过渡元素XPS分析II--数据处理

1 XPS II-- XPS analysis for transition-metal elements (II): Data processing XPS XPS Introduction to General rules for XPS analysis method, and XPS Vocabulary Shirley Tougaard Seah REELS XPS CK 3 1s22s22p63s23p63dn4s2 .. XPS * Ti2+ , 3+ , 4+ ; Fe2+,3+; Cr2+,3+,6+; Mn2+ , 3+ , 4+ ; V3+,4+,5+; Co2+,3+; Ni2+,3+ Cu1+,2+; Zn1+,2+ Sb2+,5+; Sn2+,4+ - XPS Shake-up HAS CAE (IERF) )()(EEjEj =j0(E) j(E) IERF ~ E = 0 ~ -1 E KE IERF=E-1 KE=500eV IERF= Avantage IERF= Emin J(E) Shirley Background =+maxminmaxmin1)()()()()(EEkEEkkdTTFdTTF EjEjEFk F1(E)=j(E)=j0(E) Fk+1(Emin)=0 Fk+1(Emax)=j(Emax) j(Emin)

2 3 KE smart .. Tougaard Background 222)()(')'()'()()(TCBTTKdEEEKEjEjEFiEi+= = + 2222)()(DTTCBTTKi+ = T K(T) plasmon Shake-up 3 B C D 1) Tougaard B=3250 eV2 C=1643 eV2 2) Seah-Tougaard B=1430 eV2 C=756 eV2 .. Vo i g t GL GLP GLS T 00),( ,/)()*exp()1(*EEWHMFEEDETDTMCTTMT<= = += FWHMEEmmEEmGLSEEmEEmGLP = ++ = + = ])(1/[])(2lnexp[)1(])(1/[])()1(2lnexp[220222202200 )(*)(]*)1([*00 EEGLHYEETGLGLHY>==< += + + + +049509609709809901000 Counts / sKinetic Energy (eV)Scan 979eVAl2O3/Al REELS * * REELS Tougaard B C D XPS Al2O3 XPS Al2p Al2s Tougaard B=295 C=657 D=295 eV2 + + + + + +04708090100110120130140150160 Counts / sBinding Energy (eV)

3 Al2p + + + +04708090100110120130140150160 Counts / sBinding Energy (eV)Al2p Al2s Tougaard Tougaard Al2p Al2s Al2O3/Al + + + + +047080901001101201301401501601701801902 00 Counts / sBinding Energy (eV)Al2s 0319FG Al2O3 Al Extrinsic plasmon .. Intrinsic Shake-up satelliate .. Ti V Cu Zn Cr Mn Fe Co Ni 2p53dn n=1~10 XPS XPS [PRB 12 1975 15-19] ( ) XPS XPS.

4 XPS ( ) NNLSF Cu metal + + + +05930940950960 Counts / sBinding Energy (eV)Cu2p + + + + +06930940950960970 Counts / s (Residuals 2)Binding Energy (eV)Cu2p Cu4-2Cu2p3 ACu2p1 A param (eV) Convolve Mix (%)Height (%)Exponent dEb eV rI rFWHM eV L/G I* FWHM 45% TiO2 2p1 2p3 Tougaard(3 ) plasmon + + + + +04450460470480490500 Counts / sBinding Energy (eV)Ti2p Scan010002000300040005000600070008000950 9609709809901000 Counts / sKinetic Energy (eV)Scan 979eVSurf plasmon bulk plasmon Tougaard background 0100020003000400050006000960970980990100 0 Counts / sKinetic Energy (eV)Scan 979eVTougaard 3 B=523, C=520, D=415eV2 Tougaard 3 B=59, C=180, D=40eV2 3d XPS Ti2p REELS + + + + +04450460470480490500 Counts / sBinding Energy (eV)Ti2p ScanTi2pTi2p :TiO2 + + + + + +04450460470480490500 Counts / sBinding Energy (eV)Ti2p ScanTi2pTiO2 XPS 1 Ar+ Ti x+ 2 4:1>2.

5 1, 2p1 CK 3 plasmon XPS .. + + + + + +04450460470480 Counts / s (Residuals 5)Binding Energy (eV)Ti2p Scan TiNTi2p3 TiNTi2p1 TiNSatellite TiNSatellite TiNFrom Avantage Ref Ti TiC ~ TiN TiO2 param (eV) Product Mix (%)Height (%)Exponent param (eV) Convolve Mix (%)Height (%)Exponent TiN + + + + + + + + +054504524544564584604624644664684704724 74 Counts / sBinding Energy (eV)

6 Ti2p Ti-onSiIteration = 0 Pure Ti Ref Ti TiC ~ TiN TiO2 param (eV) Convolve Mix (%)Height (%)Exponent + + + + +054504524544564584604624644664684704724 74 Counts / s (Residuals 2)Binding Energy (eV)Ti2p Ti-onSiIteration = 0Ti2p3 ATi2p1 A TiO2 Ti2p Ti Ti2p Ti + + + + + +04450460470480490500 Counts / s (Residuals 5)Binding Energy (eV)Ti2p ScanTi2p3 Scan ATi2p1 Scan + + + + + + +04450460470480490500 Counts / s (Residuals 5)Binding Energy (eV)Ti2p ScanTi2p3 ATi2p1 ATi2p3 BTi2p1 param (eV) param (eV) Smart backg BE FWHM param (eV)

7 C TiO2 = , I3/I1=1 , W3/W1=1 TiO2 XPS TiO2 Ti2p CK Ti4+ 0 - Ti2p Ti 2p eV 2p 2p 2p Eb eV TiO2 Shirley TiOx Shirley 1 TiC Shirley TiN Shirley (0 ) Sat 6 Ti ( ) TiO2/Ti + + + + + +054504524544564584604624644664684704724 74 Counts / sBinding Energy (eV)Compare-1Ti2p Scan # Ti Ti2p3/2 Ti Ti-onSi Ti TiO2+Ti Ti TiO2 Ti2p3 TiO2 1 Ti2p 2 / TiO2/Ti ( ) ~456eV TiOx TiO2 Ti + + + +054504524544564584604624644664684704724 74 Counts / s (Residuals 5)Binding Energy (eV)

8 Ti2p Scan #006Ti2p ATiO2Ti BEBEBECPSeV TPP-2M%Ty pe 000505450455460465470475 Binding Energy (eV) C 30 0, 0 05 e00040505450455460465470475 Binding Energy (eV)p g TiO2 Ti + + + +054504524544564584604624644664684704724 74 Counts / s (Residuals 2)Binding Energy (eV)Ti2p Scan #006Ti2p3 ATi2p1 ATi2p3 BTi2p1 BTi2p CTi2p3 DTi2p1 DShirley , Ti2p LS param (eV) Convolve Mix (%)Height (%)Exponent + + + + +04450460470480490500 Counts / sBinding Energy (eV)Ti2p ScanTi2pTiO2 + + + + + + + +044504524544564584604624644664684704724 74 Counts / s (Residuals 2)Binding Energy (eV)Ti2p ScanTi2p3 ATi2p1 ATi2p3 BTi2p1 BTi2p3 CTi2p1 CTiC Ti2p TiO2 : = , I3/I1=1 , W3/W1=1/2.

9 TiC/TiCx or n- TiC : = 6e V, I3/I1=1 , W3/W1=1 = 6e V, I3/I1=1 , W3/W1=1 param (eV) TiO2 TiC XPS Ti1-aTi3-aTi4-aTi5-a0204060 Amount (arb. unit)TiDLC TiCx* Ti*C/Ti*Cx DLC TiC C* (282eV) TiC/TiCx Ti C TiC TiN Ti(IV)O2 Ti(IV)C TiC TiO2 TiC/ TiO2/ TiN Ti2p + + + + + + + +054504524544564584604624644664684704724 74 Counts / s (Residuals 5)Binding Energy (eV)Ti2p ScanEtch Time = s, Etch Level = 3Ti2p3 Scan ATi2p1 Scan ATi2p3 Scan BTi2p1 Scan param (eV)

10 TiO2 TiOx + + + + + + + +0501020304050607080 Area ( )Etch Time (s)Peak Area ProfileTi2p3 Scan ATi2p3 Scan BTiO2 TiOx eV 2p 2p 2p Eb eV TiO2 Shirley TiOx Shirley 1 REF Eb ( Ti 2p) = TiO2 TiOx TiO2 Ar+ TiO2 + + + + + +044504524544564584604624644664684704724 74 Counts / s (Residuals 2)Binding Energy (eV)Ti2p ScanTi2p3 ATi2p1 ATi2p3 BTi2p1 BTi2p3 CTi2p1 CTiOC :TiC/ TiO2 param (eV) Convolve Mix (%)Height (%)Exponent TiC TiO2 TiOx eV 2p 2p 2p Eb eV TiO2 Shirley TiOx Shirley