WO2011000211A1

WO2011000211A1 - Method for preparing high density sputtering coating target by nb-doped nano indium tin oxide powder

Info

Publication number: WO2011000211A1
Application number: PCT/CN2010/000936
Authority: WO
Inventors: 郑伟; 张维佳
Original assignee: 北京航空航天大学
Priority date: 2009-06-29
Filing date: 2010-06-24
Publication date: 2011-01-06
Also published as: CN101580379B; CN101580379A

Abstract

A method for preparing high density sputtering coating target by Nb-doped nano indium tin oxide powder comprises the following steps: (1) dissolving high pure metals: high pure metal niobium, high pure metal indium and high pure metal tin are respectively dissolved into inorganic acid to form transparent solutions; (2) mixing: the obtained transparent solutions are respectively filled into containers according to the proportion; (3) chemical precipitation: the three transparent solutions are made into Nb-doped and heavily tin-doped indium hydroxide nano powder; (4) washing: the Nb-doped and heavily tin-doped tin indium hydroxide nano powder is washed by deionized water and then precipitated; (5) calcinating: the Nb-doped nano indium tin oxide powder is prepared by calcining the nano powder; (6) granulation: the Nb-doped nano indium tin oxide powder is mixed with a binder and then dried, so that Nb-doped nano indium tin oxide powder before molding can be prepared; (7) molding: the Nb-doped nano indium tin oxide powder before molding is pressed into initial blank; (8) sintering: the initial blank is sintered under the normal pressure, and the high density sputtering coating target of the Nb-doped indium tin oxide can be prepared.

Description

采用掺铌纳米铟锡氧化物粉末制备高密度溅射镀膜靶材的方法 Method for preparing high-density sputter coating target by using erbium-doped nano-indium tin oxide powder

技术领域 Technical field

本发明涉及一种粉末及靶材的制备方法，尤其涉及一种掺铌纳米铟锡氧化物 (注：以下纳米铟锡氧化物简称 ITO)粉末及高密度溅射镀膜靶材制备方法，属粉末冶金和陶瓷技术领域。背景技术 The invention relates to a method for preparing a powder and a target, in particular to a method for preparing a ytterbium-doped nano-indium tin oxide (hereinafter referred to as ITO) powder and a high-density sputter coating target, belonging to a powder. Metallurgy and ceramic technology. Background technique

液晶显示器 (LCD)及手机屏等各种显示器和太阳能电池等光电器件上都需要透明导电薄膜作为透明导电电极材料，而该薄膜的透明性和导电性是上述光电器件性能的关健因素之一。在各种透明导电膜中铟锡氧化物透明导电膜 (注：以下简称 ITO膜)性能最好。因此，被广泛应用于上述光电器件中。而制备 ITO透明导电膜的方法有真空蒸镀法、磁控溅射法、化学气相沉积法等。但是，适合于大规模化生产的方法是采用溅射靶材进行磁控溅射镀 ITO膜的方法。而所需的磁控溅射靶材有铟锡合金靶和铟锡氧化物陶瓷靶这两种。制备铟锡合金靶较容易，但磁控溅射 ITO膜在工艺上有一定难度，工艺参数对 ITO膜性能太敏感，尤其是氧成份难以控制，成品率低，不适合于大规模化生产.与此相反，制备 ITO氧化物陶瓷靶相对比较复杂，但磁控溅射 ιτο膜较容易，工艺参数与膜性能依赖性不强，因为靶本身就是铟锡氧化物，氧含量控制较容易，成品率高，适合于大规模化生产。 Transparent conductive films are required as transparent conductive electrode materials for various displays and solar cells such as liquid crystal displays (LCDs) and mobile phones, and the transparency and conductivity of the films are one of the key factors for the performance of the above-mentioned photovoltaic devices. . Indium tin oxide transparent conductive film (Note: hereinafter referred to as ITO film) has the best performance among various transparent conductive films. Therefore, it is widely used in the above photovoltaic device. The methods for preparing the ITO transparent conductive film include a vacuum evaporation method, a magnetron sputtering method, a chemical vapor deposition method, and the like. However, a method suitable for large-scale production is a method of magnetron sputtering plating of an ITO film using a sputtering target. The required magnetron sputtering targets are indium tin alloy target and indium tin oxide ceramic target. It is easy to prepare indium tin alloy target, but the magnetron sputtering ITO film has certain difficulty in the process. The process parameters are too sensitive to the performance of ITO film, especially the oxygen component is difficult to control, the yield is low, and it is not suitable for large-scale production. In contrast, the preparation of ITO oxide ceramic targets is relatively complicated, but the magnetron sputtering ιτο film is relatively easy, and the process parameters and film properties are not strong, because the target itself is indium tin oxide, and the oxygen content is easier to control. High rate, suitable for large-scale production.

一般来说， ITO膜越导电越透明其显示屏的开关速度越快且显示效果越好。而要制备出这样高性能并且可规模化生产的 ITO膜，就要求采用均匀性好且密度高的 ITO靶. 这是因为：其一，溅射出的 ITO膜电阻率低，而低密度靶内有许多孔洞，孔洞内的不确定元素在溅射过程中也进入到 ITO膜，从而影响 ITO膜导电性能；其二，低密度 ITO靶面在溅射过程中容易产生一些黑化物质称其为结瘤，这些结瘤是低价氧化铟并处在靶表面腐蚀跑道周边，在溅射过程中会引起飞弧现象 (即局部击穿放电)，这将导致 ιτο膜中出现杂质缺陷，并且由于等离子体辉光不稳定而导致溅射工艺不稳定. 为此须将靶卸下来以便清除这些黑色结瘤，这又影响了工艺的持续性和生产效率；其三，低密度 ITO靶热导率低，在溅射过程中由於存在热应力而使靶开裂；其四，高密度靶使用寿命长且靶不太厚，而低密度靶必须靶厚才能提高使用寿命,而靶面磁场强度与磁芯距离成平方反比，所以太厚的靶其表面上的磁场强度就弱，从而不能有效地进行磁控溅射；其五，均匀性好靶溅射出的膜其成份才均勾，反之亦然。而提高 ITO靶密度取决於 ITO粉末和制靶工艺。纳米级 ITO粉末和高成本的制靶工艺，则 ITO 靶相对密度可达 97%以上甚至 99%以上。 In general, the more conductive and transparent the ITO film is, the faster the switching speed of the display screen is and the better the display effect is. To produce such a high-performance and scalable ITO film, it is required to use a uniform and high-density ITO target. This is because: First, the sputtered ITO film has a low resistivity and a low-density target. There are many holes, and the uncertain elements in the holes also enter the ITO film during the sputtering process, thereby affecting the conductivity of the ITO film. Second, the low-density ITO target surface is prone to some blackening substances during the sputtering process. Nodulation, these nodules are low-priced indium oxide and are on the surface of the target to corrode the periphery of the runway, causing arcing during the sputtering process (ie, local breakdown discharge), which will cause impurity defects in the film, and The plasma glow is unstable and the sputtering process is unstable. To this end, the target must be removed to remove these black nodules, which in turn affects the process continuity and production efficiency. Third, the low-density ITO target thermal conductivity Low, cracking of the target due to thermal stress during sputtering; Fourth, the high-density target has a long service life and the target is not too thick, while the low-density target must have a target thickness to increase the service life. The intensity of the surface magnetic field is inversely proportional to the square of the magnetic core. Therefore, the strength of the magnetic field on the surface of the target is too weak, so that it can not effectively perform magnetron sputtering. Fifth, the uniformity of the film sputtered by the target is uniform. Hook, and vice versa. Increasing the ITO target density depends on the ITO powder and the target process. For nano-scale ITO powders and high-cost target processes, the relative density of ITO targets can reach 97% or more and even 99%.

一般来说，对 ΠΌ粉末具体要求是：颗粒尺寸小於 lOOnm, 比表面积大於 15m²/g并且颗粒形貌呈现球状，粒径分布范围窄，团聚少. 目前制备纳米 ITO粉末方法有：均相共沉淀法，水溶液共沉淀法，电解法，溶胶-凝胶法，喷雾燃烧法，喷雾热分解法等。 In general, the specific requirements for tantalum powder are: particle size less than lOOnm, specific surface area greater than 15m ² /g and particle morphology is spherical, narrow particle size distribution, less agglomeration. Currently, methods for preparing nano ITO powder are: Precipitation Method, aqueous solution coprecipitation method, electrolysis method, sol-gel method, spray combustion method, spray pyrolysis method, and the like.

1. 均相共沉淀法 Homogeneous coprecipitation

首先将金属铟与硝酸配制成硝酸铟并与四氯化锡或硫酸锡按一定比例混合，一般这比例要求最终制备出的 ITO粉末中 I_n20_3:Sn0₂为 9:1(重量比)，因为掺杂锡过少起不了掺杂效果，而掺过多会出现 In4S_n30₁₂绝缘相并作为载流子的散射中心而影响 ITO导电性能. 料配好后，再加入沉淀剂尿素以及去离子水配制成一定浓度的铟锡盐水溶液，经加热 70~100Ό并强烈搅拌，尿素便在溶液中均匀分解出氨水 (ΝΗ₄ΟΗ)并与铟锡盐溶液进行化学反应生成氢氧化铟 (Ιη(ΟΗ )和氢氧化锡 (Sn(OH)₄)，这两种氧化物由於不溶於水而一起沉淀下来。再用去离子水多次洗净和过滤，去掉其中的氯离子和硫酸根离子等杂质. 这时得到一种乳白色胶状的氢氧化铟和氢氧化锡混合体。然后将其加热到 100Ό左右进行烘干，去掉其中水分并研磨，便得到了纳米级氢氧化铟和氢氧化锡的混合粉末. 再经高温 600~1100°C煅烧 5~15小时，使其氧化成 In₂0₃和 Sn0₂, 这便制备出了浅黄色纳米 ITO粉末。 First, metal indium and nitric acid are formulated into indium nitrate and mixed with tin tetrachloride or tin sulfate in a certain ratio. Generally, the ratio of I _n2 0 _{3 :} Sn0 _{2 in the} finally prepared ITO powder is 9:1 (weight ratio). Because the doping of tin is too small, the doping effect can not be achieved, and if the doping is too much, the In4S _n3 0 ₁₂ insulating phase will appear as the scattering center of the carrier and affect the conductivity of the ITO. After the material is prepared, the precipitant urea is added. Deionized water is formulated into a certain concentration of indium tin salt aqueous solution. After heating 70~100Ό and vigorously stirred, urea will evenly decompose ammonia water (ΝΗ ₄ ΟΗ) in the solution and chemically react with indium tin salt solution to form indium hydroxide ( Ιη(ΟΗ) and tin hydroxide (Sn(OH) ₄ ), these two oxides are precipitated together due to their insolubility in water. They are washed and filtered several times with deionized water to remove chloride and sulfate. Impurities such as ions. At this time, a milky white colloidal mixture of indium hydroxide and tin hydroxide is obtained. Then, it is heated to about 100 Torr for drying, and the water is removed and ground to obtain nanometer indium hydroxide and hydrogen. Mixed powder of tin oxide After calcination at a high temperature of 600~1100 °C for 5-15 hours, it is oxidized to In ₂ 0 ₃ and Sn0 ₂ , thus preparing a pale yellow nano ITO powder.

制备时须注意溶液始末 PH值和温度控制。若 PH值较低，则颗粒较大并且资源使用率低，再者在沉淀的氢氧化铟锡物中含有一些 InOOH物质，该物质在煅烧过程中会形成菱形 In₂0₃相,而 ITO是属立方方铁锰矿结构；若 PH值较高，则由於碱性加重会导致来自容器玻璃的杂质硅元素介入，使 ITO粉末纯度降低. 一般 pH值取 5.5~7.5适当。煅烧温度应控制在 600~1100'C, 升温速率控制在 4〜6°C/min。另夕卜，为了提高沉淀速度以便清冼，溶液中加入少量硫酸氨 (分散剂)，若加量适当则可使颗粒形貌呈显球状有利於烧结提高靶密度；若加量过少或过量则都会使颗粒显片状或条状。在加了硫酸氨作分散剂的情况下，煅烧温度应高一些以便使残留的硫酸热解，但温度过高会晶粒长大并且可能过早进入烧结阶段，而烧结是制靶的最后工序。 . Attention should be paid to the pH and temperature control of the solution at the beginning of the preparation. If the pH is lower, the particles are larger and the resource utilization rate is lower. Further, the precipitated indium tin oxide contains some InOOH substance, which forms a diamond-shaped In ₂ 0 ₃ phase during calcination, and ITO is It is a cubic iron-manganese ore structure; if the pH value is high, the impurity silicon from the container glass will be intervened due to the increase in alkali weight, and the purity of the ITO powder is lowered. The general pH value is 5.5 to 7.5. The calcination temperature should be controlled at 600~1100'C, and the heating rate should be controlled at 4~6 °C/min. In addition, in order to increase the sedimentation speed for clearing, a small amount of ammonium sulfate (dispersant) is added to the solution. If the amount is appropriate, the particle morphology may be spherical, which is favorable for sintering to increase the target density; if the amount is too small or excessive It will make the particles appear in the form of strips or strips. In the case of adding ammonium sulfate as a dispersing agent, the calcination temperature should be higher to cause pyrolysis of residual sulfuric acid, but if the temperature is too high, the crystal grains will grow and may enter the sintering stage too early, and sintering is the final step of the target. . .

2. 水溶液共沉淀法 2. Aqueous solution coprecipitation

也是将高纯金属铟与硝酸或盐酸并加入去离子水或蒸馏水配制成硝酸铟或盐酸铟水溶液，将此与四氯化锡或硫酸锡按一定比例混合. 但直接以氨水或碳酸铵 ((NH₄)₂C0₃)作沉淀剂，从外部滴入上述铟锡盐水溶液中并进行化学反应生成乳白色的氢氧化铟和氢氧化锡而沉淀下来. 再经多次过滤与洗净后进行洪干并煅烧，便制备出纳米级的 ITO粉末。 It is also prepared by mixing high-purity metal indium with nitric acid or hydrochloric acid and adding deionized water or distilled water to make indium nitrate or indium nitrate aqueous solution. This is mixed with tin tetrachloride or tin sulfate in a certain ratio. But directly with ammonia or ammonium carbonate (( NH ₄ ) ₂ C0 ₃ ) is used as a precipitant, and is externally dropped into the above indium tin salt aqueous solution and chemically reacted to form milky white indium hydroxide and tin hydroxide to precipitate. After repeated filtration and washing, it is flooded. After drying and calcining, nano-sized ITO powder was prepared.

这种制备方法是目前制备纳米 ITO粉末时比较普遍釆用的方法. 与均相共沉淀法一样在制备时必须严格控制 pH值和温度. 一般终止 pH值为 7.5~10,这要比均相共沉淀法的大一些，这是因为从外部滴入的氨水不能迅速而均匀地与溶液内铟或锡离子进行反应所致。氨水滴入速率对最终 ITO粉末晶粒大小有重要影响. 滴入过快颗粒大且粒径分布严重不均；滴入过慢则周期长。 This preparation method is a commonly used method for preparing nano ITO powder. As with the homogeneous coprecipitation method, the pH value and temperature must be strictly controlled during preparation. Generally, the pH value is 7.5 to 10, which is more homogeneous. The coprecipitation method is larger because the ammonia water dropped from the outside cannot be quickly and uniformly reacted with indium or tin ions in the solution. The rate of ammonia influx has an important effect on the grain size of the final ITO powder. The droplets are too fast and the particles are large and the particle size distribution is severely uneven; the dropping is too slow and the period is long.

3. 电解法 3. Electrolysis

将一定比例的铟锡合金置於硝酸铵电解液中并作为阳极，其硝酸铵浓度为 0.2~5mol/L， PH H¾ 4.0-9.5, 溶液温度控制在 0~50°C之间。电解方法可以采用平板电解法和周期逆向脉冲电解法，电解电流为 100~1800A/m². 在此电解条件下，可生成氢氧化铟和亚锡酸沉淀物，再经过清冼过滤处理并干燥后，放入炉里进行 1100°C的煅烧处理，从而制备出 ITO粉末。A certain proportion of indium tin alloy is placed in an ammonium nitrate electrolyte and used as an anode. The ammonium nitrate concentration is 0.2-5 mol/L, PH H3⁄4 4.0-9.5, and the solution temperature is controlled between 0 and 50 °C. The electrolysis method may be a plate electrolysis method and a periodic reverse pulse electrolysis method, and the electrolysis current is 100 to 1800 A/m ² . Under this electrolysis condition, indium hydroxide and stannous acid precipitates may be formed. After passing through a clear filtration treatment and drying, it was placed in a furnace and calcined at 1100 ° C to prepare an ITO powder.

4. 溶胶-凝胶法 4. Sol-gel method

将丁氧基铟 (In(OC₄H₉)₃) 或异丙氧基铟 (In(OC₃H₇)₃)和丁氧基锡 (Sn(OC₄H₉)₄)或异丙氧基锡 (Sn(OC₃H₇)₄)—起混合在异丙醇 (IPA)溶剂中或无水乙醇中，并加热 100°C，回流 3 小时,从而得到 ITO溶胶。然后加入适量的水并不断搅拌,这时溶液逐渐从透明变混浊再变成乳白色的凝胶，这表明溶液在进行水解反应.为了控制这反应速度可以加入一些氨水调节溶液的 PH值，一般 PH值为 8~12。再进行烘干和煅烧工艺就可以制备出纳米级 ITO粉末. Indium butoxide (In(OC ₄ H ₉ ) ₃ ) or indium isopropoxide (In(OC ₃ H ₇ ) ₃ ) and butoxide (Sn(OC ₄ H ₉ ) ₄ ) or isopropoxy The tin (Sn(OC ₃ H ₇ ) ₄ ) is mixed in an isopropanol (IPA) solvent or anhydrous ethanol, and heated at 100 ° C for 3 hours to obtain an ITO sol. Then add an appropriate amount of water and continue to stir, then the solution gradually changes from transparent to turbid and then into a milky white gel, which indicates that the solution is undergoing hydrolysis reaction. In order to control the reaction rate, some ammonia water can be added to adjust the pH of the solution, generally PH The value is 8~12. Nano-scale ITO powder can be prepared by drying and calcining.

5. 喷雾燃烧法 5. Spray combustion method

这是一种将金属熔化并进行雾化燃烧而获得纳米级金属氧化物粉末的方法。首先将高纯金属铟和金属锡按一定比例混合并置於陶瓷坩埚中加热到 20(TC形成 In-Sn合金熔体，再将该合金熔体过热到 750Ό并引人到雾化燃烧器中，用高压氧气对其进行高效雾化，从而形成微小的合金液雾并引人到高温反应室 (135(TC-190(TC)中进行剧烈氧化燃烧，然后急冷而形成纳米级 ITO粉末。 This is a method of melting a metal and atomizing it to obtain a nano-sized metal oxide powder. First, the high-purity metal indium and the metal tin are mixed in a certain ratio and placed in a ceramic crucible and heated to 20 (TC forms an In-Sn alloy melt, and then the alloy melt is superheated to 750 Torr and introduced into the atomizing burner. It is efficiently atomized by high-pressure oxygen to form a tiny alloy liquid mist and is introduced into a high-temperature reaction chamber (135 (TC-190 (TC) for intense oxidative combustion, and then quenched to form nano-scale ITO powder.

这种制备方法的关键技术是雾化燃烧温度和时间以及高温多相流场形状的控制.这涉及到了雾化燃烧器的结构和材料以及高温氧化燃烧反应室的形状和传热介质等大量具体问题。由此可见，这是一种特殊的复杂设备。 The key technologies of this preparation method are the atomization combustion temperature and time and the control of the shape of the high-temperature multi-phase flow field. This involves a large number of specific structures and materials of the atomization burner and the shape and heat transfer medium of the high-temperature oxidation combustion reaction chamber. problem. This shows that this is a special complex device.

6. 喷雾热分解法 6. Spray thermal decomposition method

这是一种将金属盐溶液喷入高温气氛中引起溶剂蒸发和金属盐的热分解，从而直接合成氧化物粉末的方法。首先将高纯金属铟锡按一定比例混合并倒入乙酸溶剂中制成醋酸铟锡盐水溶液，再将其喷入高温容器中进行喷雾热分解而形成 ιτο粉末。 This is a method of directly synthesizing an oxide powder by spraying a metal salt solution into a high temperature atmosphere to cause evaporation of a solvent and thermal decomposition of a metal salt. First, high-purity metal indium tin is mixed in a certain ratio and poured into an acetic acid solvent to prepare an indium tin acetate aqueous solution, which is then sprayed into a high-temperature container for spray thermal decomposition to form an ιτο powder.

7. 机械研磨法 7. Mechanical grinding method

这是陶瓷粉末的传统制备方法。首先将粗糙的 In₂0₃和 Sn0₂按 9： 1 比例在球磨机容器中混合，再加入适量的去离子水或有机溶剂如无水乙醇等形成浆料，然后进行机械球磨若干个小时直到颗粒大小为 400~800nm，颗粒的平均比表面积为 5~15m²/g为止。这时再加少量的烧结剂和适量的粘结剂，然后再次机械球磨使其充分混合均匀. 将此浆料再经过喷雾干燥处理而形成 ITO粉末，但不是纳米级。制备 ITO粉末的方法约上述 7种。其中均相共沉淀法和水溶液共沉淀法以及电解液法都 ' 属液相共沉淀法，所需设备都比较简单，并且都能制备出纳米级 ITO粉末。均相共沉淀法由於采用尿素受热在液体中均匀产生氨水，所以 ITO晶粒大小均匀，主要分布在 10~30nm范围内，并且对环境污染较小，不过工艺周期长，不适合规模生产。而水溶液共沉淀法由於采用从外部加氨水，所以 ITO晶粒大小不均匀，主要分布在 10~160nm范围内，并且因氨水还造成对实验环境污染. 但由於其工艺周期短，较适合於大规模生产而被广泛采用。电解液法工艺复杂并且杂质污染相对较重些。事实上液相沉淀法都存在着杂质污染的问题。 This is a conventional preparation method of ceramic powder. First, the coarse In ₂ 0 ₃ and Sn0 ₂ are mixed in a ball mill vessel at a ratio of 9:1, and then an appropriate amount of deionized water or an organic solvent such as absolute ethanol is added to form a slurry, followed by mechanical ball milling for several hours until the particles The size is 400 to 800 nm, and the average specific surface area of the particles is 5 to 15 m ² /g. At this time, a small amount of sintering agent and an appropriate amount of binder are added, and then mechanically ball-milled again to make it fully mixed. The slurry is further subjected to spray drying treatment to form ITO powder, but not nano-scale. The method for preparing the ITO powder is about the above seven kinds. Among them, the homogeneous coprecipitation method and the aqueous solution coprecipitation method and the electrolyte method are both liquid phase coprecipitation methods, the required equipment is relatively simple, and nanometer ITO powder can be prepared. The homogeneous coprecipitation method uses ammonia to uniformly generate ammonia water in the liquid. Therefore, the ITO grains are uniform in size, mainly distributed in the range of 10 to 30 nm, and have less environmental pollution, but the process cycle is long and is not suitable for scale production. The aqueous solution coprecipitation method uses ammonia water from the outside, so the ITO grain size is not uniform, mainly distributed in the range of 10~160nm, and the ammonia environment also causes pollution to the experimental environment. However, due to its short cycle time, it is more suitable for large It is widely used in scale production. The electrolyte process is complicated and the impurity contamination is relatively heavy. In fact, the liquid phase precipitation method has the problem of impurity contamination.

无杂质污染的方法是喷雾燃烧法.这种方法由於采用过热 In-Sn 金属溶体高效雾化并充分燃烧使得气相中的金属铟和锡原子都能与氧原子进行原子级别的化学反应，所以可生成The method of impurity-free contamination is spray combustion. This method is highly atomized and charged by using a superheated In-Sn metal solution. The partial combustion causes the metal indium and tin atoms in the gas phase to undergo atomic chemical reaction with the oxygen atom, so that it can be generated

30nm量级的纳米 ITO粉末，并且燃烧反应速度极快，生产效率很高，可在 50秒内生产出 1 公斤的纳米 ΓΓΟ粉末，这特别适合於大批量生产，而且在整个工艺过程中除 In、 Sn、 0外没有任何物质介入，制备出的 ITO粉末纯度很高. 而喷雾热分解法与上述喷雾燃烧法不同，它是将金属盐溶液喷入高温容器中进行喷雾热分解而形成 ITO粉末，由於有溶剂介入，所以有杂质存在。需要指出这两种方法都存在颗粒大小不均的问题，更成问题的是所需设备特殊而昂贵，工艺操作复杂而不成熟。成熟的粉末冶金工艺方法是传统的机械研磨法，但制备纳米级 ITO粉末有困难，即使高能机械球磨法也如此.在要求不高的情况下仍广泛使用。采用溶胶凝胶法固然能制备出 30nm左右量级的纳米 ITO粉末并且所用设备和工艺操作都十分简单. 但由於有机醇锡毒性较大并且生产效率低，所以很少采用。 Nano ITO powder of the order of 30nm, and the combustion reaction rate is extremely fast, the production efficiency is very high, and 1 kg of nano bismuth powder can be produced in 50 seconds, which is especially suitable for mass production, and in addition to In during the whole process. There is no substance involved in Sn, 0, and the prepared ITO powder is of high purity. The spray pyrolysis method is different from the above spray combustion method in that a metal salt solution is sprayed into a high temperature container for spray thermal decomposition to form ITO powder. There are impurities due to solvent intervention. It is necessary to point out that both methods have problems of uneven particle size, and the problem is that the equipment required is special and expensive, and the process operation is complicated and immature. The mature powder metallurgy process is a conventional mechanical grinding process, but it is difficult to prepare nano-sized ITO powder, even for high-energy mechanical ball milling. It is still widely used under less demanding conditions. The nano-ITO powder of the order of 30 nm can be prepared by the sol-gel method and the equipment and process operations are simple. However, since the organic alcohol tin is highly toxic and has low production efficiency, it is rarely used.

一般来说，对 ITO靶具体要求是：相对密度为 97~100%，烧结后 ITO靶颗粒大小为 2~20 ιη, 横断裂强度 (机械强度)为 5~50kg/mm², 电阻率为 7 X 10·⁴~5 X 10— ⁵ Ω _cm，热传导率为 6.28- 16.75 W. m"¹. Κ·¹ , 热膨胀系数为 7 X 1(T⁶~1 X 10_⁵/°C,热电系数在室温下为 -50uV/K。要制备出这样高品质的 ITO靶，除了采用纳米级的 ITO粉末外，压靶和烧结工艺也十分关键。 In general, the specific requirements for ITO targets are: relative density of 97~100%, ITO target particle size after sintering is 2~20 ηη, transverse rupture strength (mechanical strength) is 5~50kg/mm ² , resistivity is 7 ^{X 10 · 4 ~ 5 X 10-} 5 Ω cm, a thermal conductivity of ^{6.28- 16.75 W. m "1. Κ} · 1, the thermal expansion coefficient of ^{7 X 1 (T 6 ~ 1} X 10_ 5 / ° C, the pyroelectric coefficient At room temperature, it is -50uV/K. To produce such a high-quality ITO target, in addition to the nano-scale ITO powder, the pressure target and sintering process are also critical.

压靶工艺： Pressure target process:

在纳米 ITO粉末中加入少量 (l~2wt%)粘结剂如聚乙烯醇 (PVA)和分散剂如甲基丙烯酸铰 (2%wt)等并充分搅拌使其混合均匀，在 50~100°C左右温度下进行烘干. 然后研磨并用 80目左右的金属网筛过筛. 再将过筛了的 ITO粉末装入模具中用传统成形工艺诸如模压、热压、冷等静压、热等静压等施压成形。 Add a small amount (1~2wt%) of binder such as polyvinyl alcohol (PVA) and dispersant such as methacrylic hinge (2%wt) to the nano ITO powder and stir well to mix evenly, at 50~100° Drying at a temperature of about C. Then grinding and sieving through a mesh of about 80 mesh. The sized ITO powder is placed in a mold and subjected to conventional forming processes such as molding, hot pressing, cold isostatic pressing, heat, etc. Pressure forming such as static pressure.

模压工艺成熟，操作简单并且周期短. 但由於轴向加压 (约 180Mpa)存在压力不均，容易出现分层和裂纹等现象,并且靶密度仅 60~70%, 若在氧气压 (9atm)烧结也能提高靶密度，但操作不安全；热压 (约 800〜！ 100°C， 50~150Mpa)可使 ITO靶密度大幅度提高甚至高达 99%并且无需烧结剂，这是因为粉末处於热塑性状态.但高温模具十分昂贵并且尺寸小而只能压制小样品，另外压力不均也仍然存在。冷等静压和热等静压都是在各方向施压，所以靶受压均勾，无分层和裂紋现象. 冷等静压须在 ITO粉末中添加烧结剂如 Si0₂或 Ti0₂等才可使 ITO 靶相对密度提高到 97%以上，但这又带来了杂质。冷等静压与热等静压相结合工艺是目前压靶效果最好的一种方法，可使 ITO靶相对密度高达 99%以上，但价格更昂贵。 The molding process is mature, the operation is simple and the cycle is short. However, due to the uneven pressure in the axial pressure (about 180Mpa), delamination and cracking are prone to occur, and the target density is only 60~70%, if it is at oxygen pressure (9atm). Sintering can also increase the target density, but the operation is not safe; hot pressing (about 800~! 100 °C, 50~150Mpa) can greatly increase the density of ITO target even up to 99% and no sintering agent, because the powder is at Thermoplastic state. However, high temperature molds are very expensive and small in size and can only compress small samples, and uneven pressure is still present. Cold isostatic pressing and hot isostatic pressing are applied in all directions, so the target is pressed and no delamination and cracking. Cold isostatic pressing must add sintering agent such as Si0 ₂ or Ti0 ₂ to the ITO powder. The relative density of the ITO target can be increased to over 97%, but this brings impurities. The combination of cold isostatic pressing and hot isostatic pressing is currently the best method for pressing targets, and the relative density of ITO targets can be as high as 99% or more, but the price is more expensive.

还有一种无需施高压并且可成型曲面靶的注浆成型法：先将 ln₂0₃、 Sn0₂粉末和水按一定比例混合并用球磨机研磨而形成浆料，当研磨到颗粒大小为 0.4 μ ιη~0.8 μ ιη时,再加入少量的分散剂、粘结剂 (如聚乙烯醇或聚乙二醇等)、烧结剂 (如 Α1₂0₃或 Si0₂等)、去离子水以及氨水使上述浆料的粘性系数为 100~200cps、 PH值为 7.5~10.0, 因为碱性浆料不易侵蚀通用模具材料。然后用球磨机研磨使其充分均匀混合形成最后可用浆料，其粘性系数为 1000~2000cps, 将这种浆料放在真空中进行去泡处理. 再采用压力注浆法将上述浆料注入到特定形状的石膏模中，压力为 0.1~0.2Mpa，这可减少成型的时间，更重要的是防止在 ITO 靶坯体中产生空洞. 待模具中的浆料硬化后，再将该坯体从模中取出并在室温下放置 24 小时以便尽可能除掉其中的水分，然后再进行干燥处理，这样可以防止靶裂纹. 最后进行排塑和烧结处理就可以制备出 ITO靶. 这种方法适合於制备复杂曲面结构的 ITO靶，靶相对密度可达 86%。近年来，这种方法经特殊工艺改进后，其靶相对密度可达 97%以上甚至 99%以上，但制靶周期很长。烧结工艺： There is also a grouting method that does not require high pressure and can form a curved target: firstly mix ln ₂ 0 ₃ , Sn0 ₂ powder and water in a certain ratio and grind with a ball mill to form a slurry, when ground to a particle size of 0.4 μm When ~0.8 μ ιη, add a small amount of dispersant, binder (such as polyvinyl alcohol or polyethylene glycol), sintering agent (such as Α1 ₂ 0 ₃ or SiO _{2 ,} etc.), deionized water and ammonia to make the above The viscosity coefficient of the slurry is 100~200 cps, and the pH value is 7.5~10.0, because the alkaline slurry is not easy to erode the general mold material. Then, it is ground by a ball mill to make it fully uniformly mixed to form a final usable slurry having a viscosity coefficient of 1000 to 2000 cps. The slurry is placed in a vacuum for defoaming treatment. The slurry is injected into a specific method by pressure grouting. In the shape of the plaster mold, the pressure is 0.1~0.2Mpa, which can reduce the molding time and, more importantly, prevent the ITO A void is formed in the target body. After the slurry in the mold is hardened, the body is taken out of the mold and left at room temperature for 24 hours to remove as much moisture as possible, and then dried, thereby preventing Target cracks. Finally, ITO targets can be prepared by plasticizing and sintering. This method is suitable for the preparation of ITO targets with complex curved structures with a relative density of 86%. In recent years, this method has been improved by special processes, and its target relative density can reach 97% or more and even 99% or more, but the target period is very long. Sintering process:

不管采用上述哪种成形方式，成形的 ITO靶坯都要进行排塑和烧结工艺即：将 ITO靶坯在 400 - 600Ό温度下保温 1~2个小时进行排塑即将粘结剂等排除掉. 升温速率应慢一些以防因粘结剂、分散剂、防沫剂蒸发而导致的靶裂纹. 而后在 1300~ 1600°C温度下进行烧结. 因为低於 1300Ό温度下烧结其靶相对密度仅 60%左右. 而根据 In₂0₃-Sn0₂相图，只有当温度大於 1300Ό时 Sn0₂才完全固溶於 In₂0₃中. 但当温度大於 1600Ό时则 ITO材料因蒸发 (升华）而损失严重. 显然颗粒越小，粉末***表面越大，蒸发越严重，而颗粒大则只不利於提高靶密度. 因此具体烧结 IT0靶是有相当困难。 Regardless of which of the above-mentioned forming methods, the formed ITO target blank is subjected to a plasticizing and sintering process, that is, the ITO target blank is kept at a temperature of 400 - 600 Torr for 1 to 2 hours, and the plastic is discharged to remove the binder. The heating rate should be slower to prevent target cracks caused by evaporation of binders, dispersants, and antifoaming agents. Then, sintering is performed at a temperature of 1300 to 1600 ° C. Because the target is sintered at a temperature below 1300 ° C, the relative density is only 60. According to the In ₂ 0 ₃ -Sn0 ₂ phase diagram, Sn0 ₂ is completely dissolved in In ₂ 0 ₃ only when the temperature is greater than 1300 .. However, when the temperature is greater than 1600 则, the ITO material is lost due to evaporation (sublimation). Severe. Obviously, the smaller the particle size, the larger the surface of the powder system, the more severe the evaporation, and the larger the particle is only conducive to increasing the target density. Therefore, it is quite difficult to specifically sinter the IT0 target.

解决的方法是快速烧结：将已排塑了的 ITO靶坯直接放入温度为 1600°C的高温炉里，烧结 30分钟即可. 这是因为纳米颗粒表面硬化速率远大於热传递速率，一旦颗粒全表面硬化了，颗粒内的物质就不易蒸发出来并且硬的外壳维持住了纳米颗粒原有尺寸. 当 ITO粉末颗粒为 35nm时这样制备出的 ITO靶相对密度可达 97%以上. 但要求粉末极细和粒度分布很窄，并且大样品易裂只能制备小样品。 The solution is rapid sintering: The cast ITO target blank is directly placed in a high temperature furnace at a temperature of 1600 ° C and sintered for 30 minutes. This is because the surface hardening rate of the nanoparticles is much greater than the heat transfer rate. When the particles are fully surface hardened, the particles in the particles are not easily evaporated and the hard outer shell maintains the original size of the nanoparticles. When the ITO powder particles are 35 nm, the relative density of the ITO target prepared can reach 97% or more. The powder is extremely fine and the particle size distribution is very narrow, and large samples are prone to cracking and only small samples can be prepared.

进一步提高靶密度须采用在氧气压 (l.l~10atm)下进行烧结并添加烧结剂，这是因为 ITO 靶在烧结过程中失氧而导致靶组织成分和结构变化，而在氧气压下烧结就无此变化，靶相对密度可达 97%以上。但在氧气氛环境下进行高温烧结是十分危险的，因此需要特殊而昂贵的高温炉。添加少量 0.05~2wt%烧结剂如 Ti0₂, Bi₂0₃, Si0₂等可显明地提高 ITO靶密度. 若同时添加 Si0₂和 Bi₂0₃，效果会更好。其机制是烧结剂在高温下形成液体 (例如 Bi₂0₃大约在 830Ό 温度下形成液相)并涂在 ITO颗粒表面，从而阻止了 ITO的升华，同时液体的存在有助於物质移动并伴有收缩. 然而，加入烧结剂总是会带来杂质使 IT0膜性能变差。 To further increase the target density, it is necessary to use sintering at an oxygen pressure (ll~10 atm) and add a sintering agent. This is because the ITO target loses oxygen during the sintering process, resulting in changes in the composition and structure of the target, but no sintering under oxygen pressure. With this change, the relative density of the target can reach over 97%. However, high temperature sintering in an oxygen atmosphere is very dangerous, so a special and expensive high temperature furnace is required. Adding a small amount of 0.05~2wt% sintering agent such as Ti0 ₂ , Bi ₂ 0 ₃ , Si0 _2, etc. can obviously increase the density of ITO target. If Si0 ₂ and Bi ₂ 0 ₃ are added at the same time, the effect will be better. The mechanism is that the sintering agent forms a liquid at a high temperature (for example, Bi ₂ 0 ₃ forms a liquid phase at a temperature of about 830 Å) and is coated on the surface of the ITO particles, thereby preventing the sublimation of the ITO, and the presence of the liquid contributes to the movement of the substance. There is shrinkage. However, the addition of the sintering agent always brings impurities to deteriorate the performance of the IT0 film.

发明内容 Summary of the invention

本发明的目的是提供一种惨铌纳米铟锡氧化物粉末及高密度溅射镀膜靶材制备方法，它克服了现有技术的不足，采用简单的工艺流程制备掺铌纳米铟锡氧化物粉末；通过掺铌并采用简单的制靶和烧结工艺，大幅度地提高 ITO陶瓷靶密度,并降低了产品成本。 The object of the present invention is to provide a method for preparing a nanometer indium tin oxide powder and a high-density sputter coating target, which overcomes the deficiencies of the prior art and prepares the erbium-doped nano-indium tin oxide powder by a simple process. Through erbium doping and simple target and sintering processes, the ITO ceramic target density is greatly increased and the product cost is reduced.

本发明一种掺铌纳米铟锡氧化物粉末及高密度溅射镀膜靶材制备方法，该方法包括以下步骤： The invention provides a method for preparing erbium-doped nano-indium tin oxide powder and a high-density sputter coating target, the method comprising the following steps:

(1)对高纯金属进行溶解：分别用不同的无机酸溶解高纯金属铌、高纯金属铟、高纯金属锡成透明溶液，即采用氢氟酸和硝酸混和液将高纯金属铌原料溶解成氢氟酸硝酸铌透明溶液；采用硝酸和预定量的去离子水将高纯金属铟原料溶解成硝酸铟盐水透明溶液；采用王水或浓硫酸将高纯金属锡原料溶解成氯化锡透明溶液或硫酸锡透明溶液。 (1) Dissolving high-purity metals: Dissolving high-purity metal bismuth, high-purity metal indium, high-purity metal with different inorganic acids The tin-forming transparent solution, that is, the high-purity metal ruthenium raw material is dissolved into a transparent solution of hydrofluoric acid cerium nitrate by using a mixture of hydrofluoric acid and nitric acid; the high-purity metal indium raw material is dissolved into indium nitrate brine by using nitric acid and a predetermined amount of deionized water. Transparent solution; the high-purity tin metal raw material is dissolved into a tin chloride transparent solution or a tin sulfate transparent solution by using aqua regia or concentrated sulfuric acid.

(2) 进行配料：将上述三种透明溶液按预定比例分装容器，即按 In: Sn: Nb=100: 5〜15： 0.3-2.0质量比例分装到各自容器里备用。 (2) Ingredients: Dispense the above three transparent solutions into containers according to a predetermined ratio, that is, according to In: Sn: Nb=100: 5~15: 0.3-2.0 mass ratio, and put them into their respective containers for use.

(3) 化学沉淀：采用均相共沉淀法和水热法等化学沉淀法将上述三种透明溶液按比例和规定工序，制得掺铌重掺锡的氢氧化铟纳米粉末，即先将上述硝酸铟盐水透明溶液中加入一定量的尿素或氨水和去离子水等，加温至 90°C-10(TC并不断搅拌，这时溶液 PH值逐渐上升，再滴入氯化锡或硫酸锡透明溶液以及氢氟酸硝酸铌透明溶液，直到该溶液变成白色并化学反应完成为止便停止加热，并自然沉积；较佳质量比例为 In: Sn: Nb=100: 10.6： 0.7和较佳先后顺序为在溶液 PH值为 2-3时滴入氯化锡或硫酸锡透明溶液以及氢氟酸硝酸铌透明溶液，在溶液 PH值为 2.15时滴入上述两种透明溶液其共沉淀效果和掺杂效果最好。 (3) Chemical precipitation: using the chemical precipitation method such as homogeneous coprecipitation method and hydrothermal method, the above three transparent solutions are prepared according to the ratio and the specified procedure, and the antimony-doped tin-doped indium hydroxide nanopowder is prepared, that is, the above Add a certain amount of urea or ammonia water and deionized water to the clear solution of indium nitrate brine, warm to 90 ° C -10 (TC and keep stirring, then the pH value of the solution gradually rises, then add tin chloride or tin sulfate The transparent solution and the transparent solution of bismuth hydrofluoric acid nitrate until the solution turns white and the chemical reaction is completed, the heating is stopped and naturally deposited; the preferred mass ratio is In: Sn: Nb=100: 10.6: 0.7 and preferred The order is to add a transparent solution of tin chloride or tin sulfate and a transparent solution of barium hydrogen fluoride nitrate when the pH value of the solution is 2-3, and the coprecipitation effect and doping of the above two transparent solutions are dropped when the pH value of the solution is 2.15. The best results are mixed.

(4) 清洗：用去离子水清洗数遍上述掺铌重掺锡的氢氧化铟纳米粉末并沉淀，即用去离子水洗涤直到溶液中氯离子没有为止;沉淀方式可以采用自然沉淀，或采用高速离心机进行快速沉淀，即得浆状的掺铌重掺锡的氢氧化铟白色沉淀物。 (4) Cleaning: Wash the above-mentioned antimony doped tin-doped indium hydroxide nanopowder with deionized water several times and precipitate it, that is, wash it with deionized water until the chloride ion in the solution is not available; the precipitation method can be natural precipitation, or adopt The high-speed centrifuge performs rapid precipitation to obtain a slurry-like cerium-doped tin-doped white hydroxide indium white precipitate.

(5)煅烧：将上述纳米粉末放入高温炉进行煅烧，制得掺铌纳米铟锡氧化物粉末，即将上述白色浆状沉淀物放入电阻加热干燥箱里，在 110°C下进行 24小时 -48小时干燥处理形成白色块状的掺铌氢氧化铟和氢氧化锡的混合物；此后，将此白色块状混合物放入玛瑙研磨器里进行研磨形成掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末；然后，将此白色纳米粉末装入 99瓷坩埚里，再放入到高温炉里在 600°C-90(rC下进行 6-9小时缎烧，从而制得浅黄色的掺铌纳米 ITO纳米粉末，其平均粒径为 20-40nm，其表面积为 21-46m²/g。 (5) Calcination: The above nanopowder is placed in a high temperature furnace for calcination to obtain cerium-doped nano-indium tin oxide powder, which is placed in a resistance heating drying oven at 110 ° C for 24 hours. - 48 hours drying treatment to form a mixture of white strontium-doped strontium hydroxide and tin hydroxide; thereafter, the white block mixture is placed in an agate grinder for grinding to form a mixture of cerium-doped indium hydroxide and tin hydroxide. White nano-powder; then, the white nano-powder is placed in a 99-ceramic crucible, and then placed in a high-temperature furnace at 600 ° C - 90 (rC for 6-9 hours satin burning, thereby producing a pale yellow ytterbium The nano ITO nanopowder has an average particle diameter of 20 to 40 nm and a surface area of 21 to 46 m ² /g.

(6)造粒：将上述掺铌纳米铟锡氧化物粉末加入粘合剂并干燥，制得掺铌的铟锡氧化物成型前粉末，即采用粘结剂为如聚乙稀醇等并按 3 %-5 %重量比经热水溶解后,倒入上述制得的浅黄色掺铌纳米铟锡氧化物粉末并充分搅拌形成糊状；将此糊状液体置入电阻加热干燥箱里，在 100°C-110°C下进行干燥处理 24-48小时而形成浅黄色块状物；此后，将此浅黄色块状物放入玛瑙研磨器里进行研磨，并用 40 目 -80 目不锈钢金属网筛过筛后，形成造粒后的浅黄色的掺铌 ITO粉末,即制得掺铌纳米铟锡氧化物成型前粉末，其自然休止角约 45角。 (6) granulation: adding the above-mentioned cerium-doped nano-indium tin oxide powder to a binder and drying to obtain a powder of ytterbium-doped indium tin oxide before molding, that is, using a binder such as polyethylene glycol and the like After dissolving in 3% to 5% by weight in hot water, the light yellow ytterbium-doped nano-indium tin oxide powder obtained above is poured and thoroughly stirred to form a paste; the paste liquid is placed in a resistance heating oven, Drying at 100 ° C - 110 ° C for 24-48 hours to form a pale yellow mass; thereafter, the light yellow mass is placed in an agate grinder for grinding, and 40 mesh - 80 mesh stainless steel mesh After sieving through the sieve, a granulated yttrium-doped ITO powder is formed, that is, a ytterbium-doped nano-indium tin oxide pre-molding powder having a natural angle of repose of about 45 angstroms.

(7) 成型：采用成型压机将上述掺铌的铟锡氧化物成型前粉末压制成初胚，即将上述造粒后的浅黄色的掺铌 ITO粉末放入模具中，用压力机对其模具施加压力，其施加在样品上的压强为 1000-3000 kg/cm², 从而压制成型为 ITO靶初胚，其相对密度密度为 50%-60%。 (7) Molding: The powder of the above-mentioned ytterbium-doped indium tin oxide is molded into an initial embryo by using a molding press, that is, the granulated yttrium-doped ITO powder is placed in a mold, and the mold is pressed by a press. Pressure is applied, which is applied to the sample at a pressure of 1000-3000 kg/cm ² to be press-formed into an ITO target primord with a relative density density of 50% to 60%.

(8) 烧结：将上述初胚放入髙温炉里，按一定的升温曲线进行常压烧结，即将低密度的 ITO靶初胚放入高温炉里，在大气环境下按一定的升温曲线升温即在 300°C-500°C处保温 2-5 小时以排塑处理，再快速升温至 900°C-1100°C，然后缓慢升温至 1500°C-1600°C并保温 6-10 个小时，再缓慢降温至 900°C-110(TC后，自然冷却至室温，制得高密度的 ITO靶，其相对密度在 98%以上甚至可达到 99.1 %。若要进一步提高该靶密度，则采用气压烧结，即低密度的 ITO靶初胚置于 Al₂0₃99瓷管中，再将瓷管放入高温炉里，按一定的升温曲线升温即在 300 °C -500 °C处保温 2-5 小时以排塑处理；然后将此管抽成真空，再通入氧气至管内压强为 0.2-0.6MPa，并快速升温至 900°C-1100°C，然后缓慢升温至 1400°C-1550°C并保温 3-6个小时，再缓慢降温至 900°C-1100°C后，自然冷却至室温，即得高密度的 ITO陶瓷靶，其相对密度在 99.0%以上甚至可达到 99.5 %。本发明技术与现有技术相比具有的优点及积极效果：制备掺铌纳米 ITO粉末过程中仅当硝酸铟和尿素以及去离子的水溶液的 PH值为 2.1-2.3时，滴入氯化锡和氢氟酸硝酸铌透明溶液，从而掺锡惨铌效果和共沉淀效果好，并且得到的掺铌纳米 ITO粉末的纯度高，粒度小且分布窄，成分可控，组成均匀，表面活性高，无需添加分散剂，无污染，成本低，易于实现工业化生产，更重要的是掺铌后靶密度能大幅度提高,而且靶的导电性稍有提高或不降低，因此，掺铌可视为掺杂烧结剂。附图说明 (8) Sintering: The above-mentioned primordial embryos are placed in a tempering furnace, and atmospheric pressure sintering is carried out according to a certain heating curve. The low-density ITO target primordial embryos are placed in a high-temperature furnace, and the temperature is raised according to a certain heating curve in an atmospheric environment. That is, it is kept at 300°C-500°C for 2-5 hours to be plasticized, then rapidly heated to 900°C-1100°C, then slowly heated to 1500°C-1600°C and kept for 6-10 hours. , and then slowly cool down to 900 ° C-110 (after TC, naturally cooled to room temperature, to obtain a high density ITO target, which is relatively dense The degree is above 98% and can even reach 99.1%. To further increase the target density, air pressure sintering is used, that is, the low-density ITO target primordial is placed in the Al ₂ 0 ₃ 99 porcelain tube, and then the porcelain tube is placed in a high temperature furnace, and the temperature is raised according to a certain heating curve. Heat at 300 °C -500 °C for 2-5 hours to displace the plastic; then vacuum the tube, then introduce oxygen into the tube to a pressure of 0.2-0.6 MPa, and rapidly heat up to 900 °C -1100 °C Then, slowly heat up to 1400 ° C - 1550 ° C and keep it for 3-6 hours, then slowly cool down to 900 ° C -1100 ° C, and then naturally cool to room temperature, that is, a high density ITO ceramic target, its relative density Even 99.0% can reach 99.5 %. The advantages and positive effects of the technology of the present invention compared with the prior art: in the process of preparing the erbium-doped nano ITO powder, only when the pH values of the indium nitrate and urea and the deionized aqueous solution are 2.1-2.3, tin chloride is added dropwise. The transparent solution of hydrofluoric acid cerium nitrate, so that the tin-doping effect and the co-precipitation effect are good, and the obtained erbium-doped nano-ITO powder has high purity, small particle size and narrow distribution, controllable composition, uniform composition, high surface activity, and no need Adding dispersant, no pollution, low cost, easy to realize industrial production, more importantly, the target density can be greatly improved after erbium doping, and the conductivity of the target is slightly improved or not reduced. Therefore, erbium doping can be regarded as doping. Sintering agent. DRAWINGS

图 1是本发明的工艺流程图。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a process flow diagram of the present invention.

图中符号说明 Symbol description in the figure

1、金属溶解 2、配料 3、化学沉淀 4、清洗 5、煅烧、 6、造粒 1, metal dissolution 2, ingredients 3, chemical precipitation 4, cleaning 5, calcination, 6, granulation

7、成型 8、烧结具体实施方式 7, molding 8, sintering, the specific implementation

请参阅图 1，本发明一种掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法, 列举具体实施例如下： Please refer to FIG. 1, a method for preparing a ytterbium-doped nano-indium tin oxide powder and a high-density sputter coating target thereof, and the specific implementations are as follows:

实施例一 Embodiment 1

本发明一种掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，包括以下步骤： The invention discloses a method for preparing erbium-doped nano-indium tin oxide powder and a high-density sputter coating target thereof, comprising the following steps:

步骤一：首先用氢氟酸和硝酸混和液将高纯铌原料溶解成氢氟酸硝酸铌透明溶液；用硝酸和一定量的去离子水将高纯铟原料溶解成硝酸铟盐水透明溶液；用王水将高纯锡原料溶解成氯化锡透明溶液。 Step 1: firstly dissolving the high-purity cerium raw material into a transparent solution of hydrofluoric acid cerium nitrate by using a mixed solution of hydrofluoric acid and nitric acid; dissolving the high-purity indium raw material into a transparent solution of indium nitrate brine by using nitric acid and a certain amount of deionized water; Wang Shui dissolves the high-purity tin raw material into a tin chloride transparent solution.

步骤二：将上述各透明溶液按 In: Sn: Nb=100: 8.6： 0.3比例分装到各自容器里备用。步骤三：采用均相共沉淀法将上述三种透明溶液按铌、锡、铟质量比例为 In: Sn_: Nb=100: 8.6： 0.3比例在 5000mL三口烧杯里进行混和，其混和的先后顺序为：先将硝酸铟盐水溶液与尿素和去离子水进行混和，其三者质量比为 In: (NH₂)₂CO: H₂O=100: 700: 3600；将该混和溶液加温至 96°C，待该溶液 pH值为 2.1时，滴入氯化锡透明溶液和氢氟酸硝酸铌透明溶液，用强搅伴机进行并不断搅拌，直到该溶液变成白色并化学反应完成为止便停止加热并停止搅拌，自然沉淀。 Step 2: The above transparent solutions are dispensed into respective containers in the ratio of In: Sn: Nb = 100: 8.6: 0.3 for use. Step three: by homogeneous coprecipitation clear solution according to the above three niobium, tin, indium mass ratio of _{In: Sn: Nb = 100:} 8.6: 0.3 were blended in a ratio of three 5000mL beaker, which is mixed in the order : First, the aqueous solution of indium nitrate is mixed with urea and deionized water, and the mass ratio of the three is In: (NH ₂ ) ₂ CO: H ₂ O=100: 700: 3600; The mixed solution is heated to 96 ° C, and when the pH of the solution is 2.1, a transparent solution of tin chloride and a transparent solution of bismuth hydrofluoric acid are added dropwise, and the mixture is stirred with a strong stirrer until the solution turns white. When the chemical reaction is completed, the heating is stopped and the stirring is stopped, and the precipitate is naturally precipitated.

步骤四：用去离子水洗涤 10遍并沉淀，用 5 %AgN0₃溶液检査不到氯离子。沉淀方式采用自然沉淀，产品成本低。 Step 4: Wash 10 times with deionized water and precipitate, and check for chloride ions with 5% AgN0 ₃ solution. The precipitation method adopts natural precipitation and the product cost is low.

步骤五：去掉上清液，将上述白色浆状沉淀物放入电阻加热干燥箱里，在 110°C下进行 30 小时干燥处理形成白色块状的掺铌氢氧化铟和氢氧化锡的混合物；再将此白色块状混合物放入玛瑙研磨器里进行研磨形成掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末；此后，将此白色块状混合物放入玛瑙研磨器里进行研磨，即得掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末,其平均粒径为 ₂-8nm。然后，将此白色纳米粉末装入三氧化二铝 99瓷坩埚里，再放入到高温炉里在 850Ό下进行 8小时缎烧，从而制得浅黄色的掺铌 ITO纳米粉末，其平均粒径约为 51nm，其平均比表面积约为 21m²/g。 Step 5: removing the supernatant, placing the white slurry precipitate into a resistance heating drying oven, and drying at 110 ° C for 30 hours to form a white block mixture of strontium-doped indium hydroxide and tin hydroxide; The white block mixture is then placed in an agate grinder to be ground to form a white nanopowder mixed with antimony-doped indium hydroxide and tin hydroxide; thereafter, the white block mixture is placed in an agate grinder for grinding. A white nanopowder mixed with indium hydroxide and tin hydroxide having an average particle diameter of ₂ -8 nm. Then, the white nano powder was placed in a gallium oxide 99 porcelain crucible, and then placed in a high temperature furnace at 850 Torr for 8 hours of satin burning to obtain a pale yellow erbium-doped ITO nanopowder having an average particle diameter. It is about 51 nm and has an average specific surface area of about 21 m ² /g.

步骤六：采用聚乙稀醇作为粘结剂并用 95°C去离子水溶解，按 3 %重量比加入上述掺铌纳米铟锡氧化物粉末中充分搅拌后放入电阻加热干燥箱，在 110Ό温度下干燥 30小时而形成浅黄色的块状物，此后，将此浅黄色块状物放入玛瑙研磨器里进行研磨,并用 60目不锈钢金属网筛过筛后, 制得造粒后的浅黄色的掺铌 ITO纳米粉末,其自然休止角约 45角。 Step 6: using polyethylene glycol as a binder and dissolving in deionized water at 95 ° C, adding the above-mentioned cerium-doped nano-indium tin oxide powder in a proportion of 3% by weight, stirring well, and placing it in a resistance heating drying oven at a temperature of 110 Torr. After drying for 30 hours, a pale yellow mass was formed. Thereafter, the pale yellow mass was placed in an agate grinder, ground, and sieved through a 60 mesh stainless steel mesh screen to obtain a pale yellow after granulation. The erbium-doped ITO nanopowder has a natural angle of repose of about 45 degrees.

步骤七：将上述造粒后的浅黄色的掺铌 ITO粉末放入模具中，用压力机对其模具施加压力，其施加在样品上的压强为 2300 kg/cm², 从而压制成型为 ITO靶初胚，其相对密度密度为 55%; 然后，将此低密度的 ITO靶初胚放入高温炉里，在大气环境下按一定的升温曲线升温即在 300°C处保温 3小时以排塑处理，再以 5Ό/分钟升温速度快速升温至 1000°C，再以 2。C /分钟慢速升温至 1300°C, 然后以 0.5 °C/分钟缓慢升温至 1550°C并保温 6小时，之后以 0.5 °C /分钟缓慢降温至 1300°C，再以 2°C/分钟慢速降温至 1000Ό，然后自然冷却至室温，即得黑色的高密度 ITO陶瓷靶，其相对密度在 98.4%。 Step 7: The above-mentioned granulated pale yellow erbium-doped ITO powder is placed in a mold, and a pressure is applied to the mold by a press, and the pressure applied to the sample is 2300 kg/cm ² , thereby pressing and forming into an ITO target. The initial density of the embryo is 55%. Then, the low-density ITO target embryo is placed in a high-temperature furnace, and is heated at a temperature of 300 ° C for 3 hours in a high temperature furnace. After treatment, the temperature was rapidly raised to 1000 ° C at a heating rate of 5 Ό / min, and then 2 was obtained. C / minute slowly warmed to 1300 ° C, then slowly heated to 1550 ° C at 0.5 ° C / min and held for 6 hours, then slowly cooled to 1300 ° C at 0.5 ° C / min, then 2 ° C / min Slowly cooling to 1000 Ό, and then naturally cooling to room temperature, that is, a black high-density ITO ceramic target with a relative density of 98.4%.

步骤八：若要进一步提高 ITO靶密度，则进行上述步骤一到步骤六后,可采用加压烧结即将压制成型的 ITO靶初胚置于三氧化二铝 99瓷管中，再将瓷管放入高温炉里，按一定的升温曲线升温即在 300°C处保温 3小时以排塑处理，然后将此管抽成真空，再通入氧气至管内压强为 0.2MPa，再以 5°C/分钟升温速度快速升温至 1000°C , 再以 2°C/分钟慢速升温至 1300 °C,然后以 0.5Ό/分钟缓慢升温至 1400°C并保温 6小时，之后以 0.5 Ό/分钟缓慢降温至 1300 V，再以 2Ό/分钟慢速降温至 1000'C, 然后自然冷却至室温，即得黑色的高密度 ITO陶瓷靶, 其相对密度在 99%。实施例二 Step 8: To further increase the density of the ITO target, after performing the above steps 1 to 6, the ITO target blasting of the ITO target to be pressed and pressed may be placed in a gallium oxide 99 porcelain tube, and then the porcelain tube is placed. Into the high temperature furnace, according to a certain heating curve, the temperature is raised at 300 ° C for 3 hours to plastic treatment, and then the tube is vacuumed, and then the oxygen is introduced into the tube pressure of 0.2MPa, and then 5 ° C / The temperature is rapidly increased to 1000 °C in a minute heating rate, and then slowly heated to 1300 °C at 2 °C/min, then slowly heated to 1400 °C at 0.5 Ό/min for 6 hours, then slowly cooled at 0.5 Ό/min. To 1300 V, and then slowly cooled to 1000 ° C at 2 Ό / min, and then naturally cooled to room temperature, a black high-density ITO ceramic target with a relative density of 99%. Embodiment 2

本发明一种掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，包括以下步骤- 步骤一：首先用氢氟酸和硝酸混和液将高纯铌原料溶解成氢氟酸硝酸铌透明溶液；用硝酸和一定量的去离子水将高纯铟原料溶解成硝酸铟盐水透明溶液；用王水将高纯锡原料溶解成氯化锡透明溶液。 The invention discloses a method for preparing erbium-doped nano-indium tin oxide powder and a high-density sputter coating target thereof, comprising the following steps - Step 1: firstly dissolving the high-purity cerium raw material into a transparent solution of hydrofluoric acid cerium nitrate by using a mixed solution of hydrofluoric acid and nitric acid; dissolving the high-purity indium raw material into a transparent solution of indium nitrate brine by using nitric acid and a certain amount of deionized water; Wang Shui dissolves the high-purity tin raw material into a tin chloride transparent solution.

步骤二：将上述各透明溶液按 In: Sn: Nb=100: 9.6： 0.5比例分装到各自容器里备用。步骤三：采用均相共沉淀法将上述三种透明溶液按铌、锡、铟质量比例为 In: Sn_: Nb=100: 9.6： 0.5比例在 5000mL三口烧杯里进行混和，其混和的先后顺序为：先将硝酸铟盐水溶液与尿素和去离子水进行混和，其三者质量比为 In: (NH₂)₂CO: H₂O=100: 730: 3800；将该混和溶液加温至 97°C，待该溶液 pH值为 2.2时，滴入氯化锡透明溶液和氢氟酸硝酸铌透明溶液，用强搅伴机进行并不断搅拌，直到该溶液变成白色并化学反应完成为止便停止加热并停止搅拌，自然沉淀。 Step 2: The above transparent solutions are dispensed into respective containers in the ratio of In: Sn: Nb = 100: 9.6: 0.5 for use. Step three: by homogeneous coprecipitation clear solution according to the above three niobium, tin, indium mass ratio of _{In: Sn: Nb = 100:} 9.6: 0.5 were blended in a ratio of three 5000mL beaker, which is mixed in the order : First, the aqueous solution of indium nitrate is mixed with urea and deionized water, and the mass ratio of the three is In: (NH ₂ ) ₂ CO: H ₂ O=100: 730: 3800; the mixed solution is heated to 97°. C, when the pH of the solution is 2.2, drip a transparent solution of tin chloride and a transparent solution of bismuth hydrofluoric acid nitrate, and stir with a strong stirrer until the solution turns white and the chemical reaction is completed. Heat and stop stirring, and precipitate naturally.

步骤四：用去离子水洗漆 10遍并沉淀，用 5 %AgN0₃溶液检查不到氯离子。采用高速离心机进行快速沉淀，生产效率高。 Step 4: The paint was washed 10 times with deionized water and precipitated, and the chloride ion was not detected with the 5% AgN0 ₃ solution. High-speed centrifuge for rapid precipitation and high production efficiency.

步骤五：去掉上清液，将上述白色浆状沉淀物放入电阻加热干燥箱里，在 110°C下进行 30 小时干燥处理形成白色块状的摻铌氢氧化铟和氢氧化锡的混合物；再将此白色块状混合物放入玛瑙研磨器里进行研磨形成掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末；此后，将此白色块状混合物放入玛瑙研磨器里进行研磨，即得掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末，其平均粒径为 2-6nm。然后，将此白色纳米粉末装入三氧化二铝 99瓷坩埚里，再放入到高温炉里在 850Ό下进行 8小时缎烧，从而制得浅黄色的掺铌 ITO纳米粉末，其平均粒径约为 33nm，其平均比表面积约为 28m²/g。 Step 5: removing the supernatant, placing the white slurry precipitate into a resistance heating drying oven, and drying at 110 ° C for 30 hours to form a white block mixture of strontium-doped indium hydroxide and tin hydroxide; The white block mixture is then placed in an agate grinder to be ground to form a white nanopowder mixed with antimony-doped indium hydroxide and tin hydroxide; thereafter, the white block mixture is placed in an agate grinder for grinding. A white nanopowder mixed with indium hydroxide and tin hydroxide having an average particle diameter of 2-6 nm. Then, the white nano powder was placed in a gallium oxide 99 porcelain crucible, and then placed in a high temperature furnace at 850 Torr for 8 hours of satin burning to obtain a pale yellow erbium-doped ITO nanopowder having an average particle diameter. It is about 33 nm and has an average specific surface area of about 28 m ² /g.

步骤六. · 采用聚乙稀醇作为粘结剂并用 95Ό去离子水溶解，按 4%重量比加入上述掺铌纳米铟锡氧化物粉末中充分搅拌后放入电阻加热干燥箱，在 110°C温度下千燥 30小时而形成浅黄色的块状物，此后，将此浅黄色块状物放入玛瑙研磨器里进行研磨,并用 60目不锈钢金属网筛过筛后，制得造粒后的浅黄色的惨铌 ITO纳米粉末，其自然休止角约 45角 Step 6. · Using polyethylene glycol as a binder and dissolving in 95 Ό deionized water, adding the above erbium-doped nano-indium tin oxide powder in a 4% by weight ratio, stirring well, and placing it in a resistance heating oven at 110 ° C. The mixture was dried for 30 hours at a temperature to form a pale yellow mass. Thereafter, the pale yellow mass was placed in an agate grinder for grinding and sieved with a 60 mesh stainless steel mesh screen to obtain a granulated product. Light yellow tragic ITO nanopowder with a natural angle of repose of about 45 degrees

步骤七：将上述造粒后的浅黄色的掺铌 ITO粉末放入模具中，用压力机对其模具施加压力，其施加在样品上的压强为 2600 kg/cm², 从而压制成型为 ITO靶初胚，其相对密度密度为 58%; 然后，将此低密度的 ITO靶初胚放入高温炉里，在大气环境下按一定的升温曲线升温即在 300°C处保温 3小时以排塑处理，再以 5°C/分钟升温速度快速升温至 100(TC，再以 2°C /分钟慢速升温至 1300°C, 然后以 0.5°C/分钟缓慢升温至 1550Ό并保温 6小时，之后以 0.5°C /分钟缓慢降温至 1300°C，再以 2Ό/分钟慢速降温至 ΙΟΟΟΌ, 然后自然冷却至室温，即得黑色的高密度 ΙΤΟ陶瓷靶，其相对密度在 90%。 Step 7: The above-mentioned granulated pale yellow erbium-doped ITO powder is placed in a mold, and a pressure is applied to the mold by a press, and the pressure applied to the sample is 2600 kg/cm ² , thereby pressing and forming into an ITO target. The initial density of the embryo is 58%. Then, the low-density ITO target embryo is placed in a high-temperature furnace, and is heated at a temperature of 300 ° C for 3 hours in a high temperature furnace. After treatment, the temperature was rapidly raised to 100 (TC, and then slowly heated to 1300 ° C at 2 ° C / min, then slowly heated to 1550 0.5 at 0.5 ° C / min and held for 6 hours. Slowly reduce the temperature to 1300 ° C at 0.5 ° C / min, then slowly cool to ΙΟΟΟΌ at 2 Ό / min, and then naturally cool to room temperature, that is, a black high-density tantalum ceramic target with a relative density of 90%.

步骤八：若要进一步提高 ΙΤΟ靶密度，则进行上述步骤一到步骤六后,可采用加压烧结即将压制成型的 ΙΤΟ靶初胚置于三氧化二铝 99瓷管中，再将瓷管放入高温炉里，按一定的升温曲线升温即在 300°C处保温 3小时以排塑处理，然后将此管抽成真空，再通入氧气至管内压强为 0.3MPa，再以 5°C/分钟升温速度快速升温至 1000°C，再以 2Ό/分钟慢速升温至 1300 °C,然后以 0.5°C/分钟缓慢升温至 1450Ό并保温 6小时，之后以 0.5°C/分钟缓慢降温至 1300 V ,再以 2°C/分钟慢速降温至 1000Ό, 然后自然冷却至室温，即得黑色的高密度 ITO陶瓷靶, 其相对密度在 99.3 %。实施例三 Step 8: To further increase the target density of the crucible, after performing the above steps 1 to 6, the impregnated target initial embryo to be pressed and pressed may be placed in a gallium oxide 99 porcelain tube, and then the porcelain tube is placed. Into the high temperature furnace, according to a certain heating curve, the temperature is raised at 300 ° C for 3 hours to displace the plastic treatment, and then the tube is vacuumed, and then the oxygen is introduced into the tube to a pressure of 0.3 MPa, and then 5 ° C / The temperature rises rapidly to 1000 ° C, and then slowly increases to 1300 at 2 Ό / min. °C, then slowly raise the temperature to 1450 以 at 0.5 °C / minute and keep it for 6 hours, then slowly cool down to 1300 V at 0.5 °C / minute, then slowly cool down to 1000 °C at 2 °C / minute, then naturally cool to room temperature That is, a black high-density ITO ceramic target having a relative density of 99.3%. Embodiment 3

步骤二：将上述各透明溶液按 In: Sn: Nb=100: 10.6： 0.7比例分装到各自容器里备用。步骤三：采用均相共沉淀法将上述三种透明溶液按铌、锡、铟质量比例为 In: Sn: Nb=100: 10.6： 0.7比例在 5000mL三口烧杯里进行混和，其混和的先后顺序为：先将硝酸铟盐水溶液与尿素和去离子水进行混和，其三者质量比为 In: (NH₂)₂CO: H₂O=100: 750: 4200；将该混和溶液加温至 97°C，待该溶液 pH值为 2.15时，滴入氯化锡透明溶液和氢氟酸硝酸铌透明溶液，用强搅伴机进行并不断搅拌，直到该溶液变成白色并化学反应完成为止便停止加热并停止搅拌，自然沉淀。 Step 2: The above transparent solutions are dispensed into respective containers in an In: Sn:Nb=100: 10.6:0.7 ratio for use. Step 3: The above three transparent solutions are mixed in a 5000 mL three-beat beaker according to the mass ratio of bismuth, tin and indium according to the mass ratio of bismuth, tin and indium by homogeneous coprecipitation method, and the order of mixing is : First, the aqueous solution of indium nitrate is mixed with urea and deionized water, and the mass ratio of the three is In: (NH ₂ ) ₂ CO: H ₂ O=100: 750: 4200; the mixed solution is heated to 97°. C, when the pH value of the solution is 2.15, drip a transparent solution of tin chloride and a transparent solution of bismuth hydrofluoric acid nitrate, and stir with a strong stirrer until the solution turns white and the chemical reaction is completed. Heat and stop stirring, and precipitate naturally.

步骤四：用去离子水洗涤 10遍并沉淀，用 5%AgN0₃溶液检查不到氯离子。采用高速离心机进行快速沉淀，生产效率高。 Step 4: Wash 10 times with deionized water and precipitate, and check for chloride ions with 5% AgN0 ₃ solution. High-speed centrifuge for rapid precipitation and high production efficiency.

步骤五：去掉上清液，将上述白色浆状沉淀物放入电阻加热干燥箱里，在 110°C下进行 30 小时千燥处理形成白色块状的掺铌氢氧化铟和氢氧化锡的混合物；再将此白色块状混合物放入玛瑙研磨器里进行研磨形成掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末；此后，将此白色块状混合物放入玛瑙研磨器里进行研磨，即得掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末,其平均粒径为 2-5nm。然后，将此白色纳米粉末装入三氧化二铝 99瓷坩埚里，再放入到高温炉里在 850°C下进行 8小时缎烧，从而制得浅黄色的掺铌 ITO纳米粉末，其平均粒径约为 28nm，其平均比表面积约为 32m²/g; Step 5: Remove the supernatant, place the above-mentioned white slurry precipitate in a resistance heating oven, and dry it at 110 ° C for 30 hours to form a white block mixture of strontium-doped indium hydroxide and tin hydroxide. Then, the white block mixture is placed in an agate grinder to be ground to form a white nano-powder mixed with antimony-doped indium hydroxide and tin hydroxide; thereafter, the white block mixture is placed in an agate grinder for grinding, that is, A white nanopowder mixed with indium hydroxide and tin hydroxide having an average particle diameter of 2 to 5 nm is obtained. Then, the white nano powder was placed in a gallium oxide 99 porcelain crucible, and then placed in a high temperature furnace at 850 ° C for 8 hours satin burning to obtain a pale yellow erbium-doped ITO nano powder, which averaged The particle size is about 28 nm, and the average specific surface area is about 32 m ² /g;

步骤六：采用聚乙稀醇作为粘结剂并用 95°C去离子水溶解，按 4%重量比加入上述惨铌纳米铟锡氧化物粉末中充分搅拌后放入电阻加热干燥箱，在 110'C温度下干燥 30小时而形成浅黄色的块状物，此后，将此浅黄色块状物放入玛瑙研磨器里进行研磨，并用 60目不锈钢金属网筛过筛后，制得造粒后的浅黄色的掺铌 ITO纳米粉末，其自然休止角约 45角 Step 6: Using polyethylene glycol as a binder and dissolving it in deionized water at 95 ° C, adding the above-mentioned miserable nano-indium tin oxide powder to the above-mentioned miserable nano-indium tin oxide powder, and stirring it into a resistance heating drying oven at 110' Drying at C temperature for 30 hours to form a pale yellow mass. Thereafter, the pale yellow mass was placed in an agate grinder for grinding and sieved through a 60 mesh stainless steel mesh screen to obtain a granulated product. Light yellow erbium-doped ITO nanopowder with a natural angle of repose of about 45 degrees

步骤七：将上述造粒后的浅黄色的掺铌 ITO粉末放入模具中，用压力机对其模具施加压力，其施加在样品上的压强为 2800 kg/cm², 从而压制成型为 ITO靶初胚，其相对密度密度为 60%; 然后，将此低密度的 ITO靶初胚放入高温炉里，在大气环境下按一定的升温曲线升温即在 300°C处保温 3小时以排塑处理，再以 5°C/分钟升温速度快速升温至 1000'C , 再以 1 °C /分钟慢速升温至 1300°C, 然后以 0.5°C/分钟缓慢升温至 1550Ό并保温 6小时，之后以 0.5Ό /分钟缓慢降温至 1300°C，再以 rc/分钟慢速降温至 1000°C, 然后自然冷却至室温，即得黑色的高密度 ΠΌ陶瓷靶，其相对密度在 90.1 %。 Step 7: The above-mentioned granulated pale yellow erbium-doped ITO powder is placed in a mold, and a pressure is applied to the mold by a press, and the pressure applied to the sample is 2800 kg/cm ² , thereby pressing into an ITO target. The initial density of the embryo is 60%; then, the low-density ITO target primordial is placed in a high-temperature furnace, and heated at a certain temperature rise curve in the atmosphere, that is, at 300 ° C for 3 hours to discharge plastic Treatment, and then rapidly increase the temperature to 1000 ° C at a heating rate of 5 ° C / min, then at 1 ° C /min slowly warmed to 1300 ° C, then slowly warmed to 1550 以 at 0.5 ° C / min and held for 6 hours, then slowly cooled to 1300 ° C at 0.5 Ό / min, and then slowly cooled to 1000 ° in rc / minute C, and then naturally cooled to room temperature, that is, a black high-density tantalum ceramic target having a relative density of 90.1%.

步骤八：若要进一步提高 ITO靶密度，则进行上述步骤一到步骤六后，可采用加压烧结即将压制成型的 ITO靶初胚置于三氧化二铝 99瓷管中，再将瓷管放入高温炉里，按一定的升温曲线升温即在 300Ό处保温 3小时以排塑处理，然后将此管抽成真空，再通入氧气至管内压强为 0.4MPa，再以 5 °C/分钟升温速度快速升温至 1000°C，再以 1 °C/分钟慢速升温至 1300 V, 然后以 0.5Ό/分钟缓慢升温至 1500°C并保温 6小时，之后以 0.5Ό/分钟缓慢降温至 1300 °C，再以 C/分钟慢速降温至 1000°C, 然后自然冷却至室温，即得黑色的高密度 ITO陶瓷靶, 其相对密度在 99.5%。以上所述，仅为本发明的较佳实施例而已，举凡依本发明申请专利范围所做的均等设计变，均应为本发明的技术方案所涵盖。 Step 8: To further increase the density of the ITO target, after performing the above steps 1 to 6, the ITO target blasting of the ITO target to be pressed and pressed may be placed in a gallium oxide 99 porcelain tube, and then the porcelain tube is placed. Into the high temperature furnace, according to a certain heating curve, the temperature is raised at 300 保温 for 3 hours to be plasticized, and then the tube is vacuumed, and then the oxygen is introduced into the tube to a pressure of 0.4 MPa, and then heated at 5 ° C / min. The temperature is rapidly increased to 1000 ° C, and then slowly heated to 1300 V at 1 ° C / min, then slowly heated to 1500 ° C at 0.5 Ό / min and held for 6 hours, then slowly cooled to 1300 ° at 0.5 Ό / min C, and then slowly cooled to 1000 ° C in C / minute, and then naturally cooled to room temperature, that is, a black high-density ITO ceramic target having a relative density of 99.5%. The above is only the preferred embodiment of the present invention, and all the equivalent design changes made according to the scope of the present invention should be covered by the technical solutions of the present invention.

综上所述，本发明提供了一种髙密度的铟锡氧化物陶瓷溅射靶材的制备方法，通过掺铌并采用简单的制靶工艺，可使 ITO靶的相对密度达到 99%以上。本发明制靶方法的成本低，靶性能好，可产业化生产。依法提出专利申请。 In summary, the present invention provides a method for preparing a tantalum-density indium tin oxide ceramic sputtering target. The relative density of the ITO target can be made 99% or more by erbium doping and using a simple target process. The target method of the invention has low cost, good target performance and can be industrially produced. File a patent application according to law.

Claims

权利要求书 Claim

1. 一种掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：该方法包括以下步骤： A method for preparing a cerium-doped nano-indium tin oxide powder and a high-density sputter coating target thereof, the method comprising the steps of:

(1)对高纯金属进行溶解：分别用不同的无机酸溶解高纯金属铌、高纯金属铟、高纯金属锡成透明溶液； (1) Dissolving high-purity metals: Dissolving high-purity metal lanthanum, high-purity metal indium, and high-purity metal tin into a transparent solution with different inorganic acids;

(2)进行配料：将上述三种透明溶液按预定比例分装容器； (2) Carrying out the ingredients: the above three transparent solutions are divided into containers according to a predetermined ratio;

(3)化学沉淀：采用化学沉淀法将上述三种透明溶液按比例和规定工序，制得掺铌重惨锡的氢氧化铟纳米粉末； (3) Chemical precipitation: using the chemical precipitation method, the above three transparent solutions are prepared according to the ratio and the specified procedure, and the indium hydroxide nano-powder doped with bismuth tin;

(4)清洗：用去离子水清洗数遍上述掺铌重掺锡的氢氧化铟纳米粉末并沉淀； (4) cleaning: washing the above-mentioned cerium-doped tin-doped indium hydroxide nanopowder with deionized water several times and precipitating;

(5)煅烧：将上述纳米粉末放入高温炉进行煅烧，制得惨铌纳米铟锡氧化物粉末； (5) calcination: the above nanopowder is placed in a high temperature furnace for calcination to obtain a miserable nano indium tin oxide powder;

(6)造粒：将上述掺铌纳米铟锡氧化物粉末加入粘合剂并干燥，制得掺铌的铟锡氧化物成型前粉末； (6) granulation: adding the above-mentioned cerium-doped nano-indium tin oxide powder to a binder and drying to obtain a cerium-doped indium tin oxide pre-formation powder;

(7) 成型：采用成型压机将上述掺铌的铟锡氧化物成型前粉末压制成初胚； (7) molding: using a forming press to press the above-mentioned ytterbium-doped indium tin oxide powder into an primordial;

(8)烧结：将上述初胚放入高温炉里，按一定的升温曲线进行常压烧结，制得高密度掺铌的铟锡氧化物溅射镀膜靶材；若要进一步提高该靶密度，则采用气压烧结。 (8) Sintering: The above-mentioned preliminary embryos are placed in a high-temperature furnace, and subjected to atmospheric pressure sintering according to a certain heating curve to obtain a high-density ytterbium-doped indium tin oxide sputter coating target; to further increase the target density, Air pressure sintering is used.

2. 根据权利要求 1 所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (1)中所述的不同的无机酸溶液是指：采用氢氟酸和硝酸混和液将高纯金属铌原料溶解成氢氟酸硝酸铌透明溶液；采用硝酸和预定量的去离子水将高纯金属铟原料溶解成硝酸铟盐水透明溶液；采用王水或浓硫酸将高纯金属锡原料溶解成氯化锡透明溶液或硫酸锡透明溶液。 2 . The method according to claim 1 , wherein the different inorganic acid solution described in the step (1) is : Dissolving high-purity metal ruthenium raw material into a transparent solution of hydrofluoric acid lanthanum nitrate using a mixture of hydrofluoric acid and nitric acid; dissolving the high-purity metal indium raw material into a transparent solution of indium nitrate brine using nitric acid and a predetermined amount of deionized water; Water or concentrated sulfuric acid dissolves the high-purity tin metal raw material into a tin chloride transparent solution or a tin sulfate transparent solution.

3. 根据权利要求 1所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (2)中所述的三种透明溶液按预定比例是指：按 In: Sn: Nb=100: 5〜15： 0.3-2.0质量比例分装到各自容器里。 3 . The method according to claim 1 , wherein the three transparent solutions described in the step (2) are in a predetermined ratio It means: According to In: Sn: Nb=100: 5~15: 0.3-2.0 mass ratio into the respective containers.

4. 根据权利要求 1所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (3)中所述的化学沉淀法是指：均相共沉淀法和水热法，即先将上述硝酸铟盐水透明溶液中加入一定量的尿素或氨水和去离子水，加温至 90°C-10(TC并不断搅拌，这时溶液 PH值逐渐上升，再滴入氯化锡透明溶液以及氢氟酸硝酸铌透明溶液，直到该溶液变成白色并化学反应完成为止便停止加热，并自然沉积。 4. The method of preparing erbium-doped nano-indium tin oxide powder according to claim 1 and a high-density sputter coating target thereof, The method is characterized in that: the chemical precipitation method described in the step (3) refers to: a homogeneous coprecipitation method and a hydrothermal method, that is, first adding a certain amount of urea or ammonia water and deionized water to the above transparent solution of indium nitrate brine. , warm to 90 ° C -10 (TC and continue to stir, then the pH of the solution gradually rises, then drop the tin chloride transparent solution and the transparent solution of hydrofluoric acid nitrate, until the solution turns white and the chemical reaction is completed Heating stops and naturally deposits.

5. 根据权利要求 1 所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (4)中所述的清洗并沉淀是指：用去离子水洗涤直到溶液中氯离子没有为止；沉淀方式采用自然沉淀，或采用高速离心机进行快速沉淀，即得柴状的掺铌重掺锡的氢氧化铟白色沉淀物。 The method for preparing a cerium-doped nano-indium tin oxide powder according to claim 1 or a high-density sputter coating target thereof, wherein: the cleaning and precipitation described in the step (4) is: The deionized water is washed until the chloride ions in the solution are not present; the precipitation method is carried out by natural precipitation, or rapid precipitation by a high-speed centrifuge, that is, a diesel-like antimony-doped tin-doped indium hydroxide white precipitate.

6. 根据权利要求 1所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (5)中所述的高温炉进行煅烧是指：将上述白色浆状沉淀物放入电阻加热干燥箱里，在 110Ό下进行 24小时 -48小时千燥处理形成白色块状的惨铌氢氧化铟和氢氧化锡的混合物；此后，将此白色块状混合物放入玛瑙研磨器里进行研磨形成掺铌氢氧化铟和氢氧化锡混合的白色纳米粉末；然后，将此白色纳米粉末装入 99瓷坩埚里，再放入到高温炉里在 600°C-900°C下进行 6-9小时缎烧，从而制得浅黄色的掺铌纳米 ITO纳米粉末。 The method for preparing a ytterbium-doped nano-indium tin oxide powder and a high-density sputter coating target thereof according to claim 1, wherein the calcination of the high-temperature furnace described in the step (5) is: The white slurry precipitate is placed in a resistance heating drying oven and dried at 110 Torr for 24 hours to 48 hours to form a white block mixture of indium hydroxide and tin hydroxide; thereafter, the white block is formed. The mixture is placed in an agate grinder and ground to form a white nano-powder mixed with antimony-doped indium hydroxide and tin hydroxide; then, the white nano-powder is placed in a 99-ceramic crucible and placed in a high-temperature furnace at 600°. Satin burning was carried out at C-900 ° C for 6-9 hours to obtain a pale yellow ytterbium-doped nano ITO nanopowder.

7. 根据权利要求 1 所的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (6)中所述的加入粘合剂并干燥是指：采用粘结剂为聚乙稀醇并按 3 %-5 %重量比经热水溶解后倒入上述制得的浅黄色掺铌纳米铟锡氧化物粉末并充分搅拌形成糊状；将此糊状液体置入电阻加热干燥箱里，在 100°C-110°C下进行干燥处理 24-48小时而形成浅黄色块状物；此后，将此浅黄色块状物放入玛瑙研磨器里进行研磨,并用 40 目 -80 目不锈钢金属网筛过筛后形成造粒后的浅黄色的掺铌 ITO粉末，即制得掺铌纳米铟锡氧化物成型前粉末。 7. The method for preparing ytterbium-doped nano-indium tin oxide powder according to claim 1 and a high-density sputter coating target thereof, wherein: adding the binder and drying as described in the step (6) means : using a binder of polyethylene glycol and dissolving in 3% to 5% by weight of hot water, pouring the light yellow ytterbium-doped nano-indium tin oxide powder obtained above and thoroughly stirring to form a paste; The liquid is placed in a resistance heating drying oven and dried at 100 ° C - 110 ° C for 24-48 hours to form a pale yellow mass; thereafter, the pale yellow mass is placed in an agate grinder. The powder was ground and sieved with a 40 mesh-80 mesh stainless steel mesh screen to form a granulated pale yellow erbium-doped ITO powder, thereby preparing a cerium-doped nano-indium tin oxide pre-molding powder.

8. 根据权利要求 1 所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (7)中所述的粉末压制成初胚是指：将上述造粒后的浅黄色的掺铌 ITO 粉末放入模具中，用压力机对其模具施加压力，其施加在样品上的压强为 1000-3000 kg/cm², 从而压制成型为 ITO靶初胚，其相对密度密度为 50%-60%。 8 . The method for preparing a ytterbium-doped nano-indium tin oxide powder and a high-density sputter-coated target according to claim 1 , wherein: the powder in the step (7) is pressed into the primordial index : The granulated pale yellow ytterbium-doped ITO powder is placed in a mold, and a pressure is applied to the mold by a press, and the pressure applied to the sample is 1000-3000. Kg/cm ^{2 is} thus press-formed into an ITO target primord with a relative density density of 50% to 60%.

9. 根据权利要求 1 所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (8)中所述的常压烧结是指：将低密度的 ITO靶初胚放入高温炉里，在大气环境下按一定的升温曲线升温即在 300°C-50(TC处保温 2-5小时以排塑处理，再快速升温至 900°C-110(TC，然后缓慢升温至 1500Ό-1600Ό并保温 6-10个小时，再缓慢降温至 900°C-1100°C后，自然冷却至室温，即得高密度的 ITO靶，其相对密度在 98%以上甚至可达到 99.1 %。 9. The method according to claim 1, wherein the normal pressure sintering described in the step (8) is: The low-density ITO target primordial embryo is placed in a high-temperature furnace, and is heated at a temperature rise curve in the atmosphere at 300 ° C -50 (TC for 2-5 hours for plastic treatment, and then rapidly heated to 900 ° C -110(TC, then slowly heat up to 1500Ό-1600Ό and keep it for 6-10 hours, then slowly cool down to 900°C-1100°C, then naturally cool to room temperature, which gives a high density ITO target, the relative density is More than 98% can even reach 99.1%.

10. 根据权利要求 1所述的掺铌纳米铟锡氧化物粉末及其高密度溅射镀膜靶材的制备方法，其特征在于：其步骤 (8)中所述的气压烧结是指：将压制成型的 ITO靶初胚置于 Al₂0₃99 瓷管中，再将瓷管放入高温炉里，按一定的升温曲线升温即在 300°C-50(rC处保温 2-5小时以排塑处理；然后将此管抽成真空，再通入氧气至管内压强为 0.2-0.6MPa，并快速升温至 900 °C-1100°C，然后缓慢升温至 1400°C-1550°C并保温 3-6个小时，再缓慢降温至 900°C-1100°C 后，自然冷却至室温，即得高密度的 ITO陶瓷靶，其相对密度在 99.0%以上甚至可达到 99.5 %。 10. The method for preparing ytterbium-doped nano-indium tin oxide powder and high-density sputter-coated target according to claim 1, wherein: the gas pressure sintering in the step (8) is: pressing The formed ITO target primordial is placed in an Al ₂ 0 ₃ 99 porcelain tube, and then the porcelain tube is placed in a high temperature furnace, and the temperature is raised at a temperature rise curve of 300 ° C - 50 (rC is kept at 2 to 5 hours). Plastic treatment; then pump the tube into a vacuum, then pass oxygen to the tube pressure of 0.2-0.6MPa, and quickly heat up to 900 °C-1100 °C, then slowly heat up to 1400 °C-1550 °C and keep warm 3 After -6 hours, slowly cooling to 900 ° C -1100 ° C, and naturally cooling to room temperature, a high density ITO ceramic target, the relative density of 99.0% or more can reach 99.5 %.