JPWO2006049059A1 - 金属化合物、薄膜形成用原料及び薄膜の製造方法 - Google Patents
金属化合物、薄膜形成用原料及び薄膜の製造方法 Download PDFInfo
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- JPWO2006049059A1 JPWO2006049059A1 JP2006543210A JP2006543210A JPWO2006049059A1 JP WO2006049059 A1 JPWO2006049059 A1 JP WO2006049059A1 JP 2006543210 A JP2006543210 A JP 2006543210A JP 2006543210 A JP2006543210 A JP 2006543210A JP WO2006049059 A1 JPWO2006049059 A1 JP WO2006049059A1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 39
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- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical group [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 1
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- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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)
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Abstract
Description
乾燥アルゴンガス雰囲気下で、反応フラスコにタンタラム(V)エトキシド0.246mol、脱水処理を行ったトルエン50g及び1−ジメチルアミノ−2−メチル−2−プロパノール0.271molを仕込み、常圧、塔頂温度68℃でエタノールを除去し、粗生成物を回収した(回収率100%)。得られた粗生成物から13Pa、塔頂温度103〜104℃のフラクションを回収して透明液体を得た。この精製による回収率は70%であった。得られた透明液体について以下の分析を行い、目的物である化合物No.1であることを確認した。
(1)1H−NMR(溶媒:重ベンゼン)(ケミカルシフト:多重度:H数)
(1.27:s:6H)(1.32:t:12H)(2.31:s:6H)(2.36:2H:s)(4.55:q:8H)
(2)TG−DTA(Ar流速100ml/min、昇温速度10℃/min、サンプル量11.4mg)
50質量%減少温度:193.8℃
(3)ICP−AES
化合物中のTa含有量分析値:37.1%(理論値:37.9%)
実施例1で得られた化合物No.1並びに下記に示す比較化合物1及び2について、上記実施例1と同条件でのTG−DTAにより熱挙動(50質量%減少温度及び300℃での残分)を比較した。また、化合物No.1並びに下記比較化合物1及び2について蒸気圧測定を行った。これらの結果を表1に示す。なお、蒸気圧測定は、系を一定の圧力に固定して液面付近の蒸気温度を測定し、系の圧力を変えて蒸気温度を3〜4点測定し、クラジウス−クラペイロンプロットにより、蒸気圧の式を適用して、10Torrにおける温度を算出する方法により行った。
実施例1で得られた化合物No.1並びに上記比較化合物1及び2について、熱安定性評価を行った。評価は、それぞれの化合物を密閉容器に入れ、200℃、210℃及び220℃それぞれで1時間加熱し、TG−DTAにより分解した割合を求めることにより行った。これらの結果を表2に示す。
乾燥アルゴンガス雰囲気下で、反応フラスコにニオブ(V)エトキシド0.051mol、脱水処理を行なったトルエン20g及び1−ジメチルアミノ−2−メチル−2−プロパノール0.051molを仕込み、常圧、塔頂温度140℃でエタノールを除去し、粗生成物を回収した(回収率100%)。得られた粗生成物から60〜70Pa、塔頂温度105〜115℃のフラクションを回収して淡黄色透明液体を得た。この精製による回収率は55%であった。得られた淡黄色透明液体について以下の分析を行い、目的物である化合物No.9であることを確認した。
(1)1H−NMR(溶媒:重ベンゼン)(ケミカルシフト:多重度:H数)
(1.27:s:6H)(1.32:t:12H)(2.28:s:6H)(2.35:s:2H)(4.49:q:8H)
(2)TG−DTA(Ar流速100ml/min、昇温速度10℃/min、サンプル量11.4mg)
50質量%減少温度:194.4℃
(3)ICP−AES
化合物中のNb含有量分析値:23.2%(理論値:23.8%)
実施例2で得られた化合物No.9及び比較化合物3としてのNb(OC2H5)5について、上記実施例2と同条件でのTG−DTAにより熱挙動(50質量%減少温度及び300℃での残分)を比較した。また、化合物No.9及び比較化合物3について蒸気圧測定を行った。これらの結果を表3に示す。なお、蒸気圧測定は、系を一定の圧力に固定して液面付近の蒸気温度を測定し、系の圧力を変えて蒸気温度を3〜4点測定し、クラジウス−クラペイロンプロットにより、蒸気圧の式を適用して、10Torrにおける温度を算出する方法により行なった。
図1に示すCVD装置を用いて、Pt上に以下の条件で、タンタル薄膜を製造した。製造した薄膜について、膜厚及び結晶構造の測定を蛍光X線で測定した。測定結果を以下に示す。
(製造条件)
タンタル原料:化合物No.1(原料温度;145℃、圧力;1300Pa、キャリアガス;アルゴン200sccm)、酸化ガス:酸素300sccm、反応圧力:1300Pa、反応温度(基板温度):500℃、成膜時間:25分、結晶化アニール:730℃/2min.
(結果)
膜厚;120nm、結晶構造;六方晶Ta2O5
ALD用原料として、化合物No.1のエチルシクロヘキサン溶液(0.2mol/L)を調整し、図2に示すALD装置により、以下の条件・工程で薄膜を製造した。得られた薄膜の膜厚及び結晶構造を、上記実施例2と同様にして測定した。測定結果を以下に示す。
(条件)
反応温度(基板温度);350℃、反応性ガス;水蒸気
(工程)
下記(1)〜(4)からなる一連の工程を1サイクルとして、300サイクル繰り返し、最後に700℃で3分間アニール処理を行った。
(1)気化室温度:150℃、気化室圧力1300〜1400Paの条件で気化させたALD用原料の蒸気を導入し、系圧1300 〜1400Paで1秒間堆積させる。
(2)2秒間のアルゴンパージにより、未反応原料を除去する。
(3)水蒸気を導入し、系圧力1300Paで1秒間反応させる。
(4)2秒間のアルゴンパージにより、未反応原料を除去する。
(結果)
膜厚:30nm、結晶構造:六方晶Ta2O5
Claims (11)
- 上記一般式(I)において、R2及びR3がメチル基である請求の範囲第1項記載の金属化合物。
- 上記一般式(I)において、R1がエチル基である請求の範囲第1又は4項記載の金属化合物。
- 上記一般式(II)において、R2及びR3がメチル基である請求の範囲第2項記載の金属化合物。
- 上記一般式(II)において、R1がエチル基である請求の範囲第2又は6項記載の金属化合物。
- 上記一般式(III)において、R2及びR3がメチル基である請求の範囲第3項記載の金属化合物。
- 上記一般式(III)において、R1がエチル基である請求の範囲第3又は8項記載の金属化合物。
- 請求の範囲第1〜9項のいずれかに記載の金属化合物を含有してなる薄膜形成用原料。
- 請求の範囲第10項記載の薄膜形成用原料を気化させて得た金属化合物を含有する蒸気を基体上に導入し、これを分解及び/又は化学反応させて基体上に金属含有薄膜を形成する薄膜の製造方法。
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