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PGCIMAT/UFRGS
PGCM-26Espectroscopia de Fotoelétrons
Cristiano Krug - 2009/1
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Fundamentos
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X-ray Photoelectron Spectroscopy = Electron Spectroscopy for Chemical Analysis
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4J. C. Vickerman (Ed.), Surface Analysis
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Espectroscopia
■ Originally the study of the interaction between radiation and matter as a function of wavelength.
■ Later expanded greatly to comprise any measurement of a quantity as function of either wavelength or frequency.
■ A further extension added energy as a variable, once the very close relationship E=hν for photons was realized.
■ Spectrometry is the spectroscopic technique used to assess the concentration or amount of a given species.
http://en.wikipedia.org/wiki/Spectroscopy
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Processo básico em XPS
C. Radtke, Tese de doutoramento, 2003.
BE ≈ hν - KE
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Diagrama de energia
BE ≈ hν - KE
J. F. Watts e J. Wolstenholme
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Espectro XPS
J. F. Watts e J. Wolstenholme
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A propósito...
J. F. Watts e J. Wolstenholme
Formato: n l j , j = |l±s|
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Elétrons Auger
S. J. Garrett, CEM 924; J. F. Watts e J. Wolstenholme
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Auger vs. raios X
S. J. Garrett, CEM 924
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Espectro real, XPS + Auger
S. J. Garrett, CEM 924
● Photoelectron lines● Auger lines● Peak splitting● Background● ...
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XPS: projeção de estados ocupados
H. Lüth, Solid Surfaces, Interfaces and Thin Films
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Restrição à superfície
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“Curva universal” para λ
S. J. Garrett, CEM 924
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19J. C. Vickerman (Ed.), Surface Analysis
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O processo de fotoemissão
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Instrumentação
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Fontes de raios X
H. Lüth, Solid Surfaces, Interfaces and Thin Films
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Twin anode X-ray source
S. J. Garrett, CEM 924; J. F. Watts e J. Wolstenholme
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Materiais para o ânodo
J. F. Watts e J. Wolstenholme
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Monocromador de raios X
J. F. Watts e J. Wolstenholme
Largura de linha: 0,2 a 0,4 eV
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Monocromador de raios X
J. F. Watts e J. Wolstenholme
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Radiação síncrotron
T. A. Carlson
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LNLS
www.lnls.br
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Cylindrical mirror analyser (CMA)
J. F. Watts e J. Wolstenholme
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Double-pass CMA
Handbook of XPS
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Concentric hemispherical analyser (CHA)Também chamado spherical sector
analyser (SSA)
S. J. Garrett, CEM 924
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CHA
Pass energy:
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CAEAg 3d
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34Omicron
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CRR
J. F. Watts e J. Wolstenholme
(Auger)
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36Omicron
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CRR
CAE
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38Omicron
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39J. F. Watts e J. Wolstenholme
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Resolução do CHA em modo CAE
Omicron
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41Omicron
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Detector
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Channeltron
http://www.burle.com/cgi-bin/byteserver.pl/pdf/ChannelBook.pdf
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Observações adicionais
● Lens-defined small area XPS
● Source-defined small area XPS
● XPS imaging● Serial● Parallel
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XPS imaging
J. F. Watts e J. Wolstenholme
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Interpretação de espectros
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Aplicações analíticas
● Análise Elementar● Qualitativa● Quantitativa● Discriminada (resolvida) em “estados químicos”
● Nossa abordagem:● Posição das linhas● Formato das linhas● Intensidade das linhas
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Qualitativa, XPS
Al Kα, monocromática
J. F
. W
atts
e J
. Wol
sten
holm
e
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Qualitativa, AugerJ.
F.
Wat
ts e
J.
Wol
sten
holm
e
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Identificação de linhas
● Software específico (exemplo: CasaXPS)● http://srdata.nist.gov/xps
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Tabelas “por energia”
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Tabelas “por elemento”
PH
I H
andb
ook
of X
PS
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Sinais presentes no espectro
J. C. Vickerman (Ed.), Surface Analysis
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X-ray satellites(fontes sem monocromador)
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Como identificar satélites?
● Tabelas (sempre elas...)● Trocar a fonte de raios X – com isso, os picos-
satélite têm de se deslocar● Sinais Auger não trazem satélites consigo, por
isso são distinguíveis dos próprios
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X-ray ghosts
● Source “cross-talk”● No caso de Al e Mg Kα, o fantasma está
deslocado 233 eV● Exposição de cobre sob o ânodo● Geração de raios X dentro da amostra
● Pouco prováveis! Último recurso na interpretação de espectros
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Shake-up e shake-off
● Pouco comuns● Linhas 2p de metais de
transição● C 1s de compostos
aromáticos
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Multiplet splitting
● Em fotoemissão a partir de camada fechada em presença de camada aberta
● Interação de spin● Exemplo:
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Shake-up + Multiplet...
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Extrinsic satellites/energy loss lines
Usado para estimativa de band gap: S. Miyazaki et al.,Applied Surface Science 113/114, 585 (1997).
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Background (espalhamento inelástico)
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Identificação de estados químicos
Al 2p
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Casos favoráveis em Auger
KLL de Al e Si; LMM de Cu, Zn, Ga, Ge e As
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Parâmetro Auger
● Bom para:
● Al Kα: F, Na, Cu, Zn, As, Ag, Cd, In e Te● Maior energia: Al, Si, P, S, Cl a Ti e V
● Pode-se usar radiação de freamento de uma fonte convencional (sem monocromador) para ter acesso ao sinal Auger, que aparece em valor negativo na escala de energia de ligação
'=hX − rayKEAuger−KE photoelectron
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Referências para a escala de energia de ligação
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76J. C. Vickerman (Ed.), Surface Analysis
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77J. C. Vickerman (Ed.), Surface Analysis
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Na prática
● Linhas de Au e Cu para calibrar o instrumento
● C 1s @ 284,6 eV -- carbono adventício como referência interna nos espectros
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Desdobramento spin-órbita
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/
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83J. C. Vickerman (Ed.), Surface Analysis
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84D. C. Harris e M. D. Bertolucci, Symmetry and Spectroscopy
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Ar, 3p5
Verma; Harris e Bertolucci
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Origem do deslocamento químico
J. C. Vickerman (Ed.), Surface Analysis
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Teorema de Koopmans
E B=E f n−1−E i n
E B≈− k
E B=−k−E r k −corr−rel
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Initial (ground) state effects
E B=− k
Na2S
Na2SO
4
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Melhor que o número de oxidação
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Charge potential model
E B=E B0 kq i∑
j≠i
q j /rij
E B=k qiV i
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SOS é efeito de estado inicial
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Final state effects
● Relaxation● atomic● extra-atomic
● Co 2p3/2
: Co0 < Co3+ < Co2+
● Cu 2p3/2
: Cu0 = Cu1+
● Mostly rearrangement of outer shell electrons● Extra-atomic relaxation in metals (electron
transfer) is more relevant than in ionic materials (polarization)
● Multiplet splitting and shake-up satellites are final state effects and can contribute to E
B
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Forma de linha
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Fatores relevantes
● Tempo de vida do core hole● Resolução instrumental● Satellite features
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Tempo de vida do core hole
Γ = h / τ
● Γ(C 1s ) ~ 0,1 eV● For a given element, larger for inner shell orbitals● For a given orbital, increases with atomic number● Lorentzian lineshape
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Resolução instrumental
● Energy spread of incident X-rays● Analyzer resolution● Energy spread of flooding electrons (via energy
spread in the surface potential)● Gaussian lineshapes typically assumed
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Satellite features
● Vibrational broadening● Multiplet splitting● Shake-up satellites● May or may not be resolvable from the main
photoemission peak● Typically, asymetric lineshapes● Example: asymmetric tail on high BE side of the
photoemission peak for metallic samples (due to continuous range of energy loss to excite valence band electrons into the conduction band)
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Largura de linha
Omicron
+ Echarging
2
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Simulação/ajuste de dados
● Se a resolução instrumental é dominante, picos 100% Gaussianos, mesma largura para todos os sinais
● À medida que melhora a resolução instrumental, os picos tornam-se combinações de Gaussiana e Lorentziana (Voigt)
● Para metais, deve-se considerar fator de assimetria
● Leitura obrigatória: manual do programa XPSPeak
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Análise quantitativa
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Leitura recomendada
http://www.casaxps.com/help_manual/manual_updates/TransmissionCorrection.pdf
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Quantificação
Variação do IMFP (λ) com EK
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Resolução em profundidade
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Métodos
● Desbaste (sputtering) para expor regiões originalmente enterradas
● Manipulação da equação de Beer-Lambert (variáveis acessíveis: geometria do experimento, energia cinética dos fotoelétrons)
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Espalhamento elástico
Maximum emission angle should be ~60°.
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Cuidado!
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Angle-resolved XPS (ARXPS)
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Interpretação dos dados
http://www.npl.co.uk/nanoscience/surface-+-nanoanalysis/products-and-services/arctick
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Theta ProbeTMht
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O processo de fotoemissão
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Comparação com outras técnicas(de análise elementar)
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http://www.uksaf.org/tech/list.html
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http://www.cea.com/techniques/analytical_techniques/
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EDX no microscópio eletrônico
● Profundidade de análise e resolução lateral determinadas pela energia dos elétrons primários
● No MEV, maior profundidade de análise e menor resolução lateral que XPS
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● Novos detectores permitem a identificação de elementos leves
● Espectro de boro (oxidado) obtido num MET:
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EDX em defeito de 0,2 μm
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EDX vs. SAM
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● Apenas informação elementar (sem “deslocamento químico”)
● Comparar com PIXE!
● O detector de raios X pode ser usado num instrumento XPS para XRF (“entram raios X, saem raios X”) -- especialmente útil para amostras isolantes!
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EELS
● Espectro em energia do feixe transmitido no MET● Linhas características próximas das energias de
ligação observadas em XPS
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Altíssima resolução espacial
2 nm
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● Resolução de estados químicos é possível
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Resolução de “estados eletrônicos”
D. A. Muller et al., Nature 399, 758 (1999).
thickness: 1.0 nm (ellips.)bulk-like: 0.85 nm FWHMtotal: 1.3 nm FWHMleakage: 102 A/cm2
c-Si poly-SiSiO2
Oxy
gen
sig
nal
(ar
b.
un
its)
thickness: 1.8 nm (ellips.)leakage: 10-5 A/cm2
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Espectrometria de massas
● Um mundo por si só!● Entra feixe de íons primário (várias opções!),
saem fragmentos do alvo● Detecta todos os elementos● Sensibilidade isotópica e molecular● Limite de detecção na faixa de ppb● Modos estático, dinâmico e de imageamento● Detecção de fragmentos positivos, negativos ou
neutros● Analisadores de setor magnético, tempo de voo
ou quadrupolares
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Al em lâmina de SiImpurezas em ZnSe sobre GaAs
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Espalhamento de íons
● Alta energia (RBS), baixa energia (ISS) ou energia intermediária (MEIS)
● As 3 versões estão disponíveis na UFRGS!!!● Complexidade aumenta à medida que diminui a
energia dos íons incidentes● Instrumentação diferenciada em cada caso● Em resumo, análise elementar com possível
resolução isotópica e em profundidade● Possibilidade de análise quantitativa absoluta,
sem padrões de concentração● Resolução lateral e limite de detecção variáveis
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ISS vs. RBS
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Aplicações
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2a lista de exercícios
● PMMA● Quantitativa● Fotoemissão● Aplicação