JP2009030164A - Raw material for forming strontium-containing thin film and method for preparing the same - Google Patents
Raw material for forming strontium-containing thin film and method for preparing the same Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002994 raw material Substances 0.000 title claims abstract description 33
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 28
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010409 thin film Substances 0.000 title claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 80
- 239000011734 sodium Substances 0.000 claims description 31
- 229910052700 potassium Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- IVNADBQFJRZIME-UHFFFAOYSA-N C(CC)C1=C(C(=C(C1(C)[K])C)C)C Chemical compound C(CC)C1=C(C(=C(C1(C)[K])C)C)C IVNADBQFJRZIME-UHFFFAOYSA-N 0.000 claims description 2
- XNPJIZMEHOBUHM-UHFFFAOYSA-N C(CC)C1=C(C(=C(C1(C)[Na])C)C)C Chemical compound C(CC)C1=C(C(=C(C1(C)[Na])C)C)C XNPJIZMEHOBUHM-UHFFFAOYSA-N 0.000 claims description 2
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 claims description 2
- VXNUMUQPEDLJKC-UHFFFAOYSA-N C(CC)C1=C(C(=C(C1(C)[Sr]C1(C(=C(C(=C1CCC)C)C)C)C)C)C)C Chemical compound C(CC)C1=C(C(=C(C1(C)[Sr]C1(C(=C(C(=C1CCC)C)C)C)C)C)C)C VXNUMUQPEDLJKC-UHFFFAOYSA-N 0.000 claims 3
- 229910001643 strontium iodide Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 27
- 150000003438 strontium compounds Chemical class 0.000 abstract description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 64
- 238000010926 purge Methods 0.000 description 52
- 239000000047 product Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 36
- 238000000231 atomic layer deposition Methods 0.000 description 28
- 239000010936 titanium Substances 0.000 description 25
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 24
- 229910002367 SrTiO Inorganic materials 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000005259 measurement Methods 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910004121 SrRuO Inorganic materials 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000859 sublimation Methods 0.000 description 6
- 230000008022 sublimation Effects 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- SQGUQDKNIMNMLY-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-propylcyclopenta-1,3-diene Chemical compound CCCC1C(C)=C(C)C(C)=C1C SQGUQDKNIMNMLY-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- -1 ether compound Chemical class 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- 208000035404 Autolysis Diseases 0.000 description 1
- NLZDQVUUTOVSHH-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Sr]C1(C(=C(C(=C1C)C)C)C)C)C)C)C Chemical compound CC1=C(C(=C(C1(C)[Sr]C1(C(=C(C(=C1C)C)C)C)C)C)C)C NLZDQVUUTOVSHH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010057248 Cell death Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000673 Indium arsenide Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- KQTKYCXEDDECIZ-UHFFFAOYSA-N ethylarsenic Chemical compound CC[As] KQTKYCXEDDECIZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 230000028043 self proteolysis Effects 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- ZEGFMFQPWDMMEP-UHFFFAOYSA-N strontium;sulfide Chemical compound [S-2].[Sr+2] ZEGFMFQPWDMMEP-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、化学気相成長法（Chemical Vapor Deposition法；以下、ＣＶＤ法と表す）や原子層堆積法（Atomic Layer Deposition法；以下、ＡＬＤ法と表す）により、酸化ストロンチウムや硫化ストロンチウム含有膜を形成するのに好適な原料化合物およびその製造方法ならびにストロンチウム含有薄膜の形成方法に関する。 In the present invention, a strontium oxide or strontium sulfide-containing film is formed by a chemical vapor deposition method (Chemical Vapor Deposition method; hereinafter referred to as a CVD method) or an atomic layer deposition method (hereinafter referred to as an ALD method). The present invention relates to a raw material compound suitable for formation, a production method thereof, and a formation method of a strontium-containing thin film.
ＣＶＤ法やＡＬＤ法による高誘電率のＳｒＴｉＯ3、ＳｒＢｉ2Ｔａ2Ｏ9、ＳｒＢｉ4Ｔｉ4Ｏ15等の膜は、高集積半導体装置の誘電体として期待されている。また、強誘電体膜の電極として、ＳｒＲｕＯ3膜が検討されている。
従来、これらのストロンチウムを含有する膜をＣＶＤ法やＡＬＤ法で形成する際の原料としては、ビス（ジピバロイルメタナト）ストロンチウム（Ｓｒ（Ｃ11Ｈ19Ｏ2）2；以下、Ｓｒ（ｄｐｍ）2と表す）が主に検討されてきた。
High dielectric constant films such as SrTiO 3 , SrBi 2 Ta 2 O 9 , and SrBi 4 Ti 4 O 15 by CVD or ALD are expected as dielectrics for highly integrated semiconductor devices. In addition, a SrRuO 3 film has been studied as a ferroelectric film electrode.
Conventionally, as a raw material for forming these strontium-containing films by a CVD method or an ALD method, bis (dipivaloylmethanato) strontium (Sr (C 11 H 19 O 2 ) 2 ; hereinafter referred to as Sr (dpm) ) 2 )) has been mainly studied.
しかしながら、Ｓｒ（ｄｐｍ）2は、三量体に会合しているため、蒸気圧が０．１Ｔｏｒｒ／２３１℃と非常に低く、供給上の課題を有している。
また、２３０℃以上になると熱分解が始まるため、ＡＬＤ法で成膜する場合、望ましい自己律速成長のみならず、制御困難な熱分解が同時に起きるという問題を有していた。
However, since Sr (dpm) 2 is associated with a trimer, its vapor pressure is as low as 0.1 Torr / 231 ° C., which has a supply problem.
In addition, since thermal decomposition starts at 230 ° C. or higher, when forming a film by the ALD method, there is a problem that not only desirable self-controlled growth but also thermal decomposition that is difficult to control occurs simultaneously.
したがって、より蒸気圧が高く、また、酸化剤との反応性が高く、かつ、熱安定性の高い有機ストロンチウム化合物が求められている。 Therefore, an organic strontium compound having a higher vapor pressure, higher reactivity with an oxidant, and higher thermal stability is desired.
その候補としては、例えば、公知化合物であるビス（ペンタメチルシクロペンタジエニル）ストロンチウム（Ｓｒ［Ｃ5（ＣＨ3）5］2；以下、ＳｒＣｐ* 2と表す）が挙げられる。ここで、ＳｒＣｐ* 2は、ジエチルエーテル（（Ｃ2Ｈ5）2Ｏ；以下、Ｅｔ2Ｏと表す。）やテトラヒドロフラン（Ｃ4Ｈ8Ｏ；以下、ＴＨＦと表す）等が配位した付加体ではない。 Examples of the candidate include bis (pentamethylcyclopentadienyl) strontium (Sr [C 5 (CH 3 ) 5 ] 2 ; hereinafter referred to as SrCp * 2 ), which is a known compound. Here, SrCp * 2 is an addition coordinated by diethyl ether ((C 2 H 5 ) 2 O; hereinafter referred to as Et 2 O), tetrahydrofuran (C 4 H 8 O; hereinafter referred to as THF) or the like. Not the body.
前記付加体は、熱安定性が低く、加熱とともに付加物を放出し、かつ、熱変質するため、安定した蒸気圧とならない。また、酸素原子を付加体に含んでいるため、自己分解により酸素が供給される可能性があり、ＡＬＤ法の原料としては好ましくない。 The adduct is low in thermal stability, releases an adduct with heating, and undergoes thermal alteration, and therefore does not have a stable vapor pressure. In addition, since an oxygen atom is included in the adduct, oxygen may be supplied by autolysis, which is not preferable as a raw material for the ALD method.
これに対して、付加体でないＳｒＣｐ* 2は、単量体であるため、有機ストロンチウム化合物の中では、蒸気圧が最も高いものの１つであり、また、酸化剤の水とも瞬時に反応するというＡＬＤ法の原料として好ましい性質を有している。また、５個のメチル基の影響により、有機溶媒に溶解しやすいという長所も有している。 On the other hand, since SrCp * 2 which is not an adduct is a monomer, it is one of the highest vapor pressures among organic strontium compounds, and also reacts instantly with the oxidant water. It has desirable properties as a raw material for the ALD method. In addition, it has an advantage of being easily dissolved in an organic solvent due to the influence of five methyl groups.
そこで、本発明者らは、特願２００６−３３０３５９において、ＳｒＣｐ* 2の製造方法を提案した。
しかしながら、ＳｒＣｐ* 2は、融点２０７℃であり、室温で固体であることから、上記製造方法においては、昇華操作により最終精製を行う必要があった。また、極微量の酸素、水分で変質する固体であることから、取り扱いにおいては、高価な設備と細心の操作が必要であった。
Therefore, the present inventors have proposed a method for producing SrCp * 2 in Japanese Patent Application No. 2006-330359.
However, since SrCp * 2 has a melting point of 207 ° C. and is solid at room temperature, it was necessary to perform final purification by sublimation operation in the above production method. In addition, since it is a solid that is altered by a very small amount of oxygen and moisture, expensive equipment and meticulous operation are required for handling.
したがって、精製効率が高い蒸留精製を行うことができ、また、不活性雰囲気での取扱いを容易にするためには、室温〜５０℃の温度で液体状態である化合物が求められる。
すなわち、酸素および水分に活性なシクロペンタジエニル基を有するストロンチウム化合物であって、エーテル類が付加しておらず、単量体で蒸気圧が高く、量産しやすい基を有する液体化合物が求められている。
Therefore, a compound that is in a liquid state at room temperature to 50 ° C. is required in order to perform distillation purification with high purification efficiency and to facilitate handling in an inert atmosphere.
That is, there is a need for a strontium compound having a cyclopentadienyl group that is active against oxygen and moisture, having no ethers added, a monomer, a high vapor pressure, and a group that is easily mass-produced. ing.
ところで、上述したＳｒ（ｄｐｍ）2等のβ−ジケトン系ストロンチウム錯体は、原料に金属Ｓｒを用いて合成されるが、金属Ｓｒ中には数ｐｐｍのＮａやＫが含まれており、粗製合成物中にも数ｐｐｍのＮａおよびＫが含まれる。
また、ＳｒＣｐ* 2等のシクロペンタジエニル系ストロンチウム化合物は、ＮａＣ5（ＣＨ3）5（以下、ＮａＣｐ*と表す）やＫＣ5（ＣＨ3）5（以下、ＫＣｐ*と表す）等のアルカリ金属化合物を原料に用いて合成されるため、粗製合成物中には多量のＮａまたはＫが含まれる。
これらのβ−ジケトン系ストロンチウム錯体およびＳｒＣｐ* 2は、室温付近での性状が固体であるため、蒸留による精製が難しく、原料由来のＮａやＫを効率よく除去することが難しい。
したがって、従来は、ストロンチウム含有薄膜形成用原料において、ＮａおよびＫの各含量を５０ｐｐｂ以下で得ることは困難であり、ＣＶＤやＡＬＤに適用可能なＮａおよびＫの各含量が５０ｐｐｂ以下のストロンチウム含有薄膜形成用原料はなかった。
By the way, the β-diketone strontium complex such as Sr (dpm) 2 described above is synthesized using a metal Sr as a raw material, but the metal Sr contains several ppm of Na and K, and thus is a crude synthesis. Several ppm of Na and K are also contained in the product.
Furthermore, the cyclopentadienyl system strontium compounds such SrCp * 2 is, NaC 5 (CH 3) 5 ( hereinafter, NaCp * represent) and KC 5 (CH 3) 5 (hereinafter referred to as KCp *) alkali such Since it is synthesized using a metal compound as a raw material, a large amount of Na or K is contained in the crude synthesized product.
Since these β-diketone strontium complexes and SrCp * 2 are solid in the vicinity of room temperature, they are difficult to purify by distillation, and it is difficult to efficiently remove Na and K derived from raw materials.
Therefore, conventionally, it is difficult to obtain Na and K contents of 50 ppb or less in a strontium-containing thin film forming raw material, and strontium-containing thin films having Na and K contents of 50 ppb or less applicable to CVD and ALD. There was no raw material for formation.
そこで、本発明者らは、市販のシクロペンタジエン化合物のうち、ペンタメチルシクロペンタジエンに類似した構造であるテトラメチル（ｎ−プロピル）シクロペンタジエン（Ｃ5（ＣＨ3）4（Ｃ3Ｈ7）Ｈ）を用いて合成することができる化合物であるビス（プロピルテトラメチルシクロペンタジエニル）ストロンチウム（Ｓｒ［Ｃ5（ＣＨ3）4（Ｃ3Ｈ7）］2Ｓｒ［Ｃ5（ＣＨ3）4（Ｃ3Ｈ7）］2；以下、Ｓｒ（ＰｒＭｅ4Ｃｐ）2と表す）が好ましいと考えた。 Therefore, the present inventors, among commercially available cyclopentadiene compounds, tetramethyl (n-propyl) cyclopentadiene (C 5 (CH 3 ) 4 (C 3 H 7 ) H, which has a structure similar to pentamethylcyclopentadiene. ) (Sr [C 5 (CH 3 ) 4 (C 3 H 7 )] 2 Sr [C 5 (CH 3 ) 4] (C 3 H 7 )] 2 ; hereinafter referred to as Sr (PrMe 4 Cp) 2 ).
Ｓｒ（ＰｒＭｅ4Ｃｐ）2は、特許文献１に開示されており、ＣＡＳ Ｎｏ．８８２２９６−９８−２で登録されている化合物である。
また、非特許文献１には、Ｓｒ（ＰｒＭｅ4Ｃｐ）2に、１，２−ジメトキシエタン（ＣＨ3ＯＣ2Ｈ4ＯＣＨ3；以下、ＤＭＥと表す）が付加した化合物が記載されている。
Sr (PrMe 4 Cp) 2 is disclosed in Patent Document 1, and CAS No. It is a compound registered in 882296-98-2.
Non-Patent Document 1 describes a compound in which 1,2-dimethoxyethane (CH 3 OC 2 H 4 OCH 3 ; hereinafter referred to as DME) is added to Sr (PrMe 4 Cp) 2 .
しかしながら、上記特許文献１においては、実施例７の表において、トリメチルインジウムとモノエチルアルシンを原料にしたＭＯＣＶＤでＩｎＡｓ膜を６００℃で成長させる際に、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を触媒量（＜０．２５ｍｏｌ％）共存させることが記載されているにすぎず、Ｓｒ（ＰｒＭｅ4Ｃｐ）2は微量の触媒として添加されており、膜中にＳｒは実質的に含まれていない。しかも、Ｓｒ（ＰｒＭｅ4Ｃｐ）2の製法や物性については、全く記載されていない。 However, in Patent Document 1, in the table of Example 7, when an InAs film is grown at 600 ° C. by MOCVD using trimethylindium and monoethylarsine as raw materials, Sr (PrMe 4 Cp) 2 is added in a catalytic amount ( <0.25 mol%) is described only as a coexistence, Sr (PrMe 4 Cp) 2 is added as a trace amount of catalyst, and Sr is not substantially contained in the film. Moreover, Sr For (PrMe 4 Cp) 2 of production method and properties, not described at all.
また、上記非特許文献１にも、エーテル類の付加していないＳｒ（ＰｒＭｅ4Ｃｐ）2の記載はなかった。
シクロペンタジエニル系ストロンチウム化合物は、エーテル類が付加した化合物として合成された後、エーテル類を外して得られる化合物であり、付加体を経由せずに合成することは困難である。しかも、付加したエーテル類を外すことは容易ではない。
In addition, Non-Patent Document 1 also does not describe Sr (PrMe 4 Cp) 2 to which no ethers are added.
A cyclopentadienyl-based strontium compound is a compound obtained by removing an ether after being synthesized as a compound to which an ether is added, and is difficult to synthesize without going through an adduct. Moreover, it is not easy to remove the added ethers.
したがって、これまでに、Ｓｒ（ＰｒＭｅ4Ｃｐ）2は、製造方法や物性は明らかとされておらず、これを原料として、Ｓｒを主成分として含有する薄膜は形成されたことがなかった。また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2の製造方法においては、使用するエーテル化合物種とエーテル類を外す方法が重要となる。 Therefore, until now, the manufacturing method and physical properties of Sr (PrMe 4 Cp) 2 have not been clarified, and a thin film containing Sr as a main component has never been formed using this as a raw material. Further, in the production method of Sr (PrMe 4 Cp) 2, a method of removing the ether compound species and ethers to be used is important.
また、半導体薄膜形成材料中には、Ｎａがわずかでも混入すると、半導体界面の電界の不均一や導体薄膜の腐食等、半導体特性を大きく損なうことから、有機ストロンチウム錯体中のＮａ濃度を０に近づけることが求められている。Ｋについても同様のことが求められている。 Further, if even a small amount of Na is mixed in the semiconductor thin film forming material, the semiconductor characteristics are greatly impaired such as non-uniformity of the electric field at the semiconductor interface and corrosion of the conductor thin film, so the Na concentration in the organic strontium complex is brought close to zero. It is demanded. The same is required for K.
本発明は、上記技術的課題を解決するためになされたものであり、室温〜５０℃で液体であり、蒸留精製が可能で、単量体で蒸気圧が高く、量産しやすいシクロペンタジエニル系ストロンチウム化合物によるストロンチウム含有薄膜形成用原料を提供することを目的とするものである。
また、本発明は、ＮａおよびＫの含量を低減させたストロンチウム含有薄膜を提供することをも目的とする。
また、本発明は、前記化合物の製造方法を提供することも目的とする。
The present invention has been made to solve the above technical problem, and is a liquid at room temperature to 50 ° C., can be purified by distillation, is a monomer, has a high vapor pressure, and is easy to mass-produce cyclopentadienyl. An object of the present invention is to provide a raw material for forming a strontium-containing thin film using a strontium-based compound.
Another object of the present invention is to provide a strontium-containing thin film in which the contents of Na and K are reduced.
Another object of the present invention is to provide a method for producing the compound.
本発明に係るストロンチウム含有薄膜形成用原料は、Ｓｒ（ＰｒＭｅ4Ｃｐ）2であることを特徴とする。 The raw material for forming a strontium-containing thin film according to the present invention is Sr (PrMe 4 Cp) 2 .
前記ストロンチウム含有薄膜形成用原料においては、好ましくは、ＫおよびＮａの各含量が５０ｐｐｂ以下である。 In the strontium-containing raw material for forming a thin film, each content of K and Na is preferably 50 ppb or less.
また、本発明に係るストロンチウム含有薄膜形成用原料の製造方法は、プロピルテトラメチルシクロペンタジエニルナトリウム（以下、Ｎａ（ＰｒＭｅ4Ｃｐ）と表す）もしくはプロピルテトラメチルシクロペンタジエニルカリウム（以下、Ｋ（ＰｒＭｅ4Ｃｐ）と表す）とヨウ化ストロンチウム（ＳｒＩ2）をＴＨＦ中で反応させ、Ｓｒ（ＰｒＭｅ4Ｃｐ）2のＴＨＦ付加体を生成させる工程と、ＴＨＦを留去し、トルエンで抽出してトルエン溶液とする工程と、トルエンを留去し、減圧乾燥する工程と、真空下で１００〜１６０℃に加熱し、ＴＨＦを解離除去した後、蒸留する工程とを経て、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を得ることを特徴とする。 In addition, the method for producing a raw material for forming a strontium-containing thin film according to the present invention includes propyltetramethylcyclopentadienyl sodium (hereinafter referred to as Na (PrMe 4 Cp)) or propyltetramethylcyclopentadienyl potassium (hereinafter referred to as K). (Represented as PrMe 4 Cp) and strontium iodide (SrI 2 ) in THF to produce a THF adduct of Sr (PrMe 4 Cp) 2 , distill off the THF, and extract with toluene. Sr (PrMe 4 Cp) through a process of preparing a toluene solution, a process of distilling off toluene and drying under reduced pressure, and a process of heating to 100 to 160 ° C. under vacuum to dissociate and remove THF, followed by distillation. 2 ) It is characterized by obtaining 2 .
本発明に係るストロンチウム含有薄膜形成用原料であるＳｒ（ＰｒＭｅ4Ｃｐ）2は、量産に適した液体化合物であり、本発明に係る製造方法によれば、好適に得ることができる。
また、本発明に係るストロンチウム含有薄膜形成材料であるＳｒ（ＰｒＭｅ4Ｃｐ）2は蒸気圧が高く、室温下での性状が液体であるため、蒸留精製が可能であり、半導体特性に大きな影響を与えるＮａおよびＫの含量が公知のストロンチウム含有薄膜形成材料に比べて大幅に低減される。
したがって、本発明により得られるＳｒ（ＰｒＭｅ4Ｃｐ）2を用いれば、ＣＶＤ法やＡＬＤ法により、ストロンチウム含有膜を量産することができ、また、ＮａおよびＫの含量が低減されたストロンチウム含有薄膜を形成することができる。
Sr (PrMe 4 Cp) 2 which is a raw material for forming a strontium-containing thin film according to the present invention is a liquid compound suitable for mass production, and can be suitably obtained according to the production method according to the present invention.
In addition, Sr (PrMe 4 Cp) 2, which is a strontium-containing thin film forming material according to the present invention, has a high vapor pressure and is liquid at room temperature, so that it can be purified by distillation and has a great influence on semiconductor characteristics. The content of Na and K to be provided is greatly reduced as compared with known strontium-containing thin film forming materials.
Therefore, if Sr (PrMe 4 Cp) 2 obtained by the present invention is used, a strontium-containing film can be mass-produced by a CVD method or an ALD method, and a strontium-containing thin film with reduced Na and K contents can be obtained. Can be formed.
以下、本発明について、より詳細に説明する。
本発明に係るストロンチウム含有薄膜形成用原料は、Ｓｒ（ＰｒＭｅ4Ｃｐ）2であることを特徴とするものである。
この原料化合物であるＳｒ（ＰｒＭｅ4Ｃｐ）2は、本発明に係る製造方法により、好適に得ることができる。
具体的には、Ｎａ（ＰｒＭｅ4Ｃｐ）もしくはＫ（ＰｒＭｅ4Ｃｐ）とＳｒＩ2をＴＨＦ中で反応させ、Ｓｒ（ＰｒＭｅ4Ｃｐ）2のＴＨＦ付加体を生成させる工程と、ＴＨＦを留去し、トルエンで抽出してトルエン溶液とする工程と、トルエンを留去し、減圧乾燥する工程と、真空下で１００〜１６０℃に加熱し、ＴＨＦを解離除去した後、蒸留する工程とを経ることにより、Ｓｒ（ＰｒＭｅ4Ｃｐ）2が得られる。
以下、この製造工程を順次、説明する。
Hereinafter, the present invention will be described in more detail.
The raw material for forming a strontium-containing thin film according to the present invention is Sr (PrMe 4 Cp) 2 .
This raw material compound, Sr (PrMe 4 Cp) 2 , can be suitably obtained by the production method according to the present invention.
Specifically, a step of reacting Na (PrMe 4 Cp) or K (PrMe 4 Cp) and SrI 2 in THF to produce a THF adduct of Sr (PrMe 4 Cp) 2 , and distilling off THF. Extracting with toluene to form a toluene solution, distilling off toluene and drying under reduced pressure, heating to 100 to 160 ° C. under vacuum to dissociate and remove THF, followed by distillation Thus, Sr (PrMe 4 Cp) 2 is obtained.
Hereafter, this manufacturing process is demonstrated sequentially.
まず、Ｎａ（ＰｒＭｅ4Ｃｐ）は、市販のプロピルテトラメチルシクロペンタジエン（Ｃ5（ＣＨ3）4（Ｃ3Ｈ7）Ｈ；別名：テトラメチル（ｎ−プロピル）シクロペンタジエン）（Ｓｔｒｅｍ社製、Ａｌｆａ Ａｅｓａｒ社製等）と、液体ＮＨ3中でＮａＮＨ2と反応させる方法や、ＴＨＦやＤＭＥ中でＮａＨと反応させる方法等の公知の方法により得ることができる。
Ｋ（ＰｒＭｅ4Ｃｐ）も、同様な方法で得られる。
First, Na (PrMe 4 Cp) is commercially available propyltetramethylcyclopentadiene (C 5 (CH 3 ) 4 (C 3 H 7 ) H; also known as: tetramethyl (n-propyl) cyclopentadiene) (manufactured by Strem, Alfa Aesar, etc.) and a method of reacting with NaNH 2 in liquid NH 3 or a method of reacting with NaH in THF or DME.
K (PrMe 4 Cp) can also be obtained by the same method.
次に、Ｓｒ（ＰｒＭｅ4Ｃｐ）2の合成反応溶媒であるＴＨＦに、上記により得られたＮａ（ＰｒＭｅ4Ｃｐ）もしくはＫ（ＰｒＭｅ4Ｃｐ）および無水ＳｒＩ2を溶解する。合成反応は容易に進行し、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）付加体が生成する。 Next, Na (PrMe 4 Cp) or K (PrMe 4 Cp) and anhydrous SrI 2 obtained above are dissolved in THF, which is a synthesis reaction solvent for Sr (PrMe 4 Cp) 2 . The synthesis reaction proceeds easily and an Sr (PrMe 4 Cp) 2 (THF) adduct is produced.
なお、合成反応溶媒としてＤＭＥを用いた場合は、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（ＤＭＥ）付加体が容易に生成するが、下記の比較例１に示すように、後でＤＭＥを容易に外すことができないため、ＤＭＥは適さない。
また、溶媒としてジエチルエーテルを用いた場合は、反応原料の溶解度が小さく、反応速度が低く、容積効率が悪いため、ジエチルエーテルも適さない。
In addition, when DME is used as a synthesis reaction solvent, an Sr (PrMe 4 Cp) 2 (DME) adduct is easily formed. However, as shown in Comparative Example 1 below, DME is easily removed later. DME is not suitable.
In addition, when diethyl ether is used as a solvent, diethyl ether is not suitable because the solubility of the reaction raw material is low, the reaction rate is low, and the volumetric efficiency is poor.
合成反応終了後、ＴＨＦ溶媒を留去し、トルエンでＳｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）付加体を抽出する。トルエンは、該付加体をよく溶かすが、副生成物であるヨウ化ナトリウムやヨウ化カリウムは全く溶けないため、抽出が容易である。
抽出後のトルエン溶液から、トルエンを留去し、減圧乾燥することにより、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）付加体が得られる。このＴＨＦ付加体の融点は約１３０℃である。
After completion of the synthesis reaction, the THF solvent is distilled off, and the Sr (PrMe 4 Cp) 2 (THF) adduct is extracted with toluene. Toluene dissolves the adduct well, but the by-products such as sodium iodide and potassium iodide do not dissolve at all, so that extraction is easy.
Sr (PrMe 4 Cp) 2 (THF) adduct is obtained by evaporating toluene from the extracted toluene solution and drying under reduced pressure. The melting point of this THF adduct is about 130 ° C.
この付加体を、０．００１〜０．１Ｔｏｒｒの真空下、１００〜１６０℃に加熱すると、釜内は融液状態となり、解離したＴＨＦが深冷のトラップに溜まる。トラップ内の溜まりの増加が停止したら、１６０〜１８０℃／０．０１〜０．１Ｔｏｒｒでの蒸留操作により、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を留出させる。
このようにして得られたＳｒ（ＰｒＭｅ4Ｃｐ）2は、室温にて固化することがない粘性液体である。
When this adduct is heated to 100 to 160 ° C. under a vacuum of 0.001 to 0.1 Torr, the inside of the kettle is in a melt state, and the dissociated THF accumulates in a deeply cooled trap. When the increase of the trap in the trap stops, Sr (PrMe 4 Cp) 2 is distilled by a distillation operation at 160 to 180 ° C./0.01 to 0.1 Torr.
The Sr (PrMe 4 Cp) 2 obtained in this way is a viscous liquid that does not solidify at room temperature.
上記のような方法により得られたＳｒ（ＰｒＭｅ4Ｃｐ）2を原料として用いることにより、ＣＶＤ法やＡＬＤ法により、ストロンチウム含有の酸化物膜、硫化物膜等を安定的に形成することができる。 By using Sr (PrMe 4 Cp) 2 obtained by the above method as a raw material, a strontium-containing oxide film, sulfide film or the like can be stably formed by a CVD method or an ALD method. .
また、上記のような本発明に係る製造方法によれば、ＫおよびＮａの各含量が５０ｐｐｂ以下であるＳｒ（ＰｒＭｅ4Ｃｐ）2を得ることができる。
したがって、本発明に係る製造方法により得られるＫおよびＮａの含量が少ないＳｒ（ＰｒＭｅ4Ｃｐ）2を原料として用いて、ＳｒＴｉＯ3膜、（Ｂａ，Ｓｒ）ＴｉＯ3膜、ＳｒＲｕＯ3膜等のストロンチウム含有薄膜を形成すれば、薄膜中のＫおよびＮａの各含量を従来よりも低減することができる。
Moreover, according to the manufacturing method according to the present invention as described above, Sr (PrMe 4 Cp) 2 in which each content of K and Na is 50 ppb or less can be obtained.
Therefore, strontium such as SrTiO 3 film, (Ba, Sr) TiO 3 film, SrRuO 3 film, etc., using Sr (PrMe 4 Cp) 2 having a low content of K and Na obtained by the production method according to the present invention as a raw material. If a containing thin film is formed, each content of K and Na in a thin film can be reduced rather than before.
膜形成の際のＳｒ（ＰｒＭｅ4Ｃｐ）2の供給方法としては、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を１３０〜３５０℃に加熱して流動性のある液体とし、キャリアガスをバブリングすることにより気化させる方法や、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を不活性な炭化水素溶媒に溶解して、液体マスフローメータで供給し、１５０〜３５０℃の気化器で全量気化させる方法等を用いることができる。 As a method for supplying Sr (PrMe 4 Cp) 2 during film formation, Sr (PrMe 4 Cp) 2 is heated to 130 to 350 ° C. to form a fluid liquid, and is vaporized by bubbling a carrier gas. A method, a method of dissolving Sr (PrMe 4 Cp) 2 in an inert hydrocarbon solvent, supplying the solution with a liquid mass flow meter, and vaporizing the entire amount with a vaporizer at 150 to 350 ° C. can be used.
Ｓｒ（ＰｒＭｅ4Ｃｐ）2をバブリング法で供給する場合、そのシリンダ温度は、下記実施例の温度に限ることなく、１３０〜３５０℃の間で設定することができる。そのときのキャリアガスは、不活性ガスであればよく、Ａｒの他に、Ｎ2、Ｈｅを用いることができる。また、その流量は、少なすぎても蒸気を搬送することができないが、多すぎるとシリンダ内圧を上昇させて、原料の蒸発を妨げるため、３０〜５００ｓｃｃｍであることが好ましい。 When supplying Sr (PrMe 4 Cp) 2 by the bubbling method, the cylinder temperature is not limited to the temperature of the following examples, and can be set between 130 and 350 ° C. The carrier gas at that time may be an inert gas, and N 2 and He can be used in addition to Ar. Further, the flow rate is too small to transport the vapor, but if it is too large, the cylinder internal pressure is increased and the evaporation of the raw material is prevented, so that the flow rate is preferably 30 to 500 sccm.
また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2を溶媒に溶解して、粘度を下げ、気化器に液体搬送して気化する場合、その粘度は、下記実施例の温度に限ることなく、５０ｃＰ以下であればよく、このような範囲の粘度であれば、配管および気化器内で閉塞する危険性を低くすることができる。
また、溶媒としては、溶解度が最も高いトルエンを用いることが好ましいが、低濃度溶液でよい場合には、トルエンに限らず、比較的溶解性に優れたヘキサンまたはオクタンを用いることもできる。
In addition, when Sr (PrMe 4 Cp) 2 is dissolved in a solvent to lower the viscosity and liquid is vaporized by being transported to a vaporizer, the viscosity is not limited to the temperature of the following examples, and is 50 cP or less. If the viscosity is in such a range, the risk of clogging in the piping and the vaporizer can be reduced.
As the solvent, toluene having the highest solubility is preferably used. However, when a low-concentration solution may be used, not only toluene but also hexane or octane having relatively excellent solubility can be used.
上記のような方法で気化させたＳｒ（ＰｒＭｅ4Ｃｐ）2の蒸気と、Ｔｉ（ＯｉＰｒ）4，Ｔｉ（ＯｔＢｕ）4，Ｔｉ（ＮＭｅ2）4，Ｔｉ（ＮＥｔＭｅ）4，Ｔｉ（ＮＥｔ2）4等のチタン化合物の蒸気と、酸素、オゾン、水等を酸化剤として用いれば、ＣＶＤ法やＡＬＤ法により、ＳｒＴｉＯ3膜を製造することができる。 Sr (PrMe 4 Cp) 2 vaporized by the above method, Ti (OiPr) 4 , Ti (OtBu) 4 , Ti (NMe 2 ) 4 , Ti (NEtMe) 4 , Ti (NEt 2 ) When a vapor of titanium compound such as 4 and oxygen, ozone, water or the like are used as an oxidizing agent, an SrTiO 3 film can be produced by a CVD method or an ALD method.
また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気にＢａ（ＰｒＭｅ4Ｃｐ）2蒸気を加え、Ｔｉ（ＯｉＰｒ）4，Ｔｉ（ＯｔＢｕ）4，Ｔｉ（ＮＭｅ2）4，Ｔｉ（ＮＥｔＭｅ）4，Ｔｉ（ＮＥｔ2）4等のチタン化合物の蒸気と、酸素、オゾン、水等を酸化剤として用いれば、ＣＶＤ法やＡＬＤ法により、（Ｂａ，Ｓｒ）ＴｉＯ3膜を製造することができる。 Further, Ba (PrMe 4 Cp) 2 vapor is added to Sr (PrMe 4 Cp) 2 vapor, Ti (OiPr) 4 , Ti (OtBu) 4 , Ti (NMe 2 ) 4 , Ti (NEtMe) 4 , Ti (NEt). 2 ) If a vapor of a titanium compound such as 4 and oxygen, ozone, water or the like are used as an oxidizing agent, a (Ba, Sr) TiO 3 film can be produced by CVD or ALD.
さらにまた、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気と、Ｒｕ（ＥｔＣｐ）2等のルテニウム化合物の蒸気と、酸素、オゾン、水等を酸化剤として用いれば、ＣＶＤ法やＡＬＤ法により、ＳｒＲｕＯ3膜を製造することができる。 Furthermore, if Sr (PrMe 4 Cp) 2 vapor, ruthenium compound vapor such as Ru (EtCp) 2 , oxygen, ozone, water or the like is used as an oxidizing agent, the SrRuO 3 film is formed by CVD or ALD. Can be manufactured.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
［実施例１］Ｓｒ（ＰｒＭｅ4Ｃｐ）2の製造
温度計、撹拌子、投入口、還流器を備えた１Ｌ三口フラスコに、真空アルゴン置換後、脱水脱酸素したＴＨＦ６００ｍｌと、Ｎａ（ＰｒＭｅ4Ｃｐ）７５ｇ（０．４０ｍｏｌ）を仕込み、溶解し、フラスコを水冷しながら、ＳｒＩ2粉末７２ｇ（０．２１ｍｏｌ）を加え、４０℃で８時間撹拌した。
次いで、減圧で脱溶媒し、乾燥後、脱水脱酸素したトルエン６００ｍｌを加え、加熱撹拌による抽出操作を行い、静置後、ろ過し、透明なろ液を得た。ろ液からトルエンを減圧留去し、１００℃で減圧乾燥し、融点約１３０℃の淡黄色の固体（減圧乾燥品）８９ｇを得た。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
[Example 1] Production of Sr (PrMe 4 Cp) 2 In a 1 L three-necked flask equipped with a thermometer, a stirrer, an inlet, and a reflux condenser, 600 ml of THF dehydrated and deoxygenated after vacuum argon substitution and Na (PrMe 4 Cp) were added. ) 75 g (0.40 mol) was charged and dissolved, and 72 g (0.21 mol) of SrI 2 powder was added while stirring the flask with water, followed by stirring at 40 ° C. for 8 hours.
Next, the solvent was removed under reduced pressure, and after drying, 600 ml of dehydrated and deoxygenated toluene was added, extraction operation was performed by heating and stirring, and the mixture was allowed to stand and then filtered to obtain a transparent filtrate. Toluene was distilled off from the filtrate under reduced pressure and dried under reduced pressure at 100 ° C. to obtain 89 g of a pale yellow solid (vacuum dried product) having a melting point of about 130 ° C.
この固体を高真空蒸留装置に仕込み、１１０〜１６０℃／０．１〜０．０１Ｔｏｒｒで１時間保持したところ、ＴＨＦ付加体のＴＨＦが徐々に外れ、深冷トラップに８．１ｇ溜まった。徐々に昇温し、微量の初留結晶を除去した後、１７０〜１８０℃／０．１〜０．０１Ｔｏｒｒで、主留として淡黄色の粘性液体６１ｇを得た。
この粘性液体を、再度、高真空蒸留装置に仕込み、１００〜１６０℃／０．１〜０．０１Ｔｏｒｒで約１時間保持し、微量の残留ＴＨＦを外し、１７０〜１８０℃／０．０１〜０．１Ｔｏｒｒで、主留として淡黄色の粘性液体（２回蒸留品）５６ｇを得た。
この２回蒸留品は、以下に述べる分析の結果、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（０．１３６ｍｏｌ）と同定され、その収率はＮａ（ＰｒＭｅ4Ｃｐ）に対して６８％であった。
This solid was charged in a high vacuum distillation apparatus and maintained at 110 to 160 ° C./0.1 to 0.01 Torr for 1 hour. As a result, the THF adduct was gradually removed, and 8.1 g was collected in a deep cold trap. After gradually raising the temperature and removing a small amount of the first-run crystals, 61 g of a pale yellow viscous liquid was obtained as the main fraction at 170 to 180 ° C./0.1 to 0.01 Torr.
This viscous liquid is again charged into a high-vacuum distillation apparatus and held at 100 to 160 ° C./0.1 to 0.01 Torr for about 1 hour, a trace amount of residual THF is removed, and 170 to 180 ° C./0.01 to 0 At 1 Torr, 56 g of a pale yellow viscous liquid (double distilled product) was obtained as the main distillate.
As a result of the analysis described below, this double distilled product was identified as Sr (PrMe 4 Cp) 2 (0.136 mol), and its yield was 68% with respect to Na (PrMe 4 Cp).
以下、２回蒸留品の同定分析および物性評価の方法および結果について述べる。
（１）組成分析
湿式分解して得られた液のＩＣＰ発光分光分析の結果、Ｓｒ含量は２０．７％（理論値２１．１５％）であった。
また、不純物については、Ｃａ＝１９００，Ｍｇ＜５０，Ｂａ＝１００００，Ｎａ＜５０，Ｋ＜５０，Ｃｒ＜５０，Ｆｅ＜５０，Ｃｕ＜５０，Ｎｉ＜５０（単位：ｐｐｂ）であり、高純度であることが認められた。
The method and result of identification analysis and physical property evaluation of the twice-distilled product will be described below.
(1) Composition analysis As a result of ICP emission spectroscopic analysis of the liquid obtained by wet decomposition, the Sr content was 20.7% (theoretical value: 21.15%).
As for impurities, Ca = 1900, Mg <50, Ba = 10000, Na <50, K <50, Cr <50, Fe <50, Cu <50, Ni <50 (unit: ppb), high Purity was observed.
（２）1Ｈ−ＮＭＲ
測定条件（装置：ＪＮＭ−ＥＣＡ４００（４００ＭＨｚ）、溶媒：Ｃ6Ｄ6、方法：１Ｄ）
図１に、２回蒸留品の測定結果を示す。比較のため、図２に、減圧乾燥品の結果を示す。
(2) 1 H-NMR
Measurement conditions (apparatus: JNM-ECA400 (400 MHz), solvent: C 6 D 6 , method: 1D)
FIG. 1 shows the measurement results of the double distilled product. For comparison, FIG. 2 shows the results of the vacuum dried product.
図１，２の測定スペクトルにおける各シグナルの位置とＨの個数、Ｓｒ（ＰｒＭｅ4Ｃｐ）2とＴＨＦのＨの個数の比率を考慮して、δＨ（ｐｐｍ）について、以下のように帰属を行った。
２．０１（ｓ），１．９７（ｓ） １２Ｈ
：Ｃ5（ＣＨ 3）4の−Ｃ3Ｈ7から離れたＣＨ3２個と近いＣＨ3２個
２．３９（ｔ） ２Ｈ：ＣＨ 2ＣＨ2ＣＨ3
１．３６（ｍ） ２Ｈ：ＣＨ2ＣＨ 2ＣＨ3
０．９２（ｔ） ３Ｈ：ＣＨ2ＣＨ2ＣＨ 3
３．１４（ｔ），１．２１（ｍ）：ＴＨＦの−ＯＣＨ 2ＣＨ 2ＣＨ 2ＣＨ 2−
In consideration of the position of each signal and the number of H in the measurement spectra of FIGS. 1 and 2 and the ratio of the number of H in Sr (PrMe 4 Cp) 2 and THF, the assignment of δH (ppm) is performed as follows. It was.
2.01 (s), 1.97 (s) 12H
: C 5 (C H 3)
1.36 (m) 2H: CH 2 C H 2
0.92 (t) 3H: CH 2 CH 2
3.14 (t), 1.21 (m): —OC H 2 C H 2 C H 2 C H 2 — in THF
図１に示した測定スペクトルから、２回蒸留品について、Ｓｒ１ｍｏｌに付加しているＴＨＦのｍｏｌ数は、（０．３４８＋０．４３７）／（２３．５６２＋４．１３１＋４．１３６＋６）×３８／８＝０．０９であり、平均的化学式はＳｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）0.09となった。わずかにＴＨＦが配位しているが、実質的に、Ｓｒ（ＰｒＭｅ4Ｃｐ）2とみなすことができる。 From the measurement spectrum shown in FIG. 1, the number of moles of THF added to Sr1 mol in the double-distilled product is (0.348 + 0.437) / (23.562 + 4.131 + 4.136 + 6) × 38/8 = 0. The average chemical formula was Sr (PrMe 4 Cp) 2 (THF) 0.09 . Although THF is slightly coordinated, it can be regarded substantially as Sr (PrMe 4 Cp) 2 .
なお、図２に示した測定スペクトルから、減圧乾燥品については、Ｓｒ１ｍｏｌに付加しているＴＨＦｍｏｌ数は、（２．０７６＋２．０４６）／（１１．２９６＋１．９８１＋１．８９０＋３）×３８／８＝１．０８であり、平均的化学式はＳｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）1.08となった。
また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（ＴＨＦ）1のＳｒ含量理論値が１８．０２％であるのに対して、減圧乾燥品のＳｒ含量分析値は１８．１％であった。
よって、減圧乾燥品は、約１個のＴＨＦが付加しているＳｒ（ＰｒＭｅ4Ｃｐ）2であると推定される。
From the measurement spectrum shown in FIG. 2, the THF mol number added to Sr1 mol of the dried product under reduced pressure is (2.076 + 2.046) / (11.296 + 1.981 + 1.890 + 3) × 38/8 = 1. The average chemical formula was Sr (PrMe 4 Cp) 2 (THF) 1.08 .
The theoretical value of Sr content of Sr (PrMe 4 Cp) 2 (THF) 1 was 18.02%, whereas the analytical value of Sr content of the vacuum-dried product was 18.1%.
Therefore, it is estimated that the dried product under reduced pressure is Sr (PrMe 4 Cp) 2 to which about 1 THF is added.
（３）性状と融点
２回蒸留品は、微淡黄色で、室温で非常に粘性の強い液体であり、粘度は約１０００Ｐであった。
(3) Property and melting point The double-distilled product was slightly pale yellow and was a very viscous liquid at room temperature, and the viscosity was about 1000 P.
（４）ＴＧ−ＤＴＡ
測定条件（試料重量：１４．４０ｍｇ、雰囲気：Ａｒ１気圧、昇温速度：１０．０ｄｅｇ／ｍｉｎ）
図３に、２回蒸留品の測定結果を示す。比較のため、図４に、減圧乾燥品の結果を示す。
図３，４に示すＴＧ−ＤＴＡ曲線から、２回蒸留品は、１６０℃付近まで減量はなく、除去されるＴＨＦは存在していないと推定される。
また、３００℃までに９７％蒸発していることから、分オーダーの短時間では、３００℃以下においては熱劣化することなく、ＡＬＤ法やＣＶＤ法の原料に求められる熱安定性を有していることが認められる。
(4) TG-DTA
Measurement conditions (sample weight: 14.40 mg, atmosphere: Ar 1 atm, temperature increase rate: 10.0 deg / min)
FIG. 3 shows the measurement results of the double distilled product. For comparison, FIG. 4 shows the results of the vacuum dried product.
From the TG-DTA curves shown in FIGS. 3 and 4, it is presumed that the double-distilled product has no weight loss up to around 160 ° C. and there is no THF to be removed.
In addition, since it has evaporated 97% up to 300 ° C, it has the thermal stability required for ALD and CVD materials in a short time on the order of minutes, without thermal degradation below 300 ° C. It is recognized that
（５）蒸気圧
気体飽和法測定の結果、０．１Ｔｏｒｒ／１７０℃であった。
(5) Vapor pressure It was 0.1 Torr / 170 degreeC as a result of the gas saturation method measurement.
（６）密度
密度は１．２ｇ／ｃｍ3（３０℃）であった。
(6) Density The density was 1.2 g / cm 3 (30 ° C.).
（７）溶解度
１Ｌの各溶媒に対する室温での溶解度は、トルエンに対しては３５０ｇ、ＴＨＦに対しては２８０ｇ、ヘキサンに対しては７０ｇ、オクタンに対しては７０ｇであった。
よって、トルエンに非常によく溶け、また、オクタン等にも比較的よく溶けることが認められた。
(7) Solubility The solubility at room temperature in 1 L of each solvent was 350 g for toluene, 280 g for THF, 70 g for hexane, and 70 g for octane.
Therefore, it was found that it was very well soluble in toluene and relatively well soluble in octane and the like.
［比較例１］溶媒としてＤＭＥを用いたＳｒ（ＰｒＭｅ4Ｃｐ）2の製造
温度計、撹拌子、投入口、還流器を備えた３００ｍｌ三口フラスコに、真空アルゴン置換後、脱水脱酸素したＴＨＦ１６０ｍｌと、Ｎａ（ＰｒＭｅ4Ｃｐ）１６ｇ（０．０８６ｍｏｌ）を仕込み、溶解し、フラスコを水冷しながら、ＳｒＩ2粉末１５．５ｇ（０．０４５ｍｏｌ）を加え、リフラックス下、８時間撹拌した。
次いで、減圧で脱溶媒し、乾燥後、脱水脱酸素したトルエン２００ｍｌを加え、加熱撹拌による抽出操作を行い、静置後、ろ過し、透明なろ液を得た。ろ液からトルエンを減圧留去し、１００℃で減圧乾燥したところ、初めは、淡黄色の粘い液であったが、１日後、融点約１００℃の固体１８．５ｇが得られた。
[Comparative Example 1] Production of Sr (PrMe 4 Cp) 2 using DME as a solvent A 300 ml three-necked flask equipped with a thermometer, a stirrer, a charging port, and a reflux condenser was replaced with 160 ml of dehydrated and deoxygenated THF after vacuum argon substitution. Then, 16 g (0.086 mol) of Na (PrMe 4 Cp) was charged and dissolved. While cooling the flask with water, 15.5 g (0.045 mol) of SrI 2 powder was added and stirred for 8 hours under reflux.
Next, the solvent was removed under reduced pressure, and after drying, 200 ml of dehydrated and deoxygenated toluene was added, extraction operation was performed by heating and stirring, and the mixture was allowed to stand and filtered to obtain a transparent filtrate. When toluene was distilled off under reduced pressure from the filtrate and dried under reduced pressure at 100 ° C., it was initially a pale yellow viscous liquid, but after 1 day, 18.5 g of a solid having a melting point of about 100 ° C. was obtained.
この固体を高真空蒸留装置に仕込み、１１０〜１６０℃／０．１〜０．０１Ｔｏｒｒで１時間保持したところ、ＤＭＥ付加体のＤＭＥが徐々に外れ、深冷トラップに１．２ｇ溜まった。徐々に昇温し、極微量の初留を除去した後、１７０〜１７５℃／０．１〜０．０１Ｔｏｒｒで、主留として、液体で留出し、室温で固化する淡黄色の固体（融点約５０〜８０℃）（１回蒸留品）１４．７ｇを得た。
この固体を、再度、高真空蒸留装置に仕込み、１００〜１６０℃／０．１〜０．０１Ｔｏｒｒで１時間保持した後、昇温し、１７０〜１７５℃／０．０１〜０．１Ｔｏｒｒで、主留として、液体で留出し、室温で固化する淡黄色の固体（融点約５０〜８０℃）（２回蒸留品）１２．８ｇを得た。
この２回蒸留品について、実施例１と同様にして、1Ｈ−ＮＭＲおよびＴＧ−ＤＴＡの測定を行った。
When this solid was charged in a high vacuum distillation apparatus and maintained at 110 to 160 ° C./0.1 to 0.01 Torr for 1 hour, DME adduct was gradually removed and 1.2 g was collected in a deep cold trap. After gradually raising the temperature and removing a very small amount of initial distillation, a light yellow solid (melting point of about melting point) is distilled at a temperature of 170 to 175 ° C./0.1 to 0.01 Torr as a main distillation and liquid at room temperature. 14.7 g (50 to 80 ° C.) (single distilled product) was obtained.
This solid was again charged into a high-vacuum distillation apparatus, held at 100 to 160 ° C./0.1 to 0.01 Torr for 1 hour, and then heated to 170 to 175 ° C./0.01 to 0.1 Torr. As the main distillate, 12.8 g of a pale yellow solid (melting point: about 50 to 80 ° C.) (double distilled product) that distills in liquid and solidifies at room temperature was obtained.
With respect to this double distilled product, 1 H-NMR and TG-DTA were measured in the same manner as in Example 1.
（１）1Ｈ−ＮＭＲ
図５に、２回蒸留品の測定結果を示す。
図５の測定スペクトルにおける各シグナルの位置とＨの個数、Ｓｒ（ＰｒＭｅ4Ｃｐ）2とＤＭＥのＨの個数の比率を考慮して、δＨ（ｐｐｍ）について、以下のように帰属を行った。
２．１５（ｓ），２．１２（ｓ） １２Ｈ
：Ｃ5（ＣＨ 3）4の−Ｃ3Ｈ7から離れたＣＨ3２個と近いＣＨ3２個
２．４７（ｔ） ２Ｈ：ＣＨ 2ＣＨ2ＣＨ3
１．６３（ｍ） ２Ｈ：ＣＨ2ＣＨ 2ＣＨ3
１．０８（ｔ） ３Ｈ：ＣＨ2ＣＨ2ＣＨ 3
２．６９（ｔ），２．５９（ｍ）：ＤＭＥのＣＨ 3ＯＣＨ 2ＣＨ 2ＯＣＨ 3
(1) 1 H-NMR
FIG. 5 shows the measurement results of the double distilled product.
In consideration of the position of each signal and the number of H in the measurement spectrum of FIG. 5 and the ratio of the number of H of Sr (PrMe 4 Cp) 2 and DME, the assignment of δH (ppm) was performed as follows.
2.15 (s), 2.12 (s) 12H
: 2 CH 3 and 2 close CH 3 away from —C 3 H 7 of C 5 (C H 3 ) 4 2.47 (t) 2H: C H 2 CH 2 CH 3
1.63 (m) 2H: CH 2 C H 2
1.08 (t) 3H: CH 2 CH 2
2.69 (t), 2.59 (m): DME C H 3 OC H 2 C H 2 OC H 3
図５に示した測定スペクトルから、２回蒸留品について、Ｓｒ１ｍｏｌに付加しているＤＭＥのｍｏｌ数は、（２．９２１＋１．９６１）／（１１．７２６＋１．９４５＋１．９０１＋３）×３８／１０＝１．００であり、平均的化学式はＳｒ（ＰｒＭｅ4Ｃｐ）2（ＤＭＥ）1.00となった。
また、多くの不純物によるシグナルが見られ、加熱蒸留中に、付加体の熱分解等が生じたと推測される。
また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2（ＤＭＥ）1のＳｒ含量理論値が１７．３７％であるのに対して、２回蒸留品のＳｒ含量分析値は１８．２％であった。
よって、真空加熱蒸留操作では、ＤＭＥ付加体からＤＭＥは外れにくいことが認められた。
From the measurement spectrum shown in FIG. 5, the number of moles of DME added to Sr1 mol in the double-distilled product is (2.921 + 1.961) / (11.726 + 1.945 + 1.901 + 3) × 38/10 = 1. The average chemical formula was Sr (PrMe 4 Cp) 2 (DME) 1.00 .
Further, signals due to many impurities were observed, and it is assumed that the adduct was thermally decomposed during the heating distillation.
Further, the theoretical value of Sr content of Sr (PrMe 4 Cp) 2 (DME) 1 was 17.37%, whereas the analytical value of Sr content of the double distilled product was 18.2%.
Therefore, it was recognized that DME was not easily detached from the DME adduct in the vacuum heating distillation operation.
（２）ＴＧ−ＤＴＡ
図６に、２回蒸留品の測定結果を示す。
図６に示すＴＧ−ＤＴＡ曲線から、ＤＭＥが外れる挙動は見られず、大半は、ＤＭＥ付加体のまま蒸発していると推定される。
(2) TG-DTA
FIG. 6 shows the measurement results of the double distilled product.
From the TG-DTA curve shown in FIG. 6, no DME behavior is observed, and it is estimated that most of the DME adduct is evaporated.
上記1Ｈ−ＮＭＲおよびＴＧ−ＤＴＡの測定結果から、２回蒸留品は、加熱しても、ＤＭＥは外れず、大半はＤＭＥ付加体として気化していると認められる。
すなわち、溶媒としてＤＭＥを用い、ＤＭＥ付加体を経由する方法では、純Ｓｒ（ＰｒＭｅ4Ｃｐ）2は得られなかった。
よって、市販のＳｒ（ＰｒＭｅ4Ｃｐ）2（ＤＭＥ）から、純Ｓｒ（ＰｒＭｅ4Ｃｐ）2を製造することは困難である。
From the measurement results of the above 1 H-NMR and TG-DTA, it is recognized that the double-distilled product does not come off DME even when heated, and most is vaporized as a DME adduct.
That is, pure Sr (PrMe 4 Cp) 2 could not be obtained by a method using DME as a solvent and via a DME adduct.
Therefore, it is difficult to produce pure Sr (PrMe 4 Cp) 2 from commercially available Sr (PrMe 4 Cp) 2 (DME).
［比較例２］原料としてＮａＣｐ*を用いたＳｒＣｐ* 2の製造
温度計、撹拌子、投入口、ガス出口を備えた１Ｌ三口フラスコに、真空アルゴン置換後、脱水脱酸素したＴＨＦ７５０ｍｌと、ＮａＣｐ*７９ｇ（０．５０ｍｏｌ）を仕込み、溶解し、フラスコを水冷しながら、ＳｒＩ2粉末９０ｇ（０．２４６ｍｏｌ）を加え、２５〜４０℃で２４時間撹拌した。
次いで、減圧で脱溶媒し、乾燥後、脱水脱酸素したトルエン９００ｍｌを加え、加熱撹拌する抽出操作を行い、静置後、ろ過し、透明なろ液を得た。ろ液からトルエンを減圧留去し、１００℃で減圧乾燥した。固形分をグローブボックス中で取り出し、軽く粉砕すると、淡黄色のさらさらとした粉末９８ｇが得られた。
[Comparative Example 2] Production of SrCp * 2 using NaCp * as raw material 750 ml of THF dehydrated and deoxygenated after vacuum argon substitution into a 1 L three-necked flask equipped with a thermometer, a stirrer, an inlet, and a gas outlet, and NaCp * 79 g (0.50 mol) was charged and dissolved, and 90 g (0.246 mol) of SrI 2 powder was added while stirring the flask with water, followed by stirring at 25 to 40 ° C. for 24 hours.
Next, the solvent was removed under reduced pressure, and after drying, 900 ml of dehydrated and deoxygenated toluene was added, followed by extraction with heating and stirring. After standing, the mixture was filtered to obtain a transparent filtrate. Toluene was distilled off from the filtrate under reduced pressure and dried at 100 ° C. under reduced pressure. The solid content was taken out in the glove box and lightly pulverized to obtain 98 g of a light yellow free flowing powder.
この粉末を昇華器に仕込み、１４０〜１８０℃／０．１Ｔｏｒｒで第１回目の昇華を行い、１回昇華品６５ｇを得た。
次いで、この１回昇華品を昇華器に仕込み、１４０〜１８０℃／０．１Ｔｏｒｒで第２回目の昇華を行い、純白な２回昇華品６２ｇを得た。
この２回昇華品の結晶は、以下に述べる分析の結果、ＳｒＣｐ* 2（０．１６２ｍｏｌ）と同定され、その収率はＮａＣｐ*に対して６９％であった。
This powder was charged into a sublimator and subjected to a first sublimation at 140 to 180 ° C./0.1 Torr to obtain 65 g of a once sublimated product.
Next, this once-sublimated product was charged into a sublimator and subjected to a second sublimation at 140 to 180 ° C./0.1 Torr to obtain 62 g of pure white twice-sublimated product.
As a result of the analysis described below, this twice-sublimated crystal was identified as SrCp * 2 (0.162 mol), and its yield was 69% with respect to NaCp * .
各工程で得られた固体について、実施例１と同様にして、ＩＣＰ発光分光分析による組成分析および1Ｈ−ＮＭＲの測定を行った。
その結果、Ｓｒ含量分析値（理論値２４．４７％）と、1Ｈ−ＮＭＲの全ＳｒＣｐ* 2シグナルのＨの個数およびＴＨＦシグナルのＨの個数の比率から、平均的化学式は、以下のように推定された。
減圧乾燥品： Ｓｒ含量１９．７％ ＳｒＣｐ* 2（ＴＨＦ）1.5
１回昇華品： Ｓｒ含量２２．１％ ＳｒＣｐ* 2（ＴＨＦ）0.5
２回昇華品： Ｓｒ含量２５．３％ ＳｒＣｐ* 2
また、２回昇華品について、ＩＣＰ発光分光分析の結果から、不純物は、Ｃａ＝２８００，Ｍｇ＜５０，Ｂａ＝２９０００，Ｎａ＝９４０，Ｋ＜５０，Ｃｒ＜５０，Ｆｅ＜５０，Ｃｕ＜５０，Ｎｉ＜５０（単位：ｐｐｂ）であり、実施例１に比べて、Ｎａ含量が大幅に多かった。
The solid obtained in each step was subjected to composition analysis by ICP emission spectroscopic analysis and 1 H-NMR measurement in the same manner as in Example 1.
As a result, Sr content analysis value (theoretical value 24.47%), from the total SrCp * 2 Ratio of the number of H number and THF signals H signals of 1 H-NMR, the average chemical formula is as follows Estimated.
Vacuum-dried product: Sr content 19.7% SrCp * 2 (THF) 1.5
Single sublimation product: Sr content 22.1% SrCp * 2 (THF) 0.5
Sublimation product twice: Sr content 25.3% SrCp * 2
Further, from the results of ICP emission spectroscopic analysis for the twice-sublimated product, the impurities are Ca = 2800, Mg <50, Ba = 29000, Na = 940, K <50, Cr <50, Fe <50, Cu <50. , Ni <50 (unit: ppb), and the Na content was significantly higher than that of Example 1.
［比較例３］原料としてＫＣｐ*を用いたＳｒＣｐ* 2の製造
ＮａＣｐ*に代えてＫＣｐ*を用い、それ以外は、比較例２と同様の方法で、同じモル量の原料を用いて合成を行った。
ＳｒＣｐ* 2の収率はＫＣｐ*に対して６５％であった。
実施例１と同様にして、２回昇華品について、ＩＣＰ発光分光分析による組成および不純物分析を行った。
その結果、Ｓｒ含量分析値は２５．０％（理論値２４．４７％）であり、不純物は、Ｃａ＝３０００，Ｍｇ＜５０，Ｂａ＝３１０００，Ｎａ＜５０，Ｋ＝１１００，Ｃｒ＜５０，Ｆｅ＜５０，Ｃｕ＜５０，Ｎｉ＜５０（単位：ｐｐｂ）であり、実施例１に比べて、Ｋ含量が大幅に多かった。
Using Comparative Example 3 as a raw material KCp * a instead of SrCp * 2 manufacturing NaCp * using KCp *, otherwise in the same manner as in Comparative Example 2, the synthesized using the same molar amount of the raw material went.
SrCp * 2 The yield was 65% with respect KCp *.
In the same manner as in Example 1, the sublimation product was subjected to composition and impurity analysis by ICP emission spectroscopic analysis.
As a result, the Sr content analysis value was 25.0% (theoretical value 24.47%), and impurities were Ca = 3000, Mg <50, Ba = 31000, Na <50, K = 1100, Cr <50, Fe <50, Cu <50, Ni <50 (unit: ppb), and the K content was significantly higher than that of Example 1.
［比較例４］Ｓｒ（ｄｐｍ）2の製造
温度計、撹拌羽根、還流器を備えた５００ｍｌ四口フラスコに、真空アルゴン置換後、トルエン３５０ｍｌを仕込み、次いで、ジピバロイルメタン（ｄｐｍＨ）６５．６ｇ（３５６ｍｍｏｌ）、金属Ｓｒ７．８ｇ（８９ｍｍｏｌ）を仕込み、加熱撹拌した。還流下で２４時間反応させたところ、金属片は消失した。
次いで、減圧下、溶媒および未反応のｄｐｍＨ類を留去した。さらに、１３０℃、０．０５Ｔｏｒｒで、溶存していた微量のｄｐｍＨを留去した。
残留物のうち３４ｇを高真空蒸留装置に仕込み、２３０℃／０．０２Ｔｏｒｒで蒸留し、Ｓｒ（ｄｐｍ）2３０ｇを得た。
これについて、実施例１と同様にして、ＩＣＰ発光分光分析による不純物分析を行った結果、Ｎａ＝９２０，Ｋ＝８９０（単位：ｐｐｂ）であり、実施例１に比べて、ＮａおよびＫ含量が大幅に多かった。
[Comparative Example 4] Production of Sr (dpm) 2 A 500 ml four-necked flask equipped with a thermometer, stirring blades, and reflux was charged with 350 ml of toluene after vacuum argon substitution, and then dipivaloylmethane (dpmH) 65 .6 g (356 mmol) and 7.8 g (89 mmol) of metal Sr were charged and stirred under heating. When reacted for 24 hours under reflux, the metal pieces disappeared.
Subsequently, the solvent and unreacted dpmH were distilled off under reduced pressure. Further, a trace amount of dpmH dissolved at 130 ° C. and 0.05 Torr was distilled off.
34 g of the residue was charged in a high vacuum distillation apparatus and distilled at 230 ° C./0.02 Torr to obtain 30 g of Sr (dpm) 2 .
As a result of conducting impurity analysis by ICP emission spectroscopic analysis in the same manner as in Example 1, Na = 920, K = 890 (unit: ppb). Compared to Example 1, the contents of Na and K are higher. It was much more.
［実施例２］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（１）
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2が充填されたシリンダ（Ａ）を１７０℃で、Ａｒガス１００ｓｃｃｍでバブリングし、また、Ｔｉ（ＯｉＰｒ）4が充填されたシリンダ（Ｂ）を４０℃で、Ａｒガス１００ｓｃｃｍでバブリングし、また、水が充填されたシリンダ（Ｃ）を２０℃で、Ａｒガス５０ｓｃｃｍでバブリングし、パージガスとしてＡｒ２００ｓｃｃｍを流し、各パルス１秒、パージ３秒で、ＡＬＤ操作を行った。
圧力約５ＴｏｒｒのＡＬＤ室に、基板温度３００℃のＳｉ基板を置き、（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒサイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＴｉサイクルとを交互に、各１００サイクル行い、厚さ１０ｎｍのＳｒＴｉＯ3膜を得た。
[Example 2] Formation of SrTiO 3 film by ALD method using Sr (PrMe 4 Cp) 2 (1)
The cylinder (A) filled with Sr (PrMe 4 Cp) 2 obtained in Example 1 was bubbled with 170 sc at Ar gas at 100 sccm, and the cylinder (B) filled with Ti (OiPr) 4 was used. At 40 ° C., bubbling with Ar gas at 100 sccm, and a cylinder (C) filled with water was bubbled at 20 ° C. with Ar gas at 50 sccm, Ar 200 sccm was passed as a purge gas, each pulse for 1 second, purge at 3 seconds, ALD operation was performed.
Place a Si substrate with a substrate temperature of 300 ° C. in an ALD chamber at a pressure of about 5 Torr, and perform an Sr cycle by (A pulse-purge-C pulse-purge) and a Ti cycle by (B pulse-purge-C pulse-purge). Alternately, 100 cycles were performed to obtain a SrTiO 3 film having a thickness of 10 nm.
［実施例３］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（２）
ガス導入口を含むチャンバ壁、ウエハ加熱用抵抗加熱ステージヒータ、ウエハ設置用リフタ機構を備えた成膜チャンバにて成膜した。この成膜チャンバは、圧力調整弁を介して、排気ポンプに接続し、チャンバ壁に埋め込まれたカートリッジヒータにより、チャンバ内を１６０℃に保持し、また、ステージヒータは、約０．３Ｔｏｒｒでウエハ温度が２９０℃となるように、３２０℃に設定しておく。
搬送アームを用いて、直径３００ｍｍのＳｉウエハを搬送系から成膜チャンバに導入し、ステージヒータに移載した。その後、Ａｒガス５００ｓｃｃｍを流通し、圧力調整弁によりチャンバ内圧力を１Ｔｏｒｒに保持して、ウエハ温度を昇温させた。
[Example 3] Formation of SrTiO 3 film by ALD method using Sr (PrMe 4 Cp) 2 (2)
The film was formed in a film forming chamber equipped with a chamber wall including a gas inlet, a resistance heating stage heater for heating the wafer, and a lifter mechanism for setting the wafer. This film forming chamber is connected to an exhaust pump through a pressure regulating valve, and the inside of the chamber is maintained at 160 ° C. by a cartridge heater embedded in the chamber wall. The stage heater is a wafer at about 0.3 Torr. It is set to 320 ° C. so that the temperature becomes 290 ° C.
Using the transfer arm, a Si wafer having a diameter of 300 mm was introduced from the transfer system into the film forming chamber and transferred to the stage heater. Thereafter, Ar gas (500 sccm) was circulated, and the pressure in the chamber was maintained at 1 Torr by a pressure control valve to raise the wafer temperature.
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2１００ｇを、バブリング用シリンダ（Ａ）に充填して、１６５℃に保持し、キャリアガスとしてＡｒガス５０ｓｃｃｍを流通してバブリングし、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気を得た。また、Ｔｉ（ＯｉＰｒ）4が充填されたシリンダ（Ｂ）を４５℃に保持し、Ａｒガス２００ｓｃｃｍを流通してバブリングし、Ｔｉ（ＯｉＰｒ）4蒸気を得た。また、酸化剤として水が充填されたシリンダを８０℃に保持し、出口側に高温マスフローメータを設置して、Ｈ2Ｏガスが２００ｓｃｃｍ流れるようにした（Ｃ）。さらに、パージガスとしてはＡｒ２００ｓｃｃｍを用いた。
これらの原料または酸化剤の供給（以下、パルスという）およびパージを、各パルス５秒、パージ１０秒として、以下のようなＡＬＤ操作を行った。パルスまたはパージ時、チャンバの圧力制御弁は開いているため、チャンバ内の圧力は、チャンバ内のガス流量に応じて、パルスＡ：０．３Ｔｏｒｒ、パルスＢ：０．４Ｔｏｒｒ、パルスＣ：０．５Ｔｏｒｒ、パージ：０．２Ｔｏｒｒとなる。これらのＡＬＤ操作の間、ウエハは約２９０℃に保持される。
（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒＯ形成サイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＴｉＯ2形成サイクルとを、合わせて７７サイクル、ＳｒＯ／ＴｉＯ2サイクル比＝１．３となるように行った。具体的には、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を１サイクルの一連の工程を１回とし、これを１１回繰り返し、厚さ５ｎｍのＳｒＴｉＯ3膜を形成した。
100 g of Sr (PrMe 4 Cp) 2 obtained in Example 1 was filled in a bubbling cylinder (A), maintained at 165 ° C., and bubbled by flowing Ar gas at 50 sccm as a carrier gas, and Sr (PrMe 4 Cp) to give a 2 vapor. Further, the cylinder (B) filled with Ti (OiPr) 4 was held at 45 ° C., and 200 sccm of Ar gas was circulated and bubbled to obtain Ti (OiPr) 4 vapor. Further, a cylinder filled with water as an oxidant was kept at 80 ° C., and a high-temperature mass flow meter was installed on the outlet side so that H 2 O gas flowed at 200 sccm (C). Further, Ar 200 sccm was used as the purge gas.
The following ALD operation was performed with the supply of these raw materials or oxidizing agents (hereinafter referred to as pulses) and purging with each pulse of 5 seconds and purge of 10 seconds. Since the pressure control valve of the chamber is open at the time of pulse or purge, the pressure in the chamber is changed according to the gas flow rate in the chamber, pulse A: 0.3 Torr, pulse B: 0.4 Torr, pulse C: 0. 5 Torr, purge: 0.2 Torr. During these ALD operations, the wafer is held at about 290 ° C.
SrO formation cycle by (A pulse-purge-C pulse-purge) and TiO 2 formation cycle by (B pulse-purge-C pulse-purge) are 77 cycles in total, SrO / TiO 2 cycle ratio = 1. It went so that it might become 3. Specifically, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, A series of steps of one cycle of (B pulse-purge-C pulse-purge) was performed once and this was repeated 11 times to form an SrTiO 3 film having a thickness of 5 nm.
ＸＲＦ（蛍光Ｘ線分析）法により、形成した膜の組成を調べたところ、Ｓｒ／Ｔｉ＝１．４であった。
また、Ｓｒ（ＰｒＭｅ4Ｃｐ）2の使い始めと９０ｇ使用時点で、２５枚のランニング成膜を行ったところ、その平均膜厚は５３．５Åと５０．３Å、面内膜厚分布の標準偏差は１．６％と１．３％、２５枚の面間膜厚分布の標準偏差は２．８％と３．３％であり、Ｓｒ（ＰｒＭｅ4Ｃｐ）2の使い始めとほぼ使い終わりである９０ｇ使用時点とで、成膜特性の差異はほとんどなかった。
When the composition of the formed film was examined by XRF (fluorescence X-ray analysis), Sr / Ti = 1.4.
In addition, when 25 sheets of running film were formed at the beginning of use of Sr (PrMe 4 Cp) 2 and 90 g, the average film thickness was 53.5 mm and 50.3 mm, and the standard deviation of the in-plane film thickness distribution was Are 1.6% and 1.3%, and the standard deviations of the film thickness distribution between the 25 sheets are 2.8% and 3.3%, respectively, and the use of Sr (PrMe 4 Cp) 2 is almost complete. There was almost no difference in film-forming characteristics from a certain 90 g use point.
［比較例５］ＳｒＣｐ* 2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（１）
Ｓｒ（ＰｒＭｅ4Ｃｐ）2に代えてＳｒＣｐ* 2を用い、それ以外は実施例３と同様にして成膜した。
ＳｒＣｐ* 2１００ｇの使い始めと９０ｇ使用時点で、２５枚のランニング成膜を行ったところ、その平均膜厚は５５．２Åと４３．２Åであり、膜のＳｒ／Ｔｉ比も、使い始めが１．４であるのに対して、９０ｇ使用時点では０．８であり、明らかに、ＳｒＣｐ* 2の供給量が低下していた。
[Comparative Example 5] Formation of SrTiO 3 film by ALD method using SrCp * 2 (1)
A film was formed in the same manner as in Example 3 except that SrCp * 2 was used instead of Sr (PrMe 4 Cp) 2 .
When SrCp * 2 100g started to be used and 90g was used, running film of 25 sheets was used, the average film thickness was 55.2mm and 43.2mm, and the Sr / Ti ratio of the film was also started to use. whereas the 1.4, 0.8 at 90g point of use, obviously, the supply amount of SrCp * 2 was decreased.
実施例３と比較例５から、Ｓｒ（ＰｒＭｅ4Ｃｐ）2は、バブリングの温度で液体であるため、充填量１００ｇの使用開始から終了まで、安定して蒸気を供給することができる。
一方、ＳｒＣｐ* 2はバブリングを行う温度で固体であるため、充填量１００ｇの使用開始から終了にかけて、粉体の凝集による蒸発表面積の減少、シリンダや配管のコールドスポットへの原料の凝集による伝熱不足等により、成膜原料の供給量が低下していく傾向があり、これにより、同じ成膜条件での膜厚の減少やＳｒ／Ｔｉ比の低下がもたらされていると考えられる。
From Example 3 and Comparative Example 5, since Sr (PrMe 4 Cp) 2 is a liquid at the bubbling temperature, steam can be stably supplied from the start of use to the end of the filling amount of 100 g.
On the other hand, since SrCp * 2 is a solid at the temperature at which bubbling is performed, from the start to the end of use of a filling amount of 100 g, the evaporation surface area decreases due to agglomeration of powder, and heat transfer due to agglomeration of raw materials to the cold spots of cylinders and pipes There is a tendency that the supply amount of the film forming raw material decreases due to the shortage and the like, and this is considered to cause a decrease in the film thickness and a decrease in the Sr / Ti ratio under the same film formation conditions.
［実施例４］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（３）
成膜チャンバは、実施例３と同様の条件設定とした。
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2を、バブリング用シリンダ（Ａ）に充填して、１５５℃に保持し、キャリアガスとしてＡｒガス５０ｓｃｃｍを流通してバブリングし、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気を得た。また、Ｔｉ（ＯｉＰｒ）4が充填されたシリンダ（Ｂ）を５５℃に保持し、Ａｒガス２００ｓｃｃｍを流通してバブリングし、Ｔｉ（ＯｉＰｒ）4蒸気を得た。また、酸化剤としてＯ2／Ｎ2＝５００／０．５ｓｃｃｍ混合ガスを、オゾナイザに通じて１８０ｇ／ｍ3濃度のＯ3ガスを得た（Ｃ）。さらに、パージガスとしてはＡｒ２００ｓｃｃｍを用いた。
これらのパルスおよびパージを、Ａ，Ｂパルス１０秒、Ｃパルス２秒、パージ１０秒として、以下のようなＡＬＤ操作を行った。
（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒＯ形成サイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＴｉＯ2形成サイクルとを、合わせて７７サイクル、ＳｒＯ／ＴｉＯ2サイクル比＝１．２となるように行った。具体的には、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を１サイクルの一連の工程を１回とし、これを７回繰り返し、厚さ５ｎｍのＳｒＴｉＯ3膜を形成した。
ＸＲＦ法により、形成した膜の組成を調べたところ、Ｓｒ／Ｔｉ＝１．２５であった。
[Example 4] Formation of SrTiO 3 film by ALD method using Sr (PrMe 4 Cp) 2 (3)
The film forming chamber was set to the same conditions as in Example 3.
Sr (PrMe 4 Cp) 2 obtained in Example 1 was filled into a bubbling cylinder (A), held at 155 ° C., and bubbled by flowing 50 sccm of Ar gas as a carrier gas, and Sr (PrMe 4 Cp) 2 vapor was obtained. Further, the cylinder (B) filled with Ti (OiPr) 4 was held at 55 ° C., and 200 sccm of Ar gas was circulated and bubbled to obtain Ti (OiPr) 4 vapor. Further, O 2 / N 2 = 500 / 0.5 sccm mixed gas as an oxidizing agent was passed through an ozonizer to obtain 180 g / m 3 concentration of O 3 gas (C). Further, Ar 200 sccm was used as the purge gas.
The following ALD operation was performed with these pulses and purges of A and B pulses 10 seconds, C pulses 2 seconds, and purge 10 seconds.
SrO formation cycle by (A pulse-purge-C pulse-purge) and TiO 2 formation cycle by (B pulse-purge-C pulse-purge) are 77 cycles in total, SrO / TiO 2 cycle ratio = 1. 2 was performed. Specifically, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, and (B pulse-purge-C pulse-purge) is 1 cycle. This was repeated seven times to form a 5 nm thick SrTiO 3 film.
When the composition of the formed film was examined by the XRF method, it was Sr / Ti = 1.25.
［実施例５］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（４）
成膜チャンバは、実施例３と同様の条件設定とした。
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2をトルエンに溶解し、０．４ｍｏｌ／ｌ溶液とした。その粘度は４０ｃＰであった。
この溶液を、液体供給系を用いて２００℃に加熱した気化器に誘導し、Ａｒガス２００ｓｃｃｍをキャリアガスとして、０．３ｇ／ｍｉｎの流量で、液体流量計で制御しながら気化させ、Ｓｒ（ＰｒＭｅ4Ｃｐ）2ガスを得た（Ａ）。また、Ｔｉ（ＯｉＰｒ）4を、液体供給系を用いて１００℃に加熱した気化器に誘導し、Ａｒガス２００ｓｃｃｍをキャリアガスとして、０．１ｇ／ｍｉｎの流量で、液体流量計で制御しながら気化させ、Ｔｉ（ＯｉＰｒ）4蒸気を得た。また、酸化剤としてＯ2／Ｎ2＝５００／０．５ｓｃｃｍ混合ガスを、オゾナイザに通じて１８０ｇ／ｍ3濃度のＯ3ガスを得た（Ｃ）。さらに、パージガスとしてはＡｒ２００ｓｃｃｍを用いた。
これらのパルスおよびパージを、Ａ，Ｂパルス２秒、Ｃパルス２秒、パージ５秒として、以下のようなＡＬＤ操作を行った。
（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒＯ形成サイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＴｉＯ２形成サイクルとを、合わせて９９サイクル、ＳｒＯ／ＴｉＯ2サイクル比＝１．２となるように行った。具体的には、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を１サイクルの一連の工程を１回とし、これを９回繰り返し、厚さ６．４ｎｍのＳｒＴｉＯ3膜を形成した。
[Example 5] Formation of SrTiO 3 film by ALD method using Sr (PrMe 4 Cp) 2 (4)
The film forming chamber was set to the same conditions as in Example 3.
Sr (PrMe 4 Cp) 2 obtained in Example 1 was dissolved in toluene to obtain a 0.4 mol / l solution. Its viscosity was 40 cP.
This solution is guided to a vaporizer heated to 200 ° C. using a liquid supply system, vaporized while being controlled by a liquid flow meter at a flow rate of 0.3 g / min using Ar gas of 200 sccm as a carrier gas, and Sr ( PrMe 4 Cp) 2 gas was obtained (A). Further, Ti (OiPr) 4 is guided to a vaporizer heated to 100 ° C. using a liquid supply system, and Ar gas is 200 sccm as a carrier gas, and is controlled by a liquid flow meter at a flow rate of 0.1 g / min. Vaporization gave Ti (OiPr) 4 vapor. Further, O 2 / N 2 = 500 / 0.5 sccm mixed gas as an oxidizing agent was passed through an ozonizer to obtain 180 g / m 3 concentration of O 3 gas (C). Further, Ar 200 sccm was used as the purge gas.
The following ALD operation was performed with these pulses and purges of A and B pulses 2 seconds, C pulse 2 seconds, and purge 5 seconds.
SrO formation cycle by (A pulse-purge-C pulse-purge) and TiO2 formation cycle by (B pulse-purge-C pulse-purge) are 99 cycles in total, SrO / TiO 2 cycle ratio = 1.2 It went so that it might become. Specifically, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, and (B pulse-purge-C pulse-purge) is 1 cycle. This was repeated 9 times to form a 6.4 nm thick SrTiO 3 film.
このＳｒＴｉＯ3膜を用いて、上・下部電極をともにＲｕとして、ＭＩＭ（ｍｅｔａｌ Ｉｎｓｕｌａｔｏｒ Ｍｅｔａｌ）構造を作製し、６００℃の熱処理でＳｒＴｉＯ3を結晶化させたところ、酸化膜換算膜厚は０．７ｎｍであり、電圧１Ｖ印加時のリーク電流は３．５×１０-7Ａ／ｃｍ2であった。 Using this SrTiO 3 film, an MIM (metal Insulator Metal) structure was prepared using both the upper and lower electrodes as Ru, and SrTiO 3 was crystallized by heat treatment at 600 ° C. The leakage current was 7 × 10 −7 A / cm 2 when applied with a voltage of 1 V.
［比較例６］ＳｒＣｐ* 2を用いたＡＬＤ法によるＳｒＴｉＯ3膜の形成（２）
Ｓｒ（ＰｒＭｅ4Ｃｐ）2０．４ｍｏｌ／ｌトルエン溶液に代えてＳｒＣｐ* 2０．２ｍｏｌ／ｌトルエン溶液を用い、それ以外は、実施例５と同様にして成膜した。
（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒＯ形成サイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＴｉＯ2形成サイクルとを、合わせて９９サイクル、ＳｒＯ／ＴｉＯ2サイクル比＝１．２となるように行った。具体的には、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を１サイクルの一連の工程を１回とし、これを９回繰り返し、厚さ８．２ｎｍのＳｒＴｉＯ3膜を形成した。
[Comparative Example 6] Formation of SrTiO 3 film by ALD method using SrCp * 2 (2)
A film was formed in the same manner as in Example 5 except that a SrCp * 2 0.2 mol / l toluene solution was used instead of the Sr (PrMe 4 Cp) 2 0.4 mol / l toluene solution.
The SrO formation cycle by (A pulse-purge-C pulse-purge) and the TiO 2 formation cycle by (B pulse-purge-C pulse-purge) are 99 cycles in total, SrO / TiO 2 cycle ratio = 1. 2 was performed. Specifically, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, (B pulse-purge-C pulse-purge) is 2 cycles, (A pulse-purge-C pulse-purge) is 2 cycles, and (B pulse-purge-C pulse-purge) is 1 cycle. This was repeated 9 times, and an SrTiO 3 film having a thickness of 8.2 nm was formed.
このＳｒＴｉＯ3膜を用いて、上・下部電極をともにＲｕとして、ＭＩＭ構造を作製し、６００℃の熱処理でＳｒＴｉＯ3を結晶化させたところ、酸化膜換算膜厚は０．９ｎｍであり、電圧１Ｖ印加時のリーク電流は２．４×１０-3Ａ／ｃｍ2であった。
このＳｒＴｉＯ3膜は、実施例５のＳｒＴｉＯ3膜に比べて、物理膜厚、酸化膜換算膜厚とも厚いにもかかわらず、リーク電流が大きかった。
Using this SrTiO 3 film, as the upper and lower electrodes both Ru, to prepare a MIM structure, was allowed to crystallize SrTiO 3 at heat treatment of 600 ° C., the equivalent oxide thickness is 0.9 nm, the voltage The leakage current when 1 V was applied was 2.4 × 10 −3 A / cm 2 .
This SrTiO 3 film had a larger leakage current than the SrTiO 3 film of Example 5, although the physical film thickness and the equivalent oxide film thickness were both large.
実施例５および比較例６のＳｒＴｉＯ3膜を、それぞれ膜厚５ｎｍでＳｉ基板上に成膜し、ＴＸＲＦ（全反射蛍光Ｘ線）分析によりＮａ含量を比較したところ、比較例６は実施例５の２倍であった。
このことから、ＳｒＣｐ* 2の方がＳｒ（ＰｒＭｅ4Ｃｐ）2に比べてＮａ等の不純物が多いため、電気的特性を悪化させていると考えられる。
The SrTiO 3 films of Example 5 and Comparative Example 6 were each formed on a Si substrate with a film thickness of 5 nm, and the Na content was compared by TXRF (total reflection fluorescent X-ray) analysis. It was twice.
From this, it is considered that SrCp * 2 has more impurities such as Na than Sr (PrMe 4 Cp) 2, and thus deteriorates electrical characteristics.
［実施例６］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＡＬＤ法によるＳｒＲｕＯ3膜の形成
成膜チャンバは、ステージヒータの設定を０．３Ｔｏｒｒでウエハ温度が３３０℃となるように３５０℃とし、それ以外は実施例３と同様の条件設定とした。
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2をトルエンに溶解し、０．４ｍｏｌ／ｌ溶液とした。この溶液を、液体供給系を用いて２００℃に加熱した気化器に誘導し、Ａｒガス２００ｓｃｃｍをキャリアガスとして、０．３ｇ／ｍｉｎの流量で、液体流量計で制御しながら気化させ、Ｓｒ（ＰｒＭｅ4Ｃｐ）2ガスを得た（Ａ）。また、Ｒｕ（ＥｔＣｐ）2を、液体供給系を用いて１２０℃に加熱した気化器に誘導し、Ａｒガス２００ｓｃｃｍをキャリアガスとして、０．１ｇ／ｍｉｎの流量で、液体流量計で制御しながら気化させ、Ｒｕ（ＥｔＣｐ）2蒸気を得た。また、酸化剤としてＯ2／Ｎ2＝５００／０．５ｓｃｃｍ混合ガスを、オゾナイザに通じて１００ｇ／ｍ3濃度のＯ3ガスを得た（Ｃ）。さらに、パージガスとしてはＡｒ２００ｓｃｃｍを用いた。
これらのパルスおよびパージを、Ａ，Ｂパルス１秒、Ｃパルス１秒、パージ２秒として、以下のようなＡＬＤ操作を行った。
（Ａパルス−パージ−Ｃパルス−パージ）によるＳｒＯ形成サイクルと、（Ｂパルス−パージ−Ｃパルス−パージ）によるＲｕＯ2形成サイクルとを、合わせて２４０サイクル、ＳｒＯ／ＲｕＯ2サイクル比＝１となるように行った。具体的には、（Ａパルス−パージ−Ｃパルス−パージ）を２サイクル、（Ｂパルス−パージ−Ｃパルス−パージ）を２サイクルの一連の工程を１回とし、これを６０回繰り返し、厚さ１８ｎｍのＳｒＲｕＯ3膜を形成した。
Example 6 Formation of SrRuO 3 Film by ALD Method Using Sr (PrMe 4 Cp) 2 The film formation chamber was set to 350 ° C. so that the wafer temperature would be 330 ° C. at a stage heater setting of 0.3 Torr. Other than that, the same condition setting as in Example 3 was adopted.
Sr (PrMe 4 Cp) 2 obtained in Example 1 was dissolved in toluene to obtain a 0.4 mol / l solution. This solution is guided to a vaporizer heated to 200 ° C. using a liquid supply system, vaporized while being controlled by a liquid flow meter at a flow rate of 0.3 g / min using Ar gas of 200 sccm as a carrier gas, and Sr ( PrMe 4 Cp) 2 gas was obtained (A). In addition, Ru (EtCp) 2 is guided to a vaporizer heated to 120 ° C. using a liquid supply system, and Ar gas is 200 sccm as a carrier gas while being controlled by a liquid flow meter at a flow rate of 0.1 g / min. Vaporization gave Ru (EtCp) 2 vapor. Further, O 2 / N 2 = 500 / 0.5 sccm mixed gas as an oxidizing agent was passed through an ozonizer to obtain O 3 gas having a concentration of 100 g / m 3 (C). Further, Ar 200 sccm was used as the purge gas.
These pulses and purges were A and B pulses for 1 second, C pulses for 1 second, and purge for 2 seconds, and the following ALD operation was performed.
The SrO formation cycle by (A pulse-purge-C pulse-purge) and the RuO 2 formation cycle by (B pulse-purge-C pulse-purge) are 240 cycles in total, and the SrO / RuO 2 cycle ratio = 1. I went like that. Specifically, a series of steps of (A pulse-purge-C pulse-purge) for 2 cycles and (B pulse-purge-C pulse-purge) for 2 cycles are performed once, and this is repeated 60 times. A 18 nm thick SrRuO 3 film was formed.
［実施例７］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＣＶＤ法によるＳｒＴｉＯ3膜の製造
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2が充填されたシリンダを１６０℃、内圧約５Ｔｏｒｒで、アルゴンガス５０ｓｃｃｍでバブリングし、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気をＣＶＤ室に送った。
同時に、Ｔｉ（ＮＭｅ2）4が充填されたシリンダを３０℃、内圧約５Ｔｏｒｒで、アルゴンガス５０ｓｃｃｍでバブリングし、Ｔｉ（ＮＭｅ2）4蒸気をＣＶＤ室に送った。
また、酸素ガス１００ｓｃｃｍをＣＶＤ室に送った。
ＣＶＤ室入口でこれらのガスを混合し、２Ｔｏｒｒ、３５０℃に保持したＳｉ（１００）基板上に導入したところ、３０分間で、厚さ６０ｎｍのＳｒＴｉＯ3膜が生成した。
Example 7] Sr (PrMe 4 Cp) 2 CVD method using SrTiO 3 film preparation obtained in Example 1 Sr (PrMe 4 Cp) 160 ℃ two cylinder filled with the using, in internal pressure of about 5Torr Then, argon gas was bubbled at 50 sccm, and Sr (PrMe 4 Cp) 2 vapor was sent to the CVD chamber.
At the same time, a cylinder filled with Ti (NMe 2 ) 4 was bubbled with argon gas at 50 sccm at 30 ° C. and an internal pressure of about 5 Torr, and Ti (NMe 2 ) 4 vapor was sent to the CVD chamber.
In addition, 100 sccm of oxygen gas was sent to the CVD chamber.
When these gases were mixed at the entrance of the CVD chamber and introduced onto a Si (100) substrate maintained at 2 Torr and 350 ° C., a SrTiO 3 film having a thickness of 60 nm was formed in 30 minutes.
［実施例８］Ｓｒ（ＰｒＭｅ4Ｃｐ）2を用いたＣＶＤ法によるＳｒＲｕＯ3膜の製造
実施例１で得られたＳｒ（ＰｒＭｅ4Ｃｐ）2が充填されたシリンダを１６０℃、内圧約７Ｔｏｒｒで、アルゴンガス５０ｓｃｃｍでバブリングし、Ｓｒ（ＰｒＭｅ4Ｃｐ）2蒸気をＣＶＤ室に送った。
同時に、Ｒｕ（ＥｔＣｐ）2が充填されたシリンダを３０℃、内圧約７Ｔｏｒｒで、アルゴンガス５０ｓｃｃｍでバブリングし、Ｒｕ（ＥｔＣｐ）2蒸気をＣＶＤ室に送った。
ＣＶＤ室入口でこれらのガスを混合し、５Ｔｏｒｒ、７００℃に保持したＳｒＴｉＯ3（１００）基板上に導入したところ、３０分間で厚さ８０ｎｍのＳｒＲｕＯ3膜が生成した。
Example 8] Sr (PrMe 4 Cp) 2 CVD method using SrRuO 3 film preparation obtained in Example 1 Sr (PrMe 4 Cp) 2 160 ℃ the cylinder filled with the using, in internal pressure of about 7Torr Then, argon gas was bubbled at 50 sccm, and Sr (PrMe 4 Cp) 2 vapor was sent to the CVD chamber.
At the same time, Ru (EtCp) 2 30 ℃ a cylinder filled at an internal pressure of about 7 Torr, and bubbled with argon gas 50 sccm, sent Ru (EtCp) 2 vapor to the CVD chamber.
When these gases were mixed at the entrance of the CVD chamber and introduced onto a SrTiO 3 (100) substrate maintained at 5 Torr and 700 ° C., an SrRuO 3 film having a thickness of 80 nm was formed in 30 minutes.
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| WO2012132669A1 (en) * | 2011-03-29 | 2012-10-04 | 株式会社高純度化学研究所 | Precursor for formation of europium-containing thin film, and method for forming europium-containing thin film |
| WO2012177642A2 (en) * | 2011-06-20 | 2012-12-27 | Advanced Technology Materials, Inc. | High-k perovskite material and methods of making and using the same |
| JP7114072B2 (en) * | 2018-12-06 | 2022-08-08 | 株式会社高純度化学研究所 | Bis(alkyltetramethylcyclopentadienyl)zinc, raw material for chemical vapor deposition, and method for producing thin film containing zinc |
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| JPH02225317A (en) * | 1989-02-23 | 1990-09-07 | Asahi Glass Co Ltd | Production of oxide superconductor by chemical gas phase deposition method |
| US6103002A (en) * | 1993-09-14 | 2000-08-15 | Mitsubishi Denki Kabushiki Kaisha | CVD method for forming oxide-system dielectric thin film |
| JPH06240456A (en) * | 1992-12-21 | 1994-08-30 | Kawasaki Steel Corp | Method and device for forming aluminum circuit of semiconductor device |
| KR100360494B1 (en) * | 1999-09-21 | 2002-11-13 | 삼성전자 주식회사 | Bubbler |
| US6475902B1 (en) * | 2000-03-10 | 2002-11-05 | Applied Materials, Inc. | Chemical vapor deposition of niobium barriers for copper metallization |
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| JP4626132B2 (en) * | 2003-08-29 | 2011-02-02 | 東ソー株式会社 | Method for producing Ru-containing oxide conductive thin film |
| US20070154637A1 (en) * | 2005-12-19 | 2007-07-05 | Rohm And Haas Electronic Materials Llc | Organometallic composition |
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| JP2006096732A (en) * | 2004-09-28 | 2006-04-13 | Kojundo Chem Lab Co Ltd | METHOD OF MANUFACTURING DOUBLE ALKOXIDES OF HIGH PURITY SrTa AND SrNb |
| JP2006140450A (en) * | 2004-10-05 | 2006-06-01 | Rohm & Haas Electronic Materials Llc | Organometallic compound |
| WO2008100616A2 (en) * | 2007-02-15 | 2008-08-21 | The Board Of Trustees Of The Leland Stanford Junior University | Atomic layer deposition of strontium oxide via n-propyltetramethyl cyclopentadienyl precursor |
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| US9644343B2 (en) | 2012-10-30 | 2017-05-09 | Joseph Voegele Ag | Construction machine with machine component |
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| JP5260148B2 (en) | 2013-08-14 |
| TWI447255B (en) | 2014-08-01 |
| TW200907095A (en) | 2009-02-16 |
| JP5311886B2 (en) | 2013-10-09 |
| TW200906836A (en) | 2009-02-16 |
| TWI398445B (en) | 2013-06-11 |
| JP2009030162A (en) | 2009-02-12 |
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