Anal. Chem. 1983, 55, 133R-156R (27W) Pressley, T. A.; Longbottom, J. E. Report EPA-600/4-82-008; Order No. PB82-156001, Avail. NTIS, 35 pp (1982). (28W) Pressley, T. A.; Longbottom, J. E. Report EPA-600/4-82-003; Order No. PB82-155979, Avail. NTIS, 23 pp (1982). (29W) Pressley, T. A., Longbottom, J. E. Report EPA-600/4-82-005; Order No. PB82-155995 Avali. NTIS, 24 pp (1982). (30W) Pressley, T. A,; Longbottom, J. E. Report EPA-600/4-82-008; Order No. PB82-156027, Avail. NTIS, 25 pp (1982). (31W) Preesley, T. A.; Longbottom, J. E. Report EPA-600/4-82-004; Order No. PB82-155987, Avail. NTIS, 24 pp (1982). (32W) Puijker, L. M.; Voenendaal, G.; Janssen, H. M. J.; Grleplnk, H. Fresenius’ Z . Anal. Chem., 306, 1-6 (1981); Chem. Abstr., 95, 86034k (198 1). (33W) Ramstad, l’.; Nicholson, L. W. Anal. Chem., 54, 1191-6 (1982). (34W) Rigln, V. I.Z h . Anal. Khlm., 36,1582-7 (1981); Chem. Abstr., 95, 22531611 (1981). (35W) Schuken, H. R.; Sun, 8.E. Int. J. Envlron. Anal. Chem., 70,247-63 (1981); Chem. Abstr., 96, 129428g (1982). (36W) Vaughan, C. W. Anal Chlm. Acta, 737,307-10 (1981). (37W) Voipe, G. G.; Mallet, V. N. Int. J. Environ. Anal. Chem., 8 , 291-301 (1980); Chem. Abstr., 94,1270682 (1981). (38W) Wells, D. E. ,Johnstone, S. J. J . Chromatog. Scl., 79,137-43 (1981). (39W) Wright, L. ki.; Jackson, M. D.; Lewis, R. G. Bull. Envlron. Contam. Toxicol., 28, 740-7 (1982); Chem. Abstr., 97,44000g (1982). ORGANICS-SURFACTANTS (1X) Armstrong, D. W.; Lafranchise, F.; Young, D. Anal. Chlm. Acta, 135, 165-8 (‘1982). (2X) Bhat, S. R.; Crlsp, P. T.; Eckert, J. M.; Gibson, N. A. lbld., 776, 191-3 (1980). (3X) Cosovic, 6.; Vojvodic, V. Llmnol. Oceanogr., 27,361-9 (1982). (4x1 Favretto, L.; Stancher, 6.; Tunis, F. Analyst (London), 705,833-40 (1980). (5X) Favretto, L.; Stancher, El.; Tunis, F. Inf. J . Envlron. Anal. Chem., 70, 23-33 (f981); Cbem. Abstr., 95, 192130~(1981). (6X) Helimann, H. Fresenlus’ Z . Anal. Chem., 304, 129-36 (1980); Chem. Abstr., 95,30074f (1981). (7X) Heilmann, H. ibid., 370, 224-9 (1982); Chem. Absfr., 96, 1294441 (1982). (EX) Higuchi, K.; Shimolshi, Y.; Miyata, H.; Toel, K.; Hayami, T. Analyst (London), 705,768-73 (1980). (9X) Higuchl, K.; Monya, S.;Shimolshi, Y.; Miyata, H.; Toei, K. Bunsekl Kagaku, 29, 180-3 (1980); Chem. Abstr., 93, 155581) (1980). (lox) Hunter, K. A.; Liss, P. S.; Water Res., 75,203-15 (1981); Chem. Abstr., 94, 162498m (1981). (11X) Matsueda, T. BunseklKagaku, 30,375-9 (1981); Chem. Abstr., 95, 103028d (1981). (12X) Matsueda, T.; Morimoto, M. /bid., 29,769-74 (1980); Chem. Abstr., 94. 71037u 11981). (13X) ’ Maisueda, T . Osakl, Y.; Shigee, S. /bid., 37,59-63 (1982); Chem. Abstr.. 96. 188932r (1982). (14X) Motomizu, S.; Fujwara: S.; FuJlwara, A.; Toei, K. Anal. Chem., 5 4 , 392-7 (1982). (15X) Nakae, A.; Tsuji, K.; Yemanaka, M. lbld., 52,2275-7 (1980). (16X) Petts, K. W.; Sliney, I. Water Res., 75, 129-32 (1981); Chem. Abstr., 9 4 , 145066b (1981). (17X) Shiraishi, H.; Otsuki, A.; Fuwa, K. Bull. Chem. SOC. Jpn., 55, 1410-15 (1982); Chem. Abstr., 97,43979w (1982). (18X) Taguchi, S.; Kasahara, I.;Fukushlma, Y.; Goto, K. Talanta, 28 616-18 (1981). (19X) Utsunomiya, A.; Ikeda, T.; Takamatsu, K.; Naito, S . Bunseki Kagaku, 29, 837-42 (1980); Chem. Abstr., 94,2142740 (1981).
(2OX) Yasuda, H. Nippon Kagaku Kaishi, 456-61 (1981); Chem. Abstr., 95, 67687j (1981). (21X) Zhebentyaev, A. I.Glg. Sank., 67-8 (1981); Chem. Abstr., 96, 40611p (1982). ORQANICS-M ISCELLANEOUS (1Y) Giam, C. S.; Trujlllo, D. A,; Klra, S.; Hrung, Y. Bull. Environ. Conlam. Toxicol., 25,824-7 (1980); Chem. Abstr., 94, 1 2 7 0 5 8 ~(1981). (2Y) Potin-butler, M.; Bonastre, J.; Grenier, P. Environ. Techno/. Lett., 7, 464-73 (1980); Chem. Absfr ., 94, 180375~(1981). (3Y) Rathbun, R. E.; Tai, D. Y. Water Res., 75,243-50 (1981); Chem. Abstr., 94, 180383~(1981). (4Y) Sohr, H.; Wienhold, K. Anal. Chim. Acta, 727,309-14 (1980). (5Y) Stojek, 2 . ; Osteryoung, J. Anal. Chem., 53, 847-51 (1981). (6Y) Tigwell, D. C.; Schtieffer, D. J.; Landon, L. lbld., 53,1199-202 (19181). (7Y) Zawadzka, H.; Zerbe. J.; Baraiklewicz, D. Chem. Anal., 25,469-71 (1980); Chem. Abstr., 94,52553t (1981). MISCELLANEOUS (12) Ben-Yaakov, S.; Lazar, B. Talanfa, 27, 1061-6 (1980). (22) Brueggerhoff, S.; Jackwerth, E.; Ralth, 6.; Stratmann, A,; Gonsior, B. Fresenlus’ Z . Anal. Chem., 3 7 1 , 252-8 (1982); . . Chem. Abstr., 96, 205089q (1982). (32) Cahill, T. A,; Shadoan, D. J.; Couper, C. C. Report, Order No. PE380216690, Avail NTIS, 15 pp (1980). (42) Claxton, I. R. Report, TDB-320, Avail., NTIS, 6 pp (1979). (52) Crawford, R . W. Rsport, UCRL-52532, Avall., NTIS, 30 pp (1979). (62) Crowther, J.; Evans, J. J.-Am. Works Assoc., 73, 265-70 (1981). 172) Crowther. J.: Moodv. W. B. Anal. Chim. Acta. 720.305-11 (1980). i82i Garbarino. J . R.: Ta’vlor. H. E. Aool. Soectrosc.. 34. 584-90 i1980i. i92j Garbarino, J. R.; Ttiylor, H. E. Chem. homed. Envlron . Instrum ., 7 i , 289-303 (1981); Chem. Abstr., 96,789762 (1982). (102) Garvis, D. G.; Stuermer, D. H. Water Res., 74, 1525-7 (1980); Chem. Abstr., 94,20134r (1981). (112) Gibb, J. P.; Schullnr, R. M.; Griffin, R. A. U . S . Envlron. Prot. Agency, Off. Res. Dev., (Rep.) €PA, EPA-600/9-80-070, 31-8 (1980). (122) Guest, R. L.; Blutstein, H. Anal. Chem.. 53,727-31 (1981). (132) Habib, S.; Mlnski, J. J. J. Radioanal. Chem., 63, 379-95 (1981). (142) Hiraki, K.; Nishikawa, Y. Bunseki Kagaku, 30,45-50 (1981). (152) Hirata, H.; Arai, M.; Toonooka, N. Nlppon Kagaku Kaishl, 1475-84 (1980); Chem. Abstr., 93,2 1 4 8 0 8 ~(1980). (162) Kaiser, M. L.; Kolrtyohann, S. R.; Hinderberger, E. J.; Taylor, H. E. Spectrochim. Acta, Part 6 368, 773-83 (1981); Chem. Abstr., 96, 96648y (1982). (172) Kim, J. I.; Lux, D.; Fiedler, I. Mlkrochim. Acta, 7, 137-53 (1982); Chem. Abstr., 96,574862 (1982). (182) Laxen, D. P. H.; Harrison, R. M. Anal. Chem., 53,345-50 (1981). (192) Lendermann, 6.; tiundeshagen, D. Fresenius’ Z . Anal. Chem., 3 7 0 , 415-22 119821: Chem. Abstr.. 96. 16383h 119821. (202) McCarthi’J. P.; Jackson, M. E.; Ridgway, T. H.; Caruso, J. A. A,nal. Chem., 53, 1512-16 (1981). (212) Macdonald, R. W.; McLaughlln, F. A. WaterRes., 76,95-104 (1982); Chem. Abstr., 96,1487751 (1982). (222) Massee, R.; Maessen, F. J. M. J.; De Goelj, J. J. M. Anal. Chim. Acta, 127, 181-93 (1981). (232) Owens, J. W.; Ciiadney, E. S.; Purtymun, W. D. Anal. Lett., 73, 253-60 (1980); Chem. Abstr. 93,137753n (1980). (242) Pearson, F. J.-Water Polluf. ControlFed., 53, 1243-52 (1981). (252) Salonen, K. Wal’er Res., 75, 403-6 (1981); Chem. Abstr., 95, 30092k (1981). (262) Wogman, N. A. Report, PNL-3168, Avail. NTIS. 61 pp (1979).
Surface Characterization R. Allen Bowllng and Graydon B. Larrabeel Materials Science Laboratory, Texas Instruments Incorporated, P. 0. Box 225936, MS 147, Dallas, Texas 75265
This review follows the same format used in the three earlier reviews (453,454,541). The references are in general restricted to English-language journals or easily available translations and the surface is defined as the gas-solid interface. The format sorts the information into the substrates on which the surfaces form. The abbreviations used for the various characterization techniques are shown in Table I. Reviews of specific technologies have been published over the 1981-1982 time period. The semiconductor industry continues to record the ever-increasing importance of surfaces 0003-2700/83/0355-133R$06.50/0
in device manufacture and device performance (379). The role of surfaces in the new Very Large Scale Integrated (VLSI) circuits and the militmy version of this effort, Very High Speed Inte rated Circuits (VHSIC),was reviewed for SIMS analysis (7297. The problems associated with surface analysis of Ensulators using SIMS (418) and a number of ways of controlling the surface charging problem were presented. A similar survey of characterization techniques for high-energy switch materials degredation (650)shiows the need for a “synergistic, interdisiplinary microanalytical approach”. The characterization of 0 1983 American Chemical Society
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Table I. Abbreviations AES APS
Auger electron spectroscopy appearance potential spectroscopy change in work function A@ ELL ellipsometry EELS electron energy loss spectroscopy EMP electron microprobe analysis EPR electron paramagnetic resonance ESD electron stimulated desorption ESR electron spin resonance FEM field emission microscopy FIM field ion microscopy IMMA ion microprobe mass analysis ISS ion scattering spectroscopy LEED low-energy electron diffraction MS mass spectroscopy NMR nuclear magnetic resonance Rutherford backscattering RBS RHEED reflection high-energy electron diffraction SAM scanning Auger microscopy SEM scanning electron microscopy SIMS secondary ion mass spectroscopy TD thermal desorption transmission electron microscopy TEM UHV ultrahigh vacuum UV photoelectron spectroscopy UPS XPS X-ray photoelectron spectroscopy (ESCA) XRD X-ray diffraction XRF X-rav fluorescence polycrystalline surfaces using ISS (75) and LEED (72) clearly shows that useful analytical information can be obtained on this analytically challenging substrate. The general area of characterization of adsorbates on solid surfaces was reviewed specifically for AES and XPS (55).
METALS Metal surfaces remain the most widely characterized materials systems. As has been pointed out in earlier reviews, one of the reasons for this focus is the absence of serious charging problems that plague the analysis of surfaces on insulators, glasses, ceramics, polymers, .and other organic materials. In spite of this ease of analysis, the role of surfaces on metals is recognized as paramount; and an understanding of the behavior of materials at metal surfaces and the frequent domination of the behavior and properties of metals by the surface continues to focus attention in this field. Alakli Metals. Lithium battery electrode surfaces have been examined by using XPS and SEM (24),ESCA and SEM (1016) and by electrochemical methods with SEM (137). In each case the formation of lithium compounds was observed and it was the compound that dominated the surface properties of the lithium electode. UPS spectra of lithium films exposed to various alcohols showed the formation of alkoxytype surface species in each case (796). Thin films of Li-B alloys were characterized by using RHEED (481). Lattice relaxation of Na(100) and Na(ll0) surfaces was measured by using LEED (105). The binding energy of one level in atomic cesium was measured with XPS (839). Light Metals. The oxidation of beryllium (0001) was followed in the early stages with AES and an excess of oxygen signal over stoichiometry was observed (299). The oxidation of polycrystalline boron at room temperature was investigated with EELS and AES (755, 756). Both elemental and oxidized boron were observed. Both electrical conductivity and XPS were employed in plasma CVD depositions of boron and boron carbide to show that improved properties of the coating were due to alloying of boron with carbon (354). The oxidation of magnesium has been studied with AES, LEED, and EELS (294), and LEED, EELS, ELL, and A$ (376,654). The adsorption of oxygen on magnesium surfaces has been followed with ELL (516) and XPS (334). A Mg-0 type bonding was observed but the first 4-A layer was a mixture of Mg and MgO. The early stages of oxidation of Mg, Mg-A1, and A1 were studied with XPS and the diode technique (16). Secondary electron emission as a function of oxygen partial pressure was recorded for Mg and A1 using AES (680). The temperature-dependent low-energy electron diffraction intensity 134R
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profiles from aluminum (loo),(110), and (111)were measured (954). The oxidation of (111)aluminum single crystals has been investigated by using EELS (653),XPS (740), and XPS with surface EXAFS (44,670). SIMS has been used to study oxygen adsorption on single crystal aluminum and some of its alloys (586). The interaction of oxygen with polycrystalline aluminum surfaces has been studied with EELS and secondary electron spectroscopy (714) and with AES, EELS, and ESD (136). The ESD technique was the most sensitive for the characterization of "clean" surfaces and to understand the slow growth of the first few angstroms of aluminum oxide. SIMS, AES, and XPS have been employed to determine the composition of the natural oxide film on aluminum foils (903). Surface enrichment of impurities during the oxidation process was observed with SIMS (903,211). A blue surface observed during high-temperature oxidation of Al(111) was suggested to arise from an optically excited transfer between the aluminum metal Fermi level and the aluminum oxide conduction band (381). The failure of bonds on semiconductor chips was shown to be caused by fluorine contamination, using AES, XPS, and SEM (348). Hydrogen physisorption on aluminum and alumina surfaces was investigated with EELS and no hydrogen was detected on clean aluminum but was observed on the alumina surfaces (715). The interaction of carbon monoxide on various single crystal aluminum surfaces has been investigated with AES and ESD (295),EELS (62),and LEED, AES, EELS, and A$ (483). Both hydrogen and ethylene were observed to adsorb dissociatively on Al(100) (482) and were found to be incorporated into ordered islands at intermediate exposures. Enhanced Raman scattering from aluminum f i i s indicates that two broad peaks were probably a disordered graphitic carbon layer (562). Passivation of aluminum surfaces via the reaction of various chemicals in aqueous solutions has received considerable attention. RBS (600), XPS (513, 731, 919),and AES with XPS (593,866) have been used in these passivation investigations. Surface changes during electrochemical etching were interpreted by using optical microscopy (253). The influence of additions of elements such as Cr, Cu, and Li with Al-Zn-Mg alloys on the oxidation process was investigated (210). The formation of polymer films during the etching of aluminum in CCll plasmas was studied with AES, XPS, and FTIR (651). The initial stages of oxidation of pure liquid aluminum at 973 K was studied with AES and, simultaneously, the effect of oxygen on the surface tension of liquid aluminum was measured by the sessile drop technique (343). The electronic structure of Ag on Al(100) (257), and Au, Ag, and Cu on Al(100) (256) were determined with XPS. AES profiling was used to characterize oxide films grown on A1-Cu alloys in order to establish the behavior of the interface between two layers of this same A1-Cu alloy (990). Titanium (OOO1) surface state densities were determined with appearance potential spectroscopy (629). Titanium coatings were shown to become mechanically and chemically unstable because of the formation of titanium hydride (477) and this could be avoided by high temperatures, above 400 "C. The interaction and dissociation of water on Ti(001) was characterized with UPS, photon stimulated desorption, and ESD (862). Hydrogen diffusion into and out of titanium during DC plasma discharge was investigated with in situ thermogravimetry (120). Clean samples became embrittled and desorbed hydrogen, while oxygen-contaminated samples showed limited hydrogen absorption. The migration of chlorine on a Ti-Al alloy surface during electron bombardment was observed with AES (111). Copper. A study of LEED fine structure on the low index planes of copper revealed that surface barrier resonances were present on all planes at low angles (908). The interlayer spacings in the Cu(ll0) surface were shown to exhibit a damped oscillatory deviation from the bulk value, using LEED and ISS (5). Leed analysis of Cu(100) surfaces indicated that LEED structural analysis of clean metallic surfaces can be sensitive to changes on the order of 0.02 A in atomic spacing (669). The structure of the first and second surface layers of Cu(ll0) was investigated with low-energy (keV) Ne+ and HzO+ scattering (127). This same technique was used to show the reconstruction of the oxy en covered Cu(ll0) surface (128). Clean and oxygen-coveretcopper single crystal surfaces were characterized with spectroscopic ELL in an AES/LEED UHV system (369). UPS showed no chemical interaction at 7 K between oxygen and copper films or clusters. Between 40 and
SURFACE CHARACTERIZATION manager Of me Materia$ Cheradedzah Branch hr Malerisk S c h c ~ Lahatmy of Texas IMOumens. Inc. He pinedme m m p n y in 1959 as a radlabamist. His curent wlxk is dlrected toward developing advanced tech niqurs lor ylmiconduclo( materials dlaracIerkaUon using electron h m (scanning Auger) and In microprobe techniques l a Chemical lmprfections, X.my topography. and scanning hansmirrbn electron micro$copy techniques tor physical imperfectbns. Lamabee earned a B.Sc. horn me University
eqon I). L.nabn Is a
..
. ',
r m h d hk B.S h chem kwy horn me Unlversny of Alabama and a R. Anan So-
PhD. in Chemkwy horn me Unlversw of TmnaHe held an Alexander ~n HumbOM postdoctoral research posnlm a1 me InstiMe of lnagsntc Chemkby. Unlverslty of Frankfurt. West Germany. from March 1979 lo July 1980 He JoinedTexas lnswuments Incorporated In September 1980 as a pmcBss conwol engineer I" a 8Bmlmnducta pmesing area In Janualy 1982. he -me a membsr 01 me technC cai staff in me Materla1s Wlaracterization Branch 01 me Materials Science Labwatwy of Texas Im~menls.where he k presentb responsible t a Auger and XPS inshumentah Bowling 15 a member of the EleChochemlcaI Society and lhe American Vacuum Society
100 K, molecular chemisorbed oxygen WBB observed and a t room temperature only copper oxide remained (789). Oxygen adsorption on Cu(lo0) and Cu(ll0) surfaces (857)and Cu(ll1) surfaces (858) has been investigated with UPS, EELS, LEED, and A@. Oxygen adsorption on Cu(ll0) was investigated with helium ISS (540) and with LEED and EELS (980). In the latter study single vibrational energies were observed for I6O and laO. A RHEED study of oxygen adsorption on stepped copper surfaces (612)supported the idea of enhanced stability being due to a 'fit" between the adsorption structure and the terrace width. Angle resolved UPS was used to show that on Cu(1OO) surfaces oxygen chemisorption is followed hy incorporation into the bulk and fmally hy copper(1)oxide formation (559). A similar study on Cu(ll1) was performed with highresolution EELS as a function of temperature (247). The coadsorption of oxygen and carbon on copper surfaces was studied with AES and LEED (678) and of oxygen and sulfur, with AES (32). The adsorption of water on clean and oxygen-covered Cu(ll0) was studied hy means of UPS, LEED, EELS, and A 4 (859). In this latter study the effects of temperature on the adsorption process were elucidated and dissociation of the water molecules was observed on an oxygencovered surface. Surface enhanced Raman spectroscopy has also been used to observe water adsorption on copper surfaces (728). Close packed hexagonal structures were observed with LEED during krypton and argon adsorption on Cu(ll0) (407). The same results were reported for this Xe-Cu system using angle resolved UPS (583). The adsorption of xenon on Cu(001) surfaces was investigated with ISS and the effects of various degrees of coverageon the spectra were reported (589). Two distinct stages were observed for the dissociative chemisorption of bromine on Cu(OO1) using angle resolved UPS (749). LEED and XPS were employed in studying suhmonolayers of iodine on Cu(ll1) (240). Hexagonal close packed structures were reported for cesium adsorption on Cu(100) and the presence of oxygen caused disordering of the cesium (701). LEED, AES,and UPS studies of manganese overlayers on Cu(l00) showed 4-fold hollow sites a t low coverage and disordered layer by layer growth at higher coverage (98). The same results were reported for LEED and AES studies of lead on Cu(1OO) (395). T h e epitaxial growth of thallium on Cu(100) was observed with LEED, AES, UPS, and EELS (99). Lead
and tin adsorption on Cu(100) and Cu(410) were shown to follow ordered growth patterns using LEED and AES (30). The adsorption of carbon monoxide on single-crystal copper surfaces has been followed with infrared spectroscopy (722, and LEED, EELS, and infrared 769).EELS (856).XPS (58), spectroscopy (97). Angle-resolved UPS was employed during the study of the molecular adsorption of carbon monoxide on clean and sodium-covered Cu(ll1) (558). An EELS study of nitric oxide adsorption on Cu(1OO) and 4111) was performed and distinct differences were observed for the two surfaces (981). Chemisorption of HCI and H a hy C u ( l 1 1 ) a surfaces was shown by XPS (640) to involve hydrogen abstraction with the formation of surface hydroxyl groups. Cyanide complexes on copper electrodes were measured with surface Raman spectroscopy and correlated with cyclic voltammetry (80). Ethylene and acetylene adsorption on Cu(ll1) was investiated with AES and the nature of the meta-adsorhate %ondlng determined from changes in the Auger spectra (150). Methyl, ethyl, and isopropyl alcohol adsorbed on clean Cu(ll0) faces were followed with UPS (155)and the rates of adsorption and desorption were determined. AES, EELS, and TD measurements of the interaction of cyanogen with Cu(ll1) surfaces showed dissociative adsorption, and an activation energy of 180 kJ/mol for desorption was calculated (852). The adsorption and decomposition of HNCO on Cu(ll1) and the effects of oxygen on the dissociative processes were investigated with AES,EELS, and TD (854). The same type of study was performed for formaldehyde and formic acid (115),alcohols (116),and formaldehyde and acetic acid (117) on the Cu(ll0) surface hy using XPS, UPS,and TD. Copper surfaces passivated with benzimidazole (C,H,N,) (550).henzotriazole (C6H,N,) (4801,and henzenethiol (C,H,S) ( 7 ) were analyzed in efforts to understand the film compositions. UPS spectroscopy of sulfur heterocycles adsorbed onto a Cu(ll0) surface showed marked angular dependence which suggests nonrandom orientation on the surface (907). Cu(lM))-Ni surfaces were prepared and reactivity was monitored with AES and ELL. At low nickel concentration the nickel atoms appeared to be helow the first monolayer of copper atoms and were incapable of hinding CO a t room temperature (608,730). ELL, AES, and LEED were used to study the interaction of oxygen with a Cu(ll0)-Ni surface alloy and the reaction of hydrogen and CO with the adsorbed oxygen (607). The interdiffusion of a Cu-Ni thin film was measured with AES (551). Hydrogen desorption from Ni sites on Cu(ll0)-Ni surfaces was followed with TD and the spectra showed a coverage dependence similar to that known for pure Ni(ll0) (170). Combined SIMS/XPS was used for the study of CO and oxygen adsorption on Cu-Ni and Cu surfaces (134). Combined XPS/AES showed extensive segregation of copper to the high and low index surfaces of a Cu-Ni alloy (976). A static-SIMS study of preferential sputtering on a Cu-Ni alloy surface was compared to earlier data by using AES, and it was concluded that 'different" layers were observed by each technique (918). The epitaxial growth of Cu-Cu and Ag-Cu was followed with AES by observing changes in Auger line shape (955). The electronic structure of the a-pbase of Cu-Ni alloys was investigated with UPS (54). Scanning AES was used to study the formation of brass from two separately electrodeposited layers of Cu and Zn (865). Grain houndry emhrittlement in Cu-3Al-1Si was studied with AES (984). The segregation of sulfur on the surface of Cu-Ni alloys after high-temperature treatmenta was followed with scnnning AES (425). Surface segregation on Cu-Ni and Cu-Ag alloys was investigated with XPS (391). Chromium. The initial stages of the interaction of oxygen with a Cr(ll0) surface was investigated with LEED, AES, EELS, secondary electron emission, and A 4 (776). Clean and oxidized chromium surfaces were analyzed with AES and EELS (310). EELS and secondary electron emission studies of hydrogen-covered Cr(ll0) surfaces indicated that Cr-H bonding occurred mainly via sp bonds (461). Chlorine adsorption on Cr(100) has been studied with AES, UPS, XPS, LEED, TD, and A 4 (297). A t higher chlorine exposures epitaxial growth of chromium dichloride was observed. The dissociative chemisorption of carbon monoxide on Cr(ll0) was investigated, using EELS (460). Oxide formation on (001), (Oll), (ill)! and (113) surfaces of Cr thin films was examined with scanning TEM and a mechanism for the formation of the oxides was deduced (971, 972). ANALYTICAL CHEMISTRY, VOL. 55. NO. 5, APRIL 1983
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Iron, Cobalt and Nickel. A clean Fe(ll1) surface was prepared and studied by using AES and LEED. The LEED intensity analysis was carried out with a new computational scheme designed for short interlevel spacings (829). The chemisorption of hydrogen on Fe(ll0) was studied by using EELS (68) and it was concluded that hydrogen occupies the short bridge site on Fe(ll0). A fast video LEED system monitored the dissociative adsorption of hydrogen on Fe(110) (426) enabling minimization of electron beam and contamination effects. XPS combined with thermodynamic estimations were used to develop a closed model of the boriding of iron surfaces (904). The interactions and adsorption of hydrogen and nitrogen on iron were investigated with AES and TD (271) and showed that dissociative nitrogen adsorption was the rate-limiting step of ammonia synthesis. The adsorption of nitrogen on potassium-promoted Fe(ll1) and (100) surfaces was increased by enhanced electron density due to charge transfer from potassium (272). Similar promoter action was reported for potassium plus oxygen on iron surfaces for nitrogen adsorption (696). In this latter work AES, TD, A$ were used to understand the enhanced nitrogen adsorption. The initial stages of high temperature oxidation of iron have been studied with XPS and UPS (1014),as well as with LEED and AES (953). The composition and structure of epitaxial oxide layers on Fe(ll0) crystal faces were reported (539). Mossbauer spectroscopy has been applied to the characterization of thin oxide layers on iron surfaces (830, 261). The oxidation of iron with O2and HzO has been followed with AES and XPS (926) where the rates of uptake of oxygen and water were determined. LEED, AES, TD and A$ were used to show that the heat of adsorption of potassium decreased from its initial value (Fe(llO), 57; Fe(100), 54; F e ( l l l ) , 52 kcal/mol) continuously with increasing coverage (545). The surface reaction of polycrystalline iron with H2S was studied in situ with XPS (657) over the temperature range 100-773 K and sulfidation was found to proceed at higher rates on oxidized iron than on sputter-cleaned iron. XPS, AES, and EELS studies of phosphorus on a-iron surfaces (258) detected two different phosphorus species. The chemisorption of CO on Fe(ll0) surfaces was investigated at 120 K using LEED and EELS (266). Thermal desorption of CO from Fe(ll0) induced by laser pulses was recorded with mass spectroscopy (978)and was shown to be a function of laser pulse intensity and CO coverage. The coadsorption of CO and Hz was studied by TD and X P S (84) and a new surface species was identified. EELS spectra of ammonia adsorbed on Fe(ll0) revealed three different adsorption states of molecular ammonia (269). Vibrational spectra of normal and deuterated acetylene and ethylene adsorbed on Fe(ll0) were recorded using EELS (268). EELS was also used to study the adsorption of H20 at 130 K on Fe(ll0) (69) and it was found that two different bonding configurations, OH-0 and OH-Fe, were active. The chemisorption and decompositionof propyne on clean Fe(ll0) and -(loo) was investigated with UPS (888). The nature of the passive f i i on iron has been studied by using ELL (172),XPS and SIMS (912),SIMS (649),electron diffraction (533),and XPS (518). The hydrogen storage capacities of Fe-Ti alloys were investigated with XPS and Mossbauer spectroscopy (620) and it was shown that excess Ti reduced surface sensitivity. AES and XPS were employed to show that the addition of Mn improved the hydrogenation characteristics of Fe-Ti alloys (809). Scanning AES was used to demonstrate interactive cosegregation of Sb and Ni a t grain boundaries of these iron-base alloys (325). The interaction of nickel carbonyl with evaporated iron surfaces was followed with XPS (488). The decomposition of formic acid on Fe-Ni alloys was examined with temperature programmed reaction spectroscopy (833). XPS coupled with electrochemical measurements established the composition and role of the surface of Fe-Ni alloys during dissolution and passivation (581). AES, SIMS, and XPS were used to characterize the passive film on Fe-Cr alloys (911). The (100) surface of a 50-50 Fe-Co alloy was analyzed with LEED and AES (18, 19). Superlattices formed by the interaction of iodine, water, and oxygen with the (111)surface of an Fe-Cr-Ni alloy were established with LEED, AES, and TD (323). Passive layers on amorphous Fe-Ni-Cr-Pb alloys were analyzed with AES and X P S (52,50). Anodic oxide films formed on stainless steel were analyzed with XPS, SIMS, and AES (910), and chromium enrichment in the passive film was 136R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
observed. Oxide and sulfide scales formed on sputter-deposited 304 stainless steel at 800 and 950 "C were characterized by using AES (51). An automated scanning proton microbeam (141)was used in the investigation of the oxidation of stainless steel with lSO. XPS was used in the study of Co and Ni cation inhibitors for galvanized steel (548). AES was performed on surface deposits formed on stainless steel and Inconel by exposure to plasma discharges in a tokomak (848). A cross comparison of LEED intensity data showed that sulfur atoms were adsorbed on Co(OO1) in a 4-fold site (571). The temperature-dependent oxidation of Co(OOO1) was shown with LEED and AES to form COObelow 150 "C, and exposure above 700 "C resulted in no distinct chemisorbed phase (594). AES, XPS, and FTIR studies of Co catalytic behavior showed carbon buildup during carbon monoxide decomposition which deactivated the catalyst (626). The orientation of carbon monoxide molecules chemisorbed on Co(O001) was established with angle resolved XPS and LEED (383). Chemisorption of NO and NH3 on Co was investigated with UPS, XPS, and 44 (311). Differences in the adsorption and decomposition of water on three different crystallographic surfaces of Co were measured with LEED, UPS, and TD (382). LEED analyses of various crystallographic faces of singlecrystal Ni have been performed and interpreted (185,330,331, 439,627,628,643). Hydrogen ion studies of the crystallography of Ni surfaces have been performed with RBS (841)and, when combined with channeling and blocking data revealed a missing row of atoms in the oxygen induced (2 X 1)surface of Ni(ll0). Low-energy He scattering from Ni(001) (419),and Ni(ll0) (265,555) have been used to elucidate the structures of clean and oxygen-coveredsurfaces. Surface damage on a Ni(100) surface induced by 1-keV Ar ion bombardment has been studied with LEED (949) which indicates that the damage structures consist of surface pits with a width of a few hundred angstroms and a depth of 5 atomic layers. RBS, AES, and LEED showed that on oxygen-adsorbed Ni(ll1) surfaces each oxygen atom interacts with and relaxes three nearest neighbor nickel atoms (658). The structures of oxygen-covered Ni(110) surfaces have also been investigated with LEED, EELS, AES, and 44 (592). The chemisorption of oxygen on Ni(100) at 850 "C under equilibrium conditions was performed in a solid electrolyte cell and AES was used to study the adsorption isotherms (344). The chemisorption and oxide formation was reported to follow three stages-chemisorption, oxide nucleation and lateral growth to coalescence, and thickening of coalesced oxide (400). LEED and AES were employed to establish the effects of temperature upon NiO formation and oxygen removal on Ni(ll0) (401);the activation energy of growth of NiO was found to be 5.5 kcal mol. Polycrystalline Ni oxidation was investigated with soft 4-ray APS and inverse photoemission and the results agreed well with UPS data (786). The kinetics of the initial oxidation of Ni(ll1) and (211) were measured with RHEED and X-ray emission (613). The spectrum of the vibrational frequencies of isolated adatoms and of overla ers of oxygen on Ni(100) surface were determined by using JELS (100). The oxidation of Ni(100) was studied with RBS and the results were consistent with the lateral growth of NiO islands (840). The CO, and N2 on Ni(ll0) at 20 K was shown adsorption of 02, with UPS to involve chemisorptive bonding for the first adsorbate layer (413). The adsorption of oxygen on alkali-(Na, K, Cs)-covered Ni(100) surfaces was shown to be enhanced due to increased electron charge in the surface (491). Static SIMS investigation of oxygen interaction with (001) and (111) Ni surfaces clearly demonstrated the intervention of residual hydrogenated compounds from the UHV (114). The interaction of nickel surfaces with inert gases has been measured with helium diffraction (751),UPS (435),and LEED with TD and A$ (182). The bonding of molecular nitrogen on Ni(ll0) surfaces was studied with angle resolved photoelectron spectroscopy and inelastic electron scattering (406) and the N-N and Ni-N2 stretching frequencies indicate that the Nz molecule is terminally bonded to a single nickel atom on Ni(ll0). The surface behavior of Ni(ll0) after N2 ion implantation and thermal annealing was followed by using LEED, EELS, AES, and secondary electron spectroscopy (757). Angle resolved photoelectron spectroscopy detected two ordered sulfur layers on Ni(ll1) (153). AES and SIMS were employed to detect sulfur and chlorine at grain boundries of nickel without fracturing the specimen and chlorine seg-
SURFACE CHARACTERIZATION
regation at grain bowdries was shown for the first time (312). The chemisorption of chlorine at the (110) faces of Ni, Pd, and Pt at 300 K was studied with LEED, AES, TD, and A@ (267). Iodine adsorption on Ni(100) planes was shown to form a c(2 X 2) structure and that complete desorption could only be achieved at temperatures greater than 1000 OC (444). The adsorption kinetics of hydrogen on Ni(ll1) and -(110) and the effect of preadsorption of oxygen on the sticking coefficients were reported (1000). Direct evidence of a linear relationship between the intensity ratio Ni2H+:Ni2+and the relative coverage of the surface by chemisorbed hydrogen was established with SIMS and TD (82). A molecular beam diffraction study of H2adsorptiion on Ni(ll0) revealed four homogeneous ordered phases as coverage was increased and the substrate temperature was maintained at 100 K (264). The room temperature adsorption and nature of hydrogen bonding to Ni(111)WHS determined with angle-resolved XPS (351). The effects of preaclsorbed electronegativeatoms, C1, S, and P, on the adsorption-desorption of H2 and CO on Ni(100) was studied by using LEED, AES, and TD (490). UPS was employed to confirm earlier TD data on hydrogen coadsorption with CO (506). The adsorption-desorption of Hz and CO on Ni(100), Ni(100)-p(2 X 2)s and Ni(100)-c(2 X 2)s was investigated with programmed TD (442), and the sulfur surface was shown to reduce the amount of CO adsorbed. AES, SIMS, and LEED were em loyed to compare the chemisorption behavior of Hz and d o n carbided and nitrided surfaces (489) and it was confirmed that adatom electronegativity rather than radius is primarily responsible for modification of chemisorption behavior. The interaction of CO with Ni(100) has been studied with AES and ELL and the rate of oxidation of the surface carbide was determined (473). The dissociation probability of CO on alkali-metal covered Ni(100) was shown to increase in the sequence Na, K, Cs using AES and TD (492). The dipole moment of an adsorbed CO molecule was determined to be 0.28 D with a negative end of the molecule projecting out froin the Ni(ll1) surface (147). The relationship between the secondary ion emission and CO adsorption on Ni(ll1) and Ni(100) was established by use of SIMS (191,293). The oxidation of carbidic monolayers on Ni(ll0) (783) identified a surface rearrangement at 500 K producing two carbon species which reacted with oxygen. The reaction of CO and O2on Ni(100) was shown to be stronglydependent on ordering characteristics (679). EELS was employed for the investigation of the interaction of CO with nickel surfaces (90,667). LEED was used to determine the bonding distance of c(2 X 2)-0 on Ni(001) (915). The interaction of H2 and H 2 0 with Ni-0 surfaces with static SIMS showed the presence of OH groups (113). Water interactions with nickel and oxygenprecovered nickel surfaces were studied with UPS, TD, EELS, XPS, and A@ (77-79) as well as with ESD, LEED, and T D (569). The adsorption, decomposition,and desorption of NO on Ni(ll1) was followed with XPS, UPS, AES, and LEED between 125 and 1000 K (119). ESD and LEED were combined in an investigation of the behavior of NO on Ni(ll1) and striking structural changes were seen over the 80-250 K temperature range (663). A LEED analysis of the Ni(001)-c(2 X 2)NO system at room temperature indicated dissociation of the NO molecule and random occupation by the N and 0 atoms of half the available 4-fold hollow sites (708). The structure of NI& on Ni(ll1) as determined by angle resolved UPS was a well-defined azimuthal registration with the Ni, but this could not be confirmed with ESD (568). Oxygendosed Ni(ll1) surfaces also revealed this high degree of azimuthal ordering (664). The absence of a magnetocatalytic effect for the decompositionof NHS on nickel was established (273). Increasing the NH3 coverage beyond one monolayer on Ni(ll0) produces a physisorbed monolayer (436). Angle resolved UPS was used to determine the structure and bonding of NH, chemisorbed on Ni(ll1) (804). At temperatures above 350 K only atomic nitrogen was observed to populate the Ni(ll0) surface after NH3ex osures (362). SIMS and TD $wereapplied to ethylene exposexnickel surfaces over the temperature range 80-1200 K (83). Acetylene chemisorption by Ni(100) (158) and Ni(ll1) (157) was characterized with LEED. Surface layers on nickel of nitrobenzene (145), acetonitrile (487), and stearic acid (892) have been investigated. Surface analysis of Raney nickel alloys was performed with XPS, AES, and SIMS (497). The adsorption of hydrogen on
Ni-Cu alloys was followed with flash desorption spectroscopy (834) and only at Cu concentrations greater than 25% was hydrogen coverage at saturation affected. The oxidation of Ni-Fe alloys was studied with AES and electron diffraction (349) as well as with XPS (121). Scanning AES crater edge profiling of Ni-Cr films (1023) was shown to be superior to ion sputter profiling (287). The oxidation and subsequent reduction of Ni-Cr alloys were followed with scanning AES and XPS (849). The topography and composition of nickel alloys bombarded with 10-keV He and Ar ions was determined (569). SIMS was employed to investigate the composition of oxide films that were grown on Incoloy-800 surfaces with hot steam (181). Refractory Metals. The clean V(100)-(5 X 1)surface proposed from LEED data (218) was later shown to be due to oxygen in the surface region (440,441). The preparation and characterization of the structure of a clean V(110) surface was reported (4). The permeation of hydrogen through1 vanadium over the temperature range 578-1072 K was measured and a surface oxidie layer was identified to exert a barrier to the hydrogen penetration (655). XPS was used in the preparation and characlsrization of vanadium compounds on silica gel (408,409). LEED examination of the structure of the (001) surface of Nb showed the (1X 1)diffraction pattern to prevail over the 15-1000 K temperature range (604). A method of preparing clean Nb surfaces and an understanding of the oxidation process were accomplished through the use of AES and UPS (611,457). A LEED analysis of a Mo(110) clean surface was performed and a contraction of about 1.6 f 2% from the bulk interlayer spacing was observed (324). LEED, ESD, and A$ measurements of changes in surface properties caused by the adsorption of CO, 02,and N2 on Mo(001) indicated that adsorbates, like hydrogen, induce a rearrangement of the Mo surface (81I). The presence of either oxygen or carbon was shown to severely hinder the ability of Mo(100) to dissociatively adsorb H2 or CO (502). The kinetics of the thermal desorption of CO from Mo(001) was studied by use of TJPS (810). SIMS showed that oxygen grain boundry enrichment during Mo oxidation was the cause of surface fracture (493). The structure of sulfur-adsorbed Mo(001) surfaces was determined with LEED (184) and it was shown that CO adsorption was inhibited by the sulfur overlayer. Well-defimed surface structures were generated during Clz adsorption on Mo(ll0) and a model was developed based on the LEED and AES data (186). The reactions of formaldehyde and methanol (501) and trimethylamine (963) on Mo(100) were characterized. Coatings on molybdenum for fusion reactor applications have been investigated with various surface characterization techniques (313, 675). The surface structure of single-crystal tungsten surfaces has continued to receive considerable attention. The W(OO1) surface was examined with LEED (227,280, 603,861, 9'64), EELS (40),FIM (925),and angle-resolved secondary electron spectroscopy (78511. Conflicts within the last decade of experimental data were examined, and it was concluded that the majority of the results were mutually compatible (605). LEED work has been extended to the W(110) surface (63,319). The structure of the surface barrier of W(ll0) was investigixted by the analysis of surface resonance spectra (64). The LElED fine structure accentuation induced by H2 adsorption was felt to be an indication of ordered chemisorption in interstitial sites on W(110) (66). A polarized LEED study of temperature and H2 induced reconstruction on ordering of W(lO0) was performed (967, 968). Hydrogen chemisorption on W(1110) was investigated with LEED (65), and angle-resolved IJPS (101,403). ESD was employed in a study of the adsorption of neon on tungsten (270). Auger neutralization of multiply charged neon ions at a tungsten surface was examined through observation of the ejected electron energy distributions (9'45). The coadsorption of H2 and O2 has been characterized with LEED (67) and UPS (937). The adsorption of oxygen on W(ll0) at 26 K was investigated by means of UPS and XPS (685)and atomic oxygen was first adsorbed before adsorption of molecular oxygen occurred. Chlorine adsorption on W( 110) was examined with AES, LEED, EELS, ESD, TD, and A+ (525);saturation coverage was one monolayer and a desorption energy of 3.77 eV was measured. XPS and UPS were employed in determining the horizontal and vertical configurations of molecular N 2 0 on W(ll0) and Ru(001) (932). The ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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SURFACE CHARACTERIZATION
(110) face of tungsten was found to be partially reconstructed after exposure to nitric oxide and Nz was liberated when heated to 975 K (743). The effect of spin on the final state for UPS and EELS was examined for the system a-CO/W(110) (745). The first XPS data were reported for ammonia adsorption, condensation, and decomposition on a W(110) surface (361). Chemisorption and physisorption of acetylene on W(100) at 80 K were analyzed by use of Auger energy shifts (298). The dissociative chemisorptionof sulfur on W(100) was shown to occur without surface reconstruction (705). The chemical bonding of W-Si was investigated with XPS (13). An angle-resolved investigation of Auger electrons from Cu and Au adsorbed on W(ll0) was performed (515). The epitaxial growth of Fe(ll0) on W(110) at 500 K was analyzed with LEED and AES (345). Adsorption of monolayer amounts of Bi on W(l00) surfaces has been studied with FEM and LEED (443). Pd films from zero to several monolayers on W(100) were studied with AES, LEED, TD, Aq5 (737). Selenium (703) and tellurium (702,704) adsorption on W surfaces have been studied with AES, LEED, and TD. A new metastable state of Cs adatoms on W(ll0) was reported (11). SEM observations of Cs monolayers on polycrystalline W was combined with work-function techniques to show the rapid reaction with CO and redistribution of molecular positions on gentle heating (12). Cs adsorption on an oxygen-covered W(110) surface was followed by using LEED, AES, TD, and Aq5 (700). FEM was used in a study of the coadsorption of Pb on carbon-tungsten single-crystal surfaces (638). The surface diffusion of Pb was observed in this latter work and in subsequent work (637). Synchrotron radiation photoemission spectroscopy measurements were performed on W dispenser cathodes (173). Preferential sputtering and surface segregation of W were observed in an AES study of W-Mo alloys (224). The electrocatalytic activity of cubic sodium tungsten bronze was studied, using SEM, AES, SIMS, and cyclic voltammetry (93). The chemisorption of NO on Re was studied with XPS (797) and at room temperature only dissociative adsorption occurs. AES studies of argon induced desorption of carbon from tantalum were performed (716). A variety of LEED structures were observed during chlorine adsorption on Ta(110) (864). UPS and XPS chemical shifts were seen during H2 and O2 adsorption on Ta(ll1) (937). Precious Metals. The infrared band associated with the adsorption of CO on Ru(001) was interpreted based on a random configuration of adsorbed molecules and nearest neighbor interactions (973). X P S , UPS, TD, and Aq5 were used in the study of the coadsorption of H and CO on Ru(001) (713) and the sticking coefficient of C d was observed to decrease in proportion to the amount of uncovered Ru sites. Xenon atoms were observed to adsorb on both step and terrace sites on Ru(0001) by using UPS, AES, LEED, TD, and A@ techniques (966). The chemisorption of 0 2 and NzO on Cu/Ru(001) was measured with AES and the presence of 0.02 monolayer of Cu retards the initial dissociation of N20 by 40% but had little effect on the uptake of oxygen (825). The titration of oxygen chemisorbed on Ru(001) by H2 at low pressures was characterized with AES and XPS (826). The OH stretch in the infrared spectrum of H 2 0 adsorbed on Ru(001) indicated the presence of hydrogen bonded clusters (526). The ESD angular distributions of H 0 and NH3 on Ru(001) were interpreted (191). XPS, UPd, and TD were employed in a study of the adsorption of NzO on Ru(001) (485). The adsorption of cyclohexane on Ru(001) was investigated with EELS and U P S and it was not found necessary to assume hydrogen bonding to the metal surface (396). UPS studies of the thermal desorption of CO from the Cu-covered Ru(OOO1) surface indicated that more CO adsorbs on the first Cu layer than on bulk Cu (750). The electronic properties of several oxides of Ru were determined with XPS (602). The adsorption and desorption of CO on Rh surfaces was investigated by using UPS (53), FEM and TD (339), and LEED (508). The coadsorption of Dz and CO on Rh(100) at low temperatures was followed with TD and LEED (484);they showed that the presence of CO on the surface reduces the sticking coefficient of deuterium and that the thermal desortion of deuterium is strongly influenced by postdosed CO. Thermal desorption mass spectroscopy of NO, H2, and CO coadsorption on polycrystalline Rh indicated that they coadsorb on the surface but that NO desorbs as N2 and 0 2 (609). The NO molecule was observed to adsorb dissociatively 138R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
on alumina-supported Rh (228) and the nitrogen reacts with hydroxyl groups to form a RhNH, species. Chlorine was found to adsorb readily on Rh(ll1) at 300 K via a mobile precursor state to form a chemisorbed overlayer; the activation energy of the C1 desorption was 160 kJ/mol (199). AES, flash desorption, and CO titration were used to characterize the adsorption of SO2 on Rh(ll0) and P t ( l l 0 ) (528) and heats of desorption of 225 kJ/mol were obtained. The structure of the Rh(lll)-(2 X 2)-CzHz overlayer that was obtained upon the adsorption of ethylene was determined by using a LEED intensity analysis (509). Islands of carbon created on a 90% Rh-10% Pt(ll1) surface by electron beam cracking were found to be one monolayer thick and about 60 pm in diameter (402). The adsorption of Ag, Oz, and NzO on Ag/Rh(100) was followed with AES and LEED (213) and simple site blocking explained the influence of Ag on Oz and N20 chemisorption. The adsorption of sulfur on Pd(100) (87) and on Pd(ll0) (718) was studied with LEED and AES. The interaction of 02 and H on Pd-Au alloys of various compositions was investigatecfwithAES and XPS (385),and it was observed that a hydrogen treatment at 350 "C caused complete reduction of the surface oxide. Hydrogen dissociation on clean and contaminated Pd surfaces was studied with a Pd-MOS structure (724, 723) and, when combined with XPS and Aq5, measurements were able to detect as little as 0.001 monolayer of hydrogen. The relationships between surface oxide reconstruction and bulk oxidation of Pd(100) was elucidated with LEED, AES, and EELS (686). The interaction of Oz and Hz on Pd(ll1) and polycrystalline Pd was studied over a wide range of pressures and temperatures with LEED, AES, UPS, and XPS (546) and the different steps of the formation of palladium oxide were characterized. The Pd(331) surface was found to thermally facet at temperatures reater than 900 K to a surface containing a mixture of (3205, (230), and (111) planes. The original surface could be restored with O2at 300 K and was also stabilized by the presence of sulfur contamination (219). Three types of oxides were identified that could be responsible for the known surface property modifications that occur with oxygen pretreatments. Si-stabilized oxides were also identified in this same Pd study with AES and UPS (49). The adsorption of CO and 0 on islands of Pd about 7 monolayers thick was investigatecfwith TD and AES (734) and CO was found to decompose much less on the islands grown on W(110)-c(14 X 7)-0 than on small Pd particles. AES and TD were used to show less adsorption of CO on a phosphorous-covered Pd surface than on a clean Pd surface (876). The adsorption of CO on Pd(100) was followed with infrared reflection absorption spectroscopy (687). Both TEM and TD were employed (535)to characterize the low pressure catalytic activity of evaporated Pd particles. Ethylene (326, 479) and acetylene (327) adsorption and reaction on Pd(ll1) were examined with EELS. Angle resolved photoemission was used to confirm the orientation of benzene on Pd(100) (398). The oxidation of Pd by oxygen supplied by decomposition of a poly(ethy1ene terephthalate) support film was confirmed with XPS (851). The clean (100) and (110) surfaces of Ir, Pt, and Au were shown to have stable reconstruction phases (538);the periodicity of all three (100) faces was 2 X l. The surface reconstruction of Ir(100), Pt(100), and Au(100) was found to be best described by a hexagonal rearrangement of the top monolayer based on the analysis of LEED intensities (942, 943). Cs adsorbed on clean (100) and (110) surfaces of Ir, Pt, and Au was found not to cause surface reconstruction and therefore oriented at the reconstructed surface (644). The desorption of hydrogen from Ir(100) and Ir(ll0) was investigated with field emission thermal desorption spectroscopy (233) and five desorption features were seen on the (100) face and three on the (110) face. The molecular chemisorption of Nz and the coadsorption of H2on the reconstructed Ir(ll0)-(1 X 2) surface was studied with TD, XPS, UPS, AES, and LEED (421). It was found that nitrogen was displaced by hydrogen and that the tightly bound state of hydrogen blocks virtually all N2adsorption. The adsorption and decomposition of ethylene on various Ir single-crystal surfaces over the temperature range 90-500 K was studied with FEM (1002) and compared to Pt surfaces. The chemisorption of NO on Ir(ll0) with deuterium showed the catalytic production of Ns, ND3, and DzO (422). The chemisorption and desorption of NO on Ir(ll0) was investigated with XPS, UPS, TD, AES,
SURFACE CHARACTERIZATION
LEED, and isotopic exchange (420) and approximately 35% desorbed as NO and the remainder as N2 and 02.Four distinctive thermal desorption states of water adsorbed on Hr(110)-(1 :< 2) surfaces were reported (1003). The interaction of H2and cyclopropane on the Jr(ll0) surface was studied with TD and preadsorption of hydrogen inhibits the decomposition of the cyclopropane on the surface (1004). The growth of a Pt-Re alloy on a rhenium surface was followed with XPS, UPS, AES, TD, and A$ (21). Structural defects were shown to have little effect on the adsorption of hydrogen and hydrocarbons on the Re(0001) surface (248). The surface relaxation and reconstruction of the Pt(100) surface has been followed with RBS and nuclear microanalysis (217, 671) and by LEED (378). Similar studies have been made on the Pt(110) surface (6, 286, 433) and the Pt(ll1) surface (281,733). Hydrogen chemisorptionfrom dilute acidic solutions onto Pt single crystal surfaces was examined by using an electrochemical cell directly coupled to a LEED/AES analytical system (758). Helium beam diffraction was shown to be useful for the characterization of H2 adsorption on Pt(S)-9(111) x (111)surfaces (732). Elemental fluorine adsorption on Pt(ll1) was investigated with TD and LEED (76) and at room temperature it is adsorbed with a high sticking probability. Thermal desorption first showed fluorine atoms followed by PtF2 and PtF, as exposures increased. The exposure of SO2to Pt(ll1) surfaces resulted in decomposition and a surface concentration of elemental sulfur (510); the dissociation of the SO species was the rate-determining step. LEED and AES were employed in a study of the adsorption, desorption, and decomposition of ammonia to H2 and N2 on Pt(ll1) and stepped Pt(557) surfaces (363). The appearance of the so-called Pt oxide has been correlated with the presence of oxide forming bulk impurities that segregated to the surface during O2exposure at high temperatures (110,666,779). The catalytic behavior of platinum implanted in MgO and A1203 was measured as a function of annealing temperature in argon (739). The effects of oxidizing and reducing atmospheres on the structure and surface composition of particles of Pt, Rh, Pd, and Ir and their alloys were examined with TEM and XPS (791). The formation of water from atomic oxygen and atomic hydrogen coadsorbed on Pt(ll1) was characterized with XPS and temperature programmed reaction in the 1W155 K range (290). The reaction mechanism was proposed to be the sequential addition of atomic hydrogen to oxygen and then to hydroxyl groupin to form the water product. HBr and HC1 were shown to relact with Pt(ll1) and Pt(100) surfaces to form adsorbed layers of specific mixtures of halogen atoms and hydrogen halide molecules (322). A chemisorption-induced Pt 4f surface core level shift was observed following CO adsorption using soft XPS (822). The desorption of CO+ and O+ from CO adsorbed on a recrystallized Pt ribbon was found by using ESD (204). The chemisorption and subsequent behavior of CO on Pt(ll1) surfaces have been investigated with molecular orbital studies (744),EELS and infrared absorption spectroscopy (39),studies of core level binding energy shifts (28),and low-energy molecular beam scattering (999). Surface phase transitions in CO adsorption on Pt(l1Q)have been monitored with LEED, UPS, and TD (397, 905), and the driving force was the difference in stabilities of CO adsorbed on the reconstructed and unconstructed surfaces. The rate of oxidation of CO adsorbed to high initial coverages on Pt(100) and Pt(ll1) surfaces was increased by irradiation by ultraviolet light (672). Two chemisorbed states were observed for CO adsorbed on Pt(321), using EELS, TI), AES, and LEED (598). The coadsorption of H2 and CO on recrystallized Pt was investigated with TD and ESD (202,203) and the results were interpreted as evidence for the existence of a surface species containing both H and COI. The adsorption/desorption characteristics of CQ, 0 2 , and H2 on the Pt(100)-(5 X 20) surface were examined with flash desorption spectroscopy (70). Photoemission of adsorbed CO and H 2 0 on Pt was measured by using monochromatic He and Ne discharge lines (610). The effect of sulfur on the adsorption/desorption of CO on Pt was studied with AES, TD, and modulated beam experiments (332). Large adsorption energy, vibrational frequency, and work function changes were observed for CO adsorbed on a potassium-covered Pt( 111) surface (209) and these were felt to be due to substantid charge donation from the potassium through the platinum substrate. Reconstruction was removed by either
CO or NO adsorption on Pt(ll0)-(1 X 2) surfaces and several new phases were observed to form (933). No reactions were observed to occur during programmed TD studies of coadsorbed CO and NO up to the desorption temperature of NO (341). The adsorption of NO on P t ( l l 0 ) (340) and Pt(ll1) (143) has been investigated. Angle resolved photoemission was used to elucidate the molecular structure of the species present in low and hiigh temperature phases of ethylene and acetylene on Pt(ll1) (14). FEM was employed to characterize the adsorption and desorption of ethylene and acetylene on Pt (511). Heating in the 480-830 K range of either the ethylene- or acetylenecovered surface resulted in decomposition with the breakiing of C-C and C-H bonds. The adsorption of formic acid on clean and oxygen-covered Pt(ll1) was studied with EELS and TD (38) and preadsorbed oxygen raised the yield of the formate species 6- to 7-fold. The adsorption of HNCO on Pt(ll0) was found to cause no reordering of the Pt surface and the HNCO desorbed in two stages in the temperature range 150-390 K (853). The interaction of methanol with clean and oxygen-covered Pt(ll1) surfaces was followed with EELS and TD (815), and it was observed that a methoxy species and water were formed on the preoxygenated surface. Similar studies of the decomposition pathways of the C1-CI alcohols adsorbed on Pt(ll1) were reported (817). Evidence for the formation of stable alkylidyne structures from C3-C4 unsaturated hydrocarbons adsorbed on Pt(ll1) single-crystal slurfaces was obtained by using LEED (507). The adsorption of benzene and chlorobenzeneon Pt(001) was investigated with angle-resolved photoemission (748). Fourier transform infrared spectroscopy Eihowed that benzene adsorbed on alumilna supported platinum catalysts had a Kekule structure (Le., cyclohexatriene) (364). The interaction of polar solvents in electrochemistry on Pt(100) and Pt(ll1) was studied with LEED, AES, and TD (458, 321). The relative reflectance change for the adsorbates H, Cu, and Pb on Pt(ll0) and Pb on Ag(ll0) were measured (512). The adsorption and coadsorption of potassium and oxygen on Pt(ll1) and stepped Pt(755) were studied with AES, LEED, and TD (320), and oxygen was found to thermally stabilize a potassium monolayer. The growth and chemisorption properties of Ag and Au monolayers on 1%single crystals were investigated with AES, TD, and LEED (220). The surface composition of the PtloNiw(lll)single crystal alloy was determined to be largely enriched with platinum, using AES, XPS, and ISS (89). The adsorption of CO on the (111)face of this same alloy was investigated with EELS, XPS, and UPS (445). The clean surfaces of Pt-Ni alloys with '20, 40, and 70% Ni were found to be enriched in Pt in amounts increasing with increasing platinum concentration in the bulk (806). FIM was used to characterize the behavior of fully ordered Pt3Co (1012). The interaction of CO and NO on Pt-Re alloys was reported (20). The surface segregation and surface electronic structure of Pt-Cu alloys were determined with UPS (822,823). SIMS was used to describe the oxygen adsorption phenomenon on Pt3Pb alloys (935). XPS of sputtered Pt films containing up to 17 at. % carbon was reported (232). RHEED studies of the Ag(001), Ag(llO), and Ag(ll.1) surfaces were used to explain the mechanisms causing the various peaks in the rocking curves (576). The work functims of these same three crystal faces that had been argon ion bombardment cleaned and annealed in UHV were determined as 4.14,4.22, and 4.46 eV for the (110), (loo), and (111)faces, respectively (171). ILEED was used to study the adsorption of Ar and Kr on Ag(ll1) (936). Spectroscopic ELL on the Ag(ll0) single crystal face suggested that, during oxygen adsorption, an adsorbing surface layer was formed while simultaneously the electron depletion layer, present on the clean surface, was removed (517). Between -100 and +310 O C : a sin le type of oxygen species was adsorbed on Ag(l1Q) (47) a n t above 150 "C atomic adsorbed oxygen diffuses into subsurface sites. ELL studies of O2 on a Ag(ll0) surface were found to be more readily interpreted when plasma waves and decrease in surface charge density were included in the optical treatment (478). The adsorption-desorption of oxygen, dioxygen, and superoxide on potassium-dosed Ag(100) (494)was studied with LEED, and K enhances the sticking probability of 02 by a factor of 100. LEED showed the presence of (100) oriented KC1 when K and C1 are adsorbed on Ag(100) (4%); ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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on K-dosed Ag(100) surfaces with C1, atomic oxygen is completely blocked while leaving the population of chemisorbed dioxygen unaffected. The same effect was observed during basic studies of oxygen surface chemistry on rubidium-dosed Ag(ll1) (337). EELS, TD, and XPS were used in the investigation of the adsorption of water on clean and oxygencovered Ag(ll0) surfaces (867) and water was observed to react completely with adsorbed oxygen to form hydroxyl groups. Ammonia was found to adsorb in the molecular form without dissociation on Ag(llO), using EELS and TD (336). The kinetics of the oxidation of CO over a A (111)catalyst were determined with XPS and UPS (283,2857. Surface enhanced Raman scattering was used to observe the adsorption of CO on Ag and Au evaporated films (1005). Laser-induced fluorescencewas employed to study the inelastic collisions of NO molecules with A (111) surfaces (498). ELL, LEED, and EELS studies of K afsorbed on Ag(ll1) showed nearly ionic adsorbate a t low covera e and almost neutral metallic overlayer at high coverage f275). The two-dimensional phases formed by sulfur on the (loo), (lll),and (110) faces of Ag single crystals were studied with LEED and AES (764). The adsorption of iodine on Ag(ll1) surfaces was investigated, usin XPS (982) and angle-resolved photoelectron diffraction (278
The molecular plane of chemisorbed ethylene on Ag(ll0) precovered with oxygen was shown to be parallel to the surface (46). The interaction of formic acid and its oxidation on Ag(ll0) have been characterized by using EELS (816,868). Enhanced Raman scattering of pyridine, triphenylphosphine, and ruthenium red on roughened Ag surfaces has been reported (102). Molecular SIMS was use to discover the selfhydrogenationof thiophene on Ag foil (934). UPS of ethylene chemisorbed on Ag(ll0) and benzene on Ag(ll0) and Ru(001) indicates adsorption with minimal molecular distortions (474). Vapor deposited Ag films were concluded to be covered with carbon and oxygen based on SEM, XPS, and Raman scattering (231). The oxidation of methanol to formaldehyde on oxygen-covered Ag(ll1) was followed with XPS and UPS (284).
AES was employed in the analysis of Ag films and Ag layers grown on Cu substrates (656). A monolayer condensation process for monoatomic layers of Pb deposited in UHV on Ag(ll1) was observed by using TEM (889). The oxidation of ultra-thin Pb overlayers on polycrystalline Ag was studied with XPS and UPS (164). RBS was employed to characterize electrochemicallydeposited Pb layers of up to one monolayer on polycrystalline Ag (307). The growth of Fe overlayers on Ag(100) was observed to follow an epitaxial layer-by-layer mode for three layers, using LEED and AES (847). Gold, grown epitaxially on Ag(lll), has been investigated with LEED (23) and with AES and ISS (282). The change in surface composition of Ag-Au-Pd alloys under ion bombardment was recorded by using AES (92). The reconstructed Au(ll0) surface has been studied by angle resolved 600 eV K+ ion scattering and a distorted hexagonal overlayer was proposed (692). AES was used to study grain boundary diffusion of potassium in Au films (276). Intermediate formation of AuC13 during chlorine adsorption on Au(ll1) was reported with TD, ESD, and A+ (855). The top and bottom of a thin (001) Au film were imaged by using TEM and LEED (524). Citrate ion adsorbed on Au sols was studied with surface enhanced Raman scattering (564). Segregation of Ag on the surface of Ag-Au alloys was observed with XPS (661). Ion plated Au films on Ni and Fe substrates were characterized for friction and wear through the use of XPS to analyze the surface (619). Two-dimensionalAES was used to show Ni distributed along grain boundries and on the surface of a Au-Ni-Cu film system after 300 "C heat treatment (118). SIMS was employed to show Co movement to the surface during 150-200 "C heat treatment of Co-hardened Au-electroplatefilms (795). The change in concentration with depth of a A~,&U,,~ alloy was reported (553). XRD showed a homogeneous mixture of Au and Cu crystals in autocatalytically deposited Au-Cu films (624). Other Metals. The XPS spectra of thin films of Ca, Sr, and Ba and their oxides were recorded (939). A 2% contraction from 2.64 to 2.50 A was reported for the outermost surface layer of Sc(OOO1) using LEED (916). The chemisorption of Oz, CO, and Nz on clean Mn was investigated with XPS and UPS and all three were found to adsorb dissocia140R * ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
tively (414). The surface hydroxylation of a Zn(0001)-0 surface in the 80-200 K temperature range was investigated with XPS and UPS (37). The initial diffusion of Pd into the surface region of Zn(0001) was shown to be chemically driven (279). Mossbauer spectroscopy was employed in a study of the corrosion inhibition of zinc by cobalt ions (547) and was attributed to the presence of oxidized cobalt on the surface. The facility of surface oxidation was shown to be In > Cd > Sn > Sb with XPS and AES (813). An ELL study of the growth of Cd on Cd(0001) faces showed periodic fluctuations were due to the instability of monoatomic step trains produced by spiral growth (328). The getter activity of Zr was shown to proceed by the formation of stable chemical compounds such as ZrOz,ZrHz,ZrC, etc., using XPS (536). AES was used to investigate clean and contaminated Zr surfaces and the predominant species were oxygen and carbon (214). XPS and UPS studies of the oxidation and hydridation of Zr and of a Zr-2.5% Nb alloy were performed (894). The uptake of oxygen by a clean Zr crystal was followed with AES in the temperature range 773-1008 K as a function of oxygen pressure (527). The adsorption of CO at room temperature on Al-Zr was done by using AES and gas pressure measurements (1006). An Auger microprobe was used to characterize the films formed on a NiCrAl-0.5% Zr alloy oxidized in air at 1180 "C (542) and a stoichiometric AlZ0, layer was found between an outer mixed oxide and the metal surface. The electronic states in amorphous and polycrystalline Pd-Ge alloys were measured with XPS and AES (135). UPS (665) and EELS (88) were used to investigate the interaction of Oz, Hz, and HzO with erbium surfaces. The surface of Sm metal was confirmed to be completely divalent, using UPS (333). The adsorption of Nz, NH3, and NzO on dysprosium surfaces was followed with XPS and AES (793). The electronic structure of cerium in a variety of alloys was recorded by using XPS (456). An XPS study of Gd-Co and Gd-Fe amorphous films suggested that oxides of Co and Fe were easily reduced by annealing under vacuum (824). Barium gettering was investigated with AES and XPS (950, 951) and shown to function through the formation of oxide, hydroxide, carbide, and carbonate. Submonolayers of potassium on Bi(OOO1) increased the rate of growth of epitaxial BiO(OOO1) by orders of magnitude (144). The native oxide on electropolished Sn was found to be metal free and a mixture of SnOz and SnO (94) was found by using EELS. XPS was used to study the effect of divalent ions on a Pb-selective electrode (1021). Solder adhesion failure on printed circuit boards was shown to be caused by an oxide-relatedreaction at the solder-copper interface (529) through the use of AES. The presence of oxygen adsorbed on the surface of Pb induces surface depletion of Bi and a strong segregation of Sn (252). Binding energy shifts in dilute Sn alloys were explained on the basis of XPS data (377). The surface composition of Sn-Pb alloys were determined with AES both before (304) and after ion sputtering (305,303). AES and XPS were used to determine the oxidation behavior of uranium (103) and a precursor chemisorbed oxygen species was identified at the i-ery initial stage of the oxidation reaction. SIMS, SEM, and optical microscopy were used to identify the role of contaminates and corrosion in electrochemical marking of uranium (805).
SEMICONDUCTORS Silicon. Several investigations of the structure of clean silicon surfaces have been carried out, using LEED, for Si(111)-1x 1 (249),at different temperatures for Si(100) and Si(ll1) (683) and for Si(112) (455). LEED combined wh:i AES and RBS was used to study the structural composition of Si(lOO), Si(llO), and Si(ll1) films after molecular beam epitaxial deposition and laser annealing (230). A LEED study of Si(ll1) following pulsed laser irradiation suggests that a metastable 1 x 1 surface structure is produced during the regrowth process (1024). The Si(ll1)-7 X 7 superlattice transition to 1 x 1 was shown by LEED to be to a disordered metastable surface phase rather than a true unreconstructed 1 X 1structure (81,1025). This phase transition between the 7 x 7 and 1x 1structures of Si(ll1) was also directly observed by reflection electron microscopy (689). Inelastic LEED measurements have been made on Si(OO1)-2 X 1surfaces in order to investigate the diffraction effect on inelastic scattering related to surface and bulk plasmon excitations (405, 432). Angle resolved UPS has also been used for study of the Si-
SURFACE CHARACTER IZATlI ON
(111)-7 )< 7 and -1 X I surfaces (660, 1019). The epitaxial regrowth of Si(ll1) surfaces damaged by low-energy ion bombardment has been studied by LEED (1022), and the growth behavior of epitaxial Si(ll1) was studied by high-resolution LEED (355). The epitaxial regrowth of amorphous silicon deposited on Si(ll1) was also investigated by LEED and TEM (514). EELS of a clean Si(ll1)-7 x 7 surface has been interpreted to indicate a 2dmetallic state of dangling bond surface states (45). Studies of the Si(lll)-7 x 7 surface by ISS for an ion beam incident in the [l111 direction showed that two or less layers have at most a 0.15 8,displacement parallel to the surface (212). The effect of low-energy ion bombardment on Si(211) surfaces has been investigated by ELL and AES (585). Dislocations emergent at the (111) surface of silicon crystals have been observed and analyzed by means of reflection electron microscopy (688). A number of angular resolved UPS studies of silicon surfaces have been carried out, Si(OO1) (941), and Si(lll)-2 X 1 (387, 929,930). The two-quantum photoemission yield spectrum of Si(111)was also recently reported (622).
The adsorption of various species on silicon and their effects on surface structure have been widely studied. The surface states and reactivity of hydrogen chemisorption on thermally cleaned Si(ll1) surfaces have been studied by photoemission spectroscopy with the result of new evidence for a roughsurface model (308). The chemisorption of hydrogen on Si(100)-2 x 1hail been investigated by EELS, AES, and TD (565). Hydrogen-adsorlbed Si(100)-1 X 1surfaces have been probed by ISS with the conclusion that the surface is relaxed inward over a distance of approximately 0.08 8,or about 6% of the interplanar distance (920), and hydrogen-adsorbed Si(OO1)-1 X 1 and -2 X 1 surfaces have been studied by inelastic LEED (587). SIMS was used to obtain profiles of hydrogen, carbon, nitrogen, and oxygen absorbed into evaporated amorphous silicon films after air exposure (570). Cluster model calculations for hydrogen and chlorine chemisorbed on Si(ll1)-7 X 7 have been compared to UPS spectra; it is concluded that the vacancy model with chemisorbed atoms at appropriate sites is a reasonable interpretation (410). The adsorption of fluorine on silicon has been observed by SIMS (192);and measurements of the surface extented X-ray absorption fine structure (SEXAFS) have been carried out for iodine, chlorine, and tellurium adsorbed on Si(ll1) (765, 766). Arsenic adsorption from the interaction of arsine with the Si(lO0) surface was observed by UPS (721). The adsorption of a mixture of propanal products on silicon surfaces was studied by I3C NMR (802). The amorphous-crystalline transition processes for Si(ll1) and Si(lOO),which had been annealed following damage by ion bombardment and subsequent ion implantation, were investigated by UPS and RBS ( 725).
The oxidation of amorphous silicon and hydrogenated amorphous silicon were studied by using AES and UPS (161, 475). A UPS study of disordered silicon surfaces prepared by inert ion bombardment indicates an outer surface layer containing a high density of dangling bonds (262). Oxygen adsorption on the Si(ll0) surface has been investigated by AES (633, 917). Some possible oxygen chemisorption configurations on the Si(ll1)-2 X 1surface have been deduced by UPS (871). Evidence for electron stimulated oxidation of the Si(ll1)-7 >( 7 surface has been obtained by AES and LEED (647). Differences in the oxidation of Si(lll)-7 >I: 7 and Si(lll)-2 X 1surfaces have been ascertained by U P S (870, 872). From AE13 and EELS studies of plasma-produced thin oxide films on silicon, it was concluded that the oxide properties depend slightly OH the discharge parameters (35). The chemical structure of trapped charge sites formed at the silicon-ilicon dioxide interface was investigated by XPS (356). XPS and EELS were performed on silicon with a thin top oxide layer as a function of angular variation; a small difference in the polar angular dependence was interpreted as the difference in attenuation length between incident species (429). Angular-clependent XPS core level shifts of a thin oxide on Si(ll1) were taken to indicate the existence of a siliconoxide interface of random bonding nature (288). A comparison of AES data on the silicon dioxide/Si(100) interface with semiempiricalcalculations appears to indicate that the initial oxidation is by atomic oxygen rather than by molecular oxygen (531). Studies of phosphorus pile-up at the silicon dioxide-
silicon interface have been carried out by AES; in the early stages of oxidation, the interfacial region appears to act tis a sink for phosphorus (800). A study of the electron-activated stepwise oxidation and nitridation of Si(ll1) was conducted by ESD and AES; appreciable levels of surface hydrogen which can lead to hydroxyl formation upon oxidation were found (500). A study of the initial oxidation of polycrystalline silicon was carried out with AES and angle resolved XPS (471). The oxidation of Si(ll1) was studied by high-resolution AES (537) and the growth of silicon dioxide layers from oxygen and HCl mixtures has bleen investigated by AES sputter profiling (763). The oxidation of silicon in an oxygen radio frequency plasma was studied by AES and EELS; a transition layer was found to form at the silicon and silicon dioxide interface (235). SIMS delpth profile measurements of thermally oxidized and anodically oxidized silicon layers have given indications of the origins of impurities and of the accompanying alterations in ellectrophysical surface properties (496). Measurements of the differences in chemical state of phosphorus in silicon dioxide have been made by XPS (399). SIMS and AES were used to characterize the etching of silicon and silicon dioxide by reactive ion etching; 0.6-pm lines of silicon dioxide on silicon have been produced precisely and anisotropically without imy residue or redeposition (615). Thin films of silicon dioxide, silicon nitride, and silicon oxynitride deposited by chemical vapor deposition have been analyzed by AES combined with sputter profiling (944) and by IMMA (970). Surface compositions of vacuum-deposited silicon dioxide films and thermally formed silicon dioxide layers have been determined by AES (574, 989). Changes in the surface composition of silicon and silicon dioxide induced by pulsed laser irradiation have been detected1 by AES and ESD (86). The formation of silicon nitride by implantation of nitrogen into silicon has been studied by grazing angle backscattering, AES, and EELS, the results after annealing being in good comparison with vapor deposited nitride spectra (179, 556). The reaction of Si(ll1) with nitrogen atoms a t high temperatures has been investigated by LEED (794). The nitridation of silicon and oxidized silicon has been examined by ELL and AES (375). The thermal process of nitridation of Si(ll1) by nitric oxide has been monitored by AES, XPS, UPS, LEED, and TD (988). Plasma-formed silicon nitride has been characterized by EELS and AES (384, 523). Investigations of the chemical structure of plasma-depositedand thermally grown silicon nitride have been carried out by using AES and Auger signal decomposition (566, 567), and XPS (897,1010). Low-pressure chemical vapor deposited silicon nitride and thermally grown silicon nitride films were compared by RBS, AES, and ELL (365). XPS investigations of ion implantation synthesizedsilicon nitride showed that a 1300 "C anneal for 2.5 h irr sufficient to produce silicon nitride layers having uniform depth distributions (1011). The preferential sputtering of silicon nitride by argon and helium ion bombardment was studied by AES with the conclusion that the lighter element, nitrogen, is enriched at the surface by bombardment with the heavier ion, argon, and that higher energy ions cause greater enrichment (95). Thin oxide layers art a silicon nitride and silicon interface were examined by AES depth profiles (699). The plasma etching mechanisms of silicon and aluminum have been investigated by MS and XPS (845). In addition, the adsorption and deposition of many different metals on silicon has been widely studied by various surface sensitive methods. A study of an aluminum on Si(ll1) interface lhas been carried out by XPS and AES (503). AES has been used as a probe for the aluminum on Si(ll1)-2 X 1 interf,sce electronic structure! (504). Measurements of the interlayer between aluminum and silicon dioxide have been made by ELL and AES. the interlayer thickness was found to be in the range of 1-5 A (149). EELS and AES evidence have been interpreted to indicate that aluminum deposition on a silicon dioxide film causes some reduction of the film even at room temperature, giving rise to a complex interface (236). The electronic and atomic structure of aluminum, silver, and nickel overlayers on Si(ll1) have been studied with angle resolved UPS (371). Angle resolved UPS results have also been uried to derive structural models of aluminum, silver, and nickel induced reconstructionson Si(ll1) (372). LEED, EELS, AES, TEM, and XPS investigations of thin films of gold on Si(ll1) ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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after heating conclude that gold forms a chemical bond with the silicon, forming surface phases with different electronic structures which depend on the silicon and gold concentrations (557). AES, EELS, LEED, and ISS techniques have been applied to the study of the gold on Si(ll1) interface (234),and of the silver on gold on silicon interfaces (207, 208). Gold monolayers on silicon single crystal surfaces have been produced and analyzed in terms of double scattering between a compressed Au(ll1) layer and the substrate (350). Studies of the reactions of the interface between thin films of gold on hydrogenated amorphous silicon by interference enhanced Raman scattering, TEM, and S A M have found that crystalline silicon islands with a dimension of about 1 pm grow dendritically after annealing up to 150 "C due to diffusion of silicon through the gold (921). The initial growth of gold on oxidized silicon has been investigated by AES and RHEED (25). AES and EELS have been used to observe a catalytic enhancement of silicon oxidation by the presence of a thin layer of gold on the silicon surface (205). Ordered gold and silver monolayers on a silicon substrate have been investigated by AES, LEED, and UPS with the finding that oxygen adsorption on these surfaces is considerably weaker than on clean silicon surfaces (206). A synchrotron photoemission investigation of Si(lll)/Cu, Si(lll)/Ag, Si(lll)/Au, and S i ( l l l ) / P d interfaces before and after exposure to oxygen showed that, in all cases, the oxygen interacts with silicon and not with the metal (2). In another study, synchrotron photoemission was also used to examine this enhancement of silicon reactivity to oxygen when a monolayer of silver is present on Si(ll1) (762). LEED and AES have been used to examine the structural and electronic properties of the silver adsorbed Si(ll1) surface (109,549,900, 901). The properties of the silver on Si(lll)-7 X 7 interface have also been investigated by LEED and AES (106). UPS results for silver on Si(ll1) give evidences of a chemical reaction and intermixingbetween silver and silicon even at room temperature (760). The surface structures of silver on silicon and gold on silicon have been analyzed by quantitative AES with the results interpreted to indicate that the observed data cannot be explained by the model of formation of three-dimensional island structures which are commonly referenced (913). On the other hand, LEED, AES, and angle resolved UPS data for Si(100) and Si(ll1) have shown that silver condenses on Si(ll1) according to an interlayer plus threedimensional island mechanism and that for silver on Si(100) an ordered silicon-silver interface layer is absent (367,368). LEED, AES, and ISS (772),as well as synchrotron UPS (761), have also been used by other authors to investigate the initial growth of silver layers on Si(ll1). AES measurements for polished Si(ll1) deposited with silver were made to determine the stoichiometry of surface phases; it was found that stoichiometry varies greatly, dependent upon the quantity of carbon existing on the surface (342). The initial stages of Schottky barrier formation for Pd and Ag on Si(ll1)-7 X 7 have been investigated by means of surface extended X-ray absorption fine structure (SEXAFS) (863). For 1.5 monolayers of Pd it was found that the local structure around the Pd atoms closely resembled a palladium silicide layer, and the 2.5 monolayer silver spectrum was identical with silver metal. Codeposited alloy films of Pt-Si on silicon were studied by AES with the observation that platinum appears to be depleted in the outer 200-300 A of the film (260). Evidence for interface intermixing of copper on Si(ll1) has been obtained by UPS (1). Thin layers of Pd on hydrogenated amorphous silicon have been studied by AES and XPS with the observation of a thin oxide layer with possible palladium silicides (906). Synchrotron photoemission results for Pd on Si(ll1) have also been interpreted as a silicon-silicide interface (3). RBS has been used to study silicide formation by Pd, Pt, Mo, W, and Nb which have been electron beam evaporated onto silicon (828). XPS of Ni on silicon and Pd on silicon has shown that substituted chemical interactions occur at the interface even at low temperatures (358). AES and synchrotron photoemission measurements on the nickel-silicon interface have been taken to indicate that the compound formed at room temperature contains a higher Ni concentration than for that formed at high temperatures (505). XPS and RBS have been used to study the effects of oxygen impurities on the nickel-silicon interface (359). XPS and RBS have also been applied to investigation of nickel142R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
silicon interface reactions (176). Heat treatments of Si(ll1) surfaces after monolayer coverage by Ni were found by AES, UPS, LEED, and ISS to produce three types of reconstruction of the surface (162). The chemical bonding at the interfaces of Ni and Cr with silicon was examined through synchrotron photoemission studies (300,301). Two adsorption states, one a two-dimensional phase and one a bulklike phase, for Bi on Si(100) were concluded by MS, LEED, and AES (465). Another group studying Bi adsorption on Si(ll0) surfaces by MS, LEED, and AES observed the existence of three adsorption states (694). The influence of the first adlayer structure on successive adsorption of Bi on Si(ll1) was also studied by MS and LEED (771). RBS and AES have been used to study the epitaxial crystallization of amorphous Ge on Si(100) (922). The effects of substrate reconstruction on interface formation between In and Ge overlayers and Si(lll)-2 X 1and Si(ll1)-7 X 7 substrates have been examined by synchrotron photoemission (459). Photoemission studies of Ga on Si(ll1)-2 X 1 and Sb on Si(lll)-2 x 1are indicatve of a simple interface in both cases without complex multiple binding sites or displacive reactions (306). RHEED studies have shown that Ga evaporation on Si(lO0)-2 X 1surfaces sequentially produces four different superstructures over the temperature range 350-680 'C (773). The solid-state reactions of V thin films on oxidized silicon wafers were studied by SAM (174). The Si(ll1) and Mo interface was studied with synchrotron photoemission spectroscopy and AES (759). A TEM study of Mo thin films on silicon showed the formation of silicides mainly along grain boundaries at elevated temperatures (175). UPS studies of platinum silicide on Si(100) have established that the interface state distribution is centered close to the silicon valence-band maximum (767). The electronic states and atomic structure of the palladium silicide and silicon interface have been investigated by using AES and UPS in conjunction with TEM (790). AES has been applied to the determination of the distribution of composition and impurities in magnetron sputter deposited niobium-aluminum thin films on oxidized silicon substrates (890). The damage and ion distributions resulting from ion implantation of boron in Si(ll1) have been studied by cross sectional TEM and AES (60). SIMS analyses of buried interfacial silver layers in silicon have been shown to be of a relative accuracy better than 15% as compared to RBS measurements based on silver-implanted standards (991). Deep penetration of polycrystalline silicon by high-energy phosphorus ions was shown to produce large concentrations of hole traps in MOS devices; SIMS profiles showed a large phosphorus concentrationin the deep tail of the implantations (842). Boron difluoride induced boron-doped silicon MBE layers were evaluated by SIMS with the finding that remnant fluorine is less than 2 X 10leatoms/cm3 in d cases (883). Two different thermal redistributions of implanted beryllium in silicon, dependent upon whether the implants are above or below the amorphization level, have been observed by SIMS (997). SIMS depth distributions of helium implanted in Si as a function of ion energy have shown that the range of 300 keV He ions in Si is about 1.4 pm (998). SIMS and TEM studies of implanted and laser annealed Si diode structures have been reported; the TEM analyses reveal that the crystal quality of the p-n junction region, and not of the surface, is particularly determinant for the electrical operation of the diode (572). SIMS has been used to study the slow diffusion of isotopic gallium in silicon (561). The diffusion of Te in silicon has also been investigated by SIMS; the results are suggestive of a predominantly substitutional mechanism of diffusion (437). SIMS studies were performed on Al/Si ohmic contacts for the purpose of characterizing the surface dopant concentration (193). SIMS was used to analyze the implant profile of phosphorus in p-type silicon (183). Barrier heights of yttrium and yttrium silicide on silicon diodes were correlated with interface conditions as determined by AES depth profiling (146). Cross-sectional TEM and SIMS were used to examine the arsenic distribution and to detect buried amorphous regions in megavolt arsenic implanted silicon (139). The elemental distribution of B, As, and P in silicon has been ascertained by using SIMS and neutron activation analysis (347).
The method of XPS was used to analyze the chemical composition of surface layers of silicon doped with group 6 metals (138). Automated spectroscopic ELL has been applied
SURFACE CHARACTERIZATION
to the measurement of composition and density of polycrystalline and amorphous silicon films (34). By XPS, it has been shown that films of hydrogenated or fluorinated silicon grow with a surface layer of silicon trihydride or silicon trifluoride independent of the bulk distribution of hydrogen or fluorine (552). Another XPS and U P S study of fluorinated amorphous silicon also identified the surface as mainly silicon trifluoride entities (360). EELS spectra of Si-Ge heterojunctions have been interpreted to indicate that the interface is abrupt on a microscopic level and that Ge induces extrinsic interface states in the gaps of the projected bulk band structure of silicon on the Si(ll1) surface (720). Si-Ge alloy films containing significant amounts of hydrogen were examined by XPS and IR spectroscopy (579). An aluminum impurity deposited to a thickness of less than 8 8, on a silicon surface was detected with a photo I-V technique (241). SEM has been used to study the growth of large-grain polycrystalline silicon films from the gas phase; two different formation mechanisms could be identified: a twin plane reentrant edge mechanism and a nucleation mechanism (940). Films of single crystal cobalt silicide on Si(l1Y) were analyzed by RBS, TEM, and LEED with the observation that the films are free of grain boundaries (924). The effect of high-temperature hydrogen annealing on silicon-on-sapphirefilms has been evaluated by SIMS depth profiling (893). Microtwinning in silicon-onsapphire has been observed by SEM in the backscattered electron mode when a bright source and a high pass energy filter are used (2028). The early growth of epitaxial siliconon-sapphire wasi examined by TEM; the lattice was measured to be distorted in the very early stages of growth, but the distortion decreased with growing time (366). The reactions of Cu and Fe on silicon dioxide upon heating under vacuum have been studied by XPS (392). The effects of excess phosphorus on ]plasmaetching of polycrystalline silicon were studied by SEM and TEM; where the phosphorus levels were highest, mainly at the polysilicon-free surface and at grain boundaries, the extent of plasma etching was greatest (428). EELS studies of the interface of Si(100) MOSFETS have been conducted (404). Segregated impurities localized on grain boundaries of polycrystalline silicon have been mapped by using AES; SIMS profiling has given evidence for the segregation of oxygen during high-temperature annealing (466). Neutron activation analysis (NAA) has been used to monitor the gettering behavior of individual contaminant species in Czochralski silicon following laser induced back surface damage (462). The dispersion of nickel oxide supported on boron-modified silicon has been observed by TEM and XPS (411). The composition of sputter deposited silicon and silicon carbide films was studied with XRD, LEED, EMP, and XPS (782). Iron oxide coated silicon photoelectrodes have been analyzed by AES and XRD (639). A study of the sources of transition metal contamination in silicon has been carried out by NAA (792). An AES and XPS investigation was conducted to examine the (0001) surface of silicon carbide a t various temperatures; the results indicated a significant influence of temperature on the surface (617,618). The fluorine content of amorphous rsilicon layers was determined by NAA and correlated to XPS measurements (642). Depth profiles of ion implanted and laser annealed p-n junctions in silicon have been obtained by SIMS and compared to crystallographic properties of the surface and junction with TEM; small dislocation loops a t the junction were found to degrade the junction quality (573). An AES investi ation of the surface composition of a silicon solar cell detectecfa 20 8,layer mixture of silicon oxide and chemisorbed oxygen atoms on the silicon surface (543). XPS was used to analyze the surface of silicon before and after etching in a sulfur hexafluoride plasma; no traces of sulfur were detected on the surface after etching (259). Group 3-5 Clompounds. Curved streaks in the RHEED patterns from reconstructed GaAs(001)-2 X 4 and -4 x 2
surfaces have been shown to originate from antiphase domains formed by tilted As-As dimer chains (242). Site specific densities of states for Ga and As sites in GaAs(ll0) have been derived from Auger lines; these results and XPS, SEM, and LEED investigations of these surfaces were interpreted in terms of a structure for the surface that consists of a two-phase mixture of Ga and disordered GaAs (221). LEED analysis of the GaAs(ll0) surface has been taken to indicate that the surface layer contracts by 5% of the bulk interlayer spacing
(591). Features of angular distribution XPS measurements of GaAs(ll0) and Ge(ll0) surfaces have been found to correspond well with tlhe structural characteristics of GaAs and Ge crystals, thus indicating the possible applicability of such measurements to geometric analyses (693). AES has been used to monitor the removal of carbon contamination from GEIAS substrates by exposure to ozone and ultraviolet light (599). AES has also been used to investigate the residues left on GaAs(100) surfaceai following various cleaning procedures (1026). Evidence has been obtained that EELS spectra from MBE grown GaAs(001) vary with temperature, probably because the surface arsenic concentration varies with temperature (26). Bremsstrahlung isochromat spectroscopy has been used to measure the density of unoccupied electronic states at the GaAs(ll0) surface (244). LEED patterns obtained from (111) oriented Ge and GaAs single crystals following laser irradiation sug est the regrowth of a 1 X 1metastable surface structure (1024f. AES and RHEED analyses have shown that it is possible to obtain carbon-free GaAs(100) surfaces by chemical polishing and thermal heat treatment under vacuum (646). The effects of' substrate surface cleanliness on the initial MBE growth of Gafls have also been studied by RHEED and AES (167). The surface phases of GaAs(100) and AlAs(1100) have been investigated with angle integrated photoemission; the GaAs(100) surface shows ordered reconstruction over a wide range of compositions, whereas, the AlAs(100) surface is predominantly disordered except for one reconstruction in a narrow composition range (42). These surface reconstructions of GaAs and AlAs have also been investigated with angle integrated UPS as a function of the metal to arsenic ratio (43). The surface energies of various planes of GaAs and GaP were measured by the use of a modified spark discharge method; X-ray topography analysis verified that plastic relaxation Idid not occur under the test conditions (606). The surface composition of p-type GaAs and n-type InP following varilous chemical etches have been studied by XPS (91). Schottky barrier measurements for the AlAs(110) surface have been compared with band gap calculations; an unoccupied surface antisite-defect level is predicted to lie within the band gap for A1 on the As site, probably explaining the Schottky barrier observed for n-type AlAs (17). LEED intensities have been measured for (110) and (111)faces of GaP with the conclusion that the GaP(110) face is less stable than the GaAs(110) face and that the GaP(l11) face is far more stable than the GaAs(ll1) face (544). Atom-probe field-ion microscopy was performed on the (1 11)planes of GaP with elucidation of the composition of each plane (1013). Laser induced order-disorder transitions of the InP(100) surface were examined by LEED (621). AES and EELS have been used to study the effects of ion bombardment on InP(l10) surfaces and to study the effect of different surface treatments on InP(1UO) wafers (923). AES has been used to evaluate the cleaning of InP(110) surfaces by various (cleaningmethods (836). The temperature dependence of InP and GaAs etching in a chlorine plasma has been investigated by AES;the analyses show that the etching leaves multiple layers of indium trichloride on the InP surface and leaves submonolayer levels of chlorine on GaAs (243). Precipitates in InP doped with Fe have been investigated by XRD; precipitates with a hollow center were identified as orthorhombic iron diphosphide (873). The chemisorption of Ge on GaAs(ll0) surfaces has been studied by UPS and work function measurements (3,rg). Synchrotronphotoemission measurementsof Ge on GaAs(110) surfaces suggest that the Ga-dangling-bondsurface state lies at 2.6 eV and that the exciton binding energy from the As(3d) to Ga(3d) level is approximately 1.8 eV (1030). Angular resolved UPS, EELS, and AES have been used to study GaAs(ll0) surfaces adsorbed with Al; after heat treatment, the compound AlAs is found to form at the surface (417). The adsorption of formic acid on GaAs(ll0) has been studied by EELS with the conclusion that it adsorbs as formate species (HCOO) and hydrogen (H) (596). UPS, XPS, and SIIMS investigations of oxygen and water adsorption on GaAs have shown that oxygen bonds to As sites almost exclusively while water predominantly bonds to Ga sites (975). The room temperature adsorption of oxygen on As films has been investigated by UPS; direct formation of a disordered arsenic trioxide layer is confirmed (869). The adsorption of oxygen on evaporated Ga films has also been studied by UPS between 10 and 300 K, four different states of oxygen have been found ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
1413R
SURFACE CHARACTERIZATION
depending on the temperature (788). The island state of anodic oxidation of GaAs was investigated with TEM (575). The effects of laser irradiation during oxidation for the GaAs(ll0) surface have been studied by XPS (727). The orientation dependence of oxygen adsorption on GaAs has been investigated by AES (741). AES with sputter profiling has been used to monitor the composition profiles of GaAs(100) thermal oxides; it was found that the composition at the interface was allium trioxide, gallium arsenide, and free arsenic atoms b69). XPS and AES studies of the oxidation of layered semiconductor GaSe indicate that oxygen diffuses into the layer and combines with Ga, severing the interlayer bonding between the Se and Ga atoms (430). An XPS study of the oxidation of AlAs thin films grown by MBE has shown the formation of an aluminum oxide layer; oxidaton of As was not observed until after heavy oxygen exposure (898). Oxides and their interfaces with polycrystalline InP have been investigated by using AES, SIMS, and XPS (468). The chemical composition of native oxide on etched InP has been found to be primarily indium trioxide with a small concentration of a phosphate compound (959). The oxidation of Ga films at room temperature has been studied with UPS (873). The heterojunction Ge/GaAs(llO) has been studied by synchrotron photoemission spectroscopy; evidence was found that the interface is sharp and that Ge forms a smooth overlayer at room temperature (582). XPS of the Ge/ GaAs(ll0) interface showed that half a monolayer of As, most probably bound as GeAs, and 0.03 monolayer of Ga were segregated at the crystalline film surface (625). LEED and synchrotron photoemission spectroscopy were performed on the Ge on GaAs(100) surface (74). Strong evidence for Geinduced band states on cleaved GaAs(110) has been obtained by polarization-dependent UPS (1029). UPS, LEED, and AES has been used to monitor the properties of the Ga/GaAs(llO) interface formation (108). Angular resolved UPS spectra have been obtained for the relaxed GaAs(ll0) surface and compared with theoretical calculations (597). The energy band shifts at an n-type GaAs(100) surface exposed to oxygen have been detected by UPS (388). The energy band bends at the GaAs(100) surface caused by evaporation of silicon oxide on the surface have been found by UPS to be minimal; the energy band bend was found to change mainly due to the pretreatment of the GaAs surface (389). XPS measurements have been used to determine the interface Fermi-level position in (100) and (110) GaAs samples as a function of surface treatment (346). XPS has been used to determine the band discontinuities of several heterojunctions, GaAs/AlAs (962), InAs/GaAs(100) (521),and ZnSe/GaAs(llO) and ZnSe/Ge(110) (520). Raman scattering has been employed to monitor the structure and growth of elemental arsenic deposits thermally generated during the interfacial reaction between GaAs and arsenic trioxide (799). LEED has been used to study the surface-defect structure of Ge grown epitaxially on GaAs(110) (187,188). Lightly doped p-type GaAs films grown by MBE on Cr-doped substrates have been chemically analyzed by using dynamic SIMS (190). For vapor phase epitaxial GaAs films highly doped with silicon, a linear relationship between dopant source, silane, mole fraction, and the incorporation of silicon in the film was established by SIMS (246). Residual impurities in GaAs crystals grown by the liquid encapsulated Czochralski (LEC) method in silica and BN crucibles have been measured by SIMS (189). Impurity densities and depth distributions measured by SIMS have also been reported for LEC GaAs grown in silica and PbN crucibles (994). SIMS has been used to study the incorporation of Sn and Te in MBE GaAs when SnTe is used as source; the probability of incorporation approaches unity for substrate temperatures below about 550 "C (194). Sn-doped spin-on emulsions have been used as solid diffusion sources for open tube diffusion into Cr-do ed GaAs; the Cr and Sn depth distributions were tested by S I b S (33). SIMS profiles which show the accumulation of Sn a t the growing film surface during the deposition of Sn-doped GaAs by MBE have been compared to segregation model calculations (754). SIMS has also been applied to the determination of Mg, Cr, Mn, and Fe distributions in GaAs epilayers (415,416). A SIMS study of Mn incorporation into MBE GaAs has shown that the Mn competetively surface segregates, desorbes, and complexes with As a t the surface, without any significant diffusion (237). SAM and SIMS have been used to monitor the composition profiles of n-type InP, 144R * ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
p-type InGaAs, and InGaAs/InP heterostructures (884). AES has been used to study the changes in composition produced in the surface of crystalline GaAs by low-energy ion bombardment as a function of substrate temperature; part of the data suggest that As was preferentially sputtered (835). Atom depth distributions measured by SIMS have been reported for Be, Mg, Zn, and Cd channeled in GaAs (995). A comparative study of SIMS and electrical carrier profiles by Hall measurements has been carried out for Mg-implanted GaAs (1018). The redistribution of Mn in Si and Se implanted Cr-doped GaAs has been investigated by SIMS as a function of implant dose, ener y, and anneal time; Mn was found to accumulate within a cfepth of 0.5-pm from the GaAs surface (452). Direct evidence of Cr-structural defect-oxygen interaction in Ga and As, Ga, and As and 0 ion implanted GaAs was obtained by SIMS and cross sectional TEM (770). The annealing redistribution of Cr implants in GaAs as a function of ion fluence was measured by SIMS (996). SIMS results for S-implanted GaAs suggest that implantation damage and sulfur precipitates are responsible for low electrical activation of sulfur implants a t high dose and that residual surface defects may be a limiting factor at low dose (534,1017). The postannealing concentration profiles of Fe and Cr implants in undoped InP have been obtained by SIMS (329). The anneal-induced migration of Be implanted in InP( 100) has been studied by using SIMS; Be was found to be a rapid diffusant in InP even at low fluences (676). With SIMS, the annealing characteristics of amorphizing implants of Mg and Si in InP have been examined; atomic profiles indicate that Mg and Fe are gettered out of the amorphous zone into an implant damaged, bulk region (677). SIMS has also been used to observe copper atom gettering in ion-damaged GaP (352). The depth distribution of He implanted in GaAs as a function of ion energy was studied by SIMS; the range of 300 kV He ions was about 1.4 pm (998). Synchrotron UPS measurements of the initial stages of Au, Ge, and Ga deposition on AlAs(ll0) and -(loo) surfaces have been made; Au produces a larger initial dissociation and As outdiffusion than reported for Au on GaAs, however, the net Au-A1As interdiffusion is smaller than for GaAs (73). UPS measurements have also shown high Schottky barrier heights (>1.3 eV) for GaAs(ll0) surfaces covered with about 25 monolayers of Au (726). The initial growth of Au on GaAs(001)-c(4X 4) was studied by AES and RHEED for more than 0.4 monolayer there is rapid intermixing and a tendency of As accumulation at the surface (27). XPS has been used to show that A1 and Au films on GaAs substrates interact predominantly by chemical trapping due to metal-anion bonding (121). The interfacial chemical reactions of Au, Cu, Ag, Al, Mg, Cr, and Ti metal contacts with thin native oxides on GaAs were investigated by XPS (522). The breakdown stability of Au, Al, and W Schottky barriers on GaAs was evaluated with the help of SIMS measurements (59). AES and LEED were used to study Ag on GaAs(100) surfaces (697,698),and UPS was used to study Ag on Ge(ll1) surfaces (760). A UPS, LEED, and AES study of Ag on GaAs(ll0) showed that Ag forms an abrupt interface and grow epitaxially as crystallites formin a nonuniform layer (107). Another investigation of Ag on 8aAs(OOl) by LEED, AES, and SEM concluded similar results (590). The atomic structure of A1 on GaAs(ll0) has been studied by XPS and LEED for coverages ranging from 0.5 to 8.5 monolayers; the data are indicative of an A1 for Ga replacement reaction to form AlAs (447). A LEED study of 0.5 monolayer A1 on GaAs(ll0) has shown that an ordered 1 X 1 structure results when the system is annealed at 450 OC (449). LEED intensity profiles of A1 on GaAs(ll0) as compared to MBE AlGaAs(ll0) seems to confirm a heat-induced formation of AlGaAs when Al is annealed on GaAs(ll0) (448). The composition of Sn films on GaAs has been investigated by AES (373). For W, Ta, Re, Ir, and Mo on G e s , XPS was used to monitor the interfacial chemistry during contact formation (961). The electronic structure of submonolayers of Pb on the GaAs(001) surface has been studied by angle resolved synchrotron photoemission; the studies show no significant chemical interaction between overlayer and substrate (938). The characterization of Sb overlayers on GaAs(ll0) has been carried out by use of LEED, AES, and TDS (154,446,838). RBS was used to study the growth of anodic Nb or vanadium oxide and GaAs oxide films on GaAs (148). The complex interactions at Ni/InP and Au/InP in-
SURFACE CHARACTERIZATION
terfaces were monitored by synchrotron photoemission (992). The interfacial reactions of Be/Au and Sn/Au ohmic metallizations on [nP, InGaAsP, and InGaAs have been investigated b y EMP' and cathodoluminescence imaging (142). The XPS spectra of Al, Ti, Ni, Au, Pd, Ag, and Cu on InP(110) surfaces reveal evidence for semiconductor outdiffusion, metal indiffusion, metal-anion bonding, and metal-cation alloying (122). The Au Ni/SnNi/GaAs interfaces have been investiqated by AE , to understand the ohmic contact formation; it was found that the ohmicity can be achieved without Sn due to Au-induced Ga vacancies (41). SIMS profiles of Au/Ge on GaAs allowed the redistribution of Ge into GaAs to be compared to contact resistivity profiles for the structure (10, 463). XI'S measurements of Ni, Au, and Cu on InP indicate that the interface abruptness depends on the strength and nature of interface chemical bonding (123). Synchrotron photoemission has been used to study the properties of In and Ge on GaAs(ll0) (459). The analysis of plasma grown oxyfluorides on GaAs by XPS and SIMS indicates that the molecular components of the glass following thermal annealing are gallium trifluoride and arsenic oxytrifluoride (9). The formation of structural defects in Ge-doped GaAs and AlGaAs films was investigated by TEM; it was concluded that the observed dislocation clusters did not nucleate from the threading dislocations but from GeAs and germanium diarsenic particles decorating the dislocations (960). AES was used to study the interface of vacuum-deposited tin oxide on GaAs substrates (126). The surface compoaiition of GaP has been investigated by XPS; it was found that there is sufficient potential on the surface to produce gallium oxide species which are apparently important to efficient charge transfer behavior (335). An XPF;. study of the interface formation of silicon dioxide depositel; on InSb has shLown significant interaction between the de posited and substrate species (947). RBS has been used to study the InAlAs/InGaAs interface (631,632). Other Semiconductors. LEED has been used to study the clean high !Miller index surfaces of Ge (684). LEED has been used to show that Ge vacuum cleaved along (111) planes at 30-40 K fornis some 2 X 1as well as 1X 1structures (370). Another LEED study has concluded that the 1 X 1structure is stable below about 20-40 K and that the 2 X 1 is stable above about 40-60 K (31). Electron escape depths from crystalline Ge for the electron energy range from 30 to 1250 eV have been determined by AES (316). RHEED studies of the subrnonolayer and monolayer indium-induced superstructures on GIe(ll1) (423) and Sn-induced superstructures on Ge(ll1) (424) have been performed. Angle resolved UPS measurements have been made on the Ge surface in the Ge(111)8 reconstruction (124). Oxy en adsorption of Ge(ll1) surfaces has been studied by AEB,TD,and EELS; the findings imply that at 300 K only a chemisorption oxygen state exists on the Ge(ll1) surface (878). Oxygen adsorption on alkali-metal-covered Ge(l11) surfaces were also investigated by AES, TD, and EELS; it was found that the ]presenceof alkali metals enhances the oxygen adsorption rate (879). The changes of the EELS spectrum caused by alkali metal adsorption on Ge have been taken to indicate that alkali metal deposition changes the intrinsic surface slate energy distribution (880,881). SEXAFS has beev used to study the adsorption of C1, I, and Te on Ge(ll1) and Ge(lll)--2 X 8 (765, 766). Valence band and core line investigations of the Ge-Au phase on gold-deposited Ge(ll1) have been carried out by use of synchrotron photoemission spectroscopy (719). The atomic structure of Ge(ll1) and its reactions with aluminum have been studied with LEED (1015). The XPS spectra of amorphous Si-Ge alloys were measured and compared with Raman scattering and EELS data to gain insight into the way other atoms will bond in amorphous allqys containin both Si and Ge (563). The local structure of amorphous Ge6 and GeSe was studied by using EXAFS and XPS; the analyses gave evidence for %fold coordination of Ge atoms in GeS (695). The growth of PbGeTe thin film structures by MBE has been monitored with AES (706). Chemical vapor transport of GeAs has been confirmed by XRF and EMP analvses (386). - The room temperature sta'dity against Hg evaporation from HgCdTe(l10) surfaces has been studied, using XPS and UPS; no evidence of loss was seen for periods of observation from 5 to 20 h (831). RBS has been used to monitor the near
si
surface region of HgCdTe before and after thermal processing and implantation; redistribution of Hg was observed following thermal processing (195). The process of forming plasinaanodized oxide on HgCdTe has been evaluated by using ALES and XPS; the plasma oxide was found to exhibit a decreaaiing gradient of oxygen and an increasing gradient of unoxidized Te from the surface toward the bulk (662). UPS has been used to probe the electronic structure of (110) HgCdTe (832). The surface atomic geometry of CdTe(110) has been evaluated by LEED measurements (251). CdTe has been studied by XPS and AES; the oxidized surface exhibits little or no detectable Cd signal, and the Te signal is consistent with an overlayer of elemental Te (891). The composition of anodic oxide films on HgCdTe has been characterized by several XPS studies; the results suggest that the most likely major constituent is CdTeOs (8,222,278, ;'47, 775). The formation and reduction of anodic oxides on HgCdTe have been studied by electrochemical methods and XPS (774). HgCdTe native oxide reduction by a silicon dioxide overlayer was analyzed by XPS; the data indicate a much greater ratio of reduced to oxidized Te compawd to the anodic oxide without silicon dioxide (746). AES sputter rofiies of anodic oxide f i i s on HgCdTe for composition have een determined to be complicated by nonstoichiometric sputtering (635). The oxidation of HgCdTe surfaces was foimd by XPS to be to tellurium dioxide formation at the surface (519). Another UPS and XPS study of the Oxidation of HgCdTe concluded that either tellurium dioxide or CdTeOs or both might be present (634). The compositioii of CdSeO films prepared by reactive planar magnetron sputtering has been determined by R.BS (580). XPS studies of oxygen chemisorption on thick films of CdS indicate preferential bonding of chemisorbed oxygen with sulfur (22). The oxidation of single crystal CuInSez has been investigated by using AES, SIMS, and XPS; the composition of the thermal oxide is found to be Inz03with about 10% SeOz (469). The effects of implantation and annealing on implantation-induced damage in HgCdTe were studied by RBS and SIMS (1009). RBS and SIMS have been used to observe the successful annealing of crystal damage causedl by boron implant into HgCdTe (196). SIMS and AES have shown that annealing of CdSe thin film transistors that have been fabricated with Cr source and drain electrodes causes diffusion of Cr from the electrodes into the CdSe layer, thus doping the film (130). Doping profiles in PbSnTe thin film structures have been measured by AES and an electrochemical etching technique (707). Preliminary evidence for 150-ps occupation of states up to 1.6 eV above the conduction bimd minimum in ZnTe has been obtained by picosecond tiimeresolved photoelectron spectroscopy (993). Oxide layer formation on ZnSe(ll0) surfaces has been studied by LEED; LEED patterns confirm the presence of ZnO (887). Photoemission studies of ZnSe(ll0) and ZnTe(ll0) adsorbed with oxygen have been performed (886). The composition of Zri?Pz thin films on Mg solar cells has been determined by using AES, SIMS, and XPS; evidence for the formation of Mg3P2 was obtained (467). XPS and UPS have been used to examine the electronic structure of MnCdTe monocrystals in comparison with CdTe (850). The structural properties of Cd8eS films have been determined by LEED (450). Bond structure investigations of CdsAszhave been carried out with UPS imd EELS (798). The €ormation of the CdS CuInSez interface has been studied by XPS and EELS; a ove 350 OC, rapid diffusion of Cd into the Cu-ternary was found to take place (470). The elemental composition of the GaSe SnOz heiterostructure was studied by XPS and AES (896j. The reactive interdiffusion of Cu on CdS and CdSe was investigated by using UPS, XPS, and AES; it was found to form a thick 250 A reacted layer (132). The interfaces between CdS and CdSe surfaces and various metals including Cu, Al, and Au which were deposited on them were examined by XPS and UPS (131, 133). Impurities in vapor deposited CdS crystals were investigated by SIMS (636). XPS and AES depth profiles were obtained from nonplanar CuS/CdS solar cells (96,595). By use of XPS, the states of Au and Pt impurities in vitreous and crystalline AszSe3have been studied (814). XPS has also been used to study Ag and Cu-doped amorphous AszSe3and GeSez (927, 928). SIMS has bleen employed to study the diffusive behavior of A1 and Cr thin films on CdSe; it was found that Cr diffuses more rapidly than
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ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
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SURFACE CHARACTERIZATION
A1 (801). SIMS analyses of P b and B in yttrium iron garnet epilayers have shown proof of an increase of P b in the transient region (914). XPS was used to analyze CuS films which were treated with oxidizing agents to produce patches or islands of copper sulfate (254). Metal Oxides. The hydration of the MgO surface during polishing was shown to have played a dominant role in the formation of the smooth surface (875). He diffraction from MgO(100) was studied with different He energies and different angles of incidence (752). Surface energies and surface structure of small MgO and NiO crystals were determined with TEM and EELS (198). Chemical state plots of a variety of Si-AI-0 compounds were recorded as part of a calibration of the XPS technique (957). The electronic structure of A1203 was studied with EELS, and an energy level model of both filled and empty states was constructed (682). ELL was employed in the characterization of the oxide films on Al(111) formed in the 300-600 K range with O2 at pressures from 25 to 600 torr (353). XPS measurements of an electron bombarded surface of sodium @-aluminashowed segregation of sodium to the surface (560). Thermal faceting of the rutile Ti02 surface was documented by using LEED (289). Ti02 pigments were analyzed with XPS and by titration with Hammett indicators to determine the effects of firing temperatures and Zn content (291). Large amounts of carbon were detected in hydrogen-fired TiO, using SIMS and AES (717). The effects of surface stoichiometry of clean titania powders on the adsorption of water were studied with SIMS and AES (584). Intrinsic and defect surface states on TiO,, SrTi03,and MgO single crystals were measured by using electron spectroscopic techniques (380). The hydrogen species on Ti02and SrTi03have been characterized, using the site specificity of electron-excited Auger stimulated desorption (499). Photocatalytic hydrogen production from water over platinized SrTiO, crystals was investigated with UPS, and a reduced surface species ascribed to Ti3+ and hydroxyl groups was identified (958). XPS and UPS were used to show that ion bombardment of SrTi03(100) surfaces caused these surfaces to exhibit different water adsorptive properties and that this was related to the resultant surface oxidation state of Ti (974). The dielectric properties of SrTi03 indiffused with Bi203were investigated with SEM, XPS, and TEM (302). The results of a LEED study of the VeOI3(OOl)surface as a function of oxygen coverage showed the outermost V atoms were adsorption sites for atomic oxygen in an on-top position (229). The quantitative analysis of Fe20, Fe304,and FeO by use of a derivative mode of AES and ion sputtering was reported (614). The surface cation densities of Fe,Cr2,03 solid solutions were determined with AES (530). The presence of potassium on the surface of FeO was shown to promote the dissociation of CO by using UPS, AES, and TD (476). The dissociative adsorption of oxygen on polycrystalline nickel oxide surfaces was investigated with XPS and U P S (753). The quantitative analysis of iron oxides and NiO surfaces and the effects of surface physical quality was reported (472). XPS was used to detect variations in dispersion of impregnated and ion-exchanged NiO/Si02 systems (412). The surfaces of CuO and CuzO were completely reduced to metallic Cu upon extended ultraviolet radiation (293). The decomposition of ethanol and acetaldehyde on ZnO was investigated in UHV by TD and the decomposition products indicated acetic acid as the surface intermediate species (623). The adsorption and epitaxial growth of benzeneon ZnO(1010)was studied with LEED. TD. and UPS (735). XPS was used to follow RuO, and Pi0 -electrode surface immobilization reactions wit6 thionyl chloride (532). XPS and AES were applied to the study of the surfaces of SbzO3, Sbz04,and Sb20S(317 ) . The oxidation/reduction of tin oxide films as a function of their interactions with O,,H2,NO, and H2Sat 525 K was followed with X P S (152). The mixed oxides of Te-Nb and Te-Ta were investigated with XPS and XRF and systematic differences between surface and bulk compositionswere discussed (318). The reaction of oxygen with Ta-8W-ZHf to form surface Hf02 as a function of Hf concentration was studied with AES (216). Electrochromic W 0 3 thin films were studied with SIMS and XPS (648) and UPS (393). UPS measurements of the (001) surface of W03 after exposure to atomic hydrogen indicated new states in the energy gap (125). The platinum oxide surface layers on single crystal Pt were studied in UHV with LEED and AES and surface cleanliness was shown to be crucial (778). 146R
ANALYTICAL CHEMISTRY, VOL. 55, NO. 5, APRIL 1983
The defect structure of PbO was determined with TEM (641). Laser Raman scattering was used for in situ monitoring of the surface layer formed during anodization and sulfation of tetrabasiclead sulfate (946). The composition of oxides grown on PbInAu films after rf oxidation were examined with XPS (56,57). XPS was used to characterize the surfaces of thin vacuum deposited films of bismuth oxide (238) and to determine the effect of hydrogen on the electrical and optical properties (374). The effects of Pt doping, anodization, and Pt preelectrolysis on the electrocatalytic activity of sodium tungsten bronze was reported (977). LEED was combined with ISS to characterize the surface structure formed by oxygen atoms on U02(100) (899). Other Metal Compounds. Scattering of Ne atoms from a LiF(001) surface showed broad tails that were due to inelastic scattering (812). XPS studies were carried out in order to clarify the structure of various binary silicates; i.e., Li20-, Na20-, ZnO-, MgO-, CaO-, SrO-, and BaO-Si02 (781). The electronic structure of cyanide and hexacyanoiron(I1)anions with Na and K were recorded by using XPS and X-ray emission (85). XPS spectra from clean alkaline carbonates and the species formed from ion-beam bombardment were reported (180). Aluminum perrhenate catalysts were prepared and characterized by XPS and laser Raman spectroscopy (780). The photoelectron spectrum of tetraiodosilane was recorded (673). EELS and TEM were applied to the examination of inclusions and grain boundries of a S i c ceramic (112). The reaction zone of an annealed Sic Ti fiber composite was studied with microarea AES (1027j. The composition, kinetics, and mechanism of growth of chemical vapor-deposited aluminum nitride films were determined by using RBS (711). UPS spectra of trimethyl and triethyl phosphite and phosphate were reported (169). The sulfur in a variety of sulfides was characterized with AES and XPS (554). Detection of the decomposition of a ScD2 film was performed with AES (577). AES and XRD were used to characterize the surface nitride films formed on Ti, Zr, and Hf after nitriding by rf heating to 925-1000 "C in flowing NH3 gas (226,225). RBS was used to show that TiN was an effective diffusion barrier up to 550 OC between A1 and Si (909). Oxygen atoms were shown to be preferentially adsorbed on the carbon sites at the topmost layer of TiC(001), using A$, UPS, XPS, and ISS (690). T i c field emitters were examined with FIM, FEM, and atom probe FIM (314) and the surface was shown to become enriched with carbon. The valence band structures of the trisulfides of Ti, Nb, and Ta were determined with XPS (263). The surfaces of mixed precipitates of Ti-Zr and Cu-Ag were examined with XPS (390). Surface segregation effects in TiFe were shown to play an important role in hydrogen uptake and catalytic behavior of this compound (486). The surface composition of electrodeposited chrome solar absorbing films was investigated with SIMS (846). The surface effect on the effective exchange field in fine particles of MnF2 was established with EPR (309). XPS studies of surface damage to transition metal fluorosilicates under argon ion bombardment was recorded (201). Iron boride sputtered films were investigated with Mossbauer spectroscopy,SIMS, and XRD (104). The effects of ion bombardment on the transition metal sulfides (Fe through Co and Ni) were determined with XPS (200). LEED, AES, and UPS studies of oxygen interaction with cobalt silicides (159) showed that oxygen uptake kinetics at CoSi resembles Co surfaces, whereas at CoSi2almost Si-like behavior was observed. Compositional changes of Nisi and PtSi due to Ar ion bombardment were determined with AES (1001). Photoemission studies showed that Nisi, consisted of a metallic simple-cubicsilicon crystal that was stabilized by Ni anions (163). Improvement in lateral uniformity of thermally formed NizSi was demonstrated through the use of a low-dose Xe ion implantation (986). Combined AES and XPS studies were carried out on Nisi and Pd3Si (36). The physical properties of niobium silicide films were measured with XRD and AES (768). The composition of Ni-V and Ti-Si-A1 alloys was determined by using AES and SIMS (736). XPS was used to observe the adsorption of xanthates on a thin layer of copper sulfide (742). The growth and structure of electron-beam evaporated ZnS films were determined (178), and XPS studies were performed on some CRT phosphors (837). Angle resolved UPS was employed in the characterization of a ZnSe(ll0) surface and oxygen contamination tests on the surface (255). The atomic
SURFACE CHARACTERIZATION
geometry of the ZnS(110) surface was established by use of LEED (250). The interaction of oxygen with La& single crystal surfaces has been measured (165,223,668). XPS was employed to measure the core levels and valence band level of LaH, (787). UPS spectra of CeB6and PrBBwere reported (874). The surface properties of the hydride forming alloy ErFe2were determined by using photoelectron spectroscopy and magnetic susceptibility (808). A correlation of the Auger parameter with the refractive index of various silicates was established with XPS (983). Zr was shown to be segregated to the surface of hydrogen-adsorbing ZrCrz with XPS and scanning AES (434). AES was used to determine the in-depth composition of niobium nitride formed by laser annealing of niobium metal immersed in liquid nitrogen (652). The properties of molybdenum silicide films for very large integrated circuit use were measured (427,674,827,882,979). The XPS spectrum amd band structure of RuC1, were reported (601). The surface structure and behavior of palladium silicides have been measured (48, 691). XRD and RBS were employed in the &,ructuralcharacterization of CdS films (61). The reversible AgF-LaF, interface has been studied with AES and various electrical techniques (292). The photodecomposition of AgCl has been characterized with XPS and the results were correlated to the photographic process (820). UPS and XPS were used to study the electronic structure of stoichiometricand substoichiometric TiN and ZrN (394). The effectiveness of SnClz and SnC1, in the sensitization of soda lime silicate glass for silver mirror production was investigated with XPS (712). AES was used in a study of iridium and niobium silicides deposited on single crystal Si (819). Bondings in the bulk and at the Si interface were determined for platinum silicide (357). AES, SIMS, and SEM were employed in determining the effecta of ion-implantation-induceddamage and impurities on platinum silicide (588). Tantalum silicide was characterized with AES, SIMS, and SEM for VLSI applications (168). UPS studies of WC(OOO1) were reported (860).
Carbon and Coal. LEED spectra from the (0001) face of graphite have been compared to dynamic scattering calculations; agreement is found for a top carbon layer contraction of 0.05 and a surface nearly devoid of monatomic steps (1008). UPS has been used to study the surface states on the (111)surface of diamond; no intrinsic surface states were found on the 1 X 1surface, but the results show evidence of a band of surface states on the (2 X 2)/(2 X 1)reconstructed surface (710). LE:ED has been used to provide evidence that the (111)-1 x 1 surface of diamond is terminated by hydrogen (956). Another XPS and photon-stimulated ion desorption study of diamond(ll1) verified that the mechanically polished 1 X 1 surface is hydrogen terminated and found that the reconstructed swface is hydrogen free (709). LEED and AES were used to study both clean graphite (0001) surfaces and potassium adsorbed graphite (0001) surfaces (1007). Potassium intercalated graphite was also examined by XPS (239). A high-resolution LEED study of hydrogen physisorbed on graphite at 10 K has been reported (807). Lattice parameters have been obtained for Xe and Kr monolayers on graphite by transmission high energy electron diffraction (THEED) (784). LEED has been used to investigate the adsorption of monolayers of Ne on graphite (140). A study of the electrical and chemical structure of graphite electrochemically intercalated with sulfuric acid has been carried out by XPS (777). The anodic oxidation of Ti thin films on vitreous carbon has been studied by 13EM and RBS (645). XPS and EELS have been used to examine the electronic character of diamondlike carbon films which were produced by low-ener carbon ion beam deposition (630). Hydrated graphite oxi% was found to be the product of oxy en corrosion on a carbon foil by angular distribution XP8 f1020). SIMS was used to measure the depth profiles of H and D implanted in carbon in order to study the isotopic exchange reaction in carbon (965). XPS has been used to1 monitor the effects of heat treatments on carbon fibers (738). High chloride content coal induced corrosion of liquefaction vessel components has been investigated by XPS (818). Glasses. The depletion of sodium on glass surfaces during Auger analysis has been investigated (985). An XPS and nuclear microanalysis study of compositionalchanges in glass upon electron beam irradiation has shown that Na migrated toward the inside of the tmnple and accumulated at a depth
a
comparable to the maximum electron ranges (71). XPS has been used to show that ion bombardment of a glass also results in an alteration of the sample surface; field-inducedmigration of Na and preferential sputtering appear to account for these changes (843). A SIMS study has been used to investigate the finding that the resistance of alkali borosilicate glasses to aqueous dissolution can be significantly increased by the addition of Ca, Al, and Zn ions to the solution (885). XF’S was used to study the nonbridging to bridging oxygen ration in sodium silicate glasses as it correlates with the glass density and refractive index (438). A series of sodium silicate glasses containing varying amounts of CaO have been examined by using XPS; adding CaO produces effects indicative of introduction of nonbridging oxygen into the glass matrix (948). SIMS composition profiles of boron in borosilicate glass were shown to be dependent on the mode of sample preparation; surfaces prepared by either abrasive polishing or satw cutting exhibit a boron gradient (578). XPS has been used to investigate the nonbridging oxygen content of alkali germanate and alkali germanosilicate glasses depending on the mole fraction of alkali oxide (844). The diffusion coefficient of phosphorus in phosphosilicate glass at 940-1050 O C was determined by etch rate measurements and SIMS analyses (160). A structural investigation of calcium fluorosilicate glasses was carried o a t by XPS (431). The steam corrosion of glass under polymer thin films was studied by XPS; it was found that sodium was depleted from the surface region under the polymer coating (15). Soft X-ray appearance potential spectroscopy has been applied to the study of alloy metallic glass containing Co, Ni, Fe, B, and Si (245). The electronic structures of alloy metallic glasses of Nb Rh, Nb/Ir, Ta/Rh, and Ta/Ir have been investigated by X S (215). Fast atom bombardment mass spectrometry has been applied to the analysis of silica glass surfaces (877). Catalysts. The surface electronic structure of catalyst Zr02/Si02was studied by means of XPS; the results indicate that when Zr02 is supported on SiO,! the Si-0 bond becomes stronger (464). The surface properties of a series of impregnated Co alumina catalysts were investigated by XPS, ISS, and SIM ; the reducibility of the catalysts has been shown to be directly related to the degree of metal-support interaction (177). UPS and AES have been used to study the impurity atom effect on the surface properties of sin le crystal Ni and Ru catalysts; a correlation was establishecf between the electronegativity of the impurity atom and its catalytic poisoning ability (electronic effects, as opposed to site blocking, were shown to dominate) (338). The adsorption of deuterium and CO on Cu/Ru(0001) catalyst surfaces was studied by T‘D (952). The oxidation states and composition at the surface of copper chromite catalysts have been ascertained by XI’S (151). Spectroscopiccharacterization of Wilkinson’s catalyst has been carried out by XPS; both Rh(1) and Rh(II1) were detected (156). XPS has been used to compare catalytic properties of aluminum, silica, and titania (987). TEM and XPS studies have been carried out on Fe/titania model supported catalysts following hydrogenated oxygen treatments over a range of different temperatures (895). Studies by XI’S have been made to compare the activity of Pt/TiOz and Pt/ZnO catalysts for use for methanol decomposition; XF’S confirmed that the loaded Pt of these catalysts is reduced to zero valence during reaction (902). XPS was also used to investigate the influence of the sequence of Mo and Co irnpregnation on the state and dispersion of Co in CoMo/alumina catalyst (29). Organics. Monolayers and multilayers of ferrocene derivatives deposited on metal, metal oxide, and carbon electrodes have been examined by XPS (931). UPS has been used to study the adsorption of CH and CCH, groups on surfaoes (197). X P S has been used to analyze surface functional groups introduced on polyethylene films (274). Polyethylene coated carbon black was studied by SIMS (166).
d
k
ACKNOWLEDGMENT The authors are grateful to Keith Russell for arranging the references. LITERATURE CITED (1) Abbati, I., and Grionii, M. J., J Vac. Sci. Techno/., 19, 631, 19S11. (2) Abbati, I., Rossi, G., Calliari, L., Bralcovich, L., Lindau, I., and Spicer, IN. E., J . Vac. Scl. Techno/., 21, 409, 1982.
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SURFACE CHARACTERIZATION (3) Abbatl, I., Rossl, G., Lindau, I., and Spicer, W. E., J. Vac. Sci. Technol., 79, 636, 1981. (4) Adams, D. L., and Nlelsen, H. B., Surf. Scl., 707, 305, 1981. (5) Adams, D. L., Nlelsen, H. B., Andersen, J. N., Stensgaard, I., Feldenhans, L. R., and Sorensen, J. E., Phys. Rev. Left., 49, 669, 1982. (6) Adams, D. L., Nlelsen, H. B., Van Hove, M. A., and Ignatlev, A,, Surf. Sci., 704, 47, 1981. (7) Agron, P. A., and Carlson, T. A., J. Vac. Sci. Technol., 20,815, 1982. (8) Ahearn, J. S., Davls, G. D., and Byer, N. E., J. Vac. Sci. Technol., 2 0 , 756, 1982. (9) Ahrenklel, R . K., Kazmerskl, L. L., Ireland, P. J., Jamjoum, O., Russell, P. E., Dunlavy, D., Wagner, R. S., Pattillo, S., and Jervls, T., J. Vac. Scl. Technol., 21, 434. 1982. (10) Aina, O., and Katz, W., J. Appl. Phys.; 52, 6997, 1981. (11) Akhter, P., and Venables, J. A., Surf. Scl., 702, L41, 1981. (12) Akhter, P., and Venables, J. A., Surf. Sci., 103, 301, 1981. (13) Aklmoto, K., Appl. Phys. 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