Nothing Special   »   [go: up one dir, main page]

CN101052615B - Metal compound, thin film-forming material, and method for producing thin film - Google Patents

Metal compound, thin film-forming material, and method for producing thin film Download PDF

Info

Publication number
CN101052615B
CN101052615B CN2005800377539A CN200580037753A CN101052615B CN 101052615 B CN101052615 B CN 101052615B CN 2005800377539 A CN2005800377539 A CN 2005800377539A CN 200580037753 A CN200580037753 A CN 200580037753A CN 101052615 B CN101052615 B CN 101052615B
Authority
CN
China
Prior art keywords
compound
general formula
film
metallic compound
niobium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2005800377539A
Other languages
Chinese (zh)
Other versions
CN101052615A (en
Inventor
芳仲笃也
樱井淳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adeka Corp
Original Assignee
Asahi Denka Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Denka Kogyo KK filed Critical Asahi Denka Kogyo KK
Publication of CN101052615A publication Critical patent/CN101052615A/en
Application granted granted Critical
Publication of CN101052615B publication Critical patent/CN101052615B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02183—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing tantalum, e.g. Ta2O5
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Vapour Deposition (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a metal compound represented by the general formula (I) below which is preferably used as a precursor in a thin film production method comprising a vaporization step, particularly in a CVD method including ALD. (I) (In the formula, M represents tantalum or niobium, R<1> represents an alkyl group having 1-4 carbon atoms, and R<2> and R<3> independently represent a hydrogen atom, a methyl group or a ethyl group.

Description

Metallic compound, film form the manufacture method with raw material and film
Technical field
The present invention relates to form with raw material as the novel tantalum compound and the niobium compound of part, the film that contains this tantalum compound and/or this niobium compound specific amino alcohol and used the manufacture method of this film formation with the film that contains metal of raw material.
Background technology
The film that contains tantalum or niobium mainly is used as the member of electronic units such as high dielectric capacitor, ferro-electric materials capacitor, gate insulating film, barrier film.
Manufacture method as above-mentioned film, can list MOD methods such as flame method of piling, sputtering method, ion plating method, coated heat decomposition method and sol-gel method, chemical vapor-phase growing (below, sometimes also only be designated as CVD) method etc., but contain the chemical vapor-phase growing method of ALD (ald) method owing to have and form controlled and ladder difference spreadability excellence, be suitable for producing in batches and can mixing multiple advantages such as integrated, so be best manufacture method.
In comprising the CVD method of MOD method, utilized the metallic compound of organic ligand to be used as the precursor that metal is provided to film.Low-molecular-weight pure tantalum, owing to electronegative difference between atoms metal and the Sauerstoffatom produces electric polarity, two molecules or the molecule more than two carry out combination, so volatility is poor.Relative therewith, report the metallic compound that has endways that to contain the donor groups that is coordinated in atoms metal be ether and amino alcohol as part combination can not taken place, but monomer to have bigger vapour pressure, and creating conditions of stabilizing films also is provided.For example, in patent documentation 1-5, reported and used metallic compound with amino alcohol.
Patent documentation 1: the international openly text that discloses No. 95/26355
Patent documentation 2: the spy opens the 2002-252286 communique
Patent documentation 3: the international openly text that discloses No. 01/66834
Patent documentation 4: the international openly text that discloses No. 01/78869
Patent documentation 5: the international openly text that discloses No. 01/79586
Making metallic compound gasification in the film-forming methods such as film forming CVD method, be the big and gasification easily of vapour pressure, not produce thermolysis and can stably supply with and before reaction chamber, do not decompose as the desired character of metallic compound of raw material.But though tantalum compound in the past and niobium compound have just obtained good decomposability at reaction chamber just, steam forces down, so the container and the pipe arrangement of apparatus for manufacturing thin film need be heated to than higher temperature.Therefore, because the high temperature that is applied makes material before arriving vaporizer thermolysis take place partly, produce the inner problem of stopping up or generating unwanted compound of gasifier that makes.So, up to now, do not obtain the desirable tantalum compound and the niobium compound that to gasify at low temperatures and can supply with thermally-stabilisedly.
Summary of the invention
The inventor etc. have carried out research repeatedly, found that the special metal compound that makes tertiary alcohol salt have the steric barrier effect can address the above problem.
The present invention is based on above-mentioned discovery and finishes, provide the metallic compound of representing with following general formula (I), the film that contains metallic compound to form the manufacture method of using raw material and film, the manufacture method of wherein said film is to import on the matrix containing the steam that makes described film form the metallic compound that obtains with material gasification, forms the film that contains metal thereby make its decomposition and/or chemical reaction takes place on matrix.
[Chemical formula 1]
Figure G200580037753920070510D000021
(in the formula, M represents tantalum or niobium; R 1The expression carbonatoms is 1～4 alkyl; R 2And R 3Represent hydrogen atom, methyl or ethyl respectively independently.)
Description of drawings
Fig. 1 is the synoptic diagram that is illustrated in an example of the CVD device that uses in the manufacturing of the film that contains metal of the present invention.
Fig. 2 is the synoptic diagram that is illustrated in an example of the ALD device that uses in the manufacturing of the film that contains metal of the present invention.
Embodiment
Below, metallic compound of the present invention, film are formed the manufacture method with raw material and film, preferred embodiment be described in detail according to it.
In the above-mentioned general formula of the present invention (I), as with R 1The carbonatoms of expression is 1～4 alkyl, can list methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-.
In the above-mentioned general formula (I), the terminal donor groups in the part is coordinated in atoms metal and the situation that forms ring structure is shown in the following general formula (I ').Though metallic compound of the present invention is that representative is represented with above-mentioned general formula (I), is not different from metallic compound, but comprises both notions with following general formula (I ') expression.
[Chemical formula 2]
Figure G200580037753920070510D000031
(in the formula, M, R 1, R 2And R 3Implication identical with implication in the above-mentioned general formula (I).)
As the concrete example of metallic compound of the present invention, can list following compound N o.1～No.16.
[chemical formula 3]
Figure G200580037753920070510D000041
[chemical formula 4]
Figure G200580037753920070510D000042
When in film-forming method, using metallic compound of the present invention, for above-mentioned R with the operation that makes the compound gasification 1, molecular weight little because vapour pressure is big, so be preferred, specifically, R 1Be preferably methyl or ethyl.In addition, when in not having the film-forming method that utilizes the MOD method of gasification process, using metallic compound of the present invention, above-mentioned R 1Can form reaction and select arbitrarily according to solvability, film employed solvent.
Metallic compound of the present invention is not subjected to the restriction of its manufacture method especially, can use known reaction to make, and for example, can use the synthetic method of the known common metal alkoxide that has used corresponding uncle's amino alcohol and make.As this synthetic method, can list: for example, in the presence of alkali such as sodium, sodium hydride, sodium amide, sodium hydroxide, sodium methylate, ammonia, amine, the method that the compound of inorganic salt such as metal halide, nitrate or its hydrate and correspondent alcohol is reacted; The method that the alkali metal alcoholates such as sodium alkoxide, lithium alkoxide, potassium alcoholate of inorganic salt such as metal halide, nitrate or its hydrate and correspondent alcohol compound is reacted; Make the metal alkoxide of low mass molecule alcohols such as metal methoxide salt, ethylate, isopropoxide, butanolate and the method that pure permutoid reaction takes place corresponding alkylol cpd; Inorganic salt such as metal halide, nitrate and the derivative that reactive intermediate is provided are reacted and after obtaining reactive intermediate, the method that itself and alkylol cpd are reacted.In these synthetic methods, the pure permutoid reaction of preferably metal alkoxide and uncle's amino alcohol.
Film of the present invention forms and contains the precursor of metallic compound of the present invention as film with raw material, its form forms manufacture method with the film of raw material (MOD methods such as flame method of piling, sputtering method, ion plating method, coated heat decomposition method and sol-gel method for example according to being suitable for this film, the CVD method that contains the ALD method) difference and difference can suit to select.Metallic compound of the present invention is because its physical properties, though in film forms with raw material also particularly suitable as the CVD raw material.
Forming with raw material at film of the present invention is chemical vapor-phase growing (CVD) when using raw material, the selection that can suit by the means such as conveying supply method of employed CVD method of its form.
As above-mentioned conveying supply method, following method is arranged: in material container, make the CVD material gasification by heating and/or decompression, and with as required just carrier gas such as the argon of use, nitrogen, helium be directed into the gas delivery method of hill reaction portion; State with liquid or solution is delivered to vaporizer with CVD with raw material, makes its gasification at vaporizer by heating and/or decompression, and is directed into the liquid conveying method of hill reaction portion.Under the situation of gas delivery method, the metallic compound of representing with above-mentioned general formula (I) of the present invention itself becomes the CVD raw material; Carry at liquid under the situation of method, with the metallic compound of above-mentioned general formula (I) expression itself or in organic solvent, dissolve the solution that this metallic compound forms and become the CVD raw material.
In addition, the CVD method for the multicomponent system has following method: the method that each composition of CVD raw material is gasified independently and supply with (the following single source method that also is designated as sometimes); With will be pre-mixed mixing raw material gasification that the multicomponent raw material forms and the method for supplying with (the following mixing source method that also is designated as sometimes) with required composition.Under the situation of mixing source method, the single mixture that is formed by metallic compound of the present invention or the mixture or the mixing solutions of mixing solutions, metallic compound of the present invention and other precursor are the CVD raw material.For example, mixing source as tantalum one niobium composite oxides, preferably, M is the metallic compound of the present invention of tantalum and the mixture or the mixing solutions of the metallic compound of the present invention that M is niobium, more particularly, be preferably and be selected from least a among o.1～8 of above-mentioned illustrative compound N and be selected from least a mixture or the mixing solutions of compound N among o.9～16.
, have no particular limits with the organic solvent that uses in the raw material as above-mentioned CVD, can use known common organic solvents.As this organic solvent, for example can list: alcohols such as methyl alcohol, ethanol, 2-propyl alcohol, propyl carbinol; Acetates such as vinyl acetic monomer, N-BUTYL ACETATE, acetic acid methoxyl group ethyl ester; Ether alcohol classes such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether; Ethers such as tetrahydrofuran (THF), tetrahydropyrans, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dme, dibutyl ether; Ketones such as methyl butyl ketone, methyl iso-butyl ketone (MIBK), ethyl butyl ketone, two acetone, diisobutyl ketone, Methyl amyl ketone, pimelinketone, methylcyclohexanone; Hydro carbons such as hexane, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, ethylcyclohexane, heptane, octane, toluene, dimethylbenzene; 1-dicyanopropane, 1-cyano group butane, 1-cyano group hexane, cyanocyclohexanoic alkane, cyano group benzene, 1,3-dicyano propane, 1,4-dicyanobutane, 1,6-dicyano hexane, 1,4-dicyano hexanaphthene, 1,4-dicyanobenzenes etc. has the hydro carbons of cyano group; Pyridine, lutidine etc.These organic solvents can use separately or use as two or more mixed solvents according to solvability, use temperature and the boiling point of solute, the relation of flash-point etc.When using these organic solvents, preferably making the metallic compound of the present invention in these organic solvents and the total amount of other precursor is 0.01～2.0 mol, is preferably 0.05～1.0 mol especially.
In addition, other precursor as using with metallic compound of the present invention in the CVD of multicomponent system method is not particularly limited, and can use CVD with the known general precursor that uses in the raw material.
As other above-mentioned precursor, can list and be selected from the compound that alkylol cpd, glycol compound, beta-diketone compound, cyclopentadiene compound and amine compound etc. form as a kind of or the two or more and metal in the compound group of organic ligand.In addition, metal kind as other precursor can list magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, gallium, indium, germanium, tin, lead, antimony, bismuth, silicon, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium.
In addition, form with in the raw material, as required,, can also contain nucleophilicity reagent in order to give stability to metallic compound of the present invention and other precursor at film of the present invention.As this nucleophilicity reagent; can list glycol dimethyl ether; diethylene glycol dimethyl ether; the triethylene glycol dme; gylcol ethers such as tetraethyleneglycol dimethyl ether; hexaoxacyclooctadecane-6-6; dicyclohexyl-hexaoxacyclooctadecane-6-6; octaoxacyclotetracosane-8-8; dicyclohexyl-octaoxacyclotetracosane-8-8; crown ether-like such as dibenzo-octaoxacyclotetracosane-8-8; quadrol; N; N '-Tetramethyl Ethylene Diamine; diethylenetriamine; Triethylenetetramine (TETA); tetren; penten; 1; 1; 4; 7; the 7-five methyl diethylentriamine; 1; 1; 4; 7; 10; polyamines classes such as 10-hexamethyl Triethylenetetramine (TETA), 1,4; 8; 11-tetraazacyclododecane tetradecane (cyclam); 1,4,7; 10-tetraazacyclododecanand cyclic polyamine classes such as (cyclen); methyl acetoacetate; methyl aceto acetate; etheric acid-'beta '-ketoester class or methyl ethyl diketones such as 2-methoxyl group ethyl ester, 2,4-hexane diketone; 2; 4-heptane diketone; 3; 5-heptane diketone; beta-diketon classes such as two pivaloyl methane are 0.1 mole～10 moles as the consumption of these nucleophilicity reagent of stablizer with respect to 1 mole of precursor, are preferably 1～4 mole.
The manufacture method of film of the present invention utilizes following CVD method to carry out: make metallic compound of the present invention and steam that other precursor vaporized of using as required forms and as required and the reactant gas that uses is directed on the substrate, then on substrate, make precursors decompose and/or react, thereby make film on substrate, grow and pile up.To conveying supply method, the stacking method of raw material, create conditions, manufacturing installation etc. is not particularly limited, and can use known general condition, method etc.
As the above-mentioned reactant gas that just uses as required, for example, can list: oxygen, ozone, nitrogen peroxide, nitrogen protoxide, water vapour, hydrogen peroxide, formic acid, acetate, diacetyl oxide etc. as oxidizing gas; Can list hydrogen as reducing gas; In addition, can list organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, Alkylenediamine, hydrazine, ammonia etc. as the material of making nitride.
In addition, as above-mentioned conveying supply method, can list above-mentioned gas delivery method, liquid conveying method, single source method, mixing source method etc.
In the method for single source with multiple metallic compound when the precursor, can only metallic compound of the present invention be used as precursor, also can and use metallic compound of the present invention and other precursor.With metallic compound of the present invention and other precursor and time spent, preferably film forms the related similar combination of decomposition behavior of reaction.For example, preferably combination when using as tantalum precursor and niobium combination of precursors in the method for single source can list: using M is that the metallic compound of the present invention of tantalum is as the tantalum precursor and to use M be the combination as the niobium precursor of the metallic compound of the present invention of niobium and/or tetrol salt.Using M is metallic compound of the present invention, the particularly compound N of tantalum during o.1 as the tantalum precursor, and as the niobium precursor preferably: M is metallic compound of the present invention, five (oxyethyl group) niobium, five (2-propoxy-) niobium, five (butoxy) niobiums, five (tert.-butoxy) niobium, five (tert-pentyl) niobium, five (1-methoxyl group-2-methyl-2-propoxy-) niobium of niobium.
In addition,, can list: only utilize heat that unstripped gas or unstripped gas and reactant gas are reacted, thereby make the hot CVD of film stack as above-mentioned stacking method; Use the plasma CVD of heat and plasma body; Use the optical cvd of light and heat; Use the light plasma CVD of light and heat and plasma body; The hill reaction of CVD is divided into primary process, thus the ALD (ald) that piles up with molecular level interimly.
In addition, create conditions, can list: temperature of reaction (substrate temperature), reaction pressure, stackeding speed etc. as above-mentioned.Temperature of reaction is preferably temperature that above-claimed cpd of the present invention reacts fully promptly more than 160 ℃, more preferably 250～800 ℃.In addition, reaction pressure is preferably normal atmosphere～10Pa under the situation of hot CVD or optical cvd, is preferably 10～2000Pa under the situation of using plasma body.In addition, stackeding speed can be controlled by supply conditions (gasification temperature, vapor pressure), temperature of reaction and the reaction pressure of raw material.If stackeding speed is big, then the characteristic of gained film can worsen sometimes; If stackeding speed is little, then aspect productivity, have problems sometimes, therefore be preferably 0.5～5000nm/ branch, 1～1000nm/ branch more preferably.In addition, under the situation of ALD, can control to obtain required film thickness with cycle index.And the thickness that forms the film that forms with raw material with film of the present invention suits to select according to purposes, is preferably 10～1000nm.
In addition, in the film-forming method of the present invention, behind film stack, anneal can also be carried out,, backflow (reflow) operation can also be provided with needing the ladder difference to cover under the situation of (potting) in order to obtain better electrical characteristic.The temperature of this moment is 500～1200 ℃, is preferably 600～800 ℃.
Select precursor, the reactant gas of other composition and create conditions by suitable by having used film of the present invention to form, can make the film of required kinds such as oxide ceramics, nitride ceramics, glass with the film of the film-forming method manufacturing of the present invention of raw material.Kind as the film of manufacturing can list for example tantalum pentoxide, niobium oxide, tantalum-niobium composite oxides, tantalum-titanium composite oxide, (niobium) tantalic acid (barium) strontium bismuth, tantalum nitride, niobium nitride, tantalum-niobium complex nitride, tantalum carbide, niobium carbide, tantalum-niobium double carbide, carbon, niobium metallic film separately.As the purposes of these films,, can list high dielectric capacitor film, gate insulating film, strong dielectric capacitor film, capacitor film for example as the purposes of utilizing oxide ceramics; As the purposes of utilizing nitride ceramics, can list the blocking layer; As the purposes of utilizing glass, can list opticglass such as optical fiber, light-guide wave path, image intensifer, photoswitch.
Embodiment
Below the present invention will be described in more detail with embodiment and evaluation Example, but the present invention is not subjected to any restriction of following examples etc.
The manufacturing o.1 of [embodiment 1] compound N
Under dry argon gas atmosphere, the ethanol tantalum (V) that in reaction flask, adds 0.246 mole, 50g is to remove ethanol under 68 ℃ through the toluene of processed, 0.271 mole 1-dimethylamino-2-methyl-2-propyl alcohol in normal pressure, tower top temperature, reclaims crude product (rate of recovery is 100%).Reclaiming 13Pa, tower top temperature from the crude product that obtains is 103-104 ℃ cut, thereby obtains transparent liquid.By this refining rate of recovery that is reached is 70%.Transparent liquid to gained carries out following analysis, is confirmed to be as the compound N of target compound o.1.
(analytical value)
(1) 1H-NMR (solvent: deuterium is for benzene) (chemical shift: multiplicity: the H number)
(1.27：s：6H)(1.32：t：12H)(2.31：s：6H)(2.36：2H：s)(4.55：q：8H)
(2) TG-DTA (the Ar flow velocity is that 100ml/min, heat-up rate are that 10 ℃/min, sample size are 11.4mg)
Reduce the temperature of 50 quality %: 193.8 ℃
(3)ICP-AES
Ta content analysis value in the compound: 37.1% (theoretical value is 37.9%)
The volatility evaluation o.1 of [evaluation Example 1] compound N
The compound N that embodiment 1 is obtained o.1 and the comparative compound 1 and 2 shown in following, by with the same condition of the foregoing description 1 under TG-DTA thermal behavior (reducing the residue under the temperature of 50 quality % and 300 ℃) is compared.In addition, to compound N o.1 and following comparative compound 1 and 2 carry out vapour pressure and measure.These the results are shown in table 1.In addition, vapour pressure is measured and to be carried out with following method: system is fixed as certain pressure and measures near the liquid level vapour temperature, measure 3-4 point vapour temperature by the pressure that changes system, according to one carat of amber dragon picture of Clausius, utilize the formula of vapour pressure, calculate the temperature when 10Torr.
[chemical formula 7]
Comparative compound 1 comparative compound 2
Figure G200580037753920070510D000101
[table 1]
Metallic compound Reduce the temperature of 50 quality % 300 ℃ of residues Temperature when vapour pressure is 10Torr
Compound N o.1 194℃ 0.7％ 145℃
Comparative compound 1 206℃ 1.5％ 165℃
Comparative compound 2 198℃ 1.1％ 155℃
The thermostability evaluation o.1 of [evaluation Example 2] compound N
The compound N that embodiment 1 is obtained o.1 and above-mentioned comparative compound 1 and 2 carry out the thermostability evaluation.Evaluation is carried out according to following: each compound is packed in the encloses container, respectively in 200 ℃, 210 ℃ and 220 ℃ heating 1 hour down, obtain the ratio of decomposition by TG-DTA.These results are as shown in table 2.
[table 2]
Metallic compound 200℃ 210℃ 220℃
Compound N o.1 0％ 0％ 0％
Comparative compound 1 1.8％ 8.2％ 16％
Comparative compound 2 0.9％ 2.7％ 5.9％
Can confirm by above-mentioned table 1 and 2, will o.1 compare as the compound N of metallic compound of the present invention with comparative compound, compound N molecular weight maximum o.1, and volatility is the most excellent, thermostability is also excellent.It can be said that o.1 compound N is more suitable for as CVD method tantalum precursor than compound 1 and comparative compound 2 frequently.
The manufacturing o.9 of [embodiment 2] compound N
Under dry argon gas atmosphere, the ethanol niobium (V) that in reaction flask, adds 0.051 mole, 20g is to remove ethanol under 140 ℃ through the toluene of processed and 0.051 mole 1-dimethylamino-2-methyl-2-propyl alcohol in normal pressure, tower top temperature, reclaims crude product (rate of recovery is 100%).Reclaiming 60～70Pa, tower top temperature from the crude product that obtains is 105～115 ℃ cut, thereby obtains light yellow transparent liquid.By this refining rate of recovery that is reached is 55%.Light yellow transparent liquid to gained carries out following analysis, is confirmed to be as the compound N of target compound o.9.
(analytical value)
(1) 1H-NMR (solvent: deuterium is for benzene) (chemical shift: multiplicity: the H number)
(1.27：s：6H)(1.32：t：12H)(2.28：s：6H)(2.35：s：2H)(4.49：q：8H)
(2) TG-DTA (the Ar flow velocity be 100ml/min, heat-up rate be 10 ℃/min,
Sample size is 11.4mg)
Reduce the temperature of 50 quality %: 194.4 ℃
(3)ICP-AES
Nb content analysis value in the compound: 23.2% (theoretical value is 23.8%)
The volatility evaluation o.9 of [evaluation Example 3] compound N
The compound N that obtains for embodiment 2 is the Nb (OC of compound 3 o.9 and as a comparison 2H 5) 5, by with the same condition of the foregoing description 2 under TG-DTA thermal behavior (reducing the residue under the temperature of 50 quality % and 300 ℃) is compared.In addition, o.9 compound N being carried out vapour pressure with comparative compound 3 measures.These the results are shown in table 3.In addition, vapour pressure is measured and to be carried out with following method: system is fixed as certain pressure and measures near the liquid level vapour temperature, measure 3-4 point vapour temperature by the pressure that changes system, according to one carat of amber dragon picture of Clausius, utilize the formula of vapour pressure, calculate the temperature when 10Torr.
[table 3]
Metallic compound Reduce the temperature of 50 quality % 300 ℃ of residues Temperature when vapour pressure is 10Torr
Compound N o.9 194℃ 0.2％ 169℃
Comparative compound 3 234℃ 0.2％ 190℃
Can confirm that by above-mentioned table 3 will o.9 compare with comparative compound 3 as the compound N of metallic compound of the present invention, compound N molecular weight o.9 is big, and the volatility excellence.It can be said that o.9 compound N is more suitable for as CVD method niobium precursor than compound 3 frequently.
The manufacturing of [embodiment 3] tantalum films
Use CVD device shown in Figure 1, on Pt, make tantalum films under the following conditions.Use fluorescent X-ray to measure thickness and crystalline texture to the film that makes.Measurement result is as follows.
(creating conditions)
Argon 200sccm), oxic gas the tantalum raw material: compound N is (material temperature: 145 ℃, pressure: 1300Pa, carrier gas:: oxygen 300sccm, reaction pressure: 1300Pa, temperature of reaction (substrate temperature): 500 ℃, film formation time: 25 minutes, crystallization annealing: 730 ℃/2min o.1
(result)
Thickness: 120nm, crystalline texture: hexagonal crystal Ta 2O 5
The manufacturing (ALD method) of [embodiment 4] tantalum films
Preparation compound N ethylcyclohexane solution (0.2mol/L) o.1 utilizes ALD device shown in Figure 2 as the ALD raw material, makes film by following condition and operation.Similarly measure the thickness and the crystalline texture of prepared film with the foregoing description 2.Measurement result is as follows.
(condition)
Temperature of reaction (substrate temperature): 350 ℃, reactant gas: water vapour
(operation)
A succession of operation that will be made of following (1)～(4) is as 1 circulation, and 3 minutes anneal is carried out at last in 300 circulations repeatedly under 700 ℃.
(1) will be under 150 ℃ in the vaporizer temperature, to be the ALD that gasifies under the condition of 1300～1400Pa import with the steam of raw material vaporizer pressure, is to pile up for 1 second under 1300～1400Pa at system pressure.
(2) argon by 2 seconds cleans, and removes unreacted raw material.
(3) importing water vapour, is to react for 1 second under the 1300Pa at system pressure.
(4) argon by 2 seconds cleans, and removes unreacted raw material.
(result)
Thickness: 30nm, crystalline texture: hexagonal crystal Ta 2O 5
According to the present invention, can provide the metallic compound of the precursor that is particularly suitable as film-forming method with the gasification process such as CVD method that comprise the ALD method.Not only can be by the metallic compound of the present invention of above-mentioned general formula (I) expression at the terminal dialkyl amido of introducing of part with very strong donor effect and big steric hindrance, near and introducing steric hindrance as the Sauerstoffatom of the tertiary alcohol, thereby relax and/or covered the electric polarity between atoms metal and the Sauerstoffatom, can suppress high volatilizationization and unnecessary chemical reaction by the molecule combination that suppresses metallic compound.

Claims (11)

1. with the metallic compound of following general formula (I) expression,
Figure FA20172599200580037753901C00011
In the general formula (I), M represents tantalum or niobium; R 1The expression carbonatoms is 1～4 alkyl; R 2And R 3Represent hydrogen atom, methyl or ethyl respectively independently.
2. metallic compound according to claim 1, it is with following general formula (II) expression,
Figure FA20172599200580037753901C00012
In the general formula (II), R 1, R 2And R 3Implication identical with implication in the described general formula (I).
3. metallic compound according to claim 1, it is with following general formula (III) expression,
Figure FA20172599200580037753901C00013
In the general formula (III), R 1, R 2And R 3Implication identical with implication in the described general formula (I).
4. metallic compound according to claim 1, wherein in described general formula (I), R 2And R 3It is methyl.
5. according to claim 1 or 4 described metallic compounds, wherein in described general formula (I), R 1It is ethyl.
6. metallic compound according to claim 2, wherein in described general formula (II), R 2And R 3It is methyl.
7. according to claim 2 or 6 described metallic compounds, wherein in described general formula (II), R 1It is ethyl.
8. metallic compound according to claim 3, wherein in described general formula (III), R 2And R 3It is methyl.
9. according to claim 3 or 8 described metallic compounds, wherein in described general formula (III), R 1It is ethyl.
10. film forms and to use raw mix, and it contains the metallic compound of claim 1-9 described in any one.
11. the manufacture method of film, the steam that wherein will contain the metallic compound that the described film of claim 10 formed obtain with the raw mix gasification or the claim 1-9 metallic compound described in any one imports on the matrix, forms the film that contains metal thereby make its decomposition and/or chemical reaction takes place on matrix.
CN2005800377539A 2004-11-02 2005-10-26 Metal compound, thin film-forming material, and method for producing thin film Active CN101052615B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2004318858 2004-11-02
JP318858/2004 2004-11-02
PCT/JP2005/019690 WO2006049059A1 (en) 2004-11-02 2005-10-26 Metal compound, thin film-forming material, and method for producing thin film

Publications (2)

Publication Number Publication Date
CN101052615A CN101052615A (en) 2007-10-10
CN101052615B true CN101052615B (en) 2010-07-14

Family

ID=36319071

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2005800377539A Active CN101052615B (en) 2004-11-02 2005-10-26 Metal compound, thin film-forming material, and method for producing thin film

Country Status (5)

Country Link
JP (1) JP4823069B2 (en)
KR (1) KR101128542B1 (en)
CN (1) CN101052615B (en)
TW (1) TW200619413A (en)
WO (1) WO2006049059A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4632765B2 (en) * 2004-10-21 2011-02-16 株式会社Ａｄｅｋａ Alkoxide compound, raw material for thin film formation, and method for producing thin film
JP4775996B2 (en) * 2005-03-29 2011-09-21 日本碍子株式会社 Method for producing metal oxide film
JP5148186B2 (en) * 2006-08-28 2013-02-20 東ソー株式会社 Imido complex, method for producing the same, metal-containing thin film, and method for producing the same
JP5214191B2 (en) * 2007-08-08 2013-06-19 株式会社Ａｄｅｋａ Thin film forming raw material and thin film manufacturing method
JP2024078466A (en) * 2021-04-16 2024-06-11 株式会社Adeka Thin film-forming feedstock for use in atomic layer deposition, thin film, method for producing thin film, and ruthenium compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030049943A1 (en) * 2001-09-10 2003-03-13 Choi Han-Mei Method of forming a metal oxide film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63227593A (en) * 1987-03-17 1988-09-21 Hakusui Kagaku Kogyo Kk Production of metal alkoxide solution
AU1955395A (en) 1994-03-26 1995-10-17 Drake, Simone Robert Tantalum compounds
US6015917A (en) * 1998-01-23 2000-01-18 Advanced Technology Materials, Inc. Tantalum amide precursors for deposition of tantalum nitride on a substrate
US6562678B1 (en) * 2000-03-07 2003-05-13 Symetrix Corporation Chemical vapor deposition process for fabricating layered superlattice materials
KR100385952B1 (en) * 2001-01-19 2003-06-02 삼성전자주식회사 A semiconductor capacitor having tantalum oxide as dielctric film and formation method thereof
JP4632765B2 (en) * 2004-10-21 2011-02-16 株式会社Ａｄｅｋａ Alkoxide compound, raw material for thin film formation, and method for producing thin film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030049943A1 (en) * 2001-09-10 2003-03-13 Choi Han-Mei Method of forming a metal oxide film

Also Published As

Publication number Publication date
JP4823069B2 (en) 2011-11-24
CN101052615A (en) 2007-10-10
TWI379017B (en) 2012-12-11
KR101128542B1 (en) 2012-03-23
KR20070073806A (en) 2007-07-10
JPWO2006049059A1 (en) 2008-05-29
TW200619413A (en) 2006-06-16
WO2006049059A1 (en) 2006-05-11

Similar Documents

Publication Publication Date Title
CN100595187C (en) Alkoxide compound, thin film-forming material and method for forming thin film
EP1698614B1 (en) Metal compound, material for forming thin film and method for preparing thin film
CN107428677B (en) Diazadienyl compound, raw material for forming thin film, method for producing thin film, and diazadiene compound
CN101981226B (en) Deposition of ternary oxide films containing ruthenium and alkali earth metals
CN101052615B (en) Metal compound, thin film-forming material, and method for producing thin film
CN103502202B (en) Alkoxide compound and raw material for forming thin film
KR20060058710A (en) Rare earth metal complex, material for thin-film formation, and process for producing thin film
US10882874B2 (en) Vanadium compound
EP3348667A1 (en) Chemical vapor deposition feedstock comprising organic ruthenium compound and chemical vapor deposition method using said chemical vapor deposition feedstock
KR20210094035A (en) A raw material for chemical vapor deposition containing a ruthenium complex and a chemical vapor deposition method using the raw material for chemical vapor deposition
KR20180022775A (en) A novel compound, a raw material for forming a thin film and a method for producing the thin film
CN101848917B (en) Metal compound, chemical vapor deposition material containing the same, and method for producing metal-containing thin film
JP4781012B2 (en) Metal compound having alcohol compound as ligand, raw material for forming thin film, and method for producing thin film
CN106458849A (en) Copper compound, starting material for forming thin film and method for producing thin film
EP3135664B1 (en) Alkoxide compound, raw material for forming thin film, method for producing thin film, and alcohol compound
US10920313B2 (en) Diazadienyl compound, raw material for forming thin film, and method for manufacturing thin film
WO2011083820A1 (en) Metal alkoxide compound and process for production of metal-containing thih film using the compound
US20240060177A1 (en) Indium compound, thin-film forming raw material, thin film, and method of producing same
JP2007290993A (en) STRONTIUM COMPLEX WITH ISOPROPYL OR ISOBUTYL GROUP-BEARING beta- DIKETONATO AS LIGAND, AND METHOD FOR PRODUCING METAL-CONTAINING THIN FILM USING THE STRONTIUM COMPLEX
KR20170041660A (en) Alkoxide compound, thin film-forming starting material, thin film formation method and alcohol compound
CN100390186C (en) Organic iridium compound, method for producing the compound and method for producing film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant