586

Surface Science 181 (1987) 586-595 North-Holland. Amsterdam

XPS STUDIES Kosaku KISHI,

Deprtment JUpl?l

FOR NaCl DEPOSITED Hiroya KIRIMURA

ON THE Ni(ll1)

SURFACE

and Yoshihito FUJIMOTO

Universtty, Ntshinomi.w, Hvogo 662,

of Chemtstr?/, Faculty

of Science, Kwansei-Gakuin

Received 12 June 1986; accepted for publication

15 October 1986

Vapor deposited NaCl on the Ni(ll1) surface was characterized by XPS. Three types of NaCl were found on the surface. First, the NaCl interacted strongly with Ni giving the Nals peak at 1072.2 eV, the C12p peak at 198.8 eV and the NaKLL peak at 494.3 eV. The 494.3 eV peak shifted to 493.4 eV when measured at - 500 K. The energy of the NaKLL peak and the modified Auger parameter for sodium were nearer to those for Na metal than to those for bulk NaCl. The species was assigned to NaCl which was freed from the potential of the NaCl crystal and which had a weakened Na-Cl bond. The other types were characterized by using H,O as a probe. One set of the peaks, the Nals peak at 1072.8 eV, the C12p peak at 199.6 eV and the NaKLL peak at 497.7 eV, was assigned to NaCl which was in the form of a very thin crystal. The other set, the Nals peak at 1073.5 eV, the C12p peak at 200.1 eV and the NaKLL peak at 498.5 eV, was obtained during crystal growth of NaCl as large islands upon annealing. The energies suffered from the charging effect. The effect of coadsorbing oxygen was also studied.

1. Introduction The investigation of the interaction of ionic inorganic compounds with clean surfaces of transition metals is very important in many fields of surface chemistry, such as catalytic, corrosive and electrode reactions taking place on metal surfaces and especially in gaining information about the roles of the coadsorbed species. However, very few papers have been published on XPS studies of this interaction. In the present paper, the interaction of NaCl with a Ni(ll1) surface was studied by XPS in order to obtain information about the bonding of the ionic compound with transition metal surfaces. The NaCl/Ni(lll) interface was prepared by deposition of evaporated NaCl onto the Ni(ll1) surface.

2. Experimental The experiments were carried out in an ultrahigh vacuum chamber equipped with an XPS spectrometer (Al Ka source) and LEED optics. The base pressure 0039-6028/87/$03.50 0 Elsevier Science Publishers B.V. (North-Holland Physics Publishing Division)

K. Kishr ei al. / XPS studies for NaCI on Ni(lll)

587

of the chamber was - 5 x 1O-8 Pa. All core electron binding energies, relative to the Fermi level, were calibrated against the NiZp,,, peak (852.9 eV) of the nickel single crystal. X-ray induced NaKLL Auger electrons were referred by the apparent binding energy scale used for the photoelectrons instead of using the kinetic energy scale. The photoejected electrons were collected at an angle of 30 with respect to the Ni(ll1) surface plane. The cleaning of the Ni(ll1) surface has been described in detail elsewhere [l]. Briefly, the surface of the Ni single crystal supported by a tungsten filament was cleaned by cycles of Ar ion sputtering followed by annealing at 1000 K. XPS analysis showed very little impurities of carbon and oxygen and no sulfur. NaCl was evaporated from a small piece of NaCl single crystal in a box of tantalum sheet which was electrically heated. Distilled and deionized water was degassed in a separate vacuum system by a series of freeze-pump-thaw cycles. Water vapor was admitted to the sample surface under a pressure of 10-7-10p6 Pa through a needle tube in close proximity to the surface. Oxygen gas (> 99.9%) from Takachiho Kagaku Kogyo was passed through a liquid nitrogen cooled trap before use.

3. Results and discussion In figs. 1 and 2 are shown the X-ray photoelectron spectra of Nals and 1,2,3,2 core electrons and X-ray induced NaKL,,,L,,, Auger electron Cl 2p spectra of NaCl deposited on Ni(ll1). (The C12p binding energy and intensity described below represent the energy of the C12p,,, peak and the total intensity for the overlapped Cl 2p,,, and C12p,,, peaks. The Na KL,,L,,, peak is designated as NaKLL below.) The deposition was performed at a substrate temperature of 300 K. After the deposition the intensity of the Ni 2p,,, peak decreased to 14% of that for the clean surface. Assuming a mean free path of 2.7 nm for the Ni2p,,,* p hotoelectrons (kinetic energy = 630 eV) in NaCl, the thickness of the deposited NaCl overlayers was roughly estimated as 2.6 nm according to a formula proposed by Seah and Dench [2]. As discussed below the thickness is not homogeneous over the surface and the estimated values are only the averaged approximate ones. The thick NaCl overlayers gave the Na 1s peak at 1072.8 eV, the C12p peak at 199.6 eV and the NaKLL peak at 497.7 eV as shown by curves a. The sample was then heated to 600 K until the Nals intensity was reduced to one-fourth of the initial one. The Nals peak shifted by +0.7 eV to 1073.5 eV and a shoulder appeared around 1072.2 eV (curves b). The C12p peak shifted by +0.5 eV to 200.1 eV, accompanied by a tailing at the lower binding energy side. The NaKLL moved by +0.8 eV to 498.5 eV and a new peak appeared at 493.4 eV. Curves b were measured while keeping the substrate temperature at - 500 K.

588

K. Kishr et al. / XPS studies

for NuCI on Ni(l1 I)

Fig. 1. NaKLL Auger electron and Nals photoelectron spectra for NaCl deposited on Ni(ll1). (a) NaCl with - 2.6 nm thickness; (b) measured at - 500 K and (c) at - 320 K after heating at 600 K for 20 min; (d) measured at - 470 K and (e) at - 320 K after further heating at 600 K for 5 min; (f) after desorption to submonolayer coverage by heating at 600 K and cooled to 320 K.

Curve c was obtained after the substrate was cooled to peak at 493.4 eV moved to 494.4 eV. The other peaks, significant shifts. The sample was again heated to 600 d were measured at - 470 K. The NaKLL intensity

- 320 K. The NaKLL however, did not show K for 5 min and curves decreased at 498.5 eV.

II

1500c/5s~~//..,;~, C' 2P ,J=' /"..* i*. x1/2 f a.. .--.-.__.._, .,...- .*...... : .**.,; . :...., /-

r I----

:.,:

.. ....:., : : ..

..

204 Fig. 2. C12p spectra:

200 B.E./eV

_L_~

----v,a
I

x4

196 as for fig. 1

same conditions

K. Kishi et al. / XPS studies Table Nals. 1 C12p and NaKLL

for NaCI on Ni(lI1)

589

energies

of deposited Nals

NaCl on the Ni(ll1) Cl 2~ (eV) 199.6 k/L 200.1 199.0

surface NaKLL 497.7 498.< J 493.4 ( - 500 K) 494.4 ( - 320 K) J 492.9 ( - 500 K) 494.2 ( - 300 K) 494.3 ( - 270 K) 1 495.6 - 496.0 (eV)

(ev)

Deposited multilayer NaCl on Ni(lll) Annealed at 600 K

1072.8 JI 1073.5 1072.2

Evaporation

1072.4

Deposited submonolayer NaCl on Ni(ll1) Exposure to 0, Deposited submonolayer NaCl on preoxidized Ni(ll1)

1072.2 $ 1072.0 1072.0

198.8 J 198.4 198.9

The 494.4 eV peak shifted again to 493.5 eV gaining a little in intensity. The Nals intensity decreased at 1073.5 eV and the peak at 1072.2 eV became clearer. The 493.5 eV peak returned to 494.0 eV after retooling the sample to - 330 K as shown by curve e. The variations of the binding energies are listed in table 1. The above results show that three kinds of NaCl were formed on the Ni(ll1) surface. In separate experiments, the quantity of deposited NaCl was decreased to various amounts by desorbing NaCl from the Ni(ll1) surface at an elevated temperature. Curves f of fig. 1 are an example of spectra for smaller amounts of NaCl remaining on the Ni(ll1) surface. The predominant NaKLL peak was at 494.4 eV when measured at 500 K. The Nals and the C12p peaks were located at 1072.2 and at around 199.4 eV, respectively. The C12p/Nals peak intensity ratio is significantly smaller, about one-third, than that for thick NaCl. In another extreme case NaCl was further desorbed by evaporation. The C12p/Nals peak intensity ratio was much smaller than that of a thick NaCl layer, implying that the Cl atoms were more rapidly lost from the surface than the Na atoms. The predominant NaKLL peak was located at 492.9 eV (measured at - 500 K) and at 494.2 eV (at - 300 K) as summarized in table 1. The Na 1s peak was at 1072.4 eV. The position of the C12p peak was not clear due to the very weak intensity. After exposure of the surface to 100 L O,, the Na KLL peak shifted to 495.7 eV. Instead of depositing multilayers of NaCl, a submonolayer of NaCl was deposited carefully on the clean Ni(ll1) surface, at a substrate temperature of 300 K, until the Ni 2p 3,2 peak intensity had decreased to 85% that of the clean surface. The average thickness of the NaCl layer was estimated as 0.2 nm. As

K. Ktsht et al. / XPS studies for N&I

on Ni(l I I)

175oc/5s ,(,rp -2e.Y 1 205

I,

_/.yq.. ,,.y

c 2p ...* :.:a. .. **:*.. . :. ... c ..*. *....;g

:.

cc/

I 200

h_a_,
I ,

I 195

I 75Ocl5s
., .

01s

1 6OOc/2s

/--....

Na KLL

B. E. /eV Fig. 3. NaKLL Auger electron and 0 1s and C12p photoelectron spectra. (a) Submonolayer NaCl on Ni(lll), (b) after exposure to 0 (100 L) at 300 K, (c) after subsequent 0, (100 L) exposure.

shown in fig. 3 and table 1, the NaKLL peak was predominant at 494.3 eV (measured at 270 K) at first, without annealing at elevated temperatures (curves a). The NaKLL peak showed a broad tailing at the higher binding energy side. The Nals peak was at 1072.2 eV and the C12p peak at 198.8 eV. The Cl 2p/Na 1s peak intensity ratio was nearly equal to that for a thick NaCl layer. The surface was then exposed to 0, (100 L) at 300 K. The NaKLL peak shifted from 494.3 to 495.6 eV, the Nals peak from 1072.2 to 1072.0 eV, and the Cl 2p peak from 198.8 to 198.4 eV (curves b). An 0 1s peak appeared at only by 4% with respect 529.6 eV. The Ni2p,,, p eak intensity was attenuated to that before oxygen exposure. Without the NaCl adlayer the attenuation of the Ni 2p,,, peak was - 55% after 0, exposure to the same extent. Further 0, exposure (100 L) gave substantially no spectral change. The above results reveal that the Nals peak at 1072.2 eV, the C12p peak at 198.8 eV and the NaKLL peak in the range 494.4-493.4 eV are assignable to NaCl species directly and strongly interacting with the Ni(ll1) surface and very sensitive to surface oxygen. According to the data of Nals binding energies listed by Wagner [3] the chemical shift is small, less than 2 eV. In contrast, the NaKLL lines exhibit shifts of - 6.5 eV. Therefore, the observed binding energy variations can be more effectively discussed by means of the modified Auger parameter ((Y) [4] than by the Nals energies. The (Y values are obtained as the sum of the

K. Kishi et al. / XPS studiesfor NuCI on Ni(l II) Table 2 The modified Samples Multilayer NaCl after annealing Multilayer NaCl Submonolayer NaCl at 300 K Submonolayer NaCl at 500 K Trace amount of NaCl at 500 K Submonolayer NaCl after O2 chemisorption Submonolayer NaCl on preoxidized Ni (111) Bulk NaCl ) Na metal d, ) ) ) d, a = For Ref. Ref. binding energy of photoelectrons + kinetic energy of Auger electrons. the calculation of a these values are subtracted from 1486.6 as proposed [4]. [?I].

591

Auger parameter

(cy) ) for NaCl on Ni(lll) Nals 1073.5 1072.8 1072.2 1072.2 1072.4 1072.0 1072.0 NaKLL 498.5 497.7 494.4 493.4 492.9 495.6 496.3 ) a 2061.6 2061.7 2064.4 2065.4 2066.1 2063.0 2062.3 - 2061.8 - 2065.9

in ref. [4].

photoelectron (in this case Nals) and the Auger (NaKLL) kinetic energy (both referred to the Fermi level). In using the cy values, charging effect correction and work function correction are unnecessary. The chemical shifts in the modified Auger parameter between two chemical states are related to the difference in extra-atomic relaxation energy between the two states. In table 2 are listed the (Y values calculated for NaCl deposited on Ni(lll), for NaCl powder and for Na metal. For the NaCl species giving two sets of peaks as observed in the above experiments (Nals at 1072.8 eV, Na KLL at 497.7 eV; Nals at 1073.5 eV, NaKLL at 498.5 ev>, the LYvalues were calculated as 2061.6 and 2061.7 eV, respectively. These values are substantially the same as that of NaCl powder, 2061.8 eV, implying that the chemical states of the two NaCl species are similar to that of bulk NaCl. The characterization of the species will be discussed below by examining the results of the experiments using H,O adsorption. Another set of peaks, Nals at 1072.2 eV, C12p at 198.8 eV, and NaKLL in the range 494.4-493.4 eV, gives an (Y value of 2064.4-2065.4 eV. From the data by Kowalczyk et al. [5], a value of 2065.9 eV is calculated for Na metal. (The Na 1s peak was observed at 1071.7 eV for the metal.) The (Y value for the surface species is nearer to that for the Na metal rather than to that for bulk NaCl. The chemical shifts in the (Y values reflect the difference in extra-atomic relaxation, and, in fact, the values for sodium vary from 2059.8 to 2061.9, 2062.3, 2062.8 and 2065.9 eV for NaF, NaCl, NaBr, NaI and Na metal, respectively [4]. Therefore, the large shift in the (Y value for the NaCl species must be due mainly to the screening by conduction electrons of the Ni metal. This means that NaCl interacting strongly with Ni is freed from the potential of the NaCl crystal and the increasing strength of the Na-Ni bonds is

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K. Kishl et al. / XPS studies

for N&I on N1(11 I)

accompanied by a weakening of the Na-Cl bonds and probably by a decrease in positive or negative charge on Na and Cl, respectively. The larger (Y value for NaCl at higher temperatures can be correlated with stronger bonding of Na with Ni, followed by further weakening of the Na-Cl bond. This is supported by the fact that a much larger shift of the NaKLL peak (to 492.9 eV) was observed when the C12p/Nals intensity ratio was significantly decreased from that for a thick NaCl layer after elevation of the substrate temperature; namely, when Na-Cl bond rupture occurred and part of the Cl was lost from the surface in preference to Na. In this case Na gave an (Y value of 2066.1 eV, being the same as for Na metal. Although the extra-atomic relaxation energy for Na on Ni metal may be different from that for Na on Na metal, Na from the dissociated NaCl is expected to be in a metallic state; namely, the positive charge of the Na is much reduced compared to that for bulk NaCl. Although alkali metals on transition metals are believed to donate electrons to transition metals, the electron transfer from Na to Ni may be small. From the behavior of the sticking coefficient for oxygen on the alkali-covered Ni(lOO) surface, the total electron charge transferred to Ni was found to be smaller from Na than from K and Cs [6]. However, the adsorbed Na will donate more electrons through Ni to a coadsorbed species, for example oxygen, as discussed below. The binding energy shift of the C12p peak to lower values on the interaction of NaCl with Ni corresponds well with the fact that chemisorbed chloride on evaporated Ni gives the Cl 2p peaks at lower binding energy, 198.1 eV, than bulk chloride NiCl,, 198.5 eV [7]. In other cases on evaporated Fe, Cu, Pd, Ag and Au, the chemisorbed chloride showed Cl 2p peaks at lower binding energy than those of the bulk chlorides of the respective metals and shifts of the peaks to higher binding energy with increasing coverage [7]. Such a shift was reported also for the Ag(l10) surface [8]. Oxygen chemisorption brought about a shift of the NaKLL peak to 495.6 eV and of (Y values to 2063.0 eV, irrespective of the Cl 2p/Na 1s ratio of the NaCl adlayer. For NaCl whose Na/Cl ratio is the same as that for bulk NaCl, this means a decrease in the relaxation energy for Na from Ni since Ni was coadsorbed by oxygen. For adsorbed Na from dissociated NaCl, in another extreme case, this implies the formation of a strongly bound Na-0 state surrounded by coadsorbed oxygen as has been suggested in ref. [9]. The CX value is about 1 eV larger than for the Na,O compound. The Na 1s binding energy for the submonolayer NaCl, 1072.2 eV, shifted to lower binding energy, 1072.0 eV, upon oxygen chemisorption, being a shift opposite to what one would expect in the case of increasing positive charge of Na. The opposite shift was also observed when the submonolayer NaCl lost Cl atoms from the surface upon heating. Although the positive charge of Na was expected to have decreased in this case, the binding energy shifted to a higher value, from 1072.2 to 1072.4 eV. This type of shift has been reported for K2p and K 3p

K. Kishi et al. / XPS studies for NaCl on Nz(II

I)

593

binding energies in experiments on oxygen and potassium coadsorption on Fe(ll0) [lo] and Pt(ll1) [9] and has been connected with a Madelung type effect. A small amount of NaCl was deposited on the nickel oxide layer (about three layers) on Ni(ll1) which was prepared by exposure of the clean surface to 0, (100 L) at 290 K. The broad NaKLL peak was observed centered at 496.0 eV. The Na 1s peak was at 1072.0 eV and the C12p peak at 198.9 eV. These peaks are ascribable to dispersed NaCl on preoxidized Ni. The modified Auger parameter is 2062.6 eV and near to that of bulk NaCI. This again supports the theory that the NaKLL peak can shift to 494.4 eV only when the dispersed NaCl strongly bonds to unoxidized nickel atoms. In order to characterize the remaining two sets of peaks (Na 1s: 1072.8 eV, Cl 2p: 199.6 eV, NaKLL: 497.7 eV; and Na 1s: 1073.5 eV, C12p: 200.1 eV, NaKLL: 498.5 ev), adsorption of H,O as a probe was carried out on clean and NaCl deposited surfaces. The variations of the Na Is, Cl 2p, Na KLL and 0 1s binding energies are summarized in fig. 4. The adsorbed submonolayer of H,O on the clean Ni(ll1) surface at 150 K gave the 01s peak at 532.9 eV. With a thick H,O layer (estimated as - 2 nm) on Ni(lll), the 0 1s peak was observed at 533.9 eV. The energy shift from 532.9 to 533.9 eV with increase in the thickness of the H,O layer is mainly due to the loss of the strong extra-molecular screening by the metal for upper layers of H,O from which electrons contributing to the 01s peak intensity were ejected. The smaller relaxation is expected only from the surrounding H,O molecules. The possibility of a charging effect is excluded since no shift was observed for the Ni 2p,,, peak of the Ni atoms underneath the H,O overlayers. After warming to 370 K, most of the H,O was desorbed and OH- species were formed as shown by the appearance of the 0 1s at 531.4 eV [ll]. When H,O was condensed (to 1 nm thickness) on NaCl overlayers with 1.2 nm thickness (sample A, Nals: 1072.8 eV, C12p: 199.6 eV, NaKLL: 497.7 eV with a weak peak at 494.2 eV> at 150 K, the 0 1s peak was observed at 534.0 /
Heating at 370 K Na 1s

Cl 2p

NaKLL

I 15,

0 Is

I, I I I

\\
Exposure to Hz0 at 150 K Depom;;ed lObY%72

21

\f

201 B.E. /eV

199 49Y%7

537

533

531

Fig. 4. Nals, C12p, NaKLL and 01s energy shifts for NaCl on Ni(ll1) during exposure to H,O at 150 K and heating at 370 K. [(- -): on clean Ni(ll1); (- - -): on deposited multilayer NaCI; ): on deposited multilayer NaCl after annealing at 600 K.] (-

594

K. Kzsht et ul. / XPS studies for NaCl on Ni(l II)

eV. The 01s peak was at the same energy as that for condensed H,O on Ni(ll1) at 150 K. Most of the 01s intensity was lost at 170 K but the remaining weak 01s peak showed no binding energy shift. This means that the H,O molecule both on the NaCl layer and on the condensed H,O experienced the extra-molecular relaxation to the same extent. Binding energy shifts were observed for the Nals, C12p and NaKLL peaks after condensation of H,O. These are described later. The other sample was NaCl overlayers on Ni(ll1) annealed at 600 K (sample B, Nals: 1073.5 eV, C12p: 200.2 eV, NaKLL: 498.7 eV). These peaks are all - 0.7 eV larger than the respective peaks for NaCl of sample A. Condensation of H,O (1 nm thick) on the surface at 150 K gave the 0 1s peak at 534.8 eV, being also 0.8 eV larger than those of condensed H,O on sample A and the thick H,O layers on Ni(ll1). Therefore, the energy differences between sample A and B are concluded to be due to a charging effect on sample B. Annealing of the thick NaCl layer is expected to stimulate the crystallization of the deposited NaCl and to lead to the growth of larger islands of NaCl. In the above adsorption experiments of H,O, the energies of the Nals, Cl 2p and NaKLL peaks all, except the Na KLL peak at 494.2 eV, shifted to lower energy after condensation of Hz0 (1 nm thick); (a) on sample A, Na 1s: 1072.8 + 1072.2 eV, C12p: 199.6 -+ 199.1 eV, NaKLL: 497.7 + 497.1 eV; (b) on sample B, Nals: 1073.5 -+ 1072.9 eV, C12p: 200.2 + 199.6 eV, NaKLL: 498.7 -+ 498.0 eV. These peaks returned to the position before H,O condensation when the surface was heated to 370 K, with disappearance of the 0 1s peak. The energy shifts are probably explained by variation of the work function of the sample surfaces during H,O condensation. The ejected electrons from NaCl leave into the vacuum from the surface of condensed Hz0 which leaves from the NaCl surface before H,O condensation. The weak NaKLL peak at 494.2 eV for sample A showed rather a very small shift to higher energy, unlike the other peaks, after condensation of H,O. This was due to the change of the chemical state of Na, strongly bonding to the Ni surface, in the interaction with H,O, as discussed in the effect of 0,.

Acknowledgment We wish to acknowledge tion. support of this work by The Mitsubishi Founda-

References
[l] K. Kishi and Y. Fujimoto, Surface Sci. 176 (1986) 15. [2] M.P. Seah and W.A. Dench, Surface Interface Anal. 1 (1979) 2

K. Kishi et al. / XPS studies for NaCI on Nl(I I I)

595

[3] C.W. Wagner, Faraday Disc. 60 (1975) 291. [4] C.W. Wagner, L.H. Gale and R.H. Raymond, Anal. Chem. 51 (1979) 466. [5] S.P. Kowalczyk, L. Ley, F.R. McFreely, R.A. Pollak and D.A. Shirley, Phys. Rev. B8 (1973) 3583. [6] M. Kiskinova, L. Sumev and G. Bliznakov, Surface Sci. 104 (1981) 240. [7] K. Kishi and S. Ikeda, J. Phys. Chem. 78 (1974) 107. [8] M. Bowker, J. Electron Spectrosc. Related Phenomena 28 (1983) 249. [9] G. Pirug, H.P. Bonzel and G. BrodCn, Surface Sci. 122 (1982) 1. [lo] G. Pirug, G. BrodCn and H.P. Bonzel, Surface Sci. 94 (1980) 323. [ll] K. Kishi and S. Ikeda, Chem. Letters (1972) 245.