AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of...

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AXIS Supra Getting Started Guide 39-341 Supplied by: Kratos Analytical Ltd. Wharfside, Trafford Wharf Road, Manchester, M17 1GP, UK

Transcript of AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of...

Page 1: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

AXIS Supra

Getting Started Guide39-341

Supplied by: Kratos Analytical Ltd.

Wharfside, Trafford Wharf Road,

Manchester, M17 1GP, UK

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Photoelectric effectPhotoelectric effect

Einstein, Nobel Prize 1921

Photoemission as an analytical tool

Kai Siegbahn, Nobel Prize 1981

Introduction

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XPS X-ray Photoelectron SpectroscopyESCA Electron Spectroscopy for Chemical AnalysisUPS Ultraviolet Photoelectron SpectroscopyPES Photoemission Spectroscopy

XPS, also known as ESCA, is the most widely used surface analysis technique because of its relative simplicity in use and data interpretation.

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1s

2s2p

3s

VB

Ef

Ev

Photoelectron

0

BindingEnergy

0

KineticEnergy

Photonhν

φ

Analytical Methods Analytical Methods

KE = hν - (EB+ϕ)

— Elemental identification and chemical state of element

— Relative composition of the constituents in the surface region

— Valence band structure

------ XX--ray Photoelectron Spectroscopy (XPS)ray Photoelectron Spectroscopy (XPS)

XPS spectrum:Intensities of photoelectrons versus EB or KE

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B.E. = h - K.E. - .F specν φ

e-

Vacuum level

Fermi level

core level

Fermi level

Vacuum level

φsample

φspec

K.E. = h -B.E. -ν φ.F sample

B.E.F

K.E. = h -B.E. - - ( )

= h -B.E. -

ν φφ φ

ν φ

.F sample

spec sample

.F spec

-Binding Energy Reference

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Instrumentation• Electron energy analyzer• X-ray source• Ar ion gun• Neutralizer• Vacuum system• Electronic controls• Computer system

Ultrahigh vacuum system< 10-9 Torr (< 10-7 Pa)• Detection of electrons• Avoid surface reactions/

contaminations

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A Shimadzu Group CompanyA Shimadzu Group Company Monochromated vsnon-monochromated X-ray source

Monochromated Al Kα excited Ag spectrum

Non-monochromated Mg Kα excited Ag spectrum

FWHM 0.97 eV

FWHM 0.46 eV

satell

ite

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A Shimadzu Group CompanyA Shimadzu Group Company

XPS Spectra Showing the Chemical State of Si

Si elemental

Si oxide

Si oxide Si elemental Two samples with different SiO2film thicknesses on Si substrate.

-note large chemical shift between elemental Si and silicon dioxide peaks.

d d

Si elemental

Si oxide

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A Shimadzu Group CompanyA Shimadzu Group Company

Quantitative Surface Analysis of Poly(ethylenetetraphthalate) - PET

C 1s region O 1s regionO(1) 530.8eV 51 at% O(2) 532.1eV 49 at%

C(1) 285.0eV 65 at%C(2) 286.5eV 23 at%C(3) 289.2eV 12 at%

C3C2

C1 O1O2

-(-O-C- -C-O-CH2-CH2-)-= =

O On

2223

1

32

1

1

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A Shimadzu Group CompanyA Shimadzu Group CompanyValence band Spectroscopy

Stereo isomersof PBMA only difference inValence band

Only 5minacquisition time

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A Shimadzu Group CompanyA Shimadzu Group Company Angular Dependence of XPS

0 deg (bulk sensitive)

60 degrees

45 degrees

75 degrees(surface sensitive)

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A Shimadzu Group CompanyA Shimadzu Group Company Quantitative XPS images combined with small spot analysis

Pt 1(SiO2) Pt2 (SiN)

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A Shimadzu Group CompanyA Shimadzu Group Company Quantitative XPS images

SiN

Silicate fibres

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A Shimadzu Group CompanyA Shimadzu Group Company AXIS UltraDLD

• Primary features:– 165mm hemispherical analyzer (HSA)– Concentric Spherical Mirror Analyzer (SMA)– 128 channel DLD detector for spectroscopy and

imaging– Magnetic immersion lens– Co-axial charge neutralization– Monochromatic and Achromatic X-ray sources– Automated sample manipulator– Multi-technique capability (XPS, FE-Auger, SIMS,

ISS)

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A Shimadzu Group CompanyA Shimadzu Group Company AXIS Components - magnetic lens

Co-axial chargeneutraliser(Kratos PatentEP 0 458 498 B1)

Magnetic lens(Kratos Patent EP 0 243 060 B1)

Iris

Aperture

AXIS

AXIS Ultra is designed around the established co-axial technology

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A Shimadzu Group CompanyA Shimadzu Group CompanyX-ray Monochromator -

The Rowland circle geometry

Energy dispersion ∆E ~ Rowland circle diam.

For 500 mm ~ 0.625 eVmm-1

250 mm ~ 1.25 eVmm-1

Fixed mono spotEnergy dispersivedirection, ∆E

Toroidal quartz backplane

Electron gun & x-ray anode

Rowland circle diameter

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A Shimadzu Group CompanyA Shimadzu Group Company AXIS Magnetic Lens

Charge Neutraliser Magnetic Lens

Sample

Scan Plates

Spot size apertures

ElectrostaticLens

Analyser entrance slit plate

Projector Lens

Objective Lens

Angle defining iris

sample

iris

aperture

Magnetic flux lines

photoelectrons

The magnetic immersion lens of the ‘snorkel’ type is positioned below the sample and focuses photoelectrons onto the spot size aperture.

Kratos Patent: EP 0 243 060 B1

See diagram to right

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A Shimadzu Group CompanyA Shimadzu Group Company

• High collection efficiency– large solid angle of collection– low spherical aberration therefore high magnification

(ca. x10) in both spectroscopy and imaging

• High small spot spectroscopy sensitivity

AXIS Magnetic Lens (III)

The magnetic snorkel lens focuses photoelectrons onto the spot size aperture. A set of electrostatic deflection plates enables the position of the analysis spot to be moved to a static point on the sample, or scanned to produce an image. The electrostatic lens can be used independently or in combination with the magnetic lens.

The advantages in the use of the magnetic lens include:

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A Shimadzu Group CompanyA Shimadzu Group Company AXIS Charge Neutralisation

Magnetic Lens Pole Piece

(2) Charge balance plate (-ve potential)

(1) Filament

(3) Low Energy Electron Trajectory in the Magnetic Field

Sample

1) Electrons are thermionically emitted from the charge neutraliser filament.

2) Negative potential of the charge balance plate forces the charge neutralisation electrons towards the sample. There is no direct line of sight of the filament with the sample.

3) The low energy electrons are confined by the magnetic field of the magnetic immersion lens, following an oscillating path between sample and charge balance plate.

4) As sample develops a positive charge, charge neutralisation electrons are attracted to the surface.

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A Shimadzu Group CompanyA Shimadzu Group CompanySources of charge neutralisation

electrons

(1) Low energy electrons thermionicallyemitted from the filament

(2) Low energy photoelectrons are over-focused and can return to the sample to provide charge compensation

Sample

e-

(2) (3) High energy photoelectrons are under-focused. Secondary electrons, created upon impact with the charge balance plates, return to the sample.

(3)

(1)

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A Shimadzu Group CompanyA Shimadzu Group CompanySimple ‘Universal’ Charge Neutralisation Parameters

The charge neutralisation parameters are fully software controlled, usually operated as simple ‘on’ or ‘off’.

For > 99 % of all samples run in the applications lab the neutraliser is operated under the same conditions. Therefore, samples can be left to run unattended with complete confidence that charging will not occur during data acquisition.

Normal user operation of neutraliser

Control of parameters associated with use of neutraliser

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A Shimadzu Group CompanyA Shimadzu Group CompanyNeutralisation of Rough Samples

200 microns

800 microns

Wood pulp fibres shown here in the analysis position of the spectrometer. This type of sample would traditionally be extremely difficult to neutralise, but as demonstrated by the excellent resolution on the C 1s spectrum poses no problem with the AXIS co-axial charge neutraliser.

C 1s spectrum from wood fibres

Page 23: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company AXIS Electron Optics : Selected Area

Selected area apertures

Angle defining iris

110µm analysis area 27µm analysis area

Analyser entrance slit

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A Shimadzu Group CompanyA Shimadzu Group Company

27µm analysis area

Selected area apertures

Angle defining iris

Analyser entrance slit

Beam scanning plates, x & y

AXIS Electron Optics : Selected Area and Scanned Imaging

x

yFixed x,y voltage applied to scan plates to deflect analysis position to defined position on sample.

Scanning x,y voltage applied to scan plates to deflect analysis position over defined area of sample to generate a map.

Plan view of sample

Page 25: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group CompanyIntegration of the SMA into Photoelectron Spectrometer

• Objective and projector lenses operated exactly the same as image mode

• Voltages switched from outer 2 hemispheres to inner 2

x-rays

Detector

Objective lens Retarding projector lens

Sample

HSA

I1

E0

I2

Spectroscopy modeEntrance slitintroduced

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A Shimadzu Group CompanyA Shimadzu Group Company Detector Technology

Time

∆τx

MCP

‘x’ delay line

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A Shimadzu Group CompanyA Shimadzu Group Company Delay line detector schematic

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A Shimadzu Group CompanyA Shimadzu Group Company Snap shot mode

Page 29: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Snapshot modes of operation

Pass energyeV

Energywindow

eV

Min step size Application

320 32 0.25 Full core leveleg, Cr2p, Fe 2p

160 16 0.125 Full core leveleg C1s, O1s

80 8 0.06 High resolutionat small spot

40 4 0.03 Autofocusroutine

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A Shimadzu Group CompanyA Shimadzu Group Company Snapshot mode with spot size and PE

Au 4f 500um

Au 4f 55µm Au 4f 15µm

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A Shimadzu Group CompanyA Shimadzu Group Company Ultra DLD Spectroscopy Mode

DLD

Spectral ModeStandard input lensElectrons dispersed between inner and outer hemisphere, using standard spectrometerCommon detector plane

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A Shimadzu Group CompanyA Shimadzu Group CompanyIntegration of the SMA into Photoelectron Spectrometer

• Objective lens produces magnified photoelectron image I1

• Projector lens produces image I2 retards to pass energy E0

• Magnification at detector variable from <5x to >100x

• Field of view on sample from >2mm to <100µm• Lateral resolution to <2µm

x-rays

MCPdetector

Objective lens Retarding projector lens

Sample

SMA

I1

E0

I2

Image mode

Page 33: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company

Imaging Mode

• 2 delay-line anodes arranged orthogonally.

• Position of photoelectron event defined in 2 dimensions.

• Full pulse counting photoelectron imaging.

Page 34: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company

DLD

Ultra DLD Imaging Mode

Image ModeStandard input lensElectrons pass through ‘outer’ hemisphere into SMA & back to detector planeParallel image maintainedFast, real time image

Page 35: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Imaging Performance of the SMA

• Fast Parallel XPS Imaging• as the sample is moved, so the photoelectron image

moves.

• Lateral Resolution specification < 3 µm• Fixed analyser transmission (FAT) mode

• energy resolution constant at all binding energies.• good energy resolution at all binding energies.

• ‘Real time’ chemical state XPS imaging• ability to differentiate between elements in different

chemical states.

…..Following slides attempt to illustrate these points

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A Shimadzu Group CompanyA Shimadzu Group CompanyVariable Field of View - Real Time Imaging of Au grid

2 mm fov 800 µm fov

400 µm fov 200 µm fov

• Au images acquired in less than 30 secs.

• Field of view changed by selecting predefined lens modes for a specific magnification. New f.o.v. displayed within seconds

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A Shimadzu Group CompanyA Shimadzu Group Company XPS Imaging of 5 µm Cu Bars

2.2 µm edge

25µm from centre of bars

After acquisition of the image a line scan can be generated. The line-scan can be processed to provide edge measurements, giving an indication of lateral resolution

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A Shimadzu Group CompanyA Shimadzu Group Company Examples:Cu grid

• Cu grid• horizontal bars 20µm • vertical bars 40µm

• Parallel images acquired in 1,5,10 & 20s

• Fast photoelectron images allow sample alignment

• As sample moves … image moves!!

Page 39: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company XPS Imaging of Layered Materials

• Survey of sample in cross-section showed Ti

Ti layer 8 umAl alloy

Al/SiC matrix

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A Shimadzu Group CompanyA Shimadzu Group Company Parallel images and small spot dataTi 2p image350 µm field of view

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A Shimadzu Group CompanyA Shimadzu Group Company Analysis of surface oxides

• TiAlN sample after oxidation at >9000C in air.• XPS images shows segregation of oxide

species.• Chemical state imaging shows different oxide

species.• Confirmation of oxide segregation with small

spot XPS

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A Shimadzu Group CompanyA Shimadzu Group Company Elemental imagesTi 2p image

Fe 2p image Cr 2p image

Parallel images were acquired to show the elemental distribution of the oxide species at the surface of the TiAlN material.

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A Shimadzu Group CompanyA Shimadzu Group Company Elemental & Chemical State Imaging

O 1s image at FeOx binding energy (531.8eV)

O 1s image atTiOx binding energy (529.7eV)

Fe 2p elemental Ti 2p elemental

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A Shimadzu Group CompanyA Shimadzu Group Company Small spot XPS

survey spectra acquired from 27 µm analysis area

Selected area spectra (27µm) were acquired from the sample to give a quantitative analysis of the different regions identified by parallel imaging.

Page 45: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Adhesive coverage on paper

• Inhomogeneous paper sample with uneven coverage of adhesive - lead to adhesive failure

• Optically - sample was homogenous - white

• XPS O1s image clearly identifies adhesive distribution

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A Shimadzu Group CompanyA Shimadzu Group Company O1s images variable FOV

O 1s parallel images acquired at predefined fields of view

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A Shimadzu Group CompanyA Shimadzu Group Company Chemical state images

• C 1s image allows investigation of chemistry– small spot analysis shows variation in C-H and C-O

concentrations.

• The energy resolution of Spherical Mirror Analyser (SMA) allows chemical imaging of different C 1s species.

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A Shimadzu Group CompanyA Shimadzu Group Company C1s chemical state imageCH, CC hydrocarbon

C-O bonding

55µm analysis area

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A Shimadzu Group CompanyA Shimadzu Group Company C fibre electrode

• C fibre “wool” electrode from an industrial fluorination process was analysed.

• Electrode loaded with F containing epoxy base resin.

• Coverage of resin along fibres of the electrode was investigated.

Page 50: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Large area analysis : 300x700µm

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A Shimadzu Group CompanyA Shimadzu Group Company Large area analysis

• From the large area analysis it is concluded that:– Sample inhomogeneous

• C fibre conductive• fluoro-epoxy insulating• potential differential charging removed with use of

charge neutraliser

– C 1s spectrum shows complex structure – Excellent energy resolution

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A Shimadzu Group CompanyA Shimadzu Group Company Chemical state images

F 1s image

C 1s image corresponding to C-FC 1s image corresponding to C-H

Uncovered fibres

Resin coating

Page 53: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Chemical state images

• C-C images show uncoated fibres.• C-F images show distribution of coating.• F image overlays with C-F image.

• Overlay shows C species distribution – C-C red– C-F green

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A Shimadzu Group CompanyA Shimadzu Group CompanySpectroscopy from fibres - 5µm Spectra

from Images

Spectrum from uncoated 5 µm fibre

Spectrum from coated 5 µm fibre

CC photoelectron image C-F photoelectron image

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A Shimadzu Group CompanyA Shimadzu Group Company Summary

• Multi-spectral imaging used to achieve spectra from 5µm adjacent areas

• Spectra show:• graphitic C on uncoated fibre• fluoro-epoxy resin in coating

• Demonstrates:• excellent charge compensation• chemical state image on charged sample• application of MSI for 5µm areas!

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A Shimadzu Group CompanyA Shimadzu Group Company Bond pad contamination

Al 2p photoelectron image

Optical image of Al padsin-situ

Al pad

Si substrate structure

Cross section of sample

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A Shimadzu Group CompanyA Shimadzu Group Company Bond pad contamination

• Bad adhesion had been observed in Al bond pads.• Optical images was used to identify area of know

failure.• XPS images and small spot spectra show F

contamination• Distribution of F indicates residue from plasma

etching step in production

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A Shimadzu Group CompanyA Shimadzu Group Company Al 2p and F 1s images

F 1s image showsdistribution of F on pads

Al 2p image

F 1s image

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A Shimadzu Group CompanyA Shimadzu Group Company Small spot spectroscopy

55µm spectra showAl / F on pad

Page 60: AXIS Ultra DLD Generalinfraionh.igic.bas.bg/Img/XPS.pdfVariable Field of View - Real Time Imaging of Au grid 2 mm fov 800 µm fov 400 µm fov 200 µm fov • Au images acquired in

A Shimadzu Group CompanyA Shimadzu Group Company Photoelectron images

F 1s and Al 2p imagesshow uneven distribution of F across bond pad

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A Shimadzu Group CompanyA Shimadzu Group CompanyApplications of photoelectron imaging to

micro-contact printing

• Patterning of polymer substrate (polyethylene PE) with poly(acrylic) acid PAA.– PAA impermeable, wet and dry etch resist– PAA films easily functionalised– capped with PEG can be used for bio-applications cell growth

• Oxidised PE film is prepared• PDMS stamp (optical mask) prepared with n-alkylamine• PE “stamped” with amine to passivate PE • Unpassivated regions react with PTBA• Hydrolysis of this layer leads to PAA

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A Shimadzu Group CompanyA Shimadzu Group Company µ-CP process

PE-COOCOR

PE-COOCOR

PE-COOCOR

i) PTBA ii) MeSO3H

alkyl amine

hyperbranchedPAA film

PDMS stamp

Oxidised PE substrate

alkyl amine

Passivated layer Unpassivated region

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A Shimadzu Group CompanyA Shimadzu Group Company PAA on Au films

Au 4f photoelectron image

Attenuation of Au substrategives contrast mechanism for the image.

Au substrate

PAA layer

alkyl amine

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A Shimadzu Group CompanyA Shimadzu Group Company C 1s spectra - 27µ m analysis area

PAA

C 1s from PAA layer

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A Shimadzu Group CompanyA Shimadzu Group Company Au 4f & C 1s image

Excellent correlation shown between C 1s and Au 4f images.

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A Shimadzu Group CompanyA Shimadzu Group Company High Resolution Imaging

< 3µm spatial resolution

Vision software allows retrospective line scans to be created from the parallel image. Here, a line scan has been generated from a thin scratch defect in the PAA layer.

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A Shimadzu Group CompanyA Shimadzu Group Company Fluorinated PAA on PE

PE-COOCOR

Experiment repeated usingPE substrate with PAA layer being fluorinated

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A Shimadzu Group CompanyA Shimadzu Group Company C 1s Selected Area Spectra & Images

C-Fx

C-C,C-H

Carbon chemical state overlay images.

The image is used to select the position from which the small spot spectra are acquired.

Small spot spectra