JP2018070437A - PRODUCTION METHOD OF CRYSTALLINE ZrO2 FILM, AND CRYSTALLINE ZrO2 FILM - Google Patents
PRODUCTION METHOD OF CRYSTALLINE ZrO2 FILM, AND CRYSTALLINE ZrO2 FILM Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title description 28
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000003595 mist Substances 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000012159 carrier gas Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 230000006641 stabilisation Effects 0.000 claims description 10
- 238000011105 stabilization Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 230000000087 stabilizing effect Effects 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 139
- 239000000243 solution Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 230000007704 transition Effects 0.000 description 9
- 230000001771 impaired effect Effects 0.000 description 7
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000007735 ion beam assisted deposition Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 description 2
- 239000003049 inorganic solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-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
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本発明は、光学物品、電気機器、電子部品、燃料電池、太陽電池、車両、産業用機器などに有用な結晶性ＺｒＯ２膜の製造方法および結晶性ＺｒＯ２膜に関する。 The present invention relates to an optical article, electric equipment, electronic components, fuel cells, solar cells, vehicles, a manufacturing method and a crystalline ZrO 2 film such useful crystalline ZrO 2 film industrial equipment.
ジルコニア（酸化ジルコニウム）膜は、高い耐熱性及び耐食性、低い熱及び電気伝導性等の特性を有し、耐熱用保護膜、耐食用保護膜、光学薄膜等として利用される。その形成方法としては、金属酸化物の薄膜形成方法として何れも従来から良く知られているプラズマスプレー法や真空蒸着法が一般に用いられる。
ジルコニアは、常温では単斜晶系であるが、温度を上げていくとその結晶系が正方晶系に相転移する。この相転移は可逆的なものであるが、単斜晶系から正方晶系への相転移は、約４％の体積収縮を伴うので、昇降温を繰り返すことによってジルコニアが破壊に至る場合がある。この破壊を防ぐために、ジルコニアに酸化イットリウム等の熱安定化ドーパントを固溶させ、熱的に安定化させたのが安定化ジルコニアである。
A zirconia (zirconium oxide) film has characteristics such as high heat resistance and corrosion resistance, low heat and electrical conductivity, and is used as a heat-resistant protective film, a corrosion-resistant protective film, an optical thin film, and the like. As its formation method, a plasma spray method or a vacuum deposition method, which are well known in the past as a metal oxide thin film formation method, is generally used.
Zirconia is monoclinic at normal temperature, but as the temperature is raised, the crystal system undergoes a phase transition to tetragonal system. Although this phase transition is reversible, the phase transition from the monoclinic system to the tetragonal system is accompanied by a volume shrinkage of about 4%, and thus zirconia may be destroyed by repeated heating and cooling. . In order to prevent this destruction, stabilized zirconia is obtained by dissolving a thermally stabilizing dopant such as yttrium oxide in zirconia and thermally stabilizing it.
特許文献１には、エアロゾル化ガスデポジション法を用いて、イットリア安定化ジルコニア（ＹＳＺ）粒子を基材上に堆積させることにより、ジルコニア膜を作製することが記載されている。また特許文献２には、スカンジア安定化ジルコニア膜の前駆体を焼成することによって、スカンジア安定化ジルコニア膜を作製することが記載されている。しかしながら、特許文献１および特許文献２のように、熱安定化ドーパントをドーピングすることによってジルコニア膜を熱的に安定化させた場合には、ジルコニア膜の機械的な特性の低下などが生じ、ジルコニア及びジルコニア膜が本来有しているはずの特性を十分に発揮することができないなどの問題があった。 Patent Document 1 describes that a zirconia film is produced by depositing yttria-stabilized zirconia (YSZ) particles on a substrate using an aerosolized gas deposition method. Patent Document 2 describes that a scandia-stabilized zirconia film is produced by firing a precursor of a scandia-stabilized zirconia film. However, as in Patent Document 1 and Patent Document 2, when the zirconia film is thermally stabilized by doping with a heat-stabilizing dopant, the mechanical characteristics of the zirconia film are deteriorated, resulting in zirconia. In addition, there is a problem that the characteristics that the zirconia film should originally have cannot be fully exhibited.
一方、ＹＳＺのように熱安定化ドーパントを添加することなく、熱的に安定化されたジルコニアを作製する方法が検討されている。非特許文献１には、エアロゾル化したジルコニアの原料溶液を、筒状の反応炉を通過させることによって、熱安定化ドーピングを行うことなく、正方晶の結晶構造を有する結晶性ＺｒＯ２ナノ粒子を製造することが記載されている。しかしながら、非特許文献１に記載されている方法では、溶媒が急激に蒸発するのを防ぐために、反応炉の長さを十分にとらなければならず、さらに、段階的に温度を上げて加熱するように構成する必要があるなど、製造プロセスが複雑となる問題があった。また、成膜が困難であり、粒子状になってしまう問題があった。そのため、成膜が可能であり、結晶性ジルコニア本来の性能を生かし、且つ工業上利用価値の高い結晶性ジルコニア膜が待ち望まれていた。 On the other hand, a method for producing a thermally stabilized zirconia without adding a thermally stabilizing dopant like YSZ has been studied. Non-Patent Document 1 discloses that by passing an aerosolized zirconia raw material solution through a cylindrical reactor, crystalline ZrO 2 nanoparticles having a tetragonal crystal structure are obtained without performing thermal stabilization doping. Manufacturing is described. However, in the method described in Non-Patent Document 1, in order to prevent the solvent from rapidly evaporating, it is necessary to sufficiently take the length of the reaction furnace, and further, the temperature is increased and heated in steps. There is a problem in that the manufacturing process becomes complicated, such as the need to configure. In addition, there is a problem that film formation is difficult and particles are formed. Therefore, a crystalline zirconia film that can be formed, takes advantage of the original performance of crystalline zirconia and has high industrial utility value has been awaited.
また、非特許文献２には、ＩＢＡＤ（Ｉｏｎ Ｂｅａｍ Ａｓｓｉｓｔｅｄ Ｄｅｐｏｓｉｔｉｏｎ）法を用いて、熱安定化ドーピングを行うことなく、ナノ結晶によって安定化されたＺｒＯ２のナノ粒子膜を作製することが記載されている。しかしながら、非特許文献２に記載の方法で作製されたＺｒＯ２のナノ粒子膜は、粒子径が１０ｎｍ程度の単相の結晶粒と非晶質部分とからなる粒状混相膜であり、さらに、アルゴン等の気泡が膜中に混入するなど、結晶性ＺｒＯ２相によって構成された膜ではなかった。さらに、ＩＢＡＤ法は、真空装置等の大掛かりな設備を用いる必要があるなど、非特許文献２に記載の方法では、工業的な課題が多く、また、結晶性ＺｒＯ２の非粒状膜を得ることができず、良好な非粒状の結晶性ＺｒＯ２膜を製造することが困難であった。そのため、熱安定化ドーピングを行うことなく、簡単且つ容易に、熱的に安定した非粒状の結晶性ＺｒＯ２膜を作製する方法が求められており、結晶性ＺｒＯ２の非粒状膜であって、膜質が良好である、工業的に有用な結晶性ＺｒＯ２膜が待ち望まれていた。 Non-Patent Document 2 describes that a nanoparticle film of ZrO 2 stabilized by nanocrystals is manufactured without performing thermal stabilization doping using an IBAD (Ion Beam Assisted Deposition) method. ing. However, the ZrO 2 nanoparticle film prepared by the method described in Non-Patent Document 2 is a granular mixed-phase film composed of single-phase crystal grains having a particle diameter of about 10 nm and an amorphous portion, and further, argon The film was not composed of a crystalline ZrO 2 phase, such as bubbles mixed in the film. Furthermore, the IBAD method requires the use of large-scale equipment such as a vacuum apparatus, and the method described in Non-Patent Document 2 has many industrial problems, and obtains a non-granular film of crystalline ZrO 2. It was difficult to produce a good non-granular crystalline ZrO 2 film. Therefore, there is a need for a method for producing a thermally stable non-granular crystalline ZrO 2 film easily and easily without performing thermal stabilization doping, which is a crystalline ZrO 2 non-granular film. An industrially useful crystalline ZrO 2 film with good film quality has been awaited.
本発明は、工業的有利に、熱安定化ドーピングを行うことなく、熱的に安定化された結晶性ＺｒＯ２膜を製造することができる製造方法を提供することを目的とする。 It is an object of the present invention to provide a production method that can produce a thermally stabilized crystalline ZrO 2 film without industrially advantageous thermal stabilization doping.
本発明者らは、上記目的を達成すべく鋭意検討した結果、スプレー熱分解法などによれば、アモルファスのＺｒＯ２膜が得られていたが（基板に対して原料ミストを噴射するため、基板との衝突やその際の衝突エネルギー等がアモルファス形成に影響していたのかもしれないが）、ミストＣＶＤ法を用いて結晶性ＺｒＯ２膜を成膜すると、驚くべきことに、熱安定化ドーパントを用いなくても熱的に安定化されており、室温においても相転移しない非粒状膜が得られることを見出し、特に、熱的に安定な、立方晶の結晶構造を有する結晶性ＺｒＯ２膜が簡便に得られることを見出し、このような製造方法が上記従来の問題を一挙に解決できるものであることを知見した。
また、本発明者らは、上記知見を得た後、さらに検討を重ねて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 have obtained an amorphous ZrO 2 film according to a spray pyrolysis method or the like (because the raw material mist is injected onto the substrate, The impact energy and the collision energy at that time may have influenced the amorphous formation), but surprisingly, when the crystalline ZrO 2 film is formed using the mist CVD method, the heat stabilizing dopant It has been found that a non-granular film that is thermally stabilized without using phase and does not undergo phase transition even at room temperature can be obtained, and in particular, a crystalline ZrO 2 film having a cubic crystal structure that is thermally stable Has been found that such a production method can solve the above conventional problems all at once.
In addition, after obtaining the above knowledge, the present inventors have further studied and completed the present invention.
すなわち、本発明は、以下の発明に関する。
［１］ 結晶性ＺｒＯ２膜の前駆体溶液を霧化または液滴化し、得られたミストまたは液滴を用いて、基体上に結晶性ＺｒＯ２膜を製造する方法であって、前記の霧化または液滴化後、前記ミストまたは前記液滴をキャリアガスを用いて前記基体近傍まで搬送し、ついで、前記ミストまたは前記液滴を熱反応させることにより、前記基体上に、非粒状の結晶性ＺｒＯ２膜を形成することを特徴とする結晶性ＺｒＯ２膜の製造方法。
［２］ 前記前駆体溶液がジルコニウムの有機金属錯体を含む前記［１］記載の製造方法。
［３］ 前記前駆体溶液の溶媒が有機溶媒を含む前記［１］または［２］に記載の製造方法。
［４］ 前記熱反応を、大気圧下で行う前記［１］〜［３］のいずれかに記載の製造方法。
［５］ 前記熱反応を、５００℃以下の温度で行う前記［１］〜［４］のいずれかに記載の製造方法。
［６］ 前記熱反応を、前記搬送後、前記ミストまたは液滴を加熱することにより行う前記［１］〜［５］のいずれかに記載の製造方法。
［７］ 前記［１］〜［６］のいずれかに記載の製造方法により得られた結晶性ＺｒＯ２膜。
［８］ 立方晶の結晶構造を有する前記［７］記載の結晶性ＺｒＯ２膜。
［９］ 室温において立方晶の結晶構造を有する前記［７］または［８］に記載の結晶性
ＺｒＯ２膜。
［１０］ 多結晶膜である前記［７］〜［９］のいずれかに記載の結晶性ＺｒＯ２膜。
［１１］ 膜厚が０．５μｍ以上である前記［７］〜［１０］のいずれかに記載の結晶性ＺｒＯ２膜。
［１２］ 熱安定化ドーパントを用いずに熱的に安定化された結晶性ＺｒＯ２膜であって、非粒状膜であることを特徴とする結晶性ＺｒＯ２膜。
［１３］ 立方晶の結晶構造を有する前記［１２］記載の結晶性ＺｒＯ２膜。
［１４］ 結晶性ＺｒＯ２膜を熱安定化させる方法であって、前記結晶性ＺｒＯ２膜の成膜にミストＣＶＤ法を用いることを特徴とする結晶性ＺｒＯ２膜の熱安定化方法。
［１５］ 前記［１４］記載の方法により熱安定化された結晶性ＺｒＯ２膜。
That is, the present invention relates to the following inventions.
[1] A method for producing a crystalline ZrO 2 film on a substrate by atomizing or dropping a precursor solution of a crystalline ZrO 2 film and using the obtained mist or liquid droplets, After the formation or droplet formation, the mist or the droplet is transported to the vicinity of the substrate using a carrier gas, and then the mist or the droplet is subjected to a thermal reaction to thereby form non-granular crystals on the substrate. A method for producing a crystalline ZrO 2 film, comprising forming a crystalline ZrO 2 film.
[2] The method according to [1], wherein the precursor solution contains an organometallic complex of zirconium.
[3] The production method according to [1] or [2], wherein the solvent of the precursor solution includes an organic solvent.
[4] The production method according to any one of [1] to [3], wherein the thermal reaction is performed under atmospheric pressure.
[5] The production method according to any one of [1] to [4], wherein the thermal reaction is performed at a temperature of 500 ° C. or lower.
[6] The manufacturing method according to any one of [1] to [5], wherein the thermal reaction is performed by heating the mist or droplets after the conveyance.
[7] A crystalline ZrO 2 film obtained by the production method according to any one of [1] to [6].
[8] The crystalline ZrO 2 film according to [7], which has a cubic crystal structure.
[9] The crystalline ZrO 2 film according to [7] or [8], which has a cubic crystal structure at room temperature.
[10] The crystalline ZrO 2 film according to any one of [7] to [9], which is a polycrystalline film.
[11] The crystalline ZrO 2 film according to any one of [7] to [10], wherein the film thickness is 0.5 μm or more.
[12] A thermally stabilized crystalline ZrO 2 film without using the heat stabilization dopant, crystalline ZrO 2 film, which is a non-particulate film.
[13] The crystalline ZrO 2 film according to [12], which has a cubic crystal structure.
[14] The crystalline ZrO 2 film A method of heat-stabilized, heat stabilizing method of a crystalline ZrO 2 film, which comprises using a mist CVD method in the film forming of the crystalline ZrO 2 film.
[15] A crystalline ZrO 2 film thermally stabilized by the method described in [14].
本発明の製造方法によれば、工業的有利に、熱安定化ドーピングを行うことなく、熱的に安定した非粒状の結晶性ＺｒＯ２膜を製造することができる。 According to the manufacturing method of the present invention, a thermally stable non-granular crystalline ZrO 2 film can be manufactured industrially advantageously without performing thermal stabilization doping.
本発明の結晶性ＺｒＯ２膜は、熱安定化ドーパントを用いずに熱的に安定化された結晶性ＺｒＯ２膜であって、非粒状膜であることを特長とする。前記結晶性ＺｒＯ２膜は、ＺｒＯ２結晶またはその混晶を主成分として含む膜であればそれでよく、「主成分」とは、例えば前記結晶性ＺｒＯ２膜がＺｒＯ２結晶である場合、膜中の金属元素中のＺｒの原子比が０．５以上の割合でＺｒＯ２結晶が含まれていればそれでよい。本発明においては、前記膜中の金属元素中のＺｒの原子比が０．７以上であることが好ましく、０．８以上であるのがより好ましい。 Crystalline ZrO 2 film of the present invention, there is provided a thermally stabilized crystalline ZrO 2 film without using the heat stabilization dopant, featuring that it is non-granular film. The crystalline ZrO 2 film may be any film that includes a ZrO 2 crystal or a mixed crystal thereof as a main component. For example, when the crystalline ZrO 2 film is a ZrO 2 crystal, the “main component” is a film. If the ZrO 2 crystal is contained in the atomic ratio of Zr in the metal element in the ratio of 0.5 or more, it is sufficient. In the present invention, the atomic ratio of Zr in the metal element in the film is preferably 0.7 or more, and more preferably 0.8 or more.
本発明において、「熱的に安定化された」とは、室温だけでなく、加熱しても、結晶性ＺｒＯ２膜が相転移しないことをいい、より具体的には、例えば、室温（例えば、２５℃）〜５００℃においても結晶性ＺｒＯ２膜が相転移しないことをいう。「相転移」とは、固相間の相転移のうち、結晶構造が変化する構造相転移をいう。通常、相転移の有無の確認は、Ｘ線回析法を用いて行う。 In the present invention, “thermally stabilized” means that the crystalline ZrO 2 film does not undergo phase transition even when heated, and more specifically, for example, at room temperature (for example, 25 ° C.) to 500 ° C. means that the crystalline ZrO 2 film does not undergo phase transition. "Phase transition" refers to a structural phase transition in which the crystal structure changes among the phase transitions between solid phases. Usually, the presence or absence of the phase transition is confirmed using an X-ray diffraction method.
また、本発明において、「熱安定化ドーパントを用いずに熱的に安定化された」とは、熱安定化ドーパントによって熱的に安定化されていないことを意味し、形式的にドーパントが含まれていてもよく、熱安定化の目的以外の目的でドーパント（非熱安定化ドーパント）が含まれていてもよい。例えば、電気特性を付与する目的で、ｎ型ドーパントやｐ型ドーパントが非熱安定化ドーパントとして含まれていてもよい。非熱安定化ドーパントが含まれている場合には、その含有量などは特に限定されないが、本発明においては、膜中の非熱安定化ドーパント濃度が、０．０１原子％以下であるのが好ましい。「形式的にドーパントが含まれている」とは、ドーパントが含まれている場合であっても、含まれていない場合であっても、前記結晶性ＺｒＯ２膜が熱的に安定化されていることをいう。前記非熱安定化ドーパントとしては、特に限定されないが、例えば、ニオブ、バナジウムなどが挙げられる。 Further, in the present invention, “thermally stabilized without using a heat-stabilized dopant” means that it is not thermally stabilized by a heat-stabilized dopant, and formally contains a dopant. A dopant (non-thermally stabilized dopant) may be included for purposes other than the purpose of thermal stabilization. For example, an n-type dopant or a p-type dopant may be included as a non-thermal stabilizing dopant for the purpose of imparting electrical characteristics. When a non-thermally stabilized dopant is included, the content thereof is not particularly limited, but in the present invention, the non-thermally stabilized dopant concentration in the film is 0.01 atomic% or less. preferable. “Formally containing a dopant” means that the crystalline ZrO 2 film is thermally stabilized regardless of whether or not a dopant is contained. It means being. The non-thermally stabilizing dopant is not particularly limited, and examples thereof include niobium and vanadium.
本発明において、「非粒状膜」とは、粒状ではない膜を意味し、例えばＴＥＭ観察において、粒界の確認や平均粒径の算出が困難である場合の膜をいう。また、前記結晶性ＺｒＯ２膜は、通常、層状膜であり、単層状膜であってもよいし、２以上の結晶性ＺｒＯ２層からなる多層状膜であってもよいが、本発明においては、多層状膜であるのが好ましい。また、前記結晶性ＺｒＯ２膜は、単相膜であってもよいし、２以上の結晶相を有する多相膜であってもよい。前記単相膜は、単一の結晶構造を有するＺｒＯ２相によって構成されている結晶性ＺｒＯ２膜をいう。前記多相膜は、２以上の異なる結晶構造を有するＺｒＯ２相によって構成されている結晶性ＺｒＯ２膜をいう。前記結晶構造の種類は、本発明の目的を阻害しない限り特に限定されないが、正方晶または立方晶が好ましく、立方晶がより好ましい。また、前記結晶性ＺｒＯ２膜は、単結晶からなる膜であってもよいし、多結晶からなる膜であってもよい。 In the present invention, the “non-particulate film” means a film that is not granular, and refers to a film when it is difficult to confirm grain boundaries and calculate an average particle diameter in TEM observation, for example. The crystalline ZrO 2 film is usually a layered film, may be a single layered film, or may be a multilayered film composed of two or more crystalline ZrO 2 layers. Is preferably a multilayer film. The crystalline ZrO 2 film may be a single phase film or a multiphase film having two or more crystal phases. The single phase film refers to a crystalline ZrO 2 film composed of a ZrO 2 phase having a single crystal structure. The multiphase film refers to a crystalline ZrO 2 film composed of ZrO 2 phases having two or more different crystal structures. The kind of the crystal structure is not particularly limited as long as the object of the present invention is not impaired, but tetragonal or cubic is preferable, and cubic is more preferable. The crystalline ZrO 2 film may be a single crystal film or a polycrystalline film.
前記結晶性ＺｒＯ２膜の膜厚は、特に限定されないが、本発明においては、膜厚が約０．１μｍ以上であるのが好ましく、約０．５μｍ以上であるのがより好ましい。また膜厚の上限は特に限定されないが、約１００μｍであるのが好ましく、約５０μｍであるのがより好ましい。 The film thickness of the crystalline ZrO 2 film is not particularly limited, but in the present invention, the film thickness is preferably about 0.1 μm or more, and more preferably about 0.5 μm or more. The upper limit of the film thickness is not particularly limited, but is preferably about 100 μm, and more preferably about 50 μm.
本発明においては、前記結晶性ＺｒＯ２膜がミストＣＶＤ法によって、熱安定化ドーピングせずに基体上に形成されたものであるのが好ましく、さらに、立方晶の結晶構造を有するものであるのがより好ましい。以下、前記結晶性ＺｒＯ２膜製造の好適な態様を説明する。 In the present invention, the crystalline ZrO 2 film is preferably formed on the substrate without thermal stabilization doping by the mist CVD method, and further has a cubic crystal structure. Is more preferable. Hereinafter, a preferred embodiment of the production of the crystalline ZrO 2 film will be described.
前記結晶性ＺｒＯ２膜は、結晶性ＺｒＯ２膜の前駆体溶液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を用いて基体近傍まで搬送し（搬送工程）、ついで、前記ミストまたは液滴を熱反応させることにより前記基体上に前記結晶性ＺｒＯ２膜を成膜する（成膜工程）ことにより、好適に得られる。 In the crystalline ZrO 2 film, the precursor solution of the crystalline ZrO 2 film is atomized or dropletized (atomization / droplet forming process), and the obtained mist or droplet is made near the substrate using a carrier gas. The crystalline ZrO 2 film is formed preferably on the substrate by carrying out the carrying (conveying step) and then causing the mist or droplets to undergo a thermal reaction (film forming step).
（霧化・液滴化工程）
霧化・液滴化工程は、前記前駆体溶液を霧化または液滴化する。霧化手段または液滴化手段は、前記前駆体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が、衝突エネルギーによる損傷がないためにより好ましい。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１〜１０μｍである。
(Atomization / droplet forming process)
In the atomization / droplet forming step, the precursor solution is atomized or dropletized. The atomizing means or the droplet forming means is not particularly limited as long as the precursor solution can be atomized or formed into droplets, and may be a known means. In the present invention, the atomization using ultrasonic waves is used. Means or dropletizing means are preferred. Mist or droplets obtained using ultrasonic waves have a zero initial velocity and are preferable because they float in the air.For example, instead of spraying like a spray, they can be suspended in a space and transported as a gas. A possible mist is more preferred because it is not damaged by collision energy. The droplet size is not particularly limited and may be a droplet of about several mm, but is preferably 50 μm or less, and more preferably 1 to 10 μm.
（前駆体溶液）
前記結晶性ＺｒＯ２膜の前駆体溶液は、ジルコニウムを含み、且つ霧化または液滴化が可能な溶液または分散液であれば、特に限定されない。前記前駆体溶液としては、例えば、ジルコニウムの有機金属錯体（例えばアセチルアセトナート錯体等）やハロゲン化物（例えばフッ化物、塩化物、臭化物またはヨウ化物等）を含む溶液または分散液などが挙げられる。本発明においては、立方晶の結晶構造を有する結晶性ＺｒＯ２膜を作製する場合には、前記前駆体溶液が、ジルコニウムの有機金属錯体を含むのが好ましい。ジルコニウムの有機金属錯体は、本発明の目的を阻害しない限り、特に限定されない。前記有機金属錯体としては、例えば、シアノ錯体、カルボニル錯体、シクロペンタジエン錯体、アセチルアセトナート錯体、アセチル錯体などが挙げられるが、本発明においては、前記有機金属錯体が、アセチルアセトナート錯体であるのが、より優れた膜状の立方晶ＺｒＯ２が得られるため、好ましい。また、正方晶の結晶性ＺｒＯ２膜を作製する場合には、前記前駆体溶液が、例えば、硝酸ジルコニウム、硫酸ジルコニウム、酢酸ジルコニウムなどの水溶性ジルコニウム化合物を含むのが好ましい。前駆体溶液中のジルコニウムの含有量は、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。
(Precursor solution)
The precursor solution of the crystalline ZrO 2 film is not particularly limited as long as it contains zirconium and can be atomized or formed into a droplet. Examples of the precursor solution include a solution or dispersion containing a zirconium organometallic complex (eg, acetylacetonate complex) or a halide (eg, fluoride, chloride, bromide, or iodide). In the present invention, when producing a crystalline ZrO 2 film having a cubic crystal structure, the precursor solution preferably contains an organometallic complex of zirconium. The organometallic complex of zirconium is not particularly limited as long as the object of the present invention is not impaired. Examples of the organometallic complex include a cyano complex, a carbonyl complex, a cyclopentadiene complex, an acetylacetonate complex, and an acetyl complex. In the present invention, the organometallic complex is an acetylacetonate complex. However, it is preferable because a more excellent film-like cubic ZrO 2 can be obtained. Moreover, when producing a tetragonal crystalline ZrO 2 film, the precursor solution preferably contains a water-soluble zirconium compound such as zirconium nitrate, zirconium sulfate, or zirconium acetate. The zirconium content in the precursor solution is not particularly limited as long as the object of the present invention is not impaired, but is preferably 0.001 mol% to 50 mol%, more preferably 0.01 mol% to 50 mol. %.
また、前駆体溶液は、さらに、酸や塩基等のその他添加剤が含まれていてもよい。前記酸としては、例えば、塩酸、臭化水素酸、ヨウ化水素酸などが挙げられる。
前駆体溶液の溶媒は、特に限定されず、水等の無機溶媒であってもよいし、アルコール等の有機溶媒であってもよいし、無機溶媒と有機溶媒との混合溶媒であってもよい。本発明においては、立方晶の結晶構造を有する結晶性ＺｒＯ２膜を作製する場合には、前記溶媒が有機溶媒を含むのが好ましく、アルコールを含むのがより好ましく、低級アルコール（例えば、メタノール、エタノール、プロパノール、ブタノール等）を含むのが最も好まししい。また、正方晶の結晶構造を有する結晶性ＺｒＯ２膜を作製する場合には、前記溶媒が水であるのが好ましい。前記水としては、より具体的には、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が、本発明においては、超純水が好ましい。
The precursor solution may further contain other additives such as acid and base. Examples of the acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, and the like.
The solvent of the precursor solution is not particularly limited, and may be an inorganic solvent such as water, an organic solvent such as alcohol, or a mixed solvent of an inorganic solvent and an organic solvent. . In the present invention, when producing a crystalline ZrO 2 film having a cubic crystal structure, the solvent preferably contains an organic solvent, more preferably an alcohol, and a lower alcohol (for example, methanol, (Ethanol, propanol, butanol, etc.) are most preferable. Moreover, when producing a crystalline ZrO 2 film having a tetragonal crystal structure, the solvent is preferably water. More specifically, 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. Ultrapure water is preferred.
（基体）
前記基体は、前記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、どのような形状のものであってもよく、あらゆる形状に対して有効であり、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。基板の厚さは、本発明においては特に限定されない。
(Substrate)
The substrate is not particularly limited as long as it can support the film. The material of the substrate is not particularly limited as long as the object of the present invention is not impaired, and may be a known substrate, an organic compound, or an inorganic compound. The shape of the substrate may be any shape and is effective for all shapes, for example, a plate shape such as a flat plate or a disk, a fiber shape, a rod shape, a columnar shape, a prismatic shape, A cylindrical shape, a spiral shape, a spherical shape, a ring shape and the like can be mentioned. In the present invention, a substrate is preferable. The thickness of the substrate is not particularly limited in the present invention.
前記基板は、板状であって、前記結晶性ＺｒＯ２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。前記基板としては、例えば、ガラス基板、高分子基板、金属基板、サファイア基板、ＹＳＺ基板などが挙げられるが、本発明においては、前記基板が、ｃ面サファイア基板またはＹＳＺ基板であるのが好ましい。 The substrate is not particularly limited as long as it is plate-like and serves as a support for the crystalline ZrO 2 film. It may be an insulator substrate, a semiconductor substrate, or a conductive substrate. Examples of the substrate include a glass substrate, a polymer substrate, a metal substrate, a sapphire substrate, and a YSZ substrate. In the present invention, the substrate is preferably a c-plane sapphire substrate or a YSZ substrate.
（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設置されている基体近傍まで搬送する。前記キャリアガスとしては、本発明の目的を阻害しない限り特に限定されず、例えば、酸素、オゾン、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などが好適な例として挙げられる。本発明においては、前記キャリアガスが不活性ガスであるのが好ましい。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。希釈ガスの場合には、希釈ガスの流量が、０．００１〜２Ｌ／分であるのが好ましく、０．１〜１Ｌ／分であるのがより好ましい。
(Conveying process)
In the transfer step, the mist or the droplets are transferred to the vicinity of the substrate installed in the film forming chamber with a carrier gas. The carrier gas is not particularly limited as long as the object of the present invention is not impaired. For example, oxygen, ozone, an inert gas such as nitrogen or argon, or a reducing gas such as hydrogen gas or forming gas is preferable. Can be mentioned. In the present invention, the carrier gas is preferably an inert gas. Further, the type of carrier gas may be one, but it may be two or more, and a diluent gas with a reduced flow rate (for example, 10-fold diluted gas) is further used as the second carrier gas. Also good. Further, the supply location of the carrier gas is not limited to one location but may be two or more locations. 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. In the case of a dilution gas, the flow rate of the dilution gas is preferably 0.001 to 2 L / min, and more preferably 0.1 to 1 L / min.
（成膜工程）
成膜工程では、成膜室内に設置されている基体近傍で前記ミストまたは液滴を熱反応させることによって、前記基体上に前記結晶性ＺｒＯ２膜を成膜する。熱反応は、熱でもって前記ミストまたは前記液滴が反応すればそれでよく、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。通常、前記熱反応を、前記搬送後、前記ミストまたは液滴を加熱することにより行う。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、高すぎない温度（例えば１０００℃）以下が好ましく、６５０℃以下がより好ましく、５００℃以下が最も好ましい。なお、下限は、特に限定されないが、通常、５０℃以上であり、好ましくは、１００℃以上であり、より好ましくは、３００℃以上である。本発明の製造方法によれば、例えば、原料溶液として、アセチルアセトナート錯体を用いる場合であって、立方晶の結晶構造を有する結晶性ＺｒＯ２膜を作製する場合には、５００℃以下の温度であっても良質な結晶性ＺｒＯ２膜を得ることができる。また、熱反応は、本発明の目的を阻害しない限り、真空下、非酸素雰囲気下、還元ガス雰囲気下および酸素雰囲気下のいずれの雰囲気下で行われてもよく、また、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が、本発明においては、大気圧下で行われるのが好ましい。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。
(Film formation process)
In the film forming step, the crystalline ZrO 2 film is formed on the substrate by causing the mist or droplets to undergo thermal reaction in the vicinity of the substrate installed in the film forming chamber. The thermal reaction may be performed as long as the mist or the droplet reacts with heat, and the reaction conditions are not particularly limited as long as the object of the present invention is not impaired. Usually, the thermal reaction is performed by heating the mist or droplets after the transport. In this step, the thermal reaction is usually performed at a temperature not lower than the evaporation temperature of the solvent, but is preferably not too high (for example, 1000 ° C.) or less, more preferably 650 ° C. or less, and most preferably 500 ° C. or less. In addition, although a minimum is not specifically limited, Usually, it is 50 degreeC or more, Preferably, it is 100 degreeC or more, More preferably, it is 300 degreeC or more. According to the production method of the present invention, for example, when an acetylacetonate complex is used as a raw material solution and a crystalline ZrO 2 film having a cubic crystal structure is produced, the temperature is 500 ° C. or lower. Even so, a high-quality crystalline ZrO 2 film can be obtained. Further, the thermal reaction may be performed in any atmosphere of a vacuum, a non-oxygen atmosphere, a reducing gas atmosphere, and an oxygen atmosphere as long as the object of the present invention is not impaired. Although it may be carried out under any conditions of reduced pressure and reduced pressure, it is preferably carried out under atmospheric pressure in the present invention. The film thickness can be set by adjusting the film formation time.
また、本発明においては、前記基体上にバッファ層や応力緩和層等の他の層を設けもよい。他の層の形成手段は特に限定されず、上記した結晶性ＺｒＯ２膜の形成手段と同様であってもよいし、スパッタリング、蒸着、ＣＶＤなどの公知の手段を用いてもよい。 In the present invention, other layers such as a buffer layer and a stress relaxation layer may be provided on the substrate. The means for forming the other layers is not particularly limited, and may be the same as the means for forming the crystalline ZrO 2 film described above, or a known means such as sputtering, vapor deposition, or CVD may be used.
上記のようにして結晶性ＺｒＯ２膜を製造することで、熱安定化ドーピングを行うことなく、簡単且つ容易に、熱的に安定した非粒状の結晶性ＺｒＯ２膜を得ることができる。また、上記のような好適な成膜手段によれば、立方晶の結晶構造を有する非粒状の結晶性ＺｒＯ２膜を得ることができる。 By manufacturing the crystalline ZrO 2 film as described above, a thermally stable non-granular crystalline ZrO 2 film can be obtained easily and easily without performing thermal stabilization doping. Moreover, according to the suitable film forming means as described above, a non-granular crystalline ZrO 2 film having a cubic crystal structure can be obtained.
本発明の結晶性ＺｒＯ２膜は、結晶性酸化膜が用いられる、あらゆる分野において用いることができ、従来のＺｒＯ２膜（ＹＳＺも含む）と同様にして、光学物品、電気機器、電子部品、燃料電池、太陽電池、車両、産業用機器などの種々の用途に、好適に用いることができる。 The crystalline ZrO 2 film of the present invention can be used in any field where a crystalline oxide film is used, and in the same manner as a conventional ZrO 2 film (including YSZ), an optical article, an electric device, an electronic component, It can be suitably used for various applications such as fuel cells, solar cells, vehicles, and industrial equipment.
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１を説明する。ミストＣＶＤ装置１は、キャリアガスを供給するキャリアガス源２ａと、キャリアガス源２ａ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３ａと、前駆体溶液４ａが収容されるミスト発生源４と、水５ａが入れられる容器５と、容器５の底面に取り付けられた超音波振動子６と、成膜室７と、ミスト発生源４から成膜室７までをつなぐ供給管９と、成膜室７内に設置されたホットプレート８と、熱反応後のミスト、液滴および排気ガスを排出する排気口１１とを備えている。なお、ホットプレート８上には、基板１０が設置されている。
Example 1
1. Film Forming Apparatus A mist CVD apparatus 1 used in this example will be described with reference to FIG. The mist CVD apparatus 1 includes a carrier gas source 2a for supplying a carrier gas, a flow rate adjusting valve 3a for adjusting the flow rate of the carrier gas delivered from the carrier gas source 2a, and a mist generation source in which a precursor solution 4a is accommodated. 4, a container 5 in which water 5 a is placed, an ultrasonic transducer 6 attached to the bottom surface of the container 5, a film forming chamber 7, and a supply pipe 9 connecting the mist generating source 4 to the film forming chamber 7, A hot plate 8 installed in the film forming chamber 7 and an exhaust port 11 for discharging mist, droplets and exhaust gas after thermal reaction are provided. A substrate 10 is installed on the hot plate 8.
２．前駆体溶液の作製
メタノール溶媒に、ジルコニウムアセチルアセトナートを０．０５モル／Ｌの濃度となるように混合して前駆体溶液を調整した。
2. Preparation of Precursor Solution A precursor solution was prepared by mixing zirconium acetylacetonate in a methanol solvent to a concentration of 0.05 mol / L.
３．成膜準備
上記２．で得られた前駆体溶液４ａをミスト発生源４内に収容した。次に、基板１０として、サファイア基板をホットプレート８上に設置し、ホットプレート８を作動させて成膜室７内の温度を５００℃にまで昇温させた。次に、流量調節弁３ａを開いて、キャリアガス源であるキャリアガス供給手段２ａからキャリアガスを成膜室７内に供給し、成膜室７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３．０Ｌ／分に調節した。なお、キャリアガスとして窒素を用いた。
3. Preparation of film formation The precursor solution 4a obtained in the above was accommodated in the mist generation source 4. Next, a sapphire substrate was placed on the hot plate 8 as the substrate 10, and the hot plate 8 was operated to raise the temperature in the film forming chamber 7 to 500 ° C. Next, after opening the flow rate control valve 3a, supplying the carrier gas from the carrier gas supply means 2a, which is a carrier gas source, into the film forming chamber 7, and sufficiently replacing the atmosphere in the film forming chamber 7 with the carrier gas, The flow rate of the carrier gas was adjusted to 3.0 L / min. Nitrogen was used as the carrier gas.
４．ＺｒＯ２膜の形成
次に、超音波振動子６を２．４ＭＨｚで振動させ、その振動を、水５ａを通じて前駆体井溶液４ａに伝播させることによって、前駆体溶液４ａを霧化させてミスト４ｂを生成させた。このミスト４ｂが、キャリアガスによって、供給管９内を通って、成膜室７内に導入され、大気圧下、５００℃にて、成膜室７内でミストが熱反応して、基板１０上にＺｒＯ２膜が形成された。なお、膜厚は０．５μｍであり、成膜時間は１５分間であった。
4). Formation of ZrO 2 film Next, the ultrasonic vibrator 6 is vibrated at 2.4 MHz, and the vibration is propagated to the precursor well solution 4a through the water 5a, whereby the precursor solution 4a is atomized to form the mist 4b. Was generated. The mist 4b is introduced into the film forming chamber 7 by the carrier gas through the supply pipe 9, and the mist thermally reacts in the film forming chamber 7 at 500 ° C. under atmospheric pressure. A ZrO 2 film was formed thereon. The film thickness was 0.5 μm and the film formation time was 15 minutes.
５．評価
上記４．にて得られた膜は、透明な結晶膜であった。また、Ｘ線回折装置を用いて膜の同定を実施したところ、得られた膜は、立方晶の結晶構造を有する結晶性ＺｒＯ２膜であった。Ｘ線回析結果を図２に示す。また、得られた結晶性ＺｒＯ２膜をＴＥＭ観察した。このＴＥＭ断面写真を図３に示す。図３からも明らかなとおり、得られた結晶性ＺｒＯ２膜は多層状の非粒状膜であった。
5. Evaluation 4. The film obtained in 1 was a transparent crystal film. Further, when the film was identified using an X-ray diffractometer, the obtained film was a crystalline ZrO 2 film having a cubic crystal structure. The X-ray diffraction results are shown in FIG. The obtained crystalline ZrO 2 film was observed with a TEM. This TEM cross-sectional photograph is shown in FIG. As apparent from FIG. 3, the obtained crystalline ZrO 2 film was a multilayer non-granular film.
（実施例２）
成膜時間を２５分としたこと以外は、実施例１と同様にして結晶性ＺｒＯ２膜を得た。得られた膜の膜厚は１．１μｍであった。また、実施例１と同様にして、Ｘ線回析装置を用いて膜の同定を実施したところ、得られた膜は立方晶の結晶構造を有する結晶性ＺｒＯ２膜であった。
(Example 2)
A crystalline ZrO 2 film was obtained in the same manner as in Example 1 except that the film formation time was 25 minutes. The film thickness obtained was 1.1 μm. Further, when the film was identified using an X-ray diffraction apparatus in the same manner as in Example 1, the obtained film was a crystalline ZrO 2 film having a cubic crystal structure.
本発明の結晶性ＺｒＯ２膜は、従来のＺｒＯ２膜（ＹＳＺも含む）と同様、光学物品、電気機器、電子部品、燃料電池、太陽電池、車両、産業用機器等に利用可能である。 The crystalline ZrO 2 film of the present invention can be used for optical articles, electrical equipment, electronic components, fuel cells, solar cells, vehicles, industrial equipment and the like, as with conventional ZrO 2 films (including YSZ).
１ ミストＣＶＤ装置
２ａ キャリアガス源
３ａ 流量調節弁
４ ミスト発生源
４ａ 前駆体溶液
４ｂ ミスト
５ 容器
５ａ 水
６ 超音波振動子
７ 成膜室
８ ホットプレート
９ 供給管
１０ 基板
１１ 排気口
DESCRIPTION OF SYMBOLS 1 Mist CVD apparatus 2a Carrier gas source 3a Flow control valve 4 Mist generation source 4a Precursor solution 4b Mist 5 Container 5a Water 6 Ultrasonic vibrator 7 Deposition chamber 8 Hot plate 9 Supply pipe 10 Substrate 11 Exhaust port
Claims (15)
A crystalline ZrO 2 film thermally stabilized by the method according to claim 14.
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| JPH04311571A (en) * | 1991-04-10 | 1992-11-04 | Ricoh Co Ltd | Method for forming metallic oxide film on substrate |
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| JPH04311571A (en) * | 1991-04-10 | 1992-11-04 | Ricoh Co Ltd | Method for forming metallic oxide film on substrate |
| JP2005305233A (en) * | 2004-04-19 | 2005-11-04 | Shizuo Fujita | Atomization apparatus for forming film |
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| WO2024048765A1 (en) * | 2022-08-31 | 2024-03-07 | 株式会社Gaianixx | Crystal, multilayer structure, element, electronic device, electronic apparatus and system |
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