GD-Profiler 2TM

Pulsed RF Glow Discharge Optical Emission Spectrometerwith Differential Interferometry Profiling

DiPRF GDOES

Pulsed RF Glow Discharge Optical Emission Spectrometry
with Differential Interferometry Profiling

In this context, pulsed RF
GDOES is the ideal analyticaltechnique for studying layeredmaterials as well as theirprocess control. It offers
ultrafast elemental depth profile
analysis of thin and thick layers,
conducting or isolating, with highsensitivity to all elements.

• Native oxide (few nm)• Corrosion protection• Tribological improvement

1-100 nmProtective coatings• Structure: Multilayer, Gradient,• Elemental composition• Interface details• Layer intermixing• Compound formation

Intermediate layers• Adhesion improvement• Element inter-diffusion• Substrate protection• Contamination at a buried interface

Substrate

10-1000 nm

Complex coatings

100 nm - 100 µm

Most materials today aremultilayered (automotive bodies,LED, photovoltaic thin films, harddisks, electrodes for Li batteries,
coated glasses, etc.) or they
feature surface treatments andcoatings in order to enhance
performance, to improvemechanical properties or tostrengthen corrosion resistance(nitrides, biocompatible surfaces,advanced oxides, etc.)

From multilayer sample to depth profile

1 mm

GDOES: Multilayer elemental
depth profile• Bulk composition

Large compartment

Some application domains
Li Batteries

Cationic Exchange in Glass

Nitriding

Coatings on Steel

LED

Polymers

Structured Materials

HydrogenHard Disks

2DiP, Direct measurement of thedepth as a function of time
With DiP, Differential
Interferometry Profiling, adirect measurement of thedepth as a function of time,with nanometric precision,is performed simultaneouslywith the GD analysis.

Enhance productivity
with the Sample
Mapping Unit

With a transparent
Sapphire sample thetwo DiP beams can beobserved.

www.horiba.com/GDOES

3Quantitative Elemental Depth Profile Analysis
From the First Nanometer Down to More than 150 Microns

Speed & depth resolution

Absence of matrix effects

Ultra Fast

Nanometric depth resolution

With a typical erosion rate of µm/min (2-10 nm/s),
pulsed RF GDOES is ultra fast. Researchers and users are
therefore encouraged to run multiple samples or do multiple
measurements on any specimen. The immediate feedback
allows them to check for material homogeneity, to optimize
and control each stage of their evaporation, deposition orannealing processes and to quickly react to any observedvariation. Even polymeric layers are sputtered ultra fast
without damage, due to HORIBA's patented “UFS” system.

Pulsed RF GDOES offers superb depth resolution, down to
the nanometer scale or below, made possible by the uniquecharacteristics of the advanced pulsed RF GD source andthe patented High Dynamic Detection capability of theoptical system.

This example shows analysis of Zr exposed to oxidationconditions in an atmosphere containing traces of Li. Zr
concentration naturally increases when going from the oxide
to the Zr bulk. GD signals (left) follow the concentration
changes, whilst conversely the SIMS signals (right) aremuch higher in the oxide layer.

Li

3.5 nmSub nm depth resolution
Mirror for X-ray, thinmultilayer material.
Ref: Thin Solid Films 540(2013) 96–105

Zr

CountsIntensity (a.u.)

O

Zr

Nb

102

O

Oxide/metal interface

101

1LiNb

10002000

4000

6000

Time (seconds)

00.3 nm
3.2 nmMo40 sec

20B 4C6000 secZr103

ZrO2
SI

The ionization process in SIMS is matrix dependent while
the separation of erosion and excitation in the plasma gasfor GD makes the GD nearly matrix independent.

10203040SIMS measurement

Time (seconds)

60 periods of 7 nm thick

GD measurement
The 60 layers of B4C - each 0.3nm thick – are seen andresolved. The 420nm thick structure is sputtered in 1minute!

Qualitative and quantitative depth profiles of thin and thick films
Optimum spectral coverageHigh Dynamic and Ultra-Fast Optical Detection allows simultaneous measurement ofall elements of interest in the depth profiles from ppm levels to 100%. The proprietary
HORIBA diffraction gratings allow optimum measurements of emission lines ranging
from the VUV (120 nm for H and its isotope D, 130 nm for O, etc.), to the IR for Li(670 nm) and K (766 nm).

Surface sensitive techniques (XPS or SIMS) are slow and fail to measure layers of more than 1 micrometre. For thicker
layers, SEM EDX on cross sections can be used, but require tedious preparation and cannot measure light elements.
Pulsed RF GDOES, on the other hand, rapidly sputters tens of micrometres of conductive and non-conductive materials,
measures all elements and is therefore ideal both for thin and thick layers.
Within the pulsed RF GD source, erosion and emission are spatially separated. Erosion is material dependent andmeasured with DiP. Excitation takes place in the gas phase only and uniquely relates to the plasma conditions and emission
lines intensities are directly proportional to the concentrations in the plasma. Conversion from measured signals (intensitiesvs time) to quantitative results (concentrations vs depth) is therefore straightforward.

Large Spectrum of Applications
Li Batteries

Nitriding

LEDHydrogen

Positive and negative electrodes, Thick layers
and thin surface SEI. Air sensitive sample
handling strategy with Li bell accessory.

In depth N and C measurements

Process control, depth resolution. Blue and red LED
analysis, with possible automation using the Sample
Mapping Unit.

Direct measurement of H.
H and D can also be measured simultaneously.

Ref: G. Mancuso, Colmegna, 4th GD Day
At %Ref: HORIBA Scientific Application note n°18

Ref: Fusion Engineering and Design 87 (2012) 1091– 1094

Ref: HORIBA Scientific Application note n°196060AlO

320O20Ni00Mn010F2030µm

4050Ga440LiCFe0Intensity (a.u.)

At. %40NC24681012141618µm

Emission Intensity (a.u.)

80

In

24Al
31NMg

H30
20004812Ni

DTa10Ti
02060

40100

200300400

Depth (nm)Time sState Of Charge 0 %60

Zn Coatings
AlO

C001020

Compliant with ISO 16662
Thickness, uniformity of coating, defectology.

NiLiMn4079s

50Interface 3.02 µm10060

State Of Charge 100 %Zn60Fe40

Depth resolution, uniformitycheck, repeatability

Ref: M. Penoy, Ceratizit, 6th International GD day.

Polymers

80

Hard Disks

GD SEM/EBSD Sample Preparation
Patented application of GD plasma to prepare
samples for SEM and EBSD.

%

F
30µm

5Sapphire substrate

Atomic element signal

2003

At. %

40

1P-GaN
InGaN/GaNn-GaN

20002

46810

1214

1618µmRef: S. Liang, Seagate, 2013 SCIXUS GD Workshop. Elements
for illustration only, not actual.

AlZnC

GD: 10W - 3 secCP: 5 hours

Mechanical polishing

Ho02040Etching time (min)Structured Materials

Glass Cationic Exchange
Ru11070 μm

CoTa

Pulsed operation
to avoid thermaleffects.
Deep craters.

Fe80

100 nm

0.48
LiNa

0.42

20 ≈ 30 μm

0.36

100 nm

0.30

Cr40

0.18

B

0.12

Al20 ≈ 30 μm

06

0.8

1.2

1.6

sec

Ref HORIBA Scientific notes
N° 28 & 36

180 nm

Si0.4

Long TiO2 nanotubes (over 20µm).
Structure maintained thoughout the whole erosion.

0.24

NiO

0.06

0Patented UFS mode forUltra-Fast Sputtering
Plastic DVD with 6embedded layers(100nm) resolved below
a 70 µm polymer layer.

0020406080

100120140µm7Plasma Source: It Makes the Difference

Enhance Productivity with the Sample
Mapping Unit

Source principle

Pulsed RF GDOES is sometimes too fast that it requires a permanent presencenear the instrument when multiple analyses are being made. Do you need to map
a multilayer wafer (LED, hard disk, etc.) to check coatings uniformity or to measurea batch of thin samples in an unattended manner? The Sample Mapping Unit
(SMU) is for you.

The source is central to the operation of the instrument and accounts for many of its specificcharacteristics.
• Easy Operation: sample is placed against the “O” ring and faces the anode tube in which theplasma is confined• Large Sample Compartment• Low Pressure Plasma, 13.56 MHz RF Plasma Source, Pulsable, no Ultra High Vacuum
needed; low plasma gas consumption (<0.3l/mn)•	Double Pumping: the plasma source is pumped with 2 pumps (for optimum pressure
control during the entire sputtering process – also mandatory in patented application of GD forSEM observation)

The SMU replaces the standard source compartment (it can beretrofitted onto existing units). With the SMU, manual and automatic
operations are equally available.

Without double pumping.
Local pressure at surface
is not uniform, resulting inpoor sputtering.

With double pumping.
Sample grain structure
is well resolved

Lens

Vacuum 1•	Pulse Synchronisation Acquisition of opticalsignals: enhances the Signal/Noise Ratio• Flexibility for Calibration: the selection ofSample
calibrationmaterials is easy with Pulsed RF as bulk and coatedspecimens – conductive, isolating or hybrid – can beused within the same analytical method

Ar in

λLens

λAr inAnode

AnodeAnode

Vacuum 1

Anode• Capacitive Coupling: ensured by real time
auto-matching in non-pulsed and pulsed modes(patented). Mandatory for optimum measurement ofmultilayered samples.
• Pulsed RF Operation: provides higher instantaneous
power without damage for fragile and heat sensitivematerials• Plasma Cleaning: only possible in Pulsed RF mode
it minimizes surface contamination and is crucial for
proper interpretation of extreme surface measurements
Vacuum 2(Ref: J. Anal. At. Spectrom., 2009, 24, 734–741)

Within the SMU, an XYZ stage allows the plate with multiple mounted
samples to be precisely positioned for analysis. The plate also ensuresthat the RF coupling efficiency is uniform (patented). Automatic cleaning of the anode is done when the stage is in rest position. In this rest
position, manual operation of the instrument is also possible, offering
the same flexibility as in a standard instrument – the large chamber
doors ensure easy access to the sample compartment.

150 µmVacuum 2

150 µmSampleCooling

Cooling

Principle of GD sputtering

Latest Innovations• UFS Mode (patented): Ultrafast Sputteringof polymeric materials without sample damage

8• Differential Interferometry Profiling DiP (patented):
built-in interferometer for real-time measurement ofcrater depth and erosion rates

Software screen showing a batch measurement of various samples withdifferent shapes and thicknesses (colour change is linked to thickness). SMU
measurements can be conducted with 2 and 4mm anodes.

9Optics Made for GD
Spectral range and resolution

Differential Interferometry Profiling (DiP)
Erosion rates in GDOES are material dependent, and when multi-layers aremeasured, the erosion rates change with depth. Previously, estimating erosion
rates could only be obtained from calculations (prone to uncertainties) or externalmeasurements.
Thanks to DiP, a direct measurement of the depth as a function of time, withnanometric precision, is performed simultaneously with your GD analysis.

• Wide Spectral Range of 120-800 nm• Optimised VUV/UV grating with proprietary MgF2 coating• Red/IR grating for alkali elements• Nitrogen purge optics for long-term efficiency of the optical surfaces
Flat Field
Monochromator

Flexibility• Interferometer built in the GD source• Crater depth and erosion rate measured• Laser Class 1• High-resolution monochromator with HDD detection• Flexibility to measure any N+1 element tunable• Full-spectrum coverage with Image

Cross section of the GD sourcewith DiP and specific anode andceramicHigh Dynamic, Ultra-Fast Detection
Depth sensing
beam path

Reference beampath

Patented High Dynamic Detectors for all lines
GD is fast. Reducing erosion rate degrades sensitivity,
as the amount of light is directly correlated to thequantity of material entering the plasma.
Detection must therefore be much faster and should
respond immediately to the rapid changes of concentrations from layer to layer.

Intensity as
a function of time

Only the patented High Dynamic Detector (HDD)
offers a linear dynamic acquisition range of 5x109 tomeasure all elements from sub ppm to 100% within
depth profiles.

Ni/Cu sample. The top layer contains P
and traces of Cu.

102=

Intensity as afunction of depth

Depth as afunction of time
Intensities asa function of depth

Polychromator
S

Optimum optical configuration withpolychromator and monochromator

Cu
NiP

Depth asa function of time

Intensities as afunction of time

With HDDs pre-adjustments of voltages are no longer required prior to analysis or calibration, resulting inconsiderable time saving and ease of use.

1+With a transparent
Sapphire sample thetwo DiP beams can beobserved.

Cu
NiP

Sµm

3

With HDD 1 & 2, both the low levels of Cu andthe major levels are seen and dynamic range
is above 109.

Cu
NiP

Surface Measurement and DiP windows.
In the DiP window (right) the changes of slopes reflect thechanges in erosion rates between layers. These erosion rates are
directly obtained by the interferometric measurement.

Measurement with time axis directly converted
in depth using DiP in Quantum software.

Without HDD 3, the measurement scale islimited to 0-10 V and signals of Ni and Cu
appear saturated.

11

Strategies for Handling Multiple Samples

QuantumTM: your GD Software Suite

GD operation does not require Ultra High Vacuum Sealing. Air-sensitive, small, porous or non-flat samples can therefore
be measured using dedicated holders or mounting strategies.

Large Sample Compartment
The large sample compartment helps you measure large samples but also allows theuse of various accessories for handling multiple samples.

Li Belll

IQ, Intelligent Quantification Models following ISO standards and the flexible Layer Mode, possible thanks

llto the flexibility of the pulsed RF source. Expression of results in M%, At%, depths, coating weights, layers thickness.
Built-in libraries of reference materials, erosion rates and information on optical wavelengths
Powerful data treatment functions (with task generation for batch treatment) and report generationFor air-sensitive materials or rough samples.

• All functions included (no options)• Emulation versions freely available for remote
data treatment• Time Plus function(increases measurement time during operation)• Plasma Cleaning• Pulse synchronisation detection

Small Sample Accessory
When samples are small. Also available: smaller anode diameters, Indium kit, etc.

Methodology for flexible thin films
Coated PET film on Aluminium substrate.

Elephant anode
Strategies for non-flat samples to ensure proper distance anode/sample and vacuumseal.

Sample holder for SEM cross-section preparation

Multimatrix Linear Calibrationof N with statistical information
built inThe sample's cross section is sandwiched between 2 stainless blocks placed inside
a vacuum-tight holder.
• XRF Link for direct correlation with XRF(or XPS) measurements• Online SPC (Statistical Process Control module)

1213

Surface and Beyond
We know GD and its multiple
application possibilities!
4 GD Labs
at your service
PARIS - NEW YORK - TOKYO - SHANGHAÏThe ISO Technical Committee TC 201 for Surface Analysis
has already issued three international standards for GD.
6 reference books are available, and an annual rate of over
100 scientific papers published with GD data shows thevitality of the technique in all domains of material science.
Our staff of application scientists provide dedicated solutions
and full support.

The GD plasma sputtering, though Ultra Fast, is delicate.
Incident particles have a low energy (50eV) and do not
induce structural changes in the material. Coupling GD withother techniques offering different lateral resolution
is therefore of great interest. XPS, Ellipsometry and micro-Raman measurements have beenperformed within GD craters, providing multiple andcomplementary information on the same materials.

Coupling of techniqueswith variable lateral resolutionwww.horiba.com/scientificinfo.sci@horiba.com
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Coupling to SEM, XPS or othersurface techniques