KR20090053431A - Organometallic compounds - Google Patents

Abstract

Organometallic compounds containing electron donor-substituted alkenyl ligands are provided. These compounds are particularly suitable for use as vapor deposition precursors. Also provided are methods of depositing thin films using such compounds, such as by ALD and CVD.

Organometallic compounds

Description

Organometallic Compounds {ORGANOMETALLIC COMPOUNDS}

The present invention relates generally to the field of organometallic compounds. In particular, the present invention relates to the field of organometallic compounds useful for chemical vapor deposition or atomic layer deposition of thin films.

In atomic layer deposition ("ALD") processes, conformal thin films are deposited by alternating surface exposure to the vapor of two or more types of chemical reactants. Vapor from the first precursor (or reactant) is transferred onto the surface on which the desired thin film is to be deposited. Thereafter, unreacted steam is removed from the system under vacuum. The vapor from the second precursor is then transferred onto the surface to react with the first precursor and excess second precursor vapor is removed. Each step in the ALD process typically deposits a single layer of the desired film. This series of steps is repeated until the desired film thickness is obtained. In general, the ALD process is performed at significantly lower temperatures, such as 200 to 400 ° C. The exact temperature range will depend on the specific film to be deposited and the specific precursors to be applied. ALD processes have been used for the deposition of pure metals and metal oxides, metal nitrides, metal carbide nitrides and metal silicide nitrides.

The ALD precursor must be sufficiently volatile to ensure in the reactor a concentration of precursor vapor sufficient to deposit a monolayer on the substrate surface within a reasonable time period. The precursor must also be stable enough to vaporize without premature decomposition and unwanted side reactions, while on the one hand it must be sufficiently reactive to form the desired film on the substrate. As such a balance of volatility and stability is required, adequate precursors are wholly lacking.

Conventional precursors are homomoleptic, ie have a single ligand group. Homoligand precursors provide homogeneous chemical properties and thus inherent advantages of matching and harmonizing the functionality of the ligand with the deposition process. However, using only a single ligand group may include, for example, shielding of the central metal that governs surface reactions (e.g., chemisorption) and gas phase reactions (e.g., with a second supplemental precursor), control of precursor volatility, And lack of control over other important precursor properties such as achieving the thermal stability required for the precursor. As an example, tetrakis (dialkylamino) hafnium is currently used as a chlorine-free substitute for HfCl ₄ . However, compounds in this compound group tend to degrade prematurely during storage and / or before reaching the reactor. Attempts have been made to impart thermal stability by replacing one or more dialkylamino groups with other organic groups, but they have been nearly unsuccessful because desired stability could not be achieved consistent with the functionality of the other groups. Certain alkenyl-substituted Group 14 compounds have been disclosed in US Patent Application 2004/0194703 (Shenai-Khatkhate et al.) As metalorganic chemical vapor deposition (“MOCVD”) vapor deposition precursor. These compounds may not provide the balance between the volatility and thermal stability (or other properties) required under certain ALD conditions.

There remains a need for suitable and stable precursors that provide films that meet the deposition requirements and are essentially carbon-free.

The present invention provides organometallic compounds having the general formula:

(EDG- (CR ¹ R ² ) _{y '} -CR ³ = CR ^4- (CR ⁵ R ⁶ ) _{y "} ) _n M ^{+ m} L ¹ _(mn) L ² _p

Wherein R ¹ and R ² are each independently selected from H, (C ₁ -C ₆ ) alkyl and EDG; R ³ is H, (C ₁ -C ₆ ) alkyl, EDG or EDG- (CR ¹ R ² ) _{y ′} ; R ⁴ is H or (C ₁ -C ₆ ) alkyl; R ⁵ and R ⁶ are each independently selected from H and (C ₁ -C ₆ ) alkyl; EDG is an electron donor group; M is a metal; L ¹ is an anionic ligand; L ² is a neutral ligand; y 'is 0 to 6; y ″ is 0 to 6; m is the valence of M; n is 1 to 7; and p is 0 to 3. These compounds are various vapor deposition methods, such as chemical vapor deposition (“CVD”) and in particular MOCVD Also suitable are for use as precursors in, and especially for ALD, and compositions are provided which comprise said organometallic compounds and organic solvents, which are particularly suitable for use in ALD and direct liquid injection processes.

The invention also includes providing a substrate in a reactor; Transferring the organometallic compound to a reactor in gaseous form; And depositing a film comprising a metal on the substrate. According to another embodiment, the invention provides a method of providing a substrate in a reactor; Transferring the organometallic compound as a first precursor to the reactor in gaseous form; Chemisorbing the first precursor compound onto the substrate surface; Removing the chemisorbed first precursor compound from the reactor; Transferring the second precursor in gaseous form to the reactor; Reacting the first precursor and the second precursor to form a film on the substrate; And removing the unreacted second precursor.

The following abbreviations used throughout this specification shall have the following meanings, unless the context clearly indicates otherwise: ° C = degrees Celsius; ppm = parts per million; ppb = parts per billion; RT = room temperature; M = molar; Me = methyl; Et = ethyl; i-Pr = iso-propyl; t-Bu = tertiary-butyl; c-Hx = cyclohexyl; Cp = cyclopentadienyl; Py = pyridyl; COD = cyclooctadiene; CO = carbon monoxide; Bz = benzene; Ph = phenyl; VTMS = vinyltrimethylsilane; And THF = tetrahydrofuran.

"Halogen" refers to fluorine, chlorine, bromine and iodine, and "halo" refers to fluoro, chloro, bromo and iodo. Likewise, “halogenated” refers to fluorinated, chlorinated, brominated and iodinated. "Alkyl" includes straight chain, branched and cyclic alkyl. Likewise, "alkenyl" and "alkynyl" include straight, branched and cyclic alkenyl and alkynyl, respectively.

Unless indicated otherwise, all amounts are in weight percent and all ratios are molar ratios. All numerical ranges are inclusive and combinable in any order, except where obvious, such as when the sum of numerical ranges is limited to reaching 100%.

The organometallic compound of the present invention has the general formula:

(EDG- (CR ¹ R ² ) _{y '} -CR ³ = CR ^4- (CR ⁵ R ⁶ ) _{y "} ) _n M ^{+ m} L ¹ _(mn) L ² _p

Wherein R ¹ and R ² are each independently selected from H, (C ₁ -C ₆ ) alkyl and EDG; R ³ is H, (C ₁ -C ₆ ) alkyl, EDG or EDG- (CR ¹ R ² ) _{y ′} ; R ⁴ is H or (C ₁ -C ₆ ) alkyl; R ⁵ and R ⁶ are each independently selected from H and (C ₁ -C ₆ ) alkyl; EDG is an electron donor group; M is a metal; L ¹ is an anionic ligand; L ² is a neutral ligand; y 'is 0 to 6; y ″ is 0-6; m is the valence of M; n is 1-7; and p is 0-3. wherein m ≧ n. In one embodiment, y ′ is 0-3. In other embodiments, y ″ is 0-3. In yet another embodiment, y "is 0-2, and in yet another embodiment y" is 0. Subscript “n” indicates the number of EDG-substituted alkenyl ligands in the present compound. The valence of M is typically 2-7 (ie typically m = 2-7), more typically 3-7, and more typically 3-6. In one embodiment, R ¹ to R ⁶ are each independently selected from H, methyl, ethyl, propyl, butyl and an electron donating group (“EDG”), more specifically from H, methyl, ethyl and propyl do. In other embodiments, R ⁴ , R ⁵ and R ⁶ are each independently selected from H and (C ₁ -C ₃ ) alkyl. In yet another embodiment, R ³ is EDG- (CR ¹ R ² ) _{y '} . In one embodiment, (mn) ≧ 1, ie the organometallic compound is heterologous.

Various kinds of metals may be suitably used to form the organometallic compounds herein. Typically, M is selected from Group 2-16 metals. As used herein, the term "metal" includes metalloid boron, silicon, arsenic, selenium, and tellurium, but does not include carbon, nitrogen, phosphorus, oxygen, and sulfur. In one embodiment, M is Be, Mg, Sr, Ba, Al, Ga, In, Si, Ge, Sb, Bi, Se, Te, Po, Cu, Zn, Sc, Y, La, lanthanum metal, Ti , Zr, Hf, Nb, W, Mn, Co, Ni, Ru, Rh, Pd, Ir or Pt. In another embodiment, M is Al, Ga, In, Ge, La, lanthanide metal, Ti, Zr, Hf, Nb, W, Mn, Co, Ni, Ru, Rh, Pd, Ir or Pt.

Suitable donors for EDG are those that provide π-electron stabilization to the metal. Electron donating groups may be any one comprising one or more oxygen, phosphorus, sulfur, nitrogen, alkene, alkyne and aryl groups. Salts of the electron donating groups, such as their alkali or alkaline earth metal salts, are also usable. Exemplary electron donating groups include, without limitation, hydroxyl ("-OH"), (C ₁ -C ₆ ) alkoxy ("-OR"), carbonyl ("-C (O)-"), carboxy ("-CO ₂ X "), carb (C ₁ -C ₆ ) alkoxy (" -CO ₂ R "), carbonate (" -OCO ₂ R "), amino (" -NH ₂ "), (C ₁ -C ₆ ) alkyl Amino ("-NHR"), di (C ₁ -C ₆ ) alkylamino ("-NR ₂ "), (C ₂ -C ₆ ) alkenylamino, di (C ₂ -C ₆ ) alkenylamino, ( C ₂ -C ₆ ) alkynylamino, di (C ₂ -C ₆ ) alkynylamino, mercapto ("-SH"), thioether ("-SR"), thiocarbonyl ("-C (S) -"), Phosphono (" PH ₂ "), (C ₁ -C ₆ ) alkylphosphino (" -PHR "), di (C ₁ -C ₆ ) alkylphosphino (" -PR ₂ "), vinyl ("C = C"), acetylenyl ("C≡C"), pyridyl, phenyl, furanyl, thiophenyl, aminophenyl, hydroxyphenyl, (C ₁ -C ₆ ) alkylphenyl, di (C ₁ -C ₆ ) alkylphenyl, (C ₁ -C ₆ ) alkylphenols, (C ₁ -C ₆ ) alkoxy- (C ₁ -C ₆ ) alkylphenyl, bi (phenyl) and bi (pyripyridyl) do. Electron donating groups may include other electron donating groups, such as in hydroxyphenyl, aminophenyl and alkoxyphenyl. In one embodiment, the EDG is amino, (C ₁ -C ₆ ) alkylamino, di (C ₁ -C ₆ ) alkylamino, (C ₂ -C ₆ ) alkenylamino, di (C ₂ -C ₆ ) al Kenylamino, (C ₂ -C ₆ ) alkynylamino, and di (C ₂ -C ₆ ) alkynylamino. In another embodiment, the EDG is NH ₂ , methylamino, dimethylamino, ethylamino, diethylamino, ethylmethylamino, di-iso-propylamino, methyl-iso-propylamino, allylamino, diallylamino, propargyl Amino and dipropargylamino. In another embodiment, the EDG is an aryl moiety, more particularly an aromatic heterocycle such as pyridine.

Various kinds of anionic ligands (L ¹ ) can be used in the present invention. These ligands are negatively charged. Possible ligands include, without limitation: hydrides, halides, azides, alkyls, alkenyls, alkynyls, carbonyls, dialkylaminoalkyls, iminos, hydrazidos, phosphidos, nitrosyls, nitriles (nitryl), nitrite, nitrate, nitrile, alkoxy, dialkylaminoalkoxy, siloxy, diketonate, ketoiminate, cyclopentadienyl, silyl, pyrazolate, guanidinate, Phosphoroganidinates, amidinates, phosphoramidinates, amino, alkylamino, dialkylamino and alkoxyalkyldialkylamino. Any of these ligands may be optionally substituted, for example by replacing one or more hydrogens with other substituents, such as halo, amino, disilylamino and silyl. Exemplary anionic ligands include, without limitation: (C ₁ -C ₁₀ ) alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclopentyl and cyclohexyl; (C ₂ -C ₁₀ ) alkenyl such as ethenyl, allyl, and butenyl; (C ₂ -C ₁₀ ) alkynyl, such as acetylenyl and propynyl; (C ₁ -C ₁₀ ) alkoxy such as methoxy, ethoxy, propoxy, and butoxy; Cyclopentadienyl such as cyclopentadienyl, methylcyclopentadienyl and pentamethylcyclopentadienyl; Di (C ₁ -C ₁₀ ) alkylamino (C ₁ -C ₁₀ ) alkoxy such as dimethylaminoethoxy, diethylaminoethoxy, dimethylaminopropoxy, ethylmethylaminopropoxy and diethylaminopropoxy; Silyls such as (C ₁ -C ₁₀ ) alkylsilyl and (C ₁ -C ₁₀ ) alkylaminosilyl; Alkyl amidates such as N, N'-dimethyl-methylamidineato, N, N'diethyl-methylamidineato, N, N'-diethyl-ethylamidineato, N, N ' -Di-iso-propyl-methylamidineato, N, N'-di-iso-propyl-iso-propylamidineato, N, N'-dimethyl-phenylamidineato; (C ₁ -C ₁₀ ) alkylamino, such as methylamino, ethylamino, and propylamino; Di (C ₁ -C ₁₀ ) alkylamino such as dimethylamino, diethylamino, ethylmethylamino and dipropylamino; (C ₂ -C ₆ ) alkenylamino; Di (C ₂ -C ₆ ) alkenylamino, such as diallylamino; (C ₂ -C ₆ ) alkynylamino, such as propargylamino; And di (C ₂ -C ₆ ) alkynylamino, such as dipropargylamino. If two or more L ¹ ligands are present, these ligands may be the same or different. That is, L ¹ ligands are independently selected. In one embodiment, at least one L ¹ ligand is present.

Neutral ligands (L ² ) are optional in the present compounds. These neutral ligands are not entirely charged and can function as stabilizers. Neutral ligands include, without limitation, CO, NO, alkenes, dienes, trienes, alkynes, and aromatic compounds. Exemplary neutral ligands include, without limitation: (C ₂ -C ₁₀ ) alkenes such as ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2 -Hexene, norbornene, vinylamine, allylamine, vinyltri (C ₁ -C ₆ ) alkylsilane, divinyldi (C ₁ -C ₆ ) alkylsilane, vinyltri (C ₁ -C ₆ ) alkoxysilane and Divinyldi (C ₁ -C ₆ ) alkoxysilane; (C ₄ -C ₁₂ ) dienes such as butadiene, cyclopentadiene, isoprene, hexadiene, octadiene, cyclooctadiene, norbornadiene and α-terpinene; (C ₆ -C ₁₆ ) triene; (C ₂ -C ₁₀ ) alkynes such as acetylene and propine; And aromatic compounds such as benzene, o-xylene, m-xylene, p-xylene, toluene, o-cymene, m-cymene, p-cymene, pyridine, furan and thiophene. The number of neutral ligands depends on the particular metal selected as M. Typically, the number of neutral ligands is 0-3. When two or more neutral ligands are present, these ligands may be the same or different.

The organometallic compounds herein can be prepared by a variety of methods known in the art. For example, EDG-substituted alkenyl Grignard can be reacted with a metal halide in a suitable solvent, such as an ethereal solvent such as THF or diethyl ether, to form the EDG-substituted alkenyl organometallic compounds herein. have. Alternatively, the EDG-substituted alkenyllithium compound may be reacted with a suitable metal reactant such as a metal halide, metal acetate or metal alkoxide in a suitable solvent such as hexane to form the desired EDG-substituted alkenyl organometallic compound. have.

The organometallic compounds described above are particularly suitable for use as precursors for vapor phase deposition of thin films. These compounds can be used in various CVD processes and various ALD processes. In one embodiment, two or more of these organometallic compounds may be used in a CVD or ALD process. When two or more organometallic compounds are used, these compounds contain the same metal but may have different ligands, or they may contain other metals. In other embodiments, one or more organometallic compounds herein may be used with one or more other precursor compounds.

A bubbler (also known as a cylinder) is a typical transfer device used to provide organometallic compounds herein to the deposition reactor in vapor form. This bubbler typically includes a fill port, a gas inlet port, and an outlet port connected to a vaporizer, where vaporizers are deposited when direct liquid injection is employed. Connected to the chamber. The discharge port may be connected directly to the deposition chamber. The carrier gas typically enters the bubbler through a gas input port and draws or burns the precursor vapor or precursor-containing gas stream. The conveyed vapor then exits the bubbler through the discharge port and is transferred to the deposition chamber. Various carrier gases can be used, such as hydrogen, helium, nitrogen, argon and mixtures thereof.

Depending on the specific deposition apparatus used, various bubblers can be used. If the precursor compound is a solid, the bubblers disclosed in US Pat. Nos. 6,444,038 (Rangarajan et al.) And 6,607,785 (Timmons et al.), And other designs can be used. For liquid precursor compounds, the bubblers disclosed in US Pat. Nos. 4,506,815 (Melas et al) and 5,755,885 (Mikoshiba et al), and other liquid precursor bubblers can be used. The source compound remains liquid or solid in the bubbler. Solid source compounds are typically vaporized or sublimed before being delivered to the deposition chamber. The bubbler used with the ALD process may have pneumatically actuated valves at the inlet and outlet ports to enable the quick opening and closing required to provide the required vapor pulses.

In a typical CVD process, a bubbler for supplying a liquid precursor, and any bubbler for supplying a solid precursor, will have a dip tube connected to a gas input port. In general, the carrier gas is introduced below the surface of the organometallic compound (also called a precursor or source compound), moves through the source compound and into the headspace thereon, and vapors of the source compound into the carrier gas. Carry or drag.

Precursors used in ALD processes are often liquids, low melting solids, or solids formulated in a solvent. To deal with these types of precursors, the bubbler used in the ALD process may have a dip tube connected to the discharge port. Gas enters the bubbler through the input, pressurizes the bubbler, and pushes the precursor over the dip tube to exit the bubbler.

The present invention provides a transfer device comprising the organometallic compound described above. In one embodiment, the present conveying device comprises a container having an extended cylindrical shape having an inner surface having a cross section, an upper closure portion and a lower finish, wherein the upper finish is an input opening for introducing carrier gas. having an opening and a discharge opening, the elongated cylindrical shape has a chamber comprising the organometallic compound described above.

In one embodiment, the present invention includes a container having an extended cylindrical shape having an inner surface with a cross section, an upper finish and a lower finish, wherein the upper finish is an inlet opening and outlet for introducing carrier gas. A chemical vapor deposition system having an opening, the elongated cylindrical shape having a chamber comprising an organometallic compound, the inlet opening in fluid communication with the chamber, and the chamber in fluid communication with the outlet opening. A device is provided for supplying a fluid stream saturated with an organometallic compound of:

(EDG- (CR ¹ R ² ) _{y '} -CR ³ = CR ^4- (CR ⁵ R ⁶ ) _{y "} ) _n M ^{+ m} L ¹ _(mn) L ² _p

Wherein R ¹ and R ² are each independently selected from H, (C ₁ -C ₆ ) alkyl and EDG; R ³ is H, (C ₁ -C ₆ ) alkyl, EDG or EDG- (CR ¹ R ² ) _{y ′} ; R ⁴ is H or (C ₁ -C ₆ ) alkyl; R ⁵ and R ⁶ are each independently selected from H and (C ₁ -C ₆ ) alkyl; EDG is an electron donor group; M is a metal; L ¹ is an anionic ligand; L ² is a neutral ligand; y 'is 0 to 6; y ″ is 0 to 6; m is the valence of M; n is 1 to 7; and p is 0 to 3. In another embodiment, the present invention provides a fluid stream saturated with the organometallic compounds described above. Provided are equipment for chemical vapor deposition of metal films comprising at least one device for feeding.

The deposition chamber is typically a heated vessel in which at least one, possibly multiple substrates, are placed. The deposition chamber has an outlet, which is typically connected to a vacuum pump to draw the byproduct out of the chamber and, where appropriate, to provide a reduced pressure. MOCVD can be performed under atmospheric pressure or under reduced pressure. The deposition chamber is maintained at a high temperature sufficient to induce degradation of the source compound. Typical deposition chamber temperatures are between 200 ° C. and 1200 ° C., more typically between 200 ° C. and 600 ° C., and the exact temperature is selected to be optimized to provide efficient deposition. Optionally, if the substrate is maintained at an elevated temperature or if other energy, such as plasma, is generated by the radio frequency (“RF”) source, the temperature in the deposition chamber may be reduced overall.

Suitable deposition substrates can be silicon, silicon germanium, silicon carbide, gallium nitride, gallium arsenide, indium phosphide, and the like, for electronic device manufacturing. These substrates are particularly useful for the manufacture of integrated circuits.

Deposition can continue as long as it is desired to produce a film with the desired physical properties. Typically, the film thickness will be hundreds to thousands of angstroms or more at the end of the deposition.

Accordingly, the present invention provides a method for producing a substrate comprising: a) providing a substrate in a vapor deposition reactor; b) transferring the organometallic compound described above as a precursor to the reactor in gaseous form; And c) depositing a film comprising a metal on the substrate. In a typical CVD process, the method described above further comprises decomposing the precursor in the reactor.

Thin metal-containing films are produced by ALD with near perfect stoichiometry by alternately treating the substrates one at a time with the precursor compound vapor of each element formed into the film. In an ALD process, the substrate is treated with the vapor of the first precursor at a sufficiently high temperature that the first precursor can react with the surface of the substrate, thereby allowing a single atom of the first precursor (or a metal contained therein) to the substrate surface. A layer is formed, and the surface having the first precursor atomic layer so formed is treated with the vapor of the second precursor at a sufficiently high temperature at which the second precursor reacts with the first precursor to form a single atom of the desired metal film on the substrate surface. A layer is formed. This process can continue using alternating first and second precursors until the film formed reaches a desired thickness. The temperatures used in such ALD processes are typically lower than those employed in the MOCVD process, and may be in the range of 200 to 400 ° C., but other suitable temperatures may be employed depending on the selected precursor, the film to be deposited and other criteria known to those skilled in the art. It may be.

ALD equipment typically includes a vacuum chamber means and an actuating means for providing a vacuumed atmospheric state, within which a pair of means are located, the pair of means supporting for supporting at least one substrate. Means and source means for respectively forming a source for at least two different precursor vapors, said actuating means being operatively connected with one of the pair of means to connect this one means to the other of the pair of means. It is operated to provide a single atomic layer of one precursor and then a single atomic layer of another precursor on the substrate. See US Patent No. 4,058,430 to Suntola for ALD equipment.

In another embodiment, the present invention provides a method for producing a substrate in a vapor deposition reactor; Transferring the organometallic compound described above as a first precursor to the reactor in gaseous form; Chemisorbing the first precursor compound onto the substrate surface; Removing the chemisorbed first precursor compound from the reactor; Transferring the second precursor in gaseous form to the reactor; Reacting the first precursor and the second precursor to form a film on the substrate; And removing the unreacted second precursor. The steps of alternately transferring the first and second precursors and reacting the first and second precursors are repeated until a film of the desired thickness is obtained. Removing the precursor from the reactor may comprise one or more of vacuuming the reactor under vacuum and purging the reactor using a non-reactant gas. The second precursor can be any suitable precursor that reacts with the first precursor to form the desired film. Such second precursor may optionally include other metals. Exemplary second precursors include, without limitation, oxygen, ozone, water, hydrogen peroxide, alcohols, nitrous oxide and ammonia.

When the organometallic compound of the present invention is intended to be used in an ALD process or a direct liquid injection process, it may be combined with an organic solvent. Mixtures of organic solvents are acceptable. Any organic solvent which is suitably inert to the present organometallic compound can be used. Exemplary organic solvents include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, linear alkyl benzenes, halogenated hydrocarbons, silylated hydrocarbons, alcohols, ethers, glycols, glycols, aldehydes, ketones, carboxylic acids, sulfonic acids , Phenols, esters, amines, alkylnitriles, thioethers, thioamines, cyanates, isocyanates, thiocyanates, silicone oils, nitroalkyls, alkylnitrates, and mixtures thereof. Suitable solvents include tetrahydrofuran, diglyme, n-butyl acetate, octane, 2-methoxyethyl acetate, ethyl lactate, 1,4-dioxane, vinyltrimethylsilane, pyridine, mesitylene, toluene, and Xylenes. When used in a direct liquid injection process, the concentration of organometallic compound is typically in the range of 0.05 to 0.25 M, more typically 0.05 to 0.15 M. The organometallic compound / organic solvent composition may be in the form of a solution, slurry or dispersion.

Compositions comprising the organometallic compounds herein and organic solvents are suitable for use in vapor deposition processes employing direct liquid injection. Suitable direct liquid injection processes are those described in US Patent Application 2006/0110930 (Senzaki).

According to the present invention, there is also provided a method of making an electronic device comprising the step of depositing a metal-containing film using any of the methods described above.

The present invention provides a solution that enables the use of heteroterotic precursors for vapor deposition, in particular ALD, which provides a suitable balance of functionality, the desired thermal stability, by the use of EDG-substituted alkenyl ligands, With proper center metal shielding, and well controlled surface and gas phase reactions.

The following examples are intended to illustrate various aspects of the invention.

Example  One

(1-dimethylamino) allyl (η6- p -cymene) ruthenium diisopropylacetamidinate was synthesized as follows:

Dichloro (η6- p -cymene) ruthenium dimer was reacted with lithium diisopropylacetamidinate in THF at room temperature (approximately 25 ° C.). A three-necked round bottom flask with magnet or mechanical stirring means and an efficient heating / cooling system for controlling the rate of reaction was used. After the mixture was stirred overnight at room temperature, (1-dimethylamino) allyl magnesium bromide was added at low temperature (approximately -30 ° C). The resulting mixture was then stirred overnight under a nitrogen inert atmosphere. Reagents were added in a dropwise manner and mixed slowly to control the exotherm of the reaction. The crude product was then filtered off in high yield and separated from the reactants. The target product was substantially free of organic solvents as measured by FT-NMR (<0.5 ppm) and substantially free of metallic impurities as measured by ICP-MS / ICP-OES (<10 ppb).

Example  2

Bis (1-dimethylaminoallyl) bis (cyclopentadienyl) zirconium (IV) was synthesized as follows:

Dichlorobis (cyclopentadienyl) zirconium was reacted with (1-dimethylamino) allyl magnesium bromide in THF at low temperature (approximately -30 ° C). A three-necked round bottom flask with magnet or mechanical stirring means and an efficient heating / cooling system for controlling the rate of reaction was used. The mixture was stirred at rt overnight. Next, the crude product was filtered off in high yield and then separated from the reactants. The target product was substantially free of organic solvents as measured by FT-NMR (<0.5 ppm) and substantially free of metallic impurities as measured by ICP-MS / ICP-OES (<10 ppb).

Example  3

Organometallic compounds of general formula (EDG- (CR ¹ R ² ) _{y '} -CR ³ = CR ^4- (CR ⁵ R ⁶ ) _{y "} ) _n M ^{+ m} L ¹ _(mn) L ² _p listed in the following table Compounds were prepared according to the methods described in Examples 1 and 2 above.

AMD = N, N'-dimethyl-methyl-amidinate

PAMD = N, P-dimethyl-methylphosphoamidinate

KIM = β-diketimate

BDK = β-diketonate

DMAE = dimethylaminoethyl

DMAP = dimethylaminopropyl

Ligands separated by commas in the table above represent each ligand present in the compound.

Example  4

Compositions suitable for use in ALD or direct liquid injection processes have been prepared by mixing any of the compounds of Example 3 with certain organic solvents. Specific compositions are shown in the following table. Organometallic compounds were typically present at concentrations of 0.1 M for direct liquid injection.

Claims (10)

Organometallic compounds having the general formula: (EDG- (CR ¹ R ² ) _{y '} -CR ³ = CR ^4- (CR ⁵ R ⁶ ) _{y "} ) _n M ^{+ m} L ¹ _(mn) L ² _p Wherein R ¹ and R ² are each independently selected from H, (C ₁ -C ₆ ) alkyl and EDG; R ³ is H, (C ₁ -C ₆ ) alkyl, EDG or EDG- (CR ¹ R ² ) _{y ′} ; R ⁴ is H or (C ₁ -C ₆ ) alkyl; R ⁵ and R ⁶ are each independently selected from H and (C ₁ -C ₆ ) alkyl; EDG is an electron donor group; M is a metal; L ¹ is an anionic ligand; L ² is a neutral ligand; y 'is 0 to 6; y "is 0-6; m is the valence of M; n is 1-7; and p is 0-3. The compound of claim 1, wherein L ¹ is hydride, halide, azide, alkyl, alkenyl, alkynyl, carbonyl, dialkylaminoalkyl, imino, hydrazido, phosphido, nitrosyl, nitrile , Nitrate, nitrile, alkoxy, dialkylaminoalkoxy, siloxy, diketonate, ketoiminate, cyclopentadienyl, silyl, pyrazolate, guanidinate, phosphoguanidenate, ani A compound selected from midinate, phosphoramidineate, amino, alkylamino, dialkylamino and alkoxyalkyldialkylamino. The compound of claim 1, wherein the EDG comprises one or more oxygen, phosphorous, sulfur, nitrogen, alkene, alkyne and aryl groups. The compound of claim 1, wherein M is selected from Group 2 to Group 16 metals. Providing a substrate in a vapor deposition reactor; Transferring the organometallic compound of claim 1 as a precursor to the reactor in gaseous form; And depositing a film comprising a metal on the substrate. A composition comprising the compound of claim 1 and an organic solvent. Providing a substrate in the reactor; Transferring the composition of claim 6 to a reactor using direct liquid injection; And depositing a film comprising a metal on the substrate. Providing a substrate in a vapor deposition reactor; Transferring the organometallic compound of claim 1 to the reactor in gaseous form as a first precursor; Chemisorbing the first precursor compound onto the substrate surface; Removing the chemisorbed first precursor compound from the reactor; Transferring the second precursor in gaseous form to the reactor; Reacting the first precursor and the second precursor to form a film on the substrate; And removing the unreacted second precursor. The method of claim 8, wherein the second precursor is selected from oxygen, ozone, water, peroxides, alcohols, nitrous oxide and ammonia. A transport apparatus for transporting precursors in the vapor phase in a vapor deposition reaction comprising the compound of claim 1.