JP2016166142A - Raw material for chemical vapor deposition composed of organic nickel compound and chemical vapor deposition method using the raw material for chemical vapor deposition - Google Patents
Raw material for chemical vapor deposition composed of organic nickel compound and chemical vapor deposition method using the raw material for chemical vapor deposition Download PDFInfo
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- 150000002816 nickel compounds Chemical class 0.000 title claims abstract description 43
- 239000002994 raw material Substances 0.000 title claims abstract description 43
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 165
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 79
- 239000010409 thin film Substances 0.000 claims abstract description 44
- 150000000475 acetylene derivatives Chemical class 0.000 claims abstract description 18
- 239000012495 reaction gas Substances 0.000 claims abstract description 18
- 125000001424 substituent group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000004665 trialkylsilyl group Chemical group 0.000 claims abstract description 11
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 41
- 239000003446 ligand Substances 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000005979 thermal decomposition reaction Methods 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000005755 formation reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- ZDWYFWIBTZJGOR-UHFFFAOYSA-N bis(trimethylsilyl)acetylene Chemical group C[Si](C)(C)C#C[Si](C)(C)C ZDWYFWIBTZJGOR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- HOMQMIYUSVQSHM-UHFFFAOYSA-N cycloocta-1,3-diene;nickel Chemical compound [Ni].C1CCC=CC=CC1.C1CCC=CC=CC1 HOMQMIYUSVQSHM-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- FXVDWKZNFZMSOU-UHFFFAOYSA-N 2,2,5,5-tetramethylhex-3-yne Chemical group CC(C)(C)C#CC(C)(C)C FXVDWKZNFZMSOU-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910005849 NiNx Inorganic materials 0.000 description 1
- -1 Nickel Nitride Chemical class 0.000 description 1
- 229910001295 No alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001928 direct liquid injection chemical vapour deposition Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
本発明は化学蒸着法によりニッケル薄膜又はニッケル化合物薄膜を製造するための有機ニッケル化合物からなる化学蒸着用原料に関する。詳しくは、反応ガスを使用することなく高純度のニッケル薄膜を製造することのできる化学蒸着用原料に関する。 The present invention relates to a raw material for chemical vapor deposition comprising an organic nickel compound for producing a nickel thin film or a nickel compound thin film by a chemical vapor deposition method. In detail, it is related with the raw material for chemical vapor deposition which can manufacture a high purity nickel thin film, without using reaction gas.
集積回路（ＬＳＩ、ＵＬＳＩ、ＣＰＵ）に組み込まれるトランジスタ（ＦＥＴ）やフラッシュメモリ等の各種デバイスの電極としてニッケル（Ｎｉ）薄膜が適用されている。これらの電極には、微細化、立体化といった構造面での改良と共に、低抵抗化のために不純物が排除されたニッケル薄膜であることが要求されている。このニッケル薄膜の製造として、化学蒸着法（化学気相蒸着法（ＣＶＤ法）、及び原子層蒸着法（ＡＬＤ法））が適用される。 A nickel (Ni) thin film is applied as an electrode of various devices such as a transistor (FET) and a flash memory incorporated in an integrated circuit (LSI, ULSI, CPU). These electrodes are required to be nickel thin films from which impurities are eliminated in order to reduce resistance as well as structural improvements such as miniaturization and three-dimensionalization. For the production of the nickel thin film, chemical vapor deposition (chemical vapor deposition (CVD) and atomic layer deposition (ALD)) is applied.
化学蒸着法によるニッケル薄膜製造用の原料としては、従来から多くの有機ニッケル化合物が知られている。それらの中で高純度のニッケル薄膜を製造できるものとして、特許文献１及び非特許文献１記載の有機ニッケル化合物からなる薄膜製造用原料がある。 Conventionally, many organic nickel compounds are known as raw materials for producing a nickel thin film by chemical vapor deposition. Among them, as a material capable of producing a high-purity nickel thin film, there are raw materials for producing a thin film comprising an organic nickel compound described in Patent Document 1 and Non-Patent Document 1.
特許文献１記載のニッケル薄膜製造用原料は、下記式で示される有機ニッケル化合物からなる。この原料は、反応ガスとして水素を適用することで高純度のニッケル薄膜を製造することができる。 The raw material for producing a nickel thin film described in Patent Document 1 is composed of an organic nickel compound represented by the following formula. This raw material can produce a high-purity nickel thin film by applying hydrogen as a reaction gas.
また、非特許文献１記載のニッケル薄膜製造用原料は、下記式で示される有機ニッケル化合物からなる。この原料については、反応ガスとしてアンモニアを適用することで、窒素を含有するニッケル膜（ＮｉＮｘ（ｘ＝０．０６〜０．３３））を製造することができる。このニッケル膜中の窒素は、適宜に熱処理することで除去可能であり、これにより高純度のニッケル薄膜を得ることができる。 Moreover, the raw material for nickel thin film manufacture of a nonpatent literature 1 consists of an organic nickel compound shown by a following formula. About this raw material, the nickel film | membrane (NiNx (x = 0.06-0.33)) containing nitrogen can be manufactured by applying ammonia as a reaction gas. Nitrogen in the nickel film can be removed by an appropriate heat treatment, whereby a high-purity nickel thin film can be obtained.
ところで、化学蒸着法においては、使用する有機金属化合物の種類に応じた反応ガスを原料ガスに同伴させて反応器に導入し成膜することが一般的となっている。上記従来の有機ニッケル化合物も、水素（特許文献１）やアンモニア（非特許文献１）を反応ガスとしている。薄膜の成長は、原料化合物の分解により進行するが、加熱のみで十分に分解する原料化合物はさほど多くはない。そこで、反応ガスにより原料化合物の分解をアシストして金属析出・成膜を促進する。また、反応ガスである水素やアンモニアは還元性ガスであるので、析出した金属の酸化防止の機能も有する。これらから、反応ガスの使用は高純度のニッケル薄膜を得る上で必須の要素と捉えられている。 By the way, in the chemical vapor deposition method, it is common to form a film by introducing a reaction gas corresponding to the type of the organometallic compound to be used together with the raw material gas into the reactor. The conventional organic nickel compound also uses hydrogen (Patent Document 1) or ammonia (Non-Patent Document 1) as a reaction gas. Although the growth of the thin film proceeds by decomposition of the raw material compound, there are not so many raw material compounds that are sufficiently decomposed only by heating. Accordingly, the reaction gas assists decomposition of the raw material compound to promote metal deposition and film formation. In addition, since the reactive gases such as hydrogen and ammonia are reducing gases, they also have a function of preventing the deposited metal from being oxidized. From these, use of the reaction gas is regarded as an essential element for obtaining a high-purity nickel thin film.
もっとも、反応ガスは薄膜の純度・品質を確保する上では有用であるが、成膜コストや作業安全性を考慮すれば好ましいものではない。上記で反応ガスとして挙げられた水素やアンモニアは、爆発性・腐食性・毒性が懸念されるガスであり、安全上の問題がある。そのため、成膜設備について安全対策や防食対応が要求されるので、設備コスト上昇を引き起こすこととなる。そして、従来から反応ガスを適用することなく高純度のニッケル薄膜を製造することのできる有機ルテニウム化合物の開発が求められている。 Of course, the reactive gas is useful for ensuring the purity and quality of the thin film, but it is not preferable in view of the deposition cost and work safety. Hydrogen and ammonia mentioned above as reaction gases are gases that are concerned about explosiveness, corrosiveness, and toxicity, and have safety problems. For this reason, safety measures and anticorrosion measures are required for the film forming equipment, which causes an increase in equipment costs. And development of the organoruthenium compound which can manufacture a high purity nickel thin film conventionally is not requested | required, without applying a reactive gas.
本発明は、上記のような背景のもとになされたものであり、水素等の反応ガスを使用することなくニッケルを析出させることができ、高純度のニッケル薄膜を成膜できるような有機ニッケル化合物を主成分とする化学蒸着用原料を提供する。 The present invention has been made based on the background as described above, and can deposit nickel without using a reaction gas such as hydrogen, and can form a high-purity nickel thin film. A raw material for chemical vapor deposition comprising a compound as a main component is provided.
本発明者等は、有機ニッケル化合物の熱安定性、熱分解による薄膜の形成過程、及び、反応ガスによる熱分解の促進作用の各項目について考察を行い、以下の知見を得た。 The present inventors have examined the items of thermal stability of the organonickel compound, the process of forming a thin film by thermal decomposition, and the action of promoting thermal decomposition by a reaction gas, and obtained the following knowledge.
（１）有機ニッケル化合物からの金属ニッケルの析出は、有機ニッケル化合物の熱分解により進行するものであるが、熱分解が起こり易いか否かは中心金属であるニッケルと配位子との結合力の強弱に左右される。従来の化合物は、ニッケルと配位子との結合力が強く、熱分解が容易には起こらない。そのため分解反応を促進するための反応ガスの使用が必要であった。 (1) Precipitation of metallic nickel from the organic nickel compound proceeds by thermal decomposition of the organic nickel compound, but whether or not thermal decomposition is likely to occur depends on the bonding strength between nickel as the central metal and the ligand. It depends on the strength of. Conventional compounds have a strong binding force between nickel and a ligand, and thermal decomposition does not occur easily. Therefore, it was necessary to use a reaction gas to accelerate the decomposition reaction.
（２）上記化１、化２で示した従来の有機ニッケル化合物は、２価の正電荷を有するニッケルイオンに、１価の負電荷を有する配位子が２つ配位したものである。このような有機ニッケル化合物が分解して金属膜（電荷を持たないニッケル原子の集合体）を形成するためには、次の２つのプロセスを経ることが必要と考えられる。
（ａ）中心金属と配位子間の距離が大きくなり結合が切れる。
（ｂ）中心金属、配位子が持つ電荷が中和されゼロ価になる。
(2) The conventional organonickel compounds represented by Chemical Formula 1 and Chemical Formula 2 are those in which two monovalent negatively charged ligands are coordinated to a divalent positively charged nickel ion. In order for such an organic nickel compound to decompose and form a metal film (an aggregate of nickel atoms having no charge), it is considered necessary to go through the following two processes.
(A) The distance between the central metal and the ligand is increased and the bond is broken.
(B) The charge of the central metal and ligand is neutralized to zero.
（ａ）のプロセスは、加熱温度を高くして分子の熱運動が激しくなるようにすることで達成される。一方、（ｂ）のプロセスを達成するためには、中心金属に電子を与えるための還元剤あるいは配位子から電子を取り去るための酸化剤の使用が必要である。上記化１、化２で示した従来の有機ニッケル化合物の場合、これら（ａ）、（ｂ）の双方のプロセスの達成が必要であった。 The process (a) is achieved by increasing the heating temperature so that the thermal motion of the molecules becomes intense. On the other hand, in order to achieve the process (b), it is necessary to use a reducing agent for giving electrons to the central metal or an oxidizing agent for removing electrons from the ligand. In the case of the conventional organic nickel compounds represented by the above chemical formulas 1 and 2, it is necessary to achieve both the processes (a) and (b).
本発明者等は、これらの知見から課題解決の方策として、上記（ａ）、（ｂ）のプロセスの双方の達成ではなく、（ａ）のみの達成により金属ニッケルを析出させることができる有機ニッケル化合物の採用が好適であるとした。そして、その具体的手段として、中心金属ならびに配位子が共に電荷を持たないゼロ価のニッケル錯体（有機ニッケル化合物）の適用に想到した。原料段階からゼロ価のニッケル錯体を用いれば、熱分解（上記（ａ）プロセスの達成）によりゼロ価の金属原子と配位子に分離する。分離した配位子は電荷を持たない低分子量の有機化合物であるため容易に蒸発し、気相中に拡散する。従って、上記（ｂ）のプロセス達成の有無を考慮する必要がなく、析出した金属膜の汚染の懸念もなく純粋な金属膜が得られやすくなる。 From these findings, the present inventors, as a means for solving the problem, are organic nickel capable of precipitating metallic nickel not only by the achievement of both of the processes (a) and (b) but only by the achievement of (a). Employment of a compound is considered preferable. As a specific means, the inventors have come up with the application of a zero-valent nickel complex (organic nickel compound) in which neither the central metal nor the ligand has an electric charge. If a zero-valent nickel complex is used from the raw material stage, it is separated into a zero-valent metal atom and a ligand by thermal decomposition (achievement of the above-mentioned process (a)). The separated ligand is an organic compound having a low molecular weight that has no electric charge, so it easily evaporates and diffuses into the gas phase. Therefore, it is not necessary to consider whether or not the process (b) is achieved, and a pure metal film can be easily obtained without fear of contamination of the deposited metal film.
更に、本発明者等は、加熱のみでも十分な分解を可能とするため、従来の有機ニッケル化合物よりも中心金属と配位子との結合力が弱い有機ニッケル化合物が好適であると考えた。そして、これらの条件を具備しつつ、好適な配位子としてシクロオクタジエン及びアセチレン誘導体が配位するニッケル錯体を見出し、本発明に想到した。 Further, the present inventors considered that an organic nickel compound having a weaker binding force between the central metal and the ligand than the conventional organic nickel compound is suitable in order to enable sufficient decomposition only by heating. And while satisfying these conditions, a nickel complex in which cyclooctadiene and an acetylene derivative are coordinated was found as a suitable ligand, and the present invention was conceived.
上記課題を解決する本発明は、有機ニッケル化合物からなり、化学蒸着法によりニッケル薄膜又はニッケル化合物薄膜を製造するための化学蒸着用原料において、前記有機ニッケル化合物は、次式で示される、ゼロ価のニッケルに、シクロオクタジエン及びアセチレン誘導体が配位した有機ニッケル化合物である化学蒸着用原料である。 The present invention that solves the above problems comprises an organic nickel compound, and in a chemical vapor deposition material for producing a nickel thin film or a nickel compound thin film by a chemical vapor deposition method, the organic nickel compound is represented by the following formula: It is a raw material for chemical vapor deposition which is an organic nickel compound in which cyclooctadiene and an acetylene derivative are coordinated to nickel.
以下、本発明に係る化学蒸着用原料を構成する有機ニッケル化合物について詳細に説明する。上記の通り、本発明における有機ニッケル化合物は、ニッケルにシクロオクタジエン及びアセチレン誘導体が配位した錯体である。シクロオクタジエン及びアセチレン誘導体は、いずれも電荷を持たないゼロ価の配位子である。従って、加熱による分解によってゼロ価の金属原子と配位子に分離し、反応ガスのアシストがなくとも速やかに金属ニッケルを析出させることができる。 Hereinafter, the organic nickel compound constituting the raw material for chemical vapor deposition according to the present invention will be described in detail. As described above, the organonickel compound in the present invention is a complex in which cyclooctadiene and an acetylene derivative are coordinated to nickel. Cyclooctadiene and acetylene derivatives are both zero-valent ligands having no charge. Therefore, it can be separated into zero-valent metal atoms and ligands by decomposition by heating, and metallic nickel can be rapidly deposited without the assistance of the reaction gas.
そして、配位子としてのシクロオクタジエン及びアセチレン誘導体は、ニッケル金属との結合力も弱く、加熱のみによる分解・ニッケル析出が期待できる。 Further, cyclooctadiene and acetylene derivatives as ligands have a weak binding force with nickel metal, and can be expected to decompose and precipitate nickel only by heating.
ここで、配位子であるアセチレン誘導体の置換基Ｘ１、Ｘ２は、いずれも炭素数３以上１３以下の置換基である。このように置換基が導入されたアセチレンの誘導体を配位子とするのは、錯体の安定性を調節するためである。金属の析出を容易にするためには化合物が分解しやすい結合の弱い配位子を用いれば良いが、化合物の安定性が低下しすぎると保管時（室温）でも分解が起こる、あるいは気化させる際の加熱によって分解が起こるといった問題が生じる。本発明においても、配位子として炭素数３以上１３以下の置換基を有するアセチレン誘導体を適用することで、熱分解特性を好適なものとしている。アセチレン誘導体の置換基Ｘ１、Ｘ２の炭素数は、１０以下とするのが好ましい。尚、置換基Ｘ１、Ｘ２は、炭素原子及び水素原子で構成される炭化水素基の他、炭素、水素以外の原子（窒素原子等）を含む官能基が適用される。 Here, the substituents X 1 and X 2 of the acetylene derivative which is a ligand are both substituents having 3 to 13 carbon atoms. The reason why the acetylene derivative having a substituent introduced in this way is used as a ligand is to adjust the stability of the complex. In order to facilitate the precipitation of the metal, it is sufficient to use a weakly bonded ligand that easily decomposes the compound. However, if the stability of the compound is too low, it will decompose even during storage (room temperature) or vaporize. There arises a problem that decomposition occurs due to heating. Also in this invention, the thermal decomposition characteristic is made suitable by applying the acetylene derivative which has a C3-C13 substituent as a ligand. The number of carbon atoms of the substituents X 1 and X 2 of the acetylene derivative is preferably 10 or less. In addition, as the substituents X 1 and X 2 , functional groups containing atoms other than carbon and hydrogen (such as nitrogen atoms) are applied in addition to hydrocarbon groups composed of carbon atoms and hydrogen atoms.
アセチレン誘導体として好ましいものとしては、まず、置換基Ｘ１、Ｘ２としてトリアルキルシリル基が導入された、ビス（トリアルキルシリル）アセチレンが挙げられる。この態様の有機ルテニウム化合物は、下記式で示される。 Preferred examples of the acetylene derivative include bis (trialkylsilyl) acetylene in which a trialkylsilyl group is introduced as the substituents X 1 and X 2 . The organic ruthenium compound of this embodiment is represented by the following formula.
ビス（トリアルキルシリル）アセチレンを好ましい配位子とする理由は、トリアルキルシリル基という立体的に嵩高い置換基が持つ保護効果によって錯体が適度に安定化されるためである。トリアルキルシリル基よりも嵩高い置換基を導入することで、より安定な錯体を得ることも可能であるが、安定性が高くなり過ぎると熱分解が生じ難くなる他、分子量の増加に伴う蒸気圧の低下により気化が困難となる。よって、熱分解性の確保と蒸気圧の適正化の観点から、アセチレン誘導体としてトリアルキルシリル基を導入したものを配位子とするのが好適であると判断した。 The reason why bis (trialkylsilyl) acetylene is a preferred ligand is that the complex is moderately stabilized by the protective effect of a sterically bulky substituent called a trialkylsilyl group. It is possible to obtain a more stable complex by introducing a substituent that is bulkier than the trialkylsilyl group, but if the stability becomes too high, thermal decomposition will not easily occur, and vapor accompanying an increase in molecular weight Vaporization becomes difficult due to a decrease in pressure. Therefore, from the viewpoint of ensuring thermal decomposability and optimizing the vapor pressure, it was judged that it was preferable to use a ligand having a trialkylsilyl group introduced as an acetylene derivative.
配位子であるビス（トリアルキルシリル）アセチレンについて、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は、いずれも炭素数が１以上４以下のアルキル基である。これらは全て同じアルキル基であっても良いし、相違するものであっても良い。炭素数を１以上４以下とするのは、好適な分子量の錯体として、熱分解特性と蒸気圧とのバランスを確保するためである。好適な配位子としては、２つのトリメチルシリル基（Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６の全てがメチル基）が導入されたビス（トリメチルシリル）アセチレンが挙げられる。 Regarding bis (trialkylsilyl) acetylene which is a ligand, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are all alkyl groups having 1 to 4 carbon atoms. These may all be the same alkyl group or may be different. The reason why the number of carbon atoms is 1 or more and 4 or less is to ensure a balance between thermal decomposition characteristics and vapor pressure as a complex having a suitable molecular weight. Suitable ligands include bis (trimethylsilyl) acetylene into which two trimethylsilyl groups (R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are all methyl groups) are introduced.
また、ビス（トリアルキルシリル）アセチレンに加えて、好適な配位子となるアセチレン誘導体としては、トリアルキルメチル基が導入されたビス（トリアルキルメチル）アセチレンが挙げられる。この態様の有機ルテニウム化合物は、下記式のように示される。 In addition to bis (trialkylsilyl) acetylene, examples of the acetylene derivative serving as a suitable ligand include bis (trialkylmethyl) acetylene into which a trialkylmethyl group has been introduced. The organic ruthenium compound of this embodiment is represented by the following formula.
このトリアルキルメチル基が導入されたアセチレン誘導体が配位子として好適である理由は、トリアルキルシリル基と同様であり、その嵩高さと適切な分子量による好適な分解特性が発揮される点にある。このアセチレン誘導体のＲ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２は炭素数が１以上４以下のアルキル基であるが、全て同じアルキル基であっても良いし、相違するものであっても良い。好適な配位子として、２つのｔｅｒｔ−ブチル基（Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２が全てメチル基）が導入されたビス（ｔｅｒｔ−ブチル）アセチレンが挙げられる。 The reason why the acetylene derivative introduced with the trialkylmethyl group is suitable as a ligand is the same as that of the trialkylsilyl group, in that suitable decomposition characteristics due to its bulk and appropriate molecular weight are exhibited. In this acetylene derivative, R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are alkyl groups having 1 to 4 carbon atoms, but they may all be the same or different. It may be. Suitable ligands include bis (tert-butyl) acetylene into which two tert-butyl groups (R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are all methyl groups) are introduced. .
以上の説明の通り、本発明に係る化学蒸着用原料を構成する有機ニッケル化合物は、ニッケルと配位子との適度な結合力を有することで、熱分解のみでニッケル薄膜を生成することができる。そして、電荷を持たないニッケルと電荷を持たない配位子とが錯体形成しているので、分解後の配位子の副反応による薄膜の汚染の心配もない。これらにより、成膜時に反応ガスは不要となり、反応ガスの危険性・毒性等を懸念する必要がなく成膜の効率向上、コスト削減を図ることができる。特に、窒素雰囲気下で高品位の成膜を可能とすることのメリットは大きい。 As described above, the organic nickel compound constituting the raw material for chemical vapor deposition according to the present invention has an appropriate bonding force between nickel and a ligand, and can produce a nickel thin film only by thermal decomposition. . Since nickel having no charge and a ligand having no charge are complexed, there is no fear of contamination of the thin film due to side reaction of the ligand after decomposition. As a result, no reactive gas is required at the time of film formation, and there is no need to worry about the danger or toxicity of the reactive gas, so that the efficiency of film formation can be improved and the cost can be reduced. In particular, the merit of enabling high-quality film formation in a nitrogen atmosphere is great.
また、本発明者等によれば、本発明で適用する有機ニッケル化合物は、高真空度での成膜が可能であることが確認されている。これにより、薄膜の酸化防止のため装置内を真空にすることが許容される。本発明では、ニッケル膜の酸化に配慮して還元性ガスを使用する必要もない。 Further, according to the present inventors, it has been confirmed that the organic nickel compound applied in the present invention can be formed at a high vacuum. This allows the inside of the apparatus to be evacuated to prevent oxidation of the thin film. In the present invention, it is not necessary to use a reducing gas in consideration of the oxidation of the nickel film.
本発明で適用する有機ニッケル化合物の製造方法としては、比較的入手容易なニッケル錯体であるビス（シクロオクタジエン）ニッケルを原料とし、ここに配位子となるアセチレン誘導体を反応させることで製造できる。この合成反応は、適宜の溶媒（テトラヒドロフラン（ＴＨＦ）等）にビス（シクロオクタジエン）ニッケルと、ニッケル錯体に対して過剰量（１倍以上１０倍以下）のアセチレン誘導体を添加することで進行する。この合成反応の温度は、−１００℃以上２５℃以下とするのが好ましい。 As a method for producing the organic nickel compound applied in the present invention, bis (cyclooctadiene) nickel, which is a relatively easily available nickel complex, is used as a raw material, and this can be produced by reacting with an acetylene derivative serving as a ligand. . This synthesis reaction proceeds by adding bis (cyclooctadiene) nickel to an appropriate solvent (such as tetrahydrofuran (THF)) and an excess of acetylene derivative (1 to 10 times) relative to the nickel complex. . The temperature of this synthesis reaction is preferably -100 ° C or more and 25 ° C or less.
そして、本発明に係るニッケル薄膜形成のための化学蒸着法では、原料であるニッケル化合物を真空中、加熱することにより気化させて原料ガスを発生させる。この原料ガスを基板がセットされた反応器に導入し、基板表面で加熱することで錯体を熱分解させてニッケル薄膜を形成させる方法である。 And in the chemical vapor deposition method for nickel thin film formation concerning this invention, the nickel compound which is a raw material is vaporized by heating in a vacuum, and source gas is generated. In this method, the raw material gas is introduced into a reactor on which a substrate is set and heated on the surface of the substrate to thermally decompose the complex to form a nickel thin film.
ここで、本発明に係る化学蒸着用原料は、反応ガスを使用することなく加熱のみでニッケル膜を製造することができる。つまり、反応器内が不活性ガス雰囲気であっても成膜反応を進行させることができる。この点、原料ガスを反応器へ導入する際にはキャリアガスの使用が一般的であるが、本発明ではこのキャリアガスとして不活性ガス（窒素、ヘリウム、アルゴン等）を使用することができ。そして、この不活性ガスによる原料ガス供給のみでニッケル膜を製造することができる。特に、コスト面から窒素の適用が好ましく、本発明では窒素気流下であっても高純度のニッケルを成膜できる点にメリットがある。 Here, the raw material for chemical vapor deposition according to the present invention can produce a nickel film only by heating without using a reaction gas. That is, the film forming reaction can be advanced even in an inert gas atmosphere inside the reactor. In this regard, when introducing the raw material gas into the reactor, a carrier gas is generally used. In the present invention, an inert gas (nitrogen, helium, argon, etc.) can be used as the carrier gas. And a nickel film can be manufactured only by source gas supply by this inert gas. In particular, application of nitrogen is preferable from the viewpoint of cost, and the present invention has an advantage in that high purity nickel can be formed even under a nitrogen stream.
また、上記したように、本発明に係る化学蒸着用原料は、高真空度での成膜が可能である。具体的には、反応器内の真空度を１０，０００Ｐａ以下としてニッケル膜を成膜できる。より好適な真空度は１０〜１，０００Ｐａである。このように反応器内を真空にすることで、成膜したニッケルの酸化を抑制することができる。反応器内の真空度の下限は、現実的側面から１ｐａ以上とするのが好ましい。 In addition, as described above, the chemical vapor deposition material according to the present invention can be formed at a high degree of vacuum. Specifically, the nickel film can be formed by setting the degree of vacuum in the reactor to 10,000 Pa or less. A more preferable vacuum degree is 10 to 1,000 Pa. Thus, by oxidizing the inside of the reactor, oxidation of the deposited nickel can be suppressed. The lower limit of the degree of vacuum in the reactor is preferably 1 pa or more from a practical aspect.
尚、成膜ための加熱温度は１００〜３５０℃とすることができる。１００℃未満では、成膜反応が進行し難く必要な膜厚が得られ難い。高温過ぎると、均一な膜厚の薄膜を形成し難くなり、また、膜中に不純物が混入しやすくなる。加熱温度は１５０〜２５０℃とするのがより好ましい。 In addition, the heating temperature for film-forming can be 100-350 degreeC. If it is less than 100 ° C., the film formation reaction does not proceed easily, and it is difficult to obtain a required film thickness. If the temperature is too high, it is difficult to form a thin film having a uniform thickness, and impurities are easily mixed into the film. The heating temperature is more preferably 150 to 250 ° C.
以上の通り、本発明の化学蒸着用原料によれば、反応ガスを使用することなく、不活性ガス雰囲気下及び高真空度雰囲気下であってもニッケル膜を製造することができる。本発明により成膜されたニッケル膜は、高純度・高品質である。 As described above, according to the raw material for chemical vapor deposition of the present invention, a nickel film can be produced even in an inert gas atmosphere and a high vacuum atmosphere without using a reaction gas. The nickel film formed by the present invention has high purity and high quality.
以下、本発明における最良の実施形態について説明する。本実施形態では、以下の工程によりニッケル薄膜の化学蒸着用原料である、下記の有機ニッケル化合物（［Ｎｉ（ＣＯＤ）（Ｌ）］｛１，ＣＯＤ＝１，５−シクロオクタジエン，Ｌ＝１，２−ビス（トリメチルシリル）アセチレン｝を製造した。そして、その物性評価、成膜試験を行った。 Hereinafter, the best embodiment of the present invention will be described. In the present embodiment, the following organic nickel compound ([Ni (COD) (L)] {1, COD = 1,5-cyclooctadiene, L = 1), which is a raw material for chemical vapor deposition of a nickel thin film, by the following steps. , 2-bis (trimethylsilyl) acetylene} was then evaluated for physical properties and film formation tests.
［有機ニッケル化合物の製造］
ビス（シクロオクタジエン）ニッケル（［Ｎｉ（ＣＯＤ）２］１００ｍｇ（０．３６ｍｍｏｌ）を入れた三口フラスコに、テトラヒドロフラン３．０ｍＬを加え、さらにビス（トリメチルシリル）アセチレン２７６mｇ（１．３９ｍｍｏｌ：ビス（シクロオクタジエン）ニッケルに対して３．９倍量）を加えた。そして、溶液を−１５℃に保持し１２時間攪拌して合成反応を進行させた（下記反応式）。反応終了後、溶媒を減圧留去し、残渣にメタノールを３．０ｍL加えて抽出した。更に、抽出液をろ過した後、−３５℃にて一晩静置して再結晶を行った。本実施形態に係る有機ニッケル化合物の黄色結晶１０１ｍｇ（０．３０ｍｍｏｌ）を得た。収率は８３％であった。尚、以上の操作は、窒素雰囲気にて行っている。製造した化合物について、１Ｈ及び１３Ｃ｛１Ｈ｝ＮＭＲ分析（日本電子株式会社製 ＪＮＭ−ＡＬ３００）を行った（２５℃、窒素雰囲気）。図１にその分析結果として１Ｈ−ＮＭＲスペクトルを示す。
[Production of organonickel compounds]
To a three-necked flask containing 100 mg (0.36 mmol) of bis (cyclooctadiene) nickel ([Ni (COD) 2 ]) was added 3.0 mL of tetrahydrofuran, and 276 mg (1.39 mmol: bis (cyclohexane) of bis (trimethylsilyl) acetylene was further added. Octadiene) 3.9 times the amount of nickel) was added, and the solution was kept at -15 ° C. and stirred for 12 hours to proceed the synthesis reaction (the following reaction formula). The residue was extracted by adding 3.0 mL of methanol to the residue, filtered, and then recrystallized by standing overnight at -35 ° C. Organic nickel according to this embodiment 101 mg (0.30 mmol) of a yellow crystal of the compound was obtained, and the yield was 83%, and the above operation was performed in a nitrogen atmosphere. There are, a 1 H-NMR spectrum as the analysis result 1 H and 13 C {1 H} NMR analysis was carried out (JEOL Ltd. JNM-AL300) (25 ° C., a nitrogen atmosphere) in. Figure 1.
［物性評価］
上記で製造した有機ニッケル化合物について、熱分解特性と蒸気圧を評価・測定した。熱分解特性（ＴＧ−ＤＴＡ）の分析は、エスアイアイ・ナノテクノロジー製のＴＧ／ＤＴＡ７３００を用いて、窒素気流下（１００ｃｃ（標準状態）／ｍｉｎ）、１５ｍｇの有機ニッケル化合物を昇温速度１０℃／ｍｉｎにて室温から５００℃まで加熱した際の試料の重量変化を観察した。この測定結果を図２に示す。
[Evaluation of the physical properties]
The organonickel compound produced above was evaluated and measured for thermal decomposition characteristics and vapor pressure. Analysis of thermal decomposition characteristics (TG-DTA) was performed using a TG / DTA7300 manufactured by SII Nanotechnology, under a nitrogen stream (100 cc (standard state) / min), 15 mg of an organic nickel compound at a heating rate of 10 ° C. The change in the weight of the sample was observed when heated from room temperature to 500 ° C./min. The measurement results are shown in FIG.
図２のＴＧ−ＤＴＡ曲線によれば、８３℃付近で吸熱ピークが観察されるが、このときの重量減が見られない。本実施形態の有機ニッケル化合物は、この温度で融解を開始するが、分解は生じていないことが分かる。そして、重量減は１１０℃付近から開始し、吸熱ピークが見られる約２００℃で完了している。その後の重量減は極めて緩やかであることから、この２００℃付近までの加熱でほぼ全量の化合物が分解したと考えられる。従って、本実施形態の有機ニッケル化合物は約２００℃で熱分解を完了させることができ、加熱のみで達成されることが確認できた。 According to the TG-DTA curve of FIG. 2, an endothermic peak is observed around 83 ° C., but no weight loss is observed at this time. It can be seen that the organonickel compound of this embodiment starts melting at this temperature, but no decomposition occurs. The weight loss starts around 110 ° C. and is completed at about 200 ° C. where an endothermic peak is observed. Since the subsequent weight loss is very gradual, it is considered that almost all of the compound was decomposed by heating to around 200 ° C. Therefore, it was confirmed that the organonickel compound of the present embodiment can complete the thermal decomposition at about 200 ° C. and can be achieved only by heating.
また、本実施形態の有機ニッケル化合物は常温で固体ではあるものの揮発性が高い。減圧条件では低い温度にて昇華を行うことが可能である。昇華精製を行った際の温度と圧力は４５℃、９０Ｐａであった。この結果から、本実施形態の有機ニッケル化合物は、化学蒸着用原料として好適な蒸気圧を有するものであることが確認できた。また、この有機ニッケル化合物は、低温で昇華することができること、及び、この特性を活かして昇華法での精製が可能であることが分かった。 Moreover, although the organonickel compound of this embodiment is solid at normal temperature, it has high volatility. Under reduced pressure conditions, sublimation can be performed at a low temperature. The temperature and pressure when sublimation purification was performed were 45 ° C. and 90 Pa. From this result, it was confirmed that the organonickel compound of the present embodiment has a vapor pressure suitable as a raw material for chemical vapor deposition. It was also found that this organonickel compound can be sublimated at a low temperature and can be purified by a sublimation method taking advantage of this property.
［成膜試験］
本実施形態の有機ニッケル化合物を原料として、チューブ型化学気相蒸着（ＣＶＤ）装置を用いニッケル薄膜を形成した。基板は酸化シリコン（ＳｉＯ２）基板を用いた。成膜条件は、次の通りである。尚、本発明の目的により反応ガスは使用しない。
成膜条件
試料加熱温度：５５〜６０℃
基板加熱温度：２００℃
キャリアガス：窒素１０ｓｃｃｍ
反応器圧力：７５Ｐａ
成膜時間：３０分
[Film formation test]
Using the organic nickel compound of this embodiment as a raw material, a nickel thin film was formed using a tube type chemical vapor deposition (CVD) apparatus. As the substrate, a silicon oxide (SiO 2 ) substrate was used. The film forming conditions are as follows. For the purpose of the present invention, no reaction gas is used.
Film formation conditions Sample heating temperature: 55-60 [deg.] C
Substrate heating temperature: 200 ° C
Carrier gas: nitrogen 10sccm
Reactor pressure: 75 Pa
Deposition time: 30 minutes
ニッケル膜を製造後、窒素気流下、３００℃で１時間アニーリングし、このニッケル膜についてＳＥＭ観察、面粗さ評価（ＡＦＭ）、抵抗測定、膜の組成評価（ＸＲＤ、ＸＰＳ）を行った。 After the nickel film was manufactured, it was annealed at 300 ° C. for 1 hour in a nitrogen stream, and this nickel film was subjected to SEM observation, surface roughness evaluation (AFM), resistance measurement, and film composition evaluation (XRD, XPS).
図３は、本実施形態で成膜したニッケル膜の表面及び断面写真である。これらの写真から本実施形態で形成されたニッケル膜は、連続的で平滑な薄膜である。ひび割れ、穴、島状の凝集といった欠陥は観察されなかった。また、ＡＦＭ（原子間力顕微鏡）にて薄膜の面粗さ（自乗平均面粗さ（ＲＭＳ））を測定したところ、１１ｎｍ（膜厚：約１５０ｎｍ）であった。これらから、このニッケル薄膜は、形態的に良好な状態にあるといえる。 FIG. 3 is a surface and cross-sectional photograph of the nickel film formed in this embodiment. From these photographs, the nickel film formed in this embodiment is a continuous and smooth thin film. Defects such as cracks, holes and island aggregates were not observed. Further, when the surface roughness (root mean square surface roughness (RMS)) of the thin film was measured with an AFM (atomic force microscope), it was 11 nm (film thickness: about 150 nm). From these, it can be said that this nickel thin film is in a morphologically favorable state.
また、図４にＸＲＤ（Ｘ線回折分析）によるＸ線プロファイルを示す。２θ＝４４．３°及び５２°付近に鋭いピークが観察されるが、これはｆｃｃであるニッケルの（１１１）面、（２００）面のピークである。このＸ線プロファイルには、それ以外のピークは見られず、薄膜中にはニッケル以外の合金相、化合物相の形成はないことが確認された。また、図５にはＸＰＳ（Ｘ線光電子分光分析）の分析結果を示す。この結果からも、薄膜が金属ニッケルで構成されていることが確認された。ニッケル以外のピークはほぼみられず、炭素による汚染がわずかに見られたが、それも１％未満であった。これらのＸＲＤ及びＸＰＳの結果から、本実施形態で成膜したニッケル膜は高純度のニッケルからなることが分かった。そして、本実施形態の有機ルテニウム化合物がＣＶＤ用原料として好適であることが確認できた。 FIG. 4 shows an X-ray profile by XRD (X-ray diffraction analysis). Sharp peaks are observed around 2θ = 44.3 ° and 52 °, which are peaks on the (111) plane and (200) plane of nickel which is fcc. In this X-ray profile, no other peaks were observed, and it was confirmed that no alloy phase or compound phase other than nickel was formed in the thin film. FIG. 5 shows the analysis result of XPS (X-ray photoelectron spectroscopy). Also from this result, it was confirmed that the thin film was composed of metallic nickel. Almost no peaks other than nickel were observed, and slight contamination by carbon was observed, but it was also less than 1%. From these XRD and XPS results, it was found that the nickel film formed in this embodiment was made of high-purity nickel. And it has confirmed that the organoruthenium compound of this embodiment was suitable as a raw material for CVD.
そして、ニッケル膜の比抵抗を４端子法で測定したところ、４３μΩｃｍであった。この値は、純ニッケル（比抵抗：約６μΩｃｍ）と対比すれば高い値ではあるものの、他のニッケル原料で製造される薄膜と対比しても良好な数値であった。本実施形態のニッケル膜はデバイスの電極材料としての利用可能性を示すことが確認できた。 And when the specific resistance of the nickel film was measured by the 4-terminal method, it was 43 μΩcm. Although this value is high when compared with pure nickel (specific resistance: about 6 μΩcm), it is also a good value when compared with thin films made of other nickel raw materials. It has been confirmed that the nickel film of this embodiment shows applicability as an electrode material of a device.
本発明に係る原料は、反応ガスを使用することなく、窒素気流下で高真空度の環境であってもニッケル薄膜を形成させることができる。従って、反応ガスの危険性等を気にすることなく設備設計・工程管理を進めることができ、製造コスト低減に資する。本発明は、各種デバイスの電極材料等に好適なニッケル薄膜の原料として有用である。 The raw material according to the present invention can form a nickel thin film without using a reaction gas even in a high vacuum environment under a nitrogen stream. Therefore, it is possible to proceed with the equipment design / process management without worrying about the risk of the reaction gas, etc., which contributes to a reduction in manufacturing cost. The present invention is useful as a raw material for nickel thin films suitable for electrode materials for various devices.
Claims (6)
前記有機ニッケル化合物は、次式で示される、ゼロ価のニッケルに、シクロオクタジエン及びアセチレン誘導体が配位した有機ニッケル化合物である化学蒸着用原料。
The said organic nickel compound is a raw material for chemical vapor deposition which is an organic nickel compound in which cyclooctadiene and an acetylene derivative are coordinated to zero-valent nickel represented by the following formula.
前記原料として請求項１〜請求項３のいずれか記載の化学蒸着用原料を用い、反応ガスを使用することなくニッケルを析出させる化学蒸着法。 In a chemical vapor deposition method of a nickel thin film or a nickel compound thin film in which a raw material gas consisting of an organic nickel compound is vaporized and used as a raw material gas, and the raw material gas is introduced into a reactor to deposit nickel.
A chemical vapor deposition method in which the raw material for chemical vapor deposition according to any one of claims 1 to 3 is used as the raw material, and nickel is deposited without using a reaction gas.
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