JP3128124B2 - Conductive metal oxide sintered body and use thereof - Google Patents
Conductive metal oxide sintered body and use thereofInfo
- Publication number
- JP3128124B2 JP3128124B2 JP01148348A JP14834889A JP3128124B2 JP 3128124 B2 JP3128124 B2 JP 3128124B2 JP 01148348 A JP01148348 A JP 01148348A JP 14834889 A JP14834889 A JP 14834889A JP 3128124 B2 JP3128124 B2 JP 3128124B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- oxide
- transparent conductive
- metal oxide
- conductive metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、導電性金属酸化物焼結体及びその用途に関
する。更に詳しくは、スパッタリング法、CVD法等によ
り形成される透明導電性金属酸化物薄膜及びその原材料
のに関するものである。Description: TECHNICAL FIELD The present invention relates to a conductive metal oxide sintered body and its use. More specifically, the present invention relates to a transparent conductive metal oxide thin film formed by a sputtering method, a CVD method or the like, and a raw material thereof.
［従来の技術］ 近年、太陽電池やディスプレー機器の透明電極や、帯
電防止用の導電性コーティングとして透明導電性薄膜の
需要が高まっている。このような透明導電性薄膜は、導
電性金属酸化物組成物のスパッタリング法、CVD法等に
より形成されている。[Related Art] In recent years, there has been an increasing demand for a transparent conductive thin film as a transparent electrode of a solar cell or a display device, or a conductive coating for antistatic. Such a transparent conductive thin film is formed by a sputtering method, a CVD method, or the like of a conductive metal oxide composition.
従来、このような透明導電性金属酸化物としては異種
添加元素として錫をドープした酸化インジウム（以下IT
Oと記述）、異種添加元素としてアンチモンをドープし
た酸化スズが主に用いられている。Conventionally, as such a transparent conductive metal oxide, indium oxide doped with tin as a different additive element (hereinafter referred to as IT
O), and tin oxide doped with antimony as a different additive element is mainly used.
しかし異種添加元素としてアンチモンをドープした酸
化スズは抵抗が高く（比抵抗:10mΩ・cm程度）、一方比
較的低抵抗なITOでも、比抵抗で0.2mΩ・cm程度までし
か達成されない。このような状況において、近時より低
抵抗な透明導電膜材料が熱望されている。However, tin oxide doped with antimony as a different additive element has a high resistance (specific resistance: about 10 mΩ · cm), while even a relatively low-resistance ITO can achieve a specific resistance of only about 0.2 mΩ · cm. Under such circumstances, a transparent conductive film material having a lower resistance than recently has been eagerly desired.
これまで酸化インジウムのドーパントとしては錫が最
も多く用いられているが、錫以外にもモリブデン、タン
グステン、チタン（特開昭59−204625）、亜鉛、セリウ
ム、コバルト、ニッケル（特開昭60−220505）、トリウ
ム（特開昭59−198602）、ルテニウム、鉛、銅（特開昭
59−163707）、硼素、ヒ素、アンチモン、ビスマス（特
開昭59−90307）、シリコン、ゲルマニウム（特開昭62
−202415）、アルミニウム、ガリウム（特開昭62−8456
7）、ハロゲン元素（特開昭62−142774）、テルル（特
開昭63−178414）等が検討されている。しかしいずれの
ドーパントにおいても得られる物の導電性は必ずしも十
分ではなかった。Until now, tin has been most often used as a dopant for indium oxide. In addition to tin, molybdenum, tungsten, titanium (JP-A-59-204625), zinc, cerium, cobalt, nickel (JP-A-60-220505) ), Thorium (JP-A-59-198602), ruthenium, lead and copper (JP-A-59-198602)
59-163707), boron, arsenic, antimony, bismuth (JP-A-59-90307), silicon, germanium (JP-A-62
-202415), aluminum and gallium (Japanese Patent Laid-Open No. 62-8456)
7), halogen elements (JP-A-62-142774), tellurium (JP-A-63-178414) and the like have been studied. However, the conductivity of the obtained product was not always sufficient for any of the dopants.
［問題点を解決する手段］ 本発明者等は酸化インジウムに異種添加元素をドープ
した導電性金属酸化物に関して鋭意検討を重ねた結果、
少なくともハフニウム又はニオブ成分をドーパントの一
部として含有する酸化インジウムにおいて極めて低抵抗
な透明導電膜が形成可能であることを見出だし、本発明
を完成させるに至ったものである。[Means for Solving the Problems] The present inventors have conducted intensive studies on a conductive metal oxide obtained by doping indium oxide with a different additive element.
It has been found that a transparent conductive film having extremely low resistance can be formed from indium oxide containing at least a hafnium or niobium component as a part of the dopant, and the present invention has been completed.
酸化インジウムに異種添加元素をドープすることによ
って導電性を向上させる場合、その導電性は酸化インジ
ウム中の電子密度と電子移動度によって規定される。酸
化インジウムに異種添加元素をドープしていくと電子密
度が増加し、導電性が向上するが、ドーパントの含有量
が必要以上に増大すると、電子の移動度が低下し、導電
性は再び低下する。When conductivity is improved by doping a different additive element into indium oxide, the conductivity is determined by the electron density and electron mobility in the indium oxide. The doping of indium oxide with a different additive element increases the electron density and improves the conductivity, but when the content of the dopant increases more than necessary, the electron mobility decreases and the conductivity decreases again. .
ハフニウム及び／又はニオブは、錫同様に酸化インジ
ウムにドープすることによりその電子密度を向上させる
だけでなく、ドープすることによる酸化インジウム中の
電子移動度の低下を抑制するのでドーパントとして極め
て優れている。Similar to tin, hafnium and / or niobium not only improves the electron density by doping indium oxide, but also suppresses a decrease in electron mobility in indium oxide due to doping, and is therefore extremely excellent as a dopant. .
一方、これらの成分を酸化インジウムにドープする場
合、錫成分と併用して用いることが得られる物の低抵抗
化に極めて効果的であることを見出だした。この際の酸
化インジウム中の錫成分及びハフニウム及び／又はニオ
ブ成分の含有量としては、重量換算で酸化インジウム中
のこれらの酸化物の含有量が1wt％〜20wt％、特に3wt％
〜12wt％が好ましい。また錫成分に対するハフニウム及
び／又はニオブ成分の比率にも特別の制限は無いが、特
に3wt％〜30wt％程度が好ましい。On the other hand, it has been found that when these components are doped into indium oxide, it is extremely effective to reduce the resistance of the obtained material when used in combination with the tin component. At this time, the content of the tin component and the hafnium and / or niobium component in the indium oxide is such that the content of these oxides in the indium oxide is 1 wt% to 20 wt%, particularly 3 wt% in terms of weight.
~ 12 wt% is preferred. The ratio of the hafnium and / or niobium component to the tin component is not particularly limited, but is particularly preferably about 3% to 30% by weight.
前記した量が少なすぎるとこれらの添加の効果がな
く、又必要以上に多すぎると、得られるものの低抵抗化
に悪影響を及ぼす。If the amount is too small, the effects of these additions will not be obtained. If the amount is too large, the obtained product will have an adverse effect on lowering the resistance.
このような組成の透明導電膜は極めて低抵抗であり、
かつ透明性に優れている。従来ITOによる透明導電膜に
おいては比抵抗で0.2mΩ・cm程度が限界であったが、本
発明組成の透明導電膜においてはそれ以下、特に0.18m
Ω・cm以下が可能となった。又、透明性についても、膜
の光透過率が550nmに於いて85％以上で優れたものであ
る。The transparent conductive film having such a composition has extremely low resistance,
And it is excellent in transparency. Conventionally, in the transparent conductive film of ITO, the specific resistance was limited to about 0.2 mΩcm, but in the transparent conductive film of the composition of the present invention, it was less than that, especially 0.18 m
Ω · cm or less is possible. Also, the transparency is excellent when the light transmittance of the film is at least 85% at 550 nm.
本発明中に存在する各成分は酸化物の形で存在する。 Each component present in the present invention is in the form of an oxide.
このような低抵抗の透明導電膜を形成する方法の一つ
としてスパッタリング法が考えられるが、本発明の組成
を有する焼結体は、上述した優れた透明導電膜を形成す
るターゲットとして用いることが可能である。As one method for forming such a low-resistance transparent conductive film, a sputtering method can be considered. However, the sintered body having the composition of the present invention may be used as a target for forming the above-described excellent transparent conductive film. It is possible.
本発明の組成を有する焼結体はこれをスパッタリング
することによって極めて低抵抗な透明導電膜を形成する
ことが可能であるが、当該焼結体は可能な限り高密度で
あることが好ましい。高密度のターゲットは単に機械的
強度が強いだけでなく、スパッタリングによる組成ずれ
が起り難く、導電結晶面配向性の強い、低抵抗な透明導
電膜を形成しやすい。異種元素をドーパントとした酸化
インジウムの見掛けの焼結体密度は約7g/cm3程度である
が、本発明の組成の焼結体の密度としては、5g/cm3以上
である。The sintered body having the composition of the present invention can form an extremely low-resistance transparent conductive film by sputtering, but the sintered body is preferably as dense as possible. A high-density target not only has a high mechanical strength but also is less likely to cause a composition shift due to sputtering, and is easy to form a low-resistance transparent conductive film having a strong orientation of a conductive crystal plane. The apparent density of the sintered body of indium oxide using a different element as a dopant is about 7 g / cm 3 , but the density of the sintered body having the composition of the present invention is 5 g / cm 3 or more.
このような焼結体を調製するための酸化物粉末として
は、本発明の組成を満足していれば特に制限はないが、
上述したようになるべく高密度な焼結体を得るために微
細で高分散性であることが好ましい。また本発明の焼結
体製造用の原料粉末の製造方法としては、例えば、必要
な各成分の酸化物を平均粒径0.5μｍ以下の粉末として
混合する方法、各成分を含む溶液を用いてそれらの成分
を共沈させ、共沈物を焼成するなどして複合酸化物とす
る方法等を適用可能である。The oxide powder for preparing such a sintered body is not particularly limited as long as it satisfies the composition of the present invention,
As described above, in order to obtain a sintered body as dense as possible, it is preferable to be fine and highly dispersible. Examples of the method of producing a raw material powder for producing a sintered body of the present invention include, for example, a method of mixing oxides of necessary components as a powder having an average particle diameter of 0.5 μm or less, and a method of using a solution containing each component. Is co-precipitated, and the co-precipitate is calcined to form a composite oxide.
このようにして得られた酸化物粉末は予備成型し焼結
処理を行なう。この際の焼結は、温度:1300〜1500℃、
時間:5〜20時間で大気中又は不活性雰囲気中で行なう。The oxide powder thus obtained is subjected to preliminary molding and sintering. The sintering at this time, temperature: 1300 ~ 1500 ℃,
Time: 5-20 hours in air or inert atmosphere.
［発明の効果］ このような組成の金属酸化物焼結体は、透明導電膜の
形成材として用いた場合、特に導電性において極めて優
れた性能を持つ膜を形成させることができる。[Effect of the Invention] When a metal oxide sintered body having such a composition is used as a material for forming a transparent conductive film, it is possible to form a film having extremely excellent performance especially in conductivity.
［実施例］ 以下実施例に基づき本発明を説明するが、本発明は実
施例になんら限定されるものではない。EXAMPLES Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the examples.
実施例１ 酸化インジウムに対し、異種元素酸化物ドーパントを
5wt％及び10wt％添加した２種類の複合酸化物（平均粒
径0.5μｍ）を、予備成型（100mmφx10mm厚さ）し1400
℃で焼結して焼結体ペレットを調製した。それぞれのド
ーパント組成での同一密度における比抵抗を表１に示し
た。表１より酸化ハフニウム及び／又は酸化ニオブをド
ーパントの一部として含有する酸化インジウムは酸化ス
ズ単独をドーパントとして含有する場合に比べ、より低
抵抗であることが判る。Example 1 A different element oxide dopant was added to indium oxide.
The two types of composite oxides (average particle size 0.5 μm) added with 5 wt% and 10 wt% were pre-formed (100 mmφ × 10 mm thickness) and 1400
C. to obtain a sintered body pellet. Table 1 shows the specific resistance at the same density for each dopant composition. Table 1 shows that indium oxide containing hafnium oxide and / or niobium oxide as a part of the dopant has lower resistance than the case where tin oxide alone is contained as the dopant.
実施例２ 酸化インジウム、酸化ハフニウム、酸化ニオブ、酸化
スズの複合酸化物ターゲットを用いDCマグネトロンスパ
ッタリングにより透明導電膜を調製した。透明導電膜に
おけるドーパント量としては５〜8wt％程度が最適であ
るが、これを用いてスパッタリングすると、得られる膜
中のドーパント量はターゲット中のそれより低下する傾
向があるため、ターゲット中のドーパントとして全量で
10wt％含有するものを用いた。用いたターゲットは密度
約5g/cm3、直径10cmの焼結体ターゲット（焼結温度1400
℃）を用い、スパッタガスには純アルゴン、圧力は0.6P
a、投入電力は4w/cm2とした。また基板には石英ガラス
を用い、成膜中は基板は350℃に加熱した。このような
条件において約3000Aの透明導電膜を調製した。得られ
た透明導電膜の特性を表２に示した。これらの異種元素
をドーパントの一部として用いた場合、酸化インジウム
に酸化スズのみをドープした場合のものに比べ、より低
抵抗な透明導電膜が得られた。さらに膜の光透過率は55
0nmにおいて全て85％以上で、透明性においても従来の
ものに比べて優れたものであった。Example 2 A transparent conductive film was prepared by DC magnetron sputtering using a composite oxide target of indium oxide, hafnium oxide, niobium oxide, and tin oxide. The optimum amount of the dopant in the transparent conductive film is about 5 to 8 wt%. However, when sputtering is performed using this, the amount of the dopant in the obtained film tends to be lower than that in the target. As the whole amount
What contained 10 wt% was used. The target used was a sintered compact target with a density of about 5 g / cm 3 and a diameter of 10 cm (sintering temperature 1400
° C), pure argon as sputtering gas, pressure 0.6P
a, the input power was 4 w / cm 2 . In addition, quartz glass was used for the substrate, and the substrate was heated to 350 ° C. during the film formation. Under such conditions, a transparent conductive film of about 3000 A was prepared. Table 2 shows the properties of the obtained transparent conductive film. When these different elements were used as a part of the dopant, a transparent conductive film having lower resistance was obtained as compared with the case where indium oxide was doped with only tin oxide. Furthermore, the light transmittance of the film is 55
All were 85% or more at 0 nm, and the transparency was also superior to the conventional one.
フロントページの続き (56)参考文献 特開 平２−309511（ＪＰ，Ａ) 特開 昭59−26043（ＪＰ，Ａ) 特開 昭62−12009（ＪＰ，Ａ) 特開 昭62−21751（ＪＰ，Ａ) 特開 昭60−65760（ＪＰ，Ａ) 特開 昭59−136480（ＪＰ，Ａ) 特開 昭61−55811（ＪＰ，Ａ)Continuation of front page (56) References JP-A-2-309511 (JP, A) JP-A-59-26043 (JP, A) JP-A-62-12009 (JP, A) JP-A-62-121751 (JP, A) JP-A-60-65760 (JP, A) JP-A-59-136480 (JP, A) JP-A-61-55811 (JP, A)
Claims (2)
主成分とし、焼結密度が5g/cm3以上、比抵抗が1.8mΩ・
cm以下の導電性金属酸化物焼結体。An indium oxide containing niobium and tin components as a main component, a sintered density of 5 g / cm 3 or more, and a specific resistance of 1.8 mΩ ·
Conductive metal oxide sintered body of cm or less.
主成分とし、焼結密度が5g/cm3以上、比抵抗が1.8mΩ・
cm以下の導電性金属酸化物焼結体を用いたスパッタリン
グターゲット。2. An indium oxide containing niobium and tin components as a main component, a sintering density of 5 g / cm 3 or more, and a specific resistance of 1.8 mΩ ·
A sputtering target using a conductive metal oxide sintered body of cm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01148348A JP3128124B2 (en) | 1989-06-13 | 1989-06-13 | Conductive metal oxide sintered body and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01148348A JP3128124B2 (en) | 1989-06-13 | 1989-06-13 | Conductive metal oxide sintered body and use thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10086998A Division JP3189782B2 (en) | 1998-04-13 | 1998-04-13 | Conductive metal oxide sintered body and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0315107A JPH0315107A (en) | 1991-01-23 |
| JP3128124B2 true JP3128124B2 (en) | 2001-01-29 |
Family
ID=15450754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01148348A Expired - Fee Related JP3128124B2 (en) | 1989-06-13 | 1989-06-13 | Conductive metal oxide sintered body and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3128124B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0682182U (en) * | 1993-05-11 | 1994-11-25 | 新日本製鐵株式会社 | Centrifugal air vent drainage flow rate cap and drainage device using the cap |
| WO2005086180A1 (en) * | 2004-03-09 | 2005-09-15 | Idemitsu Kosan Co., Ltd. | Thin-film transistor and thin-film transistor substrate and production methods for them and liquid crystal display unit using these and related device and method, and, sputtering target and transparent conductive film formed by using this and transparent electrode and related device and method |
| KR101328895B1 (en) * | 2009-10-26 | 2013-11-13 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Indium oxide sintered body and indium oxide transparent conductive film |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100649162B1 (en) * | 2004-10-14 | 2006-11-28 | 주식회사 삼성산업 | Demoulding Method of Mold for MSC Products |
| KR100647672B1 (en) | 2004-12-24 | 2006-11-23 | 삼성에스디아이 주식회사 | Heat-resistant transparent electrode, manufacturing method thereof and dye-sensitized solar cell having same |
| JP5167575B2 (en) * | 2005-04-22 | 2013-03-21 | 住友金属鉱山株式会社 | Oxide sintered body, sputtering target, and transparent conductive film |
| JP6155919B2 (en) * | 2013-07-11 | 2017-07-05 | 東ソー株式会社 | Composite oxide sintered body and oxide transparent conductive film |
| WO2019187269A1 (en) * | 2018-03-30 | 2019-10-03 | 三井金属鉱業株式会社 | Oxide sintered body, sputtering target, and transparent conductive film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399194A (en) * | 1981-12-30 | 1983-08-16 | Rca Corporation | Transparent conductive film |
| JPH02309511A (en) * | 1989-05-24 | 1990-12-25 | Showa Denko Kk | Transparent conductive film |
-
1989
- 1989-06-13 JP JP01148348A patent/JP3128124B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0682182U (en) * | 1993-05-11 | 1994-11-25 | 新日本製鐵株式会社 | Centrifugal air vent drainage flow rate cap and drainage device using the cap |
| WO2005086180A1 (en) * | 2004-03-09 | 2005-09-15 | Idemitsu Kosan Co., Ltd. | Thin-film transistor and thin-film transistor substrate and production methods for them and liquid crystal display unit using these and related device and method, and, sputtering target and transparent conductive film formed by using this and transparent electrode and related device and method |
| KR101328895B1 (en) * | 2009-10-26 | 2013-11-13 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Indium oxide sintered body and indium oxide transparent conductive film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0315107A (en) | 1991-01-23 |
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