Workshop on

Advancement of Group IV Nanostructures
Nanophotonics and Nanoelectronics
November 18-19, 2014
Takikawa Memorial Hall, Kobe University,
Rokkodai, Nada, Kobe 657-8501, Japan(http://www.kobe-u.ac.jp/en/access/rokko/campus.html)

Organization:
1. Japan-Czech bilateral joint research project (JSPS)
2. Smart materials team in organization of advanced science and technology, Kobe
University.

1

Program
Tuesday, November 18
13:30 Welcome address

Electronic and photonic applications I (Chair: Minoru Fujii)
13:35 Shunri Oda, Quantum Nanoelectronics Research Center, Tokyo Institute of Technology
Si quantum dots for future electronics and photonics
14:10 Tom Gregorkiewicz, Van der Waals – Zeeman Institute, University of Amsterdam
Si nanocrystals in SiO2 for spectral shaping in future photovoltaics
14:45 Stefano Ossicini, Dipartimento di Scienze e Metodi dell’Ingegneria, Università di Modena e Reggio
EmiliaSilicon nanostructures for photonics and photovoltaic applications

15:20-15:40 Break

15:40 Nobuyoshi Koshida, Graduate School of Engineering, Tokyo University of Agri. & Tech.
Diverse functional applications of nanostructured silicon

Material Synthesis (Chair: Xiaodong Pi)
16:15 Naoto Shirahata, National Institute for Materials Science (NIMS)
Organically-Terminated Silicon Nanoparticles: Synthesis, Separation by Emission and Applications

16:50 Anna Fucikova, Department of Chemical Physics and Optics, Charles University in Prague
Various ways of preparing and modifying silicon nanocrystals

17:25 Vladimir Svrcek, National Institute of Advanced Industrial Science and Technology
Surface and energy band gap engineering of silicon nanocrystals

18:15-20:00 Banquet (Ground floor)2

Wednesday, November 19
Photonics and characterization technique (Chair: Tom Gregorkiewicz)
9:00 Bernard Gelloz, Graduate School of Engineering, Nagoya University
Characteristics of nano-porous silicon luminescence and electroluminescence, and effects of various
treatments

9:35 Kenji Imakita, Graduate School of Engineering, Kobe University
CMOS-compatible nonlinear optical materials for Si photonics

10:10-10:30 Break

10:30 Jan Valenta, Faculty of Mathematics & Physics, Charles University
Special techniques of optical spectroscopy applied to Si nanostructures

11:05 Masashi Ishii, National Institute for Materials Science (NIMS)
Charge transfer dynamics of “Bright” and “Dark” Si-nc’s

Electronic and photonic applications II (Chair: Tom Gregorkiewicz)
11:40 Tomohiro Nozaki, Department of Mechanical Sciences and Engineering, Tokyo Institute of Technology
Silicon nanocrystals and hybrid solar cells

12:15-13:30 Lunch

Doping (Chair: Stefano Ossicini)
13:30 Minoru Fuji, Graduate School of Engineering, Kobe University
All-Inorganic Colloidal Silicon Nanocrystals

14:05 Xiaodong Pi, State Key Laboratory of Silicon Materials and Department of Materials Science andEngineering, Zhejiang University
Localized surface plasmon resonance of B- and P-doped Si nanocrystals3

14:40 Naoki Fukata, National Institute for Materials Science (NIMS)
Doping and characterization of impurity atoms in Si and Ge nanowires

Biological applications (Chair: Minoru Fujii)
15:15 Antonin Broz, Faculty of Medicine, Charles University
Challenges in work with nano-crystals in cell biology

15:50 Closing remark

16:00- Lab. tour (Mesoscopic materials laboratory, Kobe University)

Language: English
Participation is open to whole academic community and it is free of charge.

Organizers: Minoru FUJII, Kenji IMAKITA, Kanna AOKI, Shinya KANO
Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe
University, Rokkodai, Nada, Kobe 657-8501, JAPANfujii@eedept.kobe-u.ac.jp, Tel: +81-(0)78-803-6081

4

Abstracts

Si quantum dots for future electronics and photonics
Shunri Oda
Quantum Nanoelectronics Research Center, Tokyo Institute of Technology,
2-12-1 O-okayama, Meguro-ku,

Quantum dot structures, where electrons are confined three-dimensionally in the sub-10 nm scale,show characteristics quite different from conventional bulk structures. Recent progress in the
fabrication technology of silicon nanostructures has made possible observations of novel electricaland optical properties of silicon quantum dots, such as single electron tunneling, ballistic transport,
visible photo-luminescence and high-efficiency electron emission.
Silicon quantum dots are fabricated either by bottom-up or top-down processes. Fabrication andelectrical/opto-electrical characterization of nanocrystalline Si films by plasma processes andcoupled Si quantum dots by electron beam lithography processes are discussed.

Si nanocrystals in SiO2 for spectral shaping in future photovoltaics
T. Gregorkiewicz
Van der Waals – Zeeman Institute, University of Amsterdam
Science Park 904, 1098 XH Amsterdam, The Netherlands

The most important limitation for efficiency of photovoltaic energy conversion appears due to the mismatch
between the broad-band character of the solar radiation and the discrete operation mode of solar devices, as
determined by the specific bandgap energy of the active medium. One remedy for that would be the spectral
transformation of the solar radiation before it enters a photovoltaic device. Specifically, such a “solar
shaper” should split the large energy photons into smaller ones, whose conversion efficiency is optimal.
In my presentation, I will discuss how shaping of the solar spectrum can be achieved using layers of Si
nanocrystals with and without Er doping. In such systems efficient photon transformation can be realized byquantum cutting [1] and/or emission from Er3+ ions sensitized by Si nanocrystals [2]. I will present
evaluation of external quantum efficiency of emission from thin layers of Si nanocrystals in SiO 2 and its
evolution upon introduction of Er3+ ions. Using differently prepared materials I will evaluate how this can be
maximized. I will also discuss energy efficiency of solar shapers based on Si nanocrystals and Er3+ ions. In a
separate part, I will discuss also strategies how Si nanocrystals can be employed for quantum “pasting” bywhich low-energy photons could be used in photovoltaic conversion by a standard Si solar cell.
[1] M.T. Trinh et al., Nature Photonics 6, 316-321 (2012).
[2] S. Saeed et al., Nature Communications 5:4665 (2014)

Silicon nanostructures for photonics and photovoltaic applications
Stefano Ossicini
CNR-INFM-S3 “nanoStructures and bioSystems at Surfaces”, Dipartimento di Scienze e Metodidell’Ingegneria, Università di Modena e Reggio Emilia, via Amendola 2 Pad. Morselli, I-42100
Reggio Emilia, Italy
stefano.ossicini@unimore.it
In recent years particular attention has been devoted to Silicon nanocrystals and nanowires, apowerful class of nanostructures which is opening new substantial opportunities for photonics andphotovoltaics. These nanostructures are zero- and one-dimensional materials with diameter fromfew to some tenths of nanometers. They present unique size dependent electronic, optical andtransport properties that are intrinsically associated with their low dimensionality and quantum
confinement effect (QCE). In particular we have performed several ab-initio calculations in theframework of Density Functional Theory and Many-Body Perturbation Theory for free and silica
embedded Si nanocrystals and for Si and Si-Ge nanowires. Among the different results we willconcentrate, here, on Si nanocrystals and on SiGe nanowires.
In this latter case we show that efficient n- and p-type doping can be achieved in coaxial SiGe
nanowires , taking advantage of the band offset of the Si/Ge interface. A one-dimensional electron(hole) gas is created at the band-edge and the carrier density is uniquely controlled by the impurity
concentration with no need of thermal activation. Additionally, SiGe core-shell nanowires provide
naturally the separation between the different types of carriers, electron and holes, a property
ideally suited for photovoltaic applications.
In the first case, the opportunity of doping and codoping of Si nanocrystals embedded in a SiO2
matrix or passivated by H or OH groups has been considered in order to tune their transport and/or
optical properties. Moreover we will show how the interaction between nanocrystals is a promisingroute to foster the establishment of third generation photovoltaics due to multiple exciton generation.

Diverse Functional Applications of Nanostructured Silicon
Nobuyoshi Koshida
Graduate School of Engineering, Tokyo University of Agri. & Tech.,
Koganei, Tokyo 184-8588, Japan,
e-mail: koshida@cc.tuat.ac.jp
URL: http://www.tuat.ac.jp/~koslab/
Along with the continuing development of ULSI for large-capacity and lower-power
information processing, silicon technology has been explored toward functional
applications in photonics, acoustics, MEMS, sensing, biometric, and biomedical area.
Here we show that nanostructured silicon is a platform for the emerging diverse streams.
A typical fabrication method of nanosilicon is a wet process termed electrochemical
anodization. Depending on the anodization conditions and the type of silicon substrates,
two kinds of structures are formed in the etched layers: interconnected nanodots andperiodically arrayed nanopores. Prepared quantum-sized silicon dots which behave as aquasi-direct wide-gap semiconductor provide opportunities for silicon photonics: efficient
light emitter in visible to uv range and photovoltaic conversion in the short wavelength
region. Analyses of observed avalanche photoconduction indicate that the impact
ionization rate in nanosilicon dots is considerably higher than that in bulk silicon. The hot
electron effect leads to the development of ballistic cold cathode. The usefulness as anenergetic planar electron emitter has been demonstrated in vacuum (parallel EB
lithography), in atmospheric-pressure gases (electron attachment), and in solutions(ballistic electro-deposition of thin metal and group-IV films). The extremely lowered
thermal conductivity of nanosilicon induces efficient thermo-acoustic effect with a broadband response. This is useful as a full-digital speaker and an analytical tool of bioacoustic communications. The nanosilicon layer with high aspect-ratio periodic
nanopores is useful as a template for fabricating Ni nanowire arrays with a significantly
high magnetic anisotropy. Some topics on these functional properties of nanosilicon are
discussed, including their device applications.

Organically-Terminated Silicon Nanoparticles: Synthesis, Separation by Emission and Applications
Naoto Shirahata1,2
1

WPI-MANA, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047, 2PRESTO, Scienceand Technology Agency (JST), 4-1-8 Honcho Kawaguchi, 332-0012, Japan E-mail: shirahata.naoto@nims.go.jp

Optical use of colloidal nanoparticles of silicon (npSi) and germanium (npGe) has gained increasing
attention for its possible contributions to building a sustainable society that ideally uses resources and energy
with high efficiency without causing damage to the environment or human health. Full control innanostructures such as crystalline phase, surface and size of the NPs allows the tuning the color in a verybroad range of emission wavelength from near-UV (300 nm~) through full color of visible to near-IR(~1030 nm for npSi and ~1270 nm for npGe). However, the story does not end here. Unlike the direct
bandgap semiconductors, PL origin of npSi is still not very clear and under debate. The yet-to-be-definedmechanism becomes a big obstacle for ease in access to emission tuning. As a result, research on
luminescent Si is a matter for fundamental study. A lot of reports regarding the emission is very interesting
counter-intuitive and even confusing and to reach in a unified conclusion. From the reported literatures
emission of npSi can be divided into two distinct regions. First region is in the emission range from near-UV
to Aqua (em= 300−500 nm), and another region is Green to NIR (em= 500−1030 nm) region. There is a
discontinuity or wall between these two regions. These two kind of different emission zone, covered by npSi
are being prepared by fundamentally different preparation approaches. To the best of our knowledge,
unfortunately, there are no reports which break this barrier or discontinuity smoothly by a single preparation
method. In the present talk, I will start my talk by describing the synthesis of npSi with diamond cubic
lattice structures. A critical size of npSi to form a diamond cubic lattice lies in the range between 1.1 and 1.2
nm. Thus, we can see the size dependent photoluminescence spectra in the range between 500 nm and 1130
nm through the control over the size of diamond cubic npSi in the ranging from 1.1-1.2 nm to 5.2 nm. On
the other hand, we see the size-dependent NUV-Aqua emissions when npSi do not have diamond cubic
lattices. Commonly, the NUV-Aqua emitting npSi are prepared by any solution synthesis under room
temperature and subsequent column separation by emission color. The discovery of color-tunable emission
from free-standing npSi kindled the development and study of luminescent forms of Si for its potential
applications. I will show herein several applications including light-emitting diodes.
1. For reviews, see: a) B. Ghosh and N. Shirahata, “Solution-Processable White-Light-Emitting Germanium
Nanocrystals”, Sci. Technol. Adv. Mater. 2014, 15, 014207 (1-14) b) N. Shirahata, “Colloidal Si
nanocrystals: A controlled organic-inorganic interface and its implications of color-tuning and chemical
design toward sophisticated architectures”, Phys. Chem. Chem. Phys. 2011, 13, 7284-7294. c) N.
Shirahata, A. Hozumi, T. Yonezawa, “Monolayer-derivative Functionalization of Non-oxidized Silicon
Surfaces”, Chem. Rec. 2005, 5, 145-159
2. B. Ghosh, Y. Masuda, Y. Wakayama, Y. Imanaka, J. Inoue, K. Hashi, Deguchi, H. Yamada, Y. Sakka, S.
Ohki, T. Shimizu, and N. Shirahata, “Hybrid White Light Emitting Diode Based on Silicon
Nanocrystals”, Adv. Funct. Mater. 2014 (DOI: 10.1002/adfm.201401795)
3. N. Shirahata, D. Hirakawa, Y. Masuda, and Y. Sakka, “Size-Dependent Color-Tuning of Efficiently
Luminescent Germanium Nanoparticles”, Langmuir 2013, 29, 7401-7410
4. N. Shirahata, “Solution-Processable White-Light-Emitting Germanium Nanocrystals”J. Sol. Stat. Chem.
2014, 214, 74-78
5. B. Ghosh, Y. Sakka, and N. Shirahata, “Efficiently Green-Luminescent Germanium Nanocrystals”, J.
Mater. Chem. A 2013, 1, 3747-3751
6. N. Shirahata, D. Hirakawa, and Y. Sakka, “Interfacial-related Color Tuning of Colloidal Si Nanocrystals”,
Green Chem. 2010, 12, 2139-2141
7. N. Shirahata and Y. Sakka, “Controlled Organic/Inorganic Interface Leading to the Size-tunable
Luminescence from Si Nanoparticles”, J. Cer. Soc. Jpn. 2010, 118, 932-939
8. N. Shirahata, T. Tsuruoka, T. Hasegawa, and Y. Sakka, “Size-Tunable UV-Luminescent Silicon
Nanocrystals”, Small 2010, 6, 915-921
9. N. Shirahata, M. R. Linford, S. Furumi, L. Pei, Y. Sakka, R. J. Gates, M. C. Asplund, “Laser-derived
One-Pot Synthesis of Silicon Nanocrystals Terminated with Organic Monolayers”, Chem. Commun. 2009,4684-4686

Title: Various ways of preparing and modifying silicon nanocrystals
Anna Fucikova, Department of Chemical Physics and Optics, Charles University in Prague
Czech RepublicContact: anna.fucikova@email.cz
In this presentation we would like to summarize various methods of silicon nanocrystals
preparation and present the pros and cons of each method. Especially we concentrate on
preparation of nanocrystals from hydrogen silsesquioxane (HSQ). The silicon nanocrystals
are formed from HSQ molecules annealed at 1000°C in inert Ar atmosphere with 5% H2. I
this way, we obtain silicon nanocrystals in silicon oxide matrix. The nanocrystals are released
from the matrix by HF etching and need to be stabilized in order to prevent the nanocrystals
from deterioration. In the stabilization process the surface Si-H group is usually replacedby an organic group. This process can be initiated by light, high temperature,
microwaves, or radicals. The properties of passivated nanocrystals are varying greatly inquantum efficiency, PL peak position and width.
In cooperation with J. Linnros group we also developed a method for direct
passivation of silicon nanocrystals in the annealing step.
The individual
silicon nanocrystals exhibited significantly narrow emission peak at room
temperature (average linewidth ~ 25 meV) compared to silicon nanocrystals
embedded in a silicon oxide shell (150 meV), when studied by single dot
spectroscopy. The luminescence from produced nanocrystals covers a broad
spectral range from 530-720 nm (1.7-2.3 eV). Blinking and spectral hoppingof individual nanocrystals were also detected. The silicon nanocrystals
did not show any deterioration of luminescence for at least 16 months.

Surface and energy band gap engineering of silicon nanocrystals
Vladimir Svrcek1, Mickael Lozach1, Somak Mitra2 Davide Mariotti2,
1

National Institute of Advanced Industrial Science and Technology, Research Center for Photovoltaic
Technologies, Tsukuba, Japan.
2
University of Ulster, Nanotechnology & Integrated Bio-Engineering Centre-NIBEC, Newtownabbey,
UK.
st nd
In 1 /2 generation devices, every absorbed photon can only generate one electron-hole pair whereby
in devices with carrier multiplication (CM), more than one electron-hole pair can be formed for every
photon absorbed. CM has been demonstrated to occur in PbSe, PbS, PbTe, CdSe, InAs and Si quantum
dots (Si QDs) [1]. In this context, silicon as a raw material represents an attractive solution; however
CM in Si QDs is triggered only for high energy photons (above ~2 eV) [2] and the indirect nature ofsilicon still plays a role in limiting the absorption coefficient.
In this talk we discuss how surface engineering and alloying bulk Si with another material offers
another opportunity to challenge the nature of silicon’s indirect energy band gap in Si QDs. In thisrespect the atmospheric generated plasmas present unique opportunities. In particular atmosphericpressure confined plasma (e.g. microplasmas) has allowed substantial promising advances for both QDs
surface engineering and synthesis. Firstly, here we would like to report on recent strategies forsurfactant free surface engineering of Si QDs that have employed microplasma interactions withcolloids [3]. The surface characteristics achieved via microplasma processing contributed to improve
optoelectronic properties, add to our understanding of Si QDs fundamental properties [4-6] and madepossible the fabrication of photovoltaic devices with improved efficiencies [7]. Secondly we discuss theapproaches how to engineer the energy band gap and direct transition in Si QDs by alloying withenvironmental friendly and abundant element (e.g, tin). Confined plasmas generated in the liquid by
ns/fs laser pulses allowed the growth of the silicon–tin QDs via kinetic pathways. In particular wewould like to report on the synthetic feasibility of semiconducting alloyed silicon–tin QDs where thesilicon–tin alloys at quantum confinement size have the potential to undergo a real transition fromindirect to direct narrower energy bandgap, compared to corresponding elemental Si QDs [8].
Acknowledgements This work was partially supported by a NEDO and JSPS projects, international
network through the Leverhulme Trust Grant.
References
1. P. V. Kamat J. Phys. Chem. Lett. 2013, 4, 908
2. D. Timmerman et al. Nat. Nanotechnol. 2011, 6, 710L18
3. V. Svrcek et al. Applied Physics Letters 2010, 97, 161502
4. D. Mariotti, et al Adv. Funct. Mat. 2012 ,22, 954.
5.
6.
7.
8.

V. Svrcek et al. J. Phys. Chem. C 2013, 117, 10939
V. Svrcek et al. Adv. Funct. Mater. 2013, 23, 6051
V. Svrcek et al. Appl.Phys.Lett. 2012 , 100, 223904
V. Svrcek et al. Nanoscale, 2013, 5, 6725

Characteristics of nano-porous silicon luminescence and electroluminescence, andeffects of various treatments.
Gelloz Bernard

Nano porous silicon can be prepared by electrochemical etching of silicon wafers inhydrofluoric acid. Luminescent layers can be obtained when the porous structure
contains crystallites whose sizes are lower than the Bohr radius in silicon (~4 nm).
Regarding optoelectronic applications, compared to other nano-silicon materials
obtained by planar technologies, porous silicon has a set of key advantages, such as (i)the ease and low-cost of manufacture, (ii) the ability to form quickly thick layers(limited only for the silicon substrate thickness), and (iii) easy modulation of index forphotonic crystal formation. However, it also has critical limitations, such as (i)mechanical weakness of high porosity layers, (ii) an easily contaminated exposed
surface (it is an opened structure) leading to poor stability, and (iii) a difficult control offeature size distribution within the porous silicon skeleton.
This presentation reviews the luminescence and electroluminescence properties ofporous silicon. In addition, various treatments used in a view to enhancing theircharacteristics (such as efficiency, stability, color) are reviewed.

CMOS-compatible nonlinear optical materials for Si photonics
Kenji Imakita
Graduate School of Engineering, Kobe University
In recent years, nonlinear optical phenomena in Si-based materials have attracted
significant attentions due to the possible optoelectronic applications such as all opticalsignal routing, wavelength converter, electro-optic modulator, and so on. It is wellknown that Si crystal shows small third order nonlinearity compared to direct bandgap
semiconductors due to the indirect bandgap nature, and exhibits no second ordernonlinearity due to the centrosymmetric structure. These motivate researchers to
explore new CMOS-compatible materials with large second or third order nonlinearity.
This work consists of two parts. The first part is on the third order nonlinear opticalproperties of phosphorous(P)- or boron(B)-doped silicon nanocrystals embedded in SiO2
thin films prepared by a sputtering method. A z-scan method and a pump-probe opticalkerr gate method were used to evaluate the nonlinear refractive index (n2), two photon
absorption coefficient (), and the time response of the third order optical nonlinearity.
The values of n2 and  of our undoped samples were the order of 10-12 cm2/W and 10-9
cm/W, respectively. Regardless of P- or B-doping, n2 and  were found to be enhanced
about 5 times by the doping. The time response of the optical nonlinearity was fasterthan our time resolution of 100 femtoseconds. The results indicate that doping of Si
nanocrystals can be a promising tool to improve the nonlinear optical properties.
The second part is on the second order nonlinearity of CMOS-compatible amorphousthin films. Until recently, it was believed that amorphous materials do not show second
order nonlinearity due to the centrosymmetric structure. However, a few kinds ofamorphous thin films prepared by conventional deposition systems, such as SiN thinfilms prepared by plasma enhanced chemical vapor deposition and silicon monoxide(SiO) thin films prepared by an electron beam deposition, have been reported to exhibit
large second order nonlinearity. In this work, we investigated the second ordernonlinearity of Ge-doped SiO2 amorphous thin films prepared by a sputtering method.
It was found that the second-order nonlinearity of SiO2, which vanishes in theelectric-dipole approximation, can be significantly enhanced by Ge doping. The observed
maximum value of d33 is 8.2 pm/V, which is 4 times larger than d22 of β-BaB2O4 crystal.
Strong correlation was observed between the deff values and the electron spin resonancesignals arising from GePb centers, suggesting that GePb centers are the most probableorigin of the large second-order nonlinearity.

Special techniques of optical spectroscopy applied to Si nanostructures
Jan Valenta
Department of Chemical Physics & Optics, Faculty of Mathematics & Physics, Charles University,
Prague 2, Czechia
jan.valenta@mff.cuni.cz
Light-emitting silicon nanostructures have been studied for more than 25 years, but the full understandingof electronic and optical properties is still not achieved. We believe that application of advanced techniquesof optical spectroscopy can move forward our knowledge of Si nanostructures. Namely the following
techniques have great potential: single-nano-object spectroscopy, non-linear optical spectroscopy,
quantum yield measurement etc. All these techniques require careful calibration and reliable sample
preparation, otherwise severe artefacts could distort the obtained results. In this contribution we shalldiscuss some critical aspects of these spectroscopy techniques.

Charge transfer dynamics of “Bright” and “Dark” Si-nc’s
Masashi Ishii
National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047, JapanISHII.Masashi@nims.go.jp“Bright” Si-nc’s can be investigated with optical measurements such as photoluminescence.
However, how can we investigate “Dark” Si-nc’s? From the fact that charge transfer decides “Bright”
or “Dark” of Si-nc’s, we adopt electronic measurement techniques for complete understanding of
nano-systems including “Bright” and “Dark” Si-nc’s.
To discuss dynamics of the charge transfer, we performed electronic frequency response
analyses (FRA). By using the FRA, we can precisely probe specific charge behaviors withresponse time  from ~ps to ~s. We found that Si-nc systems have charge responses in s ~ msregion [1-3]: The faster electron-hole recombination process with  ~ s is a reason of intenseemission of Si-nc’s, the activation process of a dopant level with  ~ ms fills the Si-nc’s with charges,
and Auger recombination with  ~ 100 ms emits the filled charges and quenches the luminescence.
I talk various charge behaviors in photo-excited Si-nc’s and approach the factors determining“Bright” and “Dark” of the Si-nc’s.
This work was supported by KAKENHI, Grand-in-Aid for Scientific Research (26420287).
[1] M. Ishii, I. Crowe, M. Halsall, A. Knights, R. Gwilliam, and B. Hamilton, J. Appl. Phys. 116,
063513 (2014).
[2] M. Ishii, I. Crowe, M. Halsall, A. Knights, R. Gwilliam, and B. Hamilton, Jpn. J. Appl. Phys. 53,
031302 (2014).
[3] M. Ishii, I. Crowe, M. Halsall, A. Knights, R. Gwilliam, and B. Hamilton, Appl. Phys. Lett. 101,
242108 (2012).

Silicon nanocrystals and hybrid solar cells.
Tomohiro Nozaki and Yi Ding
Department of Mechanical Sciences and Engineering, Tokyo Institute of Technology
tnozaki@mech.titech.ac.jp

This paper presents synthesis method of highly crystalline silicon nanocrystals (Si NCs)
and application to organic/inorganic hybrid solar cell. Si NCs with mean size of 6 nm weresynthesized from chlorinated silicon precursor (SiCl4) using flow-type, non-thermal VHF (70 MHz)
plasma reactor. Si NCs, as an electron acceptor, were blended with p-type organic semiconductormaterials (P3HT or PTB7) using appropriate solvent, producing stable Si NCs containing inks. After
spin casting on ITO substrate and evaporation of metal contact, it forms bulk heterojunction (BHJ)
type organic/inorganic hybrid solar cells with isolated Si NCs in the polymer matrix. Performancewas evaluated under 1-SUN (100 mW/cm2), resulting in short circuit current of 11.5 mA/cm2, open
circuit voltage of 0.62 V, and power conversion efficiency of 3.7%. The electronic band structure
and its tunability by size and surface termination; -Cl (as produced), -H (HF treatment), -O(controlled oxidation) is the key to maximizing the power conversion capability of the device.
Examining the performance of those devices would offer valuable insights into the electronic band
structure of Si NCs and their tunability. Successful fabrication of highly efficient and inexpensive
solar cell with Si NCs is the important goal to meet the future energy demand.

All-Inorganic Colloidal Silicon Nanocrystals
Minoru Fujii
Department of Electrical and Electronic Engineering, Graduate School of Engineering,
Kobe University, Rokkodai, Nada, Kobe, 657-8501, Japan
Colloidal dispersions of semiconductor nanocrystals (NCs) can be used as “inks” forlow-cost, solution-based deposition of films for optoelectronic applications. A common
feature of colloidal NCs is capping of the surface with organic ligands which stericallyor electrostatically stabilize NCs in solution. However, long organic ligands hinder
charge carrier transport of films fabricated from these NCs. Processes for ligand
removal or exchange in solution or during film formation have been employed.
Unfortunately, these techniques cannot be applied to Si, because Si forms covalentbonds with organic ligands. We have recently developed a novel method to stabilize
Si-NCs in solution without organic ligand passivation.[1] The strategy to attain solution
dispersibility is heavy doping of B and P simultaneously on the surface of Si-NCs. The
heavily B and P doped shell induces negative potential on the surface, which prevents
agglomeration of NCs in polar solvents due to the electrostatic repulsion. In thepresentation, I will discuss the results of structural characterization andphotoluminescence properties of B and P codoped colloidal Si-NCs. I will also discuss
the electrical transport properties of NC films produced from the colloid. [1] J. Phys.
Chem. C 116, 17969 (2012), J. Phys. Chem. C 117, 6807 (2013), J. Phys. Chem. C 117,
11850 (2013).

Localized surface plasmon resonance of B- and P-doped Si nanocrystals
Xiaodong Pi
State Key Laboratory of Silicon Materials and Department of Materials Science andEngineering, Zhejiang University, Hangzhou, Zhejiang 310027, China

We have produced Si nanocrystals (NCs) that are rather heavily doped with B and P
by means of a gas-phase approach [1]. It is found that localized surface plasmon
resonance (LSPR) occurs to both B- and P-doped Si NCs [2,3]. We bothexperimentally and computationally show that the so-called Drude model traditionallyused to describe the LSPR of noble metal NCs also works for the LSPR ofsemiconductor NCs if the dielectric screening and carrier effective mass ofsemiconductor NCs are considered. Significantly, electronic properties such as dopant
activation and free carrier behavior can be elucidated by investigating the LSPR of
doped Si NCs with the synergy of experiments and calculations. We clearly
demonstrate that B-doped Si NCs are better positioned for the practical use of LSPR
than P-doped Si NCs. The current findings may help advance the Si-NC-based
plasmonics.

[1] S. Zhou, X. D. Pi, Z. Y. Ni, Q. B. Luan, Y. Y. Jiang, C. H. Jin, T. Nozaki, and D.
Yang, Particle and Particle Systems Characterization, in press (2014).
[2] X. D. Pi and C. Delerue, Physics Review Letters 111, 177402 (2013).
[3] S. Zhou, X. D. Pi, Z. Y. Ni, Y. Ding, D. Yang, C. Delerue and T. Nozaki,
submitted.

Doping and characterization of impurity atoms in Si and Ge nanowires

N. Fukata1, T. Sekiguchi1, Y. Bando1, K. Murakami2, and Zhong Lin Wang3
1 National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Japan
2 Institute of Applied Physics, University of Tsukuba, Tsukuba 305-8573, Japan
3 School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA
30332-0245, USA

-1

-1

11

10

Intensity (arb. units)

Intensity (arb. units)

Intensity (arb. units)

Silicon and germanium nanowires (SiNWs and GeNWs) are of great interest in the fields of both
fundamental and application research. In this study, we investigated doping and their characterizaionin SiNWs and GeNWs.
SiNWs were synthesized by laser ablation and GeNWs were synthesized by CVD method.
Micro-Raman scattering measurements were performed at room temperature with a 532-nm
excitation light. Electron spin resonance (ESR) measurements were carried out at 4.2 K.
A Raman peak was observed at about 618 cm-1 for SiNWs(a)synthesized by using a Si target with B. The peak frequency is(b) 618cm Si 640cm Si
in good agreement with that of a local vibrational mode of B
618
B
B
in Si crystal. The Fano broadening due to a coupling between
the discrete optical phonon and a continuum of interband hole
640
excitations was also observed in the optical phonon peak,which indicates heavily B doping. The observation of B local
600 620 640 660-1
Raman shift (cm )vibrational peaks and Fano broadening were observed for the-1
618cm
B-doped SiNWs
first time in our experiments [1,2]. These results prove that B
atoms were doped in substitutional sites of the crystalline Si
undoped SiNWs
core of SiNWs [1,2]. ESR measurements were also performed
500
550
600
650
700
-1
to investigate defects and P donor/conduction electrons inRaman shift (cm )P-doped SiNWs. The observation of ESR signal due toSi
g=2. 006(c)conduction electrons clearly showed that P atoms were doped
P
P-doped SiNWs
Ni2P=10 mol%in substitutional sites of the crystalline Si core of SiNWs [2,3].
The codoping of B and P were also investigated and theg=1. 998
compensation effect in SiNWs was detected [4]. The
segregation behaviors of B and P were investigated by using
undoped
SiNWs
B local vibrational peaks and Fano broadening for B-doped
SiNWs, while an ESR signal of conduction electrons wasused for P-doped SiNWs. The results showed that the
segregation of B is faster than that of P. Raman local
318 319 320 321 322 323 324
vibrational peaks and Fano resonance due to B acceptors andMagnetic field (mT)P donors were also observed for B-doped and P-doped
Fig. 1. (a) Raman spectra observed for B-doped and
GeNWs, showing the formation of p-type and n-type GeNWs.
undoped SiNWs. (b) The magnification of (a). (c)ESR signals observed for P-doped and undoped
The segregation of B and P were investigated for B-doped and
SiNWs.
P-doped SiNWs [5]. The results showed that the segregationof B is faster than that of P [6]. Recently, we also

succeeded in growing Si/Ge and Ge/Si core-shell NWs and proving site-selective
doping in Si/Ge and Ge/Si core-shell NWs [7].
References:[1] N. Fukata et al., Appl. Phys. Lett. 89 (2006) 203109. [2] N. Fukata, Adv. Mater. 21 (2009) 2829.
[3] N. Fukata, Appl. Phys. Lett. 90 (2007) 153117. [4] N. Fukata et al., Appl. Phys. Lett. 93 (2008)
203106. [5] N. Fukata et al., ACS NANO 4 (2010) 3807. [6] N. Fukata et al., NANO Lett. 11 (2011)
651. [7] N. Fukata et al., ACS NANO 6 (2012) 3278.

Challenges in work with nano-crystals in cell biology
Antonin Broz, Lucie Ostrovska, Marie Hubalek-Kalbacova
Institute of Inherited Metabolic Disorders, 1st Faculty of Medicine, Charles University Prague
Si nano-crystals (NC) are an alternative to quantum dots and organic fluorophores used incell biology, histology and medicine for fluorescent staining. Before utilization of these fluorescent
NC in biomedicine it is necessary to investigate their toxicity in vitro and fluorescence performance inbiological environment. There are several challenges in work with NCs in biological experiments.
Well-defined colloid concentration and NC size enable determination of minimal
concentration of NCs for suitable detection in microscope setups used for imaging in cell biology. It
also allows to define correctly the toxicity of NCs. Closely related to the issue of NC colloid
concentration is the quantum yield of NCs which should be as high as possible. The less living cell
culture is illuminated the less stress the cells undergo during an experiment. The illumination issue isassociated with the spectral characteristics of the NCs. UV light used for excitation of Si NCs canseverely damage cell structures resulting in cell death. Another challenge in manipulation with NCs istheir sterility and transportation conditions. Alcohols often used as a basis for NC colloids canprevent the colloid from bacterial infection and aggregation of NCs but they are also toxic for humancells. All these issues have to be addressed when preparing NCs for the biological experiments and it
all places demands on cooperation and correct communication between physicists preparing NCs
and cell biologists performing cell experiments.