CN101341155A - Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film - Google Patents
Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film Download PDFInfo
- Publication number
- CN101341155A CN101341155A CNA2006800452445A CN200680045244A CN101341155A CN 101341155 A CN101341155 A CN 101341155A CN A2006800452445 A CNA2006800452445 A CN A2006800452445A CN 200680045244 A CN200680045244 A CN 200680045244A CN 101341155 A CN101341155 A CN 101341155A
- Authority
- CN
- China
- Prior art keywords
- film
- hafnium
- cyclopentadienyl
- compound
- general formula
- 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.)
- Granted
Links
- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 83
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 39
- 150000002363 hafnium compounds Chemical class 0.000 title abstract 2
- 239000010409 thin film Substances 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 48
- 230000015572 biosynthetic process Effects 0.000 claims description 41
- -1 methyl cyclopentadienyl Chemical group 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 17
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000012808 vapor phase Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 238000002309 gasification Methods 0.000 description 14
- YWATTXMDZQWERV-UHFFFAOYSA-N CN(C)[Hf] Chemical compound CN(C)[Hf] YWATTXMDZQWERV-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IUBCUJZHRZSKDG-UHFFFAOYSA-N C(C)N(C)[Hf] Chemical compound C(C)N(C)[Hf] IUBCUJZHRZSKDG-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000009834 vaporization Methods 0.000 description 8
- 230000008016 vaporization Effects 0.000 description 8
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Images
Classifications
-
- 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
- C07F17/00—Metallocenes
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Electrodes Of Semiconductors (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed is a hafnium compound which is in a liquid state at room temperature and has excellent stability. Also disclosed is a technique for stably forming a high-quality hafnium thin film for which a raw material can be stably supplied. Specifically disclosed is a hafnium thin film-forming material which is composed of a compound represented by the following general formula [I]: LHf(NR<1>R<2>)3 [I] In the formula, L represents a cyclopentadienyl group or a substituted cyclopentadienyl group, and R<1> and R<2> respectively represent an alkyl group. R<1> and R<2> may be the same as or different from each other.
Description
Technical field
The present invention relates to form the technology that hafnium is a film.
Background technology
Someone motion use four halogenation hafniums, four (dialkyl amido) hafnium, four (alkoxyl group) hafniums or four (beta-diketon) hafnium, forming hafnium by chemical vapor-phase growing method or atomic shell control growing method is film.
Yet, when the formation hafnium is film, must make the above-claimed cpd gasification.So, above-claimed cpd is heated for gasification.
But four halogenation hafniums and four (beta-diketon) hafnium are solid.Therefore be difficult to gasification, be difficult to supply stable gas.That is, be difficult to stable supplying raw material, therefore can't stablize and form high-quality hafnium is film.
The thermostability of four (dialkyl amido) hafnium is low.Therefore decompose during heating and gasifying.So be difficult to supply stable gas.That is, be difficult to stable supplying raw material, therefore can't stablize and form high-quality hafnium is film.
The stability of four (alkoxyl group) hafnium is also poor.For example, only be just to preserve to decompose.Therefore be difficult to supply stable gas.That is, be difficult to stable supplying raw material, therefore can't stablize and form high-quality hafnium is film.
Patent documentation 1: TOHKEMY 2005-298467
Patent documentation 2: TOHKEMY 2005-294421
Patent documentation 3: TOHKEMY 2004-137223
Patent documentation 4: TOHKEMY 2004-137222
Summary of the invention
Invent problem to be solved
Therefore, problem to be solved by this invention is the problems referred to above.Hafnium based compound for liquid and rich stability particularly is provided under the normal temperature, and can stablize supply raw material, it is stable that to form high-quality hafnium be the technology of film.
The method of dealing with problems
Find when furtheing investigate: LHf (NR in order to address the above problem
1R
2)
3The rich stability of the compound of expression, but also gasification easily, can form high-quality hafnium by chemical vapor-phase growing method or atomic shell control growing method is film.
Realized the present invention based on above-mentioned knowledge.
That is, the problems referred to above are resolved by a kind of compound, and this compound is characterised in that: represent with following general formula [I].
The problems referred to above particularly are resolved by following compound, and this compound is characterised in that: in general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl; R
1, R
2Be methyl or ethyl.
The problems referred to above are that the material of film is resolved by forming hafnium also, and it is film that this material is used to form hafnium, it is characterized in that: the compound that is following general formula [I] expression.
The problems referred to above are that the material of film is resolved by forming hafnium also, and it is film that this material is used to form hafnium, it is characterized in that: contain the compound of following general formula [I] expression and the solvent of dissolving above-claimed cpd.
General formula [I]:
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
The problems referred to above are that the material of film is resolved by forming hafnium particularly, and this material is the material that above-mentioned formation hafnium is a film, it is characterized in that: in the above-mentioned general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl, and R
1, R
2Be methyl or ethyl.The problems referred to above are that the material of film is resolved by forming hafnium, and this material is characterised in that: the compound of wherein above-mentioned general formula [I] is CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3[Cp=cyclopentadienyl, MeCp=methyl cyclopentadienyl, EtCp=ethyl cyclopentadienyl, Me=methyl, Et=ethyl].
The problems referred to above are that the material of film is resolved by forming hafnium also, this material is the material that above-mentioned formation hafnium is a film, and wherein solvent is the compound of the amine compound of 2～40 (particularly below 20) for one or more are selected from hydrocarbon system compound and the carbonatoms that carbonatoms is 5～40 (particularly below 15).
The material that above-mentioned formation hafnium is a film is the material of film especially for forming hafnium by chemical vapor-phase growing method or atomic shell control growing method.
The problems referred to above are that the method for film is resolved by forming hafnium also, and the method is characterized in that: using above-mentioned formation hafnium is the material of film, and utilizing the chemical vapor-phase growing method to form hafnium on substrate is film.
The problems referred to above are that the method for film is resolved by forming hafnium also, and the method is characterized in that: using above-mentioned formation hafnium is the material of film, and utilizing atomic shell control growing method to form hafnium on substrate is film.
The invention effect
According to the present invention, can form hafnium well is film.That is, being used to form hafnium is the rich stable and gasification easily of raw material of film, therefore can stablize to supply raw material, and the high-quality hafnium of stable formation is a film.
The accompanying drawing summary
Fig. 1 is CpHf (NMe
2)
3The NMR collection of illustrative plates.
Fig. 2 is the CVD schematic representation of apparatus.
Fig. 3 is (MeCp) Hf (NMe
2)
3The NMR collection of illustrative plates.
Fig. 4 is (EtCp) Hf (NMe
2)
3The NMR collection of illustrative plates.
Fig. 5 is CpHf (NMeEt)
3The NMR collection of illustrative plates.
Fig. 6 is (MeCp) Hf (NMe
2)
3The TG-DTA curve.
Nomenclature
1 container
2 gasifiers
3 well heaters
4 substrates
5 decomposition reaction furnaces
6 well heaters
7 vacuum pumps
The best mode that carries out an invention
Novel cpd of the present invention is the compound of following general formula [I] expression, and L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl in the particularly following general formula [I], and R
1, R
2Compound for methyl or ethyl.Wherein have: CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3
General formula [I]:
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
Above-claimed cpd is particularly useful as and forms hafnium is the material of film.Wherein, be the material of film with acting on by chemical vapor-phase growing method or atomic shell control growing method formation hafnium.The compound of above-mentioned general formula [I] expression is when forming hafnium and be the material of film, and this compound is separately preferred or to use with the form of mixtures of its solvent of dissolving.Ie in solution (solute (general formula [I])+solvent) form.Solvent is preferably one or more and is selected from carbonatoms be 5～40 hydrocarbon system compound of (particularly 5～15) and carbonatoms be 2～40 compound of amine compound of (particularly 2～20).Wherein, preferred solvent is: hydrocarbon system solvent, for example n-decane, normal heptane, normal hexane, the tetradecane, dimethylbenzene, toluene; Amine series solvent, for example triethylamine, two (trimethyl silyl) amine, diethylamine, pyridine.With respect to the compound of 100 mass parts general formulas [I] expression, the amount of solvent is 1～10000 mass parts, preferred especially 100～2000 mass parts.That is, by using above-mentioned solvent successfully to carry out raw material supply.Still it should be noted that CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3Deng compound why most preferably, to be because be the membranous excellence of film by the hafnium of these compound formation.
The method that formation hafnium of the present invention is a film is as follows: using above-mentioned formation hafnium is the material of film (compound of above-mentioned general formula [I] expression or contain the solution of compound shown in the above-mentioned general formula [I]), and utilizing the chemical vapor-phase growing method to form hafnium on substrate is film; Perhaps, using above-mentioned formation hafnium is the material of film (compound shown in the above-mentioned general formula [I] or contain the solution of compound shown in the above-mentioned general formula [I]), and utilizing atomic shell control growing method to form hafnium on substrate is film.
Still it should be noted that, in the present invention, hafnium be film except that the Hf film, for example also have the hafnia film.This film is by carrying out obtaining under the environment at oxygenant when the material filming that is film with formation hafnium of the present invention.In addition, can also obtain by being used in combination ozone gas.And the environment during according to film forming (gas) determines that suitably hafnium is the composition of film.When for example under nitriding atmosphere, carrying out film forming, form hafnium nitride film.
Below providing specific embodiment describes.
[novel cpd CpHf (NMe
2)
3Synthetic]
Under nitrogen atmosphere, 29g four (dimethylamino) hafnium and 5.3g cyclopentadiene were stirred 1 hour in 70mL benzene.With this vlil 2 hours, benzene was heated up in a steamer in decompression afterwards.Remaining yellow liquid carries out the underpressure distillation of 0.1 holder under 70～80 ℃, obtain the 25g yellow liquid.
The boiling point of this yellow liquid is 75 ℃/0.2 holder.
In addition, the result who is measured by NMR, collection of illustrative plates show following resonance line.
1H-NMR(C
6D
6)：3.0(s，18H)，6.0(s，5H)
Still it should be noted that Fig. 1 is the NMR collection of illustrative plates of cyclopentadienyl three (dimethylamino) hafnium.
And judged by above-mentioned reaction formation and NMR collection of illustrative plates: the gained yellow liquid is cyclopentadienyl three (dimethylamino) hafnium [CpHf (NMe
2)
3].
Next, with 150g CpHf (NMe
2)
3Pack in the container, be heated to 100 ℃, supply argon gas (carrier gas) with 500ml/ minute ratio simultaneously.CpHf (the NMe of gasification
2)
3Pass through heating tube (Heating temperature is 100 ℃, 120 ℃, 150 ℃) together with carrier gas, be recycled to retrieving arrangement.Still it should be noted that arrange in the system this moment is vacuum.
CpHf (the NMe that measures so operation and reclaim
2)
3The NMR collection of illustrative plates, confirm the resolvent amount at each temperature.As a result, the resolvent amount is zero under all temperature of 100 ℃, 120 ℃ and 150 ℃.That is, judge CpHf (NMe
2)
3Rich stability.
In addition, measure CpHf (NMe
2)
3TG-DTA the time, vaporization rate is 88.6%.Be the vaporization rate height, judge thus: CpHf (NMe
2)
3Be that easy gasification, the suitable Hf of formation are the material of film.
[Hf is the formation of film]
Fig. 2 is used to form the schematic representation of apparatus that Hf is a film.
Among Fig. 2,1 is that container, 2 is that gasifier, 3 is that well heater, 4 is that substrate, 5 is that decomposition reaction furnace, 6 is that well heater, 7 is a vacuum pump.
Using being installed on of Fig. 2 to make Hf on the substrate 5 is film.
That is, with CpHf (NMe
2)
3Pack in the container 1, with ratio the supply of nitrogen of 0.1g/ minute (positive delivery gas).CpHf (the NMe of positive delivery
2)
3Gasification imports in the decomposition reaction furnace 5 in gasifier 3.With well heater 6 gasifier 3 and pipe arrangement are heated to 120～130 ℃.Still it should be noted that arrange in the system this moment is vacuum.In addition, substrate 4 is heated to 400 ℃.As a result, on substrate 4, form film.
The inner evenness excellence of the film of as above operating and forming.In addition, verify, confirm that this film is the Hf film by ICP-MS.
[novel cpd (MeCp) Hf (NMe
2)
3Synthetic]
Under nitrogen atmosphere, 10g four (dimethylamino) hafnium and 2g methyl cyclopentadiene were stirred 1 hour in 35mL benzene.With this vlil 2 hours, benzene was heated up in a steamer in decompression afterwards.Remaining yellow liquid carries out the underpressure distillation of 0.1 holder under 70～80 ℃, obtain the 11g yellow liquid.
The boiling point of this yellow liquid is 72 ℃/0.1 holder.
In addition, the result who is measured by NMR, collection of illustrative plates show following resonance line.
1H-NMR(C
6D
6)：2.1(s，3H)，3.0(s，18H)，5.8(m，2H)，5.9(m，2H)
Still it should be noted that Fig. 3 is the NMR collection of illustrative plates of methyl cyclopentadienyl three (dimethylamino) hafnium.
And judged by above-mentioned reaction formation and NMR collection of illustrative plates: the gained yellow liquid is methyl cyclopentadienyl three (dimethylamino) hafnium [(MeCp) Hf (NMe
2)
3].
Next, with 150g (MeCp) Hf (NMe
2)
3Pack in the container, be heated to 100 ℃, supply argon gas (carrier gas) with 500ml/ minute ratio simultaneously.(MeCp) Hf (NMe of gasification
2)
3Pass through heating tube (Heating temperature is 100 ℃, 120 ℃, 150 ℃) together with carrier gas, be recycled to retrieving arrangement.Still it should be noted that arrange in the system this moment is vacuum.
(MeCp) Hf (NMe that measures so operation and reclaim
2)
3The NMR collection of illustrative plates, confirm the resolvent amount at each temperature.As a result, the resolvent amount is zero under all temperature of 100 ℃, 120 ℃ and 150 ℃.That is, judge (MeCp) Hf (NMe
2)
3Rich stability.
In addition, measure (MeCp) Hf (NMe
2)
3TG-DTA the time, vaporization rate is 97.3%.Be the vaporization rate height, judge thus: (MeCp) Hf (NMe
2)
3Be that easy gasification, the suitable Hf of formation are the material of film.Still it should be noted that Fig. 6 is (MeCp) Hf (NMe
2)
3The TG-DTA curve.
[Hf is the formation of film]
In embodiment 1, use (MeCp) Hf (NMe
2)
3Replaced C pHf (NMe
2)
3And operate equally, on substrate 4, form film.
The inner evenness excellence of the film of so operating and obtaining.In addition, verify, confirm that this film is the Hf film by ICP-MS.
[novel cpd (EtCp) Hf (NMe
2)
3Synthetic]
Under nitrogen atmosphere, 25g four (dimethylamino) hafnium and 7g ethyl cyclopentadiene were stirred 1 hour in 60mL benzene.With this vlil 2 hours, benzene was heated up in a steamer in decompression afterwards.Remaining yellow liquid carries out the underpressure distillation of 0.1 holder under 70～80 ℃, obtain the 19g yellow liquid.
The boiling point of this yellow liquid is 78 ℃/0.2 holder.
In addition, the result who is measured by NMR, collection of illustrative plates show following resonance line.
1H-NMR(C
6D
6)：1.1(t，3H)，2.5(q，2H)，3.0(s，18H)，5.9(m，2H)，6.0(m，2H)
Still it should be noted that Fig. 4 is the NMR collection of illustrative plates of ethyl cyclopentadienyl three (dimethylamino) hafnium.
And judged by above-mentioned reaction formation and NMR collection of illustrative plates: the gained yellow liquid is ethyl cyclopentadienyl three (dimethylamino) hafnium [(EtCp) Hf (NMe
2)
3].
Next, with 150g (EtCp) Hf (NMe
2)
3Pack in the container, be heated to 100 ℃, supply argon gas (carrier gas) with 500ml/ minute ratio simultaneously.(EtCp) Hf (NMe of gasification
2)
3Pass through heating tube (Heating temperature is 100 ℃, 120 ℃, 150 ℃) together with carrier gas, be recycled to retrieving arrangement.Still it should be noted that arrange in the system this moment is vacuum.
(EtCp) Hf (NMe that measures so operation and reclaim
2)
3The NMR collection of illustrative plates, confirm the resolvent amount at each temperature.As a result, the resolvent amount is zero under all temperature of 100 ℃, 120 ℃ and 150 ℃.That is, judge (EtCp) Hf (NMe
2)
3Rich stability.
In addition, measure (EtCp) Hf (NMe
2)
3TG-DTA the time, vaporization rate is 94.8%.Be the vaporization rate height, judge thus: (EtCp) Hf (NMe
2)
3Be that easy gasification, the suitable Hf of formation are the material of film.
[Hf is the formation of film]
In embodiment 1, use (EtCp) Hf (NMe
2)
3Replaced C pHf (NMe
2)
3And operate equally, on substrate 4, form film.
The inner evenness excellence of the film of so operating and obtaining.In addition, verify, confirm that this film is the Hf film by ICP-MS.
[novel cpd CpHf (NMeEt)
3Synthetic]
Under nitrogen atmosphere, 63g four (methylethyl amino) hafnium and 10g cyclopentadiene were stirred 1 hour in 140mL benzene.With this vlil 2 hours, benzene was heated up in a steamer in decompression afterwards.Remaining yellow liquid carries out the underpressure distillation of 0.1 holder under 80～90 ℃, obtain the 36g yellow liquid.
The boiling point of this yellow liquid is 85 ℃/0.2 holder.
In addition, the result who is measured by NMR, collection of illustrative plates show following resonance line.
1H-NMR(C
6D
6)：1.0(t，9H)，2.9(s，9H)，3.2(q，6H)，6.1(s，5H)
Still it should be noted that Fig. 5 is the NMR collection of illustrative plates of cyclopentadienyl three (methylethyl amino) hafnium.
And judged by above-mentioned reaction formation and NMR collection of illustrative plates: the gained yellow liquid is cyclopentadienyl three (methylethyl amino) hafnium [CpHf (NMeEt)
3].
Next, with 150g CpHf (NMeEt)
3Pack in the container, be heated to 100 ℃, supply argon gas (carrier gas) with 500ml/ minute ratio simultaneously.The CpHf (NMeEt) of gasification
3Pass through heating tube (Heating temperature is 100 ℃, 120 ℃, 150 ℃) together with carrier gas, be recycled to retrieving arrangement.Still it should be noted that arrange in the system this moment is vacuum.
The CpHf (NMeEt) that measures so operation and reclaim
3The NMR collection of illustrative plates, confirm the resolvent amount at each temperature.As a result, the resolvent amount is zero under all temperature of 100 ℃, 120 ℃ and 150 ℃.That is, judge CpHf (NMeEt)
3Rich stability.
In addition, measure CpHf (NMeEt)
3TG-DTA the time, vaporization rate is 90.1%.Be the vaporization rate height, judge thus: CpHf (NMeEt)
3Be that easy gasification, the suitable Hf of formation are the material of film.
[Hf is the formation of film]
In embodiment 1, use CpHf (NMeEt)
3Replaced C pHf (NMe
2)
3And operate equally, on substrate 4, form film.
The inner evenness excellence of the film of so operating and obtaining.In addition, verify, confirm that this film is the Hf film by ICP-MS.
In embodiment 1, except use when the film forming n-decane as solvent, operate equally.As a result, on substrate 4, form film.
The inner evenness excellence of the film of so operating and obtaining.In addition, verify, confirm that this film is the Hf film by ICP-MS.
Be film forming in embodiment 1, in embodiment 6, carry out film forming according to atomic shell control growing method according to the chemical vapor-phase growing method.
As a result, formed the Hf film of inner evenness excellence.
Be film forming in embodiment 2, in embodiment 7, carry out film forming according to atomic shell control growing method according to the chemical vapor-phase growing method.
As a result, formed the Hf film of inner evenness excellence.
Be film forming in embodiment 3, in embodiment 8, carry out film forming according to atomic shell control growing method according to the chemical vapor-phase growing method.
As a result, formed the Hf film of inner evenness excellence.
Embodiment 9
Be film forming in embodiment 4, in embodiment 9, carry out film forming according to atomic shell control growing method according to the chemical vapor-phase growing method.
As a result, formed the Hf film of inner evenness excellence.
Embodiment 10
Operate similarly to Example 1, obtain sec.-propyl cyclopentadienyl three (dimethylamino) hafnium.
Then, use sec.-propyl cyclopentadienyl three (dimethylamino) hafnium, operate similarly to Example 1, on substrate 4, form film.
The film of so operating and obtaining is compared relatively poor with the film of embodiment 1, but the inner evenness excellence.
Embodiment 11
Operate similarly to Example 1, obtain sec.-propyl cyclopentadienyl three (methylethyl amino) hafnium.
Then, use sec.-propyl cyclopentadienyl three (methylethyl amino) hafnium, operate similarly to Example 1, on substrate 4, form film.
The film of so operating and obtaining is compared relatively poor with the film of embodiment 1, but the inner evenness excellence.
Embodiment 12
Operate similarly to Example 1, obtain ethyl cyclopentadienyl three (diethylin) hafnium.
Then, use ethyl cyclopentadienyl three (diethylin) hafnium, operate similarly to Example 1, on substrate 4, form film.
The film of so operating and obtaining is compared relatively poor with the film of embodiment 1, but the inner evenness excellence.
Embodiment 13
Operate similarly to Example 1, obtain sec.-propyl cyclopentadienyl three (diethylin) hafnium.
Then, use sec.-propyl cyclopentadienyl three (diethylin) hafnium, operate similarly to Example 1, on substrate 4, form film.
The film of so operating and obtaining is compared relatively poor with the film of embodiment 1, but the inner evenness excellence.
Embodiment 14
Operate similarly to Example 1, obtain methyl cyclopentadienyl three (methylethyl amino) hafnium.
Then, use methyl cyclopentadienyl three (methylethyl amino) hafnium, operate similarly to Example 1, on substrate 4, form film.
The inner evenness excellence of the film of so operating and obtaining.In addition, verify, confirm that this film is the Hf film by ICP-MS.
Comparative example 1
In embodiment 1, except using four (methylethyl amino) hafnium replaced C pHf (NMe
2)
3In addition, operate equally, on substrate 4, form film.
The film of so operating and obtaining is compared with the film of embodiment 1, and inner evenness is relatively poor.
Comparative example 2
In embodiment 1, except using four (oxyethyl group) hafnium replaced C pHf (NMe
2)
3In addition, operate equally, on substrate 4, form film.
The film of so operating and obtaining is compared with the film of embodiment 1, and inner evenness is relatively poor.
Comparative example 3
In embodiment 1, except using four (beta-diketon) hafnium replaced C pHf (NMe
2)
3In addition, operate equally, on substrate 4, form film.
The film of so operating and obtaining is compared with the film of embodiment 1, and inner evenness is relatively poor.
Comparative example 4
In embodiment 1, except using HfCl
4Replaced C pHf (NMe
2)
3In addition, operate equally, on substrate 4, form film.
The film of so operating and obtaining is compared with the film of embodiment 1, and inner evenness is relatively poor.
Industrial applicability
To use hafnium be the field of film, such as particularly useful in the semiconductor applications etc.
Claims (20)
1. compound is characterized in that: with following general formula [I] expression,
General formula [I]
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
2. the compound of claim 1, it is characterized in that: in above-mentioned general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl; R
1, R
2Be methyl or ethyl.
3. the compound of claim 1 is characterized in that: the compound of above-mentioned general formula [I] expression is for being selected from CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3Any, wherein Cp=cyclopentadienyl, MeCp=methyl cyclopentadienyl, EtCp=ethyl cyclopentadienyl, Me=methyl, Et=ethyl.
4. forming hafnium is the material of film, and it is film that this material is used to form hafnium, it is characterized in that: be the compound of following general formula [I] expression,
General formula [I]
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
5. the formation hafnium of claim 4 is the material of film, it is characterized in that: in the above-mentioned general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl; R
1, R
2Be methyl or ethyl.
6. the formation hafnium of claim 4 is the material of film, it is characterized in that: the compound of above-mentioned general formula [I] expression is for being selected from CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3Any, wherein Cp=cyclopentadienyl, MeCp=methyl cyclopentadienyl, EtCp=ethyl cyclopentadienyl, Me=methyl, Et=ethyl.
7. the formation hafnium of claim 4 is the material of film, it is characterized in that: except the compound that contains above-mentioned general formula [I] expression, also contain the solvent of the compound of the above-mentioned general formula of dissolving [I] expression.
8. the formation hafnium of claim 7 is the material of film, it is characterized in that: solvent is that 5～40 hydrocarbon system compound and carbonatoms are the compound of 2～40 amine compound for one or more are selected from carbonatoms.
9. the formation hafnium of claim 4 is the material of film, it is characterized in that: it is film that this material is used for forming hafnium by the chemical vapor-phase growing method.
10. the formation hafnium of claim 4 is the material of film, it is characterized in that: it is film that this material is used for forming hafnium by atomic shell control growing method.
11. forming hafnium is the method for film, it is film that this method utilizes the chemical vapor-phase growing method to form hafnium on substrate, it is characterized in that: use the compound of following general formula [I] expression,
General formula [I]
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
12. the formation hafnium of claim 11 is the method for film, it is characterized in that: in the above-mentioned general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl; R
1, R
2Be methyl or ethyl.
13. the formation hafnium of claim 11 is the method for film, it is characterized in that: the compound of above-mentioned general formula [I] expression is for being selected from CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3Any, wherein Cp=cyclopentadienyl, MeCp=methyl cyclopentadienyl, EtCp=ethyl cyclopentadienyl, Me=methyl, Et=ethyl.
14. the formation hafnium of claim 11 is the method for film, it is characterized in that: use the solution of compound dissolution in solvent with above-mentioned general formula [I] expression.
15. the formation hafnium of claim 14 is the method for film, it is characterized in that: solvent is that 5～40 hydrocarbon system compound and carbonatoms are the compound of 2～40 amine compound for one or more are selected from carbonatoms.
16. forming hafnium is the method for film, it is film that this method utilizes atomic shell control growing method to form hafnium on substrate, it is characterized in that: use the compound of following general formula [I] expression,
General formula [I]
LHf(NR
1R
2)
3
Wherein, L is the cyclopentadienyl of cyclopentadienyl or replacement; R
1, R
2Be alkyl, R
1And R
2Differ from one another or identical.
17. the formation hafnium of claim 16 is the method for film, it is characterized in that: in the above-mentioned general formula [I], L is cyclopentadienyl, methyl cyclopentadienyl or ethyl cyclopentadienyl; R
1, R
2Be methyl or ethyl.
18. the formation hafnium of claim 16 is the method for film, it is characterized in that: the compound of above-mentioned general formula [I] expression is for being selected from CpHf (NMe
2)
3, (MeCp) Hf (NMe
2)
3, (EtCp) Hf (NMe
2)
3, CpHf (NMeEt)
3Any, wherein Cp=cyclopentadienyl, MeCp=methyl cyclopentadienyl, EtCp=ethyl cyclopentadienyl, Me=methyl, Et=ethyl.
19. the formation hafnium of claim 16 is the method for film, it is characterized in that: use the solution of compound dissolution in solvent with above-mentioned general formula [I] expression.
20. the formation hafnium of claim 19 is the method for film, it is characterized in that: solvent is that 5～40 hydrocarbon system compound and carbonatoms are the compound of 2～40 amine compound for one or more are selected from carbonatoms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005351450 | 2005-12-06 | ||
| JP351450/2005 | 2005-12-06 | ||
| PCT/JP2006/323754 WO2007066546A1 (en) | 2005-12-06 | 2006-11-29 | Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101341155A true CN101341155A (en) | 2009-01-07 |
| CN101341155B CN101341155B (en) | 2012-03-07 |
Family
ID=38122694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800452445A Active CN101341155B (en) | 2005-12-06 | 2006-11-29 | Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP5128289B2 (en) |
| KR (1) | KR101367827B1 (en) |
| CN (1) | CN101341155B (en) |
| TW (1) | TWI415855B (en) |
| WO (1) | WO2007066546A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062792A (en) * | 2020-08-05 | 2020-12-11 | 芯越芯(南京)电子科技有限公司 | Production method of tris (dimethylamine) cyclopentadiene hafnium |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2432363B (en) | 2005-11-16 | 2010-06-23 | Epichem Ltd | Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition |
| EP2029790A1 (en) | 2006-06-02 | 2009-03-04 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing |
| US7956207B2 (en) * | 2006-09-28 | 2011-06-07 | Praxair Technology, Inc. | Heteroleptic organometallic compounds |
| CN101815807B (en) * | 2007-09-14 | 2012-06-13 | 西格玛-奥吉奇有限责任公司 | Methods of preparing thin films by atomic layer deposition using monocyclopentadienyl trialkoxy hafnium and zirconium precursors |
| KR101560755B1 (en) | 2007-09-14 | 2015-10-15 | 시그마 알드리치 컴퍼니 엘엘씨 | Methods of preparing titanium containing thin films by atomic layer deposition using monocyclopentadienyl titanium-based precursors |
| KR20120093165A (en) | 2009-08-14 | 2012-08-22 | 레르 리키드 쏘시에떼 아노님 뿌르 레？드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 | Hafnium- and zirconium-containing precursors and methods of using the same |
| US8765220B2 (en) | 2009-11-09 | 2014-07-01 | American Air Liquide, Inc. | Methods of making and deposition methods using hafnium- or zirconium-containing compounds |
| TW201402586A (en) * | 2012-05-25 | 2014-01-16 | Air Liquide | Hafnium-containing precursors for vapor deposition |
| US9499571B2 (en) | 2014-12-23 | 2016-11-22 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Germanium- and zirconium-containing compositions for vapor deposition of zirconium-containing films |
| US9663547B2 (en) | 2014-12-23 | 2017-05-30 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Silicon- and Zirconium-containing compositions for vapor deposition of Zirconium-containing films |
| US10106568B2 (en) | 2016-10-28 | 2018-10-23 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Hafnium-containing film forming compositions for vapor deposition of hafnium-containing films |
| KR102033540B1 (en) | 2017-04-27 | 2019-10-17 | (주)디엔에프 | Metal triamine compound, its preparation method and composition for depositing a metal-containing thin film comprising the same |
| KR102259874B1 (en) * | 2019-12-23 | 2021-06-03 | (주)원익머트리얼즈 | Method for forming dielectric film using organometallic compound precursor having cyclopentadiene and use in semiconductor manufacturing thereof |
| KR102562274B1 (en) * | 2020-12-17 | 2023-08-01 | 주식회사 이지티엠 | Organometallic precursor compounds |
| KR20220157741A (en) * | 2021-05-21 | 2022-11-29 | 주식회사 아이켐스 | Novel hafnium compound, precursor composition comprising the same, thin film using the same and deposition method of the same |
| JPWO2023282104A1 (en) * | 2021-07-07 | 2023-01-12 |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1272939B (en) | 1995-02-01 | 1997-07-01 | Enichem Spa | METALLOCENIC CATALYST SUPPORTED FOR THE (CO) POLYMERIZATION OF OLEFINS |
| US5527752A (en) * | 1995-03-29 | 1996-06-18 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the production of polyolefins |
| DE19736449A1 (en) * | 1997-08-21 | 1999-02-25 | Gfe Met & Mat Gmbh | Composite |
| JP4868639B2 (en) * | 2000-06-12 | 2012-02-01 | 株式会社Ａｄｅｋａ | Raw material for chemical vapor deposition and method for producing thin film using the same |
| JP2002069027A (en) * | 2000-08-25 | 2002-03-08 | Kojundo Chem Lab Co Ltd | HAFNIUM ALKOXYTRIS(beta-DIKETONATE), METHOD FOR MANUFACTURING THE SAME AND METHOD FOR MANUFACTURING OXIDE FILM USING THE SAME |
| JP4644359B2 (en) * | 2000-11-30 | 2011-03-02 | ルネサスエレクトロニクス株式会社 | Deposition method |
| JP2003020305A (en) * | 2001-07-10 | 2003-01-24 | Sumitomo Chem Co Ltd | Catalyst for olefin polymerization |
| JP2003218107A (en) * | 2002-01-24 | 2003-07-31 | Hitachi Ltd | Method for forming insulation film and film formation device |
| JP2003332327A (en) * | 2002-05-16 | 2003-11-21 | Japan Pionics Co Ltd | Gasification supply method |
| US20040168627A1 (en) * | 2003-02-27 | 2004-09-02 | Sharp Laboratories Of America, Inc. | Atomic layer deposition of oxide film |
| KR100995451B1 (en) * | 2003-07-03 | 2010-11-18 | 삼성전자주식회사 | Organic Thin Film Transistor comprising Gate Insulator having Multi-layered Structure |
| JP2005171291A (en) * | 2003-12-09 | 2005-06-30 | Tosoh Corp | Titanium-containing thin film and production method therefor |
| JP4457881B2 (en) * | 2003-12-25 | 2010-04-28 | Ｔｄｋ株式会社 | Rare earth magnets |
| JP2005187356A (en) * | 2003-12-25 | 2005-07-14 | Mitsubishi Materials Corp | Organic metal compound and its solution raw material and method for forming metal-containing film using the compound |
-
2006
- 2006-11-29 CN CN2006800452445A patent/CN101341155B/en active Active
- 2006-11-29 WO PCT/JP2006/323754 patent/WO2007066546A1/en active Application Filing
- 2006-11-29 JP JP2007549083A patent/JP5128289B2/en active Active
- 2006-11-29 KR KR1020087008011A patent/KR101367827B1/en active IP Right Review Request
- 2006-11-30 TW TW095144383A patent/TWI415855B/en active
-
2012
- 2012-10-01 JP JP2012219892A patent/JP5548748B2/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062792A (en) * | 2020-08-05 | 2020-12-11 | 芯越芯(南京)电子科技有限公司 | Production method of tris (dimethylamine) cyclopentadiene hafnium |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI415855B (en) | 2013-11-21 |
| JPWO2007066546A1 (en) | 2009-05-14 |
| JP5548748B2 (en) | 2014-07-16 |
| KR20080077086A (en) | 2008-08-21 |
| JP5128289B2 (en) | 2013-01-23 |
| KR101367827B1 (en) | 2014-02-26 |
| TW200728311A (en) | 2007-08-01 |
| CN101341155B (en) | 2012-03-07 |
| WO2007066546A1 (en) | 2007-06-14 |
| JP2013047391A (en) | 2013-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101341155B (en) | Hafnium compound, hafnium thin film-forming material and method for forming hafnium thin film | |
| CN103097394B (en) | Molybdenum (IV) acid amides precursor and its purposes in ald | |
| US8568530B2 (en) | Use of cyclopentadienyl type hafnium and zirconium precursors in atomic layer deposition | |
| KR100988973B1 (en) | Metal complexes of tridentate beta-ketoiminates | |
| JP5957017B2 (en) | Novel group 4B organometallic compound and method for producing the same | |
| CN102712662A (en) | Hafnium- and zirconium-containing precursors and methods of using the same | |
| KR101841444B1 (en) | Group 5 metal compounds, preparing methods thereof, precursor compositions including the same for film deposition, and depositing methods of film using the same | |
| JP2006516031A (en) | Chemical vapor deposition precursors for the deposition of tantalum-based materials | |
| TWI469988B (en) | The novel 4b group metalorganic compounds and the preparations thereof | |
| CN101111502B (en) | Tantalum compound, method for producing same, tantalum-containing thin film and method for forming same | |
| CN106103456A (en) | Organic germanium amines and the method with its deposition thin film | |
| JP2020143316A (en) | Indium compound and method for forming indium-containing film using the indium compound | |
| KR101772478B1 (en) | Organic group 13 precursor and method for depositing thin film using thereof | |
| JP6979032B2 (en) | A transition metal compound, a method for producing the same, and a composition for thin film deposition containing a transition metal containing the same. | |
| US11495453B2 (en) | Vapor deposition precursor having excellent thermal stability and reactivity and preparing method therefor | |
| JP2016037654A (en) | Film formation material and film formation method | |
| TWI272275B (en) | Novel bismuth compound, process of producing the same, and process of producing a film | |
| KR101306810B1 (en) | Novel tungsten aminoalkoxide compounds, preparation method thereof and process for the formation of thin films using the same | |
| KR20220039318A (en) | New Group 4 organometallic precursor compound with excellent thermal stability, manufacturing method thereof, and thin film formation method using the same. | |
| JP4711113B2 (en) | CH3AlH2: L manufacturing method, Al-based film forming material, Al-based film forming method, and Al-based wiring film forming method | |
| KR102631512B1 (en) | Novel Organometallic Compounds for deposition of thin film | |
| KR100634814B1 (en) | Precursors of novel titanium oxide and preparation method thereof | |
| CN107660204A (en) | The method for preparing indazole derivative |
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 |