Journal of Electron Spectroscopy and Related Phenomena, 17 (1979) 275-278 0 Elsewer Sclentlfic Pubhshmg Company, Amsterdam - Prmted In The

Netherlands

Data bank

XPS INTENSITY RATIOS FOR Fe, Nl, Pd AND Cd METALS

E SOBCZAK

and K PERSY * of Scaences, Warsaw (Poland)

Instztute of Physics. Polzsh Academy

* Instztute of Technacal Physrcs, Techntcal Unwersrty, Vrenna (Austrra)

This communlcatlon presents the XPS lme mtenslty measurements for outer electron subshells m Fe, Nl, Pd and Cd metals for the photon energes of the Ka emlsslon lmes of magnesium at 1254eV and of alummum at 1487 eV usmg a GCA McPherson ESCA 36 spectrometer (without retardmg field), the angle between the mcommg photon and the outgomg electron IS 90. Before photoemlsslon measurements the metal samples were etched by ion bombardment. The integral mtensltles I, and Ii of photoelectron lmes from z-th and I-th subshells were measured assummg a linear behavlour of the background. The mtenslty ratlo I, /I, of photoelectron lmes from the z-th and I-th subshells of the gwen atom can be wntten [ 1,2,3] as Ii r,=, 0, . -.-.- 0, 4 + 4 + p, AK A, Rz R, (1)

where o, 1s the total photolomzatlon cross-section of the z-th subshell, 0, 1s the asymmetry parameter, X, w the mean free path for melastlc scattenng of electrons wlvch 1s proportional todc , and R, 1sthe correction factor due to the energy w&h of the spectrometer sht bemg proportional to the kmetlc energy Ekin of the photoelectrons The expementally determined photolonlzatlon cross-section ratio 1s therefore even by

(2)
The asymmetry parameter p = 2 for s-electrons at energres far from the threshold [ l] Although p IS not accurately known for the p- and d-subshells discussed here, typical values of 0 for large kmetlc energy are about 1 5 for p-subshells [ 1,4] and m the range 1 O-l 5 for d-subshells [ 1,51

276 TABLE 1 RATIOS FOR Fe AND Nl LEVELS 3Pi3s Fe Nl 29 30 2 74 11 AT Mg Kcu(1254 eV) VBI~P Nl 13 14 0 65a 22 Fe 0 31 0 32 0 15a 21 Nl 0 44 0 45 0 24a 19

INTENSITY

VB/3s Fe 0 95 10 0 37 27

I, l4
(aq).X,t (w?j)theoly expt /theory

31 32 2 48 13

TABLE 2 INTENSITY

RATIOS
3d/4s

FOP Pd AND Cd LEVELS 4PJ4S Cd 36 68 363 19 Pd 36 3 6 323 11 Cd 33 3 4 332 10 VB 14s Pd 56 6 1 243a 25

AT Mg Ka (1254 eV) VBI~P Cd 57 6 1 318* 19 Pd 16 16 075a 21 Cd 17 17 09Sa 17 VBI3d Pd 0 16 0 095 O075a 12 Cd 0 16 009 0,090a 10

Pd

414
(cq/~~j)~~~~ (~fbj)theQry expt /theory

37 64 326 2.0

a The sum of (J&j and us=

In Tables 1 and 2 the expenmental XPS mtenslty ratios and the derived cross-sectlon ratros at Mg Kac are compared with the theoretlcal photoionlzation cross-section ratios gwen by Scofleld [S] . Analogous results obtamed at the Al Karphoton energy are shown m Tables 3 and 4. The expenmental results agree reasonably well with theory for ratios of p to s mner subshell photoemission as well as for ratios of d-core to d-valence band photoemission Larger discrepancies are revealed for the photoemlsslon of dcore and d-valence electrons relative s- and p-subshells The expernnental mtenslty ratios of d/s and d/p photoemlssron are about twme the theoretical ratios The expenmental errors due to the area peak measurements (about lo%), and the p correction (below 10%) are small compared to these dlscrepancles Multielectron effects are not expected to be so strong as to decrease by a factor of two the measured s- and p-subshell photoemlsslon Sohd state effects like hybndlzatron of s and d orbltals also can not be considered as reasons for the discrepancies, smce they should decrease the expernnental mtensity of the d-valence band compared to the photolonlzatlon crosssections for s and d outer subshells m free atoms. Therefore theoretical crosssections for s and p photoemisslon, which together are a small contnbutlon

277

TABLE 3 INTENSITY

RATIOS

FOR Fe AND Nl LEVELS VBJ3s Nl 31 32 2 48 13 Fe 0 66 0 73 0 2ga 26

AT Al KCU(1487 eV)

3P/3s

VBI3p

Fe &II, (O;/OJ)expt (wq)thfmY expt /theory 26 27 2 24 12

N1 10 11 0 51a 22

Fe 0 25 0 26 0 132a 20

Nl 0 32 0 33 0 205a 16

a The sum of o&j and 04~ TABLE 4 RATIOS

3dJ4s

INTENSITY

FOR Pd AND 4Pl4S Cd 32 56 292 19 Pd 38 40 315 13

Cd LEVELS VB/4s Cd 37 39 3 25 12 Pd 43 47 207a 23

AT Al Ka! (1487 eV) VBI3d Cd 12 12 087a 14 Pd 0 14 0 10 0077 12 Cd 0 14 0 09 0093 10

VW4p

Pd IElI, (a$~,).,,~ (wJ~J)u-y expt /theory a The

SUIIl Of

Cd 45 49 2 73a 18

Pd 11 11 0 66a 17

30 49 268 18
u&j

and 0~

to the total atomic photolonlzatlon cross-section, seem to be 1 5-2 tnnes lower than the expenmental values The unique XPS mvestlgatlons [7] of Cd and Sr free atoms also show that the intensity ratios of Cd 3d5,* /Cd 3p3,2 and Sr 3d/Sr 3p3,* core subshells are about 1.5 tunes bigger than the theoretical values

ACKNOWLEDGEMENT

One of the authors (E S ) would hke to thank the Austrian Academy of Sciences for havmg gwen her an opportunity to perform measurements in Vienna.

REFERENCES 1 2 J W Cooper and S T Manson, Phys Rev, B L Henke, Phys Rev A, 6 (1972) 94 177 (1969) 157

278 3 4 5 6 7 V I Nefedov, N P Sergushm, I M Band and M B Trzhaskovskaya, J Electron Spectrosc Relat Phenom , 2 (1973) 383 S T Manson, J Electron Spectrosc Relat Phenom , 1 (1972) 413 M 0 Krause, Phys Rev, 177 (1969) 151 J H Scofleld, J Electron Spectrosc ReIat Phenom , 8 (1976) 129 W Mehlhorn, B Breuckmann and D Hausamann, Phys Scr , 16 (1977) 177