JP2017206746A - Manufacturing method of oxide sintered body and oxide sintered body - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 48
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 43
- 239000011733 molybdenum Substances 0.000 claims abstract description 43
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 28
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052738 indium Inorganic materials 0.000 claims abstract description 22
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 24
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 238000007738 vacuum evaporation Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- 238000007733 ion plating Methods 0.000 description 14
- 238000007906 compression Methods 0.000 description 13
- 230000006835 compression Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000007740 vapor deposition Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 230000005525 hole transport Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910017299 Mo—O Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000000313 electron-beam-induced deposition Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- -1 aromatic amine compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
本発明は、酸化インジウムを主原料とする真空蒸着用の酸化物焼結体の製造方法と酸化物焼結体に関する。 The present invention relates to a method for manufacturing an oxide sintered body for vacuum vapor deposition using indium oxide as a main raw material and the oxide sintered body.
酸化物透明導電膜は、高い導電性と特に可視光領域における高い透過率を有するため、液晶ディスプレイ（ＬＣＤ）、有機エレクトロルミネッセンス（有機ＥＬ）表示装置等の表示素子、太陽電池、発光ダイオード（ＬＥＤ）における透明電極等の材料のほか、自動車窓の熱線反射膜、帯電防止膜、防曇用透明発熱体等に広く利用されている。 Oxide transparent conductive films have high conductivity and high transmittance, particularly in the visible light region. Therefore, display elements such as liquid crystal displays (LCD) and organic electroluminescence (organic EL) display devices, solar cells, and light emitting diodes (LEDs) In addition to materials such as transparent electrodes in (3), it is widely used for heat ray reflective films, antistatic films, antifogging transparent heating elements for automobile windows, and the like.
近年、これらの中でもＬＣＤや有機ＥＬ表示装置の技術開発が進み、高い表示性能と、高い省エネルギー性を実現する製品が数多く提供されている。これらのＬＣＤや有機ＥＬ表示装置は、小型かつ薄く作製することが可能であり、特に、携帯電話、ＰＤＡ（Personal Digital Assistant）、パーソナルコンピュータ等のディスプレイとして広く使用されている。 In recent years, among these, technological development of LCD and organic EL display devices has progressed, and many products that realize high display performance and high energy saving are provided. These LCDs and organic EL display devices can be made small and thin, and are particularly widely used as displays for mobile phones, PDAs (Personal Digital Assistants), personal computers, and the like.
有機ＥＬ表示装置を構成する有機ＥＬ素子は、有機化合物を利用した発光素子であり、近年、その性能の向上は目覚ましいものがある。この有機ＥＬ素子は、電子及び正孔の再結合によって発光するものであるが、この際、正孔輸送層への正孔注入効率は、正孔輸送層のイオン化ポテンシャルと陽極（透明電極）の仕事関数（真空準位とフェルミ準位のエネルギ差）の大きさに依存する。すなわち、正孔輸送層のイオン化ポテンシャルとの関係で、より高い仕事関数を有する陽極を使用することにより、正孔輸送層への正孔注入効率を高めることができる。 An organic EL element constituting an organic EL display device is a light emitting element using an organic compound, and in recent years, the performance has been remarkably improved. This organic EL element emits light by recombination of electrons and holes. At this time, the efficiency of hole injection into the hole transport layer is determined by the ionization potential of the hole transport layer and the anode (transparent electrode). It depends on the magnitude of the work function (energy difference between vacuum level and Fermi level). That is, the efficiency of hole injection into the hole transport layer can be increased by using an anode having a higher work function in relation to the ionization potential of the hole transport layer.
正孔輸送物質としては、さまざまな有機化合物が提案されているが、それらの中でも芳香族アミン系化合物、特にトリフェニルアミン誘導体や、カルバゾール誘導体が優れた機能を有するものとして知られている。ここで、トリフェニルアミン誘導体であるトリフェニルアミンのイオン化ポテンシャルは５．５ｅＶ〜５．６ｅＶの範囲にあり、カルバゾール誘導体であるポリビニルカルバゾールのイオン化ポテンシャルは５．８ｅＶ程度である。 Various organic compounds have been proposed as the hole transport material, and among them, aromatic amine compounds, particularly triphenylamine derivatives and carbazole derivatives are known as having excellent functions. Here, the ionization potential of triphenylamine, which is a triphenylamine derivative, is in the range of 5.5 eV to 5.6 eV, and the ionization potential of polyvinylcarbazole, which is a carbazole derivative, is about 5.8 eV.
一方、陽極に用いられる酸化物透明導電膜としては、酸化インジウム系の酸化物膜、酸化亜鉛系の酸化物膜、酸化スズ系の酸化物膜が知られている。これらのうち、酸化インジウム系の酸化物膜の一種である、スズをドープした酸化インジウム（酸化インジウムスズ；ＩＴＯ）膜は、特に低抵抗の膜が容易に得られることから、広く利用されている。 On the other hand, as an oxide transparent conductive film used for an anode, an indium oxide-based oxide film, a zinc oxide-based oxide film, and a tin oxide-based oxide film are known. Among these, tin-doped indium oxide (indium tin oxide; ITO) film, which is a kind of indium oxide-based oxide film, is widely used because a low-resistance film can be easily obtained. .
しかしながら、ＩＴＯの仕事関数は４．６ｅＶ〜５．０ｅＶにとどまるため、上記の正孔輸送物質との間には０．５ｅＶ〜１．２ｅＶ程度のエネルギー障壁が存在し、正孔輸送層への正孔注入効率を向上させることはできない。 However, since the work function of ITO is only 4.6 eV to 5.0 eV, an energy barrier of about 0.5 eV to 1.2 eV exists between the hole transport material and the hole transport layer. The hole injection efficiency cannot be improved.
これに対して、特許文献１では、インジウム及びモリブデンを含む酸化物、または酸化インジウム及び酸化タングステンを含む酸化物を使用することによって、５．０ｅＶを超える仕事関数が得られるとの記載がある。特に、モリブデンを含むものに関しては、モリブデンの添加量が多いほど、仕事関数が増加する傾向がみられることが記載されている。一方、特許文献２には、インジウムとモリブデンと酸素からなる焼結体とその製造方法が記載されている。 On the other hand, Patent Document 1 describes that a work function exceeding 5.0 eV can be obtained by using an oxide containing indium and molybdenum or an oxide containing indium oxide and tungsten oxide. In particular, for those containing molybdenum, it is described that the work function tends to increase as the addition amount of molybdenum increases. On the other hand, Patent Document 2 describes a sintered body made of indium, molybdenum, and oxygen and a manufacturing method thereof.
また、Ｉｎ−Ｍｏ−Ｏ膜は、その膜の構成元素を含む酸化物焼結体のタブレット（すなわち、Ｉｎ−Ｍｏ−Ｏの酸化物焼結体のタブレット）を原料として用いて、電子ビーム蒸着法、イオンプレーティング法や高密度プラズマアシスト蒸着法等の各種真空蒸着法で製造することができる。生産性の向上や製造コストの低減を考慮すると、高速で成膜する必要があるが、特に、電子ビーム蒸着法やイオンプレーティング法、高密度プラズマアシスト蒸着法で製造することにより、導電性や透過性に優れた非晶質Ｉｎ−Ｍｏ−Ｏ膜を高速に製造することができる。このような成膜法では、原料である酸化物焼結体タブレットに与えるエネルギー量を増やすことによって高速成膜が可能となる。 Further, the In—Mo—O film is formed by using an oxide sintered body tablet containing the constituent elements of the film (that is, an In—Mo—O oxide sintered body tablet) as a raw material, and electron beam evaporation. It can be manufactured by various vacuum deposition methods such as a method, an ion plating method and a high density plasma assisted deposition method. Considering improvement in productivity and reduction in manufacturing cost, it is necessary to form a film at a high speed, but in particular, by conducting electron beam evaporation, ion plating, and high-density plasma assisted evaporation, conductivity and An amorphous In—Mo—O film having excellent permeability can be manufactured at high speed. In such a film formation method, high-speed film formation is possible by increasing the amount of energy applied to the oxide sintered body tablet as a raw material.
しかし、非晶質Ｉｎ−Ｍｏ−Ｏ膜を高速で成膜するために、電子ビーム等のエネルギーを連続して多量に酸化物焼結体タブレットに与えると、長時間の連続成膜時に膜組成の変動（経時変化）が生じて、一定の特性の膜が製造できないという現象が生じる。この現象は、焼結体中に含まれるＭｏＯ３やＭｏＯ２等の高蒸気圧成分に起因するものであることから、成膜を中断して、未使用の酸化物焼結体タブレットに交換する必要があり、生産性を悪くする要因となっていた。 However, in order to form an amorphous In-Mo-O film at a high speed, if a large amount of energy such as an electron beam is continuously applied to the oxide sintered tablet, the film composition is formed during a long continuous film formation. This causes a phenomenon that a film having a certain characteristic cannot be manufactured. Since this phenomenon is caused by high vapor pressure components such as MoO 3 and MoO 2 contained in the sintered body, the film formation is interrupted and replaced with an unused oxide sintered body tablet. It was necessary and was a factor that deteriorated productivity.
特許文献３には、電子ビーム蒸着法や、イオンプレーティング法、高密度プラズマアシスト蒸着法等の真空蒸着法により酸化物透明導電膜を製造する際に、多量のエネルギーを投入しても、割れやクラックが発生することのない酸化物焼結体とその製造方法、及び酸化物焼結体をタブレットとする製造方法が紹介されている。当該特許文献３には、ＭｏＯ３やＭｏＯ２を含まないようにすれば、長時間の連続成膜時に膜組成の変動（経時変化）が生じることによって、一定の特性の膜が製造できないという現象がおきないとの記載がある。 Patent Document 3 discloses that even when a large amount of energy is applied when a transparent oxide conductive film is manufactured by a vacuum deposition method such as an electron beam deposition method, an ion plating method, or a high density plasma assisted deposition method, An oxide sintered body that does not cause cracks and its production method, and a production method using the oxide sintered body as a tablet are introduced. According to Patent Document 3, if MoO 3 or MoO 2 is not included, a film composition having a certain characteristic cannot be manufactured due to a change in film composition (time-dependent change) during long-time continuous film formation. There is a description that does not occur.
しかしながら、特許文献１には、蒸着源として用いる酸化物ペレットの製法に関して具体的な記述がない。一方、特許文献２には、インジウムとモリブデンと酸素からなる焼結体とその製造方法が記載されているが、モリブデンの添加量は、モリブデンがインジウムに対して原子数比で０．００３〜０．２０の範囲に限られており、モリブデンのより高添加量の領域ついての検討がされていない。 However, Patent Document 1 does not specifically describe a method for producing oxide pellets used as a deposition source. On the other hand, Patent Document 2 describes a sintered body composed of indium, molybdenum and oxygen and a method for producing the same. The amount of molybdenum added is 0.003 to 0 in terms of the atomic ratio of molybdenum to indium. .20 is limited, and no study has been made on regions with higher amounts of molybdenum.
また、特許文献３では、モリブデンの組成範囲は、モリブデンがインジウムに対する原子数比で０．００１以上０．０６０以下の領域に限られており、よりモリブデン添加量が高い領域についての記載がない。モリブデン添加量が高い組成範囲において、特許文献３の製法で酸化物焼結体を生成する場合、ＭｏＯ2やＭｏＯ３よりはＩｎ２Ｏ３に近いものの、Ｉｎ２（ＭｏＯ４）３がＩｎ２Ｏ３より昇華しやすいため、長時間の連続成膜時において、膜組成の変動（経時変化）が生じて、一定の特性の膜が製造できないという現象が生じる。特に、モリブテン濃度が高い酸化物焼結体からなるタブレットを用いて、真空蒸着法で酸化物透明導電膜を成膜する際に、大量のエネルギーをタブレットに投入することによって、タブレットに割れやクラックが発生することが問題となっていた。 Further, in Patent Document 3, the composition range of molybdenum is limited to a region in which molybdenum has an atomic ratio with respect to indium of 0.001 or more and 0.060 or less, and there is no description of a region where the amount of molybdenum added is higher. In the composition range where the amount of molybdenum added is high, when an oxide sintered body is produced by the manufacturing method of Patent Document 3, In 2 (MoO 4 ) 3 is In 2 , although it is closer to In 2 O 3 than MoO 2 or MoO 3. Since it is more easily sublimated than O 3 , the film composition fluctuates (changes with time) during continuous film formation for a long time, resulting in a phenomenon that a film having a certain characteristic cannot be manufactured. In particular, when a transparent oxide conductive film is formed by vacuum deposition using a tablet made of an oxide sintered body with a high molybdenum concentration, cracking or cracking can occur in the tablet by applying a large amount of energy to the tablet. It was a problem to occur.
本発明は、上記課題に鑑みてなされたものであり、モリブテン濃度が高い酸化物焼結体からなるタブレットを用いて、真空蒸着法により酸化物透明導電膜を製造する際に、割れやクラックの発生を抑制することの可能な、新規かつ改良された酸化物焼結体の製造方法、及び酸化物焼結体を提供することを目的とする。 This invention is made | formed in view of the said subject, When manufacturing an oxide transparent conductive film by a vacuum evaporation method using the tablet which consists of an oxide sintered compact with a high molybdenum concentration, a crack and a crack are produced. It is an object of the present invention to provide a novel and improved method for producing an oxide sintered body capable of suppressing the generation, and an oxide sintered body.
本発明の一態様は、真空蒸着用の酸化物焼結体の製造方法であって、酸化インジウム粉と三酸化モリブテン粉の混合物に水系溶媒を加えて湿式調合してスラリーを作製する工程と、前記スラリーを乾燥して造粒粉を作製する工程と、前記造粒粉を成形してから酸素濃度が体積比で３０％以上である焼成雰囲気中で所定の温度で焼結して酸化物焼結体タブレットを作製する工程と、を含み、前記スラリーを作製する際に、モリブデンの量がインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％となるように、前記酸化インジウム粉と前記三酸化モリブデン粉を湿式調合することを特徴とする。 One aspect of the present invention is a method for producing an oxide sintered body for vacuum deposition, the step of adding a water-based solvent to a mixture of indium oxide powder and molybdenum trioxide powder to prepare a slurry, and The slurry is dried to produce granulated powder, and after the granulated powder is formed, the oxide concentration is sintered by sintering at a predetermined temperature in a firing atmosphere in which the oxygen concentration is 30% or more by volume. A step of producing a bonded tablet, and when producing the slurry, the indium oxide powder so that the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio (Mo / In + Mo) to indium The molybdenum trioxide powder is prepared by a wet process.
本発明の一態様によれば、モリブテン濃度が高い酸化物焼結体タブレットにおいて、所定量のモリブデンを含有させ、密度を所定の範囲にすることによって、真空蒸着法によって高いエネルギーをタブレットに投入しても割れやクラックの発生を抑制して、安定した成膜が実現される。 According to one aspect of the present invention, in an oxide sintered body tablet having a high molybdenum concentration, a predetermined amount of molybdenum is contained, and the density is set to a predetermined range, whereby high energy is input to the tablet by vacuum deposition. However, it is possible to suppress the generation of cracks and cracks and realize stable film formation.
このとき、本発明の一態様では、焼結する際の前記所定の温度は、５００℃以上６００℃以下であることとしてもよい。 At this time, in one embodiment of the present invention, the predetermined temperature at the time of sintering may be 500 ° C. or more and 600 ° C. or less.
このようにすれば、酸化インジウムに固溶しない酸化モリブデン相の残存や、化合物相となる前に酸化モリブデンが昇華することを抑制するので、所望の組成の酸化物焼結体を確実に作製できる。 In this way, it is possible to reliably produce an oxide sintered body having a desired composition because the molybdenum oxide phase that does not form a solid solution in indium oxide and the sublimation of molybdenum oxide before becoming a compound phase are suppressed. .
また、本発明の一態様では、前記造粒粉を成形してから焼結する際に、前記焼成雰囲気中で成形した前記造粒粉を５時間以上２０時間以下保持して焼結することとしてもよい。 Moreover, in one aspect of the present invention, when the granulated powder is molded and then sintered, the granulated powder molded in the firing atmosphere is held for 5 hours to 20 hours and sintered. Also good.
このようにすれば、酸化インジウムに固溶しない酸化モリブデン相の残存や、化合物相となる前に酸化モリブデンが昇華することを抑制した上で、所望の組成の酸化物焼結体の製造コストを低減できる。 In this way, it is possible to reduce the manufacturing cost of the oxide sintered body having a desired composition while suppressing the remaining molybdenum oxide phase that does not dissolve in indium oxide and the sublimation of molybdenum oxide before becoming a compound phase. Can be reduced.
また、本発明の他の態様は、少なくともインジウムとモリブテンを含む真空蒸着用の酸化物焼結体であって、三酸化モリブデンを固溶したインジウム酸化物が含まれ、前記モリブデンの量が前記インジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％であることを特徴とする。 Another aspect of the present invention is an oxide sintered body for vacuum vapor deposition containing at least indium and molybdenum, and includes indium oxide in which molybdenum trioxide is dissolved, and the amount of molybdenum is the indium. The atomic ratio (Mo / In + Mo) is 30 at% to 60 at%.
本発明の他の態様によれば、モリブテン濃度が高い酸化物焼結体タブレットにおいて、所定量のモリブデンを含有させ、密度を所定の範囲にすることによって、真空蒸着法によって高いエネルギーをタブレットに投入しても割れやクラックの発生を抑制できる。 According to another aspect of the present invention, in a sintered oxide tablet with a high molybdenum concentration, a predetermined amount of molybdenum is contained, and the density is set within a predetermined range, whereby high energy is input to the tablet by vacuum deposition. Even so, the generation of cracks and cracks can be suppressed.
このとき、本発明の他の態様では、真空蒸着用タブレットとして適用した際に、圧縮強度が５．３８ｋＮ以上を有することとしてもよい。 At this time, in another aspect of the present invention, when applied as a vacuum deposition tablet, the compression strength may be 5.38 kN or more.
このように、酸化物焼結体タブレットの圧縮強度を所定の値以上とすることによって、各蒸着法の装置へタブレットを連続的に投入可能となるので、安定した成膜を持続させることができる。 In this way, by setting the compressive strength of the oxide sintered body tablet to a predetermined value or more, it becomes possible to continuously put the tablet into the apparatus of each vapor deposition method, so that stable film formation can be maintained. .
また、本発明の他の態様では、酸化モリブデンの単相及び金属相が含まれていないこととしてもよい。 In another embodiment of the present invention, the molybdenum oxide single phase and metal phase may not be included.
このようにすれば、モリブデン添加量が高い組成範囲でも、タブレットに大量のエネルギーを投入した際におけるタブレットの割れやクラックの発生を抑制できる。 If it does in this way, even if it is a composition range with a high molybdenum addition amount, generation | occurrence | production of the crack of a tablet and a crack at the time of supplying a lot of energy to a tablet can be suppressed.
以上説明したように本発明によれば、モリブテン濃度が高い酸化物焼結体からなるタブレットを用いて、真空蒸着法により酸化物透明導電膜を製造する際に、大量のエネルギーをタブレットに投入しても、タブレットに割れやクラックの発生を抑制できる。このため、成膜を中断することなく、連続的にタブレットを供給し安定して成膜できるようになる。 As described above, according to the present invention, when producing a transparent conductive oxide film by vacuum deposition using a tablet made of an oxide sintered body having a high molybdenum concentration, a large amount of energy is charged into the tablet. However, it is possible to suppress the generation of cracks and cracks in the tablet. For this reason, it becomes possible to supply the tablet continuously and stably form the film without interrupting the film formation.
以下、本発明の好適な実施の形態について詳細に説明する。なお、以下に説明する本実施形態は、特許請求の範囲に記載された本発明の内容を不当に限定するものではなく、本実施形態で説明される構成の全てが本発明の解決手段として必須であるとは限らない。 Hereinafter, preferred embodiments of the present invention will be described in detail. The present embodiment described below does not unduly limit the contents of the present invention described in the claims, and all the configurations described in the present embodiment are essential as means for solving the present invention. Not necessarily.
本発明者らは、仕事関数を高めるためにモリブテン濃度を高めた酸化物焼結体からなるタブレットを電子ビーム蒸着法や、イオンプレーティング法、高密度プラズマアシスト蒸着法等の各種真空蒸着法に用いる蒸着源用のタブレットとして用いた場合に、当該タブレットに大量のエネルギーを投入しても、該タブレットに割れやクラックの発生がしないように、酸化モリブデン相（ＭｏＯ３やＭｏＯ２等）やその金属相がなく、安定に連続成膜することができる強度を有する酸化物焼結体を得ることを目的に鋭意研究を重ねた。 The inventors of the present invention applied a tablet made of an oxide sintered body having a high molybdenum concentration in order to increase the work function to various vacuum deposition methods such as an electron beam deposition method, an ion plating method, and a high density plasma assisted deposition method. When used as a tablet for a deposition source to be used, a molybdenum oxide phase (MoO 3 or MoO 2 or the like) or its so that the tablet does not crack or crack even when a large amount of energy is input to the tablet. Intensive research has been conducted with the aim of obtaining an oxide sintered body having a metal phase and a strength capable of stably and continuously forming a film.
その結果、モリブデンを固溶したインジウム酸化物を含有した酸化物焼結体タブレットにおいて、所定量のモリブデンを含有させて密度を所定の範囲にすると、高いエネルギーをタブレットに投入しても割れることなく、前述した各種真空蒸着法で成膜が実現可能となることを見出した。また、酸化物焼結体タブレットの圧縮強度が所定の値以上であると、各蒸着法の装置へタブレットを連続的に投入することが可能となり、安定した成膜を持続させることができることも見出した。本発明は、これらの知見に基づいて、更に研究を行った結果、本発明を完成するに至った。 As a result, in an oxide sintered tablet containing indium oxide in which molybdenum is dissolved, if a predetermined amount of molybdenum is included and the density is in a predetermined range, even if high energy is applied to the tablet, it does not crack. The inventors have found that film formation can be realized by the various vacuum deposition methods described above. It has also been found that if the compressive strength of the oxide sintered body tablet is equal to or higher than a predetermined value, it is possible to continuously put the tablet into an apparatus for each vapor deposition method and to maintain stable film formation. It was. As a result of further studies based on these findings, the present invention has been completed.
以下、本発明の一実施形態に係る酸化物焼結体の製造方法について、図面を使用しながら詳細に説明する。図１は、本発明の一実施形態に係る酸化物焼結体の製造方法の概略を示すフロー図である。 Hereinafter, the manufacturing method of oxide sinter concerning one embodiment of the present invention is explained in detail, using a drawing. FIG. 1 is a flowchart showing an outline of a method for producing an oxide sintered body according to an embodiment of the present invention.
本発明の一実施形態に係る酸化物焼結体の製造方法は、電子ビーム蒸着法やイオンプレーティング法、高密度プラズマアシスト蒸着法等の真空蒸着用の酸化物焼結体の製造方法である。本実施形態の酸化物焼結体の製造方法は、図１に示すように、スラリーを作製する工程Ｓ１１と、当該スラリーを乾燥造粒して造粒粉を作製する工程Ｓ１２と、当該造粒粉を成形したものを焼成雰囲気中で所定の温度で焼結して、酸化物焼結体タブレットを作製する工程Ｓ１３とを含む。かかる工程Ｓ１１乃至Ｓ１３を経て、Ｉｎ−Ｍｏ−Ｏの酸化物焼結体のタブレットが作製される。 A method for producing an oxide sintered body according to an embodiment of the present invention is a method for producing an oxide sintered body for vacuum vapor deposition such as an electron beam vapor deposition method, an ion plating method, and a high density plasma assisted vapor deposition method. . As shown in FIG. 1, the manufacturing method of the oxide sintered body of the present embodiment includes a step S11 for producing a slurry, a step S12 for producing a granulated powder by drying and granulating the slurry, and the granulation. Sintering what shape | molded powder | flour at predetermined | prescribed temperature in baking atmosphere, and producing step S13 which produces an oxide sintered compact tablet. Through these steps S11 to S13, an In-Mo-O oxide sintered body tablet is manufactured.
本実施形態では、スラリーを作製する際に、モリブデンの量がインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％となるように、酸化インジウム粉と三酸化モリブデン粉を湿式調合することを特徴とする。具体的には、平均粒径１μｍ以下の酸化インジウム粉と、モリブデンの量がインジウムに対する原子数比で３０ａｔ％〜６０ａｔ％となるように平均粒径５μｍ以下の三酸化モリブデン粉と、水系溶媒を加えて湿式で調合することによって、スラリーを作製する。 In this embodiment, when preparing the slurry, wet blending of the indium oxide powder and the molybdenum trioxide powder is performed so that the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio (Mo / In + Mo) to indium. It is characterized by. Specifically, an indium oxide powder having an average particle size of 1 μm or less, a molybdenum trioxide powder having an average particle size of 5 μm or less, and an aqueous solvent so that the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio to indium. In addition, the slurry is prepared by wet blending.
スラリーの作製で調合する際に、モリブデンがＭｏ／Ｉｎ＋Ｍｏ原子数比で３０ａｔ％よりも少ないと、化合物相（Ｉｎ２（ＭｏＯ４）３）の化合物相が少なくなることから、一定の強度を得るための焼結性を保てない。一方、モリブデンがＭｏ／Ｉｎ＋Ｍｏ原子数比で６０ａｔ％を上回ると、酸化モリブデン相（ＭｏＯ３やＭｏＯ２等）が現れ、前述したように一定の特性の成膜ができなくなる。 When preparing the slurry for preparation, if the molybdenum is less than 30 at% in the Mo / In + Mo atomic ratio, the compound phase (In 2 (MoO 4 ) 3 ) is reduced in compound phase, thereby obtaining a certain strength. Therefore, the sinterability cannot be maintained. On the other hand, if molybdenum exceeds 60 at% in terms of the Mo / In + Mo atomic ratio, a molybdenum oxide phase (MoO 3 , MoO 2, etc.) appears, and it becomes impossible to form a film with certain characteristics as described above.
工程Ｓ１１でスラリーを作製したら、スプレードライヤー装置を用いることによって、当該スラリーを乾燥造粒して造粒粉を作製する（工程Ｓ１２）。そして、当該造粒粉を成形してから酸素濃度が体積比で３０％以上である焼成雰囲気中において、所定の温度で焼結して酸化物焼結体タブレットを作製する（工程Ｓ１３）。具体的には、得られた造粒粉を成形した後に、酸素濃度が体積比で３０％以上である焼成雰囲気中において、５００〜６００℃で５〜２０時間保持して焼結する。 After producing the slurry in step S11, the slurry is dried and granulated by using a spray dryer device to produce granulated powder (step S12). And after shaping | molding the said granulated powder, it sinters by predetermined temperature in the baking atmosphere whose oxygen concentration is 30% or more by volume ratio, and produces an oxide sintered compact tablet (process S13). Specifically, after the obtained granulated powder is molded, it is sintered by holding at 500 to 600 ° C. for 5 to 20 hours in a firing atmosphere in which the oxygen concentration is 30% or more by volume.
５００℃より下回る温度や５時間を下回る保持時間で焼結した場合、酸化インジウムに固溶しない酸化モリブデンが残り、前述したように成膜時に一定の特性の膜が得られない。一方、６００℃を超える温度や２０時間を超える保持時間で焼結した場合、化合物相となる前に酸化モリブデンが昇華してしまい、所望の組成から外れてしまう。また、製造コストにおいても好ましくない。こうした条件を外れた場合には、本発明の一実施形態に係る酸化物焼結体タブレットが得られ難い。 When sintering at a temperature lower than 500 ° C. or a holding time lower than 5 hours, molybdenum oxide that does not dissolve in indium oxide remains, and as described above, a film having certain characteristics cannot be obtained during film formation. On the other hand, when sintering is performed at a temperature exceeding 600 ° C. or a holding time exceeding 20 hours, molybdenum oxide is sublimated before becoming a compound phase, and is deviated from a desired composition. Moreover, it is not preferable also in manufacturing cost. When these conditions are not met, it is difficult to obtain an oxide sintered body tablet according to an embodiment of the present invention.
このように、本発明の一実施形態に係る酸化物焼結体の製造方法で作製された酸化物焼結体は、少なくともインジウムとモリブテンを含む真空蒸着用の酸化物焼結体であって、三酸化モリブデンを固溶したインジウム酸化物を含み、モリブデンの量がインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％であり、その酸化物焼結体を真空蒸着用タブレットとして適用した際に、その圧縮強度が酸化物焼結体の量産設備ラインの連続供給に耐えうるタブレット強度とされる５．３８ｋＮ以上を有するものとなる。 Thus, the oxide sintered body produced by the method for producing an oxide sintered body according to one embodiment of the present invention is an oxide sintered body for vacuum vapor deposition containing at least indium and molybdenum, Indium oxide containing molybdenum trioxide as a solid solution is included, and the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio (Mo / In + Mo) to indium, and the oxide sintered body was applied as a tablet for vacuum deposition. In this case, the compression strength is 5.38 kN or more, which is tablet strength that can withstand continuous supply of mass production equipment lines of oxide sintered bodies.
すなわち、本実施形態では、モリブテン濃度が高い酸化物焼結体タブレットにおいて、所定量のモリブデンを含有させ、密度を所定の範囲にすることによって、真空蒸着法によって高いエネルギーをタブレットに投入しても、タブレットの割れやクラックの発生を抑制して、安定した成膜が実現される。 That is, in this embodiment, in the oxide sintered body tablet having a high molybdenum concentration, a predetermined amount of molybdenum is contained, and the density is set to a predetermined range, so that high energy can be input to the tablet by vacuum deposition. Stable film formation is realized by suppressing the occurrence of cracks and cracks in the tablet.
換言すると、本実施形態の製法で作製された酸化物焼結体からなるタブレットを電子ビーム蒸着法や、イオンプレーティング法、高密度プラズマアシスト蒸着法等の真空蒸着法における蒸着源として用いると、大量のエネルギーをタブレットに投入しても、タブレットに割れやクラックが発生しない。このため、成膜を中断することなく、連続的にタブレットを供給し安定して成膜することができるようになる。 In other words, when a tablet made of an oxide sintered body produced by the manufacturing method of the present embodiment is used as a deposition source in a vacuum deposition method such as an electron beam deposition method, an ion plating method, a high density plasma assisted deposition method, Even if a large amount of energy is input to the tablet, the tablet does not break or crack. For this reason, it becomes possible to supply the tablet continuously and stably form the film without interrupting the film formation.
また、本実施形態の酸化物焼結体タブレットは、ホットプレス焼結法を用いないので、低コストで成膜できる上に、酸化物焼結体タブレットの圧縮強度を所定の値以上とすることによって、各蒸着法の装置へタブレットを連続的に投入可能となるので、安定した成膜を持続させることが可能となる。 Moreover, since the oxide sintered body tablet of this embodiment does not use the hot press sintering method, it can form a film at low cost, and the oxide sintered body tablet has a compressive strength of a predetermined value or more. Thus, it is possible to continuously put the tablet into the apparatus for each vapor deposition method, so that stable film formation can be maintained.
さらに、本実施形態の酸化物焼結体の製造方法で作製された酸化物焼結体は、酸化モリブデンの単相及び金属相が含まれていないので、モリブデン添加量が高い組成範囲でも、タブレットに大量のエネルギーを投入した際におけるタブレットの割れやクラックの発生を抑制できる。また、本実施形態の酸化物焼結体の製造方法で作製された酸化物焼結体を用いて酸化物透明導電膜を成膜すると、得られた酸化物透明導電膜が経時変化のない安定した品質の膜とすることができる。すなわち、本実施形態の酸化物焼結体からなるタブレットを各種の真空蒸着法に用いることによって、表示デバイスに好適に用いることができる酸化物透明導電膜を高速で安定的に成膜できるので、生産性を向上させることができる。 Furthermore, since the oxide sintered body produced by the method of manufacturing an oxide sintered body according to the present embodiment does not include a single phase and a metal phase of molybdenum oxide, even in a composition range where the amount of molybdenum added is high, the tablet The tablet can be prevented from cracking and cracking when a large amount of energy is supplied to the tablet. Moreover, when an oxide transparent conductive film is formed using the oxide sintered body produced by the method of manufacturing an oxide sintered body according to the present embodiment, the obtained oxide transparent conductive film is stable without change over time. The film can be made with a high quality. In other words, by using a tablet made of the oxide sintered body of the present embodiment for various vacuum deposition methods, an oxide transparent conductive film that can be suitably used for a display device can be stably formed at high speed. Productivity can be improved.
次に、本発明の一実施形態に係る酸化物焼結体の製造方法、及び酸化物焼結体について実施例により詳しく説明する。なお、本発明は、これらの実施例に限定されるものではない。 Next, a method for manufacturing an oxide sintered body according to an embodiment of the present invention and the oxide sintered body will be described in detail with reference to examples. The present invention is not limited to these examples.
＜実施例１＞
実施例１では、はじめに、平均粒径０．８μｍの酸化インジウム粉にインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％となるように三酸化モリブデン粉（高純度化学製）と混合し、純水と分散剤（ポリカルボン酸アンモニウム塩）とバインダー（ポリビニルアルコール）と金型成形時の潤滑剤（ステアリン酸）を加えて、固形分率０．６０％のスラリーを作製した。このスラリーをスプレードライヤー（大川原化工機(株)製 Ｌ−８ｉ）を用いて乾燥・造粒を行った。得られた造粒粉をφ３０ｍｍの円筒状の金型に入れ、上から１２０ｋＮの圧力をかけて成形した。得られた成形体に対し、酸素濃度が体積比で４０％となるように導入して６００℃で２０時間保持して焼結し、酸化モリブデンを含むＩＭｏＯタブレットを作製した。
<Example 1>
In Example 1, first, indium oxide powder having an average particle diameter of 0.8 μm was mixed with molybdenum trioxide powder (manufactured by High-Purity Chemical) so that the atomic ratio to indium was 30 at% (Mo / In + Mo). Water, a dispersant (polycarboxylic acid ammonium salt), a binder (polyvinyl alcohol), and a lubricant for molding (stearic acid) were added to prepare a slurry having a solid content of 0.60%. The slurry was dried and granulated using a spray dryer (L-8i, manufactured by Okawara Chemical Co., Ltd.). The obtained granulated powder was put into a cylindrical mold having a diameter of 30 mm and molded by applying a pressure of 120 kN from above. The obtained molded body was introduced so that the oxygen concentration became 40% by volume, and held at 600 ° C. for 20 hours to sinter, thereby producing an IMoO tablet containing molybdenum oxide.
作製したＩＭｏＯタブレットを引張圧縮試験機（（株）今田製作所製ＳＤＷＳ−２０１２型）を用いて、圧縮強度を測定した。測定時は、真空蒸着装置のタブレット連続供給ラインを想定し、測定するタブレット面にφ１０ｍｍのアルミ製チップの治具を装着し、測定したところ、１１．１ｋＮであり、目標である５．３８ｋＮ以上あることが確認された。また、得られ焼結体タブレットをＸ線回折装置（X’Pert-PRO スペクトリス(株)製）にて分析したところ、Ｉｎ２Ｏ３相及びＩｎ２（ＭｏＯ４）３相が検出され、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相は、確認されなかった。また、このタブレットを用いてイオンプレーティング成膜を行い、成膜時の加熱によるタブレットの割れ欠けは、発生しなかった。 The compressive strength of the produced IMoO tablet was measured using a tensile and compression tester (SDWS-2012 type, manufactured by Imada Seisakusho Co., Ltd.). At the time of measurement, assuming a tablet continuous supply line of a vacuum vapor deposition apparatus, a jig with an aluminum chip of φ10 mm was mounted on the tablet surface to be measured, and when measured, it was 11.1 kN, which is a target of 5.38 kN or more. It was confirmed that there was. Moreover, when the obtained sintered body tablet was analyzed with an X-ray diffractometer (manufactured by X'Pert-PRO Spectris Co., Ltd.), In 2 O 3 phase and In 2 (MoO 4 ) 3 phase were detected and oxidized. A molybdenum phase (MoO 3 or MoO 2 ) and a metal phase were not confirmed. Further, ion plating film formation was performed using this tablet, and cracking and chipping of the tablet due to heating during film formation did not occur.
＜実施例２＞
実施例２では、使用する三酸化モリブデン粉を酸化インジウム粉のインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で５０ａｔ％とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。その際のタブレット圧縮強度は、９．０ｋＮであり、目標とする圧縮強度以上であることが確認された。また、得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相及びＩｎ２（ＭｏＯ４）３相が検出され、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相は、確認されなかった。また、このタブレットを用いてイオンプレーティング成膜を行い、成膜時の加熱によるタブレットの割れ欠けは発生しなかった。
<Example 2>
In Example 2, an IMoO tablet was produced using the same conditions as in Example 1 except that the molybdenum trioxide powder used was 50 at% in terms of the atomic ratio of indium oxide powder to indium (Mo / In + Mo). The tablet compression strength at that time was 9.0 kN, which was confirmed to be equal to or higher than the target compression strength. Moreover, when X-ray diffraction analysis was performed on the obtained sintered body tablet, an In 2 O 3 phase and an In 2 (MoO 4 ) 3 phase were detected, and a molybdenum oxide phase (MoO 3 or MoO 2 ) and a metal phase were It was not confirmed. In addition, ion plating film formation was performed using this tablet, and cracking and chipping of the tablet due to heating during film formation did not occur.
＜実施例３＞
実施例３では、使用する三酸化モリブデン粉を酸化インジウム粉のインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で６０ａｔ％とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。その際のタブレット圧縮強度は、８．７ｋＮであり、目標とする圧縮強度以上であることが確認された。また、得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相及びＩｎ２（ＭｏＯ４）３相が検出され、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相は、確認されなかった。また、このタブレットを用いてイオンプレーティング成膜を行い、成膜時の加熱によるタブレットの割れ欠けは、発生しなかった。
<Example 3>
In Example 3, an IMoO tablet was prepared using the same conditions as in Example 1 except that the molybdenum trioxide powder used was 60 at% in terms of the atomic ratio of indium oxide powder to indium (Mo / In + Mo). The tablet compression strength in that case was 8.7 kN, and it was confirmed that it was more than the target compression strength. Moreover, when X-ray diffraction analysis was performed on the obtained sintered body tablet, an In 2 O 3 phase and an In 2 (MoO 4 ) 3 phase were detected, and a molybdenum oxide phase (MoO 3 or MoO 2 ) and a metal phase were It was not confirmed. Further, ion plating film formation was performed using this tablet, and cracking and chipping of the tablet due to heating during film formation did not occur.
＜比較例１＞
比較例１では、使用する三酸化モリブデン粉を酸化インジウム粉のインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で２０ａｔ％とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。その際のタブレット圧縮強度は、３．８ｋＮであり、目標とする圧縮強度を得ることができなかった。また、得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相及びＩｎ２（ＭｏＯ４）３相が検出され、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相は確認されなかったが、このタブレットを用いてイオンプレーティング成膜を行った際に、欠けが発生した。
<Comparative Example 1>
In Comparative Example 1, an IMoO tablet was produced using the same conditions as in Example 1 except that the molybdenum trioxide powder used was 20 at% in terms of the atomic ratio of indium oxide powder to indium (Mo / In + Mo). The tablet compression strength at that time was 3.8 kN, and the target compression strength could not be obtained. Moreover, when the obtained sintered compact tablet was subjected to X-ray diffraction analysis, an In 2 O 3 phase and an In 2 (MoO 4 ) 3 phase were detected, and a molybdenum oxide phase (MoO 3 and MoO 2 ) and a metal phase were confirmed. Although not done, chipping occurred when ion plating film formation was performed using this tablet.
＜比較例２＞
比較例２では、使用する三酸化モリブデン粉を酸化インジウム粉のインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で７０ａｔ％とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。得られたタブレットは表面が粗になっており、圧縮強度は測定できなかった。得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相とＩｎ２（ＭｏＯ４）３相及び酸化モリブデン相（ＭｏＯ３）が検出された。また、所望の組成比、寸法から大きく外れ、イオンプレーティング成膜は実施できなかった。
<Comparative example 2>
In Comparative Example 2, an IMoO tablet was produced using the same conditions as in Example 1 except that the molybdenum trioxide powder used was 70 at% in terms of the atomic ratio of indium oxide powder to indium (Mo / In + Mo). The obtained tablet had a rough surface, and the compressive strength could not be measured. When the obtained sintered tablet was analyzed by X-ray diffraction, an In 2 O 3 phase, an In 2 (MoO 4 ) 3 phase, and a molybdenum oxide phase (MoO 3 ) were detected. Further, the composition greatly deviated from the desired composition ratio and dimensions, and ion plating film formation could not be performed.
＜比較例３＞
比較例３では、焼結する際の焼結温度を４５０℃、焼結時間を３５時間とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。その際のタブレット圧縮強度は、０．３０ｋＮであり、目標とする圧縮強度を得ることができなかった。また、得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相とＩｎ２（ＭｏＯ４）３相及び酸化モリブデン相（ＭｏＯ３）が検出された。このタブレットを用いてイオンプレーティング成膜を行った際に、欠けが発生した。
<Comparative Example 3>
In Comparative Example 3, an IMoO tablet was produced using the same conditions as in Example 1 except that the sintering temperature during sintering was 450 ° C. and the sintering time was 35 hours. The tablet compression strength at that time was 0.30 kN, and the target compression strength could not be obtained. Moreover, when the obtained sintered compact tablet was analyzed by X-ray diffraction, an In 2 O 3 phase, an In 2 (MoO 4 ) 3 phase, and a molybdenum oxide phase (MoO 3 ) were detected. Chipping occurred when ion plating film formation was performed using this tablet.
＜比較例４＞
焼結する際の焼結温度を７００℃、焼結時間を４時間とした以外は、実施例１と同じ条件を用いてＩＭｏＯタブレットを作製した。その際のタブレット圧縮強度は、４．０ｋＮであり、目標とする圧縮強度を得ることができなかった。また、得られた焼結体タブレットをＸ線回折分析したところ、Ｉｎ２Ｏ３相及びＩｎ２（ＭｏＯ４）３相が検出され、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相は、確認されなかったが、所望の組成比、寸法から大きく外れ、イオンプレーティング成膜は、実施できなかった。
<Comparative Example 4>
An IMoO tablet was produced using the same conditions as in Example 1 except that the sintering temperature during sintering was 700 ° C. and the sintering time was 4 hours. At that time, the tablet compression strength was 4.0 kN, and the target compression strength could not be obtained. Moreover, when X-ray diffraction analysis was performed on the obtained sintered body tablet, an In 2 O 3 phase and an In 2 (MoO 4 ) 3 phase were detected, and a molybdenum oxide phase (MoO 3 or MoO 2 ) and a metal phase were Although not confirmed, the composition greatly deviated from the desired composition ratio and dimensions, and ion plating film formation could not be performed.
前述した本発明の一実施形態に係る酸化物焼結体の製造方法によって作製した酸化物焼結体の各実施例及び各比較例の測定結果について、以下の表１に示す。 Table 1 below shows the measurement results of Examples and Comparative Examples of the oxide sintered body produced by the method of manufacturing an oxide sintered body according to the embodiment of the present invention described above.
表１に示すように、実施例１乃至３と比較例１及び２の測定結果より、モリブデンの量がインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％となるように、酸化インジウム粉と三酸化モリブデン粉を湿式調合して作製したスラリーを乾燥造粒して得られた造粒粉を焼結することによって、酸化モリブデン相（ＭｏＯ３やＭｏＯ２）及び金属相が含まれずに、真空蒸着時に必要とされる一定の圧縮強度、すなわち、その圧縮強度が酸化物焼結体の量産設備ラインの連続供給に耐えうるタブレット強度とされる５．３８ｋＮ以上を有する焼結性が確保された酸化物焼結体タブレットとすることができることが分かった。 As shown in Table 1, from the measurement results of Examples 1 to 3 and Comparative Examples 1 and 2, indium oxide is used so that the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio (Mo / In + Mo) to indium. By sintering the granulated powder obtained by dry granulating the slurry prepared by wet-mixing the powder and molybdenum trioxide powder, the molybdenum oxide phase (MoO 3 and MoO 2 ) and the metal phase are not included , Sinterability with a certain compressive strength required at the time of vacuum deposition, that is, a compressive strength of 5.38 kN or more, which is a tablet strength that can withstand continuous supply of mass production equipment lines of oxide sintered bodies, is ensured It turned out that it can be set as the made oxide sintered compact tablet.
また、実施例１乃至３と比較例３及び４の測定結果より、焼結する際の温度を５００℃以上６００℃以下とすることによって、酸化インジウムに固溶しない酸化モリブデン相の残存や、化合物相となる前に酸化モリブデンが昇華することによる成膜不可となる不具合が抑制されるので、所望の組成の酸化物焼結体を確実に作製できることが分かった。 Further, from the measurement results of Examples 1 to 3 and Comparative Examples 3 and 4, by setting the temperature at the time of sintering to 500 ° C. or more and 600 ° C. or less, the remaining molybdenum oxide phase not dissolved in indium oxide or the compound It has been found that an oxide sintered body having a desired composition can be reliably produced because a problem that the film formation is impossible due to the sublimation of molybdenum oxide before it becomes a phase is suppressed.
さらに、実施例１乃至３と比較例３及び４の測定結果より、造粒粉を成形してから焼結する際に、焼成雰囲気中で成形した造粒粉を５時間以上２０時間以下保持して焼結することによって、酸化インジウムに固溶しない酸化モリブデン相の残存や、化合物相となる前に酸化モリブデンが昇華することを抑制した上で、所望の組成の酸化物焼結体の製造コストを低減できることが分かった。 Furthermore, from the measurement results of Examples 1 to 3 and Comparative Examples 3 and 4, when the granulated powder is molded and then sintered, the granulated powder molded in the firing atmosphere is held for 5 hours or more and 20 hours or less. Sintering suppresses the remaining molybdenum oxide phase that does not dissolve in indium oxide and the sublimation of molybdenum oxide before it becomes a compound phase, and the manufacturing cost of an oxide sintered body with a desired composition. It was found that can be reduced.
以上の結果から、本発明の一実施形態に係る酸化物焼結体の製造方法を用いることで、モリブデンの量が原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％とモリブデン濃度が高い酸化物焼結体タブレットにおいて、酸化モリブデン相（ＭｏＯ３やＭｏＯ２等）やその金属相がなく、電子ビーム蒸着法、イオンプレーティング法、高密度プラズマアシスト蒸着法等の真空蒸着法により酸化物透明導電膜を製造する際の多量のエネルギー投入や、連続成膜時のタブレット供給ラインにおける割れやクラックに耐えうる強度を有する酸化物焼結体が作製されることが分かった。また、本発明の一実施形態に係る酸化物焼結体の製造方法で作製された酸化物焼結体を用いて、得られた酸化物透明導電膜が経時変化のない安定した品質の膜となることが分かった。 From the above results, by using the method for manufacturing an oxide sintered body according to one embodiment of the present invention, the amount of molybdenum is 30at% to 60at% in atomic ratio (Mo / In + Mo), and the molybdenum concentration is high. Sintered material tablet does not have molybdenum oxide phase (MoO 3 or MoO 2 etc.) or its metal phase, and transparent oxide by vacuum deposition such as electron beam deposition, ion plating, high density plasma assisted deposition It has been found that an oxide sintered body having a strength sufficient to withstand cracks and cracks in a tablet supply line during continuous film formation can be produced when producing a conductive film. In addition, using the oxide sintered body produced by the method for producing an oxide sintered body according to one embodiment of the present invention, the obtained oxide transparent conductive film has a stable quality film that does not change with time. I found out that
なお、上記のように本発明の各実施形態及び各実施例について詳細に説明したが、本発明の新規事項及び効果から実体的に逸脱しない多くの変形が可能であることは、当業者には、容易に理解できるであろう。従って、このような変形例は、全て本発明の範囲に含まれるものとする。 Although the embodiments and examples of the present invention have been described in detail as described above, it will be understood by those skilled in the art that many modifications can be made without departing from the novel matters and effects of the present invention. It will be easy to understand. Therefore, all such modifications are included in the scope of the present invention.
例えば、明細書又は図面において、少なくとも一度、より広義又は同義な異なる用語と共に記載された用語は、明細書又は図面のいかなる箇所においても、その異なる用語に置き換えることができる。また、酸化物焼結体の構成、及び酸化物焼結体の製造方法の動作も本発明の各実施形態及び各実施例で説明したものに限定されず、種々の変形実施が可能である。 For example, a term described with a different term having a broader meaning or the same meaning at least once in the specification or the drawings can be replaced with the different term in any part of the specification or the drawings. Further, the structure of the oxide sintered body and the operation of the method for producing the oxide sintered body are not limited to those described in the embodiments and examples of the present invention, and various modifications can be made.
Ｓ１１ スラリーを作製する工程、Ｓ１２ スラリーを乾燥造粒する工程、Ｓ１３ 造粒粉を焼結する工程 S11 Slurry manufacturing process, S12 Slurry drying granulation process, S13 Sintering granulated powder process
Claims (6)
酸化インジウム粉と三酸化モリブテン粉の混合物に水系溶媒を加えて湿式調合してスラリーを作製する工程と、
前記スラリーを乾燥して造粒粉を作製する工程と、
前記造粒粉を成形してから酸素濃度が体積比で３０％以上である焼成雰囲気中で所定の温度で焼結して酸化物焼結体タブレットを作製する工程と、を含み、
前記スラリーを作製する際に、モリブデンの量がインジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％となるように、前記酸化インジウム粉と前記三酸化モリブデン粉を湿式調合することを特徴とする酸化物焼結体の製造方法。 A method for producing an oxide sintered body for vacuum deposition,
Adding a water-based solvent to a mixture of indium oxide powder and molybdenum trioxide powder and preparing a slurry by wet preparation; and
Drying the slurry to produce granulated powder;
Forming an oxide sintered body tablet by sintering at a predetermined temperature in a firing atmosphere in which the oxygen concentration is 30% or more by volume ratio after forming the granulated powder,
When the slurry is prepared, the indium oxide powder and the molybdenum trioxide powder are wet-mixed so that the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio to indium (Mo / In + Mo). A method for producing an oxide sintered body.
三酸化モリブデンを固溶したインジウム酸化物が含まれ、前記モリブデンの量が前記インジウムに対する原子数比（Ｍｏ／Ｉｎ＋Ｍｏ）で３０ａｔ％〜６０ａｔ％であることを特徴とする酸化物焼結体。 An oxide sintered body for vacuum deposition containing at least indium and molybdenum,
An oxide sintered body comprising indium oxide in which molybdenum trioxide is dissolved, wherein the amount of molybdenum is 30 at% to 60 at% in terms of the atomic ratio to the indium (Mo / In + Mo).
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| CN103682015A (en) * | 2012-09-20 | 2014-03-26 | 海洋王照明科技股份有限公司 | Molybdenum doped indium oxide conductive film, preparation method and application thereof |
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| JP2000072526A (en) * | 1998-09-04 | 2000-03-07 | Idemitsu Kosan Co Ltd | Target for transparent conductive coat, transparent conductive glass, and transparent conductive film |
| JP2007246318A (en) * | 2006-03-15 | 2007-09-27 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact, method for manufacturing the same, method for manufacturing oxide transparent conductive film, and oxide transparent conductive film |
| JP2013131560A (en) * | 2011-12-20 | 2013-07-04 | Sumitomo Metal Mining Co Ltd | Transparent conductive film laminate, manufacturing method of the same, thin film solar cell, and manufacturing method of the same |
| CN103682015A (en) * | 2012-09-20 | 2014-03-26 | 海洋王照明科技股份有限公司 | Molybdenum doped indium oxide conductive film, preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200020855A (en) | 2018-08-09 | 2020-02-26 | 제이엑스금속주식회사 | Oxide thin film formed using the oxide sputtering target, its manufacturing method, and this oxide sputtering target |
| KR20210116686A (en) | 2018-08-09 | 2021-09-27 | 제이엑스금속주식회사 | Oxide sputtering target, manufacturing method thereof, and oxide thin film formed using the sputtering target |
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| JP6531718B2 (en) | 2019-06-19 |
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