JP2011162440A - Ito sintered compact, ito sputtering target and method for manufacturing the same - Google Patents
Ito sintered compact, ito sputtering target and method for manufacturing the same Download PDFInfo
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本発明は、ＩＴＯ燒結体、ＩＴＯスパッタリングターゲット及びその製造方法、特に高い強度を有するＩＴＯ燒結体、この燒結体を用いたスパッタリングターゲット及びその製造方法に関する。 The present invention relates to an ITO sintered body, an ITO sputtering target and a method for producing the same, particularly an ITO sintered body having high strength, a sputtering target using the sintered body, and a method for producing the same.
近年、液晶表示装置等の表示装置や透明電極等の技術分野で、ＩＴＯ透明導電膜が広く使用されている。このＩＴＯ透明導電膜は、操作が簡便であるという点から、スパッタリング法により形成されることが多くなっている。ＩＴＯスパッタリングターゲットを用いて得られたＩＴＯ透明導電性膜は、その透明性と導電性とに優れていることから、半導体技術分野で注目されている。 In recent years, ITO transparent conductive films have been widely used in technical fields such as display devices such as liquid crystal display devices and transparent electrodes. This ITO transparent conductive film is often formed by a sputtering method because it is easy to operate. An ITO transparent conductive film obtained by using an ITO sputtering target is attracting attention in the field of semiconductor technology because of its excellent transparency and conductivity.
この場合、ＩＴＯ燒結体からなるスパッタリングターゲット材を銅材料等からなるバッキングプレート部材へ接合することにより、スパッタリングプロセスで用いるスパッタリングターゲットが作製されるが、このターゲット材の強度が弱いと接合時やスパッタプロセス中に割れてしまうという問題が生じる。 In this case, a sputtering target used in a sputtering process is produced by bonding a sputtering target material made of an ITO sintered body to a backing plate member made of a copper material or the like. The problem of cracking during the process arises.
そのため、例えば、ターゲットの割れの防止等を意図したものとして、燒結密度９０％以上１００％以下、燒結粒径１μｍ以上２０μｍ以下である高密度ＩＴＯ燒結体からなるスパッタリングターゲットが提案されている(例えば、特許文献１参照)。この場合、酸化インジウムと酸化スズとの混合粉末を特定の燒結温度で燒結することにより、目的とする燒結密度及び燒結粒径を有するＩＴＯ燒結体を得ており、実際に得られている燒結体の抗析力は１７〜２３ｋｇ／ｍｍ２である。 Therefore, for example, a sputtering target composed of a high-density ITO sintered body having a sintered density of 90% to 100% and a sintered particle diameter of 1 μm to 20 μm has been proposed as intended for prevention of target cracking (for example, , See Patent Document 1). In this case, by sintering a mixed powder of indium oxide and tin oxide at a specific sintering temperature, an ITO sintered body having a target sintering density and a sintered particle size is obtained, and the sintered body actually obtained is obtained. The segregation force is 17-23 kg / mm 2 .
また、Ｓｎが固溶した酸化インジウム粉末を、真空中で熱処理したのち粉末とし、この粉末を成形後燒結してＩＴＯスパッタリングターゲットを得ることが提案されている(例えば、特許文献２参照)。この場合、得られたターゲットの抗折力は１５〜１８ｋｇ／ｍｍ２である。しかし、この程度の抗折力では、必ずしも接合時やスパッタプロセス中の割れを防止できないことがある。 In addition, it has been proposed that an indium oxide powder in which Sn is dissolved is heat-treated in a vacuum and then formed into a powder, which is sintered after molding to obtain an ITO sputtering target (see, for example, Patent Document 2). In this case, the bending strength of the obtained target is 15 to 18 kg / mm 2 . However, this level of bending strength may not always prevent cracking during bonding or during the sputtering process.
本発明の課題は、上述の従来技術の問題点を解決し、高い強度を有するＩＴＯ燒結体、ＩＴＯスパッタリングターゲット及びその製造方法を提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art and provide an ITO sintered body having high strength, an ITO sputtering target, and a method for producing the same.
本発明のＩＴＯ燒結体は、酸化スズと酸化インジウムとを含むＩＴＯ燒結体において、酸化スズを８〜１２重量％、並びに元素の周期表の２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物を０．００１〜０．１重量％含み、残部が酸化インジウムであることを特徴とする。 The ITO sintered body of the present invention is an ITO sintered body containing tin oxide and indium oxide, tin oxide is 8 to 12% by weight, and at least one element of group 2a and group 4a elements of the periodic table of elements The oxide is 0.001 to 0.1% by weight, and the balance is indium oxide.
本発明のＩＴＯ燒結体はまた、酸化スズと酸化インジウムとを含むＩＴＯ燒結体において、酸化スズを８〜１２重量％、並びに元素の周期表の２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物を０．０１〜０．１重量％含み、残部が酸化インジウムであることを特徴とする。 The ITO sintered body of the present invention is also an ITO sintered body containing tin oxide and indium oxide. It is characterized by containing 0.01 to 0.1% by weight of elemental oxide and the balance being indium oxide.
２ａ族及び４ａ族元素の酸化物は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｚｒ及びＨｆの酸化物であることが好ましい。 The oxides of group 2a and group 4a elements are preferably oxides of Mg, Ca, Sr, Ba, Ti, Zr and Hf.
２ａ族及び４ａ族元素の酸化物は、燒結体の結晶粒界に分散して存在している。 The oxides of Group 2a and Group 4a elements are present dispersed in the crystal grain boundaries of the sintered body.
本発明のＩＴＯスパッタリングターゲットは、上記ＩＴＯ燒結体からなることを特徴とする。 The ITO sputtering target of the present invention is characterized by comprising the above ITO sintered body.
本発明のＩＴＯスパッタリングターゲットの製造方法は、酸化インジウム、酸化スズ、並びに元素の周期表の２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物を、酸化スズ８〜１２重量％、元素の周期表の２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物０．００１〜０．１重量％、並びに酸化インジウム残部の割合で配合して混練した後、乾燥造粒し、この造粒粉を静水圧プレスし、次いで大気中で焼成することを特徴とする。この２ａ族及び４ａ族元素の酸化物は、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｚｒ及びＨｆの酸化物であることが好ましい。 The manufacturing method of the ITO sputtering target of the present invention comprises indium oxide, tin oxide, and an oxide of at least one element selected from elements 2a and 4a of the periodic table of elements, tin oxide 8 to 12% by weight, After mixing and kneading at a ratio of 0.001 to 0.1% by weight of an oxide of at least one element of elements 2a and 4a of the periodic table of elements and the remainder of indium oxide, dry granulation is performed. The granulated powder is hydrostatically pressed and then fired in the air. The oxides of Group 2a and Group 4a elements are preferably oxides of Mg, Ca, Sr, Ba, Ti, Zr and Hf.
本発明によれば、高い強度を有するＩＴＯ燒結体及びＩＴＯスパッタリングターゲットを提供できるという効果を奏する。 According to the present invention, it is possible to provide an ITO sintered body and an ITO sputtering target having high strength.
本発明によれば、酸化インジウム及び酸化スズに対して特定の元素の酸化物を特定量配合することにより、高い強度を有するＩＴＯ燒結体及びこの燒結体からなるＩＴＯスパッタリングターゲットを提供できる。すなわち、酸化スズ及び酸化インジウムを含むＩＴＯ燒結体において、酸化スズを５〜１５重量％、好ましくは８〜１２重量％、並びに周期表の２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物を０．００１〜０．１重量％、好ましくは０．０１〜０．１重量％含み、残部が酸化インジウムである高強度燒結体及びこの燒結体からなるＩＴＯスパッタリングターゲットを提供できる。ここで、２ａ族及び４ａ族元素のうちの少なくとも１種の元素の酸化物とは、２ａ族及び４ａ族元素のいずれか一方の少なくとも１種の元素の酸化物、又は２ａ族及び４ａ族元素のそれぞれの少なくとも１種の元素の酸化物(この場合、少なくとも２種の元素の酸化物となる)を意味する。すなわち、２ａ族元素だけの場合も４ａ族元素だけの場合も、両方の場合も含まれる。 According to the present invention, an ITO sintered body having high strength and an ITO sputtering target made of this sintered body can be provided by blending a specific amount of an oxide of a specific element with indium oxide and tin oxide. That is, in an ITO sintered body containing tin oxide and indium oxide, tin oxide is 5 to 15% by weight, preferably 8 to 12% by weight, and at least one element of group 2a and group 4a elements of the periodic table. It is possible to provide a high-strength sintered body containing 0.001 to 0.1% by weight, preferably 0.01 to 0.1% by weight of oxide, with the balance being indium oxide, and an ITO sputtering target made of this sintered body. Here, the oxide of at least one element of Group 2a and Group 4a elements is an oxide of at least one element of Group 2a and Group 4a elements, or Group 2a and Group 4a elements Means an oxide of at least one element (in this case, an oxide of at least two elements). That is, both the case of only the group 2a element and the case of only the group 4a element are included.
本発明によれば、酸化スズ含量を８〜１２重量％の範囲とすることが好ましいが、酸化スズ含量が７重量％以下及び１３重量％以上であるＩＴＯスパッタリングターゲットを用いてスパッタリングすると、得られるＩＴＯ膜の膜抵抗が高くなる傾向がある。 According to the present invention, the tin oxide content is preferably in the range of 8 to 12% by weight, but obtained by sputtering using an ITO sputtering target having a tin oxide content of 7% by weight or less and 13% by weight or more. The film resistance of the ITO film tends to increase.
２ａ族元素の酸化物は、Ｍｇ、Ｃａ、Ｓｒ及びＢａの酸化物であり、また、４ａ族元素の酸化物は、Ｔｉ、Ｚｒ及びＨｆの酸化物である。 Group 2a element oxides are oxides of Mg, Ca, Sr and Ba, and group 4a element oxides are oxides of Ti, Zr and Hf.
本発明で使用する酸化インジウムとしては、ＢＥＴ比表面積が５〜１５ｍ２／ｇである粉末を使用することが好ましく、酸化スズとしては、ＢＥＴ比表面積が５〜１５ｍ２／ｇである粉末を使用することが好ましく、また、２ａ族及び４ａ族元素の酸化物としては、ＢＥＴ比表面積が５〜１０ｍ２／ｇである粉末を使用すること好ましい。これらのＢＥＴ比表面積の範囲内の酸化物粉末を使用すれば、均一な燒結体が得られる。 As the indium oxide used in the present invention, a powder having a BET specific surface area of 5 to 15 m 2 / g is preferably used, and as the tin oxide, a powder having a BET specific surface area of 5 to 15 m 2 / g is used. Moreover, it is preferable to use the powder whose BET specific surface area is 5-10 m < 2 > / g as an oxide of 2a group and 4a group element. If an oxide powder within the range of these BET specific surface areas is used, a uniform sintered body can be obtained.
上記酸化物粉末を適宜選択して、それぞれを所定量配合し、大気(空気)雰囲気中又は空気と酸素との混合雰囲気中で１５００〜１６００℃で焼成すれば、高い強度を有するＩＴＯ燒結体を得ることができ、この燒結体からＩＴＯスパッタリングターゲットを得ることができる。 The above oxide powder is appropriately selected, each is blended in a predetermined amount, and fired at 1500 to 1600 ° C. in the atmosphere (air) atmosphere or in a mixed atmosphere of air and oxygen, an ITO sintered body having high strength can be obtained. An ITO sputtering target can be obtained from this sintered body.
かくして得られた燒結体は、ＥＰＭＡ(Electron Probe Micro Analyzer)によって観測したところ、その母相(酸化インジウム及び酸化ジルコニウム)のＩＴＯ燒結粒子の結晶粒界に２ａ族元素の酸化物及び／又は４ａ族元素の酸化物が分散して存在していることが分かる。図１にその結晶構造を模式的に示す。燒結体をバッキングプレートへ接合する時の燒結体の割れ又はスパッタリングプロセス中のターゲットの割れは、クラックの起点から粒界を通じてその割れが拡がって生じるが、本発明のＩＴＯ燒結体及びこの燒結体から得られたＩＴＯスパッタリングターゲットの場合は強度が非常に高いためか、その割れは結晶粒界に存在する分散粒子が抑えているものと考えられる。一般的に強度が高いと割れ難くなることは知られている。 The sintered body thus obtained was observed by EPMA (Electron Probe Micro Analyzer). As a result, the oxide of the group 2a element and / or the group 4a group was present at the crystal grain boundary of the ITO sintered particles of the parent phase (indium oxide and zirconium oxide). It can be seen that elemental oxides are dispersed. FIG. 1 schematically shows the crystal structure. Cracking of the sintered body when the sintered body is bonded to the backing plate or cracking of the target during the sputtering process is caused by the crack spreading from the starting point of the crack through the grain boundary. From the ITO sintered body of the present invention and this sintered body, In the case of the obtained ITO sputtering target, the strength is very high, or the cracks are considered to be suppressed by the dispersed particles existing at the crystal grain boundaries. In general, it is known that if the strength is high, it is difficult to break.
次に、本発明を実施例及び比較例に基づいて説明する。 Next, this invention is demonstrated based on an Example and a comparative example.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．０１ｗｔ％、酸化マグネシウム０．０１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 A BET specific surface area of 10 m 2 / g tin oxide 10 wt%, zirconium oxide 0.01 wt%, magnesium oxide 0.01 wt%, and a BET specific surface area of 15 m 2 / g indium oxide balance are blended. As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．０１ｗｔ％、酸化カルシウム０．０１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 BET specific surface area of 10 m 2 / g tin oxide 10 wt%, zirconium oxide 0.01 wt%, calcium oxide 0.01 wt%, and BET specific surface area of 15 m 2 / g indium oxide balance are blended. As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．０５ｗｔ％、酸化カルシウム０．０５ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.05 wt% of zirconium oxide, 0.05 wt% of calcium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the dispersant. As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．０５ｗｔ％、酸化ハフニウム０．０２ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10% by weight of tin oxide having a BET specific surface area of 10 m 2 / g, 0.05% by weight of zirconium oxide, 0.02% by weight of hafnium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g, As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．００２ｗｔ％、酸化マグネシウム０．００２ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.002 wt% of zirconium oxide, 0.002 wt% of magnesium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the dispersant. As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．００１ｗｔ％、酸化マグネシウム０．００１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.001 wt% of zirconium oxide, 0.001 wt% of magnesium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the dispersant. As a surfactant, 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．００１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.001 wt% of zirconium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g were mixed with the surfactant as a dispersant in 0%. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.1 wt% of zirconium oxide, and the balance of indium oxide having a BET specific surface area of 15 m 2 / g were mixed. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A test piece of 3 × 4 × 40 mm was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化カルシウム０．００１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.001 wt% of calcium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g were mixed. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化カルシウム０．０１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。 10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.01 wt% of calcium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the surfactant as a dispersant. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化カルシウム０．１ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。
(比較例１)
A 10 wt% tin oxide having a BET specific surface area of 10 m 2 / g, a 0.1 wt% calcium oxide, and a balance of indium oxide having a BET specific surface area of 15 m 2 / g were mixed. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
(Comparative Example 1)
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．５ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。
(比較例２)
10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.5 wt% of zirconium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the surfactant as a dispersant. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
(Comparative Example 2)
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化ジルコニウム０．０００５ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１に従って４点曲げ試験を実施した。また、燒結体のバルク抵抗値を公知の４探針法にて測定した。
(比較例３)
10 wt% of tin oxide having a BET specific surface area of 10 m 2 / g, 0.0005 wt% of zirconium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g were mixed with a surfactant as a dispersant in 0%. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A 3 × 4 × 40 mm test piece was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk resistance value of the sintered body was measured by a known four-probe method.
(Comparative Example 3)
ＢＥＴ比表面積１０ｍ２／ｇの酸化スズ１０ｗｔ％、酸化カルシウム０．５ｗｔ％、及びＢＥＴ比表面積１５ｍ２／ｇの酸化インジウム残部を配合し、この配合物に、分散剤としての界面活性剤を０．５ｗｔ％、バインダーとしてのＰＶＡを１ｗｔ％、所定量の水を加えて、スラリー濃度が７５ｗｔ％になるようにし、これをボールミル中で混練した。得られたスラリーをスプレードライヤーにて乾燥造粒し、造粒粉を得た。この造粒粉をゴム型へ投入し、静水圧プレス(２ｔ／ｃｍ２)でプレスして成形体を得た。この成形体を１６００℃大気雰囲気中で焼成し燒結体を得、かくして得られた燒結体から３×４×４０ｍｍの試験片を切り出してＪＩＳ Ｒ１６０１従って４点曲げ試験を実施した。また、燒結体のバルク表面抵抗値を公知の４探針法にて測定した。 10 wt% tin oxide having a BET specific surface area of 10 m 2 / g, 0.5 wt% calcium oxide, and the remainder of indium oxide having a BET specific surface area of 15 m 2 / g are mixed with the surfactant as a dispersant. 0.5 wt%, 1 wt% of PVA as a binder, and a predetermined amount of water were added so that the slurry concentration became 75 wt%, and this was kneaded in a ball mill. The obtained slurry was dried and granulated with a spray dryer to obtain granulated powder. This granulated powder was put into a rubber mold and pressed with an isostatic press (2 t / cm 2 ) to obtain a molded body. This molded body was fired in an air atmosphere at 1600 ° C. to obtain a sintered body. A test piece of 3 × 4 × 40 mm was cut out from the sintered body thus obtained, and a four-point bending test was performed according to JIS R1601. Further, the bulk surface resistance value of the sintered body was measured by a known 4-probe method.
上記した実施例１〜１１及び比較例１〜３で得られたＩＴＯ燒結体の試験片に対して測定した曲げ強度(ＭＰａ)及びバルクの表面抵抗値(ｍΩ)を以下の表１に纏めて示す。なお、表１中では、２ａ族及び４ａ族元素の酸化物及びその添加量(ｗｔ％)についても纏めて示す。 Table 1 below summarizes the bending strength (MPa) and bulk surface resistance (mΩ) measured for the ITO sintered specimens obtained in Examples 1 to 11 and Comparative Examples 1 to 3 described above. Show. In Table 1, the oxides of Group 2a and Group 4a elements and their addition amount (wt%) are also shown.
(表１)
本発明によれば、高い強度を有するＩＴＯ燒結体、この燒結体からなるＩＴＯスパッタリングターゲットを提供できるので、このターゲットを用いてスパッタリング法で形成されるＩＴＯ透明導電膜を適用する技術分野、例えば、液晶表示装置等の表示装置や透明電極等の技術分野で広く利用可能である。 According to the present invention, an ITO sintered body having high strength and an ITO sputtering target made of this sintered body can be provided. Therefore, a technical field in which an ITO transparent conductive film formed by sputtering using this target is applied, for example, It can be widely used in the technical fields of display devices such as liquid crystal display devices and transparent electrodes.
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| JP2002284570A (en) * | 2001-03-23 | 2002-10-03 | Tosoh Corp | Oxide sintered compact and sputtering target |
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| KR101945145B1 (en) * | 2016-03-14 | 2019-02-01 | 제이엑스금속주식회사 | Oxide sintered compact |
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