US005403620A United States Patent (19) 11 Patent Number: 5,403,620 Kaesz. et al. 45 Date of Patent: Apr. 4, 1995

54 CATALYSIS IN ORGANOMETALLIC CVD 2688-2689, J. Am. Chem. Soc vol 110, No. 8 (no OF THIN METAL FILMS month). 75) Inventors: Herbert D. Kaesz; Robert F. Hicks, Kaplin, Yu A. et al. "Decomposition of Nickelocene in both of Los Angeles, Calif. Presence of Hydrogen' Jan. 1980, pp. 118-121, UDC. 547.1' 174, c. 1980, Plenum Publishing Corp., translated 73 Assignee: Regents of The University of from Zharnal Obshchei Khimir, 50, 118 (1980). California, Oakland, Calif. Egger, K. W., “Cyclopentadienyl-Metal Complexes II *) Notice: The portion of the term of this patent Mass Spectrometric and Gas Phase Kinetic Studies on subsequent to Jul. 14, 2009 has been the Thermal Stability and the Structure of disclaimed. (CH3)3PtC5H5", 24(1970) pp. 501-506, J. Organome tallic Chemistry no month. 21 Appl. No.: 959,384 Miller, Timothy M. et al., “Heterogeneous, Platinum 22 Filed: Oct. 13, 1992 Catalyzed Hydrogenation of (Diolofin)dialkylplatinum 51) Int. Cl...... C23C 16/00 (II)Complexes: Kinetics', 1988, pp. 3146-3156, J. Amer 52) U.S.C...... 427/252; 427/123; Chem Soc vol 110 #10 no month. 427/124; 427/255.2; 427/255.7; 427/554 Primary Examiner-Shrive Beck 58) Field of Search ...... 427/123, 124, 554, 255.2, Assistant Examiner-Vi Duong Dang 427/255.7, 252 Attorney, Agent, or Firm--George F. Bethel; Patience 56 References Cited K. Bethel U.S. PATENT DOCUMENTS 57 ABSTRACT 3,622,367 11/1971 Haag. 427/123 4,915,988 4/1990 Erbil. 427/255.2 A process for CVD including plasma enhanced and 5,091,210 2/1992 Mikoshiba ...... 427/124 laser induced CVD using one or more precursor film 5,130,172 7/1992 Hicks ...... 427/252 forming metal compounds as the major film forming 5,154,949 10/1992 Shindo ...... 427/255.2 metal precursor, for example organotungsten, which is admixed with minor amounts of a precursor catalytic OTHER PUBLICATIONS metal compound, for example, an organoplatinum com Houle, F. A. et al., "Surface Processes Leading to Car pound, as a precursor to a catalytic metal in the pres bon Contamination of Photochemically Deposited Cop ence of hydrogen gas to provide improved purity of per Films' Nov./Dec. 1986, A4(6)pp. 2452-2458, J. Vac Sci. deposited metal films having residual amounts of the Gozum, John E. et al., "Tailored Organometallics as catalytic metal incorporated therein. Precursors for the Chem. Vapor Deposition of High -Purity Palladium and Platinum Thin Films', 1988, pp. 25 Claims, 3 Drawing Sheets

OOO

4.O O

2OO

O O 25 4O 55 7O 85 OO 29 U.S. Patent Apr. 4, 1995 Sheet 1 of 3 5,403,620

8983 R S.

K

O O O O O O OT 3O O8 &O 3 & (quo) AISueu U.S. Patent Apr. 4, 1995 Sheet 2 of 3 5,403,620

anS

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oupE his O C) O aub ab s Ol 8 (?)

O V

O CN

(%) uolSOduoo Ouov U.S. Patent Apr. 4, 1995 Sheet 3 of 3 5,403,620

FIG 3 Table . Atomic composition Of films

Tungsten (%) Platinum (%). Carbon (%). Oxygen (%) Depth (A) W WIPt WPt W WIPt W WIPt

O 44.9 54.6 19 46.2 39.0 5.9 4.2 190 66.6 88.6 3.4 24.6 5.7 3.5 2.0 380 67.3 89.8 3.6 24.5 4.8 3.4 1.6 570 67.4 90.9 2.3 249 4.8 34 1.8 760 66.7 90.9 2.6 25.5 5.1 32 1.5 950 65.7 88.9 4.2 26.2 4.8 2.2 1.8 1140 63.3 90.1 3.3 26.1 4.7 1.2 1.7 1330 39.5 89.9 4.0 11.3 5.1 3.3 1.8 1520 15.3 89.3 3.6 4.6 5.1 5.6 1.8 1900 89.2 4.1 4.7 1.8

2280 88.1 4.1 5.9 1.7 2660 84.1 5.2 8.9 1.7 3040 73.6 10.2 13.8 2.2 3420 58.3 15.2 24.2 2.1

"type of film. 5,403,620 1. 2 For instance, the use of metal carbonyl compounds in CATALYSSN ORGANOMETALLC CVD OF CVD applications typically introduces carbon and oxy THIN METAL FILMS gen contaminants. Localized laser heating at high tem peratures of small deposited metal "dots' as shown by BACKGROUND OF THE INVENTION 5 Houle et al in their work with deposited tungsten ap pears to essentially clean in the center with impurities 1. Field of the Invention on the periphery of the dot area. This invention relates to chemical vapor deposition The three major chemical processes for achieving (CVD) of thin metal films, and in particular to the cata CVD can be generally classified as reduction, thermal lyzed removal of heteroatoms during the deposition of 0 decomposition, and displacement. metals from precursor film forming metal compounds in Reduction involves exposing the volatile metal com the presence of hydrogen. pound during or after deposition on the substrate to 2. Description of the Prior Art hydrogen or equivalent reducing gas. Theoretically, the The deposit of thin coatings of metals onto various hydrogen reacts with the nonmetal portion of the com substrates are important in several industries. For exam 15 pound to yield volatile hydrocarbon byproducts and to ple, one of the most important applications is in the leave the metal film behind on the substrate. production of integrated circuits in the microelectronics Thermal decomposition involves heating the sub industry. In this respect, one of the most important strate to cause the hydrocarbon portion of the volatile criteria is the purity of the deposited thin metal film. metal compound to decompose to volatile hydrocar The presence of even small amounts of carbon, oxygen 20 bons and leave the surface of the substrate while leaving and other heteroatom contaminants can markedly affect the metal on the surface. the performance of the finished electronic component. Displacement involves use of a surface material or The term "heteroatom' as used herein and in the surface absorbed species on the substrate to react with appended claims is meant to include all atoms except the volatile metal compound to yield volatile by metal atoms. 25 products and deposit metal on the exposed surface. Various methods have been used for purposes of All of the above techniques suffer from the introduc depositing a thin metal coating onto a substrate includ tion of impurities during the decomposition reaction of ing for example precipitation from liquid solution, sput the precursor metal compound or to produce corrosive tering, and chemical vapor deposition (CVD), and byproducts in depositing the metal film. plasma enhanced CVD. 30 In recent years, improved purity of thin metal films In addition to purity, it is often desirable to selec deposited by CVD involved the use of organometallics tively deposit a metal film on a portion of the surface of as the volatile compound. See Gozum, J. et al., "Tai a semiconductor or other electronic component. This is lored Organometallics as Precursors for the Chemical particularly the case for purposes of providing intercon Vapor Deposition of High-Purity Palladium and Plati nects to various circuit elements which require selective 35 num. Thin Films,” J. Am. Chen. Soc., 110, 2688 (1988). deposition in small voids in the substrate surface of the In the above referenced article bis(allyl)palladium, electronic component. bis(2-methylallyl)palladium, and (cyclopentadienyl)(al The use of liquid solution precipitation of precursor lyl) palladium were investigated for CVD at 250 C. compounds followed by metal deposition has some and 10 Torr. The cyclopentadienyl compound advantages. However, it has generally been unsatisfac yielded CVD palladium films having about 5 mol % tory for purposes of complete and contiguous deposi residual carbon as a contaminant. However, it was also tion since it is difficult to insure that the solution will found that at a similar temperature and pressure, the penetrate the small voids which are necessary to insure cyclopentadienyl complex CPPtMe3(cyclopen film quality and proper adherence to the substrate. Ad tadienyl)(trimethyl)platinum(IV) produced high qual ditionally, the purity of the deposited coating is often 45 ity platinum films that were not significantly contami not as high as is necessary for some commercial applica nated with carbon. In some cases a large amount of tions. Sputtering has also been rejected in many in carbon is incorporated by the process. For example, stances since the quality of the coating as well as the titanium carbide films have been deposited using tet uniformity of the coating has often been less than com raneopentyltitanium (TiCH2C(CH3)34) at approxi mercially acceptable. Also, this method requires that 50 mately 350° C. The deposited Ti contained sufficient the extra metal introduced be chemically etched away carbon to form a separate TiC phase. in subsequent treatments. Organometallic compounds have also been evaluated Chemical vapor deposition, has provided more uni for other purposes. For example, in Egger, K., "Cy form deposition of thin metal films and is more reliable clopentadienyl-Metal Complexes II. Mass Spectromet for conformal coverage in the deposition of metal films 55 ric and Gas Phase Kinetic Studies on the Thermal Sta on convoluted surfaces. Despite the advantages of bility and the Structure of (CH3)3Pt-Cshs,” J. Organo CVD, the degree of purity of the deposited metal films metallic Chemistry, 24, 501 (1970), the structure of cy has often been less than desired. clopentadienyl(trimethyl)platinum(IV) was reported. Chemical vapor deposition has produced films which The article concluded that the cyclopentadienyl group have been contaminated with unacceptable levels of 60 was at bonded. Studies of the hydrogenation of (1,5 carbon and oxygen and other heteroatoms that are de cyclooctadiene) dimethylplatinum has also been re rived from decomposition of hydrocarbon and oxocar ported. Miller, T. et al., “Heterogeneous, Platinum-Cat bon moieties of the volatile CVD precursor com alyzed Hydrogenation of (Diolefin)dialkylplatinum(II) pounds. Complexes: Kinetics,” J. Am. Chem. Soc., 3146 (1988) These precursor compounds are typically organome (and two subsequent articles by the same author). Hy tallic compounds with hydrocarbon, carbonyl, and hy drogenation of nickelocene (C5H5)2Ni) has also been dride ligands that are used in organometallic chemical reported. Kaplin, Y. et al., “Decomposition of Nickelo vapor deposition processes (OMCVD). cene in Presence of Hydrogen,' UDC 547.1174, c. 1980 5,403,620 3 4 Plenum Publishing Corp., translated from Zhurnal atom contaminants than hitherto possible. As used Obshchei Khimi, 50, 118 (1980). None of these articles, herein and in the appended claims the term “liquid however, report any special benefits of using these com CVD” refers to use of a solution deposited precursor pounds in CVD. compound in the CVD process. In our newly issued patent U.S. Pat. No. 5,130,172 5 It is a further object of the invention to provide a thin there is described the low temperature deposition of metal film, especially tungsten having up to 5-10 mol % organometallic compounds onto substrates. The pro of another catalytic metal such as platinum, and other cess includes coating onto various substrates such as Group VIII transition metals such as ruthenium, os glass or silicon, at least one metal that can readily cycle mium, cobalt, rhodium, iridium, nickel, and palladium. between two oxidation states and that is also a hydroge 10 nation catalyst capable of facilitating the hydrogenation It is a further object of the invention to provide a of hydrocarbon ligands of precursor organometallic process for the deposit of tungsten and/or other metals compounds. During the process the substrate is main having dissolved therein or alloyed with, or heteroge tained at a relatively low temperature in the range of neously admixed, one or more of the above catalytic metals. about room temperature up to about 190 C. depending 15 on the substrate. It is also an object of the invention to provide a pro The precursor organometallic compound of our pa cess wherein tungsten and/or other metals can be de tent which is vaporized or dissolved has the general posited on a substrate from precursor film forming formula metal compounds and the purity improved by including 20 precursor catalytic metal compounds which catalyze LMRn the removal of carbon from the deposited tungsten and other metal films and at the same time remain as a dis wherein L is hydrogen, ethylene, allyl, methylallyl, solved portion of the tungsten or other metal films, or at butadienyl, pentadienyl, cyclopentadienyl, methycy the metal surface or at grain boundaries. clopentadienyl, cyclohexadienyl, hexadienyl, cyclohep 25 It is a further object of the invention to provide a tatrienyl, or derivatives of said compounds having at process for controlling the amount of heteroatom such least one alkyl side chain having less than five carbon as carbon in the deposit of metal films in which one atOmS, precursor would introduce carbon during metal deposi M is a metal which can readily cycle between two tion while another precursor would deposit the pure oxidation states and can catalyze hydrogenation of hy 30 metal. Such depositions can be simultaneous or sequen drocarbon ligands of the organometallic compound tial. such as cobalt, rhodium, iridium, nickel, palladium, It is another object of the invention to provide metal platinum, osmium, ruthenium. films comprising a mixture of two metals with up to 10 R is methyl, ethyl, propyl, or butyl, mol % of a catalytic metal. n is a number from 0 to the valence of said metal, 35 It is a further object of the invention to provide a m is a number from 0 to the valence of the metal, and method for the laser induced deposition of pure metal m plus n must equal the valence of the metal. films using precursor film forming metal compounds During the process the substrate is continuously ex and precursor catalytic metal compounds in the pres posed to hydrogen gas and the organometallic com ence of hydrogen gas wherein the laser beam is directed pound at a temperature in the range of about room on the substrate at an incident angle ranging from per temperature to about 190 C. depending on the organo pendicular to parallel. metallic compound. During the course of reaction, a It is also an object of the invention to provide a pro layer of the metal from the organometallic compound is cess for deposition of pure metals from precursor film deposited on the surface of the substrate which at the forming metal compounds in the presence of precursor same time catalytically hydrogenates the hydrocarbon 45 catalytic metal compounds and hydrogen gas wherein ligand of the organometallic compound to provide sig the precursor catalytic metal compound is first depos nificant purity of the deposited metal compared with ited on the substrate from a solvent solution followed by prior art processes. In the above process, the best results evaporation and thermal decomposition to leave the were obtained using CpPtMe3 or MeCpPtMe3. catalytic metal on the substrate, followed by CVD de A particular advantage of the process is that in most 50 cases the process takes place at a relatively low temper position of a metal from precursor film forming metal ature and the carbon impurity can be kept as low as 3.5 compounds in the presence of hydrogen gas. The above mol % or less. process is referred to herein and in the claims as "liquid However, following the above process using a heated CVD'. substrate of, for example, silicon or glass and an organo 55 It is also an object of the invention to provide pro metallic compound wherein the metal is comprised of a cesses for the deposition of pure metal films onto sub refractory metal such as tungsten and in the presence of strates by various combinations of gas CVD and liquid hydrogen gas, it has been found that the deposited tung CVD processes, using precursor film forming metal sten metal is contaminated significantly with carbon, as compounds and precursor catalytic metal compounds in much as 30 mol % to 40 mol % depending on the reac the presence of hydrogen gas. tion conditions. Thus, the presence of the hydrogen It is also an object of the invention to selectively reducing gas is insufficient in the case of tungsten or deposit metals onto a substrate using precursor film ganometallics to prevent the contamination of the de forming metal compounds and catalytic amounts of a posited tungsten film with carbon. precursor catalytic metal compound in the presence of Thus, it is an object of the invention to provide a 65 hydrogen gas. In this manner, the process can be used to method for depositing metal films, and especially tung provide a patterned deposition of metals either from the sten metal films by both liquid and gas phase CVD. gas phase deposition, either sequentially or simulta Such metal films contain significantly reduced hetero neously or by the liquid phase deposition of precursor 5,403,620 5 6 compounds to deposit either the metals or catalytic due to their low electrical resistivity. Of lesser interest metals or both or all sequentially or simultaneously. are hafnium, thorium, titanium, uranium, vanadium, and zirconium due to their high electrical resistivity, al SUMMARY OF THE INVENTION though the invention process can be used advanta The invention includes the deposition of a thin layer 5 geously to improve the purity of these and other depos of tungsten and other metals onto a substrate with ited metal films for a variety of other applications. greatly improved purity levels. The precursor film forming metal compounds, for The process includes using one or more precursor example, bis(cyclopentadienyl)dihydrotungsten, film forming metal compound as the major film forming (C5H5)2WH2, and the precursor catalytic metal com metal precursor, for example organotungsten, which is 10 pounds, for example CpptMe3 are each separately admixed with minor amounts of a precursor catalytic mixed with helium, argon or other inert gas preferably metal compound, for example, an organoplatinum com to the point of saturation. The two gases are then prefer pound, as a precursor to a catalytic metal in the pres ably mixed together, as in a manifold, prior to introduc ence of hydrogen gas and wherein the substrate is tion into the reaction chamber. The use of the inert gas heated to bring about deposition of the film forming 15 prevents premature decomposition, especially of the metal and catalysis by the catalytic metal for removal of precursor catalytic metal compounds in the presence of carbon and other heteroatom contaminants as volatile hydrogen gas. hydrocarbon byproducts from the deposited metal film. Alternatively, the precursor film forming metal com The invention process also includes the liquid phase pounds can be introduced with a stream of hydrogen deposition of the precursor followed by metal deposi 20 gas, while the more reactive precursor catalytic metal tion as well as gas phase deposition, sequentially or compound is preferably introduced by a stream of inert simultaneously to control and or to tailor deposited gaS. metal films and metal admixtures. Laser induced CVD Hydrogen gas is separately introduced into the reac and plasma enhanced CVD are also included in the tion chamber, preferably near to the substrate. Excel invention. 25 lent results have been obtained using approximately The invention also includes the improved purity equal volume portions of the hydrogen gas and the metal films, especially tungsten metal films having rela mixture taken as a whole of the inert gas saturated with tively minor amounts of a catalytic metal dissolved, the precursor film forming metal compounds and the admixed, or alloyed therein. inert gas saturated with the precursor catalytic metal 30 compounds. DESCRIPTION OF THE DRAWINGS Saturation of the inert gas is effected by passage of FIG. 1 shows the X-ray diffraction pattern of tung the inert gas over the precursor film forming metal sten film deposited on silicon in accordance with the compounds or over the precursor catalytic metal con invention process. pounds. FIG. 2 shows an Auger depth profile of a deposited 35 The relative amounts of the precursor film forming W/Pt film. metal compounds and the precursor catalytic metal Table 1 shows a comparison of a W/Pt film deposited compounds are controlled by the flow rates. The pre according to the invention with a W film deposited cursor catalytic metal compounds are included to pro according to a prior art process. vide up to 10 mol %, with from 0.1-5 mol% being most preferred. The exact amount will depend upon the iden OETALED DESCRIPTION OF THE tity of the precursor film forming metal compounds and INVENTION of the precursor catalytic metal compounds used. It is intended that any procedure normally followed All of the gases are preferably directed in a stream for chemical vapor deposition (CVD) or liquid vapor across the surface of the substrate. The substrate is deposition can be used in carrying out the process of the 45 heated to and maintained at a temperature sufficiently invention. Deposition by means of laser photodeposi high to cause decomposition of the precursor film form tion is also used and is an additional process element of ing metal compounds. The exact temperature will de the invention. pend upon the identity and chemical, thermal, and sta Preferably, a reaction chamber is used having a bility makeup of the compounds used under the reaction means for introduction of gaseous substances. If desired, 50 conditions. A temperature of approximately 200-400 the reaction chamber can be provided with a window C., has given good results using in the case of made of a special quartz material such as Spectrosyl TM (C5H5)2WH2 on various substrates. or Carbosyl TM which permits the passage of infrared Heating of the substrate is preferably by means of an light for purposes of heating of the substrate. infrared lamp which is focused through the quartz win The reaction chamber also includes a susceptor or 55 dow in order to specifically heat the substrate. other support for holding the substrate onto which the The precursor film forming metal compound gas tungsten is to be deposited. mixture and the precursor catalytic metal compound The substrates, for example, can be comprised among gas mixture are preferably prewarmed to a temperature others of glass, fused silica, sapphire (001), silicon (100) of approximately 60' C. and GaAs (100). Cleaning of the substrates by degreas The pressure within the reaction chamber during the ing, acid or other etching prepares the surface of the reaction can be ambient but is more preferably a dy substrate for the deposition process by removing impu namic vacuum so that the stream of gases is constantly rities which can interfere with the deposition process. passing over and contacting the substrate surface onto The process is particularly suitable for deposition of which the film forming metal such as tungsten and the metals which are capable of resisting high temperatures 65 catalytic metal, such as platinum are being continuously and which preferentially form refractory carbides in the deposited. presence of carbon. Such metals of greatest interest In some cases, a preliminary surface treatment with include tungsten, molybdenum, niobium, and tantalum the catalytic metal is feasible. Alternatively, the cata 5,403,620 7 8 lytic metal deposited from the catalytic metal precursor hydride, (C5H5)2TiH2BH2; bis(cyclopentadienyl)dime in the early part of the CVD process is sufficient to thyltitanium, (C5H5)2Ti(CH3)2; bis(cyclopentadienyl)- yield relatively pure metal film. methylvanadium, (C5H5)2VCH3; 1,1'-dimethylvanado In some cases the precursor metal compound or com cene, (C5H4CH3)2V; bis(2,4-dimethylpentadienyl)- pounds and/or the precursor catalytic metal compound vanadium, (C5H3(CH3)2)2V; bis(cyclopentadienyl)- can be introduced into a plasma in plasma-enhanced dihydrotungsten, (C5H5)2WH2; trisbutadienetungsten, CVD processes. (C4H6)3W; hexamethyltungsten, (CH3)6W; and bis(cy The precursor from which the film forming metal is clopentadienyl)(cyclobutadiene)Zirconium, deposited is one or more vaporizable or soluble precur (C5H5)22rcH4. sor film forming metal compounds having the formula O Examples of the precursor organocatalyst metal com LMRn. The precursor film forming metal compounds pound comprise among others: is included as a major component of a gas mixture CpPtMe3; CpPt(allyl); CpPt(methylallyl); MeCpPt which is admixed with a minor amount of at least one (methylallyl); CpPt(CO)CH3; MeCpPt(CO)CH3; bisal vaporizable precursor catalytic metal compound having lylPd; (methylallyl)Pd(allyl); bis(2-methylallyl)pal the formula 5 ladium; (cyclopentadienyl)(allyl)palladium; IMRn. (CH3C5H4)PtMe3; (C3H5)3Rh; (C3H5)3Ir; Cpr(hexadi ene); (C5H5)Ir(C6Hs); (C5(CH3)5)Ir(ethylene)2; In the above formulas, L is a T-bonding organic ii (C5H7)Ir(C8H8); (CH3C5H4)2Ni; (cyclopentadienyl)- gand such as ethylene, allyl, methylallyl, butadienyl, (cyclohexadienyl)cobalt, (C5H5)Co(C5H7); pentadienyl, cyclopentadienyl, methycyclopentadienyl, 20 (CH3C5H4)Co(MeCp); (C5H5)CoCp; (cy cyclohexadienyl, hexadienyl, cycloheptatrienyl, or clobutadienyl)(cyclopentadienyl)cobalt, alkyl or alkyl silyl or fluorinated derivatives of such (C4H4)CoC5H5; bis(cyclopentadienyl)cobalt; compounds having sufficient volatility of the precursor (C5H5)2Co; bis(methylcyclopentadienyl)cobalt, metal compound to be of utility in CVD or liquid CVD; (CH3C5H4)2Co; cyclopentadienyl(1,3-hexadienyl)- M is a precursor metal such as a transition metal, Ti 25 cobalt, (C5H5)CoC6H7; (cyclopentadienyl)(5-methyl (titanium), Zr (zirconium), Hf (hafnium), V (vanadium), cyclopentadienyl)cobalt, (C5H5)CoC5H4CH3; Nb (niobium), Ta (tantalum), Cr (chromium), Mo (mo (C5H5)Co(CO)2; (C6Hs)CoCp; bis(ethylene)(pentame lybdenum), W (tungsten), Mn (manganese), Re (Rhe thylcyclopentadienyl)cobalt, ((CH3)5Cs)Co(C2H2)2; nium), Fe (iron), Ru (ruthenium), Os (osmium), or a triallylchromium, (C3H4)3Cr, bis(cyclopentadienyl)- main group metal such as Al (aluminum), Ga (gallium), 30 chromium, (C5H5)2Cr; (cycloheptatrienyl)(cyclopen In (indium), Si (silicon), Ge (germanium), Sn (tin), or a tadienyl)chromium, (C7H7)Cr(C5H5); bis(cyclopen lanthanide or actinide metal such as La (lanthanum), Nd tadienyl)iron, (C5H5)2Fe; (2,4-cyclohexadienyl)(cy (neodymium), Sm (samarium), U (uranium), Pu (pluto clopentadienyl)iron, (C6H)Fe(C5H5); (cyclopen n1um; tadienyl)(methylcyclopentadienyl)iron, M' is a metal selected from the group of metals that 35 can catalyze hydrogenation and hydrogenolysis reac (C5H5)Fe(C5H4CH3);bis(methylcyclopentadienyl)iron, tions of unsaturated and saturated organic ligands, L (CH3C5H4)2Fe; (cycloheptatrienyl)(cyclopentadienyl)- and R, to yield volatile byproducts and also can cata manganese, (C5H5)Mn(C7H8); (benzene)(cyclopen lyze the hydrogenation of surface carbon to methane as tadienyl)manganese, (C5H5)Mn(C6H6); ethenylosmo in Fischer-Tropsch catalysis in the presence of hydro cene, (C5H5)Os(C5H4CHCH2); 1,1'-dimethylosmocene, gen, and consisting among others of the Group VIII (C5H4CH3)2Os; vinylosmocene, transition metals of Co (cobalt), Rh (rhodium), Ir (irid (C5H5)O5(C5H4CH2CH3); bis(cyclopentadienyl)hy ium), Ni (nickel), Pd (palladium), Pt (platinum), Fe dridorhenium, (C5H5)2ReH; hexamethylrhenium, (iron), Ru (ruthenium), and and Os (osmium); (CH3)6Re; HRe(CO)5; cyclopentadienyl(methylcy R is a G-bonding ligand radical such as hydrogen, 45 clopentadienyl)ruthenium, (C5H5)Ru(C5H4CH3); ru methyl, ethyl, n- or iso- propyl, n-, sec-, or t-butyl, thenocenylacetylene, (C5H5)Ru(C5H4CCH); vinyiru benzyl, phenyl, and silylated and fluorinated derivatives thenocene, (C5H5)Ru(C5H4CHCH2); bis(methylcy having sufficient volatility or solubility of the precursor clopentadienyl)ruthenium, Ru(CH3C5H4)2; ethylru metal compound to be of utility in CVD or liquid CVD; thenocene, (C5H5)Ru(C5H4CH2CH3). n is a number from 0 to the valence of said metal, 50 Examples of the preferred precursor film forming m is a number from 0 to the valence of the metal, metal compounds include: where m plus n allow a stable configuration of the pre bis(cyclopentadiene)dihydrotungsten, (C5H5)2WH2; cursor metal compound to allow the precursor com trisbutadienetungsten, (C4H6)3W. pound to be either volatile or soluble. The preferred precursor catalytic metal compounds Examples of the precursor film forming metal com 55 ae pounds include but are not limited to: CpPtMe3 or MecpPtMe3. bis(cyclopentadienyl)-dihydromolybdenum, By the term "soluble' as used herein and in the ap (C5H5)2MoH2; bis(cyclopentadienyl)(ethylene)molyb pended claims is meant to have sufficient solubility to denum, (C5H5)2MoC2H2; tris(butadiene)molybdenum, enable the precursor compound to be dissolved in an (C4H5)3Mo; tris(cyclobutadienyl)molybdenum, organic solvent. Examples of such organic solvents (C4H4)3Mo; dicylopentadienyltrihydroniobium, includes among others hexane, cyclohexane, tetrahy (C5H5)2NbH3; bis(cyclopentadienyl)niobiumborohy drofuran, 1,2-dimethoxyethane, acetonitrile, and the dride, (C5H5)2NbH2BH2; bis(cyclopentadienyl)hy like. dro(ethylene)niobium, (C5H5)2NbHC2H2; bis(cy The solution is applied to the surface of the substrate clopentadienyl)allylniobium, (C5H5)2NbC3H4; pen 65 and the solvent removed by evaporation. Thermal heat tamethyltantalum, Ta (CH3)5; bis(cyclopentadienyl)- ing and/or laser induced decomposition in the presence trihydrotantalum, (C5H5)2Tahs; bis(cyclopentadienyl)- of hydrogen gas and the catalytic metal causes the metal trimethyltitanium, (C5H5)2Ti(CH3)3; titanocene boro film to be formed. 5,403,620 10 The precursor film forming metal compounds for Grignard reagent. Solvent was removed at 0° C. under metal film forming are included in major amounts with 10-2 torr vacuum. 50 ml pentane was used to extract relatively minor amounts of the precursor catalytic the product from the raw product, and the pentane was metal compounds. With respect to the amount of the removed at 15-20 C. and 10-2 torr to give the crude precursor catalytic metal compounds, there can be in product. The crude product was then purified by subli cluded up to about 10 mol %. mation at 15 torr and 50° C. with a cold finger at 10 C. The invention will be more easily understood by for about 30 minutes. reference to the following examples which are pres Compounds (e) to (i) were prepared using similar ented for the purpose of illustrating the invention and procedures. are in no way intended to constitute a limitation thereof. 10 EXAMPLE 1. EXAMPLE 2 PREPARATION OF PRECURSOR FILM DEPOSITION OF TUNGSTEN IN THE FORMING METAL COMPOUNDS AND PRESENCE OF HYDROGEN AND AN PRECURSOR CATALYTIC METAL, 15 ORGANOPLATINUM CATALYST COMPOUNDS The reaction materials were prepared from precur The following precursor film forming metal com sors. The organotungsten compound, Cp2WH2 was pounds and precursor catalytic metal compounds were prepared from WCl6 following the procedure outlined prepared: by M. L. H. Green, J. A. McCleverty, L. Pratt and G. (a) CpPtMe3 20 Wilkinson, J. Chem. Soc., 4854 (1961); see also Organo (b) (CH3C5H4)PtMe3 metallic Syntheses, J. J. Eisch and R. B. King, Eds., Vol. (c) (C3H5)3Rh 1, Transition Metal Compounds, R. B. King, Ed. (Aca (d) (C3H5)3Ir demic Press, New York, N.Y., 1965) 79. (e) HRe(CO)5 The precursor CplptMe3 was prepared from K2PtCl6 (f) (CH3C5H4)2Ni 25 according to the method described by Z. Xue, H. Thri (g) (C5H5)2CoCP dandam, H. D. Kaesz and R. F. Hicks, Chem. Mater., 4, (h) (C5H5)Co(C6H); (i) (CH3C5H4)Co(MeCp); 162 (1992). Alternatively, the CpPtMe3 can be pur where Cp is cyclopentadienyl; Me is methyl; (C6H) is chased directly from Strem Chemical Company, New cyclohexadiene; and MeCp is methylcyclopentadiene. 30 buryport, Mass. Compound (a) was prepared from PtMe3I and NaCp The reaction chamber was comprised of a glass tube using the procedure described in Robinson, S. and having a diameter of 2.5 cm. The tungsten was depos Shaw, B., J. Chem. Soc., 277, 1529 (1965), except that ited on both glass and silicon (100) substrates. Prior to toluene was used instead of benzene as the solvent, and deposition, the glass was washed in ethylene chloride the reaction was started at -77 C. The yield obtained 35 and methanol, rinsed in deionized water, and dried in was 52%. Compound (a) was also obtained using the air. The silicon wafers were similarly prepared but de Robinson and Shaw procedure. ionized after water rinsing, also included etching for 10 Compound (b) was prepared as follows: 445 mg seconds in 10% by volume hydrofluoric acid, rinsing PtMe3I in 25 ml ethyl ester dried over potassium and again in water, and then drying in air. benzene was added dropwise at -78 C. under nitrogen The substrate was placed within the glass tube. The to 1.5 ml of approximately 1.1 M MeCpNa. The solu section of the tube containing the substrate which was tion was slowly raised back to room temperature over about 3 cm long, was heated to 380-20 C. by means 12 hours while stirring. Ethyl ether and THF were of heating tape wrapped uniformly around the tube. removed at -20 to -30 C, leaving an oily residue The Cp2WH2 was placed 5 cm upstream of the sub that sublimed at room temperature. A cold finger at 45 strate and was heated to 100-150° C. by a resistance -15 C. gave 62 mg of a yellow compound. The resi heater located directly underneath the tube. At these due was extracted with pentane and filtrated in air. The temperatures the vapor pressure of Cp2WH2 is ~ 0.01 pentane was removed at -20 C. Torr. During the deposition period, hydrogen was fed Compound (c) was prepared as follows: 100 mg at 8 cm/min, and argon was fed at 16 cm/min. The RhCl3 anhydrous was stirred in 50 ml ethyl ether dried 50 over potassium and benzophenone and added to a ten argon was passed through a glass frit containing times excess of allylMgCl (2.0 M in THF (Aldrich)). CpptMe3 at 23° C. so that the argon became saturated After stirring for 12 hours, dry ice was added to the with 0.045 Torr of the precursor catalytic metal com decomposed excess allylMgCl, and the mixture was pound. dried under vacuum at -15 C. Pentane was then used 55 The argon and the hydrogen were purified prior to to exhaust the residue and pentane was removed at reaction by passing through a deoxygenating catalyst about 5 degrees centigrade by water evaporation. After (OXYSORBTM, Altec Associates, Inc.) and 13X mo sublimation (cold finger at temperature of running wa lecular sieves. The relative ratios or percentages by ter, flask at room temperature), a yellow solid formed volume of the Cp2WH2 and CpptMe3 were 90/10 mol on the cold finger. %. The gases were flowed over the substrate for a Compound (d) was prepared as follows: 0.200 g IrCl3 period ranging from 6 to 20 hours. in 4 ml toluene was dried and added dropwise under Using the silicon (100) substrates, it was found that argon gas to 3.4 ml of 2MallylMgClin THF (Aldrich) tungsten decomposed more readily than on the glass at -78 degrees C. The black IrCl3 remained undis substrates. For example, the glass surface was covered solved. The solution was then raised to room tempera 65 with a transparent brown layer of material after 6 hours ture and heated on a water bath to 50 C. for 10 hours. of deposition. After the same amount of time, the silicon The solution was dark and no precipitate formed. A few was covered with a uniform, highly reflective metal lumps of dry ice were added to destroy any remaining film. 5,403,620 11 12 It was estimated that the growth rate of the films was Table 1 shown below compares the compositions of between 0.05 and 0.15 A/s. The films exhibited excel W/Pt films deposited according to example 2 and W lent adherence to the silicon as demonstrated by the fact films deposited according to example 3. that they could not be removed by cellophane tape An examination of Table 1 indicates that when tung application. 5 sten is deposited without the organoplatinum catalyst, The structure and composition of the deposited W/Pt the composition of the film is 71.8% W, 25.1% C, and films were analyzed by X-ray diffraction, scanning elec 3.1% O. Thus, there is significantly decreased carbon tron microscopy, and Auger electron spectroscopy contamination (25.1% C compared to 5.3% C) and with depth profiling. A 4-point probe was used to deter decreased contamination with oxygen (3.1% O com mine the sheet resistivity and a depth profiling measure 10 pared to 1.8% O) when the precursor catalytic metal ment yielded the thickness of the films deposited. compound is codeposited with the tungsten precursor. It was found that the deposited films are amorphous These results demonstrate the advantage of including and comprised of 100-500A clusters as shown by scan small amounts of CpPtMe3 or equivalent precursor ning electron micrographs. It was also found that the catalytic metal compounds for codeposition to enhance clusters could be converted into microcrytallites by 5 the purity of transition metal films obtained by chemical annealing in hydrogen at 750° C. Vapor deposition. FIG. 2 shows an Auger depth profile of the W/Pt EXAMPLE 4 film. The bulk film is sputtered from 20 to 140 minutes LASER PHOTODEPOSITION after which the Sisignal appears due to sputtering of the 20 silicon substrate. FIG. 2 does not show the atomic con Using the reaction chamber substantially as described tribution from the silicon. The film produced was found in Example 3, glass, silicon, fused silica, sapphire (001), to contain 89.6% W, 3.3% Pt, 5.3% C, and 1.8% O. It and GaAs (100) substrates are deposited with tungsten is believed that this is the highest purity tungsten film using Cp2WH2 and CpPtMe3 in the presence of hydro ever produced from the thermal decomposition of an 25 gen. Organotungsten precursor. The substrates are prepared in the same manner as It is believed that the high purity is a consequence of described in Example 3. the catalytic hydrogenation and hydrogenolysis of the A stream of argon gas is separately passed over crys hydrocarbon ligands by the codeposited platinum. tals of Cp2WH2 and over crystals of CpPtMe3 to satu The above results demonstrate that increased purity 30 rate the argon gas with the respectively compounds. of tungsten films can be effected by including small Hydrogen gas is introduced into the reaction cham amounts of CpptMe to improve the purity of transition ber in proximity to a laser beam, and gas flow is parallel metal films obtained by chemical vapor deposition of to the surface of the substrate. precursor film forming metal compounds. All photolyses are carried out at atmospheric pres 35 sure with the laser beam perpendicular to the surface. EXAMPLE 3 An alternative deposition using the laser beam parallel DEPOSITION OF TUNGSTEN FROM to the surface to induce a gas phase reaction that surface ORGANOTUNGSTEN IN THE ABSENCE OF A deposits metal can also be used as well as laser beam PRECURSOR CATALYST METAL COMPOUND deposition at angles between parallel and perpendicular 40 to the surface. This example is presented for purposes of comparison The laser is a 308 nm line of a XeCl excimer laser or only and is not in accordance with the process of the the 351 and 364 nm lines of an argon ion laser. invention. The deposition is first carried out by irradiating a The procedure of Example 2 was repeated except circle 1 mm in diameter with 2.6 m/pulse at 10 Hz that tungsten was deposited from Cp2WH2 in the pres 45 using the 308 nm band. Visible mirrors are formed on ence of hydrogen but without the presence of an or the substrates in about 10 minutes. The deposited films ganoplatinum catalyst. have a thickness of about 1000 angstroms. Hydrogen was fed to the reactor upstream of the Photodeposition is carried out under CW conditions precursor at 2 cm/min (at 20 C.). with fluences of 4-5 mW/mm2 at laser wave lengths of X-ray diffraction, scanning electron microscopy, and 50 35i and 364 nm. Using the same flow rates, mirror-like Auger electron spectroscopy with depth profiling was deposits are observed in about 10 minutes. also used to analyze the structure and composition of Analysis of the films using Auger electron spectros the W films deposited. A four-point probe was used to copy showed substantially the same pure films as ob measure sheet resistivity and film thickness was deter tained following the process of Example 3. mined with depth profiling measurements. 55 The substrate is patterned using a mask and a 40 mm The film thickness was 1,450 A. lens for the laser. The image is focussed below the sur FIG. 1 shows the X-ray diffraction pattern of tung face of the substrate in order to minimize the focus, and sten film deposited on silicon (100) after annealing in hence deposition, on the cell windows. Successful pat hydrogen at 750° C. for 2 hours. As shown, the sharp terned depositions are obtained. lines near 26 = 40,58, 73, and 87 are due to W metal. 60 Laser induced and plasma enhanced metal deposition A silicon substrate shows a broad peak at 69. No peaks can also be used in combination with various combina were found for tungstensilicide. tions of gas phase CVD and liquid CVD as above de It was found that the sheet resistivity of the unan scribed. nealed W films averaged 544 u().cm. This is com Various modifications of the invention are contem pared with the value for bulk tungsten metal of 5.6 65 plated which will be obvious to those skilled in the art LO.cm. It is believed that the high resistivity is proba and which can be resorted to without departing from bly due to the amorphous nature of the deposit as well the spirit and scope of the invention as defined in the as the poor contact between adjacent metal clusters. following appended claims. 5,403,620 13 14 We claim: form. on said surface a metal film M containing 1. A process for the chemical vapor deposition of at catalytic metal M" without causing substantial im least one metal onto a substrate comprising: purities from the ligands of said precursor com a) exposing said substrate to a fluid mixture contain pounds to be formed on said surface and incorpo ing a major amount of at least one vaporizable or rated on or within said metal film. soluble precursor film forming metal compound 2. A process according to claim 1 wherein said pre having the formula cursor catalytic metal compounds LMRn comprise 0.1 to 10 mol % relative to said precursor film forming InMRn. compounds LMRn and both being introduced in a 10 stream of inert gas. and to a fluid containing a minor amount of at least one 3. A process according to claim 1 wherein said pre vaporizable or soluble precursor catalytic metal com cursor film forming metal compounds comprise: pound having the formula bis(cyclopentadienyl) dihydromolybdenum, LMR (C5H5)2MoH2; bis(cyclopentadienyl)(ethylene)- 15 molybdenun, (C5H5)2MoC2H2; tris(butadiene)- molybdenun, (C4H5)3Mo; tris(cyclobutadienyl)- wherein L is a 7t-bonding organic ligand consisting of molybdenum, (C4H4)3Mo; dicylopentadienyltrihy ethylene, allyl, methylallyl, butadienyl, pentadie droniobium, (C5H5)2NbH3; bis(cyclopentadienyl)- nyl, cyclopentadienyl, methycyclopentadienyl, niobiumborohydride, (C5H5)2NbH2BH2; bis(cy cyclohexadienyl, hexadienyl, cycloheptatrienyl, or 20 clopentadienyl)hydro(ethylene)niobium, alkyl or alkylsilyl or fluorinated derivatives of said (C5H5)2NbHC2H2; bis(cyclopentadienyl)allylni precursor catalytic metal compounds having suffi obium, (C5H5)2NbC3H4; pentamethyltantalum, cient volatility of the precursor metal compound to Ta(CH3)s; bis(cyclopentadienyl)trihydrotantalum, be of utility in gaseous CVD or liquid CVD; (C5H5)2Tahs; bis(cyclopentadienyl)trimethyl M is a precursor metal consisting of a transition 25 titanium, (C5H5)2Ti(CH3)3; titanocene borohy metal, Ti (titanium), Zr (zirconium), Hf (hafnium), dride, (C5H5)2TiH2BH2; bis(cyclopentadienyl)- V (vanadium), Nb (niobium), Ta (tantalum), Cr dimethyltitanium, (C5H5)2Ti(CH3)2; bis(cyclopen (chromium), Mo (molybdenum), W(tungsten), Mn tadienyl)methylvanadium, (C5H5)2VCH3; 1,1'- (manganese), Re (Rhenium), Fe (iron), Ru (ruthe dimethylvanadocene, (C5H4CH3)2V; bis(2,4-dime nium), Os (osmium), or a main group metal consist 30 ing of Al (aluminum), Ga (gallium), In (indium), a thylpentadienyl)vanadium, (C5H3(CH3)2)2V; bis(- group 4a element consisting of Si (silicon), Ge cyclopentadienyl)dihydrotungsten, (C5H5)2WH2; (germanium), Sn (tin), or a lanthanide or actinide trisbutadienetungsten, (C4H6)3W; hexamethyl metal consisting of La (lanthanum), Nd (neodym tungsten, (CH3)6W; and bis(cyclopentadienyl)(cy ium), Sm (samarium), U (uranium), Pu (plutonium; 35 clobutadiene)zirconium, (C5H5)2ZrC4H4. M' is a metal selected from the group of metals that 4. A process according to claim 1 wherein said pre can catalyze hydrogenation and hydrogenolysis cursor catalytic metal compounds comprise: reactions of unsaturated and saturated organic li CpPtMe3; Cpt(allyl); Cppt(methylallyl); MeCpPt gands, L and R, to yield volatile byproducts and (methylallyl); CpPt(CO)CH3; MeCpPt(CO)CH3; also can catalyze the hydrogenation of surface bisallylPd; (methylallyl)Pd(allyl); bis(2-methylal carbon to methane in the presence of hydrogen, lyl)palladium; (cyclopentadienyl)(allyl)palladium; and consisting of the Group VIII transition metals (CH3C5H4)PtMe3; (C3H5)3Rh; (C3H5)3Ir; Cpr(- of Co (cobalt), Rh (rhodium), Ir (iridium), Ni hexadiene); (C5H5)Ir(C6Hs); (Cs(CH3)5)Ir(e- (nickel), Pd (palladium), Pt (platinum), Fe (iron), thylene)2: (C5H7)Ir(C8H8); (CH3C5H4)2Ni; (cy Ru (ruthenium), and Os (osmium); 45 clopentadienyl)(Cyclohexandienyl)cobalt, R is a o-bonding ligand radical consisting of hydro (C5H5)Co(C5H7); (CH3C5H4)Co(MeCp); gen, methyl, ethyl, n- or iso-propyl, n-, sec-, or t (C5H5)CoCp; (cyclobutadienyl)(cyclopen butyl, benzyl, phenyl, and silylated and fluorinated tadienyl)cobalt, (C4H4)Co(C5H5); bis(cyclopen derivatives having sufficient volatility or solubility tadienyl)cobalt; (C5H5)2Co; bis(methylcyclopen of the precursor metal compound to be of utility in 50 tadienyl)cobalt, (CH3C5H4)2Co; cyclopen CVD or liquid CVD; tadienyl(1,3-hexadienyl)cobalt, (C5H5)Co(C5H7); n is a number from 0 to the valence of said metal, (cyclopentadienyl)(5-methyl-cyclopentadienyl)- m is a number from 0 to the valence of the metal, cobalt, (C5H5)Co(C5H4CH3); (C5H5)Co(CO)2; where m plus n allow a stable configuration of the (C6Hs)CoCp; bis(ethylene)s(pentamethylcy precursor metal compound to allow the precursor 55 clopentadienyl)cobalt, ((CH3)5Cs)Co(C2H2)2; trial compound to be either volatile or soluble in an lylchromium, (C3H4)3Cr; bis(cyclopentadienyl)- organic solvent; chromium, (C5H5)2Cr; (cycloheptatrienyl)(cy (b) exposing said substrate to hydrogen gas; and clopentadienyl)chromium, (C7H7)Cr(C5H5); bis(- (c) maintaining said substrate throughout the reaction cyclopentadienyl)iron, (Cshs)2Fe; (2,4-cyclohex at a temperature sufficiently high to decompose adienyl)(cyclopentadienyl)iron, (C6H7)Fe(C5H5); said precursor film forming metal compounds and (cyclopentadienyl)(methylcyclopentadienyl)iron, said precursor catalytic metal compounds; (C5H5)Fe(C5H4CH3); bis(methylcyclopentadienyl (d) reacting said precursor film forming metal com )iron, (CH3C5H4)2Fe; (cycloheptatrienyl)(cy pound and said precursor catalytic metal com clopentadienyl) manganese, (Cshs)Mn(C7H8); pound in the presence of hydrogen gas in a manner 65 (benzene) (cyclopentadienyl)manganese, to cause decomposition of precursor metal com (C5H5)Mn(C6H6); vinylosmocene, pound LMRn, and of the catalyst metal com- . (C5H5)Os(C5H4CHCH2); 1,1'-dimethylosmocene, pound LM'Rn on the surface of said substrate to (C5H4CH3)2Os; ethylosmocene, 5,403,620 15 16 (C5H5)Os(C5H4CH2CH3); bis(cyclopentadienyl)- and to a fluid containing a minor amount of at least one hydridorhenium, (C5H5)2ReH; hexamethylr vaporizable or soluble precursor catalytic metal com henium, (CH3)6Re; HRe(CO)5; cyclopentadienyl(- pound having the formula methylcyclopentadienyl)ruthenium, (C5H5)Ru(C5H4CH3); ruthenocenylacetylene, (C5H5)Ru(C5H4CCH); vinylruthenocene, (C5H5)Ru(C5H4CHCH2); bis(methylcyclopen wherein L is a at-bonding organic ligand consisting of tadienyl)ruthenium, Ru(CH3C5H4)2; ethylrutheno ethylene, allyl, methylallyl, butadienyl, pentadie cene, (C5H5)Ru(C5H4CH2CH3). nyl, cyclopentadienyl, methycyclopentadienyl, 5. A process according to claim 1 wherein said pre O cyclohexadienyl, hexadienyl, cycloheptatrienyl, or cursor film forming metal compounds comprise: alkyl or alkylsilyl or fluorinated derivatives of said bis(cyclopentadienyl)dihydrotungsten, (C5H5)2WH2, precursor catalytic metal compounds having suffi or trisbutadienetungsten, (C4H5)3W. cient volatility of the precursor metal compound to 6. A process according to claim 1 further comprising: be of utility in CVD or liquid CVD; annealing said deposited metal films to convert the 5 M is a precursor metal consisting of a transition metal films into a dense mat of small crystallites. metal, Ti (titanium), Zr (zirconium), Hf (hafnium), 7. A process according to claim 1 wherein said pre V (vanadium), Nb (niobium), Ta (tantalum), Cr cursor catalytic metal compound is CpptMe3 or (chromium), Mo (molybdenum), W(tungsten), Mn MeCpPtMe3. (manganese), Re (Rhenium), Fe (iron), Ru (ruthe 8. A process according to claim 1 wherein said pre 20 nium), Os (osmium), or a main group metal such as cursor catalytic metal compounds and said precursor Al(aluminum), Ga (gallium), In (indium), a group film forming metal compounds are each mixed with an 4a element consisting of Si (silicon), Ge (germa inert gas prior to introduction into said reaction cham nium), Sn (tin), or a lanthanide or actinide metal ber and wherein said precursor catalytic metal com consisting of La (lanthanum), Nd (neodymium), pounds/inert gas mixture, said precursor film forming 25 Sm (samarium), U (uranium), Pu (plutonium; metal compounds/inert gas mixture, and said hydrogen M" is a metal selected from the group of metals that gas are directed in a continuous stream over said sub can catalyze hydrogenation and hydrogenolysis Strate. reactions of unsaturated and saturated organic li 9. A process according to claim 8 wherein said inert gands, L and R, to yield volatile byproducts and gas is mixed with said precursor catalytic metal com 30 also can catalyze the hydrogenation of surface pounds and with said precursor film forming metal carbon to methane in the presence of hydrogen, compounds by separately passing a stream of said inert and consisting of the Group VIII transition metals gas over each of said compounds to saturate said inert of Co (cobalt), Rh (rhodium), Ir (iridium), Ni gas with said precursor catalytic metal compounds and (nickel), Pd (palladium), Pt (platinum), Fe (iron), with said precursor film forming metal compounds. 35 Ru (ruthenium), and Os (osmium); 10. A process according to claim 1 wherein said sub R is a ot-bonding ligand radical consisting of hydro strate is heated to a temperature in the range of about gen, methyl, ethyl, n- or iso-propyl, n-, sec-, or t 180 C. to about 400 C. and said reaction gases are at a butyl, benzyl, phenyl, and silylated and fluorinated temperature in the range of ambient to about 150 C. derivatives having sufficient volatility or solubility 11. A process according to claim 1 wherein said sub of the precursor metal compound to be of utility in strate is comprised of a substance stable to the tempera CVD or liquid CVD; ture and partial pressure of hydrogen and the tempera n is a number from 0 to the valence of said metal, ture of the process. m is a number from 0 to the valence of the metal, 12. A process according to claim 1 wherein two dif 45 where m plus n allow a stable configuration of the ferent precursor film forming metal compounds as de precursor metal compound to allow the precursor fined in step (a) are included in the process to provide compound to be either volatile or soluble in an an alloy or mixture of two different metals having resid organic solvent; ual amounts of the catalytic metal deposited within the (b) exposing said substrate to hydrogen gas; and metal alloy or mixture. SO (c) exposing said substrate to irradiation from a laser 13. A process according to claim 1 in which two or beam at a wavelength sufficient to cause said pre more different metals are deposited onto a substrate in a cursor film forming metal compounds and said sequential process by following steps (a), (b), (c), and precursor catalytic metal compounds to react with (d) to deposit the first layer of metal having a minor said hydrogen gas; and, amount of the catalytic metal therein and then subse 55 (d) depositing said metal films on the surface of said quently depositing another different metal on the first substrate without causing substantial heteroatom metal by repeating steps (a), (b), (c), and (d) of claim 1 impurities from the organic portion of said precur until the total number of deposited metal layers has been sor film forming metal compounds or from said formed. precursor catalytic metal compounds to be formed 14. A process for depositing at least one film of a on said surface. metal onto a substrate comprising: 15. A process according to claim 14 wherein step (c) a) exposing said substrate to a gas or liquid mixture comprises exposing said substrate to irradiation from a containing a major amount of at least one vaporiz laser beam disposed at an incident angle from perpen able or soluble precursor film forming metal com dicular to parallel to said substrate surface and at a pound having the formula 65 wavelength sufficient to cause one or both of said pre cursor film forming metal compounds and said precur sor catalytic metal compounds to react in the gas phase and in proximity to said substrate to react with said 5,403,620 17 18 hydrogen on the substrate surface and deposit said gands, L and R, to yield volatile byproducts and metal film on the surface of said substrate. also can catalyze the hydrogenation of surface 16. A process according to claim 14 in which two or carbon to methane in the presence of hydrogen, more different metals are deposited onto a substrate in a and consisting of the Group VIII transition metals sequential process by following steps (a), (b), (c), and of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (d) to deposit the first layer of metal having a minor (nickel), Pd (palladium), Pt (platinum), Fe (iron), amount of the catalytic metal therein and then subse Ru (ruthenium), and Os (osmium); quently depositing another different metal on the first R is a o-bonding ligand radical consisting of methyl, metal by repeating steps (a), (b), (c), and (d) of claim 1 ethyl, n- or iso-propy, n-, sec-, or t-butyl, benzyl, until the total number of deposited metal layers has been 10 formed. phenyi, and silylated and fluorinated derivatives 17. A process according to claim 14 wherein one or having sufficient volatility or solubility of the pre more of the precursor metal compounds are selectively cursor metal compound to be of utility in CVD or deposited to form a pattern. liquid CVD; 18. In a process for depositing a metal film from a n is a number from 0 to the valence of said metal, vaporizable or soluble precursor compound containing 15 m is a number from 0 to the valence of the metal, a metal to be deposited onto a substrate in the presence where m plus n allow a stable configuration of the of hydrogen gas, the improvement which comprises: precursor metal compound to allow the precursor exposing said substrate simultaneously or sequentially compound to be either volatile or soluble; to at least one vaporizable or soluble precursor (b) exposing said substrate to hydrogen gas; and compound containing a metal which can be depos (c) maintaining said substrate throughout the reaction ited as a metal film and a metal which can catalyze at a temperature sufficiently high to decompose hydrogenation and hydrogenolysis reactions of said precursor film forming metal compounds and unsaturated and saturated organic ligands to yield said precursor catalytic metal compounds; volatile byproducts and which can also catalyze 25 (d) reacting said precursor film forming metal com the hydrogenation of surface carbon to methane in pounds and said precursor catalytic metal com the presence of hydrogen to cause the metal from pounds in the presence of hydrogen gas in a man the catalyst compound to be incorporated within ner to cause deposition of metals M from said two the deposited metal film as a dissolved portion, or more precursor film forming metal compounds, alloy, or at the metal surface, or at grain bound 30 and of the catalyst metal M' from said precursor aS 19. A process for controlling the amount of carbon in catalytic metal compounds on the surface of said particular and oxygen in metal films produced by chem substrate without causing substantial impurities ical vapor deposition on substrates comprising: from the organic portion of said precursor film a) exposing said substrate to a fluid mixture contain forming metal compounds or of said precursor ing a major amount of two or more vaporizable or 35 catalytic metal compounds to be formed on said soluble precursor film forming metal compounds surface and to be incorporated within said metal M having the formula layer. 20. A process according to claim 19 wherein M in LMRn each of said two or more precursor film forming metal 40 compounds is different. and to a fluid containing a minor amount of at least one 21. A process according to claim 19 wherein M in vaporizable or soluble precursor catalytic metal com each of said two or more separate precursor film form pound having the formula ing metal compounds is the same. 22. A process according to claim 19 wherein said LMRn 45 deposition steps are simultaneous. wherein L is a 7T-bonding organic ligand consisting of 23. A process according to claim 19 wherein said ethylene, allyl, methylallyl, butadienyl, pentadie deposition steps are sequential. nyl, cyclopentadienyl, methycyclopentadienyl, 24. In a process for plasma-enhanced CVD of metal cyclohexadienyl, hexadienyl, cycloheptatrienyl, or 50 films wherein controlled amounts of one or more pre alkyl or alkylsilyl or fluorinated derivatives of said cursor film forming metal compounds in gaseous form compounds having sufficient volatility of the pre are introduced into a reaction chamber in the vicinity of cursor metal compound to be of utility in CVD or a heated substrate and wherein said precursor film liquid CVD; forming metal compounds in gaseous form are exposed M is a precursor metal consisting of a transition 55 to a means for activating and sustaining a plasma con metal, Ti (titanium), Zr (zirconium), Hf (hafnium), tained and fed by said precursors in gaseous form, to V (vanadium), Nb (niobium), Ta (tantalum), Cr cause deposition of a metal film on said substrate, the (chromium), Mo (molybdenum), W (tungsten), Mn improvement which comprises: (manganese), Re (Rhenium), Fe (iron), Ru (ruthe adding controlled amounts of hydrogen gas and of at nium), Os (osmium), or a main group metal consist least one vaporizable precursor catalytic metal ing of Al (aluminum), Ga (gallium), In (indium), Si compound containing a metal which can catalyze (silicon), Ge (germanium), Sn (tin), or a lanthanide hydrogenation and hydrogenolysis reactions of or actinide metal consisting of La (lanthanum), Nd unsaturated and saturated organic ligands to yield (neodymium), Sm (samarium), U (uranium), Pu volatile byproducts and which can also catalyze (plutonium; 65 the hydrogenation of surface carbon to methane in M' is a metal selected from the group of metals that the presence of hydrogen to cause the metal from can catalyze hydrogenation and hydrogenolysis the precursor catalytic metal compound to be in reactions of unsaturated and saturated organic li corporated within the deposited metal film as a 5,403,620 19 20 dissolved portion, alloy, or at the metal surface, or ing of Al(aluminum), Ga (gallium), In (indium), a at grain boundaries. group 4a element comprising Si (silicon), Ge (ger 25. A process for the deposition of metal films of manium), Sn (tin), or a lanthanide or actinide metal enhanced purity which comprises: consisting of La (lanthanum), Nd (neodymium), (a) forming a solution of a precursor catalytic metal 5 Sm (samarium), U (uranium), Pu (plutonium; compound having the formula; M' is a metal selected from the group of metals that can catalyze hydrogenation and hydrogenolysis LMR reactions of unsaturated and saturated organic li gands, L and R, to yield volatile byproducts and (b) wetting the surface of a substrate with said solu 10 also can catalyze the hydrogenation of surface tion; carbon to methane in the presence of hydrogen, (c) evaporating solvent from said solution on said and consisting of the Group VIII transition metals surface; of Co (cobalt), Rh (rhodium), Ir (iridium), Ni (d) heating said substrate in the presence of hydrogen (nickel), Pd (palladium), Pt (platinum), Fe (iron), gas to cause decomposition of said precursor cata 15 lytic metal compound and cause deposition of cata Ru (ruthenium), and Os (osmium); lytic metal M on the surface of said substrate with R is a ot-bonding ligand radical consisting of hydro out causing substantial impurities from the hetero gen, methyl, ethyl, n- or iso-propyl, n-, sec-, or t atom portion of said precursor catalytic metal com butyl, benzyl, phenyl, and silylated and fluorinated pound to be formed on said surface; derivatives having sufficient volatility or solubility (e) exposing said substrate having said catalytic metal of the precursor metal compound to be of utility in M' thereon to a fluid mixture containing at least CVD or liquid CVD; one vaporizable or soluble precursor film forming n is a number from 0 to the valence of said metal, metal M compound having the formula m is a number from 0 to the valence of the metal, 25 where m plus n allow a stable configuration of the LMRn precursor metal compound to allow the precursor compound to be either volatile or soluble in an wherein L is a 7t-bonding organic ligand consisting of organic solvent; ethylene, allyl, methylallyl, butadienyl, pentadie (f) exposing said substrate to hydrogen gas; and nyl, cyclopentadienyl, methycyclopentadienyl, (g) maintaining said substrate throughout the reaction cyclohexadienyl, hexadienyl, cycloheptatrienyl, or 30 at a temperature sufficiently high to decompose alkyl or alkylsilyl or fluorinated derivatives of said said precursor metal compounds; compounds having sufficient volatility of the pre (h) reacting said precursor metal compound in the cursor metal compound to be of utility in CVD or presence of hydrogen gas in a manner to cause liquid CVD; 35 deposition of metal M, on the surface of said sub M is a precursor metal consisting of a transition strate without causing substantial impurities from metal, Ti (titanium), Zr (zirconium), Hf (hafnium), the organic portion of said precursor film forming V (vanadium), Nb (niobium), Ta (tantalum), Cr metal compound or of said precursor catalytic (chromium), Mo (molybdenum), W (tungsten), Mn metal compound to be formed on said surface and (manganese), Re (Rhenium), Fe (iron), Ru (ruthe incorporated within said metal M layer. nium), Os (osmium), or a main group metal consist k : k x:

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