Lecture22 SurfaceCharacterization

Unlessotherwisenoted,sourceInformationforthefollowingslides: 1) B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2nd edition(SanDiego:ElsevierAcademicPress.2004). 2) Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedical Application,MIT,http://ocw.mit.edu,

SurfaceCharacterizationof Biomaterials:VacuumTechniques

XrayPhotoelectronSpectroscopy (XPS)
Ejected Photoelectron Incident X-ray
Free elevel Fermi level
Valence Band Conduction Band

KE h BE Spec

2p 2s

L2,L3 L1

1s

Physicalbasis:photoionizationandemissionof corelevelelectronsuponirradiationwithXrays XPSspectrallinesareidentifiedbytheshellfrom whichtheelectronwasejected(1s,2s,2p,etc) Surfacesensitive(1 10nm) Quantitative countingelectrons!But accuracy dependsonthequalityoftheatomicsensitivity factors Sampledegradationisanissue!

Enablesanalysisofcomplexsurfacechemistries Automatedhighthroughput(atleastforhigh vacuumtechniques)

XPS

AreaunderpeakIiproportionalto numberofelectronsejected(&to numberofatomspresent) Onlyelectronsinthenearsurface regionescapewithoutlosing energybyinelasticcollision Sensitivity:dependsonelement. Elementspresentinconcentrations >0.1atom%aregenerally detectable(H&Heexceptions, nondetectable)

HighResolutionXPS

HighResolutionXPS

Quantification:PeakFitting
High Resolution C 1s and O 1s Spectra of p(S-co-MMA) Brush
C2 C2 C2 m C1 C1 C4 n C5 O
O

O O1

O O2

C3 CH3

CH3

C3 C4 C2 C5 C1

O2 O1

Survey Method

High Resolution Method

FMMA

8(O / C ) exp 3(O / C ) exp 2

FMMA

8( I O C / I C ) exp 3( I O C / I C ) exp 1

where (O / C ) exp is the O/C ratio obtained from XPS

Ton-That et al. Polymer 2001, 42, 1121.

where ( I O C / I C ) is the ratio of the carbonyl C to the total C

XPS CopolymerComposition Gradient

X-ray photoelectron spectroscopy (XPS) was used to map the surface composition of the statistical copolymer brush gradients Spectra collected at 4 mm intervals along the gradient substrate
C 1s C 1s envelope O 1s

Survey Spectra

High Resolution Spectra

XPS CopolymerComposition Gradient

X-ray photoelectron spectroscopy (XPS) was used to map the surface composition of the statistical copolymer brush gradients Spectra collected at 4 mm intervals along the gradient substrate
C 1s O 1s

Survey Spectra

DepthProfilingwithXPSatDepths>10nm

SIMS

SIMS

SIMS

SIMSModesofOperation

SIMSModesofOperation:
ExampleofStaticMode

SIMSModesofOperation:
ExampleofDynamicMode