JP4504271B2 - Method for producing indium oxide-zinc oxide sintered target - Google Patents
Method for producing indium oxide-zinc oxide sintered target Download PDFInfo
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- JP4504271B2 JP4504271B2 JP2005192739A JP2005192739A JP4504271B2 JP 4504271 B2 JP4504271 B2 JP 4504271B2 JP 2005192739 A JP2005192739 A JP 2005192739A JP 2005192739 A JP2005192739 A JP 2005192739A JP 4504271 B2 JP4504271 B2 JP 4504271B2
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- indium oxide
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- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000000843 powder Substances 0.000 claims description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 45
- 229910003437 indium oxide Inorganic materials 0.000 claims description 32
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 5
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims 1
- 241000519995 Stachys sylvatica Species 0.000 description 25
- 238000001354 calcination Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Description
本発明は、酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法に関し、特に、大型サイズの焼結体であっても均一でむらがなく、高密度でしかもホワイトスポット等の色むらが少ないものが得られ、歩留りが著しく向上する酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法に関するものである。 The present invention relates to a method for producing a target of an indium oxide-zinc oxide sintered body, and in particular, even a large size sintered body is uniform and has no unevenness, high density and little color unevenness such as white spots. Is obtained, and the manufacturing method of the indium oxide-zinc oxide based sintered compact target in which the yield is remarkably improved.
現在、液相ディスプレイ装置（ＬＣＤ）を始めとする表示ディバイスには透明導電膜材料として酸化インジウム−酸化錫（ＩＴＯ）が広く用いられている。ＩＴＯ透明導電膜は、通常ＩＴＯ焼結体ターゲットを用いてスパッタ法で作製されている。このＩＴＯ膜は、低抵抗で透明性に優れ、エッチング性が良いなど優れた材料であるが、エッチングに強酸が必要であったり、ＴＦＴ−ＬＣＤに用いた場合、金属電極との間で電池反応を起こしたり、耐湿性が低いという問題を有していた。
この耐湿性を改善し、かつＩＴＯと同等の導電性と透明性を有する材料として酸化インジウム−酸化亜鉛系の材料の焼結体ターゲットおよびその製造方法が特許文献１に提案されている。この特許文献１に開示されている焼結体の製造方法は比較的小さい物品を対象としているが、実際の工業生産で用いられる焼結体ターゲットの大きさはこれよりはるかに大きい。このような従来の製造方法で大型サイズ、例えば５インチ×１５インチ以上の焼結体を作製した場合、十分に高密度な焼結体（相対密度９５％以上）が得られない、又は、焼結体の周辺部と中央部で色むらが発生する、などの問題が残されている。特に色むらのあるターゲットをスパッタに用いると、得られる膜の抵抗値にばらつきが生じるため、実際には焼結体の外側部分を研削して色むら部分を取り除いてからターゲットとして使用しているのが現状である。
この問題を改善し、かつＩＴＯと同等の導電性と透明性を有する材料として酸化インジウム−酸化亜鉛系の材料の焼結体ターゲット及びその製造方法が特許文献２に提案されている。特許文献２に開示されている焼結体の製造方法は、原料の酸化亜鉛を４００〜８００℃で仮焼して、粉砕して使用するものであるが、この場合には、焼結体ターゲットの体表面にホワイトスポット（白色斑点）と呼ばれる色むらが発生する、などの問題が残されている。特にホワイトスポットと呼ばれる色むらのあるターゲットをスパッタに用いると、スパッタリング途中でアーキングなどの異常放電を起こして成膜出来なくなるなどの問題が発生する場合がある。ここで、ホワイトスポットとは、周辺部より色が薄く、０．５〜５ｍｍφ程度の直径を有しており、この部分の抵抗値は周囲の抵抗値より大きい場合がある。
Patent Document 1 proposes a sintered body target of an indium oxide-zinc oxide based material as a material having improved moisture resistance and having the same conductivity and transparency as ITO, and a method for producing the same. The method for manufacturing a sintered body disclosed in Patent Document 1 targets relatively small articles, but the size of a sintered body target used in actual industrial production is much larger than this. When a sintered body having a large size, for example, 5 inches × 15 inches or more is produced by such a conventional manufacturing method, a sufficiently high density sintered body (relative density of 95% or more) cannot be obtained or sintered. Problems remain such as uneven color in the periphery and center of the ligature. In particular, if a target with uneven color is used for sputtering, the resistance value of the resulting film will vary, so in practice, the outer part of the sintered body is ground to remove the uneven color part and then used as the target. is the current situation.
Patent Document 2 proposes a sintered body target of an indium oxide-zinc oxide based material as a material that improves this problem and has the same conductivity and transparency as ITO, and a manufacturing method thereof. The method for producing a sintered body disclosed in Patent Document 2 is a method in which the raw material zinc oxide is calcined at 400 to 800 ° C. and pulverized for use. In this case, the sintered body target is used. Problems such as color unevenness called white spots (white spots) remain on the body surface. In particular, when an uneven color target called a white spot is used for sputtering, an abnormal discharge such as arcing may occur during the sputtering, which may cause a problem that the film cannot be formed. Here, the white spot is lighter in color than the peripheral part and has a diameter of about 0.5 to 5 mmφ, and the resistance value of this part may be larger than the surrounding resistance value.
本発明は、前記の課題を解決するためになされたもので、大型サイズの焼結体を作製した場合でも相対密度９５％以上の高密度のものが得られ、かつ焼結体ターゲット表面のホワイトスポットと呼ばれる色むらの発生を抑制した酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems. Even when a large-sized sintered body is produced, a high-density one having a relative density of 95% or more is obtained, and the surface of the sintered body target is white. It aims at providing the manufacturing method of the indium oxide zinc oxide type sintered compact target which suppressed generation | occurrence | production of the color nonuniformity called a spot.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、出発原料として酸化インジウム−酸化亜鉛粉末を用い、以下の方法にて、酸化インジウム−酸化亜鉛系焼結体ターゲットの製造することにより前記の目的を達成することを見出し本発明を完成したものである。 As a result of intensive studies to achieve the above object, the inventors of the present invention used an indium oxide-zinc oxide powder as a starting material and manufactured an indium oxide-zinc oxide based sintered target by the following method. As a result, the inventors have found that the above object can be achieved and completed the present invention.
すなわち、本発明は、以下の内容を特徴とするものである。
（１）酸化インジウム粉末と酸化亜鉛粉末の混合粉末（酸化インジウム−酸化亜鉛粉末）を４００℃〜８００℃で仮焼し、得られた酸化インジウムと酸化亜鉛が結合した粉末（酸化インジウム−酸化亜鉛仮焼粉末）をプレス成形後、酸素雰囲気下で１２５０℃〜１４５０℃で焼結する酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法。
（２）酸化インジウム−酸化亜鉛粉末を４００℃〜８００℃で仮焼し、得られた酸化インジウム−酸化亜鉛仮焼粉末を粉砕処理した後に酸化インジウム粉末を混合、又は得られた酸化インジウム−酸化亜鉛仮焼粉末に酸化インジウム粉末を混合した後に粉砕処理し、この混合粉末をプレス成形後、酸素雰囲気下で１２５０℃〜１４５０℃で焼結する酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法。
（３）前記酸化インジウム−酸化亜鉛仮焼粉末のＢＥＴ表面積が４〜１０ｍ2／ｇである前記（１）又は（２）に記載の酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法。
（４）前記酸化インジウム−酸化亜鉛仮焼粉末中の酸化インジウム含有量が２０〜９５重量％である前記（１）又は（２）に記載の酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法。
That is, the present invention is characterized by the following contents.
(1) A mixed powder of indium oxide powder and zinc oxide powder ( indium oxide-zinc oxide powder ) is calcined at 400 ° C. to 800 ° C., and the obtained powder indium oxide and zinc oxide combined ( indium oxide-zinc oxide) after press forming a calcined powder), indium oxide sintered at 1250 ° C. to 1450 ° C. in an oxygen atmosphere - zinc oxide-based sintered body target manufacturing method.
(2) Indium oxide-zinc oxide powder is calcined at 400 ° C. to 800 ° C., and the obtained indium oxide-zinc oxide calcined powder is pulverized and then mixed with indium oxide powder , or obtained indium oxide-oxidation A method for producing an indium oxide-zinc oxide sintered body target in which indium oxide powder is mixed with calcined zinc powder and then pulverized, and the mixed powder is press-molded and sintered at 1250 ° C. to 1450 ° C. in an oxygen atmosphere. .
(3) The method for producing an indium oxide-zinc oxide based sintered target according to (1) or (2), wherein the indium oxide-zinc oxide calcined powder has a BET surface area of 4 to 10 m 2 / g.
(4) the indium oxide - method of manufacturing a zinc oxide-based sintered body target - indium oxide according to the indium oxide content of the zinc oxide calcined powder is 20 to 95% by weight (1) or (2) .
本発明の酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法よると、大型サイズの焼結体を作製した場合でもであっても均一で色むらがなく、相対密度９５％以上の高密度のものが得られ、かつ焼結体ターゲット表面のホワイトスポット等の色むらの発生を抑制できる。 According to the method for producing an indium oxide-zinc oxide based sintered body target of the present invention, even when a large size sintered body is produced, there is no color unevenness and a relative density of 95% or more is high. Can be obtained, and color unevenness such as white spots on the surface of the sintered compact target can be suppressed.
以下、本発明の製造方法を詳細に説明する。
本発明の酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法は、酸化インジウム（Ｉｎ2Ｏ3）−酸化亜鉛（ＺｎＯ）粉末を４００℃〜８００℃で仮焼し、得られた酸化インジウム−酸化亜鉛仮焼粉末をプレス成形後、１２５０℃〜１４５０℃で焼結する。
Hereinafter, the production method of the present invention will be described in detail.
The indium oxide-zinc oxide based sintered body target manufacturing method of the present invention is obtained by calcining indium oxide (In 2 O 3 ) -zinc oxide (ZnO) powder at 400 ° C. to 800 ° C. After the zinc oxide calcined powder is press-molded, it is sintered at 1250 ° C to 1450 ° C.
本発明においては、まず、酸化インジウム−酸化亜鉛粉末を仮焼する。酸化亜鉛粉末のみを仮焼した場合、次工程の粉砕工程で、粉砕できない粉が混入したり、二次粒子が成長したりした原料粉末が混入した場合、ターゲット表面にホワイトスポット（白色斑点）と呼ばれる色むらが出来易くなる。
酸化インジウム−酸化亜鉛粉末を仮焼することにより、粉末の混合性が良くなり次工程での粉砕が容易になったり、酸化亜鉛が完全に酸化されて亜酸化体が除かれ、亜鉛が昇華しにくくなる。仮焼温度は通常４００〜８００℃、好ましくは４００〜６００℃である。仮焼温度が８００℃以上と高くなると酸化インジウムと酸化亜鉛の反応が起こり粒子の凝結が強くなり、その後の粉砕を行う場合に粉砕がしにくくなる。仮焼時間は２時間以上が好ましい。
In the present invention, first, indium oxide-zinc oxide powder is calcined. When only zinc oxide powder is calcined, in the next pulverization process, when powder that cannot be pulverized or raw material powder that has grown secondary particles is mixed, white spots (white spots) on the target surface Color unevenness called becomes easy to be made.
By calcining the indium oxide-zinc oxide powder, the powder mixability is improved and pulverization in the next process is facilitated, or the zinc oxide is completely oxidized to remove the suboxide and the zinc is sublimated. It becomes difficult. The calcination temperature is usually 400 to 800 ° C, preferably 400 to 600 ° C. When the calcining temperature is as high as 800 ° C. or higher, the reaction between indium oxide and zinc oxide occurs, and the particles are strongly condensed. When the subsequent pulverization is performed, the pulverization becomes difficult. The calcining time is preferably 2 hours or more.
また、本発明においては、仮焼粉砕後の酸化インジウム−酸化亜鉛はＢＥＴ表面積が４〜１０ｍ2／ｇの範囲であればホワイトスポットが効果的に抑制でき、ＢＥＴ表面積が６〜８ｍ2／ｇであるとさらに好ましい。
さらに、酸化インジウム−酸化亜鉛仮焼粉末中の酸化インジウム含有量が２０〜９５重量％であると、高密度化（相対密度で９５％以上。ここで、相対密度は、酸化インジウム、酸化亜鉛の真密度を重量配分して求めた理論密度を100％とした相対値である。）及びホワイトスポット等の色むら抑制の効果が特に著しく表われる。
In the present invention, indium oxide after calcination milling - White spot so long as zinc oxide BET surface area of 4~10m 2 / g can be effectively suppressed, a BET surface area of 6-8 m 2 / g Is more preferable.
Furthermore, when the content of indium oxide in the indium oxide-zinc oxide calcined powder is 20 to 95% by weight, the density is increased (relative density is 95% or more. Here, the relative density is indium oxide or zinc oxide. This is a relative value with the theoretical density obtained by weight distribution of the true density as 100%.) And the effect of suppressing color unevenness such as white spots is particularly remarkable.
仮焼後、得られた酸化インジウム−酸化亜鉛仮焼粉末を、プレス成形する。プレス成形の条件としては、特に制限されないが、例えば、冷間静水圧（ＣＩＰ）等の手段によりプレス成形を行えばよい。 After the calcination, the obtained indium oxide-zinc oxide calcination powder is press-molded. The conditions for press molding are not particularly limited, but for example, press molding may be performed by means such as cold isostatic pressure (CIP).
プレス成形後、得られた成型体を１２５０℃〜１４５０℃の温度で焼結する。この焼結を行う際に、雰囲気を酸素雰囲気にしておくことにより十分な高密度（相対密度９５％以上）を得ることを確実にすることができ、特に８００℃〜焼結温度（１２５０℃〜１４５０℃）の間の酸素濃度が重要である。焼結温度が１２５０℃未満では焼結体は高密度とはならず、ターゲット表面にホワイトスポットが発生したり、色むらが発生したりすることがある。また、１４５０℃を越えるとＺｎＯが昇華して組成むらや組成ずれが生じる。焼結時間は２時間以上が好ましい。
また、高温になると酸化インジウム−酸化亜鉛の酸化物が酸素を遊離する場合があり、酸素雰囲気下で焼結を行うことによりこの酸素の遊離を抑えることが出来る。
その後、得られた焼結体は平面研削による面出し加工及び色むら部分除去のための外周部切断の機械加工を経て製品としてのターゲットが得られる。
After the press molding, the obtained molded body is sintered at a temperature of 1250 ° C to 1450 ° C. When performing this sintering, it is possible to ensure that a sufficiently high density (relative density of 95% or more) is obtained by keeping the atmosphere in an oxygen atmosphere, and in particular, 800 ° C. to sintering temperature (1250 ° C. to The oxygen concentration between 1450 ° C.) is important. When the sintering temperature is less than 1250 ° C., the sintered body does not have a high density, and white spots may be generated on the target surface or color unevenness may occur. On the other hand, when the temperature exceeds 1450 ° C., ZnO is sublimated, resulting in uneven composition and compositional deviation. The sintering time is preferably 2 hours or more.
In addition, indium oxide-zinc oxide oxide may liberate oxygen at high temperatures, and the liberation of oxygen can be suppressed by sintering in an oxygen atmosphere.
Thereafter, the obtained sintered body is subjected to surface processing by surface grinding and machining of the outer peripheral portion for removing the uneven color portion to obtain a target as a product.
また、本発明は、上記方法において、酸化インジウム−酸化亜鉛粉末を仮焼した後、得られた酸化インジウム−酸化亜鉛仮焼粉末を粉砕処理した後に酸化インジウム（Ｉｎ2Ｏ3）粉末を混合、又は得られた酸化インジウム−酸化亜鉛仮焼粉末に酸化インジウム粉末を混合した後に粉砕処理する工程を有していても、ホワイトスポット等の色むら抑制の他、前記と同様の効果が得られ好ましい。
酸化インジウム−酸化亜鉛仮焼粉末の粉砕、及び酸化インジウム粉末の混合方法としては、特に限定されず、ボールミル等の公知の方法によればよく、粉砕と混合を同時に行ってもよく、別々に行ってもよい。混合後の酸化インジウムと酸化亜鉛との混合割合は特に限定されないが、２０：８０〜９５：５であると好ましい。また、これらの粉末の混合中又は粉砕混合後に、必要に応じてポリビニルアルコール（ＰＶＡ）水溶液等のバインダーを添加してもよい。
また、前記粉砕・混合工程を行う場合にも、酸化インジウム−酸化亜鉛仮焼粉末中の酸化インジウム含有量が２０〜９５重量％であると、高密度化（相対密度で９５％以上）及びホワイトスポット等の色むら抑制の効果が特に著しく表われる。
Further, in the above method, the present invention, after calcining the indium oxide-zinc oxide powder in the above method, pulverizing the obtained indium oxide-zinc oxide calcined powder, and then mixing indium oxide (In 2 O 3 ) powder, Alternatively, even if the obtained indium oxide-zinc oxide calcined powder has a step of pulverizing after mixing indium oxide powder, the same effect as described above is obtained in addition to suppressing color unevenness such as white spots. .
The method for pulverizing the indium oxide-zinc oxide calcined powder and the method for mixing the indium oxide powder is not particularly limited, and may be a known method such as a ball mill, and the pulverization and mixing may be performed simultaneously or separately. May be. The mixing ratio of indium oxide and zinc oxide after mixing is not particularly limited, but is preferably 20:80 to 95: 5. Moreover, you may add binders, such as polyvinyl alcohol (PVA) aqueous solution, as needed during the mixing of these powders, or after grinding | pulverization mixing.
Further, when the pulverization / mixing step is performed, if the indium oxide content in the indium oxide-zinc oxide calcined powder is 20 to 95% by weight, the density is increased (relative density is 95% or more) and white. The effect of suppressing color unevenness such as spots is particularly remarkable.
次に、実施例を用いて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
実施例１〜４及び比較例１〜２
表１に記載した酸化インジウム−酸化亜鉛粉末の混合比及び仮焼温度で２時間仮焼後、得られた酸化インジウム−酸化亜鉛仮焼粉末のＢＥＴ表面積を測定した。その後、仮焼粉末をジルコニア（ＺｒＯ2）ボールを用いたボールミルで乾式で２４時間混合した。次いで、この混合物にバインダーとしてＰＶＡ水溶液を加え、６インチ×２０インチ×１６ｍｍ厚サイズの平板状に圧力８００ｋｇｆ／ｃｍ2で金型を用いてプレス成形した。得られた成形体を焼結時間８時間、大気圧中で酸素を導入しながら表１に記載の焼結温度で焼成し焼結体を得た。
なお、比較例１及び２については、仮焼を行わなかった。
得られた焼結体の相対密度を測定し、ホワイトスポット（白色斑点）の判定については、研削加工により所定の厚みまで表面研削後、目視にて径０．５ｍｍφ以上のホワイトスポットの数を数えた。それらの結果を表１に示す。
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Examples 1-4 and Comparative Examples 1-2
After calcining for 2 hours at the indium oxide-zinc oxide powder mixing ratio and calcining temperature described in Table 1, the BET surface area of the obtained indium oxide-zinc oxide calcined powder was measured. Thereafter, the calcined powder was mixed in a dry manner in a ball mill using zirconia (ZrO 2 ) balls for 24 hours. Next, an aqueous PVA solution was added as a binder to this mixture, and press-molded into a flat plate having a size of 6 inches × 20 inches × 16 mm using a mold at a pressure of 800 kgf / cm 2 . The obtained compact was fired at the sintering temperature shown in Table 1 while introducing oxygen at atmospheric pressure for a sintering time of 8 hours to obtain a sintered body.
In Comparative Examples 1 and 2, no calcination was performed.
The relative density of the obtained sintered body is measured, and for the determination of white spots (white spots), the number of white spots having a diameter of 0.5 mmφ or more is visually counted after surface grinding to a predetermined thickness by grinding. It was. The results are shown in Table 1.
表１に示すように、実施例１〜４の焼結体はいずれも相対密度が高く、ホワイトスポットも発生していないのに対し、仮焼を行わなかった比較例１〜２では、高密度が得られる場合もあるがホワイトスポットの多いものであった。 As shown in Table 1, all of the sintered bodies of Examples 1 to 4 have a high relative density and no white spots are generated. In some cases, there were many white spots.
実施例５〜８及び比較例３〜５
表２に記載した酸化インジウム−酸化亜鉛粉末を表２に記載の仮焼温度で２時間仮焼後、得られた酸化インジウム−酸化亜鉛仮焼粉末のＢＥＴ表面積を測定した。その後、得られた仮焼粉末に酸化インジウム粉末を加えて表２に記載の酸化インジウム（Ｉｎ2Ｏ3）量となるように混合し、ジルコニア（ＺｒＯ2）ボールを用いたボールミルで乾式で２４時間混合した。次いで、この混合物にバインダーとしてＰＶＡ水溶液を加え、湿式粉砕を行い、スプレードライヤーにて造粒した後、８インチ×２０インチ×１８ｍｍ厚サイズの平板状に圧力８００ｋｇｆ／ｃｍ2で金型を用いてプレス成形した。得られた成形体を焼結時間８時間、大気中で表２に記載の焼結温度で焼成し、焼結体を得た。
なお、比較例３及び４については、出発原料として酸化インジウム−酸化亜鉛粉末の代わりに酸化亜鉛粉末を用い、比較例５では仮焼した酸化インジウム及び酸化亜鉛粉末を用いず、仮焼していない粉末のみを用いた。
得られた焼結体の相対密度を測定し、ホワイトスポット（白色斑点）の判定については、研削加工により所定の厚みまで表面研削後、目視にて径０．５ｍｍφ以上のホワイトスポットの数を数えた。それらの結果を表２に示す。
Examples 5-8 and Comparative Examples 3-5
The indium oxide-zinc oxide powder described in Table 2 was calcined at the calcining temperature described in Table 2 for 2 hours, and then the BET surface area of the obtained indium oxide-zinc oxide calcined powder was measured. Thereafter, indium oxide powder is added to the obtained calcined powder and mixed so that the amount of indium oxide (In 2 O 3 ) shown in Table 2 is reached, and then dried in a ball mill using zirconia (ZrO 2 ) balls. Mixed for hours. Next, an aqueous PVA solution is added to this mixture as a binder, wet pulverized, granulated with a spray dryer, and then formed into a flat plate having a size of 8 inches x 20 inches x 18 mm using a mold at a pressure of 800 kgf / cm 2. Press molded. The obtained molded body was fired at a sintering temperature shown in Table 2 in the atmosphere for 8 hours with a sintering time to obtain a sintered body.
In Comparative Examples 3 and 4, zinc oxide powder was used as a starting material instead of indium oxide-zinc oxide powder, and in Comparative Example 5, calcined indium oxide and zinc oxide powder were not used and calcined. Only powder was used.
The relative density of the obtained sintered body is measured, and for the determination of white spots (white spots), the number of white spots having a diameter of 0.5 mmφ or more is visually counted after surface grinding to a predetermined thickness by grinding. It was. The results are shown in Table 2.
表２に示すように、実施例５〜８の焼結体はいずれも相対密度が高く、ホワイトスポットも発生していないのに対し、一方、酸化亜鉛のみを仮焼した比較例３ではホワイトスポットが発生し、比較例２では密度も低くホワイトスポットの多いものしか得られていない。一段焼結の比較例３では、高密度のものも得られるが、ホワイトスポットの多いものであった。 As shown in Table 2, all of the sintered bodies of Examples 5 to 8 have a high relative density and no white spots are generated. On the other hand, in Comparative Example 3 in which only zinc oxide was calcined, white spots were used. In Comparative Example 2, only a low density and a large number of white spots were obtained. In Comparative Example 3 of single-stage sintering, a high-density one was obtained, but there were many white spots.
以上詳細に説明したように、本発明の酸化インジウム−酸化亜鉛系焼結体ターゲットの製造方法よると、大型サイズの焼結体を作製した場合でも均一でむらがなく、相対密度９５％以上の高密度のものが得られ、かつ焼結体ターゲット表面のホワイトスポット等の色むらの発生を抑制でき、歩留りが著しく向上するため実用性の高い製造方法である。
As described above in detail, according to the method for producing an indium oxide-zinc oxide based sintered body target of the present invention, even when a large size sintered body is produced, there is no unevenness, and the relative density is 95% or more. This is a highly practical manufacturing method because a high-density product can be obtained and the occurrence of uneven color such as white spots on the surface of the sintered compact target can be suppressed, and the yield is significantly improved.
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| JPH06236711A (en) * | 1992-12-15 | 1994-08-23 | Idemitsu Kosan Co Ltd | Conductive material and manufacture thereof |
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| JPH06236710A (en) * | 1992-12-15 | 1994-08-23 | Idemitsu Kosan Co Ltd | Conductive material and manufacture and manufacture thereof |
| JPH09111444A (en) * | 1995-10-13 | 1997-04-28 | Mitsui Mining & Smelting Co Ltd | Production of indium oxide-zinc oxide based sintered body target |
| JP2001011613A (en) * | 1999-06-29 | 2001-01-16 | Mitsui Mining & Smelting Co Ltd | Production of sputtering target containing zinc oxide |
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| JPH06236711A (en) * | 1992-12-15 | 1994-08-23 | Idemitsu Kosan Co Ltd | Conductive material and manufacture thereof |
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| JPH06236710A (en) * | 1992-12-15 | 1994-08-23 | Idemitsu Kosan Co Ltd | Conductive material and manufacture and manufacture thereof |
| JPH09111444A (en) * | 1995-10-13 | 1997-04-28 | Mitsui Mining & Smelting Co Ltd | Production of indium oxide-zinc oxide based sintered body target |
| JP2001011613A (en) * | 1999-06-29 | 2001-01-16 | Mitsui Mining & Smelting Co Ltd | Production of sputtering target containing zinc oxide |
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