Laser-Assisted Dynamics on Metallic Surfaces
using Ultrafast X-Rays
byLuis Miaja Avila
B.S., Tecnológico de Monterrey, 2002

A thesis submitted to the
Faculty of the Graduate School of the
University of Colorado in partial fulfillmentof the requirements for the degree ofDoctor of Philosophy
Department of Physics
2009This thesis entitled:
Laser-Assisted Dynamics on Metallic Surfaces using Ultrafast X-Rays
written by Luis Miaja Avila
has been approved for the Department of Physics

Prof. Henry C. Kapteyn

Prof. Margaret M. Murnane

Date

The final copy of this thesis has been examined by the signatories, and we find thatboth the content and the form meet acceptable presentation standards of scholarly
work in the above mentioned discipline.

iii
Miaja Avila, Luis (Ph.D., Physics)
Laser-Assisted Dynamics on Metallic Surfaces using Ultrafast X-Rays
Thesis directed by Prof. Margaret M. Murnane and Prof. Henry C. Kapteyn

Time-resolved photoelectron spectroscopy is a powerful technique for the study ofreal-time electron dynamics on metallic surfaces. These studies are performed in pumpprobe geometries, where a pump pulse excites a dynamic process and a time-delayedprobe monitors changes in the system. Furthermore, recent progress in ultrafast lasers
and high-harmonic generation has opened up a new area of surface science, where these
two light sources are the standard tools for the study of ultrafast surface dynamics. Another critical discovery that has made it possible to study high-energy and femtosecond
time-scale atomic dynamics is the laser-assisted photoelectric effect. However, until 2005
this effect had only been observed in gas-phase atomic systems, limiting its applicability
to the study of isolated atoms or molecules.
Using time-resolved photoelectron spectroscopy, this thesis presents work demonstrating that the physics of the laser-assisted photoelectric effect can be expanded tosolid-state systems. This result represents the laser-assisted version of the original manifestation of the photoelectric effect. This thesis also presents experimental data showing that laser-assisted photoemission from surfaces can be distinguished from otherlaser-surface interaction phenomena, such as hot electron excitation, above-thresholdphotoemission, and space-charge acceleration.
Additionally, by using surface laser-assisted photoemission and laser-assisted Auger
decay, a direct measurement of the lifetime of core-excited states of an atom adsorbed
onto a surface is presented. Finally, this research demonstrates that using a dressing
laser at longer wavelengths dramatically reduces above-threshold photoemission andspace-charge effects while enhancing the surface laser-assisted photoemission signal.

Dedication

Para mi amá y mi apá.
Para mi mejor amiga y esposa Tamra.

v

Acknowledgements

During the last six and a half years I’ve had the fortune to work with so many
wonderful people to whom I’ll be always grateful. First of all I would like to thankmy advisors, Henry Kapteyn and Margaret Murnane. Their guidance and support
were fundamental for the development of this work. It has been my honor to work forthem. It has also been a pleasure to work and learn from Martin Aeschlimann, mythird advisor and life coach. His support and passion for science sparked my interest in
surface science. I also give my acknowledgment to John Gland, another great advisorand friend to whom I owe all the chemistry I know, and Michael Bauer, a great scientist
I wish I had worked with more closely. Also, I would like to thank Dan Dessau andJim and Lorrie Shepard for their friendship, support, and encouragement to come to
Boulder for grad school.
I would also like to thank the two amazing post-docs with whom I worked, Tim
Lei and Guido Saathoff. Thanks to Tim for introducing me to surface science, forteaching me how to run the experiments, and for always being patient with me. Thanks
to Guido for showing me that patience and optimism are fundamental to make things
happen, and for all his help and suggestions to get these experiments to work. I will
always be amazed with his incredible understanding of science.
I would also like to acknowledge Ra’anan Tobey, Dave Gaudiosi, Ariel Paul andAmy Lytle, four great grad students and friends from whom I’ve learned a lot. Stefan
Mathias is another great friend and coworker who helped me get these experiments

vi
running. I want to thank all the KM group members who made the lab a fun place
to work: Mark Siemens, Richard Sandberg, Jing Yin, Mike Grisham, Etienne Gagnon,
Erez Gershgoren, Steffen Hädrich, Jim Holtsnider, Daisy Raymondson, Chan La-ovorakiat, Arvinder Sandhu, Xibin Zhou, Robynne Lock, Oren Cohen, Nick Wagner,
Andrea Wüest, Scott Hoch, Rachael and Matt Tearle, Tenio Popmintchev, Alon Bahabad, Qing Li, Paul Arpin, Mike Gerrity, Ethan Townsend, Matt Seaberg, Craig Hogle,
Kim Reid. From KM Labs I would like to acknowledge: Sterling Backus, Hsiao-hua Liu,
Neil Anderson, Dirk Mueller, and Kendall Read. I also want to thank other friends from
JILA: my best friend Manuel Castellanos Beltrán, Javier von Stecher, Nathan FlowersJacobs, Konrad Lehnert, and many others I may have forgotten.
And of course I must acknowledge the fantastic staff at JILA: Todd Asnicar, Hans
Green, Blaine Horner, Tom Foote, Kim Hagen, Tracy Keep, James Fung-A-Fat, Dave
Alchenberger, Leslie Czaia, Pam Leland, Lisa Roos, Randall Holliness, Brian and Agnes
Lynch, Dave Erickson, Jeff Sauter, Mike Paige, J. R. Raith, Ed Holliness, Joel Frahm,
Jim McKown, Carl Sauer, David Tegart, Julie Phillips, Lynn Hogan, Sam Jarvis, Andy
Hytjan, Doug Hogoboom, Peter Ruprecht, Corinne Hammond.
Finally I would like to pay the greatest tribute to my family. To my parents andsiblings for being a great source of motivation and inspiration. And to my wife Tamrafor her smile, love, and eternal support.

viiContents

Chapter
1 Introduction

1

2 Theory

10

2.1

High-Harmonic Generation . . . . . . . . . . . . . . . . . . . . . . . . .

10

2.1.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

10

2.1.2

Theoretical treatment . . . . . . . . . . . . . . . . . . . . . . . .

11

2.1.3

Phase-matching . . . . . . . . . . . . . . . . . . . . . . . . . . . .

19

Laser-Assisted Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . .

23

2.2.1

Volkov wave . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

23

2.2.2

Laser-assisted scattering . . . . . . . . . . . . . . . . . . . . . . .

26

2.2.3

Laser-assisted photoelectric effect . . . . . . . . . . . . . . . . . .

30

2.2

3 Experimental Setup

34

3.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

34

3.2

EUV and IR Beamlines . . . . . . . . . . . . . . . . . . . . . . . . . . .

34

3.2.1

IR beamline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

36

3.2.2

EUV beamline . . . . . . . . . . . . . . . . . . . . . . . . . . . .

37

3.3

UHV Chamber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

40

3.4

Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

43

3.5

Finding Temporal and Spatial Overlap . . . . . . . . . . . . . . . . . . .

45

viii
4 Laser-Assisted Photoemission from Surfaces

49

4.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

49

4.2

Aspects of Surface LAPE . . . . . . . . . . . . . . . . . . . . . . . . . .

49

4.2.1

Momentum conservation and ground state dispersion . . . . . . .

50

4.2.2

Resonant interband and intraband transitions . . . . . . . . . . .

51

4.2.3

Non-resonant interband transitions . . . . . . . . . . . . . . . . .

52

4.2.4

Dressed band structure . . . . . . . . . . . . . . . . . . . . . . .

53

4.2.5

Competing strong field effects . . . . . . . . . . . . . . . . . . . .

53

4.3

Above-Threshold Photoemission . . . . . . . . . . . . . . . . . . . . . .

56

4.4

Extraction of the Sideband Structure . . . . . . . . . . . . . . . . . . . .

58

4.5

Laser Intensity Dependence of LAPE from Surfaces . . . . . . . . . . . .

71

4.6

Hot Electrons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

75

4.7

Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

78

5 Direct Measurement of Core-Level Relaxation Dynamics in Complex Systems

80

5.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

80

5.2

Sample Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

84

5.3

Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . .

84

5.4

Conclusion

92. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

6 Laser-Assisted Photoemission with Long-Wavelength IR Pulses

94

6.1

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

94

6.2

Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . .

96

6.3

Conclusion

7 Outlook
7.1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
103

Angle-Resolved Photoemission with High Harmonics . . . . . . . . . . . 103
7.1.1

Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

ix
7.1.2

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

7.1.3

ARPES using femtosecond high harmonic light . . . . . . . . . . 107

7.1.4

Energy distribution curves . . . . . . . . . . . . . . . . . . . . . . 109

7.1.5

Momentum distribution curves . . . . . . . . . . . . . . . . . . . 112

7.1.6

Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

7.2

Chemisorbed System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

7.3Interatomic Coulombic Decay . . . . . . . . . . . . . . . . . . . . . . . . 116

7.4

Double Auger Decay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

8 Conclusion

120

Bibliography

122

Appendix
A Laser-Assisted Dynamics

133

A.1 Ponderomotive Potential and Maximal Classical Excursion . . . . . . . . 133
A.2 Volkov Wave Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
A.3 S-Matrix Element in Laser-Assisted Scattering . . . . . . . . . . . . . . 136
B Time-of-Flight Electron Analyzer

138

B.1 Electron Analyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
B.2 Time to Energy Conversion . . . . . . . . . . . . . . . . . . . . . . . . . 139

xFiguresFigure1.1

Schematic representation of bichromatic 2PPE. The electron is excitedfrom the occupied initial state |ii to the intermediate state |ni and final
state |f i by the pump (3hν) and probe (hν) laser pulses. (i) Electrons
are detected as a function of kinetic energy for fixed delay td between
pump and probe pulses or (ii) for a fixed kinetic energy as a function of
the time delay between pump and probe pulses. Adapted from reference [1].

1.2Electromagnetic spectrum with emphasis on the extreme ultraviolet andsoft x-ray portions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.3

2

4

The principle behind the laser-assisted photoemission process for atoms
in the “soft photon” limit. LAPE is described in two steps. First, theground state electron is photoemitted into an excited state in the continuum by the XUV pulse, neglecting the influence of the IR field. Then,the photoemitted electron evolves as a free electron in the IR field, unaffected by the atomic potential. This results in a redistribution of theelectrons in the continuum by absorption and stimulated emission of IR
photons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5

xi
1.4

Compilation of experiments that studied LAPE from atoms. a) Upper:
HHG photoelectron spectra of He obtained in the presence (solid line)
and absence (dashed line) of the laser pulse. Notice the appearance ofsidebands in the presence of the laser pulse. Lower: Height of the 11 eV
PE peak as a function of delay. Gaussian fit (FWHM = 138 fs) to the datais shown as a solid curve and indicates a soft x-ray pulse duration of 120
fs. From reference [2]. b) Upper: Temporal evolution of Kr photoelectron
spectra following core excitation. Note the manifestation of sidebands atboth the 4p and Auger peaks. Lower: Temporal evolution of the 4p andAuger sideband heights. The lifetime of the Kr core hole can be obtained
from these data. Adapted from reference [3]. c) Left: Experimental setup
for the observation LAPE using the FEL and an optical laser. Right: Partof the photoelectron spectrum in the region of the He 1s−1 main line andthe high-energy sideband. From reference [4]. . . . . . . . . . . . . . . .

7

2.1

Pictorial representation of the three-step model. From reference [5].

11

2.2

Photoionization processes for different laser intensities: a) multiphoton. .

absorption (γ À 1), b) tunneling (γ < 1), and c) above barrier ionization(γ ¿ 1). The gray line corresponds to the Coulomb potential, while theblue line corresponds to the Coulomb potential modified by the laser field. 13
2.3

Possible paths for the electron during rescattering as a function of laser
phase, and several selected values of the phase of the laser at ionization.
Intersection with the x-axis indicates the possibility of recombination.
Adapted from reference [6]. . . . . . . . . . . . . . . . . . . . . . . . . .

2.4

16

Energy of the returning electron as a function of laser phase. The red
dotted line indicates the maximum kinetic energy (3.17 Up ) at phase valueof ≈ 18◦ . Adapted from reference [7]. . . . . . . . . . . . . . . . . . . . .

17

xii
2.5

Normalized HHG intensity as a function of phase mismatch. Adaptedfrom reference [7]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.6

21

The high-harmonic and laser light go out of phase as they propagate
through the medium. The coherence length Lc is defined as the length
over which HHG and laser light remain in phase. If phase matching(∆k = 0, red) is achieved, the signal will increase quadratically. Larger
phase mismatch values (shorter coherence lengths) result in lower HHG
signal (blue → ∆k = π/(2Lc ), and green → ∆k = π/Lc ). . . . . . . . . .

3.1

Experimental setup for observing the laser-assisted photoelectric effectfrom surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.2

22

35

Picture of a HHG waveguide v-groove holder engineered by the KapteynMurnane group. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

37

3.3

Reflectivity curve for a single Mg:SiC multilayer mirror. . . . . . . . . .

38

3.4

Reflectivity curve for a single Si:Mo multilayer mirror. . . . . . . . . . .

39

3.5

Transmission of the aluminum and zirconium filters. The green curve
represents the transmission of an oxidized aluminum filter. . . . . . . . .

3.6

39

Geometry for the photoemission measurements: p-polarized IR light impinges on the Pt sample at an angle θ with respect to the surface normal.
ϑ = 90 − θ is the angle of the polarization vector with respect to thesurface normal. The detector is titled by 20◦ with respect to the planeof incidence. The corresponding observation angle ϑ with respect to thesurface normal is given by cos φ = cos 20◦ cos ϑ. . . . . . . . . . . . . . .

3.7

TDS for Pt(111) covered with O2 . The rate of temperature increase is 5
K/sec. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.8

42

44

Schematic of the phosphor screen, Pt(111), BBO and quartz crystals holder. 46

xiii
3.9

Schematic of experimental setup for finding temporal overlap when the
IR pulse wavelength is different than 780 nm. In this case we use of the
optical Kerr effect to find time zero. . . . . . . . . . . . . . . . . . . . .

4.1

48

Calculated IR intensity required to generate first order sideband heightsof A1 =0.1 for wavelengths of 800 nm and 1600 nm, respectively, as afunction of the kinetic energy of the electrons. For kinetic electron energies of 36 eV and an 800 nm dressing wavelength, laser intensities greaterthan 1011 W/cm2 are required. . . . . . . . . . . . . . . . . . . . . . . .

4.2

55

Multiphoton-induced photoemission spectra taken at different laser intensities ranging from 130 to 590 GW/cm2 using IR light only. ATP(above threshold photoemission) and space-charge acceleration generate
electrons with kinetic energies of tens of eV. . . . . . . . . . . . . . . . .

4.3

57

Observed photoelectron spectra from Pt(111) as a function of time-delay
between the IR and EUV beams. For -100 fs time delays, the EUV-only
spectrum (dashed line) is also shown. A slight shift of the spectrum
due to IR-induced space-charge can be seen, but this does not change
the shape of the spectrum and can thus be corrected for. The strong
modification at the Fermi edge of the time zero spectrum is due to laserassisted photoemission. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.4

60

Calculated LAPE response function using equation 4.3 assuming the generation of two sidebands. . . . . . . . . . . . . . . . . . . . . . . . . . . .

61

xiv
4.5

Photoemission spectrum at zero time delay between the EUV and IR
fields, taken from the data shown in figure 4.3. Observed photoemission
spectrum with (red line) and without (black line) the IR pulse present.
The blue line shows the fit to the EUV+IR curve by convolving the LAPE
response function from equation 4.3 with the unperturbed spectrum. The
inset shows the LAPE response function associated with the fit. . . . . .

4.6

63

Identical spectrum to that shown in figure 4.5, where the positive andnegative first-order sideband heights are allowed to vary during the fit.
However, no significant asymmetry is generated as a result of this fit. . .

4.7

64

(a) The solid line shows the square of the Bessel function A1 = J12 (x),plottedversus x2 ∝ I. The dotted line depicts the asymptote behavior for small
x: A∗1 = x2 /4. For a cross-correlation measurement, a linear intensity
dependence of A1 is required, which is only fulfilled for small x. (b)Measured cross-correlation of the IR (with 30 fs pulse duration) and the
expected ≈ 10 fs duration EUV pulses as a function of time delay. The
measured sideband heights A1 are replaced by the corresponding valuesA∗1 of the asymptote, so that linear intensity dependence is ensured forall data points. A Gaussian fit yields 33 ± 2 fs, limited by the duration of
the IR pulse duration. A Gaussian fit to the uncorrected A1 data yields
37 ± 3 fs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.8

65

LAPE spectrum taken at a different sample angle of ϑ = 5◦ . Due to thelarger d-band peak at this angle, the negative sideband is more clearlyvisible. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.9

66

LAPE time series for EUV+IR pulse separations between -40 fs and 40 fs
in steps of 5 fs. The black lines show the EUV-only data. The EUV+IR
spectra (red lines) are corrected for a 0.1 eV space-charge shift. The bluelines show the symmetric fits. . . . . . . . . . . . . . . . . . . . . . . . .

68

xv
4.10 Amplitude of the first-order (blue circles) and second-order (red squares)
sideband intensity versus time delay. The fits result in FWHM of 37 ± 5
fs and 35 ± 3 fs for the first- and second-order sidebands, respectively. .

69

4.11 Positive and negative sideband heights (upper curve) and depletion of
the d-band peak (lower curve) versus time delay. The Gaussian fits yield
36 ± 4 fs for the positive sideband, 37 ± 6 fs for the negative sideband,and 38 ± 5 fs for the depletion signal, respectively. . . . . . . . . . . . .

70

4.12 First-order sideband height as a function of the sample angle. The sample
is shown to influence the effective dressing field, because the componentof the electric field perpendicular to the surface is reduced due to boundary conditions. The data agree with the expected cos2 reduction in theeffective intensity. The inset illustrates the definition of the sample angle(surface normal) for 0◦ and 90◦ with respect to the IR polarization. . . .

72

4.13 Photoemission due to both EUV+IR (red lines) and EUV-only (blacklines) light at time zero as well as EUV+IR for a delay of -100 fs (bluelines) for different IR laser intensities. The -100 fs curves show the influence of the space-charge induced by the IR-induced low-energy electrons
on the XUV photoelectrons around the Fermi edge. At low intensities,
it results in a shift to higher energies due to acceleration. At the highest
intensity shown, the space-charge also changes the shape of the spectrum. 73

xvi
4.14 Extracted sideband intensity A1 as a function of the effective IR beam
peak intensity, perpendicular to the surface. The influence of the sample angle has been taken into account. The sideways intensity follows
the theoretically expected square of the first-order Bessel function. The
maximum of the curve is a factor of two higher than expected from theargument of the Bessel function (equation 4.1). This is within our experimental uncertainty in the determination of the effective dressing intensity
because of insufficient knowledge of the spatial overlap between EUV and
IR pulses on the sample. . . . . . . . . . . . . . . . . . . . . . . . . . . .

75

4.15 (a) Photoemission spectra around the Fermi edge for s-polarized IR lightat high laser intensity (1012 W/cm2 ). The electric field at the surface
vanishes in this case, so that no dressing is expected. However due tothe absorption of IR light, a hot electron distribution is excited, and isvisible at the Fermi edge for relative time delays later than -60 fs (timezero in this measurement). (b) Photoemission spectra for p-polarized IR
light at half the intensity applied in a) (5 × 1011 W/cm2 ). Hot electrons
are visible at positive time delays. LAPE can be observed at -40 fs (timezero), clearly dominating the hot electron distribution and distinguishable
by its step-like shape. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

77

4.16 Excess hot electrons (dots) at the Fermi edge for s-polarized IR light.
These hot electrons follow a sharp rise and slow exponential decay. The
fit (dashed) yields a lifetime of about 270 ± 60 fs. This behavior is also
found for the average kinetic energy (solid line) and is consistent withexpected hot electron lifetimes. . . . . . . . . . . . . . . . . . . . . . . .

78

xvii
4.17 Excess hot electrons (dots) at the Fermi edge for p-polarized IR light. In
this case, the excess electrons show a two component structure. For large
time delays they decay exponentially. The fit results in a lifetime of 260± 80 fs, in agreement with the value found for s-polarized light (270 ± 60fs). Around time zero, the electron distribution exhibits a peak which isdue to LAPE. The average kinetic energy, which is insensitive to LAPE,
still follows the exponential decay behavior characteristic of hot electron
decay. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1

79

Schematic of the experiment. Ultrafast SXR and IR pulses are focused
into a Xe/Pt(111) surface, where the kinetic energy of the photoemitted
electrons is measured by a time-of-flight detector. An electron from theXe N4 (4d) shell is ejected by the SXR, followed by filling of the corehole by an O2,3 (5p) shell electron and ejection of a secondary (Auger)
electron from the O2,3 shell. In the presence of the IR beam, sidebands
appear in the photoelectron spectrum of both Xe and Pt. By comparing
the sideband amplitude vs time delay for the Pt and Xe, we can extract
the lifetime of the Xe 4d core hole. . . . . . . . . . . . . . . . . . . . . .

83

5.2

Photoelectron spectra for clean (red) and Xe dosed Pt (blue). . . . . . .

85

5.3

Photoelectron spectra for Xe/Pt(111) with (red) and without (black) the
presence of the IR pulse. . . . . . . . . . . . . . . . . . . . . . . . . . . .

86

xviii
5.4

Extraction of the LAPE/LAAD sideband amplitudes for Xe/Pt(111) atzero time delay between the IR and SXR beams. (a) Photoelectron spectra near the Pt d-band; (b) near the Xe Auger N OO bands; and (c) near
the Xe 4d peaks. The red and black lines represent the spectra with andwithout the IR pulse, respectively. The blue lines show the fit to the
SXR+IR curve when the LAPE response function from equation 4.3 isconvolved with the SXR-only spectrum. The insets show the extracted
LAPE/LAAD response function associated with the fit, demonstrating
the dependence of the sideband amplitudes on the photoelectron energy.

5.5

87

Photoelectron spectra from Xe/Pt(111) as a function of time delay. Negative time delays denote that the SXR pulse arrives after the IR pulse.
The time evolution of the redistribution of electrons due to the IR dressing at the Pt d-band and at the Xe Auger photoelectron peaks can beobserved. The spectra shown in the lineouts correspond to the photoelectron spectrum at zero (red) and at -50 (black) fs time delay between
the SXR and the IR pulses. . . . . . . . . . . . . . . . . . . . . . . . . .

5.6

89

Sideband height vs time delay for the Pt d-band and Xe Auger photoelectrons. The sideband height for the Pt d-band (red curve) corresponds
to a cross-correlation between the SXR and the IR pulses. In contrast,
the Auger sideband height (black curve) is clearly shifted by 5.9 ± 0.2 fs
with respect to time zero, and is also broadened with respect to the Pt
d-band curve. The shift and broadening are due to the inherent lifetimeof the Xe 4d core hole. From these curves we extract a Xe 4d core-hole
lifetime of 7.1 ± 1.1 fs.

5.7. . . . . . . . . . . . . . . . . . . . . . . . . . .

91

Xe 4d photoelectron lines measured at 117.0 eV photon energy. The solidline shows the result of the least-square fit to the data points given bycircles. Figure reproduced from reference [8]. . . . . . . . . . . . . . . .

92

xix
6.1

Laser-assisted photoelectric effect with (a) 780 nm and (b) 1300 nm driving pulses. Both spectra are measured at zero time delay between the
EUV and IR pulses. The red and black lines represent the photoemission spectra with and without the IR pulse present, respectively. The
blue lines show the fit to the EUV+IR curve when the LAPE response
function from equation 4.3 is convolved with the EUV-only spectrum.
The insets show the LAPE response functions associated with the fit. In(a) the 780 nm pulses with peak intensity I780nm = 1.4 × 1011 W/cm2
generate sidebands A1(780nm) = 0.13 ± 0.01, while in (b) the 1300 nm
pulses with peak intensity I1300nm = 2.4 × 1010 W/cm2 generate sidebands A1(1300nm) = 0.18 ± 0.01. Compared with the 780 nm pulses, the1300 nm pulses create a greater LAPE signal at much lower intensities.

6.2

97

Photoemission spectra with EUV pulses and (a) 780 nm pulses (b) 1300
nm pulses. Black curves represent the spectra with the EUV light only,
while red curves represent the spectra in the presence of both EUV and
IR pulses at zero time delay. In the lower energy range, the difference
between the red and black curves is caused by above threshold photoemission. At the Fermi edge, the difference is caused by the laser-assisted
photoelectric effect. The intensity required for 780 nm pulses to obtainobservable LAPE signal introduces a large amount of photoelectrons in
the low energy range up to 23 eV. In contrast, with the 1300 nm pulses,
the intensity used produces ATP photoelectrons with kinetic energies ofless than 7 eV. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

99

xx
6.3

Comparison of the space-charge effect around the Fermi edge at -100 fs
time delay. For 780 nm pulses, the large amount of low-energy photoelectrons generated through ATP causes a shift of the whole spectrum aroundthe Fermi edge. This effect is greatly suppressed with 1300 nm pulses,
because fewer photoelectrons are generated from the IR pulse throughATP at this wavelength. . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

7.1

Angle resolved PE-spectra of the Shockley surface state and a series ofquantum-well states of 40 ML Ag/Cu(111) recorded at photon energiesof (a) 6 eV (4th harmonic of the Ti:Sapphire oscillator) and (b) 21.22 eV(He I line of the discharge VUV-lamp). An increase in photon energy
enables access to electronic states at higher binding energies and extends
the experimentally accessible momentum space. . . . . . . . . . . . . . . 106

7.2

Photoemission maps of the Cu(111) sp-band at finite angle with (a) the
He II line and (b) the HHG light source, after selecting the 27th harmonic. The analyzer resolution was set to 200 meV. The HHG-spectrum
is broadened due to the energy bandwidth of 801 ± 10 meV of the fsHHG pulses. The red lines mark the integration areas for the energy andmomentum distribution curves as shown in figures 7.3 and 7.4. Note that
there are no harmonic sidebands observable. . . . . . . . . . . . . . . . . 109

xxi
7.3

(a) Electron distribution curves EDC extracted from the photoemission−1

maps in figure 7.2 (kk = 1.15 Å

). (b) Gaussian fits of the sp-band

peak. The deconvolution of the Gaussian of the sp-band peak in the
HHG-spectrum with the Gaussian linewidth of the sp-band peak in the
He II spectrum gives a Gaussian bandwidth of 801 ± 10 meV for the
HHG-light. (c) EDC extracted from the photoemission maps in figure−1

7.2 at a different kk value (kk = 1.25 Å

). The blue EDC is derived byconvoluting the original He II spectrum with a Gaussian of 801 meV tomimic the broadening due to the bandwidth of the HHG light. . . . . . 110
7.4

Momentum distribution curves (MDCs) extracted from the photoemission maps in figure 7.2. The MDC marked by open squares was derived
after convoluting the He II EDCs with the HHG bandwidth of 801 meV
for all different kk values. . . . . . . . . . . . . . . . . . . . . . . . . . . 113

7.5a) Experimental Auger-electron spectrum of atomic cesium after background substraction (from reference [9]). b) Photoabsorption spectra of
the C 1s → 2π transition for gas-phase CO and CO adsorbed on Pt(111)(from reference [10]). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116

7.6a) After excitation, the inner valence (inner) hole is localized in monomer
A. b) Emission of an outer valence (outer) electron from monomer B after
the transition of energy from the neighboring monomer A. c) Doubly
ionized cluster with two outer valence holes localized in two different butneighboring monomers. Adapted from reference [11]. . . . . . . . . . . . 117

B.1 Geometrical schematics of a Time-of-Flight (TOF) analyzer. . . . . . . . 138
B.2 Conversion from the acquired time of flight distribution N (t) to an energy
spectrum N (E). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

xxii
B.3 Time of flight (top) to energy (bottom) conversion. The direct opticalreflection of the sample induces the optical peak, which is used as time
zero. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

Chapter 1
Introduction

An important motivation for the study of surfaces is the fundamental understanding of heterogeneous catalysis. The idea that the presence of a solid could accelerate achemical reaction without modifying the solid was what triggered the development of
the field of surface science. Since then, the goal of surface science has been to build
an understanding of electronic, atomic and molecular dynamics on surfaces. Over theyears, different experimental techniques have been developed to better explore the interaction between adsorbates (atoms or molecules) and surfaces. These techniques include
low-energy electron diffraction (LEED), used for the determination of surface structure;
inverse photoemission spectroscopy (IPS), which studies the unoccupied electronic structure of surfaces, thin films, and adsorbates; Auger electron spectroscopy (AES), used forthe characterization of surface adsorbates; and ultraviolet and x-ray photoelectron spectroscopies (UPS and XPS, respectively), which measure the elemental composition andelectronic state of the solid. These last two techniques have been extensively applied insurface science because of their excellent surface sensitivity. Surface sensitivity in UPS
and XPS arises from the idea that emitted electrons usually have energies ranging from
20 eV to 2 keV, and at these values, electrons have a short mean free path in a solid.
The escape depth of electrons [12] is therefore localized to within a few nanometers of
the target surface, thus probing only the first few layers of the solid.
However, techniques that can directly observe the dynamics of adsorbates on sur-2
faces were not developed until later. The main difficulty in resolving these processes
comes from the characteristically short time scale, between femtoseconds and picoseconds, for an adsorbate to vibrate, rotate or translate. Typical light sources for XPS
emit photons with “long” pulse durations of several tens of picoseconds, while UPS
helium lamps emit photons continuously. Therefore, conventional UPS and XPS techniques cannot be utilized in this case. The development of femtosecond Ti:Sapphirelaser systems was crucial for the improved understanding of surface processes. The ultrashort pulse duration delivered by these laser systems allowed the real-time study ofdynamic surface processes through pump-probe techniques such as time-resolved two-

Emission rate

photon photoemission (TR-2PPE), see figure 1.1.
(ii)

(i)
E F +4hν
Ef

|f>
hν

EnergyE vac
E n |n>Kin. energy

Pump-probe delay

Emission rate

3hν

EF
Ei

|i>

0
td
Pump-probe delay

Figure 1.1: Schematic representation of bichromatic 2PPE. The electron is excited fromthe occupied initial state |ii to the intermediate state |ni and final state |f i by the pump(3hν) and probe (hν) laser pulses. (i) Electrons are detected as a function of kinetic
energy for fixed delay td between pump and probe pulses or (ii) for a fixed kinetic
energy as a function of the time delay between pump and probe pulses. Adapted fromreference [1].

3
Two-photon photoemission (2PPE) [13,14] spectroscopy has the unique capabilityof directly observing electrons with specific energy and momentum within the skin-depthof a surface. In addition, 2PPE combines characteristics of traditional photoemission
and inverse photoemission spectroscopies, which makes it the method of choice for the
study of ultrafast electron dynamics at surfaces. Initial experiments with picosecond
time-resolution focused on the electron-phonon scattering in metals [15] and the dynamics of thermalized band-edge carriers in semiconductors [16]. Improvements in energy
and time resolution allowed the study of unoccupied bands and surface states in metals [13]. With the further development of ultrafast lasers, time-resolved two-photon
photoemission became a powerful tool to analyze the dynamics of non-thermalized electrons (“hot electrons”) and unoccupied surface states directly in the time domain [17].
The first applications of TR-2PPE on femtosecond time scales included measurements ofelectron-electron scattering rates in metals [17–19] and image-potential-state lifetimes
on metallic surfaces [20]. Further applications of ultrafast lasers in TR-2PPE led tothe discovery of a novel mechanism of adsorbate desorption from metal surfaces in the
femtosecond time regime, mediated by direct charge transfer of “hot electrons” [21, 22].
This opened a new pathway in photochemical reactions.
The photon energy used in these TR-2PPE experiments must be lower than thework function of the substrate, thus below 5 - 6 eV. In this energy regime, TR-2PPE
experiments only probe a relatively restricted bandwidth of the surface electronic states,
specifically those unoccupied states located a few electronvolts around the Fermi edge.
Nevertheless, the study of deeper electron levels is also important because these levels
contain information on the surface structure and the chemical and magnetic state of thesurface. In order to perform these studies, the ultrafast photon sources need to extend
their excitation energies into the extreme-ultraviolet (EUV) and x-ray regions of thespectrum (see figure 1.2).
In the late eighties, Rhodes [23], Manus [24] and coworkers described for the first4

Figure 1.2: Electromagnetic spectrum with emphasis on the extreme ultraviolet andsoft x-ray portions.

time the generation of high-order harmonics (HHG) and reported the conversion of theTi:Sapphire amplifier output to ultrashort coherent light pulses in the VUV, EUV and
x-ray regions of the spectrum. So far, HHG photon energies on the order of 1 keV [25–28]
and pulse durations as short as 80 attoseconds [29–31] have been observed. It is thislatter property that makes HHG a unique tool for the study of dynamic processes whenhigh temporal resolution is required. Therefore, using a high-order harmonic source ina surface science PE experiment within a pump-probe scheme provides exciting insights
into dynamic surface processes on extremely short time scales. Haight et al., pioneered
the use of HHG in surface science by demonstrating that HHG can be used as a lightsource for valence- and core-level photoelectron spectroscopy [32]. They recognized
the two main advantages of an HHG light source compared to conventional, shortwavelength light sources. Namely, that the harmonic source is both small-scale (tabletop) and tunable, and that the short pulse structure is capable of real-time experiments
on a femtosecond scale.
To date, high harmonic generation has been successfully used to study electron
relaxation in materials [33–36], surface adsorbate dynamics [37, 38], photoacoustic dynamics [39], and molecular dissociation [40]. More recently, high harmonics have been

5
used as a pump beam to study x-ray-induced molecular dynamics [41]. Although photon energies > 1 keV can be generated using high harmonic emission, the photon flux
is too low above 100 eV to be employed routinely in experiments.
Time-resolved experiments using ultrafast high-harmonic light have also been
greatly expanded by the application of laser-assisted, strong-field dynamic processes.
When an electron is photoejected in the presence of an intense laser field of 1011 W/cm2 ,the electron is accelerated by the laser field. If the interaction occurs continuously over
several optical cycles, the electron undergoes oscillations. This leads to ponderomotiveenergy shifts, and, in the presence of atomic nuclei or solids that can absorb momentum, to the generation of sidebands in the photoelectron spectrum. These sidebands

continuum

correspond to the absorption and stimulated emission of photons from the laser field.

ħωIR

ħωXUV
E=0

ground state

Figure 1.3: The principle behind the laser-assisted photoemission process for atoms in
the “soft photon” limit. LAPE is described in two steps. First, the ground state electron
is photoemitted into an excited state in the continuum by the XUV pulse, neglecting
the influence of the IR field. Then, the photoemitted electron evolves as a free electronin the IR field, unaffected by the atomic potential. This results in a redistribution of
the electrons in the continuum by absorption and stimulated emission of IR photons.

This laser-assisted photoeffect (figure 1.3) is considered to result from “dressing”
of the free-electron wave function; i.e., the electron evolves in a state where the free

6electron is driven by the IR laser field. These dressed states are known as Volkov waves.
Laser-assisted electron dynamics were first observed in electron-atom scattering in thepresence of a strong CO2 laser field [42]. Later, this process was applied to time-resolved
measurements of laser-assisted Auger decay (LAAD) [43], using ultrashort-pulse, soft
x-ray plasma sources [44]. Laser-assisted photoemission (LAPE) was first observed
by Glover et al. [2], using high harmonic sources. In these experiments, atoms were
simultaneously irradiated by XUV and intense infrared (IR) light. The presence of
the IR laser modifies the XUV photoelectron spectrum. In both cases, LAAD and
LAPE, the observation of laser-assisted dynamics indicates the emission time of thephotoelectrons or Auger electrons. By varying the time delay between the XUV and IR
pulses, the LAPE signal provides an exact timing synchronization between the pulses,
as well as providing a cross-correlation between the laser and XUV fields.
More recently, LAPE and LAAD have been combined to measure ultrafast, corelevel dynamics in Krypton atoms [3]. In this experiment, LAPE provides time zero while
LAAD yields the emission-time behavior of the delayed Auger electrons. In this way,
the lifetime of an M-shell vacancy in Krypton could be measured directly in the time
domain. Figure 1.4 contains a compilation of experimental results of LAPE from atoms.
It has also been shown that with XUV pulse durations in the sub-optical cycle domain,
LAPE becomes sensitive to the IR electric field rather than the intensity envelope,
giving rise to sub-femtosecond resolution in time-resolved experiments [29, 30, 45–47].
Recently, LAPE has been successfully demonstrated with femtosecond XUV pulses fromthe free-electron laser FLASH at DESY in Hamburg [4].
However until 2006, laser-assisted photoemission and laser-assisted Auger decay
had only been observed in gas-phase atomic systems. This limits the applicabilityof the physics of laser-assisted dynamics to the study of isolated atoms or molecules.
Furthermore, this constraint also represents a practical limit to the use of LAPE for
XUV pulse characterization, since both atomic photoionization cross-sections and the

7
a)

b)

c)

Figure 1.4: Compilation of experiments that studied LAPE from atoms. a) Upper: HHG
photoelectron spectra of He obtained in the presence (solid line) and absence (dashedline) of the laser pulse. Notice the appearance of sidebands in the presence of the laser
pulse. Lower: Height of the 11 eV PE peak as a function of delay. Gaussian fit (FWHM= 138 fs) to the data is shown as a solid curve and indicates a soft x-ray pulse durationof 120 fs. From reference [2]. b) Upper: Temporal evolution of Kr photoelectron spectra
following core excitation. Note the manifestation of sidebands at both the 4p and Auger
peaks. Lower: Temporal evolution of the 4p and Auger sideband heights. The lifetimeof the Kr core hole can be obtained from these data. Adapted from reference [3]. c)
Left: Experimental setup for the observation LAPE using the FEL and an optical laser.
Right: Part of the photoelectron spectrum in the region of the He 1s−1 main line andthe high-energy sideband. From reference [4].

8obtainable photon flux from high-harmonic sources decrease rapidly with increasing
photon energy. The result has been that, due to the low target densities in the gas phase,current XUV pulse duration measurements are limited to photon energies below 100 eV.
Other approaches for characterizing ultrashort XUV pulses, such as the autocorrelation
using two-photon absorption [48, 49], are even more experimentally challenging at very
high photon energies. To date, these techniques have only been demonstrated at photon
energies lower than 50 eV.
Our group reported the first observation of the laser-assisted photoelectric effectin solid-state systems [50]. In our work, a clean Pt(111) single crystal was used as thesolid surface, since it exhibits a large density of d-states at the Fermi edge, with a characteristic peak-like structure in the XUV photoelectron spectrum. In the presence ofan intense laser field, sidebands appeared in the Pt(111) photoemission spectrum. We
showed that the modification of the photoelectron spectrum by LAPE can be distinguished from simple heating of the electrons by the IR beam in three ways: i) by varying
the laser polarization, ii) by measuring the mean energy of the photo-ejected electrons
and verifying that it does not change, and iii) by successfully fitting the photoelectron
spectrum to theory. We also demonstrated that surface LAPE can be used to measure
the pulse duration of XUV pulses. Since then, surface LAPE has been successfully
combined with attosecond soft x-ray pulses [51] and with femtosecond XUV pulses fromthe FLASH free-electron laser [52]. Recently, we reported the first direct time-resolved
observation of core-level relaxation dynamics in a complex surface-adsorbate system bycombining surface LAPE and LAAD [53].
This thesis presents a detailed description of the above mentioned experimental
results. The work presented here is organized as follows: Chapter 2 discusses the theoryof high-harmonic generation and laser-assisted photoemission. Chapter 3 presents a
detailed overview of the experimental setup used for the observation of surface LAPE.
Chapter 4 reports the first experimental observation of surface LAPE and distinguishes

9surface LAPE form other laser-surface interaction phenomena. The results presented inchapter 4 agree with the atomic-based model presented in chapter 2. By combining surface LAPE and laser-assisted Auger decay, chapter 5 presents the direct time-resolved
measurement of a core-excited state lifetime of an atom adsorbed onto a surface. This
result is fundamental for the understanding of charge-transfer processes between substrates and adsorbates. Chapter 6 shows that using a dressing laser at longer wavelengths dramatically reduces undesirable laser-surface phenomena while enhancing thesignal from surface LAPE. These results enable ultrafast studies of surface-adsorbate
systems and attosecond electron dynamics over a wider energy range. Chapter 7 proposes future experiments for the study of electron dynamics on surfaces. This chapter
places special emphasis on future modifications to the experimental setup that will allow
the parallel detection of energy and momentum of the photoemitted electrons. Finally,
chapter 8 summarizes the experimental results presented in this thesis.

Chapter 2Theory2.1

High-Harmonic Generation

2.1.1

Introduction

The last two decades have been a revolutionary period in the development of
ultrashort light sources in the extreme-ultraviolet (EUV) and soft x-ray (SXR) regionsof the electromagnetic spectrum. This has happened in part due to the improvement of a
new generation of ultrafast lasers [54,55], which can generate pulses with durations of ≤10 fs. When these intense femtosecond laser pulses are focused into a gas, the interaction
between the light pulse and the electrons of the atoms in the gas is so strongly nonlinearthat high harmonics of the laser frequency are radiated. The high-energy photons fromthis process extend into the soft x-ray region of the spectrum [5,28]. Since all the atoms
experience a similar coherent light field, the x-ray emissions from individual atoms arecoherent. Therefore, a coherent x-ray beam is emitted in the forward direction, colinearwith the fundamental laser light.
Because of the ultrashort pulse duration at short wavelengths of the light pulses
generated through high-harmonic generation (HHG), a new window through which toobserve nature is available. Due to the short wavelength, HHG light allows the imaging
of small features, since the resolution of an optical system is proportional to the wavelength of the light [56]. Analogously, HHG light sources allow for the writing of small

11patterns via photolithography. Furthermore, ultrafast x-ray pulses have the potential
to directly monitor atomic motion in chemical and material reactions [36, 37, 40, 41, 57].
Over the last several years, high-harmonic generation has progressed from a novel
nonlinear process to a robust table-top source of ultrafast high-energy photons. A
fundamental part of this improvement was based on the better understanding of thisprocess. In the next section the theoretical treatment of HHG will be reviewed.
2.1.2

Theoretical treatment

As mentioned before, high-harmonic generation is a term used to describe thenonlinear interaction between an intense laser pulse and a medium (usually a gas) that
results in the generation of harmonics of the driving laser field. This process can be
distinguished from low-order harmonics in that it cannot be described by perturbation
theory. Some of the unique characteristics of high-harmonic generation are:
• A sharp cutoff where the high-harmonics signal drops rapidly.
• A long plateau of harmonics with similar intensities.
• Intense low-order harmonics, whose intensities follow perturbation theory.

Femtosecond pulse

Gas

X-ray
Accelerated electron

Figure 2.1: Pictorial representation of the three-step model. From reference [5].

The theory of HHG has been the subject of extensive investigation over the lasttwo decades. An intuitive physical interpretation of HHG has been developed, primarily

12by Ken Kulander, Paul Corkum, and co-workers, that explains HHG as a three-step“rescattering” process [58, 59]:(1) Ionization of the atom.
(2) Classical acceleration of the free electron by the laser field.
(3) Recombination of the electron with the parent ion.
The first step in the HHG process occurs when the electric field of the driving
laser is sufficient to ionize the target atom. There are three ways to ionize an atom:
multiphoton, tunnel, and above barrier ionization (see figure 2.2). The Keldysh parameter, γ, is the common yardstick used to determine which of these various ionization
processes occurs [60]. It is defined as the ratio of the laser frequency to the tunnelingfrequency.
sωlaserγ==
ωtunnel

Ip
,
2Up

(2.1)

where Ip is the ionization potential of the atom, and Up is the ponderomotive potential
or the energy gained by the electron in an oscillating field (see Appendix A). In termsof the laser intensity I in W/cm2 and the wavelength λ in µm, the ponderomotive
potential, in electronvolts, is given by:Up ≈ 9.33 × 10−14 Iλ2 ,(2.2)

If the laser intensity is small (γ À 1), then multiphoton ionization is dominant. In
this regime, the effective potential is only slightly modified from the Coulomb potential
by the laser field and ionization occurs by the absorption of N photons (figure 2.2(a)).
In this case, the ionization can be treated as a perturbative process. Tunnel ionization
becomes the dominant process at larger laser intensities, where γ < 1 (figure 2.2(b)).
In this regime, the effective potential is severly distorted by the laser field, allowing thea)13
EnergyPositionb)

EnergyPositionc)EnergyPosition

Figure 2.2: Photoionization processes for different laser intensities: a) multiphoton
absorption (γ À 1), b) tunneling (γ < 1), and c) above barrier ionization (γ ¿ 1). The
gray line corresponds to the Coulomb potential, while the blue line corresponds to the
Coulomb potential modified by the laser field.

14electron to tunnel through the atom. An expression for the tunnel ionization probabilityof an atom in an oscillating field, which is known as ADK ionization rate, was developedby Ammosov, Delone, and Krainov [61]. For the typical situation of neutral Argon(Ip = 15.76 eV) interacting with an 800 nm laser pulse, tunnel ionization becomes
the dominant mechanism for intensities Ip > 1014 W/cm2 . Tyical intensities in HHG
experiments are > 1014 −1016 W/cm2 , making tunnel ionization the dominant ionization
mechanism. For very intense optical pulses (γ ¿ 1), the Coulomb barrier may besuppressed below the ionization potential while there still exists a large population in
the ground state (figure 2.2(c)). This regime is called above-barrier ionization.
After ionization, the next step is the acceleration of the free electron in the laser
field. The assumption that the electron is free after ionization is justified because
outside of the atomic potential, the laser field is much greater than the Coulomb potential. Furthermore, the electron and the field, due to the large number of statesavailable to the electron, may be treated classically. The electric field is given byE(t) = E0 cos (ωt)êx + αE0 sin (ωt)êy , where E0 is the field strength, ω is the laser
frequency and α is the ellipticity (±1 for circularly polarized light, 0 for linearly polarized light), and the electron’s equations of motion (equations 2.3–2.6) are obtained byintegrating F(t) = ma = eE(t),eE0sin ωt + v0x
ωmeE0x(t) = − 2 cos ωt + v0x t + x0ω m
αeE0vy (t) = −cos ωt + v0yωm
αeE0y(t) = − 2 sin ωt + v0y t + y0ω mvx (t) =

(2.3)
(2.4)
(2.5)
(2.6)

where v0x , v0y , x0 , and y0 can be evaluated from the initial condition of the tunneling
electron. It is assumed that as the electron tunnels through the barrier into the continuum, it does so with zero velocity at the position where the ionization potential and15
the Coulomb + laser potential are equal. This position is usually a few Å, while theelectron’s excursion in the field is a few nm. Thus, the electron is considered to be at
the origin when it tunnels into the continuum. From equations 2.3–2.6 it is possible tosee that if the light is circularly polarized, the electron will not return to the positionof the parent ion. For high-harmonic generation linearly polarized light has to be used,since the electron must return to the parent ion.
Equations 2.3–2.6 demonstrate that the kinetic energy of the returning electron
will depend on the phase of the driving laser field at the time the electron tunnels
through the barrier. Figure 2.3 shows a one dimensional calculation of the trajectoryof the free electron for several initial phases of the laser field. This calculation showsthat if the electron is emitted between 0◦ and 90◦ phase, it will return to the position of
the parent ion. Furthermore, it is also possible to calculate the energy of the returning
electron as a function of the phase of the laser pulse when the electron tunnels throughthe barrier (see figure 2.4). Notice that during its excursion in the laser field, theelectron can gain energy up to ≈ 3.17Up . This happens when the electron is released
into the field with a phase of ≈ 18◦ . It is possible for an electron to gain more energy
than 3.17Up , but that would require for the electron to be released at a phase of ≈ 180◦or to stay in the laser field longer than one optical cycle (2.6 fs for 800 nm light), where
the ionization probability is very low [58].
The final step in the three-step model is the recombination process. An electron
returning to the parent ion can scatter elastically, ionize the ion collisionally, or emit a
photon via recombination with the ion. If the electron recombines with the parent ion
in the ground state and emits a photon, conservation of energy dictates that the photon
cannot have more energy than Ip + 3.17Up . This is known as the HHG cutoff (equation
2.7) and determines the maximum photon energy that can be emitted through HHG.

hνmax = Ip + 3.17Up

(2.7)

16

2
0 rad

1

0.07 rad−1

2

x/ (eE/mω )00.31 rad−2−3

0.72 rad−4
2.36 rad−5

2.09 rad−6

1.57 rad

−7
−8
0

0.5

1

1.5

2

2.5

3

3.5

4

Laser phase (rad)Figure 2.3: Possible paths for the electron during rescattering as a function of laser
phase, and several selected values of the phase of the laser at ionization. Intersection
with the x-axis indicates the possibility of recombination. Adapted from reference [6].

17

3.5
3

KE / UP

2.5
2
1.5
1
0.5
0

0

1/8
1/4
3/8
Laser phase at release (rad)1/2

Figure 2.4: Energy of the returning electron as a function of laser phase. The red dottedline indicates the maximum kinetic energy (3.17 Up ) at phase value of ≈ 18◦ . Adaptedfrom reference [7].

18This emission of light upon recombination can be calculated with the dipole operator d(t) = hψ|e r(t)|ψi [59]. The phase of the dipole operator is given by exp [−iS(ti , tf )],where S(ti , tf ), the quasi-classical action (equation 2.8), is the phase accumulated by
the electron in the laser field,

S(ti , tf ) =

Z tf
ti

Ã
dt00

[p(ti , tf ) − A(t00 )]2
+ Ip
2

!
(2.8)

where p(ti , tf ) is the momentum corresponding to an electron ionized at time ti andrecombined at tf , A(t) is the vector potential of the laser field, Ip is the ionization
potential of the atom, and ti and tf are the ionization and recombination times, respectively. The stationary points of this phase determine which trajectories have the mostsignificant contribution to the dipole moment. For a given harmonic, the dominant contribution comes from two trajectories: one with a short return time, and one with a long
return time. Therefore, these two trajectories contribute photons of the same energy.
Thus quasi-classical action also determines the phase of the emitted harmonic [62]:Φat = qωtf − S(ti , tf )/h̄

(2.9)

where ω is the driving laser angular frequency, and q is the harmonic order. Equation
2.9 shows that the phase of the emitted harmonics is dependent on the intensity of the
IR driving field; therefore, by modulating the laser intensity, it should be possible toadjust the phase relation between the driving field and the harmonic field.
The single atom response is proportional to the absolute square of the Fouriertransform of the dipole operator d(ω) = F {d(t)}. References [58] and [59] contain|d(ω)|2 plots where the same qualitative behavior of high-harmonic generation is shown:a sharp cutoff, a long plateau, and a perturbative behavior for the low order harmonics.
This three-step process will repeat itself for every half cycle of the driving field,
therefore generating odd harmonics of the driving field. This is due to symmetry con-

19siderations in the nonlinear optical process - the generation of even harmonics requires a
medium without inversion symmetry, which does not exist in a gas. If the symmetry is
broken by introducing a second pulse of a different wavelength, it is possible to generate
even and odd harmonics of the driving field.

2.1.3

Phase-matching

High-harmonic generation has proven to be a practical and useful light sourcefor photoelectron spectroscopy [63]; however, the limited photon flux generated through
HHG can limit its application in different research areas. The efficiency of HHG has been
limited by the fact that the process is not phase-matched, in that the propagation speedof the x-rays and the fundamental light are different from each other. This limits theinteraction length over which the electric field of the x-rays can build constructively. The
highest conversion efficiencies reported to date are on the order of 10−5 to 10−6 [5, 64].
From classical nonlinear optics, the field of the q th harmonic, after propagating
through a nonlinear medium of length L, is
Z L
Eq ∝

0

Efn d(z) exp [−i∆kz]dz(2.10)

where Ef is the driving field, n is the effective order of the nonlinear process, d(z) is
the nonlinear coefficient, ∆k = qkf − kq is the phase mismatch, and kf and kq are thewave vectors of the fundamental field and the q th harmonic, respectively. As can beseen from equation 2.10 and figure 2.5, the intensity of the q th harmonic at the exitof the medium is maximized when ∆k = 0. Furthermore, integrating equation 2.10,
under the assumption that Efn and d(z) are independent of the propagation directionz, allows us to obtain the relation between the intensity of the q th harmonic and thephase mismatch,

20Ã
Eq ∝ L2 sinc2

!
∆kL
.
2

(2.11)

Figure 2.6 shows the harmonic signal growth as a function of the medium lengthfor different phase mismatch values. When ∆k = 0, the harmonic signal grows quadratically with medium length, while for ∆k 6= 0 the harmonic intensity oscillates. Theseoscillations can be described in terms of a characteristic length, the coherence length:

Lc =

π
∆k

(2.12)

The coherence length is defined as the length necessary for a phase shift of π todevelop between the signal generated at two different positions along the propagation
direction. In other words, it is the length over which the harmonic signal increases
before being converted back into the fundamental field. As seen in figure 2.6, a larger
phase mismatch results in a shorter coherence length and less harmonic signal.
Early attempts at phase matching involved adjusting the laser to either focus
before or after a gas jet of a noble gas [65]. However, by using a gas jet of noble gas,
the interaction length is limited by the size of the jet, so efficient generation of highharmonics is not achieved. Later, phase matching by pressure tuning in a hollow, gasfilled waveguide was demonstrated [66, 67]. For HHG in a hollow waveguide, the phasemismatch originates from three dispersion mechanisms: i) the neutral gas (∆kn ), ii) the
free electrons (∆kp ), and iii) the waveguide (∆kw ). At the high-harmonic wavelengths,
it is assumed that the neutral gas has an index of refraction ≈ 1, and that the HHG
signal is generated with a small spatial profile such that it does not interact with the
waveguide. Under these assumptions, the phase mismatch in a hollow waveguide is:∆k = ∆kn + ∆kp + ∆kw=

Ã

λ
2πqP δn (1 − η) ηP Natm re
−
qλ −
λPatm
Patm
q

(2.13)!
−

qu2nm λ4πa2(2.14)

21

Normalized Intensity

1

0.8

0.6

0.4

0.2

0
0

0.5

1

1.5

2

2.5

3

∆kL/2 (rad)Figure 2.5: Normalized HHG intensity as a function of phase mismatch. Adapted fromreference [7].

22

4
3.5

Intensity (a.u.)

3
2.5
2
1.5
1
0.5
0
0

0.5

1
Medium length (L/Lc)

1.5

2

Figure 2.6: The high-harmonic and laser light go out of phase as they propagate throughthe medium. The coherence length Lc is defined as the length over which HHG andlaser light remain in phase. If phase matching (∆k = 0, red) is achieved, the signal will
increase quadratically. Larger phase mismatch values (shorter coherence lengths) resultin lower HHG signal (blue → ∆k = π/(2Lc ), and green → ∆k = π/Lc ).

23where λ is the fundamental wavelength, q is the harmonic order, re is the classical electron radius, unm is a constant corresponding to the propagation mode in the waveguide,a is the waveguide radius, η is the fractional level of ionization, P is the gas pressure,
Patm is the atmospheric pressure, δn = ngas − 1 is the deviation of the neutral gas index
of refraction from that of a vacuum, and Natm is the gas density at atmospheric pressure.
For small values of η there exists a pressure for which ∆k = 0, but for large η phasematching is not possible and quasi-phase matching techniques are necessary [68, 69].

2.2

Laser-Assisted Dynamics
This section will show how the conventional field-free calculations can be modified

to handle the presence of a strong field. It will also emphasize the nature of the wave
function of a free electron in a laser field, known as a Volkov wave function. This section
follows closely the work of Madsen [70].

2.2.1

Volkov wave

Strong fields are well-described by the time-dependent vector potentialA(r, t) = A0 cos(ωt − k · r),(2.15)

with k being the wave vector of magnitude k determined by the dispersion relation
ω = kc, and A0 the amplitude along the polarization vector of the field ². The electricfield E associated with the vector potential of equation 2.15 is given byE(r, t) = −∂A(r, t).
∂t(2.16)

This sections uses atomic units h̄ = me = e = a0 = 1, where e is the electron
charge, me is the electron mass, and a0 is the Bohr radius. The laser light is assumed
to be linearly polarized. The Coulomb gauge with ∇ · A = 0 and vanishing scalarpotential are also utilized through this section. The coupling between the laser and24
the electron is expressed by replacing the momentum operator of the electron with theminimal coupled momentum, p̂ → p̂ + A(r, t) [70]. Hence, the dipole approximation,exp(ik · r) ∼ 1, may be applied very accurately. Consequently, the Hamiltonian isH0 =(p̂ + A(t))2
p̂ 2
A(t)2
=
+ A(t) · p̂ +,222(2.17)

where the vector potential is only time dependent.
In cases where the interaction of the electron with the field is represented as inequation 2.17, the interaction is described by the velocity gauge. Even though a variety
of gauges exist [71, 72], physical observables are independent of the gauge chosen. The
Hamiltonian in equation 2.17 can be rewriten as

H00 =

p̂ 2
+ r · E (t).
2(2.18)

In cases where the interaction of the electron with the field is represented as in equation
2.18, the interaction is described by the length gauge.
As approximations are introduced, one gauge may be more accurate for a description of the physics. As an example, the length gauge probes regions where the wave
functions change rapidly with r, which in this case are typically positions close to the
nucleus.
In this case the velocity gauge will be used because the mathematics are simpler
to handle. Therefore, solving the time-dependent Schrödinger equation for positiveenergies,
"
#
∂
p̂ 2
A(t)2
i ψ(r, t) =+ A(t) · p̂ +ψ(r, t).
∂t22(2.19)

Where, if not for the coupling terms introduced by the external field, the solution toequation 2.19 would be the usual plane waves ψ0 (r , t) = (2π)−3/2 exp i(q · r − q 2 t/2)
with p̂ 2 ψ0 (r , t) = q 2 ψ0 (r , t). By direct substitution it can be verified that

25

!#
"
Z t Ã 2
0 )2
A(t
1
q
ψV (r , t) =exp i q · r −dt0+ A(t0 ) · q +22(2π)3/20(2.20)

is a solution to equation 2.19. This solutions is called a Volkov wave after the author who
first considered the wave function of a free (relativistic) electron in an electromagnetic
field [73].
Before proceeding, it would be useful to introduce (see Appendix A)

Up =

A20
E2
= 02
4
4ω

(2.21)

α0 =

A0
E0
=− 2
ω
ω

(2.22)

where Up stands for the ponderomotive potential - the kinetic energy of an electron in
the laser field averaged over an optical cycle - and α0 denotes the maximal classicalexcursion of the electron in its oscillatory motion in the field.
By evaluating the integrals in equation 2.19 and by using Up and α0 , the Volkov
wave may be written in a different way (see Appendix A):

!#
Ã
"
Up
1
q2
ψV (r , t) =sin 2ωt −+ Up t .
exp i q · r − q · α0 sin ωt −2ω2(2π)3/2(2.23)

In equation 2.23 the first term of the exponent describes the plane wave motion of
the electron with energy q2 /2 as indicated by the presence of this factor in the last term.
The rest of the terms in the exponent are due to the interaction of the electron withthe laser field. The Up t and Up /(2ω) sin 2ωt terms describe an oscillating and constantenergy shift gained by the electron in the presence of the field, while the second term
describes the oscillatory motion of the electron of amplitude α0 along the direction of
the field’s polarization.

26
Unfortunately, the expression in equation 2.23 is not well-suited for the calculationof the matrix elements due to the sinusoidal time-dependence of the exponent. A simpler
exponential form may be obtained by introducing a sum over the generalized Bessel
functions Jn (u, v). The form of the generating function of these functions [74, 75]∞Xeinφ Jn (u, v) = exp i(u sin φ + v sin 2φ),(2.24)n=−∞may immediately be used in equation 2.23. Thus, the expression for the Volkov wave is
Ã
!
∞
X
Up
1
iq·r
−i(q 2 /2+Up +nω)tψV (r , t) =e.
e
Jn α0 · q,2ω(2π)3/2n=−∞(2.25)As shall be seen, the Volkov wave function in equation 2.25 allows a simple evaluation of the time integrals occurring in the matrix elements.

2.2.2

Laser-assisted scattering

Laser-assisted elastic electron scattering is a process of the typeeq i + Ai → eq f + Ai ,(2.26)

where atom A remains in its initial state Ai during the collision while the electron
exchanges ` quanta with the laser field to change energy from qi2 /2 to
qf2

qi2
+ `ω
2

(2.27)

q f = q i + Q,

(2.28)

2=and momentum from q i towhere Q is the momentum transfer to the electron. This kind of process, known as
free-free transition has been intensively studied experimentally and theoretically overthe last two decades [76]. In a simple way, the electron-atom interaction is modeled by27
a potential V , and the scattering is described by perturbation theory. Where if not forthe presence of the field, the transition matrix element in the first Born approximation
would simply be the matrix element of the potential sandwiched between two planewaves. However, the laser field turns the plane waves into Volkov waves, and the Smatrix element reads [77](S − 1)B
f i = −i

Z ∞
−∞

(f )

(i)

dthψV | V | ψV i.

(2.29)

Substituting the expression for the Volkov waves in equation 2.25 into equation
2.29 and using the summation formula∞X

Jn∓k (u, v)Jk (u0 , v 0 ) = Jn (u ± u0 , v ± v 0 ),(2.30)k=−∞it is possible to derive (see Appendix A)(S − 1)B
f i = −2πi

X

TfBi (`),(2.31)`

with TfBi (`) the (transition) T -matrix for a scattering process with the exchange of `photons

TfBi (`) = J` (−α0 · Q)Ṽ (Q),(2.32)and Ṽ (Q) the Fourier transform of the potential

1Ṽ (Q) =(2π)3Z
dr e−iQ·r V (r ).

(2.33)

In equation 2.31 the delta function expressing energy conservation has been suppressed, and the energy balance is given by equation 2.28.
The matrix element in equation 2.33 is the field-free T -matrix element in the first
Born approximation. Thus, the differential cross-section for the exchange of ` photons
reads

28

dσ B
dσ B (`)= J`2 (α0 · Q).
dΩdΩ

(2.34)

Equation 2.34 expresses the laser-assisted cross-section in terms of the field-freecross-section and a Bessel function of integer order `. The amplitude of the vector α0in equation 2.34 is related to the amplitude of the electric field by E0 = ω 2 α0 as follows
from equation 2.22. In the SI system, one atomic unit of field strength is given by
Eau = e/(4π²0 a20 ) with ²0 as the vacuum permittivity. In this case, Eau = 5.14 × 109
V/cm. The corresponding unit of intensity is the time-averaged Poynting vector Iau =|Eau |2 /(2µ0 c), where µ0 is the vacuum permeability, and the factor 1/2 comes from thetime-averaging. When the values are substituted, Iau = 3.51 × 1016 W/cm2 . For fieldstrengths and intensities on the order of Eau and Iau , the force exerted on the electronsby the laser field matches the strength of the field from the atomic nucleus.
The laser field does not need to be very strong to result in a nonperturbative
coupling to the field. The point is that the coupling to the field enters through α0 · Q.
The larger the argument of the Bessel function, the more likely are high-order multiphoton processes. This result arises from the behavior of the Bessel function. The
instantaneous kinetic momentum p(t) of an electron in the spatially uniform vector
potential A(t) is given byp(t) = q + A(t),(2.35)

where q is a constant vector that represents the time-averaged value of p(t). An electronwith time-averaged momentum q i will arrive at a scattering center at some time t andhence with incident momentum p i determined by equation 2.35. Scattering is assumed
to take place instantaneously (that is, in a time short compared with 1/ω) and elasticallyfrom an incident momentum p i to a final momentum p f . Thus A(t) has the same value
immediately after the collision as it had immediately before, and the time-averaged final

29
momentum q f is determined by equation 2.35. Therefore,q f − q i = p f (t) − p i (t) = Q,

(2.36)

qf2 − qi2 = −2Q · A(t),(2.37)

and, because p2f = p2i ,In a typical process q f and q i are regarded as the observables. Equation 2.37
then determines the value of A(t) at which the scattering took place, and equation 2.35
determines the values of p f and p i (and hence the energy) involved in the interaction
with the scatterer.
In laser-assisted electron scattering, the role of the laser is to redistribute theelectron intensity in different photon-exchange channels. This role may be seen formallyby applying the summation formula

Jn (u, v) =∞X

Jn−2k (u)Jk (v),(2.38)k=−∞for the Bessel functions from which it follows that
X dσ B (`)
`

dΩ

=

dσ B
.
dΩ

(2.39)

This relation means, for example, that the cross-section for the exchange of zero
photons is not equal to the field-free cross-section. Only in the limit of vanishing fields
it is possible to find α0 · Q ∼ 0, and J` (0) = δ`,0 , from which the field-free cross-section
can be obtained.
It has been shown [78] that equation 2.34 holds for the exact scattering crosssection in the limit that the photon energy is small compared to the kinetic energyof the electron. In this limit the theory predicts that the ratio of the laser-assisted
cross-section to the field-free cross-section is given by the square of the Bessel function

30

dσ(`)
= J`2 (α0 · Q).
dΩ(2.40)

Equation 2.40 is attractive because it allows a straightforward comparison withexperiment, and this theory accounts well for data taken in experiment.

2.2.3

Laser-assisted photoelectric effect

The laser-assisted photoelectric effect is the process

γ + A → A+ + (e + `h̄ω),(2.41)

where a high-energy photon γ is absorbed by an atom in the presence of a laser field. In
the final state the continuum electron exchanges photons with the assisting laser field.
The Born approximation for the S-matrix expression for a transition from theinitial atomic wave function Φ0 to a final Volkov wave function ψV is(S − 1)B
f i = −iZ ∞−∞dthψV | Aγ (t) · p̂ | Φ0 i,(2.42)

where Φ0 = φ(r )eiEb t with Eb as the binding energy of the initial electron wave function.
Here Aγ (t) is the vector potential for the high-energy photon. In this process, the dipole
approximation is introduced both for the laser field and the high-energy photon field.
The strength of the coupling between the high-energy photon field and the electron isassumed to be sufficiently weak so that only the co-rotating (energy conserving part) of
the interaction contributes. That is, in the matrix element of equation 2.42, the vector
potential Aγ (t) = Aγ,0 cos(ωγ t) is replaced by Aγ (t) = Aγ,0 /2 exp(−iωγ t).
As before, by substituting the expression for the Volkov waves from equation 2.25
into equation 2.42, the following S-matrix element can be derived(S − 1)B
f i = −2πi

X`

Tf i (`),(2.43)

31
where
Ã
!
Up
1
Tf i (`) = Aγ,0 · q f φ̃0 (q f )J` α0 · q f ,22ω

(2.44)and φ̃0 (q (`)) the Fourier transform of the initial atomic state φ0 :1
φ̃0 (q ) =(2π)3/2Z
dr e−iq ·r φ0 (r ).

(2.45)The energy conservation implicit in equation 2.43 is
qf2
2+ Up + `ω = ωγ − Eb .

(2.46)

With the (2π)−3/2 normalization chosen for the Volkov waves, the relation between the transition matrix element and the scattering amplitude is

ff i (`) = (2π)2 Tf i (`).

(2.47)The differential cross-section dσ/dΩ = (qf /qi )|f |2 with qi = qf (` = 0) is¯!¯2Ãqf (2π)4 ¯¯
Up ¯¯
dσ(`)
=
¯A0,γ · q f φ̃0 (q f )J` α0 · q f ,¯ .
dΩ
qi 4 ¯2ω ¯(2.48)The total cross-section in the `th channel is obtained by integration over the angularRvariables, σ(`) = dΩqf /qi |f |2 .
To the extent that the dependence of q f on ` can be neglected, equation 2.48
reduces to
Ã
!
U
dσ(`)
dσ
p
= J`2 α0 · q f ,
,
dΩ
2ω dΩ

(2.49)

with dσ/dΩ as the laser field-free differential photoionization cross-section. This result
is similar to the result expressed by equation 2.34 for laser-assisted scattering.

32
The typical signature of the presence of an assisting laser field is the square ofa Bessel function. From equation 2.49 it is possible to obtain an approximate expression for the differential probability that the photoelectric effect is accompanied by theexchange of n laser photons
Ã
!
U
dPn
dσ(n)
p
=P
= Jn2 α0 · q f ,
,
dΩ
dσ(`)
2ω
`

(2.50)

where the summation formula, equation 2.30, together with the result J0 (0, 0) = 1 wasused.
If the dependence of q f on the number of exchanged photons is retained, theresults are more involved. As an example, consider the probability that the photoelectriceffect is accompanied by the exchange of n laser photons

σ(n)Pn = P.
` σ(`)(2.51)

Assuming that the main effect of the assisting field is to redistribute the probability current into different photon-exchange channels, it is possible to approximatePthe sum ` σ(`) by the total field-free cross-section σF F and use Pn = σ(n)/σF F toobtain the probability. In this approach, the influence of the laser field A on the initialstate, as well as the influence of the sample potential φ on the final continuum state,
are neglected. The former is justified even for weakly bound systems as long as φ is a
short-range potential [74], while the latter holds in the soft photon limit. Thus, the ratioof the laser-assisted and the field-free photoemission cross-section can be derived [70] as
follows:Ã!
³´
Udσ(n)/dΩpPn == Jn2 α0 · q f ,≈ Jn2 α0 · q f
dσ/dΩ
2ω

(2.52)In the approximation of equation 2.52 the ponderomotive potential is neglected.
As is the case in the soft photon limit, the target atom properties cancel and the prob-

33
ability depends only on the electron and laser field properties. It is therefore expected
that, to the extent that the soft photon limit approximation is justified, the target
properties are negligible.
In summary, the laser-assisted photoelectric effect can be considered to result
from “dressing” of the free-electron wave function. When an electron is photoejectedin the presence of an intense laser field, the electron is accelerated by the laser field. If
the interaction occurs continuously over several optical cycles, the electron undergoes
oscillations. This leads to ponderomotive energy shifts, and, in the presence of atomic
nuclei or solids that can absorb momentum, to the generation of sidebands in the photoelectron spectrum. The appearance of sidebands corresponds to the absorption andstimulated emission of photons from the laser field.

Chapter 3
Experimental Setup

3.1

Introduction
The dynamics of an electronic excitation and the following relaxation process

can be followed directly by using the pump-probe technique. Experimentally, this isrealized by controlling the time delay between the pump and probe pulses: A first laser
pulse (pump) excites the system under investigation and a second time delayed pulse(probe) samples the excited state of the system. By varying this time delay after aspectrum has been acquired, it becomes possible to follow the temporal evolution of
the excitation process and its subsequent relaxation into the steady state. With theavailability of fs-laser and HHG photons, a whole range of time-resolved techniques
have become available. As photoemission samples electronic states, time-resolved x-ray
photoelectron spectroscopy is able to sample the evolution of excited states above theFermi level and in some cases laser induced changes at the core levels.
The time-resolved EUV photoemission spectrometer that we have used for our
experiments (see figure 3.1) consists of two major components - an ultra-high vacuum(UHV) chamber and the EUV and IR beamlines.

3.2

EUV and IR Beamlines
The laser system used for these experiments is a commercial multipass Ti:sapphire

amplifier (KM Labs “Dragon”). At an energy per pulse of 2 mJ and a repetition rateRoughNoble Gas

Ti:Sapphire Laser System
2 mJ/pulse @ 2 KHz, 25 fs

Rough
70 l/sDelay Stage

Chopper

EUV Multilayer
Reflector Pair

Gate
Valve

Al/Zr
FilterWindow

IR

EUV

ED
/A
ug
e

LE

Gas Doserr

Low Lux Camera

Sputter Gun

Pt(111)

TOF

1000 l/s

Photo DiodeIR Filter

RGA

35

Figure 3.1: Experimental setup for observing the laser-assisted photoelectric effect fromsurfaces.

36of 2 kHz, this laser produces 25 fs pulses with a central wavelength of 780 nm. The
laser beam is directed through a beam splitter, which separates the beam into two.
Depending on the experiment approximately 10 - 30 % of the energy is used for the
IR beam, while the remaining energy is used for the EUV beam. Since in this thesis
a number of experiments using different EUV and IR wavelengths are discussed, eachwill be examined separately.

3.2.1

IR beamline

The IR beam (10 - 30% of the laser energy) is directed through a computercontrolled delay stage in order to control the time delay between EUV and IR pulses.
These pulses are then loosely focus into the UHV chamber and subsequently redirectedto the sample at a small (≈ 1◦ ) angle with respect to the EUV beam. The IR beam
spot size at the sample is varied between 0.2 and 1.2 mm by moving a focusing lens.
The IR beam is chopped at a frequency of 1 kHz, and the electron detector is gatedto record EUV+IR and EUV-only spectra alternately. This allows us to distinguishemission caused solely by the IR beam from two-color (EUV+IR) photoemission.
Furthermore, in order to experimentally verify the wavelength dependence oflaser-assisted photoemission, we performed experiments with two different IR wavelengths:• 780 nm: Chapters 4 and 5 discuss experiments where the IR wavelength is
780 nm (the fundamental frequency of the laser system). In these experiments,
the IR pulse duration is broadened to 35 - 40 fs by dispersion as it propagates
through various optical elements in the delay line.
• 1300 nm: The experiment discussed in chapter 6 studies the dependence of
the LAPE sideband height for different IR wavelengths. We used an opticalparametric amplifier (OPA) [79] to convert the 780 nm light into 1300 nm light.

37
In this experiment, the pulse duration of the IR beam is ≈ 90 fs.

3.2.2

EUV beamline

The remaining 70 - 90 % laser energy is up-converted by phase matched highharmonic generation (see section 2.1) in a noble gas-filled, hollow waveguide [66] (seefigure 3.2). Just as with the IR beam, the experiments discussed below make use of thetwo different EUV energies:• 43 eV (27th harmonic, 29 nm): In this case, Argon is the noble gas used toefficiently generate this photon energy through HHG. The argon pressure inside the hollow waveguide is ≈ 45 torr. This photon energy was used for theexperiments discussed in chapters 4 and 6.
• 91 eV (57th harmonic, 13.5 nm): ≈ 500 torr of Helium is used to generate thisphoton energy. The experiment covered in chapter 5 makes use of this photon
energy.

Figure 3.2: Picture of a HHG waveguide v-groove holder engineered by the KapteynMurnane group.

Since HHG produces a semi-continuum spectrum, frequency discrimination isneeded in order to use the HHG photons for photoemission. In our experiments, we38
use a pair of multilayer mirrors [80], one flat and one curved, to spectrally select thedesired harmonic and to focus the EUV beam onto the Pt surface with a spot size of
approximately 100 µm. For the 43 eV photons, this pair of multilayer mirrors is made byperiodically growing magnesium and silicon carbide (silicon and molybdenum for the 91
eV photons) thin-films on a superpolished glass substrate to form a Bragg reflector for
the incoming photons. The wavelength with the maximum reflectivity is equal to twice
the thickness of the Mg:SiC (Si:Mo) stack of the multilayer mirrors. Figure 3.3 shows
the reflectivity vs wavelength plot of a single Mg:SiC multilayer mirror. The wavelengthof the maximum reflectivity of the multilayer mirror is near the 27th harmonic of thedriving 780 nm pulse. Figure 3.4 shows the reflectivity curve for a Si:Mo multilayer
mirror. Experimentally the photon flux at the 27th harmonic is higher than at the57th harmonic; however, the multilayer mirrors for the shorter wavelength photons havehigher reflectivity.

Reflectivity (%)

0.4

0.3

27th
harmonic

0.2

29th
harmonic

25th
harmonic
0.1

0.0
40

42
44
Photon Energy (eV)46

Figure 3.3: Reflectivity curve for a single Mg:SiC multilayer mirror.

Additionally, a 200 nm thick aluminum or zirconium filter is used to maintaina pressure differential between the high-order harmonic generation cell and the UHV

39

0.6

Reflectivity (%)

0.5
57th
harmonic

0.4
0.3

59th
harmonic

0.2
0.1

88

90

92
Photon energy (eV)94

96

Figure 3.4: Reflectivity curve for a single Si:Mo multilayer mirror.

Aluminum
Zirconiumoxidized AlTransmission (%)

0.6

0.4

0.2

0.0
20

40

60
Photon energy (eV)

80

100

Figure 3.5: Transmission of the aluminum and zirconium filters. The green curve represents the transmission of an oxidized aluminum filter.

chamber, and to block the copropagating IR light while transmitting the EUV beam.
The aluminum filter transmits the 43 eV photons, while the zirconium filter transmits
the 91 eV light (see figure 3.5).

40

3.3

UHV Chamber
The UHV chamber is pumped by a 500 l/s turbo pump (Balzers TMU-520-SG)

and a 270 l/s ion pump (Varian VacIon Plus 300 noble diode) to achieve a base vacuum
pressure of under 1×10−10 mbar after a standard UHV bake out. To prevent the earth’s
magnetic field from penetrating into the vacuum chamber, the chamber is shieldedinternally by double layers of µ-metal. This prevents the course of photoelectrons frombeing distorted by external magnetic fields. A platinum(111) single crystal is mounted
inside the chamber by spot-welding it onto two parallel tantalum heating wires, which
are in turn spot-welded to a manipulator mounted vertically from the top port of thechamber (see figure 3.8). The manipulator has the capability of performing three-axis
translational and azimuthal rotational motion with respect to the platinum sample.
In addition, the manipulator’s inner tube can be filled with liquid nitrogen, providing
cooling for the sample.
A high current power supply (HP 6269B) is connected to the manipulator anddrives the tantalum wires that heat the platinum sample. A proportional-integralderivative (PID) temperature controller (Omega CN77000) controls this power supply.
A K-type thermocouple is also spot-welded to the back of the platinum sample for measuring the sample’s instantaneous temperature. The measured temperature feeds into
the PID temperature controller as a feedback signal to control the high current power
supply. Using this feedback control scheme, the electrical heating can be nicely balanced by the liquid nitrogen cooling; therefore, the sample temperature can be reliably
controlled over a wide temperature range, from 79 to 1200 K, and the temperature canbe increased or decreased at a rapid rate.
A custom-built, time-of-flight (TOF), electronic kinetic energy analyzer is used
for detection (see Appendix B). Two shielding layers of µ-metal are installed around theinner wall of the TOF tube to insulate it from the earth’s magnetic field. The total tube

41
length is Ltube = 600 mm and the inner diameter is 40 mm, which provides an electron
collection solid angle of S ' 2×10−3 sterradians. At the end of the TOF tube, a custombuilt, large area (40 mm), fast-response detector detects the electrons. A double microchannel plate (MCP) is used at the front of the detector to obtain the gain necessary todetect single electrons. The MCPs amplify the single electron signal to detectable signal
levels (∼ 100 mV) by a secondary electron cascade process . The detector has timing
resolution of about 200 ps. Impedance matching of the whole electron detector allows it
to operate with a GHz frequency bandwidth. The key ideas of impedance matching are
adapted from the design of A. Stolow [81], and a cone-shape anode design ensures thatthe fast electronic signal propagates into the coaxial cable with no noticeable reflection.
The output signal is subsequently delivered to a high frequency pre-amplifier, followed
by a constant fraction discriminator (ORTEC 9327), ensuring that the electron arrival
time is independent of output signal intensity fluctuations. An all solid-state time-todigital converter (TDC) (ACAM AM-F1) measures the electron flight times, referenced
to a start signal from the laser system.
The real electron flight time is actually referenced to the moment when the EUV
pulse arrives at the sample, also the moment when the sample starts to emit electrons.
This moment appears on the TOF spectrum as an EUV scattered light peak. The peakis a result of the EUV pulse being scattered/reflected from the sample surface, with thescattered EUV light then triggering the detector. There is a 2 ns time delay between
this EUV peak and the real start time, resulting from the propagation of the EUV
light from the sample to the detector. This time difference is negligible since the fastest
photoelectrons need more than 150 ns to reach the detector. By subtracting the timeof the EUV start peak from the measured flight time, the actual electron kinetic energy
Ekin can be calculated (see Appendix B).
As shown in figure 3.6, the EUV and IR beams irradiate the sample at a variable
angle θ with respect to the surface normal. In order to prevent light reflected off the42sample from hitting the detector, the TOF tube is tilted up with respect to the planeof incidence by an angle of 20◦ . Consequently the observation angle φ with respect tothe surface normal is given by cos φ = cos 20◦ cos(90 − θ).

TOF

Pt sample

20°
ϕθ
surface normal

p-polarization
laser beam

Figure 3.6: Geometry for the photoemission measurements: p-polarized IR light impinges on the Pt sample at an angle θ with respect to the surface normal. ϑ = 90 − θis the angle of the polarization vector with respect to the surface normal. The detector
is titled by 20◦ with respect to the plane of incidence. The corresponding observation
angle ϑ with respect to the surface normal is given by cos φ = cos 20◦ cos ϑ.

For standard surface diagnostics, the UHV chamber is equipped with a Low Energy Electron Diffraction (LEED) Spectrometer and an Auger Electron Spectrometer(AES) (OCI BDL800IR), which monitor the condition of the sample’s surface. The
diffraction pattern of the LEED can reveal the local order of the sample surface, while
surface contamination can be seen using the AES. A residual gas analyzer (RGA) (Leybold Inficon Transpector) is installed on the UHV chamber for monitoring the ambientchamber gas content. In addition, Thermal Desorption Spectra (TDS) [82] can be takenby the RGA, measuring the partial pressure of a target molecule while the temperatureof the sample is steadily raised.

43

3.4

Sample Preparation
For sample preparation and cleaning, an argon ion sputter gun is installed in

the UHV main chamber. The sputter gun can be used to remove the topmost several
mono-layers of the platinum sample, and therefore sample surface contaminations are
simultaneously removed. Rapid thermal annealing can subsequently be performed toreconstruct the surface order. However, on a day to day basis, we usually obtain athermal desorption spectrum of oxygen adsorbed on Pt(111) to assess the cleanliness ofthe sample.
Thermal desorption spectroscopy is a well-known and commonly used techniquefor characterizing chemical reaction processes on surfaces. The idea of TDS is to adsorb
the molecules under study to the metal surface at a low, non-reactive temperature.
The temperature of the metal surface is subsequently increased at a constant rate toa temperature well above the temperature where the adsorbates react and desorb. By
measuring the yield of the desorbing molecular species and the corresponding desorbing
temperatures, information about adsorption energy of the adsorbates, activation energy,
and the reaction channels of the chemical reactions can be extracted. For oxygen on
platinum (111), TDS can help us understand the oxygen chemisorbed states and theircorresponding properties.
Figure 3.7 shows the TDS spectrum of O2 on Pt(111) taken using our setup.
Oxygen was initially dosed onto the platinum sample at 77 K, to saturation coverage.
Two distinct desorption peaks can be observed in the TDS spectrum: an intense α-O2
peak at 145 K, and a weaker high temperature β-O2 peak (the symbols of α and β
are used for identification purposes only; the oxygen molecules desorbing from thesetwo peaks are the same). The TDS spectrum of O2 /Pt can be explained by superoxo
oxygen (O−2 ) dominating at the bridge site at high coverage, when oxygen is dosed tofull coverage at liquid nitrogen temperature. When the surface temperature is heated44

O2 desorption signal (a.u.)

14x10

-9

TDS
O2 /Pt(111)

12
10

α-O2

8
6
4
β-O2

2

x5
0
200

400

600
Temperature (K)

800

1000

Figure 3.7: TDS for Pt(111) covered with O2 . The rate of temperature increase is 5
K/sec.

above 145 K, a large fraction of oxygen molecules desorb from the platinum surface,since the oxygen molecules have gained enough energy to overcome the energy barrier fordesorption. Once some of the oxygen molecules desorb, the oxygen coverage becomesmuch lower on the platinum surface, and there will not be enough oxygen molecules
left on the surface to cluster at adjacent bridge sites. The oxygen molecules now tend
to move from the bridge site to the three-fold hollow sites to lower their total energy,
2−leading to a state transition from the superoxo (O−2 ) into the peroxo (O2 ) state forthe remaining oxygen molecules. When the surface temperature increases above 200 K,
the intermolecular bond of the adsorbed oxygen molecule will gain enough energy to bebroken. This causes the oxygen molecule to dissociate into two identical oxygen atoms,
and the two oxygen atoms absorb on two different three-fold hollow sites on a platinum
surface. Since atomic oxygen has a much higher adsorption energy, it will remain on
the platinum surface until the surface temperature reaches temperatures higher than
600 K. Finally, the atomic oxygen will desorb and recombine to form oxygen molecules

45
and leave the platinum surface.
In our experimental setup we use a custom-built gas doser for precision gas dosing.
The major benefit of using a gas doser versus using a gas leak valve is that a doser allows
a much higher local pressure to be created around the sample area while keeping the restof the chamber in high vacuum. This also minimizes the opportunity for gas molecules
to adsorb at the UHV main chamber wall, preventing prolonged pump down times aftergas dosing. In addition, if experimentally required, continuous gas dosing to the sample
would not cause serious problems. Maintaining the high vacuum condition of the restof the system is needed to ensure the functionality of other highly sensitive equipment.
For example, the working pressure of the MCP electronic detector must be lower than1 × 10−6 mbar.

3.5

Finding Temporal and Spatial Overlap
The spatial and temporal overlap between the EUV and the IR beams at the

sample is obtained using a multi-step procedure. A preliminary spatial overlap is obtained by moving the sample holder (figure 3.8) so that the EUV and IR beams hit aphosphor screen that is moved in place of the Pt(111) surface. The beams are observed
and aligned using a CCD camera that images the phosphor from outside the chamber.
The temporal overlap is obtained by moving the sample holder to another position, where the beams pass through a beta barium borate (β-barium borate, BBO),
frequency-doubling crystal. The aluminum filter in the EUV beamline is replaced by athin (0.355 mm) sapphire window to allow the IR light from the high-harmonic EUV
beamline into the UHV chamber. A cross-correlation between the two IR fields thenlocates time zero. The position of time zero must be corrected for the sapphire window
group delay, which is 934 fs. At this point, the Pt(111) sample is moved into place. Since
the position of the phosphor screen along the light direction is not exactly the same as
the Pt(111) sample, the spatial overlap must be readjusted. This is done using LAPE

46

Cold
sourcePt(111)

Ta wires

PhosphorscreenQuartzcrystalBBO
crystalFigure 3.8: Schematic of the phosphor screen, Pt(111), BBO and quartz crystals holder.

(see section 4.4) itself, by observing the highest-energy photoelectrons as a measure of
spatial and temporal overlap.
However, the above mentioned procedure can only be used for experiments where
780 nm light is used for the IR beam. In the experiments from chapter 6 we used
1300 nm light to “dress” the electrons photoemitted by the EUV light. Therefore, themethod described above on how to find temporal overlap cannot be used. Instead wemade use of the optical Kerr effect [83].

47
The optical Kerr effect is a change in the refractive index of a material in responseto an electric field. In our case, the electric field is due to the light itself. It is distinct
from the Pockels effect in that the induced index change is directly proportional to thesquare of the electric field instead of to the magnitude of the field. Under the influence of
the applied field, the material becomes birefringent, with different indices of refraction
for light polarized parallel to or perpendicular to the applied field. The difference inindex of refraction, ∆n, is given by∆n = nk − n⊥ = KE 2 λ0

(3.1)

where λ0 is the wavelength of the light, K is the Kerr constant, E is the amplitude ofthe electric field, nk is the index of refraction in the direction of the applied, and n⊥ is
the index at right angles to E . This difference in index of refraction causes the material
to act like a waveplate when light is incident on it in a direction perpendicular to theelectric field. If the material is placed between two “crossed” (perpendicular) linear
polarizers, no light will be transmitted when the electric field is turned off, while nearly
all of the light will be transmitted for some optimum value of the electric field. Higher
values of the Kerr constant allow complete transmission to be achieved with a smaller
applied electric field. This effect only becomes significant with very intense beams suchas those from ultrafast lasers.
In order to find time zero through the optical Kerr effect, we move the sample
holder to a position where both beams pass through a quartz crystal. We place two“crossed” polarizers in the probe 1300 nm beamline, while we set the pump 780 nm
light polarization at 45◦ from the probe light polarization (figure 3.9). We then monitor
the intensity of the probe beam while changing the optical path-length of the pumpbeamline. When both pulses hit the quartz crystal at the same time, the intensityof the probe beam after the second polarizer increases. A measurement of the probe48
light intensity versus time locates temporal overlap between both pulses. As mentioned
before, in order to find time zero between the EUV pulse and the 1300 nm pulse, weneed to correct for the delay induced by the sapphire window.

Δt ≠ 0polarizer
s-pol

probe
quartzcrystalp-pol

pump
45° froms-polpolarizer

detectorpolarizer

detectorΔt = 0polarizer
s-pol

probe
quartzcrystalpump
45° froms-pol

Figure 3.9: Schematic of experimental setup for finding temporal overlap when the IR
pulse wavelength is different than 780 nm. In this case we use of the optical Kerr effectto find time zero.

Chapter 4
Laser-Assisted Photoemission from Surfaces

4.1

Introduction
The purpose of this chapter is to extract from EUV+IR photoemission data

unambiguous signatures of all the processes that occur when a surface is illuminatedsimultaneously with an EUV and intense IR fields, i.e. above-threshold photoemission,
heating of the valence electron distribution, and LAPE. Above-threshold photoemission
and hot electrons are so-called initial state effects (i.e. signal originates from atoms thathave not interacted with the EUV light), whereas LAPE is a f inal state effect in that
it is specific to the EUV-excited atoms. Comparing the relative magnitudes of theseeffects allows us to develop methods to single-out the continuum free-free transitions
corresponding to LAPE. We found that LAPE is the dominant process over a wide
range of IR intensities and polarizations typically employed in experiments investigating
charge-transfer dynamics in surfaces and surface-adsorbate systems. This result shows
the feasibility of extending the variety of time-resolved measurements using LAPE thathave been observed and employed in atomic and molecular samples, to solid surfaces.

4.2

Aspects of Surface LAPEIn principle, the concept of the laser-assisted photoelectric effect should apply

not only to atoms but to solid surfaces as well. It should also result in the convolutionof sideband shifts onto the entire continuous EUV photoemission spectrum from the50solid. However, due to the manifold different excitation paths and energy dissipation
channels, the interpretation of energy shifts in the photoemission spectra from solid
surfaces is more complicated than in the gas phase. The following sections discusspossible influences of the strong IR light on the photoemission spectra from solids.

4.2.1

Momentum conservation and ground state dispersion

A basic difference between photoemission from crystal surfaces, when comparedto photoemission from atoms, concerns the exchange of momentum. This is restricted tointeger multiples of the reciprocal lattice vector h̄G in a crystal, due to the periodicityof the lattice. However, the presence of a surface removes the periodicity in one halfspace and softens momentum conservation. In the case of EUV photoemission, theelectrons have a very short escape depth on the order of 5 Å, according to the universal
curve [12, 84]. They thus sense only one or two atomic layers. The surface can thenact as a continuous source or sink of momentum normal to the surface [85], and theelectron can be excited into a surface state, often called inverse LEED state. Along thesurface normal, the latter is essentially a plane wave. For an IR laser pulse impinging
on a metal surface, the electric field components parallel to the surface nearly vanish
because of the boundary conditions. The remaining field, i.e. the component that isable to dress the photoemitted electrons, thus points along the surface normal, where
the surface can balance momentum conservation. In this direction, the interaction of
the emitted electron with the IR laser can be described by replacing the plane wave
part of the LEED final state by a Volkov wave.
However in EUV photoemission, part of the spectrum arises from direct transitions, e.g., the emission from d-bands into s-bands in transition metals. This photoemission process conserves the momentum qk parallel to the surface. As the “dressing”
is associated with a momentum change along the surface normal, the direction of emission of the electron is changed, except for electrons emitted normal to the surface.

51
For angle-resolved photoemission spectroscopy with infinite resolution, or laser-assisted
photoemission, the detected sidebands stem from electrons emitted from different initial states and at slightly different angles compared with the electrons that did not loseor gain photons of energy h̄ω from the IR field. Due to the dispersion of the valencebands in solids, the corresponding energies can be shifted leading to a deviation of the
sideband energy spacing compared with the IR photon energy. However, in the soft
photon limit, the relative momentum change associated with the exchange of a photon
between the photoelectron and the IR field is small. At an observation angle of 45◦ , the−1absorption or emission of a 1.6 eV photon by a 36 eV electron leads to ∆kk = 0.05 Å,which is about 0.02 of the total Brillouin zone. The corresponding energy shift due todispersion is at most 50 meV, which is significantly smaller than the IR photon energy(1.59 eV) and even below the energy resolution of our detector. Thus, we neglect thesedispersion energy shifts in this work.

4.2.2

Resonant interband and intraband transitions

Another difference between atoms and surfaces is the quasi-free behavior of electrons in a band, due to the delocalization of the electrons from individual ions. At the
Fermi edge of Pt, however, the energy spectrum is dominated by d-bands, which deviatesignificantly from the free-electron like sp-bands. Due to the strong localization of thed-electrons to the crystal ions, the d-bands are narrow and exhibit only low dispersion.
They can be described in the tight binding approximation and resemble bound electrons in atoms [86]. Ground state dressing of the d-electrons is therefore neglected in
the soft photon limit for the same reasons as in atoms [87]. For the broader sp-bands,
the tight binding approximation does not hold. Although the electrons can move freely,
they cannot respond to the IR light in the same way as electrons in the continuum.
At low frequencies, the interaction of light with a metal is dominated by intraband
absorption. In this process, which corresponds to the classical IR absorption picture,52electrons can absorb any photon energy from the IR field and are promoted into unoccupied levels above the Fermi edge. This mechanism thus only affects a small fractionof the electrons in a narrow window around the Fermi edge, and does not lead to sideband peaks. Moreover, resonant kk -conserving interband transitions are only possible
in certain directions when energy and momentum conservation are fulfilled. Contrary
to the case of continuum electrons, only absorption is possible from the ground statesince stimulated emission is forbidden by the Pauli principle, as the lower lying states
are filled. The presence of such resonant interband transitions should thus be visible
by an enhancement of the positive sideband; i.e., conduction-band electrons can absorb
photons from the laser field. The dependence of this contribution on the EUV+IR timedelay should follow the lifetime of the intermediate states, which is approximately 100
fs for transition metals [88]. Both effects are not observed in our experiment.

4.2.3

Non-resonant interband transitions

Due to the high IR intensities applied in LAPE experiments, non-resonant IRinterband transitions into virtual levels occur, which can serve as intermediate states
for multiphoton ionization. Such transitions have been studied theoretically in atoms in
different limiting cases. For electrons in excited Rydberg states of atoms, non-resonant
absorption and emission of microwave photons into virtual states can lead to dressing
analogous to the continuum [89]. As unoccupied real levels above and below the initial
Rydberg state are densely spaced, both absorption and emission are equally likely,
which leads to symmetric sidebands. For electrons in an atomic ground state, symmetricsidebands can occur when the photon energy of the dressing beam is considerably smaller
than the spacing between the atomic levels. In this case, which is usually fulfilled only
for light in the far IR or microwave region, the distance of the virtual states after
absorption and emission are approximately equally spaced from the closest unoccupied
level [90].

53
In our experiment, the electrons are in the ground state and the photon energy is
not resonant with any direct interband transition on a Pt(111) surface. Non-resonant
absorption is closer to resonance with an unoccupied real state than stimulated emission,
since unoccupied levels are only available above the ground state. Dressing of theground state is thus expected to preferentially enhance the positive sideband leading
to asymmetric amplitudes. In the light-metal interaction volume, however, the electron
number reaches the same order of magnitude as the number of photons per pulse appliedin our experiment. As a consequence, only a very small fraction of the electrons is excited
into the virtual states, leading only to a negligible contribution to the positive sideband
in the EUV photoemission spectrum. This is in contrast to gaseous atoms where theatom density is usually much lower than the photon density. In the case of dressing of
the final state, only the small number of photoemitted electrons plays a role - so thatin the continuum a significant fraction of the electrons can be dressed.

4.2.4

Dressed band structure

Theoretical investigations of intense field effects in solids predict the openingof band gaps [91, 92] whenever direct multiphoton transitions are possible. These bandgaps are closely related to the intensity-dependent Autler-Townes splitting [93] of atomic
levels in the presence of a resonant or near-resonant strong laser beam. At a photon
energy of 1.6 eV, the laser is not resonant with any direct interband transition [94],so that ground state dressing is expected to play a minor role in our experiment. The
strong IR laser thus influences the electrons only after photoemission, leading to thefinal state dressing picture similar to the experiments done in gaseous atoms.

4.2.5

Competing strong field effects

For applications of LAPE in EUV pulse duration measurements, the sideband
amplitude range, after equation 2.50 An = Jn2 (x) for small values of the argument x, is54of special interest. In SI units x can be written assx=16πα IEkin.
4me h̄ ωIR

(4.1)

For small x, A1 can be approximated by A1 ≈ x2 /4 leading to

A1 ∝

IEkin
4 .
ωIR

(4.2)

In this regime, the sideband height depends linearly on the IR laser intensity,
which makes it a suitable observable for EUV+IR cross-correlation measurements as well
as for time resolved spectroscopy. Additionally, A1 depends on the kinetic energy Ekinof the dressed electron and on the IR photon energy ωIR . Figure 4.1 shows the intensity
required to generate 1st-order sideband amplitudes of A1 = 0.1 versus the photoelectrons
kinetic energies Ekin for 800 nm light. For kinetic energies below 100 eV, an intensity ofat least 1011 W/cm2 is necessary. For slower electrons, the required intensity increases
dramatically. This intensity range is only 1 to 2 orders of magnitude below the damage
threshold of metal surfaces. Also, the excitation of non-thermal hot electrons leads
to changes in the spectra similar to those caused by the photoelectric effect. Finally,
the illumination of metal surfaces at such high intensities leads to significantly stronger
electron emission and higher kinetic energies than from gaseous atoms, due to fieldenhancement and space-charge-induced Coulomb explosion.
In past work, it was shown that above-threshold photoemission (ATP) can besignificant from surfaces at much lower laser intensities than in atoms, due to fieldenhancement effects [95]. Above-threshold photoemission is the photoemission of electrons from a surface by absorption of more photons than is required to overcome thework function. This effect can be understood, similar to LAPE, by the rate-limiting
multi-photon ionization of the sample through absorption of the minimum number ofphotons needed, and followed by redistribution of these electrons in the continuum by55
13

800 nm
1600 nm2

Intensity (W/cm )

10

10

10

10

12

11

10

0

10

20

30

40
50
60
electron energy (eV)

70

80

90

100

Figure 4.1: Calculated IR intensity required to generate first order sideband heightsof A1 =0.1 for wavelengths of 800 nm and 1600 nm, respectively, as a function of the
kinetic energy of the electrons. For kinetic electron energies of 36 eV and an 800 nm
dressing wavelength, laser intensities greater than 1011 W/cm2 are required.

absorption of additional photons [96]. For ultrashort Ti:sapphire laser pulses at 780 nm,
intensities on the order of 1014 W/cm2 are needed to cause a substantial emission ofelectrons by multiphoton ionization of gaseous atoms; i.e. above-threshold ionization.
However, it has been known for a long time that surface plasmons can lead to substantial field enhancement (up to a factor of 103 ) corresponding to intensity enhancementsof 106 on a metal surface [95]. This effect results in phenomena such as surface enhanced Raman scattering. Although forbidden by energy and momentum conservationon perfectly flat surfaces, these surface plasmons can be excited on rough surfaces. Dueto the corresponding field enhancement, ATP can happen at intensities as low as 108
W/cm2 [95]. These enhancements not only lead to higher kinetic energies of the ATP
electrons from surfaces than the ATI electrons from atoms, but also the number of electrons is considerably larger. Additionally, the first step in ATP, multiphoton ionization,is stronger than in atoms, because of the low ionization potential (work function) of

56
atoms. Finally, the sample particle density is higher than in typical experiments on
atoms. As a consequence, many electrons can be emitted from a very small volume ofthe solid sample by a single intense laser pulse, which leads to a Coulomb explosion as
the electrons repel each other [35, 97]. This way, some of the electrons are accelerated
and can gain a significant amount of extra kinetic energy, while others are decelerated
and may not escape the surface. Surface preparation thus plays a major role in theability to successfully observe LAPE.

4.3

Above-Threshold Photoemission
As was discussed above, the IR laser intensity at 800 nm required to generate

sidebands is on the order of 1011 W/cm2 . Since the parallel component of the electricfield nearly vanishes at the surface of a good conductor, the laser polarization mustbe perpendicular to the surface. Figure 4.2 shows a photoemission spectrum taken
for p-polarized IR light as the laser intensity is varied around 1011 W/cm2 . No EUV
light was incident in this measurement. Since the ponderomotive potential at these
intensities is <0.1 eV and is much less than the work function of Pt (5.8 eV), no “channelclosing” occurs, and at least 4 IR photons are required to photoeject electrons from thesurface. The lowest intensity curve shows multiphoton photoemission by 4 photons, witha small contribution of above-threshold photoemission by 5 photons. As the intensity is
increased, two effects can be observed. First, above threshold photoemission becomesstronger. The 5-photon edge increases and new channels with 6 and 7 photons appear.
However at higher laser intensities, the separation of subsequent edges is measurablylarger than the IR photon energy. This occurs because the number of photoelectrons
increases dramatically and leads to a Coulomb explosion of the electron cloud, due
to their mutual repulsion [35]. As a result, faster electrons at the front of the cloudare accelerated, while slower electrons at the back are decelerated. This effect alreadybecomes very strong at the moderate laser intensities applied here.

57

Figure 4.2: Multiphoton-induced photoemission spectra taken at different laser intensities ranging from 130 to 590 GW/cm2 using IR light only. ATP (above thresholdphotoemission) and space-charge acceleration generate electrons with kinetic energies
of tens of eV.

In contrast to experiments on gaseous samples, the higher target densities andlower ionization potentials in solids lead to stronger multiphoton ionization, abovethreshold photoemission, and as a consequence, to stronger space-charge acceleration.
To detect LAPE from solids with Ti:sapphire laser pulses at 800 nm, EUV photon energies of at least 30 to 40 eV are required so that the photoejected electrons corresponding
to the Fermi edge have energy significantly higher than the IR-induced ATP electrons.
However, even if the EUV photoelectron Fermi edge lies beyond the high energy ATPelectrons, its shape can still be altered by the space-charge if too many IR-induced electrons are emitted. It is therefore important to reduce space-charge effects as much as
possible.
The measurement shown here was performed on a sample that was cleaned as
described before. This is necessary since any surface roughness can lead to strong
local enhancements of the IR field at the surface [95], which dramatically increases the

58
number and energy of IR-ejected electrons. Due to the strong susceptibility of theseeffects to surface roughness, the IR-induced electron spectra differ strongly from day today, and figure 4.2 can thus only be taken as an example. We observe the creation of
hot spots on the Pt(111) surface resulting from IR laser intensities above 1012 W/cm2
at pulse duration ∼ 30 fs. These hot spots result in a huge increase in high energy
electrons resulting from the IR field. Apart from using shorter pulse durations to raise
this damage threshold, the use of lower IR photon energy as the dressing field would help
to circumvent this problem. In the present experiment, however, IR-induced electrons
can be kept sufficiently low by thorough sample preparation and by restricting the IR
laser intensity to moderate values.

4.4

Extraction of the Sideband Structure
As mentioned before, LAPE has been extensively studied in the gas phase, where

the discrete nature of the photoelectron spectrum makes the sidebands easy to distinguish. To extract this peak-like sideband structure from the continuous spectra of solid
surfaces, the EUV+IR spectrum must be deconvolved from the EUV-only spectrum
using a fitting procedure. Figure 4.3 shows a series of photoelectron spectra aroundthe Fermi edge, at an IR peak intensity on the order of 1011 W/cm2 and for relative
time delays between the IR and EUV beams ranging from -100 fs to +100 fs. Negative
time delays denote that the EUV pulse arrives after the IR pulse. The IR beam waspolarized in the plane of incidence (p-polarized). The EUV-only spectrum is only shownfor the -100 fs measurement (dashed line). At this time delay, both the EUV-only, as
well as the EUV+IR spectra, show the typical d-band structure of clean Pt(111). ThisPt d-band peak near the Fermi edge, although 0.9 eV wide, is nevertheless a very useful characteristic peak around which to observe sidebands. While the spectral shapeis unaffected by the presence of the IR field, the EUV+IR spectrum is slightly shiftedto higher electron energies as compared to the EUV-only spectrum, due to the space-

59
charge induced Coulomb explosion. We have observed this space-charge-induced shift
to be present for time delays between at least -1 ps and +1 ps. This can be explained by
the fact that the photo-emitted electrons are traveling slowly enough that they do notescape from the range of the space-charge field of the IR-induced electron cloud during
the time frame of the experiment. Thus, the EUV photoelectron energies are slightly
shifted even when the IR pulse comes considerably after the EUV. This space-charge
effect increases strongly with the IR intensity. At very high intensities it not only shifts
the EUV+IR spectra, but also changes its shape (see e.g. figure 4.13). However in figure
4.3, the space-charge effect is rather low, indicating an effective IR intensity in the low
1011 W/cm2 range. The space-charge shift is determined from the -100 fs curves andall EUV+IR spectra are corrected for it before subsequent analysis.
In the photoemission spectrum shown in figure 4.3 near that which corresponds tozero time delay between the laser and EUV pulses, we observe a very strong shape change
at the Fermi edge. Insight into the origin of this change can be gained by calculating the
average kinetic energy of the photoelectrons above 20 eV, both with and without the IR
pulse present. (Below 20 eV photoelectron kinetic energies, the EUV+IR spectrum isdominated by low-energy electrons from above-threshold photoemission.) No significant
IR-induced increase of the average kinetic energy was found around zero fs. Indeed, thecalculated average photoelectron kinetic energies with and without the IR were identical,
within 0.1 meV, at all time delays. This indicates an essentially equal redistributionof electrons to lower and to higher kinetic energies in the presence of the IR field thatmodifies the photoelectron spectra. Consquently, this result excludes interpretationsof a photoelectron spectrum modified by image potential states, ground state dressing,or hot electrons [98], since in all cases the average kinetic energy should be increasedby the presence of the IR field. We therefore interpret the Fermi edge modificationnear time zero to be the result of the laser-assisted photoelectric effect. Viewed in a
perturbative two-step model, the electrons photo-emitted by the EUV beam can absorb

60

6000

Time Delay (fs)

5000

100
80
60

counts

4000

40
20

3000

0
- 20

2000

- 40
- 60

1000

- 80
-100

0
25

30
35
electron energy (eV)40

Figure 4.3: Observed photoelectron spectra from Pt(111) as a function of time-delay
between the IR and EUV beams. For -100 fs time delays, the EUV-only spectrum(dashed line) is also shown. A slight shift of the spectrum due to IR-induced spacecharge can be seen, but this does not change the shape of the spectrum and can thus
be corrected for. The strong modification at the Fermi edge of the time zero spectrum
is due to laser-assisted photoemission.

61
or emit photons from the IR field, leading to sidebands in the photoelectron spectrum.
In an atomic system, the EUV photoelectron spectrum consists of discrete atomic peaks,
and the LAPE sidebands are easily distinguished. From a surface, the photoemission
spectrum consists of a continuous distribution due to the band structure of the solid.
Nevertheless, the high density-of-states at the Fermi edge for Pt(111) allows sideband
peaks to be discerned at ± 1.6 eV.

LAPE response

1.0
without IRwith IR

0.8
0.6
0.4
0.2
0.0
-4

-2

0
E-E0 (eV)24Figure 4.4: Calculated LAPE response function using equation 4.3 assuming the generation of two sidebands.

To quantitatively extract the sideband intensities in the case of photoemission
from Pt in the presence of an intense IR field, we modeled the absorption and emissionof up to two IR photons by a photo-electron of kinetic energy E0 by

f (E − E0 ) =1 − 2A1 − 2A2 (E−E0 )2 /2σ2
√
e
+
2
!
Ã 2πσ
X
A1
A
2
2
2
2
2
√
e(E−E0 ±h̄ω) /2σ + √e(E−E0 ±2h̄ω) /2σ
(4.3)
2
2
2πσ
2πσ
±

(see Figure 4.4). Since the kinetic energies of the affected electrons are large compared62
to the IR photon energy (soft photon limit), we assume that the influence of the groundstate on the free-free transitions is negligible. In particular, this LAPE response function
is considered independent of the electron’s kinetic energy over the fit range around the
Fermi edge. Consequently, the EUV+IR spectrum is expected to be generated by aconvolution of the EUV-only spectrum with the LAPE response function of equation 4.3.
We therefore fit this convolution to the combined EUV+IR photoemission spectrum,
allowing the sideband intensities A1 and A2 , as well as the width σ and the peakseparation h̄ω, to be fit parameters. The factor in front of the first Gaussian peak ischosen to normalize the response function to 1. The parameters A1 and A2 thus give thefraction of electrons scattered into the first and second sidebands respectively. Figure
4.5 shows the result for zero time delay between the IR and EUV beams. The black line
gives the photoemission spectrum without the IR pulse present. The red line shows thephotoemission spectrum with the IR pulse present. Finally, the blue line shows the fit to
the EUV+IR curve by convolving the LAPE response function from equation 4.3 withthe unperturbed spectrum. The inset of figure 4.5 shows the LAPE response function
associated with the resulting fit parameters: A1 = 0.241 ± 0.004; A2 = 0.013 ± 0.003;√
σ = 0.23 ± 0.02 eV; and h̄ω = 1.59 ± 0.02 eV. The inset is multiplied by 2πσ 2 , sothat the peak heights reflect the corresponding intensity parameters A1 and A2 .
The fit to the sideband separation of h̄ω = 1.59 eV corresponds very well to thephoton energy of the IR beam, while the width σ reflects closely the convolution of
the laser bandwidth (≈ 0.1 eV) and the detector resolution at the high energy partof the photoelectron spectrum (≈ 0.2 eV). Initially, we allowed the response function
to be asymmetric using different intensity parameters A±
1,2 for the positive and negative sidebands. However, this fit generally yielded sideband heights that were identical
for the high- and low-energy sidebands, as would be expected for the LAPE in thisweak-field regime (see figure 4.6). The quality of the resulting fit strongly supports theinterpretation of these data as surface LAPE. This is further corroborated by the fact

63
0.6

√ 2π σf(E-E0)

1200

0.4



counts

1000
800
600

0.2
0.0

400

-4
0
4
E-E0 (eV)

EUV+IREUV only
fit

200
0
25

30

35
electron energy (eV)40

Figure 4.5: Photoemission spectrum at zero time delay between the EUV and IR fields,
taken from the data shown in figure 4.3. Observed photoemission spectrum with (redline) and without (black line) the IR pulse present. The blue line shows the fit to the
EUV+IR curve by convolving the LAPE response function from equation 4.3 with theunperturbed spectrum. The inset shows the LAPE response function associated withthe fit.

that no sidebands are observed when the polarization of the IR light is perpendicular to the direction of detection (s-polarized, see figure 4.15a). However, hot electrons
can be observed for both polarizations of the IR field. These hot electron-energy distributions persist for significantly longer times than the LAPE response (hundreds offemtoseconds), and are discussed below.
By fitting the photoelectron spectra for all other time delays, with h̄ω and σ
fixed to the values derived from the time zero photoemission spectrum, we determine
the strengths A1 of the first-order sideband as a function of delay between the IR and
EUV pulses (figure 4.7b). The small error bars show the large sensitivity of the fit to
the sideband heights, which is due to the fact that the positive sidebands show up in aregion well beyond the Fermi edge where the EUV-only spectrum exhibits a small countrate. For a cross-correlation measurement, an observable which is linear in the laser

64
0.5

√ 2π σf(E-E0)

1200

800



counts

1000

600

0.4
0.3
0.2
0.1
0.0
-4

400

EUV+IREUV only
fit

200

0
4
E-E0 (eV)

0
25

30

35
electron energy (eV)40

45

Figure 4.6: Identical spectrum to that shown in figure 4.5, where the positive andnegative first-order sideband heights are allowed to vary during the fit. However, nosignificant asymmetry is generated as a result of this fit.

intensity IL is required. As shown in figure 4.7a, A1 fulfills this requirement for small
IL , where A1 is approximated by the asymptote A∗1 = x2 /4, and, following equation 4.1,
x2 ∝ IL . For larger intensities, however, A1 levels off and exhibits a sublinear behavior.
To ensure a linear dependence for all data points, the sideband heights A1 are thus
replaced by the corresponding values A∗1 of the asymptote. A Gaussian fit yields afull width at half maximum of 33 ± 2 fs, in accordance with the expected EUV pulse
duration of ∼ 10 fs and the IR pulse duration on the order of 35 fs, respectively [50].
Figure 4.8 shows a LAPE measurement at an angle of about ϑ = 5◦ (see figure3.6) between the IR polarization (p-polarized) and the surface normal, close to grazing
incidence. At this sample angle, which corresponds to an observation angle of about
20◦ with respect to the surface normal, the d-band peak at the Fermi edge is evenmore pronounced than in the previous geometry, and it dominates the broader d-bandstructure at 30 eV. As a result, the sideband characteristics of the LAPE process become
even more obvious. The steps due to the first- and second-order positive sidebands are

65

a)

0.8
2

A1 = J1 (x)2A1, A1*0.6

A1* = x /4

0.4

0.2

0.0
0.0

b)

0.5

1.0

1.5
2
x

2.0

2.5

3.0

sideband height A1, A1*

0.4
A1
A1*
fit

0.3

0.2

0.1

0.0
-100

-50

0

50

100

Time Delay (fs)Figure 4.7: (a) The solid line shows the square of the Bessel function A1 = J12 (x),plottedversus x2 ∝ I. The dotted line depicts the asymptote behavior for small x: A∗1 = x2 /4.
For a cross-correlation measurement, a linear intensity dependence of A1 is required,
which is only fulfilled for small x. (b) Measured cross-correlation of the IR (with 30 fs
pulse duration) and the expected ≈ 10 fs duration EUV pulses as a function of timedelay. The measured sideband heights A1 are replaced by the corresponding values A∗1of the asymptote, so that linear intensity dependence is ensured for all data points.
A Gaussian fit yields 33 ± 2 fs, limited by the duration of the IR pulse duration. A
Gaussian fit to the uncorrected A1 data yields 37 ± 3 fs.

66
more pronounced and the first-order negative sideband is visible. Moreover, like in theprevious data set, the EUV+IR spectrum can again be reproduced from the EUV-only
data by convolution with the symmetric sideband function of equation 4.3. This result
has been found at several other sample angles as well, which are not shown here. The
universal applicability of this fit procedure to data taken at different sample angles
excludes band structure effects, e.g. the opening of band gaps [91, 92], from being thecause of the observed IR-induced modifications to the photoemission spectra.

1400√ 2π σf(E-E0)

1200



counts

1000
800

0.6
0.4
0.2
0.0

600
400

-4 -2 0 2 4
E-E0 (eV)

EUV+IREUV only
fit

200
0
28

30

32

34
36
electron energy (eV)

38

40

42

Figure 4.8: LAPE spectrum taken at a different sample angle of ϑ = 5◦ . Due to thelarger d-band peak at this angle, the negative sideband is more clearly visible.

Figure 4.9 shows a time series of LAPE spectra (red curves) between -40 fs and
40 fs in steps of 5 fs. The black curves represent the EUV-only spectra and the blue
curves are the fits. In this data set, the space-charge turns out to be stronger than in theprevious measurement. This may be due to higher surface roughness, which depends onthe cleaning procedure and thus changes from day to day. The corresponding shift tohigher energies of the EUV+IR spectra with respect to the EUV-only curve is alreadycorrected-for in figure 4.9. In addition, the data at -40 fs (where the EUV pulse comes

67
after the IR pulse) reveal a slight smearing of the EUV+IR spectrum, caused by the
space-charge induced Coulomb explosion. Despite this smearing, the fit procedure still
qualitatively reproduces the EUV+IR spectra, especially the step-like structure in the
spectra that show strong LAPE. Quantitatively however, the space-charge distortion
will lead to systematic deviations of the fit parameters A1 and A2 . These sideband
heights are plotted versus time delay in figure 4.10. A1 grossly follows the expected
Gaussian cross-correlation characteristics as in the previous data set. However, it does
not go to zero at the wings, primarily because of the space-charge effects. Moreover,the background is not constant, but is higher for large time delays. This backgroundis most likely composed of a constant part, due to the space-charge effect, and above
time zero, a time-dependent part from hot electrons. These effects will be discussed in
more detail in the following sections, but they will not be taken it into account in thediscussion of the present data set. A tentative Gaussian fit of the A1 curve in figure
4.10 yields a width of 38 ± 5 fs, similar to the previous measurement.
Due to the larger number of data points, the present time series makes it possible
to investigate the time dependence of the smaller second-order sideband height A2 (seefigure 4.10). It follows a similar Gaussian curve with a width of 35 ± 3 fs, in agreementwith the time dependence expected from the pulse lengths. Despite the contributions
from hot electrons and space-charge, we can perform a coarse check of equation 2.50 bycomparing the maxima of A1 and A2 . For the observed Amax
= 0.25 ± 0.02 we expect,1
after An = Jn2 (x), an accompanying Amax
= 0.026 ± 0.06, which agrees reasonably with2
the measured value of 0.038 ± 0.002.
Figure 4.11 shows an alternative analysis of the data using the d-band peak at the
Fermi edge. After subtraction of the EUV-only curves in figure 4.8 from the EUV+IR
data, two maxima arise around 34 eV and 37 eV, originating from the the positive andnegative first-order sidebands, respectively. Additionally, the depletion of the d-band
peak leads to a minimum in the subtracted data. These three extrema are plotted68Time Delay (fs)
5000

40
35
30
25

4000

20

counts

15
10

3000

5
0
- 5
- 10
- 15

2000

- 20
- 25

1000

- 30
EUV+IREUV only
fit

- 35
- 40

0
30

32

34
36
38
electron energy (eV)40

Figure 4.9: LAPE time series for EUV+IR pulse separations between -40 fs and 40 fs
in steps of 5 fs. The black lines show the EUV-only data. The EUV+IR spectra (redlines) are corrected for a 0.1 eV space-charge shift. The blue lines show the symmetric
fits.

69

Sideband Intensities A1,2

0.25
A1
A2
fit

0.20
0.15
0.10
0.05

-40

-20

0
Time Delay (fs)20

40

Figure 4.10: Amplitude of the first-order (blue circles) and second-order (red squares)
sideband intensity versus time delay. The fits result in FWHM of 37 ± 5 fs and 35 ± 3
fs for the first- and second-order sidebands, respectively.

versus time delay in figure 4.11. Gaussian fits result in widths of 36 ± 4 fs for the
positive sideband, 37 ± 6 fs for the negative sideband, and 38 ± 5 fs for the 0th order,
which agree with each other and with the pulse widths within their error margins. In
summary, dressing of pronounced peak-like structures in the electron spectra of solids
can be detected by a direct comparison of the EUV-only and the EUV+IR data andby monitoring the sideband heights or, more sensitively, by the depletion of the photoemission peak. Alternatively, if the structure is more complicated, the convolutionof the EUV-only data with a sideband function has to fit to the EUV+IR data. In
any case, the dressing makes it possible to measure the time when electrons are ejectedfrom surfaces or adsorbates by photoemission or subsequent Auger decay. To achieve
optimum time resolution, other IR-induced effects such as space-charge acceleration or
hot electron excitation must be minimized.
As scattering of photo-emitted electrons within the material leads to large angle

sideband intensity (a.u.)

70
500
0
-500
-1000
positive sideband
negative sideband
carrier

-1500

-40

-20

0
Time Delay (fs)20

40

Figure 4.11: Positive and negative sideband heights (upper curve) and depletion of thed-band peak (lower curve) versus time delay. The Gaussian fits yield 36 ± 4 fs for the
positive sideband, 37 ± 6 fs for the negative sideband, and 38 ± 5 fs for the depletion
signal, respectively.

and energy changes, scattered electrons are effectively removed from the part of thespectrum near the Fermi edge that we analyze. The observed electrons thus essentiallyoriginate from a thin layer defined by their ≈ 5 Å mean free path. We believe thatthe finite transit time through this layer ultimately limits the resolution of surfaceLAPE for characterizing EUV pulses or for measuring ultrafast inner-shell electron
dynamics in solids. In our case, this value is < 200 attoseconds, and thus does not
limit our measurement. Still higher resolution could be obtained by increasing the EUV
photon energy, and thus the emitted photoelectron energies, so that they escape more
quickly. Therefore, this result also opens up new possibilities for studying femtosecondto-attosecond correlated electron dynamics in solids.

71

4.5

Laser Intensity Dependence of LAPE from Surfaces
To study the intensity dependence of the first-order sidebands, we first investi-

gated the influence of the sample on the effective intensity on the surface. To this end,
the IR light was p-polarized and the surface was rotated horizontally to three different
angles ϑ between the IR polarization and the surface normal. ϑ = 0◦ denotes grazing
incidence with the polarization being perpendicular to the surface. ϑ = 90◦ denotes
normal incidence and parallel polarization with respect to the surface. Figure 4.12
shows the amplitude A1 of the first-order sideband extracted at three different angles.
Towards ϑ = 90◦ , A1 decreases strongly. This sample angle dependence can be fit witha cos2 consistent with the assumption that only the electric field exactly at the surface
interacts with the photoemitted electron. As the parallel component Ek vanishes here,
only the perpendicular field E⊥ = Ein cos ϑ remains. For moderate laser intensities, A1
is linear in IL and therefore follows Iin cos2 ϑ.
Figure 4.13 depicts a series of photoemission spectra taken at different IR peakintensities. EUV+IR (red lines) and EUV-only (black lines) at time zero as well as
EUV+IR at -100 fs time delay (blue) are shown. The -100 fs curves reflect the influenceof the space-charge of the IR-induced low-energy electrons on the EUV photoelectrons
around the Fermi edge. At low intensities, it results in a shift to higher energies due toacceleration, whereas the shape of the spectrum is unaffected. At the highest intensity
shown, the space-charge also changes the shape of the spectrum. After correcting forthe space-charge shifts using the -100 fs spectra, the sideband heights A1 are determinedusing the fit procedure described in the previous section, and results are shown in figure
4.14. The measurement taken near 600 GW/cm2 is still below the damage thresholdof the surface. However, at this intensity the space-charge created by the IR beam on
the sample starts changing the shape of the EUV+IR spectrum as compared to the
EUV-only spectrum, making the extraction of the sideband amplitude more difficult.

72

0.25

90°

sideband height A1

0.20

TOF
0.15

0°
p-polarizedlaser beam

0.10

0.05

0.00
0

20

40
60
sample angle ϑ(°)

80

100

Figure 4.12: First-order sideband height as a function of the sample angle. The sample
is shown to influence the effective dressing field, because the component of the electricfield perpendicular to the surface is reduced due to boundary conditions. The dataagree with the expected cos2 reduction in the effective intensity. The inset illustrates
the definition of the sample angle (surface normal) for 0◦ and 90◦ with respect to the
IR polarization.

We thus used a EUV+IR spectrum taken at -100 fs as a background spectrum for the
convolution, since it shows the same distortions due to the space-charge effect as the
EUV+IR spectrum, but does not exhibit the sidebands. This procedure leads to thelarger uncertainty for this data point. At even higher laser intensities, electrons fromATP begin to overlap with the Fermi edge in the spectra and bury the LAPE signature.
However, such high laser intensities are only necessary for testing the validity of thesimple theoretical description of surface LAPE given earlier.
The laser intensity is also corrected for the sample angle, so that it corresponds
to the perpendicular component of the electric field. This corrected laser intensity√
dependence is then fit to An = Jn2 (a I). Here, a is a fit parameter and n = 1 denotes
the number of absorbed or emitted IR photons. Qualitatively, we find excellent agree-

73

IR peak intensity2(GW/cm )
526
10000

439
395

8000

counts

351
6000

307
263

4000

219
175

2000

132
EUV+IR (0fs)
EUV-only
EUV+IR (-100fs)

88

0
20

25

35
30
electron energy (eV)40

Figure 4.13: Photoemission due to both EUV+IR (red lines) and EUV-only (black lines)
light at time zero as well as EUV+IR for a delay of -100 fs (blue lines) for different IR
laser intensities. The -100 fs curves show the influence of the space-charge induced by
the IR-induced low-energy electrons on the XUV photoelectrons around the Fermi edge.
At low intensities, it results in a shift to higher energies due to acceleration. At thehighest intensity shown, the space-charge also changes the shape of the spectrum.

74
ment between our data and this model. The quantitative comparison is limited by theknowledge of the actual IR beam intensity. The peak IR intensity corresponding to
the perpendicular electric field at the surface was calculated by taking into account the
sample angle. This intensity is likely to be an overestimation of the effective dressing
intensity for two reasons. First, the EUV beam spot size is estimated to be a significant
fraction of the IR beam spot size. And second, a possible misalignment of the spatial
EUV+IR overlap would decrease the effective intensity. From the kinetic energies of theelectrons around the Fermi edge and the laser photon energy, the first-order sideband
amplitude is expected to peak at 540 GW/cm2 . From the fit we find the maximum of
the Bessel function at 960 GW/cm2 , which is within our error margin for the effective
intensity. Note also that our highest data point has an amplitude of A1 = 0.30, very
close to the maximum of the square of the first order Bessel function of 0.348. Thisshows that essentially all detected photoelectrons are dressed.
For applications such as measurement of pulse duration or surface electron dynamics, it is desirable to use lower IR pulse intensities in the linear regime, where thecross-correlation A1 (τ ) directly reflects the time behavior under study. At these laser
intensities, we found LAPE to be the dominant process. The presence of space-charge induces only a small overall shift in the spectra that can be corrected for. Above thresholdphotoemission can be suppressed below 600 GW/cm2 by using a flat surface [95]. The
excitation of hot electrons has been found to cause significantly smaller modificationsof the photoemission spectrum than LAPE even at rather high laser intensities [99].
However, the presence of such hot electrons can be distinguished from LAPE since theirpresence increases the average electron kinetic energy around the Fermi edge.
Our data show that laser-assisted photoemission from a Pt(111) surface can beobserved for IR intensities up to 600 GW/cm2 , below what is needed to observe heating,ATP, or desorption at metal surfaces [37]. This result is important for applications ofsurface LAPE to the study of attosecond electron dynamics in solids and in surface-

75
0.35
sideband amplitude A1

0.30
0.25
0.20
0.15
0.10
0.05
0.00
0

200

400
600
800
2
IR peak intensity (GW/cm )

1000

1200

Figure 4.14: Extracted sideband intensity A1 as a function of the effective IR beam
peak intensity, perpendicular to the surface. The influence of the sample angle has beentaken into account. The sideways intensity follows the theoretically expected squareof the first-order Bessel function. The maximum of the curve is a factor of two higher
than expected from the argument of the Bessel function (equation 4.1). This is within
our experimental uncertainty in the determination of the effective dressing intensity
because of insufficient knowledge of the spatial overlap between EUV and IR pulses on
the sample.

adsorbate systems.

4.6

Hot Electrons
At high IR laser intensities (IL > 5 × 1011 W/cm2 ), a significant number ofelectrons within the conduction band will be excited, resulting in a non-equilibrium hot
electron distribution at the Fermi edge. The number of excited electrons depends only
on the laser fluence absorbed by the metal. Hot electron excitation is thus expected
regardless of the polarization, although energy coupling onto the surface can vary, tosome extent, with polarization. In order to observe hot electrons, but suppress LAPE, weacquired the time series of photoemission spectra shown in figure 4.15a using s-polarized
IR light at a high intensity of about 1012 W/cm2 . For time delays greater than -60 fs, a76slight influence of the IR laser light is observed in the EUV+IR spectra. However, thiseffect is considerably smaller than in the previous measurements with p-polarized light.
We analyze these excess electrons in two different ways. First we subtract the EUV-only
spectra from the corresponding EUV+IR spectra. The difference in these spectra show
a peak above the Fermi edge stemming from the excess electrons. Figure 4.16 shows
the integrated area of this peak versus time delay. The second approach to analyze
these data is by calculating the average kinetic energies hEkin,IR i and hEkin,EUV i above
the ATP distribution (i.e. >33 eV in this case). In figure 4.16, the solid line shows,
as a function of time delay, the normalized difference (hEkin,IR i-hEkin,EUV i)/hEkin,EUV i,i.e. the laser-induced increase of the kinetic energy. After proper scaling, the curves
are shown to follow the same characteristics: an increase in electrons > EF at -60 fs
followed by an exponential decay as the time delay increases. In this case, the IR pulse
serves as a pump for the process observed here. This time behavior is fundamentallydifferent from the cross-correlation found for LAPE, and indicates the excitation of acomparatively long-lived hot electron distribution.
Figure 4.15b shows another time series taken with p-polarized IR light at a laser
intensity of 5 × 1011 W/cm2 , which is half the intensity used with the s-polarized lightdata discussed above. These data clearly show a LAPE signal at -40 fs, visible again
as a comparably strong step-like modification of the Fermi edge. In addition, excess
electrons are visible beyond the Fermi edge for time delays exceeding the EUV+IR
cross-correlation time. We again corrected for the small space-charge effect and thenevaluated the excess electrons and the kinetic energy increase (figure 4.17). In thismeasurement, the time dependence of the excess electrons exhibits a two-component
structure. We ascribe the peak at -40 fs to LAPE. The corresponding spectrum could
be fitted in the way described above. The subsequent slow decay is due to hot electrons.
A fit yields a decay time of about 260 fs, in agreement with the measurement using spolarized light. The kinetic energy curve reflects only the hot electron contribution to

77

a)

Time Delay (fs)b)

Time Delay (fs)

200

200

6000
6000

180

5000

180

160

160

140

140

120

5000

120

100

100

80

80

60

4000

60

4000

20
0
3000

40

countscounts

40

20
0
3000

- 20

- 20

- 40

- 40

- 60
2000

- 80

- 60
2000
- 80

-100

-100

-120
-140

1000

-120
-140

1000

-160

-160

EUV+IREUV only

-180
-200

0

0
26

28

30

32

34

36

electron energy (eV)

38

40

26

28

30

32

34

36

38

40

electron energy (eV)Figure 4.15: (a) Photoemission spectra around the Fermi edge for s-polarized IR lightat high laser intensity (1012 W/cm2 ). The electric field at the surface vanishes in thiscase, so that no dressing is expected. However due to the absorption of IR light, a
hot electron distribution is excited, and is visible at the Fermi edge for relative timedelays later than -60 fs (time zero in this measurement). (b) Photoemission spectra forp-polarized IR light at half the intensity applied in a) (5 × 1011 W/cm2 ). Hot electrons
are visible at positive time delays. LAPE can be observed at -40 fs (time zero), clearly
dominating the hot electron distribution and distinguishable by its step-like shape.

78
the excess electrons since LAPE does not change the net kinetic energy. This showsthat the slow decay can be attributed to electrons that gain kinetic energy on average,

Hot Electron Distribution (a.u.)whereas the peak is due to electrons that are redistributed symmetrically due to LAPE.

600

400

increase of mean kin. energy
excess electronsexp. fit to excess electrons

200

0
-150

-100

-50

0
50
Time Delay (fs)

100

150

200

Figure 4.16: Excess hot electrons (dots) at the Fermi edge for s-polarized IR light. These
hot electrons follow a sharp rise and slow exponential decay. The fit (dashed) yields a
lifetime of about 270 ± 60 fs. This behavior is also found for the average kinetic energy(solid line) and is consistent with expected hot electron lifetimes.

4.7

Conclusion
In this chapter the laser-assisted photoelectric effect from a solid surface was in-vestigated. By illuminating a Pt(111) sample simultaneously with ultrashort 1.6 eV and
42 eV pulses, we observed sidebands in the extreme ultraviolet photoemission spectrum.
Sideband amplitudes were extracted very accurately from the continuous spectra over awide range of laser intensities. Our results agree with a simple model, in which LAPE is
described by EUV photoemission followed by the interaction of the photoemitted electron with the laser field. This strong effect can definitively be distinguished from otherlaser surface interaction phenomena, such as hot electron excitation, above-threshold

Hot Electron Distribution (a.u.)

79

1000
increase of mean kin. energy
excess electronsexp. fit to excess electrons

800
600
400
200
0
-200

-100

0
Time Delay (fs)

100

200

Figure 4.17: Excess hot electrons (dots) at the Fermi edge for p-polarized IR light. In
this case, the excess electrons show a two component structure. For large time delays
they decay exponentially. The fit results in a lifetime of 260 ± 80 fs, in agreementwith the value found for s-polarized light (270 ± 60 fs). Around time zero, the electron
distribution exhibits a peak which is due to LAPE. The average kinetic energy, whichis insensitive to LAPE, still follows the exponential decay behavior characteristic of hotelectron decay.

photoemission and space-charge acceleration.

Chapter 5
Direct Measurement of Core-Level Relaxation Dynamics in Complex
Systems

5.1

Introduction
The results presented in chapter 4 are important for the study of ultrafast,

femtosecond-to-attosecond time-scale electron dynamics in solids and surface-adsorbate
systems. By studying the evolution of the sideband height at different time delays between EUV and IR pulses, we can extract information about the electron dynamics. If
the electron to be studied is directly photoemitted by the EUV pulse, then the temporal evolution of the sideband height allows us to characterize the EUV pulse duration.
However, if the electron under study is a secondary electron, which means the electron
is photoemitted some time after the EUV pulse hits the sample, then the temporal evolution of the sideband height encodes information about the time it took for the electron
to be photoemitted. In the case of adsorbates (atoms or molecules), a comparison of thetime it takes for this electron to be photoemitted while the atom/molecule is absorbed
on a substrate or in gas phase gives us information about charge-transfer time scales
between the adsorbate and the substrate.
Charge-transfer processes between substrates and adsorbates are of great importance in many areas of surface science [100]. Various approaches have been used
to obtain information about charge-transfer time scales, including line-shape analysis [101], core-hole clock spectroscopy [102, 103], and direct time-domain pump-probe

81
experiments [104,105]. Line-shape analysis has been successfully applied to the study ofcore-hole lifetimes in isolated molecules and atoms, where spectral lineshapes are mainly
homogeneously broadened. Thus, the spectral linewidth is unambiguously related to the
dynamics of simple decay processes, because no further energy and momentum dissipation processes exist.
However, in the case of adsorbates on solid surfaces, inhomogeneous contributions
due to the substrate (distortions, dislocations, and impurities) and adsorbate-substrate
vibrations can increase the linewidth. Charge-transfer processes between the adsorbate
and substrate can increase the homogeneous linewidth. For adsorbate states, in general,a clear separation between homogeneous and inhomogeneous broadening is not always
possible. Time domain measurements promise to directly observe dynamics unalteredby additional inhomogeneous contributions. However, these experiments require a time
resolution comparable to typical electronic charge-transfer time scales, which are often
in the range of a few fs, and in some cases can even be sub-femtosecond. As a result,real time experiments [106] have proven to be very challenging.
Core-hole clock spectroscopy is a method that seeks to overcome the limitations of pure energy- or time-domain methods, by using a sequence of energy-resolved
measurements in conjunction with an adsorbate core level as an internal “reference
clock” for investigating fast electron relaxation dynamics [102, 103]. This approachhas demonstrated that adsorbate-to-substrate electron transfer processes can proceedon attosecond-to-femtosecond timescales. However, this technique requires accurate
knowledge of core-hole lifetimes in adsorbate-substrate systems, which may differ fromthe core-hole lifetime of the same atom/molecule in the gas phase. In investigations todate, the lifetime of these core states has been inferred through energy-domain measurements, assuming that the lifetime of these states is not changed from that of a free
atom measured using high resolution atomic spectroscopy.
The first time-resolved studies of electronic and charge-transfer dynamics at sur-82
faces investigated valence band resonances of chemisorbed and physisorbed atoms andmolecules on metallic surfaces [107,108]. These efforts reported a strong influence of thesubstrate on the resonance lifetimes, even for physisorbed systems, due to good overlap of the electronic wavefunctions. These experiments used time-resolved two-photon
photoemission, driven by a combination of ultraviolet and infrared (UV+IR) photons
with energies up to a few eV. Therefore, these studies explored adsorbate states in thevalence and conduction bands just below the vacuum level. To date however, investigations of core energy levels have been performed only in the energy domain [109].
Recently, the development of high-harmonic generation (HHG) sources [5, 25, 110] hasmade it possible to access the ultrafast dynamics of both valence and core levels [37,98].
Here we present the first time-domain measurement of Auger decay from a complex materials system - an adsorbate on a surface (Xe/Pt(111)), see figure 5.1. Bycomparing laser-assisted photoemission from a Pt substrate with the delayed laserassisted Auger decay from Xe, we measure the core-hole lifetime for the 4d vacancy inatomic Xe absorbed on a Pt(111) surface to be 7 ± 1 fs. This measurement is possible
despite the many complexities that result from the metallic substrate, such as above
threshold photoemission, hot electrons, and space-charge effects. It is also the firstmeasurement of the lifetime of core holes in Xe/Pt, since there exists no spectroscopic
measurement of the linewidth of these transitions. The extracted lifetime for the Xe/Pt
4d core-hole is consistent with high-resolution linewidth measurements of Xe in thegas phase, clearly validating our approach. Furthermore, our results demonstrate thattime-resolved measurements are possible that can definitively identify the nature of any
spectral broadening in more tightly bound systems, such as chemisorbed systems. Thismeasurement is the first time-domain observation of highly excited states in a complex
system, i.e. not in an isolated atom environment.
As mentioned in chapters 2 and 4, in a laser-assisted process, an atom is irradiated simultaneously by an ultrafast soft x-ray (SXR) and a laser beam. Characteristic

83Electron
Kinetic Energy

IR laser

LAAD
Auger

TOF

LAAD

O2,3 (5p)O1 (5s)Soft X-Ray
N4 (4d)XePt(111)Figure 5.1: Schematic of the experiment. Ultrafast SXR and IR pulses are focused
into a Xe/Pt(111) surface, where the kinetic energy of the photoemitted electrons ismeasured by a time-of-flight detector. An electron from the Xe N4 (4d) shell is ejectedby the SXR, followed by filling of the core-hole by an O2,3 (5p) shell electron and ejectionof a secondary (Auger) electron from the O2,3 shell. In the presence of the IR beam,
sidebands appear in the photoelectron spectrum of both Xe and Pt. By comparing the
sideband amplitude vs time delay for the Pt and Xe, we can extract the lifetime of theXe 4d core hole.

84
sidebands appear surrounding the SXR photoemission peaks, corresponding to simultaneous absorption and emission of laser photons. The magnitude and shape of thesesidebands change as the time delay between the SXR and laser beams is changed, encoding information about the underlying electron dynamics.

5.2

Sample Preparation
Before dosing the surface with Xenon, the Pt surface was cleaned via three cyclesof oxygen annealing at 450 ◦ C and flashing to 1000 ◦ C. After dosing the Pt(111) surface with a monolayer of Xe at a temperature of 84 ◦ K, three distinct features can be
distinguished in the photoelectron spectrum (see figure 5.2). Around the Fermi edge,
corresponding to photoelectron kinetic energies of ∼ 85 eV, we observe the d-band of Pt.
At photoelectron kinetic energies between 22 and 26 eV, we detect the Xe 4d core-levels,
while at energies between 35 and 42 eV, we observe the Xe NOO Auger electrons. These
Auger electrons are emitted when an electron from the Xe N4 (4d) shell is ejected by
a 90.8 eV SXR, followed by filling of the core-hole by an O2,3 (5p) shell electron andejection of a secondary (Auger) electron from the O2,3 shell, as shown in figure 5.1.

5.3

Results and Discussion
In the presence of an intense laser field, sidebands appear in the Xe/Pt(111)

photoemission spectrum (see figure 5.3) over the entire energy range. By comparing the
sidebands surrounding the Pt d-band peaks (corresponding to the fast process of direct
photoemission), with the sidebands surrounding the Auger peaks of Xe (corresponding
to the slower process of Auger decay), we can directly measure the lifetime of the 4d corehole of Xe/Pt(111). In this way, we take advantage of the precise timing information
inherent in laser-assisted photoemission.
In order to extract the sideband height from our data we follow the same steps
described in section 4.4. However, for low IR intensities, careful comparison of theory

85
Xe 4d
core-levels

clean Pt(111)
Xe/Pt(111)counts600

400

Pt d-band

Xe NOO Auger

200

0
20

30

40

50
60
electron kinetic energy (eV)

70

80

90

Figure 5.2: Photoelectron spectra for clean (red) and Xe dosed Pt (blue).

and experiment have shown that the sideband height can be modeled by the square ofa Bessel function A1 = J12 (x) [70], with the argument given by equation 4.1.
For small intensities, A1 approaches the asymptote A∗1 = x2 /4, and becomeslinear in the IR laser intensity I:

A∗1 ≈

IEkin
4 .
ωIR

(5.1)

Here, Ekin represents the kinetic energy of the photoemitted electron, and ωIR
the IR photon energy. In this linear regime, A1 directly provides a suitable observableto follow the electron dynamics. At higher intensities, however, A1 levels off and showsa sub-linear behavior. To obtain a signal linear in I throughout the entire intensity
range, we project the sideband heights onto the asymptote by replacing all measured
A1 by the corresponding values [99].
Figure 5.4 shows photoemission spectra for the case of SXR only, as well as the
optimal overlap of both IR and SXR beams in space and time on the Xe/Pt(111) sample.

80
40
0

5

10

15

20x10

3

20

30

Xe 4d
core-levels

Xe NOO Auger

5060electron kinetic energy (eV)70

Pt d-band

SXR-only
SXR+IR

90

86

countsFigure 5.3: Photoelectron spectra for Xe/Pt(111) with (red) and without (black) the
presence of the IR pulse.

87
0.8

1400

0.6
√ 2π σ f(E-E0)

a 1600

0.4



1200

Extracted LAPE sidebands

Counts

1000

0.2

800
0.0

Pt d-band

600

-4

0
E-E0 (eV)4400
SXR+IRSXR only
fit

200
0
76

78

80

82
84
Electron energy (eV)8688b 40000.8

Extracted LAAD sidebands

0.6

0.4



√ 2π σ f(E-E0)

3500

3000
Counts

90

0.2

2500

0.0
-4

}

2000

0
E-E0 (eV)4

Xe NOO Auger electrons
SXR+IRSXR only
fit

1500

34

36

38

40
Electron energy (eV)4244c 18x10346

Extracted LAPE sidebands
0.8

16√ 2π σ f(E-E0)

0.6

0.4



14

Counts

12

0.2

10

0.0
-4

8

0
E-E0 (eV)4}6

SXR+IRSXR onlyfit

420

Xe 4d core-levels

22

24Electron energy (eV)26

28

Figure 5.4: Extraction of the LAPE/LAAD sideband amplitudes for Xe/Pt(111) atzero time delay between the IR and SXR beams. (a) Photoelectron spectra near thePt d-band; (b) near the Xe Auger N OO bands; and (c) near the Xe 4d peaks. The redand black lines represent the spectra with and without the IR pulse, respectively. The
blue lines show the fit to the SXR+IR curve when the LAPE response function fromequation 4.3 is convolved with the SXR-only spectrum. The insets show the extracted
LAPE/LAAD response function associated with the fit, demonstrating the dependenceof the sideband amplitudes on the photoelectron energy.

88
These spectra clearly show strong sidebands surrounding the Pt d-band, with weaker
but still detectable sidebands surrounding the Xe Auger N OO peaks and the Xe 4d
peaks.
Equation 5.1 implies that the ratio of the sideband heights of the Pt d-band andthe Xe 4d peaks should be equal to the ratio of their corresponding photoelectron kinetic
energies:
Ekin(d-band)A∗d−band=.
∗AXe
Ekin(Xe)(5.2)

To verify this experimentally, one can consider the first-order sideband height at
the Pt d-band (A∗d−band ), with a value of 0.26 ± 0.01, for a photo-emitted electron kinetic
energy of 85.1 eV. For the first-order sidebands surrounding the Xe 4d peak (A∗Xe ), theirheight is 0.08 ± 0.01, corresponding to an electron kinetic energy of 24.8 eV. Thus, thesideband height ratio yields 3.43 ± 0.02, while the electron kinetic energy ratio is 3.4.
This good agreement of the extracted sideband heights with that predicted by theory,
coupled with the excellent agreement of the fit from equation 4.3 and the experimental
data over a very broad energy range (blue and red curves of figure 5.4), confirms thatlaser-assisted photoemission (LAPE) and laser-assisted Auger decay (LAAD) processes
are responsible for all the large changes in the SXR photoemission spectrum of Xe/Pt
in the presence of an intense IR beam.
Figure 5.5 shows a series of photoelectron spectra at a peak IR laser intensity of
1.3 × 1011 W/cm2 , for relative time delays of -50 fs to 50 fs between the SXR and IR
beams. Negative time delay corresponds to the SXR pulse arriving after the IR pulse.
The IR beam polarization was chosen parallel to the direction of detection in order tomaximize the laser-assisted photoemission sidebands. Due to the low intensity of the
IR beam used in this experiment, we do not observe above-threshold photoemission
effects [95, 96] at the kinetic energies of the Xe 4d peaks, or space-charge effects [35, 97]

(fs)

l ay
De

40

20

0

-20

-40

Pt d-band
phototelectrons

90

80

Xe Auger
photoelectrons

70

ron
Elect

50

V
gy (e
ener

)

40

0 fs delay-50 fs delay

30

89

Figure 5.5: Photoelectron spectra from Xe/Pt(111) as a function of time delay. Negative
time delays denote that the SXR pulse arrives after the IR pulse. The time evolutionof the redistribution of electrons due to the IR dressing at the Pt d-band and at the
Xe Auger photoelectron peaks can be observed. The spectra shown in the lineouts
correspond to the photoelectron spectrum at zero (red) and at -50 (black) fs time delay
between the SXR and the IR pulses.

90
at the Fermi edge. In figure 5.5, the time evolution of the redistribution of electrons
can be observed, both at the Pt d-band and in the region of the Xe Auger peaks. The
spectra shown in the lineouts correspond to the photoelectron spectrum at zero (red)and at -50 (black) fs time delay between the SXR and IR pulses.
For each time delay, the sideband height at the Pt d-band and at the Xe Auger
peaks are independently obtained. The results for the projected first-order sideband
amplitudes are plotted in figure 5.6. The left and right axes have been scaled withrespect to each other in order to match the ratio between the kinetic energies of thePt d-band and the Auger peaks. The time evolution of the sideband height for the Pt
d-band electrons (A∗d−band ) corresponds to a cross-correlation between the SXR and theIR pulses. A Gaussian fit yields a FWHM value of 36.1 ± 1.5 fs, centered at time zero.
Since our IR pulse duration is 35.5 ± 1.2 fs, measured using the Frequency Resolved
Optical Gating technique [111], we obtain a SXR pulse duration of 6.6 ± 6.1 fs fromthe cross-correlation signal.
In contrast to the sideband signal extracted from the Pt d-band (red curve), thesideband signal corresponding to the Xe Auger electrons (A∗Auger ) (black curve) is clearlyshifted by ∼ 6 fs with respect to time zero. Moreover, a Gaussian fit yields a broadened
FWHM of 40.1 ± 2.1 fs. The observed time shift and broadening are the result of
the inherent lifetime of the Xe 4d core-hole. By fitting the Auger sideband curve withthe convolution of a decaying exponential and the direct photoelectron cross-correlation
obtained from the Pt d-band data, we obtain a Xe 4d core-hole lifetime of 7.1 ± 1.1 fs.
Thus, by comparing laser-assisted photoemission and Auger decay, the characteristic
delay of the Auger emission can be precisely measured, making it possible to obtain
fairly good resolution even using a relatively long 35 fs IR pulse.
Achieving temporal overlap between the SXR and the IR pulses during the dataacquisition time was of crucial importance to accurately extract the core-hole lifetime. In
order to test the stability of the temporal overlap, we acquired our data in 10 increasing

91

0.25

Xe 4d-1 lifetime = 7.1 ± 1.1 fs

FWHM EUV = 6.6 ± 6.1 fs
FWHM IR = 35.5 ± 1.2 fs

0.12
0.10

0.20

0.08

0.15

0.06

0.10

0.04

0.05

0.02

0.00

0.00

-40

-20

0

20

*
Projected Sideband height A Auger*
Projected Sideband height A d-band

Δt = 5.9 ± 0.2 fs

40

Delay (fs)Figure 5.6: Sideband height vs time delay for the Pt d-band and Xe Auger photoelectrons. The sideband height for the Pt d-band (red curve) corresponds to a crosscorrelation between the SXR and the IR pulses. In contrast, the Auger sideband height(black curve) is clearly shifted by 5.9 ± 0.2 fs with respect to time zero, and is alsobroadened with respect to the Pt d-band curve. The shift and broadening are due tothe inherent lifetime of the Xe 4d core hole. From these curves we extract a Xe 4dcore-hole lifetime of 7.1 ± 1.1 fs.

time-delay scans, each with time duration of 45 minutes. The IR beam was chopped
at 1 kHz, and the TOF detector was gated to record SXR+IR and SXR-only spectra,
alternately. The peak of the LAPE signal (from the Pt d-band electrons curve) for allscans was compared to extract a slow time-zero jitter between the SXR and the IR
pulses. Combining this time jitter, which is mainly caused by mechanical vibrations in
our experimental setup, with the statistical error obtained from our fit, we can determine
the core-hole lifetime with an accuracy of ± 1.1 fs.
As mentioned before, our measured Xe 4d core-hole lifetime is consistent with arecent gas phase energy-domain measurement (see figure 5.7), that measured a widthof 111 ± 3meV (6.3 ± 0.2 fs) for Xe 4d states [8]. The close correspondence between
our measurements and previous energy-domain measurements demonstrates that this

92
technique can extract core-hole lifetimes in the time domain [53], thereby identifying thenature of any spectral broadening in more tightly bound systems, such as chemisorbed

Intensity (10 3 counts)

systems.

Xe

4d 3/28
4d 3/2
6
4
2
0
48

50

Kinetic energy (eV)Figure 5.7: Xe 4d photoelectron lines measured at 117.0 eV photon energy. The solidline shows the result of the least-square fit to the data points given by circles. Figure
reproduced from reference [8].

5.4Conclusion
By comparing laser-assisted photoemission from a Pt(111) substrate with the de-layed laser-assisted Auger decay from Xe, we report the first time-domain measurementof a core-hole lifetime of a complex system - in this case an adsorbate on a substrate.
Furthermore, we have experimentally proven the validity of equation 5.1 as a good the-93
oretical model for describing LAPE from surfaces. Future experiments can investigate
more tightly bonded chemisorbed systems. In these systems, the stronger chemicalbond (and hence enhanced charge-transfer process) between substrate and adsorbate is
known to influence the linewidth, broadening it compared with the isolated atom case.
As well as uncovering the mechanisms that influence charge-transfer at surfaces, theseexperiments will also provide an exact surface core-hole lifetime as a reference for othercharge-transfer techniques such as core-hole clock spectroscopy.

Chapter 6
Laser-Assisted Photoemission with Long-Wavelength IR Pulses

6.1

Introduction
As mentioned in chapter 4, for ultrashort Ti:sapphire laser pulses at a wavelengthof 780 nm, intensities on the order of 1011 W/cm2 are typically required to generate
observable LAPE signals. At such high intensities, the IR laser can itself lead to electron
emission through multiphoton and above-threshold ionization (ATI), or in the case ofemission from a solid surface, above-threshold photoemission (ATP). These multiphoton
emission processes often result in a large flux of electrons from the sample that can
obscure the detection of sidebands. These processes are so-called initial state effects(i.e. signal originates overwhelmingly from atoms that have not interacted with the
EUV light), whereas LAPE is a f inal state effect in that these processes are specific to
the EUV-excited atoms.
The ATP process is particularly problematic for ultrafast measurements of surface
electron dynamics. In ATI and ATP processes, electrons can absorb many more photons
than the photoionization threshold, and thus are ejected at high kinetic energies. In thecase of ATI in atoms, these electrons generally still have sufficiently low kinetic energies
that they are separated in energy from the EUV-induced electrons, and thus are not amajor problem. However, past work has shown that ATP from surfaces can be significant
at much lower laser intensities than in atoms, due to field enhancement effects [95]. For
example, in the series of experiments discussed here, 780 nm IR pulses with a peak

95
intensity of 1.4 × 1011 W/cm2 generate ATP photoelectrons with kinetic energy up to
23 eV. These ATP electrons can make it impossible to detect the LAPE signal fromdynamic processes that generate free electrons with low kinetic energies. Processes suchas Auger decay [53] and interatomic Coulombic decay [112,113] often result in low-energy
electrons, and thus their spectroscopic signatures are buried in a large background of
ATP electrons. Furthermore, the high flux of ATP electrons from a very small surface
area leads to a Coulomb explosion of the electron cloud, in which fast electrons areaccelerated and slow electrons are decelerated because of Coulomb repulsion between
them [35, 97]. This space-charge effect can distort the photoelectron energy spectrum
and also smear the LAPE signal [99]. Thus, for many studies in time-resolved surface
electronic dynamics, it is critical to identify approaches for reducing ATP and spacecharge initial state effects. Moreover, even in the case of time-resolved studies in isolated
atoms, there are cases where a reduction in ATI signal can be desirable.
This chapter shows that the use of a strong-field dressing laser pulse at longer
IR wavelengths dramatically reduces ATP and space-charge effects while maintaining
a robust surface LAPE signal. Comparing LAPE photoemission spectra from a cleanPt(111) surface taken using 780 nm and 1300 nm dressing wavelengths demonstrates
that the LAPE signal is significantly enhanced while the number and kinetic energies of
ATP electrons are reduced and the space-charge effects are suppressed. This remarkable
improvement results from the favorable wavelength scaling of both the LAPE and ATP
effects combined. Therefore, this new approach to laser-assisted photoemission allows
us to probe ultrafast dynamics in solids and surface-adsorbate systems over a large
final-state energy range. In particular, this methodology promises to make possible thestudy of time-resolved, low kinetic-energy processes on surfaces for the first time.

96

6.2

Results and Discussion
As discussed in chapter 4, for low IR intensities, careful comparison of theory andexperiment [70, 96] has shown that the sideband height can be modeled by the squareof a Bessel function A1 = J12 (x), with the argument given by equation 4.1. And, for asmall argument x, A1 can be approximated by A1 ≈ x2 /4 leading to equation 4.2:

A1 ∝

IEkin
4 .
ωIR

Equation 4.2 shows that the amplitude of the LAPE sidebands can be increased by
1) increasing the IR intensity I, 2) increasing the kinetic energy Ekin of the electron to be
dressed, or 3) decreasing the frequency ωIR of the dressing field. Option one, increasing
the IR intensity, is generally undesirable because it increases the ATP electron flux andmay also damage or induce desorption from the surface [95]. Option two, increasing thephotoelectron kinetic energy, is not generally applicable. For processes such as Auger
decay or interatomic Coulombic decay, the ejected electron kinetic energy is determinedby the energy level structure of the system, and cannot be varied by changing the energyof the incoming photons. Therefore, the best option for increasing the LAPE signal levelis to tune the wavelength of the IR dressing pulses to wavelengths longer than the 780
nm wavelength typical of a Ti:Sapphire laser. This approach is particularly compelling
given the λ4 dependence from 4.2. Tuning to longer wavelengths can be done in astraightforward way using an optical parametric amplifier (OPA) [79]. This approach isalso desirable since the OPA process can be used to generate pulses significantly shorter
than the (Ti:sapphire) driving laser. However up to this point, the predicted scaling of
the LAPE process to longer wavelengths has not been verified experimentally, and thewavelength dependence of processes such as ATP had not been systematically explored.
Figure 6.1 shows the observed photoemission spectra in the energy region near
the Fermi edge in the case of illumination of a clean Pt(111) crystal. Here, the EUV and97a) 780 nm√ 2π σf(E-E0)

1200

800



Counts

1000

600

0.6
0.4
0.2
0.0

400

-4 -2 0 2 4
E-E0 (eV)EUV-only
EUV+IR
fit

200
0
28

30

32

34
36
Electron energy (eV)3840b) 1300 nm
0.6√ 2π σf(E-E0)

2000



Counts

1500

1000

0.4
0.2
0.0
-2
0
2
E-E0 (eV)EUV-only
EUV+IR
fit

500

0
28

30

32

34
36
Electron energy (eV)38

40

Figure 6.1: Laser-assisted photoelectric effect with (a) 780 nm and (b) 1300 nm driving
pulses. Both spectra are measured at zero time delay between the EUV and IR pulses.
The red and black lines represent the photoemission spectra with and without the IR
pulse present, respectively. The blue lines show the fit to the EUV+IR curve when the
LAPE response function from equation 4.3 is convolved with the EUV-only spectrum.
The insets show the LAPE response functions associated with the fit. In (a) the 780
nm pulses with peak intensity I780nm = 1.4 × 1011 W/cm2 generate sidebands A1(780nm)= 0.13 ± 0.01, while in (b) the 1300 nm pulses with peak intensity I1300nm = 2.4 × 1010
W/cm2 generate sidebands A1(1300nm) = 0.18 ± 0.01. Compared with the 780 nm pulses,
the 1300 nm pulses create a greater LAPE signal at much lower intensities.

98
IR pulses are temporally coincident, so that the photoemitted electrons experience thepeak dressing laser intensity. The red and black lines give the photoemission spectrawith and without the IR pulse present, respectively. The blue lines show the fit to
the EUV+IR curve using the fitting procedure introduced in section 4.4. The insets offigure 6.1 show the LAPE response function associated with the resulting fit parameters.
In figure 6.1a 780 nm pulses were used to drive LAPE, while in figure 6.1b 1300 nm
pulses were used. The figure demonstrates that LAPE driven by 1300 nm pulses showsnotably larger sidebands than when 780 nm pulses were used, even though the 1300 nm
laser intensity was much lower than the 780 nm laser intensity. Therefore, these data
directly indicate that the use of 1300 nm pulses very significantly enhances the LAPE
signal [114].
In addition to increasing the strength of the LAPE signal, the lower-intensityof the 1300 nm pulses also dramatically reduces ATP photoelectrons. This happens
both because the intensity is lower and because longer-wavelength photons have lessenergy, thus ATP requires a larger number of photons. This leads to a considerably
smaller cross-section for ATP. Theoretical calculations of the ATP cross-section dependon other factors such as the IR intensity, the IR polarization, the work function of
the sample, and the time duration of the pulses. Detailed discussions can be found inreferences [115–118]. Figure 6.2 shows EUV-only and EUV+IR spectra over the fullenergy range for the cases where LAPE was driven by 780 and 1300 nm pulses. ATP
is the main contributor to the difference in the low-energy range. By comparing thedifference in the low-energy range in both spectra, we find that the lower-intensity 1300
nm pulses introduce significantly fewer electrons with lower kinetic energies than thehigher-intensity 780 nm pulses. Thus, ATP is suppressed when lower-intensity, longerwavelength pulses are applied.
The suppression of ATP, without a reduction of the LAPE signal, is especially useful for studying dynamics in surface-adsorbate systems. In many interesting processes

99a) 800 nm
30x10

3EUV-only
EUV+IRCounts

25
20
15
10
5
0
0

10

20
Electron energy (eV)

30

40

20
Electron energy (eV)3040b) 1300 nm
20x10

3

EUV-only
EUV+IRCounts

15

10

5

0
0

10

Figure 6.2: Photoemission spectra with EUV pulses and (a) 780 nm pulses (b) 1300 nm
pulses. Black curves represent the spectra with the EUV light only, while red curves
represent the spectra in the presence of both EUV and IR pulses at zero time delay.
In the lower energy range, the difference between the red and black curves is caused
by above threshold photoemission. At the Fermi edge, the difference is caused by thelaser-assisted photoelectric effect. The intensity required for 780 nm pulses to obtainobservable LAPE signal introduces a large amount of photoelectrons in the low energy
range up to 23 eV. In contrast, with the 1300 nm pulses, the intensity used produces
ATP photoelectrons with kinetic energies of less than 7 eV.

100
in these systems, the electrons to be studied are photoemitted with low kinetic energies.
When longer-wavelength IR pulses are used, ATP generates fewer low-energy electrons,
therefore offering a wider energy range in which to detect an unobscured LAPE signal.
Furthermore, IR-induced multiphoton or thermal desorption of the adsorbate will also
be strongly suppressed.
Besides these improvements, strongly reduced space-charge effects using 1300 nm
dressing pulses were also observed (see figure 6.3). In the combined EUV+IR spectrum
using 780 nm dressing pulses, a clear shift of the photoemission spectrum to higher
energies is seen with respect to the EUV-only spectrum. As explained before, this shift
is caused by the Coulomb repulsion of the numerous photoelectrons generated as a resultof ATP. In contrast, space-charge effects are suppressed in the 1300 nm spectrum. This
leads to a more accurate calculation of the LAPE signal and eliminates the need tocorrect for space-charge shifts in the LAPE sideband fit, as was done with the data
shown in figure 6.1a.
In addition to the advantages mentioned above, the results allow us to exper−4
imentally verify the ωIR
dependence of the LAPE sideband strength. Equation 4.2

shows that at low-dressing laser intensities, the first-order sideband height is directly
proportional to the intensity of the driving pulse and the kinetic energy of the electron
to be dressed, while it is inversely proportional to the frequency of the driving pulse
to the fourth power. Using our experimental results from figure 6.1 we can verify the
relationship -4
A1(1300nm) I780nm
ω780nm.
=4
A1(780nm) I1300nm
ω1300nm(6.1)

The predicted frequency ratio yields 7.7, while the experimentally determinedfactor on the right side of equation 6.1 yields 8.0 ± 0.4. This excellent agreement
between our experimental data and equation 6.1 demonstrates that the theoretical model

101a) 780 nm
1600
1400

Counts

1200
1000
800
600
400
EUV-only
EUV+IR

200
0
28

30

32
34
Electron energy (eV)

36

38

32
34
Electron energy (eV)3638b) 1300 nm
2000

Counts

1500

1000

500

EUV-only
EUV+IR

0
28

30

Figure 6.3: Comparison of the space-charge effect around the Fermi edge at -100 fs timedelay. For 780 nm pulses, the large amount of low-energy photoelectrons generated
through ATP causes a shift of the whole spectrum around the Fermi edge. This effectis greatly suppressed with 1300 nm pulses, because fewer photoelectrons are generated
from the IR pulse through ATP at this wavelength.

102
presented in references [70, 119] is correct for describing LAPE from surfaces. The 4% discrepancy found in our data is mainly caused by errors in the measurement of thebeam size and the spatial overlap between the EUV and IR beams on the sample.

6.3

Conclusion
This chapter reports data that clearly demonstrate several advantages to using

longer-wavelength pulses to drive the laser-assisted photoelectric and Auger effects fromsurfaces. In previous work studying electron dynamics in surface-adsorbate systems,
using the correct IR dressing laser intensity was a critical issue. This is because therange of intensities over which LAPE signal could be observed without introducing too
much ATP, was quite narrow. By moving to a dressing wavelength of 1300 nm, theenhanced LAPE signal, suppressed ATP, and reduced space-charge noise dramatically
improve the range of laser intensities over which good LAPE signals can be observed.
This new approach to LAPE and LAAD will therefore be critical for enabling timeresolved studies of ultrafast electronic processes at surfaces.

Chapter 7
Outlook

7.1

Angle-Resolved Photoemission with High Harmonics

7.1.1

Motivation

Currently, our electron detector cannot resolve the emission angles of the photoelectrons emitted from the sample. In many surface science experiments, resolving theemission angle is not critical to understanding the details behind the mechanism understudy. For some experiments, however, obtaining angular information and therefore
the dispersion of the electronic band structure, will improve our understanding of theprocesses occurring on the sample. The development of electron analyzers capable ofrecording in parallel the kinetic energy Ekin and the momentum kk of the photoemitted
electrons, allows the investigation of the sample’s electronic band-structure Ekin (kk ).
The results shown in this section were performed with one of these new detectors
in the laboratory of Prof. Martin Aeschlimann at the University of Kaiserslautern.
This experiment is a result of the ongoing collaboration between the Kapteyn/Murnane,
Aeschlimann and Bauer groups.

7.1.2

Introduction

In recording the momentum-resolved electronic structure E(k) of a surface, angleresolved photoemission spectroscopy (ARPES) has emerged as a leading experimental

104
technique. ARPES identifies static key properties of complex systems, such as adsorbed
molecules [120] or high-temperature super conductors [121]. The ultrafast dynamics inthese systems associated with nuclear motion or phase-transition after intense laser
irradiation, provide valuable information on fundamental physical properties. Theseultrafast dynamics can be mapped by the measurement of E(k) as a function of timeusing femtosecond time-resolved ARPES. In particular, by recording the energy distribution as well as the momentum distribution of the photoemitted electrons, a completecharacterization of the different steps involved in these processes becomes possible. To
drive such an experiment, powerful femtosecond and attosecond light sources in the
EUV-regime, such high-order harmonic generation, are required.
In the past, exclusively time-of-flight (TOF) electron analyzers have been usedin photoemission spectroscopy (PES) experiments in combination with HHG, because
they exhibit a relatively high detection efficiency [40, 50, 98, 122, 123]. The drawback ofthese types of analyzers is their restricted energy resolution for kinetic electron energies
beyond 10 eV, which is the energy regime typically probed in conventional EUV-PES.
Furthermore, in their conventional configuration, these analyzers are only efficient interms of energy detection. With respect to mapping of angular distribution of photoemitted electrons, only very specific and complex TOF configurations (for instancemulti anode-systems) can provide the required efficiency. In order to achieve reasonable
time- and angle-resolved PES (TR-ARPES), a parallel detection for energy and momentum of the photoemitted electrons is indispensable. In recent years, hemisphericalenergy analyzers have been developed which are equipped for parallel (and therefore
efficient) detection of a multitude of energy channels, as well as momentum channels, ofphotoemitted electrons. This development has enabled an electron analyzer system forangle-resolved photoemission spectroscopy using a low-repetitive, low-intensity, HHG
light source with high-energy and high-angular resolution independent of the electron
kinetic energy.

105
The main challenge for this experiment is to show that ARPES at a reasonablecount rate can be performed using a kHz fs-HHG source. This section, presents thefirst ARPES data achieved using a 1 kHz HHG light source and a hemispherical energy
analyzer, equipped with a 2D-detector for parallel energy and momentum detection[124]. The results show that ARPES using high harmonic light at a photon energy of
41.85 eV can be performed with an angular resolution better than 0.6◦ (corresponding to−10.03 Å

at Ekin = 36 eV). A comparison of the HHG PES-spectra with corresponding

data recorded with a conventional He discharge lamp (hν = 40.81 eV) allows us todetermine that the total bandwidth of the HHG-light transmitted by the non-dispersive
monochromator is 801 ± 10 meV, which is capable of supporting EUV pulses as short
as 3 fs.
In comparison with femtosecond light sources in the visible or VUV regime, theuse of high-harmonic light for time-resolved experiments has three main advantages:• The high photon energies delivered by the HHG source extend the information
accessible by time-resolved photoemission experiments to deeper-lying electronic
states, even into the regime of classical core-level spectroscopy.
• The use of intense femtosecond pump-pulses in time-resolved photoemission
experiments often gives rise to a parasitic electron background in the kinetic
energy range of up to about 10 eV, resulting from multiphoton photoemission
processes [63,98]. Therefore, to extract the relevant primary (probe) photoemission signal out of this background, the significantly higher photon energy (andconsequently electron kinetic energy) delivered by a HHG source is desirable.
• Finally, for a given acceptance angle of the energy analyzer, the use of highphoton energies significantly extends the accessible momentum range of thephotoemitted electrons.

106

Figure 7.1: Angle resolved PE-spectra of the Shockley surface state and a series ofquantum-well states of 40 ML Ag/Cu(111) recorded at photon energies of (a) 6 eV (4thharmonic of the Ti:Sapphire oscillator) and (b) 21.22 eV (He I line of the discharge
VUV-lamp). An increase in photon energy enables access to electronic states at higher
binding energies and extends the experimentally accessible momentum space.

This last issue is highlighted in figure 7.1, which displays angle-resolved photoemission data of ultrathin silver films (40 ML) on Cu(111), recorded at photon energiesof 6 eV (fourth harmonic of the Ti:Sapphire oscillator, figure 7.1a) and 21.22 eV (He I
line of the discharge VUV-lamp, figure 7.1b). The plots map the kinetic energy distribution of the photoemitted electrons as a function of the emission angle θ. The series ofdispersive states visible in both maps are due to the Shockley surface state (top-mostfeature) and quantum well states (higher binding energy states), the latter ones localized within the silver film [125,126]. The component of the electron momentum parallel

107
to the surface, kk , is conserved in the photoemission process. For a given emission angle
θ and kinetic energy Ekin , its absolute value can be calculated to:
r
kk =

2me
Ekin sin θ.
h̄2

(7.1)

This equation directly implies that for a given analyzer acceptance angle, a higher
electron kinetic energy allows for a deeper view into momentum-space. The apparent
difference in the dispersion of the quantum well states as a function of the emission
angle between figure 7.1a and figure 7.1b is a direct consequence of this property. The
constant acceptance angle of ± 7◦ for both measurements transforms into a kk interval−1of about ± 0.09 Å

for initial state energies close to the Fermi edge at 6 eV excitation−1(Ekin ≈ 2 eV), and into a kk interval of about ± 0.25 Å

for the same initial states but

for excitation energies of 21 eV (Ekin ≈ 16 eV). In terms of probing transient changes inE(k) within time-resolved photoemission experiments, the use of ultrashort EUV pulses
instead of UV-pulses will obviously extend the accessible states not only with respect
to energy but also with respect to momentum.
7.1.3

ARPES using femtosecond high harmonic light

Figure 7.2 shows two photoemission maps of the Cu(111) surface for momentum−1

values between 0.7 Å

−1

and 1.52 Å

(corresponding to electron emission angles between

13.3◦ and 28.3◦ ). The left spectrum (figure 7.2a) has been recorded with the He II lineof the gas-discharge lamp with a photon energy of hν = 40.81 eV. The right spectrum(figure 7.2b) is the corresponding photoemission map recorded with the 27th harmonicof a Ti:sapphire laser system, corresponding to an energy of hν = 41.85 eV. For both
maps, identical analyzer settings have been used, corresponding to an energy resolutionof 200 meV. Two dominant features can be identified in the two spectra: the barely
dispersive copper 3d-bands between 2 eV and 4 eV binding energy, and the sp-band−1

which splits off the d-band at about 0.85 Å

. The sp-band is characterized by its

108
distinct parabolic dispersion. Contributions to the HHG-spectrum due to lower andhigher order harmonics are not visible in the spectrum. The upper limit of such acontribution can be deduced from the intensity ratio between the dominant d-bandfeature at 3 eV binding energy and the signal from the adjacent harmonics located at± 3.1 eV from this feature (see figure 7.3a).
This estimation shows that any contribution from the 29th harmonic is suppressedby a ratio of better than 1:25, while the corresponding value for the 25th harmonic isbetter than 1:7. The increased suppression of the 29th harmonic in comparison to themeasured/calculated multilayer mirror reflectivity is achieved by tuning the high-energy
cutoff of the harmonic generation process right above the 27th order. The residual
photon flux of the 27th harmonic available for photoemission spectroscopy after thealuminium filter and the monochromator is ∼ 8 × 103 photons/pulse compared to ∼ 107
photons/pulse delivered by the HHG lightsource. Therefore, the integration time for
the HHG-spectrum is raised to about 50 minutes in comparison to 10 seconds for theconventional He II spectrum. Nevertheless, these spectra show that the high harmoniclight source is suitable for reasonable mapping of the electronic band structure of asurface.
Evident however, is an overall energy broadening of the photoemission featuresin the HHG spectrum in comparison to the He II spectrum. Due to the rather low
HHG-light intensity after the monochromator, the broadening cannot be attributed tospace-charge effects, as will be discussed in the following subsection. Therefore, thebroadening only reflects the intrinsic bandwidth of the femtosecond HHG light pulses(time-bandwidth product for Gaussian-shaped and bandwidth-limited pulses ≈ 0.44).
The achievable time-resolution of a time-resolved ARPES experiment will be discussed
in the following subsection. Furthermore, it will be demonstrated that in comparison
to the results obtained with the He II light source, the momentum resolution is notaffected by the excitation with the HHG light.

109

Figure 7.2: Photoemission maps of the Cu(111) sp-band at finite angle with (a) the He
II line and (b) the HHG light source, after selecting the 27th harmonic. The analyzer
resolution was set to 200 meV. The HHG-spectrum is broadened due to the energy
bandwidth of 801 ± 10 meV of the fs-HHG pulses. The red lines mark the integration
areas for the energy and momentum distribution curves as shown in figures 7.3 and 7.4.
Note that there are no harmonic sidebands observable.

7.1.4

Energy distribution curves

Energy distribution curves (EDC) from the He II data and the HHG data, as
shown in figure 7.3a, have been derived from the PE-maps (figure 7.2) by a signal
integration along kk , as indicated by the red marked area centred around kk = 1.15
−1Å

. Both d-bands and sp-bands are clearly resolved as peaks at about 3 eV binding

energy and right at the Fermi-level, respectively. All spectral features, d-bands, sp-band
peak, and Fermi edge, are strongly broadened in the HHG-spectrum in comparison to
the He II spectrum.

110

Figure 7.3: (a) Electron distribution curves EDC extracted from the photoemission−1
maps in figure 7.2 (kk = 1.15 Å ). (b) Gaussian fits of the sp-band peak. The deconvolution of the Gaussian of the sp-band peak in the HHG-spectrum with the Gaussian
linewidth of the sp-band peak in the He II spectrum gives a Gaussian bandwidth of 801± 10 meV for the HHG-light. (c) EDC extracted from the photoemission maps in figure−1
7.2 at a different kk value (kk = 1.25 Å ). The blue EDC is derived by convoluting
the original He II spectrum with a Gaussian of 801 meV to mimic the broadening due
to the bandwidth of the HHG light.

With the use of a low-repetition, high-intensity light source for photoemission
spectroscopy, one must be aware of space-charge effects leading to distortions in thephotoemission spectrum. As a consequence of using pulsed radiation with high fluencies, the photomitted electrons leave the surface in short pulses with a fairly highelectron density. Space-charge effects due to the Coulomb repulsion between the electrons within such a pulse distort the spectral distribution of these electrons and result

111
in a considerable loss in both energy resolution and angular resolution [35, 127]. The
strength of these distortions is governed by the number of photoemitted electrons andthe kinetic energy of the electrons.
A comparison of photoemission spectra recorded with different incident photon
yields enables the quantification of space-charge effects. The number N of photoemitted
electrons per pulse and area A in this experiment is about 2 orders of magnitude larger
than in the experiments done with the monochromator (see figure 7.3). The difference(quadratic subtraction) of the width of the d-band feature in both spectra is, however,less than 500 meV. Based on this result, an upper value can be given for the space-chargeq √broadening in the spectra recorded with the monochromator following the N/ A
dependence, as given in reference [35]. This shows that the maximum contribution
to the energy broadening for the experiments with a single harmonic is 56 meV. The
quadratic addition of this value to the intrinsic linewidth of d-band and sp-band feature
as deduced from the He II spectrum results in a line broadening of the peak FWHM well
below 5 meV, a value that cannot be resolved with the analyzer settings (pass energy)
used in the experiments.
The comparison of the sp-band peak width of the He II and the HHG spectrum
can therefore be used to determine the bandwidth of the EUV-pulse. For both spectra,
gaussian fits were performed to the sp-band peak and the corresponding peak FWHM
(see figure 7.3b) was determined. Quadratic subtraction of the He II-spectrum FWHM
from the HHG-spectrum FWHM gives the lower limit for the spectral bandwidth of the
HHG radiation. This value is equal to the HHG bandwidth, since the contribution of
the He II light linewidth to the spectral broadening of the EDC is negligible. For the He
II sp-band peak, a FWHM of 0.51 eV was measured in comparison to 0.95 eV derived
from the HHG-spectrum. This gives a bandwidth-value for the HHG radiation of 0.801± 10 eV. To verify the validity of this approach we convolved the He II EDC at a−1

different kk (kk = 1.25 Å) with a Gaussian representing the HHG spectra distribution

112
with the derived bandwidth of 801 meV. A comparison of the resulting EDC withthe corresponding HHG EDC is shown in figure 7.3c. The convolution result matches
perfectly with the measured Fermi-edge distribution and the sp-band peak (blue linein (c)). The differences in the d-band peak between convolved EDC and the measured
HHG-EDC can be assigned to the different polarizations of the two light sources used in
the experiment (unpolarized for the discharge lamp and p-polarized for the HHG-light)
due to polarization and state sensitive transition matrix elements.
The bandwidth of the EUV-HHG pulses of 801 ± 10 meV is capable of supportinga temporal pulse width of 3 fs. This value is the upper limit of time-resolution achievablein a pump-probe experiment using the described HHG beamline. Since there are nofurther dispersive elements in the beamline, it can be assumed (without measurement)that this pulse length is actually operative in our experiment. Using chirped or shaped
laser pulses should further narrow the HHG bandwidth in the future [128].

7.1.5

Momentum distribution curves

Figure 7.4 shows the momentum distribution curves (MDCs) derived from the
red-lined areas of figure 7.2 at an energy just below the Fermi-level. As was the casefor the EDC, a clear broadening in comparison to the He II-MDC was observed. In
the following, it will be shown that this broadening is related to the energy broadeningof the PE-spectrum by the bandwidth of the HHG radiation and that the momentum
resolution is not affected by the use of the femtosecond HHG pulse. Let us first consider
the momentum spread in the PE spectrum due the momentum vector of the HHGlight itself. The total momentum added by the absorption of a 42 eV photon to an−1electron is about 0.02 Å

. The momentum spread delivered by the different frequency

components contributing to the selected harmonic is consequently much smaller (0.0004−1Å

for 801 meV bandwidth) and therefore cannot account for the observed broadeningof the HHG-MDC.

113

Figure 7.4: Momentum distribution curves (MDCs) extracted from the photoemission
maps in figure 7.2. The MDC marked by open squares was derived after convoluting
the He II EDCs with the HHG bandwidth of 801 meV for all different kk values.

Another point to consider with respect to momentum resolution is the spot sizeof the EUV light at the surface, which determines the source diameter for photoemitted electrons. In our setup, the HHG-light is focused by the second mirror of themonochromator to a spot-size of about 100 µm to guarantee a high angular resolution.
By comparison, the He II light is not focused onto the sample and exhibits a beam
diameter of 600 µm. Therefore, the spot size cannot account for the broadening of the
MDC trace, either. To check to what extent the spectral energy broadening due tothe finite bandwidth of the HHG affects the MDC, the following convolution procedure
was performed. EDCs for a series of kk values measured with the He II lamp wereconvolved with a 801 meV Gaussian to again mimic the energy broadening of the HHG
EDCs. From these EDC-series, we then extract a purely “energy broadened” MDC andcompare this spectrum with the measured HHG-MDC (see figure 7.4). Evidently, thesimulated and measured MDC agree almost perfectly. Therefore, it can be concluded

114
that the use of the HHG-light source does not degrade the momentum resolution of the
ARPES experiment.
A detailed specification of the analyzer’s momentum resolution using the He discharge lamp (beam diameter of 600 µm) shows an effective angle resolution of 0.6◦ ,−1

corresponding to a momentum resolution of 0.03 Å

at a kinetic energy of 36 eV. Dueto the smaller HHG spot size in comparison to the He II light, we expect that theangular resolution in the HHG experiment even exceeds this value.

7.1.6

Conclusions

This section presented angle-resolved photoemission spectra recorded by excitation with femtosecond high harmonic light using a 2D imaging energy analyzer forparallel energy and momentum detection. The bandwidth of the transmitted EUV
light is 801 ± 10 meV, and thus broad enough to support pulses as short as 3 fs. By
these means, an angular resolution in the HHG photoemission experiment of better−1than < 0.03Å

could be achieved. Yet, the relatively long integration times required

to record a complete photoemission map are somewhat unsatisfactory. This constraintcan, however, be overcome by some modifications to the experimental setup. Femtosecond amplifier systems with equivalent pulse specifications as the system used in thiswork but driven at repetition rates as high as 20 kHz are commercially available andwill reduce typical measurement times by a factor of 20.
Finally, at the Kapteyn/Murnane group we have acquired a 2D imaging energy
analyzer similar to the one described in this section, and will install it in the next few
months. Besides reproducing these results, future prospects of time-resolved ARPES
include studies of ultrafast processes of systems characterized by transient changes inthe electronic structure E(k). This may include, for instance, the ultrafast dynamics
associated with highly correlated systems such as high-temperature superconductors,
the interaction of adsorbates and surfaces, or the dynamics of phase transitions such as

115
laser-induced melting processes in conventional metals.

7.2

Chemisorbed System
As was shown in chapter 5, the dynamics of the excitation and decay of acore electron of an adsorbed atom or molecule are still poorly understood. The corephotoionization process is accompanied by vibrational or electronic excitation, chargetransfer from the substrate, and internal rearrangement. This process can leave theadsorbate-substrate complex in a variety of possible excited states immediately after
ionization. The lifetime of these excited states compared to the lifetime of the core holewill dictate the nature of the radiationless decay spectra.
In chapter 5 a proof of principle experiment was performed to show that the corehole lifetime of an adsorbate on a substrate can be directly measured. In the immediate
future, we want to expand this study to more tightly bonded chemisorbed systems.
In these systems, the stronger chemical bond (and hence enhanced charge-transfer) between substrate and adsorbate is known to influence the linewidth broadening comparedwith an isolated atom. The two systems that we are contemplating are Cs/Pt(111) [9]and CO/Pt(111) [10]. Cs adsorbed on Pt(111) (figure 7.5(a)) is the experimentally
simplest system to study. In this case, we will use 91 eV photons to create a core holeand follow its dynamics through surface LAPE, just as we did with Xe/Pt(111). Carbon monoxide adsorbed onto Pt(111) (figure 7.5(b)) is an interesting system to study;
however, it is experimentally harder. Two reasons why CO/Pt(111) is a more complex
system to study are: 1) The photon energy necessary for the generation of a core holeis around 300eV, and 2) the estimated core-hole lifetime is about 1 - 2 fs, which meansthat in order to time-resolve this process we would need IR pulses shorter than 30 fs.
This would require the use of self-phase modulation fibers to compress the IR pulse
duration to < 10 fs.

116

a)

b)

Figure 7.5: a) Experimental Auger-electron spectrum of atomic cesium after backgroundsubstraction (from reference [9]). b) Photoabsorption spectra of the C 1s → 2π transition for gas-phase CO and CO adsorbed on Pt(111) (from reference [10]).

7.3

Interatomic Coulombic Decay
The Interatomic Coulombic Decay (ICD) process with its underlying dynamics

was theoretically predicted over a decade ago [112]. Recently, its occurrence was experimentally confirmed in large Ne clusters [129] as well as in Ne2 [130]. The Interatomic
Coulombic Decay is a fast decay process occurring via electron emission in loosely boundinner valence ionized atomic or molecular clusters. The mechanism that is the basis of

117
the ICD is an efficient energy transfer between neighboring monomers. The theoretical
approach from Cederbaum predicts that after excitation the inner valence hole localized in one of the monomers is filled by an outer valence electron of the same monomer.
The energy gained in this transition is transferred to a neighboring monomer, whichuses it to emit one of its outer valence electrons (see figure 7.6). ICD is different from
Auger decay since the electron does not emerge from the excited particle, but from its
neighbor. Furthermore, this emission is not mediated by the overlap of the participatingwaves functions but rather by an energy transfer via a virtual photon.

a)

b)

ICD

c)

outer

outer

outer

outer

outer

outer

inner

inner

inner

inner

inner

inner

core

core

core

core

core

core

A

B

A

B

A

B

Figure 7.6: a) After excitation, the inner valence (inner) hole is localized in monomer
A. b) Emission of an outer valence (outer) electron from monomer B after the transition of energy from the neighboring monomer A. c) Doubly ionized cluster with twoouter valence holes localized in two different but neighboring monomers. Adapted fromreference [11].

The efficiency of the energy transfer mechanism on which the ICD is based isstrongly dependent on the nuclear distance between monomers, so that basically only
neighboring monomers are involved in the process. In particular, if the monomers
are very close to each other, the double ionization potential is too high and the ICD
is energetically forbidden; if they are too far apart the energy transfer mechanism is
not effective. Through energy domain measurements, the lifetime of the inner valence
ionized state has been assumed to be on the order of a few to one hundred fs. Consequently, nuclear dynamics and electronic decay can occur on comparable time scales

118
and interplay significantly.
Because there is an interest in obtaining a value for the lifetime of the inner valence
ionized state, we propose the time-resolved study of the electron dynamics involved in
the interatomic Coulombic decay using laser-assisted photoemission. This experiment
would be similar to the one presented in chapter 5, with the difference being we would
have to dose Ne onto the Pt(111) surface. We would follow the temporal behaviorof the sideband heights for the Pt d-band and the ICD electrons; thus, obtaining avalue for the lifetime of the ICD process. However, this experiment presents certain
difficulties: 1) In order to dose Ne onto the Pt(111) surface, we would need to cool
down the sample to ≈ 14 ◦ K, which is something that we cannot do at the moment.
2) The characteristic energies of the ICD electrons are a few eV, which means that inorder to see the appearance of sidebands we would have to be careful that ATP does notmask the LAPE signal. As was demonstrated in chapter 6 by using longer-wavelength
light the ATP signal can be reduced; thus, we might need to use IR wavelengths longer
than 2000 µm. Although we have encountered the above mentioned difficulties, we havebeen working on the required changes to the experimental setup for the temporal study
of ICD.

7.4

Double Auger Decay
As was discussed in chapter 5, deep inner shells are known to decay by cascade

emission of Auger electrons, corresponding to transitions between successive inner-shelllevels. The first accessible inner shell, on the other hand, is expected to decay byemission of a single Auger electron only. However, a weaker channel was discovered innoble gases, with emission of two electrons, known as the double Auger process [131]. Itsinterest lies in the strong electron correlation from which it originates. One importantquestion concerns its dynamics: is it a direct double Auger process where both Auger
electrons are emitted simultaneously, or is it a cascade process with subsequent emission

119of electrons?
This question could be answered by studying the temporal evolution of the LAPE
signal from the Auger and double Auger electrons. This experiment would be similar
to the one presented in chapter 5, except that in this case we need to be concerned withthe signal from the ATP electrons. The kinetic energy of the double Auger electrons isin the order of a few eV. Therefore, in order to study the dynamics of the double Auger
decay we would have to combine our results from chapters 5 and 6. Current studiesof this effect in Xe atoms suggest that the dominant path is a cascade process with arapid (6 fs) ejection of a first Auger electron followed by the slower (> 23 fs) emissionof a second Auger electron [132].

Chapter 8
Conclusion

This thesis reports the first experimental observation of laser-assisted photoemission from a surface, its potential for the study of charge transfer in adsorbate-substrate
systems, and a full comparison of surface LAPE with an atomic-based theoretical approach.
The observation of surface laser-assisted photoemission is significant for threereasons. First, it represents new physics - the extension of atomic dressed states to surface dressed states is not obvious, because of complex spatially-dependent laser electricfields present at the surface. Second, surface LAPE will make it possible to characterize lower-flux and higher-energy XUV pulses, since the target atoms are orders ofmagnitude more dense on a surface compared to a gas. Finally, surface LAPE has thepotential to study ultrafast, femtosecond-to-attosecond time-scale electron dynamics
in solids and in surface-adsorbate systems. This is in contrast with measurements todate in atomic systems, where dynamics are generally only homogeneously broadened
and where time-domain studies have duplicated information that can be obtained fromspectroscopic studies.
This work also presents the first direct time-resolved observation of the lifetimeof core-excited states of an atom adsorbed onto a surface. The ability to directly measure the core-hole lifetime of an adsorbate on a substrate is of utmost importance forspectroscopic techniques such as core-hole clock spectroscopy, which use this value as a

121
reference for investigating fast electron relaxation dynamics. Our results demonstratethat time-resolved measurements that can identify the nature of any spectral broadening
in more tightly bound systems, such as chemisorbed systems, are possible.
Furthermore, the results shown in this thesis agree with a simple atomic-based
theoretical model. Surface LAPE can be distinguished from other laser-surface interaction phenomena, such as hot electron excitation, above-threshold photoemission, andspace-charge acceleration. By using longer-wavelength IR pulses it has been possible
to simultaneously increase the surface LAPE signal and suppress the undesirable processes of above-threshold photoemission, therefore enabling ultrafast studies of surfaceadsorbate systems and attosecond electron dynamics over a wider energy range.

Bibliography[1] M. Weinelt, “Time-resolved two-photon photoemission from metal surfaces,”
Journal of Physics: Condensed Matter, vol. 14, no. 43, pp. R1099–R1141, 2002.
[2] T. E. Glover, R. W. Schoenlein, A. H. Chin, and C. V. Shank, “Observation oflaser assisted photoelectric effect and femtosecond high order harmonic radiation,”
Physical Review Letters, vol. 76, no. 14, pp. 2468–2471, 1996.
[3] M. Drescher, M. Hentschel, R. Kienberger, M. Uiberacker, V. Yakovlev, A. Scrinzi,
T. Westerwalbesloh, U. Kleineberg, U. Heinzmann, and F. Krausz, “Time-resolved
atomic inner-shell spectroscopy,” Nature, vol. 419, pp. 803–807, 2002.
[4] M. Meyer, D. Cubaynes, P. O’Keeffe, H. Luna, P. Yeates, E. T. Kennedy, J. T.
Costello, P. Orr, R. Taieb, A. Maquet, S. Dusterer, P. Radcliffe, H. Redlin, A. Azima, E. Plonjes, and J. Feldhaus, “Two-color photoionization in xuv free-electron
and visible laser fields,” Physical Review A (Atomic, Molecular, and Optical
Physics), vol. 74, no. 1, p. 011401, 2006.
[5] H. C. Kapteyn, M. M. Murnane, and I. P. Christov, “Extreme nonlinear optics:
Coherent x rays from lasers,” Physics Today, vol. 58, no. 3, pp. 39–44, 2005.
[6] A. L. Lytle, “Phase matching and coherence of high-order harmonic generation inhollow waveguides,” Ph.D. dissertation, University of Colorado, 2008.
[7] D. M. Gaudiosi, “High power ultrafast laser design and high-order harmonic generation in capillary discharge plasmas,” Ph.D. dissertation, University of Colorado,2007.
[8] M. Jurvansuu, A. Kivimki, and S. Aksela, “Inherent lifetime widths of ar 2p-1, kr
3d-1, xe 3d-1, and xe 4d-1 states,” Physical Review A, vol. 64, no. 1, p. 12502,
2001.
[9] H. Aksela and S. Aksela, “Auger-electron spectrum of atomic cesium in the 1575-ev energy range,” Phys. Rev. A, vol. 28, no. 5, pp. 2851–2858, 1983.
[10] R. Murphy, E. W. Plummer, C. T. Chen, W. Eberhardt, and R. Carr, “Dynamics
of adsorbate core-hole decay. ii. lifetimes,” Physical Review B, vol. 39, no. 11, p.
7517, 1989.

123[11] S. Scheit, H.-D. Meyer, and L. S. Cederbaum, “The interatomic coulombic decay
in ne2,” Journal of Physics: Conference Series, vol. 4, p. 277, 2005.
[12] M. P. Seah and W. A. Dench, “Quantitative electron spectroscopy of surfaces: A
standard data base for electron inelastic mean free paths in solids,” Surface andInterface Analysis, vol. 1, pp. 2–11, 1979.
[13] K. Giesen, F. Hage, F. J. Himpsel, H. J. Riess, and W. Steinmann, “Two-photon
photoemission via image-potential states,” Phys. Rev. Lett., vol. 55, no. 3, pp.
300–303, 1985.
[14] T. FAUSTER, “2-photon photoemission,” PROGRESS IN SURFACE SCIENCE,
vol. 46, no. 2-3, pp. 177–186, 1994.
[15] R. Yen, J. M. Liu, N. Bloembergen, T. K. Yee, J. G. Fujimoto, and M. M. Salour,“Picosecond laser interaction with metallic zirconium,” Applied Physics Letters,
vol. 40, no. 2, pp. 185–187, 1982.
[16] R. T. Williams, T. R. Royt, J. C. Rife, J. P. Long, and M. N. Kabler, “Picosecond
time-resolved photoelectron spectroscopy of znte,” Journal of Vacuum Science andTechnology, vol. 21, no. 2, pp. 509–513, 1982.
[17] W. S. Fann, R. Storz, H. W. K. Tom, and J. Bokor, “Electron thermalization ingold,” Phys. Rev. B, vol. 46, no. 20, pp. 13 592–13 595, 1992.
[18] C. A. Schmuttenmaer, M. Aeschlimann, H. E. Elsayed-Ali, R. J. D. Miller, D. A.
Mantell, J. Cao, and Y. Gao, “Time-resolved two-photon photoemission fromcu(100): Energy dependence of electron relaxation,” Phys. Rev. B, vol. 50, no. 12,
pp. 8957–8960, 1994.
[19] W. S. Fann, R. Storz, H. W. K. Tom, and J. Bokor, “Direct measurement of
nonequilibrium electron-energy distributions in subpicosecond laser-heated gold
films,” Phys. Rev. Lett., vol. 68, no. 18, pp. 2834–2837, 1992.
[20] R. W. Schoenlein, J. G. Fujimoto, G. L. Eesley, and T. W. Capehart, “Femtosecond studies of image-potential dynamics in metals,” Phys. Rev. Lett., vol. 61,
no. 22, pp. 2596–2599, 1988.
[21] H. Petek, M. J. Weida, H. Nagano, and S. Ogawa, “Real-Time Observation ofAdsorbate Atom Motion Above a Metal Surface,” Science, vol. 288, no. 5470, pp.
1402–1404, 2000.
[22] A. G. Borisov, J. P. Gauyacq, A. K. Kazansky, E. V. Chulkov, V. M. Silkin,
and P. M. Echenique, “Long-lived excited states at surfaces: cs/cu(111) andcs/cu(100) systems,” Phys. Rev. Lett., vol. 86, no. 3, pp. 488–491, 2001.
[23] A. MCPHERSON, G. GIBSON, H. JARA, U. JOHANN, T. LUK, I. MCINTYRE, K. BOYER, and C. RHODES, “Studies of multiphoton production of
vacuum ultraviolet-radiation in the rare-gases,” JOURNAL OF THE OPTICALSOCIETY OF AMERICA B-OPTICAL PHYSICS, vol. 4, no. 4, pp. 595–601,
1987.

124
[24] M. FERRAY, A. LHUILLIER, X. LI, L. LOMPRE, G. MAINFRAY, and
C. MANUS, “Multiple-harmonic conversion of 1064-nm radiation in raregases,” JOURNAL OF PHYSICS B-ATOMIC MOLECULAR AND OPTICALPHYSICS, vol. 21, no. 3, pp. L31–L35, 1988.
[25] C. Spielmann, “Generation of coherent x-rays in the water window using 5femtosecond laser pulses,” Science, vol. 278, no. 5338, pp. 661–664, 1997.
[26] J. Zhou, J. Peatross, M. M. Murnane, H. C. Kapteyn, and I. P. Christov, “Enhanced high-harmonic generation using 25 fs laser pulses,” Phys. Rev. Lett.,
vol. 76, no. 5, pp. 752–755, 1996.
[27] E. Seres, J. Seres, F. Krausz, and C. Spielmann, “Generation of coherent soft-xray radiation extending far beyond the titanium l edge,” Phys. Rev. Lett., vol. 92,
no. 16, p. 163002, 2004.
[28] J. Seres, E. Seres, A. Verhoef, G. Tempea, C. Strelill, P. Wobrauschek,
V. Yakovlev, A. Scrinzi, C. Spielmann, and F. Krausz, “Source of coherent kiloelectronvolt x-rays,” NATURE, vol. 433, no. 7026, p. 596, 2005.
[29] P. Paul, E. Toma, P. Breger, G. Mullot, F. Auge, P. Balcou, H. Muller, and
P. Agostini, “Observation of a train of attosecond pulses from high harmonic
generation,” SCIENCE, vol. 292, no. 5522, pp. 1689–1692, 2001.
[30] M. Hentschel, R. Kienberger, C. Spielmann, G. Reider, N. Milosevic, T. Brabec,
P. Corkum, U. Heinzmann, M. Drescher, and F. Krausz, “Attosecond metrology,”
NATURE, vol. 414, no. 6863, pp. 509–513, 2001.
[31] E. Goulielmakis, M. Schultze, M. Hofstetter, V. S. Yakovlev, J. Gagnon, M. Uiberacker, A. L. Aquila, E. M. Gullikson, D. T. Attwood, R. Kienberger, F. Krausz,
and U. Kleineberg, “Single-cycle nonlinear optics,” Science, vol. 320, no. 5883, pp.
1614–1617, 2008.
[32] R. HAIGHT and D. PEALE, “Tunable photoemission with harmonics of subpicosecond lasers,” REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 65, no. 6, pp.
1853–1857, 1994.
[33] F. Quere, S. Guizard, P. Martin, G. Petite, H. Merdji, B. Carré, J.-F. Hergott,and L. Le Déroff, “Hot-electron relaxation in quartz using high-order harmonics,”
Phys. Rev. B, vol. 61, no. 15, pp. 9883–9886, 2000.
[34] A. Rettenberger, P. Leiderer, M. Probst, and R. Haight, “Ultrafast electron transport in layered semiconductors studied with femtosecond-laser photoemission,”
Phys. Rev. B, vol. 56, no. 19, pp. 12 092–12 095, 1997.
[35] S. Passlack, S. Mathias, O. Andreyev, D. Mittnacht, M. Aeschlimann, and
M. Bauer, “Space charge effects in photoemission with a low repetition, high intensity femtosecond laser source,” Journal of Applied Physics, vol. 100, p. 024912,
2006.

125
[36] K. Read, H. Karlsson, M. Murnane, H. Kapteyn, and R. Haight, “Excitation
dynamics of dye doped tris(8-hydroxy quinoline) aluminum films studied using
time-resolved photoelectron spectroscopy,” JOURNAL OF APPLIED PHYSICS,
vol. 90, no. 1, pp. 294–300, 2001.
[37] M. Bauer, C. Lei, K. Read, R. Tobey, J. Gland, M. M. Murnane, and H. C.
Kapteyn, “Direct observation of surface chemistry using ultrafast soft-x-ray
pulses,” Physical Review Letters, vol. 87, no. 2, p. 25501, 2001.
[38] C. Lei, M. Bauer, K. Read, R. Tobey, Y. Liu, T. Popmintchev, M. M. Murnane,and H. C. Kapteyn, “Hot-electron-driven charge transfer processes on o2/pt(111)
surface probed by ultrafast extreme-ultraviolet pulses,” Phys. Rev. B, vol. 66,
no. 24, p. 245420, 2002.
[39] R. I. Tobey, E. H. Gershgoren, M. E. Siemens, M. Murnane, H. Kapteyn,
T. Feurer, and K. A. Nelson, Probing of thermal acoustic transients in materials
using EUV radiation, in Ultrafast Phenomena XIV, edited by T. Kobayashi, T.
Okada, T. Kobayashi, K. A. Nelson and S. D. Silvestri. Niigata, Japan: SpringerVerlag.
[40] L. Nugent-Glandorf, M. Scheer, D. Samuels, V. Bierbaum, and S. Leone, “Ultrafast photodissociation of br-2: Laser-generated high-harmonic soft x-ray probingof the transient photoelectron spectra and ionization cross sections,” JOURNAL
OF CHEMICAL PHYSICS, vol. 117, no. 13, pp. 6108–6116, 2002.
[41] E. Gagnon, P. Ranitovic, X.-M. Tong, C. L. Cocke, M. M. Murnane, H. C.
Kapteyn, and A. S. Sandhu, “Soft x-ray-driven femtosecond molecular dynamics,” SCIENCE, vol. 317, no. 5843, pp. 1374–1378, 2007.
[42] A. Weingartshofer, J. K. Holmes, G. Caudle, E. M. Clarke, and H. Krüger, “Direct
observation of multiphoton processes in laser-induced free-free transitions,” Phys.
Rev. Lett., vol. 39, no. 5, pp. 269–270, 1977.
[43] J. M. Schins, P. Breger, P. Agostini, R. C. Constantinescu, H. G. Muller, G. Grillon, A. Antonetti, and A. Mysyrowicz, “Observation of laser-assisted auger decay
in argon,” Physical Review Letters, vol. 73, no. 16, pp. 2180–2183, 1994.
[44] M. M. Murnane, H. C. Kapteyn, and R. W. Falcone, “High-density plasmas produced by ultrafast laser pulses,” Phys. Rev. Lett., vol. 62, no. 2, pp. 155–158,
1989.
[45] A. Baltuska, T. Udem, M. Uiberacker, M. Hentschel, E. Goulielmakis, H. R.
Gohle Ch, V. S. Yakovlev, A. Scrinzi, T. W. Hansch, and F. Krausz, “Attosecond
control of electronic processes by intense light fields,” Nature, vol. 421, no. 6923,
pp. 611–5, 2003.
[46] R. Kienberger, E. Goulielmakis, M. Uiberacker, A. Baltuska, V. Yakovlev, F. Bammer, A. Scrinzi, T. Westerwalbesloh, U. Kleineberg, and U. Heinzmann, “Atomic
transient recorder,” Nature, vol. 427, pp. 817–821, 2004.

126[47] J. Itatani, F. Quéré, G. L. Yudin, M. Y. Ivanov, F. Krausz, and P. B. Corkum,“Attosecond streak camera,” Phys. Rev. Lett., vol. 88, no. 17, p. 173903, 2002.
[48] T. Sekikawa, A. Kosuge, T. Kanai, and S. Watanabe, “Nonlinear optics in theextreme ultraviolet,” NATURE, vol. 432, no. 7017, pp. 605–608, 2004.
[49] P. Tzallas, D. Charalambidis, N. Papadogiannis, K. Witte, and G. Tsakiris, “Direct observation of attosecond light bunching,” NATURE, vol. 426, no. 6964, pp.
267–271, 2003.
[50] L. Miaja-Avila, C. Lei, M. Aeschlimann, J. L. Gland, M. M. Murnane, H. C.
Kapteyn, and G. Saathoff, “Laser-assisted photoelectric effect from surfaces,”
Physical Review Letters, vol. 97, no. 11, p. 113604, 2006.
[51] A. L. Cavalieri, N. Muller, T. Uphues, V. S. Yakovlev, A. Baltuska, B. Horvath,
B. Schmidt, L. Blumel, R. Holzwarth, and S. Hendel, “Attosecond spectroscopy
in condensed matter,” Nature, vol. 449, no. 7165, pp. 1029–32, 2007.
[52] A. Pietzsch, F. A, hlisch, M. Beye, M. Deppe, F. Hennies, M. Nagasono, E. Suljoti,
W. Wurth, C. Gahl, D. K, brich, and A. Melnikov, “Towards time resolved corelevel photoelectron spectroscopy with femtosecond x-ray free-electron lasers,” New
Journal of Physics, no. 10, p. 033004, 2008.
[53] L. Miaja-Avila, G. Saathoff, S. Mathias, J. Yin, C. L. o vorakiat, M. Bauer,
M. Aeschlimann, M. M. Murnane, and H. C. Kapteyn, “Direct measurement ofcore-level relaxation dynamics on a surface-adsorbate system,” Physical Review
Letters, vol. 101, p. 046101, 2008.
[54] S. Backus, C. Durfee, M. Murnane, and H. Kapteyn, “High power ultrafast lasers,”
REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 69, no. 3, pp. 1207–1223, 1998.
[55] I. Walmsley, L. Waxer, and C. Dorrer, “The role of dispersion in ultrafast optics,”
REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 72, no. 1, pp. 1–29, 2001.
[56] R. L. Sandberg, A. Paul, D. A. Raymondson, S. Haedrich, D. M. Gaudiosi,
J. Holtsnider, R. I. Tobey, O. Cohen, M. M. Murnane, and H. C. Kapteyn, “Lensless diffractive imaging using tabletop coherent high-harmonic soft-x-ray beams,”
PHYSICAL REVIEW LETTERS, vol. 99, no. 9, 2007.
[57] R. Tobey, E. Gershgoren, M. Siemens, M. Murnane, H. Kapteyn, T. Feurer, and
K. Nelson, “Nanoscale photothermal and photoacoustic transients probed withextreme ultraviolet radiation,” APPLIED PHYSICS LETTERS, vol. 85, no. 4,
pp. 564–566, 2004.
[58] K. C. Kulander, K. J. Schafer, and J. L. Krause, ”Dynamics of short-pulse
exicitation, ionization and harmonic conversion, in Super-Intense Laser-Atom
Physics, B. Piraux, A. LHuillier, and K. Rzazewski, Eds. New York: Plenum.
[59] P. Corkum, “Plasma perspective on strong-field multiphoton ionization,” PhysicalReview Letters, vol. 71, no. 13, pp. 1994–1997, 1993.

127[60] L. KELDYSH, “Ionization in field of a strong electromagnetic wave,” SOVIETPHYSICS JETP-USSR, vol. 20, no. 5, p. 1307, 1965.
[61] M. V. Ammosov, N. B. Delone, and V. P. Krainov, “Tunnel ionization of complex
atoms and of atomic ions in an alternating electromagnetic field,” Sov. Phys.
JETP, vol. 64, no. 6, pp. 1191–1194, 1986.
[62] M. Lewenstein, P. Salières, and A. L’Huillier, “Phase of the atomic polarizationin high-order harmonic generation,” Phys. Rev. A, vol. 52, pp. 4747–4754, 1995.
[63] M. Bauer, “Femtosecond ultraviolet photoelectron spectroscopy of ultra-fast surface processes,” Journal of Physics D: Applied Physics, vol. 38, no. 16, pp. R253–
R267, 2005.
[64] T. Brabec and F. Krausz, “Intense few-cycle laser fields: Frontiers of nonlinear
optics,” Reviews of Modern Physics, vol. 72, no. 2, pp. 545–591, 2000.
[65] P. Balcou and A. L’Huillier, “Phase-matching effects in strong-field harmonic
generation,” Phys. Rev. A, vol. 47, no. 2, pp. 1447–1459, 1993.
[66] A. Rundquist, C. Durfee, Z. Chang, C. Herne, S. Backus, M. Murnane, and
H. Kapteyn, “Phase-matched generation of coherent soft x-rays,” SCIENCE, vol.
280, no. 5368, pp. 1412–1415, 1998.
[67] C. G. Durfee, A. R. Rundquist, S. Backus, C. Herne, M. M. Murnane, and H. C.
Kapteyn, “Phase matching of high-order harmonics in hollow waveguides,” Phys.
Rev. Lett., vol. 83, no. 11, pp. 2187–2190, 1999.
[68] E. A. Gibson, A.Paul, N. Wagner, R. Tobey, D. Gaudiosi, S. Backus, I. P. Christov,
A. Aquila, E. M. Gullikson, D. T. Attwood, M. M. Murnane, and H. C. Kapteyn,“Coherent soft x-ray generation in the water window with quasi-phase matching,”
Science, vol. 302, no. 5642, pp. 95–98, 2003.
[69] A. Paul, R. Bartels, R. Tobey, H. Green, S. Weiman, I. Christov, M. Murnane, H. Kapteyn, and S. Backus, “Quasi-phase-matched generation of coherent
extreme-ultraviolet light,” Nature, vol. 421, no. 6918, pp. 51–54, 2003.
[70] L. B. Madsen, “Strong-field approximation in laser-assisted dynamics,” American
Journal of Physics, vol. 73, p. 57, 2005.
[71] K. Rzazewski and K. Wdkiewicz, “Gauge-independent canonical formalism for
nonrelativistic electrodynamics,” Annals of Physics, vol. 130, pp. 1–13, 1980.
[72] L. B. Madsen, “Gauge invariance in the interaction between atoms and few-cycle
laser pulses,” Phys. Rev. A, vol. 65, no. 5, p. 053417, May 2002.
[73] D. Wolkov, “ber eine klasse von lsungen der diracschen gleichung,” Z. Phys.,vol. 94, pp. 250–260, 1935.
[74] H. R. Reiss, “Effect of an intense electromagnetic field on a weakly bound system,”Phys. Rev. A, vol. 22, no. 5, pp. 1786–1813, 1980.

128[75] M. R. Spiegel, Mathematical Handbook of Formulas and Tables.
McGraw-Hill.

New York:[76] F. Ehlotzsky, A. Jaron, and J. Z. Kaminski, “Electron-atom collisions in a laser
field,” Phys Rep, vol. 297, pp. 63–153, 1998.
[77] C. J. Joachain, Quantum Collision Theory. Amsterdam: North-Holland/Elsevier,
1975.
[78] N. M. Kroll and K. M. Watson, “Charged-particle scattering in the presence of astrong electromagnetic wave,” Phys. Rev. A, vol. 8, no. 2, pp. 804–809, Aug 1973.
[79] G. Cerullo and S. D. Silvestri, “Ultrafast optical parametric amplifiers,” Review
of Scientific Instruments, vol. 74, no. 1, pp. 1–18, 2003.
[80] D. Attwood, Soft X-Rays and Extreme Ultraviolet Radiation: Principles andApplications. New York: Cambridge University Press, 1999.
[81] A. Stolow, “Gigahertz bandwidth ultrahigh vacuum 50 omega coaxial high-voltage
coupling capacitor for photoelectron spectroscopy,” REVIEW OF SCIENTIFICINSTRUMENTS, vol. 67, no. 5, pp. 1777–1780, 1996.
[82] P. Redhead, “Thermal desorption of gases,” VACUUM, vol. 12, no. 4, pp. 203–211,
1962.
[83] G. Fowles, Introduction to Modern Optics. New York: Dover Publication, 1989.
[84] S. Tanuma, T. Shiratori, T. Kimura, K. Goto, S. Ichimura, and C. Powell, “Experimental determination of electron inelastic mean free paths in 13 elemental
solids in the 50 to 5000 ev energy range by elastic-peak electron spectroscopy,”
SURFACE AND INTERFACE ANALYSIS, vol. 37, no. 11, pp. 833–845, 2005.
[85] B. FEUERBACHER and R. WILLIS, “Photoemission and electron states at cleansurfaces,” JOURNAL OF PHYSICS C-SOLID STATE PHYSICS, vol. 9, no. 2,
pp. 169–216, 1976.
[86] R. HAYDOCK and M. KELLY, “Surface densities of states in tight-binding approximation,” SURFACE SCIENCE, vol. 38, no. 1, pp. 139–148, 1973.
[87] A. Cionga, V. Florescu, A. Maquet, and R. Taı̈eb, “Target dressing effects inlaser-assisted x-ray photoionization,” Phys. Rev. A, vol. 47, no. 3, pp. 1830–1840,
1993.
[88] A. Mönnich, J. Lange, M. Bauer, M. Aeschlimann, I. A. Nechaev, V. P. Zhukov,
P. M. Echenique, and E. V. Chulkov, “Experimental time-resolved photoemission
and ab initio study of lifetimes of excited electrons in mo and rh,” Physical Review
B (Condensed Matter and Materials Physics), vol. 74, no. 3, p. 035102, 2006.
[89] J. E. Bayfield, L. D. Gardner, Y. Z. Gulkok, and S. D. Sharma, “Spectroscopic
study of nonresonant photon absorption by highly excited hydrogen atoms in astrong microwave field,” Phys. Rev. A, vol. 24, no. 1, pp. 138–143, 1981.

129[90] H. R. Reiss, “Analytically simple dressing of bound-state wave functions,” Phys.
Rev. A, vol. 39, no. 5, pp. 2449–2455, 1989.
[91] N. Tzoar and J. I. Gersten, “Theory of electronic band structure in intense laser
fields,” Phys. Rev. B, vol. 12, no. 4, pp. 1132–1139, 1975.
[92] F. H. M. Faisal and J. Z. Kamiński, “Floquet-bloch theory of high-harmonic generation in periodic structures,” Phys. Rev. A, vol. 56, no. 1, pp. 748–762, 1997.
[93] S. H. Autler and C. H. Townes, “Stark effect in rapidly varying fields,” Phys.
Rev., vol. 100, no. 2, pp. 703–722, 1955.
[94] G. LESCHIK, R. COURTHS, H. WERN, S. HUFNER, H. ECKARDT, andJ. NOFFKE, “Band-structure of platinum from angle resolved photoemission experiments,” SOLID STATE COMMUNICATIONS, vol. 52, no. 2, pp. 221–225,
1984.
[95] M. Aeschlimann, “Observation of surface enhanced multiphoton photoemission
from metal surfaces in the short pulse limit,” The Journal of Chemical Physics,
vol. 102, no. 21, p. 8606, 1995.
[96] H. G. Muller, H. B. L. van den Heuvell, and M. J. van der Wiel, “Dressing ofcontinuum states after mpi of xe in a two-colour experiment,” Journal of physics.
B. Atomic and molecular physics, vol. 19, no. 21, pp. L733–L739, 1986.
[97] G. Petite, P. Agostini, R. Trainham, E. Mevel, and P. Martin, “Origin of the highenergy electron emission from metals under laser irradiation,” Physical Review B,
vol. 45, no. 21, p. 12210, 1992.
[98] P. Siffalovic, M. Drescher, M. Spieweck, T. Wiesenthal, Y. C. Lim, R. Weidner,
A. Elizarov, and U. Heinzmann, “Laser-based apparatus for extended ultraviolet femtosecond time-resolved photoemission spectroscopy,” Review of Scientific
Instruments, vol. 72, p. 30, 2001.
[99] G. Saathoff, L. Miaja-Avila, M. Aeschlimann, M. M. Murnane, and H. C. Kapteyn,“Laser-assisted photoemission from surfaces,” Physical Review A, vol. 77, p.
022903, 2008.
[100] P. A. Brhwiler, O. Karis, and N. Mrtensson, “Charge-transfer dynamics studied
using resonant core spectroscopies,” Reviews of Modern Physics, vol. 74, no. 3, p.
703, 2002.
[101] T. Fauster and W. Steinmann, In Photonic Probes of Surfaces, ser. Electromagnetic Waves: Recent Developments in Research. Amsterdam: North-Holland,
1995, vol. 2.
[102] C. Keller, M. Stichler, G. Comelli, F. Esch, S. Lizzit, D. Menzel, and W. Wurth,“Femtosecond dynamics of adsorbate charge-transfer processes as probed by highresolution core-level spectroscopy,” Physical Review B, vol. 57, no. 19, pp. 11 951–
11 954, 1998.

130[103] A. Fhlisch, P. Feulner, F. Hennies, A. Fink, D. Menzel, D. Sanchez-Portal, P. M.
Echenique, and W. Wurth, “Direct observation of electron dynamics in the attosecond domain,” Nature, vol. 436, no. 7049, pp. 373–376, 2005.
[104] M. Wolf, “Femtosecond dynamics of electronic excitations at metal surfaces,”
Surface Science(Netherlands), vol. 377, pp. 343–349, 1997.
[105] M. Bauer, S. Pawlik, and M. Aeschlimann, “Femtosecond lifetime investigationsof excited adsorbate states: atomic oxygen on cu (111),” Surf. Sci, vol. 377, p.
350354, 1997.
[106] L. Bartels, G. Meyer, K. H. Rieder, D. Velic, E. Knoesel, A. Hotzel, M. Wolf, and
G. Ertl, “Dynamics of electron-induced manipulation of individual co molecules
on cu(111),” Physical Review Letters, vol. 80, no. 9, p. 2004, 1998.
[107] M. Bauer, S. Pawlik, and M. Aeschlimann, “Resonance lifetime and energy of an
excited cs state on cu(111),” Physical Review B, vol. 55, no. 15, p. 10040, 1997.
[108] A. Hotzel, K. Ishioka, E. Knoesel, M. Wolf, and G. Ertl, “Can we control lifetimes of electronic states at surfaces by adsorbate resonances?” Chemical Physics
Letters, vol. 285, no. 3-4, pp. 271–277, 1998.
[109] G. Kaindl, T. C. Chiang, and T. Mandel, “Surface effects on energies of auger
electrons from xe (111),” Physical Review B, vol. 28, no. 6, pp. 3612–3614, 1983.
[110] Z. Chang, A. Rundquist, H. Wang, M. M. Murnane, and H. C. Kapteyn, “Generation of coherent soft x rays at 2.7 nm using high harmonics,” Physical Review
Letters, vol. 79, no. 16, pp. 2967–2970, 1997.
[111] R. Trebino, Frequency-Resolved Optical Gating: The Measurement of Ultrashort
Laser Pulses. Kluwer Academic Publishers, 2002.
[112] L. S. Cederbaum, J. Zobeley, and F. Tarantelli, “Giant intermolecular decay andfragmentation of clusters,” Phys. Rev. Lett., vol. 79, no. 24, pp. 4778–4781, 1997.
[113] G. Ohrwall, M. Tchaplyguine, M. Lundwall, R. Feifel, H. Bergersen, T. Rander,
A. Lindblad, J. Schulz, S. Peredkov, S. Barth, S. Marburger, U. Hergenhahn,
S. Svensson, and O. Bjorneholm, “Femtosecond interatomic coulombic decay infree neon clusters: Large lifetime differences between surface and bulk,” PhysicalReview Letters, vol. 93, no. 17, 2004, 173401.
[114] L. Miaja-Avila, J. Yin, S. Backus, G. Saathoff, M. Aeschlimann, M. M. Murnane,and H. C. Kapteyn, “Ultrafast studies of electronic processes at surfaces using thelaser-assisted photoelectric effect with long-wavelength dressing light,” PhysicalReview A (Atomic, Molecular, and Optical Physics), vol. 79, no. 3, p. 030901,
2009.
[115] J. P. Girardeau-Montaut and C. Girardeau-Montaut, “Theory of ultrashort nonlinear multiphoton photoelectric emission from metals,” Physical Review B,
vol. 51, no. 19, p. 13560, 1995.

131[116] R. Daniele, G. Ferrante, E. Fiordilino, and S. Varro, “Photoelectric effect from a
metal-surface - a revisited theoretical-model,” Journal of the Optical Society ofAmerica B-Optical Physics, vol. 9, no. 10, pp. 1916–1921, 1992.
[117] S. Varro and F. Ehlotzky, “The multiphoton photo-effect and harmonic generation
at metal surfaces,” Journal of Physics D-Applied Physics, vol. 30, no. 22, pp.
3071–3078, 1997.
[118] F. Bisio, M. Nyvlt, J. Franta, H. Petek, and J. Kirschner, “Mechanisms of highorder perturbative photoemission from cu(001),” Physical Review Letters, vol. 96,
no. 8, p. 087601, 2006.
[119] J. C. Baggesen and L. B. Madsen, “Theory for time-resolved measurements oflaser-induced electron emission from metal surfaces,” Physical Review A (Atomic,
Molecular, and Optical Physics), vol. 78, no. 3, p. 032903, 2008.
[120] H. Steinruck, “Angle-resolved photoemission studies of adsorbed hydrocarbons,”
JOURNAL OF PHYSICS-CONDENSED MATTER, vol. 8, no. 36, pp. 6465–6509,
1996.
[121] A. Damascelli, Z. Hussain, and Z. Shen, “Angle-resolved photoemission studiesof the cuprate superconductors,” REVIEWS OF MODERN PHYSICS, vol. 75,
no. 2, pp. 473–541, 2003.
[122] M. Bauer, C. Lei, R. Tobey, M. Murnane, and H. Kapteyn, “Time-resolved ups:
a new experimental technique for the study of surface chemical reactions on femtosecond time-scales,” SURFACE SCIENCE, vol. 532, pp. 1159–1165, 2003.
[123] G. Tsilimis, J. Kutzner, and H. Zacharias, “Photoemission study of clean and c(4x 2)-2co-covered pt (111) using high-harmonic radiation,” APPLIED PHYSICS
A-MATERIALS SCIENCE & PROCESSING, vol. 76, no. 5, pp. 743–749, 2003.
[124] S. Mathias, L. Miaja-Avila, M. M. Murnane, H. Kapteyn, M. Aeschlimann,and M. Bauer, “Angle-resolved photoemission spectroscopy with a femtosecondhigh harmonic light source using a two-dimensional imaging electron analyzer,”
REVIEW OF SCIENTIFIC INSTRUMENTS, vol. 78, no. 8, p. 083105, 2007.
[125] T. Chiang, “Photoemission studies of quantum well states in thin films,”
SURFACE SCIENCE REPORTS, vol. 39, no. 7-8, pp. 181–235, 2000.
[126] S. Mathias, M. Wiesenmayer, M. Aeschlimann, and M. Bauer, “Quantumwell wave-function localization and the electron-phonon interaction in thin ag
nanofilms,” PHYSICAL REVIEW LETTERS, vol. 97, no. 23, p. 236809, 2006.
[127] X. Zhou, B. Wannberg, W. Yang, V. Brouet, Z. Sun, J. Douglas, D. Dessau,
Z. Hussain, and Z. Shen, “Space charge effect and mirror charge effect in photoemission spectroscopy,” JOURNAL OF ELECTRON SPECTROSCOPY AND
RELATED PHENOMENA, vol. 142, no. 1, pp. 27–38, 2005.
[128] R. Bartels, S. Backus, I. Christov, H. Kapteyn, and M. Murnane, “Attosecond
time-scale feedback control of coherent x-ray generation,” CHEMICAL PHYSICS,
vol. 267, no. 1-3, pp. 277–289, 2001.

132[129] S. Marburger, O. Kugeler, U. Hergenhahn, and T. Möller, “Experimental evidence
for interatomic coulombic decay in ne clusters,” Phys. Rev. Lett., vol. 90, no. 20,
p. 203401, 2003.
[130] T. Jahnke, A. Czasch, M. S. Schöffler, S. Schössler, A. Knapp, M. Käsz, J. Titze,
C. Wimmer, K. Kreidi, R. E. Grisenti, A. Staudte, O. Jagutzki, U. Hergenhahn,
H. Schmidt-Böcking, and R. Dörner, “Experimental observation of interatomic
coulombic decay in neon dimers,” Phys. Rev. Lett., vol. 93, no. 16, p. 163401,
2004.
[131] T. A. Carlson and M. O. Krause, “Experimental evidence for double electron
emission in an auger process,” Phys. Rev. Lett., vol. 14, no. 11, pp. 390–392,
1965.
[132] F. Penent, J. Palaudoux, P. Lablanquie, L. Andric, R. Feifel, and J. H. D. Eland,“Multielectron spectroscopy: The xenon 4d hole double auger decay,” Phys. Rev.
Lett., vol. 95, no. 8, p. 083002, 2005.

Appendix A
Laser-Assisted Dynamics

A.1

Ponderomotive Potential and Maximal Classical Excursion
The ponderomotive potential Up is defined as the kinetic energy of an electronin the E field, averaged over an optical cycle. Using Newton’s second law (in atomic
units), F = r̈ , where F = E , we can extract ṙ by
Z
ṙ =

dtE ,

(A.1)

E =−

∂
A,
∂t

(A.2)

where the electric field E is given by

therefore,ṙ = −A
Now we can calculate the averaged kinetic energy of the electron

(A.3)

134

*
hKEi =
*

1 2
ṙ
2

+

i2
1h
− A0 cos(ωt − k · r )
=
2
*
+
1 2
=
A cos2 (ωt − k · r )
2 0
*
+
1 2
=
A cos2 (ωt − k · r )2 0hKEi =+

A20
E2= 02 = Up .
4
4ω

(A.4)

From Newton’s second law we can also obtain the maximal classical excursion α0of the electron in its oscillatory motion in the field. Starting from equation A.3

ṙ

= −A

ṙ

= −A0

r

A0
= −
sin(ωt − k · r ),
ωZ t

dt0 cos(ωt0 − k · r )

0

(A.5)
where the maximum value of sin(ωt − k · r ) = 1. Thus, the maximal classical excursion
α0 is

α0 =

A.2

A0
E0
=− 2 .
ωω

(A.6)

Volkov Wave Function
In this section we will derive the Volkov wave as a function of generalized Bessel

functions. We will start from equation 2.20 and solve the integrals!#"
Z t Ã 2A(t0 )2
1
0
0 q+ A(t ) · q +.
ψV (r , t) =exp i q · r −dt22(2π)3/2
0

(A.7)

135
First integral:
Z t

dt0

0

q2
q2
= t.
2
2

(A.8)

Second integral:Z t

dt0 A(t0 ) · q

Z t
=

0

0

= q·

dt0 q · A0 cos(ωt0 )A0sin(ωt)ω= q · α0 sin(ωt).

(A.9)

Third integral:

Z t
dt
0

0 2
0 A(t )

2

Z t

=
=
=
=
=

A2
dt0 0 cos2 (ωt0 )2
0Z
A20 t 0dt cos2 (ωt0 )2 0Zi
A20 t 0 h
dt 1 + cos(2ωt0 )4 0Ã
!
sin(2ωt)
A20
t+
4
2ω
Ã
!
sin(2ωt)
Up t +.
2ω

(A.10)

By inserting the solved integrals A.8-A.10 into equation A.7, the Volkov wave
function is given by

"
Ã
!#
Up
1
q2
ψV (r , t) =exp i q · r − q · α0 sin(ωt) −sin(2ωt) −+ Up t , (A.11)2ω
2(2π)3/2
which is the same as equation 2.23. We can now make use of equation 2.24 to rewrite
the Volkov wave function in terms of generalized Bessel functions

136

ψV (r , t) ==ψV (r , t) =

A.3

´
# ³ 2
"
q
−i
+U
t
U
1
p
p
2
eiq ·r exp(−i) q · α0 sin(ωt) +sin(2ωt) e
3/2
2ω
(2π)
´
Ã
! ³ 2
∞
q
X
+U
t
−i
U
1
p
p
2
eiq ·re−inωt Jn q · α0 ,
e
3/2
2ω
(2π)
n=−∞
³
´ Ã
!
∞
q2
X
−i
+U
+nω
t
U
1
p
p
2
eiq ·re
Jn q · α 0 ,.
(A.12)2ω(2π)3/2n=−∞

S-Matrix Element in Laser-Assisted Scattering
Here we will derive the S-Matrix element in the case of laser-assisted scattering. If

we substitute the initial and final Volkov wave functions of equation 2.25 into equation
2.29 we obtain(S − 1)B
fi

Z ∞
= −i
−∞

(f )

Z ∞
= −i

dt
∞

(i)

dthψV | V | ψV i
XÃJn q f · α 0 ,

n,m

!

Ã

! ³ q2UpUp
Jm q i · α0 ,
e
2ω
2ω
+

i

q2
f
− 2i +(n−m)ω
2

¯ ¯
¯ ¯ 1
1
iq f ·r ¯ ¯×eeiq i ·r .
¯V ¯¯ ¯ (2π)3/2(2π)3/2*´
t(A.13)

If we introduce the momentum transfer q f = q i + Q, the last factor of equation
A.13 can be identified as the Fourier transform Ṽ (Q) defined in equation 2.33:

¯ ¯
+
¯ ¯ 1
1
iq f ·r ¯ ¯
iq i ·ree¯V ¯¯ ¯ (2π)3/2(2π)3/2
Z
1
d3 rV ei(q f −q i )·r
(2π)3
Z
1
d3 rV eiQ·r .
(2π)3*Ṽ (Q) ==Ṽ (Q) =(A.14)
Thus, the time integral in equation A.13 is readily evaluated

137

!
qi2
= −i2πδ−+ (n − m)ω
2
2
n,m
Ã
! Ã
!
Up
Up
×Jn q f · α0 ,Jm q i · α0 ,Ṽ (Q).
2ω
2ω
X(S − 1)B
fi

Ã

qf2

(A.15)We define the new summation index ` = m − n, and equation A.15 reads

Ã

!
qi2
= −i2π
δ
−
+ `ω
2
2
n,`
Ã
!
Ã
!
Up
Up
J`+n q i · α0 ,Ṽ (Q).
×Jn q f · α0 ,2ω2ωX(S − 1)Bfi

qf2(A.16)The summation formula∞X

Jn∓k (u, v)Jk (u0 , v 0 ) = Jn (u ± u0 , v ± v 0 )(A.17)k=−∞

may be applied to the product of generalized Bessel functions and the summation overn, and we obtain(S − 1)Bfi(S − 1)B
fi

! Ã
!
Up
Up
qi2
−
+ `ω J` α0 · q i − α0 · q f ,−Ṽ (Q)= −i2π
δ
2
2
2ω 2ω
`
Ã
!
! Ã
X
qf2
qi2
= −i2πδ−+ `ω J` α0 · (q i − q f ), 0 Ṽ (Q)
2
2
`
Ã
!
! Ã
X
qf2
qi2
δ
= −i2π−+ `ω J` − α0 · Q Ṽ (Q)(A.18)
2
2
X

Ã

qf2

`

where Jn (u, 0) = Jn (u) was used to relate the generalized Bessel function to the ordinaryone.

Appendix B
Time-of-Flight Electron Analyzer

B.1

Electron Analyzer
When count rates are low, it is advantageous to try to detect every emitted

electron within the energy range of interest. Using a pulsed photon source, the timeof-flight analyzer (TOF) can be employed (figure B.1), where in theory every single
electron is counted.
MCP
Detector

Decoupling
capacitor

Photonv ~ l flight / tflighte-

Samplel samplel driftAnodel flight
Figure B.1: Geometrical schematics of a Time-of-Flight (TOF) analyzer.

This is basically a stop watch technique triggered by a pulse from the light sourceand stopped when the photoelectron is detected after flying through a defined drift
stretch. One of the limiting factors of such an analyzer is the restriction on the maximal
count rate, since every single electron has to be registered and counted by the electronics.

139
The electronics have a certain dead time where they cannot register events.

B.2

Time to Energy Conversion
A time-of-flight analyzer physically measures the time of flight of a particle, i.e.

electron, and not its energy Ekin . Therefore, the acquired data has to be normalized
into an energy-dependent spectrum. The conversion from a time of flight distribution,
to an energy-dependent spectrum is made by calculating the energy axis according to
the kinetic energy. Here, each time bin ti corresponds to a certain Ei width which varies
in bin width according to a 1/t2 law (since Ekin = me l2 /(2t2 )). To obtain the number of
events N (Ei ) per energy bin Ei as a function of the counts N (ti ) in the correspondingtime bin, the counts have to be renormalized (figure B.2).
N(t3 )
N(t)N(E)

N(E 3 )
t
t3

E

Δt

ΔE

E3

Figure B.2: Conversion from the acquired time of flight distribution N (t) to an energy
spectrum N (E).

The total number of events, i.e. the surface under the spectral curves, is the samefor the time and energy domain. For the counts N in every bin of width ∆t or ∆E this
is
¯
¯ ¯
¯
¯
¯ ¯X
¯X
¯
¯ ¯
¯
N (Ei ) · ∆E ¯
N (ti ) · ∆t¯ = ¯
¯
¯
¯ ¯
¯
i

and converting to infinitesimal notation,

i

(B.1)

140
¯Z
¯ ¯Z
¯
¯
¯ ¯
¯
¯
¯ ¯
¯
¯ N (t) · dt¯ = ¯ N (E) · dE ¯.
¯
¯ ¯
¯

(B.2)

Differentiating both sides by dt,¯¯¯ dE ¯me l2¯¯
N (t) = N (E) · ¯·¯ = N (E) ·¯ dt ¯e t3(B.3)

gives a way to renormalize the counts N (Ei ) in every energy bin Ei

N (Eikin ) =e t3i· · N (ti )me l 2(B.4)

1 me l2··2 e t2i

(B.5)

with

Eikin =
where
• l = ldrif t + lsample .
• N (ti ): Measured counts in bin ti .

• N (Ei ): Calculated number of counts in bin Ei .
• l: Total drift length of the electron.
• ldrif t : Length of the TOF tube.
• lsample : Distance from the sample to the entrance of the TOF.
• ti : Time of flight of the electron over the drift stretch.
• tstop−start : Elapsed time between the laser trigger and electron detection.
• toptical start : Elapsed time between the laser trigger and the optical detection
peak.

141
• me : Electron mass.
• e: Electron charge.
From equation B.5 it is clear that the bin width Eikin is not constant, but instead
proportional to −1/t2 . This means that it decreases with an increase in flight time andbinding energy.
The MCP detector can detect not only particles, but also photons. This is used
to obtain the time zero (optical peak, see figure B.3) for calculating the time of flightti . The sensitivity of the MCP increases for shorter wavelengths, so that when using
high order harmonics the optical back scattering from the harmonic beam on the sample
is enough to induce a significant signal on the MCP. Thus, the time of flight ti is thedifference between the time evolved between the trigger and the detection tstop−start andthe optical peak in the flight time spectrum toptical start , which remains constant within
an experiment:Ãti = tstop−start −!
ldrif t + lsample
toptical start −
.
c

(B.6)

The last term in equation B.6 refers to the time correction due to the time elapsed
between registering the optical peak at the MCO and its arrival at the sample surface.
This time delay of a pulse traveling at the speed of light is in our case ∼ 2 ns andtherefore virtually negligible compared with the electrons’ flight time.

142

12x10

3

d-bandpeaks

Counts N(t flight)

108
6

Optical
peak
Fermi
edge

4
2
0
0

Counts N(Ekin)200x10200

400
t flight (ns)

600

800

3

150

100
d-band
peaks

Fermi
edge

50

0
5

10

15
20
25
30
Electron kinetic energy (eV)35

Figure B.3: Time of flight (top) to energy (bottom) conversion. The direct opticalreflection of the sample induces the optical peak, which is used as time zero.