measured by

Nanolab Technologies
www.nanolab1.com
XPS Services
Director of XPS Services: Vince Crist, PhD
Tel #: 1-408-433-3320 xtn 136 or 116
E-mail: vincec@nanolab1.com

Samples Received at Nanolab: xxx, 2013

Data-Report E-mailed: xxx, 2013
Job#: ORD - XXXXX

Key Capabilities of K-Alpha:

Surface chemistry (<100 ), >1MCPS, atom% accuracies ~5%, elemental composition, high energy resolution chemical states, 128
channel SnapShot detector makes profiles and maps 4-5X faster than scanned mode, SnapShot parallel mode spectra , 2 methods to
control charging of insulators, beam sizes down to 30, angle-resolve XPS, AR-PROCESS, rotated depth profiles, depth profiling using
500 V Ar+ for minimal degradation, line profiles, time studies, degradation studies, glove box, very gentle ion cleaning

Thermo K-Alpha
Monochromatic XPS System
Thermo K-Alpha
Mono XPS System

Purpose (Objective):
Xxx
Sample Names/Descriptions
Names:
XPS Analyses Requested:
xxx
Interpretation of Spectra, Profiles - Observations, Notes and Suggestions:
Xxx
Please call or e-mail us for any questions regarding the data and the report. We welcome on-site visits to work with us while collecting
your data-report or to discuss future or current analysis needs.

Analysis Conditions:
Standard X-ray beam size is our 400 x 600 spot. The smallest spot size available is 30 .
Samples were not exposed to X-rays until measurement was started to minimize the chance of degradation
Charge compensation, if used, was a combined beam of low voltage Ar+ and e-
X-rays are monochromatic Al K 1486 eV (8.3383 ). The X-ray angle of incidence is 30
Electron take-off-angle is 90 that gives a depth of information, depending on material, between 60 and 120
Other Details:
An Appendix lists practical information about XPS limits, contamination, sources of contamination and more.
Chemical state assignments are based on the 40,000 monochromatic XPS spectra stored in the SpecMaster Database of Monochromatic XPS Spectra
Free of charge, Nanolab will provide you will a copy of a spectral data processing software called SDP v4.3 for a period of 6 months when you submit a request for SDP by e-mail.
Overlaid spectra, if requested, are found just after the surface composition tables.
Detection limits for XPS range from 0.1 to 0.2 atom% (i.e. 1000-2000 ppm) for most elements.
Because XPS measurements are normally done once, the statistical confidence level is modest, roughly 75%.
Your data and report will be retained for at least one year.

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Thermo K-Alpha
Mono XPS System

Uncertainty in Atom % value in the surface composition table, shown above, depends on intensity of signal: strong signals are +/- 10% of the value shown, weak
signals are +/- 30% of the value shown. The actual depth of information depends on atomic number (Z) and electron Take-Off-Angle (TOA) . The standard
electron TOA on the K-Alpha XPS is a 90 deg angle which gives a depth of information ranging from 60-120 Angstroms, which depends on elements in the material.
The limit for detection for most elements is roughly parts per thousand (ppth). The standard detection limits range from: 0.1-1.0 atom % for nearly all elements.
XPS does not easily measure ppm level. XPS is often done only once, so statistical accuracy is limited.. Samples are rarely, but sometimes damaged by X-rays
during analysis (eg PVC, nitro-cellulose). Samples can lose gases and liquids in UHV. XPS detects all elements, except H or He. Please read the appendix for
additional information on XPS, contamination, energy resolution settings, data quality, calibration, and reference energies.

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Mono XPS System

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Mono XPS System

High energy resolution spectra are peak-fitted to resolve the presence or absence of chemical states of many elements. Peak-fitting depends on the FWHM of the
chemical states so FWHM are important to the peak-fitting process. Nanolab uses pass energy and step size settings that allows us to maximize the detection of
multiple species within a peak-fit envelop. The conditions that Nanolab uses produces FWHM that range from 1.0 to 1.5 eV. When a FWHM is >1.8 eV, we
normally add another peak. Uncertainty in the Binding Energy (BE) values listed in the chemical states table, shown above, is roughly +/-0.1 to +/-0.3 eV. Peaks
(signals) that have obvious peak maxima are slightly more accurate. Raw peak-fit BE values are rounded from 2 decimal places (e.g. 0.xx) down to 1 decimal
place. Chemical state assignments are often due to the presence of 1-3 different chemical states / chemical species that have the same or very nearly the same BE.
The chemical state assignments shown at the top of each column are based on BEs listed in various sources of BE, including the XPS SpecMaster Pro Database
System. The BE difference between chemical states for an element depends on the degree of electron polarization between the atoms that affect the element of
interest. As a result, chemical shifts that are relative to the elemental form can be as small as 0.1 eV to as much as 5.0 eV. Page 5
Thermo K-Alpha
Mono XPS System

When to use XPS ?

We have a problem feature, bigger than 50 across, and the chemistry is unknown = use Survey Spectra
The chemistry of the top 5-10 nm (50-100 ) is contaminated - has the wrong chemistry = use Survey Spectra
The thicknesses and chemistry of a multi-layered film (0-1 ) needs to be analyzed = use Depth Profiling
The chemistry at the top surface seems to be segregated or diffused due to heat processing = use Line Profiling
The XY distribution of elements in the top 10 nm seems to be wrong = use XY Mapping
We need to measure a chemical state profile of a very thin oxide with no Ar+ damage = Angle Resolved XPS
Thickness of chemicals in the top layer is unknown, and needs to be measured = use Chemical State Spectra
We changed our process chemistry and need to check chemistry of the top 10 nm = use Chemical State Spectra
A competitor has a new product that we want to analyze = use Survey Spectra Mode Depth Profiling

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Thermo K-Alpha
Mono XPS System
Thermo K-Alpha
Mono XPS System

Samples 1-xx
As Received

N
F
C
Fe
Sn
O
S
Cl
Cu
Si
Al
W
Y
Ni
Hf
Ti
Mg
Mo
Na

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Thermo K-Alpha
Mono XPS System

C 1s O 1s

xxx

Ti 2p N 1s

Analyzed for: Page 9

Thermo K-Alpha
Mono XPS System

F 1s Si 2p

xxx

xx xx

Analyzed for: Page

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Thermo K-Alpha
Mono XPS System

Survey and Chemical State Spectra

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Thermo K-Alpha
Mono XPS System

Xxx As Received

Survey

+ + Page 12
Thermo K-Alpha
Mono XPS System

Xxx As Received

+ +
*The expanded view of the survey spectra is provided to more clearly reveal the presence or absence of weak signals in the 0-
500 eV or the 500-1100 eV range where many contaminants, if present, will appear as very weak signals. Page
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Thermo K-Alpha
Mono XPS System

Xxx As Received

+ +
*The expanded view of the survey spectra is provided to more clearly reveal the presence or absence of weak signals in the 0-
500 eV or the 500-1100 eV range where many contaminants, if present, will appear as very weak signals. Page
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Thermo K-Alpha
Mono XPS System

C 1s O 1s

xx xx

Analyzed for: Page

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Thermo K-Alpha
Mono XPS System

xx xx

xx xx

Analyzed for: Page

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Thermo K-Alpha
Mono XPS System

Reference Data
from XPS SpecMaster Database

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Mono XPS System

Reference Spectra

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Thermo K-Alpha
Mono XPS System
Thermo K-Alpha
Mono XPS System

Constants, Variables and Limits

Depth of information varies from 10 to 120
Depth of information depends on Electron Take-Off-Angle (TOA) and the inelastic mean free path (IMFP) of electrons which
varies with the element analyzed
XPS Limit for Detection is usually: parts per thousand (ppth) (XPS does not easily measure ppm level)
Lowest Detected Concentration: 0.1-1.0 atom % for nearly all elements
Ultimate Level of Detection Limit: Requires extremely long analysis (10 hr) to detect 100 ppm
Detection of Li, Be, and B require longer analysis times because they give weak signals
Uncertainty in Atom % value depends on intensity of signal: Strong signals are ~ +/- 10%, weak signals are +/- 30%
XPS measurements are usually done only once, so statistical accuracy of any value is limited.
XPS identifies chemical states, not molecular structure (chemical states are similar to oxidation states, but are not)
XPS directly measures differences in electron density between adjacent atoms (electron polarization)
Samples are rarely, but sometimes degraded by X-rays during analysis (eg PVC, nitro-cellulose)
Samples can lose gases (O2, N2, CO, CO2) and liquids (water, elastomers, solvents) after entering UHV
XPS can be used to analyze heavy oils or solution residues smeared onto aluminum foil or other smooth surfaces
XPS uses monochromatic Aluminum X-rays with 1.486 keV energy (8.3383 )
Charge compensation is achieved by using low voltage electrons (0.1-5.0eV) and low voltage Ar ions
Vertical (depth) resolution varies from 1-2 nm
XPS detects all elements, except H or He

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Mono XPS System

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Thermo K-Alpha
Mono XPS System

Design and Capabilities of K-Alpha

This XPS instrument is a ThermoScientific system manufactured in 2009 by Thermo Fisher Scientific
The smallest beam size on the K-Alpha is 30 micron in diameter.
The largest beam size on the K-Alpha is 400 x 600 microns for general work.
The standard electron Take-Off-Angle (TOA) on the K-Alpha XPS is a 90 deg angle that gives information from 60-120
depending on material
Max sample size: 50 x 40 x 15 mm (wdt)
The electron collection angle is: 60
The electron detector has 128 channels which can be scanned or measured in parallel to produce SnapShot spectra
The X-ray angle of incidence on the standard sample mount is: 30
The tilt stage can be rotated from -90 to +90 deg.
The azimuthal rotation stage produces depth profiles with improved interface resolution especially for crystalline materials
The K-Alpha XPS uses monochromatic Aluminum X-rays with 1.486 keV energy (8.3383 )
Charge compensation uses low voltage electrons (0.1 to 5.0 eV) and low voltage Ar ions
With ion beam etching, a depth profile down to 5,000 is common with or without rotation
Vertical (depth) resolution varies from 1-2 nm
When the analysis area is smaller than 50 microns, we recommend using a FE-Auger that has a hemispherical energy
analyzer and an electron retardation lens which allow us to measure chemical states and to obtain reliable atom%s
The ultimate vacuum, produced by using turbo-molecular and a titanium sublimation pumps, is 5x10(-10) torr
The usual working pressure is roughly 5x10(-8) torr
The argon ion gun on the K-Alpha is programmed to give argon ions with voltages between 3000 and 200 volts

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Thermo K-Alpha
Mono XPS System

Instrument Calibration
The reference BEs used to calibrate the BE scale are Cu 2p3 at 932.67 eV and Au 4f7 at 83.98 eV. Checking reference
energies is a simple process because the sample stage inside the analysis chamber holds pure samples of Copper (Cu),
Gold (Au) and Silver (Ag).
X-ray beam size and alignment with the desired analysis area is checked by using the ZnS phosphor that is permanently
resident on the sample stage inside the analysis chamber.
Charge referencing of insulators, if needed, is done by setting the hydrocarbon C 1s peak max to 285.0 eV.
The instrument transmission function, which affects atom% quantification results, is verified by generating atom% values
from the four major peaks (Cu 2p1, Cu 2p3, Cu 3s and Cu 3p) of freshly ion etched Copper (Cu)

Data Quality and Reliability

The step size for survey spectra is set to either 1.1 or 1.3 eV per channel. This step size allows us to maximize the data
quality (S/N) of survey spectra since they are used to detect the expected strong signals as well as the very weak signals
that are contaminants. Survey spectra range from -10 to 1,100 eV. Few signals appear above 1100 eV. When key
signals above 1,100 eV are needed, the range is expanded to 1,400 eV. Spectra run with smaller step sizes and larger
ranges make it difficult to detect weak signals and are a waste of time.
The BEs produced from survey spectra are accurate to roughly +/- 1 eV and are not normally useful for chemical state
identification. It is possible to identify a few chemical states by looking at peak BEs in a survey spectrum.
For most chemical state spectra, it would be sufficient to use a Pass Energy of 90 eV which gives a Ag 3d5 FWHM = 1.1
eV because the natural FWHM of most chemical compounds when analyzed under practical conditions, are larger than 1.2
eV. Even so, we prefer to use a pass energy = 50 eV, which produces a Ag 3d5 FWHM = 0.8 eV. This level of energy
resolution is more than sufficient to resolve chemical states of all chemical compounds.
The step size for chemical state spectra is 0.1 eV per step (channel). Because peak-fitting extrapolates the data points,
the relative error in the peak maxima BEs is <0.1 eV.
We deliberately designed our survey spectra to detect those weak XPS signals that might be contaminants.
In the appendix, there are charts that show the Signal/Noise (S/N) ratios as a function of the number of scans. To help
customers to identify their desired level of S/N we normally collect data based on square numbers (e.g. 22, 32, 42, 52).

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Thermo K-Alpha
Mono XPS System

Survey Spectra (aka wide scan spectra)

Survey spectra are collected by using a pass energy = 200 eV. The maximum pass energy is 500 eV.
The usual X-ray beam size is 400 um x 600 um.
The step size for survey spectra is set to either 1.1 or 1.3 eV per channel.
The electron take-off-angle for a non-tilted sample is 90 deg.
Signal is collected until the signal to noise ratio gives a 0.05 atom% detection limit for most elements

Chemical State Spectra (aka high resolution spectra)

The step size is 0.1 eV per step (channel).
Spectra windows are normally 20 eV wide.
The pass energy is normally set to 50 eV which produces a Ag 3d5 FWHM = 0.8 eV.
The smallest pass energy on the K-Alpha is 5 eV which produces a Ag 3d5 FWHM <0.47 eV.

Depth Profiles
The argon ion etch crater is roughly 4 mm x 2 mm for all depth profiles.
The etch rate of thermally grown SiO2 is used as a rough measure of etch depth.
Ar ion etching is normally done at 1 kV, which gives an etch rate between 1.2 and 1.4 Ang/sec for SiO2. If a 3 kV etch rate
is used, then the etch rate is between 2.6 and 2.8 Ang/sec.
Depth profiles are collected by using the parallel SnapShot mode at a pass energy of 150 eV which produces a 20 eV
window.
The normal angle of incidence of Ar+ is 30 deg
The normal X-ray beam size is 400 um x 600 um

Sample Preparation & Carbon Removal by Very Light Ion Etch

Wafers that are larger than the sample stage are held by a pair of wafer tweezers, turned upside down, scribed on the
back at the edge with a diamond or carbide tip and then cleaved by using a standard wafer cleaving tool
Samples that are larger than the sample mount are carefully cut or broken to a suitable size.
Clean room twill cloth is placed under any sample while cleaving it or cutting it
The adventitious carbon on any as-received surface of any sample can be selectively removed by exposing it to a 0.5 or
1.0 kV Ar+ ion beam for 3-5 seconds. This method removes roughly 80-90% of the adventitious carbon and does not
harm the surface.

General
We deliberately designed our survey spectra to detect those weak XPS signals that might be contaminants.
In this appendix, there are charts that show the Signal/Noise (S/N) ratios as a function of the number of scans. To help
customers to identify their desired level of S/N we normally collect data based on square numbers (e.g. 22, 32, 42, 52).
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Thermo K-Alpha
Mono XPS System

Survey Spectra
Relative sensitivity factors (RSFs), which are used to generate atom%s, are based on Scofields theoretically calculated
photo-ionization cross-sections by using a self-consistent central field potential model
The instrument transmission function (TF) aka instrument response function (IRF) uses an exponent of 1.0 for pass energies
ranging from 10 to 200 eV.

Chemical State Spectra

Charge referencing is done by setting the hydrocarbon C 1s peak max to 285.0 eV. Please note that charge referencing of
native oxide materials is not used (or recommended) as native oxides are thin enough to allow electrons to tunnel through
the grain boundaries and effect charge compensation of thin insulating overlayers.
The BEs produced from survey spectra are accurate to roughly +/- 1 eV and are not normally useful for chemical state
identification.

Chemical State Assignments

Chemical state assignments are made by referring to one or more references that include the:
SpecMaster XPS Database of 40,000 Monochromatic XPS Spectra (XPS International LLC)
Handbook of Monochromatic XPS Spectra The Elements and Native Oxides (Wiley & Sons)
Handbook of Monochromatic XPS Spectra - Semiconductors (Wiley & Sons)
Handbook of Monochromatic XPS Spectra - Polymers and Polymers Damaged by X-rays (Wiley & Sons)
Handbook of X-ray Photoelectron Spectroscopy 2nd edition (PHI)
Internal reference spectra collected from various pure chemicals
Reference BE data in NIST database are useful as a rough guide for BEs, but can have errors >0.4 eV for conductors and
>1.0 eV for insulators. This problem is due to the way the XPS machines were operated at universities over many years
time, and due to the various reference BEs recommended by the XPS instrument makers. We recommend caution when
using this database. For critical work, we recommend buying or making your own reference material and then analyzing
them.

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Mono XPS System

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Thermo K-Alpha
Mono XPS System

Common Surface Contaminants

Carbon & oxygen are normal contaminants on all materials (comes from air, contact w containers etc)
Carbon mainly present as hydrocarbon with 2-3 C-O moieties (eg organic alcohol, ketone, ester or acid)
Carbon is very loosely attached & easily etched off (3-5 sec argon ion etch at 2-3 keV)
Carbon is between 5 to 50 angstrom thick (see above)
Oxygen present mainly as oxide or hydroxide (water is also common for metal oxides)
S, Cl, Na, Ca, and Si are also very common contaminants (eg Ag often has S and Cl)
Silicon is often present as oil, lubricant, plasticizer, etc. (causes many problems for many industries)
Gloves easily contaminate surfaces with silicone and others (especially soft latex gloves)

Material Type Typical Amount of Carbon Contamination

Metals 40-60 atom %
Ceramics 30-50 atom %
Semiconductors & glasses 20-40 atom %
Polymers 5-10 atom %
Gold (special case) 60-80 atom %

COMMON SOURCES of SURFACE CONTAMINATION

Silicone products: the worlds most common contaminant
Material production & handling: S, Cl, C, O, Na, Ca, K, N & F
Cleaning baths, gears, rollers & lubricants: heavy carbon-based oils, long chain organic acids/salts
Plastic gloves: Si, Ca, Na, Mg, S, Cl, R4NX, SO4, CO3
Clean room materials: HCl, HF, H2SO4, HNO3 & NH4Cl fumes, clean room gloves, plastic gloves
Forbidden clean room materials: cosmetic powders, hair treatments, residual cigarette smoke,
HV sputter chamber shields: Fe, Cr, W, Ta, Cu, O ...
Antistatic or anti-caking additives: Sn, Ca, O, SO4, CO3
Adhesives: silicone products, cyano (CN) groups, epoxies (C,O, trace N)
Elastomers: organic esters (COOR), acetates (CH3COOR), glycols (C-OH), silicones
Mold release agents & slip agents: silicone oil, oleic acid, heavy hydrocarbons
Soaps: long chain fatty acids, esters, aromatics, Ca, Na, O
Water Stains: Ca, C, O, Na, Fe, SO4
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Thermo K-Alpha
Mono XPS System

Aluminum Foil (Kitchen) Contamination Caused by Gloves

As Received
Un-gloved hands will contaminate products with various organic oils, NaCl, water and other
chemicals which a worker has unknowingly touched. To avoid such contamination, the worker
Control sample of
aluminum foil as
usually wears plastic, nylon or clean room gloves. We have tested for contamination from gloves
received by wearing them and touching kitchen aluminum foil.

Al C O Si N Na Cl S Ca F Zn
Clean Al foil 29 29 41 --- --- --- --- --- --- --- ---
Clean Al foil 30 21 48 0.3 --- --- --- ---
Fingerprint / Al 6.6 76 16 0.6 0.6 0.7 0.1 --- --- --- ---

#1 plastic/nylon 23 33 40 3.8 --- --- 0.6 --- --- --- ---

#2 off-white latex 22 40 34 2.1 --- 0.4 --- --- 0.3 ---
#3 yellow latex 2.2 50 23 24.0 --- --- 0.3 --- --- --- ---
#4 pink PE 20 53 26 --- 0.6 --- --- --- --- --- ---
Aluminum Foil (Kitchen) #5 pink latex 19 42 33 5.8 --- 0.3 --- --- --- --- ---
After Glove Touch #6 yellow latex 23 42 33 --- 0.6 0.5 --- 1.1 --- --- ---
#7 opaque vinyl 27 41 32 --- --- 0.5 --- --- 0.1 --- ---
Control sample of
aluminum foil touched #8 clean rm nylon 29 22 47 1.4 0.1 0.3 --- --- --- --- ---
by latex glove #9 blk conductive 14 53 32 0.9 0.3 --- --- --- --- --- ---
#10 white latex 7.4 54 26 10.0 --- 0.2 0.8 1.1 --- ---
#11 yellow latex 2 21 36 39 2.9 0.4 --- --- --- 0.1 --- 0.3
#12 clear PE 17 53 29 1 0.2 --- --- --- --- ---
#13 white PE 27 25 47 0.4 0.5 --- 0.1 --- --- --- ---

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Thermo K-Alpha
Mono XPS System

Extended Analysis Time and # of Scans improves

Detection Limits by decreasing S/N. 50 scans takes
1 hour and increases S/N by 300% (3X).

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Thermo K-Alpha
Mono XPS System

Overlay of Ag 3d5 Signal (normalized) for

Pass Energies 10-160 eV

Performance from Dirty Silver (Ag) Surface

Pass Energy FWHM Relative
of Ag 3d5 Count Rate
160 1.6 1000X
140 1.5 900X
120 1.3 800X
100 1.2 650X
90 1.1 560X
80 1.0 500X
70 1.0 400X
60 0.9 320X
50 0.8 250X
40 0.7 170X
30 0.7 100X
20 0.6 52X
10 0.6 20X

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Mono XPS System

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Mono XPS System

Energy Difference = 1.0 eV between peak maxima (i.e. a chemical shift of 1.0 eV)

Energy Difference = 1.0 eV between peak maxima (i.e. a chemical shift of 1.0 eV)
Counts of shifted spectra decreased by 2X

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Thermo K-Alpha
Mono XPS System

Energy Difference = 1.0 eV between peak maxima (i.e. a chemical shift of 1.0 eV)
Counts of shifted spectra decreased by 3X

Energy Difference = 1.0 eV between peak maxima (i.e. a chemical shift of 1.0 eV)
Counts of shifted spectra decreased by 4X

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