TW201250033A - Oxide sintered body, method for manufacturing same, and target using same - Google Patents

Oxide sintered body, method for manufacturing same, and target using same Download PDF

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Publication number
TW201250033A
TW201250033A TW101107657A TW101107657A TW201250033A TW 201250033 A TW201250033 A TW 201250033A TW 101107657 A TW101107657 A TW 101107657A TW 101107657 A TW101107657 A TW 101107657A TW 201250033 A TW201250033 A TW 201250033A
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Taiwan
Prior art keywords
powder
oxide
sintered body
oxide powder
target
Prior art date
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TW101107657A
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Chinese (zh)
Inventor
Kunihiko Nakata
Shohei Hotta
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Sumitomo Chemical Co
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Publication date
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Publication of TW201250033A publication Critical patent/TW201250033A/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/645—Pressure sintering
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04B35/6455—Hot isostatic pressing
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C04B2235/3237—Substoichiometric titanium oxides, e.g. Ti2O3
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • C04B2235/662—Annealing after sintering
    • C04B2235/664—Reductive annealing
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    • C04B2235/79—Non-stoichiometric products, e.g. perovskites (ABO3) with an A/B-ratio other than 1

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  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Physical Vapour Deposition (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

Provided are: a target; a method for manufacturing the target; an oxide sintered body that is useful for manufacturing the target; and a method for manufacturing the oxide sintered body; the target making it possible, even if DC sputtering is used, to form at high productivity a zinc-oxide-based transparent electroconductive film having a similar level of electroconductivity as AZO or GZO and exceptional chemical durability. This oxide sintered body substantially comprises zinc, titanium, oxygen, and at least one additional trace element (TE) selected from the group consisting of aluminum, gallium, and indium, the titanium being derived from low-valence titanium oxide represented by the formula TiO2-X (X = 0.1 to 1).

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201250033 六、發明說明·· 【發明所屬之技術領域】201250033 VI. INSTRUCTIONS··· TECHNICAL FIELD OF THE INVENTION

本發明係關於對於依據濺鍍法'離子蒸鍍法、脈衝雷 射沉積（PLD: Pulse Laser Deposition)法' 電子束（EB :Electron Beam)蒸鍍法等所進行之氧化鋅系透明導電膜 的形成爲有用之氧化物燒結體及其製造方法，靶材及其製 造方法，以及氧化鋅系透明導電膜的製造方法。 【先前技術】 兼具導電性與光穿透性之透明導電膜，以往除了應用 在太陽能電池、液晶顯示元件、其他各種感光元件中的電 極等之外，亦應用在汽車車窗或建築用加熱線反射膜、防 帶電膜、冷凍橱窗等中的防霧用透明發熱體等之廣泛用途 中。尤其是低電阻且導電性佳之透明導電膜，爲人所知者 乃適合於太陽能電池，或是液晶、有機電激發光、無機電 激發光等之液晶顯示元件，或是觸控面板等。 以往，透明導電膜，爲人所知者例如有摻雜銻的氧化 錫（ΑΤΟ )膜或摻雜氟的氧化錫（FTO )膜等之氧化錫（ Sn〇2 )系薄膜；摻雜鋁的氧化鋅（ΑΖΟ )膜或摻雜鎵的氧 化鋅（GZO )膜等之氧化鋅（ZnO )系薄膜；以及摻雜錫 的氧化銦（ITO : Indium Tin Oxide )膜等之氧化銦（ Ιη203 )系薄膜。當中最被應用在工業上者爲氧化銦系透 明導電膜，尤其是ITO膜爲低電阻且導電性佳，故已廣泛 地達到實用化。 201250033 例如，當藉由濺鍍法來形成如ITO般之氧化物膜時， —般是採用由構成膜之金屬元素所構成之合金靶材（ΙΤΟ 膜時爲In-Sn合金），或是將含有構成膜之金屬元素的氧 靶材（ITO膜時爲由In-Sn-。惟使用合金靶材時，所形 中的氧氣所供給，所以氣體 結果有時難以一定地保持與 膜速度或是所得之膜的特性 面，使用氧化物靶材時，供 身所供給，僅有不足份是由 以氣體環境中的氧氣量變動 以抑制，其結果乃容易製造 膜特性之透明導電膜。因此 用氧化物靶材（亦即氧化物 導電膜，做爲該必要原料之 所以較昂貴且有資源枯竭之 種可取代IT0膜之可泛用於 可藉由濺鍍法進行工業上的 受到矚目，而積極進行可提 言’非專利文獻1中，係報 種摻雜劑摻雜於ZnO之作法 化物燒結或混合而成之氧化物 〇所構成之燒結體或混合體） 成之膜中的氧全部由氣體環境 環境中的氧氣量容易變動。其 氣體環境中的氧氣量相依之成 (比電阻、穿透率）。另一方 給至膜之氧的一部分由靶材本 氣體環境中的氧氣所供給，所 ，與使用合金靶材時相比可加 出具有一定膜厚且具有一定的 ，工業上所使用之靶材，係採 燒結體或氧化物混合體）。 ITO膜等之氧化銦系透明 In (銦），由於爲稀有金屬， 疑慮。因此，近年來係期待一 工業上的透明導電膜。當中， 製造之氧化鋅系透明導電膜乃 高該導電性能之硏究。具體而 告一種爲了提高導電性而將各 • 10 201250033 〔先前技術文獻〕 〔非專利文獻〕 〔非專利文獻1〕月刊Display，1999年9月號，p 〜「ZnO系透明導電膜的動向」 【發明內容】 (發明所欲解決之課題） 本發明者們發現到，若不用4價的氧化鈦（Ti02 ( ))’而是使用低原子價氧化鈦作爲摻雜劑的鈦源時， 可進一步增加有用於化學耐久性的改良之鈦含量。此外 亦發現到該低原子價氧化鈦爲低電阻，且對太陽能電池 的透明導電膜而言爲有益之近紅外線的穿透性亦佳。然 ’本發明者們亦發現到，與以往所應用之AZO或GZO 比’由一般鈦摻雜的氧化鋅（TZO )所構成之靶材的導 性差’所以當使用ΤΖΟ的靶材並藉由直流（DC )濺鍍 成膜時，無法增快成膜速度，生產性較A Ζ Ο或G Z 0更 之問題。 本發明之課題在於提供~種即使藉由DC濺鍍法， 可生產性佳地形成具有與AZO或GZO同等程度的導電 且化學耐久性佳之氧化鋅系透明導電膜之靶材及其製造 法。 此外，本發明之課題在於提供一種有用於製造該靶 之氧化物燒結體及其製造方法。再者，本發明之課題在 提供一種可生產性佳地製造出具有與AZO或GZO同等 IV 則 等 而 相 電 來 差 亦 性 方 材 於 程 201250033 度的導電性且化學耐久性佳之氧化鋅系透明導電膜之方法 (用以解決課題之手段） 本發明者們係爲了解決上述課題而進行精心探討，結 果發現到下列第（1 )項〜第（1 8 )項的具體手段，因而 完成本發明。 (1) 一種氧化物燒結體，其特徵爲實質上由鋅，鈦 ，氧，與選自由鋁、鎵及銦所組成之群組的至少1種微量 添加元素（TE )所構成之氧化物燒結體，該鈦係來自由式 :Ti〇2-x ( x = 0.1〜1)表示之低原子價氧化鈦。 (2) 如第（1)項之氧化物燒結體，其中該氧化物燒 結體具有5.3g / cm3以上的密度，並且具有12ιηΩ · cm以 下的比電阻。 (3 )如第（1 )項或第（2 )項之氧化物燒結體，其 中該至少1種微量添加元素（TE)相對於該鋅、該鈦及該 至少1種微量添加元素（TE )的合計之原子數比[TE/ ( Zn+Ti+TE)]，超過 0.001 且未達 0.005。 (4 )如第（1 )項至第（3 )項中任一項之氧化物燒 結體，其中該鈦相對於該鋅' 該鈦及該至少1種微量添加 元素（TE )的合計之原子數比[Ti/ ( Zn+ Ti + TE )]，超 過0.02且爲0.1以下。 (5) —種方法，其爲製造出如第（1)項至第（4) 項中任一項之氧化物燒結體之方法，其係包含： 201250033 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 以及將藉由該成形步驟所得之成形體，在真空中、還 原氣體環境中或非活性氣體環境中，於600。〇〜1 5 00 °C中 進行燒結之步驟； (A)由式：TiO2-X(X=0.1〜1)表示之低原子價氧 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B )由式：Ti02.x ( X = 0.1〜1 )表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (6) —種方法，其爲製造出如第（1)項至第（〇 項中任一項之氧化物燒結體之方法，其係包含： 使含有以下所示之（A )或（B )的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於600°C〜1 5 00 °C中進行燒結之步驟，以 及 將藉由該燒結步驟所得之燒結體，在非活性氣體環境 中、真空中或還原氣體環境中進行退火處理之步驟； (A) 由式：Ti02_x ( X= 0.1〜1 )表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 由式：ΤίΟ2·χ(Χ=0·1〜1)表示之低原子價氧 -9- 201250033 化鈦粉，與選自由氧化鋁粉'氧化•鎵粉及氧化銦粉所組成 之群組的至少1種粉’與氫氧化鋅粉之混合粉。 (7) 如第（5)項之方法，其中該退火處理是在選自 由氮氣環境、氬氣環境、氮氣環境、二氧化碳氣體環境及 氫氣環境所組成之群組的至少一種氣體環境中進行。 (8) —種方法，其爲製造出如第（1)項至第（4) 項中任一項之氧化物燒結體之方法，其係包含： 將含有以下所示之（A)或（B)的混合粉之原料粉放 入於石墨製的模材中，在真空中或非活性氣體環境中，於 600°C〜1 500°C中進行加壓燒結之步驟； (A) 由式：表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦玢所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 由式：Ti〇2.x(x=〇.i〜1)表示之低原子價氧 化駄粉’與選自由氧化鋁粉 '氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (9) 如第（8)項之方法’其中該加壓燒結步驟爲熱 模壓燒結步驟。 (1 〇 ) 種靶材’其特徵係加工如第（1 )項至第（4 )項中任一項之氧化物燒結體而得。 (11) ~~種方法’其爲製造出如第（1〇)項之靶材之 方法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， -10- 201250033 將藉由該成形步驟所得之成形體，在真空中、還原氣 體環境中或非活性氣體環境中，於600 °C〜1500 °C中進行 燒結之步驟，以及 加工該燒結步驟中所得之氧化物燒結體而得靶材之步 驟； (A)由式：Ti〇2.x(X=〇.l〜1)表示之低原子價氧 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B )由式：Ti02.x ( x = 0.1〜1 )表示之低原子價氧 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (12) —種方法，其爲製造出如第（1〇)項之靶材之 方法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於6 0 0 t〜1 5 0 0 °C中進行燒結之步驟， M藉由該燒結步驟所得之燒結體，在非活性氣體環境 中 '真空中或還原氣體環境中進行退火處理之步驟，以及 力口 I該退火處理步驟中所得之氧化物燒結體而得靶材 之步驟； (A)由式·· τίΟ2·χ(Χ=0·1〜1)表示之低原子價氧 化i太粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， -11 - 201250033 (B )由式：Ti02.x ( χ = 〇·ι〜1 )表示之低原子價氧 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (13) —種方法，其爲製造出如第（1〇)項之靶材之 方法，其係包含： 將含有以下所示之（A)或（B)的混合粉之原料粉放 入於石墨製的模材中，在真空中或非活性氣體環境中，於 600°C〜1 500°C中進行加壓燒結之步驟，以及 加工該加壓燒結步驟中所得之氧化物燒結體而得靶材 之步驟； (A) 由式：TiO2-X(X=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 由式：ΤίΟ2·χ(Χ=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (14) 如第（10)項之靶材，其係使用在依據濺鍍法 所進行之成膜。 (15) —種如第（1〇)項之靶材的使用方式，其係用 作爲濺鍍靶材。 (16) —種方法，其爲製造出氧化鋅系透明導電膜之 方法，其係包含： 使含有以下所示之（Α)或（Β)的混合粉之原料粉成 形之步驟， -12- 201250033 將藉由該成形步驟所得之成形體’在真空中、還原氣 體環境中或非活性氣體環境中，於600°C〜1 500°C中進行 燒結之步驟， 加工該燒結步驟中所得之氧化物燒結體而得靶材之步 驟，以及 使用該靶材來形成透明導電膜之步驟； (A) 由式：TiO2-X(X=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 由式：ΤίΟ2·χ(Χ=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (17)—種方法，其爲製造出氧化鋅系透明導電膜之 方法，其係包含： 使含有以下所示之（Α)或（Β)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於600°C〜1500°C中進行燒結之步驟， 將藉由該燒結步驟所得之燒結體，在非活性氣體環境 中、真空中或還原氣體環境中進行退火處理之步驟， 加工該退火處理步驟中所得之氧化物燒結體而得靶材 之步驟，以及 使用該靶材來形成透明導電膜之步驟； (A)由式：Ti〇2.x(X=〇.l〜1)表示之低原子價氧 -13- 201250033 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B)由式：TiO2-X(X=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 (18)—種方法，其爲製造出氧化鋅系透明導電膜之 方法，其係包含： 將含有以下所示之（A)或（B)的混合粉之原料粉放 入於石墨製的模材中，在真空中或非活性氣體環境中，於 600°C〜1 500°C中進行加壓燒結之步驟， 加工該加壓燒結步驟中所得之氧化物燒結體而得靶材 之步驟，以及 使用該靶材來形成透明導電膜之步驟； (A) 由式：TiO2_x(X=0.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 由式：Τί〇2·χ(Χ=〇.1〜1)表示之低原子價氧 化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所組成 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 發明之效果： 藉由本發明所得之氧化物燒結體及靶材，係可生產性 佳地形成具有與AZO或GZO同等程度的導電性之氧化鋅 系透明導電膜。尤其是，藉由使用本發明之氧化物燒結體 -14 - 201250033 ，即使在DC濺鍍法中，亦可在穩定的放電狀態下生產性 佳地成膜，而穩定地製造出兼具有優異導電性及化學耐久 性之鈦摻雜的氧化鋅系透明導電膜。此外，如此製造之透 明導電膜，亦具有非以稀有金屬的銦爲必要之優點，故產 業上極爲有用。 【實施方式】 (氧化物燒結體） 本發明之氧化物燒結體，實質上由鋅，來自特定的氧 化鈦之鈦，氧，與微量添加元素（選自由鋁、鎵及銦所組 成之群組的至少1種）所構成。在此，所謂「實質上J ， 係意味著構成氧化物燒結體之全部原子的99%以上由鋅， 鈦，氧，與微量添加元素所構成。本發明之氧化物燒結體 ，較佳者，構成氧化物燒結體之全部原子的9 9.9%以上由 鋅，鈦，氧，與微量添加元素所構成。 本發明之氧化物燒結體，當具有5.3g/cm3以上的密 度時，使用其所得之靶材的導電性優異，故較佳。當氧化 物燒結體具有5.3g / cm3以上的密度時，相對密度約爲 95%以上。本發明之氧化物燒結體，尤佳係具有5.3 g/ cm3 〜5.6g/cm3 的密度，更佳具有 5.5g/cm3 〜5.6g/cm3 的密度。 本發明之氧化物燒結體，通常具有12γπΩ · cm以下 的比電阻。DC濺鑛時的成膜速度，係與作爲濺鍍靶材之 氧化物燒結體的比電阻相依。當氧化物燒結體的比電阻較 -15- 201250033 高時，藉由DC濺鍍有時無法生產性佳地成膜。AZO或GZO 等之燒結體，通常具有12m Ω · cm以下的比電阻，可增 大投入電力，故可進行高速成膜使生產效率提高。考量到 成膜性或生產性時，本發明之氧化物燒結體的比電阻愈低 愈佳，具體而言，較佳爲ΙΟπιΩ . cm以下，尤佳未達l〇m Ω · cm，更佳未達 8ηιΩ . cm。 本發明之氧化物燒結體中所含有的鈦，爲摻雜劑的主 成分，微量添加元素（選自由鋁、鎵及銦所組成之群組的 至少1種）具有降低比電阻之作用。 本發明之氧化物燒結體中所含有的鈦，係來自由式： Ti〇2_x ( X= 0.1〜1 )表示之低原子價氧化鈦。此等當中， 較佳是由3價的鈦所構成之氧化鈦（III ) ( Ti203 ( X = 0.5))及由2價的鈦所構成之氧化鈦（II) (TiO(X=l ))，尤佳爲氧化鈦（in)。 低原子價氧化鈦，不僅如TiO ( II )及Ti203 ( III ) 般之具有整數原子價之氧化鈦，只要是由式：Ti〇2.x ( X =0· 1〜1 )表示之氧化鈦即可，亦包含Ti305、Ti407、 7^6〇11、1^5〇9、1^8〇15等。由式：1^〇21(父=0.1〜1)表 示之低原子價氧化駄，可爲低原子價氧化欽的混合物。此 般低原子價氧化鈦，通常是在氫氣環境等之還原氣體環境 中，使用碳等作爲還原劑來加熱二氧化鈦（Ti〇2)而得。 藉由調節氫濃度、還原劑的量、加熱溫度等，可控制低原 子價氧化鈦之混合物的比率。該低原子價氧化鈦的結構， 可藉由X射線繞射儀（X-Ray Diffration，XRD ) 、X射線 -16- 201250033The present invention relates to a zinc oxide-based transparent conductive film which is subjected to a sputtering method, an ion deposition method, a pulsed laser deposition (PLD: Pulse Laser Deposition) method, an electron beam (EB: Electron Beam) vapor deposition method, or the like. A useful oxide sintered body, a method for producing the same, a target, a method for producing the same, and a method for producing a zinc oxide-based transparent conductive film. [Prior Art] A transparent conductive film having both conductivity and light transmittance has been applied to automotive windows or architectural heating in addition to electrodes used in solar cells, liquid crystal display elements, and various other photosensitive elements. A wide range of applications such as a line-reflecting film, an antistatic film, and a transparent heat generating body for antifogging in a refrigerating window. In particular, a transparent conductive film having low resistance and good electrical conductivity is known as a solar cell, a liquid crystal display element such as a liquid crystal, an organic electroluminescence, or an inorganic electroluminescence, or a touch panel. Conventionally, a transparent conductive film is known, for example, a tin oxide (ΑΤΟ) film such as a germanium-doped tin oxide (ΑΤΟ) film or a fluorine-doped tin oxide (FTO) film; and an aluminum doped film; A zinc oxide (ZnO) film such as a zinc oxide (ΑΖΟ) film or a gallium-doped zinc oxide (GZO) film; and an indium oxide (ITO) system such as a tin-doped indium oxide (ITO: Indium Tin Oxide) film film. Among them, those which are most commonly used in the industry are indium oxide-based transparent conductive films, and in particular, ITO films have low electrical resistance and good electrical conductivity, and thus have been widely put into practical use. 201250033 For example, when an oxide film such as ITO is formed by sputtering, an alloy target composed of a metal element constituting the film is generally used (In-Sn alloy when ruthenium film), or An oxygen target containing a metal element constituting the film (In-Sn- when the ITO film is used. However, when the alloy target is used, oxygen is supplied in the form, so that the gas may be difficult to maintain the film speed or When the oxide target is used as the characteristic surface of the obtained film, the supply is supplied to the body, and only the insufficient portion is suppressed by the amount of oxygen in the gas atmosphere, and as a result, the transparent conductive film is easily produced. An oxide target (ie, an oxide conductive film, which is an expensive material and has a resource depletion as a necessary raw material, can be used in place of the IT0 film, and can be widely used for industrial attention by sputtering. Actively, it can be said that 'Non-Patent Document 1 is a sintered body or a mixture of oxides prepared by sintering or mixing a dopant doped with ZnO.) Gas environment ring The amount of oxygen in the gas is easily changed. The amount of oxygen in the gas environment depends on it (specific resistance, permeability). The other part of the oxygen supplied to the membrane is supplied by the oxygen in the gas environment of the target. When an alloy target is used, a target having a certain film thickness and having a certain industrial use can be added, and a sintered body or an oxide mixture can be used. The indium oxide-based transparent In (indium) such as an ITO film is a rare metal and is a concern. Therefore, in recent years, an industrial transparent conductive film has been expected. Among them, the zinc oxide-based transparent conductive film produced is high in the conductivity. Specifically, in order to improve the conductivity, each of the above-mentioned items is required. 10 201250033 [Prior Art Document] [Non-Patent Document] [Non-Patent Document 1] Monthly publication, September 1999 issue, p ~ "The movement of the ZnO-based transparent conductive film" SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The present inventors have found that when a tetravalent titanium oxide (Ti02 ( ))' is used instead of a low-valent titanium oxide as a dopant titanium source, Further improved titanium content for chemical durability is added. Further, it has been found that the low-valent titanium oxide has a low electrical resistance and is excellent in the penetration of near-infrared rays for a transparent conductive film of a solar cell. However, the inventors have also found that the AZO or GZO used in the past has a poorer conductivity than the target made of zinc oxide (TZO) doped with general titanium, so when using a target of ruthenium When direct current (DC) is sputtered into a film, the film formation speed cannot be increased, and the productivity is more problematic than A Ζ Ο or GZ 0. An object of the present invention is to provide a target for producing a zinc oxide-based transparent conductive film having electrical conductivity equivalent to AZO or GZO and having good chemical durability, and a method for producing the same, by a DC sputtering method. Further, an object of the present invention is to provide an oxide sintered body for producing the target and a method for producing the same. Further, an object of the present invention is to provide a zinc oxide system which is excellent in productivity and has good electrical conductivity and is excellent in electrical conductivity and has a conductivity of about the same as that of AZO or GZO. The method of the transparent conductive film (means for solving the problem) The inventors of the present invention have carefully studied the above problems, and as a result, found the following specific means (1) to (18), thus completing the present invention. invention. (1) An oxide sintered body characterized by substantially sintering an oxide composed of zinc, titanium, oxygen, and at least one trace addition element (TE) selected from the group consisting of aluminum, gallium, and indium. The titanium is derived from a low valence titanium oxide represented by the formula: Ti〇2-x (x = 0.1 to 1). (2) The oxide sintered body of the item (1), wherein the oxide sintered body has a density of 5.3 g / cm 3 or more and has a specific resistance of 12 η Ω · cm or less. (3) The oxide sintered body according to item (1) or (2), wherein the at least one trace addition element (TE) is relative to the zinc, the titanium, and the at least one trace addition element (TE) The total atomic ratio [TE/(Zn+Ti+TE)] exceeds 0.001 and does not reach 0.005. (4) The oxide sintered body according to any one of (1) to (3), wherein the titanium is a total of atoms of the titanium and the at least one trace addition element (TE) The number ratio [Ti/(Zn + Ti + TE )] exceeds 0.02 and is 0.1 or less. (5) A method of producing an oxide sintered body according to any one of the items (1) to (4), which comprises: 201250033 comprising (A) or The step of forming the raw material powder of the mixed powder of (B), and the shaped body obtained by the forming step, in a vacuum, a reducing gas atmosphere or an inert gas atmosphere, at 600.烧结~1 00 °C in the step of sintering; (A) by the formula: TiO2-X (X = 0.1~1) expressed as low valence titanium oxide powder 'and selected from alumina powder, gallium oxide powder and oxidation At least one powder of the group consisting of indium powder, mixed with zinc oxide powder, (B) low-valent titanium oxide powder represented by the formula: Ti02.x (X = 0.1~1), and selected from oxidation A powder of at least one powder of a group consisting of aluminum powder, gallium oxide powder and indium oxide powder, and a powder of zinc hydroxide powder. (6) A method of producing an oxide sintered body according to any one of the items (1), wherein the method comprises: (A) or (B) a step of forming a raw material powder of the mixed powder, and subjecting the formed body obtained by the forming step to sintering in an atmosphere or an oxidizing gas atmosphere at 600 ° C to 1 500 ° C, and The step of annealing the sintered body obtained by the sintering step in an inert gas atmosphere, in a vacuum or in a reducing gas atmosphere; (A) low valence oxidation represented by the formula: Ti02_x (X = 0.1~1) Titanium powder, and at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, mixed powder with zinc oxide powder, (B) by: ΤίΟ2·χ (Χ=0· 1~1) indicates a low valence oxy-9-201250033 titanium powder, and at least one powder selected from the group consisting of alumina powder 'oxidized gallium powder and indium oxide powder' and zinc hydroxide powder (7) The method according to item (5), wherein the annealing treatment is selected from the group consisting of a nitrogen atmosphere and an argon atmosphere Performing in at least one gas environment of a group consisting of a nitrogen atmosphere, a carbon dioxide gas environment, and a hydrogen atmosphere. (8) A method of manufacturing any one of items (1) to (4) A method of oxidizing a sintered body, comprising: placing a raw material powder containing a mixed powder of (A) or (B) shown below in a mold made of graphite, in a vacuum or an inert gas atmosphere, a step of pressure sintering at 600 ° C to 1 500 ° C; (A) a low-valent titanium oxide powder represented by the formula: and a group selected from the group consisting of alumina powder, gallium oxide powder, and indium oxide oxide a group of at least one powder, a powder mixed with zinc oxide powder, (B) a low valence yttrium oxide powder represented by the formula: Ti〇2.x (x=〇.i~1) and selected from alumina powder a mixture of at least one powder of a group consisting of gallium oxide powder and indium oxide powder, and a powder of zinc hydroxide powder. (9) The method of item (8) wherein the pressure sintering step is hot press sintering The step (1 〇) of the target material is obtained by processing the oxide sintered body according to any one of the items (1) to (4). 1) A method for producing a target material according to item (1), which comprises the steps of: forming a raw material powder containing the mixed powder of (A) or (B) shown below , -10- 201250033 The step of sintering the formed body obtained by the forming step in a vacuum, a reducing gas atmosphere or an inert gas atmosphere at 600 ° C to 1500 ° C, and processing the sintering step a step of obtaining a target by the oxide sintered body obtained; (A) a low-valent titanium oxide powder represented by the formula: Ti〇2.x (X=〇.l~1) and selected from the group consisting of alumina powder, At least one powder of a group consisting of gallium oxide powder and indium oxide powder, and a powder mixed with zinc oxide powder, (B) a low-valent titanium oxide powder represented by the formula: Ti02.x (x = 0.1~1) 'mixed powder with at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. (12) A method of producing a target material according to item (1), comprising: forming a raw material powder containing the mixed powder of (A) or (B) shown below a step of sintering in a gaseous environment or an oxidizing gas atmosphere at 600 to 150 ° C by a shaped body obtained by the forming step, M by the sintered body obtained by the sintering step a step of performing an annealing treatment in a vacuum or a reducing gas atmosphere in an inert gas atmosphere, and a step of obtaining a target by the oxide sintered body obtained in the annealing treatment step; (A) τίΟ2·χ(Χ=0·1~1) represents a low valence oxidized i-powder' and at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc oxide Powder mixed powder, -11 - 201250033 (B ) by the formula: Ti02.x ( χ = 〇 ·ι ~1 ) is a low atomic valence titanium oxide powder 'selected from alumina powder, gallium oxide powder and indium oxide powder At least one powder of the group formed, and a mixed powder of zinc hydroxide powder. (13) A method of producing a target material according to item (1), which comprises: placing a raw material powder containing a mixed powder of (A) or (B) shown below In the graphite molding material, the step of pressure sintering is performed at 600 ° C to 1 500 ° C in a vacuum or in an inert gas atmosphere, and the oxide sintered body obtained in the pressure sintering step is processed. a step of a target; (A) a low-valent titanium oxide powder represented by the formula: TiO2-X (X = 0.1 to 1), and a group selected from the group consisting of alumina powder, gallium oxide powder, and indium oxide powder At least 1 powder, mixed powder with zinc oxide powder, (B) low-valent titanium oxide powder represented by the formula: ΤίΟ2·χ (Χ=0.1~1), and selected from alumina powder, gallium oxide powder and oxidation A mixed powder of at least one powder of the group consisting of indium powder and zinc hydroxide powder. (14) The target material of item (10) is used for film formation according to the sputtering method. (15) A method of using a target such as the item (1), which is used as a sputtering target. (16) A method for producing a zinc oxide-based transparent conductive film, comprising: a step of forming a raw material powder containing a mixed powder of (Α) or (Β) shown below, -12- 201250033 The oxidation of the shaped body obtained by the forming step in a vacuum, in a reducing gas atmosphere or in an inert gas atmosphere at 600 ° C to 1 500 ° C to process the oxidation obtained in the sintering step a step of obtaining a target by sintering a body, and a step of forming a transparent conductive film using the target; (A) a low-valent titanium oxide powder represented by the formula: TiO2-X (X=0.1 〜1), and At least one powder of a group consisting of free alumina powder, gallium oxide powder and indium oxide powder, and a powder mixed with zinc oxide powder, (B) is represented by a formula: ΤίΟ2·χ (Χ=0.1~1) The atomic-valent titanium oxide powder and a mixed powder of at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. (17) A method for producing a zinc oxide-based transparent conductive film, comprising: forming a raw material powder containing a mixed powder of (Α) or (Β) shown below, by using The formed body obtained by the forming step is subjected to sintering in an atmosphere or an oxidizing gas atmosphere at 600 ° C to 1500 ° C, and the sintered body obtained by the sintering step is in an inert gas atmosphere. a step of annealing in a vacuum or a reducing gas atmosphere, a step of processing the oxide sintered body obtained in the annealing step to obtain a target, and a step of forming a transparent conductive film using the target; (A) :Ti〇2.x (X=〇.l~1) indicates a low valence oxy-oxyl-13-201250033 titanium powder, and at least one selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder 1 powder, mixed powder with zinc oxide powder, (B) low-valent titanium oxide powder represented by the formula: TiO2-X (X=0.1~1), and selected from alumina powder, gallium oxide powder and indium oxide A powder of at least one powder of the group consisting of powder and zinc hydroxide powder. (18) A method for producing a zinc oxide-based transparent conductive film, comprising: placing a raw material powder containing the mixed powder of (A) or (B) shown below in a mold made of graphite a step of performing pressure sintering in a vacuum or an inert gas atmosphere at 600 ° C to 1 500 ° C to process the oxide sintered body obtained in the pressure sintering step to obtain a target. And a step of forming the transparent conductive film using the target; (A) a low-valent titanium oxide powder represented by the formula: TiO2_x (X = 0.1 to 1), and selected from the group consisting of alumina powder, gallium oxide powder, and indium oxide powder At least one powder of the group formed, and a mixed powder of zinc oxide powder, (B) a low atomic weight titanium oxide powder represented by the formula: Τί〇2·χ (Χ=〇.1~1), and A mixed powder of at least one powder of a group consisting of free alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. According to the oxide sintered body and the target obtained by the present invention, a zinc oxide-based transparent conductive film having conductivity equivalent to AZO or GZO can be formed with good productivity. In particular, by using the oxide sintered body-14 - 201250033 of the present invention, even in the DC sputtering method, it is possible to form a film with good productivity in a stable discharge state, and to stably produce both excellent. A titanium-doped zinc oxide-based transparent conductive film having electrical conductivity and chemical durability. Further, the transparent conductive film thus produced also has an advantage that it is not necessary to use indium of a rare metal, and is therefore extremely useful in the industry. [Embodiment] (Oxide sintered body) The oxide sintered body of the present invention is substantially composed of zinc, titanium derived from specific titanium oxide, oxygen, and a trace addition element selected from the group consisting of aluminum, gallium, and indium. At least one of them is composed. Here, "substantially J" means that 99% or more of all atoms constituting the oxide sintered body are composed of zinc, titanium, oxygen, and a trace amount of an additive element. The oxide sintered body of the present invention is preferably, 9.9% or more of all the atoms constituting the oxide sintered body are composed of zinc, titanium, oxygen, and a trace amount of an additive element. When the oxide sintered body of the present invention has a density of 5.3 g/cm 3 or more, the obtained When the oxide sintered body has a density of 5.3 g / cm 3 or more, the relative density is about 95% or more. The oxide sintered body of the present invention, particularly preferably 5.3 g / cm 3 The density of 5.6 g/cm 3 is more preferably 5.5 g/cm 3 to 5.6 g/cm 3 . The oxide sintered body of the present invention usually has a specific resistance of 12 γ π Ω · cm or less. It is dependent on the specific resistance of the oxide sintered body as a sputtering target. When the specific resistance of the oxide sintered body is higher than -15-201250033, it is sometimes impossible to form a film by DC sputtering. Sintered body of GZO, etc., usually has 12m Ω · cm Since the specific resistance can increase the input electric power, high-speed film formation can be performed to improve the production efficiency. When the film forming property or productivity is considered, the specific resistance of the oxide sintered body of the present invention is preferably lower, specifically, It is preferably ΙΟπιΩ.cm or less, particularly preferably less than 10 μm Ω · cm, more preferably less than 8 ηι Ω. cm. The titanium contained in the oxide sintered body of the present invention is a main component of the dopant, and is added in a trace amount. The element (selected from at least one of the group consisting of aluminum, gallium, and indium) has a function of lowering the specific resistance. The titanium contained in the oxide sintered body of the present invention is derived from the formula: Ti〇2_x (X= 0.1 to 1) is a low atomic valence titanium oxide. Among these, titanium oxide (III) composed of trivalent titanium (Ti203 (X = 0.5)) and oxidation by divalent titanium are preferred. Titanium (II) (TiO(X=l)), especially preferably titanium oxide (in). Low atomic valence titanium oxide, not only TiO ( II ) and Ti203 ( III ), but also has an integral valence of titanium oxide, as long as It is a titanium oxide represented by the formula: Ti〇2.x (X =0·1~1), and also contains Ti305, Ti407, 7^6〇11, 1^5〇9 1^8〇15, etc. The formula: 1^〇21 (parent=0.1~1) indicates a low valence yttrium oxide, which can be a mixture of low valence valences. Such low valence titanium oxide is usually In a reducing gas atmosphere such as a hydrogen atmosphere, carbon dioxide or the like is used as a reducing agent to heat titanium dioxide (Ti〇2). By adjusting the hydrogen concentration, the amount of the reducing agent, the heating temperature, and the like, a mixture of low-valent titanium oxides can be controlled. The ratio. The structure of the low-valent titanium oxide can be obtained by X-ray Diffration (XRD), X-ray -16-201250033

先電子分先 ί我（X-Ray Photoelectron Spectroscopy，XPS )等之儀器分析來確認。First, the electrons are first analyzed by instrumental analysis such as X-Ray Photoelectron Spectroscopy (XPS).

本發明之氧化物燒結體中’較佳者，微量添加元素（ TE )相對於鋅、鈦及微量添加元素（te )的合計之原子 數比[TE/ (Zn+Ti+TE)]，超過 o.ool 且未達 〇〇〇5。 當微量添加元素（TE)的原子數比[te/ (Zn+Ti+TE)] 位於上述範圍時，可在不會損及將氧化物燒結體形成爲靶 材後之膜的特性下’進一步使氧化物燒結體的比電阻達到 低電阻化。較佳者’微量添加元素（TE )的原子數比[TE / (Zn+Ti+TE)]爲 0.0015 〜〇.〇〇45，尤佳爲 0.002 〜 0.004 ° 本發明之氧化物燒結體中，較佳者，鈦相對於鋅、鈦 及至少1種微量添加元素（TE)的合計之原子數比[Ti/ (Zn+Ti+TE)]’超過0.02且爲0.1以下。當鈦的原子 數比[Ti/ ( Zn + Ti + TE )]位於上述範圍時，可提升燒結 體的強度，且容易加工爲靶材。再者，可進一步提升所形 成之導電膜的化學耐久性、導電性及透明性。較佳者，駄 的原子數比[Ti/ (Zn+Ti+TE)]爲 〇.〇3 〜0.09。 本發明之氧化物燒結體，較佳是由氧化鋅相與鈦酸鋅 化合物相所構成，或是由鈦酸鋅化合物相所構成。如此， 在氧化物燒結體中含有鈦酸鋅化合物相時，可提升燒結體 的強度，即使例如在嚴苛條件（高電力等）下成膜作爲靶 材時，亦不易產生龜裂。 鈦酸鋅化合物相，可含有：ZnTi03、Zn2Ti04、鈦元 -17- 201250033 素固溶於ZnTi03或Zn2Ti〇4的鋅部位者；從ZnTi03或 Zn2Ti〇4產生氧缺損者；Zn/Ti比僅從ΖηΉ03或Zn2Ti04 的化合物產生些許偏移之非計量化學組成者等。 氧化鋅相，可含有：ZnO、或是鈦、鋁、鎵或銦固溶 於ZnO者；從ZnO產生氧缺損者；由於鋅缺損而從ZnO 成爲非計量化學組成者等。氧化鋅相，通常具有纖鋅（ Wurtzite)礦型結構。 本發明之氧化物燒結體，較佳係實質上不含有氧化鈦 的結晶相。當氧化物燒結體含有氧化鈦的結晶相時，會有 所得之膜的比電阻等物性產生變動而缺乏均一性之疑慮。 如上述般，例如當Ti/ ( Zii+ Ti + TE)之値爲〇.1以下時 ，通常氧化鈦會完全與氧化鋅反應，使氧化物燒結體中不 易生成氧化鈦的結晶相。所謂氧化鈦的結晶相，具體而言 ，除了 Ti2〇3和TiO之外，亦含有Zn等其他元素固溶於 此等結晶的性質。 製造本發明之氧化物燒結體之方法並無特別限定，例 如’可藉由後述製造方法而理想地製得本發明之氧化物燒 結體。 (製造氧化物燒結體之方法） 製造本發明之氧化物燒結體之第1方法（以下有時僅 記載爲「本發明之第1製造方法」），係包含：使含有以 下所不之（A)或（B)的混合粉之原料粉成形之步驟，以 及將藉由成形步驟所得之成形體，在真空中、還原氣體環 -18- 201250033 境中或非活性氣體環境中，於600 °C〜1500 °C中 之步驟； (A )由式：Ti02.x ( Χ = 0. 1〜1 )表示之低 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦 之群組的至少1種粉，與氧化鋅粉之混合粉， (B)由式：Ti〇2.x(X=〇.l〜1)表示之低 化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦 之群組的至少1種粉，與氫氧化鋅粉之混合粉。 製造本發明之氧化物燒結體之第2方法（以 記載爲「本發明之第2製造方法」），係包含： 述（A)或（B)之原料粉成形之步驟，將藉由成 得之成形體，在大氣環境中或氧化氣體環境中， 〜1 500 °C中進行燒結之步驟，以及將藉由燒結步 燒結體，在非活性氣體環境中、真空中或還原氣 進行退火處理之步驟。 本發明之第1及第2製造方法中，係使用i 或（B )的混合粉作爲原料粉，較佳係使用·· (A')氧化鈦（III)粉，與選自由氧化鋁粉 粉及氧化銦粉所組成之群組的至少1種粉，與氧 混合粉，或是 (B1)氧化鈦（III)粉，與選自由氧化鋁粉 粉及氧化銦粉所組成之群組的至少1種粉，與氫 之混合粉。In the oxide sintered body of the present invention, the atomic ratio [TE/(Zn+Ti+TE)] of the total amount of trace addition elements (TE) to zinc, titanium and trace addition elements (te) is more than O.ool and not up to 5. When the atomic ratio [TE/(Zn+Ti+TE)] of the trace addition element (TE) is in the above range, the characteristics of the film after the oxide sintered body is formed into a target can be prevented from being further improved. The specific resistance of the oxide sintered body is reduced in resistance. Preferably, the atomic ratio [TE / (Zn + Ti + TE)] of the trace additive element (TE) is 0.0015 to 〇.〇〇45, and particularly preferably 0.002 to 0.004 ° in the oxide sintered body of the present invention, Preferably, the atomic ratio [Ti/(Zn+Ti+TE)]' of titanium in total of zinc, titanium, and at least one trace addition element (TE) exceeds 0.02 and is 0.1 or less. When the atomic ratio of titanium [Ti/(Zn + Ti + TE )] is in the above range, the strength of the sintered body can be improved and it is easy to process into a target. Further, the chemical durability, conductivity, and transparency of the formed conductive film can be further improved. Preferably, the atomic ratio of 駄 [Ti/(Zn+Ti+TE)] is 〇.〇3 to 0.09. The oxide sintered body of the present invention is preferably composed of a zinc oxide phase and a zinc titanate compound phase, or a zinc titanate compound phase. When the zinc oxynitride compound phase is contained in the oxide sintered body, the strength of the sintered body can be increased, and cracking is less likely to occur even when a film is formed as a target under severe conditions (such as high electric power). The zinc titanate compound phase may contain: ZnTi03, Zn2Ti04, titanium element-17-201250033, which is dissolved in the zinc portion of ZnTi03 or Zn2Ti〇4; the oxygen defect is generated from ZnTi03 or Zn2Ti〇4; the Zn/Ti ratio is only The compound of ΖηΉ03 or Zn2Ti04 produces a slight offset of the non-metering chemical composition and the like. The zinc oxide phase may contain: ZnO, or titanium, aluminum, gallium or indium which is solid-solubilized in ZnO; oxygen-depleted from ZnO; and non-metering chemical composition from ZnO due to zinc deficiency. The zinc oxide phase usually has a Wurtzite mineral structure. The oxide sintered body of the present invention preferably contains substantially no crystal phase of titanium oxide. When the oxide sintered body contains a crystal phase of titanium oxide, there is a concern that the physical properties such as the specific resistance of the obtained film fluctuate and the uniformity is lacking. As described above, for example, when the enthalpy of Ti/( Zii + Ti + TE) is 〇.1 or less, the titanium oxide is usually completely reacted with zinc oxide, and a crystal phase of titanium oxide is not easily formed in the oxide sintered body. The crystal phase of titanium oxide, specifically, in addition to Ti2〇3 and TiO, also contains other elements such as Zn which are solid-solubilized in such crystals. The method for producing the oxide sintered body of the present invention is not particularly limited. For example, the oxide sintered body of the present invention can be desirably produced by a production method described later. (Method of Producing Oxide Sintered Body) The first method of producing the oxide sintered body of the present invention (hereinafter, simply referred to as "the first production method of the present invention") includes the following (A) Or (B) the step of forming the raw material powder of the mixed powder, and the shaped body obtained by the forming step, in a vacuum, in a reducing gas ring -18-201250033 or in an inert gas atmosphere at 600 ° C a step of ~1500 ° C; (A) a formula of: Ti02.x ( Χ = 0. 1~1 ) indicating a reduced titanium powder ' and a group selected from the group consisting of alumina powder, gallium oxide powder and indium oxide At least one powder, a mixed powder with zinc oxide powder, (B) a reduced titanium powder represented by the formula: Ti〇2.x (X=〇.l~1) and selected from alumina powder, gallium oxide powder And a mixed powder of at least one powder of the group of indium oxide and zinc hydroxide powder. The second method of producing the oxide sintered body of the present invention (described as "the second production method of the present invention") includes the step of forming the raw material powder of (A) or (B), which is obtained by The formed body is subjected to sintering in an atmosphere or an oxidizing gas atmosphere at a temperature of ～1,500 ° C, and is annealed in an inert gas atmosphere, a vacuum or a reducing gas by a sintering step sintered body. step. In the first and second production methods of the present invention, a mixed powder of i or (B) is used as the raw material powder, and preferably (A') titanium oxide (III) powder is used, and is selected from alumina powder. And at least one powder of the group consisting of indium oxide powder, mixed with oxygen, or (B1) titanium oxide (III) powder, and at least one selected from the group consisting of alumina powder and indium oxide powder 1 kind of powder, mixed with hydrogen.

氧化鋅粉，通常使用具有纖鋅礦結構之ZnO 進行燒結 原子價氧 粉所組成 原子價氧 粉所組成 下有時僅 使含有上 形步驟所 於 600°C 驟所得之 體環境中 :述（A ) 、氧化鎵 化鋅粉之 、氧化鎵 氧化鋅粉 等粉末， -19" 201250033 此外，亦可使用預先在還原氣體環境中燒結該ZnO使其產 生氧缺損者。再者’氫氧化鋅粉可爲非晶賛或具有結晶結 構者。 氧化鈦粉，係使用由上述式：TiO2_x(X=0.1〜1)表 示之氧化鈦粉末，較佳係使用Ti2〇3 ( III )粉末。此係由 於Ti203 ( III )的結晶結構爲三方晶，通常與此混合之氧 化鋅，如上述般具有六方晶的纖綷礦結構，可使結晶結構 的對稱性達到一致，於固相燒結時容易取代固溶之故。 氧化鋁粉並無特別限定，可使用一般的α -氧化鋁等 粉末。氧化鎵粉並無特別限定，可使用一般的α-氧化鎵 等粉末。氧化銦粉並無特別限定，可使用一般的氧化銦等 粉末。 用作爲原料粉之化合物（粉）的平均粒徑，較佳分別 爲5 /z m以下。 混合粉中之各粉的混合比率，可因應所使用之化合物 (粉）的種類來適當地設定。例如，在最終所得之氧化物 燒結體中，可適當地設定使原子數比位於上述範圍。此時 ，考量到鋅的蒸氣壓較鈦更高，燒結時容易逸散，較佳係 以使鋅的量較所期望之氧化物燒結體的目的組成（Zn與 Ti之原子數比）更多之方式來設定混合比率。具體而言， 鋅的逸散容易度係因燒結時的氣體環境而有所不同，例如 在使用氧化鋅粉時，在大氣中或氧化氣體瓌境中，僅會引 起氧化鋅粉本身的逸散，但在還原氣體環境中進行燒結時 ，氧化鋅被還原而成爲較氧化鋅更易逸散之金屬鋅，而使 -20- 201250033 鉢的消失量增加。惟如後述般，一旦於燒結後在還原氣體 環境中進行退火處理時，在進行退火處理之時點中已成爲 複合氧化物’所以鋅不易逸散。因此，關於相對於目的組 成需增加何種程度的鋅量者，只需考量燒結的氣體等來設 定即可’例如在大氣中或氧化氣體環境中進行燒結時，設 定在成爲所期望之原子數比的量之約1.0倍〜1.05倍，在 還原氣體環境中進行燒結時，設定在成爲所期望之原子數 比的量之約1 . 1倍〜1 · 3倍。用作爲原料粉之化合物（粉 )’可分別僅爲1種或2種以上。 本發明之第1製造方法及第2製造方法中所包含之使 原料粉成形之步驟中的成形方法，並無特別限制，例如可 列舉出將原料粉與水系溶劑混合，並藉由濕式混合充分地 將所得之漿液混合後，進行固液分離、乾燥及粒化，並使 所得之粒化物成形之方法。 濕式混合，例如可藉由採用有硬質Zr02球等之濕式 球磨機或振動硏磨機來進行，使用濕式球磨機或振動硏磨 機時之混合時間，較佳約爲1 2小時〜7 8小時。雖可直接 將原料粉進行乾式混合，但尤佳者爲濕式混合。關於固液 分離、乾燥及粒化，可別可採用一般所知的方法。 使所得之粒化物成形時，例如可將粒化物放入於模框 並加壓而成形。此外，在使進行乾式混合所得之原料粉或 進行濕式混合後進行乾燥所得之原料粉成形時，例如可將 原料粉放入於模框並加壓而成形。加壓方法，可列舉出採 用冷均壓模壓等的冷成形機之方法，或是單軸模壓。不論 -21 - 201250033 是冷均壓模壓或單軸模壓，當壓力過低時，均有無法形成 穩定的模壓成型體之疑慮’壓力過筒時’成型體變得容易 斷裂。壓力’在冷均壓模壓的情形時，通常爲5 〇MPa以上 200MPa以下’較佳爲l〇〇MPa以上200MPa以下，在單軸 模壓的情形時，通常爲1 OMPa以上500MPa以下，_彳圭胃 2 0MPa以上50MPa以下。當使用熱模壓等進行熱加壓來成 形時，不僅製造成本上較爲不利，且有難以得到大型燒結 體之疑慮。成塑體的形狀或尺寸並無特別限定，例如可列 舉出圓筒、直方體等。當得到粒化物作爲成形體時，可在 乾燥後使用一般所知的方法來粒化，但此時較佳係將黏合 劑與原料粉一同混合。黏合劑例如可使用聚乙烯醇、乙酸 乙烯酯、乙基纖維素等。 本發明之第1製造方法及第2製造方法中，藉由成形 步驟所得之成形體的燒結，係在非活性氣體環境（例如氮 氣、氬氣、氨氣、氖氣等）、真空、還原氣體環境（例如 二氧化碳、氫氣、氨等）、大氣及氧化氣體環境（氧濃度 較大氣更高之氣體）中的任一種氣體環境中，在60CTC〜 1 500 °C中進行。尤佳是在氧化氣體環境（氧濃度較大氣更 闻之氣體環境）中’在1000 C〜1500 °C中進行。在大氣或 氧化氣體環境中進行燒結時，可進一步在非活性氣體環境 中、真空中、還原氣體環境中進行退火處理。該退火處理 ’係用以使氧化物燒結體產生氧缺損以降低比電阻而進行 者。在非活性氣體環境中、真空中或還原氣體環境中進行 燒結時’當期望進一步降低比電阻時，可在燒結後進行退 -22- 201250033 火處理。 當燒結溫度未達600 °C時’燒結無法充分地進行，而 使靶材密度降低，另一方面，超過丨5 〇 〇它時，氧化鋅本身 會分解而消失。上述任一氣體環境中，尤佳均在1〇〇(rc〜 1300C進行燒結。將成形體升溫至上述燒結溫度時，就使 燒結速度達到均一來看’較佳係將升溫速度在6〇〇。(：爲止 前設爲5°C/分〜10°C/分’超過600°C至1500 °C爲止， 係設爲1 °C /分〜4 °C /分。 在任一氣體環境中進行燒結時，燒結時間（亦即燒結 溫度下的保持時間），較佳係設爲3小時〜1 5小時》當燒 結時間未達3小時時，燒結密度容易變得不足，而有所得 之氧化物燒結體的強度降低之傾向，另—方面，超過15 小時時’燒結體的晶粒成長變得顯著，並且有導致空孔的 粗大化以及最大空孔徑的增大化之傾向，其結果具有燒結 密度降低之疑慮。 燒結步驟中的燒結方法並無特別限制，例如可列舉出 常壓燒結法、微波燒結法、毫波燒結法等。 製造本發明之氧化物燒結體之第3方法（以下有時僅 記載爲「本發明之第3製造方法」），係包含：將前述原 料粉放入於石墨製的模材中，在真空中或非活性氣體環境 中，於600 °C〜l5〇〇°C中進行加壓燒結之步驟。 前述加壓燒結之方法，例如可列舉出熱模壓法、熱等 靜壓加壓（HIP : Hot Isostatic Pressing)法、放電電發燒 結法等。 •23- 201250033 加壓燒結時的氣體環境’爲真空（例如2Pa以下）或 非活性氣體環境（例如氮氣、氬氣、氦氣、氖氣等），較 佳爲真空。加壓燒結時施加於原料粉之壓力，較佳爲 20MPa〜150MPa，尤佳爲 30MPa〜lOOMPa»加壓燒結時 的燒結溫度，較佳爲1〇〇〇 °C〜1600 °C，尤佳爲11〇〇。(：〜 1400 °C »加壓燒結時間，可因應燒結溫度和原料粉的量等 來適當地調整，通常爲30分鐘〜4小時，尤佳爲1小時〜 2小時》 藉由本發明之第3製造方法所得之氧化物燒結體，爲 了進一步降低比電阻，可在非活性氣體環境中、真空中或 還原氣體環境中進行退火處理。 本發明之第1、第2或第3製造方法的說明中所提及 之退火處理的方法，例如可列舉出一邊導入氮氣、氬氣、 氯氣、二氧化碳、氫氣等之非氧化氣體一邊在常壓下加熱 之方法，以及在真空下（較佳爲2Pa以下）加熱之方法等 。就製造成本之觀點來看，一邊導入非氧化氣體一邊在常 壓下進行之方法較有利。 退火溫度（加熱溫度）較佳爲1 0 0 0 °C〜1 4 0 0 °C，尤佳 爲1 100°C〜1 3 00°C。退火時間（加熱時間）較佳爲7小時 〜1 5小時，尤佳爲8小時〜12小時。退火溫度未達1 〇〇〇 °(：時，會有由退火處理所進行之氧缺損不足之疑慮，另一 方面，退火溫度超過1 400 °C時，鋅容易逸散，而有所得之 氧化物燒結體的組成（Zn與Ti之原子數比）與所期望的 比率成爲不同之疑慮。 -24- 201250033 藉由本發明之第1、第2或第3製造方法所得之氧化 物燒結體，通常具有5.3g/ cm3以上的密度，且具有12m Ω · cm以下的比電阻。 (靶材） 本發明之靶材，爲各種成膜方法中所使用之靶材，尤 其使用在由濺鍍法（較佳爲量產性佳之DC濺鍍法）所進 行之成膜中的靶材。本發明之靶材，係將上述本發明之氧 化物燒結體加工爲既定形狀及既定尺寸而得。 加工本發明之氧化物燒結體而得靶材之方法並無特別 限制，可適當地採用一般所知的方法。例如對氧化物燒結 體施以平面硏磨等之後，切斷爲既定尺寸並貼著於支撐座 ’藉此可得本發明之靶材。可因應必要，將複數片氧化物 燒結體排列爲分割形狀而構成大面積的靶材（複合靶材） 〇 本發明之靶材，較佳係用作爲濺鍍靶材，尤佳係用作 爲DC濺鑛的靶材。 使用本發明之靶材來製造透明導電膜之方法並無特別 限制，可適當地採用一般所知的方法。例如可藉由濺鍍法 、離子蒸鍍法、脈衝雷射沉積（PLD )法、電子束（eb ) 蒸鍍法，使用本發明之靶材來製造透明導電膜。本發明之 形成氧化鋅系透明導電膜之方法，較佳爲濺鍍法，尤佳爲 DC濺鍍法。 使用本發明之氧化物燒結體或本發明之靶材所形成之 -25- 201250033 透明導電膜，乃兼具優異的導電性與化學耐久性（耐熱性 、耐濕性、耐藥性（耐鹼性、耐酸性等））。此般透明導 電膜，可較佳地使用在例如液晶顯示器、電漿顯示器、無 機EL (電激發光）顯示器、有機EL顯示器、電子紙等的 透明電極；太陽能電池之光電轉換元件的窗電極；透明觸 控面板等之輸入裝置的電極；電磁屏蔽罩的電磁遮蔽膜等 用途。此外，使用本發明之氧化物燒結體或本發明之靶材 所形成之透明導電膜，亦可作爲透明電波吸收體、紫外線 吸收體、或透明半導體裝置而與其他金屬膜或金屬氧化膜 組合應用。 〔實施例〕 以下係列舉出實施例及比較例來具體地說明本發明。 惟本發明在不脫離該目的及主旨之範圍內，並不限定於下 列實施例。 實施例中，燒結體和透明導電膜的比電阻，係以下列 方法來求取。 <比電阻> 比電阻，係使用電阻率儀（三菱化學股份有限公司製 「LORESTA-GP，MCP-T610」），並藉由四端子四探針法 來測定。詳細而言，將4根針狀電極直線地放置在樣本上 ，使一定的電流於外側的兩探針間與內側的兩探針間流通 ，並測定內側的兩探針間所產生之電位差來求取電阻。 -26- 201250033 (實施例1 ) 將氧化鋅粉末（ZnO :和光純藥工業股份有限公司製 ，特級）、氧化鈦（m)粉末（Ti203 :高純度化學硏究 所股份有限公司製，純度99.99% )及氧化鋁粉末（Al2〇3 :住友化學股份有限公司製，純度99.99% )，以使原子 數比計成爲 Zn: Ti: Al=96.8: 3: 0_2(Ti/ (Zn+Ti + Al) =0.03，且 Al/ (Zn+Ti+Al) = 0.002 )之方式來 調配而得混合物。接著將所得之混合物放入於模具，藉由 單軸模壓以成形壓500kg/cm2來成形，而得直徑100mm 及厚度5mm的圓盤狀成形體。將該成形體，於常壓（ 1 .0 1 3 2 5 · 102kPa )的氬氣環境下，在1 200°C中燒結4小 時而得氧化物燒結體（1)。 藉由能量分散型螢光X射線裝置（島津製作所股份有 限公司製「EDX-700L」），來分析所得之氧化物燒結體 (1 )，可得知Zn與Ti與A1之原子數比Zn : Ti : Al = 96.8 ： 3 ： 0.2 ( Ti/ ( Zn + Ti + A1 ) = 0.03，且 Al/ ( Zn + Ti + A1 ) = 0.002 )。該燒結體的密度爲5.41§/(：1113, 比電阻爲5ιηΩ · cm。 接著將所得之氧化物燒結體（1 )加工爲5 0mm φ 的 圓盤狀而得靶材，使用該靶材，藉由DC濺鍍法使透明導 電膜成膜，而得透明導電基板。亦即，將透明基板（厚度 7mm的無鹼玻璃：Corning公司製的Eagle XG)與所得之 IG材設置在濺鑛裝置（Canon Anelva Engineering股份有 -27 - 201250033 限公司製「E-200」）內，以12sccm導入氬氣（純度 99.9995 %以上，Ar純氣體= 5N)，在壓力0.5Pa、投入電 力100W、基板溫度25 0 °C的條件下進行濺鍍，而在基板 上形成具有5 00 nm的膜厚之透明導電膜。成膜速度極爲高 速，所得之透明導電膜的比電阻爲4.4x1 0_4Ω · cm之低電 阻。因此，鋁的微量添加相對於透明導電膜完全無影響。 (實施例2) 使用氧化鎵粉末（Ga203 :住友化學股份有限公司製 ，純度99.99% )來取代氧化鋁粉末，除此之外，其他與 實施例1相同而得氧化物燒結體（2 )。 與實施例1相同地分析所得之氧化物燒結體（2 )， 可得知Zn與Ti與Ga之原子數比Zn : Ti : Ga= 96.8 : 3 ：0.2(Ti/ (Zn+Ti+Ga) = 0.03，且 Ga/ (Zn+Ti + Ga) = 0.002 )。氧化物燒結體（2 )的密度爲5.41g / cm3 ，比電阻爲6ιώΩ · cm。 然後，除了使用氧化物燒結體（2 )之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法，在基板上形成具有膜厚5 OOnm之透明導電膜 。成膜速度極爲高速，所得之透明導電膜的比電阻爲4.4X 1 (Γ4 Ω · cm之低電阻。因此，鎵的微量添加相對於透明導 電膜完全無影響。 (實施例3) -28- 201250033 使用氧化銦粉末（Ιη203 :高純度化學硏究所股 限公司製，純度99.99% )來取代氧化鋁粉末，並且 原子數比計成爲 Zn : Ti : In= 96.7 : 3 : 0.3 ( Ti/ ( Ti+In) = 0.03，且 In/ (Zn+Ti+In) = 0.003)之 來調配，除此之外，其他與實施例1相同而得氧化物 體（3)。 與實施例1相同地分析所得之氧化物燒結體（3 可得知Zn與Ti與In之原子數比Zn : Ti : In= 96.7 ： 0.3 ( Ti/ (Zn+Ti+In) = 0.03，且 In/ ( Zn + Ti + = 0.003 )。氧化物燒結體（3)的密度爲5.41g/cm3 電阻爲9χηΩ . cm。 然後，除了使用氧化物燒結體（3 )之外，其他 施例1相同而製作出靶材，並且與實施例1相同地 DC濺鏟法，在基板上形成具有膜厚5 00nm之透明導 。成膜速度極爲高速，所得之透明導電膜的比電阻爲 1 (Γ4 Ω · cm之低電阻。因此，銦的微量添加相對於透 電膜完全無影響。 (實施例4) 上述實施例1中，進一步使用上述氧化鎵粉末， 以使原子數比計成爲Zn : Ti : A1 : Ga= 96.6 : 3 : C 0.2 ( Ti/ ( Zn + Ti + A1 + Ga ) = 0.03，且（A1 十 Ga (Zn + Ti + A1 + Ga ) = 0.0 04 )之方式來調配，除此 ，其他與實施例1相同而得氧化物燒結體（4 )。 份有 以使 Zn + 方式 燒結 )， 3 : In ) ’比 與實 藉由 電膜 4.4x 明導 並且 • 2 : )/ 之外 -29- 201250033 與實施例1相同地分析所得之氧化物燒結體（4 可得知Zn與Ti與A1與Ga之原子數比Zn: Ti: A: 96.6 ： 3: 0.2 ： 0.2 ( Ti/ (Zn+Ti+Al+Ga) = 0.03 (Al+Ga) / (Zn+Ti+Al+Ga ) =〇.〇〇4)。氧化 結體（4)的密度爲5.41g/cm3’比電阻爲4ιηΩ . cm 然後，除了使用氧化物燒結體（4 )之外，其他 施例1相同而製作出靶材，並且與實施例1相同地 DC濺鍍法，在基板上形成具有膜厚500nm之透明導 。成膜速度極爲高速，所得之透明導電膜的比電阻爲 1 (Γ4 Ω . cm之低電阻。因此，鋁及鎵的微薰添加相對 明導電膜完全無影響。 (實施例5) 將上述氧化鋅粉末、上述氧化鋁粉末及氧化鈦（ 粉末（TiO :高純度化學硏究所股份有限公司製， 99.99%)，以使原子數比計成爲Zn:Ti:Al=90.7: 0.3 (Ti/ (Zn+Ti+Al) = 0.09，且 Al/ (Zn+Ti )=0.00 3 )之方式投入於球磨機使其微粉末化。接 除球粒及乙醇，將所得之混合粉末放入於由石墨所構 模具（壓模），於真空下（約IPa)，藉由以石墨所 之沖壓機，以40MPa的壓力加壓，在1〇〇〇°C下進行 時的加熱處理，而得直徑100mm及厚度5mm的圓盤 化物燒結體（5 )。 與實施例1相同地分析所得之氧化物燒結體（5 G a = ，且 物燒 〇 與實 藉由 電膜 4 Αχ 於透 II) 純度 9 ： + Α1 著去 成之 構成 4小 型氧 )， -30- 201250033 可得知Zn與Ti與AI之原子數比Zn: Ti: Α1=9〇·7: 9: 0.3 (Ti/ (Zn+Ti+Al) =0.09,且 Al/ (Zn+Ti+Al )=0.003 )。氧化物燒結體（5 )的密度爲5.49g/ cm3 ’ 比電阻爲ΙΟηιΩ · cm。 然後，除了使用氧化物燒結體（5 )之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法，在基板上形成具有膜厚500nm之透明導電膜 。成膜速度極爲高速，所得之透明導電膜的比電阻爲】.3>< 1 Ο·3 Ω . cm之低電阻。因此，鋁的微量添加相對於透明導 電膜完全無影響。 (實施例6) 使用氧化鎵粉末（Ga203 :住友化學股份有限公司製 ，純度99.99% )來取代氧化鋁粉末，除此之外，其他與 實施例5相同而得氧化物燒結體（6 )。 與實施例1相同地分析所得之氧化物燒結體（6 )， 可得知Zn與Ti與Ga之原子數比Zn: Ti: Ga=90.7: 9 :0.3 (Ti/ ( Zn + Ti + Ga ) =0.09，且 Ga/ ( Zn + Ti +Zinc oxide powder, usually composed of ZnO having a wurtzite structure and consisting of oxyvalent oxygen powder composed of sintered valence oxygen powder, sometimes only in the body environment obtained by the above-mentioned step at 600 ° C: A), powder of gallium zinc oxide powder, gallium oxide zinc oxide powder, etc., -19" 201250033 In addition, it is also possible to use the ZnO which is previously sintered in a reducing gas atmosphere to cause oxygen deficiency. Further, the zinc hydroxide powder may be amorphous or have a crystal structure. As the titanium oxide powder, a titanium oxide powder represented by the above formula: TiO2_x (X = 0.1 to 1) is used, and a Ti2?3 (III) powder is preferably used. Since the crystal structure of Ti203 ( III ) is trigonal, the zinc oxide which is usually mixed with the above has a hexagonal fibrite structure as described above, so that the symmetry of the crystal structure can be made uniform, and it is easy to be sintered during solid phase sintering. Replace solid solution. The alumina powder is not particularly limited, and a general powder such as α-alumina can be used. The gallium oxide powder is not particularly limited, and a general powder such as α-gallium oxide can be used. The indium oxide powder is not particularly limited, and a general powder such as indium oxide can be used. The average particle diameter of the compound (powder) used as the raw material powder is preferably 5 / z m or less. The mixing ratio of each of the powders in the mixed powder can be appropriately set depending on the type of the compound (powder) to be used. For example, in the finally obtained oxide sintered body, the atomic ratio can be appropriately set in the above range. At this time, it is considered that the vapor pressure of zinc is higher than that of titanium, and it is easy to escape during sintering, and it is preferable to make the amount of zinc more than the intended composition of the oxide sintered body (the atomic ratio of Zn to Ti). The way to set the mixing ratio. Specifically, the ease of diffusion of zinc varies depending on the gas environment during sintering. For example, when zinc oxide powder is used, in the atmosphere or in an oxidizing gas environment, only the dispersion of the zinc oxide powder itself is caused. However, when sintering is carried out in a reducing gas atmosphere, zinc oxide is reduced to become metal zinc which is more likely to escape than zinc oxide, and the amount of disappearance of -20-201250033 增加 is increased. However, as described later, when annealing is performed in a reducing gas atmosphere after sintering, the composite oxide is formed at the time of annealing treatment, so that zinc is not easily dissipated. Therefore, regarding the amount of zinc to be added to the target composition, it is only necessary to consider the amount of the sintered gas or the like to be set, for example, when sintering is performed in the atmosphere or in an oxidizing gas atmosphere, the desired number of atoms is set. The amount of the ratio is about 1.0 to 1.05 times, and when it is sintered in a reducing gas atmosphere, it is set to about 1.1 times to 1⁄3 times the amount of the desired atomic ratio. The compound (powder) used as the raw material powder may be used alone or in combination of two or more. The molding method in the step of molding the raw material powder included in the first production method and the second production method of the present invention is not particularly limited, and examples thereof include mixing the raw material powder with an aqueous solvent and wet mixing. After the obtained slurry is sufficiently mixed, solid-liquid separation, drying, and granulation are carried out, and the obtained granules are molded. The wet mixing can be carried out, for example, by using a wet ball mill or a vibratory honing machine having a hard Zr02 ball or the like, and the mixing time when using a wet ball mill or a vibrating honing machine is preferably about 12 hours to 7 8 . hour. Although the raw material powder can be directly mixed dry, it is especially preferred to wet mix. Regarding solid-liquid separation, drying, and granulation, a generally known method can be used. When the obtained granules are molded, for example, granules can be placed in a mold frame and pressed to form. Further, when the raw material powder obtained by dry mixing or the raw material powder obtained by dry-mixing and drying is formed, for example, the raw material powder may be placed in a mold frame and pressurized to be molded. The pressurization method may be a method using a cold forming machine such as cold press molding or a single-axis molding. Regardless of whether -21 - 201250033 is cold-pressure molding or uniaxial molding, when the pressure is too low, there is a concern that a stable molded body cannot be formed. When the pressure is over-pressed, the molded body is easily broken. When the pressure is in the case of cold-pressure molding, it is usually 5 〇 MPa or more and 200 MPa or less, preferably l MPa or more and 200 MPa or less. In the case of uniaxial molding, it is usually 1 OMPa or more and 500 MPa or less. The stomach is 20 MPa or more and 50 MPa or less. When it is formed by hot pressurization using hot stamping or the like, it is not only disadvantageous in terms of manufacturing cost, but also has a fear that it is difficult to obtain a large sintered body. The shape or size of the molded body is not particularly limited, and examples thereof include a cylinder, a rectangular parallelepiped and the like. When the granulated product is obtained as a shaped body, it can be granulated after drying by a generally known method, but in this case, it is preferred to mix the binder together with the raw material powder. As the binder, for example, polyvinyl alcohol, vinyl acetate, ethyl cellulose or the like can be used. In the first production method and the second production method of the present invention, the sintering of the molded body obtained by the molding step is carried out in an inert gas atmosphere (for example, nitrogen, argon, ammonia, helium, etc.), vacuum, and reducing gas. The environment (for example, carbon dioxide, hydrogen, ammonia, etc.), the atmosphere, and the oxidizing gas atmosphere (gas having a higher oxygen concentration and higher gas) are carried out at 60 CTC to 1 500 °C. It is particularly preferable to carry out in an oxidizing gas atmosphere (a gas atmosphere having a relatively high oxygen concentration) at 1000 C to 1500 °C. When sintering is carried out in an atmosphere or an oxidizing gas atmosphere, the annealing treatment may be further carried out in an inert gas atmosphere, in a vacuum, or in a reducing gas atmosphere. This annealing treatment is performed to cause the oxide sintered body to generate oxygen defects to lower the specific resistance. When sintering is carried out in an inert gas atmosphere, in a vacuum or in a reducing gas atmosphere, when it is desired to further reduce the specific resistance, it is possible to carry out the -22-201250033 fire treatment after sintering. When the sintering temperature is less than 600 °C, the sintering does not proceed sufficiently, and the density of the target is lowered. On the other hand, when it exceeds 丨5 〇 氧化, the zinc oxide itself decomposes and disappears. In any of the above gas environments, it is preferable to carry out sintering at 1 〇〇 (rc to 1300 C. When the molded body is heated to the above-mentioned sintering temperature, the sintering speed is made uniform), and the heating rate is preferably 6 〇〇. (: Set to 5 °C / min to 10 °C / min before the end of 600 ° C to 1500 ° C, set to 1 ° C / min ~ 4 ° C / min. In any gas environment When sintering, the sintering time (that is, the holding time at the sintering temperature) is preferably set to 3 hours to 15 hours. When the sintering time is less than 3 hours, the sintered density tends to become insufficient, and the obtained oxide is obtained. In the other hand, when the strength of the sintered body is lowered, the grain growth of the sintered body becomes remarkable, and the coarsening of the pores and the increase of the maximum pore diameter tend to occur, and the result is sintering. The method of sintering in the sintering step is not particularly limited, and examples thereof include a normal pressure sintering method, a microwave sintering method, and a milli-wave sintering method. The third method of producing the oxide sintered body of the present invention (hereinafter, Only described as "the first aspect of the present invention" (3) A method for producing a product comprising: placing the raw material powder in a graphite mold material, and performing pressure sintering in a vacuum or an inert gas atmosphere at 600 ° C to 15 ° C Examples of the pressure sintering method include a hot press method, a hot isostatic pressing (HIP) method, and a discharge electro-elastic sintering method. • 23-201250033 Gas atmosphere during pressure sintering A vacuum (for example, 2 Pa or less) or an inert gas atmosphere (for example, nitrogen, argon, helium, neon, etc.) is preferably a vacuum. The pressure applied to the raw material powder during pressure sintering is preferably 20 MPa to 150 MPa. More preferably, the sintering temperature at the time of pressure sintering of 30 MPa to 100 MPa is preferably 1 〇〇〇 ° C to 1600 ° C, particularly preferably 11 〇〇. (: ~ 1400 ° C » pressure sintering time, can be adapted The sintering temperature and the amount of the raw material powder are appropriately adjusted, and are usually 30 minutes to 4 hours, and more preferably 1 hour to 2 hours. The oxide sintered body obtained by the third production method of the present invention is further reduced in specific resistance. Can be in an inert gas environment, true Annealing treatment in a medium or reducing gas atmosphere. The annealing treatment method mentioned in the description of the first, second or third manufacturing method of the present invention may, for example, introduce nitrogen gas, argon gas, chlorine gas or carbon dioxide. a method of heating a non-oxidizing gas such as hydrogen gas under normal pressure, and a method of heating under vacuum (preferably 2 Pa or less), etc., from the viewpoint of production cost, while introducing a non-oxidizing gas under normal pressure The method is more advantageous. The annealing temperature (heating temperature) is preferably from 1 0 0 ° C to 1 40 ° C, particularly preferably from 1 100 ° C to 1 300 ° C. The annealing time (heating time) is preferably from 7 hours to 15 hours, and more preferably from 8 hours to 12 hours. When the annealing temperature is less than 1 〇〇〇° (:, there is a concern that the oxygen deficiency caused by the annealing treatment is insufficient. On the other hand, when the annealing temperature exceeds 1 400 °C, the zinc is easily dispersed, and the obtained oxidation is obtained. The composition of the sintered body (the atomic ratio of Zn to Ti) is different from the desired ratio. -24- 201250033 The oxide sintered body obtained by the first, second or third production method of the present invention is usually It has a density of 5.3 g/cm 3 or more and a specific resistance of 12 m Ω · cm or less. (Target) The target of the present invention is a target used in various film forming methods, particularly in sputtering method ( The target material in the film formation by the DC sputtering method which is preferably mass-produced. The target material of the present invention is obtained by processing the above-described oxide sintered body of the present invention into a predetermined shape and a predetermined size. The method of obtaining the target material by the oxide sintered body of the invention is not particularly limited, and a generally known method can be suitably employed. For example, after the oxide sintered body is subjected to planar honing or the like, it is cut into a predetermined size and attached thereto. Supporting seat ' thereby obtaining the invention A target material may be formed by arranging a plurality of oxide sintered bodies into a divided shape to form a large-area target (composite target). The target of the present invention is preferably used as a sputtering target, and is particularly preferable. The method for producing a transparent conductive film using the target of the present invention is not particularly limited, and a generally known method can be suitably employed, for example, by sputtering, ion evaporation, or the like. A transparent conductive film is produced by using a target of the present invention by a pulsed laser deposition (PLD) method or an electron beam (eb) evaporation method. The method for forming a zinc oxide-based transparent conductive film of the present invention is preferably a sputtering method. Particularly preferred is a DC sputtering method. The -25-201250033 transparent conductive film formed by using the oxide sintered body of the present invention or the target of the present invention has excellent electrical conductivity and chemical durability (heat resistance, moisture resistance) Properties, drug resistance (alkali resistance, acid resistance, etc.). Such a transparent conductive film can be preferably used, for example, in liquid crystal displays, plasma displays, inorganic EL (electroluminescence) displays, organic EL displays, and electronics. Transparent electricity such as paper a window electrode of a photoelectric conversion element of a solar cell; an electrode of an input device such as a transparent touch panel; an electromagnetic shielding film of an electromagnetic shielding cover; and the use of the oxide sintered body of the present invention or the target of the present invention The transparent conductive film formed may be used in combination with another metal film or a metal oxide film as a transparent electromagnetic wave absorber, an ultraviolet absorber, or a transparent semiconductor device. [Embodiment] The following series are given by way of examples and comparative examples. The present invention is not limited to the following examples without departing from the spirit and scope of the invention. In the examples, the specific resistance of the sintered body and the transparent conductive film is obtained by the following method. The specific resistance > specific resistance was measured by a four-terminal four-probe method using a resistivity meter ("LORESTA-GP, MCP-T610" manufactured by Mitsubishi Chemical Corporation). Specifically, four needle electrodes are placed linearly on the sample, and a constant current flows between the two probes on the outer side and the two probes on the inner side, and the potential difference generated between the inner two probes is measured. Find the resistance. -26-201250033 (Example 1) Zinc oxide powder (ZnO: Wako Pure Chemical Industries, Ltd., special grade), titanium oxide (m) powder (Ti203: High Purity Chemical Research Institute Co., Ltd., purity 99.99) %) and alumina powder (Al2〇3: manufactured by Sumitomo Chemical Co., Ltd., purity 99.99%), so that the atomic ratio is Zn: Ti: Al = 96.8: 3: 0_2 (Ti / (Zn + Ti + Al) ) = 0.03, and Al/(Zn + Ti + Al) = 0.002 ) was formulated to obtain a mixture. Then, the obtained mixture was placed in a mold, and molded by a uniaxial molding at a molding pressure of 500 kg/cm 2 to obtain a disk-shaped formed body having a diameter of 100 mm and a thickness of 5 mm. This molded body was sintered at 1,200 ° C for 4 hours under an argon atmosphere under normal pressure (1.03 3 2 5 · 102 kPa) to obtain an oxide sintered body (1). The obtained oxide sintered body (1) was analyzed by an energy dispersive fluorescent X-ray apparatus ("EDX-700L" manufactured by Shimadzu Corporation), and the atomic ratio of Zn to Ti and A1 was known to be Zn: Ti : Al = 96.8 : 3 : 0.2 ( Ti / ( Zn + Ti + A1 ) = 0.03, and Al / ( Zn + Ti + A1 ) = 0.002 ). The density of the sintered body was 5.41 § / (: 1113, and the specific resistance was 5 ηη Ω · cm. The obtained oxide sintered body (1) was processed into a disk shape of 50 mm φ to obtain a target, and the target was used. A transparent conductive film is formed by a DC sputtering method to obtain a transparent conductive substrate, that is, a transparent substrate (an alkali-free glass having a thickness of 7 mm: Eagle XG manufactured by Corning Co., Ltd.) and the obtained IG material are placed in a sputtering apparatus. (Canon Anelva Engineering shares -27 - 201250033 limited company "E-200"), argon gas (purity 99.9995% or more, Ar pure gas = 5N) is introduced at 12sccm, at a pressure of 0.5Pa, input power 100W, substrate temperature Sputtering was carried out at 25 ° C, and a transparent conductive film having a film thickness of 500 nm was formed on the substrate. The film formation speed was extremely high, and the specific resistance of the obtained transparent conductive film was 4.4 x 1 0_4 Ω · cm. Therefore, the trace addition of aluminum has no effect at all on the transparent conductive film. (Example 2) Alumina powder was replaced with gallium oxide powder (Ga203: manufactured by Sumitomo Chemical Co., Ltd., purity: 99.99%). , other with embodiment 1 The oxide sintered body (2) was obtained in the same manner. The obtained oxide sintered body (2) was analyzed in the same manner as in Example 1, and the atomic ratio of Zn to Ti and Ga was found to be Zn: Ti : Ga = 96.8 : 3 : 0.2 (Ti / (Zn + Ti + Ga) = 0.03, and Ga / (Zn + Ti + Ga) = 0.002 ). The oxide sintered body (2) has a density of 5.41 g / cm 3 and a specific resistance of 6 ώ Ω · cm. Then, a target material was produced in the same manner as in Example 1 except that the oxide sintered body (2) was used, and a film thickness of 50,000 nm was formed on the substrate by DC sputtering as in Example 1. The transparent conductive film has a high film formation speed, and the specific resistance of the obtained transparent conductive film is 4.4X 1 (low resistance of Γ4 Ω · cm. Therefore, the trace addition of gallium has no influence at all on the transparent conductive film. (Example 3 -28- 201250033 The alumina powder was replaced with indium oxide powder (Ιη203: manufactured by the company of High Purity Chemical Research Institute, purity 99.99%), and the atomic ratio was Zn : Ti : In = 96.7 : 3 : 0.3 ( Ti / ( Ti + In ) = 0.03 , and In / (Zn + Ti + In) = 0.003) to be formulated, otherwise, the same as in the first embodiment The oxide body (3) was obtained. The obtained oxide sintered body was analyzed in the same manner as in Example 1 (3, the atomic ratio of Zn to Ti and In was found to be Zn: Ti : In = 96.7 : 0.3 ( Ti / (Zn + Ti) +In) = 0.03, and In/ ( Zn + Ti + = 0.003 ). The oxide sintered body (3) had a density of 5.41 g/cm3 and a resistance of 9 χηΩ·cm. Then, a target material was produced in the same manner as in Example 1 except that the oxide sintered body (3) was used, and a transparent sputtering method having a film thickness of 500 nm was formed on the substrate by the DC sputtering method as in Example 1. The film formation speed is extremely high, and the specific resistance of the obtained transparent conductive film is 1 (Γ4 Ω·cm low resistance. Therefore, the trace addition of indium has no influence at all on the electricity transmission film. (Example 4) In the above Example 1 Further, the above gallium oxide powder is used so that the atomic ratio is Zn : Ti : A1 : Ga = 96.6 : 3 : C 0.2 ( Ti / ( Zn + Ti + A1 + Ga ) = 0.03 , and (A1 ten Ga ( In the same manner as in Example 1, the oxide sintered body (4) was obtained in the same manner as in Example 1 except that Zn + Ti + A1 + Ga ) = 0.0 04 ). The parts were sintered in a Zn + manner, 3 : In ) 'The ratio of the Zn and Ti and the A1 and Ga are analyzed in the same manner as in the first embodiment except that the ratio is 4.4x and the other is -29-201250033. Atomic number ratio Zn: Ti: A: 96.6 : 3: 0.2 : 0.2 ( Ti / (Zn + Ti + Al + Ga) = 0.03 (Al + Ga) / (Zn + Ti + Al + Ga ) = 〇. 4) The density of the oxidized body (4) is 5.41 g/cm3', and the specific resistance is 4 ηηΩ. cm. Then, except for using the oxide sintered body (4), the other examples 1 are identical to produce a target, and Embodiment 1 identically DC In the plating method, a transparent guide having a film thickness of 500 nm is formed on the substrate. The film formation speed is extremely high, and the specific resistance of the obtained transparent conductive film is 1 (Γ4 Ω·cm low resistance. Therefore, the addition of aluminum and gallium to the micro-smoke is relatively The conductive film of the present invention has no effect at all. (Example 5) The zinc oxide powder, the above alumina powder, and titanium oxide (powder (TiO: 99.99%, manufactured by High Purity Chemical Research Co., Ltd.) were used to make the atomic ratio In the manner of Zn:Ti:Al=90.7:0.3 (Ti/(Zn+Ti+Al)=0.09, and Al/(Zn+Ti)=0.00 3 ), it is put into a ball mill to be finely powdered. Granules and ethanol, the obtained mixed powder is placed in a mold (die) made of graphite, under vacuum (about IPa), and pressed at a pressure of 40 MPa by a press machine made of graphite, at 1 Torr. The heat treatment at the time of 〇°C was carried out to obtain a disk-formed sintered body (5) having a diameter of 100 mm and a thickness of 5 mm. The obtained oxide sintered body (5 G a = , and the material was burned) was analyzed in the same manner as in Example 1. And the actual membrane 4 Αχ through the II) purity 9 : + Α1 to form a small oxygen () 4, -30- 20 1250033 It is known that the atomic ratio of Zn to Ti and AI is Zn: Ti: Α1=9〇·7: 9: 0.3 (Ti/ (Zn+Ti+Al) =0.09, and Al/(Zn+Ti+Al) =0.003 ). The oxide sintered body (5) had a density of 5.49 g/cm3' and a specific resistance of ΙΟηιΩ·cm. Then, a target material was produced in the same manner as in Example 1 except that the oxide sintered body (5) was used, and a transparent film having a film thickness of 500 nm was formed on the substrate by DC sputtering as in Example 1. Conductive film. The film formation speed is extremely high, and the specific resistance of the obtained transparent conductive film is a low resistance of .3><1 Ο·3 Ω·cm. Therefore, the trace addition of aluminum has no effect at all on the transparent conductive film. (Example 6) An oxide sintered body (6) was obtained in the same manner as in Example 5 except that the alumina powder was replaced by a gallium oxide powder (Ga203: manufactured by Sumitomo Chemical Co., Ltd., purity: 99.99%). The obtained oxide sintered body (6) was analyzed in the same manner as in Example 1, and the atomic ratio of Zn to Ti and Ga was found to be Zn: Ti: Ga = 90.7: 9 : 0.3 (Ti / ( Zn + Ti + Ga ) =0.09, and Ga/ ( Zn + Ti +

Ga ) = 0.003 )。氧化物燒結體（6)的密度爲5.49g/cm3 ，比電阻爲ΙΟπιΩ . cm。 然後，除了使用氧化物燒結體（6)之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法’在基板上形成具有膜厚500ηιη之透明導電膜 。成膜速度極爲高速’所得之透明導電膜的比電阻爲15χ -31 - 201250033 1〇-3Ω . cm之低電阻。因此’鎵的微量添加相對於透明導 電膜完全無影響。 (實施例7) 上述實施例5中’進一步使用上述氧化鎵粉末，並且 以使原子數比計成爲Zn : Ti : A1 : Ga= 90.4 : 9 : 0.2 : 0.2(Ti/ (Zn+Ti+Al+Ga) =0.09’ 且（Al+Ga) / (Zn + Ti + A1 + Ga ) = 0.004 )之方式來調配，除此之外 ，其他與實施例5相同而得氧化物燒結體（7 )。 與實施例1相同地分析所得之氧化物燒結體（7 )， 可得知Zn與Ti與A1與Ga之原子數比Zn : Ti : AI : Ga = 90.4: 9: 0.2: 0.2 (Ti/ (Zn+Ti+Al+Ga) = 0.09 » 且（Al+Ga) / (Zn+Ti+Al+Ga) = 0.004 )。氧化物 燒結體（7)的密度爲5.49g/cm3，比電阻爲ΙΟπιΩ . cm ο 然後，除了使用氧化物燒結體（7)之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法，在基板上形成具有膜厚5 0 0 nm之透明導電膜 。成膜速度極爲高速，所得之透明導電膜的比電阻爲1.3x 1(Γ3 Ω · cm之低電阻。因此，鋁及鎵的微董添加相對於透 明導電膜完全無影響。 (實施例8) 將上述氧化鋅粉末、上述氧化鈦（II)粉末、及上述 -32- 201250033 氧化銦粉末，以使原子數比計成爲Zn : Ti : In = 96.2 : 3.4 ： 0.4(Ti/ (Zn+Ti+In) = 0.034，且 In/ (Zn+Ti + In) = 0.0 04 )之方式來調配而得混合物。接著將所得之 混合物放入於模具，藉由單軸模壓以成形壓500kg/ cm2 來成形，而得直徑l〇〇mm及厚度5mm的圓盤狀成形體。 將該成形體，於常壓（1.01325· 102kP a)的大氣環境下， 在140(TC中燒結4小時而得氧化物燒結體（8 )。 與實施例1相同地分析所得之氧化物燒結體（8 )， 可得知Zn與Ti與In之原子數比Zn : Ti : In= 96.2 : 3.4 :0.4 (Ti/ (Zn+Ti+In) = 0.034，且 In/ (Zn+Ti + In) = 0.004 )。氧化物燒結體（8)的密度爲5.52g/Cm3 ’比電阻爲8ιηΩ . cm。 然後，除了使用氧化物燒結體（8)之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法，在基板上形成具有膜厚5 0 Onm之透明導電膜 。成膜速度極爲高速，所得之透明導電膜的比電阻爲4· lx 10_4Ω _ cm之低電阻。因此，銦的微量添加相對於透明導 電膜完全無影響。 (實施例9 ) 上述實施例8中，進一步使用上述氧化鋁粉末，並且 以使原子數比計成爲Zn: Ti: In: Α1=96·2: 3.4: 0_2: 0.2 (Ti/ (Zn+Ti+In+Al) = 0.034，且（In+Al) / (Zn+ Ti+ In+ Al) = 0.0 0 4 )之方式來調配，除此之外， -33- 201250033 其他與實施例8相同而得氧化物燒結體（9 )。 與實施例1相同地分析所得之氧化物燒結體（9 )， 可得知Zn與Ti與In與A1之原子數比Zn : Ti : In : A1 = 96.2 : 9 : 3.4 : 0.2 ： 0.2 ( Ti / ( Zn + Ti + In + A1 )= 0.034，且（in+Al) / (Zn+Ti+In+Al) = 0.004 )。 氧化物燒結體（9)的密度爲5.52g/cm3，比電阻爲8ιηΩ • cm ° 然後，除了使用氧化物燒結體（9)之外，其他與實 施例1相同而製作出靶材，並且與實施例1相同地藉由 DC濺鍍法，在基板上形成具有膜厚5 00nm之透明導電膜 。成膜速度極爲高速，所得之透明導電膜的比電阻爲4.lx 1 (Τ4 Ω _ cm之低電阻。因此，銦及鋁的微量添加相對於透 明導電膜完全無影響。 (比較例1 ) 使用氧化鈦（IV )粉末（Ti〇2 :和光純藥工業股份有 限公司製，純度99.99% )來取代氧化鈦（III )粉末，不 使用氧化鋁粉末，並且以使原子數比計成爲Zn: Ti=97: 3(Ti/ (Zn+Ti) = 0.03)之方式來調配，除此之外，其 他與實施例1相同而得氧化物燒結體（C 1 )。 與實施例1相同地分析所得之氧化物燒結體（C 1 )， 可得知Zn與Ti之原子數比Zn : Ti = 97 : 3 ( Ti/ ( Zn + Ti ) = 0.03 )。氧化物燒結體（Cl )的密度爲5.3 8g/ cm3 ，比電阻爲6.21ίΩ · cm。 -34- 201250033 接著使用氧化物燒結體（c 1 )，與實施例1相同而製 作出靶材，並且與實施例1相同地藉由DC濺鍍法嘗試形 成透明導電膜。然而，由於所得之靶材（氧化物燒結體（ C 1 ))的電阻高，故無法成膜。該靶材，雖然可藉由即使 是絕緣體的靶材亦可成膜之RF濺鍍法來成膜，但在適合 於工業生產之DC濺鍍法中無法成膜。 (比較例2) 以使原子數比計成爲Zn : Ti= 91 : 9 ( Ti/ ( Zii+ Ti )=0.09 )之方式來調配氧化鋅粉末及氧化鈦（IV)粉末 ，除此之外，其他與比較例1相同而得氧化物燒結體（C2 )° 與實施例1相同地分析所得之氧化物燒結體（C2 ) ’ 可得知Zn與Ti之原子數比Zn : Ti= 91 : 9 ( Ti/ ( Zn + Ti) =0.09)。氧化物燒結體（C2)的密度爲5.30g/cm3 ，比電阻爲測定臨限以上（超負載）之極高電阻。 接著使用氧化物燒結體（C2 )，與實施例1相同而製 作出靶材，並且與實施例1相同地藉由DC濺鍍法嘗試形 成透明導電膜。然而，由於所得之靶材（氧化物燒結體（ C2))的電阻高，故無法成膜。該靶材，雖然可藉由即使 是絕緣體的靶材亦可成膜之RF濺鍍法來成膜，但在適合 於工業生產之DC濺鍍法中無法成膜。 (比較例3) -35- 201250033 使用氧化鈦（IV )粉末來取代氧化鈦（ 使用氧化鋁粉末，並且以使原子數比計成爲 9(Ti/ (Zn+Ti) =0.09)之方式來調配， 他與實施例5相同而得氧化物燒結體（C 3 ) 與實施例1相同地分析所得之氧化物燒 可得知Zn與Ti之原子數比Zn : Ti= 91 : S Ti) = 0.09)。氧化物燒結體（C3)的密度: ，比電阻爲測定臨限以上（超負載）之極高 接著使用氧化物燒結體（C3)，與實施 作出靶材，並且與實施例1相同地藉由DC 成透明導電膜。然而，由於所得之靶材（氧 C3))的電阻高，故無法成膜。該靶材，雖 是絕緣體的靶材亦可成膜之RF濺鍍法來成 於工業生產之DC濺鍍法中無法成膜。 Π)粉末，不 Zn ： Ti = 91 ： 除此之外，其 〇 結體（C3 )， (Ti/ ( Zn + % 5.49g / cm3 電阻。 例1相同而製 濺鍍法嘗試形 化物燒結體（ 然可藉由即使 膜，但在適合 -36-Ga ) = 0.003 ). The oxide sintered body (6) had a density of 5.49 g/cm3 and a specific resistance of ΙΟπιΩ.cm. Then, a target material was produced in the same manner as in Example 1 except that the oxide sintered body (6) was used, and a transparent film having a film thickness of 500 nm was formed on the substrate by DC sputtering as in Example 1. Conductive film. The film formation speed is extremely high. The specific resistance of the obtained transparent conductive film is 15 χ -31 - 201250033 1 〇 -3 Ω. Therefore, the microaddition of gallium has no effect at all on the transparent conductive film. (Example 7) In the above Example 5, 'the above gallium oxide powder was further used, and the atomic ratio was Zn : Ti : A1 : Ga = 90.4 : 9 : 0.2 : 0.2 (Ti / (Zn + Ti + Al) Oxide sintered body (7) was obtained in the same manner as in Example 5 except that +Ga) = 0.09' and (Al + Ga) / (Zn + Ti + A1 + Ga ) = 0.004 ) . The obtained oxide sintered body (7) was analyzed in the same manner as in Example 1, and the atomic ratio of Zn to Ti and A1 to Ga was found to be Zn: Ti : AI : Ga = 90.4: 9: 0.2: 0.2 (Ti/ ( Zn+Ti+Al+Ga) = 0.09 » and (Al+Ga) / (Zn+Ti+Al+Ga) = 0.004 ). The density of the oxide sintered body (7) was 5.49 g/cm3, and the specific resistance was ΙΟπιΩ. cm ο Then, the target was produced in the same manner as in Example 1 except that the oxide sintered body (7) was used, and In the same manner as in Example 1, a transparent conductive film having a film thickness of 500 nm was formed on the substrate by DC sputtering. The film formation speed is extremely high, and the specific resistance of the obtained transparent conductive film is 1.3 x 1 (low resistance of Γ3 Ω · cm. Therefore, the addition of aluminum and gallium has no effect at all on the transparent conductive film. (Example 8) The zinc oxide powder, the titanium oxide (II) powder, and the above -32 to 201250033 indium oxide powder are made to have an atomic ratio of Zn : Ti : In = 96.2 : 3.4 : 0.4 (Ti / (Zn + Ti + The mixture was prepared by in) = 0.034, and In / (Zn + Ti + In) = 0.0 04 ). The resulting mixture was placed in a mold and formed by uniaxial molding at a forming pressure of 500 kg/cm 2 . A disk-shaped molded body having a diameter of 10 mm and a thickness of 5 mm was obtained. The molded body was sintered at 140 (TC for 4 hours) under atmospheric pressure (1.01325·102 kPa). The obtained oxide sintered body (8) was analyzed in the same manner as in Example 1, and the atomic ratio of Zn to Ti and In was found to be Zn : Ti : In = 96.2 : 3.4 : 0.4 (Ti / (Zn) +Ti+In) = 0.034, and In/(Zn+Ti + In) = 0.004 ). The density of the oxide sintered body (8) is 5.52 g/cm 3 'the specific resistance is 8 ηηΩ · cm. A target material was produced in the same manner as in Example 1 except that the oxide sintered body (8) was used, and a film thickness of 50 Onm was formed on the substrate by DC sputtering as in Example 1. The transparent conductive film has a high film formation speed, and the specific resistance of the obtained transparent conductive film is a low resistance of 4·lx 10_4 Ω_cm. Therefore, the trace addition of indium has no influence at all on the transparent conductive film. (Example 9) In Example 8, the above alumina powder was further used, and the atomic ratio was determined to be Zn: Ti: In: Α1 = 96·2: 3.4: 0_2: 0.2 (Ti / (Zn + Ti + In + Al) = Oxide sintered body (9) was obtained in the same manner as in Example 8 except that (In+Al) / (Zn + Ti + In + Al) = 0.0 0 4 ) was blended. The obtained oxide sintered body (9) was analyzed in the same manner as in Example 1, and the atomic ratio of Zn to Ti and In to A1 was found. Zn : Ti : In : A1 = 96.2 : 9 : 3.4 : 0.2 : 0.2 ( Ti / ( Zn + Ti + In + A1 ) = 0.034, and (in + Al) / (Zn + Ti + In + Al) = 0.004 ). The oxide sintered body (9) had a density of 5.52 g/cm 3 and a specific resistance of 8 ηη Ω • cm °, and then a target was produced in the same manner as in Example 1 except that the oxide sintered body (9) was used, and In the same manner as in Example 1, a transparent conductive film having a film thickness of 500 nm was formed on the substrate by DC sputtering. The film formation speed is extremely high, and the specific resistance of the obtained transparent conductive film is 4.lx 1 (low resistance of Τ4 Ω_cm. Therefore, the trace addition of indium and aluminum has no influence at all on the transparent conductive film. (Comparative Example 1) A titanium oxide (IV) powder (Ti〇2: manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.99%) was used in place of the titanium oxide (III) powder, and no alumina powder was used, and the atomic ratio was determined to be Zn: An oxide sintered body (C 1 ) was obtained in the same manner as in Example 1 except that Ti = 97: 3 (Ti / (Zn + Ti) = 0.03). The same analysis as in Example 1 was carried out. The obtained oxide sintered body (C 1 ) has an atomic ratio of Zn to Ti of Zn : Ti = 97 : 3 ( Ti / ( Zn + Ti ) = 0.03 ). The density of the oxide sintered body (Cl ) is 5.3 8 g / cm 3 , specific resistance was 6.21 ίΩ · cm. -34 - 201250033 Next, using the oxide sintered body (c 1 ), a target was produced in the same manner as in Example 1, and was sprayed by DC as in Example 1. The plating method attempts to form a transparent conductive film. However, since the obtained target (oxide sintered body (C 1 )) has high electrical resistance, it cannot be formed. The film can be formed by RF sputtering using a target of an insulator, but it cannot be formed by a DC sputtering method suitable for industrial production. (Comparative Example 2) The zinc oxide powder and the titanium oxide (IV) powder were prepared so that the atomic ratio was Zn : Ti = 91 : 9 ( Ti / ( Zii + Ti ) = 0.09 ), and otherwise the same as in Comparative Example 1. The obtained oxide sintered body (C2) was analyzed in the same manner as in Example 1 to obtain an atomic ratio of Zn to Ti: Zn : Ti = 91 : 9 ( Ti / ( Zn + ) Ti) = 0.09) The density of the oxide sintered body (C2) is 5.30 g/cm3, and the specific resistance is extremely high resistance above the measurement limit (overload). Next, the oxide sintered body (C2) is used, and examples The target was produced in the same manner, and a transparent conductive film was attempted by DC sputtering in the same manner as in Example 1. However, since the obtained target (oxide sintered body (C2)) had high electric resistance, it could not be formed. Membrane. Although the target can be formed by RF sputtering by forming a target of an insulator, it is suitable for industrial production. In the DC sputtering method, film formation was impossible. (Comparative Example 3) -35- 201250033 The titanium oxide (IV) powder was used instead of titanium oxide (using alumina powder, and the atomic ratio was 9 (Ti/ (Zn+) Ti(=0.09) was prepared in the same manner as in Example 5, and the obtained oxide sintered body (C3) was analyzed in the same manner as in Example 1. The atomic ratio of Zn to Ti was found to be Zn: Ti = 91 : S Ti) = 0.09). Density of the oxide sintered body (C3): The specific resistance is extremely high above the measurement threshold (overload), and then the oxide sintered body (C3) is used, and the target is made and the same as in the first embodiment. The DC is a transparent conductive film. However, since the obtained target (oxygen C3) has high electrical resistance, film formation cannot be achieved. This target material, which is an insulator target, can also be formed into a film by RF sputtering to form a film in a DC sputtering method which is industrially produced. Π) powder, not Zn : Ti = 91 : In addition to this, the tantalum body (C3 ), (Ti / ( Zn + % 5.49g / cm3 resistance. Example 1 is the same as the sputtering method to try to form a sintered body (But by even the film, but at -36-

Claims (1)

201250033 七、申請專利範圍： 1. 一種氧化物燒結體，其特徵爲實質上由鋅，鈦，氧 ，與選自由鋁、鎵及銦所組成之群組的至少1種微量添加 元素（TE )所構成之氧化物燒結體， 該鈦係來自由式：Ti02.x ( X= 0· 1〜1 )表示之低原子 價氧化鈦。 2 .如申請專利範圍第1項之氧化物燒結體，其中前述 氧化物燒結體具有5.3g/cm3以上的密度，並且具有12m Ω · cm以下的比電阻。 3 .如申請專利範圍第1或2項之氧化物燒結體，其中 前述至少1種微量添加元素（TE )相對於前述鋅、前述鈦 及前述至少1種微量添加元素（TE )的合計之原子數比 [TE/ (Zn+Ti+TE)]，超過 0.001 且未達 0.005。 4. 如申請專利範圍第1至3項中任一項之氧化物燒結 體，其中前述鈦相對於前述鋅、前述鈦及前述至少1種微 量添加元素（TE)的合計之原子數比[Ti/ (Zn+Ti+TE )]，超過0.02且爲0.1以下。 5. —種方法，其爲製造出如申請專利範圍第1至4項 中任一項之氧化物燒結體之方法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟，以及 將藉由該成形步驟所得之成形體，在真空中、還原氣 體環境中或非活性氣體環境中，於60〇°C〜1 500 °C中進行 燒結之步驟； -37- 201250033 (A) 前述由式：TiO2-X(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：TiO2.x(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 6. —種方法，其爲製造出如申請專利範圍第1至4項 中任一項之氧化物燒結體之方法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於60(TC〜1 5 00 °C中進行燒結之步驟，以 及 將藉由該燒結步驟所得之燒結體，在非活性氣體環境 中、真空中或還原氣體環境中進行退火處理之步驟： (A) 前述由式：TiO2_x(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：Ti02.x(X=〇.l〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 7. 如申請專利範圍第5項之方法，其中前述退火處理 是在選自由氮氣環境、氬氣環境、氦氣環境、二氧化碳氣 體環境及氫氣環境所組成之群組的至少一種氣體環境中進 -38- 201250033 行。 8 .—種方法，其爲製造出如申請專利範圍第1至4項 中任一項之氧化物燒結體之方法，其係包含： 將含有以下所示之（A )或（B )的混合粉之原料粉放 入於石墨製的模材中，在真空中或非活性氣體環境中，於 6 00°C〜150CTC中進行加壓燒結之步驟； (A) 前述由式：TiO2-X(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：ΤίΟ2·χ(Χ=0·1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 9 .如申請專利範圍第8項之方法，其中前述加壓燒結 步驟爲熱模壓燒結步驟。 1 〇 · —種靶材，其特徵係加工如申請專利範圍第1至4 項中任一項之氧化物燒結體而得。 1 1 · 一種方法，爲製造出如申請專利範圍第1 〇項之靶 材之方法，其係包含： 使含有以下所示之（A )或（Β )的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在真空中、還原氣 體環境中或非活性氣體環境中，於600 t：〜1500 °C中進行 燒結之步驟，以及 加工該燒結步驟中所得之氧化物燒結體而得祀材之步 -39- 201250033 驟； (A) 前述由式：Ti〇2.x(X=〇.l〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：TiO2.x(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 12. —種方法，其爲製造出如申請專利範圍第1〇項之 靶材之方法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於6 0 0 °C〜1 5 0 0 °C中進行燒結之步驟， 將藉由該燒結步驟所得之燒結體，在非活性氣體環境 中、真空中或還原氣體環境中進行退火處理之步驟，以及 加工該退火處理步驟中所得之氧化物燒結體而得靶材 之步驟； (A) 前述由式：Ti〇2.x(x=o.i〜1)表示之低原子 價氧化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：Ti〇2.x(X=0.1〜1)表示之低原子 價氧化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 13. —種方法，其爲製造出如申請專利範圍第10項之 -40- 201250033 靶材之方法，其係包含： 將含有以下所示之（A)或（B)的混合粉之原料粉放 入於石墨製的模材中’在真空中或非活性氣體環境中，於 600°C〜1 500°C中進行加壓燒結之步驟，以及 加工該加壓燒結步驟中所得之氧化物燒結體而得靶材 之步驟； (A) 前述由式：Ti02_x(X=〇.l〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：TiO2.x(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 14.如申請專利範圍第10項之靶材，其係使用在依據 濺鍍法所進行之成膜。 1 5 . —種如申請專利範圍第1 0項之靶材的使用方式， 其係用作爲濺鍍靶材。 16.—種方法，其爲製造出氧化鋅系透明導電膜之方 法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在真空中、還原氣 體環境中或非活性氣體環境中’於600°C〜1 5 00 °C中進行 燒結之步驟， 加工該燒結步驟中所得之氧化物燒結體而得靶材之步 -41 - 201250033 驟，以及 使用該靶材來形成透明導電膜之步驟； (A )前述由式：Ti02-x (Χ=0.〗〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (Β)前述由式：TiO2.x(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 17.—種方法，其爲製造出氧化鋅系透明導電膜之方 法，其係包含： 使含有以下所示之（A)或（B)的混合粉之原料粉成 形之步驟， 將藉由該成形步驟所得之成形體，在大氣環境中或氧 化氣體環境中，於600 °C〜1 5 00 °C中進行燒結之步驟， 將藉由該燒結步驟所得之燒結體，在非活性氣體環境 中、真空中或還原氣體環境中進行退火處理之步驟， 加工該退火處理步驟中所得之氧化物燒結體而得靶材 之步驟，以及 使用該靶材來形成透明導電膜之步驟； (A) 前述由式：TiO2.x(X=0.1〜1)表示之低原子 價氧化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：Ti〇2.x(x=〇.l〜1)表示之低原子 價氧化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 -42- 201250033 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 18. —種方法，其爲製造出氧化鋅系透明導電膜之方 法，其係包含： 將含有以下所示之（A)或（B)的混合粉之原料粉放 入於石墨製的模材中，在真空中或非活性氣體環境中，於 6 0 0 °C〜1 5 0 0 °C中進行加壓燒結之步驟， 加工該加壓燒結步驟中所得之氧化物燒結體而得靶材 之步驟，以及 使用該靶材來形成透明導電膜之步驟； (A) 前述由式：TiO2-X(X=0.1〜1)表示之低原子 價氧化鈦粉，與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氧化鋅粉之混合粉， (B) 前述由式：TiO2-x(X=0.1〜1)表示之低原子 價氧化鈦粉’與選自由氧化鋁粉、氧化鎵粉及氧化銦粉所 組成之群組的至少1種粉，與氫氧化鋅粉之混合粉。 -43- 201250033 四、指定代表圖： (一） 本案指定代表圖為：無 (二） 本代表圖之元件符號簡單說明：無 201250033 五 本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無201250033 VII. Patent application scope: 1. An oxide sintered body characterized by substantially at least one trace addition element (TE) selected from the group consisting of aluminum, gallium and indium. The oxide sintered body composed of the low-valent titanium oxide represented by the formula: Ti02.x (X = 0·1 to 1). 2. The oxide sintered body according to claim 1, wherein the oxide sintered body has a density of 5.3 g/cm3 or more and a specific resistance of 12 mΩ·cm or less. 3. The oxide sintered body according to claim 1 or 2, wherein the at least one trace addition element (TE) is atomic to the total of the zinc, the titanium, and the at least one trace addition element (TE). The ratio [TE/(Zn+Ti+TE)] exceeds 0.001 and does not reach 0.005. 4. The oxide sintered body according to any one of claims 1 to 3, wherein the atomic ratio of the titanium to the total of the zinc, the titanium, and the at least one trace addition element (TE) is [Ti / (Zn + Ti + TE )], exceeding 0.02 and being 0.1 or less. A method of producing an oxide sintered body according to any one of claims 1 to 4, which comprises: mixing a mixture containing (A) or (B) shown below The step of forming the powder raw material powder, and the step of sintering the molded body obtained by the forming step in a vacuum, a reducing gas atmosphere or an inert gas atmosphere at 60 ° C to 1 500 ° C ; -37- 201250033 (A) The above formula: TiO2-X (X=0.1~1) represents a low valence titanium oxide powder, and is selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder. At least one powder, a mixed powder with zinc oxide powder, (B) a low atomic weight titanium oxide powder represented by the formula: TiO2.x (X = 0.1 to 1), and selected from alumina powder, gallium oxide powder And a mixed powder of at least one powder of the group consisting of indium oxide powder and zinc hydroxide powder. A method of producing an oxide sintered body according to any one of claims 1 to 4, which comprises: mixing a mixture containing (A) or (B) shown below The step of forming the powder raw material powder, the step of sintering the molded body obtained by the forming step in an atmosphere or an oxidizing gas atmosphere at 60 (TC to 1 500 ° C), and The step of annealing the sintered body obtained in the sintering step in an inert gas atmosphere, in a vacuum or in a reducing gas atmosphere: (A) The low-valent titanium oxide powder represented by the formula: TiO2_x (X=0.1 〜1) And at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and a powder mixed with zinc oxide powder, (B) the above formula: Ti02.x (X=〇.l ～1) A low-atomic titanium oxide powder and a mixed powder of at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. The method of claim 5, wherein the annealing treatment is selected from a nitrogen atmosphere, argon In at least one gas environment consisting of a group consisting of environment, helium environment, carbon dioxide gas environment and hydrogen environment, enter -38-201250033. 8. A method, which is manufactured as in the scope of claims 1 to 4 The method of any one of the oxide sintered bodies, comprising: placing a raw material powder containing a mixed powder of (A) or (B) shown below in a graphite molded material, in a vacuum or inactive a step of pressure sintering in a gas atmosphere at 600 ° C to 150 CTC; (A) a low valence titanium oxide powder represented by the formula: TiO2-X (X = 0.1 to 1), and selected from alumina At least one powder of the group consisting of powder, gallium oxide powder and indium oxide powder, and a powder mixed with zinc oxide powder, (B) the above formula: ΤίΟ2·χ (Χ=0·1~1) is low a valent atomic titanium oxide powder, and a mixed powder of at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. 9. As claimed in claim 8 The method wherein the pressure sintering step is a hot stamping sintering step. 1 〇·- a target, The characterization is obtained by processing the oxide sintered body according to any one of claims 1 to 4. 1 1 · A method for producing a target according to the first aspect of the patent application, which comprises : a step of forming a raw material powder containing a mixed powder of (A) or (Β) shown below, using a shaped body obtained by the forming step in a vacuum, a reducing gas atmosphere or an inert gas atmosphere, The step of sintering at 600 t: 1500 ° C, and the processing of the oxide sintered body obtained in the sintering step to obtain a coffin step - 39 - 201250033; (A) The above formula: Ti 〇 2. x (X=〇.l~1) represents a low valence titanium oxide powder, and a powder mixed with at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc oxide powder (B) The low-valent titanium oxide powder represented by the formula: TiO2.x (X=0.1 to 1), and at least one selected from the group consisting of alumina powder, gallium oxide powder, and indium oxide powder. Powder, mixed powder with zinc hydroxide powder. 12. A method of producing a target material according to the first aspect of the patent application, comprising the step of: forming a raw material powder containing the mixed powder of (A) or (B) shown below And sintering the formed body obtained by the forming step in an atmosphere or an oxidizing gas atmosphere at 600 ° C to 150 ° C, and sintering by the sintering step a step of annealing in an inert gas atmosphere, in a vacuum or a reducing gas atmosphere, and a step of processing the oxide sintered body obtained in the annealing step to obtain a target; (A) the above formula: Ti 〇2.x (x=oi~1) represents a low valence titanium oxide powder 'and at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc oxide powder Mixed powder, (B) The above formula: Ti〇2.x (X=0.1~1) represents a low valence titanium oxide powder 'and a group selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder At least one powder, mixed with zinc hydroxide powder. A method for producing a target material according to claim 10, wherein the raw material powder containing the mixed powder of (A) or (B) shown below is contained. Putting it into a graphite mold material to perform pressure sintering in a vacuum or an inert gas atmosphere at 600 ° C to 1 500 ° C, and processing the oxide sintering obtained in the pressure sintering step a step of obtaining a target; (A) a low-valent titanium oxide powder represented by the formula: Ti02_x (X=〇.l~1), and a powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder a mixture of at least one powder of the group and zinc oxide powder, (B) a low-valent titanium oxide powder represented by the formula: TiO2.x (X = 0.1 to 1), and selected from alumina powder, A mixed powder of at least one powder of a group consisting of gallium oxide powder and indium oxide powder, and zinc hydroxide powder. 14. The target material of claim 10, which is used for film formation according to a sputtering method. 1 5 . A method of using a target as claimed in claim 10, which is used as a sputtering target. 16. A method for producing a zinc oxide-based transparent conductive film, comprising: forming a raw material powder containing a mixed powder of (A) or (B) shown below, by using the method The formed body obtained by the forming step is subjected to sintering in a vacuum, a reducing gas atmosphere or an inert gas atmosphere at 600 ° C to 1 500 ° C to process the oxide sintered body obtained in the sintering step. Step of obtaining the target -41 - 201250033, and the step of forming the transparent conductive film using the target; (A) the low atomic valence titanium oxide represented by the formula: Ti02-x (Χ=0.〗~1) Powder, mixed powder of at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc oxide powder, (Β) the above formula: TiO2.x (X=0.1~ 1) A low-atomic titanium oxide powder and a mixed powder of at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. 17. A method for producing a zinc oxide-based transparent conductive film, comprising: forming a raw material powder containing a mixed powder of (A) or (B) shown below, by using the method The formed body obtained by the forming step is subjected to sintering in an atmosphere or an oxidizing gas atmosphere at 600 ° C to 1 500 ° C, and the sintered body obtained by the sintering step is in an inert gas atmosphere. a step of annealing in a vacuum or a reducing gas atmosphere, a step of processing the oxide sintered body obtained in the annealing step to obtain a target, and a step of forming a transparent conductive film using the target; (A) a low valence titanium oxide powder represented by the formula: TiO2.x (X=0.1 〜1) and at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc oxide Powder mixed powder, (B) The above formula: Ti〇2.x (x=〇.l~1) indicates low atomic weight titanium oxide powder' and is selected from alumina powder, gallium oxide powder and indium oxide powder -42- 201250033 Group of at least 1 powder, with zinc hydroxide The mixed powder. 18. A method for producing a zinc oxide-based transparent conductive film, comprising: placing a raw material powder containing a mixed powder of (A) or (B) shown below in a graphite molding material In the vacuum or in an inert gas atmosphere, the step of pressure sintering is performed at 60 ° C to 1 500 ° C, and the oxide sintered body obtained in the pressure sintering step is processed to obtain a target. a step of forming a transparent conductive film using the target; (A) a low-valent titanium oxide powder represented by the formula: TiO2-X (X=0.1 to 1), and an oxide selected from the group consisting of alumina powder At least one powder of a group consisting of gallium powder and indium oxide powder, and a powder mixed with zinc oxide powder, (B) the low-valent titanium oxide powder represented by the formula: TiO2-x (X=0.1 to 1) 'mixed powder with at least one powder selected from the group consisting of alumina powder, gallium oxide powder and indium oxide powder, and zinc hydroxide powder. -43- 201250033 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201250033 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention. :no
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
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JP3030913B2 (en) * 1991-04-15 2000-04-10 住友金属鉱山株式会社 Manufacturing method of ITO sintered body
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JP5003600B2 (en) * 2008-06-13 2012-08-15 住友金属鉱山株式会社 Oxide sintered body, target, transparent conductive film obtained using the same, and conductive laminate
WO2011102425A1 (en) * 2010-02-18 2011-08-25 住友化学株式会社 Oxide sintered body, oxide mixture, manufacturing methods for same, and targets using same
JP2011184715A (en) * 2010-03-05 2011-09-22 Sumitomo Chemical Co Ltd Zinc oxide based transparent conductive film forming material, method for producing the same, target using the same, and method for forming zinc oxide based transparent conductive film
JP2011207742A (en) * 2010-03-09 2011-10-20 Sumitomo Chemical Co Ltd Zinc oxide transparent conductive film forming material, method of manufacturing the same, target using the same and method of forming zinc oxide transparent conductive film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN107109630A (en) * 2014-12-26 2017-08-29 株式会社半导体能源研究所 The manufacture method of sputtering target material
US10316404B2 (en) 2014-12-26 2019-06-11 Semiconductor Energy Laboratory Co., Ltd. Method for manufacturing sputtering target

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