CN101511773A - Organometallic compounds having sterically hindered amides - Google Patents

Abstract

This invention relates to organometallic compounds represented by the formula M(NR1R2)X wherein M is a metal or metalloid, R1 is the same or different and is a hydrocarbon group or a heteroatom-containing group, R2 is the same or different and is a hydrocarbon group or a heteroatom-containing group; R1 and R2 can be combined to form a substituted or unsubstituted, saturated or unsaturated cyclic group; R1 or R2 of one (NR1R2) group can be combined with R1 or R2 of another (NR1R2) group to form a substituted or unsubstituted, saturated or unsaturated cyclic group; x is equal to the oxidation state of M; and wherein said organometallic compound has (i) a steric bulk sufficient to maintain a monomelic structure and a coordination number equal to the oxidation state of M with respect to anionic ligands, and (ii) a molecular weight sufficient to possess a volatility suitable for vapor deposition.; a process for producing the organometallic compounds, and a method for producing a film or coating from organometallic precursor compounds.

Description

Organometallic compound with sterically hindered amides

Technical field

[0001] the present invention relates to contain sterically hindered amides organometallic compound, make the method for the organometallic compound contain sterically hindered amides and make the method for film or coating by the Organometallic precursor compounds that contains sterically hindered amides.

Background technology

[0002] in the semi-conductive manufacturing or the course of processing, use chemical Vapor deposition process on substrate such as wafer or other surface, to form material film.In chemical vapour deposition, chemical vapor deposition precursor is also referred to as chemical vapor-deposited compound, decomposes the film that has required composition with formation through heat, chemistry, photochemistry mode or by plasma-activated method.For example, the chemical vapor deposition precursor of gas phase can contact with the substrate of the temperature that is heated to above the precursors decompose temperature so that form metal or metal oxide film on substrate.Preferably, chemical vapor deposition precursor is volatile, heat decomposable and can produces uniform thin film under chemical vapor deposition conditions.

[0003] semi-conductor industry considers various uses is used the film of various different metals at present.Many organometallic complexs have been considered to form the potential precursor of these films.In industry, need to develop new compound and explore the potentiality of the chemical vapor deposition precursor that they use as thin film deposition.

[0004] lanthanon sill is the candidate material of the high-k dielectrics in the semiconducter device of future generation as oxide compound, silicate, aluminate and silicon/aluminum ox nitride (oxynitrides).But, because the inherent nature of lanthanon, as the participation of bigger atomic radius (comparing), f orbitals and tendency (Cotton, the F.A. of right+3 oxidation state with transition metal; Wilkenson, G.W.Advanced Inorganic Chemistry; People such as Schumann, Chem.Rev.2002,102,1851), the group of the lanthanides system usually have high ligancy and form dipolymer, higher oligopolymer and/or with the adducts of other molecule.This situation is the situation of many amide-based systems, and has seriously limited the availability that has the enough volatile stable compounds of chemical vapour deposition and atomic layer deposition applications.

[0005] U.S. Patent Application Publication Nos.US 2002/0187644 A1 and US2002/0175393 A1 disclose the metal amide precursor composition with the regulation effectiveness that is used to form dielectric film (as gate-dielectric, high-k metal oxide and ferroelectric metal oxide compound), and relate to the low temperature chemical vapor deposition method of utilizing said composition to deposit this type of dielectric film.

[0006] when developing by chemical vapour deposition or the film forming method of atomic layer deposition method, still needing preferably at room temperature is liquid, have enough vapour pressures, have suitable thermostability (promptly, for chemical Vapor deposition process, can on the substrate of heating, decompose, but can in course of conveying, not decompose, and for atomic layer deposition method, can thermolysis, but when contacting, can react with co-reactant), can form uniform thin film and stay the precursor of the undesired impurity of minute quantity (if any) (for example, halogenide, carbon etc.).Therefore, still need to develop new compound and explore chemical gas phase that they use as thin film deposition or the potentiality of atomic layer deposition precursor.Therefore, need in the art to provide and have some or the preferred precursor of all above-mentioned characteristics.

Summary of the invention

[0007] the present invention partly relates to formula M (NR ₁R ₂) _xShown organometallic compound, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume (steric bulk) of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition).

[0008] the present invention also partly relates to the method for making organometallic compound, comprise that (i) makes nitrogenous compound and basic metal in first jar, or the compound of alkali metal containing, or alkaline-earth metal, or the compound of alkaline including earth metal in the presence of the solvent and the reaction conditions that is being enough to make first reaction mixture comprise base material (basematerial) react down, (ii) described base material is added to and contain metal source compound and choose wantonly in second jar that contains amine compound, (iii) in described second jar, make described base material and described metal source compound and optional described amine compound be enough to make under the reaction conditions of second reaction mixture that comprises described organometallic compound and react, and (iv) from described second reaction mixture, separate described organometallic compound; Wherein said organometallic compound is by formula M (NR ₁R ₂) _xExpression, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition).This organometallic compound yield that is obtained by method of the present invention may be 60% or higher, preferred 75% or higher, more preferably 90% or higher.

[0009] the present invention further partly relates to (the NR by breakdown M ₁R ₂) _xShown Organometallic precursor compounds is made the method for film, coating or powder, and wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition); Make film, coating or powder thus.Usually, the decomposition of described Organometallic precursor compounds is heat, chemistry, photochemistry or plasma-activated.

[0010] the present invention further partly relates to the Organometallic precursor mixture again, and it comprises (a) formula M (NR ₁R ₂) _xShown Organometallic precursor compounds, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition); (b) one or more different Organometallic precursor compounds (for example, contain hafnium, aluminiferous, contain strontium, baric, titaniferous Organometallic precursor compounds).

[0011] The present invention be more particularly directed to comprise " next generation " sedimentation of acid amide type lanthanon precursor.These precursors may have the advantage above other known precursors.These contain the lanthanum material and can be used for multiple use, as dielectric medium, blocking layer and electrode, and compare with other metallic film in many cases and show improved character (thermostability, required form, less diffusion, low seepage, less electric charge capture or the like).

[0012] the present invention has several advantages.For example, method of the present invention can be used for generating the chemical structure with change and the organometallic compound of physical properties.The film that is generated by this organometallic compound precursor can deposit to lack incubation time (incubation time), and shows good slickness by the film of this organometallic compound precursor deposition.

[0013] The present invention be more particularly directed to be used for the chemical vapour deposition and the atomic layer deposition precursor of device of future generation, especially, in room temperature, promptly 20 ℃ is preferred for the Organometallic precursor of liquid down.

[0014] Organometallic precursor compounds of the present invention can provide with other material (for example, as Al ₂O ₃Material) collaborative (in tandem) be used to relate to the required character of atomic layer deposition precursor of the purposes of nanometer laminated structure.

Detailed Description Of The Invention

[0015] as implied above, the present invention relates to formula M (NR ₁R ₂) _xShown organometallic compound, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition).Organometallic compound of the present invention is a liquid under 20 ℃ preferably.

[0016] keep the monosomy of this organo-metallic molecule to verify in realizing that sufficient volatility is important.Dipolymer, oligopolymer or the formation that contains other thing class of two or more metal centers make this compound too big, and therefore, the molecular weight of increase can limit the application as precursor.

[0017] be important as the spatial volume of this organo-metallic molecule that bulky amide ligands gave to other thing class (they can limit volatility) that prevents to form dipolymer, oligopolymer or contain two or more metal centers.In addition, this spatial volume prevents that ligancy is higher than the central element oxidation state, this (for example helps to prevent to form volatility is lower and polarity is higher thing class, so-called " ate (root of ester or salt) " compound, if they exist, then can introduce basic metal (for example Li) and halogen (for example Cl) in reaction process).Be noted that in some cases the coordination of little neutral molecule (for example diethyl ether, Trimethylamine 99) is higher than the central element oxidation state although technically ligancy is increased to, and may produce the precursor with acceptable matter, and within the scope of the invention.

[0018] spatial volume of organometallic compound of the present invention is preferably greater than the spatial volume of three (diethylamino) lanthanums or three (diisopropylaminoethyl) lanthanum.

[0019] requirement of sufficient volatility has been limited the molecular weight of this organo-metallic molecule.Although a kind of molecule may be monomer and have the ligancy that equals the central element oxidation state, if this part too big (for example high molecular), owing to lack vapour pressure, this compound may can not be used as precursor.Organo-metallic molecule of the present invention preferably is not the neutral molecule of dipolymer, oligopolymer or other thing class that contains two or more metal centers.

[0020] organometallic compound of the present invention have usually be lower than about 1000, preferably be lower than about 750, the molecular weight more preferably less than about 500.

[0021] organometallic compound of the present invention has the fusing point that is enough to tackle vapour deposition (vapordeposition).This organometallic compound has usually and is lower than about 200 ℃, preferably is lower than about 100 ℃, more preferably less than about 50 ℃ fusing point.

[0022] organometallic compound of the present invention has the volatility that is suitable for vapour deposition (vapordeposition).Organometallic compound of the present invention has the volatility of at least 0.1 holder under 200 ℃ usually, preferably the volatility of at least 0.1 holder under 150 ℃, the more preferably volatility of at least 0.1 holder under 100 ℃.

[0023] organometallic compound of the present invention shows the thermostability that is enough to tackle vapour deposition (vapordeposition).This organometallic compound has the thermostability that is less than the described organometallic compound of about 1 weight % under 100 ℃ through decomposition in 1 day usually, be preferably under 100 ℃ and decomposed the thermostability that is less than the described organometallic compound of about 1 weight %, more preferably under 100 ℃, be less than the thermostability of the described organometallic compound of about 1 weight % through decomposition in 1 year through 1 month.

[0024] common, R ₁And R ₂Identical or different, and be hydrogen, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, tert-pentyl, cyclohexadienyl, adamantyl, phenyl, benzyl, silyl, dimetylsilyl, diethylsilane base, trimethyl silyl, triethylsilyl, dimethylethylsilyl, diethylmethyl silyl or the like independently.

[0025] common, R ₁And R ₂Identical or different, and be hydrogen, alkyl independently; Replacement or unsubstituted, saturated or undersaturated hydrocarbon, aromatic hydrocarbons, clicyclic hydrocarbon, aromatic heterocycle, cycloaliphatic heterocycle, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamines (polyamine), nitrile; Or its mixture.R ₁And R ₂Can also comprise replacement or unsubstituted, saturated or undersaturated ring-type amido or amino, for example '-aziridino (aziridinyl), azetidine base (azetidinyl), pyrrolidyl (pyrrolidinyl), thiazolidyl (thiazolidinyl), piperidyl (piperidinyl), pyrryl (pyrrolyl), pyridyl (pyridinyl), pyrimidyl (pyrimidinyl), pyrrolinyl (pyrrolinyl), pyrazolyl (pyrazolyl), thiazolyl (thiazolyl) oxazolyl (oxazolyl), imidazolyl (imidazolyl), tetrahydroglyoxaline ketone group (imidazolidinonyl), imidazolidinethione base (imidazolidinethionyl), quinolyl (quinolinyl), isoquinolyl (isoquinolinyl), carbazyl (carbazolyl), triazolyl (triazolyl), indyl (indolyl) and purine radicals (purinyl).Each R ₁And R ₂Preferably identical or different, and be hydrogen, alkyl or its mixture independently.

[0026] normally the 2nd family (for example Sr, Ba), the 3rd family (for example Sc, Y), the 13rd family (Al, Ga) or lanthanon (for example La, Ce, Pr, Nd, Dy, Er and Yb) of M.M also can be the 1st, 4,5,6,7,8,9,10,11,12,14,15,16,17,18 family or actinide elementss.M is preferably selected from the 2nd family's element, the 13rd family's element, the 14th family's element, transition metal or lanthanon.M more preferably is selected from Sr, Ba, Sc, Y, Al, Ga, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.

[0027] exemplary organometallic compound of the present invention comprises for example three (two (cyclohexyl) amino) lanthanum, three (tertiary butyl sec.-propyl) amino) lanthanum, three (two (dimetylsilyl) amino) lanthanum, three ((trimethyl silyl) (dimethylethylsilyl) amino) lanthanum, three (two (tertiary butyl) amino) lanthanum, three (two (tert-pentyl) amino) lanthanum, three (tert-pentyl-tertiary butyl amino) lanthanum, three (tertiary butyl trimethyl silyl amino) lanthanum, three (two (dimethylethylsilyl) amino) lanthanum or the like.Preferred organometallic compounds comprises for example amination lanthanum (lanthanum amide).

[0028] in one embodiment of the invention, this organometallic compound comprises for example three (two (dimetylsilyl) amino) lanthanum, three ((trimethyl silyl) (dimethylethylsilyl) amino) lanthanum and three (two (dimethylethylsilyl) amino) lanthanum.

[0029] in another embodiment of the present invention, this organometallic compound comprises for example three (two (cyclohexyl) amino) lanthanum, three (tertiary butyl sec.-propyl) amino) lanthanum, three (two (tertiary butyl) amino) lanthanum, three (two (tert-pentyl) amino) lanthanum, three (tert-pentyl-tertiary butyl amino) lanthanum and three (tertiary butyl trimethyl silyl amino) lanthanum.

[0030] exemplary organometallic compound of the present invention can be expressed from the next:

[0031] Organometallic precursor compounds of the present invention can be (homo-leptic) that all joins type, promptly all R groups are identical, as three (two (tert-pentyl) amino) lanthanum, or (heteroleptic) of mixed matching, be that the one or more of R group differ from one another, as three (tertiary butyl trimethyl silyl amino) lanthanum.

[0032] as implied above, the invention still further relates to the method for making organometallic compound, comprise that (i) makes nitrogenous compound and basic metal in first jar, or the compound of alkali metal containing, or alkaline-earth metal, or the compound of alkaline including earth metal is in the presence of the solvent and be enough to make under the reaction conditions of first reaction mixture that comprises base material and react, (ii) described base material is added to and contain metal source compound and choose wantonly in second jar that contains amine compound, (iii) in described second jar, make described base material and described metal source compound and optional described amine compound be enough to make under the reaction conditions of second reaction mixture that comprises described organometallic compound and react, and (iv) from described second reaction mixture, separate described organometallic compound; Wherein said organometallic compound is by formula M (NR ₁R ₂) _xExpression, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition).This organometallic compound yield that is obtained by method of the present invention can be 60% or higher, preferred 75% or higher, more preferably 90% or higher.

[0033] in method as herein described, this metal source compound, for example pure metal, metal halide, metal species halogenide (metal pseudohalide) or the like starting material can be selected from multiple compound known in the art.The present invention most preferably is selected from the metal of Sr, Ba, Sc, Y, Al, lanthanon or the like at this.Illustrative metal source compounds comprises for example La (CF ₃SO ₃) ₃, LaCl ₃, LaBr ₃, LaI ₃, SrCl ₂Or the like.Other illustrative metal source compounds comprises for example La (OiPr) ₃Or the like.Preferred metal source compound comprises for example lanthanide halides and lanthanon fluoroform sulphonate.These metal source compound starting material can normally contain any compound or the pure metal of central metal atom.

[0034] is used for synthetic method of the present invention and also can utilizes fluoroform sulphonate Base Metal source compound with organometallic compound of bulky amide ligands.Although most of metal amides (metalloamide) compound it is reported by metal halide (LaCl for example ₃) synthetic, but slowly maybe can not detect because of the bigger spatial shape of part with the speed of reaction of bulky amide compound.Therefore, this trifluoromethanesulfonic acid salt compound with better leavings group is more suitable for this purposes.In addition, (for example Cl) compares with halogenide, and gained trifluoromethanesulfonic acid radical ion can not be retained in the coordination sphere (coordination sphere) (for example bridging), and therefore more is applicable to manufacturing neutral monomer thing class.In addition, the solubleness of the raising of this bulky amide and fluoroform sulphonate can allow to use hydrocarbon solvent (for example toluene), and this may be desirable under the debatable situation of coordination that contains heteroatomic solvent (for example tetrahydrofuran (THF) or ether) and required compound.

[0035] the raw-material concentration of metal source compound can change in wide region, and only need be the necessary minimum of given metal concentration of reacting and providing needs to use with this base material and optional amine compound, the basis of the necessary amount of metal of its formation (furnish) organometallic compound of the present invention at least.Usually, according to the size of reaction mixture, about 1 mmole or more be low to moderate about 10,000 mmoles or higher metal source compound starting material concentration should be enough to most methods.

[0036] in method as herein described, amine compound can be selected from multiple compound known in the art.Illustrative amine compounds comprises for example diisopropylamine, two-tert.-amylamine, tertiary butyl isopropylamine, two-tert-butylamine, dicyclohexylamine, tertiary butyl trimethyl silyl amine, diethyl tetramethyl-disilazane or the like.Preferred amine compound starting material can be by formula NR ₃R ₄R ₅Expression, wherein R ₃, R ₄And R ₅Identical or different separately, and be hydrogen, alkyl independently; Replacement or unsubstituted, saturated or undersaturated hydrocarbon, aromatic hydrocarbons, clicyclic hydrocarbon, aromatic heterocycle, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamines, nitrile; Or its mixture.This amine compound can comprise ring-type and chelating system.This amine compound can also comprise the HCl salt of amine, as ammonium chloride, dimethylammonium chloride or the like.R ₃, R ₄And R ₅Preferred separately identical or different and be hydrogen, alkyl or its mixture independently.Preferred amine compound comprises for example two-tert.-amylamine, tertiary butyl isopropylamine, two-tert-butylamine, tertiary butyl trimethyl silyl amine and diethyl tetramethyl-disilazane.

[0037] the raw-material concentration of this amine compound can change in wide region, and only need be to react necessary minimum with these alkali starting material and metal source compound.Usually, according to the size of reaction mixture, about 1 mmole or more be low to moderate about 10,000 mmoles or higher amine compound starting material concentration should be enough to most methods.

[0038] in method as herein described, the alkali starting material can be selected from multiple compound known in the art.Exemplary alkali comprises pKa greater than about 10, be preferably greater than about 20, any alkali more preferably greater than about 25.This base material is preferably diisopropylaminoethyl lithium, two-tert-pentyl lithium amide, tertiary butyl sec.-propyl lithium amide, two-tertiary butyl lithium amide, two-tertiary butyl sodium amide, dicyclohexyl lithium amide, tertiary butyl trimethyl silyl lithium amide, two (ethyl dimetylsilyl) lithium amide or the like.Lithium amide (lithium amides) is preferred alkali starting material.

[0039] the raw-material concentration of this alkali can change in wide region, and only need be to react necessary minimum with these amine compound starting material and metal source compound.Usually, according to the size of first reaction mixture, about 1 mmole or more be low to moderate about 10,000 mmoles or higher alkali starting material concentration should be enough to most methods.

[0040] in one embodiment, these alkali starting material can original position generate, for example, and lithiated amides (lithiated amide) or the like.From the purity angle, owing to eliminated the needs that separate and handle any reactive solid, original position is useful with the metal source compound reaction immediately after generating the alkali starting material in reactor.It is also comparatively cheap.

[0041] under the alkali starting material that generate the in position situation in place, metal source compound, for example La (CF ₃SO ₃) ₃Interpolation can add by liquid or solid, or in some cases, carry out with solvent solution or slurry form more easily.Although some metal source compound be moisture-sensitive and under inert atmosphere such as nitrogen, use, its degree is usually than amine compound, for example lithiated amides, amine and analogue are much lower.In addition, the finer and close and easier transfer of many metal source compound.

[0042] these alkali starting material can be by the prepared in reaction of the compound of the compound of nitrogenous compound and basic metal or alkali metal containing or alkaline-earth metal or alkaline including earth metal.Can prepare this alkali starting material by traditional method as known in the art.

[0043] used solvent can be any saturated and undersaturated hydrocarbon, aromatic hydrocarbons, aromatic heterocycle, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, thioesters, lactone, acid amides, amine, polyamines (polyamine), nitrile, silicone oil (silicone oils), other aprotic solvent or above-mentioned one or more mixture in the method for the present invention; More preferably pentane, heptane, octane, nonane, decane, dimethylbenzene, tetramethyl-benzene, glycol dimethyl ether, diglyme (diglyme), hydrofluoric ether and above-mentioned one or more mixture; Most preferably be hexane, ether, THF, benzene, toluene and above-mentioned one or more mixture.Can use any suitable solvent that can suitably disturb anticipation reaction unfriendly.If desired, can use the mixture of one or more different solvents.The amount of solvent for use is inessential to the present invention, need be the amount that is enough to the reactive component in the solubilizing reaction mixture only.Usually, the amount of solvent can for about 5 weight % of reaction mixture starting material gross weight to about 99 weight % or more.

[0044] reaction conditions of the reaction method of this base material, this metal source compound and optional this amine compound as temperature, pressure and duration of contact, also can greatly change, and can use any suitable combination of this type of condition in this article.Temperature of reaction can be the reflux temperature of any aforementioned solvents, more preferably about-80 ℃ to about 150 ℃, most preferably is about 20 ℃ to about 80 ℃.Usually this is reflected under the environmental stress and carries out, duration of contact can for several seconds or several minutes to several hours or more.Reactant can add in the reaction mixture, or mixes with any order.For institute in steps, used churning time can be about 0.1 to about 400 hours, preferably approximately 1 to 75 hour, more preferably about 4 to 16 hours.In the embodiment of the present invention of in single jar, carrying out, before reacting, this base material is not separated from first reaction mixture with metal source compound and the amine compound of choosing wantonly.In preferred embodiments, metal source compound is added in first reaction mixture at ambient temperature or under being higher than the temperature of envrionment temperature.

[0045] organometallic compound of being made by the reaction of this base material, this metal source compound and optional amine compound can be selected from multiple compound.For the present invention, organometallic compound comprises having metal-compound of nitrogen key.Exemplary organometallic compound comprises for example metal amino thing (metal amides), metal amine (metal amines) or the like.

[0046] organometallic compound of the present invention also can be by pot process preparation.This pot process is particularly suitable for scale operation, because it can use identical device, some identical reagent and the processing parameter that can be adapted to the manufacturing multiple product easily to carry out.Synthetic this organometallic compound of the technology that this method uses all operations to carry out in single container, and the approach of making this organometallic compound does not require the separation intermediate complex.The U.S. Patent Application Serial No.10/678 that submits on October 6th, 2003 has described an a kind of pot process in 074, and this application is incorporated herein by this reference.

[0047] for the organometallic compound of making by method of the present invention, can pass through recrystallization, more preferably by extractive reaction residue (for example hexane) and chromatography, most preferably purify by distillation and distillation.

[0048] those of skill in the art will recognize that can be in scope or do not deviate from as following claims mentally under the more specifically specified situation of the present invention, the method that this paper describes in detail is made many changes.

[0049] example that can be used for characterizing the technology of this organometallic compound that forms by above-mentioned synthetic method comprises, but be not limited to analytical gas chromatography, nucleus magnetic resonance, thermogravimetric analysis, inductively coupled plasma mass spectrometry method, dsc, vapour pressure and viscosity measurement.

[0050] relative vapour pressure of above-mentioned organometallic compound precursor or relative viscosity can be by thermogravimetric analysis commercial measurements known in the art.Equilibrium vapor pressure also can for example be measured by all gas of finding time from sealed vessel, after this compound steam is introduced this container, and such measuring stress as known in the art.

[0051] organometallic compound precursor as herein described is preferably in room temperature, and promptly 20 ℃ is liquid, and is well suited for in-situ preparing powder and coating.For example, liquid organometallic compound precursor can be applied on the substrate, be heated to the temperature that is enough to decompose this precursor then, on this substrate, form metal or coating of metal oxides thus.Can Liquid precursor be applied on the substrate by japanning, spraying, dip-coating or other technology known in the art.Can be in stove, with hot rifle, heat by this substrate of electrically heated or by alternate manner known in the art.Form the first layer thus by spreading this precursor of organometallic compound precursor, heating and decomposition, carry out at least once other coating and heating with identical or different precursor then, can obtain layered coating.

[0052] aforesaid liquid organometallic compound precursor also can atomize and spray on the substrate.Available atomizing and spray equipment are as known in the art as nozzle, atomizer and other.

[0053] in a preferred embodiment of the invention, aforesaid organometallic compound is used in vapour deposition (the gas phase deposition) technology to form powder, film or coating.This compound can be used as single source precursor or can with one or more other precursors, for example with using by the steam that heats at least a other organometallic compound or metal complex deposits yields.In given method, also can use more than one aforesaid organometallic compound precursor.

[0054] as implied above, the present invention relates to the Organometallic precursor mixture, it comprises (a) formula M (NR ₁R ₂) _xShown Organometallic precursor compounds, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition); (b) one or more different Organometallic precursor compounds (for example, contain hafnium, aluminiferous, contain strontium, baric, titaniferous Organometallic precursor compounds).

[0055] can in the presence of other gaseous component, deposit.In one embodiment of the invention, in the presence of at least a non reactive carrier gas, carry out thin film deposition.The example of non-reactive gas comprises rare gas element, as nitrogen, argon gas, helium and under processing condition not with other gas of this organometallic compound precursors reaction.In other embodiments, in the presence of at least a reactant gas, carry out thin film deposition.Some reactant gases of available include but not limited to, hydrazine (hydrazine), oxygen, hydrogen, air, oxygen-rich air, ozone (O ₃), nitrous oxide (N ₂O), water vapour, organic vapor, ammonia and other.As known in the art, oxidizing gas is as air, oxygen, oxygen-rich air, O ₃, N ₂Having of O or oxidisability organic compound steam is beneficial to the formation metal oxide film.

[0056] as implied above, the present invention also part relates to the method for making film, coating or powder.This method comprises that at least a organometallic compound precursor of the following decomposition that further describes makes the step of film, coating or powder thus.More particularly, the present invention partly relates to (the NR by breakdown M ₁R ₂) _xShown Organometallic precursor compounds is made the method for film, coating or powder, and wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition (vapor deposition); Make film, coating or powder thus.Usually, the decomposition of described Organometallic precursor compounds is heat, chemistry, photochemistry or plasma-activated.

[0057] can carry out sedimentation as herein described and comprise film, powder or the coating of single metal, or comprise film, powder or the coating of single metal oxide with formation.Also can deposit mixed film, powder or coating, for example mixed metal oxide film.Can be for example by using several Organometallic precursors (wherein at least a be selected from above-mentioned organometallic compound) to form mixed metal oxide film.

[0058] can carry out the gas phase membrane deposition and have desired thickness with formation, for example about 1 nanometer is to the thin film layer that surpasses 1 millimeter.Precursor as herein described is particularly useful for making film, and for example thickness is the films of about 10 nanometers to about 100 nanometers.Film of the present invention for example can be considered for making metal electrode, particularly as the n-channel metal electrodes in the logic, as being used for the electrode for capacitors of DRAM purposes and as dielectric materials.

[0059] this method also is applicable to the preparation layered film, and wherein two-layer at least phase or composition are different.The example of layered film comprises metal-insulator semiconductor, and metal-insulator-metal type.

[0060] in one embodiment, the present invention relates to comprise through heat, chemistry, photochemistry mode or the steam by the above-mentioned organometallic compound precursor of the plasma-activated decomposition method of film forming step on substrate thus.For example, make steam that this compound produces with have be enough to make the organometallic compound decomposition and on substrate the substrate of film forming temperature contact.

[0061] this organometallic compound precursor can be used in the chemical vapour deposition, or more specifically, is used in the Metalorganic chemical vapor deposition method known in the art.For example, above-mentioned organometallic compound precursor can be used in normal atmosphere and the Low Pressure Chemical Vapor Deposition.This compound can be used in the hot wall chemical vapor deposition (heating the entire reaction chamber in the method), and is used in the cold or warm wall type chemical vapour deposition (in this technology only heated substrate).

[0062] above-mentioned organometallic compound precursor also can be used in plasma body or the auxiliary chemical Vapor deposition process of photon, wherein uses energy or electromagnetic energy from plasma body to activate this chemical vapor deposition precursor respectively.This compound also can be used in ionic fluid, the auxiliary chemical Vapor deposition process of electron beam, wherein respectively ionic fluid or electron beam is led substrate for the energy that is applied to the chemical decomposition vapor deposition precursor.Also can use laser-assisted chemical Vapor deposition process, wherein with the laser guide substrate to realize the photolysis of this chemical vapor deposition precursor.

[0063] method of the present invention can be in various CVD (Chemical Vapor Deposition) reactor known in the art, for example heat or cold wall reactor, plasma body is auxiliary, bundle is auxiliary (beam-assisted) or laser-assisted reactor in carry out.

[0064] can use the example of the substrate of method of the present invention coating to comprise solid substrate, as metal substrate, for example Al, Ni, Ti, Co, Pt, Ta; Metal aluminate; Metal silicide, for example TiSi ₂, CoSi ₂, NiSi ₂Semiconductor material, for example Si, SiGe, GaAs, InP, diamond, GaN, SiC; Isolator, for example SiO ₂, Si ₃N ₄, HfO ₂, Ta ₂O ₅, Al ₂O ₃, barium strontium (BST); Blocking material, for example TiN, TaN; Or comprising on the substrate of combination of materials.In addition, film or coating can formed on glass, pottery, plastics, the thermoset polymerization material and on other coating or thin film layer.In preferred embodiments, thin film deposition is at the substrate that is used to make or process electronic package.In other embodiments, use substrate load stable low-resistivity (resistivity) conductor deposit or optical clear film (optically transmitting film) in the presence of oxygenant at high temperature.

[0065] can on substrate, carry out method of the present invention with deposit film with smooth planar surface.In one embodiment, in wafer manufacturing or processing, carry out this method with deposit film on the used substrate.For example, can on comprising, carry out this method with deposit film as groove, hole (holes) or through hole (vias) and so on patterns of features substrate.In addition, method of the present invention also can with other step in wafer manufacturing or the processing, for example shelter, etching and other step be integrated.

[0066] chemical vapour deposition film can be deposited into desired thickness.For example, formed film can preferably less than 500 nanometers, be more preferably less than 200 nanometer thickness less than 1 micron thickness.Also can make the film less than 50 nanometer thickness, for example thickness is about 1 film to about 20 nanometers.

[0067] above-mentioned organometallic compound precursor also can be used in the method for the invention, thereby form film by ald (ALD) or atomic shell nucleation (ALN) technology, during this period, substrate is exposed in the ALT pulse of precursor, oxygenant and inert gas stream.For example in U.S. Patent No. 6,287,965 and U.S. Patent No. 6,342,277 in the successive layers deposition technique has been described.The disclosure of these two patents all is incorporated herein by this reference fully.

[0068] for example, in the cycle, substrate progressively is exposed at an ALD: a) rare gas element; B) carry the rare gas element of precursor vapor; C) rare gas element; And d) separately or with the oxygenant of rare gas element.Usually, each step can as weak point (for example, Millisecond) the equipment permission and as processing requirement length (for example, several seconds or several minutes).The time length of one-period may be as little to several milliseconds and reach several minutes.Can to several hours period, repeat this cycle for several minutes.The film of making can be several nanometer thin or thicker, for example 1 millimeter (mm).

[0069] method of the present invention also can use supercutical fluid to carry out.Use the example of the Film forming method of the present known supercutical fluid in this area to comprise chemical fluid deposition; Supercritical fluid delivery-electroless plating; The supercutical fluid electroless plating; With overcritical immersion deposition.

[0070] chemical fluid deposition processes for example is well suited for making high purity films and is fit to cover complex surface and fills high aspect ratio (aspect-ratio) feature.For example in U.S. Patent No. 5,789, chemical fluid deposition has been described in 027.In U.S. Patent No. 6,541, also described the use supercutical fluid among the 278B2 and formed film.The disclosure of these two patents is incorporated herein by this reference fully.

[0071] in one embodiment of the invention, the patterned substrate of heating is at solvent, as closely critical (near critical) or supercutical fluid, and for example near critical or supercritical CO ₂Be exposed to one or more organometallic compound precursors under existing.At CO ₂Situation under, under pressure that is higher than about 1000psig and about at least 30 ℃ temperature, provide solvent fluid.

[0072] precursors decompose is to form metallic film on substrate.This reaction also produces organic materials by this precursor.This organic materials is dissolved by solvent fluid and removes from substrate easily.Also can be for example by using oxidizing gas to form metal oxide film.

[0073] in an example, in being housed, the reaction chamber of one or more substrates carries out sedimentation.By for example heating whole chamber, substrate is heated to temperature required with stove.Can be for example by this chamber be applied the steam that vacuum is made organometallic compound.For low-boiling compound, this chamber can be enough hot, so that compound vaporization (vaporization).Along with the substrate surface of steam Contact Heating, its decomposition also forms metal or metal oxide film.As mentioned above, the organometallic compound precursor can use separately or with one or more components, be used in combination as other Organometallic precursor, inert carrier gas or reactant gas.

[0074] makes in the system of film by method of the present invention can be used for, starting material directional later exhaust mix manifold containing can be fed to process gas in the deposition reactor with manufacturing, in this reactor, carry out film growth.Starting material include but not limited to, carrier gas, reactant gas, sweeping gas, precursor, etch/clean and other.Use mass flow control device known in the art, valve, pressure converter and other device to realize the accurate control that process gas is formed.Exhaust manifold can be transported to vacuum pump with gas and the by-pass stream of leaving deposition reactor.Can use discharge (abatement) system of vacuum pump downstream from waste gas, to remove any hazardous material.This depositing system can be furnished with the in-situ analysis system that allows to measure the process gas composition, comprises the residual gas analysis device.Control and data collecting system can be monitored various processing parameters (for example temperature, pressure, flow velocity etc.).

[0075] above-mentioned organometallic compound precursor can be used for making film that comprises single metal or the film that comprises single metal oxide.Also can deposit mixed film, for example mixed metal oxide film.This class film is for example by using several Organometallic precursors to make.Metallic film can for example not use carrier gas, steam or other oxygen source to form yet.

[0076] film that forms by method as herein described can be by technology known in the art, for example by X-ray diffraction, Auger spectroscopy, the sub-optical emission spectrography of X-ray photoelectric, atomic force microscopy, scanning electron microscopy and other characterized by techniques known in the art.Also can be by the resistivity and the thermostability of methods known in the art MEASUREMENTS OF THIN.

[0077] ald of silicate and aluminate and chemical vapour deposition can be used for many materials of future generation (for example as dielectric chloric acid lanthanum).

[0078] various modifications and changes of the present invention are that those skilled in the art are conspicuous, it being understood that this class is revised and change is included in the spirit and scope of the application's extent of competence and claims.

Claims (22)

1. formula M (NR ₁R ₂) _xShown organometallic compound, wherein M is metal or metalloid, R ₁Identical or different, and be alkyl or contain heteroatomic group, R ₂Identical or different, and be alkyl or contain heteroatomic group; R ₁And R ₂Can replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; (NR ₁R ₂) R of group ₁Or R ₂Can with another (NR ₁R ₂) R of group ₁Or R ₂Replace or unsubstituted, saturated or undersaturated cyclic group in conjunction with forming; X equals the oxidation state of M; And wherein said organometallic compound has (i) to be enough to keep the ligancy relative with anion ligand of the spatial volume of monomer structure and the oxidation state that equals M and (ii) to be enough to have the volatile molecular weight that is suitable for vapour deposition.

2. the organometallic compound of claim 1, it has is enough to tackle the thermostability of vapour deposition and the fusing point that is enough to tackle vapour deposition.

3. the organometallic compound of claim 1, its spatial volume is greater than the spatial volume of three (diethylamino) lanthanums or three (diisopropylaminoethyl) lanthanum.

4. the organometallic compound of claim 1, it has less than about 1000 molecular weight with less than about 200 ℃ fusing point.

5. the organometallic compound of claim 1, it has in the volatility of 200 ℃ of 0.1 holder with at 100 ℃ decomposed the thermostabilitys that are less than the described organometallic compound of about 1 weight % through 1 day at least.

6. the organometallic compound of claim 1, it is a liquid at 20 ℃.

7. the organometallic compound of claim 1, wherein M is selected from the 2nd family's element, the 13rd family's element, the 14th family's element, transition metal or lanthanon, each R ₁And R ₂Identical or different, and be alkyl independently; Replacement or unsubstituted, saturated or undersaturated hydrocarbon, aromatic hydrocarbons, clicyclic hydrocarbon, aromatic heterocycle, cycloaliphatic heterocycle, haloalkane, silylanizing hydrocarbon, ether, polyethers, thioether, ester, lactone, acid amides, amine, polyamines, nitrile; Or its mixture.

8. the organometallic compound of claim 1, wherein M is selected from Sr, Ba, Sc, Y, Al, Ga, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and each R ₁And R ₂Identical or different, and be replacement or unsubstituted alkyl, clicyclic hydrocarbon, silylanizing hydrocarbon or its mixture independently.

9. the organometallic compound of claim 1 is selected from three (two (cyclohexyl) amino) lanthanum, three (tertiary butyl sec.-propyl) amino) lanthanum, three (two (dimetylsilyl) amino) lanthanum, three ((trimethyl silyl) (dimethylethylsilyl) amino) lanthanum, three (two (tertiary butyl) amino) lanthanum, three (two (tert-pentyl) amino) lanthanum, three (tert-pentyl-tertiary butyl amino) lanthanum, three (tertiary butyl trimethyl silyl amino) lanthanum and three (two (dimethylethylsilyl) amino) lanthanum.

10. make the method for the organometallic compound of claim 1, comprise that (i) makes nitrogenous compound and basic metal in first jar, or the compound of alkali metal containing, or alkaline-earth metal, or the compound of alkaline including earth metal is in the presence of the solvent and be enough to make under the reaction conditions of first reaction mixture that comprises base material and react, (ii) described base material is added to and contain metal source compound and choose wantonly in second jar that contains amine compound, (iii) in described second jar, make described base material and described metal source compound and optional described amine compound be enough to make under the reaction conditions of second reaction mixture that comprises described organometallic compound and react, and (iv) from described second reaction mixture, separate described organometallic compound.

11. the method for claim 10, wherein metal source compound comprises pure metal, metal halide or metal species halogenide, base material has the pKa greater than about 10, and amine compound comprises diisopropylamine, two-tert.-amylamine, tertiary butyl isopropylamine, two-tert-butylamine, dicyclohexylamine, tertiary butyl trimethyl silyl amine or diethyl tetramethyl-disilazane.

12. the method for claim 10, wherein metal source compound comprises La (CF ₃SO ₃) ₃, LaCl ₃, LaBr ₃, LaI ₃Or SrCl ₂Base material comprises diisopropylaminoethyl lithium, two-tert-pentyl lithium amide, tertiary butyl sec.-propyl lithium amide, two-tertiary butyl lithium amide, two-tertiary butyl sodium amide, dicyclohexyl lithium amide, tertiary butyl trimethyl silyl lithium amide or two (ethyl dimetylsilyl) lithium amide, and amine compound comprises diisopropylamine, two-tert.-amylamine, tertiary butyl isopropylamine, two-tert-butylamine, dicyclohexylamine, tertiary butyl trimethyl silyl amine or diethyl tetramethyl-disilazane.

13. the method for claim 10, wherein this organometallic compound yield is 60% or higher.

14. make the method for film, coating or powder by the Organometallic precursor compounds that decomposes claim 1, make this film, coating or powder thus.

15. the method for claim 14, the decomposition of wherein said Organometallic precursor compounds are heat, chemistry, photochemistry or plasma-activated.

16. the method for claim 14 wherein makes described Organometallic precursor compounds vaporization, and the steam importing is equipped with in the deposition reactor of substrate.

17. the method for claim 16, wherein said substrate is made of the material that is selected from metal, metal silicide, metal aluminate, semi-conductor, isolator and blocking material.

18. the method for claim 16, wherein said substrate is a patterned wafers.

19. the method for claim 14, wherein said film, coating or powder are by the gas phase deposition technology manufacturing.

20. the method for claim 14, wherein said film, coating or powder are by chemical vapour deposition or ald manufactured.

21. comprise the Organometallic precursor compounds of (a) claim 1 and the mixture of (b) one or more different Organometallic precursor compounds.

22. the mixture of claim 21, wherein said one or more other Organometallic precursor compounds be selected from contain hafnium, aluminiferous, contain strontium, baric or titaniferous Organometallic precursor compounds.