CN101155640A - Organoaluminum precursor compounds - Google Patents

Abstract

This invention relates to organoaluminum precursor compounds represented by the formula (I): wherein R<SUB>1</SUB>, R<SUB>2</SUB>, R<SUB>3</SUB> and R<SUB>4</SUB> are the same or different and each represents hydrogen or an alkyl group having from 1 to about 3 carbon atoms, and R<SUB>5</SUB> represents an alkyl group having from 1 to about 3 carbon atoms. This invention also relates to processes for producing the organoaluminum precursor compounds and a method for producing a film or coating from the organoaluminum precursor compounds.

Description

Organoaluminum precursor compounds

Invention field

The method that the present invention relates to Organoaluminum precursor compounds, the described Organoaluminum precursor compounds of preparation reaches the method for preparing aluminium or pellumina or coating from described Organoaluminum precursor compounds.

Background of invention

Make or the process of processing semiconductor in use chemical vapour sedimentation method on ground for example wafer or other surfaces) go up the film that forms material.In chemical vapour deposition, chemical vapor deposition precursor (being also referred to as the chemical vapour deposition compound) is by heat, chemistry, photochemistry or the plasma-activated film with required composition that is decomposed to form.For example the vapor phase chemical vapor deposition precursor can contact with the ground that is heated above the precursors decompose temperature and form metal or metal oxide film on ground.Preferred chemical vapor deposition precursor is volatility, heat decomposable and can produce uniform film under the chemical vapour deposition condition.

Semicon industry generally considers to use the film of various metals in various application.Think that many metal-organic complexs are for forming the possible precursor of these films.Need to develop new compound in the sector and explore it as the possibility of film deposition with chemical vapor deposition precursor.Current chemical vapour deposition has many shortcomings with aluminum precursor, comprises high viscosity, low stability, pyrophorisity, low-vapor pressure and expensive.

United States Patent (USP) 5,880,303 disclose formula H ₂Al{ (R ¹) (R ²) NC ₂H ₄NR ³Volatile molecules in coordination amino/amine (amido/amine) aluminium alkane complex compound, wherein R ¹, R ²And R ³Be hydrogen or alkyl independently of one another with 1-3 carbon atom.It is said that these aluminium complexs show high thermal stability and deposit high-quality aluminium film at low temperatures.Also it is said, these aluminium complexs can be on metal or other electrically conductive substrates deposition of aluminum film optionally.But these aluminium complexs at room temperature or be solid or for high viscosity liquid.

Aluminium oxide (Al ₂O ₃) film is used in the application that semicon industry requires chemical inertness, high-termal conductivity and radiation resistance.It is used in the manufacturing of LCD, electroluminescent display, solar cell, bipolar device and silicon-on-insulator (SOI) device.In addition, aluminium oxide is used as wear-resisting and corrosion resistant coating in the instrument manufacturing.Most of aluminum chemistry vapor deposition precursors are pyrophorisities, and this makes it be difficult to operation.Those of nonflammable (as amine-aluminium alkane) have the problem that storage life is short, viscosity is high and steam forces down.Need exploitation to have the nonflammable alumina precursor of low viscosity, high vapour pressure and long storage life.

Pass through in chemical vapour deposition or the film forming method of atomic layer deposition method in exploitation, need to continue such precursor, it preferably at room temperature is a liquid, have enough vapour pressures, having suitable heat endurance (promptly for chemical vapour deposition, decomposes on the ground that has heated rather than decomposes in course of conveying; For ald, not thermal decomposition, but when being exposed to coreagent, react), can form uniform film, and stay (if existence) unwanted impurity (for example halide, carbon etc.) hardly.Therefore, continue to need to develop new compound and explore it as the possibility of film deposition with chemical evapn or atomic layer deposition precursor.Therefore, there is a need in the field to provide precursor with some or preferred whole above-mentioned characteristics.

The invention summary

The present invention relates to the Organoaluminum precursor compounds of following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-.Described Organoaluminum precursor compounds adopts chelating amine protection aluminium atom, thereby makes the not spontaneous combustion of described precursor compound.

The invention still further relates to the method for the Organoaluminum precursor compounds of preparation following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes aluminum source compound and organic diamine compound in the presence of the solvent and be enough to produce under the reaction condition of the reactant mixture that comprises described Organoaluminum precursor compounds and react, and (ii) separates described Organoaluminum precursor compounds from described reactant mixture.The yield of the Organoaluminum precursor compounds that is obtained by this method of the present invention can be 60% or higher, and preferred 75% or higher, more preferably 90% or higher.

Select as another kind, the present invention relates to prepare the method for the Organoaluminum precursor compounds of following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes organic diamine compound and alkaloid substance in the presence of the solvent and be enough to produce under the reaction condition of first reactant mixture that includes the organic diamines salt compound and react, (ii) in described first reactant mixture, add aluminum source compound, described organic diamine salt compound and described aluminum source compound are reacted under the reaction condition that is enough to produce second reactant mixture that comprises described organo-aluminum compound, and (iv) from described second reactant mixture, separate described organo-aluminum compound.The same with top method, the yield of the organo-aluminum compound that is obtained by this method of the present invention can be 60% or higher, and preferred 75% or higher, more preferably 90% or higher.

The invention still further relates to a kind of method for preparing film, coating or powder, thereby described method is by decomposing Organoaluminum precursor compounds preparation film, coating or the powder of following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-.Usually, the decomposition of described Organoaluminum precursor compounds is by heat, chemistry, photochemistry or plasma-activated.

The present invention also relates to the Organometallic precursor mixture, described Organometallic precursor mixture comprises the Organoaluminum precursor compounds of (i) following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, with (ii) one or more different Organometallic precursor compounds (as the Organometallic precursor compounds that contains hafnium, contains tantalum or contain molybdenum).

The present invention also partly relates to the deposition of aluminum precursor.Aluminium oxide (Al of the present invention ₂O ₃) film can be used for requiring in the semicon industry in the multiple application of chemical inertness, high-termal conductivity and radiation resistance.Aluminum oxide film is useful in the manufacturing of LCD, electroluminescent display, solar cell, bipolar device and silicon-on-insulator (SOI) device.In addition, aluminium oxide can be used as wear-resisting and corrosion resistant coating in the instrument manufacturing.

Organoaluminum precursor compounds of the present invention is to have low viscous free-pouring liquid.This makes described Organoaluminum precursor be easy to be used for existing bubbling type chemistry dispensing system.Organoaluminum precursor compounds of the present invention also has long storage life and excellent heat endurance, and this makes it be applicable to chemical vapour deposition and ald, its not spontaneous combustion in addition, and this makes the easier and safety of its operation, shipment and storage.

Organoaluminum precursor of the present invention is down liquid and has low viscosity in room temperature (promptly 20 ℃).It can easily distribute in existing chemical vapour deposition is used in bubbler and the direct liquid infusion system.Such precursor is not required to be fluid is flowed and heating extraly.The long storage life that described Organoaluminum precursor has makes it can expand the scale of production and make client on-the-spotly to store economically need worry decomposition in a large number and not.The precursor that great majority contain aluminium is a pyrophorisity.The nature of danger of spontaneous combustion chemicals requires special operation, suitable training and the equipment of protectiveness.Organoaluminum precursor of the present invention is non-hypergolic, this means that it can also can load and transport in air under minimum special installation and training in the operation of realization safety.

The present invention has some other benefits.For example, method of the present invention can be used for producing the organo-aluminum compound precursor with different chemical constitutions and physical property.Deposition from the film (being aluminium and pellumina) that described organo-aluminum compound precursor generates can be carried out in short time, and has good slickness from the film of described organo-aluminum compound precursor deposition.

Detailed Description Of The Invention

As mentioned above, the present invention relates to the Organoaluminum precursor compounds of following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-.R ₁, R ₂, R ₃, R ₄And R ₅In available exemplary alkyl comprise for example methyl, ethyl, n-pro-pyl and isopropyl.

Exemplary Organoaluminum precursor compounds of the present invention comprises for example dimethylethylethylen,diamine ,diamine dimethyl aluminium, dimethylethylethylen,diamine ,diamine aluminium methyl, trimethyl ethylenediamine dimethyl aluminium, triethyl group ethylenediamine dimethyl aluminium, diethylmethylethylen,diamine dimethyl aluminium, dimethyl propyl ethylenediamine dimethyl aluminium, dimethylethylethylen,diamine ,diamine diisopropyl aluminium etc.

As mentioned above, the present invention also relates to prepare the method (being referred to herein as " method A ") of the Organoaluminum precursor compounds of following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes aluminum source compound and organic diamine compound in the presence of the solvent and be enough to produce under the reaction condition of the reactant mixture that comprises described Organoaluminum precursor compounds and react, and (ii) separates described Organoaluminum precursor compounds from described reactant mixture.The yield of the Organoaluminum precursor compounds that is obtained by this method of the present invention can be 60% or higher, and preferred 75% or higher, more preferably 90% or higher.

Owing to can use identical equipment to carry out, reactant that some is identical and technological parameter can easily be fit to make the product of wide region, so this method A is specially adapted to large-scale production.Described method provides the method for using wherein all operations to carry out in single container synthetic Organoaluminum precursor compounds, and the route of synthetic Organoaluminum precursor compounds does not need the separation of intermediates complex compound.

The aluminum source compound raw material that adopts among the method A can be selected from multiple compound known in the art.This exemplary class aluminum source compound comprises for example Me ₃Al, Me ₂AlH, Et ₃Al, Et ₂MeAl, Et ₂AlH, ⁱPr ₃Al etc.

The concentration of the aluminum source compound raw material that adopts among the method A can change in wide region, only needs with organic diamine compound reaction and the given aluminum concentration that needs usefulness is provided and supplies with required minimum of the fundamental quantity of the required aluminium of organo-aluminum compound of the present invention at least.Usually for most of technologies, according to the scale of reactant mixture, the concentration of aluminum source compound raw material be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

The organic diamine raw materials of compound that adopts among the method A can be selected from multiple compound known in the art.Exemplary organic diamine compound comprises for example dimethylethylethylen,diamine ,diamine, trimethyl ethylenediamine, triethyl group ethylenediamine, diethylmethylethylen,diamine, dimethyl propyl ethylenediamine etc.Preferred organic diamine raw materials of compound comprises dimethylethylethylen,diamine ,diamine, diethylmethylethylen,diamine etc.

The concentration of the organic diamine raw materials of compound that adopts among the method A can change in wide region, only needs and required minimum of alkali raw material reaction.Usually for most of technologies, according to the scale of reactant mixture, the concentration of organic diamine raw materials of compound be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

The solvent that adopts among the method A can be the mixture of any saturated and undersaturated hydrocarbon, aromatic hydrocarbons, aromatic heterocycle compounds, alkyl halide, silylated hydrocarbon, ether, polyethers, thioether, ester, thioesters, lactone, acid amides, amine, polyamine, nitrile, silicone oil, other aprotic solvent or one or more above-mentioned solvents; More preferably ether, pentane or dimethoxy-ethane; Most preferably hexane or toluene.Can use any suitable solvent that does not excessively influence anticipation reaction unfriendly.If desired, can use the mixture of one or more different solvents.For the present invention, the consumption of solvent is not crucial, only needs to be enough to the amount of each reactive component in the solubilizing reaction mixture.The amount of usual solvents can account for about 5% weight of reactant mixture raw material gross weight to about 99% weight or more.

The reaction condition (for example temperature, pressure and time of contact) of organic diamine compound and aluminum source compound reaction also can have very big variation among the method A, can use any suitable combination of these conditions herein.Reaction temperature can be the reflux temperature of any above-mentioned solvent, more preferably about-80 ℃ to about 150 ℃, most preferably is about 20 ℃-Yue 80 ℃.Usually described being reflected under the ambient pressure carried out, and time of contact can be from about several seconds or several minutes extremely several hours or longer.Can any order add in the reactant mixture reactant or mixing.For all steps, mixing time can be about 0.1-about 400 hours, was preferably about 1-75 hour, more preferably about 4-16 hour.

As mentioned above, the present invention also relates to prepare the method (being referred to herein as " method B ") of the Organoaluminum precursor compounds of following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes organic diamine compound and alkaloid substance in the presence of the solvent and be enough to produce under the reaction condition of first reactant mixture that includes the organic diamines salt compound and react, (ii) in described first reactant mixture, add aluminum source compound, described organic diamine salt compound and described aluminum source compound are reacted under the reaction condition that is enough to produce second reactant mixture that comprises described organo-aluminum compound, and (iv) from described second reactant mixture, separate described organo-aluminum compound.

The yield of the organo-aluminum compound that is obtained by this method of the present invention can be 60% or higher, and preferred 75% or higher, more preferably 90% or higher.Owing to can use identical equipment to carry out, reactant that some is identical and technological parameter can easily be fit to make the product of wide region, so this method B is specially adapted to large-scale production.Described method provides the method for using wherein all operations to carry out in single container synthetic organo-aluminum compound, and the route of synthetic organo-aluminum compound does not need the separation of intermediates complex compound.

The organic diamine raw materials of compound that adopts among the method B can be selected from multiple compound known in the art.Exemplary organic diamine compound comprises for example dimethylethylethylen,diamine ,diamine, trimethyl ethylenediamine, triethyl group ethylenediamine, diethylmethylethylen,diamine, dimethyl propyl ethylenediamine etc.Preferred organic diamine raw materials of compound comprises dimethylethylethylen,diamine ,diamine, diethylmethylethylen,diamine etc.

The concentration of the organic diamine raw materials of compound that adopts among the method B can change in wide region, only needs and required minimum of alkali raw material reaction.Usually for most of technologies, according to the scale of reactant mixture, the concentration of organic diamine raw materials of compound be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

The alkali raw material that adopts among the method B 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.Alkaloid substance is preferably n-BuLi, t-BuLi, MeLi, NaH, CaH etc.

The concentration of the alkali raw material that adopts among the method B can change in wide region, only needs and required minimum of organic diamine raw materials of compound reaction.Usually for most of technologies, according to the scale of first reactant mixture, the alkali material concentration be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

In the embodiment of method B, but described organic diamine salt compound original position generates, for example lithiumation organic diamine such as lithiumation dimethylethylethylen,diamine ,diamine, lithiumation trimethyl ethylenediamine, lithiumation triethyl group ethylenediamine, lithiumation diethylmethylethylen,diamine, lithiumation dimethyl propyl ethylenediamine etc.Original position generation organic diamine salt compound is favourable from the purity angle in reaction vessel before and then reacting with aluminum source compound, because of it has eliminated the needs that separate and handle any reactive solid.It is also more cheap.

After original position generates the organic diamine salt compound, aluminum source compound such as Me ₂The adding of AlCl can be by adding that solid carries out or adding as solvent solution or slurry more easily in some cases.Though some aluminum source compound is to wetting responsive and using under inert atmosphere such as nitrogen, its sensitivity is usually far below organic diamine salt compound such as lithiumation dimethylethylethylen,diamine ,diamine etc.In addition, many aluminum source compound density are higher, are easier to transmit.

Organic diamine salt compound from the method B of the prepared in reaction of organic diamine raw materials of compound and alkali raw material can be selected from multiple compound.Exemplary organic diamine salt compound comprises for example lithiumation dimethylethylethylen,diamine ,diamine, lithiumation trimethyl ethylenediamine, lithiumation triethyl group ethylenediamine, lithiumation diethylmethylethylen,diamine, lithiumation dimethyl propyl ethylenediamine etc.

The concentration of the organic diamine salt compound that adopts among the method B can change in wide region, only need with aluminum source compound reaction to provide organo-aluminum compound of the present invention required minimum.Usually for most of technologies, according to the scale of reactant mixture, the concentration of organic diamine salt compound be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

The aluminum source compound raw material that adopts among the method B can be selected from multiple compound known in the art.This exemplary class aluminum source compound comprises for example Me ₂AlCl, Me ₂AlBr, Me ₂AlF, Et ₂AlCl, EtMeAlCl, ⁱPr ₂AlCl etc.

The concentration of the aluminum source compound raw material that adopts among the method B can change in wide region, only needs with organic diamine salt compound reaction and the given aluminum concentration that needs usefulness is provided and supplies with required minimum of the fundamental quantity of the required aluminium of organo-aluminum compound of the present invention at least.Usually for most of technologies, according to the scale of reactant mixture, the concentration of aluminum source compound raw material be about 1 mM more be low to moderate about 10,000 mMs or higher should be enough.

The solvent that adopts among the method B can be the mixture of any saturated and undersaturated hydrocarbon, aromatic hydrocarbons, aromatic heterocycle compounds, alkyl halide, silylated hydrocarbon, ether, polyethers, thioether, ester, thioesters, lactone, acid amides, amine, polyamine, nitrile, silicone oil, other aprotic solvent or one or more above-mentioned solvents; More preferably ether, pentane or dimethoxy-ethane; Most preferably hexane or toluene.Can use any suitable solvent that does not excessively influence anticipation reaction unfriendly.If desired, can use the mixture of one or more different solvents.For the present invention, the consumption of solvent is not crucial, only needs to be enough to the amount of each reactive component in the solubilizing reaction mixture.The amount of usual solvents can account for about 5% weight of reactant mixture raw material gross weight to about 99% weight or more.

The reaction condition (for example temperature, pressure and time of contact) of alkali raw material and organic diamine compound reaction also can have very big variation among the method B, can use any suitable combination of these conditions herein.Reaction temperature can be the reflux temperature of any above-mentioned solvent, more preferably about-80 ℃ to about 150 ℃, most preferably is about 20 ℃-Yue 80 ℃.Usually described being reflected under the ambient pressure carried out, and time of contact can be from about several seconds or several minutes extremely several hours or longer.Can any order add in the reactant mixture reactant or mixing.For all steps, mixing time can be about 0.1-about 400 hours, was preferably about 1-75 hour, more preferably about 4-16 hour.

The reaction condition (for example temperature, pressure and time of contact) of organic diamine salt compound and aluminum source compound reaction also can have very big variation among the method B, can use any suitable combination of these conditions herein.Reaction temperature can be the reflux temperature of any above-mentioned solvent, more preferably about-80 ℃ to about 150 ℃, most preferably is about 20 ℃-Yue 80 ℃.Usually described being reflected under the ambient pressure carried out, and time of contact can be from about several seconds or several minutes extremely several hours or longer.Can any order add in the reactant mixture reactant or mixing.For all steps, mixing time can be about 0.1-about 400 hours, was preferably about 1-75 hour, more preferably about 4-16 hour.In embodiment of in single jar, carrying out of the present invention, with the aluminum source compound reaction before the organic diamine salt compound from first reactant mixture, do not separate.In preferred embodiments, aluminum source compound is in environment temperature or be higher than under the temperature of environment temperature and be added in first reactant mixture.

Method of the present invention is preferred for preparing the organo-aluminum compound precursor with different chemical structures and physical property.Can adopt multiple reactive material in the method for the present invention.

For Organoaluminum precursor compounds by method preparation of the present invention, can be by recrystallization, more preferably by extracting (for example using hexane) reaction residue and chromatography, most preferably carrying out purifying by distillation and distillation.

Person skilled in the art will recognize that under the situation of scope of the present invention that does not depart from following claims regulation more specifically or aim and can carry out various variations the method that this paper describes in detail.

The example that can be used for characterizing the technology of the Organoaluminum precursor compounds that forms by above-mentioned synthetic method includes but not limited to gas chromatography, nuclear magnetic resonance, thermogravimetry, inductivity coupled plasma mass spectrometry, differential scanning calorimetry, vapour pressure and viscosimetric analysis.

The relative vapour pressure of above-mentioned organo-aluminum compound precursor or relative volatility can be measured by thermogravimetric analysis technology known in the art.Equilibrium vapor pressure also can followingly be measured, and for example by all gas of finding time from the container of sealing, subsequently the steam of described compound is introduced in the container, and method is as known in the art measured pressure.

Preferred organo-aluminum compound precursor as herein described is down liquid and is highly suitable for in-situ preparing powder and coating in room temperature (promptly 20 ℃).For example liquid organo-aluminum compound precursor can be coated on ground, be heated to the temperature that is enough to decompose described precursor subsequently, thereby on ground, form aluminium or aluminum oxide coating layer.Can carry out by paint, spraying, dip-coating or by other technologies known in the art to ground applying liquid precursor.Can be in baking oven, use heating gun, heat by the electrical heating ground or by additive method known in the art.Can be by being coated with the machine aluminium compound precursor, heat subsequently and decompose, thereby form ground floor, use identical or different precursor to apply other coatings of one deck and heating at least subsequently, obtain laminated coating.

Liquid organo-aluminum compound precursor (for example above-mentioned precursor) is also aerosolizable and be sprayed on the ground.Spendable atomizing and spray equipment (for example nozzle, sprayer etc.) are known in the art.

In embodiment preferred of the present invention, in gas phase deposition technology, use organo-aluminum compound (for example above-claimed cpd) to form powder, film or coating.Described compound can be used as the precursor of single source or can use with one or more other precursors, for example with using by the steam that heats at least a other organo-metallic compounds or metal complex deposits yields.In a kind of given method, also can use more than a kind of organo-metallic compound precursor (for example above-mentioned precursor).

As mentioned above, the present invention relates to the Organometallic precursor mixture, described Organometallic precursor mixture comprises the Organoaluminum precursor compounds of (i) following formula representative

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, with (ii) one or more different Organometallic precursor compounds (as the Organometallic precursor compounds that contains hafnium, contains tantalum or contain molybdenum).

Can in the presence of other gaseous components, deposit.In one embodiment of the invention, film is deposited under at least a non reactive carrier gas existence and carries out.The example of non-reactive gas comprise inert gas (for example nitrogen, argon gas, helium) and under process conditions not with other gases of organo-aluminum compound precursors reaction.In other embodiments, film is deposited under at least a reactant gas existence and carries out.Spendable partial reaction gas includes but not limited to hydrazine, oxygen, hydrogen, air, oxygen-enriched air, ozone (O ₃), nitrous oxide (N ₂O), water vapour, organic vapor, ammonia etc.As known in the art, oxidizing gas (for example air, oxygen, oxygen-enriched air, O ₃, N ₂The having steam of O or oxidisability organic compound) is beneficial to the formation metal oxide film.

As mentioned above, the present invention also partly relates to the method for preparing film, coating or powder.Thereby described method comprises the step of decomposing at least a preparation of organo-aluminum compound precursor film, coating or powder, and this point further describes hereinafter.

Can carry out sedimentation as herein described and form film, powder or coating or the film that comprises single metal oxide, powder or the coating that comprises single metal.Also can deposit hybrid films, powder or coating, for example mixed metal oxide film.For example by using several Organometallic precursors (wherein at least a be selected from above-mentioned organo-aluminum compound) can form mixed metal oxide film.

Can carry out gas phase membrane and deposit the rete that forms desired thickness (for example about 1nm is to surpassing 1mm).Precursor as herein described is used in particular for preparing film, and for example thickness is the film of the about 100nm of about 10nm-.Think that film of the present invention for example can be used for making metal electrode, particularly in logic, be used as the n-channel metal electrodes, in DRAM uses, be used as electrode for capacitors and be used as dielectric substance.

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

In one embodiment, the present invention relates to a kind of like this method, on ground, form the step of film thereby described method comprises the steam by heat, chemistry, photochemistry or the above-mentioned organo-aluminum compound precursor of plasma-activated decomposition.The steam that for example described compound produces and temperature are enough to make the ground of described organo-aluminum compound decomposition to contact and form film on grounds.

Described organo-aluminum compound precursor can be used for chemical vapour deposition, perhaps more particularly, is used for organometallic chemical vapor deposition process known in the art.For example above-mentioned organo-aluminum compound precursor can be used in normal pressure and the low pressure chemical vapor deposition method.Described compound can be used for hot wall chemical vapour deposition (the wherein method that the entire reaction chamber is heated) and cold wall or warm wall type chemical vapour deposition (wherein only heating the technology of ground).

Above-mentioned organo-aluminum compound precursor also can be used in plasma or the light assistant chemical vapor deposition method, wherein uses energy or electromagnetic energy activating chemical vapor deposition precursors from plasma respectively.Described compound also can be used in ion beam, the electron beam assistant chemical vapor deposition method, wherein respectively ion beam or electron beam is led ground so that the energy of chemical decomposition vapor deposition precursors to be provided.Also can use laser assistant chemical vapor deposition method, wherein with the laser guide ground to influence the photolysis of chemical vapor deposition precursor.

Can carry out method of the present invention in various chemical vapour deposition reactors, hot wall for example known in the art or cold wall reactor, plasma are assisted, light beam is auxiliary or the laser auxiliary reactor.

Can use the example of the ground of method coating of the present invention to comprise solid substrates, for example metal substrate, for example Al, Ni, Ti, Co, Pt, Ta; Metal silicide, for example TiSi ₂, CoSi ₂, NiSi ₂Semi-conducting material, for example Si, SiGe, GaAs, InP, diamond, GaN, SiC; Insulator, for example SiO ₂, Si ₃N ₄, HfO ₂, Ta ₂O ₅, Al ₂O ₃, barium strontium titanate (BST); Barrier material, for example TiN, TaN; Or on the ground of the combination that comprises various materials.In addition, can and on other coatings or rete, form film or coating at glass, pottery, plastics, thermoset copolymer material.In preferred embodiments, be used to make or process deposited film on the ground of electronic component.In other embodiments, use ground to support under the high temperature low resistivity conductor deposit or light-transmissive film stable in the presence of oxidant.

Can on ground, come deposited film with the inventive method with level and smooth flat surfaces.In one embodiment, be used to make or the ground of processed wafer on come deposited film with described method.For example can comprise that various features for example come deposited film with described method on the figuratum ground in ditch, hole or road.In addition, method of the present invention also can be used in combination with other steps of manufacturing or processed wafer (for example shelter, etching etc.).

Chemical vapor deposition films can be deposited as required thickness.For example the film of Xing Chenging can preferably less than 500 nanometers, be more preferably less than 200 nanometer thickness less than 1 micron thickness.Also can produce the film less than 50 nanometer thickness, for example thickness is the film of about 20 nanometers of about 0.1-.

Above-mentioned organo-aluminum compound precursor also can be used for method of the present invention forming film by ald (ALD) or atomic layer nucleation (ALN) technology, during ground is exposed to the ALT pulse of precursor, oxidant and inert gas flow.Sequential layer deposition techniques for example sees and is set forth in United States Patent (USP) 6,287,965 and United States Patent (USP) 6,342,277.Two pieces of disclosed contents of patent are attached to herein by quoting in full.

For example in the cycle, adopt mode progressively that ground is exposed to: a) inert gas at an ALD; B) carry the inert gas of precursor vapor; C) inert gas; And d) independent oxidant or oxidant and inert gas.Common each step can be as short as equipment and allow (for example millisecond) and grow to arts demand (for example several seconds or several minutes).The duration of one-period can be as short as millisecond and grow to several minutes.In time, repeat this cycle from a few minutes to a few hours.The film of preparation can be several nanometer thin or thicker, for example 1 millimeter (mm).

Also can use supercritical fluid to carry out method of the present invention.This area example of the film sedimentation of known use supercritical fluid usually comprises chemical fluid deposition; Supercritical fluid transmission-chemical deposition; The supercritical fluid chemical deposition; With overcritical immersion deposition.

For example chemical fluid deposition processes is highly suitable for preparing high purity films and covers complex surface and fill the high aspect ratio element.Chemical fluid deposition is for example seen and is set forth in United States Patent (USP) 5,789,027.Use supercritical fluid formation film also to see and be set forth in United States Patent (USP) 6,541,278B2.These two pieces of disclosed contents of patent are attached to herein by quoting in full.

In one embodiment of the invention, (for example near critical or supercritical fluid is as nearly critical or supercritical CO at solvent ₂) exist down, the figuratum ground that has heated is exposed to one or more organo-aluminum compound precursors.Using CO ₂Situation under, the pressure of donor solvent fluid surpasses about 1000psi (gauge pressure), temperature is at least about 30 ℃.

Precursors decompose forms aluminium or pellumina on ground.Described reaction also produces organic substance by precursor.Described organic substance is dissolved in the solvent fluid easily to be removed from ground.For example, also can form pellumina by using oxidizing gas.

In one embodiment, in comprising the reative cell of one or more grounds, carry out depositing operation.By heating whole chamber (for example adopting oven process) ground is heated to required temperature.For example, can produce the steam of organo-aluminum compound by vacuum is executed in the chamber.For low-boiling compound, can make this chamber enough hot with the gasification compound.When steam contacted the surface of bottom material that has heated, its decomposition also formed aluminium or pellumina.As mentioned above, the organo-aluminum compound precursor can use separately or be used in combination with one or more components (for example other Organometallic precursors, inert carrier gas or reactant gas).

Prepare in the system of film by method of the present invention can be used for, raw material can be guided into gas blend manifold, produce process gas, be supplied to deposition reactor, carry out the film growth at this.Raw material includes but not limited to carrier gas, reactant gas, purge gas, precursor, etch/clean etc.Service property (quality) flow controller, valve, pressure sensor and other devices known in the art are the composition of control process gas accurately.Exhaust manifold can be delivered to vavuum pump with gas and the by-pass that comes out from deposition reactor.Can use the waste disposal system of vacuum pump downstream from the gas of discharging, to remove any harmful material.Sedimentary system can be equipped with in-situ analysis system, comprises residual gas analyser, and it can measure the composition of process gas.Control and data acquisition system can be monitored various technological parameters (for example temperature, pressure, flow velocity etc.).

Can use above-mentioned organo-aluminum compound precursor preparation to comprise the film of single aluminium or comprise the film of single aluminium oxide.Also can deposit hybrid films, for example mixed metal oxide film.For example by using several Organometallic precursors to produce this type of film.For example also can form metal film by not using carrier gas, steam or other oxygen sources.

Can use characterized by techniques known in the art by the film that method as herein described forms, for example by X-ray diffraction, Auger power spectrum, x-ray photoelectron emission power spectrum, atomic force microscopy, scanning electron microscopy and other technologies known in the art.Also can measure the resistivity and the heat endurance of film by methods known in the art.

Various change of the present invention and to change those skilled in the art be obvious it should be understood that these changes and variation are included in the aim and scope of the scope of asking in this and claims.

Embodiment 1

Synthesizing of dimethylethylethylen,diamine ,diamine dimethyl aluminium (DMEEDDMA)

Under the nitrogen inert atmosphere, 5 milliliters of trimethyl aluminium/30 milliliter dry toluenes are cooled to 0 ℃.In this solution, dropwise add 8.5 milliliters of dimethylethylethylen,diamine ,diamine.Reactant added hot reflux 2 hours, at room temperature stirred 12 hours again.Removal of solvent under reduced pressure, remaining product under reduced pressure distills.Discard the light fraction in the distillation, only stay pure DMEEDDMA.

Embodiment 2

The another kind of synthetic method of DMEEDDMA

Under the nitrogen inert atmosphere, 22 milliliters of dimethylethylethylen,diamine ,diamine/250 milliliter hexanes are cooled to 0 ℃.In this solution, dropwise add 51 milliliters of n-BuLis.Make solution be warming up to room temperature and stirred 12 hours, obtain yellow liquid and colorless solid.Again this solution is cooled to 0 ℃, and dropwise adds 9 milliliters of Me ₂AlCl.Allow solution be warming up to room temperature and stirred 16 hours.Solids removed by filtration thing and removal of solvent under reduced pressure from solution.The NMR of solution shows the DMEEDDMA that has produced band impurity.

Embodiment 3

The heat endurance of DMEEDDMA

The heat endurance of DMEEDDMA is assessed by silicon chip is exposed in about 330 ℃ the mixture that only contains argon gas and DMEEDDMA steam.Argon gas with 100 standard cubic centimeters evaporates DMEEDDMA down at 40 ℃.The DMEEDDMA evaporimeter remains on 50 holders with the needle-valve between evaporimeter and deposition reactor.Equipment therefor is seen and is set forth in J.Atwood, D.C.Hoth, D.A.Moreno, C.A.Hoover in this experiment, S.H.Meiere, D.M.Thompson, G.B.Piotrowski, M.W.Litwin, J.Peck, ElectrochemicalSociety Proceedings 2003-08, (2003) 847.Deposition reactor remains on 5 holders.The argon gas merging (total flow that is mixture is 460 standard cubic centimeters) of the material that will come out from the DMEEDDMA evaporimeter before silicon chip exposes and 360 other standard cubic centimeters.Silicon chip is exposed in this mixture did not have electrodeposition substance after 15 minutes.This shows that the heat endurance of DMEEDDMA under 330 ℃ enough is used for Atomic layer deposition method and should be self limiting.

Embodiment 4

Carry out the ald of aluminium from DMEEDDMA

For determining that DMEEDDMA is used for the performance of Atomic layer deposition method, is exposed to silicon chip DMEEDDMA and the H that separates by argon purge ₂In the ALT pulse of O.Pellumina is in about 330 ℃ of deposit.Atomic layer deposition cycle was made up of 4 steps: (1) DMEEDDMA and argon gas, (2) argon purge, (3) H ₂O and argon gas and (4) argon purge.The duration in 4 steps was respectively 10/20/10/20 second.

The growth of film dual wavelength pyrometer in-situ monitoring.Pyrometer uses radiation emitted to measure temperature.Growth for Thin Film is introduced long mutually and destructive interference to this radiation, thereby causes certain fluctuation pattern when following the tracks of apparent silicon temperature.These temperature fluctuations (increase or subtract) can be used to detect the growth in situ of film.The temperature fluctuation that pyrometer records is at above-mentioned use DMEEDDMA and H ₂Be verified in the 4 step atomic layer deposition process of O.By eliminate water (only argon gas) in the 3rd step, fluctuation stops (being that temperature no longer increases or subtracts).This shows that this method is a self limiting.

The result shows that DMEEDDMA is the suitable material standed for by the ald pellumina.The result means that DMEEDDMA also can be used for by the chemical vapor deposition deposition of aluminium oxide.The suitable oxygen co-reactant that contains comprises H when using the DMEEDDMA deposition of aluminium oxide in chemical vapour deposition or Atomic layer deposition method ₂O, oxygen, ozone and alcohol.

Claims (16)

1. the Organoaluminum precursor compounds of a following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-.

2. the Organoaluminum precursor compounds of claim 1, wherein R ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen, methyl, ethyl, n-pro-pyl or isopropyl separately, R ₅Represent methylidene, ethyl, n-pro-pyl or isopropyl.

3. the Organoaluminum precursor compounds of claim 1, it is liquid down at 20 ℃.

4. the Organoaluminum precursor compounds of claim 1, described precursor compound is selected from dimethylethylethylen,diamine ,diamine dimethyl aluminium, dimethylethylethylen,diamine ,diamine aluminium methyl, trimethyl ethylenediamine dimethyl aluminium, triethyl group ethylenediamine dimethyl aluminium, diethylmethylethylen,diamine dimethyl aluminium, dimethyl propyl ethylenediamine dimethyl aluminium and dimethylethylethylen,diamine ,diamine diisopropyl aluminium.

5. method for preparing the Organoaluminum precursor compounds of following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes aluminum source compound and organic diamine compound in the presence of the solvent and be enough to produce under the reaction condition of the reactant mixture that comprises described Organoaluminum precursor compounds and react, and (ii) separates described Organoaluminum precursor compounds from described reactant mixture.

6. the method for claim 5, the yield of wherein said Organoaluminum precursor compounds is 60% or higher.

7. the method for claim 5, wherein said aluminum source compound is selected from Me ₃Al, Me ₂AlH, Et ₃Al, Et ₂MeAl, Et ₂AlH and ⁱPr ₃Al.

8. the method for claim 5, wherein said organic diamine compound is selected from dimethylethylethylen,diamine ,diamine, trimethyl ethylenediamine, triethyl group ethylenediamine, diethylmethylethylen,diamine and dimethyl propyl ethylenediamine.

9. method for preparing the Organoaluminum precursor compounds of following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-, described method comprises that (i) makes organic diamine compound and alkaloid substance in the presence of the solvent and be enough to produce under the reaction condition of first reactant mixture that includes the organic diamines salt compound and react, (ii) in described first reactant mixture, add aluminum source compound, described organic diamine salt compound and described aluminum source compound are reacted under the reaction condition that is enough to produce second reactant mixture that comprises described organo-aluminum compound, and (iv) from described second reactant mixture, separate described organo-aluminum compound.

10. the method for claim 9, the yield of wherein said Organoaluminum precursor compounds is 60% or higher.

11. the method for claim 9, wherein said organic diamine compound is selected from dimethylethylethylen,diamine ,diamine, trimethyl ethylenediamine, triethyl group ethylenediamine, diethylmethylethylen,diamine and dimethyl propyl ethylenediamine.

12. the method for claim 9, wherein said alkaloid substance is selected from n-BuLi, t-BuLi, MeLi, NaH and CaH.

13. the method for claim 9, wherein said organic diamine salt compound are selected from lithiumation dimethylethylethylen,diamine ,diamine, lithiumation trimethyl ethylenediamine, lithiumation triethyl group ethylenediamine, lithiumation diethylmethylethylen,diamine and lithiumation dimethyl propyl ethylenediamine.

14. the method for claim 9, wherein said aluminum source compound is selected from Me ₂AlCl, Me ₂AlBr, Me ₂AlF, Et ₂AlCl, EtMeAlCl and ⁱPr ₂AlCl.

15. a method for preparing film, coating or powder, thus described method is by decomposing Organoaluminum precursor compounds preparation film, coating or the powder of following formula representative:

R wherein ₁, R ₂, R ₃And R ₄Identical or different, represent hydrogen separately or have the alkyl of about 3 carbon atoms of 1-, R ₅Representative has the alkyl of about 3 carbon atoms of 1-.

16. the method for claim 15, the decomposition of wherein said Organoaluminum precursor compounds is by heat, chemistry, photochemistry or plasma-activated carrying out.