Science 141 (1984) 240-254 North-Holland, Amsterdam

Department Received



and R.J. MADIX
University, Stanford, 21 February CaIijotxia 1984 94305, USA

of Chemical Engineering, 25 October 1983; accepted


for publicatidn

The oxidation of gold has been studied under UHV conditions by AES, XPS, and TDS. The previously reported adsorbed oxygen state, which formed by heating the sample above 600 K in 10W5 Torr of oxygen and which remained after subsequent heating to 1100 K in vacua, has been shown to result from the reaction of oxygen with silicon diffusing from the bulk. No oxygen adsorption was detected on a clean sample for oxygen pressures up to 10m4 Torr and sample temperatures between 300-600 K. Chemisorption of oxygen atoms could be induced by placing a hot platinum filament close to the sample during exposure to oxygen. The activation energy for desorption of this oxygen state was estimated from the thermal desorption spectra to be about 163 kJ mol-‘. The chemisorbed oxygen atoms and the oxygen associated with silicon were distinguished by different O(ls) binding energies (529.2 and 532.3 eV respectively) and by different O(KVV) Auger fine structure.

1. Introduction In the last decade several investigators have published conflicting results concerning the interaction of oxygen with gold surfaces [l-4]. While all of the studies agree that no oxygen is adsorbed on the clean gold surface at room temperature, there is marked disagreement over the behavior at higher temperatures. Schrader [l] studied the oxidation of a (111) gold surface in 5 X lob7 Torr of oxygen at several temperatures between 373 and 873 K and concluded that activated adsorption of oxygen occurred to form a disordered chemisorbed layer. Chesters and Somorjai [2] in their study of the oxidation of Au(ll1) and Au(S)-(6(111) X (100)) reached similar conclusions. They also observed new diffraction features which they attributed to the. adsorbed oxygen in a square surface oxide mesh. The stepped surface behaved identically to the (111) surface; no enhancement of the rate of adsorption by the steps was observed. In both of these studies the authors found that the surface oxide was remarkably stable, disappearing only upon heating the sample above 1073 K for several hours. It was noted [1,2] that this behavior was very different from that observed for bulk gold oxide, Au,O,, which cannot be formed by direct reaction of oxygen and gold and which decomposes near 410 K. The greater 0039-6028/84/$03.00 0 Elsevier Science Publishers B.V. (North-Holland Physics Publishing Division)

S.8 kcal mol-’ [7] and -0. However. in general. which are . The irreproducibility in results for the formation of the strongly bound oxide on gold is analogous to the confusion in the literature over the existence of very stable bulk oxides of other noble metals such as platinum or palladium.151. a different state of oxygen was detected by these authors after exposing the foil to atomic oxygen.6]. / Adrorption of oxygen on gold 241 stability of the surface oxide compared to the bulk oxide was attributed to the coordinative unsaturation of the surface metal atoms which causes the heat of formation of the surface oxide to be much larger than the heat of formation pf the bulk oxide [l].9 kcal mol-’ [8] respectively. calcium was below the limit of detection by AES (the intensity of the Ca(KW) transition in CaO is larger than the O(KW) transition by a factor of 1. since in each study mentioned above. In this context several studies have shown that calcium at the surface of gold can lead to greatly increased rates of adsorption of oxygen [4. How- . Spillover implies that oxygen bound to calcium should have a similar stability to oxygen bound to gold. In sharp contrast to the above results Eley and Moore [3] found that a clean polycrystalline gold sample exposed to 3 X lop5 Torr of oxygen for an hour at temperatures between 300-1000 K did not adsorb oxygen. forming CaO at the surface [4] while another suggested that spillover of oxygen from calcium to gold could occur leading to a much higher O/Ca ratio than expected for CaO formation [6]. rather than due to oxygen spillover from calcium.O. D. should be compared when looking for periodic trends in the adsorbate-substrate binding energy. This seems unlikely in view of the heats of formation of bulk CaO and Au. E.N. Canning et al. this state desorbed between 500-600 K without conversion to the strongly bound state. which is unfortunate since ideally the zero coverge limiting value of the activation energy. which may alter the activity of the surface towards oxygen adsorption.ll] although a recent study of the oxidation of platinum disputes this [12].. may explain some of the differences in the above results. This very stable state of adsorbed oxygen was also reported by Bazhutin et al. Reported activation energies for desorption of chemisorbed oxygen from surfaces of group VIII and Ib metals are collected in table 1. The results presented below suggest that a higher O/Ca ratio than that expected for CaO was probably due to the undetected presence of silicon which also reacts with oxygen. for the contradictory results for the oxidation of gold. [5] after heating a gold foil to 900 K in 5 X lo-’ Torr of oxygen. The presence of impurities. so Ca should be more easily detected than oxygen). Several reports have indicated that silicon must be present for these oxygen states to form [lO. The role of lateral interactions among adsorbed oxygen atoms has not been quantitatively determined in all of these studies. In the absence of spillover it is unlikely that surface calcium was responsible. These studies disagree on the maximum oxygen coverage attained in the presence of calcium.3 [9]. One study indicated that all the oxygen was associated with calcium.

references are indicated by the numbers in parentheses. In addition the state of chemisorbed oxygen atoms bonded to gold. formed only by prior dissociation of O. W E (kJ mol-‘) looo-1100 234 Ir [37] Tp W E (kJ mol-‘) 900-1100 230-270 ever the reported activation energies do show periodic trends similar to those observed for the stabilities of the bulk oxides shown in table 2.) 923 K [40] Au (Au. The results given below show that the stable high temperature oxide state on gold is attributable to the undetected presence of silicon. which diffuses out of the bulk and reacts with oxygen to form a very stable SiO. Canning et al.) 423 K [40] (Ag. layer at temperatures above 300 K. / Adsorption of oxygen gold on Table 1 Collected activation energies for oxygen atom recombination and desorption and the temperatures of the peaks in the desorption spectra.) 1320 K [39] . According to periodic trends then..tO. The metal-oxygen interaction energy increases from right to left in each period and decreases moving down each group. evacuated by an ion pump to an ultimate pressure of Table 2 Decomposition Rh (F&O) 1300 K [8] (PdO) 1148 K [40] (Rho. XPS and TDS. the data for gold are from the present work co Stable oxide Rh 1341 Ni Stable oxide Pd [35] 830-900 230 Pt [38] 690-800 200 cu Stable oxide Ag [361 SOL-600 173 AU 654 163 T. Experimental The experiments were performed in a vacuum system consisting of a stainless steel bell jar. surface oxides of gold which are stable above 1000 K in UHV certainly would not be expected to form.) Ir (IrO. has been characterized by AES.O. 2.242 N. D.S.O) 450 K VI temperatures for bulk metal oxides decomposing Pd to metal and oxygen Ag in air 1373 K [40] .

In order to induce adsorption of atomic oxygen on the clean gold surface.) peak was then 83.5 V was employed. the binding energy of the Au(4f.N. a platinum filament was placed at 1 cm from the surface during the oxygen dose. The Auger spectra were excited by an electron beam with a primary energy of 2 keV. The energy scale of the Auger spectra was referenced to the Fermi level of the sample and adjustment for the work function of the spectrometer was made by setting the energy of the gold N. The spectra were collected digitally in a Tracer Northern signal analyser which enabled co-adding of scans to improve the signal-to-noise ratio of the spectra. A double pass CMA (PHI) was used to record the Auger and photoelectron spectra. Mg Ka radiation (400 W at grazing incidence) was employed to excite the photoelectrons. A clean sample was obtained by cycles of oxidation (PO. In this way the calcium and silicon impurities in the near surface region were reduced to below the limits of detection by AES after 70-80 h treatment. prolonged annealing of the sample at 900 K for 2 h would again lead to the detection of silicon at the surface. / Adsorption of oxygen on gold 243 8 x lo-” Torr after bake out. with dimensions 10 mm diameter x 2 mm thick. The heating rate was found to be constant over the temperature range for which 0. Continued treatment over the course of several weeks sufficiently depleted the sample of silicon to allow thermal desorption spectra to be obtained without segregation of impurities to the surface. but for high resolution spectra 0. The sample.N. The X-ray photoelectron spectra were recorded using the CMA in the constant pass energy mode (P = 50 eV).. incident along the surface normal. . No measurable increase in the sample tempertature was produced by the hot filament. However. At 1400 K no deposition of platinum was detected. = 10m6torr.8 eV [14]. The temperature ramp was provided by a current jump through the heating filament.O. For filament temperatures above 1450 K platinum metal was deposited on the gold and was detected by the growth of new Auger features at 1967 and 2044 eV. After several cycles of ion bombardment and annealing the LEED pattern showed that the surface had faceted. The sample was heated radiatively by a tungsten filament mounted behind it.S. transition to 239 eV [13]. T= 900 K for 1 h) and argon ion bombardment with the sample at room temperature. Thermal desorption spectra were recorded using a UT1 mass spectrometer in line of sight to the crystal to monitor the oxygen flux from the surface. The binding energy scale of each spectrum was referenced to the sample Fermi level.. desorption occurred.. A precise characterization of the surface atomic structure has thus not been attempted.D. The gold sample was cut from a gold rod which was found to be a twinned crystal. Canning et al. though high background intensity and poorly defined diffraction spots indicated a large amount of surface disorder remained. A peak-to-peak modulation of 2 V was used routinely. was mounted in a tantallum holder with a chromel-alumel thermocouple held in physical contact with the edge of the crystal.

the sample to oxgyen at 600 K: (a) clean surface: (b) . / Adsorption of oxygen on gold 3.244 N. After several weeks of further cleaning no oxygen was adsorbed by this procedure.1. Results and discussion 3. (d) 900 L 0. However the amount of oxygen adsorbed in this state depended on the previous history of the sample. 1. D. Canning et al..S.. The adsorbed oxygen was retained even after heating the sample to 1000 K for 1 h in vacuum. Auger spectra recorded after exposing (c) 100 L 0. However. Thermal oxidation of gold Exposing a clean sample to oxygen partial pressures between 10-6-10-’ Torr for 1 h at room temperature did not lead to any detectable adsorption of oxygen. initially if the sample was heated to 600 K at 10W6 Torr oxygen pressure. XI x4 (b) f (Cl dN(E) dE i ji 30 130 230 KE/eV 330 430 5301 1550 1650 33 L 0. Fig.. adsorption did occur. suggesting the role of impurities.

indicates that all of the adsorbed oxygen was associated with the silicon and further supports the SiO. / Adsorption of oxygen on gold 245 Although calcium was not detectable following the prolonged heat treatment that led to the formation of the adsorbed oxygen state. .N. Detection of silicon was particularly difficult since the most intense silicon Auger feature (at 94 eV for pure silicon) shifts to 78 eV in SiO. The ratio of the intensities of the Si(KLL) transition at 1605 eV to the O(KW) transition at about 508 eV was identical to that in SiO. a careful examination of the Auger spectra showed that silicon was present whenever the oxygen was detected (fig. Spectrum 2b followed annealing of the sample to 600 K for 20 min. 2.S. The two transitions at 88 and 94 eV have been observed previously for silicon atoms in a metallic envionment [16]. stoichiometry. which shows the effect of exposing a surface with some segregated silicon present to oxygen at room temperature. The AU (b 1 (a 1 c 30 50 70 so KE/cV 110 130 1550 1650 Fig. exposure 1000 L. exposure 2000 L. The effect of room temperature oxidation on the silicon Auger spectra: (a) clean gold surface. Spectrum 2a was recorded after ion bombardment of the surface and no silicon could be detected. to be given below. The silicon KLL transition was detected at 1618 eV. [15] and so is obscured by the gold transition at 69 eV. (d) 0. This is clearly illustrated in fig. 2. 1). After exposing this surface to 1000 L of oxygen at room temperature spectrum 2c was recorded. (b) sample annealed to 600 K for 20 min. D. Spectrum 2d was taken after an additional 1000 L exposure. Canning et al. [13]. Further spectroscopic evidence. (c) 0.

Y:.% .A:-~‘.. T.600 K). :.:: ‘:.” j-l ii) Xl . (c) after exposing the clean gold sample to oxygen with a hot Pt filament close to the surface._ .....:i <:. :..._.. . !.... : I:’ . ‘..:si.. 3. / Adsorprion of oxygen on gold Au(4f-I ‘._’ .:’ (. I’ I :t ..1”!...2 .. .. : r .... .I . I.’ ‘t ..‘I i: ‘I. k. ‘* ‘I..P. _._..__ . ‘. P_____.-.. .C.. .3 :’ .I : ..._. . ?: . I ........’+.... I ‘.:::“-% .c x2 " I __. 1’ ‘\ :: 1: r: I ” . .F... ‘. ...J .._ .“. . ..... ..I ... .. 12 1 i) A?.I’ ‘.. I ( ‘: ..: ..A’ ‘k... . v.I x2 e-.: r: 1 . ‘i :‘.. ‘. .i..Y+ . 4358c/s j 1... (i) Au(4f) and (ii) O(k) XPS spectra: (a) clean gold surface. $f’ “I b) . . +c\” ‘..:. .. I !’ I I. . n._ (C ) . . I.iC.246 N.. _.c’ ......_.. ‘I’ 1: . : _.. ‘..: .’ :. . . . .<. . .‘..2’ i.: 52 9.....S. :* ... -.\ \ . .c+ >: . . ... I: X’ “__......: c. : I.. ..i __..~w:. . (a 1 524 544 549 8Wev Fig.$j@’ ” 529 534 539 :.i’ .. . (b) after heating the sample in oxygen (1000 L.. :\ ‘_ .: ‘?.. .’ . .. . .... Y.‘.wi’- O(lS) 82 Xl ‘“.: ...’ 1: \ ” . ._. . ‘1.s .: . ‘i.. .....\i .:’ : .: .>:. ... :. D... :.i .....--..sM. 980~1s ::: . Canning et al.:’ :‘.. .. :: ‘1.: + 1.’ _ _ --.:’ :f j.i 532.. (a) . ..-‘... I.(4 f5.‘. .‘. . ...I :. .PG I..G’ :: +. ..+ .. .. .___ (b ) .!. . :c i. ...“..: (C ) :c ..

the resolution was 2 eV. High resolution O(KW) Auger spectra for the oxygen state produced by: (a) heating the gold sample in oxygen (30 L. Canning et al. T= 300 K) and is identical to the spectrum of Cu. 460 480 KE/eV 500 520 540 Fig. leading to the apparent disappearance of the transitions at 88 and 94 eV indicating that the oxygen was bonding to the silicon. These results agree with a recent report that gold monolayers and multilayers can catalyse the oxidation of silicon surfaces at room temperature leading to complete oxidation of silicon atoms alloyed with the gold to SiO. [13]. Further evidence that the strongly bound oxygen state formed upon heating a gold crystal in oxygen is due to the formation of SiO.N. Both spectra were recorded under identical conditions.O. T= 600 K). Spectrum (c) was recorded following the oxidation of a Cu(ll1) surface (300 L. The shift in the Si(KLL) transition from 1618 to 1605 eV is consistent with the formation of SiO. 3 and by the oxygen Auger spectra in fig.D. Oxygen adsorption caused the growth of an O(KW) feature and large shifts of the Si(KW) features.S. . 4. is given by the XPS results shown in fig.0 eV dN(E) dE Au-O (b) 440 . (b) exposing the room temperature sample to oxygen atoms. These spectra were recorded following an oxygen dose of 1000 L with the sample at 600 K. / Aakorption of oxygen on gold 247 Si(KLL) transition was unaltered in intensity following the oxygen treatment but was shifted to 1605 eV. [17]. 4. The XPS spectrum 3(ii)b shows a single O(ls) peak with a FWHM of 2.

The Auger O(KVV) lineshape of the thermally induced oxygen state shown in fig. on gold (532:3 k 0. have previously been investigated [19] and account for the difference in the Auger spectra for the strongly bound oxygen state reported in this study and that reported by the Russian workers mentioned earlier [5]. / Adsorption of oxygen on gold which is close to the instrumental resolution of 1. Such beam-induced effects for SiO.248 N.S. The XPS and AES spectra of this new oxygen state are compared with those of the strongly bound oxygen state in figs. 3 and 4. [19]. (429. The O(ls) binding energy of this state was 532. but no chemical shift due to oxide formation was observed (fig. Canning et al.2. This binding energy is close to that expected for SiO. [20] for the adsorbed oxygen state on gold produced by exposing the sample to oxygen in a microwave discharge. This contrasts with the noticeable chemical shift of the Au (4f) levels produced by a similar coverage of oxygen following adsorption of oxygen atoms on the clean surface (see below).2) estimated from the known Si(2p)-O(ls) separation in pure SiO. The width of the oxygen peak suggests that only one chemical form of oxygen is present. D.4 eV higher in binding energy than .3 k 0. 3. The O(ls) binding energy of 529. Adsorption of atomic oxygen When the clean gold surface at room temperature was exposed to oxygen in the presence of a platinum filament at 1400 K a new adsorbed oxygen state was detected with very different physical characteristics from the thermally produced oxygen state.6 eV [IS]) and the previously reported Si(2p) binding energy of oxidized silicon in the presence of gold multilayers (103. It was noticed that for a high coverage of this oxygen state prolonged exposure to the electron beam when recording the oxygen Auger spectrum led to a shift of the main negative feature from 504 to 509 eV. The absence of a chemical shift of the Au(4f) features following the formation of the thermally induced adsorbed oxygen state indicates that no gold oxides are present. 4a is identical to that of pure SiO. At 1400 K no platinum deposition on the gold could be detected so that the new oxygen state was not associated with surface platinum. 3(i)b). The single O(ls) XPS peak suggests all of the oxygen is associated with the surface silicon. The silicon XPS was too weak to be detected in our experiments. . The binding energy of the O(ls) electrons and the fine structure of the O(KVV) Auger transitions are consistent with the presence of SiO. The Si(KW) and Si(KLL) Auger spectra from this “oxidized” surface indicate that silicon is present and is chemically associated with oxygen.8 eV. The Au(4f) features were attenuated following oxygen exposure and the formation of this strongly bound oxygen state.0 eV [17]).2 eV is typical for atomic oxygen bound to metal surfaces and compares well with that reported by Evans et al. showing small shoulders about 1. The Au(4f) transitions were affected by the presence of adsorbed atomic oxygen.2 eV.

O. A much larger shift would be predicted from the data for inorganic complexes.8 X lOi atoms cm-* [27]).. The spectrum is compared with that for chemisorbed oxygen on copper [25] in fig. However..ion [24]. while for CuO it is not fully resolved from the major intra-atomic feature at 514 eV owing to the broader valence band of CuO compared to Cu. / Adwrption of oxygen on gold 249 the main peaks following oxidation..0 84. Consequently the formal oxidation state of the surface gold atoms associated with formation of the surface oxide is not clear from the observed binding energy shift alone. 4.0 87. the sensitivity of this feature to the oxidation state of gold must remain a matter of speculation. however. an increase in the covalent character of the metal-oxygen bond in the oxides compared to the metal-ligand bond in the inorganic complexes may well lead to a reduction in the binding energy shifts for a given formal oxidation state of the metal. making determination of the stoichiometry of the surface oxide difficult.) feature compared to the clean metal [23]. A comparison of this binding energy shift with those observed for mono-nuclear and polynuclear gold complexes [21. attributing it to the presence of Au+ ions. 4.N. which exhibits a binding energy shift of 1. The overall shape and position of the fine structure in the O(KW) Auger spectrum of this oxygen species on gold is typical of atomic oxygen adsorbed on metal surfaces and has been interpreted in terms of the closed shell 02.5 +1. with that reported for the (2 x 2) oxygen adlayer on Pt(ll1) (corresponding to a coverage of 3. Second. causing variations in the binding energy shifts for the two environments for a given oxidation state.9 0.9 eV for the Au (4f. On copper the feature at 520 eV has been assigned to an interatomic Auger transition involving the metal valence electrons [26] and its width has been shown to be sensitive to the oxidation state of the metal: Cu.5 +3. After Table 3 The dependence of the binding energy of the Au(4f.) gold from data in refs.0 . First. Canning et al.O.S.7 +os level on the formal oxidation state (OS) of 85.O gives a well defined feature as in fig. The maximum coverage of chemisorbed atomic oxygen was’estimated by comparison of the Auger peak-to-peak height ratio O(515 eV)/Au(239 eV). which was 2. This seems to be true for Au. Several factors may limit the validity of this comparison.22] (summarized in table 3) suggests a formal oxidation state of + 1 for the surface gold atoms. relaxation effects for the gold atoms at the surface may differ from those in inorganic complexes.. where it is seen that all the features are identical. in the absence of UPS data for different oxidation states of gold and without O(KW) spectra for bulk Au203.22] BE (eV) OS 83.D. It is tempting to interpret the 520 eV feature in the case of gold in a similar manner.0 at saturation. [21.

.0 k 0. This implies there is an energy barrier to the formation of the bulk oxide from the surface oxide.) and O(ls) photoelectron binding energies are somewhat different.D.. The oxygen-to-gold intensity ratio together with published atomic sensitivity factors [14] gave the ratio of oxygen to gold in this layer as 2. suggesting that the oxygen has not penetrated deep into the gold lattice. The shifted Au(4f.S. assuming that the sample surface was atomically smooth.8 eV [23]. which corresponds to a relative coverage of at least two monolayers. It is difficult to determine unambiguously if all the oxygen is present just as chemisorbed atoms at the metal surface or if a true oxide layer has begun to form on the metal...2 eV. Canning et al. It was further assumed that the oxygen forms a homogeneous layer with all the gold atoms in the layer characterized by this shifted peak. A comparison of the XPS intensity ratio of the O(ls) signal at saturation and the Au(4p. suggesting that a thin layer of gold oxide has begun to form... chemisorbed oxygen atoms and to unreactive oxygen atoms which had penetrated the surface of the crystal lattice [30]. assigned respectively to reactive. This is considerably different from the O(ls) binding energy previously reported for bulk Au. These results can be compared with those for oxygen adsorption on Ag(ll0) where two O(ls) signals were observed at 529. However. The observation that the oxide layer stops growing at an oxygen coverage of about 2.9 x 1Or5 atoms cm-* was obtained. A single O(ls) peak with a binding energy characteristic of adsorbed atomic oxygen was observed at 529. ..z) intensity ratio of the (2 X 2)0 adlayer [27] gives a similar coverage estimate of 2. This surface oxide must be somewhat different from the bulk oxide since the Au(4f.) peak and the O(ls) peak.2 and 531..O. / Adwption ofoxygen gold on correction for the relative sensitivity of the Au(239 eV) and the Pt(237 eV) transitions of the clean metals [13].250 N.0 indicates that it is a superficial oxide stabilized by the surface.5. The XPS spectra support this contention.) feature in the spectrum of the oxidized surface.) signal of the clean surface recorded under the same conditions with the O(ls): Pt(4p. a coverage of 2. Au and Pt on photon energy. The ionization cross sections of the elements calculated by Scofield [28] were used to make these corrections.) spectrum normalized to the unshifted Au(4f.. at 531. It was assumed that the features in the difference spectrum were only due to the chemical shift of the 4f levels of gold atoms associated with oxygen.. A stoichiometry for the surface oxide layer may be estimated from a comparison of the intensity of the chemically shifted Au(4f...2 eV. the oxide layer which is formed can be rapidly and completely removed by reaction with formic acid at room temperature [29]. after allowance was made for the dependence of the ionization cross sections of 0. The high oxygen concentration and the observation of a chemical shift of the Au(4f) levels are consistent with formation of an oxide at the surface since oxygen chemisorption usually ceases at much lower coverages and does not produce noticeable chemical shifts of the metal core levels.2) peak intensity was obtained by subtraction of a clean surface Au(4f.5 X 1015 atoms cm-2.

Canning et al. 5. S. XPS and AES showed that the oxygen completely desorbed upon heating the crystal above 670 K.N. Thermal desorption spectra following the adsorption of atomic oxygen on the gold surface for varying initial coverages up to saturation. The heating rate was 21. At intermediate coverages .5 K s-l. / Adsorption of oxygen on gold 251 I 495 544 592 640 688 735 T/K Fig. D. 5 for varying initial coverges of adsorbed atomic oxygen. Thermal desorption spectra are shown in fig. The mass spectrometer was tuned to m/e 32.

The observation that oxygen will not adsorb at room temperature on gold indicates that adsorption is activated. If the dissociative adsorption of oxygen on gold were non-activated this desorption activation energy would be equal to the heat of adsorption. Since the rate of recombination of atomic oxygen is expected to be second order in the atomic oxygen concentration. It is not clear why the high temperature state was lost with increasing coverage. -c 38 kcal mall’. which is just a little lower than the activation energy for desorption of oxygen from silver [31].) the desorption activation energy is larger than the heat of adsorption by Ea. 4. Both adsorbed atomic oxygen and oxygen associated with silicon on the gold surface have been characerized by XPS and high resolution Auger spectroscopy. First. from Si which diffuses out of the crystal on heating and is not due to an activated adsorption of oxygen. For a clean crystal no adsorption was detected following oxygen exposures in excess of 5 x lo5 L and for crystal temperatures up to 600 K where rates of desorption of adsorbed atomic oxygen become significant. is probably attributable to the formation of SiO.. / Adsorption of oqgen on gold two desorption rate maxima were observed. This activation energy for . Canning et al. Summary In conclusion it has been shown that the strongly bound oxide on gold. = 3 x 1O-3 [31].D. if adsorption is activated (with activation energy E. the apparent first order behavior of the desorption peak at 654 K must result from the presence of attractive lateral interactions between oxygen atoms in a manner similar to that observed for oxygen on Ag(ll0) [31]. Comparison of Ed with the heat of formation of bulk gold oxide indicates that 0 < E. The desorption activation energy is much larger than the heat of formation of the bulk gold oxide. An estimate of the activation energy for oxygen atom recombination and desorption was extracted from the data by applying Redhead’s formula for the activation energy of a first order desorption process and assuming a pre-exponential factor of lOI s-’ [32]. It was shown that gold will adsorb oxygen atoms at room temperature and that the activation energy for recombination and desorption of these atoms was about 163 kJ mol-‘.252 N. Second. This indicates that the sticking probability for oxygen on this gold sample must be below 10p5. This yield a value Ed = 162. Further desorption studies form structurally well defined surfaces are in progress to clarify this point. and this may be traced to two causes. a much smaller value than that observed for Ag(ll0) where S. heats of adsorption of oxygen on noble metals are often larger than the heat of formation of the bulk oxide due to the unique properties of the surface environment [32]. The inability of gold to adsorb oxygen under our experimental conditions is attributable to an activation barrier to adsorption. As the initial coverage was increased the lower temperature maxima grew without a shift in position and the higher temperature peak was removed entirely.S. previously reported by several authors.5 kJ mol-‘.

However. 2nd ed. Hilaire. Eden Prairie. M. 59 (1977) 456.L. Surface Sci. These results also raise questions on the nature of the adsorbed oxygen states which have been observed following the high pressure oxidation of gold samples. N. Comsa. Surface Sci. D-34. Commandre. Schrader.I. Commandre and J.E. 118 (1982) 32. Canning et al. Battistoni. Naldini. Maire. administered American Chemical Society for partial support of this research. (CRC Press. Savchenko. Moore. Acknowledgement made to the Donors of the Petroleum Research Fund. Cros. Handbook of X-Ray Photoelectron Spectroscopy (Perkin-Elmer. 29. Sotto and G. M. Evans. Surface Sci. H. Surface Sci. C.M. J.A. 5. Surface Sci. Tricker. 102 (1981) L14.A. 64 (1977) 209. Legare. Bazhutin. Surface Sci.J. Eley and P. Mattogno. F. Ishizaka. formation. Chesters and G. D. 2 (1970) 112. Franken and G. Hor and G. L. S. Electron Spectrosc. 91 (1980) 175. Appl. Pirug. G. A. Brewer and G. MN. J. Somorjai. A.M. 63rd ed. Reaction Kinetics Catalysis Letters 104 (1979) 337. Surface Sci. Hass. J.B. S. 76 (1978) L599. 1983) p. D. Surface Sci. S. P.J. / Ahorption of oxygen on gold 253 adsorption might be measured by studying the adsorption at higher oxygen pressures than those accessible in our UHV apparatus or by employing molecular beam techniques. E. J. Surface Sci. Acknowledgements The authors gratefully acknowledge the support of the National Foundation through grant NSF CPE 80-23815Al. 1976). 84 (1979) 355. D. A. M.K.S. (Physical Electronics. Derrien and F. Surface Sci. p. Niehus and G. Faraday Disc. . M. Surface Sci. C. 103 (1981) L109. Hopefully careful XPS and AES studies will resolve some of these questions. Surface Sci. Somorjai. in: Transition Metals.A.P. Derrien and M. 52 (1975) 21. the results presented here indicate that great care must be taken in cleaning the samples for any attempt to measure this activation energy to be successful and to avoid interference form SiO. Surface Sci. Colloid Interface Sci. Handbook of Auger Electron Spectroscopy. 1979). Handbook of Chemistry and Physics. Ringeisen. Vol. Salvan. Bonzel. Shih. B. Thomas. 112 (1981) 207. Carriere and B. Zanoni and L. Boreskov and V. M.B. J.D.E. Schrader. 78 (1978) L227. M. 58 (1974) 97. H. Iwata and Y. International Review of Science: Inorganic Chemistry Series 2. Derrien. Kamigaki. Related Phenomena 28 (1982) 23.A. Parry. Part 1. Evans.N. R. A. Salmeron.E. Science is also by the References [l] [2] [3] [4] [S] [6] [7] [8] [9] [lo] [ll] [12] [13] [14] [15] 1161 [17] [18] [19] [20] 1211 M. 104 (1981) 625. G. Walters and J. L. 124 (1983) L35. Lang. Navrotsky.

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