CN116425514A - 一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用 - Google Patents

一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用 Download PDF

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CN116425514A
CN116425514A CN202310244635.5A CN202310244635A CN116425514A CN 116425514 A CN116425514 A CN 116425514A CN 202310244635 A CN202310244635 A CN 202310244635A CN 116425514 A CN116425514 A CN 116425514A
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oxide
doped indium
indium oxide
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CN116425514B (zh
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葛春桥
陈露
李强
杨进明
柳春锡
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Zhongshan Zhilong New Material Technology Co ltd
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Abstract

本发明属于光伏电池技术领域，提供了一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用，本发明采用特定含量的SnO2、TiO2、CeO2、X的氧化物、ZrO2、HfO2对氧化铟进行掺杂制得多元氧化物掺杂氧化铟基靶材，X为V、Nb、Cr、Mo、Ta、W中的一种或几种，总掺杂浓度较低，降低烧结温度，多元氧化物掺杂氧化铟基靶材的密度在7.080‑7.121g/m3之间，晶粒尺寸9.8‑12.8μm，靶材具有低掺杂、高密度的特点，由其所制得的TCO薄膜，迁移率达到在43‑75cm2/(V.s)之间，透光率(@400‑1200nm)达到88.5‑90.8％，同时满足高透光率和高迁移率的要求。

Description

一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用
技术领域
本发明涉及光伏电池技术领域，更具体地，涉及一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用。
背景技术
氧化铟(In2O3)基靶材(简称为ITO靶材)制备的透明导电氧化物薄膜(简称为TCO薄膜)，主要包括In、Sb、Zn和Cd的氧化物及其复合多元氧化物薄膜材料。由于具有禁带宽、电阻率低、可见光区光透射率高和红外光谱区光反射率高等优良的光电特性，长期以来被广泛应用于平板显示器、太阳能电池、有机发光二极管、低辐射玻璃、特殊功能窗涂层、透明薄膜晶体管及柔性电子器件等领域。
不同元素掺杂的氧化铟基靶材，制备的TCO薄膜光电性能各异。随着面板显示、光伏电池等行业的发展，对TCO薄膜提出了更高的光学性能与电学性能要求。纯In2O3靶材制备的TCO薄膜，其迁移率高达80-150cm2/V.S，但其烧结温度过高(In2O3熔点2000℃)，一般通过掺杂氧化物来降低烧结温度。低掺杂浓度的ITO靶材，由于铟含量仍然较高，烧结温度需高达1850-1950℃，才能制备出适合PVD溅射镀膜所需的高密度靶材，能耗较高，且对烧结设备的要求较高。传统的ITO靶材，SnO2作为助烧物的加入，可以降低ITO靶材的烧结温度，但会对薄膜的透光性能及电学性能造成影响，且掺杂浓度过高会造成晶界散热及生成不导电的In4Sn3O12二次相。
因此，亟需开发一种掺杂浓度低、密度高的靶材，且由其所制得的TCO薄膜具有较高的迁移率和透光率。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种多元氧化物掺杂氧化铟基靶材及其制备方法和应用，本发明提供的多元氧化物掺杂氧化铟基靶材，密度在7.080-7.121g/m3之间，晶粒尺寸9.8-12.8μm，靶材具有低掺杂、高密度的特点；靶材使用物理气相沉积溅射镀膜，制得的TCO薄膜的迁移率43-75cm2/(V.s)之间，透光率(@400-1200nm)达到88.5-90.8％，同时满足高迁移率和高透光率的要求。
本发明的第一方面提供一种多元氧化物掺杂氧化铟基靶材。
具体地，一种多元氧化物掺杂氧化铟基靶材，按照质量份计，包括如下组分：
Figure BDA0004125518780000021
所述多元氧化物掺杂氧化铟基材料还包括ZrO2 0-200ppm和HfO2 0-50ppm，ZrO2的质量不为零，HfO2的质量不为零。
为了制备高密度低掺杂的氧化铟基靶材，本发明通过掺杂SnO2、TiO2、ZrO2作为助烧物，有效降低烧结温度。配位数为6的四价Ce离子半径为0.101nm，接近配位数为6的三价In(0.094nm)，掺杂点位晶格微应变化小，与In2O3相比，CeO2具有较大的标准生成焓，可以减少氧缺位的密度，从而提高结晶度，CeO2的加入，使得Ti、Zr多元掺杂体系的四方相结构稳定，减少了晶界散射对载流子传输的影响。TiO2经典的结构为锐钛矿型和晶红石型，同时掺杂CeO2，通过CeO2与TiO2、ZrO2、HfO2之间的同价掺杂，可以提高TiO2的高温稳定性，且不会发生晶格畸变，从而提高靶材的热稳定性和结晶度，晶粒尺寸较均匀，从而提高致密度；TiO2、ZrO2、HfO2的掺杂，还在保持高迁移率的同时提高薄膜的可见光和近红外透过率；但ZrO2及HfO2的掺杂量过多和过少效果均不佳，过多会引起靶材的热膨胀，且造成较多的氧空位，过少或者不加则达不到增强靶材密度的效果。另外，本发明还同时掺杂高价元素氧化物(V(+5)、Nb(+5)、Cr(+6)、Mo(+6)、Ta(+5)、W(+6))，掺杂的高价离子与氧化物中被替代离子的化合价相差较大，每个掺杂离子较Sn4+提供了更多的自由载流子，提高了掺杂效率，在相同掺杂浓度下，可获得较高的自由载流子浓度，提高迁移率。
优选地，所述多元氧化物掺杂氧化铟基靶材，按照质量份计，包括如下组分：
Figure BDA0004125518780000022
Figure BDA0004125518780000031
进一步优选地，所述多元氧化物掺杂氧化铟基靶材，按照质量份计，包括如下组分：
Figure BDA0004125518780000032
优选地，所述多元氧化物掺杂氧化铟基材料还包括ZrO2 100-200ppm和HfO2 20-50ppm。
进一步优选地，所述多元氧化物掺杂氧化铟基材料还包括ZrO2 125-200ppm和HfO225-50ppm。
优选地，所述ZrO2和HfO2的质量比为(3-5)：1。
进一步优选地，所述ZrO2和HfO2的质量比为(3-4.5)：1。
更优选地，所述ZrO2和HfO2的质量比为(3-4)：1。
优选地，所述X的氧化物包括V2O5、Nb2O5、CrO3、MoO3、Ta2O5、WO3中的一种或几种。
本发明的第二方面提供一种多元氧化物掺杂氧化铟基靶材的制备方法。
一种多元氧化物掺杂氧化铟基靶材的制备方法，包括如下步骤：
将各组分混合，制得混合料，喷雾干燥，制得混合氧化物粉体，注入模具内静压成型，制得靶材素胚，脱脂，烧结，制得所述多元氧化物掺杂氧化铟基靶材。
优选地，所述将各组分混合后，还包括研磨。
优选地，所述研磨后还包括添加粘结剂和/或增塑剂。
优选地，所述添加粘结剂和/或增塑剂后，还包括过滤。
优选地，所述研磨包括先采用Φ0.40-0.80mm锆珠研磨6-10h，转速为400-800rpm，再使用Φ0.10-0.50mm锆珠研磨6-10h，转速为600-1000rpm。
进一步优选地，所述研磨包括先采用Φ0.60-0.80mm锆珠研磨8-10h，转速600-800rpm，再使用Φ0.30-0.50mm锆珠研磨8-10h，转速800-1000rpm。
优选地，所述粘结剂为聚乙烯醇(PVA)。
优选地，所述增塑剂为聚乙二醇(PEG)。
优选地，所述粘结剂的质量占混合料的总质量的0.4-2.5％。
优选地，所述增塑剂的量占混合料的总质量的0.1-2％。
优选地，所述混合氧化物粉体的比表面积为5-25m2/g，松装密度为1.00-1.60g/cm3。
优选地，所述静压成型的成型压力100-200MPa。静压强化后为靶材素坯。
优选地，所述烧结的温度为1500-1650℃，所述烧结的时间为240-300h。
优选地，所述烧结的气氛为氧气气氛或氮气气氛。
本发明的第三方面提供一种多元氧化物掺杂氧化铟基靶材的应用。
一种多元氧化物掺杂氧化铟基靶材在光伏电池领域中的应用。
一种透明导电氧化物薄膜，包括采用所述多元氧化物掺杂氧化铟基靶材制得的。
一种透明导电氧化物薄膜的制备方法，包括如下步骤：
将所述多元氧化物掺杂氧化铟基靶材采用溅射镀膜制得所述透明导电氧化物薄膜。
优选地，所述溅射镀膜为物理气相沉积溅射镀膜。
优选地，所述溅射镀膜的功率为50-500W。
相对于现有技术，本发明的有益效果如下：
(1)本发明采用特定含量的SnO2、TiO2、CeO2、X的氧化物、ZrO2、HfO2对氧化铟进行掺杂制得多元氧化物掺杂氧化铟基靶材，X为V、Nb、Cr、Mo、Ta、W中的一种或几种，本发明相对现有的ITO靶材，总掺杂浓度较低，有效降低烧结温度，CeO2有助于提高结晶度，从而提高靶材致密度和均匀性，掺杂了X的氧化物，提高掺杂效率，多元氧化物掺杂氧化铟基靶材的密度在7.080-7.121g/m3之间，晶粒尺寸9.8-12.8μm，靶材具有低掺杂、高密度的特点；
(2)本发明利用多元氧化物掺杂氧化铟基靶材通过物理气相沉积(PVD)溅射镀膜沉积的TCO薄膜，迁移率达到43-75cm2/(V.s)之间，透光率达到88.5-90.8％(@400-1200nm)，同时满足高透光率和高迁移率的要求，具有优异的光电性能，该种靶材可以直接应用于显示面板、光伏电池等行业中。
具体实施方式
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。
实施例1
一种多元氧化物掺杂氧化铟基靶材，其组分及其含量如表1所示。
上述多元氧化物掺杂氧化铟基靶材的制备方法，包括如下步骤：
S1、氧化铟粉体的制备：
将铟锭(4N5)溶解，金属铟用稀HCl溶解，生成InCl3溶液；将此溶液加热并加入稍过量的氨水使之生成沉淀，和母液一起再在加热熟化6.5h；过滤后洗涤沉淀直至没有Cl-，在室温下干燥得到In(OH)3；将In(OH)3高温煅烧后形成In2O3粉体，测得粉体的比表面积值位于5-20m2/g之间，D50值≤3μm；
S2、混合粉体的制备：
将制备的In2O3粉与其余掺杂氧化物粉末混合，制得混合料；先使用Φ0.60mm锆珠研磨8h，转速600rpm，再使用Φ0.30mm锆珠研磨8h，转速800rpm；添加粘结剂(PVA)和增塑剂(PEG)后搅拌过滤，其中粘结剂质量占混合料总质量的2.0％，增塑剂质量占混合料总质量的0.5％；喷雾干燥，制得混合氧化物粉体，测得粉末的比表面积值5-25m2/g，其松装密度1.00-1.60g/cm3；氧化物粉末的纯度为4N；
S3、素胚成型：
使用旋转靶模具，将粉末注入模具内，使用湿式液压机，成型压力180MPa，静压强化，制得靶材素坯；
S4、脱脂与烧结：
靶材素坯脱脂后，在氧气气氛下进行高温烧结，烧结温度最高为1650℃，烧结时间为280h，制得多元氧化物掺杂氧化铟基靶材。
实施例2-16和对比例1-9
实施例2-16和对比例1-9与实施例1的区别在于，组分及其含量不同，如表1所示。
表1各实施例和对比例的组分及其含量
Figure BDA0004125518780000061
备注：表1中ZrO2、HfO2含量单位为ppm，其余氧化物含量单位为质量份。
产品效果测试
1、加工绑定：
分别将上述各实施例和对比例制备的靶材按图纸尺寸加工后，与钛管绑定，并进行超声波验伤，无暗裂纹。然后进行后续的镀膜测试。
2、镀膜测试：
靶材密度由阿基米德排水法测得。
在清洗过的玻璃基板上，分别采用上述各实施例和对比例制得的靶材使用溅射镀膜沉积TCO薄膜，镀膜功率150W，溅射气体为Ar，镀膜气氛为H2/O2混合气体，沉积膜厚80mm，使用霍尔效应测试仪测试薄膜的迁移率，使用紫外分光光度计测试薄膜的透光率。
各实施例和对比例制得的靶材，以及由其制得的TCO薄膜的性能测试结果如表2所示。
表2各实施例和对比例的性能测试结果
Figure BDA0004125518780000071
由上表可知，本发明实施例1-16制得的多元氧化物掺杂氧化铟基靶材，密度在7.080-7.121g/m3之间，晶粒尺寸9.8-12.8μm，靶材具有低掺杂、高密度的特点。靶材使用PVD溅射镀膜，制得的TCO薄膜的迁移率在43-75cm2/(V.s)之间，透光率(@400-1200nm)达到88.5-90.8％。实施例15调整了ZrO2与HfO2的质量比为1：1，导致密度稍有所下降。实施例16调整了ZrO2与HfO2的质量比为7：1，导致迁移率稍有所下降。根据上述效果，本发明设置ZrO2掺杂量在0-200ppm之间(ZrO2的含量不为零)，HfO2掺杂量在0-50ppm之间(HfO2的含量不为零)，ZrO2和HfO2的质量比在(3-5)：1之间，制备的靶材效果为佳。
对比例1由于只掺杂了SnO2，且掺杂浓度较低，相同烧结工艺下，烧结温度严重不够，靶材密度过低。与实施例2相比，对比例2未掺杂HfO2，靶材密度稍低，导致沉积的TCO薄膜迁移率及透光率下降。与实施例8相比，对比例3未掺杂TiO2，缺少了助烧作用，与对比例1相同，制备的靶材的密度过低。与实施例2相比，对比例4未掺杂CeO2，晶格间的应力较大，气孔较多，致密度略低。与实施例3相比，对比例5未掺杂ZrO2，TCO薄膜光电性能下降。对比例6的ZrO2与HfO2掺杂过多，过多的Zr的存在，使得Ce4+被还原为Ce3+，弱化了CeO2的掺杂作用，沉积的TCO薄膜迁移率较低。对比例7中ZrO2与HfO2的比例为1：4，沉积的TCO薄膜迁移率及透光率降低。对比例8、对比例9分别增加了ZrO2与HfO2的含量，导致沉积薄膜的光电性能降低。

Claims (10)

1.一种多元氧化物掺杂氧化铟基靶材，其特征在于，按照质量份计，包括如下组分：
Figure FDA0004125518770000011
X的氧化物0.1-3份，所述X为V、Nb、Cr、Mo、Ta、W中的一种或几种；
所述多元氧化物掺杂氧化铟基材料还包括ZrO2 0-200ppm和HfO2 0-50ppm，所述ZrO2的质量不为零，HfO2的质量不为零。
2.根据权利要求1所述多元氧化物掺杂氧化铟基靶材，其特征在于，按照质量份计，包括如下组分：
Figure FDA0004125518770000012
X的氧化物0.1-1份。
3.根据权利要求1所述多元氧化物掺杂氧化铟基材料，其特征在于，还包括ZrO2100-200ppm和HfO2 20-50ppm。
4.根据权利要求1所述多元氧化物掺杂氧化铟基材料，其特征在于，所述ZrO2和HfO2的质量比为(3-5)：1。
5.根据权利要求1所述多元氧化物掺杂氧化铟基材料，其特征在于，所述X的氧化物包括V2O5、Nb2O5、CrO3、MoO3、Ta2O5、WO3中的一种或几种。
6.权利要求1-5任一项所述的多元氧化物掺杂氧化铟基靶材的制备方法，包括如下步骤：
将各组分混合，制得混合料，喷雾干燥，制得混合氧化物粉体，注入模具内静压成型，制得靶材素胚，脱脂，烧结，制得所述多元氧化物掺杂氧化铟基靶材。
7.根据权利要求1所述的制备方法，其特征在于，所述烧结的温度为1500-1650℃，所述烧结的时间为240-300h。
8.权利要求1-5任一项所述的多元氧化物掺杂氧化铟基靶材在光伏电池领域中的应用。
9.一种透明导电氧化物薄膜，其特征在于，包括采用权利要求1-5任一项所述的多元氧化物掺杂氧化铟基靶材制得。
10.权利要求9所述的透明导电氧化物薄膜的制备方法，其特征在于，包括如下步骤：
将所述多元氧化物掺杂氧化铟基靶材采用溅射镀膜制得所述透明导电氧化物薄膜。
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