TWI634079B - Indium hydroxide powder and indium oxide powder - Google Patents

Indium hydroxide powder and indium oxide powder Download PDF

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TWI634079B
TWI634079B TW103146308A TW103146308A TWI634079B TW I634079 B TWI634079 B TW I634079B TW 103146308 A TW103146308 A TW 103146308A TW 103146308 A TW103146308 A TW 103146308A TW I634079 B TWI634079 B TW I634079B
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indium
plane
powder
hydroxide powder
indium oxide
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菅本憲明
木部龍夫
川上哲史
岩佐剛
加茂哲郎
水沼昌平
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住友金屬鑛山股份有限公司
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Abstract

得到高密度的燒結體。使用將氫氧化銦粉預燒所得之氧化銦粉。其中，氫氧化銦粉係藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，(442)面之配向指數為0.5以下，並且相對於上述(200)面之配向指數，上述(400)面之配向指數之比為1.5以上，且並沒有出現(220)面及(420)面之繞射峰。 A high-density sintered body was obtained. The indium oxide powder obtained by calcining the indium hydroxide powder was used. Among them, the indium hydroxide powder has an alignment index of (200) plane and (400) plane obtained by Wilson's formula of 2.0 or more, and an alignment index of (442) plane is 0.5 or less, and is relative to the (200) plane As for the alignment index, the ratio of the above (400) plane alignment index is 1.5 or more, and there are no diffraction peaks on the (220) plane and (420) plane.

Description

氫氧化銦粉及氧化銦粉 Indium hydroxide powder and indium oxide powder

本發明係關於能製作出高密度之氧化銦錫濺鍍靶材(ITO濺鍍靶材)的氫氧化銦粉及氧化銦粉。尚，本專利申請為以於2014年3月11日在日本所申請之日本專利申請號特願2014-47507號作為基礎來主張優先權，且藉由參照此申請來引用於本申請。 The present invention relates to an indium hydroxide powder and an indium oxide powder capable of producing a high-density indium tin oxide sputtering target (ITO sputtering target). Still, this patent application claims priority based on Japanese Patent Application No. 2014-47507 filed in Japan on March 11, 2014, and is incorporated herein by reference with reference to this application.

近年，作為太陽能電池用途與觸控面板用途之透明導電膜的利用增加，伴隨此濺鍍靶材等、透明導電膜形成用材料的需求也增加。於此等之透明導電膜形成用材料中，主要使用氧化銦系燒結材料，作為主原料係使用氧化銦粉。為得到高密度靶材，用於濺鍍靶材之氧化銦粉係盡可能比表面積經控制，且分散性為良好者為較佳。 In recent years, the use of transparent conductive films for solar cell applications and touch panel applications has increased, and the demand for transparent conductive film forming materials, such as sputtering targets, has also increased. Among these materials for forming a transparent conductive film, an indium oxide-based sintered material is mainly used, and indium oxide powder is used as a main raw material. In order to obtain a high-density target, the indium oxide powder used for the sputtering target has a specific surface area controlled as much as possible, and a good dispersibility is preferred.

氧化銦粉之製造方法為，主要將硝酸銦水溶液或氯化銦水溶液等之酸性水溶液，以胺水等之鹼性水溶液中和後，將產生之氫氧化銦的沉澱乾燥後預燒，藉由所謂的中和法來製造。 The manufacturing method of indium oxide powder is that an acidic aqueous solution such as an indium nitrate aqueous solution or an indium chloride aqueous solution is neutralized with an alkaline aqueous solution such as amine water, and the resulting indium hydroxide precipitate is dried and then calcined. So-called neutralization method.

在中和法中，提案有為抑制氧化銦粉的凝 聚，利用添加鹼於70~95℃之高溫的硝酸銦水溶液中而得到針狀的氫氧化銦粉之方法(例如，參照專利文獻1。)。此方法為利用將針狀的氫氧化粉進行預燒而可得到凝聚較少之氧化銦粉。 In the neutralization method, it is proposed to suppress the coagulation of indium oxide powder. Polymerization is performed by adding a base to an indium nitrate aqueous solution at a high temperature of 70 to 95 ° C. to obtain needle-shaped indium hydroxide powder (for example, refer to Patent Document 1). In this method, the needle-shaped hydroxide powder is calcined to obtain indium oxide powder with less aggregation.

然而，以中和法製造之氧化銦粉，會產生粒 徑或粒度分布容易變不均，在製造濺鍍靶材時，靶材的密度不會變高，且密度不均之問題，與產生濺鍍時容易發生異常放電之問題。另外，中和法中會有氧化銦粉製造後發生大量的氮排水之緣故而使排水處理成本變高之問題。 However, indium oxide powder produced by the neutralization method will produce particles The diameter or particle size distribution is likely to become uneven. When manufacturing a sputtering target, the density of the target does not become high, and the problem of uneven density and the problem of abnormal discharge easily occur during sputtering. In addition, in the neutralization method, there is a problem that a large amount of nitrogen drainage occurs after the indium oxide powder is manufactured, thereby increasing the cost of drainage treatment.

作為改善此種問題之方法，提案有藉由將金 屬銦作電解處理而產生氫氧化銦的沉澱後，將其預燒而製造氧化銦粉之方法，即所謂的電解法(例如，參照專利文獻2。)。電解法中，與中和法相比，除氧化銦粉製造後的氮排水量可大幅減少之外，也可將得到之氧化銦粉的粒徑均一化。 As a way to improve such problems, the proposal The method of producing indium oxide powder by indium metal electrolytic treatment to produce precipitation of indium hydroxide, which is calcined, is the so-called electrolytic method (for example, refer to Patent Document 2). Compared with the neutralization method, in the electrolytic method, in addition to the greatly reduced nitrogen drainage after the indium oxide powder is manufactured, the particle size of the obtained indium oxide powder can also be uniformized.

然而，藉由電解法所得到之氫氧化銦粉，係 有因電解液的pH值近似於中性而非常細微且容易凝聚等之問題。將其預燒而得到之氧化銦粉雖一次粒徑較均一，但此等粒子容易變為凝聚較強之凝聚粉。藉由凝聚，此種氧化銦粉係粒度分布之範圍變得較廣，故有阻礙靶材之高密度化之問題。 However, the indium hydroxide powder obtained by the electrolytic method is a There is a problem that the pH value of the electrolytic solution is nearly neutral, and it is very fine and easily aggregates. Although the primary particle diameter of the indium oxide powder obtained by pre-firing is relatively uniform, these particles easily become agglomerated powder with strong aggregation. The range of the particle size distribution of such indium oxide powders is widened by agglomeration, so there is a problem that the density of the target material is hindered.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Literature]

〔專利文獻1〕日本特許第3314388號公報 [Patent Document 1] Japanese Patent No. 3314388

〔專利文獻2〕日本特許第2829556號公報 [Patent Document 2] Japanese Patent No. 2829556

於此，本發明係為鑑於上述情事而所提案出來者，且以提供一種可得到高密度的燒結體之氫氧化銦粉及將其預燒而得到之氧化銦粉為目的。 Herein, the present invention has been proposed in view of the foregoing circumstances, and an object thereof is to provide an indium hydroxide powder capable of obtaining a high-density sintered body and an indium oxide powder obtained by calcining the same.

達成上述目的之本發明的氫氧化銦粉，其特徵係藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，(442)面之配向指數為0.5以下，並且相對於(200)面之配向指數的(400)面之配向指數之比為1.5以上，且並不具有(220)面及(420)面之繞射峰。 The indium hydroxide powder of the present invention that achieves the above-mentioned object is characterized in that the orientation indexes of the (200) plane and (400) plane obtained by Wilson formula are each 2.0 or more, and the orientation index of the (442) plane is 0.5 or less. And the ratio of the (400) plane alignment index to the (200) plane alignment index is 1.5 or more, and does not have diffraction peaks for the (220) plane and (420) plane.

達成上述目的之本發明的氧化銦粉，其特徵係BET值為10~15m2/g，且粒度分佈之累積粒度10%粒徑(D10)為0.2μm以上，累積粒度90%粒徑(D90)為2.7μm以下。 The indium oxide powder of the present invention which achieves the above-mentioned object is characterized by a BET value of 10 to 15 m 2 / g, and a cumulative particle size of 10% of the particle size distribution (D10) is 0.2 μm or more, and a cumulative particle size of 90% (D90) ) Is 2.7 μm or less.

本發明係於特定之結晶面，亦即(200)面、(400)面及(442)面上進行配向，將具有特定之配向指 數之結晶性較高之氫氧化銦粉預燒而得到比表面積經控制之分散性良好的氧化銦粉。藉此，本發明係經由使用此氧化銦粉而得到相對密度較高之燒結體者。 The present invention is oriented on a specific crystal plane, that is, the (200) plane, the (400) plane, and the (442) plane. Several indium hydroxide powders with higher crystallinity are pre-fired to obtain indium oxide powders with a controlled specific surface area and good dispersibility. Accordingly, the present invention is one which uses this indium oxide powder to obtain a sintered body having a relatively high density.

〔圖1〕圖1為表示應用本發明之氧化銦粉的製造方法之流程圖。 [Fig. 1] Fig. 1 is a flowchart showing a method for manufacturing the indium oxide powder to which the present invention is applied.

〔實施發明之形態〕 [Form of Implementing Invention]

以下說明關於應用本發明之氫氧化銦粉及氧化銦粉。尚，本發明並無特別限制，並不限制以下之詳細說明者。關於應用本發明之氫氧化銦粉及氧化銦粉之實施形態，經由下例之順序來詳細說明。 The following describes the indium hydroxide powder and the indium oxide powder to which the present invention is applied. However, the present invention is not particularly limited and is not limited to those described in detail below. The embodiments of the indium hydroxide powder and the indium oxide powder to which the present invention is applied will be described in detail through the sequence of the following examples.

1.氧化銦粉之製造方法 1. Manufacturing method of indium oxide powder

1-1.氫氧化銦粉之生成步驟 1-1. Formation steps of indium hydroxide powder

1-2.氫氧化銦粉之回收步驟 1-2. Recovery steps of indium hydroxide powder

1-3.氫氧化銦粉之乾燥步驟 1-3. Drying steps of indium hydroxide powder

1-4.氫氧化銦粉 1-4. Indium hydroxide powder

1-5.氧化銦粉之生成步驟 1-5. Generation steps of indium oxide powder

1-6.氧化銦粉 1-6. Indium oxide powder

2.濺鍍靶材之製造方法 2. Manufacturing method of sputtering target

1.氧化銦粉之製造方法 1. Manufacturing method of indium oxide powder

氧化銦粉之製造方法，係如圖1所示，具有下例之步驟：藉由電解法生成氫氧化銦粉之氫氧化銦粉之生成步驟S1、回收所生成之氫氧化銦粉之回收步驟S2、乾燥經回收之氫氧化銦粉之乾燥步驟S3、與將經乾燥之氫氧化銦粉預燒後而得到氧化銦粉之氧化銦粉之生成步驟S4。 The manufacturing method of indium oxide powder is shown in FIG. 1 and has the following steps: Step S1 of generating indium hydroxide powder that generates indium hydroxide powder by electrolytic method, and step of recovering the generated indium hydroxide powder S2. A step S3 of drying the recovered indium hydroxide powder, and a step S4 of generating an indium oxide powder after pre-firing the dried indium hydroxide powder.

氫氧化銦粉係如後述般，使用含銦之陽極、使用硝酸銨水溶液作電解液、將電解液之pH值控制為2.5~4.0、液溫控制為20~60℃之範圍所生成，藉由X射線繞射所得之結晶面方位係配向於(200)面、(400)面以及(442)面之結晶性較高者。氫氧化銦粉其特徵係藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，優先配向於(400)面，相對於(200)面之配向指數的(400)面之配向指數之比為1.5以上，(442)面之配向指數為0.5以下，且並不具有(220)面及(420)面之繞射峰。將此種之氫氧化銦粉預燒而得到之氧化銦粉為比表面積經控制且分散性良好者。 The indium hydroxide powder is produced by using an anode containing indium, using an aqueous solution of ammonium nitrate as an electrolytic solution, and controlling the pH value of the electrolytic solution to 2.5 to 4.0 and the liquid temperature to be in a range of 20 to 60 ° C. The orientation of the crystal plane obtained by X-ray diffraction is aligned with the higher crystallinity of the (200) plane, (400) plane, and (442) plane. The characteristics of the indium hydroxide powder are that the orientation indexes of the (200) plane and (400) plane obtained by Wilson's formula are each 2.0 or more, and are preferentially aligned to the (400) plane, and ( The ratio of the alignment index of the 400) plane is 1.5 or more, the alignment index of the (442) plane is 0.5 or less, and there are no diffraction peaks of the (220) plane and (420) plane. The indium oxide powder obtained by pre-firing such indium hydroxide powder is one having a controlled specific surface area and good dispersibility.

(1-1)氫氧化銦粉之生成步驟 (1-1) Production steps of indium hydroxide powder

氫氧化銦粉之生成步驟S1中，使含有銦之陽極與陰極浸漬於電解液，藉由電解反應來生成氫氧化銦粉。 In the step S1 of generating indium hydroxide powder, an anode and a cathode containing indium are immersed in an electrolytic solution, and an indium hydroxide powder is generated by an electrolytic reaction.

關於陽極，例如可使用金屬銦等，為抑制氧化銦粉之雜質的混入，盡可能高純度者較佳。關於陰極，可使用導電性之金屬及碳電極等，例如可使用將不溶性之 鈦以鉑塗佈者等。 As the anode, for example, metal indium can be used, and in order to suppress the incorporation of impurities of the indium oxide powder, it is preferable that the purity is as high as possible. As the cathode, conductive metals and carbon electrodes can be used, for example, insoluble Titanium is coated with platinum.

關於電解液，可使用水溶性之硝酸鹽、硫酸 鹽、氯化物鹽等之一般的電解質鹽之水溶液。其中使用硝酸銨水溶液時，藉由氧化銦粉之生成步驟S4中之預燒，硝酸離子、銨離子可作為氮化合物去除，故可防止雜質成分的混入。另一方面，於電解液中，使用氯化銨和硫酸銨時，會混入氯化物離子和硫酸離子等之雜質成分。因此，關於電解液，使用硝酸銨水溶液為較佳。 For the electrolyte, water-soluble nitrate and sulfuric acid can be used. Aqueous solutions of common electrolyte salts such as salts and chloride salts. When an aqueous ammonium nitrate solution is used, the nitrate ions and ammonium ions can be removed as nitrogen compounds by the pre-baking in the step S4 of indium oxide powder generation, so the mixing of impurity components can be prevented. On the other hand, when ammonium chloride and ammonium sulfate are used in the electrolytic solution, impurity components such as chloride ions and sulfate ions are mixed. Therefore, as for the electrolytic solution, an aqueous ammonium nitrate solution is preferably used.

電解液的濃度設定在0.1~2.0mol/L之範圍 為較佳。電解液的濃度比0.1mol/L較低時，電解液的導電度會下降，電解電壓會上升，故會有通電部發熱、電力成本變高等之問題，故較不佳。另一方面，電解液的濃度比2.0mol/L較高時，藉由電解所生成之氫氧化銦粉會粗大化，故粒徑之偏差會變大，故較不佳。因此，電解液的濃度設定在0.1~2.0mol/L之範圍為較佳。 The concentration of the electrolyte is set in the range of 0.1 to 2.0 mol / L Is better. When the concentration of the electrolytic solution is lower than 0.1 mol / L, the conductivity of the electrolytic solution will decrease, and the electrolytic voltage will increase. Therefore, there will be problems such as heating of the current-carrying part and higher power cost, which is not good. On the other hand, when the concentration of the electrolytic solution is higher than 2.0 mol / L, the indium hydroxide powder generated by the electrolysis will be coarsened, so the variation in the particle size will become large, which is not good. Therefore, the concentration of the electrolytic solution is preferably set in a range of 0.1 to 2.0 mol / L.

電解液的pH值設定在pH2.5~4.0之範圍為 較佳。電解液比pH4.0較高時，生成之氫氧化銦粉會出現所需之(200)面、(400)面以及(442)面以外之(220)面、(420)面之繞射峰。該種氫氧化銦粉為在結晶性會產生紊亂，會成為一次粒徑細微化、且具有凝聚性之粉末，結果為粒度分布之幅度會變廣。又，電解液比pH2.5較低時，在陰極中會析出金屬的銦，氫氧化銦粉的生產效率會下降。因此，電解液的pH值設定在pH2.5~4.0之範圍為較佳。 The pH of the electrolyte is set in the range of pH 2.5 to 4.0 as Better. When the electrolyte is higher than pH 4.0, the generated indium hydroxide powder will have diffraction peaks on the (200) plane, (400) plane, and (220) plane and (420) plane other than the (442) plane. . This kind of indium hydroxide powder is a powder that causes turbulence in crystallinity, becomes a powder with a reduced primary particle size, and has cohesiveness. As a result, the range of the particle size distribution becomes wider. When the electrolytic solution is lower than pH 2.5, metal indium is precipitated in the cathode, and the production efficiency of indium hydroxide powder is reduced. Therefore, it is preferable to set the pH value of the electrolytic solution in the range of pH 2.5 to 4.0.

電解液的液溫為20~60℃之範圍較佳。電解 液的溫度比20℃較低、或比60℃較高時，會出現所需之(200)面、(400)面以及(442)面以外之(220)面、(420)面之繞射峰。而且，電解液的溫度比20℃較低時，氫氧化銦粉的結晶性會產生紊亂，會成為一次粒徑細微化、且具有凝聚性之粉末，結果為粒度分布之幅度會變廣。又，電解液的溫度比60℃較高時，為促進粒子成長，一次粒徑會變大。粒徑之差異會對凝聚之程度給予影響，故結果為包含不同粒徑之氫氧化銦粉時，粒度分布之幅度會變廣。因此，電解液的液溫設定在20~60℃之範圍為較佳。 The liquid temperature of the electrolytic solution is preferably in a range of 20 to 60 ° C. electrolysis When the temperature of the liquid is lower than 20 ° C or higher than 60 ° C, the required diffraction of the (200) plane, (400) plane, and (220) plane, (420) plane other than the (442) plane will appear. peak. In addition, when the temperature of the electrolytic solution is lower than 20 ° C, the crystallinity of the indium hydroxide powder is disturbed, and the primary particle size becomes finer and the powder has cohesiveness. As a result, the range of the particle size distribution becomes wider. When the temperature of the electrolytic solution is higher than 60 ° C, the primary particle diameter becomes larger in order to promote particle growth. The difference in particle size affects the degree of agglomeration, so the result is that when indium hydroxide powders with different particle sizes are included, the size of the particle size distribution becomes wider. Therefore, the liquid temperature of the electrolytic solution is preferably set in a range of 20 to 60 ° C.

電解條件雖無特別限制，電流密度在3~15A /dm2進行者為較佳。電流密度比3A/dm2較低時，氫氧化銦粉的生產效率會下降。電流密度比15A/dm2較高時，因電解電壓會上升容易產生液溫上升，會發生金屬銦的表面不動態化而難以電解等之問題。因此，電流密度設定在3~15A/dm2為較佳。 Although the electrolysis conditions are not particularly limited, it is better to perform the current density at 3 ~ 15A / dm 2 . When the current density is lower than 3A / dm 2 , the production efficiency of indium hydroxide powder will decrease. If the current density is higher than 15A / dm 2 , the temperature of the liquid is likely to rise due to an increase in the electrolytic voltage, and problems such as the surface of the metal indium not being dynamic and difficult to electrolyze may occur. Therefore, the current density is preferably set to 3 to 15 A / dm 2 .

(1-2)氫氧化銦粉之回收步驟 (1-2) Recovery steps of indium hydroxide powder

氫氧化銦粉之回收步驟S2，係將氫氧化銦粉之生成步驟S1中所生成之氫氧化銦粉從電解液進行固液分離，以純水清洗經分離之氫氧化銦粉後，再次進行固液分離而回收。固液分離方法係可列舉藉由例如旋轉過濾、離心分離、壓濾、加壓過濾、減壓過濾等之過濾。尚，不特別限 制清洗次數，視需要進行複數次。 The recovery step S2 of the indium hydroxide powder is the solid-liquid separation of the indium hydroxide powder generated in the step S1 of generating the indium hydroxide powder from the electrolytic solution, and the separated indium hydroxide powder is washed with pure water and then performed again. Solid-liquid separation and recovery. Examples of the solid-liquid separation method include filtration by spin filtration, centrifugation, pressure filtration, pressure filtration, and reduced pressure filtration. Not limited The cleaning times can be adjusted as many times as necessary.

(1-3)氫氧化銦粉之乾燥步驟 (1-3) Drying step of indium hydroxide powder

氫氧化銦粉之乾燥步驟S3中，進行回收後之氫氧化銦粉之乾燥。乾燥方法雖無特別限制，例如以噴霧乾燥機、空氣對流型乾燥爐、紅外線乾燥爐等之乾燥機來進行。乾燥條件係若可去除氫氧化銦粉之水分並無特別限制，但例如乾燥溫度為80~150℃之範圍較佳。乾燥溫度比80℃較低時，乾燥會變不完全。乾燥溫度比150℃較高時，會從氫氧化銦變成氧化銦，於次步驟之氧化銦粉之粒度分布的調整會變得不方便。又，乾燥時間係因溫度而異，但大約10~24小時。 In the step S3 of drying the indium hydroxide powder, the recovered indium hydroxide powder is dried. Although the drying method is not particularly limited, for example, it is performed with a dryer such as a spray dryer, an air convection-type drying furnace, or an infrared drying furnace. The drying conditions are not particularly limited if the moisture of the indium hydroxide powder can be removed, but for example, the drying temperature is preferably in the range of 80 to 150 ° C. When the drying temperature is lower than 80 ° C, drying becomes incomplete. When the drying temperature is higher than 150 ° C, it will change from indium hydroxide to indium oxide, and the adjustment of the particle size distribution of the indium oxide powder in the next step will become inconvenient. The drying time varies depending on the temperature, but it is about 10 to 24 hours.

(1-4)氫氧化銦粉 (1-4) Indium hydroxide powder

氫氧化銦粉係藉由上述之電解條件所生成，且配向於結晶面方位為(200)面、(400)面以及(442)面之結晶性較高者。氫氧化銦粉係藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，(442)面之配向指數為0.5以下，相對於(200)面之配向指數的(400)面之配向指數之比為1.5以上。所得之氫氧化銦粉係不具有(220)面及(420)面之繞射峰。此種氫氧化銦粉為凝聚被抑制，且粒度分布為狹窄者。結晶相的測定係使用X射線繞射裝置進行測定。配向指數係使用藉由X射線繞射來求得之各自的面指數之繞射強度，而藉由 Wilson式來計算。 The indium hydroxide powder is generated by the above-mentioned electrolysis conditions, and the crystallinity of the orientation of the crystal plane is (200) plane, (400) plane, and (442) plane is higher. The indium hydroxide powder is obtained by Wilson's formula, and the alignment index of the (200) plane and (400) plane is 2.0 or more, and the alignment index of the (442) plane is 0.5 or less. The ratio of the (400) plane alignment index is 1.5 or more. The obtained indium hydroxide powder did not have diffraction peaks on the (220) plane and the (420) plane. Such indium hydroxide powder is one whose aggregation is suppressed and the particle size distribution is narrow. The measurement of the crystal phase was performed using an X-ray diffraction device. The alignment index uses the diffraction intensity of the respective surface indices obtained by X-ray diffraction, and Wilson formula to calculate.

(1-5)氧化銦粉之生成步驟 (1-5) Generation steps of indium oxide powder

氧化銦粉之生成步驟S4中，藉由氫氧化銦粉之乾燥步驟S3將乾燥後之氫氧化銦粉預燒而生成氧化銦粉。雖適宜地決定預燒條件，但例如在預燒溫度600~800℃、預燒時間1~10小時進行者為較佳。 In the step S4 of generating indium oxide powder, the dried indium hydroxide powder is pre-fired through the drying step S3 of the indium hydroxide powder to generate indium oxide powder. Although the calcination conditions are appropriately determined, it is preferable to perform the calcination at a calcination temperature of 600 to 800 ° C. and a calcination time of 1 to 10 hours, for example.

預燒溫度比600℃較低時，氧化銦粉之BET值會超過15m2/g，一次粒子會太小，故變為具有凝聚性之粉末。因此，所得到之氧化銦粉中，無法得到高密度之燒結材料，例如氧化銦錫(ITO)燒結材料。預燒溫度比800℃較高時，氧化銦粉之BET值會未達10m2/g，一次粒徑會變大，粒子間產生之空洞會變大，故燒結性會下降。因此，所得到之氧化銦粉中，無法得到高密度之燒結材料。因此，為得到高密度之燒結材料，預燒溫度設定在600℃~800℃之範圍為較佳。 When the calcination temperature is lower than 600 ° C, the BET value of the indium oxide powder will exceed 15 m 2 / g, and the primary particles will be too small, so it will become a cohesive powder. Therefore, in the obtained indium oxide powder, a high-density sintered material such as an indium tin oxide (ITO) sintered material cannot be obtained. When the calcination temperature is higher than 800 ° C, the BET value of the indium oxide powder will not reach 10 m 2 / g, the primary particle size will increase, and the voids generated between the particles will increase, so the sinterability will decrease. Therefore, in the obtained indium oxide powder, a high-density sintered material cannot be obtained. Therefore, in order to obtain a high-density sintered material, it is preferable to set the calcination temperature in the range of 600 ° C to 800 ° C.

(1-6)氧化銦粉 (1-6) Indium oxide powder

所得到之氧化銦粉為比表面積之BET值經控制在10~15m2/g之範圍內，粒度分佈之累積粒度10%粒徑(D10)為0.2μm以上，累積粒度90%粒徑(D90)為2.7μm以下。此種氧化銦粉為比表面積經控制，分散性良好，凝聚較少，故可生成高密度之燒結材料。 The BET value of the specific surface area of the obtained indium oxide powder is controlled within a range of 10 to 15 m 2 / g, the cumulative particle size of the particle size distribution is 10%, and the particle size (D10) is 0.2 μm or more, and the cumulative particle size is 90% (D90) ) Is 2.7 μm or less. This kind of indium oxide powder has a controlled specific surface area, good dispersibility and less agglomeration, so it can form a high density sintered material.

尚，氧化銦粉之生成步驟S4中，將氫氧化銦 粉設為更所需之粒徑而視需要亦可進行碎解或粉碎。又，此氧化銦粉之生成步驟S4中，於氫氧化銦粉之電解之際，於電解液中使用硝酸銨時，會產生硝酸銨之分解，可防止氧化銦粉的混入。 In step S4 of generating indium oxide powder, indium hydroxide is The powder is set to a more desirable particle size and may be disintegrated or pulverized if necessary. In addition, in the step S4 of generating indium oxide powder, when ammonium nitrate is used in the electrolytic solution during the electrolysis of the indium hydroxide powder, decomposition of ammonium nitrate occurs, which can prevent the mixing of indium oxide powder.

如上述，氧化銦粉之製造方法中，藉由使用 包含銦之陽極之電解反應而得到氫氧化銦粉之際，作為電解液，藉由例如使用硝酸銨水溶液，控制電解液的pH值成為2.5~4.0、液溫成為20~60℃之範圍，可得到配向於(200)面、(400)面以及(442)面之結晶性較高之氫氧化銦粉。所得到之氫氧化銦粉為凝聚被抑制，粒度分布之狹窄者。氧化銦粉之製造方法中，藉由將所得到之氫氧化銦粉預燒，比表面積為10~15m2/g之範圍內，且分散性良好，可製造D10為0.2μm以上、D90為2.7μm以下之粒度分布狹窄之氧化銦粉。因此，使用所得到之氧化銦粉來製造濺鍍靶材時，可得到高密度之燒結體。 As described above, in the method for producing indium oxide powder, when an indium hydroxide powder is obtained by an electrolytic reaction using an anode containing indium, as an electrolytic solution, for example, an ammonium nitrate aqueous solution is used to control the pH value of the electrolytic solution to 2.5. Indium hydroxide powder having a crystallinity of ~ 4.0 and a liquid temperature in the range of 20 to 60 ° C can be obtained on the (200) plane, (400) plane, and (442) plane. The obtained indium hydroxide powder was one in which aggregation was suppressed and the particle size distribution was narrow. In the manufacturing method of indium oxide powder, the obtained indium hydroxide powder is calcined, and the specific surface area is in the range of 10 to 15 m 2 / g and the dispersibility is good. Indium oxide powder with narrow particle size distribution below μm. Therefore, when a sputtering target is produced using the obtained indium oxide powder, a high-density sintered body can be obtained.

又，此氧化銦粉之製造方法中，與中和法相 比，可抑制氧化銦粉之製造後之氮排水量。 In addition, in the manufacturing method of this indium oxide powder, Ratio, it can suppress the nitrogen drainage amount after the production of indium oxide powder.

2.濺鍍靶材之製造方法 2. Manufacturing method of sputtering target

濺鍍靶材之製造方法係，首先，以所需之比例，將藉由上述之氧化銦粉之製造方法所得到之氧化銦粉，與氧化錫粉等之靶材的其他原料混合而製作造粒粉。其次，使用造粒粉，藉由例如冷壓法來製作成型體。其次，在大氣壓下例如於1300~1600℃之溫度範圍內將成型體進行燒 結。其次，視所需進行將燒結體之平面和側面研磨等之加工。接著，藉由將燒結體結合於Cu製之底板，可得到氧化銦錫濺鍍靶材(ITO濺鍍靶材)。 The method for manufacturing a sputtering target is to first prepare an indium oxide powder obtained by the above indium oxide powder manufacturing method and other raw materials of the target material such as tin oxide in a desired ratio. Grain powder. Next, using a granulated powder, a compact is produced by, for example, a cold pressing method. Next, the molded body is fired under the atmospheric pressure, for example, in a temperature range of 1300 to 1600 ° C. Knot. Next, if necessary, the surface and side surfaces of the sintered body are polished. Next, by bonding the sintered body to a Cu base plate, an indium tin oxide sputtering target (ITO sputtering target) can be obtained.

濺鍍靶材之製造方法中，成為原料之氧化銦 粉之比表面積為經控制，分散性良好者，故可得到高密度之燒結體，且可使濺鍍靶材之密度變高。因此，濺鍍靶材在加工中不會產生破裂缺陷，且可抑制濺鍍時產生的異常放電。 Indium oxide as raw material in the manufacturing method of sputtering target The specific surface area of the powder is controlled and has good dispersibility, so a high-density sintered body can be obtained, and the density of the sputtering target can be increased. Therefore, the sputtering target does not generate crack defects during processing, and abnormal discharges generated during sputtering can be suppressed.

〔實施例〕 [Example]

以下，說明關於應用本發明之具體的實施 例，但本發明不限制於此等之實施例。 Hereinafter, specific implementations related to the application of the present invention will be described. Examples, but the invention is not limited to these examples.

<實施例1> <Example 1>

實施例1中，首先，將作為電解液使用之硝酸銨水溶液之濃度調整至0.5mol/L、pH值調整至3.5、液溫調整至40℃。pH值係藉由添加於電解液之硝酸量來調整。電解液之液體量設定在100L。 In Example 1, first, the concentration of the ammonium nitrate aqueous solution used as the electrolytic solution was adjusted to 0.5 mol / L, the pH value was adjusted to 3.5, and the liquid temperature was adjusted to 40 ° C. The pH is adjusted by the amount of nitric acid added to the electrolyte. The liquid amount of the electrolyte was set at 100L.

其次，使用經調整之電解液，進行氫氧化銦之電解。陽極係使用純度99.99%之金屬銦板，陰極係使用不溶性之Ti/PT電極。電流密度係設定在10A/dm2。其次，對所得到之氫氧化銦漿料做反復過濾與清洗之中，以100℃、15小時進行乾燥，得到3.6kg之氫氧化銦粉。藉由電解氫氧化銦粉之晶析效率為100%。 Next, electrolysis of indium hydroxide was performed using the adjusted electrolytic solution. The anode system uses a metal indium plate with a purity of 99.99%, and the cathode system uses an insoluble Ti / PT electrode. The current density was set at 10 A / dm 2 . Next, the obtained indium hydroxide slurry was repeatedly filtered and washed, and dried at 100 ° C. for 15 hours to obtain 3.6 kg of indium hydroxide powder. The crystallization efficiency by electrolytic indium hydroxide powder is 100%.

其次，對所得到之氫氧化銦粉進行X射線繞 射測定(PANalytical公司製，X’Pert-PRO)，由各結晶面之繞射峰強度來評價配向指數。配向指數係藉由Wilson式來求得。 Second, X-ray-wound the obtained indium hydroxide powder The radiometric measurement (X'Pert-PRO, manufactured by PANalytical Co., Ltd.) evaluates the alignment index based on the diffraction peak intensity of each crystal plane. The alignment index is obtained by Wilson formula.

其次，將所得到之氫氧化銦粉以700℃進行5 小時預燒。 Next, the obtained indium hydroxide powder was subjected to 5 ° C at 700 ° C. Burn-in hours.

使用比表面積測定裝置(macsorb1210：股份 有限公司Mountech製)來測定氧化銦粉之比表面積亦是BET值(氣體吸附法)。 Using specific surface area measuring device (macsorb1210: shares Mountech Co., Ltd.) to measure the specific surface area of the indium oxide powder is also a BET value (gas adsorption method).

之後，將氧化錫粉33g混合於所得到之氧化 銦粉967g之後，藉由冷壓法得到成型體，在大氣壓下以1400℃、30小時進行燒結，製作氧化銦錫之燒結體。燒結體之相對密度，係藉由阿基米德法來測定。 Thereafter, 33 g of tin oxide powder was mixed with the obtained oxide. After 967 g of indium powder, a compact was obtained by a cold pressing method, and sintered at 1400 ° C. for 30 hours under atmospheric pressure to produce a sintered compact of indium tin oxide. The relative density of the sintered body was measured by the Archimedes method.

<實施例2~7及比較例1~9> <Examples 2 to 7 and Comparative Examples 1 to 9>

實施例2、3及比較例5、6係製作與實施例1同樣之氫氧化銦粉，且調整氫氧化銦粉之預燒溫度如表2所示來製作氧化銦粉及燒結體。 Examples 2, 3, and Comparative Examples 5 and 6 produced the same indium hydroxide powder as in Example 1, and adjusted the calcination temperature of the indium hydroxide powder as shown in Table 2 to produce indium oxide powder and sintered bodies.

實施例4~7及比較例1~4、7~9，係調整電 解液之硝酸銨濃度、pH值、液溫如表1所示，調整氫氧化銦粉之預燒溫度如表2所示，除外為製作與實施例1同樣之氫氧化銦粉、氧化銦粉及燒結體。 Examples 4 to 7 and Comparative Examples 1 to 4, 7 to 9 The ammonium nitrate concentration, pH value, and liquid temperature of the solution are shown in Table 1. The pre-baking temperature of the indium hydroxide powder is adjusted as shown in Table 2, except that the same indium hydroxide powder and indium oxide powder as in Example 1 were prepared. And sintered bodies.

下列之表1中顯示氫氧化銦粉之配向指數及 晶析效率，表2中，顯示氧化銦粉之BET值、燒結體之 相對密度。 The following Table 1 shows the orientation index of indium hydroxide powder and Crystallization efficiency, Table 2 shows the BET value of indium oxide powder and the sintered body. Relative density.

由表1、2中顯示之結果，實施例1~7中， 可得到高結晶性之氫氧化銦粉，其為藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，(442)面之配向指數為0.5以下，且相對於(200)面之配向指數的(400)面之配向指數之比為1.5以上。又，實施例1~7中，沒有出現(220)面及(420)面之繞射峰。 From the results shown in Tables 1 and 2, in Examples 1 to 7, High crystallinity indium hydroxide powder can be obtained. The orientation indices of the (200) plane and (400) plane obtained by Wilson's formula are each 2.0 or more, and the orientation index of the (442) plane is 0.5 or less. The ratio of the (400) plane alignment index on the (200) plane alignment index is 1.5 or more. In Examples 1 to 7, diffraction peaks of the (220) plane and the (420) plane did not appear.

又，實施例1~7中，使用生成之氫氧化銦 粉，經由於600℃~800℃之溫度範圍進行預燒，可得到 BET值為10~15m2/g之範圍、D10為0.2μm以上、D90為2.7μm以下之粒度分布狹窄之氧化銦粉。實施例1~7為與比較例相比，燒結體之相對密度變為極高密度。 In addition, in Examples 1 to 7, the prepared indium hydroxide powder was used to perform a calcination in a temperature range of 600 ° C to 800 ° C, and a BET value in a range of 10 to 15 m 2 / g and a D10 of 0.2 μm or more were obtained. D90 is indium oxide powder with narrow particle size distribution below 2.7μm. In Examples 1 to 7, the relative density of the sintered body was extremely high compared to the comparative example.

另一方面，比較例1中，將電解液之pH值設 定在2.0，除外製作與實施例1相同之氫氧化銦粉。該結果，比較例1中，經由電解步驟於陽極析出金屬/銦，無法得到氫氧化銦粉，且晶析效率為0%。 On the other hand, in Comparative Example 1, the pH value of the electrolytic solution was set It was set at 2.0, except that the same indium hydroxide powder as in Example 1 was produced. As a result, in Comparative Example 1, metal / indium was precipitated at the anode through the electrolytic step, no indium hydroxide powder was obtained, and the crystallization efficiency was 0%.

另一方面，比較例2~4中，於氫氧化銦粉會 出現所需之(200)面、(400)面以及(442)面以外之(420)面之繞射峰，結晶性會產生紊亂，成為具有凝聚性之粉末。比較例2~4中，以預燒溫度700℃製作之氧化銦粉之BET值為10~15m2/g之範圍內，D10為0.4μm以上、D90為4.2μm以上，粒度分布會變廣。因此，比較例2~4中，燒結性會下降，燒結體之相對密度會變低。 On the other hand, in Comparative Examples 2 to 4, diffraction peaks at the (200) plane, (400) plane, and (420) plane other than the (442) plane appear in the indium hydroxide powder, and crystallinity occurs. Disorders and become a cohesive powder. In Comparative Examples 2 to 4, the BET value of the indium oxide powder prepared at a calcination temperature of 700 ° C. was in the range of 10 to 15 m 2 / g, D10 was 0.4 μm or more, and D90 was 4.2 μm or more, and the particle size distribution was widened. Therefore, in Comparative Examples 2 to 4, the sinterability was lowered, and the relative density of the sintered body was lowered.

又，如比較例5所示，於氫氧化銦粉之預燒 溫度500℃時，氧化銦粉之BET值會增加，同時變成具有凝聚性之粉末。又，比較例5亦係D10為0.4μm、D90為6.7μm，且粒度分布會變廣。比較例6中，以預燒溫度930℃製作之氧化銦粉之BET值會變過低，同時D10為0.5μm、D90為9.8μm，且粒度分布會變廣。此種比較例5、6中，燒結性會下降，燒結體之相對密度會變低。 In addition, as shown in Comparative Example 5, the calcination of indium hydroxide powder At a temperature of 500 ° C, the BET value of the indium oxide powder will increase and it will become a cohesive powder. In Comparative Example 5, D10 was 0.4 μm and D90 was 6.7 μm, and the particle size distribution was widened. In Comparative Example 6, the BET value of the indium oxide powder prepared at a calcination temperature of 930 ° C. became too low, while D10 was 0.5 μm and D90 was 9.8 μm, and the particle size distribution was broadened. In such Comparative Examples 5 and 6, the sinterability was lowered, and the relative density of the sintered body was lowered.

又，比較例7、8中，於氫氧化銦粉會出現所 需之(200)面、(400)面以及(442)面以外之面之繞射峰，結晶性會產生紊亂，會變為具有凝聚性之粉末。並 且，比較例7、8中，以預燒溫度1100℃製作之氧化銦粉之BET值會變太低，會變為D10為0.5μm、0.3μm，D90為14.8μm、10.2μm，且粒度分布會變廣。此種比較例7、8中，燒結性會下降，燒結體之相對密度會變非常低。 In Comparative Examples 7 and 8, indium hydroxide powder appeared. The diffraction peaks of the surfaces other than the (200) plane, (400) plane, and (442) plane are required, the crystallinity will be disordered, and it will become a cohesive powder. and Moreover, in Comparative Examples 7 and 8, the BET value of the indium oxide powder prepared at a calcination temperature of 1100 ° C would become too low, D10 would be 0.5 μm, 0.3 μm, D90 would be 14.8 μm, 10.2 μm, and the particle size distribution would be Will become wider. In such Comparative Examples 7 and 8, the sinterability was reduced, and the relative density of the sintered body was extremely low.

又，比較例9中，可得到雖配向於(200) 面，但不配向於(400)面及(422)面之氫氧化銦粉，會變為具有凝聚性之粉末。比較例9中，以預燒溫度700℃製作之氧化銦粉之BET值為10~15m2/g之範圍內，但D10為0.4μm、D90為12.6μm，粒度分布會變廣，會變為具有凝聚性之粉末。此種比較例9中，燒結性會下降，燒結體之相對密度會變低。 Moreover, in Comparative Example 9, indium hydroxide powder that was aligned on the (200) plane but not on the (400) and (422) planes was obtained, and the powder became cohesive. In Comparative Example 9, the BET value of the indium oxide powder prepared at a calcination temperature of 700 ° C was in the range of 10 to 15 m 2 / g, but D10 was 0.4 μm and D90 was 12.6 μm, and the particle size distribution was broadened and changed to Cohesive powder. In such Comparative Example 9, the sinterability was lowered, and the relative density of the sintered body was lowered.

由以上之結果，經由使用含有銦之陽極，使 用作為電解液之硝酸銨水溶液，控制電解液成為pH值2.5~4.0、液溫20~60℃之範圍，來進行電解反應而生成氫氧化銦粉之方法，明白可得到配向於(200)面、(400)面以及(442)面，結晶性較高，粒度分布為狹窄之氫氧化銦粉。接著，使用此氫氧化銦粉，可得到比表面積經控制之分散性良好之氧化銦粉，經由使用此氧化銦粉明白可得到高密度之燒結體。 From the above results, by using an anode containing indium, An ammonium nitrate aqueous solution as an electrolytic solution is used to control the electrolytic solution to a pH value of 2.5 to 4.0 and a liquid temperature of 20 to 60 ° C, and a method for performing an electrolytic reaction to generate indium hydroxide powder is understood to be able to be aligned on the (200) surface , (400) plane and (442) plane, indium hydroxide powder with high crystallinity and narrow particle size distribution. Next, using this indium hydroxide powder, an indium oxide powder having a controlled specific surface area and good dispersibility can be obtained, and it is understood that a high density sintered body can be obtained by using this indium oxide powder.

Claims (2)

一種氫氧化銦粉，其特徵係藉由Wilson式求得之(200)面及(400)面之配向指數為各自2.0以上，(442)面之配向指數為0.5以下，並且相對於上述(200)面之配向指數，上述(400)面之配向指數之比為1.5以上，且並不具有(220)面及(420)面之繞射峰，前述氫氧化銦粉係藉由使用20~40℃液溫之電解液的電解來製造。An indium hydroxide powder characterized by the orientation index of the (200) plane and (400) plane obtained by Wilson's formula being 2.0 or more, the orientation index of the (442) plane is 0.5 or less, and is ) Plane alignment index, the ratio of the (400) plane alignment index is 1.5 or more, and does not have the diffraction peaks of the (220) plane and (420) plane. The aforementioned indium hydroxide powder uses 20 ~ 40 Manufactured by electrolysis of electrolyte at a liquid temperature of ℃. 一種氧化銦粉，其係藉由將如請求項1之氫氧化銦粉進行預燒而得到，其特徵係BET值為10~15m2/g，且粒度分佈之累積粒度10%粒徑(D10)為0.2μm以上，累積粒度90%粒徑(D90)為2.7μm以下。An indium oxide powder obtained by pre-firing the indium hydroxide powder as claimed in claim 1, characterized by a BET value of 10 to 15 m 2 / g, and a cumulative particle size distribution of 10% particle size (D10 ) Is 0.2 μm or more, and the 90% cumulative particle size (D90) is 2.7 μm or less.
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