JPH09176841A - Sputtering target - Google Patents
Sputtering targetInfo
- Publication number
- JPH09176841A JPH09176841A JP7333208A JP33320895A JPH09176841A JP H09176841 A JPH09176841 A JP H09176841A JP 7333208 A JP7333208 A JP 7333208A JP 33320895 A JP33320895 A JP 33320895A JP H09176841 A JPH09176841 A JP H09176841A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- thin film
- sputtering target
- silver
- sputtering
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銀系薄膜上にスパ
ッタリング法にて耐湿性に優れた透明薄膜を成膜する際
に適用されるスパッタリングターゲットに係わり、特
に、上記透明薄膜を効率的に成膜でき、しかも透明薄膜
の成膜時に上記銀系薄膜が損傷を受け難いスパッタリン
グターゲットの改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sputtering target applied when a transparent thin film excellent in moisture resistance is formed on a silver-based thin film by a sputtering method. The present invention relates to an improvement of a sputtering target which can be formed into a film and is less likely to damage the silver-based thin film when forming a transparent thin film.
【０００２】[0002]
【従来の技術】銀系薄膜の表面にＩＴＯ薄膜等の透明薄
膜を設けて構成される多層薄膜は極めて高い導電性を有
するため、この高い導電性を利用して銀系の多層薄膜を
様々な分野に応用する技術が提案されている。2. Description of the Related Art Since a multilayer thin film formed by providing a transparent thin film such as an ITO thin film on the surface of a silver-based thin film has a very high conductivity, various silver-based multilayer thin films can be utilized by utilizing this high conductivity. Technologies applied to the field have been proposed.
【０００３】例えば、特公平1- 12663号公報または特開
昭61-25125号公報は、銀被膜を薄膜化させて透明性を確
保し、その表面にＩＴＯ薄膜を積層して多層構造とした
透明導電膜を提案している。この透明導電膜はＩＴＯ単
体の薄膜に較べてその導電率が極めて高いため、例え
ば、ＩＴＯ薄膜はその膜厚が 250nmの場合 8Ω／□程度
の面積抵抗率を有するのに対し、上記多層構造の透明導
電膜はその合計膜厚が高々90nmであっても 5Ω／□程度
の低い面積抵抗率を実現することができる。[0003] For example, Japanese Patent Publication No. 1-12663 or Japanese Patent Laid-Open No. 61-25125 discloses a transparent thin film made of a silver film to ensure transparency, and an ITO thin film is laminated on the surface thereof to form a multilayer structure. A conductive film is proposed. Since this transparent conductive film has an extremely high conductivity as compared with a thin film of ITO alone, for example, an ITO thin film has an area resistivity of about 8 Ω / □ when the film thickness is 250 nm, whereas it has the above-mentioned multilayer structure. Even if the total film thickness of the transparent conductive film is at most 90 nm, it is possible to realize a low sheet resistivity of about 5 Ω / □.
【０００４】また、このような銀系多層薄膜の高い導電
率と透明性とに着目して、特開昭63- 173395号公報は、
同様の層構成を有する多層薄膜を透明な電磁波シールド
膜として利用する技術を提案している。Further, paying attention to the high conductivity and transparency of such a silver-based multilayer thin film, JP-A-63-173395 discloses that:
A technique is proposed in which a multilayer thin film having the same layer structure is used as a transparent electromagnetic wave shield film.
【０００５】また、1982年日本で開催された第７回ＩＣ
ＶＭにおいては、同様の層構成を有する銀系多層薄膜が
長波長側の光を遮断する性能に優れていることに着目し
て、上記銀系多層薄膜を熱線反射膜に適用する技術を提
案している。The 7th IC held in Japan in 1982
In VM, focusing on the fact that a silver-based multilayer thin film having the same layer structure is excellent in the ability to block light on the long wavelength side, a technique for applying the silver-based multilayer thin film to a heat ray reflective film is proposed. ing.
【０００６】[0006]
【発明が解決しようとする課題】しかし、上記銀系多層
薄膜においては、ＩＴＯ薄膜の酸化インジウムの存在下
で積層界面等から侵入した空気中の水分が銀およびＩＴ
Ｏの薄膜と化合し易く、その表面に反応物が生成されて
シミ状の欠陥を生じ、例えば、ディスプレイの透明電極
に適用した場合、その表示画面に欠陥等が生じ易い問題
点があった。However, in the above-mentioned silver-based multi-layered thin film, in the presence of indium oxide of the ITO thin film, moisture in the air that has entered from the stacking interface or the like causes silver and IT.
There is a problem that it is easy to combine with a thin film of O, and a reaction product is generated on the surface thereof to cause spot-like defects.
【０００７】これに対し、上記ＩＴＯ薄膜に代えて、あ
るいはＩＴＯ薄膜の上に更に積層して、ＳｉＯ2 から成
る薄膜を適用した場合、この薄膜が空気中の水分を遮断
するため、水分による銀薄膜の損傷を防止することが可
能である。On the other hand, when a thin film made of SiO 2 is applied instead of the ITO thin film or further laminated on the ITO thin film, this thin film blocks moisture in the air, and therefore silver caused by moisture is used. It is possible to prevent damage to the thin film.
【０００８】但し、このＳｉＯ2 薄膜は電気絶縁性であ
るため、直流（ＤＣ）スパッタリングによる成膜が不可
能で高周波（ＲＦ）スパッタリングに頼らざるを得な
い。しかし、ＲＦスパッタリングによる成膜において
は、その成膜速度がＤＣスパッタリングに較べて著しく
遅く、かつ、銀薄膜がスパッタリング中に発生したプラ
ズマのダメージを受けて凝集し、ＳｉＯ2 薄膜の成膜時
に銀薄膜が損傷を受け易いという問題があった。However, since this SiO 2 thin film is electrically insulative, it cannot be formed by direct current (DC) sputtering and must rely on high frequency (RF) sputtering. However, in the film formation by RF sputtering, the film formation speed is significantly slower than that in DC sputtering, and the silver thin film is damaged by the plasma generated during the sputtering and aggregates to form silver during the film formation of the SiO 2 thin film. There is a problem that the thin film is easily damaged.
【０００９】本発明は、このような問題点に着目してな
されたもので、その課題とするところは、耐湿性に優れ
た透明薄膜を効率的に成膜でき、しかもこの成膜時に上
記銀系薄膜が損傷を受け難いスパッタリングターゲット
を提供することにある。The present invention has been made by paying attention to such a problem. The problem is that a transparent thin film having excellent moisture resistance can be efficiently formed, and at the time of this film formation, the above silver is used. The purpose of the present invention is to provide a sputtering target in which the system thin film is not easily damaged.
【００１０】このような技術的課題に鑑みて、本発明者
らは、上記銀系多層薄膜の一部を構成するＩＴＯ薄膜に
代えて種々の透明薄膜の成膜を試みその特性を検討した
ところ、酸化インジウムに酸化セリウムを添加した混合
酸化物の薄膜が、銀系薄膜挟持構成の導電性透明薄膜の
耐湿性向上に大きく効果のあることを見い出した。In view of such technical problems, the present inventors have tried to form various transparent thin films in place of the ITO thin film which constitutes a part of the above-mentioned silver-based multi-layered thin film, and have examined their characteristics. It was found that a mixed oxide thin film obtained by adding cerium oxide to indium oxide has a great effect on improving the moisture resistance of a conductive transparent thin film having a silver-based thin film sandwich structure.
【００１１】同時に、酸化セリウムが高屈折率であるこ
とから、酸化インジウムと酸化セリウムの混合酸化物の
屈折率も、酸化セリウムの添加割合に従って高屈折率と
なり、このため、銀系薄膜挟持構成の透明薄膜の透過率
を従来構成より大きく向上せしめることも見い出した。At the same time, since cerium oxide has a high refractive index, the refractive index of the mixed oxide of indium oxide and cerium oxide also becomes a high refractive index according to the addition ratio of cerium oxide. It was also found that the transmittance of the transparent thin film can be greatly improved compared to the conventional structure.
【００１２】酸化インジウムに酸化セリウムを添加した
混合酸化物のターゲットは導電性があるため、酸化セリ
ウムのセリウム元素の量が、混合酸化物中の総金属元素
量のおよそ30at％（原子パーセント）位まではＤＣスパ
ッタリングやＲＦ−ＤＣ重畳スパッタリング等の直流ス
パッタリングの適用が可能である。Since the target of the mixed oxide in which cerium oxide is added to indium oxide is conductive, the amount of cerium element in cerium oxide is about 30 at% (atomic percent) of the total amount of metal elements in the mixed oxide. Until then, DC sputtering such as DC sputtering or RF-DC superimposed sputtering can be applied.
【００１３】酸化セリウム添加量が高くなるに従い、急
激にターゲットの導電率が悪化し、ＤＣスパッタリング
に向かなくなる。特に、60at％（原子パーセント）を超
えると、熱衝撃によりターゲットにクラックが入るとい
う問題があった。As the amount of cerium oxide added increases, the electrical conductivity of the target deteriorates rapidly and DC sputtering becomes difficult. In particular, if it exceeds 60 at% (atomic percentage), there is a problem that the target is cracked by thermal shock.
【００１４】すなわち、酸化インジウムと酸化セリウム
の混合酸化物は、酸化セリウムが十分な導電性をもたな
いことから、酸化セリウムの混合比率を高めるに従い、
その混合酸化物のターゲットの導電性が急激に低下し、
直流スパッタリングが困難な導電性の低いターゲットと
なる。That is, in the mixed oxide of indium oxide and cerium oxide, since cerium oxide does not have sufficient conductivity, as the mixing ratio of cerium oxide is increased,
The conductivity of the mixed oxide target drops sharply,
It becomes a target with low conductivity, which makes DC sputtering difficult.
【００１５】加えて、酸化インジウムと酸化セリウムの
混合酸化物のターゲットは、ＩＴＯ（酸化インジウムと
酸化スズ）と比較すると、ＩＴＯのターゲットほど充填
密度があがりにくく、充填密度に伴うスパッタリングレ
ートの点で不十分なものがあった。In addition, compared with ITO (indium oxide and tin oxide), the mixed oxide target of indium oxide and cerium oxide has a lower packing density than the ITO target, and in terms of the sputtering rate accompanying the packing density. There was something inadequate.
【００１６】[0016]
【課題を解決するための手段】本発明者らは、高添加の
酸化セリウムの混合酸化物ターゲットにおいても直流ス
パッタリング（通常のＤＣの他、ＲＦ−ＤＣ、ＤＣパル
ススパッタ等含む）が可能な導電性をターゲットに付与
するために、酸化スズ（ＳｎＯ2 ）の少量添加が有効で
あることを発見した。The inventors of the present invention have made it possible to conduct direct current sputtering (including ordinary DC, RF-DC, DC pulse sputtering, etc.) even in a highly-doped cerium oxide mixed oxide target. It was discovered that the addition of a small amount of tin oxide (SnO 2 ) is effective for imparting the property to the target.
【００１７】すなわち、請求項１に係わる発明は、銀系
薄膜を挟持する構成の導電膜の透明薄膜を成膜する際に
適用されるスパッタリングターゲットを前提とし、酸化
インジウムと酸化セリウムを基材とする混合酸化物に、
各々基材の混合割合より少ない量にて酸化スズを含有せ
しめた混合酸化物とすることを特徴とするスパッタリン
グターゲットである。That is, the invention according to claim 1 is premised on a sputtering target applied when forming a transparent thin film of a conductive film having a structure in which a silver-based thin film is sandwiched, and indium oxide and cerium oxide are used as base materials. Mixed oxide to
A sputtering target comprising a mixed oxide containing tin oxide in an amount smaller than the mixing ratio of the respective substrates.
【００１８】酸化スズの添加量は、そのスズ元素量に
て、混合酸化物の総金属元素に対し 0.1at％（原子パー
セント）の若干量添加から効果があり、また、 5at％
（原子パーセント）を超える量では逆に導電率の低下が
見られる。なお、 5at％（原子パーセント）を超える量
ではターゲットの密度低下も見られる。The amount of tin oxide added is effective from the addition of a small amount of 0.1 at% (atomic percentage) with respect to the total metal elements of the mixed oxide, and 5 at%.
On the contrary, when the amount exceeds (atomic percentage), the conductivity is decreased. In addition, when the amount exceeds 5 at% (atomic percent), the density of the target also decreases.
【００１９】すなわち、請求項４に係わる発明は、酸化
スズのスズ元素の量が、混合酸化物の総金属元素に対
し、 0.1at％（原子パーセント）から 5at％（原子パー
セント）の範囲内にあることを特徴とする。That is, in the invention according to claim 4, the amount of tin element of tin oxide is within the range of 0.1 at% (atomic percent) to 5 at% (atomic percent) with respect to the total metal elements of the mixed oxide. It is characterized by being.
【００２０】また、スパッタリング時の成膜レートを高
くし生産性を上げるため、スパッタリングターゲットの
密度を上げることが重要となる。また、ＩＴＯと比較し
導電率に劣るターゲットをＤＣスパッタリングで同じよ
うな条件で使用するためには、耐熱衝撃性に優れたター
ゲットとすることが必要である。In addition, it is important to increase the density of the sputtering target in order to increase the film formation rate during sputtering and increase productivity. Further, in order to use a target having a conductivity lower than that of ITO in DC sputtering under the same conditions, it is necessary to make the target excellent in thermal shock resistance.
【００２１】本発明者らは、高密度で、かつ、微粒組織
であるために靱性に優れ、スパッタリング成膜時に割れ
難いターゲットとするため、酸化チタンの少量添加が有
効であることを発見した。The present inventors have discovered that the addition of a small amount of titanium oxide is effective in order to obtain a target which is excellent in toughness due to its high density and fine grain structure and which is not easily broken during sputtering film formation.
【００２２】すなわち、請求項２に係わる発明は、酸化
インジウムと酸化セリウムを基材とする混合酸化物に、
各々基材の混合割合より少ない量にて酸化チタンを含有
せしめた混合酸化物のターゲットであることを特徴とす
る。That is, the invention according to claim 2 provides a mixed oxide comprising indium oxide and cerium oxide as a base material,
Each of the targets is a mixed oxide target containing titanium oxide in an amount smaller than the mixing ratio of the base material.
【００２３】酸化チタンの添加量は、耐アルカリ性を要
求しない用途であれば、酸化インジウムや酸化セリウム
の基材と同程度の量を加えても良い。しかし、表示装置
用の電極を含め、耐アルカリ性を必要とする用途が多い
ものである。酸化チタンは、強アルカリに溶解し易く、
これを 5at％（原子パーセント）を超えるレベルで混合
酸化物中に添加することは、例えば、アルカリ洗浄等で
その導電膜に著しいダメージを与えてしまう。The amount of titanium oxide added may be approximately the same as that of the base material of indium oxide or cerium oxide if the application does not require alkali resistance. However, there are many applications that require alkali resistance, including electrodes for display devices. Titanium oxide is easily dissolved in strong alkali,
If this is added to the mixed oxide at a level exceeding 5 at% (atomic percentage), the conductive film is significantly damaged by, for example, alkali cleaning.
【００２４】また、混合酸化物のターゲットの密度を向
上するには、酸化チタンのチタン元素量にて混合酸化物
の総金属元素に対し、 0.1at％（原子パーセント）の若
干量添加から効果がある。In order to improve the density of the target of the mixed oxide, addition of a small amount of 0.1 at% (atomic percentage) to the total metal elements of the mixed oxide in the titanium element amount of titanium oxide is effective. is there.
【００２５】すなわち、請求項５に係わる発明は、酸化
チタンのチタン元素の量が、混合酸化物の総金属元素に
対し、 0.1at％（原子パーセント）から 5at％（原子パ
ーセント）であることを特徴とする。That is, in the invention according to claim 5, the amount of titanium element of titanium oxide is 0.1 at% (atomic percent) to 5 at% (atomic percent) with respect to the total metal elements of the mixed oxide. Characterize.
【００２６】本発明者らは、さらに、酸化インジウムと
酸化セリウムを基材とする混合酸化物に、酸化スズと酸
化チタンの両方を少量ずつ添加することにより導電性の
向上とターゲット密度の向上の効果がともに得られるこ
とを発見した。The present inventors have further improved the conductivity and the target density by adding small amounts of both tin oxide and titanium oxide to a mixed oxide based on indium oxide and cerium oxide. I found that the effect can be obtained together.
【００２７】すなわち、請求項３に係わる発明は、酸化
インジウムと酸化セリウムを基材とする混合酸化物に、
各々基材の混合割合より少ない量にて酸化スズと酸化チ
タンを含有せしめた混合酸化物のターゲットであること
を特徴とするスパッタリングターゲットである。That is, the invention according to claim 3 provides a mixed oxide having indium oxide and cerium oxide as a base material,
The sputtering target is a mixed oxide target containing tin oxide and titanium oxide in an amount smaller than the mixing ratio of the base materials.
【００２８】透明薄膜にて銀系薄膜を挟持する構成の導
電膜において、屈折率の高い透明薄膜を用いることによ
り、該導電膜の透過率を向上せしめる。特に、屈折率が
空気（屈折率ｎ＝１）より高い液晶材料（屈折率ｎ＝
1.5〜 1.6程度）と導電膜が実質的に接触する構成の液
晶表示素子では、屈折率の高い透明薄膜を用いること
が、透過率の高い液晶表示素子とする上で極めて有効で
あることを本発明者らは見い出した。By using a transparent thin film having a high refractive index in a conductive film having a structure in which a silver-based thin film is sandwiched between transparent thin films, the transmittance of the conductive film is improved. In particular, a liquid crystal material having a refractive index higher than that of air (refractive index n = 1) (refractive index n =
For a liquid crystal display element with a structure in which the conductive film is in substantial contact with a conductive film (about 1.5 to 1.6), it is extremely effective to use a transparent thin film with a high refractive index for a liquid crystal display element with a high transmittance. The inventors have found out.
【００２９】高屈折率の無機酸化物である酸化セリウム
（ＣｅＯ2 ）と、酸化インジウムの混合酸化物による透
明薄膜にて、銀系薄膜を挟持する有用な構成を本発明者
らは提案している。The present inventors have proposed a useful structure in which a silver-based thin film is sandwiched between transparent thin films of a mixed oxide of cerium oxide (CeO 2 ) which is an inorganic oxide having a high refractive index and indium oxide. There is.
【００３０】また、酸化セリウムの酸化インジウムに対
する添加は、該導電膜の耐湿性を大幅に向上せしめる。
酸化セリウムのセリウム元素の量が 5at％（原子パーセ
ント）を超えるに従い、該導電膜の耐湿性は徐々に向上
していく。Also, the addition of cerium oxide to indium oxide significantly improves the moisture resistance of the conductive film.
As the amount of the cerium element of cerium oxide exceeds 5 at% (atomic percentage), the moisture resistance of the conductive film is gradually improved.
【００３１】酸化チタンや酸化スズをこの混合酸化物に
添加することにより、割れにくいターゲットに成形する
ことができるが、酸化セリウムのセリウム元素の量が、
60at％（原子パーセント）を超えると、導電性が低下し
直流スパッタにて成膜しにくいターゲットとなる。By adding titanium oxide or tin oxide to this mixed oxide, it is possible to form a target which is hard to break, but the amount of cerium element of cerium oxide is
If it exceeds 60 at% (atomic percentage), the conductivity will decrease and it will be a target that is difficult to form a film by DC sputtering.
【００３２】すなわち、請求項６に係わる発明は、酸化
セリウムのセリウム元素の量が、混合酸化物の総金属元
素に対し、 5〜60at％（原子パーセント）であることを
特徴とする。That is, the invention according to claim 6 is characterized in that the amount of the cerium element of cerium oxide is 5 to 60 at% (atomic percentage) based on the total metal elements of the mixed oxide.
【００３３】液晶表示装置用導電膜を前提とする場合
は、上記透明薄膜の屈折率が、およそ2.1〜 2.4の範囲
内にあることが望ましく、また、強酸などのエッチャン
トでエッチングしてパターン形成できることが望まし
い。これらの仕様をほぼ満たす範囲の酸化セリウムのセ
リウム元素のさらに望ましい添加量は、総金属元素に対
し10〜40at％（原子パーセント）である。When the conductive film for a liquid crystal display device is assumed, the transparent thin film preferably has a refractive index within the range of about 2.1 to 2.4, and can be patterned by etching with an etchant such as strong acid. Is desirable. A more desirable addition amount of the cerium element of cerium oxide in a range that substantially meets these specifications is 10 to 40 at% (atomic percent) with respect to the total metal elements.
【００３４】すなわち、請求項７に係わる発明は、酸化
セリウムのセリウム元素の量が、混合酸化物の総金属元
素に対し、10〜40at％（原子パーセント）であることを
特徴とする。That is, the invention according to claim 7 is characterized in that the amount of the cerium element of cerium oxide is 10 to 40 at% (atomic percentage) with respect to the total metal elements of the mixed oxide.
【００３５】本発明によるスパッタリングターゲットの
評価結果および、本発明のスパッタリングターゲットを
用いて成膜した銀系薄膜を挟持する構成の導電膜の評価
結果を以下に記す（表１）に示す。The evaluation results of the sputtering target according to the present invention and the evaluation results of the conductive film having a structure in which a silver-based thin film formed using the sputtering target of the present invention is sandwiched are shown below (Table 1).
【００３６】[0036]
【表１】 [Table 1]
【００３７】なお、導電膜のパタニングが不必要な用
途、例えば反射防止膜、電磁波シールド膜、液晶表示素
子でもＴＦＴと対向する共通側の電極等の場合は、（表
１）の評価項目から導電膜のエッチング加工性を除くこ
とになる。For applications in which the patterning of the conductive film is unnecessary, such as an antireflection film, an electromagnetic wave shielding film, and an electrode on the common side facing the TFT in a liquid crystal display element, etc., the conductivity is determined from the evaluation items in Table 1. The etching processability of the film will be excluded.
【００３８】また、（表１）において、導電膜の耐湿性
は、温度23℃、湿度50％の条件で１ケ月間放置し、肉眼
および顕微鏡のいずれかの観察によっても外観上の変化
が見られないものを○とし、また、肉眼観察では変化が
観察されなかったが、顕微鏡観察ではシミが観察された
ものを△とし、肉眼観察でシミが観察されたものを×と
評価した。Further, in (Table 1), the moisture resistance of the conductive film is changed by the naked eye or the observation of a microscope for 1 month under the condition of the temperature of 23 ° C. and the humidity of 50%. Those that were not observed were evaluated as ◯, changes that were not observed by macroscopic observation, but those that were observed by microscopic observation were evaluated as Δ, and those that were observed by visual observation were evaluated as x.
【００３９】本発明に係わるスパッタリングターゲット
には、前記した酸化物以外の酸化物を含ませることも可
能である。例えば、ＳｉＯ2 、ＧｅＯ2 、Ｓｂ2 Ｏ5 、
Ｂｉ 2 Ｏ3 等の半金属の酸化物、あるいは、ＭｇＯ、Ｚ
ｎＯ、Ｇａ2 Ｏ3 、Ａｌ2 Ｏ 3 、ＨｆＯ2 、ＺｒＯ2 、
Ｔａ2 Ｏ5 等の金属酸化物があげられる。Sputtering target according to the present invention
The oxide may contain oxides other than those mentioned above.
Noh. For example, SiOTwo, GeOTwo, SbTwoOFive,
Bi TwoOThreeOxide of semi-metal such as MgO, Z
nO, GaTwoOThree, AlTwoO Three, HfOTwo, ZrOTwo,
TaTwoOFiveMetal oxides such as
【００４０】なお、上記導電膜としては、銀単体から構
成される薄膜の他、銀を主成分としこれに他の金属元素
等を添加して構成される銀系合金の薄膜等が利用でき
る。このような添加元素としては、例えばＣｕ、Ｐｄ、
Ｎｉ、Ｚｎ、Ｃｄ、Ｍｇ、Ｉｎ、Ａｌ、Ｔｉ、Ｚｒ、Ｃ
ｅまたはＳｉ等が適用できる。As the conductive film, not only a thin film made of simple silver but also a thin film of a silver-based alloy composed mainly of silver and added with another metal element or the like can be used. Examples of such additional elements include Cu, Pd,
Ni, Zn, Cd, Mg, In, Al, Ti, Zr, C
e or Si can be applied.
【００４１】そして、これら銀系薄膜が厚さ20nm以下の
場合、この銀系薄膜と上記透明薄膜とで構成される銀系
多層薄膜は光透過率と導電率に優れたものになるため、
例えば、透明電磁波シールド膜、液晶ディスプレイ等の
透明電極、あるいは太陽電池の光入射側に設けられる透
明電極等に適用することができる。When these silver-based thin films have a thickness of 20 nm or less, the silver-based multilayer thin film composed of this silver-based thin film and the transparent thin film has excellent light transmittance and electrical conductivity.
For example, it can be applied to a transparent electromagnetic wave shield film, a transparent electrode such as a liquid crystal display, or a transparent electrode provided on the light incident side of a solar cell.
【００４２】また、銀系薄膜が厚さ20nmを超えた場合に
は、この銀系薄膜の高い光反射率を利用して、例えば、
反射型液晶ディスプレイの光反射膜や光反射性電極、あ
るいは太陽電池の光入射側とは反対側の面に設けられる
光反射電極として利用することが可能である。When the thickness of the silver-based thin film exceeds 20 nm, the high light reflectance of this silver-based thin film is utilized to
It can be used as a light reflecting film or a light reflecting electrode of a reflective liquid crystal display, or as a light reflecting electrode provided on the surface of the solar cell opposite to the light incident side.
【００４３】次に、本発明に係わるスパッタリングター
ゲットの製造方法について説明する。まず、酸化インジ
ウム、酸化セリウム、酸化スズ、酸化チタン等の酸化物
粉末の適量に対し有機バインダー、分散剤および溶剤
（水または有機溶剤）を加え、ボールミル等の粉砕装置
を使用して粉砕し微細化すると共にこれら粉末を均一に
混合する。粉砕および混合は、上記各酸化物の平均粒径
が 2μｍ以下となるまで行うことが望ましい。通常、10
〜50時間である。Next, a method of manufacturing the sputtering target according to the present invention will be described. First, add an organic binder, dispersant and solvent (water or organic solvent) to an appropriate amount of oxide powder such as indium oxide, cerium oxide, tin oxide, titanium oxide, etc., and pulverize with a pulverizing device such as a ball mill to obtain fine particles. And mix the powders uniformly. It is desirable that the pulverization and mixing be performed until the average particle diameter of each oxide is 2 μm or less. Usually 10
~ 50 hours.
【００４４】なお、上記分散剤は、各酸化物の粒子の凝
集を防止して平均粒径 2μｍ以下の微粒子状態で安定に
分散させるものである。The above-mentioned dispersant prevents the particles of each oxide from aggregating and stably disperses them in the form of fine particles having an average particle size of 2 μm or less.
【００４５】十分に粉砕、混合した後、乾燥し整粒を行
う。整粒の粒径は 10 〜 100μｍとするのが、より良い
流動性、成形性を得るため好ましい。整粒粉末を用いて
ターゲット形状に成形を行う。成形圧力は、 500Ｋｇｆ
／cm2 以上の圧力で行い、成形体密度が 3.5ｇ／cm3 を
超える圧力を選ぶことが好ましい。なお、ターゲット形
状および厚みは任意である。After being sufficiently crushed and mixed, it is dried and sized. The particle size of the sized particles is preferably 10 to 100 μm in order to obtain better fluidity and moldability. It shape | molds in a target shape using the sized powder. Molding pressure is 500 Kgf
It is preferable to carry out at a pressure of not less than / cm 2 and to select a pressure at which the density of the molded body exceeds 3.5 g / cm 3 . The target shape and thickness are arbitrary.
【００４６】こうして成形された混合物を焼成し、有機
バインダーや分散剤等不要成分を除去すると共に、上記
酸化物を焼結して本発明に係わるスパッタリングターゲ
ットを得ることができる。焼成は電気炉等で行うことが
でき、その温度は1000〜1600℃でよく、好ましくは1200
〜1500℃である。1000℃より低いとターゲットが緻密な
焼結体とならず、導電性と光透過性に優れた透明薄膜を
成膜することが困難となり、また、ターゲットの強度や
寿命が低下する。他方、1600℃を超えると酸化チタンや
酸化セリウムが解離し、またはこれら酸化チタンや酸化
セリウムと導電性透明金属酸化物とが反応して、成膜さ
れる透明薄膜の導電性と光透過性とを損なうことがあ
る。なお、焼成時間は10〜40時間程度でよい。また、得
られたスパッタリング用ターゲットの形状が不適当な場
合には、研削盤で研削したりダイヤモンドカッターで切
断して必要な形状に成形すればよい。The mixture thus formed can be fired to remove unnecessary components such as an organic binder and a dispersant, and the above oxide can be sintered to obtain a sputtering target according to the present invention. Firing can be performed in an electric furnace or the like, the temperature may be 1000 ~ 1600 ℃, preferably 1200
~ 1500 ℃. If the temperature is lower than 1000 ° C., the target does not become a dense sintered body, and it becomes difficult to form a transparent thin film excellent in conductivity and light transmittance, and the strength and life of the target decrease. On the other hand, when the temperature exceeds 1600 ° C., titanium oxide or cerium oxide is dissociated, or these titanium oxide or cerium oxide reacts with a conductive transparent metal oxide, and the conductivity and the light transmittance of the transparent thin film to be formed. May be damaged. The firing time may be about 10 to 40 hours. If the shape of the obtained sputtering target is inappropriate, the target may be ground by a grinder or cut by a diamond cutter to be formed into a required shape.
【００４７】次に、本発明に係わるスパッタリングター
ゲットの使用方法について以下説明する。すなわち、本
発明に係わるスパッタリングターゲットは、ＤＣスパッ
タリングやＲＦ−ＤＣスパッタリング等の直流スパッタ
リング法、ＲＦ（高周波）スパッタリング法等のターゲ
ットとして使用し、銀系薄膜を水分から保護する透明薄
膜を成膜するために適用される。Next, a method of using the sputtering target according to the present invention will be described below. That is, the sputtering target according to the present invention is used as a target for a DC sputtering method such as DC sputtering or RF-DC sputtering, or an RF (radio frequency) sputtering method to form a transparent thin film that protects a silver-based thin film from moisture. Applied for.
【００４８】この際、上記スパッタリングターゲットの
導電性を生かして、成膜速度が大きく、しかも銀系薄膜
を損傷させることのない、ＤＣスパッタリングやＲＦ−
ＤＣスパッタリング等直流スパッタリング法を適用する
ことが好ましい。また、銀系薄膜の劣化を防止するため
成膜装置内部の水分は少ない方が好ましく、また、透明
薄膜のエッチング適性を確保するため、 180℃以下また
は室温の基板温度で成膜することが望ましい。At this time, by utilizing the conductivity of the sputtering target, the film formation rate is high, and DC sputtering or RF- that does not damage the silver-based thin film.
It is preferable to apply a DC sputtering method such as DC sputtering. Further, it is preferable that the water content inside the film forming apparatus is low in order to prevent deterioration of the silver-based thin film, and in order to ensure the etching suitability of the transparent thin film, it is desirable to form the film at a substrate temperature of 180 ° C. or lower or room temperature. .
【００４９】また、本発明に係わるスパッタリングター
ゲットは、スパッタリング法を利用して、銀系薄膜とそ
の基板（例えば、ガラス板、プラスチック材料等）との
密着力を増大させる透明薄膜（接着層として機能する）
を設けるために利用することもできる。この場合、上記
透明薄膜は銀系薄膜と基板との間に設けられる。The sputtering target according to the present invention utilizes the sputtering method to increase the adhesion between the silver-based thin film and its substrate (eg, glass plate, plastic material, etc.) and the transparent thin film (functions as an adhesive layer). Do)
Can also be used to provide. In this case, the transparent thin film is provided between the silver-based thin film and the substrate.
【００５０】請求項１〜５に記載の発明に係わるスパッ
タリングターゲットによれば、酸化インジウムと酸化セ
リウムを基材とする混合酸化物に、ターゲットの導電性
を向上せしめる酸化スズを少量、および、ターゲットの
密度を向上せしめる酸化チタンを少量添加するため、導
電性のある、かつ、高密度で靱性に優れたターゲットを
提供し得る。According to the sputtering target of the invention described in any one of claims 1 to 5, the mixed oxide having indium oxide and cerium oxide as a base material contains a small amount of tin oxide for improving the conductivity of the target, and the target. Since a small amount of titanium oxide is added to improve the density, it is possible to provide a conductive target having a high density and excellent toughness.
【００５１】このため、ＤＣスパッタリングやＲＦ−Ｄ
Ｃスパッタリング等の直流スパッタリング法の適用が可
能となり、安定した放電が高いスパッタレートにて確保
できる。本発明により、高屈折率の透明薄膜を熱的ダメ
ージの少ない直流スパッタリングにて成膜することが可
能となり、このことにより、高性能（高透過率、低反射
率、低抵抗）の導電膜が提供できる。For this reason, DC sputtering and RF-D
A DC sputtering method such as C sputtering can be applied, and stable discharge can be secured at a high sputtering rate. According to the present invention, it is possible to form a transparent thin film having a high refractive index by direct-current sputtering with little thermal damage, which allows a high-performance (high transmittance, low reflectance, low resistance) conductive film to be formed. Can be provided.
【００５２】[0052]
【発明の実施の形態】本発明の実施の形態につき、以下
に記す実施例により説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to the following examples.
【００５３】[0053]
【実施例】以下に、本発明の実施例について詳細に説明
する。 ＜実施例１＞実施例１に係わるスパッタリングターゲッ
トは、酸化インジウムに酸化セリウムをセリウム元素換
算で約30at％（原子パーセント）となる混合酸化物に、
酸化スズをスズ元素換算で 0.1〜 5at％（原子パーセン
ト）添加して、ターゲットの比抵抗（電気伝導度の逆
数）とターゲット密度を測定し、以下に記す（表２）を
得た。Embodiments of the present invention will be described below in detail. <Example 1> The sputtering target according to Example 1 is a mixed oxide of indium oxide and cerium oxide in an amount of about 30 at% (atomic percentage) in terms of cerium element.
0.1 to 5 at% (atomic percentage) of tin oxide was added in terms of tin element, and the specific resistance (reciprocal of electric conductivity) and target density of the target were measured to obtain the following (Table 2).
【００５４】[0054]
【表２】 [Table 2]
【００５５】上記の（表２）に示すように、酸化スズを
少量添加することで、ターゲットの比抵抗が下がった。As shown in the above (Table 2), the specific resistance of the target was lowered by adding a small amount of tin oxide.
【００５６】＜実施例２＞実施例２に係わるスパッタリ
ングターゲットは、酸化インジウムに酸化セリウムをセ
リウム元素換算で約30at％（原子パーセント）となる混
合酸化物に、酸化チタンをチタン元素換算で 0.1〜 5at
％（原子パーセント）添加して、ターゲットの比抵抗
（電気伝導度の逆数）、ターゲット密度、およびターゲ
ットの粒径を測定し、以下に記す（表３）を得た。<Embodiment 2> The sputtering target according to Embodiment 2 is a mixed oxide of indium oxide containing about 30 at% (atomic percentage) of cerium oxide in terms of cerium element, and titanium oxide of 0.1 to about 0.1 in terms of titanium element. 5at
% (Atomic percent) was added, and the target specific resistance (reciprocal of electrical conductivity), target density, and target particle size were measured, and the following (Table 3) was obtained.
【００５７】[0057]
【表３】 [Table 3]
【００５８】上記の（表３）に示すように、酸化チタン
を少量添加することで、ターゲットの密度が大きく向上
し、粒径が微細となった。As shown in the above (Table 3), by adding a small amount of titanium oxide, the density of the target was greatly improved and the particle size became finer.
【００５９】＜実施例３＞実施例３に係わるスパッタリ
ングターゲットは、酸化インジウム、酸化セリウム、酸
化スズ、酸化チタンの混合酸化物からなり、各々組成は
混合酸化物中の総金属元素に対し、インジウム元素を6
8.5at％（原子パーセント）、セリウム元素を30.0at％
（原子パーセント）、スズ元素を 1.0at％（原子パーセ
ント）、チタン元素を 0.5at％（原子パーセント）とし
た。<Embodiment 3> The sputtering target according to Embodiment 3 is composed of a mixed oxide of indium oxide, cerium oxide, tin oxide and titanium oxide, each of which has a composition based on the total metal elements in the mixed oxide. 6 elements
8.5at% (atomic percent), cerium element 30.0at%
(Atomic percent), tin element was 1.0 at% (atomic percent), and titanium element was 0.5 at% (atomic percent).
【００６０】そして、このスパッタリングターゲット
は、以下の方法で製造されている。すなわち、平均粒径
が各々約 2μｍの酸化インジウム粉末と、酸化セリウム
と、酸化スズと、酸化チタンとを所定量計量し、かつ、
少量のパラフィンを添加して湿式ボールミルにより24時
間粉砕すると共に混合した。The sputtering target is manufactured by the following method. That is, indium oxide powder having an average particle diameter of about 2 μm, cerium oxide, tin oxide, and titanium oxide are weighed in predetermined amounts, and
A small amount of paraffin was added, and the mixture was ground by a wet ball mill for 24 hours and mixed.
【００６１】次に、これを乾燥し、50〜70μｍに整粒
後、金型に充填しプレス成形した。次いで、これを電気
炉に入れ、酸素雰囲気下で1400℃、10時間の条件で焼成
し上記パラフィンを除去すると共に、混合酸化物を焼結
させた。そして、平面研削盤で研削し、次にダイヤモン
ドカッターで成形して上記スパッタリングターゲットを
製造した。このターゲットの比抵抗は 2×10-2Ω-cm 、
密度は 6.9であった。Next, this was dried, and after being sized to 50 to 70 μm, it was filled in a mold and press-molded. Then, this was placed in an electric furnace and fired under an oxygen atmosphere at 1400 ° C. for 10 hours to remove the paraffin and sinter the mixed oxide. Then, the above sputtering target was manufactured by grinding with a surface grinder and then molding with a diamond cutter. The resistivity of this target is 2 × 10 -2 Ω-cm,
The density was 6.9.
【００６２】このスパッタリングターゲットを銅のバッ
キングプレートにボンディングし、ＤＣマグネトロンス
パッタリング装置の内部に収容し、真空排気した。厚さ
0.7mmのガラス板上に、厚さ34nmの透明薄膜、厚さ15nm
の銀薄膜、厚さ35nmの透明薄膜の３層の導電膜を連続し
て成膜した。This sputtering target was bonded to a copper backing plate, housed inside a DC magnetron sputtering apparatus, and evacuated. thickness
Transparent thin film with a thickness of 34 nm, thickness of 15 nm on a 0.7 mm glass plate
The silver thin film and the transparent conductive thin film having a thickness of 35 nm were continuously formed in three layers.
【００６３】こうして得られた導電膜付きガラス基板の
断面を図１に記す。図１中、10はガラス基板、11は透明
薄膜、12は銀薄膜、13は透明薄膜をそれぞれ示してい
る。A cross section of the glass substrate with a conductive film thus obtained is shown in FIG. In FIG. 1, 10 is a glass substrate, 11 is a transparent thin film, 12 is a silver thin film, and 13 is a transparent thin film.
【００６４】次に、導電膜付きガラス基板を、 200℃、
1時間の条件で熱処理し、導電膜の面積抵抗値と、波長
545nmでの透過率を測定したところ、面積抵抗値は 2.7
Ω／□、透過率は約97％であった。なお、透明薄膜の屈
折率は、およそ 2.3であった。Next, the glass substrate with a conductive film is placed at 200 ° C.
Heat treatment under the condition of 1 hour, and the area resistance value of the conductive film and the wavelength
When the transmittance at 545 nm was measured, the sheet resistance value was 2.7.
Ω / □, the transmittance was about 97%. The refractive index of the transparent thin film was about 2.3.
【００６５】また、この導電膜付きガラス基板を、25℃
の室内に１ケ月間放置した後、導電膜を肉眼で観察した
ところ、その表面に外観の変化は全く観察されなかっ
た。Further, this glass substrate with a conductive film was placed at 25 ° C.
When the conductive film was observed with the naked eye after being left in the room for 1 month, no change in appearance was observed on the surface.
【００６６】[0066]
【発明の効果】請求項１〜７に係わる本発明によれば、
高密度、かつ、導電性のあるターゲットであるため、高
い成膜レートで安定したＤＣスパッタリングが可能とな
り、同時に高屈折率の透明薄膜が成膜可能であるため、
銀系薄膜を挟持する構成の導電膜を、従来にない高い性
能で提供できる。例えば、透明薄膜が 2.3前後の高屈折
率であるため、 3Ω／□弱の低抵抗の導電膜を80nm強の
極めて薄い膜厚にて、導電膜が形成できることとなっ
た。According to the present invention according to claims 1 to 7,
Since it is a high-density and conductive target, stable DC sputtering can be performed at a high film formation rate, and at the same time, a transparent thin film having a high refractive index can be formed.
It is possible to provide a conductive film having a structure in which a silver-based thin film is sandwiched, with high performance that has never been achieved. For example, since the transparent thin film has a high refractive index of around 2.3, it was possible to form a conductive film having a low resistance of less than 3Ω / □ and an extremely thin film thickness of more than 80 nm.
【００６７】加えて、本発明の導電性のあるターゲット
により、耐熱性の低いプラスチック等の基板上や、有機
のカラーフィルター上にも高速度で効率よく導電膜が形
成できる。In addition, the conductive target of the present invention enables a conductive film to be formed efficiently at a high speed even on a substrate such as plastic having low heat resistance or on an organic color filter.
【００６８】本発明は、酸化セリウムの高含有率にもか
かわらず、スパッタリングターゲットにＤＣスパッタリ
ングに十分な導電性および強度が確保できるため、結果
として高価な酸化インジウムの使用量を大きく減らすこ
とができる。According to the present invention, despite the high content of cerium oxide, the sputtering target can secure sufficient conductivity and strength for DC sputtering. As a result, the amount of expensive indium oxide used can be greatly reduced. .
【００６９】従って、このスパッタリングターゲットを
適用することにより、従来にない高い性能の導電膜を、
従来にない低コストで提供できる。Therefore, by applying this sputtering target, a conductive film of high performance which has never been obtained can be obtained.
It can be provided at a low cost that has never been seen before.
【００７０】[0070]
【図１】実施例に係わる導電膜付きガラス基板の断面説
明図。FIG. 1 is an explanatory cross-sectional view of a glass substrate with a conductive film according to an example.
10 ガラス基板 11 透明薄膜 12 銀系薄膜 13 透明薄膜 10 Glass substrate 11 Transparent thin film 12 Silver-based thin film 13 Transparent thin film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岸 俊人 東京都港区新橋５丁目11番３号 住友金属 鉱山株式会社内 (72)発明者 高梨 昌二 東京都港区新橋５丁目11番３号 住友金属 鉱山株式会社内 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Toshihito Kishi 5-11-3 Shimbashi, Minato-ku, Tokyo Sumitomo Metal Mining Co., Ltd. (72) Inventor Shoji Takanashi 5-11-3 Shimbashi, Minato-ku, Tokyo Sumitomo Metal Mining Co., Ltd.
Claims (7)
膜を成膜する際に適用されるスパッタリングターゲット
において、酸化インジウムと酸化セリウムを基材とする
混合酸化物に、各々基材の混合割合より少ない量にて酸
化スズを含有せしめた混合酸化物の焼結体であることを
特徴とするスパッタリングターゲット。1. A sputtering target applied when forming a transparent thin film of a conductive film having a structure in which a silver-based thin film is sandwiched, in a mixed oxide containing indium oxide and cerium oxide as base materials, A sputtering target, which is a sintered body of a mixed oxide containing tin oxide in an amount smaller than the mixing ratio.
膜を成膜する際に適用されるスパッタリングターゲット
において、酸化インジウムと酸化セリウムを基材とする
混合酸化物に、各々基材の混合割合より少ない量にて酸
化チタンを含有せしめた混合酸化物の焼結体であること
を特徴とするスパッタリングターゲット。2. In a sputtering target applied when forming a transparent thin film of a conductive film having a structure in which a silver-based thin film is sandwiched, a mixed oxide containing indium oxide and cerium oxide as base materials is added to each of the base materials. A sputtering target, which is a mixed oxide sintered body containing titanium oxide in an amount smaller than the mixing ratio.
膜を成膜する際に適用されるスパッタリングターゲット
において、酸化インジウムと酸化セリウムを基材とする
混合酸化物に、各々基材の混合割合より少ない量にて酸
化スズと酸化チタンを含有せしめた混合酸化物の焼結体
であることを特徴とするスパッタリングターゲット。3. In a sputtering target applied when forming a transparent thin film of a conductive film having a structure in which a silver-based thin film is sandwiched, a mixed oxide containing indium oxide and cerium oxide as base materials is added to each of the base materials. A sputtering target, which is a sintered body of a mixed oxide containing tin oxide and titanium oxide in an amount smaller than the mixing ratio.
総金属元素に対し 0.1〜 5at％（原子パーセント）であ
ることを特徴とする請求項１または３に記載のスパッタ
リングターゲット。4. The sputtering target according to claim 1, wherein the amount of tin element of tin oxide is 0.1 to 5 at% (atomic percent) with respect to the total metal elements of the mixed oxide.
物の総金属元素に対し 0.1〜 5at％（原子パーセント）
であることを特徴とする請求項２または３に記載のスパ
ッタリングターゲット。5. The amount of titanium element of titanium oxide is 0.1 to 5 at% (atomic percent) with respect to the total metal elements of the mixed oxide.
The sputtering target according to claim 2 or 3, wherein
酸化物の総金属元素に対し 5〜60at％（原子パーセン
ト）であることを特徴とする請求項１、２、３、４また
は５に記載のスパッタリングターゲット。6. The amount of cerium element of cerium oxide is 5 to 60 at% (atomic percentage) based on the total metal elements of the mixed oxide, according to claim 1, 2, 3, 4 or 5. The sputtering target described.
酸化物の総金属元素に対し10〜40at％（原子パーセン
ト）であることを特徴とする請求項１、２、３、４また
は５に記載のスパッタリングターゲット。7. The method according to claim 1, wherein the amount of cerium element of cerium oxide is 10 to 40 at% (atomic percentage) based on the total metal elements of the mixed oxide. The sputtering target described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33320895A JP3445891B2 (en) | 1995-12-21 | 1995-12-21 | Sputtering target |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33320895A JP3445891B2 (en) | 1995-12-21 | 1995-12-21 | Sputtering target |
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| Publication Number | Publication Date |
|---|---|
| JPH09176841A true JPH09176841A (en) | 1997-07-08 |
| JP3445891B2 JP3445891B2 (en) | 2003-09-08 |
Family
ID=18263533
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33320895A Expired - Fee Related JP3445891B2 (en) | 1995-12-21 | 1995-12-21 | Sputtering target |
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| Country | Link |
|---|---|
| JP (1) | JP3445891B2 (en) |
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