JP5128289B2 - Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method - Google Patents
Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method Download PDFInfo
- Publication number
- JP5128289B2 JP5128289B2 JP2007549083A JP2007549083A JP5128289B2 JP 5128289 B2 JP5128289 B2 JP 5128289B2 JP 2007549083 A JP2007549083 A JP 2007549083A JP 2007549083 A JP2007549083 A JP 2007549083A JP 5128289 B2 JP5128289 B2 JP 5128289B2
- Authority
- JP
- Japan
- Prior art keywords
- hafnium
- thin film
- based thin
- film forming
- cphf
- 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
Links
- 239000010409 thin film Substances 0.000 title claims description 81
- 229910052735 hafnium Inorganic materials 0.000 title claims description 72
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims description 71
- 150000001875 compounds Chemical class 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 40
- 239000000463 material Substances 0.000 title claims description 38
- 239000000758 substrate Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- -1 amine compound Chemical class 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000010408 film Substances 0.000 description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 21
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000009834 vaporization Methods 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000006200 vaporizer 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
- ZYLGGWPMIDHSEZ-UHFFFAOYSA-N dimethylazanide;hafnium(4+) Chemical compound [Hf+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C ZYLGGWPMIDHSEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- SJHWIROHRNJCSQ-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C(C)(C)C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C SJHWIROHRNJCSQ-UHFFFAOYSA-N 0.000 description 2
- YPCXNVPDXZXKME-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[Hf](N(C)CC)(N(C)CC)N(CC)C Chemical compound C(C)(C)C1(C=CC=C1)[Hf](N(C)CC)(N(C)CC)N(CC)C YPCXNVPDXZXKME-UHFFFAOYSA-N 0.000 description 2
- IJJIBWRHCHHBEV-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)N(CC)CC Chemical compound C(C)(C)C1(C=CC=C1)[Hf](N(CC)CC)(N(CC)CC)N(CC)CC IJJIBWRHCHHBEV-UHFFFAOYSA-N 0.000 description 2
- SVXNXAKDMINOTQ-UHFFFAOYSA-N C(C)N(C)[Hf](C1(C=CC=C1)C)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Hf](C1(C=CC=C1)C)(N(CC)C)N(CC)C SVXNXAKDMINOTQ-UHFFFAOYSA-N 0.000 description 2
- TYYSTSWNSKHYFT-UHFFFAOYSA-N C(C)N(C)[Hf](C1C=CC=C1)(N(CC)C)N(CC)C Chemical compound C(C)N(C)[Hf](C1C=CC=C1)(N(CC)C)N(CC)C TYYSTSWNSKHYFT-UHFFFAOYSA-N 0.000 description 2
- QZANQQCQYLHXLS-UHFFFAOYSA-N C(C)N(CC)[Hf](C1(C=CC=C1)CC)(N(CC)CC)N(CC)CC Chemical compound C(C)N(CC)[Hf](C1(C=CC=C1)CC)(N(CC)CC)N(CC)CC QZANQQCQYLHXLS-UHFFFAOYSA-N 0.000 description 2
- JIGXARPLYFNBCG-UHFFFAOYSA-N C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C Chemical compound C1(C=CC=C1)[Hf](N(C)C)(N(C)C)N(C)C JIGXARPLYFNBCG-UHFFFAOYSA-N 0.000 description 2
- ZXXWMOMXTOZQFP-UHFFFAOYSA-N CN(C)[Hf](C1(C=CC=C1)C)(N(C)C)N(C)C Chemical compound CN(C)[Hf](C1(C=CC=C1)C)(N(C)C)N(C)C ZXXWMOMXTOZQFP-UHFFFAOYSA-N 0.000 description 2
- CXQYVOGCLGBONO-UHFFFAOYSA-N CN(C)[Hf](C1(C=CC=C1)CC)(N(C)C)N(C)C Chemical compound CN(C)[Hf](C1(C=CC=C1)CC)(N(C)C)N(C)C CXQYVOGCLGBONO-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
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 description 2
- 150000002362 hafnium Chemical class 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 0 CCC*(*1)C=CS1C1CC(*CC)CC1 Chemical compound CCC*(*1)C=CS1C1CC(*CC)CC1 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BFIMXCBKRLYJQO-UHFFFAOYSA-N ethanolate;hafnium(4+) Chemical compound [Hf+4].CC[O-].CC[O-].CC[O-].CC[O-] BFIMXCBKRLYJQO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 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
- 239000007800 oxidant agent Substances 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
- 239000008096 xylene Substances 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 System
-
- 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
Description
【技術分野】
【０００１】
本発明はハフニウム系薄膜形成技術に関する。
【背景技術】
【０００２】
テトラハロゲン化ハフニウム、或いはテトラキス（ジアルキルアミノ）ハフニウム、若しくはテトラキス（アルコキシ）ハフニウム、又はテトラキス（β−ジケトン）ハフニウムを用い、化学気相成長方法あるいは原子層制御成長方法によって、ハフニウム系薄膜を形成することが提案されている。
【０００３】
ところで、ハフニウム系薄膜の形成に際しては、前記化合物を気化させる必要が有る。そして、気化の為、前記化合物は加熱される。
【０００４】
しかしながら、テトラハロゲン化ハフニウムやテトラキス（β−ジケトン）ハフニウムは固体である。この為、気化が困難であり、安定したガス供給が出来難い。すなわち、原料の安定供給が困難であることから、高品質なハフニウム系薄膜を安定して形成することが出来ない。
【０００５】
テトラキス（ジアルキルアミノ）ハフニウムは熱安定性が低い。従って、加熱して気化した際、分解する。この為、安定したガス供給が出来難い。すなわち、原料の安定供給が困難であることから、高品質なハフニウム系薄膜を安定して形成することが出来ない。
【０００６】
テトラキス（アルコキシ）ハフニウムも安定性が悪い。例えば、保存しているだけでも分解してしまう。この為、安定したガス供給が出来難い。すなわち、原料の安定供給が困難であることから、高品質なハフニウム系薄膜を安定して形成することが出来ない。
【特許文献１】
特開２００５−２９８４６７
【特許文献２】
特開２００５−２９４４２１
【特許文献３】
特開２００４−１３７２２３
【特許文献４】
特開２００４−１３７２２２
【発明の開示】
【発明が解決しようとする課題】
【０００７】
従って、本発明が解決しようとする課題は、前記の問題点を解決することである。特に、常温で液体であり、そして安定性に富んでおり、原料の安定供給が行え、高品質なハフニウム系薄膜を安定して形成できる技術を提供することである。
【課題を解決するための手段】
【０００８】
前記課題を解決する為の検討を、鋭意、推し進めて行く中、ＬＨｆ（ＮＲ１Ｒ２）３で表される化合物は、安定性に富んでおり、そして気化も容易であり、化学気相成長方法や原子層制御成長方法によって高品質なハフニウム系薄膜を形成できることを見出すに至った。
【０００９】
前記知見を基にして本発明が達成されたものである。
【００１０】
すなわち、前記の課題は、下記の一般式［Ｉ］で表されることを特徴とする化合物によって解決される。
【００１１】
特に、一般式［Ｉ］におけるＲ１，Ｒ２がメチル基またはエチル基であることを特徴とする化合物によって解決される。
【００１２】
又、ハフニウム系薄膜を形成する為の材料であって、
下記の一般式［Ｉ］で表される化合物であることを特徴とするハフニウム系薄膜形成材料によって解決される。
【００１３】
又、ハフニウム系薄膜を形成する為の材料であって、
下記の一般式［Ｉ］で表される化合物と、
前記化合物を溶解する溶媒
とを含有する
ことを特徴とするハフニウム系薄膜形成材料によって解決される。
【００１４】
一般式［Ｉ］
ＣｐＨｆ（ＮＲ１Ｒ２）３
（但し、Ｃｐはシクロペンタジエニル基、Ｒ１，Ｒ２はアルキル基であり、Ｒ１とＲ２とは互いに異なっていても同じであってもよい。）
特に、上記のハフニウム系薄膜形成材料であって、Ｒ１，Ｒ２がメチル基またはエチル基であることを特徴とするハフニウム系薄膜形成材料によって解決される。
【００１５】
中でも、上記一般式［Ｉ］の化合物がＣｐＨｆ（ＮＭｅ２）３，ＣｐＨｆ（ＮＭｅＥｔ）３〔Ｃｐ＝シクロペンタジエニル基、Ｍｅ＝メチル基、Ｅｔ＝エチル基〕であることを特徴とするハフニウム系薄膜形成材料によって解決される。
【００１６】
又、上記のハフニウム系薄膜形成材料であって、溶媒が炭素数５〜４０（特に、１５以下）の炭化水素系化合物及び炭素数２〜４０（特に、２０以下）のアミン系化合物の群の中から選ばれる一つ又は二つ以上の化合物であるハフニウム系薄膜形成材料によって解決される。
【００１７】
上記のハフニウム系薄膜形成材料は、特に、化学気相成長方法または原子層制御成長方法によってハフニウム系薄膜を形成する為の材料である。
【００１８】
又、前記の課題は、上記ハフニウム系薄膜形成材料を用いて化学気相成長方法により基板上にハフニウム系薄膜を形成することを特徴とするハフニウム系薄膜形成方法によって解決される。
【００１９】
又、前記の課題は、上記ハフニウム系薄膜形成材料を用いて原子層制御成長方法により基板上にハフニウム系薄膜を形成することを特徴とするハフニウム系薄膜形成方法によって解決される。
【発明の効果】
【００２０】
本発明によれば、ハフニウム系薄膜が良好に形成できる。すなわち、ハフニウム系薄膜を形成する為の原料が安定性に富み、かつ、気化し易いことから、原料の安定供給が行え、高品質なハフニウム系薄膜が安定して形成される。
【図面の簡単な説明】
【００２１】
【図１】ＣｐＨｆ（ＮＭｅ２）３のＮＭＲスペクトル
【図２】ＣＶＤ装置の概略図
【図３】（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３のＮＭＲスペクトル
【図４】（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３のＮＭＲスペクトル
【図５】ＣｐＨｆ（ＮＭｅＥｔ）３のＮＭＲスペクトル
【図６】（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３のＴＧ−ＤＴＡチャート
【符号の説明】
【００２２】
１ 容器
２ 気化器
３ 加熱器
４ 基板
５ 分解反応炉
６ 加熱器
７ 真空ポンプ
【発明を実施するための最良の形態】
【００２３】
本発明になる新規化合物は下記の一般式［Ｉ］で表される化合物である。特に、下記の一般式［Ｉ］におけるＲ１，Ｒ２がメチル基またはエチル基の化合物である。中でも、ＣｐＨｆ（ＮＭｅ２）３，ＣｐＨｆ（ＮＭｅＥｔ）３である。
一般式［Ｉ］
ＣｐＨｆ（ＮＲ １ Ｒ ２ ） ３
（但し、Ｃｐはシクロペンタジエニル基、Ｒ１，Ｒ２はアルキル基であり、Ｒ１とＲ２とは互いに異なっていても同じであってもよい。）
【００２４】
上記化合物は、特に、ハフニウム系薄膜形成材料として用いられる。中でも、化学気相成長方法や原子層制御成長方法によってハフニウム系薄膜を形成する為の材料として用いられる。上記一般式［Ｉ］で表される化合物がハフニウム系薄膜形成材料として用いられる場合、該化合物化合物は、単独、又は該化合物を溶解する溶媒との混合物の形態で用いられることが好ましい。即ち、溶液（溶質（一般式［Ｉ］）＋溶媒）形態のものである。溶媒は、好ましくは炭素数５〜４０（特に、５〜１５）の炭化水素系化合物及び炭素数２〜４０（特に、２〜２０）のアミン系化合物の群の中から選ばれる一つ又は二つ以上の化合物である。中でも、好ましいのは、炭化水素系の溶媒では、例えばノルマルデカン、ノルマルヘプタン、ノルマルヘキサン、テトラデカン、キシレン、トルエンが挙げられ、又、アミン系の溶媒では、例えばトリエチルアミン、ビス（トリメチルシリル）アミン、ジエチルアミン、ピリジンが挙げられる。溶媒の量は、一般式［Ｉ］で表される化合物１００質量部に対して溶媒が１〜１００００質量部、特に１００〜２０００質量部が好ましい。すなわち、斯かる溶媒を用いることによって材料の供給がスムーズに行われる。尚、ＣｐＨｆ（ＮＭｅ２）３，（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３，（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３，ＣｐＨｆ（ＮＭｅＥｔ）３等の化合物が最も好ましいのは、これ等の化合物により形成されたハフニウム系薄膜の膜質が優れていたからによる。
【００２５】
本発明になるハフニウム系薄膜形成方法は、上記のハフニウム系薄膜形成材料（上記一般式［Ｉ］で表される化合物、又は上記一般式［Ｉ］で表される化合物を含む溶液）を用い、化学気相成長方法により基板上にハフニウム系薄膜を形成する方法である。或いは、上記のハフニウム系薄膜形成材料（上記一般式［Ｉ］で表される化合物、又は上記一般式［Ｉ］で表される化合物を含む溶液）を用い、原子層制御成長方法により基板上にハフニウム系薄膜を形成する方法である。
【００２６】
尚、本発明において、ハフニウム系薄膜とは、Ｈｆ膜の他にも、例えば酸化ハフニウム膜が有る。このような膜は、本発明になるハフニウム系薄膜形成材料を成膜するに際して、酸化剤の環境下で行うことによって得られる。又、オゾンガスを併用することによっても得られる。そして、成膜時の環境（ガス）によってハフニウム系薄膜の組成が適宜決まる。例えば、窒化雰囲気下で成膜が行われると、窒化ハフニウム薄膜が出来る。
【００２７】
以下、具体的実施例を挙げて説明する。
【実施例１】
【００２８】
〔新規化合物ＣｐＨｆ（ＮＭｅ２）３の合成〕
２９ｇのテトラキス（ジメチルアミノ）ハフニウムと、５．３ｇのシクロペンタジエンとを７０ｍＬのベンゼン中で、窒素雰囲気下において、１時間掛けて攪拌した。この溶液を２時間掛けて加熱還流した後、ベンゼンを減圧留去した。残った黄色液体を７０〜８０℃で０．１Ｔｏｒｒの減圧蒸留し、２５ｇの黄色液体を得た。
この黄色液体は、沸点が７５℃／０．２Ｔｏｒｒの液体であった。
又、ＮＭＲで測定した結果、スペクトルは以下の共鳴線を示した。
1Ｈ−ＮＭＲ（Ｃ６Ｄ６）：３．０（ｓ、１８Ｈ），６．０（ｓ、５Ｈ）
尚、図１はシクロペンタジエニルトリス（ジメチルアミノ）ハフニウムのＮＭＲスペクトルである。
そして、上記反応形態およびＮＭＲスペクトルから、得られた黄色液体はシクロペンタジエニルトリス（ジメチルアミノ）ハフニウム［ＣｐＨｆ（ＮＭｅ２）３］であることが判った。
【００２９】
次に、１５０ｇのＣｐＨｆ（ＮＭｅ２）3を容器中に入れて１００℃に加熱すると共に、アルゴンガス（キャリアーガス）を５００ｍｌ／分の割合で供給した。気化したＣｐＨｆ（ＮＭｅ２）３は、キャリアーガスと共に加熱配管（加熱温度は１００℃，１２０℃，１５０℃）を経て、回収装置に回収された。尚、この時、系内は真空に排気されている。
このようにして回収されたＣｐＨｆ（ＮＭｅ２）３のＮＭＲスペクトルを測定し、各温度における分解物量を確認した。その結果、１００℃，１２０℃及び１５０℃の全ての温度において、分解物量は０であった。すなわち、ＣｐＨｆ（ＮＭｅ２）３は安定性に富んだものであることが判った。
又、ＣｐＨｆ（ＮＭｅ２）３のＴＧ−ＤＴＡを測定した処、気化率は８８．６％であった。すなわち、高い気化率であることから、気化し易い材料であり、Ｈｆ系薄膜を形成するのに好適な材料であることが判った。
【００３０】
〔Ｈｆ系薄膜の形成〕
図２は、Ｈｆ系薄膜を成膜する為の装置の概略図である。
図２中、１は容器、２は気化器、３は加熱器、４は基板、５は分解反応炉、６は加熱器、７は真空ポンプである。
そして、図２の装置を用いて基板５上にＨｆ系薄膜を作製した。
すなわち、容器１内にＣｐＨｆ（ＮＭｅ２）３を入れて、窒素ガス（圧送ガス）を０．１ｇ／分の割合で供給した。圧送されたＣｐＨｆ（ＮＭｅ２）３は気化器３で気化され、分解反応炉５に導かれた。気化器３及び配管は加熱器６にて１２０〜１３０℃に加温されている。尚、この時、系内は真空に排気されている。又、基板４は４００℃に加熱されている。その結果、基板４上に膜が形成された。
上記のようにして形成された膜は、面内均一性に優れたものであった。
又、ＩＣＰ−ＭＳで調べた結果、Ｈｆ薄膜であることが確認された。
【参考例１】
【００３１】
〔新規化合物（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３の合成〕
１０ｇのテトラキス（ジメチルアミノ）ハフニウムと、２ｇのメチルシクロペンタジエンとを３５ｍＬのベンゼン中で、窒素雰囲気下において、１時間掛けて攪拌した。この溶液を２時間掛けて加熱還流した後、ベンゼンを減圧留去した。残った黄色液体を７０〜８０℃で０．１Ｔｏｒｒの減圧蒸留し、１１ｇの黄色液体を得た。
この黄色液体は、沸点が７２℃／０．１Ｔｏｒｒの液体であった。
又、ＮＭＲで測定した結果、スペクトルは以下の共鳴線を示した。
1Ｈ−ＮＭＲ（Ｃ６Ｄ６）：２．１（ｓ、３Ｈ），３．０（ｓ、１８Ｈ），５．８（ｍ、２Ｈ），５．９（ｍ、２Ｈ）
尚、図３はメチルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウムのＮＭＲスペクトルである。
そして、上記反応形態およびＮＭＲスペクトルから、得られた黄色液体はメチルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウム［（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３］であることが判った。
【００３２】
次に、１５０ｇの（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３を容器中に入れて１００℃に加熱すると共に、アルゴンガス（キャリアーガス）を５００ｍｌ／分の割合で供給した。気化した（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３は、キャリアーガスと共に加熱配管（加熱温度は１００℃，１２０℃，１５０℃）を経て、回収装置に回収された。尚、この時、系内は真空に排気されている。
このようにして回収された（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３のＮＭＲスペクトルを測定し、各温度における分解物量を確認した。その結果、１００℃，１２０℃及び１５０℃の全ての温度において、分解物量は０であった。すなわち、（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３は安定性に富んだものであることが判った。
又、（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３のＴＧ−ＤＴＡを測定した処、気化率が９７．３％であった。すなわち、高い気化率であることから、気化し易い材料であり、Ｈｆ系薄膜を形成するのに好適な材料であることが判る。尚、図６は（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３のＴＧ−ＤＴＡチャートである。
【００３３】
〔Ｈｆ系薄膜の形成〕
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに（ＭｅＣｐ）Ｈｆ（ＮＭｅ２）３を用いて同様に行い、基板４上に膜を形成した。
【参考例２】
【００３４】
〔新規化合物（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３の合成〕
２５ｇのテトラキス（ジメチルアミノ）ハフニウムと、７ｇのエチルシクロペンタジエンとを６０ｍＬのベンゼン中で、窒素雰囲気下において、１時間掛けて攪拌した。この溶液を２時間掛けて加熱還流した後、ベンゼンを減圧留去した。残った黄色液体を７０〜８０℃で０．１Ｔｏｒｒの減圧蒸留し、１９ｇの黄色液体を得た。
この黄色液体は、沸点が７８℃／０．２Ｔｏｒｒの液体であった。
又、ＮＭＲで測定した結果、スペクトルは以下の共鳴線を示した。
1Ｈ−ＮＭＲ（Ｃ６Ｄ６）：１．１（ｔ、３Ｈ），２．５（ｑ、２Ｈ），３．０（ｓ、１８Ｈ），５．９（ｍ、２Ｈ），６．０（ｍ、２Ｈ）
尚、図４はエチルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウムのＮＭＲスペクトルである。
そして、上記反応形態およびＮＭＲスペクトルから、得られた黄色液体はエチルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウム［（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３］であることが判った。
【００３５】
次に、１５０ｇの（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３を容器中に入れて１００℃に加熱すると共に、アルゴンガス（キャリアーガス）を５００ｍｌ／分の割合で供給した。気化した（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３は、キャリアーガスと共に加熱配管（加熱温度は１００℃，１２０℃，１５０℃）を経て、回収装置に回収された。尚、この時、系内は真空に排気されている。
このようにして回収された（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３のＮＭＲスペクトルを測定し、各温度における分解物量を確認した。その結果、１００℃，１２０℃及び１５０℃の全ての温度において、分解物量は０であった。すなわち、（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３は安定性に富んだものであることが判った。
又、（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３のＴＧ−ＤＴＡを測定した処、気化率は９４．８％であった。すなわち、高い気化率であることから、気化し易い材料であり、Ｈｆ系薄膜を形成するのに好適な材料であることが判った。
【００３６】
〔Ｈｆ系薄膜の形成〕
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに（ＥｔＣｐ）Ｈｆ（ＮＭｅ２）３を用いて同様に行い、基板４上に膜を形成した。
【実施例２】
【００３７】
〔新規化合物ＣｐＨｆ（ＮＭｅＥｔ）３の合成〕
６３ｇのテトラキス（メチルエチルアミノ）ハフニウムと、１０ｇのシクロペンタジエンとを１４０ｍＬのベンゼン中で、窒素雰囲気下において、１時間掛けて攪拌した。この溶液を２時間掛けて加熱還流した後、ベンゼンを減圧留去した。残った黄色液体を８０〜９０℃で０．１Ｔｏｒｒの減圧蒸留し、３６ｇの黄色液体を得た。
この黄色液体は、沸点が８５℃／０．２Ｔｏｒｒの液体であった。
又、ＮＭＲで測定した結果、スペクトルは以下の共鳴線を示した。
1Ｈ−ＮＭＲ（Ｃ６Ｄ６）：１．０（ｔ、９Ｈ），２．９（ｓ、９Ｈ），３．２（ｑ、６Ｈ），６．１（ｓ、５Ｈ）
尚、図５はシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウムのＮＭＲスペクトルである。
そして、上記反応形態およびＮＭＲスペクトルから、得られた黄色液体はシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウム［ＣｐＨｆ（ＮＭｅＥｔ）３］であることが判った。
【００３８】
次に、１５０ｇのＣｐＨｆ（ＮＭｅＥｔ）３を容器中に入れて１００℃に加熱すると共に、アルゴンガス（キャリアーガス）を５００ｍｌ／分の割合で供給した。気化したＣｐＨｆ（ＮＭｅＥｔ）３は、キャリアーガスと共に加熱配管（加熱温度は１００℃，１２０℃，１５０℃）を経て、回収装置に回収された。尚、この時、系内は真空に排気されている。
このようにして回収されたＣｐＨｆ（ＮＭｅＥｔ）３のＮＭＲスペクトルを測定し、各温度における分解物量を確認した。その結果、１００℃，１２０℃及び１５０℃の全ての温度において、分解物量は０であった。すなわち、ＣｐＨｆ（ＮＭｅＥｔ）3は安定性に富んだものであることが判った。
又、ＣｐＨｆ（ＮＭｅＥｔ）３のＴＧ−ＤＴＡを測定した処、気化率は９０．１％であった。すなわち、高い気化率であることから、気化し易い材料であり、Ｈｆ系薄膜を形成するのに好適な材料であることが判った。
【００３９】
〔Ｈｆ系薄膜の形成〕
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりにＣｐＨｆ（ＮＭｅＥｔ）３を用いて同様に行い、基板４上に膜を形成した。
このようにして得られた膜は、面内均一性に優れたものであった。又、ＩＣＰ−ＭＳで調べた結果、Ｈｆ薄膜であることが確認された。
【実施例３】
【００４０】
実施例１において、成膜に際して、溶媒としてノルマルデカンを用いた以外は同様に行った。その結果、基板４上に薄膜が形成された。
このようにして得られた膜は、面内均一性に優れたものであった。又、ＩＣＰ−ＭＳで調べた結果、Ｈｆ薄膜であることが確認された。
【実施例４】
【００４１】
実施例１においては化学気相成長方法によって成膜された場合であるが、実施例３においては原子層制御成長方法によって成膜が行われた。
その結果、面内均一性に優れたＨｆ薄膜が形成されていた。
【実施例８】
【００４３】
【実施例５】
【００４４】
実施例２においては化学気相成長方法によって成膜された場合であるが、実施例５においては原子層制御成長方法によって成膜が行われた。
その結果、面内均一性に優れたＨｆ薄膜が形成されていた。
【参考例３】
【００４５】
実施例１と同様に行い、イソプロピルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウムを得た。
そして、イソプロピルシクロペンタジエニルトリス（ジメチルアミノ）ハフニウムを用い、実施例１と同様に行って基板４上に膜を形成した。
このようにして得られた膜は、実施例１の膜に比べたならば劣るものの、面内均一性に優れたものであった。
【参考例４】
【００４６】
実施例１と同様に行い、イソプロピルシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウムを得た。
そして、イソプロピルシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウムを用い、実施例１と同様に行って基板４上に膜を形成した。
このようにして得られた膜は、実施例１の膜に比べたならば劣るものの、面内均一性に優れたものであった。
【参考例５】
【００４７】
実施例１と同様に行い、エチルシクロペンタジエニルトリス（ジエチルアミノ）ハフニウムを得た。
そして、エチルシクロペンタジエニルトリス（ジエチルアミノ）ハフニウムを用い、実施例１と同様に行って基板４上に膜を形成した。
このようにして得られた膜は、実施例１の膜に比べたならば劣るものの、面内均一性に優れたものであった。
【参考例６】
【００４８】
実施例１と同様に行い、イソプロピルシクロペンタジエニルトリス（ジエチルアミノ）ハフニウムを得た。
そして、イソプロピルシクロペンタジエニルトリス（ジエチルアミノ）ハフニウムを用い、実施例１と同様に行って基板４上に膜を形成した。
このようにして得られた膜は、実施例１の膜に比べたならば劣るものの、面内均一性に優れたものであった。
【参考例７】
【００４９】
実施例１と同様に行い、メチルシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウムを得た。
そして、メチルシクロペンタジエニルトリス（メチルエチルアミノ）ハフニウムを用い、実施例１と同様に行って基板４上に膜を形成した。
【比較例１】
【００５０】
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに、テトラキス（メチルエチルアミノ）ハフニウムを用いた以外は同様に行い、基板４上に膜を形成した。
このようにして得られた膜は、実施例１のものに比べて、面内均一性に劣るものであった。
【比較例２】
【００５１】
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに、テトラキス（エトキシ）ハフニウムを用いた以外は同様に行い、基板４上に膜を形成した。
このようにして得られた膜は、実施例１のものに比べて、面内均一性に劣るものであった。
【比較例３】
【００５２】
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに、テトラキス（β−ジケトン）ハフニウムを用いた以外は同様に行い、基板４上に膜を形成した。
このようにして得られた膜は、実施例１のものに比べて、面内均一性に劣るものであった。
【比較例４】
【００５３】
実施例１において、ＣｐＨｆ（ＮＭｅ２）３の代わりに、ＨｆＣｌ４を用いた以外は同様に行い、基板４上に膜を形成した。
このようにして得られた膜は、実施例１のものに比べて、面内均一性に劣るものであった。
【産業上の利用可能性】
【００５４】
ハフニウム系薄膜が用いられる分野、例えば半導体分野などにおいて特に有用である。【Technical field】
[0001]
The present invention relates to a hafnium-based thin film forming technique.
[Background]
[0002]
A hafnium-based thin film is formed by a chemical vapor deposition method or an atomic layer controlled growth method using tetrahalogenated hafnium, tetrakis (dialkylamino) hafnium, tetrakis (alkoxy) hafnium, or tetrakis (β-diketone) hafnium. It has been proposed.
[0003]
By the way, when forming the hafnium-based thin film, it is necessary to vaporize the compound. The compound is then heated for vaporization.
[0004]
However, tetrahalogenated hafnium and tetrakis (β-diketone) hafnium are solid. For this reason, vaporization is difficult and stable gas supply is difficult. That is, since it is difficult to stably supply raw materials, a high-quality hafnium-based thin film cannot be stably formed.
[0005]
Tetrakis (dialkylamino) hafnium has low thermal stability. Therefore, it decomposes when heated and vaporized. For this reason, it is difficult to supply a stable gas. That is, since it is difficult to stably supply raw materials, a high-quality hafnium-based thin film cannot be stably formed.
[0006]
Tetrakis (alkoxy) hafnium also has poor stability. For example, even if it is stored, it will be decomposed. For this reason, it is difficult to supply a stable gas. That is, since it is difficult to stably supply raw materials, a high-quality hafnium-based thin film cannot be stably formed.
[Patent Document 1]
JP-A-2005-298467
[Patent Document 2]
JP-A-2005-294421
[Patent Document 3]
JP 2004-137223 A
[Patent Document 4]
JP 2004-137222 A
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0007]
Therefore, the problem to be solved by the present invention is to solve the above-mentioned problems. In particular, the object is to provide a technique that is liquid at normal temperature and has high stability, can stably supply raw materials, and can stably form a high-quality hafnium-based thin film.
[Means for Solving the Problems]
[0008]
While studying to solve the above problems is eagerly pursued, the compound represented by LHf (NR 1 R 2 ) 3 is rich in stability, is easy to vaporize, and is chemical vapor deposition. We have found that high-quality hafnium-based thin films can be formed by this method and atomic layer controlled growth method.
[0009]
The present invention has been achieved based on the above findings.
[0010]
That is, the above problem is solved by a compound represented by the following general formula [I].
[0011]
In particular, it is solved by a compound characterized in that R 1 and R 2 in the general formula [I] are a methyl group or an ethyl group.
[0012]
Also, a material for forming a hafnium-based thin film,
This is solved by a hafnium-based thin film forming material characterized by being a compound represented by the following general formula [I].
[0013]
Also, a material for forming a hafnium-based thin film,
A compound represented by the following general formula [I]:
This is solved by a hafnium-based thin film forming material comprising a solvent for dissolving the compound.
[0014]
Formula [I]
CpHf (NR 1 R 2 ) 3
(However, Cp is a cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)
In particular, this is solved by the hafnium-based thin film forming material described above, wherein R 1 and R 2 are a methyl group or an ethyl group.
[0015]
Among them, the compound of the above general formula [I] is CpHf (NMe 2 ) 3 , CpHf (NMeEt) 3 [Cp = cyclopentadienyl group, Me = methyl group, Et = ethyl group] It is solved by the system thin film forming material.
[0016]
The hafnium-based thin film forming material is a hydrocarbon compound having 5 to 40 carbon atoms (particularly 15 or less) and an amine compound having 2 to 40 carbon atoms (particularly 20 or less). This is solved by a hafnium-based thin film forming material which is one or more compounds selected from the inside.
[0017]
The above-mentioned hafnium-based thin film forming material is a material for forming a hafnium-based thin film, in particular, by a chemical vapor deposition method or an atomic layer control growth method.
[0018]
In addition, the above-mentioned problem is solved by a hafnium-based thin film forming method characterized in that a hafnium-based thin film is formed on a substrate by a chemical vapor deposition method using the hafnium-based thin film forming material.
[0019]
Further, the above-mentioned problems are solved by a hafnium-based thin film forming method, characterized in that a hafnium-based thin film is formed on a substrate by an atomic layer controlled growth method using the hafnium-based thin film forming material.
【Effect of the invention】
[0020]
According to the present invention, a hafnium-based thin film can be formed satisfactorily. That is, since the raw material for forming the hafnium-based thin film has high stability and is easily vaporized, the raw material can be stably supplied, and a high-quality hafnium-based thin film can be stably formed.
[Brief description of the drawings]
[0021]
FIG. 1 NMR spectrum of CpHf (NMe 2 ) 3 FIG. 2 Schematic diagram of a CVD apparatus FIG. 3 NMR spectrum of (MeCp) Hf (NMe 2 ) 3 FIG. 4 (EtCp) Hf (NMe 2 ) 3 of NMR spectra [Figure 5] CPHF (NMeEt) 3 NMR spectrum 6 (MeCp) Hf (NMe 2) 3 of TG-DTA chart [description of symbols]
[0022]
1
[0023]
The novel compound according to the present invention is a compound represented by the following general formula [I]. In particular, R 1 and R 2 in the following general formula [I] are compounds having a methyl group or an ethyl group. Among them, CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 are used.
Formula [I]
CpHf (NR 1 R 2 ) 3
(However, Cp is a cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)
[0024]
The above compound is used particularly as a hafnium-based thin film forming material. Among them, it is used as a material for forming a hafnium-based thin film by a chemical vapor deposition method or an atomic layer control growth method. When the compound represented by the general formula [I] is used as a hafnium-based thin film forming material, the compound compound is preferably used alone or in the form of a mixture with a solvent that dissolves the compound. That is, it is in the form of a solution (solute (general formula [I]) + solvent). The solvent is preferably one or two selected from the group consisting of a hydrocarbon compound having 5 to 40 carbon atoms (particularly 5 to 15) and an amine compound having 2 to 40 carbon atoms (particularly 2 to 20 carbon atoms). One or more compounds. Among them, preferred are hydrocarbon-based solvents such as normal decane, normal heptane, normal hexane, tetradecane, xylene, and toluene, and amine-based solvents include, for example, triethylamine, bis (trimethylsilyl) amine, and diethylamine. And pyridine. The amount of the solvent is preferably 1 to 10,000 parts by mass, particularly preferably 100 to 2000 parts by mass with respect to 100 parts by mass of the compound represented by the general formula [I]. That is, by using such a solvent, the material can be supplied smoothly. The compounds such as CpHf (NMe 2 ) 3 , (MeCp) Hf (NMe 2 ) 3 , (EtCp) Hf (NMe 2 ) 3 , CpHf (NMeEt) 3 are most preferably formed by these compounds. This is because the quality of the hafnium-based thin film was excellent.
[0025]
The hafnium-based thin film forming method according to the present invention uses the above-mentioned hafnium-based thin film forming material (the compound represented by the general formula [I] or the solution containing the compound represented by the general formula [I]), In this method, a hafnium-based thin film is formed on a substrate by a chemical vapor deposition method. Alternatively, the above-mentioned hafnium-based thin film forming material (the compound represented by the above general formula [I] or the solution containing the compound represented by the above general formula [I]) is used on the substrate by the atomic layer controlled growth method. This is a method of forming a hafnium-based thin film.
[0026]
In the present invention, the hafnium-based thin film includes, for example, a hafnium oxide film in addition to the Hf film. Such a film can be obtained by forming the hafnium-based thin film forming material according to the present invention in an oxidizing agent environment. It can also be obtained by using ozone gas in combination. The composition of the hafnium-based thin film is appropriately determined depending on the environment (gas) during film formation. For example, when film formation is performed in a nitriding atmosphere, a hafnium nitride thin film can be formed.
[0027]
Hereinafter, specific examples will be described.
[Example 1]
[0028]
[Synthesis of Novel Compound CpHf (NMe 2 ) 3 ]
29 g of tetrakis (dimethylamino) hafnium and 5.3 g of cyclopentadiene were stirred in 70 mL of benzene for 1 hour in a nitrogen atmosphere. This solution was heated to reflux for 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure at 70 to 80 ° C. and 0.1 Torr to obtain 25 g of a yellow liquid.
This yellow liquid was a liquid having a boiling point of 75 ° C./0.2 Torr.
Moreover, as a result of measuring by NMR, the spectrum showed the following resonance lines.
1 H-NMR (C 6 D 6 ): 3.0 (s, 18H), 6.0 (s, 5H)
FIG. 1 is an NMR spectrum of cyclopentadienyltris (dimethylamino) hafnium.
Then, from the above reaction forms and NMR spectra, the resulting yellow liquid was found to be cyclopentadienyl tris (dimethylamino) hafnium [CpHf (NMe 2) 3] .
[0029]
Next, 150 g of CpHf (NMe 2 ) 3 was put in a container and heated to 100 ° C., and argon gas (carrier gas) was supplied at a rate of 500 ml / min. Vaporized CpHf (NMe 2 ) 3 was recovered together with the carrier gas through a heating pipe (heating temperatures: 100 ° C., 120 ° C., 150 ° C.) in a recovery device. At this time, the system is evacuated to a vacuum.
The NMR spectrum of CpHf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the amount of decomposition products was 0 at all temperatures of 100 ° C., 120 ° C., and 150 ° C. That is, it was found that CpHf (NMe 2 ) 3 is rich in stability.
Further, when TG-DTA of CpHf (NMe 2 ) 3 was measured, the vaporization rate was 88.6%. That is, since it has a high vaporization rate, it has been found that it is a material that is easily vaporized and a material that is suitable for forming an Hf-based thin film.
[0030]
[Formation of Hf-based thin film]
FIG. 2 is a schematic view of an apparatus for forming an Hf-based thin film.
In FIG. 2, 1 is a container, 2 is a vaporizer, 3 is a heater, 4 is a substrate, 5 is a decomposition reaction furnace, 6 is a heater, and 7 is a vacuum pump.
Then, an Hf-based thin film was produced on the
That is, CpHf (NMe 2 ) 3 was put in the
The film formed as described above was excellent in in-plane uniformity.
Moreover, as a result of examining by ICP-MS, it was confirmed that it was a Hf thin film.
[ Reference Example 1 ]
[0031]
[Synthesis of Novel Compound (MeCp) Hf (NMe 2 ) 3 ]
10 g of tetrakis (dimethylamino) hafnium and 2 g of methylcyclopentadiene were stirred in 35 mL of benzene for 1 hour in a nitrogen atmosphere. This solution was heated to reflux for 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure at 70 to 80 ° C. and 0.1 Torr to obtain 11 g of a yellow liquid.
This yellow liquid was a liquid having a boiling point of 72 ° C./0.1 Torr.
Moreover, as a result of measuring by NMR, the spectrum showed the following resonance lines.
1 H-NMR (C 6 D 6 ): 2.1 (s, 3H), 3.0 (s, 18H), 5.8 (m, 2H), 5.9 (m, 2H)
FIG. 3 is an NMR spectrum of methylcyclopentadienyltris (dimethylamino) hafnium.
Then, from the above reaction forms and NMR spectra, the resulting yellow liquid was found to be methyl cyclopentadienyl tris (dimethylamino) hafnium [(MeCp) Hf (NMe 2 ) 3].
[0032]
Next, 150 g of (MeCp) Hf (NMe 2 ) 3 was put in a container and heated to 100 ° C., and argon gas (carrier gas) was supplied at a rate of 500 ml / min. Vaporized (MeCp) Hf (NMe 2 ) 3 was recovered together with a carrier gas through a heating pipe (heating temperatures: 100 ° C., 120 ° C., 150 ° C.) in a recovery device. At this time, the system is evacuated to a vacuum.
The NMR spectrum of (MeCp) Hf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the amount of decomposition products was 0 at all temperatures of 100 ° C., 120 ° C., and 150 ° C. That is, it was found that (MeCp) Hf (NMe 2 ) 3 is rich in stability.
Further, when TG-DTA of (MeCp) Hf (NMe 2 ) 3 was measured, the vaporization rate was 97.3%. That is, since it has a high vaporization rate, it can be seen that it is a material that is easily vaporized and is a material that is suitable for forming an Hf-based thin film. FIG. 6 is a TG-DTA chart of (MeCp) Hf (NMe 2 ) 3 .
[0033]
[Formation of Hf-based thin film]
In Example 1, a film was formed on the
[ Reference Example 2 ]
[0034]
[Synthesis of Novel Compound (EtCp) Hf (NMe 2 ) 3 ]
25 g of tetrakis (dimethylamino) hafnium and 7 g of ethylcyclopentadiene were stirred in 60 mL of benzene for 1 hour in a nitrogen atmosphere. This solution was heated to reflux for 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure at 70 to 80 ° C. and 0.1 Torr to obtain 19 g of a yellow liquid.
This yellow liquid was a liquid having a boiling point of 78 ° C./0.2 Torr.
Moreover, as a result of measuring by NMR, the spectrum showed the following resonance lines.
1 H-NMR (C 6 D 6 ): 1.1 (t, 3H), 2.5 (q, 2H), 3.0 (s, 18H), 5.9 (m, 2H), 6.0 (M, 2H)
FIG. 4 is an NMR spectrum of ethylcyclopentadienyltris (dimethylamino) hafnium.
From the above reaction form and NMR spectrum, it was found that the obtained yellow liquid was ethylcyclopentadienyltris (dimethylamino) hafnium [(EtCp) Hf (NMe 2 ) 3 ].
[0035]
Next, 150 g of (EtCp) Hf (NMe 2 ) 3 was placed in a container and heated to 100 ° C., and argon gas (carrier gas) was supplied at a rate of 500 ml / min. Vaporized (EtCp) Hf (NMe 2 ) 3 was recovered together with the carrier gas through a heating pipe (heating temperatures: 100 ° C., 120 ° C., 150 ° C.) in a recovery device. At this time, the system is evacuated to a vacuum.
The NMR spectrum of (EtCp) Hf (NMe 2 ) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the amount of decomposition products was 0 at all temperatures of 100 ° C., 120 ° C., and 150 ° C. That is, it was found that (EtCp) Hf (NMe 2 ) 3 was rich in stability.
Further, when TG-DTA of (EtCp) Hf (NMe 2 ) 3 was measured, the vaporization rate was 94.8%. That is, since it has a high vaporization rate, it has been found that it is a material that is easily vaporized and a material that is suitable for forming an Hf-based thin film.
[0036]
[Formation of Hf-based thin film]
In Example 1, it carried out in a similar manner using the CpHf (NMe 2) 3 instead of (EtCp) Hf (NMe 2) 3, to form a film on the
[Example 2 ]
[0037]
[Synthesis of Novel Compound CpHf (NMeEt) 3 ]
63 g of tetrakis (methylethylamino) hafnium and 10 g of cyclopentadiene were stirred in 140 mL of benzene for 1 hour in a nitrogen atmosphere. This solution was heated to reflux for 2 hours, and then benzene was distilled off under reduced pressure. The remaining yellow liquid was distilled under reduced pressure at 80 to 90 ° C. and 0.1 Torr to obtain 36 g of a yellow liquid.
This yellow liquid was a liquid having a boiling point of 85 ° C./0.2 Torr.
Moreover, as a result of measuring by NMR, the spectrum showed the following resonance lines.
1 H-NMR (C 6 D 6 ): 1.0 (t, 9H), 2.9 (s, 9H), 3.2 (q, 6H), 6.1 (s, 5H)
FIG. 5 is an NMR spectrum of cyclopentadienyltris (methylethylamino) hafnium.
From the above reaction form and NMR spectrum, it was found that the obtained yellow liquid was cyclopentadienyltris (methylethylamino) hafnium [CpHf (NMeEt) 3 ].
[0038]
Next, 150 g of CpHf (NMeEt) 3 was put in a container and heated to 100 ° C., and argon gas (carrier gas) was supplied at a rate of 500 ml / min. Vaporized CpHf (NMeEt) 3 was recovered together with a carrier gas through a heating pipe (heating temperatures: 100 ° C., 120 ° C., 150 ° C.) in a recovery device. At this time, the system is evacuated to a vacuum.
The NMR spectrum of CpHf (NMeEt) 3 recovered in this way was measured, and the amount of decomposition products at each temperature was confirmed. As a result, the amount of decomposition products was 0 at all temperatures of 100 ° C., 120 ° C., and 150 ° C. That is, it was found that CpHf (NMeEt) 3 is rich in stability.
Further, when TG-DTA of CpHf (NMeEt) 3 was measured, the vaporization rate was 90.1%. That is, since it has a high vaporization rate, it has been found that it is a material that is easily vaporized and a material that is suitable for forming an Hf-based thin film.
[0039]
[Formation of Hf-based thin film]
A film was formed on the
The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of examining by ICP-MS, it was confirmed that it was a Hf thin film.
[Example 3 ]
[0040]
In Example 1, film formation was performed in the same manner except that normal decane was used as a solvent. As a result, a thin film was formed on the
The film thus obtained was excellent in in-plane uniformity. Moreover, as a result of examining by ICP-MS, it was confirmed that it was a Hf thin film.
[Example 4 ]
[0041]
In Example 1, the film was formed by the chemical vapor deposition method, but in Example 3, the film was formed by the atomic layer controlled growth method.
As a result, an Hf thin film excellent in in-plane uniformity was formed.
[Example 8]
[0043]
[Example 5 ]
[0044]
In Example 2 , the film was formed by the chemical vapor deposition method, but in Example 5 , the film was formed by the atomic layer controlled growth method.
As a result, an Hf thin film excellent in in-plane uniformity was formed.
[ Reference Example 3 ]
[0045]
In the same manner as in Example 1, isopropylcyclopentadienyltris (dimethylamino) hafnium was obtained.
Then, using isopropylcyclopentadienyltris (dimethylamino) hafnium, a film was formed on the
The film thus obtained was excellent in in-plane uniformity, although inferior to the film of Example 1.
[ Reference Example 4 ]
[0046]
In the same manner as in Example 1, isopropylcyclopentadienyltris (methylethylamino) hafnium was obtained.
A film was formed on the
The film thus obtained was excellent in in-plane uniformity, although inferior to the film of Example 1.
[ Reference Example 5 ]
[0047]
In the same manner as in Example 1, ethylcyclopentadienyltris (diethylamino) hafnium was obtained.
Then, a film was formed on the
The film thus obtained was excellent in in-plane uniformity, although inferior to the film of Example 1.
[ Reference Example 6 ]
[0048]
In the same manner as in Example 1, isopropylcyclopentadienyltris (diethylamino) hafnium was obtained.
A film was formed on the
The film thus obtained was excellent in in-plane uniformity, although inferior to the film of Example 1.
[ Reference Example 7 ]
[0049]
In the same manner as in Example 1, methylcyclopentadienyltris (methylethylamino) hafnium was obtained.
A film was formed on the
[Comparative Example 1]
[0050]
A film was formed on the
The film thus obtained was inferior in in-plane uniformity as compared with that of Example 1.
[Comparative Example 2]
[0051]
A film was formed on the
The film thus obtained was inferior in in-plane uniformity as compared with that of Example 1.
[Comparative Example 3]
[0052]
A film was formed on the
The film thus obtained was inferior in in-plane uniformity as compared with that of Example 1.
[Comparative Example 4]
[0053]
A film was formed on the
The film thus obtained was inferior in in-plane uniformity as compared with that of Example 1.
[Industrial applicability]
[0054]
This is particularly useful in a field where a hafnium-based thin film is used, such as a semiconductor field.
Claims (17)
下記の一般式［Ｉ］で表される化合物である
ことを特徴とするハフニウム系薄膜形成材料。
一般式［Ｉ］
ＣｐＨｆ（ＮＲ １ Ｒ ２ ） ３
（但し、Ｃｐはシクロペンタジエニル基、Ｒ１，Ｒ２はアルキル基であり、Ｒ１とＲ２とは互いに異なっていても同じであってもよい。）A material for forming a hafnium-based thin film,
A hafnium-based thin film forming material, which is a compound represented by the following general formula [I].
Formula [I]
CpHf (NR 1 R 2 ) 3
(However, Cp is a cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)
ことを特徴とする請求項１のハフニウム系薄膜形成材料。 2. The hafnium-based thin film forming material according to claim 1 , wherein R 1 and R 2 in the general formula [I] are a methyl group or an ethyl group.
ことを特徴とする請求項１のハフニウム系薄膜形成材料。The compound represented by the general formula [I] is selected from the group consisting of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 [where Cp = cyclopentadienyl group, Me = methyl group, Et = ethyl group]. The hafnium-based thin film forming material according to claim 1, which is any one selected.
ことを特徴とする請求項１のハフニウム系薄膜形成材料。2. The hafnium-based thin film forming material according to claim 1, further comprising a solvent that dissolves the compound represented by the general formula [I] in addition to the compound represented by the general formula [I].
ことを特徴とする請求項４のハフニウム系薄膜形成材料。The hafnium-based compound according to claim 4, wherein the solvent is one or two or more compounds selected from the group consisting of a hydrocarbon compound having 5 to 40 carbon atoms and an amine compound having 2 to 40 carbon atoms. Thin film forming material.
ことを特徴とする請求項１のハフニウム系薄膜形成材料。2. The hafnium-based thin film forming material according to claim 1, which is a material for forming a hafnium-based thin film by a chemical vapor deposition method.
ことを特徴とする請求項１のハフニウム系薄膜形成材料。2. The hafnium-based thin film forming material according to claim 1, which is a material for forming a hafnium-based thin film by an atomic layer controlled growth method.
下記の一般式［Ｉ］で表される化合物が用いられる
ことを特徴とするハフニウム系薄膜形成方法。
一般式［Ｉ］
ＣｐＨｆ（ＮＲ １ Ｒ ２ ） ３
（但し、Ｃｐはシクロペンタジエニル基、Ｒ１，Ｒ２はアルキル基であり、Ｒ１とＲ２とは互いに異なっていても同じであってもよい。）A method of forming a hafnium-based thin film on a substrate by a chemical vapor deposition method,
A method for forming a hafnium-based thin film, wherein a compound represented by the following general formula [I] is used.
Formula [I]
CpHf (NR 1 R 2 ) 3
(However, Cp is a cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)
ことを特徴とする請求項８のハフニウム系薄膜形成方法。9. The method of forming a hafnium-based thin film according to claim 8, wherein R 1 and R 2 in the general formula [I] are a methyl group or an ethyl group.
ことを特徴とする請求項８のハフニウム系薄膜形成方法。The compound represented by the general formula [I] is selected from the group consisting of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 [where Cp = cyclopentadienyl group, Me = methyl group, Et = ethyl group]. 9. The method for forming a hafnium-based thin film according to claim 8, which is any one selected.
ことを特徴とする請求項８のハフニウム系薄膜形成方法。9. The hafnium-based thin film forming method according to claim 8, wherein a solution in which the compound represented by the general formula [I] is dissolved in a solvent is used.
ことを特徴とする請求項１１のハフニウム系薄膜形成方法。The hafnium-based compound according to claim 11, wherein the solvent is one or two or more compounds selected from the group consisting of a hydrocarbon compound having 5 to 40 carbon atoms and an amine compound having 2 to 40 carbon atoms. Thin film forming method.
下記の一般式［Ｉ］で表される化合物が用いられる
ことを特徴とするハフニウム系薄膜形成方法。
一般式［Ｉ］
ＣｐＨｆ（ＮＲ １ Ｒ ２ ） ３
（但し、Ｃｐはシクロペンタジエニル基、Ｒ１，Ｒ２はアルキル基であり、Ｒ１とＲ２とは互いに異なっていても同じであってもよい。）A method of forming a hafnium-based thin film on a substrate by an atomic layer controlled growth method,
A method for forming a hafnium-based thin film, wherein a compound represented by the following general formula [I] is used.
Formula [I]
CpHf (NR 1 R 2 ) 3
(However, Cp is a cyclopentadienyl group, R 1 and R 2 are alkyl groups, and R 1 and R 2 may be different or the same.)
ことを特徴とする請求項１３のハフニウム系薄膜形成方法。The compound represented by the general formula [I] is selected from the group consisting of CpHf (NMe 2 ) 3 and CpHf (NMeEt) 3 [where Cp = cyclopentadienyl group, Me = methyl group, Et = ethyl group]. The hafnium-based thin film forming method according to claim 13, which is selected.
ことを特徴とする請求項１３のハフニウム系薄膜形成方法。14. The hafnium-based thin film forming method according to claim 13, wherein a solution in which the compound represented by the general formula [I] is dissolved in a solvent is used.
ことを特徴とする請求項１６のハフニウム系薄膜形成方法。The hafnium-based compound according to claim 16, wherein the solvent is one or two or more compounds selected from the group consisting of a hydrocarbon compound having 5 to 40 carbon atoms and an amine compound having 2 to 40 carbon atoms. Thin film forming method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007549083A JP5128289B2 (en) | 2005-12-06 | 2006-11-29 | Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005351450 | 2005-12-06 | ||
| JP2005351450 | 2005-12-06 | ||
| JP2007549083A JP5128289B2 (en) | 2005-12-06 | 2006-11-29 | Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method |
| 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 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012219892A Division JP5548748B2 (en) | 2005-12-06 | 2012-10-01 | Hafnium-based thin film forming method and hafnium-based thin film forming material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2007066546A1 JPWO2007066546A1 (en) | 2009-05-14 |
| JP5128289B2 true JP5128289B2 (en) | 2013-01-23 |
Family
ID=38122694
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007549083A Active JP5128289B2 (en) | 2005-12-06 | 2006-11-29 | Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method |
| JP2012219892A Active JP5548748B2 (en) | 2005-12-06 | 2012-10-01 | Hafnium-based thin film forming method and hafnium-based thin film forming material |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012219892A Active JP5548748B2 (en) | 2005-12-06 | 2012-10-01 | Hafnium-based thin film forming method and hafnium-based thin film forming material |
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) |
Families Citing this family (17)
| 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 |
| WO2007140813A1 (en) * | 2006-06-02 | 2007-12-13 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes 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 |
| US8221852B2 (en) * | 2007-09-14 | 2012-07-17 | Sigma-Aldrich Co. Llc | Methods of atomic layer deposition using titanium-based precursors |
| EP2191034B1 (en) * | 2007-09-14 | 2013-03-13 | Sigma-Aldrich Co. LLC | Methods of preparing thin films by atomic layer deposition using monocyclopentadienyl triamino zirconium precursors |
| EP2464652A4 (en) * | 2009-08-14 | 2013-01-09 | Air Liquide | Hafnium- and zirconium-containing precursors and methods of using the same |
| EP2499274B1 (en) | 2009-11-09 | 2016-04-20 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Deposition methods using hafnium-containing compounds |
| TW201402586A (en) * | 2012-05-25 | 2014-01-16 | Air Liquide | Hafnium-containing precursors for vapor deposition |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| KR20240031321A (en) * | 2021-07-07 | 2024-03-07 | 가부시키가이샤 아데카 | Compounds, raw materials for forming thin films, thin films and methods for producing thin films |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229146A (en) * | 1997-08-21 | 1999-08-24 | Gfe Metalle & Materialien Gmbh | Composite material |
| 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 |
| JP2002069641A (en) * | 2000-06-12 | 2002-03-08 | Asahi Denka Kogyo Kk | Raw material for chemical vapor deposition and method for producing thin film using the same |
| JP2002167672A (en) * | 2000-11-30 | 2002-06-11 | Nec Corp | Film deposition method |
| 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 |
| JP2005026698A (en) * | 2003-07-03 | 2005-01-27 | Samsung Electronics Co Ltd | Organic tft including gate insulating film of multilayer structure |
| JP2005171291A (en) * | 2003-12-09 | 2005-06-30 | Tosoh Corp | Titanium-containing thin film and production method therefor |
| JP2005210094A (en) * | 2003-12-25 | 2005-08-04 | Tdk Corp | Rare earth magnet |
Family Cites Families (5)
| 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 |
| JP2003020305A (en) * | 2001-07-10 | 2003-01-24 | Sumitomo Chem Co Ltd | Catalyst for olefin polymerization |
| US20040168627A1 (en) * | 2003-02-27 | 2004-09-02 | Sharp Laboratories Of America, Inc. | Atomic layer deposition of oxide film |
| 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 KR KR1020087008011A patent/KR101367827B1/en active IP Right Review Request
- 2006-11-29 JP JP2007549083A patent/JP5128289B2/en active Active
- 2006-11-30 TW TW095144383A patent/TWI415855B/en active
-
2012
- 2012-10-01 JP JP2012219892A patent/JP5548748B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11229146A (en) * | 1997-08-21 | 1999-08-24 | Gfe Metalle & Materialien Gmbh | Composite material |
| JP2002069641A (en) * | 2000-06-12 | 2002-03-08 | Asahi Denka Kogyo Kk | 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 |
| JP2002167672A (en) * | 2000-11-30 | 2002-06-11 | Nec Corp | Film deposition method |
| 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 |
| JP2005026698A (en) * | 2003-07-03 | 2005-01-27 | Samsung Electronics Co Ltd | Organic tft including gate insulating film of multilayer structure |
| JP2005171291A (en) * | 2003-12-09 | 2005-06-30 | Tosoh Corp | Titanium-containing thin film and production method therefor |
| JP2005210094A (en) * | 2003-12-25 | 2005-08-04 | Tdk Corp | Rare earth magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101341155B (en) | 2012-03-07 |
| CN101341155A (en) | 2009-01-07 |
| JP5548748B2 (en) | 2014-07-16 |
| JPWO2007066546A1 (en) | 2009-05-14 |
| KR101367827B1 (en) | 2014-02-26 |
| TWI415855B (en) | 2013-11-21 |
| WO2007066546A1 (en) | 2007-06-14 |
| JP2013047391A (en) | 2013-03-07 |
| TW200728311A (en) | 2007-08-01 |
| KR20080077086A (en) | 2008-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5128289B2 (en) | Hafnium-based compound, hafnium-based thin film forming material, and hafnium-based thin film forming method | |
| KR101659725B1 (en) | Volatile dihydropyrazinyl and dihydropyrazine metal complexes | |
| EP2609102B1 (en) | Molybdenum (iv) amide precursors and use thereof in atomic layer deposition | |
| JP6596737B2 (en) | Metal complexes containing amidoimine ligands | |
| JP5161787B2 (en) | Cyclopentadienyl-type hafnium and zirconium precursors and their use in atomic layer deposition | |
| EP2644741B1 (en) | Methods of preparing titanium containing thin films by atomic layer deposition using monocyclopentadienyl titanium-based precursors | |
| US9045509B2 (en) | Hafnium- and zirconium-containing precursors and methods of using the same | |
| JP2010539710A (en) | Thin film preparation method by atomic layer growth using hafnium precursor and zirconium precursor | |
| US9121093B2 (en) | Bis-ketoiminate copper precursors for deposition of copper-containing films and methods thereof | |
| KR102327450B1 (en) | group Ⅳ transition metal compounds, method for their preparation, and composition for thin film deposition containing them | |
| KR102286114B1 (en) | Group iv transition metal compounds, preparation method thereof and process for the formation of thin films using the same | |
| JP4289141B2 (en) | ORGANIC SILICON COMPOUND, SOLUTION RAW MATERIAL, AND METHOD FOR FORMING SILICON-CONTAINING FILM USING THE COMPOUND | |
| KR20220113029A (en) | Group iv transition metal compounds, preparation method thereof and process for the formation of thin films using the same | |
| KR20150059129A (en) | Organo group 14 metalloid azide compounds and method of thin film deposition using them as precursors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090918 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090918 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120704 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120830 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20121003 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20121031 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5128289 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151109 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |