JP2014065645A - Ito powder and production method thereof - Google Patents

Ito powder and production method thereof Download PDF

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JP2014065645A
JP2014065645A JP2012213762A JP2012213762A JP2014065645A JP 2014065645 A JP2014065645 A JP 2014065645A JP 2012213762 A JP2012213762 A JP 2012213762A JP 2012213762 A JP2012213762 A JP 2012213762A JP 2014065645 A JP2014065645 A JP 2014065645A
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tin
ito powder
indium
ito
powder
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JP5949395B2 (en
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Takehiro Yonezawa
岳洋 米澤
Kazuhiko Yamazaki
和彦 山崎
Ai Takenoshita
愛 竹之下
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Mitsubishi Materials Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data

Abstract

PROBLEM TO BE SOLVED: To provide ITO powder the powder compact of which is made to have the volume resistivity lower than before while dispensing with post treatment in a powder state thereof.SOLUTION: The ITO powder being a sample is packed in a sample holder belonging to an X-ray diffraction apparatus and the sample-packed sample holder is irradiated with an X-ray in a range of 2θ/θ=15-90 degrees to obtain a diffraction line. When a lattice constant, crystallite size and a lattice strain are refined by using the obtained diffraction line, the obtained lattice strain is within 0.2-0.8.

Description

本発明は、圧粉体にしたときに低い体積抵抗率を示すＩＴＯ粉末及びその製造方法に関するものである。本明細書において、ＩＴＯとはインジウム錫酸化物(Indium Tin Oxide)をいう。   The present invention relates to an ITO powder showing a low volume resistivity when it is made into a green compact and a method for producing the same. In this specification, ITO refers to indium tin oxide.

ＩＴＯは、Ｉｎ２Ｏ３に錫(Ｓｎ)をドープした化合物であり、１０２０〜１０２１ｃｍ−３の高いキャリア濃度を有し、スパッタリング法等の気相法で成膜したＩＴＯ膜では、１×１０−４Ωｃｍ程度の低い抵抗率が得られる。しかしながら、ＩＴＯ粉末の状態では、通常、その抵抗値は高抵抗であり、１０Ωｃｍ以上の範囲にある（例えば、特許文献１及び２参照。）。ＩＴＯ粉末の抵抗値を低下させるために、特許文献１又は２に記載された方法では、アルコキシド法により調製されたＩＴＯ粉末をアルコールガス又はヒドラジン水化物ガスを含有する不活性ガス雰囲気中で２００〜４５０℃の温度で加熱して、脱酸素を行い、酸素の格子欠陥を生じさせている。これらの方法によれば、１００ｋｇｆ／ｃｍ２（９．８０ＭＰａ）の圧力を加えたとき、０．０１〜０．５０Ωｃｍの範囲に低抵抗化されたＩＴＯ粉末が得られる。 ITO is a compound in which tin (Sn) is doped into In 2 O 3 , has a high carrier concentration of 10 20 to 10 21 cm −3 , and an ITO film formed by a vapor phase method such as a sputtering method, A resistivity as low as 1 × 10 −4 Ωcm is obtained. However, in the state of ITO powder, the resistance value is usually high resistance and is in the range of 10 Ωcm or more (see, for example, Patent Documents 1 and 2). In order to reduce the resistance value of the ITO powder, in the method described in Patent Document 1 or 2, the ITO powder prepared by the alkoxide method is 200 to 200 in an inert gas atmosphere containing alcohol gas or hydrazine hydrate gas. Deoxygenation is performed by heating at a temperature of 450 ° C., thereby causing oxygen lattice defects. According to these methods, when a pressure of 100 kgf / cm 2 (9.80 MPa) is applied, an ITO powder having a low resistance in the range of 0.01 to 0.50 Ωcm can be obtained.

またＩＴＯ粉末を低抵抗化する別の方法として、塩化インジウム及び塩化錫の混合水溶液を、混合の最終ｐＨが２〜８となる量のアンモニウム炭酸塩と５℃〜９５℃で混合することによってインジウムと錫の水酸化物を共沈させ、得られた沈殿を４００℃〜９５０℃で３０〜８時間加水分解する方法が開示されている（例えば、特許文献３参照）。この製造方法によれば５０ｋｇｆ／ｃｍ２（４．９０ＭＰａ）の圧力を加えたとき、比抵抗が７０Ωｃｍ以下若しくは１５Ωｃｍ以下のＩＴＯ粉末が得られる。またこの方法では、塩化錫として４価錫化合物であるＳｎＣｌ４水溶液を用いている。 Another method for reducing the resistance of ITO powder is to mix indium chloride and tin chloride with indium carbonate in an amount such that the final pH of mixing is 2 to 8 at 5 ° C. to 95 ° C. And a method of hydrolyzing the resulting precipitate at 400 ° C. to 950 ° C. for 30 to 8 hours (for example, see Patent Document 3). According to this manufacturing method, when a pressure of 50 kgf / cm 2 (4.90 MPa) is applied, an ITO powder having a specific resistance of 70 Ωcm or less or 15 Ωcm or less is obtained. In this method, SnCl 4 aqueous solution which is a tetravalent tin compound is used as tin chloride.

特開平５−０２４８３７号公報（特許請求の範囲、段落［０００５］、[００１０]、[００１１]）JP-A-5-024837 (Claims, paragraphs [0005], [0010], [0011]) 特開平５−１９３９４０号公報（特許請求の範囲、段落［０００５］、[００１０]、[００１１]）JP-A-5-193940 (Claims, paragraphs [0005], [0010], [0011]) 特開平５−２０１７３１号公報（特許請求の範囲、段落[００１２]〜[００１５]）JP-A-5-201731 (Claims, paragraphs [0012] to [0015])

ＩＴＯ粉末を低抵抗化するために、特許文献１及び２の方法では、ＩＴＯ粉末をアルコールガス又はヒドラジン水化物ガスを含有する不活性ガス雰囲気中で加熱する後処理が必要があった。また従来の方法では、塩化錫として４価錫化合物であるＳｎＣｌ４を用いるか、或いはＳｎＣｌ２を用いている。即ち、単一の価数の原料を使用しているため、ＩｎイオンとＳｎイオンのイオン半径の違いにより、前駆体（例えば、水酸化物など）が不安定となり、Ｓｎ化合物が析出しやすく、十分にＳｎをドープすることができなかった。 In order to reduce the resistance of the ITO powder, the methods of Patent Documents 1 and 2 require post-treatment of heating the ITO powder in an inert gas atmosphere containing alcohol gas or hydrazine hydrate gas. In the conventional method, SnCl 4 that is a tetravalent tin compound is used as tin chloride, or SnCl 2 is used. That is, since a raw material having a single valence is used, the precursor (for example, hydroxide) becomes unstable due to the difference in ionic radius between In ions and Sn ions, and Sn compounds are likely to precipitate. Sn could not be sufficiently doped.

本発明の目的は、粉末状態での後処理を要することなく、ＩＴＯ粉末の圧粉体において従来より低い体積抵抗率を得ることができるＩＴＯ粉末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 provide an ITO powder capable of obtaining a lower volume resistivity than conventional ones in a green compact of an ITO powder without requiring post-treatment in a powder state, and a method for producing the same.

本発明の第１の観点は、ＢｒｕｋｅｒＡＸＳ社製、Ｘ線回折装置Ｄ８ Ａｄｖａｎｃｅを用いて、この装置に付属する試料ホルダーに実施例１〜５及び比較例１、２で得られた各ＩＴＯ粉末を充填して２θ／θ＝１５〜９０ｄｅｇの範囲でＸ線を照射し、得られた回折線からＲｉｅｔｖｅｌｄ解析ソフトであるＴＯＰＡＳ（ＢｒｕｋｅｒＡＸＳ社製）を使用し、プロファイル関数としてＦＰを用いたＰａｗｌｅｙ法にて解析し、ローレンツ関数成分の半値幅から結晶子サイズと格子歪を算出したときの格子歪が０．２〜０．８の範囲にあることを特徴とするＩＴＯ粉末である。   The first aspect of the present invention is that each ITO powder obtained in Examples 1 to 5 and Comparative Examples 1 and 2 is attached to a sample holder attached to this apparatus using an X-ray diffraction apparatus D8 Advance manufactured by Bruker AXS. Fill and irradiate X-rays in the range of 2θ / θ = 15 to 90 deg., And use the TOPAS (manufactured by Bruker AXS), which is Rietveld analysis software, from the obtained diffraction lines, and the Pawley method using FP as a profile function The ITO powder is characterized in that the lattice strain is in the range of 0.2 to 0.8 when the crystallite size and the lattice strain are calculated from the half width of the Lorentz function component.

また本発明の第２の観点は、第１の観点に基づく発明であって、３価インジウム化合物と錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成する工程と、前記沈殿物を純水又はイオン交換水で洗浄する工程と、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製する工程と、前記スラリーを乾燥する工程と、前記乾燥したインジウム水錫酸化物を焼成してインジウム錫酸化物を得る工程とを含むＩＴＯ粉末を製造する方法の改良である。その特徴ある点は、前記錫化合物が４価錫化合物と２価錫化合物の混合物であって、Ｓｎ４＋：Ｓｎ２＋の錫イオン比が９０：１０〜１０：９０の範囲にあることにある。 A second aspect of the present invention is an invention based on the first aspect, wherein an alkaline aqueous solution is mixed with a mixed aqueous solution of a trivalent indium compound and a tin compound to produce a coprecipitated hydroxide of indium and tin. A step, a step of washing the precipitate with pure water or ion-exchanged water, a step of discarding a supernatant of the precipitate and preparing a slurry in which indium tin hydroxide particles are dispersed, and a step of drying the slurry And improving the method for producing ITO powder, comprising firing the dried indium water tin oxide to obtain indium tin oxide. The characteristic point is that the tin compound is a mixture of a tetravalent tin compound and a divalent tin compound, and the tin ion ratio of Sn 4+ : Sn 2+ is in the range of 90:10 to 10:90.

また本発明の第３の観点は、第２の観点に基づく発明であって、前記４価錫化合物がＳｎＣｌ４水溶液であり、前記２価錫化合物がＳｎＣｌ２・２Ｈ２Ｏ粉末であるＩＴＯ粉末の製造方法である。
また本発明の第４の観点は、第１の観点のＩＴＯ粉末又は第２若しくは第３の方法により製造されたＩＴＯ粉末を溶媒に分散させて分散液を製造する方法である。
更に本発明の第５の観点は、第４の観点の分散液からＩＴＯ膜を製造する方法である。 The third aspect of the present invention is an invention based on the second aspect, wherein the tetravalent tin compound is an SnCl 4 aqueous solution, and the divalent tin compound is SnCl 2 .2H 2 O powder. It is a manufacturing method.
A fourth aspect of the present invention is a method for producing a dispersion by dispersing the ITO powder of the first aspect or the ITO powder produced by the second or third method in a solvent.
Furthermore, a fifth aspect of the present invention is a method for producing an ITO film from the dispersion liquid according to the fourth aspect.

本発明の第１の観点のＩＴＯ粉末は、所定のＸ線回折装置で所定の条件でＸ線を照射し、得られた回折線から所定の解析ソフトを使用し、プロファイル関数としてＦＰを用いたＰａｗｌｅｙ法にて解析し、ローレンツ関数成分の半値幅から結晶子サイズと格子歪を算出した格子歪が０．２〜０．８の範囲にある。格子歪が大きいほど、圧粉体にしたときに低い体積抵抗率を得ることができる。具体的には、格子歪が０．２〜０．８の範囲にあるＩＴＯ粉末は、この圧粉体に４．９ＭＰａ（５０ｋｇｆ／ｃｍ２）の圧力を加えたときの圧粉体の体積抵抗率は０．２０Ωｃｍ以下にすることができる。 The ITO powder according to the first aspect of the present invention irradiates X-rays with a predetermined X-ray diffractometer under predetermined conditions, uses predetermined analysis software from the obtained diffraction lines, and uses FP as a profile function. The lattice strain obtained by analyzing by the Pawley method and calculating the crystallite size and the lattice strain from the half width of the Lorentz function component is in the range of 0.2 to 0.8. The larger the lattice strain, the lower the volume resistivity when the green compact is made. Specifically, the ITO powder having a lattice strain in the range of 0.2 to 0.8 has a volume resistance of the green compact when a pressure of 4.9 MPa (50 kgf / cm 2 ) is applied to the green compact. The rate can be 0.20 Ωcm or less.

また本発明の第２の観点のＩＴＯ粉末の製造方法では、インジウムと錫の共沈水酸化物を生成する工程で、錫化合物が４価錫化合物と２価錫化合物の混合物であって、Ｓｎ４＋：Ｓｎ２＋の錫イオン比が９０：１０〜１０：９０の範囲である。この範囲にすることによりインジウム錫水酸化物の前駆体の構造が安定するものと考えられ、これにより、この前駆体中に取り込まれるＳｎの量が増加し、Ｉｎ２Ｏ３の格子歪を増加させて、ＩＴＯ粉末からなる圧粉体の低い体積抵抗率を得ることができる。 In the method for producing ITO powder according to the second aspect of the present invention, in the step of producing a coprecipitated hydroxide of indium and tin, the tin compound is a mixture of a tetravalent tin compound and a divalent tin compound, and Sn 4+ : Tin ion ratio of Sn 2+ is in the range of 90:10 to 10:90. This range is considered to stabilize the structure of the indium tin hydroxide precursor, thereby increasing the amount of Sn incorporated into the precursor and increasing the lattice strain of In 2 O 3. Thus, a low volume resistivity of the green compact made of ITO powder can be obtained.

更に本発明の第３の観点のＩＴＯ粉末の製造方法では、ＳｎＣｌ４水溶液とＳｎＣｌ２・２Ｈ２Ｏ粉末とを混合して錫含有水溶液を調製する。この４価錫化合物と２価錫化合物の組合せは汎用性やコストの点で優れている。 Further in the manufacturing method of the third aspect of the ITO powder of the present invention, by mixing a SnCl 4 solution and SnCl 2 · 2H 2 O powder to prepare a tin-containing aqueous solution. This combination of a tetravalent tin compound and a divalent tin compound is excellent in terms of versatility and cost.

ＩＴＯ粉末の圧粉体の抵抗率を測定する装置の模式図である。It is a schematic diagram of the apparatus which measures the resistivity of the green compact of ITO powder. ＩＴＯの格子歪の逆数とその抵抗率との関係を示す図である。It is a figure which shows the relationship between the reciprocal number of the lattice distortion of ITO, and its resistivity.

次に本発明を実施するための形態を説明する。ＩＴＯ粉末の抵抗率は、このＩＴＯ粉末から作られるＩＴＯ膜の特性を評価するうえで重要な指標である。特にＩＴＯ膜を導電性シートや電極として使用する場合には、高い導電性、即ち低い抵抗率が求められる。   Next, the form for implementing this invention is demonstrated. The resistivity of the ITO powder is an important index for evaluating the characteristics of the ITO film made from the ITO powder. In particular, when an ITO film is used as a conductive sheet or electrode, high conductivity, that is, low resistivity is required.

このＩＴＯはＩｎ２Ｏ３に錫(Ｓｎ)を固溶させた固溶体であり、Ｉｎサイトに置換固溶したＳｎ原子１つに対し、１つのキャリア電子が生成することで、高い導電性を発現させることができる。また、Ｉｎ３＋のイオン半径（Ｓｈａｎｎｏｎ半径）が０．８０Åであり、Ｓｎ４＋のイオン半径（Ｓｈａｎｎｏｎ半径）がこれより小さい０．６９Åであることから、Ｉｎ２Ｏ３のＩｎサイトへＳｎが固溶すると、Ｉｎ２Ｏ３の結晶格子に歪が生じると考えられる。従って、これら二つを総合すると、置換したＳｎが多い、即ちＳｎから生成したキャリア電子が多い程、Ｉｎ２Ｏ３の結晶格子の格子歪が大きくなると考えられる。 This ITO is a solid solution in which tin (Sn) is dissolved in In 2 O 3 , and one carrier electron is generated for one Sn atom substituted and dissolved in the In site, thereby exhibiting high conductivity. Can be made. In addition, since the ion radius of In 3+ (Shannon radius) is 0.80Å and the ion radius of Sn 4+ (Shannon radius) is 0.69Å, which is smaller than this, Sn is fixed to the In site of In 2 O 3. It is considered that distortion occurs in the crystal lattice of In 2 O 3 when dissolved. Therefore, when these two are combined, it is considered that the more the substituted Sn, that is, the more carrier electrons generated from Sn, the greater the lattice strain of the crystal lattice of In 2 O 3 .

図２に示すように、Ｉｎ２Ｏ３の結晶格子の格子歪の逆数とＩＴＯ粉末の圧粉体の体積抵抗率に直線関係が得られることから、格子歪が大きいほど、圧粉体の低い体積抵抗率を得ることができる。この高い格子歪を作り出すためには、前駆体であるインジウム錫水酸化物をより安定な構造にして、Ｉｎ２Ｏ３への錫(Ｓｎ)の固溶量を増加することが必要になる。 As shown in FIG. 2, since a linear relationship is obtained between the reciprocal of the lattice strain of the crystal lattice of In 2 O 3 and the volume resistivity of the green compact of the ITO powder, the larger the lattice strain, the lower the green compact. Volume resistivity can be obtained. In order to produce this high lattice strain, it is necessary to increase the solid solution amount of tin (Sn) in In 2 O 3 by making the precursor indium tin hydroxide a more stable structure.

Ｉｎ２Ｏ３への錫(Ｓｎ)の固溶に関して、Ｉｎ３＋とＳｎ４＋とＳｎ２＋の各イオン半径に着目すると、前述したように、Ｉｎ３＋のイオン半径（Ｓｈａｎｎｏｎ半径）が０．８０Åであり、Ｓｎ４＋のイオン半径（Ｓｈａｎｎｏｎ半径）がこの０．８０Åより小さい０．６９Åである。一方、Ｓｎ２＋のイオン半径（Ｓｈａｎｎｏｎ半径）は０．８０Åより大きい１．１８Åである。このＩｎ３＋とＳｎ４＋とＳｎ２＋の各イオン半径の差異から、錫化合物を４価錫化合物と２価錫化合物との混合物とした場合、Ｉｎ３＋よりイオン半径が小さいＳｎ４＋が固溶することにより生じる歪を、Ｉｎ３＋よりイオン半径が大きいＳｎ２＋が緩和することで、インジウム錫水酸化物の構造が安定するものと推察される。この前駆体の構造が安定になれば、この前駆体中に取り込まれるＳｎの量が増加し、Ｉｎ２Ｏ３の結晶格子の格子歪を増加させて、ＩＴＯ粉末からなる圧粉体の低い体積抵抗率を得ることができる。 Regarding the solid solution of tin (Sn) in In 2 O 3 , focusing on the ionic radii of In 3+ , Sn 4+ and Sn 2+ , as described above, the ionic radius (Shannon radius) of In 3+ is 0.80 前述. Yes, the ion radius of Sn 4+ (Shannon radius) is 0.69 Å which is smaller than 0.80 こ の. On the other hand, the ion radius (Shannon radius) of Sn 2+ is 1.18 Å, which is larger than 0.80 Å. From the difference in ionic radii of In 3+ , Sn 4+ and Sn 2+ , when the tin compound is a mixture of a tetravalent tin compound and a divalent tin compound, Sn 4+ having an ionic radius smaller than that of In 3+ is dissolved. It is presumed that the structure of indium tin hydroxide is stabilized by the relaxation of Sn 2+ having an ionic radius larger than that of In 3+ . If the structure of the precursor becomes stable, the amount of Sn incorporated into the precursor increases, increasing the lattice strain of the crystal lattice of In 2 O 3 and reducing the volume of the green compact made of ITO powder. Resistivity can be obtained.

本発明のＩＴＯ粉末の格子歪は０．２〜０．８の範囲にある。０．２未満ではＩｎ２Ｏ３への錫(Ｓｎ)の固溶量が少なく、低い体積抵抗率が得られない。また０．８を超える値は本発明の製造方法では得られていない。 The lattice strain of the ITO powder of the present invention is in the range of 0.2 to 0.8. If it is less than 0.2, the solid solution amount of tin (Sn) in In 2 O 3 is small, and a low volume resistivity cannot be obtained. Moreover, the value exceeding 0.8 is not obtained by the manufacturing method of the present invention.

本発明のＩＴＯ粉末は、以下の方法で製造される。先ず、３価インジウム化合物に４価錫化合物と２価錫化合物の混合物を混合して混合水溶液を調製する。この混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成し、この沈澱を乾燥し、焼成した後、得られたインジウム錫酸化物を粉砕することにより得られる。３価インジウム化合物としては３塩化インジウム（ＩｎＣｌ３）、硝酸インジウム(Ｉｎ(ＮＯ３)３)、酢酸インジウム(Ｉｎ(ＣＨ３ＣＯＯ)３)などが挙げられ、４価錫化合物としては、４塩化錫（ＳｎＣｌ４）水溶液、臭化スズ(ＳｎＢｒ４)などが挙げられ、２価錫化合物としては、２塩化錫（ＳｎＣｌ２・２Ｈ２Ｏ）、硫酸錫(ＳｎＳＯ4)、臭化スズ(ＳｎＢｒ２)などが挙げられる。この４価錫化合物と２価錫化合物の組合せとして、ＳｎＣｌ４水溶液とＳｎＣｌ２・２Ｈ２Ｏ粉末とを混合することが汎用性やコストの点で好ましい。アルカリ水溶液としては、アルカリ金属の残留の心配のない、アンモニア（ＮＨ３）水、炭酸水素アンモニウム（ＮＨ４ＨＣＯ３）水などが挙げられる。 The ITO powder of the present invention is produced by the following method. First, a mixed aqueous solution is prepared by mixing a trivalent indium compound with a mixture of a tetravalent tin compound and a divalent tin compound. This mixed aqueous solution is mixed with an aqueous alkaline solution to form a coprecipitated hydroxide of indium and tin, dried and calcined, and then pulverized indium tin oxide obtained. Examples of the trivalent indium compound include indium trichloride (InCl 3 ), indium nitrate (In (NO 3 ) 3 ), indium acetate (In (CH 3 COO) 3 ), and the tetravalent tin compound includes tetrachloride. tin (SnCl 4) solution, tin tetrabromide (SnBr 4). Examples of the divalent tin compound, stannic chloride (SnCl 2 · 2H 2 O) , tin sulfate (SnSO 4), tin bromide (SnBr 2 ). As a combination of the tetravalent tin compound and the divalent tin compound, it is preferable in terms of versatility and cost to mix an SnCl 4 aqueous solution and SnCl 2 · 2H 2 O powder. Examples of the alkaline aqueous solution include ammonia (NH 3 ) water, ammonium hydrogen carbonate (NH 4 HCO 3 ) water, and the like, which do not cause the concern of residual alkali metal.

３価インジウム化合物に混合する４価錫化合物と２価錫化合物の混合物の両者の混合割合は、Ｓｎ４＋：Ｓｎ２＋の錫イオン比で９０：１０〜１０：９０の範囲である。この範囲外となる、Ｓｎ４＋が多すぎてＳｎ２＋が少なすぎる場合にはＳｎの水酸化物が析出しやすく、Ｓｎがドープされないため、導電性が低い不具合があり、Ｓｎ４＋が少なすぎてＳｎ２＋が多すぎる場合にはＳｎＯが析出しやすく、Ｓｎがドープされないため、導電性が低い不具合がある。好ましくは１５：８５〜８５：１５の範囲である。言い換えれば、３価インジウム化合物に混合する錫化合物が４価錫化合物のみの場合も、２価錫化合物のみの場合もＳｎがドープされにくい不具合がある。 The mixing ratio of both the tetravalent tin compound and the mixture of the divalent tin compound mixed with the trivalent indium compound is in the range of 90:10 to 10:90 in the Sn 4+ : Sn 2+ tin ion ratio. When there is too much Sn 4+ and too little Sn 2+ outside this range, Sn hydroxide is likely to precipitate, and Sn is not doped, so there is a problem of low conductivity, and Sn 4+ is too little. When there is too much Sn 2+, SnO is likely to precipitate and Sn is not doped, so that there is a problem of low conductivity. Preferably it is the range of 15: 85-85: 15. In other words, both the case where the tin compound mixed with the trivalent indium compound is only the tetravalent tin compound and the case where only the divalent tin compound is used have a problem that Sn is hardly doped.

インジウムと錫の水酸化物を共沈させるときの反応液の最終ｐＨを３．５〜９．３、好ましくはｐＨ５．０〜８．０、液温を５℃以上、好ましくは液温１０℃〜８０℃に調整することによって、インジウム錫の共沈水酸化物を沈澱させることができる。アルカリ水溶液の混合は、上記混合水溶液にアルカリ水溶液を滴下し、上記ｐＨ範囲に調整しながら行われるか、或いは上記混合水溶液とアルカリ水溶液とを同時に水に滴下し、上記ｐＨ範囲に調整しながら行われる。   The final pH of the reaction solution when coprecipitating indium and tin hydroxide is 3.5 to 9.3, preferably pH 5.0 to 8.0, and the solution temperature is 5 ° C. or more, preferably 10 ° C. By adjusting to ˜80 ° C., a coprecipitated hydroxide of indium tin can be precipitated. The mixing of the alkaline aqueous solution is performed while dropping the alkaline aqueous solution into the mixed aqueous solution and adjusting it to the pH range, or simultaneously dropping the mixed aqueous solution and the alkaline aqueous solution into water and adjusting the pH range. Is called.

上記共沈インジウム錫水酸化物の生成後、この沈殿物を純水又はイオン交換水で洗浄し、上澄み液の抵抗率が少なくとも５０００Ω・ｃｍ、好ましくは少なくとも５００００Ω・ｃｍになるまで洗浄する。上澄み液の抵抗率が５０００Ω・ｃｍより低いと塩素等の不純物が十分に除去されておらず、高純度のインジウム錫酸化物粉末を得ることができない。抵抗率が５０００Ω・ｃｍ以上となった上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得る。   After the coprecipitated indium tin hydroxide is formed, the precipitate is washed with pure water or ion-exchanged water and washed until the supernatant has a resistivity of at least 5000 Ω · cm, preferably at least 50000 Ω · cm. If the resistivity of the supernatant liquid is lower than 5000 Ω · cm, impurities such as chlorine are not sufficiently removed, and high-purity indium tin oxide powder cannot be obtained. The supernatant liquid of the precipitate having a resistivity of 5000 Ω · cm or more is discarded to obtain a highly viscous slurry in which indium tin hydroxide particles are dispersed.

このスラリーを、大気中、好ましくは窒素やアルゴンなどの不活性ガス雰囲気下、１００〜２００℃の範囲で２〜２４時間乾燥した後、大気中２５０〜８００℃の範囲で０．５〜６時間焼成炉にて焼成する。この焼成により形成された凝集体をハンマーミルやボールミルなどを用いて粉砕してほぐし、ＩＴＯ粉末を得る。このＩＴＯ粉末を５０〜９５質量部の無水エタノールと５〜５０質量部の蒸留水を混合した表面処理液に入れて含浸させた後、ガラスシャーレに入れて窒素ガス雰囲気下、２００〜４００℃の範囲で０．５〜５時間加熱すると、表面改質処理したＩＴＯ粉末が得られる。   The slurry is dried in air, preferably in an inert gas atmosphere such as nitrogen or argon, in the range of 100 to 200 ° C. for 2 to 24 hours, and then in the air in the range of 250 to 800 ° C. for 0.5 to 6 hours. Firing in a firing furnace. Aggregates formed by this firing are pulverized using a hammer mill, ball mill, or the like, and ITO powder is obtained. The ITO powder was impregnated with a surface treatment solution in which 50 to 95 parts by mass of absolute ethanol and 5 to 50 parts by mass of distilled water were mixed, and then placed in a glass petri dish under a nitrogen gas atmosphere at 200 to 400 ° C. When heated in the range for 0.5 to 5 hours, ITO powder subjected to surface modification treatment is obtained.

次に本発明の実施例を比較例とともに詳しく説明する。   Next, examples of the present invention will be described in detail together with comparative examples.

＜実施例１＞
〔表面改質処理したＩＴＯ粉末の製法〕
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液に、濃度５５質量％の四塩化錫（ＳｎＣｌ４）水溶液と二塩化錫（ＳｎＣｌ２２Ｈ２Ｏ）粉末とを混合した錫含有水溶液を添加し、攪拌して原料液を調製した。このとき、錫含有水溶液はＳｎ４＋：Ｓｎ２＋の錫イオン比で表１に示す割合で四塩化錫と二塩化錫を混合して調製した。また原料液は錫含有水溶液を錫（Ｓｎ）：インジウム（Ｉｎ）の質量比を表１に示すように混合した。 <Example 1>
[Production of surface-modified ITO powder]
A tin-containing aqueous solution prepared by mixing an aqueous solution of indium chloride (InCl 3 ) having an In metal concentration of 24% by mass with an aqueous solution of tin tetrachloride (SnCl 4 ) having a concentration of 55% by mass and tin dichloride (SnCl 2 2H 2 O) powder. The mixture was added and stirred to prepare a raw material solution. At this time, a tin-containing aqueous solution was prepared by mixing tin tetrachloride and tin dichloride at a ratio shown in Table 1 with a Sn 4+ : Sn 2+ tin ion ratio. The raw material solution was prepared by mixing a tin-containing aqueous solution as shown in Table 1 with a mass ratio of tin (Sn): indium (In).

４５℃に加温した純水中に、上記原料液と２５質量％のアンモニア（ＮＨ３）水溶液とをｐＨを調整しながら同時に滴下した。このとき反応温度を４５℃、最終の反応液のｐＨを８．０に調整した。生成したインジウム錫共沈水酸化物である沈殿物をイオン交換水によって繰り返し傾斜洗浄を行った。上澄み液の抵抗率が５０００Ω・ｃｍ以上になったところで、上記沈殿物の上澄み液を捨て、インジウム錫水酸化物粒子が分散した粘度の高いスラリーを得た In purified water was heated to 45 ° C., and the and the raw material solution and 25% by weight of ammonia (NH 3) solution was simultaneously added dropwise to adjust the pH. At this time, the reaction temperature was adjusted to 45 ° C., and the pH of the final reaction solution was adjusted to 8.0. The generated precipitate of indium tin coprecipitated hydroxide was repeatedly washed with ion-exchanged water using an inclined exchange. When the resistivity of the supernatant liquid became 5000 Ω · cm or more, the supernatant liquid of the precipitate was discarded, and a highly viscous slurry in which indium tin hydroxide particles were dispersed was obtained.

このスラリーを、大気中、１１０℃で１０時間乾燥した後、大気中６００℃で３時間焼成し、凝集体を粉砕してほぐし、ＩＴＯ粉末を得た。このＩＴＯ粉末を無水エタノールと蒸留水を混合した表面処理液(混合比率はエタノール９５質量部に対して蒸留水５質量部)に入れて含浸させた後、ガラスシャーレに入れて窒素ガス雰囲気下、４００℃にて２時間加熱して表面改質処理したＩＴＯ粉末を得た。   The slurry was dried in air at 110 ° C. for 10 hours, and then calcined in air at 600 ° C. for 3 hours. The aggregate was pulverized and loosened to obtain ITO powder. This ITO powder was impregnated in a surface treatment liquid (mixing ratio of 5 parts by mass of distilled water with respect to 95 parts by mass of ethanol) mixed with absolute ethanol and distilled water, and then placed in a glass petri dish under a nitrogen gas atmosphere. An ITO powder having been surface-modified by heating at 400 ° C. for 2 hours was obtained.

〔ＩＴＯ膜の製造〕
この表面改質処理したＩＴＯ粉末２０ｇを、蒸留水（０．０２０ｇ）、トリエチレングリコール−ジ−２−エチルヘキサノエート[３Ｇ]（２３．８ｇ）、無水エタノール（２．１ｇ）、リン酸ポリエステル（１．０ｇ）、２−エチルヘキサン酸（２．０ｇ）、２，４−ペンタンジオン（０．５ｇ）の混合液に入れて分散させた。調製した分散液を無水エタノールで固形分であるＩＴＯ粉末の含有量が１０質量％になるまで希釈した。この希釈した分散液をスピンコーティングにより石英ガラス板に塗布して成膜し、厚さ０．２μｍのＩＴＯ膜を得た。 [Production of ITO film]
20 g of this surface-modified ITO powder was added to distilled water (0.020 g), triethylene glycol-di-2-ethylhexanoate [3G] (23.8 g), absolute ethanol (2.1 g), phosphoric acid The mixture was dispersed in a mixed solution of polyester (1.0 g), 2-ethylhexanoic acid (2.0 g), and 2,4-pentanedione (0.5 g). The prepared dispersion was diluted with absolute ethanol until the content of ITO powder as a solid content was 10% by mass. This diluted dispersion was applied to a quartz glass plate by spin coating to form a film, and an ITO film having a thickness of 0.2 μm was obtained.

＜実施例２〜５＞
実施例１と同じ塩化インジウムと四塩化錫と二塩化錫を用いて、表１に示す錫イオン比で、四塩化錫と二塩化錫を混合して錫含有水溶液を調製し、かつ表１に示す質量比で、この錫含有水溶液と原料液とを混合した。上記錫イオン比と上記質量比を変えた以外は、実施例１と同様にして、表面改質したＩＴＯ粉末を得た。 <Examples 2 to 5>
Using the same indium chloride, tin tetrachloride and tin dichloride as in Example 1, tin tetrachloride and tin dichloride were mixed at a tin ion ratio shown in Table 1 to prepare a tin-containing aqueous solution. The tin-containing aqueous solution and the raw material liquid were mixed at the indicated mass ratio. A surface-modified ITO powder was obtained in the same manner as in Example 1 except that the tin ion ratio and the mass ratio were changed.

＜比較例１＞
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液に、濃度５５質量％の四塩化錫（ＳｎＣｌ４）水溶液を添加混合し、ＩｎＣｌ３−ＳｎＣｌ４混合溶液を調製した。このとき、混合溶液は錫（Ｓｎ）：インジウム（Ｉｎ）の質量比が表１に示すように混合した。以下、実施例１と同様にして、表面改質したＩＴＯ粉末を得た。 <Comparative Example 1>
An aqueous solution of tin tetrachloride (SnCl 4 ) having a concentration of 55% by mass was added to and mixed with an aqueous solution of indium chloride (InCl 3 ) having an In metal concentration of 24% by mass to prepare an InCl 3 -SnCl 4 mixed solution. At this time, the mixed solution was mixed such that the mass ratio of tin (Sn): indium (In) was as shown in Table 1. Thereafter, a surface-modified ITO powder was obtained in the same manner as in Example 1.

＜比較例２＞
Ｉｎ金属濃度が２４質量％の塩化インジウム（ＩｎＣｌ３）水溶液に、二塩化錫（ＳｎＣｌ２２Ｈ２Ｏ）粉末を添加混合し、ＩｎＣｌ３−ＳｎＣｌ２混合溶液を調製した。このとき、混合溶液は錫（Ｓｎ）：インジウム（Ｉｎ）の質量比が表１に示すように混合した。以下、実施例１と同様にして、表面改質したＩＴＯ粉末を得た。 <Comparative example 2>
Tin dichloride (SnCl 2 2H 2 O) powder was added to and mixed with an indium chloride (InCl 3 ) aqueous solution having an In metal concentration of 24 mass% to prepare an InCl 3 -SnCl 2 mixed solution. At this time, the mixed solution was mixed such that the mass ratio of tin (Sn): indium (In) was as shown in Table 1. Thereafter, a surface-modified ITO powder was obtained in the same manner as in Example 1.

＜比較試験＞
〔ＩＴＯ粉末の格子歪〕
ＢｒｕｋｅｒＡＸＳ社製、Ｘ線回折装置Ｄ８ Ａｄｖａｎｃｅを用いて、この装置に付属する試料ホルダーに実施例１〜５及び比較例１、２で得られた各ＩＴＯ粉末を充填して２θ／θ＝１５〜９０ｄｅｇの範囲でＸ線を照射し、得られた回折線からＲｉｅｔｖｅｌｄ解析ソフトであるＴＯＰＡＳ（ＢｒｕｋｅｒＡＸＳ社製）を使用し、プロファイル関数としてＦＰを用いたＰａｗｌｅｙ法にて解析し、ローレンツ関数成分の半値幅から結晶子サイズと格子歪を算出した。測定は、ＣｕＫａを管球として用い、４０ｋＶ、４０ｍＡとし、特定Ｘ線（波長１．５４Å）でステップ間隔を０．０５ｄｅｇとして行った。その結果を表１に示す。 <Comparison test>
[Lattice strain of ITO powder]
Using the X-ray diffractometer D8 Advance manufactured by BrukerAXS, the sample holder attached to the apparatus was filled with each ITO powder obtained in Examples 1 to 5 and Comparative Examples 1 and 2, and 2θ / θ = 15 to The X-ray is irradiated in the range of 90 deg., And the obtained diffraction lines are analyzed by the Pawley method using FP as a profile function using TOPAS (manufactured by BrukerAXS), which is Rietveld analysis software, and half of the Lorentz function component. The crystallite size and lattice strain were calculated from the value width. The measurement was performed using CuKa as a tube, 40 kV, 40 mA, a specific X-ray (wavelength 1.54 mm) and a step interval of 0.05 deg. The results are shown in Table 1.

〔ＩＴＯ粉末の体積抵抗率〕
実施例１〜５及び比較例１、２で得られた各ＩＴＯ粉末の体積抵抗率を図１に示す測定装置（三菱化学アナリティック製 MCP-PD51）を用いて測定した。その結果を表１に示す。具体的には、各ＩＴＯ粉末の体積抵抗率の測定は、図１に示す、内径φが２５ｍｍのシリンダー１にＩＴＯ粉末２．００ｇを充填し、４．９ＭＰａ（５０ｋｇｆ／ｃｍ２）の圧力を加えて、実施例１〜５及び比較例１、２で得られたＩＴＯ粉末の抵抗率をそれぞれ測定した。圧力は図示しない圧力センサにより、抵抗率は直流４端子法で測定した。図１において、２はＩＴＯ粉末の圧粉体である。 [Volume resistivity of ITO powder]
The volume resistivity of each ITO powder obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured using a measuring apparatus (MCP-PD51 manufactured by Mitsubishi Chemical Analytic) shown in FIG. The results are shown in Table 1. Specifically, the volume resistivity of each ITO powder is measured by filling 2.00 g of ITO powder in a cylinder 1 having an inner diameter φ of 25 mm shown in FIG. 1 and applying a pressure of 4.9 MPa (50 kgf / cm 2 ). In addition, the resistivity of the ITO powder obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured. The pressure was measured by a pressure sensor (not shown), and the resistivity was measured by a DC four-terminal method. In FIG. 1, 2 is a green compact of ITO powder.

Figure 2014065645
Figure 2014065645

＜評価＞
表１から明らかなように、４価錫化合物のみの比較例１及び２価錫化合物のみの比較例２では、ＩＴＯ粉末の格子歪がそれぞれ０．１５５、０．０７５であり、この場合には体積抵抗率が０．２３９Ωｃｍ、０．２０１Ωｃｍであったのに対して、Ｓｎ４＋：Ｓｎ２＋の錫イオン比が９０：１０〜１０：９０の範囲にある実施例１〜５では、ＩＴＯ粉末の格子歪が０．２〜０．８の範囲にあり、この場合には体積抵抗率は０．２０Ωｃｍ以下の範囲にあった。これにより格子歪が０．２〜０．８の範囲のＩＴＯ粉末は体積抵抗率が低いことが立証された。 <Evaluation>
As apparent from Table 1, in Comparative Example 1 containing only the tetravalent tin compound and Comparative Example 2 containing only the divalent tin compound, the lattice strain of the ITO powder was 0.155 and 0.075, respectively. In Examples 1 to 5 where the Sn 4+ : Sn 2+ tin ion ratio is in the range of 90:10 to 10:90, while the volume resistivity was 0.239 Ωcm and 0.201 Ωcm, the ITO powder The lattice strain was in the range of 0.2 to 0.8. In this case, the volume resistivity was in the range of 0.20 Ωcm or less. This proved that the ITO powder having a lattice strain in the range of 0.2 to 0.8 has a low volume resistivity.

Claims (5)

Ｘ線回折装置に付属する試料ホルダーに試料となるＩＴＯ粉末を充填して２θ／θ＝１５〜９０ｄｅｇの範囲でＸ線を照射し、得られた回折線から格子定数、結晶子サイズ、格子歪の精密化を行った結果、得られた格子歪が０．２〜０．８の範囲にあることを特徴とするＩＴＯ粉末。   A sample holder attached to the X-ray diffractometer is filled with ITO powder as a sample and irradiated with X-rays in the range of 2θ / θ = 15 to 90 deg. From the obtained diffraction lines, the lattice constant, crystallite size, and lattice distortion As a result of the refinement of the ITO, the obtained lattice strain is in the range of 0.2 to 0.8. ３価インジウム化合物と錫化合物の混合水溶液にアルカリ水溶液を混合して、インジウムと錫の共沈水酸化物を生成する工程と、前記沈殿物を純水又はイオン交換水で洗浄する工程と、前記沈殿物の上澄み液を捨ててインジウム錫水酸化物粒子が分散したスラリーを調製する工程と、前記スラリーを乾燥する工程と、前記乾燥したインジウム水錫酸化物を焼成してインジウム錫酸化物を得る工程とを含むＩＴＯ粉末を製造する方法において、
前記錫化合物が４価錫化合物と２価錫化合物の混合物であって、Ｓｎ４＋：Ｓｎ２＋の錫イオン比が９０：１０〜１０：９０の範囲にあることを特徴とする請求項１記載のＩＴＯ粉末の製造方法。 A step of mixing an aqueous alkaline solution with a mixed aqueous solution of a trivalent indium compound and a tin compound to produce a coprecipitated hydroxide of indium and tin, a step of washing the precipitate with pure water or ion-exchanged water, and the precipitation Discarding the supernatant of the product to prepare a slurry in which indium tin hydroxide particles are dispersed, drying the slurry, and firing the dried indium tin oxide to obtain indium tin oxide In a method for producing an ITO powder comprising:
The tin compound is a mixture of a tetravalent tin compound and a divalent tin compound, and a tin ion ratio of Sn 4+ : Sn 2+ is in a range of 90:10 to 10:90. Production method of ITO powder. 前記４価錫化合物がＳｎＣｌ４水溶液であり、前記２価錫化合物がＳｎＣｌ２・２Ｈ２Ｏ粉末である請求項２記載の製造方法。 The production method according to claim 2 , wherein the tetravalent tin compound is an SnCl 4 aqueous solution, and the divalent tin compound is SnCl 2 · 2H 2 O powder. 請求項１記載のＩＴＯ粉末又は請求項２若しくは３記載の方法により製造されたＩＴＯ粉末を溶媒に分散させて分散液を製造する方法。   A method for producing a dispersion by dispersing the ITO powder according to claim 1 or the ITO powder produced by the method according to claim 2 or 3 in a solvent. 請求項４記載の分散液からＩＴＯ膜を製造する方法。   A method for producing an ITO film from the dispersion according to claim 4.
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