CN108698932B - 氧化物烧结体及氧化物透明导电膜 - Google Patents

氧化物烧结体及氧化物透明导电膜 Download PDF

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CN108698932B
CN108698932B CN201780012335.7A CN201780012335A CN108698932B CN 108698932 B CN108698932 B CN 108698932B CN 201780012335 A CN201780012335 A CN 201780012335A CN 108698932 B CN108698932 B CN 108698932B
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oxide
sintered body
transparent conductive
oxide sintered
film
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CN108698932A (zh
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秋池良
土田裕也
仓持豪人
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Tosoh Corp
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Tosoh Corp
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Abstract

本发明的目的在于，提供能够得到在宽波长域的范围内显示更低的光吸收特性，且低电阻的氧化物透明导电膜的氧化物烧结体、及氧化物透明导电膜。一种氧化物烧结体，具有铟、铪、钽及氧作为构成元素，其中，使用在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％的氧化物烧结体。

Description

氧化物烧结体及氧化物透明导电膜
技术领域
本发明涉及氧化物烧结体、溅射靶、以及氧化物透明导电膜及其制造方法。
背景技术
氧化物透明导电膜为低电阻且在可见光区域内具有较高的透射率，因此，被用于液晶等显示元件、太阳能电池等各种受光元件的电极，另外，被用在汽车用、建筑材料用的热射线反射膜、抗静电膜或冷藏展示柜等防雾用透明发热体等各种领域。其中，添加有锡的氧化铟膜也被作为ITO(Indium Tin Oxide)膜广泛利用。
近年来，作为用于最大限地引出元件特性的一种方法，根据要求协调电特性、光学特性是极其重要的，特别是积极地进行与液晶等显示元件或太阳能电池等各种用途对应的物性的最优化。
在上述的ITO膜中，尝试通过调整锡的添加量，调节电特性、光学特性。但是，在该方法中，难以同时改善如电阻那样的电特性和如透射率、光吸收率那样的光学特性这两者。例如，非专利文献1中公开有In2O3－SnO2系透明导电膜的电光学特性的SnO2量依赖性。据此，In2O3－SnO2系透明导电膜在SnO2量为10wt％左右时电阻变得最低。但是，在这样的SnO2量，由于等离子体波长向短波长侧位移，因此，在红外区域吸收率大，透射率降低。
近年来，在上述的元件中，多将高分子膜或有机系材料组装入元件结构内，因此，寻求与现存工艺相比大幅降低制膜或元件制造工艺的最高温度，需要液晶等分子不分解，能够使用大量的树脂、聚合物基板的在150℃以下的温度下能够实现低电阻的透明导电膜。
专利文献1、2中公开有由铟和包含铪、钽的金属元素中的至少一种元素和氧构成的氧化物烧结体。但是，专利文献1、2均只公开有单独添加了上述金属元素的例子。
专利文献3、4中公开有氧化铟中含有绝缘性氧化物的溅射靶，作为绝缘性氧化物，例示了氧化铪、氧化钽。但是，任一文献对于添加了氧化铪、氧化钽的实施例均完全没有记载。
现有技术文献
专利文献
专利文献1:日本特开平9－209134号公报
专利文献2:日本特开平9－150477号公报
专利文献3:日本特开2003－105532公报
专利文献4:日本特开2004－149883公报
非专利文献
非专利文献1:TOSOH Research&TechnologyReview、47、pp.11－20(2003)
发明内容
发明所要解决的问题
本发明的目的在于，提供在150℃以下的低温工艺中，在与有机物在结构上不可分的基材或有机基材上也能够实现低电阻的透明导电膜用氧化物烧结体、溅射靶、透明导电膜及该带膜基材、以及它们的制造方法。
用于解决问题的技术方案
鉴于这种情况，本发明者们进行了深入研究，结果发现，通过在氧化铟中以特定的比率添加特定的元素，可以得到一种氧化物烧结体，该氧化物烧结体用将制膜、元件制造的工艺的最高温度抑制在低温的制造工艺可以形成实现了充分低的电阻的氧化物透明导电膜，并因此完成了本发明。
即，本发明在于以下的[1]～[6]。
[1]一种氧化物烧结体，具有铟、铪、钽及氧作为构成元素，其特征在于，在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。
[2]根据上述[1]所述的氧化物烧结体，其特征在于，氧化物烧结体的相对密度为97％以上，且平均结晶粒径为8μm以下。
[3]根据上述[1]或[2]所述的氧化物烧结体，其特征在于，含有低于1at％的不可避免的杂质而成。
[4]一种溅射靶，其特征在于，包含上述[1]～[3]所述的氧化物烧结体。
[5]一种氧化物透明导电膜的制造方法，其特征在于，使用上述[4]所述的溅射靶进行溅射。
[6]一种氧化物透明导电膜，在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。
具体实施方式
以下，详细说明本发明的优选的实施方式。
本实施方式的氧化物烧结体的特征在于，在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。在本说明书中，“at％”是指“原子％”。即，本实施方式的氧化物烧结体中，Hf相对于In、Hf及Ta的合计的原子比(原子数的比率)为0.2～3.0at％，Ta相对于In、Hf及Ta的合计的原子比(原子数的比率)为0.02～1.3at％。
通过设为这种组成范围，能够用将制膜、元件制造的工艺的最高温度抑制在低温的制造工艺形成能够实现充分低的电阻的氧化物透明导电膜。
从更适于低温工艺这种观点来看，Hf/(In+Hf+Ta)的下限优选为0.5at％，更优选为0.7at％。从同样的观点来看，Hf/(In+Hf+Ta)的上限优选为2.5at％。
从更适于低温工艺这种观点来看，Ta/(In+Hf+Ta)的下限优选为0.1at％，更优选为0.2at％。从同样的观点来看，Ta/(In+Hf+Ta)的上限优选为1.0at％。
在本实施方式中，从以更高的水准实现氧化物透明导电膜的低的电阻率的观点来看，优选Hf/(In+Hf+Ta)为0.5～2.5at％。
本实施方式的氧化物烧结体的铟的含量，相对于金属元素的合计，优选为96at％以上，更优选为97at％以上，进一步优选为98at％以上。
本实施方式的氧化物烧结体及氧化物透明导电膜也可以含有不可避免的微量的杂质。作为这种杂质，可举出具有In、Hf及Ta以外的金属元素的氧化物等的化合物。氧化物烧结体中的这些杂质的合计含量，换算为金属元素，相对于In、Hf及Ta的合计，优选为1at％以下，更优选为0.5at％以下，进一步优选为0.1at％以下，特别优选为低于0.05at％。
本实施方式的氧化物烧结体的相对密度优选为97％以上，更优选为99％以上。具有这种相对密度的氧化物烧结体用作溅射靶的情况下，能够进一步降低溅射中的异常放电。
本发明的氧化物烧结体的相对密度如下算出。即，将In、Hf及Ta分别换算为In2O3、HfO2及Ta2O5的氧化物求出重量比率。在此，将求出的In2O3、HfO2及Ta2O5的重量比率分别设为a(％)、b(％)、及c(％)。接着，分别使用真密度In2O3：7.18g/cm3、HfO2：9.68g/cm3、Ta2O5：8.73g/cm3，算出理论密度A(g/cm3)。
A＝(a+b+c)/((a/7.18)+(b/9.68)+(c/8.73))
氧化物烧结体的烧结密度B(g/cm3)按照JIS－R1634－1998，通过阿基米德法测定。
相对密度(％)作为烧结密度B(g/cm3)相对于算术上求出的理论密度A(g/cm3)的相对值，通过下式求出。
相对密度(％)＝(B/A)×100
本发明的氧化物烧结体的平均结晶粒径优选为8μm以下，进一步优选为6μm以下。通过设为这种平均结晶粒径，可以提高氧化物烧结体的强度。从制造的容易性的观点来看，平均结晶粒径的下限优选为0.01μm，更优选为0.5μm，进一步优选为2μm。
此外，本发明的烧结体中的粒子的平均结晶粒径的测定如下进行。即，将本发明的氧化物烧结体切割为适当的大小后，对观察面进行表面抛光，接着利用稀盐酸溶液进行化学蚀刻，使粒界明确。使用EPMA、SEM/EDS、XRD等对该试样拍摄烧结体的抛光面的观察照片。求出观察照片的500个以上颗粒的长径，将其算术平均值作为平均结晶粒径。
接着，对本发明的氧化物烧结体的制造方法进行说明。
在本发明中，原料粉末的混合方法没有特别限定，具有：制备含有成为铟源的粉末、成为铪源的粉末及成为钽源的粉末的成型用的混合粉末的混合工序；将混合粉末成型而制作成成型体的成型工序；焙烧成型体而得到氧化物烧结体的焙烧工序。
以下，详细说明各工序。
在混合工序中，制备含有铟、铪、及钽的氧化物的混合粉末。在本实施方式中，原料粉末的混合方法没有特别限定，可以将成为铟源的粉末、成为铪源的粉末及成为钽源的粉末同时混合，或者也可以预先混合一部分后，进而追加余部进行混合。
作为混合方法，优选首先预先混合成为铪源的粉末和成为钽源的粉末，进行预烧的方法。作为原料粉末没有特别限定，氧化铪、氧化钽合适，但也可以使用通过焙烧而成为氧化铪、氧化钽的铪、钽的无机、有机盐等。特别是如果考虑处理性，则优选使用氧化物粉末。如果考虑处理性，则这些粉末的粒径优选为平均1次粒径为1.5μm以下，进一步优选为0.1～1.5μm。通过使用这种粉末，可以得到烧结体密度的改善效果。
在此，预混合方法没有特别限定，可例示使用了氧化锆、氧化铝、尼龙树脂等的球、珠的干式、湿式的介质搅拌型磨机、无介质的容器旋转式混合、机械搅拌式混合等混合方法。具体而言，可举出球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机、V型混合机、桨叶式混合机、双轴行星搅拌式混合机等。此外，在使用湿式法的球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机等的情况下，需要对粉碎后的浆料进行干燥。该干燥方法没有特别限定，例如可例示过滤干燥、流动层干燥、喷雾干燥等。另外，在使用金属盐溶液、醇盐溶液作为原料的情况下，使自溶液中析出的沉淀类干燥。优选所得的预混合粉末在800～1200℃进行预烧。预烧温度更优选为1000～1200℃，时间在1～3小时是充分的。所得的预烧粉末通过破碎处理等，使平均1次粒径为0.5μm以下。破碎等处理方法没有特别限定，可例示使用了氧化锆、氧化铝、尼龙树脂等的球、珠的干式、湿式的介质搅拌型磨机等的混合方法。具体而言，可举出球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机等。此外，在使用湿式法的球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机等的情况下，需要对破碎后的浆料进行干燥。其干燥方法没有特别限定，例如可例示过滤干燥、流动层干燥、喷雾干燥等。
接着，以成为最终组成的方式混合氧化铟粉末和所述预混合粉末，得到成型用混合粉末。通过使用氧化铟粉末，可减少工序的复杂性、粉末处理等附加操作。在铟源是氧化物以外的物质的情况、例如为硝酸盐、氯化物、碳酸盐等的情况下，进行预烧制成氧化物后使用。如果考虑处理性，则这些粉末的粒径优选为平均1次粒径1.5μm以下，进一步优选为0.1～1.5μm。通过使用这种粉末，得到烧结体密度的改善效果。
在此，混合方法没有特别限定，可例示使用了氧化锆、氧化铝、尼龙树脂等的球、珠的干式、湿式的介质搅拌型磨机、无介质的容器旋转式混合、机械搅拌式混合等混合方法。具体而言，可举出球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机、V型混合机、桨叶式混合机、双轴行星搅拌式混合机等。此外，在使用湿式法的球磨机、珠磨机、磨碎机、振动磨机、行星式磨机、喷射式磨机等的情况下，需要对粉碎后的浆料进行干燥。该干燥方法没有特别限定，例如，可例示过滤干燥、流动层干燥、喷雾干燥等。
所得的粉末为平均1次粒径1.5μm以下，更优选为0.1～1.5μm成为成型用粉末。另外，也可以进一步通过造粒处理等改善成型工序中的操作性。这些操作在成型性、烧结性的改善上起到效果。
在混合工序中，成为铟源的粉末、成为铪源的粉末、及成为钽源的粉末的使用量在以金属元素的原子比表示成型用的混合粉末的组成(最终组成)时，优选处于以下的范围。即，Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。
通过设为这种组成范围，可以用将制膜、元件制造的工艺的最高温度抑制在低温的制造工艺形成能够实现充分低的电阻的氧化物透明导电膜。
在成型工序中，将在混合工序获得的成型用的混合粉末成型。成型方法可适当选择能够成型为目标形状的成型方法，没有特别限定。例如，可例示挤压成型法、及浇注成型法等。成型压力可以在不产生裂纹等而能够制作可处理的成型体的范围内适当设定，没有特别限定。成型体的成型密度优选尽可能高。因此，也可使用冷等静压成型(CIP)等方法。此时，根据需要，也可以使用用于改善成型性的有机系的添加剂。
在成型时使用添加剂的情况下，为了去除残存于成型体中的水分、有机系的添加剂，优选在焙烧工序前在80～500℃的温度下实施加热处理。该处理温度只要根据残存的水分、添加剂的量及种类适当选择即可。
在焙烧工序中，对通过成型工序所得的成型体进行焙烧。对于升温速度没有特别限定，从缩短焙烧时间和防裂纹的观点来看，优选为10～400℃/小时。用于烧结的保持温度(烧结保持温度)优选为1400℃以上且低于1650℃，更优选为1500℃以上且1625℃以下。通过设为这种焙烧条件，能够得到更高密度的氧化物烧结体。保持时间优选为1小时以上，更优选为3～10小时。由此，能够得到更高密度且平均结晶粒径小的氧化物烧结体。对于降温速度，只要在通常的范围内设定，则没有特别限定，从缩短焙烧时间和防裂纹的观点来看，优选为10～500℃/小时。
焙烧时的气氛优选为含有氧的气氛。特别优选在氧气流中进行焙烧。特别优选将烧结时将氧导入炉内时的氧流量(L/min)和成型体的重量(投料量、kg)之比(成型体的重量/氧流量)设为1.0[kg/(L/min)]以下。由此，能够得到更高密度的氧化物烧结体。
本发明的氧化物烧结体的制造方法不限定于上述的方法。例如也可以在混合工序不进行预混合及预烧，而将成为铟源的粉末、成为铪源的粉末及成为钽源的粉末一起混合，调整成型用的混合粉末。
本实施方式的溅射靶的特征在于，包含上述的氧化物烧结体。这种溅射靶因为制膜时的放电特性优异，所以能够抑制异常放电而稳定地进行制膜。该溅射靶具有与氧化物烧结体同样的组成及结构。
在本实施方式中，可以将氧化物烧结体直接用作溅射靶，也可以将氧化物烧结体加工成规定的形状用作溅射靶。
溅射靶的溅射面的表面粗糙度以中心线平均粗糙度(Ra)计优选为3μm以下，更优选为2μm以下。由此，可进一步抑制制膜时的异常放电的次数，可进行稳定的制膜。中心线平均粗糙度可通过用粒度号不同的磨石等对成为溅射面的复合氧化物烧结体的表面进行机械加工的方法、或利用喷砂等进行喷射加工的方法等来调整。中心线平均粗糙度能够通过例如利用表面性状测定装置评价测定面来求出。
可以使用本实施方式的溅射靶，通过溅射法来制膜。作为溅射法，能够适当选择DC溅射法、RF溅射法、AC溅射法、DC磁控溅射法、RF磁控溅射法、或离子束溅射法等。这些中，从可大面积、均匀且高速地制膜的观点来看，优选DC磁控溅射法、及RF磁控溅射法。
溅射时的温度没有特别限定，根据使用的基材的耐热性适当设定。例如，在以无碱玻璃为基材的情况下，通常优选为250℃以下，在以树脂制薄膜为基材的情况下，通常优选为150℃以下。在使用石英、陶瓷、或金属等耐热性优异的基材的情况下，也可在这些温度以上的温度下制膜。
溅射时的气氛气体通常使用惰性气体、例如氩气。根据需要，也可以使用氧气、氮气、或氢气等。
本实施方式的氧化物透明导电膜能够通过使用了上述的溅射靶的溅射制膜而得。即，本实施方式的氧化物透明导电膜通过进行对包含氧化物烧结体的溅射靶进行溅射制膜的工序而能够获得。
本实施方式的氧化物透明导电膜即使是将制膜、元件制造的工艺的最高温度抑制为低于200℃、特别是低于180℃这种低温的制造工艺，也能够实现更充分低的电阻。进而，可得到高温、高湿环境下的耐久性优异的氧化物透明导电膜。
通过上述的方法而得的氧化物透明导电膜的组成反映用于溅射的靶的组成。即，通过使用包含上述的氧化物烧结体的溅射靶，Hf/(In+Hf+Ta)为0.2～3.0at％。另外，得到Ta/(In+Hf+Ta)具有0.02～1.3at％的组成的氧化物透明导电膜。
即，本实施方式的氧化物透明导电膜具有与溅射靶及氧化物烧结体同等的组成。
因此，氧化物透明导电膜包含具有铟、铪、钽及氧作为构成元素的氧化物。氧化物透明导电膜中的铟的含量、铪的含量、钽的含量的优选的范围与氧化物烧结体相同。
从本实施方式的氧化物透明导电膜用制膜、元件制造的工艺的最高温度抑制在低温的制造工艺能够实现充分低的电阻的观点来看，Hf/(In+Hf+Ta)的下限优选为0.5at％，更优选为0.7at％。从同样的观点来看，Hf/(In+Hf+Ta)的上限优选为2.5at％，更优选为2.1at％。
从本实施方式的氧化物透明导电膜用制膜、元件制造的工艺的最高温度抑制在低温的制造工艺能够实现充分低的电阻的观点来看，Ta/(In+Hf+Ta)的下限优选为0.1at％，更优选为0.3at％。另外，从同样的观点来看，Ta/(In+Hf+Ta)的上限优选为1.0at％。
在本实施方式中，从以更高的水准实现氧化物透明导电膜的低的电阻率的观点来看，优选Hf/(In+Hf+Ta)为0.5～2.5at％。另外，优选Ta/(In+Hf+Ta)为0.1～1.0at％。
氧化物透明导电膜根据用途形成适当的膜厚来使用。例如，在用于太阳能电池等各种受光元件的电极、显示元件的TFT、CF、有机EL元件的透明电极等的情况下，多使用具有100nm～300nm程度的膜厚的氧化物透明导电膜。在液晶等显示元件、特别是触摸面板的用途中，除了玻璃基板外，还多采用使用了高分子薄膜挠性基板。在这种用途中，形成膜厚为5～50nm程度的非常薄的膜使用。另外，由于形成层叠了耐热性低的材料的结构，或使用高分子薄膜，因此要求将制膜工艺的最高温度抑制在低温。
本发明的氧化物透明导电膜，能够适宜地作为与基材一起构成的、包含氧化物透明导电膜的层叠基材来使用。
在此，基材可举出包括无碱玻璃、石英等的玻璃基材、树脂制的高分子薄膜基材、陶瓷或金属的基材等。特别是在面向显示元件的情况下视认性极其重要，因此，包括无碱玻璃、石英等的玻璃基材、树脂制的高分子薄膜基材是适宜的。
这种层叠基材适宜作为与多个功能零件一起构成的元件来使用。例如，适合用作太阳能电池等光学元件，FPD、触摸面板等显示元件。特别是上述的显示元件适宜装入电子设备内使用，特别适于如移动设备那种小型高性能电子设备。
以上，说明了本发明的优选的实施方式，但本发明不限定于上述的实施方式。
发明效果
本发明的氧化物烧结体能够用作溅射靶。而且，通过使用该靶进行溅射，能够抑制溅射中的异常放电，制造本发明的氧化物透明导电膜。本发明的氧化物透明导电膜即使在150℃以下的工艺温度中也能够实现300μΩ·cm以下这种极低的电阻率，因此，不仅使一般的电子元件的制造工艺容易化，而且可适宜用于使用了有机基材的元件、有机半导体元件。
实施例
参照以下的实施例，更具体地说明本发明，但本发明不限定于这些实施例。
[实施例1～20]
根据表1所示的组成，利用以下的方法制作烧结体、溅射靶、透明导电膜。
＜氧化物烧结体的制作＞
作为原料粉末，准备纯度99.99重量％、平均粒径0.5μm的氧化铟粉末，纯度99.9重量％、平均粒径0.2μm的氧化铪粉末，纯度99.9重量％、平均粒径0.2μm的氧化钽粉末。以达到表1中记载的原子比的方式秤量这些原料粉末并利用干式球磨机混合，得到成型用的混合粉末。混合粉末的平均粒径为0.2μm。
将该混合粉末按以下的顺序成型制作成型体。首先，使用直径150mm的模型，以0.3ton/cm2加压，将混合粉末成型。接着，进行以3.0ton/cm2加压的CIP成型，得到圆柱形状的成型体。将该成型体配置在调整为纯氧气氛的烧结炉内，在以下的条件下进行烧结，制作圆板形状的氧化物烧结体。这样，得到各实施例、各比较例及各参考例的氧化物烧结体。此外，保持时间是在烧结保持温度下保持的时间。
(焙烧条件)
·升温速度：50℃/小时
·烧结保持温度：1600℃
·保持时间：5小时
·烧结气氛：从升温开始前(室温)至达到降温时的100℃，将纯氧气体导入炉内
·降温速度：100℃/小时
·成型体的重量/氧流量：0.9[kg/(L/min)]
＜氧化物烧结体的评价＞
(组成)
使用市售的ICP发光分析装置，通过ICP发光分析法将各实施例、各比较例及各参考例的氧化物烧结体的组成定量。然后，求出原子比。其结果示于表1。此外，氧化物烧结体的组成大体与成型用的混合粉末的组成相同。
(相对密度)
求出各实施例、各比较例及各参考例的氧化物烧结体的相对密度。相对密度是在将氧化物烧结体的理论密度设为A，将烧结密度设为B时，通过下述式求出的值。理论密度A及烧结密度B的测定方法如上述。测定结果示于表1。
相对密度(％)＝(B/A)×100
(平均结晶粒径)
测定构成各实施例、各比较例及各参考例的氧化物烧结体的结晶粒子的平均结晶粒径。平均结晶粒径的测定方法如上述。但是，氧化物烧结体的抛光面的观察照片(倍率：1000～5000倍)使用扫描电子显微镜来拍摄。求出在该观察照片中500个粒子的长径。将求出的长径的算术平均值作为平均结晶粒径。测定结果示于表1。
(三点弯曲强度)
烧结体的强度根据JIS－R－1601测定三点弯曲强度。
＜溅射靶及氧化物透明导电膜的制作＞
将在各实施例、各比较例及各参考例中制作的氧化物烧结体加工成圆板形状(直径：4英寸＝101.6mm)。在用作溅射靶时，成为溅射面的面使用平面磨床和金刚石磨石进行了抛光。抛光时通过改变磨石的粒度号，调整中心线平均粗糙度(Ra)。这样制作溅射靶。使用市售的表面性状测定装置(装置名Surftest SV－3100，Mitutoyo制)测定制作的溅射靶的溅射面的Ra。其结果如表1所示。
使用所得的溅射靶，通过DC磁控溅射法在下述的条件下在基板上制膜。制膜后，在以下的条件进行后处理，得到氧化物透明导电膜。
(制膜条件)
·装置：DC磁控溅射装置
·磁场强度：1000Gauss(靶正上、水平成分)
·基板温度：室温(25℃)
·到达真空度：8×10－5Pa
·制膜时的气氛：氩气
·溅射时的气压：0.5Pa
·DC功率：200W
·膜厚：30nm
·使用基板：无碱玻璃(康宁(CORNING)公司制EAGLE XG玻璃厚度0.7mm)
(制膜后的后处理条件)
制膜后将带透明导电膜的基板进行在大气中以150℃进行60分钟加热的热处理。此时的升温速度为50℃/min。
＜氧化物透明导电膜的评价＞
(膜厚)
薄膜的厚度使用DEKTAK3030(Sloan社制)测定。
(电阻率)
薄膜的电阻率使用HL5500(日本Bio-Rad Laboratories社制)测定。
(透光率)
基板上形成有氧化物透明导电膜的试样的透光率使用分光光度计(商品名：U－4100、株式会社日立High-Technologies社制)，测定从波长240nm至2600nm的范围，示出在显示器件中重要的波长400～800nm的透光率的平均值。
所得的透明导电膜的电阻率和透光率的测定结果示于表1。
[比较例1～10]
根据表1所示的组成，利用与实施例1～20同样的方法制作烧结体、溅射靶、透明导电膜。
[参考例1]
根据表1所示的组成，将焙烧时的保持时间设为15小时，利用除此以外的条件与实施例1～20同样的方法制作烧结体、溅射靶、透明导电膜。
[参考例2]
根据表1所示的组成，将焙烧时的保持时间设为25小时，利用除此以外的条件与实施例1～20同样的方法制作烧结体、溅射靶、透明导电膜。
测定结果示于表1。
[表1]
Figure BDA0001770705940000141
[参考例3]
将添加元素设为Sn，利用与实施例1～20同样的方法制作烧结体、溅射靶、透明导电膜。评价结果示于表2。从该结果可知，即使与添加目前一般使用的Sn的In2O3(ITO)相比较，本发明也能够在低温工艺实现低的电阻。
[表2]
Figure BDA0001770705940000151
上面虽然参照特定的实施方式详细地说明了本发明，但对于本领域技术人员来说明显可知，在不脱离本发明的本质范围能够增加各种变更、修正。
此外，将2016年2月22日申请的日本专利申请2016－031403号及2016年11月16日申请的日本专利申请2016－223540号的说明书、权利要求的范围、附图及摘要的全部内容引用于此，作为本发明的说明书的公开而编入。
产业上的可利用性
根据本发明，能够提供溅射靶及适宜用作溅射靶的氧化物烧结体。而且，通过使用该溅射靶进行溅射，能够抑制在制膜中的靶的破损的同时，制作氧化物透明导电膜。本发明的氧化物透明导电膜在将氧化物透明导电膜的制膜、元件制造的工艺的最高温度抑制在低温的制造工艺能够实现低电阻。因此，例如通过用于太阳能电池，与目前比较，能够抑制光学损失、光吸收产生的发热。另外，本发明的氧化透明导电膜在用低温的制膜工艺制作时，具有低的电阻率和高的透射率，因此，例如能够适合用于除玻璃基板外，使用薄膜等挠性基板的触摸面板用途。另外，由于本发明的氧化物透明导电膜具有高的耐久性，因此能够适合用于各种装置用途。

Claims (6)

1.一种氧化物烧结体，其特征在于，由铟、铪、钽及氧作为构成元素而构成，在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。
2.根据权利要求1所述的氧化物烧结体，其特征在于，
氧化物烧结体的相对密度为97％以上，且平均结晶粒径为8μm以下。
3.根据权利要求1或2所述的氧化物烧结体，其特征在于，
其含有低于1at％的不可避免的杂质。
4.一种溅射靶，其特征在于，
其包含权利要求1～3所述的氧化物烧结体。
5.一种氧化物透明导电膜的制造方法，其特征在于，
使用权利要求4所述的溅射靶进行溅射。
6.一种氧化物透明导电膜，其特征在于，由铟、铪、钽及氧作为构成元素而构成，在将铟、铪及钽分别用In、Hf及Ta表示时，以原子比计Hf/(In+Hf+Ta)为0.2～3.0at％，Ta/(In+Hf+Ta)为0.02～1.3at％。
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