JP5896121B2 - Oxide sputtering target and protective film for optical recording medium - Google Patents
Oxide sputtering target and protective film for optical recording medium Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims description 39
- 230000001681 protective effect Effects 0.000 title claims description 25
- 230000003287 optical effect Effects 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
- 238000004544 sputter deposition Methods 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000007373 indentation Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 D 50 = 1 μm) Chemical compound 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
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- 235000012239 silicon dioxide Nutrition 0.000 description 2
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- 238000004528 spin coating Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012856 weighed raw material Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
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- Physical Vapour Deposition (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Manufacturing Optical Record Carriers (AREA)
Description
本発明は、Ｂｌｕ−ｒａｙ Ｄｉｓｃ（登録商標）等に用いる光記録媒体用保護膜を成膜するための酸化物スパッタリングターゲット及びこれを用いて作製した光記録媒体用保護膜に関するものである。 The present invention relates to an oxide sputtering target for forming a protective film for an optical recording medium used for Blu-ray Disc (registered trademark) and the like, and to a protective film for an optical recording medium produced using the oxide sputtering target.
近年、写真や動画の高画質化に伴い、光記録媒体等へ記録する際のデジタルデータが増大し、記録媒体の高容量化が求められ、既に、高記録容量の光記録媒体として二層記録方式により５０ＧＢの容量を有したＢｌｕ−ｒａｙ Ｄｉｓｃ（登録商標：以下、ＢＤと称す）が販売されている。このＢＤは、今後もさらなる高容量化が望まれており、記録層の多層化による高容量化の研究が盛んに行われている。 In recent years, with the improvement of the picture quality of photographs and moving images, digital data when recording on an optical recording medium or the like has increased, and there has been a demand for an increase in the capacity of the recording medium. A Blu-ray Disc (registered trademark: hereinafter referred to as BD) having a capacity of 50 GB is on the market. In the future, it is desired to further increase the capacity of this BD, and research on increasing the capacity by increasing the number of recording layers has been actively conducted.
上記従来の技術には、以下の課題が残されている。
有機色素を記録層に用いたタイプの記録媒体では、無機物を記録層とした場合と比較して、記録層の変形が大きいため、特許文献１の段落番号００５８にも記載されているように、色素と隣り合う保護層には低い硬度が必要である。そのため、従来では、適度に柔らかい膜であるＺｎＳ−ＳｉＯ２やＩＴＯが採用されている。
しかしながら、ＺｎＳ−ＳｉＯ２には、特許文献２の段落番号０００４にも記載があるように、硫黄（Ｓ）が含まれていると、硫黄と反射膜中の金属とが反応して反射率が低下し、保存性が低くなるという不都合がある。また、ＩＴＯについては、スパッタの際にパーティクルが多く、記録媒体のディスクに悪影響を与える上、生産設備の清掃が大変であり、生産性が悪いという問題があった。
The following problems remain in the conventional technology.
In the recording medium of the type using the organic dye for the recording layer, since the deformation of the recording layer is large compared to the case where the inorganic substance is used as the recording layer, as described in paragraph No. 0058 of Patent Document 1, The protective layer adjacent to the dye must have a low hardness. Therefore, conventionally, ZnS—SiO 2 and ITO, which are moderately soft films, are employed.
However, as described in paragraph No. 0004 of Patent Document 2, when ZnS—SiO 2 contains sulfur (S), sulfur reacts with the metal in the reflective film, resulting in a reflectivity. There is an inconvenience that the storage stability is lowered. In addition, ITO has many particles when it is sputtered, which adversely affects the disk of the recording medium, and the production equipment is difficult to clean, resulting in poor productivity.
本発明は、前述の課題に鑑みてなされたもので、光記録媒体保護膜形成用として、保存性が高く、柔らかく割れ難い膜を成膜可能であると共に、直流スパッタが可能でパーティクルも少ない酸化物スパッタリングターゲット及びこれを用いて作製した光記録媒体用保護膜を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems, and can be used for forming a protective film for an optical recording medium, which can form a film that is highly storable, soft and difficult to break, and that can be directly sputtered and has few particles. It is an object of the present invention to provide an object sputtering target and a protective film for an optical recording medium produced using the same.
本発明者らは、ＺｎＯ系のスパッタリングターゲットについて研究を進めたところ、原料にＳｉＯ２と、Ｉｎ２Ｏ３とを加えることにより、直流スパッタで反射率の変化が少なく柔らかく割れ難い膜が成膜できることを見出した。 The inventors of the present invention have made researches on a ZnO-based sputtering target, and by adding SiO 2 and In 2 O 3 to the raw material, a soft and difficult-to-crack film is formed by DC sputtering with little change in reflectance. I found out that I can do it.
したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。すなわち、第１の発明に係る酸化物スパッタリングターゲットは、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなることを特徴とする。 Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems. That is, the oxide sputtering target according to the first invention has In: 0.15 at% or more, Si: 7 at% or more, Total of In and Si: 39 at% or less, and the balance is Zn and inevitable with respect to the total metal component amount. It consists of impurities.
この酸化物スパッタリングターゲットでは、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなる成分組成の酸化物であるので、比抵抗が低く安定した直流スパッタが可能であり、反射率の変化が少なく高い保存性を有していると共に柔らかく割れ難い膜を成膜することができる。
なお、ＺｎＯ中に固溶したＩｎによるキャリアの発生によりターゲットの比抵抗を下げることができると共に、さらに成膜された膜の熱拡散率が向上して熱的損傷を軽減可能と考えられる。
In this oxide sputtering target, In: 0.15 at% or more, Si: 7 at% or more, total of In and Si: 39 at% or less with respect to the total metal component amount, oxidation of the component composition consisting of Zn and inevitable impurities as the balance Therefore, a stable direct current sputtering with a low specific resistance is possible, a change in reflectance is small, a film having high storability and being soft and difficult to break can be formed.
Note that it is considered that the specific resistance of the target can be lowered by the generation of carriers by solid solution of In in ZnO, and the thermal diffusivity of the formed film can be further improved to reduce thermal damage.
なお、Ｉｎの含有量を０．１５ａｔ％以上とした理由は、０．１５ａｔ％未満であると、直流スパッタが不安定になり、膜の割れが発生し易くなるためである。また、上記Ｓｉの含有量を７ａｔ％以上とした理由は、７ａｔ％未満であると、膜の硬度（後述する押し込み硬さ）が８００ｍｇｆ／μｍ２以上になり、硬くなってしまうためである。さらに、ＩｎおよびＳｉの合計含有量を３９ａｔ％以下とした理由は、３９ａｔ％を超えると、原料に加えるＩｎ２Ｏ３またはＳｉＯ２が多くなり過ぎてＺｎＯと複合酸化物を多量に作り、ターゲットの比抵抗が高くなって、ＤＣスパッタができなくなるためである。 The reason why the In content is set to 0.15 at% or more is that when it is less than 0.15 at%, direct current sputtering becomes unstable and cracking of the film easily occurs. The reason why the Si content is 7 at% or more is that when it is less than 7 at%, the hardness of the film (indentation hardness described later) becomes 800 mgf / μm 2 or more and becomes hard. Furthermore, the reason why the total content of In and Si is 39 at% or less is that if it exceeds 39 at%, too much In 2 O 3 or SiO 2 is added to the raw material to produce a large amount of ZnO and composite oxide, and the target This is because the specific resistance becomes high and DC sputtering cannot be performed.
第２の発明に係る酸化物スパッタリングターゲットは、第１の発明に記載の酸化物スパッタリングターゲットにおいて、Ｓｉ：２５ａｔ％以上であることを特徴とする。
すなわち、この酸化物スパッタリングターゲットでは、Ｓｉ：２５ａｔ％以上であるので、膜の硬度（押し込み硬さ）が７００ｍｇｆ／μｍ２以下の、柔らかく割れ難い膜を成膜することができる。
An oxide sputtering target according to a second invention is characterized in that in the oxide sputtering target according to the first invention, Si: 25 at% or more.
That is, in this oxide sputtering target, since Si: 25 at% or more, a soft and difficult-to-break film having a film hardness (indentation hardness) of 700 mgf / μm 2 or less can be formed.
第３の発明に係る光記録媒体用保護膜は、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなる成分組成の酸化物であることを特徴とする。 The protective film for an optical recording medium according to the third invention is In: 0.15 at% or more, Si: 7 at% or more, the sum of In and Si: 39 at% or less with respect to the total metal component amount, the balance being Zn and inevitable It is an oxide having a component composition made of impurities.
第４の発明に係る光記録媒体用保護膜は、第３の発明に記載の光記録媒体用保護膜において、Ｓｉ：２５ａｔ％以上であることを特徴とする。
また、第５の発明に係る光記録媒体用保護膜は、第１又は第２の発明に係る酸化物スパッタリングターゲットを用いてスパッタリングすることにより成膜されたことを特徴とする。
The protective film for an optical recording medium according to a fourth invention is the protective film for an optical recording medium according to the third invention, wherein Si: 25 at% or more.
The protective film for an optical recording medium according to the fifth invention is formed by sputtering using the oxide sputtering target according to the first or second invention.
すなわち、これらの光記録媒体用保護膜では、反射率の変化が小さく保存性が高いと共に、柔らかく割れ難い特性を有しており、有機色素の記録層を使用したＢＤの保護膜として好適である。 That is, these protective films for optical recording media are suitable as a protective film for BD using a recording layer of an organic dye, since the change in reflectance is small and the storage property is high and the film is soft and difficult to break. .
本発明によれば、以下の効果を奏する。
すなわち、本発明に係る酸化物スパッタリングターゲットによれば、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなる成分組成の酸化物であるので、安定した直流スパッタが可能であり、高い保存性を有していると共に柔らかく割れ難い膜を成膜することができる。
したがって、本発明の酸化物スパッタリングターゲットで成膜された光記録媒体用保護膜は、有機色素の記録層を使用したＢＤ用の誘電体保護膜として好適である。
The present invention has the following effects.
That is, according to the oxide sputtering target according to the present invention, In: 0.15 at% or more, Si: 7 at% or more, total of In and Si: 39 at% or less with respect to the total metal component amount, the balance being Zn and inevitable Since it is an oxide having a component composition made of impurities, stable direct current sputtering is possible, and a film that has high storage stability and is hard to break can be formed.
Therefore, the protective film for optical recording media formed with the oxide sputtering target of the present invention is suitable as a dielectric protective film for BD using an organic dye recording layer.
以下、本発明の酸化物スパッタリングターゲット及び光記録媒体用保護膜の一実施形態を説明する。 Hereinafter, an embodiment of the oxide sputtering target and the protective film for an optical recording medium of the present invention will be described.
本実施形態の酸化物スパッタリングターゲットは、例えばＢＤの有機色素で形成された記録層に積層される誘電体保護膜を作製するためのスパッタリングターゲットであって、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなる成分組成に設定されている。
なお、直流（ＤＣ）スパッタをするためにはスパッタリングターゲットの比抵抗を、１Ω・ｃｍ以下とすることが望ましい。特に、安定したスパッタを行うためには、０．１Ω・ｃｍ以下が望ましく、さらに望ましくは０．０１Ω・ｃｍ以下である。
The oxide sputtering target of the present embodiment is a sputtering target for producing a dielectric protective film laminated on a recording layer formed of, for example, an organic dye of BD, and has In: 0 with respect to the total amount of metal components. .15 at% or more, Si: 7 at% or more, total of In and Si: 39 at% or less, and the balance is set to a component composition consisting of Zn and inevitable impurities.
In order to perform direct current (DC) sputtering, the specific resistance of the sputtering target is desirably 1 Ω · cm or less. In particular, in order to perform stable sputtering, it is preferably 0.1 Ω · cm or less, and more preferably 0.01 Ω · cm or less.
また、本実施形態の酸化物スパッタリングターゲットを用いてスパッタリングにより成膜された光記録媒体用保護膜は、上記ターゲットと同様に、全金属成分量に対してＩｎ：０．１５ａｔ％以上、Ｓｉ：７ａｔ％以上、ＩｎおよびＳｉの合計：３９ａｔ％以下、残部がＺｎおよび不可避不純物からなる成分組成の酸化物である。 Further, the protective film for an optical recording medium formed by sputtering using the oxide sputtering target of the present embodiment is In: 0.15 at% or more with respect to the total metal component amount, Si: 7 at% or more, total of In and Si: 39 at% or less, the balance being an oxide having a component composition consisting of Zn and inevitable impurities.
本実施形態の酸化物スパッタリングターゲットを製造する方法の一例について詳述すれば、まず酸化亜鉛と、二酸化ケイ素と、酸化インジウムとの各原料粉末を所定の比率になるように秤量する。 If an example of the method of manufacturing the oxide sputtering target of this embodiment is explained in full detail, first, each raw material powder of a zinc oxide, a silicon dioxide, and an indium oxide will be measured so that it may become a predetermined ratio.
この秤量した原料粉末とその３倍量（重量比）のジルコニアボール（直径５ｍｍ）とをポリ容器に入れ、ボールミル装置にて２４時間湿式混合する。なお、この際の溶媒には、例えばアルコールを用いる。次に、得られた混合粉末を乾燥後、例えば目開き：２５０μｍの篩にかけ、９００〜１２５０℃、望ましくは１０００〜１１５０℃にて２〜９時間、１５０〜３５０ｋｇｆ／ｃｍ２の圧力にて真空または不活性ガス雰囲気中でホットプレスし、スパッタリングターゲットとする。 This weighed raw material powder and its three times (weight ratio) zirconia balls (diameter 5 mm) are put in a plastic container and wet-mixed for 24 hours in a ball mill apparatus. In addition, alcohol is used for the solvent in this case, for example. Next, the obtained mixed powder is dried and then, for example, sieved through a sieve of 250 μm and vacuumed at 900 to 1250 ° C., preferably 1000 to 1150 ° C. for 2 to 9 hours, and a pressure of 150 to 350 kgf / cm 2 . Alternatively, hot pressing is performed in an inert gas atmosphere to obtain a sputtering target.
上記本実施形態に基づいて実際に作製した酸化物スパッタリングターゲットの実施例について、評価を行った結果を説明する。
［実施例］
酸化亜鉛（化学式：ＺｎＯ、Ｄ５０＝１μｍ）と、二酸化ケイ素（化学式：ＳｉＯ２、Ｄ５０＝２μｍ）と、酸化インジウム（化学式：Ｉｎ２Ｏ３、Ｄ５０＝１１μｍ）との各原料粉末を、表１に示す所定の比率になるように秤量した。
The result of having evaluated about the Example of the oxide sputtering target actually produced based on the said this embodiment is demonstrated.
[Example]
Each raw material powder of zinc oxide (chemical formula: ZnO, D 50 = 1 μm), silicon dioxide (chemical formula: SiO 2 , D 50 = 2 μm), and indium oxide (chemical formula: In 2 O 3 , D 50 = 11 μm) is used. The sample was weighed so as to have a predetermined ratio shown in Table 1.
この秤量した原料粉末とその３倍量（重量比）のジルコニアボール（直径５ｍｍ）とをポリ容器に入れ、ボールミル装置にて２４時間湿式混合した。なお、この際の溶媒には、アルコールを用いた。次に、得られた混合粉末を乾燥後、目開き：２５０μｍの篩にかけ、１１００℃にて２時間、３５０ｋｇｆ／ｃｍ２の圧力にて真空中でホットプレスし、実施例１〜７のスパッタリングターゲットを作製した。なお、ターゲットサイズは、直径１２５ｍｍ×厚さ５ｍｍとした。 The weighed raw material powder and 3 times its amount (weight ratio) of zirconia balls (diameter 5 mm) were placed in a plastic container and wet mixed in a ball mill apparatus for 24 hours. In addition, alcohol was used for the solvent in this case. Next, the obtained mixed powder was dried, sieved through a sieve of 250 μm, hot-pressed in vacuum at 1100 ° C. for 2 hours at a pressure of 350 kgf / cm 2 , and the sputtering targets of Examples 1 to 7 Was made. The target size was 125 mm diameter x 5 mm thickness.
なお、比較例として、Ｉｎ２Ｏ３を含有しないもの（比較例１）と、本発明の成分組成割合の設定範囲外としたもの（比較例２，３）についても、表１に示す組成で同様にスパッタリングターゲットを作製した。さらに、従来のＺｎＳ−ＳｉＯ２（比較例４）及びＩＴＯ（比較例５）のスパッタリングターゲットを用意した。ＺｎＳ−ＳｉＯ２は三菱マテリアル製のＺＳＳＯターゲット（２０ｍｏｌ％ＳｉＯ２）、ＩＴＯは三菱マテリアル製のＩＴＯターゲット（１０ｗｔ％ＳｎＯ２）である。
これらの実施例及び比較例のスパッタリングターゲットを用いて、以下の成膜条件により実施例１〜７及び比較例１〜５の光記録媒体用保護膜を成膜した。
スパッタリングターゲットの金属組成を表２に、光記録媒体用保護膜の金属組成を表３に示す。
As comparative examples, those not containing In 2 O 3 (Comparative Example 1) and those outside the setting range of the component composition ratio of the present invention (Comparative Examples 2 and 3) also have the compositions shown in Table 1. Similarly, a sputtering target was produced. Furthermore, conventional sputtering targets of ZnS—SiO 2 (Comparative Example 4) and ITO (Comparative Example 5) were prepared. ZnS—SiO 2 is a ZSSO target (20 mol% SiO 2 ) manufactured by Mitsubishi Materials, and ITO is an ITO target (10 wt% SnO 2 ) manufactured by Mitsubishi Materials.
Using the sputtering targets of these Examples and Comparative Examples, protective films for optical recording media of Examples 1 to 7 and Comparative Examples 1 to 5 were formed under the following film forming conditions.
Table 2 shows the metal composition of the sputtering target, and Table 3 shows the metal composition of the protective film for an optical recording medium.
＜成膜条件＞
・電源：パルスＤＣ５００Ｗ（一部、高周波（ＲＦ）スパッタ）
・全圧：０．４Ｐａ
・スパッタガス：Ａｒ＝４７．５ｓｃｃｍ、Ｏ２：２．５ｓｃｃｍ（比較例４のみＡｒ＝５０ｓｃｃｍ、Ｏ２＝０ｓｃｃｍ）
・ターゲット−基板（ＴＳ）距離：７０ｍｍ
<Film formation conditions>
・ Power supply: Pulse DC500W (partially, radio frequency (RF) sputtering)
・ Total pressure: 0.4Pa
Sputtering gas: Ar = 47.5 sccm, O 2 : 2.5 sccm (only Comparative Example 4 Ar = 50 sccm, O 2 = 0 sccm)
-Target-substrate (TS) distance: 70 mm
「評価」
各実施例・比較例のスパッタリングターゲットについて、密度比、比抵抗、異常放電回数、パーティクルの量、膜の押し込み硬さ、膜の割れ、膜の比抵抗、膜のＸＲＤ及び反射率の変化を求めた。
＜密度比測定＞
密度比は、焼結体を所定寸法に機械加工した後、重量を測定し嵩密度を求めた後、理論密度で割ることで、算出した。尚、理論密度は原料の重量に基づいて以下のようにして求めた。
"Evaluation"
For the sputtering target of each example / comparative example, the density ratio, specific resistance, number of abnormal discharges, amount of particles, film indentation hardness, film cracking, film specific resistance, film XRD, and change in reflectance are obtained. It was.
<Density ratio measurement>
The density ratio was calculated by machining the sintered body to a predetermined size, measuring the weight to determine the bulk density, and then dividing by the theoretical density. The theoretical density was determined as follows based on the weight of the raw material.
＜比抵抗測定＞
スパッタリングターゲットおよび膜の比抵抗測定は、三菱化学製抵抗測定器ロレスタＧＰを用いて測定した。
<Specific resistance measurement>
The specific resistance of the sputtering target and the film was measured using a resistance measuring instrument Loresta GP manufactured by Mitsubishi Chemical.
＜反射率の変化＞
ポリカーボネート上にＡｇ９８．１Ｎｄ１．０Ｃｕ０．９合金をスパッタし、特許文献１に記載の下記色素を成膜した基板を用い、その上に上述の条件において各実施例及び比較例の保護膜を厚さ１４ｎｍ成膜した。その後、８０℃、８５％の恒温恒湿器に１００時間放置して、その前後の反射率の変化を測定した。なお、反射率の測定には、紫外可視分光光度計（日本分光株式会社製Ｖ−５５０）を用いた。また、波長４０５ｎｍの光に対する反射率を求めた。
<Change in reflectance>
A substrate in which an Ag 98.1 Nd 1.0 Cu 0.9 alloy was sputtered on polycarbonate and the following dye described in Patent Document 1 was formed on the substrate, and each of the Examples and Comparative Examples was formed on the above-described conditions. A protective film having a thickness of 14 nm was formed. Then, it was left for 100 hours in a constant temperature and humidity chamber at 80 ° C. and 85%, and the change in reflectance before and after that was measured. In addition, the ultraviolet visible spectrophotometer (JASCO Corporation V-550) was used for the measurement of a reflectance. Moreover, the reflectance with respect to the light of wavelength 405nm was calculated | required.
・色素：上記基板に成膜した色素は、下記構造式で表される配位子Ａと二価のＮｉとからなる含金アゾ色素Ａと、配位子Ｂと二価のＣｏとからなる含金アゾ色素Ｂとを７０：３０重量％比となるように混合し、オクタフルオロペンタノール（ＯＦＰ）で１．０重量％に希釈した混合溶液をスピンコートで成膜した。なお、スピンコートは、上記混合溶液を基板中央付近に１．５ｇ環状に塗布し、基板を１２００ｒｐｍで７秒間回転させ色素を延伸し、その後、９２００ｒｐｍで３秒回転させ色素を振り切ることによる塗布を行った。なお、塗布後には基板を８０℃の環境下に１時間保持することで溶媒であるＯＦＰを蒸発除去した。 -Dye: The dye formed on the substrate comprises a metal-containing azo dye A composed of a ligand A represented by the following structural formula and divalent Ni, a ligand B, and divalent Co. The metal-containing azo dye B was mixed at a ratio of 70:30 wt%, and a mixed solution diluted to 1.0 wt% with octafluoropentanol (OFP) was formed by spin coating. In spin coating, 1.5 g of the above mixed solution is applied in the vicinity of the center of the substrate, the substrate is rotated at 1200 rpm for 7 seconds to stretch the dye, and then rotated at 9200 rpm for 3 seconds to shake off the dye. went. After coating, the OFP as the solvent was removed by evaporation by holding the substrate in an environment of 80 ° C. for 1 hour.
＜膜の押し込み硬さ＞
上述の条件において基板をコーニング社製１７３７ガラス、膜厚を５００ｎｍとして成膜を行い、押し込み加重を３５ｍｇｆとし超微小押し込み硬さ試験機（エリオニクス社製ＥＮＴ−１１００ａ）にて測定を行った。なお、基板は２７℃の装置内にセットし、１時間以上経過してから測定した。なお、１０点測定の平均値を測定値とした。
<Indentation hardness of film>
Under the above-mentioned conditions, the substrate was formed with 1737 glass made by Corning, the film thickness was 500 nm, the indentation load was 35 mgf, and measurement was performed with an ultra-fine indentation hardness tester (ENT-1100a, Elionix). The substrate was set in a 27 ° C. apparatus and measured after 1 hour or more had elapsed. In addition, the average value of 10-point measurement was made into the measured value.
＜膜の割れ＞
上述の条件において、厚さ０．１ｍｍのＰＥＴフィルムに１００ｎｍの膜厚で成膜し、フィルムを１０回折り曲げた後、膜表面を顕微鏡により倍率１０００倍にて観察して割れの有無を調べた。
＜異常放電とパーティクル＞
上述の条件において１２時間スパッタを行い異常放電の回数を計測した。その後、スパッタチャンバーを解放し、チャンバー内のパーティクルを確認した。
＜膜のＸＲＤ＞
試料の準備：試料はＳｉＣ−Ｐａｐｅｒ（ｇｒｉｔ １８０）にて湿式研磨、乾燥の後、測定試料とした。
装置：理学電気社製（ＲＩＮＴ−Ｕｌｔｉｍａ／ＰＣ）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：４０ｍＡ
走査範囲（２θ）：５°〜８０°
スリットサイズ：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、受光（ＲＳ）０.８ｍｍ
測定ステップ幅：２θで０.０２度
スキャンスピード：毎分２度
試料台回転スピード：３０ｒｐｍ
これらの各評価結果を、表４に示す。
<Membrane cracking>
Under the above-mentioned conditions, a film of 100 nm was formed on a PET film having a thickness of 0.1 mm, the film was bent 10 times, and then the surface of the film was observed with a microscope at a magnification of 1000 to check for cracks. .
<Abnormal discharge and particles>
Sputtering was performed for 12 hours under the above conditions, and the number of abnormal discharges was measured. Thereafter, the sputtering chamber was released, and particles in the chamber were confirmed.
<XRD of membrane>
Preparation of sample: The sample was wet-polished with SiC-Paper (grit 180) and dried, and then used as a measurement sample.
Equipment: Rigaku Electric (RINT-Ultima / PC)
Tube: Cu
Tube voltage: 40 kV
Tube current: 40 mA
Scanning range (2θ): 5 ° -80 °
Slit size: Divergence (DS) 2/3 degree, Scattering (SS) 2/3 degree, Light reception (RS) 0.8mm
Measurement step width: 0.02 degrees at 2θ Scan speed: 2 degrees per minute Sample stage rotation speed: 30 rpm
These evaluation results are shown in Table 4.
これらの結果からわかるように、本発明の実施例は、いずれも比抵抗が０．１Ω・ｃｍ以下であり、異常放電回数が非常に少ないと共にパーティクルの量も少なかった。これに対して比較例１，４では、比抵抗が高くて測定可能範囲外であり、直流スパッタができなかった。また、比較例２についても、比抵抗が高く、直流スパッタができなかった。比較例５については、パーティクルの量が多かった。なお、本発明の実施例及び比較例は、いずれも密度は９０％以上であった。 As can be seen from these results, all of the examples of the present invention had a specific resistance of 0.1 Ω · cm or less, the number of abnormal discharges was very small, and the amount of particles was small. On the other hand, in Comparative Examples 1 and 4, the specific resistance was high and out of the measurable range, and DC sputtering could not be performed. Further, Comparative Example 2 also had a high specific resistance and could not be DC sputtered. In Comparative Example 5, the amount of particles was large. In addition, as for the Example and comparative example of this invention, all had a density of 90% or more.
また、保護膜の柔らかさを示す膜の押し込み硬さについては、比較例１，３で８００ｍｇｆ／μｍ２を超えてしまっており、これら比較例１，３では、膜の割れが生じていた。これらに対し、本発明の実施例はいずれも８００ｍｇｆ／μｍ２以下であり、比較例１，３に比べて柔らかい膜が得られ、膜の割れが生じていない。なお、ＩＴＯ膜である比較例５では、膜の割れが発生している。
さらに、反射率の変化については、ＺｎＳ−ＳｉＯ２の比較例４が大きく変化しているのに対し、本発明の実施例は、いずれも１．０％以下の少ない変化率であり、高い保存性が得られている。
なお、本実施例の保護膜は、常温でアモルファスである。
Further, the indentation hardness of the film indicating the softness of the protective film exceeded 800 mgf / μm 2 in Comparative Examples 1 and 3, and in Comparative Examples 1 and 3, the film was cracked. On the other hand, all of the examples of the present invention are 800 mgf / μm 2 or less, and a soft film is obtained as compared with Comparative Examples 1 and 3, and the film is not cracked. In Comparative Example 5, which is an ITO film, the film is cracked.
Furthermore, with respect to the change in reflectance, the comparative example 4 of ZnS-SiO 2 is greatly changed, whereas the examples of the present invention all have a low change rate of 1.0% or less and high storage. Sex has been obtained.
Note that the protective film of this example is amorphous at room temperature.
次に、代表的に本発明の実施例１，３のスパッタリングターゲットについて、Ｘ線回折（ＸＲＤ）した結果を図１に示す。なお、図１の上段が実施例１であり、下段が実施例３である。この結果からわかるように、ＺｎＯに帰属する回折ピークと、ＳｉＯ２とＺｎＯとの複合酸化物であるＺｎ２ＳｉＯ４とに帰属する回折ピークが検出され、ＺｎＯ及びＺｎ２ＳｉＯ４の相の存在が確認された。 Next, the results of X-ray diffraction (XRD) of the sputtering targets of Examples 1 and 3 of the present invention are shown in FIG. The upper part of FIG. 1 is Example 1, and the lower part is Example 3. As can be seen from this result, a diffraction peak attributed to ZnO and a diffraction peak attributed to Zn 2 SiO 4 which is a composite oxide of SiO 2 and ZnO were detected, and the presence of phases of ZnO and Zn 2 SiO 4 was detected. Was confirmed.
また、実施例１，３のスパッタリングターゲットについて、ＥＰＭＡ（フィールドエミッション型電子線プローブ）にて、反射電子像（ＣＰ）および各元素の組成分布を示す元素分布像を観察した。上記反射電子像および元素分布像をそれぞれ図２及び図３に示す。
なお、ＥＰＭＡによる元素分布像は、本来カラー像であるが、白黒像に変換して記載しているため、濃淡の淡い部分（比較的白い部分）が所定元素の濃度が高い部分となっている。
これら画像から、実施例１，３のスパッタリングターゲットは、ＺｎＯとＺｎ２ＳｉＯ４と酸化ケイ素との相からなり、ＩｎがＺｎＯ相に選択的に分散していることがわかる。
Moreover, about the sputtering target of Example 1, 3, the reflected electron image (CP) and the element distribution image which shows the composition distribution of each element were observed by EPMA (field emission type electron beam probe). The reflected electron image and the element distribution image are shown in FIGS. 2 and 3, respectively.
The element distribution image by EPMA is originally a color image, but is described after being converted into a black and white image, and thus a light and dark portion (relatively white portion) is a portion where the concentration of the predetermined element is high. .
From these images, it can be seen that the sputtering targets of Examples 1 and 3 are composed of phases of ZnO, Zn 2 SiO 4 and silicon oxide, and In is selectively dispersed in the ZnO phase.
なお、本発明を、スパッタリングターゲットとして利用するためには、面粗さ：５．０μｍ以下、より好ましくは１．０μｍ以下、粒径：２０μｍ以下より好ましくは１０μｍ以下、金属系不純物濃度：０．１原子％以下、より好ましくは０．０５原子％以下、抗折強度：５０ＭＰａ以上、より好ましくは１００ＭＰａ以上であることが好ましい。上記各実施例は、いずれもこれらの条件を満たしたものである。
また、本発明の技術範囲は上記実施形態および上記実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。
例えば、上記実施形態および上記実施例では、加圧焼結をホットプレスによって行っているが、他の方法としてＨＩＰ法（熱間等方加圧式焼結法）等を採用しても構わない。
In order to use the present invention as a sputtering target, the surface roughness is 5.0 μm or less, more preferably 1.0 μm or less, the particle size is 20 μm or less, more preferably 10 μm or less, and the metal impurity concentration is 0.00. 1 atomic% or less, more preferably 0.05 atomic% or less, bending strength: 50 MPa or more, more preferably 100 MPa or more. Each of the above-described embodiments satisfies these conditions.
The technical scope of the present invention is not limited to the above-described embodiment and examples, and various modifications can be made without departing from the spirit of the present invention.
For example, in the above embodiment and the above examples, pressure sintering is performed by hot pressing, but as another method, a HIP method (hot isostatic pressing method) or the like may be employed.
Claims (2)
ＺｎＯ相及びＺｎ２ＳｉＯ４相を有し、
前記ＺｎＯ相にＩｎが固溶していることを特徴とする酸化物スパッタリングターゲット。 In: 0.15 at% or more, Si: 25 at% or more, total of In and Si: 39 at% or less with respect to the total metal component amount, the balance is made of Zn and inevitable impurities,
Having a ZnO phase and a Zn 2 SiO 4 phase,
An oxide sputtering target, wherein In is dissolved in the ZnO phase.
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| JP2001195789A (en) * | 2000-01-06 | 2001-07-19 | Mitsubishi Materials Corp | Sputtering target for forming optical recording medium protective film free from sputtering crack |
| JP2001316805A (en) * | 2000-05-08 | 2001-11-16 | Mitsubishi Materials Corp | Sputtering target for formation of optical logging protection film capable of dc sputtering |
| JP2002133718A (en) * | 2000-10-30 | 2002-05-10 | Ricoh Co Ltd | Optical recording medium |
| JP4198918B2 (en) * | 2002-02-14 | 2008-12-17 | 日鉱金属株式会社 | Sputtering target mainly composed of zinc sulfide and method for producing the sputtering target |
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