TWI324186B - Deposition processes using group 8 (viii) metallocene precursors - Google Patents

Description

1324186 (1) 玖, invention description [Technical field to which the invention belongs] This application claims to apply for U.S. Provisional Application No. 60/42 2,94 6 on January 31, 2002; application on October 31, 2002 US Provisional Application No. 60/422,947; application for US Provisional Application No. 60 / 42 6, 2 84 on the day of the month of 2002; application for the US Provisional Application No. 60/ on November 18, 2002 No. 4, No. 6, No. 1, No. 60/46,320, filed on February 7, 2003; US Provisional Application No. 60/453, 7] No. 8 on April 18, 2003; U.S. Provisional Application No. 60/453,719, filed on Apr. 18, 2003; and U.S. Provisional Application No. 60/4 5 3 5 7 1 7, filed on April 18, 2003. All teachings of the above-referenced applications are incorporated herein by reference. [Prior Art] A chemical vapor deposition (CVD) method is used to form a thin film of a material on a substrate such as a wafer or other surface during the manufacture or processing of a semiconductor. In CVD, a CVD precursor, also known as a CVD compound, is thermally, chemically, photochemically decomposed or activated by plasma to form a film having the desired composition. For example, the vapor phase C V D precursor can be contacted with a substrate heated to a temperature above the decomposition temperature of the precursor to form a metal or metal oxide film on the substrate. Films comprising ruthenium (Ru), ruthenium oxide (Ru〇2) or iron (Fe) have good electrical conductivity, high work function, are chemically and thermally stable, and chemically diffuse between the anti-layer-5-(2) 1324186 and Many dielectric substrate materials are compatible. Ru and Ru Ο 2 films, for example, have been studied as thin film electrode materials for semiconductor devices such as DRAM (Dynamic Random Access Memory) devices. An example of a film prepared from a ruthenium-based precursor is described in U.S. Patent No. 6,440,495 issued to Wade et al. on Aug. 27, 2002; U.S. Patent issued to Vaartstra et al. No. 6,074,945; U.S. Patent Application Publication No. 2002/010,282, filed on Aug. 1, 2002, the disclosure of which is incorporated herein by reference in its entirety, in its entirety, in Precursor chemical vapor deposition 'Rapid heat and other short-time processing techniques III, Electronics, Dielectric Science and Technology' and High Temperature Materials chapter, Journal No. 2 - 1 Book 235 - 242 '201 The meeting of the Electrochemical Association. The teachings of the above-referenced patents, published patent applications, and entireties are hereby incorporated by reference. Bis (pentaPto) cyclopentadienyl) ruthenocene and symmetrical diethyl-substituted ferrocene (1,1-diethyl fluorene) have been studied as A possible precursor for the ruthenium-based film is formed by CVD techniques. These compounds have been prepared by several synthetic routes. An existing method for forming hafnocene includes the reaction of RuC13·ΧΗ20 with cyclopentadiene in the presence of Zn to produce hafnocene, ZnCl2 and HCl, as shown in Fig. 1A. A similar method, using ethyl-substituted cyclopentadiene, has been used to prepare 1' Γ-diethyl fluorene, as shown in Figure 1 。. Generally, the yield obtained by this method is about 70%. (3) (3) 1324186 As shown in Figure 1 C, the non-lightly substituted ferrocene has also been made by cyclopentadiene, chloro(cyclopentadienyl)bis(indolylphenylphosphine) ruthenium (U) and Preparation of sodium hydride (NaH) in benzene. The chlorine (cyclopentadienyl) bis(triphenyl-)pyrene (II) precursor has been synthesized by the reaction of antimony trichloride and triphenylphosphine in ethanol. Another method for the use of alpha to hafnium includes a metal transfer reaction of a bis(alkylcyclopentanyl) iron compound with RUCl3.XH2? and results in a low yield of 1,1 -alkyl ferrocene钌 'Formation of ferric chloride (F^Cj3) and iron species that are difficult to separate. Monosubstituted/ethylidene §j ', such as 1 _-ethyl decyl fluorene, is formed as an impurity during the synthesis of hydrazine, .1 diethylene fluorene. Tertiary-butyl (cyclopentane-yl) (cyclopentane-based) nails have also been reacted by a thermal mixture of bis(cyclopentadienyl)phosphonium chloride and polyphosphoric acid, with tertiary Butanol is then prepared by distillation. 3 Tang Chang' The above synthetic formula is often associated with special operating techniques of low yield, competitive dimerization, separation of mismatched products, and hazardous reagents (eg, NaH). Furthermore, as seen in Figures A and b, these synthetic methods involve the addition of two cyclopentadienyl rings and are therefore suitable for the preparation of unsubstituted zirconium or symmetrically substituted ruthenium,] Monoethyl ferrocene. Both pentylene and 1' 1-diethyl fluorene have a lower vapor pressure (less than 10 Torr at 1 °C). At room temperature, the hafnocene is a solid and the 1' 1 diethylbifluorene is a liquid. Generally, a more volatile CVD precursor is preferred because it is a precursor that is liquid rather than solid at room temperature. In addition to the 'required -8- (4) 1324186 CVD raw average square metal [hair layer or / or seedless species selected bag-like ring less one base precursor is also thermally decomposable under appropriate CVD conditions Uniform film. Therefore, there is a need to continue to study nail-based CVD precursors and new methods. There is also a need for a process for preparing a film comprising ruthenium or other Group 8. The present invention is generally related to a kind of material, such as a deposition method of, for example, a sputum material, such as

箄弟8 (VIII VIII brother 8 (VIII) gold _ oxide. The private symmetry replaces it - the u method includes the substitute - the pentylene dam precursor, -7 ~ ^ 稽 the formation of the metallocene precursor迦1 / 迺CpmCd# — + 钌 (Ru), hungry (〇) and iron (:., including at least ~ substituent D1 of the first metal pentylene group (for example, 茚基j^代The second is taken as a substituent D, and the second is taken as a part '· and CP, as a part (for example, fluorenyl). : ^ α 二录基 or 】 and Dl, which are different from each other and X;

CalHbiXcl ; C^Hb2Xc2 ( c= 〇) c a, Hblx

Ca2Hb2Xc2〇CalHblXc]; and can produce a film (VIII) film, a coating metal and at least one. The asymmetry p Μ is one. C ρ is an alkenyl group, or the species includes to cyclopentadiene.

Ca2Hb2Xc2 ( c= 〇) 〇c Ca2Hb2Xc2〇( C= 0 ) C alHb.Xcla|Hblxcl : and (5) (5) 1324186 where X is a halogen atom or a nitro group (no2); a 1 is from 2 to 8 Integer; bl is an integer from 0 to 2 (al) + l-cl; c 1 is an integer from 0 to 2 ( a 1 ) + 1 - b 1; b 1 + c 1 is at least 1; a2 is from 0 To an integer of 8; b2 is from .0 to? ( a2 ) +1 — an integer of c2 ; c2 is an integer from 0 to 2 ( a2 ) +1- b2 . In one embodiment, the invention is directed to a method of depositing a film. The method comprises the steps of decomposing a vapor of an asymmetric metallocene or a metallocene-like compound, wherein the decomposition is deposited thermally, chemically, photochemically or by plasma activation and the metallocene or halometallocene compound has The above formula CpMCp', thereby forming a material. In a preferred embodiment, D 1 is X; C a 1 H b ] X c 1 ·

Ca2Hb2XC2 ( C= Ο ) CalHblXcl ; C a 2 H b 2 X c 2 0 C a I H b ] X c ]'

Ca2Hb2Xc2 (C=O) OCalHblXcl; or Ca2Hb2Xc2〇(C=O) CalHblXcl; where X is fluorine (F), chlorine (Cl), bromine (Br), iodine (I) or ( -10- (6) (6 1324186 a 1 is an integer from 2 to 8; bl is an integer from 〇 to 2(al) + l-cl; cl is an integer from 0 to 2 (al) +1 - bl; b 1 + c 1 is At least 1 ; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2 ( a2 ) +1 - c2 ; c2 is an integer from 0 to 2 (a2) +1 - b2, and D丨 is: X ; C a 丨 H b ] X c 1 ;

Ca2Hb2Xc2 ( C = 0 ) CalHblXcl ;

Ca2Hb2.Xc2〇Ca|HblXcl;

Ca2Hb2Xc2(C=0) OCajHblXcI' or Ca2Hb2Xc2〇( C = 0 ) CalHblXcl ; where X is F, Cl ' Br, I or N〇2 ; a 1 is an integer from 1 to 8; bl is from 〇 to 2 (al +1 - an integer of cl; cl is an integer from 0 to 2 (al) + l-bl; b 1 + c 1 is at least 1; a 2 is an integer from 0 to 8; b2 is from 0 to 2 ( A2) an integer of +l-c2; c2 is an integer from 0 to 2 (a2) +1 - b2. A specific example of a metallocene compound used in the process of the present invention -11 - (7) 1324186 is 1-methyl, 1'-ethyl fluorene.

At least one of Cp or Cp' may include one or, C>2, d3, d4, D5, D2', d3, D4, which provides additional options and flexibility for the existing method of preparing a film by CVD. It is liquid at room temperature and has a vapor pressure higher than that of the conventionally known 'for example, 1-methyl, 1 '-ethyl-diethyldiethyldifluorene. Higher vapor pressures increase productivity and lower film manufacturing costs. Modification of the ring by cyclopentane in the compounds of the invention corrects such properties as solubility, vapor pressure, reaction pathway, reduction/oxidation potential, geometric distribution. Thus, a particular precursor can be selected for use in addition to carbon, and many of the precursors described herein, substituted for one metallocene, do not contain non-phase+ atoms and are generally free of impurities. Metal oxide formation may be facilitated in some other organic substituents. DETAILED DESCRIPTION OF THE INVENTION A more detailed description of the foregoing and other objects, features and embodiments of the invention will be set forth. These patterns are not necessarily proportional to many additional substituents, such as and d5. Ru — , 〇 s — , F e — some. Some of these compounds, the vapor pressure of the precursor. Pour; 钌 has a higher than 1,1 '. There is an economic advantage. The functionalization of the cyclopentadienyl alkenyl ring is decomposed, burned, and the like, preferably in the form of electrons and electrons. In addition to hydrogen, for example, an alkyl group is taken as an example of its decomposition, the presence of an oxygen atom in the form of a film, coating or powder is more readily known from the following invention, as the same reference text in the drawings Refers to 'emphasis to illustrate the principles of this -12-(8) (8) 1324186 invention. The invention is generally directed to a method for making a film, coating or powder. The method comprises the step of decomposing at least one asymmetrically substituted Group 8 (V I π ) metallocene compound ‘ further described below. As used herein, the term "metallocene" refers to an organometallic coordination compound of a sandwich type structure having a structure similar to ferrocene, in which the transition metal is a π-bond (electrons are extended on the ring and The lower orbital shift) to 7? η - the coordination ring, usually the aromatic moiety 'CP and Cp', where η represents the number of carbon atoms bonded to the ring portion of the transition metal. In a preferred embodiment, both 'CP and CP' are independently selected from cyclopentadienyl or fluorenyl (fused phenyl and cyclopentadienyl rings). If all of the carbon atoms in the cyclopentadienyl ring are involved in the bonding to the transition metal, then these moieties are described as 7-5-coordination. Therefore, the full description of ferrocene will be (77 5 - CU5) 2Fe. Figure 2A shows the phase-error configuration of a metallocene in which the ruthenium is a Group 8 (V ill ) metal, for example, ruthenium, hungry or iron. The metallocene may also have a cross-over configuration as shown in Figure 2B. As used herein, the formula is not intended to describe a particular metallocene configuration. The π n -coordination moiety other than the cyclopentadienyl group herein means ''like cyclopentadienyl hydrazine. Additional relative ionic groups may be present in the compound to balance the charge and form a neutral molecule, as is known in the art. The metallocene compound useful in the process of the invention may have the formula CpMCp, wherein M is Ru, 〇s or Fe and wherein Cp and Cp are cyclopentadienyl or cyclopentadienyl (eg, hydrazine) Base) part. Each Cp and -13-(9)1324186 C p ' is substituted and different from C ρ and C p 1 . More specifically, in each Cp and (Η) atom is substituted by a substituent, D 1 and D ! and D Γ are different from each other and independently: X ; C a IH b 1 X c 1 1 Ca2Hb2Xc2 ( C = Ο Ca,HblXc Ca2Hb2Xc2〇Ca|HblXcl > Ca2Hb2Xc2 ( O) OCalHbi: Ca2Hb2Xc2〇( C = O ) CalHbl : wherein x is a halogen atom or a nitro group (no2 ) a 1 is an integer from 1 to 8; b ] From 0 to [J 2 ( a 1 ) + 1 — c 1 cl is from 0 to 2 ( al ) +1 - bl b 1 + c 1 is at least 1; a2 is an integer from 0 to 8; b 2 is From 0 to IJ 2 ( a 2 ) + 1 — c 2 c2 is from 0 to 2 ( a2 ) +1 - b2 as used herein, the substituents D 1 and D of the integer range of branches. For example, a branched Cl - C8 alkyl group. In a specific embodiment of the invention,

In the Cp' portion, at least one hydrogen D!' is replaced. SB r±n Β Θ . cl, and integers; integers; integers; integers. Included. Linear and 〇] and/or D!' can be used for straight chain and D 1 is: -14 - X ; (10) (10) 1324186 C a I H b 1 X C 1 >

Ca2Hb2Xc2 ( C = 0) Ca|HblXcl 1 C a 2 H b 2 X c 2 〇 C a I H b 1 X c 1

Ca2Hb2Xc2 (C 2 O) OCa|HblXcl, and

Ca2Hb2Xc2〇(C=0) CalHblXcl 1 wherein X is a halogen atom such as fluorine (F), chlorine (C), bromine (Br or iodine (I); a 1 is an integer from 2 to 8; bl is from 0 To the integer of J2(al)+l-cl; cl is an integer from 0 to U2(al)+l-bl; bl+cl is at least 1; a2 is an integer from 0 to 8; b2 is from 0 to 〇 2 (a2) + l-c2 integer; c2 is an integer from 0 to lj 2 ( a2 ) +1 - b2; and D], is: X;

CalHblXcl >

Ca2Hb2Xc2 ( C = Ο ) Ca, HblXcl ; C a 2 Η b 2 X c 2 〇 C a I Η b ] X c 1 1

Ca2Hb2Xc2 ( C= O) OCa|HblXcI ; and

Ca2Hb2Xc2〇( C= 0) CalHblXcl ' where X is a halogen atom; -15 - (11) (11)1324186 a 1 is an integer from 1 to 8; bl is from 〇 to 2(al) +1—c] Integer; cl is an integer from 0 to 2 (al) +1 - bl; b 1 + c 1 is at least 1; a2 is an integer from 0 to 8; b2 is from 0 to 2 (a2) + l-c2 Integer; c2 is an integer from 0 to !j 2 ( a2 ) +1 — b2 . In one example, D is selected from the group consisting of: C a i H b 1 X c 1 >

Ca2Hb2Xc2 (C-0) CalhbjXcl 'Ca2Hb2Xc2〇C2iHblXc 丨;

Ca2Hb2Xc2 (C=O) OCa|Hb]Xcl; or Ca2Hb2Xc2〇(C=O) Ca,Hb)Xci; wherein X is a halogen atom, such as F 'C] ' Br or I; a 1 is from 1 to 8 Integer; bl is an integer from 0 to 2(al) +l-cl; c 1 is an integer from 0 to 2 ( a 1 ) + 1 - b 1; b 1 + c 1 is equal to or greater than 1; a2 is from An integer from 0 to 8; b2 is an integer from 0 to 2 ( a2 ) +1 - c2 ; c2 is an integer from 0 to 2 ( a2 ) +1 — b2 ; b2 + c2 is equal to or greater than 1 ; : -16 - (12) (12)1324186 C a IH b 1 X c 1 '

Ca2Hb2Xc2 ( c = 0 ) CalHblXc]; C a 2 H b 2 X c 2 0 C a I H b ] X c 1 >

Ca2Hb2Xc2 ( C = 0) OCa|HblXcl,

Ca2Hb2Xc2〇(C=0) CalHb]Xcl 'wherein X is a halogen atom, such as F, c], Br or I; a 1 is an integer from 1 to 8; b 1 is from 0 to !J 2 (a 1 ) + ] - an integer of c 1; : cl is an integer from 0 to 2 (al) +; l - bl; b 1 + c 1 is equal to or greater than 1; a2 is an integer from 0 to 8; b2 is from 0 To 2(a2)+l—the integer of c2; c2 is an integer from 0 to 2 ( ) +1 - b2; 2b2 +C.2 is equal to or greater than 1. In another example, D i is a halogen atom, X ' for example, F, C1, Br or I; and D]' is selected from:

CalHblXcl ;

Ca2Hb2Xc2 ( C = 0) CaiHb] Xcl,

Ca2Hb2Xc2〇CalHblXcl;

Ca2Hb2Xc2 (C=0) OCalHblXc): C a 2 H b 2 X c 2 〇( C = 0 ) C a IH b JX c 1 ; wherein X is a halogen atom; -17 - (13) (13) 1324186 a 1 Is an integer from 2 to 8; b 1 is an integer from 0 to 2 ( a 1 ) + I — c 1 ; cl is an integer from 0 to 2 (al) + l-bl; b 1 + c 1 is equal to or More than 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to !J2(a2)+l-c2; c2 is an integer from 0 to 2 ( ά2 ) +1 — b2; 2b2+c2 is equal to or Greater than 1. An example of the structural formula (C p M C p ') of the metallocene compound of the present invention is shown in Fig. 3. Optionally, one or both of the C ρ and CP' moieties of the inventive metallocene or halocene-like compound further comprise one or more additional substituents, D >:. In one example, at least one of _ C ρ and C ρ ' is a polysubstituted cyclopentadienyl or fluorenyl moiety. The generalized structural formula of the CpMCp' metallocene compound of the present invention is shown in Fig. 4. D, and D" are selected independently as described above. D2, D3, D4, D5, D^, D3', D, and D5' are independently selected from: C a IH b 1 X ci : C a 2 H b 2 X c 2 ( C = 0 ) C a IH bi X c 】;

Ca2Hb2Xc2OCalHblXcl;

Ca2Hb2Xc2 ( C = O) 〇CaiHblXcI, or Ca2Hb2X〇2〇( C= 0) Ca|Hb]Xcl where a ] is an integer from 〇 to 8; -18 - (14) 1324186 b 1 is from 0 to 2 ( a 1 ) + 1 - an integer of c 1 ; cl is an integer from 0 to 2 (al) + l-bl; b 1 + c 1 is equal to or greater than 1; a2 is an integer from 0 to 8; b2 is from 0 To an integer of 2(a2)+l-c2; c2 is an integer from 0 to 2 (a2) +1 - b2; 2b2+c2 is equal to or greater than 1. Specific examples of the mercapto-metallocene compound which can be used in the present invention are shown in Table 1 and in Figure 5. -19 - (15) 1324186 (15)

Table 1 1-methyl, fluorenyl-ethyl decyl fluorene 1,2-dimethyl, fluorenyl-ethyl decyl fluorene 1-methyl, fluorenyl-propyl dimethyl sulfonium methyl, hydrazine, 3-diethyl Dimethyl hydrazine. 1-methyl, hydrazine-isopropyl bromomethyl, hydrazine, 2-diethyl fluorenyl 1-methyl, hydrazine-butyl ferrocene 1-methyl, hydrazine-ethyl , 3-propyl ferrocene 1-methyl]'-dibutyl butyl fluorenyl 1-methylpropyl, 3-ethyl decyl fluorene]-methyl, hydrazine-tertiary butyl ferrocene Ethyl, hydrazine-methyl, 3-propyl decyl bromide ethyl, fluorenyl propyl fluorenylmethyl, hydrazine-ethyl, 2-propyl decyl fluorene. 1-ethyl, r-isopropyl Methyl hydrazine, hydrazine-propyl, 2-ethyl fluorenyl 1-ethyl, r-butyl ferrocene 1-ethyl, hydrazine-methyl 52-propyl ferrocene, ethyl, r- Diethyl butyl ferrocene 1-methyl, hydrazine-propyl ferrocene. 1-ethyl, 1'-tertiary butyl fluorenyl 1-methyl, ethyl decyl propyl 3r-isopropyl二 钌 钌 钌 1,3-dimethyl-Γ-ethyl decyl 钌 1-propyl 4'-butyl ferrocene 1:2: Γ-dimethyl-3'-ethyl ferrocene. 1-propyl, fluorene-tert-butyl ferrocene 1-butyl-indole-ethenyl fluorenyl. 1-propyl, fluorene-tertiary butyl钌 乙基 乙基 乙基 乙基 乙基 甲 甲 甲 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Second butyl ferrocene 1,2,3:4-tetramethyl-fluorene-ethyl decyl quinone. 1-isopropyl, hydrazine-tris, butyl butyl fluorenyl 1-ethyl fluorenyl, Γ-ethoxy ferrocene. 1-butyl, butyl butyl fluorenyl 1-difluoromethyl- hydrazine-ethyl dimethyl fluorene 1-butyl hydrazine - tert-butyl butyl ferrocene Fluoromethyl, 2,3,4-fluoro-indenyl-trifluoromethyl octafluorene 1-secondary butyl ferrocene, fluorene-tertiary butyl ferrocene 1-vinyl-fluorene-fluoride 1,1,3,3,3-trimethylmenterene-1-ethoxymethyl-anthracene: 2'-diethyl fluorene], hydrazine, 2-trimethyl fluorenyl 1-ethyl propyl hydrazine U-dimethyl, Γ-ethyl dimethyl sulfonium 1, hydrazine, 2,4-triethyl-3: ethyl fluorenyl fluorene - 20- (16) (16) 1324186 can be used The metallocene compound of the present invention also includes a hungry compound and an iron-based compound similar to the compounds shown in Table 1 or Figure 5. Similarly, the process of the present invention can be used to form a ruthenium metal comprising other 77 n coordinated aromatic moieties. Suitable metallocene compounds for use in the process of the present invention are not disclosed in U.S. Patent Application, by David M & Pson and Cynthia A. Hoover, under the name asymmetric Group 8 (VIII') metallocene compound, At the same time, the agent's lawsuit case number D — 2 ] 2 6 6 is applied at the same time. All the teachings are quoted by the party; A suitable synthetic method for preparing a metallocene compound for use in the process of the present invention is disclosed by David Thompson and Cynthia A. Hoover in the U.S. Patent Application. The agent litigation case number D - 2 1 2C, which was applied at the same time as this case, is all incorporated in this article. The metal salt may be a metal (111) salt such as, for example, a metal halide (e.g., chloride, bromide, iodide, fluoride), a metal nitrate, and other suitable metal salts. The ruthenium is a Group 8 (Vlil) metal, for example, Ru, 〇S or Fe. Usually, the metal salt is abbreviated as ΜΧη. As used herein, 'M.Xn does not exclude such waters including hydration and is known in the art as a metal salt compound that can be clearly expressed ("other than 〇) . Thus, in a particular example, the abbreviation FeX3, as used herein, includes water-free and hydrated iron salts that can be used to form ferrocene or ferrocene-like compounds. The metal (Μ) salt (X) may be a metal (丨丨j) salt, for example, such as -21 - (17) (17) 1324186 'metal halide (for example, chloride, bromide 'iodide' fluoride) 'Metal nitrates and other suitable metal salts. The metal is clearly represented by the formula MXn or, if hydrated water is present, represented by ΜΧη·μΗ20, Μ is Ru, Os or Fe. Use a metal salt, for example, for example,

FeX3 · 77 HaO or FeX3 to form a ferrocene or ferrocene-like compound. The ligand (L) is typically an electron pair donor compound. A neutral electron pair of a precursor 'e.g., for example, triphenylphosphine (pPh3) is used in one example. It is also possible to use tricyclohexylphosphine and other phosphines of the general formula PR3, as well as the phosphite triester 'P(OR)3, wherein R is a phenyl 'cyclohexyl group, an alkyl group or a branched chain group' such as a tertiary one base. Other suitable electron pair donors include amine 'phosphates', carbonyl compounds 'olefins, polyolefins, phosphine phosphines' amides and others.

The Cp compound is a precursor of the Cp moiety in the above CpMCp compound. Preferably, the Cp compound is HCp', for example, cyclopentane or oxime. The Cp component may also be provided as a salt of a pentane-alkyl group or a sulfhydryl anion, for example, potassium cyclopentyl-alkyl (KC p ), naphthoquinone (NaCp), and penta pentylene (LiCp). and other. Suitable cations for use with the cyclopentadienyl anion in the synthetic methods described herein include trimethyl sandstone (TMS) 'Na, Li, K, Mg, Ca and T1. The gas atoms in at least one of the Cp moieties are replaced by a radical, as described above. Specific examples of HCp include methylcyclopentadiene, ethylcyclopentadiene, n-propyl or isopropylcyclopentadiene 'n-butyl-, sec-butyl- or tertiary Cyclopentadiene or halo-cyclopentadiene.

The Cp compound may also be substituted by two or more, for example, it may be di--22-(18)(18)1324186 'tri-, tetra-, and penta-substituted cyclopentadiene. Specific examples of the substituents D2, 〇3, D4 and D5 are as described above. The Μ X n , L and H C P components may each be provided in neat form or optionally in a suitable solvent. Preferred solvents which can be used in the process of the invention include alcohols such as, for example, 'ethanol, methanol, isopropanol and other alcohols. It is also possible to use ethyl acetate, tetrahydrofurfuran (THF), saturated or unsaturated hydrocarbons, aromatic heterocyclic rings, haloalkanes, alkylation hydrocarbons, ethers, polyether sulfides, esters, lactones, decylamines. , amines, polyamines, nitriles, fluorenones and other aprotic solvents. A combination of solvents can also be used. The concentrations of 'MXn., L and Cp are typically selected as known in the art. For example, the molar concentration of MXn in a suitable solvent can range from about 〇 1 M to the net. The molar concentration of L in a suitable solvent may range from about .〇 _;! M to the net. The molar concentration of Cp in a suitable solvent can range from about 〇"μ" to the net. If a net phosphine is used, it is generally believed that the reaction will be exothermic. Methods and systems for dissipating substantial mass of reaction heat per unit volume are known in the art. The three ingredients can be combined in any order. In one example, the metal component and the HCp component are simultaneously added to the L component. In another embodiment, the metal component and the H C p component are combined to form a mixture. The mixture is then combined with the L component, for example, by adding the L component to the mixture. In another embodiment, all ingredients are combined at the same time. The typical molar ratio of HCp to ΜΧη used ranges from about 50 to about 1, preferably from about 12 to about 2 and most preferably from about 7 to about 5. Typically, the molar ratio of L to Μ X η ranges from about 8 to about 0, preferably from -23-(19) (19) 1324186 from about 6 to about 2 and most preferably from about 5 to about 3.5. If a large excess of HCp is used, the reaction is forced to form a (Cp) 2M product. The temperature should preferably be near the boiling point of the solvent used or the boiling point of the reaction mixture. Other suitable temperatures can be determined experimentally by routine experimentation. Generally, the reaction 'can be carried out at a temperature from above the freezing point of the reaction composition to about the boiling point range. For example, the reaction can range from about -1 to 0. (: to a temperature in the range of about 1.25 ° C. The reaction time is usually determined depending on the temperature and the concentration of various reactants, and may range, for example, from about 5 minutes to about 96 hours. The intermediate component formed by the reaction of MX, L and HCp can be represented by the formula CpMLfX, wherein .f = 1 or 2. In one example, CpMLfX is isolated from the process known in the art, for example, as a solid. , CpMLfX, and then reacted with Cp, a compound: preferably in the presence of a solvent. The CpM composition preferably includes an anion of the Cp' moiety of the above compound of the present invention. The counter ion may include trimethylmethanyl (TMS), Na. , Li, K, Mg, Ca, T.1. Specific examples of cyclopentadienyl compounds which may be used include, but are not limited to, sodium cyclopentadienide or lithium, methylcyclopentadienylation Sodium or lithium., sodium isopropylcyclopentadienide or lithium and others. It is also possible to use a Cp' moiety: a di- or poly-substituted anion (for example, two, one, four or one) Cyclopentadienyl anion). Unsubstituted anthracene or cycloalkyne can also be used. The anion of a cyclosaturated hydrocarbon, a heterocyclic ring or an aromatic ring is as described above. In a specific example, the intermediate compound is CpRu(PPh3)2C1. It reacts with a Cp-cut salt. The recommended Cp% salt includes NaCp^LiCp1. -24 - (20) 1324186 (Cp1) 2Mg, TMS(Cp') and (Cp,) Ding 1. Examples of suitable glutinous agents include benzene, toluene, xylene 'pentaquinone', petroleum ether, aromatic Heterocyclic 'saturated or unsaturated hydrocarbons, haloalkanes, alkyl ethers, ethers, polyethers, thioethers, esters, lactones, decylamines, amines, polyamines, nitriles, ketenes, and others. The range of the molar concentration of the Cp f component in the solvent may range from about 〇·μμ to about 3 · 5 ', preferably from about 〇 5 Μ to about 2.5 Μ and the best in the range About 1.4 to about 1. 8 范 范 · 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型 典型6 to about! Range of 2. In another example, not only the intermediate product CpMLfX·. After it forms a solution, a Cp' compound, such as the above salt, is added to a solution comprising .CpMLiX. C p · composition and intermediate The reaction between the species C p ML f X (either singly or without singly) is carried out, for example, at temperatures generally as described above and results in the formation of Cp MC p, the product. The reaction time is usually determined by temperature and concentration of various reactants. 'and may range from about 15 minutes to about 6 days. When synthesizing a structure of the CpRuCp' type, one of the rings containing a ketone, an ester or an ether functional property is generally preferred to have a greater number of ketones. A ring of vinegar or ether is regarded as a Cp' ring, and it is added to an intermediate product as a TMS salt. The product of the reaction 'CpMCp1' can be distinguished and purified by methods known in the art, such as, for example, 'solvent (eg, hoist) extraction followed by distillation 'sublimation or chromatography, or directly by steaming, sublimation or Chromatography. Recrystallization, ultracentrifugation, and other techniques can also be used. Or -25-(21)(21)1324186, the product can be used as a reaction mixture without further isolation and purification. A method of forming a compound of the invention is described by the chemical reaction shown in Figure 6. In the method shown in Figure 6, MC13·βΗ20, triphenylphosphine and D-substituted cyclopentadiene are reacted under reflux in ethanol to form intermediate compound CpM(PPh3) 2C1, which is then substituted with D,'- The sodium cyclopentadienide reacts to form CpMCp^.

Either or both of Cp and oxime or Cp' may include an additional substituent, Dx, for example, 'for example, the above group. Either or two of Cp and/or Cp1 may be or be a two-"three-one" tetra- or five-substituted cyclopentadiene moiety. It can be formed to form a special two-substituted asymmetric ferrocene, that is, I monomethyl, 1 'monoethyl fluorene or (methyl-cyclopentadienyl) ethylcyclopentadienyl The synthetic scheme of 钌) is shown in FIG. As shown in Figure 7, 'RuC〗 3 · ΧΗ20, triphenyl lin and methylcyclopentadiene are reacted in ethanol under reflux to form intermediate compound chlorine (methylcyclopentadienyl) bis(diphenylphosphine)钌(Π) or (t?5-C5H4C2H5) Ru(PPh3) 2C1 'which is then reacted with sodium ethylcyclopentadienide to form 丨-methyl, :!, monoethyl fused nail _. Examples of techniques that can be used to characterize compounds formed by the above synthetic methods include, but are not limited to, analytical gas chromatography, nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), induced coupling plasma mass spectrometry ( ICPMS) 'Vapor pressure and viscosity measurement. The relative vapor pressure or relative volatility of the above precursors can be measured by thermogravimetric analysis techniques known in the art. The equilibrium vapor pressure can also be measured, -26-(22) (22) 1324186 by, for example, drawing all of the gas from the closed vessel, after which the vapor of the compound is directed to the vessel and the measured pressure as known in the art. Not specific to the special mechanism, it is generally believed that the specific functionalization of the Cp and Cp 'rings to formulate the properties of Group 8 (VIII) metallocenes, such as solubility 'vapor pressure, decomposition' combustion and other reaction pathways, reduction/oxidation potential , geometry, preferred orientation and electron density distribution. For example, it is generally believed that the larger substituent D! and/or D > 1 promotes an increase in the entropy of the component and is compared to the previously disclosed compound. The metallocene compound described herein is more likely to be liquid at room temperature. In the process of the present invention, the above metallocene compound is decomposed and the organic portion is removed, resulting in the formation of a film, coating or powder of a Group 8 (VIII) metal group or a Group 8 (VIII) ' metal oxide group. . The precursors described herein which are liquid at room temperature are well suited for the in situ preparation of powders and coatings. For example, the liquid precursor is applied to the substrate and then heated to a temperature sufficient to decompose the precursor, thereby removing the organic groups and forming a metal or metal oxide coating on the substrate. The application of the liquid precursor to the substrate can be impregnated by painting 'spray' or by other techniques known in the art. Heating can be carried out in an oven, using a heat gun, by electrically heating the substrate, or by other methods known in the art. The layered coating can be obtained by coating the precursor, and heating and decomposing it, thereby forming a first layer, followed by coating at least one other coating of the same or different precursors, and heating. Liquid metallocene precursors such as those described above can also be atomized and sprayed onto the substrate. Atomizing and spraying devices that can be used, such as nozzles, sprayers, and the like, are known in the art. -27- (23) (23) 1324186 In a preferred embodiment of the invention, a metallocene or a metallocene-like compound, such as the above, is used in vapor deposition techniques for forming powders, films or coatings. . The compound can be used as a single source precursor or can be used with one or more other precursors, for example, with steam generated by heating at least one other organometallic compound or metal complex. More than one metallocene precursor, such as those described above, can also be used in the given process. The deposition can be carried out in the presence of other gas phase components. In a particular embodiment of the invention, the film deposition is carried out in the presence of at least one non-reactive carrier gas. Examples of non-reactive gases include inert gases such as nitrogen, argon, ruthenium and other gases which do not react with the precursor under process conditions. In other embodiments, film deposition is carried out in the presence of at least one reactive carrier gas. Some reactive gases that may be used include, but are not limited to, hydrazine, oxygen, hydrogen, air, oxygen-enriched air, ozone (〇 3 ) '- nitrous oxide (N 2 0 ), water vapor, organic vapors, and others. As is known in the art, the presence of an oxidizing gas such as, for example, air, oxygen, oxygen-enriched air, helium 3, N20 or a vapor of an oxidizing organic compound facilitates the formation of a metal oxide film. It is generally believed that the presence of oxygen atoms in the D*'D!', Dx and Dx' organic groups also facilitates the formation of metal oxides. The deposition methods described herein can be performed to form a thin film 'powder or coating comprising a single metal, For example, an 'Os-film, or a film, powder or coating comprising a single metal oxide (eg, 'Ru〇2) film, powder or coating β can be deposited 'eg, a mixed metal oxide film. A mixed metal oxide film can be formed, e.g., by using several organic gold -28-(24) 1324186 precursors, at least one of which is selected from the above metallocene or dimeric compounds. A vapor phase thin film deposition may be performed to form a thin film layer of a desired thickness (for example, a range of 1 n m to 1 m m ). The precursors described herein can be used to prepare films, for example, films having a thickness ranging from about 1 Ο ηηη to about a range. The tantalum film, for example, can be considered as a genus electrode, particularly as a logic P-channel metal electrode, and as a capacitor electrode for application. This method is also suitable for preparing layered films in which the layers or compositions of the layers are different. Examples of layered films include metal-semiconductor (MIS) and metal-insulator-metal (M.IM). In one embodiment, the invention relates to a method for thermal, chemical, photochemical or plasma activation. The step of decomposing the above-mentioned halocene metallocene precursor (for example, one of the compounds shown in Table 1) to form a film on the substrate. For example, a vapor produced by a compound (which is a liquid at a warmer temperature) and a base having a temperature sufficient to cause decomposition of the metallocene and formation of a film comprising a metal of Group 8 (VIII) or (VIII) metal oxide on a substrate. Material contact. The precursors can be used in CVD or, more particularly, metal-organic chemical vapor deposition (MOCVD) known in the art. For example, the precursors described above can be used in atmospheric pressure, as well as in press CVD processes. Compounds can be used in hot wall CVD, where the entire reaction chamber is heated, and in cold or warm CVD, a technique in which only the substrate is heated. The metallocene is at least 10 0. nm from the fabrication of gold DRAM. A second insulator comprising a genus or a gas, which is used in the group 8 of the genus, for the method of lowering one of its wall types -29-(25) (25) 1324186. The above precursors can also be used for plasma Or light-assisted CVD methods in which energy or electromagnetic energy, respectively derived from plasma, is used to activate the CVD precursor. The compound can also be used in ion beam, electron beam assisted CVD methods where the ion beam or electron beam is directed to the substrate separately for application to the energy of the decomposition of the C V D precursor. A laser-assisted CVD method can also be used where laser light is directed at the substrate to produce a photoreactive reaction of the CVD precursor. The process of the present invention can be carried out in a variety of CVD reactors, such as, for example, 'hot or cold wall reactors, plasma-assisted, beam-assisted or laser-assisted reactors, as is known in the art. Precursors which are often liquid at room temperature during the CVD manufacturing process are preferred and several of the above asymmetric ferrocene compounds have properties which make them suitable as CVD precursors. 1-Methyl 5 r -ethyl fluorene, for example, having a melting point of 2 °c. · 1-Ethyl, I'-isopropyltetramethane has a melting point of 3 °c; 1-methyl, monoisopropyl fluorene is a liquid at room temperature. The previously used symmetric 1,2 _diethyl fluorene has a melting point of 6 ° C, while 1-ethyl ferrocene has a melting point of 12 ° C. Examples of the substrate which can be coated using the method of the present invention include solid substrates such as metal substrates such as 'Al, Ni, Ti, Co, Pt, Ta; metal tellurides such as TiSi2, CoSi2, NiSi2; semiconductor materials, For example, Si, SiGe 'GaAs 'InP, diamond, GaN, SiC; insulator, for example, Si〇2 'Si3n4, Hf〇2, Ta205, Al2〇3, barium titanate total (BST); barrier material, for example, TiN , TaN; or on a substrate comprising a combination of materials. In addition, the film or coating can be formed on glass, ceramic, plastic 'thermoset poly-30-(26) 1324186 composites and on other coatings or film layers. In a comparative example, thin film deposition is used in the fabrication or processing of electronic components. In other embodiments, the substrate is used to support low resistivity conductor deposits that are stable at oxidant temperatures, such as Ru〇2 films, or Optical transmission film, such as 'Ru〇2. The method of the present invention can be carried out to deposit a flat planar film on a substrate. In a preferred embodiment, a film is deposited on a substrate for wafer fabrication or processing to deposit a film in a feature, such as a channel, hole or via. In addition, the method of the present invention can also be deposited with other steps in the crystallography (such as reticle, etching, and the like), and the CVD or Μ OCVD film can be deposited to a desired thickness to form a film that is less than 1 micron thick. Good less than 5 0 0 Nai is 200 nm thick. It is also possible to produce thin films having a thickness of less than 50 nm and having a thickness of between about 20 and about 30 nm. The above asymmetric metallocene compound can also be used in the present invention for atomic layer deposition (ALD). Or atomic layer nucleation techniques to form a film during which the substrate is exposed to alternating pulses of precursor, oxidant flow. Subsequent layer deposition techniques are described in Example No. 6,287,965, issued to Kang Patent No. 6,34252 7 on September 2, 2001, and the teachings of the two patents dated January 29, 2002 are incorporated by reference. In this article. For example, in an ALD cycle, the substrate is exposed to: a) an inert gas; b) carrying a precursor vapor on a substrate that is specifically implemented. Underneath, at high Ru metal or with smooth, line the method. For example, a circle can be fabricated or fabricated on a substrate. . For example, the rice and the better film, for example, the method of the invention (ALN) agent and inert gas such as the US patent et al. and the United States Sherman ° (with step-by-step inert gas -31 - (27) (27) 1324186 ;c) an inert gas; and d) an oxidizing agent, alone or together with an inert gas. In general, each step can be as short as the equipment allows (eg, micron) and as long as the method requires (eg, 'several seconds or minutes. One cycle can be as short as microseconds and as long as minutes. The cycle can be repeated A period of time ranging from a few minutes to an hour. The resulting film may be thin or thicker, for example, 1 micron (mm). The process of the invention may also be carried out using a supercritical liquid. Currently known in the art. Examples of thin film deposition methods using supercritical liquids include chemical fluid deposition (CFD); supercritical fluid transport-chemical agglomeration (SFT-CD); supercritical fluid chemical deposition (SFCD); and supercritical immersion deposition ( SFID) CFD methods, for example, are well suited for the preparation of high purity films and are suitable for filling complex surfaces and high aspect ratio features. CFD is described, for example, in U.S. Patent No. 5,789,027, issued to Watkins on August 4, 1998. Et al. The use of a supercritical liquid to form a film is also described in U.S. Patent No. 6,541,27,8 B2, issued to Morita et al. on Apr. 2, 003. The teachings of the two patents are incorporated by reference. In one embodiment of the invention, the thermal mapping substrate is exposed to one or more precursors, such as one or more precursors as shown in Table 1, for example, 1-methyl '1' - Ethyl fluorene, in the presence of a solvent such as a critical or supercritical liquid, for example, near critical or supercritical co2. In the case of c 〇 2, the solvent liquid is provided at a pressure above about 1 000 psig and at least A temperature of about 30 ° C. The precursor is decomposed to form a thin film of Group 8 (VIII) -32-(28) (28) 1324186 on the substrate. The reaction is also produced from the Cp and Cp' portions of the precursor. Organic material. The organic material is dissolved in a solvent liquid and easily removed from the substrate. It is also possible to form a metal oxide film, for example by using an oxidant. In one embodiment, the deposition method covers one or more substrates. The substrate is heated in a reaction chamber. The substrate is heated to a desired temperature by heating the entire chamber, for example, 'using a furnace. The vapor of the metallocene compound can be produced, for example, by applying a vacuum to the chamber. For low boiling compounds, The chamber can be hot enough to cause the combination Evaporation of a substance. When a vapor contacts a surface of a thermal substrate, it decomposes and forms a metal or metal oxide film. As described above, the metallocene or metallocene-like precursor may be used alone or in combination with one or more components. For example, a combination of other organometallic precursors, an inert carrier gas, or a reactive gas. Use, -, -, - - A schematic representation of a system that can be used in a film prepared by the method of the present invention. In Figure 8. As shown in Figure 8, the feedstock is directed to a gas-blending manifold to produce a process gas supply to the deposition reactor where film growth occurs, including but not limited to carrier gas, reactive gas , flushing gas, precursors, etching/cleaning gases and others. The precise control of the process gas composition is accomplished using mass-flow controllers (MFCs), valves, pressure transducers, and other devices known in the art. Also shown in Figure 8 is an exhaust manifold that delivers gas leaving the deposition reactor and bypassing the vacuum pump. The mitigation system, the vacuum pump downflow, is used to remove any hazardous materials from the exhaust gases. The deposition system installs an in situ analysis system, including a residual gas analyzer that allows measurement of the method gas composition. The control and data acquisition system monitors various -33- (29) (29) 1324186 method parameters (eg, temperature, pressure, flow rate, etc.). Shown in Figure 9 is a schematic representation of apparatus 10, which is an example of a suitable apparatus that can be used to prepare a process gas for film deposition by the method of the present invention. Apparatus 1 includes a vaporizer 12 in which a liquid or solid precursor is vaporized by methods known in the art. The temperature of the precursor, which determines its vapor pressure, is monitored by a thermocouple and controlled by a heating wire. The appropriate mathematical equations for the relationship between vapor pressure versus temperature for a compound are:

1 η P s a t — A — B / T where lnPsat is the natural logarithm of saturated vapor pressure, a and B experimental or theoretically derived constants, and T is the absolute temperature (Kelvin). A carrier gas, such as nitrogen, is supplied to the vaporizer 12 from a gas source 14 (e.g., a gas tank). The desired carrier gas flow rate is controlled by MFC 16. The pressure of the carrier gas was measured by a pressure gauge 18. Valves 2 0 and 22 are used to control the flow rate of the gas supplied to the vaporizer 12. Valves 24 and 26 are used to control the flow rate of the vaporized precursor and the carrier gas exiting the vaporizer. Closing the bypass valve 28 directs the carrier gas to the vaporizer 丨2. The needle valve 30, located in the downstream of the vaporizer .12, is used to control the total pressure inside the vaporizer and the flow rate of the process gas supplied to the deposition reactor 32. It is assumed that the gas leaving the vaporizer is fully saturated (i.e., the partial pressure is equal to the vapor pressure). The flow rate of the precursor can be determined using the carrier gas flow rate: total pressure and precursor vapor pressure. FIG. 10 is a schematic diagram of a deposition reactor 32. A process gas comprising a carrier gas and a vapor phase precursor is introduced via inlet 34. Multiple inlets or wells can also be used for separate injections of method gases, vapors or supercritical fluids. -34- (30) (30) 1324186 Thin films are deposited on substrate 36. The fixed gap spacing is maintained between the bottom of the inlet 3 4 and the upper end of the substrate 36. The substrate 36 is loaded on the molybdenum sensor. The 8 8 sensor 38 is a wafer capable of holding the sample, for example, having a diameter of up to 3 〃. The reactor can be modified to deposit a thin film on a larger substrate (eg, on a 200 or 300 micron (mnl) wafer). The temperature of the sensor is measured using a thermocouple · 4 , and controlled by a tungsten-halogen lamp 42. The deposition reactor pressure was monitored using a capacitance manometer 4 4 . During film deposition, the substrate .36 is heated to the desired temperature and the gas is contacted with the process gas. A vacuum pump is used to reduce the pressure within the deposition reactor. .

In other examples, the reaction chamber is equipped with in situ analysis and/or automatic method control and data acquisition. Method piping and chamber wall isothermal control can also be provided..V Typically, the pressure in the deposition reactor 32 ranges from about 〇.〇1 to 76-〇. Preferably, from about 0. 1 to about. The range of 760 Torr and preferably ranges from about 1 Torr to about 50 Torr. Generally, the film is deposited in a range from about 75 ° C to about 7 ° C, preferably from about 2 5 0 ° C to 4 5 (temperature in the range of TC. As known in the art, oxidizing gases such as, for example, air, oxygen, oxygen-enriched air, ozone (03), nitrous oxide (N20) or oxidation The presence of a vapor of an organic compound facilitates the formation of a metal oxide film. Other techniques for forming a metal oxide film can also be used, as is known in the art. The oxidant partial pressure is typically from about 0 to about 50 Torr. The range of the oxidant to the precursor may range from 0 to 0.000. The above precursor may be used to prepare a film comprising a single metal, for example, -35- (31) (31) 1324186 0 s - film, Or a film comprising a single metal oxide (for example, Ru ◦ 2 ). It is also possible to deposit a mixed film, such as a mixture. Metal oxide film. For example, by using several organometallic precursors, at least one of them is selected from the above-mentioned metallocene or a metallocene-like compound. A metal thin film can also be formed, for example, by No source of carrier gas, vapor or other oxygen is used. The films formed by the methods described herein can be characterized by techniques known in the art, for example, by X-ray diffraction (XRD), Eurasian spectroscopy X-ray photoelectron emission spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy, and other techniques known in the art. The resistance of the film can also be measured by methods known in the art. Rate and thermal stability. '' . . . . . . . . . Example [Example] Example - Example 1 Step A. A 5-liter five-neck round bottom flask was installed through a mechanical stirring paddle of the center neck. 2 · 0 liters) and PP h 3 (420 μg, 1.6 m). Two 500 ml three-necked flasks were connected via a positive displacement pump via a Teflon ® (perfluorinated polymer, DuPont) tube. Two necks of a 5-liter four-neck flask The remaining neck of the 5 liter flask was fitted with a condenser. The heating mantle was placed under a 5 liter flask and the solution was stirred and heated to reflux. All triphenylphosphine was dissolved in ethanol at reflux. The system was flushed with nitrogen at reflux. 0 min. -36- (32) (32) 1324186 During this time, a 500 ml round bottom flask was charged with RuC] 3. ΧΗ20 (] gram, 0.40 mM), ethanol (300 ml) and Teflon® ( Perfluorinated polymer, DuPont's coated magnetic stir bar. The ethanol solution immediately appeared brown/orange. In order to dissolve all RuC13 · ΧΗ20, it is necessary to heat the solution. This solution is passed through a septum and into a solution by inserting a needle attached to a 1 lb/gauge square 吋 (Psig) nitrogen source and by pulsing the septum with another needle to reduce excess pressure. Spray for 30 minutes. · Manufacture of acetonitrile/dry ice bath and another 5 0.0 ml flask dipped in this bath for a long time. Freshly distilled methylcyclopentadiene (190 g, 270 ml, 2.4 mol, freshly distilled under nitrogen) was then cannulated into a cooled flask. After the nitrogen injection of the triphenylphosphine and antimony trichloride in ethanol solution is completed, the contents of the two 500 ml flasks are pumped at a separate rate with a positive displacement pump... 5 . So that after 5 minutes, two joins are completed. To accomplish this, the ethylcyclopentadiene was pumped at a rate of 45 ml/min and the ethanol trichlorination was pumped at a rate of 50 ml/min. After the addition was completed, the solution was refluxed for an additional 2 hours. During this time, small orange crystals were observed to accumulate on the meniscus of the solution on the wall of the 2-liter flask. Step B. After stirring for 2 hours, separate two positive displacement chestnuts and Teflon ® (perfluorinated polymer, DuPont) tubes were separated from the 5 liter flask. The distillation side arm was attached to one of the necks of the flask and about 1 liter of ethanol was removed via distillation. The mechanical agitation and orange crystals were stopped and settled at the bottom of the flask. The solution was cooled to room temperature over 3 hours -37 - (33) (33) 丄 324186. The solution was then removed from the flask by inserting a glass tube having a coarse filter plate attached to its terminal and a reduced pressure was used to pull the solution through the filter plate and out of the flask. The crystals were washed with heptane (300 mL) and the heptane was removed in a similar manner. Three washes were performed.

Step C All openings to the flask were closed with a rubber septum and the flask was evacuated and refilled three times with nitrogen. T H F (500 ml, anhydrous) was introduced into the flask in a cannula and mechanical stirring was started. A solution of ethylcyclopentaquinone lithium (500 ml, 1.2 Μ, 〇 60 mol) in THF was then cannulated into a 5 liter flask. The contents were heated to reflux and stirred for 4 hours. After refluxing for 4 hours, the stirring was stopped and the solution was transferred to a 2-liter one-neck round bottom flask. This solution was concentrated on a rotary evaporator to a volume of about 20.0 ml. The viscous liquid was then transferred to a 250 ml round bottom flask. A 250 ml round bottom flask was fitted with a short diameter distillation connection tube with a vigreux dent and a 0 0 ml storage bottle receiver. The liquid and clear yellow liquid were distilled under vacuum, containing some of the methyl, triphenylphosphine methyl,], ethyl octagonal nails (determined by G C M S). The spin-belt distillation of the yellow liquid provided 84.6 g (82% yield) of triphenylphosphine-free 1-methyl, 1, monoethyl fluorene, >99% purity (GCMS, 1H NMR), and the remaining impurities were It is attributed to 1'1, dimethyl dimethyl fluorene and 1,1,-diethyl fluorene. The TG study showed that this liquid had less than 〇. 〇i % nonvolatile residue -38- (34) (34) 1324186 Example 2 A 2 liter three-necked round bottom flask was charged with Teflon ® (perfluorinated polymer, DuPont) Stir bar, ethanol (1.0 L) and PPh3 (2 63 g, Mo's 5 equivalents). A 250 ml dropping funnel, a 150 ml heated water jacket dropping funnel and a condenser were attached to the three necks of a 2-liter flask. It is important to note that the two dropping funnels are fitted with a Teflon® valve that allows it to be isolated from the pressure of the round bottom flask. The rubber septum was attached to the top of the dropping funnel of a 150 ml heated water jacket. The top end of the condenser is fitted with a T connection tube and connected to an inert atmosphere. The heating mantle was placed under a 2-liter 3-neck flask and the solution was stirred and heated to reflux. All triphenylphosphine was dissolved in ethanol at reflux. The system was flushed with nitrogen for 30 minutes during reflow. During this time, the 500 ml Erlenmeyer flask was charged with Ru C13 · X H2.0 (. 50 g '〇 2〇 Moel), ethanol (150 ml, 1 equivalent) and Teflon ® ( & m Polymer, DuPont) coated magnetic stir bar. The ethanol solution immediately appeared brown/orange. In order to dissolve all of the RUC]3··20, it is necessary to gently heat the solution. This solution was poured into a 250 ml dropping funnel and a drip dispenser was fitted with a silicone septum. This solution was sprayed with nitrogen for 3 minutes by inserting a needle connected to a 1-2 psig nitrogen source through the septum and into the solution and by puncturing the septum with another needle to relieve excess pressure. A methanol/dry ice bath was made in a dropping funnel of 15 ml of heated water jacket. The inside of the dropping funnel was flushed with nitrogen for 30 minutes in the same manner as another dropping funnel. Methylcyclopentadiene (96.2 grams ' 1.2 moles, 6 equivalents distilled twice under nitrogen atmosphere) was piped through a rubber septum into a cooled dropping funnel. -39- (35) (35) 1324186 After rinsing in a 2 liter-round bottom flask for 3 hours, open two separate dropping funnels and the rest of the system of Teflon® valve and simultaneously add two solutions dropwise. Both solutions were added to the ethanol pph3 solution over a 20 minute period. The solution was refluxed throughout the period. The solution quickly appeared dark orange brown. After the addition was completed, the solution was refluxed for an additional 2 hours. During this time, small orange crystals of CpRu (PPh3) 2C1 were observed to accumulate on the liquid surface of the solution on the wall of the 2-liter flask. The conduit having a coarse porous filter plate attached to its terminal is connected to a positive displacement pump. The porous end of the tube was immersed in the reactor and all of the liquid was pumped out of a 2 liter round bottom flask. The dropping funnel was removed from the reactor at this stage. Install the K-head distillation connection tube on one side and the rubber septum on the other side. The flask was evacuated and refilled three times with nitrogen. Under nitrogen, 'anhydrous toluene (1.0 liter) was passed through a rubber septum into a 5 liter flask. The dark opaque solution is heated to reflux and the K-head distillation connection tube is opened to distill off a portion of the solvent. The distillate was collected until the head temperature reached 1 〇 9 ° C (note that in the same experiment: this consumes different volumes of solvent - typically 400 - 600 ml of liquid is important). The solution is then cooled to below reflux. The flask was then charged with additional toluene to obtain a volume of about 600 ml of toluene. A lithium ethylcyclopentadienide slurry (35 g, hydrazine: 35 moles, 400 ml) of toluene was then introduced into the reaction pot as a cannula. After the addition, the solution was stirred at 8 ° C for 4 hours. At this stage, the flask was removed from the glove box and most of the toluene was removed using a κ-head steaming connection. The remaining liquid (about 400 ml) was decanted into a 1. liter round bottom flask. This round bottom flask was fitted with a short diameter distillation connection tube with a Vigre dent and a distillation -40 - (36) 1324186. The liquid collected from the Vigre column was re-distilled and obtained 4 4 g of a clear yellow liquid, 1 , > 99% purity (GCMS). TGA study less than 0.01% non-volatile residue. Example 3 A lithium bottom flask prepared as follows (ethylcyclopentadienide) was charged with T ef 1 〇η · ® (perfluorinated polymeric rod. The live plug connection tube., with hot wall and rubber on the neck of the flask. The nitrogen/vacuum manifold was attached to the flask and refilled with nitrogen three times. Anhydrous toluene (passing through the rubber septum into the flask and beginning to agitate to the outer °C of the jacketed flask with the na 1 gene tube) was circulated through the jacketed flask. Outside the wall. Once distilled ethylcyclopentadiene (in the Vigrow column with a cannula into the flask (1 2 7 grams, 1 , 3 5 Mo maintained at a temperature below 〇 ° C) (about 2 join n-Butyllithium (800° halo; liter, in the yard). The fine white alkylene oxide during the addition of n-butyllithium) becomes apparent in solution. This material can be used as a suspension or via a suspension. It is used as a solid. Example 4 Spin-belt distillation steams the book base under vacuum, 丨 '-ethyl ferrocene' shows that this liquid has. 2 liters of three-neck plus rounds 'DuPont' hot-wall connecting tube of the stirring piece Install to the stem connection tube and hollow 1 · 0 liters) and then use the casing. Cooling fluid And the liquid cooling jacket is connected (^ i 5 a toluene reaches 1.0 ° C, the central portion of the new distillation) ears). When stirring, in an hourly) slowly in the casing of the .614, 1.2 8 Mo precipitate (ethyl cyclopentane filtration and solvent removal single-41 - (37) (37) 1324186 in nitrogen gloves In a box, a 25 ml flask was charged with ΤΗF (50 ml, anhydrous 'no inhibitor'), chloro (ethylcyclopentadienyl) bis(triphenylphosphine) ruthenium (II) (3.22 g, 0.004 mol, 1 Equivalent) and Teflon ® (perfluorinated polymer, DuPont) stir bar. Stir the solution and slowly add isopropylcyclopenta-salted sodium burgundy THF solution (0.20M' 30 ml, u Equivalent). Dark red after the addition of the solution. In 30 minutes, the liquid surface appeared yellow. Stir the solution overnight. Take an aliquot (1..0 ml) from the solution and analyze by GC/MS. Observed with 1 - B一一] 'Isopropyl ferrocene consistently has a mass of 3 〇] g / mol. Also observed with alkyl cyclopentadiene dimer two 1 'I1 - diethyl two . The other peaks of the same quality of the presence of 1 ' 1 '-diisopropyl fluorenone and triphenylphosphine.. Then the THF was removed from the flask under reduced pressure. The 250 ml flask was fitted with a vacuum-applied short-diameter distillation connection tube, and the contents of the flask were distilled under reduced pressure (~0.1 Torr). A pale yellow liquid (0.72 g) was collected. This liquid was then analyzed by chromatography. Purification by method. A pentane solution of ruthenium gel was used. The column has a diameter of 0 · 7 5 和 and a length of 6 。. It is separated from 0 · 5 3 g of 99+% pure 1-ethyl-1' by chromatography. - isopropyl ferrocene (41% yield) Example 5 In a nitrogen glove box, a 250 ml flask was charged with THF (50 mL, anhydrous, no inhibitor), chloro (methylcyclopentadiene) bis (three Phenylphosphine) ruthenium (II) (5.02 g, 0.007 mol, 1 eq.) and Tef]on® (perfluoro-42- (38) (38) 1324186 polymer "DuPont" stir bar. Stirring solution And slowly add isopropylcyclopentadienide in burgundy-colored THF solution (0-20 M '50 ml' ι·5 eq.). After adding the solution, it appears dark red. In 30 minutes, the liquid surface appears yellow. The solution was stirred overnight. One aliquot (1.0 ml) was taken from the solution and analyzed by GC/MS. It was observed with 1-methyl-indole-isopropyl钌 - resulting in a mass of 28 7 g / mol. Also observed with alkyl cyclopentadiene dimer, 1 ' Γ dimethyl dimethyl fluorene, 1,], one or two different The other peaks of the same quality of propyl hafnocene and triphenylphosphine were present. Then the THF solvent was removed from the flask under reduced pressure. 2 50 ml flask was fitted with a cloth. 'And under reduced pressure (~〇·]. tray.) Distillate the contents of the bottle. Collect a light yellow liquid (1.78 g). This liquid was then purified by chromatography. A pentane solution of hydrazine gel was used. Column. It has a diameter of 〇 75 和 and a length of 6 。. Separated by chromatography 1 · 〇 3 : gram 98 + % pure 1-methyl 〗 〖 -isopropyl isopropyl bismuth (53% yield) Example 6 in a nitrogen glove box, 250 ml flask Into bis(propylcyclopentadienyl)magnesium (5.15 g, 0.02 mol, 1 equivalent), chloro (methylcyclopentadienyl) bis(triphenylphosphine) ruthenium (II) (5.02 g, 〇.007 Mohr,] Equivalent) and Teflon ® (perfluorinated polymer, DuPont) stir bar. Toluene (120 ml, anhydrous, no inhibitor) was placed in a 250 ml round bottom flask with a cannula and the contents were stirred. After the addition of the solvent, the solution appeared 溁-43-(39) (39) 1324186 red. The toluene solvent was then removed from the flask under reduced pressure. The toluene solvent was removed under reduced pressure and the flask was mounted with a short diameter distillation connection. The distillate was collected and GC/MS showed that the main section from the short diameter distillation was 8 8 7 % pure 1-propyl plant - ethyl ferrocene. Example 7 The vapor pressure of the ruthenium precursor was measured. The vapor pressure in the temperature range (2 5 _ 7 〇 ° C ) ' ( MeCp ) ( EtCp ) Ru is at least twice the vapor s of (EtCp ) .2Ru. Approximately 1 gram of (MeCp) ( EtCp ) Ru was placed in the vaporizer with an inert glove atmosphere. Prior to deposition, the substrate p was ultrasonically treated at room temperature: the substrates were first treated with H20, then:::I.·5 - NH4〇h: H7C>2:H?_0, then The most HA rinse interval afterwards! minute. The substrate is then dried using nitrogen. Sample introduction and removal from the reactor are accomplished using a loading and unloading lock equipped with a magnetically coupled transfer arm. Once the substrate is loaded and placed on the heater, film deposition is performed in the following sequence. First, the substrates are heated to the desired temperature. The samples are then exposed to a process gas comprising a precursor (etc.) and any co-reaction % (^ $ Oxygenating Agent). The two super-purity (Ujjp) is greater than 99.9 99%, nitrogen is used as a carrier and the gas is removed. UHp oxygen is used as the oxidizing gas. UHP nitrogen vaporization precursor, (methylcyclopentane) - (ethyl cyclopentadienyl) hydrazine. -44 - (40) (40) 1324186 Example 8 A tantalum film was deposited on a cerium oxide (SiO 2 ) / cerium (Si) substrate, such as the apparatus shown in Figures 9 and 10. The reaction conditions and results are summarized in Table 2. During all of these experiments, the total flow rate of the gas was 750 standard cubic centimeters per minute (seem) and the precursor flow rate was 0.4 seem. The temperature of the substrate was measured using a dual one-wavelength pyrometer manufactured by WiI, iamson Corporation, Concord, Mass. The pressure in the reactor was measured using a MKS instrument capable of measuring 0.1 to LI 100 Torr and manufactured by Andover, Mass., B a r a i r ο η electric quantity m ο η 〇 m e t e r. The gap is the distance between the method gas inlet tube and the substrate to be coated, expressed as 吋. The oxygen flow rate and the remaining gas were adjusted to nitrogen according to the ratio in Table 2. 02 • The ratio of precursor to the flow rate of oxygen divided by the molar flow rate of the precursor in the process gas. As seen in Table 2, the time during which the substrate was exposed to the complete process gas mixture (vapor, 02 reactant gas, N 2 carrier gas) varied between 15 and 60 minutes. · -45 - 1324186

<N漱骢 first attempt, no visible deposition, first successful deposition pyrometer output vibration, indicating film growth uniformity better than operation (b) no visible deposition 琅 1 1 1 1 4H Sao trn deposited thin film deposited film to increase uniformity by increasing the gap 1 Increase uniformity by reducing 〇2/precursor ratio to about 50 1 _1 Growth of Ru film repeat at lower temperature and higher pressure (d To see if the precursor disappears during operation (e) 〇 2/precursor. The ratio of the product is 500 500 crevice, 吋1—^ CS (N Pi CN CS (N CN P Η 240 360 360 S m 280 360 deposition time) , minutes § iT) iTi iT) operation 3 S -46- (42) 1324186

The thickness of the deposited film was measured by cross-sectional scanning electron microscopy (S EM ). The sheet resistance, and the corresponding resistivity, were measured using a 4-point probe. Elemental composition is determined by a variety of techniques, including energy dispersive spectroscopy (EDS) and XPS. Figures 1 and 12 show cross-sectional views of the 75 degree tilt of the sample from run (d), collected by scanning electron microscopy. It was found that the film formed under the condition of operation (d) has good properties regarding thickness uniformity and resistivity. The tantalum film is about 200 nanometers (nm) thick. The sheet resistance was measured by the 4-point probe method as 〇 1 1 Q / s q. This produces a resistivity of .2 2 u Ω cm. The spectral dispersion obtained by energy dispersive spectroscopy (EDS) is shown in Fig. 3, confirming that the film of ruthenium is present on the SiO 2 /Si substrate. It is expected that thinner films can be produced by reducing the sinking time, for example, 20 to 30 nm thick. Example 9

Experimental runs a - f (described in Example 8) and additional runs 1 - 3 2 are shown in Table 3. Experiments were performed using, for example, the preparations described in Figures 9 and 10. As seen in Table 3, the substrate comprised Si〇2./Si, alumina, and patterned wafers. All film deposition experiments were performed using a nitrogen stream of 1 〇〇 standard cubic centimeter per minute through a precursor vaporizer. The gap is used to operate c - f and the operation 1 - 3 2 is 2 吋. (Run a _ b with a gap). The carburetor pressure is 25 Torr at 1 5 and 18 and 50 Torr in all other cases. -47- 1324186

嗽嗽注旺mq ήτΧ line q. _ y shirt S 1 u Moved the first successful growth of the pyrometer vibration, indicating that the film growth has no visible growth 0 (3⁄4" Gull O ✓ ΜΊ §i^ Sao Songsong艄 its growth appears to be faster than 2 I tray operation without visible growth sm growth Ru film growth Rii film increases uniformity by increasing the gap by reducing the 02/precursor ratio to about 50 to increase uniformity | The RU film is grown at low temperature and higher pressure and repeats (d) to see if the precursor disappears during operation (e). Increase the pressure 1 to drive the new load and change the transfer tube to repeat (d) and (1)! EtCp) 2Ru precursor repeat (1) Repeat at 350C substrate temperature (2) ~ s M field 1ι is (N imn 〇 1 · · 銶 _ using (EtCp) 2Ru with the same parameters as (4) · Run in 5 minutes Time repeat (4) 睢i Run Η Φ for the spirit S w it : i key! 〇 ◎ name S pay 潞 jfeOJ r^> 〇] ε| z$S dimension p Ο 〇〇〇〇〇〇〇〇〇 Ο 〇〇 o s s 〇〇 〇〇 Ή Ή 关 关 关 关 CS CS CS CS CN CS CS CN <Ν CN rs S ^乸ν〇m .v〇cn 〇VO CO 〇〇〇CN S ΓΟ S m 〇IT) (^) tn 〇ΓΟ Ο ι〇m 〇in 〇o cn 狴馘ο m § vi »〇 Mr-Η V) ; Precursor (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru | (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp) Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (EtCp)2Ru (EtCp)2Ru (MeCp)(EtCp)Ru (EtCp)2Ru |(MeCp)(EtCp)Ru (MeCp)(EtCp)Ru # rt JD 〇X5 ο Cm OJ m inch »〇VO OO

-48 - (44)1324186 Note No obvious advantages ☆μ G job post very rough film growth looks very poor vaporizer error (250 Torr) s DU pressure on nucleation density and growth rate meaning Φ stuffing stimulate S 51 _ seeking solution jn Κπ mm il sprinkle η φ ®b ι/-) 1 m 德Λ e 粜1? pr wear 踹Μ ti tiS S t=. ΓΤ ^ Γ 1 舔 in 20 Torr pressure and lower substrate temperature The effect of the lower operation uses the determination of Ru02 from (c) the nucleation 1 density 1 such as (6) the substrate of the Dave Thompson's pharyngeal treatment, at a chamber pressure higher than the above-mentioned operation level 2 (2 托i To 200 trays according to the operation (13) to increase the force [] 02 ratio to complete the Ru deposition | to repeat the chamber pressure at 20 Torr (13) a. a® Egon ii B s stretch VKr U__ _ -3⁄43⁄43⁄4 s 兜 pocket_z$ Warming in higher chamber pressure air drying (ad) repetition (17) possible shortening time interval Csl 〇1, ο 〇〇〇〇〇Ο ο 〇SI shouting insects f «Η ο production one ο 〇〇〇〇t- 〇 ο ο ο r Η 〇 it it 四 四 四 四 四 四 四 四 四 四 四 四 四 & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm CO cn m expansion Φ Κη § <N 卜rH m yn (N precursor (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru |(MeCp)(EtCp)Ru ( MeCp)(EtCp)Ru(MeCp)(EtCp)Ru(MeCp)(EtCp)Ru(MeCp)(EtCp)Ru . (MeCp)(EtCp)Ru Run# as Ο t—^ CN m 寸rH r—< Ό r- 00 -49- 1324186

® Γε 撇m Good deposition deposits look good and good deposits thieves < plastic similar to 20030311 A, slightly thinner thick film growth similar to 20030312A, slightly thinner changes not much better deposition, around Thickness s tm at 20 Torr pressure and 2 minutes deposition time repeat (17) Thin film deposition of ruthenium oxide layer with high 02 flow is repeated at 2 Torr (20) Repeat (13) Repeat with (EtCp) 2Ru precursor ( 22) g Λ Μ m Ο CN 1 Μ gl gl mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm mm ϋ listen to the 80C vaporizer repeat (27) with (MeCpEtCp)Ru precursor at 80C repeat (27) with (MeCpEtCp)Ru precursor at 90C repeat (29) continue to decrease at the lowest deposition rate at lower substrate temperatures Substrate temperature 睇〇〇〇〇〇o 〇〇§·· § § 冢. Oxygen flow, sccni 〇〇〇〇〇os 〇(N 〇1—^ 〇CN Ο <Ν 〇CN 〇CN 1 〇S : mtj 变纪 l^-R 〇(Ν S (N (N oi (N N (N N (N N N N &i < N CN (ΝΪ m inch CS si ^ 〇m (Ν 〇 〇mmom ΓΛ σ\ η ΓΟ m cn m ΓΛ cn CN ro m C^i CO 〇m 〇On CS deposition time, minutes <N m to ο ο ΓνΪ wo κη ο 〇 precursor (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru(MeCp)(EtCp)Ru(MeCp)(EtCp)Ru(EtCp)2Ru(MeCp)(EtCp)Ru(MeCp)(EtCp)Ru(MeCp)(EtCp)Ru (EtCp)2Ru (EtCp)2Ru —___1 (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru (MeCp)(EtCp)Ru Run# σ\ ro <Ν 〇〇<N Os (N <N ΓΟ -50- (46) (46) 1324186 The ALD experiment in Run 11 was performed as follows. The patterned wafer substrate was exposed to one containing (1) nitrogen purge; (2) nitrogen and precursor; a nitrogen purge; and (4) a nitrogen and oxygen process gas stream. The total cycle time of the experiment (all 4 steps), the operation n is 1 〇 seconds (3 seconds for steps 1 and 3, 2 seconds for steps 2 and 4) ° method cycle (all 4 steps) repeat 1 0 8 0 Times, all periods are 18 minutes. The resulting film had a thickness of about 6 5 n m ° in operation 26, and the ALD 'total deposition time was 120 minutes in the same manner. The deposited material is not composed of 倂 倂 but is composed of discontinuous nanocrystals of straight van 彳 彳 A 5 〇 to 300 nm. . * * Example 1 0 'Measurement use〗 - The properties of the film deposited by methyl-Germanium-Ethyl lanthanum and compared to the film produced using 1,1 diethyl ferrocene. The film is deposited on a 3-inch wafer using, for example, a device as described above. The wafer temperature is 3 30 °c, the precursor vaporization temperature is 700-190 °C, the chamber pressure is 2 Torr, the oxygen flow rate is 2 0 0 sccm, and the nitrogen flow rate is 5 50 sc c. m. It was 5 minutes and the film growth rate was I 〇 - 60 nm / min. The sheet resistance was measured by a four-point probe 'perpendicular to the principal plane and 5 intervals (main plane = 0 m m ). The results are shown in Figures 14, 15 and 16. Figure 14 depicts the measured sheet resistance as a function of vaporizer temperature for films deposited from (EtCp) 2Ru and (EtCp) (MeCp) Ru. The vaporizer temperature was changed while all other experimental conditions (temperature, pressure, etc.) were fixed. -51 - (47) (47)1324186 These data are measured at the center of the substrate. This figure shows that films deposited using (EtCp)(MeCp) Ru exhibit lower sheet resistance compared to (EtCp) Au deposited films. This can be attributed to the higher concentration of '(EtCp)(MeCp) Ru in the process gas compared to (EtCp) 2ru at the same vaporizer temperature. The difference in the concentration of this precursor is due to the difference in vapor pressure. Wafer cracking and film thickness as measured by cross-sectional SEM are shown in Figure 5. Under the same conditions, the film produced from 1-methyl, hydrazine, and ethyl octafluorene was thicker than the film formed by the use of 1,2-diethyl ferrocene after the same period of time. This result is also attributed to the higher vapor pressure of 1-methyl, 1,2-ethyl fluorene. The resistivity of these films, shown in Fig. 16., is calculated using the measurement of film resistance and thickness. X-ray diffraction data was also obtained and indicated that the crystals observed in the SEM data consisted of Ru. In addition, X-ray ray electronic spectral data is collected as a function of film depth. These data indicate that the presence of oxygen is close to the surface of the film and that the amount of oxygen present in the film is reduced, as one is deeper into the film. It is shown that - deep oxygen is present in the monomethyl group, and the film produced by 1,2-ethyl decanofluorene is less than the film formed from 1,1 -diethyl fluorene. The present invention has been particularly shown and described with reference to the preferred embodiments thereof. It is understood by those skilled in the art that various changes in form and detail may be made without departing from the scope of the invention as included in the appended claims. -52- (48) 1324186 [Simple Description of the Drawings] Figure 1A illustrates a prior art synthesis path for forming an unsubstituted ferrocene. Figure 1B depicts a prior art synthetic route for the formation of i,r-diethylmentifluorene.

Figure 1c illustrates another prior art method for forming an unsubstituted ferrocene. Figure 2 A shows the molecular formula of a metallocene in a phase-displacement configuration. Figure 2B shows the molecular formula of the dimetallocene in the crossover configuration. Figure 3 is a structural formula of a disubstituted metallocene compound. Figure 4 shows a generalized structural formula of a metallocene which can be used in the process of the present invention. Figure 5 shows an exemplary asymmetric hafnocene compound.

Figure 6 illustrates a synthetic process that can be used to form a metallocene precursor that can be used in the process of the present invention. Figure 7 shows a synthetic process which can be used to form 1-methyl 3 oxime-ethyl decanofluorene. Figure 8 is a schematic illustration of a thin film deposition system that can be used to carry out specific embodiments of the method of the present invention. Figure 9 is a schematic representation of an apparatus for vaporizing a liquid or solid precursor in a gas miscible manifold for chemical vapor deposition of a film. Figure 10 is a schematic view of a thin film deposition reactor which can be used to carry out the embodiment of the present invention - 53-(49) (49) 1324186. Figures 11 and 12 are scanning images showing a cross-sectional image of a tantalum film produced by the inventive method. Electron micrograph. Figure 13 is an energy dispersive spectrum of a ruthenium film produced on a SiO 2 /Si substrate using the method of the present invention. Figure 14 is a graph showing the measurement of sheet resistance as a function of vaporizer temperature using a film deposited using a monomethyl, 1'-ethyl ferrocene precursor and a film deposited using ruthenium-diethyl fluorene. . Figure 15 is a plot of film thickness as a function of vaporizer temperature for a 1 -methyl, 1 'ethylidene lanthanum precursor deposited as compared to a film deposited with ruthenium-diethyl fluorene. 16 is the use of 1-methyl, r-ethyl ferrocene precursors and! The resistivity of the film deposited by ^ ~ diethyl ferrocene is plotted as a function of vaporization. -54-

Claims (1)

(1) (1) 1324186 Pickup, Patent Application 1. A method of preparing a film comprising the step of decomposing at least one precursor in the presence of a substrate, wherein the decomposition is thermal, chemical, actinic or plasma-activated And the precursor has 'the general formula cp MC p % wherein Μ is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted ring comprising at least one substituent D ! pentadienyl or fluorenyl Part: Cp' is a second substituted cyclopentadienyl or indenyl moiety comprising at least one substituent D, ' wherein Di and D are different; . . . D 1 is selected from: X : C a IH h ] X c ] > 』Ca2Hb2Xc2 ( C= 0 ) Ca,HblXcl ; Ca2Hb2Xc2〇Ca]HblXcl · Ca2Hb2$c2 ( C-2 0) OCalHb丨Xc】; and Ca2Hb2Xc2〇( C = 0 ) Ca,HblXC]; Wherein X is a halogen atom; a 1 is an integer from 2 to 8; bl is an integer from 0 to 2 (al) +] - cl; cl is an integer from 〇 to 2 (al) + l_bl; -55 - ( 2) (2) 1324186 b 1 + c 1 is at least 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2 ( a2 ) +1 - c2 ; c2 is from 0 to 2 ( a2 ) + 1 - the integer of b2; and DI -^ΞΕ t ±r · 1P P · X ; C 2 ) H b ] XC 1 ' Ca2Hb2Xc2 ( C = O ) Ca, HblXc,; Ca2Hb2Xc.2〇Ca 丨HblXcl; CaaHbaXcaCC^O) OCaiHb】Xci' and Ca2Hb2Xc2〇(C =0) Ca|HblXcI, _ where X is F, Cl, Br or I; a 1 is an integer from 1 to S; . b 1 is an integer from 0 to 2 ( a 1 ) + 1 - c 1 ; cl is An integer from 0 to 2 ( a 1 ) + 1 - b 1 ; b 1 + c ] is equal to or greater than 1; a2 is an integer from 0 to 8; b 2 is from 0 to 2 ( a 2 ) + ] — c An integer of 2; c.2 is an integer from 0 to 2 (a2) +1 - b2; and b2 + c2 is equal to or greater than 1, thereby forming a film on the substrate. 2. The method of claim 1, wherein one or two of the Cp and Cp' moieties comprise at least one additional substituent, Dx, selected from the group consisting of: -56 - X (3) X (3) 1324186 C a 1 H b 1 X c 1 ' Ca2Hb2Xc2 CC = 0 ) Ca, Hb) Xcl ; C a 2 H b 2 X c 2 0 C a IH b 1 X c 1 ' Ca2Hb2Xc2 ( C = 0 ) OCalHblXcl ; and ' Ca2Hb2Xc2〇 ( C = 0) CalHblXcl ; where X is F, Cl, Br or I; a 1 is an integer from 0 to 8; b 1 is an integer from 0 to 2 ( a 1 ) + 1 - c 1 ; From 0 to 2 ( a 1 ) + 1 — an integer of b 1 ; 丨b Bu c 1 is equal to or greater than .1 a2 is an integer from 0 to 8; b2 is from 0 to 2 ( a2 ) +1 — c2 An integer; c2 is an integer from 0 to 2 ( a2 ) +1 - b2 ; and b 2 + c 2 is equal to or greater than 1. 3. The method of claim 1, wherein the precursor is vaporized and the vapor directly enters a deposition reactor that houses the substrate. 4. The method of claim 1, wherein the substrate is a patterned wafer. 5. The method of claim 1, wherein the vapor of the precursor is combined with a carrier gas. 6. The method of claim 1, wherein the vapor of the precursor is mixed with an oxidizing component selected from the group consisting of oxygen 'ozone and nitrous oxide. -57 - (4) rI324186 7. The method of claim 1, wherein the precursor is methyl, 1 '-ethyl ferrocene. 8. The method of claim 1, wherein the film comprises at least one material selected from the group consisting of base metals, starved metals, ferrous metals 'yttria, oxidized hunger and iron oxide. 9. The method of claim 1, wherein the decomposition is carried out in the presence of a solvent liquid close to a critical or supercritical liquid. 10. The method of claim 5, wherein the film is formed on the substrate by continuous chemical vapor deposition, atomic layer nucleation or atomic layer deposition. -58 -