JP2019070180A - Film deposition method - Google Patents
Film deposition method Download PDFInfo
- Publication number
- JP2019070180A JP2019070180A JP2017196465A JP2017196465A JP2019070180A JP 2019070180 A JP2019070180 A JP 2019070180A JP 2017196465 A JP2017196465 A JP 2017196465A JP 2017196465 A JP2017196465 A JP 2017196465A JP 2019070180 A JP2019070180 A JP 2019070180A
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- Prior art keywords
- film
- substrate
- group
- raw material
- film forming
- Prior art date
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Links
- 238000000151 deposition Methods 0.000 title abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000012159 carrier gas Substances 0.000 claims abstract description 31
- 230000000737 periodic effect Effects 0.000 claims abstract description 29
- 239000003595 mist Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 229910052800 carbon group element Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052795 boron group element Inorganic materials 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052696 pnictogen Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract 4
- 239000010408 film Substances 0.000 description 101
- 239000000758 substrate Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
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- 238000010790 dilution Methods 0.000 description 10
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- 239000002019 doping agent Substances 0.000 description 7
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
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- 239000010703 silicon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229920001709 polysilazane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
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- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
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- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
本発明は、酸素を含有しない非酸化物（例えば、リン化物、窒化物等）を主成分とする皮膜を成膜する方法に関する。 The present invention relates to a method of forming a film containing non-oxide containing no oxygen (for example, phosphide, nitride and the like) as a main component.
炭化物、硫化物、ホウ化物、リン化物または窒化物等のような非酸素化合物の皮膜は、耐腐食性、耐磨耗性、バリア性、絶縁性などにおいて優れた特性を示すことから、電子部品・電気機器部品、工業部材など幅広い分野での活用が期待されており、その需要が高まっている。 Coatings of non-oxygen compounds such as carbides, sulfides, borides, phosphides or nitrides exhibit excellent properties in corrosion resistance, wear resistance, barrier properties, insulation properties, etc.・ Use in a wide range of fields such as electrical equipment parts and industrial parts is expected, and the demand is increasing.
特許文献１では、プラズマＣＶＤ法を用いて、窒化物半導体層上に半絶縁性のシリコン窒化膜を形成することが記載されている。このように成膜することで、耐圧に優れたシリコン窒化膜を形成している。しかしながら、特許文献１に記載のプラズマＣＶＤ法は、真空装置が必要であるため、コストが増大し、工業的に有用な方法とはいえず、プラズマが基板や膜表面に悪影響を及ぼして、特性が劣化してしまう問題もあった。また、このようにして得られた膜は、酸化の影響を受けやすく、機能安定性や耐食性において満足のいくものではなかった。 Patent Document 1 describes that a semi-insulating silicon nitride film is formed on a nitride semiconductor layer using a plasma CVD method. By forming the film in this manner, a silicon nitride film excellent in withstand voltage is formed. However, since the plasma CVD method described in Patent Document 1 requires a vacuum device, the cost increases and it can not be said that it is an industrially useful method, and the plasma adversely affects the substrate and the film surface, resulting in characteristics. Was also a problem that In addition, the film thus obtained was susceptible to oxidation, and was not satisfactory in functional stability and corrosion resistance.
一方、大気圧下においても成膜することが可能で、より簡便な成膜方法として、ミストＣＶＤ法が注目されており、例えば、酸化鉄、酸化インジウムまたは酸化ガリウム膜等の酸化物薄膜を成膜することについて、近年盛んに検討がされている（非特許文献１および特許文献２）。ミストＣＶＤ法は、大気圧下において密着性や機能安定性に優れた酸化物薄膜を容易に成膜できることが知られているが、２種以上の元素からなる多元系の非酸化物膜を成膜する場合には、基板や石英管の酸素の影響も受けることがあり、膜の一部または全部が酸化されてしまう問題があった。特に、アルミニウム、ケイ素またはチタン等の酸化されやすい元素の非酸化物を成膜する場合には、酸化膜が形成されてしまうなど、良質な非酸化物膜を安定的に成膜することが困難であった。そのため、非酸化物の皮膜を簡便且つ安定的に成膜することができる成膜方法が待ち望まれていた。 On the other hand, the mist CVD method attracts attention as a film formation method which can be formed even under atmospheric pressure and is a simpler film formation method. For example, an oxide thin film such as an iron oxide, indium oxide or gallium oxide film is formed. The membrane formation has been actively studied in recent years (Non-Patent Document 1 and Patent Document 2). It is known that the mist CVD method can easily form an oxide thin film having excellent adhesion and functional stability under atmospheric pressure, but it is possible to form a multicomponent non-oxide film composed of two or more elements. In the case of forming a film, the film may be influenced by oxygen in the substrate or the quartz tube, and there is a problem that a part or all of the film is oxidized. In particular, when forming a non-oxide of an element which is easily oxidized such as aluminum, silicon or titanium, it is difficult to stably form a good non-oxide film, for example, an oxide film is formed. Met. Therefore, a film forming method capable of forming a non-oxide film easily and stably has been desired.
本発明は、簡単かつ容易に、工業的有利に、良質な非酸化物（例えば、リン化物、窒化物など）の皮膜を成膜できる方法を提供することを目的とする。 An object of the present invention is to provide a method capable of forming a film of good quality non-oxide (for example, phosphide, nitride and the like) easily and easily in an industrially advantageous manner.
本発明者らは、上記目的を達成すべく鋭意検討した結果、第１の元素と、第１の元素とは異なる第２の元素とを含有する原料を霧化または液滴化し、得られたミストまたは液滴をキャリアガスで搬送し、ついで該ミストまたは液滴を熱反応させて、第１の元素と第２の元素との化合物を含む皮膜を成膜する方法において、第１の元素が周期律表第１４族又は第１５族の元素であり、第２の元素が、Ｄブロック元素又は周期律表第１３族元素若しくは第１４族元素であり、前記熱反応を、不活性ガス又は還元性ガスの雰囲気下で行って成膜すると、驚くべきことに、得られた皮膜が酸化されることなく、良質な非酸化膜の皮膜を成膜でき、得られた皮膜が、耐腐食性等に優れていること等を種々知見し、このような成膜方法が従来の問題を一挙に解決できるものであることを見出した。
また、本発明者らは、上記知見を得た後、さらに検討を重ね、本発明を完成させるに至った。
As a result of intensive studies to achieve the above object, the present inventors obtained atomization or dropletization of a raw material containing a first element and a second element different from the first element. A method of forming a film containing a compound of a first element and a second element by transporting mist or droplets with a carrier gas and then thermally reacting the mist or droplets, wherein the first element is a film It is an element of periodic table group 14 or 15 and the second element is a D block element or periodic table group 13 or 14 element, and the heat reaction is carried out using an inert gas or reduction When the film formation is carried out in an atmosphere of a corrosive gas, it is possible to form a film of a good quality non-oxide film without causing the oxidation of the obtained film surprisingly, and the obtained film has corrosion resistance etc. Found out that the film deposition method like this It was found to be those that can be solved.
In addition, after obtaining the above-mentioned findings, the present inventors repeated studies and came to complete the present invention.
すなわち、本発明は、以下の発明に関する。
［１］ 第１の元素と、第１の元素とは異なる第２の元素とを含有する原料を霧化または液滴化し、得られたミストまたは液滴をキャリアガスで搬送し、ついで該ミストまたは液滴を熱反応させて、第１の元素と第２の元素との化合物を含む皮膜を成膜する方法であって、第１の元素が周期律表第１４族又は第１５族の元素であり、第２の元素が、Ｄブロック元素又は周期律表第１３族元素若しくは第１４族元素であり、前記熱反応を、不活性ガス又は還元性ガスの雰囲気下で行うことを特徴とする成膜方法。
［２］ 前記原料が、第１の元素と第２の元素とを含む化合物である前記［１］記載の成膜方法。
［３］ 前記原料が、第１の元素の化合物および第２の元素の化合物である前記［１］記載の成膜方法。
［４］ 第１の元素が周期律表第１５族元素である前記［１］〜［３］のいずれかに記載の成膜方法。
［５］ 第１の元素が窒素である前記［１］〜［４］のいずれかに記載の成膜方法。
［６］ 第２の元素が、周期律表の第４周期Ｄブロック元素又は第１３族元素若しくは第１４族元素である前記［１］〜［５］のいずれかに記載の成膜方法。
［７］ 第２の元素が、周期律表第１４族元素である前記［１］〜［６］のいずれかに記載の成膜方法。
［８］ 前記原料溶液中の第１の元素と第２の元素との原子比が、１：２〜１０：１である前記［１］〜［７］のいずれかに記載の成膜方法。
［９］ 前記熱反応を、不活性ガスの雰囲気下で行う前記［１］〜［８］のいずれかに記載の成膜方法。
［１０］ 前記熱反応を、５００℃以上の温度で行う前記［１］〜［９］のいずれかに記載の成膜方法。
That is, the present invention relates to the following inventions.
[1] A raw material containing a first element and a second element different from the first element is atomized or formed into droplets, and the resulting mist or droplets are carried by a carrier gas, and then the mist Or a method of forming a film containing a compound of the first element and the second element by thermally reacting the droplets, wherein the first element is an element of Group 14 or Group 15 of the periodic table And the second element is a D block element or a periodic table group 13 element or a group 14 element, and the thermal reaction is performed under an atmosphere of an inert gas or a reducing gas. Deposition method.
[2] The film forming method according to the above [1], wherein the raw material is a compound containing a first element and a second element.
[3] The film forming method according to [1], wherein the raw material is a compound of a first element and a compound of a second element.
[4] The film forming method according to any one of the above [1] to [3], wherein the first element is a periodic table group 15 element.
[5] The film forming method according to any one of the above [1] to [4], wherein the first element is nitrogen.
[6] The film forming method according to any one of the above [1] to [5], wherein the second element is a fourth period D block element or a group 13 element or a group 14 element of the periodic table.
[7] The film forming method according to any one of the above [1] to [6], wherein the second element is a periodic table group 14 element.
[8] The film forming method according to any one of the above [1] to [7], wherein the atomic ratio of the first element to the second element in the raw material solution is 1: 2 to 10: 1.
[9] The film forming method according to any one of the above [1] to [8], wherein the thermal reaction is performed in an atmosphere of an inert gas.
[10] The film forming method according to any one of the above [1] to [9], wherein the thermal reaction is performed at a temperature of 500 ° C. or more.
本発明の成膜方法は、簡単且つ容易に、工業的有利に、非酸化物（例えば、リン化物、窒化物など）の皮膜を成膜することができる。 According to the film forming method of the present invention, a non-oxide (for example, phosphide, nitride, etc.) film can be formed easily and easily industrially advantageously.
本発明の成膜方法は、第１の元素と、第１の元素とは異なる第２の元素とを含有する原料を霧化または液滴化し（霧化・液滴化工程）、得られたミストまたは液滴をキャリアガスで搬送し（搬送工程）、ついで該ミストまたは液滴を熱反応させて、主成分に第１の元素と第２の元素との化合物を含む皮膜を基体上に成膜する（成膜工程方法であって、第１の元素が周期律表第１４族又は第１５族の元素であり、第２の元素が、Ｄブロック元素又は周期律表第１３族元素若しくは第１４族元素であり、前記熱反応を、不活性ガス又は還元性ガスの雰囲気下で行うことを特長とする。 The film forming method of the present invention is obtained by atomizing or dropletizing a raw material containing a first element and a second element different from the first element (atomization / dropletization step), The mist or droplets are transported by a carrier gas (transport step), and then the mist or droplets are thermally reacted to form a film containing the compound of the first element and the second element as the main component on the substrate. Forming a film (in the film forming step method, the first element is an element of Group 14 or Group 15 of the Periodic Table, the second element is a D block element or a Group 13 element of Periodic Table, or It is a Group 14 element, and is characterized in that the thermal reaction is performed under an atmosphere of an inert gas or a reducing gas.
以下、本発明の好ましい態様について説明するが、本発明はこれら好ましい態様に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to these preferred embodiments.
（基体）
前記基体は、前記皮膜を支持できるものであれば特に限定されない。前記基体の材料も、本発明の目的を阻害しない限り特に限定されず、公知の基体であってよく、有機化合物であってもよいし、無機化合物であってもよい。前記基体の形状としては、例えば、平板や円板等の板状、繊維状、棒状、円柱状、角柱状、筒状、螺旋状、球状、リング状などが挙げられるが、本発明においては、基板が好ましい。また、本発明においては、前記基体が、凹凸形状を有する立体物であるのが好ましく、前記立体物としては、例えば、多孔質体などが挙げられ、より具体的には、ハニカム構造を有する多孔質体などが好適な例として挙げられる。前記基体が、このような立体物であっても、本発明によれば凹凸内部の隅々に至るまで均一に成膜することができる。
(Substrate)
The substrate is not particularly limited as long as it can support the film. The material of the substrate is also not particularly limited as long as the object of the present invention is not impaired, and the substrate may be a known substrate, may be an organic compound, or may be an inorganic compound. Examples of the shape of the substrate include plates such as flat plates and disks, fibers, rods, cylinders, prisms, cylinders, spirals, spheres, rings, etc. In the present invention, A substrate is preferred. In the present invention, the substrate is preferably a three-dimensional object having a concavo-convex shape, and examples of the three-dimensional object include a porous body, and more specifically, a porous material having a honeycomb structure. A substrate is mentioned as a suitable example. According to the present invention, even if the substrate is such a three-dimensional object, the film can be formed uniformly to every corner inside the unevenness.
また、前記基板は、板状であって、膜の支持体となるものであれば特に限定されない。絶縁体基板であってもよいし、半導体基板であってもよいし、導電性基板であってもよい。前記基板の形状は、特に限定されず、略円形状（例えば、円形、楕円形など）であってもよいし、多角形状（例えば、３角形、正方形、長方形、５角形、６角形、７角形、８角形、９角形など）であってもよく、様々な形状を好適に用いることができる。また、本発明においては、前記基板が、表面に凹凸形状を有する基板であるのも好ましく、このような凹凸形状を有する基板上であっても、良好に皮膜を成膜することができる。また、本発明においては、大面積の基板を用いることもでき、このような大面積の基板を用いることによって、前記単結晶膜の面積を大きくすることができる。本発明においては、前記基板が、コランダム構造を有する結晶物、β―ガリアを有する結晶物、六方晶の結晶構造を有する結晶物、正方晶の結晶構造を有する結晶物を主成分として含む基板であるのも好ましい。コランダム構造を有する結晶物を主成分として含む基板は、基板中の組成比で、コランダム構造を有する結晶物を５０％以上含むものであれば、特に限定されないが、本発明においては、７０％以上含むものであるのが好ましく、９０％以上であるのがより好ましい。コランダム構造を有する結晶を主成分とする基板としては、例えば、サファイア基板（例：ｃ面サファイア基板）や、α型酸化ガリウム基板などが挙げられる。β−ガリア構造を有する結晶物を主成分とする基板としては、例えばβ−Ｇａ２Ｏ３基板、又はＧａ２Ｏ３とＡｌ２Ｏ３とを含みＡｌ２Ｏ３が０ｗｔ％より多くかつ６０ｗｔ％以下である混晶体基板などが挙げられる。六方晶の結晶構造を有する結晶物を主成分とする基板としては、例えば、ＳｉＣ基板、ＺｎＯ基板、ＧａＮ基板等が挙げられる。正方晶の結晶構造を有する基板としては、例えば、主面が（１００）結晶面又は（２００）結晶面の正方晶の結晶構造を有している基板などが挙げられる。前記基板の厚さは、本発明においては特に限定されないが、好ましくは、５０〜２０００μｍであり、より好ましくは２００〜８００μｍである。 Further, the substrate is not particularly limited as long as it is plate-like and serves as a film support. It may be an insulator substrate, a semiconductor substrate, or a conductive substrate. The shape of the substrate is not particularly limited, and may be substantially circular (for example, circular, elliptical, etc.), or polygonal (for example, triangular, square, rectangular, pentagonal, hexagonal, heptagonal , Octagons, and hexagons), and various shapes can be suitably used. Further, in the present invention, it is preferable that the substrate is a substrate having a concavo-convex shape on the surface, and even on a substrate having such a concavo-convex shape, a film can be formed favorably. In the present invention, a large-area substrate can also be used, and the area of the single crystal film can be increased by using such a large-area substrate. In the present invention, the substrate comprises, as a main component, a crystal having a corundum structure, a crystal having β-gallia, a crystal having a hexagonal crystal structure, or a crystal having a tetragonal crystal structure. It is also preferable to be present. The substrate containing the crystalline substance having the corundum structure as the main component is not particularly limited as long as it contains 50% or more of the crystalline substance having the corundum structure in the composition ratio in the substrate, but 70% or more in the present invention It is preferable to contain, and 90% or more is more preferable. As a board | substrate which has a crystal | crystallization which has a corundum structure as a main component, a sapphire substrate (example: c surface sapphire substrate), an alpha-type gallium oxide substrate etc. are mentioned, for example. As a substrate having a crystalline substance having a β-gallia structure as a main component, for example, a β-Ga 2 O 3 substrate, or containing Ga 2 O 3 and Al 2 O 3 , Al 2 O 3 is more than 0 wt% and 60 wt% And the like. As a board | substrate which has a crystalline substance which has a hexagonal crystal structure as a main component, a SiC substrate, a ZnO substrate, a GaN substrate etc. are mentioned, for example. Examples of the substrate having a tetragonal crystal structure include a substrate having a tetragonal crystal structure in which the main surface is a (100) crystal plane or a (200) crystal plane. The thickness of the substrate is not particularly limited in the present invention, but is preferably 50 to 2000 μm, more preferably 200 to 800 μm.
（原料）
原料は、第１の元素と、第１の元素とは異なる第２の元素とを少なくとも含有しており、霧化または液滴化が可能なものであれば、特に限定されない。本発明においては、前記原料は、通常、溶媒とともに原料溶液として用いられる。原料溶液中の前記原料の含有量は、本発明の目的を阻害しない限り特に限定されないが、好ましくは、０．００１モル％〜５０モル％であり、より好ましくは０．０１モル％〜５０モル％である。また、前記原料溶液中の第１の元素と第２の元素との混合割合も、特に限定されないが、本発明においては、前記原料溶液中の前記原料溶液中の第１の元素と第２の元素との原子比が、１：１０〜２０：１であるのが、より良好に第１の元素と第２の元素との化合物を成膜できるため、好ましく、１：２〜１０：１であるのがより好ましい。
(material)
The raw material contains at least the first element and the second element different from the first element, and is not particularly limited as long as it can be atomized or formed into droplets. In the present invention, the raw material is usually used as a raw material solution together with a solvent. The content of the raw material in the raw material solution is not particularly limited as long as the object of the present invention is not impaired, but preferably 0.001 mol% to 50 mol%, more preferably 0.01 mol% to 50 mol. %. Further, the mixing ratio of the first element and the second element in the raw material solution is not particularly limited, but in the present invention, the first element and the second element in the raw material solution in the raw material solution are not particularly limited. It is preferable that the atomic ratio to the element is 1:10 to 20: 1, because a compound of the first element and the second element can be formed more favorably. It is more preferable that there be.
第１の元素は、周期律表の第１４族又は第１５族の元素であれば、特に限定されない。ここで、「周期律表」は、国際純正応用化学連合（Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｐｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）（ＩＵＰＡＣ）にて定められた周期律表を意味する。周期律表の第１４族の元素としては、例えば、炭素（Ｃ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）、スズ（Ｓｎ）または鉛（Ｐｂ）等が挙げられる。本発明においては、第１４族の元素が、炭素またはケイ素であるのが、非酸化物の皮膜をより良好に成膜できるため、好ましく、ケイ素であるのがより好ましい。周期律表の第１５族の元素としては、例えば、窒素（Ｎ）リン（Ｐ）、ヒ素（Ａｓ）、アンチモン（Ｓｂ）またはビスマス（Ｂｉ）等が挙げられる。本発明においては、第１５族の元素が、窒素またはリンであるのが、非酸化物の皮膜をより良好に成膜できるため、好ましく、窒素であるのがより好ましい。 The first element is not particularly limited as long as it is an element of Group 14 or Group 15 of the periodic table. Here, the "periodic table" means the periodic table defined by International Union of Pure and Applied Chemistry (IUPAC). Examples of the element of Group 14 of the periodic table include carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb) and the like. In the present invention, it is preferable that the element of Group 14 be carbon or silicon, because a non-oxide film can be formed better, silicon is more preferable. As an element of Group 15 of the periodic table, for example, nitrogen (N) phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi) and the like can be mentioned. In the present invention, it is preferable that the element of Group 15 be nitrogen or phosphorus, because a non-oxide film can be formed better, nitrogen is more preferable.
第２の元素は、Ｄブロック元素又は周期律表第１３族元素若しくは第１４族元素であれば、特に限定されない。「Ｄブロック元素」は、３ｄ、４ｄ、５ｄ、および６ｄ軌道を満たす電子を有する元素をいう。前記Ｄブロック元素としては、例えば、スカンジウム（Ｓｃ）、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、イットリウム（Ｙ）、ジルコニウム（Ｚｒ）、ニオブ（Ｎｂ）、モリブデン（Ｍｏ）、テクネチウム（Ｔｃ）、ルテニウム（Ｒｕ）、ロジウム（Ｒｈ）、パラジウム（Ｐｄ）、銀（Ａｇ）、カドミウム（Ｃｄ）、ルテチウム（Ｌｕ）、ハフニウム（Ｈｆ）、タンタル（Ｔａ）、タングステン（Ｗ）、レニウム（Ｒｅ）、オスミウム（Ｏｓ）、イリジウム（Ｉｒ）、白金（Ｐｔ）、金（Ａｕ）、水銀（Ｈｇ）、ローレンシウム（Ｌｒ）、ラザホージウム（Ｒｆ）、ドブニウム（Ｄｂ）、シーボーギウム（Ｓｇ）、ボーリウム（Ｂｈ）、ハッシウム（Ｈｓ）、マイトネリウム（Ｍｔ）、ダームスタチウム（Ｄｓ）、レントゲニウム（Ｒｇ）またはコペルニシウム（Ｃｎ）などが挙げられる。本発明においては、前記Ｄブロック元素が、周期律表の第４周期Ｄブロック元素（スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、または亜鉛）であるのが、第１の元素と第２の元素との化合物をより良好に成膜することができるため、好ましい。周期律表第１３族元素としては、ホウ素（Ｂ）、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）またはタリウム（Ｔｌ）などが挙げられる。周期律表第１４族元素としては、上記した周期律表第１４族の元素等が挙げられる。本発明においては、第２の元素が、第４周期Ｄブロック元素又は第１３族元素若しくは第１４族元素であるのが好ましく、周期律第１４族元素であるのがより好ましい。 The second element is not particularly limited as long as it is a D block element or a periodic table group 13 element or a group 14 element. "D block element" refers to an element having electrons that satisfy the 3d, 4d, 5d, and 6d orbitals. Examples of the D block element include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and copper. (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), laurenthium (Lr), razarhodium (Rf), dovenium (Db), seaborgium (Sg), bouriu (Bh), hassium (Hs), meitnerium (Mt), darmstadtium (Ds), and the like roentgenium (Rg) or Copernicium (Cn). In the present invention, the D block element is the fourth period D block element of the periodic table (scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper or zinc). It is preferable because the compound of the element of (1) and the second element can be deposited better. The periodic table group 13 element includes boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl) and the like. Examples of the periodic table group 14 element include the above-mentioned periodic table group 14 elements and the like. In the present invention, the second element is preferably a fourth period D block element, a group 13 element or a group 14 element, and more preferably a periodic group 14 element.
本発明においては、第１の元素が周期律表第１５族の元素であって、第２の元素が周期律表第１４族の元素であるのが、好ましい。このような好ましい第１の元素と第２の元素との組み合わせを用いることにより、前記皮膜がより酸化されにくく、より耐食性に優れた前記皮膜を得ることができる。 In the present invention, it is preferable that the first element be an element of Group 15 of the periodic table and the second element be an element of Group 14 of the periodic table. By using such a combination of the first element and the second element, it is possible to obtain the film which is more resistant to oxidation and more excellent in corrosion resistance.
前記原料は、第１の元素と、第１の元素とは異なる第２の元素とを少なくとも含有すればそれでよく、第１の元素および第２の元素以外の他の元素を含んでいてもよい。本発明においては、前記原料が第１の元素と第２の元素とを含む化合物であるのが好ましい。このような好ましい原料を用いることにより、第１の元素と第２の元素との化合物を含む皮膜をより良好に成膜することができる。また、本発明においては、前記原料が第１の元素の化合物および第２の元素の化合物であるのも好ましい。このような原料を用いることにより、第１の元素と第２の元素との化合物を含む皮膜を良好に成膜することができる。また、本発明においては、前記皮膜が、主成分に第１の元素と第２の元素との化合物を含むのが好ましい。ここで、「主成分」とは、例えば、前記皮膜が主成分に窒化チタンを含む場合には、膜中の元素中の窒素およびチタンの原子比が、０．５以上の割合で窒化チタンが含まれていればそれでよい。本発明においては、前記膜中の元素中の窒素およびチタンの原子比が、０．７以上であるのが好ましく、０．８以上であるのがより好ましい。第１の元素と第２の元素とを含む化合物は、第１の元素と第２の元素とを含んでいれば、特に限定されず、無機化合物であってもよいし、有機化合物であってもよい。また、第１の元素の化合物は、第１の元素を含んでいれば、特に限定されず、無機化合物であってもよいし、有機化合物であってもよい。第２の元素の化合物は、第２の元素を含んでいれば、特に限定されず、無機化合物であってもよいし、有機化合物であってもよい。また、本発明においては、第１の元素が窒素であり、前記皮膜が、第２の元素の窒化物を含むのが、より良好に成膜を行うことができるため、好ましく、第１の元素がリンであり、前記皮膜が、第２の元素のリン化物を含むのも、より良好に成膜を行うことができるため好ましい。 The raw material may contain at least the first element and the second element different from the first element, and may contain the first element and another element other than the second element. . In the present invention, the raw material is preferably a compound containing a first element and a second element. By using such a preferable raw material, a film including a compound of the first element and the second element can be formed more favorably. In the present invention, it is also preferable that the raw material is a compound of the first element and a compound of the second element. By using such a raw material, a film containing a compound of the first element and the second element can be favorably formed. Further, in the present invention, the film preferably contains a compound of the first element and the second element as the main component. Here, “main component” means, for example, when the film contains titanium nitride as the main component, titanium nitride is used at an atomic ratio of nitrogen and titanium in the elements in the film of 0.5 or more. That is fine if it is included. In the present invention, the atomic ratio of nitrogen and titanium in the elements in the film is preferably 0.7 or more, more preferably 0.8 or more. The compound containing the first element and the second element is not particularly limited as long as it contains the first element and the second element, and may be an inorganic compound or an organic compound. It is also good. The compound of the first element is not particularly limited as long as it contains the first element, and may be an inorganic compound or an organic compound. The compound of the second element is not particularly limited as long as it contains the second element, and may be an inorganic compound or an organic compound. Further, in the present invention, it is preferable that the first element is nitrogen, and the film contains a nitride of the second element, because film formation can be performed better, and the first element is preferable. Is preferable and the film contains a phosphide of the second element because the film can be formed more favorably.
前記溶媒は、特に限定されず、公知の溶媒であってよい。水等の無機溶媒であってもよいし、アルコールまたはエーテル等の有機溶媒であってもよい。前記水としては、具体的には、例えば、純水、超純水、水道水、井戸水、鉱泉水、鉱水、温泉水、湧水、淡水、海水などが挙げられる。本発明においては、前記溶媒が、有機溶媒であるのが、少なくとも第１の元素と第２の元素とを含む多元系の皮膜をより良好に成膜できるので、好ましく、酸素原子非含有有機溶媒であるのがより好ましい。前記酸素原子非含有有機溶媒としては、例えば、炭化水素系溶媒または芳香族系溶媒等が挙げられる。前記炭化水素系溶媒としては、例えば、ヘキサン、ヘプタン、オクタン、デカリン等の脂肪族炭化水素系溶媒またはシクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素系溶媒等が挙げられる。前記芳香族系溶媒としては、例えば、トルエン、キシレン、トリメチルベンゼン類、エチルベンゼン、エチルトルエン、エチルキシレン、ジエチルベンゼン、プロピルベンゼン等のアルキルベンゼン類、あるいはメチルナフタレン、エチルナフタレン、ジメチルナフタレン等のアルキルナフタレン類、その他アルキルビフェニル類、アルキルアントラセン類、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族類等が挙げられる。 The solvent is not particularly limited, and may be a known solvent. It may be an inorganic solvent such as water or an organic solvent such as alcohol or ether. Specific examples of the water include pure water, ultrapure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, seawater and the like. In the present invention, it is preferable that the solvent is an organic solvent, since a multi-component film containing at least the first element and the second element can be formed better, and the organic solvent containing no oxygen atom is preferable. Is more preferred. Examples of the oxygen atom non-containing organic solvent include hydrocarbon solvents and aromatic solvents. Examples of the hydrocarbon-based solvent include aliphatic hydrocarbon-based solvents such as hexane, heptane, octane and decalin, and alicyclic hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. Examples of the aromatic solvents include alkylbenzenes such as toluene, xylene, trimethylbenzenes, ethylbenzene, ethyltoluene, ethylxylene, diethylbenzene and propylbenzene, and alkylnaphthalenes such as methylnaphthalene, ethylnaphthalene and dimethylnaphthalene, Other examples include alkylated biphenyls, alkylanthracenes, halogenated aromatics such as chlorobenzene, dichlorobenzene and trichlorobenzene.
また、前記原料溶液には、ドーパントが含まれていてもよい。原料溶液にドーパントを含ませることにより、イオン注入等を行わずに、結晶構造を壊すことなく、前記皮膜の導電性を容易に制御することができる。前記ドーパントとしては、特に限定されず、公知のドーパントであってよい。前記ドーパントの濃度は、通常、約１×１０１６／ｃｍ３〜１×１０２２／ｃｍ３であってもよいし、また、ドーパントの濃度を例えば約１×１０１７／ｃｍ３以下の低濃度にしてもよいし、ドーパントを約１×１０２０／ｃｍ３以上の高濃度で含有させてもよい。 In addition, the raw material solution may contain a dopant. By including the dopant in the raw material solution, the conductivity of the film can be easily controlled without breaking the crystal structure without performing ion implantation or the like. The dopant is not particularly limited, and may be a known dopant. The concentration of the dopant may generally be about 1 × 10 16 / cm 3 to 1 × 10 22 / cm 3 , and the concentration of the dopant may be low, for example, about 1 × 10 17 / cm 3 or less. The dopant may be contained at a high concentration of about 1 × 10 20 / cm 3 or more.
（霧化・液滴化工程）
霧化・液滴化工程は、原料溶液を霧化または液滴化する。原料溶液の霧化手段または液滴化手段は、原料溶液を霧化または液滴化できさえすれば特に限定されず、公知の手段であってよいが、本発明においては、超音波を用いる霧化手段または液滴化手段が好ましい。超音波を用いて得られたミストまたは液滴は、初速度がゼロであり、空中に浮遊するので好ましく、例えば、スプレーのように吹き付けるのではなく、空間に浮遊してガスとして搬送することが可能なミストであるので衝突エネルギーによる損傷がないため、非常に好適である。液滴サイズは、特に限定されず、数ｍｍ程度の液滴であってもよいが、好ましくは５０μｍ以下であり、より好ましくは０．１〜１０μｍである。
(Atomization / droplet formation process)
In the atomization / droplet formation step, the raw material solution is atomized or formed into droplets. The means for atomizing or dropletizing the raw material solution is not particularly limited as long as it can atomize or drop the raw material solution, and may be a known means, but in the present invention, a mist using ultrasonic waves is used. Means of dropletization or dropletization are preferred. The mist or droplet obtained by using ultrasonic waves is preferable because it has an initial velocity of zero and floats in the air, and for example, it is possible to float in a space and carry it as a gas rather than spraying it like a spray. As it is a possible mist, it is very suitable because it is not damaged by collision energy. The droplet size is not particularly limited, and may be about several mm, but preferably 50 μm or less, more preferably 0.1 to 10 μm.
（搬送工程）
搬送工程では、キャリアガスでもって前記ミストまたは前記液滴を成膜室内に搬送する。前記キャリアガスは、通常、不活性ガスまたは還元性ガスであり、より具体的に例えば、窒素やアルゴン等の不活性ガス、または水素ガスやフォーミングガス等の還元ガスが好適な例として挙げられる。また、キャリアガスの種類は１種類であってよいが、２種類以上であってもよく、流量を下げた希釈ガス（例えば１０倍希釈ガス等）などを、第２のキャリアガスとしてさらに用いてもよい。また、キャリアガスの供給箇所も１箇所だけでなく、２箇所以上あってもよい。キャリアガスの流量は、特に限定されないが、０．０１〜２０Ｌ／分であるのが好ましく、１〜１０Ｌ／分であるのがより好ましい。希釈ガスを用いる場合には、希釈ガスの流量が、０．００１〜１０Ｌ／分であるのが好ましく、０．１〜１０Ｌ／分であるのがより好ましい。
(Transporting process)
In the transfer step, the mist or the droplets are transferred into the film forming chamber with a carrier gas. The carrier gas is usually an inert gas or a reducing gas, and more specifically, an inert gas such as nitrogen or argon, or a reducing gas such as hydrogen gas or a forming gas can be mentioned as a preferable example. In addition, although one kind of carrier gas may be used, two or more kinds may be used, and a dilution gas with a reduced flow rate (for example, 10-fold dilution gas etc.) is further used as a second carrier gas. It is also good. Further, the carrier gas may be supplied not only to one place, but also to two or more places. The flow rate of the carrier gas is not particularly limited, but is preferably 0.01 to 20 L / min, and more preferably 1 to 10 L / min. When a dilution gas is used, the flow rate of the dilution gas is preferably 0.001 to 10 L / min, and more preferably 0.1 to 10 L / min.
（成膜工程）
成膜工程では、成膜室内で前記ミストまたは液滴を、不活性ガス又は還元性ガスの雰囲気下で熱反応させることによって、前記基体上に、皮膜を成膜する。熱反応は、熱でもって前記ミストまたは液滴が反応すればそれでよく、化学反応であってもよいし、物理反応であってもよい。その他の反応であってもよい。本発明においては、前記熱反応を不活性ガス又は還元性ガスの雰囲気下で行うことが肝要であり、通常、不活性ガス又は還元性ガスで成膜室内を置換した後、成膜室を開放せずに、その雰囲気を維持したまま、熱反応を行う。従来、ミストＣＶＤ法でも金属酸化膜の成膜に例えば窒素ガスがキャリアガスとして用いられていたが、大気圧開放系で成膜するので、成膜室に流入した酸素の影響も受けていたが、このようにすることによって、酸素の悪影響を避けることができる。反応条件等も本発明の目的を阻害しない限り特に限定されない。本工程においては、前記熱反応を、通常、溶媒の蒸発温度以上の温度で行うが、５００℃以上がより好ましく、５５０℃以上が最も好ましい。また、例えば、第１の元素が窒素である場合には、前記熱反応を、７５０℃以上で行うのが好ましい。また、熱反応は、不活性ガス又は還元性ガスの雰囲気下で行われれば、本発明の目的を阻害しない限り、大気圧下、加圧下および減圧下のいずれの条件下で行われてもよい。本発明においては、前記熱反応を、不活性ガスの雰囲気下で行うのが好ましく、大気圧下で且つ不活性ガスの雰囲気下で行うのがより好ましい。なお、膜厚は、成膜時間を調整することにより、設定することができる。
(Deposition process)
In the film forming step, a film is formed on the substrate by thermally reacting the mist or the droplets in an atmosphere of an inert gas or a reducing gas in a film forming chamber. The thermal reaction may be any reaction if the mist or droplets react with heat, and may be a chemical reaction or a physical reaction. It may be other reaction. In the present invention, it is important to carry out the thermal reaction under an atmosphere of inert gas or reducing gas, and usually, the inside of the film forming chamber is replaced with the inert gas or reducing gas, and then the film forming chamber is opened. Thermal reaction is performed without maintaining the atmosphere. Conventionally, nitrogen gas, for example, was used as a carrier gas for metal oxide film deposition even in the mist CVD method, but since the film was formed by an atmospheric pressure release system, it was also affected by oxygen flowing into the deposition chamber. By doing so, the adverse effects of oxygen can be avoided. The reaction conditions and the like are not particularly limited as long as the object of the present invention is not impaired. In the present step, the thermal reaction is usually carried out at a temperature equal to or higher than the evaporation temperature of the solvent, preferably 500 ° C. or higher, and most preferably 550 ° C. or higher. Also, for example, when the first element is nitrogen, it is preferable to carry out the thermal reaction at 750 ° C. or higher. Also, the thermal reaction may be performed under any pressure of atmospheric pressure, under pressure and under reduced pressure, as long as the object of the present invention is not impaired if it is performed under an atmosphere of inert gas or reducing gas. . In the present invention, the thermal reaction is preferably carried out under an atmosphere of an inert gas, and more preferably under atmospheric pressure and under an atmosphere of an inert gas. Note that the film thickness can be set by adjusting the film formation time.
上記のようにして成膜することにより、簡単且つ容易に、工業的有利に非酸化物（例えば、リン化物、窒化物など）の皮膜を成膜することができる。また、得られた皮膜は、耐腐食性、耐摩耗性およびバリア性に優れており、工業的に有用なものである。前記皮膜は、そのままで又は必要に応じて表面処理等が施されて、各種機器若しくは部材又はその部品等に用いられる。前記機器としては、電子機器又は光学機器などが好適な例として挙げられる。前記電子機器又は光学機器としては、例えば、光学物品、電気機器、電子部品、燃料電池、太陽電池、車両、産業用機器などが挙げられる。前記部材としては、例えば、超硬工具類又は金型類等の超硬材などが挙げられる。 By forming the film as described above, it is possible to easily and easily form a film of non-oxide (for example, phosphide, nitride and the like) industrially advantageously. Moreover, the obtained film is excellent in corrosion resistance, abrasion resistance and barrier property, and is industrially useful. The film is used as it is or, if necessary, subjected to surface treatment and the like, to various devices or members or parts thereof. As said apparatus, an electronic apparatus or an optical apparatus etc. are mentioned as a suitable example. Examples of the electronic device or optical device include an optical article, an electric device, an electronic component, a fuel cell, a solar cell, a vehicle, and an industrial device. Examples of the member include cemented carbide tools and cemented carbide materials such as molds.
以下、本発明の実施例を説明するが、本発明はこれらに限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
（実施例１）
１．成膜装置
図１を用いて、本実施例で用いたミストＣＶＤ装置を説明する。ミストＣＶＤ装置１９は、基板２０を載置するサセプタ２１と、キャリアガスを供給するキャリアガス供給手段２２ａと、キャリアガス供給手段２２ａから送り出されるキャリアガスの流量を調節するための流量調節弁２３ａと、キャリアガス（希釈）を供給するキャリアガス（希釈）供給手段２２ｂと、キャリアガス（希釈）供給手段２２ｂから送り出されるキャリアガスの流量を調節するための流量調節弁２３ｂと、原料溶液２４ａが収容されるミスト発生源２４と、水２５ａが入れられる容器２５と、容器２５の底面に取り付けられた超音波振動子２６と、内径４０ｍｍの石英管からなる供給管２７と、供給管２７の周辺部に設置されたヒーター２８とを備えている。サセプタ２１は、石英からなり、基板２０を載置する面が水平面から傾斜している。成膜室となる供給管２７とサセプタ２１をどちらも石英で作製することにより、基板２０上に形成される膜内に装置由来の不純物が混入することを抑制している。
Example 1
1. Film Forming Apparatus The mist CVD apparatus used in the present embodiment will be described with reference to FIG. The mist CVD apparatus 19 comprises a susceptor 21 for mounting the substrate 20, a carrier gas supply means 22a for supplying a carrier gas, and a flow rate control valve 23a for adjusting the flow rate of the carrier gas delivered from the carrier gas supply means 22a. A carrier gas (dilution) supply means 22b for supplying a carrier gas (dilution), a flow control valve 23b for adjusting the flow rate of the carrier gas delivered from the carrier gas (dilution) supply means 22b, and a raw material solution 24a , The container 25 into which the water 25a is put, the ultrasonic transducer 26 attached to the bottom of the container 25, the supply pipe 27 consisting of a quartz tube having an inner diameter of 40 mm, and the periphery of the supply pipe 27 And a heater 28 installed in the The susceptor 21 is made of quartz, and the surface on which the substrate 20 is placed is inclined from the horizontal surface. By making both the supply pipe 27 and the susceptor 21 to be the film forming chamber from quartz, the contamination of the device-derived impurities into the film formed on the substrate 20 is suppressed.
２．原料溶液の作製
ポリシラザンをキシレンに混合し、これを原料溶液２４ａとした。なお、原料溶液中のポリシラザンと、キシレンとの体積比は、１：１とした。
2. Preparation of Raw Material Solution Polysilazane was mixed with xylene to obtain a raw material solution 24a. The volume ratio of polysilazane to xylene in the raw material solution was 1: 1.
３．成膜準備
上記２．で得られた原料溶液２４ａをミスト発生源２４内に収容した。次に、基板２０として、サファイア基板をサセプタ２１上に設置し、ヒーター２８を作動させて成膜室２７内の温度を７５０℃にまで昇温させた。次に、流量調節弁２３ａ、２３ｂを開いて、キャリアガス源であるキャリアガス供給手段２２ａ、２２ｂからキャリアガスを成膜室２７内に供給し、成膜室２７の雰囲気をキャリアガスで十分に置換した後、キャリアガスの流量を１０Ｌ／ｍｉｎに、キャリアガス（希釈）の流量を１０Ｌ／ｍｉｎに調節した。なお、キャリアガスとして窒素を用いた。
3. Preparation for film formation The raw material solution 24 a obtained in the above was contained in the mist generation source 24. Next, a sapphire substrate was placed on the susceptor 21 as the substrate 20, and the heater 28 was operated to raise the temperature in the film forming chamber 27 to 750 ° C. Next, the flow control valves 23a and 23b are opened, and the carrier gas is supplied from the carrier gas supply means 22a and 22b, which is a carrier gas source, into the film forming chamber 27, and the atmosphere in the film forming chamber 27 is sufficiently After the replacement, the flow rate of the carrier gas was adjusted to 10 L / min, and the flow rate of the carrier gas (dilution) was adjusted to 10 L / min. In addition, nitrogen was used as carrier gas.
４．皮膜の形成
次に、超音波振動子２６を２．４ＭＨｚで振動させ、その振動を、水２５ａを通じて原料溶液２４ａに伝播させることによって、原料溶液２４ａを微粒子化させて原料微粒子を生成した。この原料微粒子が、キャリアガスによって成膜室２７内に導入され、大気圧下、７５０℃にて、供給管２７内でミストが反応して、基板２０上に透明な皮膜が形成された。なお、得られた膜の膜厚は３５０ｎｍであった。また、得られた膜の外観写真を、図２に示す。
4. Formation of Film Next, the ultrasonic transducer 26 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material solution 24a through the water 25a to make the raw material solution 24a into fine particles to generate raw material fine particles. The raw material fine particles were introduced into the film forming chamber 27 by the carrier gas, and the mist reacted in the supply pipe 27 at 750 ° C. under atmospheric pressure to form a transparent film on the substrate 20. The film thickness of the obtained film was 350 nm. Moreover, the external appearance photograph of the obtained film | membrane is shown in FIG.
（評価）
上記で得られた皮膜につき、エネルギー分散型Ｘ線分析装置（ＥＤＳ：Ｅｎｅｒｇｙ Ｄｉｓｐｅｒｓｉｖｅ Ｘ−ｒａｙ Ｓｐｅｃｔｒｏｍｅｔｅｒ）およびＸ線回折装置を用いて膜の同定を行ったところ、得られた膜は、α―Ｓｉ３Ｎ４であった。また、テスターを用いて電気伝導性を評価したところ、絶縁体であった。
(Evaluation)
The film obtained above was subjected to film identification using an energy dispersive X-ray spectrometer (EDS) and an X-ray diffractometer, and the obtained film was α-Si. It was 3 N 4. Moreover, when electrical conductivity was evaluated using a tester, it was an insulator.
（実施例２）
基板に代えて、図３（ａ）に示すハニカム基材を用いたこと、原料にリンを用いたこと、キャリアガスの流量を５．０Ｌ／ｍｉｎとしたこと、キャリアガス（希釈）を用いなかったこと、成膜温度を５００℃としたこと以外は、実施例１と同様にして、皮膜を成膜した。結果を図３（ｂ）に示す。図３（ｂ）から明らかな通り、ハニカム基材であっても凹凸内部にいたるまで均一に成膜された黒色の皮膜が得られた。
(Example 2)
Instead of the substrate, the honeycomb substrate shown in FIG. 3A is used, phosphorus is used as the raw material, the flow rate of the carrier gas is 5.0 L / min, and the carrier gas (dilution) is not used. A film was formed in the same manner as in Example 1 except that the film forming temperature was set to 500 ° C. The results are shown in FIG. 3 (b). As is clear from FIG. 3 (b), even with the honeycomb substrate, a black film was uniformly formed to the inside of the unevenness.
本発明の成膜方法は、電子部品・電気機器部品、光学・電子写真関連装置、工業部材など、非酸化物膜（例えば、リン化物、窒化物など）が用いられるあらゆる分野に有用である。 The film forming method of the present invention is useful in all fields where non-oxide films (for example, phosphides, nitrides and the like) are used, such as electronic parts / electrical parts, optical / electrophotographic related devices, industrial members and the like.
１９ ミストＣＶＤ装置
２０ 基板
２１ サセプタ
２２ａ キャリアガス供給手段
２２ｂ キャリアガス（希釈）供給手段
２３ａ 流量調節弁
２３ｂ 流量調節弁
２４ ミスト発生源
２４ａ 原料溶液
２５ 容器
２５ａ 水
２６ 超音波振動子
２７ 供給管
２８ ヒーター
２９ 排気口
19 mist CVD apparatus 20 substrate 21 susceptor 22a carrier gas supply means 22b carrier gas (dilution) supply means 23a flow control valve 23b flow control valve 24 mist generation source 24a raw material solution 25 container 25a water 26 ultrasonic transducer 27 supply pipe 28 heater 29 Exhaust port
Claims (10)
The film forming method according to any one of claims 1 to 9, wherein the thermal reaction is performed at a temperature of 500 ° C or higher.
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| CN201811147185.3A CN109628910B (en) | 2017-10-07 | 2018-09-29 | Method of forming film |
| US16/151,461 US10927458B2 (en) | 2017-10-07 | 2018-10-04 | Method of forming film |
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