JP4279707B2 - Sputtering target and protective film for optical information recording medium - Google Patents
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- 230000003287 optical effect Effects 0.000 title claims description 39
- 238000005477 sputtering target Methods 0.000 title claims description 24
- 230000001681 protective effect Effects 0.000 title claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 238000007496 glass forming Methods 0.000 claims description 17
- 238000002834 transmittance Methods 0.000 claims description 14
- 239000010410 layer Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 29
- 239000010408 film Substances 0.000 description 22
- 239000011241 protective layer Substances 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001552 radio frequency sputter deposition Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Description
本発明は、スパッタ膜の非晶質性が安定であり、記録層との密着性、機械特性に優れ、かつ透過率が高く、また非硫化物系で構成されているため、隣接する反射層、記録層の劣化が生じ難い光情報記録媒体用保護膜及びこれらに適用できるパッタリングターゲットに関する。 In the present invention, since the amorphousness of the sputtered film is stable, the adhesiveness with the recording layer is excellent, the mechanical properties are high, and the transmittance is high. The present invention relates to a protective film for an optical information recording medium in which deterioration of a recording layer hardly occurs and a patching target applicable to these.
従来、主として相変化型の光情報記録媒体の保護層に一般的に使用されるZnS−SiO2は、光学特性、熱特性、記録層との密着性等において、優れた特性を有し、広く使用されている。
しかし、今日Blue-Rayに代表される書き換え型DVDは、さらに書き換え回数の増加、大容量化、高速記録化が強く求められている。
Conventionally, ZnS-SiO 2 generally used mainly for the protective layer of phase change type optical information recording media has excellent characteristics such as optical characteristics, thermal characteristics, adhesion to the recording layer, etc. in use.
However, today, rewritable DVDs represented by Blue-Ray are strongly required to increase the number of rewrites, increase the capacity, and increase the recording speed.
光情報記録媒体の書き換え回数等が劣化する原因の一つとして、保護層ZnS−SiO2に挟まれるように配置された記録層材への、ZnS−SiO2からの硫黄成分の拡散が挙げられる。
また、大容量化、高速記録化のため高反射率で高熱伝導特性を有する純AgまたはAg合金が反射層材に使用されるようになったが、このような反射層も保護層材であるZnS−SiO2と接するように配置されている。
したがって、この場合も同様に、ZnS−SiO2からの硫黄成分の拡散により、純AgまたはAg合金反射層材も腐食劣化して、光情報記録媒体の反射率等の特性劣化を引き起こす要因となっていた。
One of the causes of deterioration of the number of times of rewriting of the optical information recording medium is diffusion of sulfur components from ZnS-SiO 2 to the recording layer material arranged so as to be sandwiched between the protective layers ZnS-SiO 2. .
In addition, pure Ag or Ag alloy having high reflectivity and high thermal conductivity has been used for the reflective layer material for increasing the capacity and recording speed, but such a reflective layer is also a protective layer material. They are arranged in contact with the ZnS-SiO 2.
Accordingly, in this case as well, due to the diffusion of the sulfur component from ZnS-SiO 2 , the pure Ag or Ag alloy reflective layer material also corrodes and becomes a factor causing deterioration in characteristics such as reflectance of the optical information recording medium. It was.
これら硫黄成分の拡散防止対策として、反射層と保護層、記録層と保護層の間に、窒化物や炭化物を主成分とした中間層を設けた構成にすることも行なわれている。しかし、これは積層数の増加となり、スループット低下、コスト増加になるという問題を発生している。
上記のような問題を解決するため、保護層材に硫化物を含まない酸化物のみの材料へと置き換え、ZnS−SiO2と同等以上の光学特性、非晶質安定性を有する材料系を見出すことが急務となっていた。
In order to prevent diffusion of these sulfur components, an intermediate layer mainly composed of nitride or carbide is provided between the reflective layer and the protective layer and between the recording layer and the protective layer. However, this causes an increase in the number of layers, resulting in a problem that throughput decreases and costs increase.
In order to solve the above problems, the protective layer material is replaced with an oxide-free material that does not contain sulfides, and a material system having optical properties equal to or better than ZnS-SiO 2 and amorphous stability is found. It was an urgent need.
以上のようなことから、酸化物系保護層材、透明導電材あるいは光学薄膜が提案されている（特許文献１〜３参照）。
しかし、特許文献１〜３は、光学特性及び非晶質性が劣る領域を含む問題があった。
However, Patent Documents 1 to 3 have a problem including a region where optical properties and amorphousness are inferior.
本発明は、膜の非晶質性が安定であり、記録層との密着性、機械特性に優れ、且つ透過率が高く、非硫化物系で構成することにより、隣接する反射層、記録層の劣化が生じ難い光情報記録媒体用保護膜及びその製造方法並びにこれらに適用できるパッタリングターゲットに関するものであり、 これによって、光情報記録媒体の特性の向上を大幅に改善することを目的とする。 In the present invention, the amorphousness of the film is stable, the adhesiveness to the recording layer, the mechanical properties are excellent, and the transmittance is high. The present invention relates to a protective film for an optical information recording medium in which degradation of the optical information hardly occurs, a method for manufacturing the protective film, and a patching target applicable to these, and aims to greatly improve the characteristics of the optical information recording medium .
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、従来の保護層材ZnS−SiO2を、下記に提示する硫化物を含まない酸化物のみの材料へと置き換え、かつZnS−SiO2と同等の光学特性及び非晶質安定性を確保し、光情報記録媒体の特性改善が可能であるとの知見を得た。 In order to solve the above problems, the present inventors conducted extensive research, and as a result, replaced the conventional protective layer material ZnS-SiO 2 with a sulfide-free oxide-only material presented below, In addition, the inventors have obtained knowledge that optical characteristics and amorphous stability equivalent to those of ZnS-SiO 2 can be secured and the characteristics of the optical information recording medium can be improved.
本発明はこの知見に基づき、１）ZrO２又はHfO２の何れか１種又は２種を主成分とし、さらにガラス形成酸化物を添加した材料から成り、透過率９０％以上（波長４０５ｎｍ）及び屈折率１．８〜２．４（波長４０５ｎｍ）を有する光情報記録媒体用保護膜を形成するためのスパッタリングターゲット、２）ZrO２又はHfO２の何れか１種又は２種を主成分とし、さらにガラス形成酸化物を添加した材料から成り、透過率９０％以上（波長４０５ｎｍ）及び屈折率１．８〜２．４（波長４０５ｎｍ）を有し、薄膜状態で非晶質安定であることを特徴とする光情報記録媒体用保護膜を形成するためのスパッタリングターゲット、３）ガラス形成酸化物を5〜50mol％添加した材料から成ることを特徴とする１又は２記載のスパッタリングターゲット、４）ガラス形成酸化物として、SiO2を添加したことを特徴とする１〜３のいずれかに記載のスパッタリングターゲットを提供する。 Based on this knowledge, the present invention is composed of 1) one of ZrO 2 and HfO 2 as a main component and a material to which a glass-forming oxide is added, and has a transmittance of 90% or more (wavelength 405 nm); Sputtering target for forming a protective film for optical information recording medium having a refractive index of 1.8 to 2.4 (wavelength 405 nm), 2) One or two of ZrO 2 and HfO 2 as a main component, Further, it is made of a material added with a glass-forming oxide, has a transmittance of 90% or more (wavelength 405 nm), a refractive index of 1.8 to 2.4 (wavelength 405 nm), and is amorphous in a thin film state. 3. A sputtering target for forming a protective film for an optical information recording medium, characterized by comprising 3) a material to which 5 to 50 mol% of a glass-forming oxide is added. 3) The sputtering target according to any one of 1 to 3, wherein SiO 2 is added as a glass-forming oxide.
また、本発明は、５）相対密度が90%以上であることを特徴とする１〜４のいずれかに記載のスパッタリングターゲット、６）上記１〜５のいずれかに記載のスパッタリングターゲットを用いて形成することを特徴とする透過率90％以上（波長405nm）及び屈折率1.8〜2.4（波長405nm）を有する光情報記録媒体用保護膜を提供する。 Moreover, this invention uses 5) the sputtering target in any one of 1-4 characterized by relative density being 90% or more, and 6) the sputtering target in any one of said 1-5. Provided is a protective film for an optical information recording medium having a transmittance of 90% or more (wavelength 405 nm) and a refractive index of 1.8 to 2.4 (wavelength 405 nm).
上記によって、従来の保護層材ZnS−SiO2を、硫化物を含まない酸化物のみの材料へと置き換えることによって、隣接する反射層、記録層等への硫黄による劣化を抑制すると共に、ZnS−SiO2と同等又はそれ以上の光学特性及び非晶質安定性を備え、記録層との密着性、機械特性に優れ、且つ透過率が高いという優れた特性を持つ光情報記録媒体用保護膜及びこれらに適用できるパッタリングターゲットを提供できる。
また、本材料系を使用することにより、光情報記録媒体の特性改善が可能となるという優れた効果を有する。
As described above, the conventional protective layer material ZnS-SiO 2 is replaced with an oxide-only material that does not contain sulfide, thereby suppressing deterioration of the adjacent reflective layer, recording layer, etc. due to sulfur, and ZnS- comprising a SiO 2 equal to or more optical characteristics and amorphous stability, adhesiveness to the recording layer, superior mechanical properties, and protection optical information recording medium film transmittance has excellent properties of high and A sputtering target applicable to these can be provided.
Further, the use of this material system has an excellent effect that the characteristics of the optical information recording medium can be improved.
本発明のスパッタリングターゲットは、ZrO２又はHfO２の何れか１種又は２種を主成分とし、さらにガラス形成酸化物を添加した材料から成る。特に、ガラス形成酸化物を5〜50mol％添加することが望ましく、また通常ガラス形成酸化物としては、SiO2を使用する。ガラス形成酸化物としては、その他、B2O3あるいはケイ酸化物ガラスを使用することもできるが、短波長側の吸収が少ない純SiO2が望ましく、また製法上でも有利（最適）なのは、純SiO2である。 The sputtering target of the present invention is made of a material mainly containing any one or two of ZrO 2 and HfO 2 and further added with a glass-forming oxide. In particular, it is desirable to add 5 to 50 mol% of a glass forming oxide, and SiO 2 is usually used as the glass forming oxide. In addition, B 2 O 3 or silicate glass can be used as the glass-forming oxide, but pure SiO 2 with less absorption on the short wavelength side is desirable, and the advantage (optimum) in terms of the production method is pure SiO 2 .
本発明の大きな特徴は、薄膜状態で非晶質安定であることである。ガラス形成酸化物5mol％未満の添加では、非晶質安定性の十分な効果が得られず、また50mol％を超える添加では、光学特性（屈折率、透過率）が不適となって、良好な特性が得ることができない。したがって、ガラス形成酸化物を5〜50mol％の範囲の添加とするのが望ましい。 A major feature of the present invention is that it is amorphous in a thin film state. Addition of less than 5 mol% of glass-forming oxide does not provide a sufficient effect of amorphous stability, and addition of more than 50 mol% results in inadequate optical properties (refractive index, transmittance) and is favorable. Characteristics cannot be obtained. Therefore, it is desirable to add glass-forming oxide in the range of 5 to 50 mol%.
この材料は、光学特性及び膜の非晶質性が安定しており、相変化型光記録媒体の保護層材に適している。成膜には、高周波スパッタリングを使用する。
本材料は、上記の通り非晶質性が安定し、透過率を向上させることが出来るため、書換え速度の速い相変化記録媒体や青色レーザー系の相変化記録媒体用保護層材に適する。
This material is stable in optical characteristics and amorphousness of the film, and is suitable as a protective layer material for a phase change optical recording medium. For film formation, high frequency sputtering is used.
Since this material is stable in amorphousness and can improve the transmittance as described above, it is suitable for a phase change recording medium having a fast rewrite speed or a protective layer material for a phase change recording medium of a blue laser system.
また、本発明のスパッタリングターゲットは、相対密度が90%以上とすることが可能である。密度の向上は、スパッタ膜の均一性を高め、またスパッタリング時のパーティクルの発生を抑制できる効果を有する。
上記に述べるスパッタリングターゲットを使用して、少なくとも薄膜として光情報記録媒体構造の一部を形成する光情報記録媒体用保護膜を提供することができる。さらに、上記スパッタリングターゲットを使用して、少なくとも薄膜として光情報記録媒体の構造の一部を形成し、且つ記録層又は反射層と隣接して配置されている光情報記録媒体を作製することができる。
Further, the sputtering target of the present invention can have a relative density of 90% or more. The improvement in density has the effect of improving the uniformity of the sputtered film and suppressing the generation of particles during sputtering.
By using the sputtering target described above, it is possible to provide a protective film for an optical information recording medium that forms at least a part of the optical information recording medium structure as a thin film. Furthermore, by using the sputtering target, it is possible to produce an optical information recording medium in which a part of the structure of the optical information recording medium is formed as at least a thin film and is disposed adjacent to the recording layer or the reflective layer. .
さらに、本発明のスパッタリングターゲットを使用して形成された薄膜は、光情報記録媒体の構造の一部を形成し、記録層又は反射層と隣接して配置されるが、上記の通り、ＺｎＳを使用していないので、Ｓによる汚染がなく、保護層に挟まれるように配置された記録層材への硫黄成分の拡散がなくなり、これによる記録層の劣化がなくなるという著しい効果がある。
また、大容量化、高速記録化のため、高反射率で高熱伝導特性を有する純ＡｇまたはＡｇ合金が反射層材に使用されるようになったが、この隣接する反射層への硫黄成分の拡散も無くなり、同様に反射層材が腐食劣化して、光情報記録媒体の反射率等の特性劣化を引き起こす原因が一掃されるという優れた効果を有する。
Furthermore, the thin film formed using the sputtering target of the present invention forms a part of the structure of the optical information recording medium and is arranged adjacent to the recording layer or the reflective layer. Since it is not used, there is no contamination due to S, and there is no significant diffusion of sulfur component into the recording layer material arranged so as to be sandwiched between protective layers, thereby eliminating the deterioration of the recording layer.
In addition, pure Ag or Ag alloy having high reflectivity and high thermal conductivity has been used for the reflective layer material in order to increase the capacity and increase the recording speed, but the sulfur component to the adjacent reflective layer has been used. Diffusion is also eliminated, and the reflective layer material is similarly corroded and has an excellent effect of eliminating the cause of deterioration of characteristics such as reflectance of the optical information recording medium.
本発明のスパッタリングターゲットは、平均粒径が５μｍ以下である各構成元素の酸化物粉末を、常圧焼結又は高温加圧焼結することによって製造することができる。これによって、相対密度が９０％以上を有するスパッタリングターゲットが得られる。
使用する酸化物原料粉末は、化学量論的酸化物を使用する。すなわち酸素量の少ない酸化物粉末又は酸化物粉末に同種元素（金属）粉末を混合して、全体として酸素量を少なくする等の手法は採らない。
これによって、密度の高い均一なターゲットとすることができる。また、スパッタリング時に酸素量を常時調節する等の煩雑な工程を不要とし、さらに酸化膜の組成変動や面内バラツキが防止できるという著しい利点がある。密度の高く均一なターゲットは、スパッタ時に下記に示すパーティクル発生防止効果を有する。
The sputtering target of the present invention can be produced by atmospheric pressure sintering or high temperature pressure sintering of oxide powders of each constituent element having an average particle size of 5 μm or less. Thereby, a sputtering target having a relative density of 90% or more is obtained.
The oxide raw material powder used is a stoichiometric oxide. That is, there is no method of reducing the amount of oxygen as a whole by mixing an oxide powder with a small amount of oxygen or the same kind of element (metal) powder into an oxide powder.
As a result, a uniform target with high density can be obtained. Further, there is a significant advantage that a complicated process such as constantly adjusting the amount of oxygen at the time of sputtering is not required, and further, composition variation and in-plane variation of the oxide film can be prevented. A high density and uniform target has the following particle generation preventing effect during sputtering.
さらに、本発明のスパッタリングターゲットを使用することにより、生産性が向上し、品質の優れた材料を得ることができ、光ディスク保護膜をもつ光記録媒体を低コストで安定して製造できるという著しい効果がある。
本発明のスパッタリングターゲットの密度向上は、空孔を減少させ結晶粒を微細化し、ターゲットのスパッタ面を均一かつ平滑にすることができるので、スパッタリング時のパーティクルやノジュールを低減させ、さらにターゲットライフも長くすることができるという著しい効果を有し、品質のばらつきが少なく量産性を向上させることができる。
Furthermore, by using the sputtering target of the present invention, productivity is improved, a material with excellent quality can be obtained, and an optical recording medium having an optical disk protective film can be manufactured stably at low cost. There is.
The improvement in the density of the sputtering target of the present invention can reduce the number of vacancies, refine the crystal grains, and make the sputtering surface of the target uniform and smooth, thereby reducing particles and nodules during sputtering, and further improving the target life. It has a remarkable effect that it can be lengthened, and there is little variation in quality, so that mass productivity can be improved.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１−７）
４Ｎ相当で５μｍ以下のＳｉＯ２粉及び４Ｎ相当で平均粒径５μｍ以下のＺｒＯ２粉及びＨｆＯ２粉を準備し、表１に示す組成となるように調合し、平均粒径１μｍ相当まで湿式微粉砕した後、バインダーを添加してスプレードライヤーで造粒した。この造粒粉を冷間で加圧成形し、酸素雰囲気、１５００°Ｃで常圧焼結し、この焼結材を機械加工でターゲット形状に仕上げた。このターゲットの成分組成を表１に示す。
なお、表１に示す実施１〜３については、ＺｒＯ ２ 系であり、本願発明であるＨｆＯ ２ 系に直接関係する発明に該当しないが、参考として掲げる。
(Example 1-7)
4N equivalent SiO 2 powder of 5 μm or less and 4N equivalent ZrO 2 powder and HfO 2 powder having an average particle size of 5 μm or less were prepared and prepared so as to have the composition shown in Table 1. After grinding, a binder was added and granulated with a spray dryer. This granulated powder was pressure-formed cold and sintered under normal pressure in an oxygen atmosphere at 1500 ° C., and the sintered material was finished into a target shape by machining. The component composition of this target is shown in Table 1.
Note that Examples 1 to 3 shown in Table 1 are ZrO 2 systems and do not fall under the invention directly related to the HfO 2 system of the present invention, but are listed as a reference .
上記の仕上げ加工した６インチφサイズのターゲットを使用して、スパッタリングを行った。スパッタ条件は、ＲＦスパッタ、スパッタパワー１０００Ｗ、Ａｒガス圧０．５Ｐａとし、目標膜厚１５００Åで成膜した。
成膜サンプルの透過率（波長４０５ｎｍ）％、屈折率（波長４０５ｎｍ）、非晶質性（成膜サンプルのアニール処理（６００°Ｃ×３０ｍｉｎ、Ａｒ雰囲気）を施した、ＸＲＤ（Ｃｕ−Ｋα、４０ｋＶ、３０ｍＡ）による測定における２θ＝２０−６０°の範囲の未成膜ガラス基板に対する最大ピーク強度で表した）の測定した結果等を、まとめて表１に示す。
Sputtering was performed using the above-mentioned 6-inch φ-sized target that was finished. The sputtering conditions were RF sputtering, sputtering power 1000 W, Ar gas pressure 0.5 Pa, and a target film thickness of 1500 mm.
XRD (Cu-Kα, film-formed sample annealed (600 ° C. × 30 min, Ar atmosphere) subjected to transmittance (wavelength 405 nm)%, refractive index (wavelength 405 nm), amorphous (film sample annealing) Table 1 summarizes the measurement results and the like of the maximum peak intensity with respect to an undeposited glass substrate in the range of 2θ = 20-60 ° in the measurement at 40 kV, 30 mA).
以上の結果、実施例１−７のスパッタリングターゲットは、相対密度は９０以上に達し、安定したＲＦスパッタができた。
また、スパッタ膜の透過率は、９５〜９８％（４０５ｎｍ）に達し、屈折率は１．８〜２．１であり、また特定の結晶ピークは見られず、安定した非晶質性（１．０〜１．１）を有していた。
さらに、本実施例のターゲットは、ＺｎＳを使用していないので、硫黄の拡散・汚染による光情報記録媒体の特性劣化は生じない。また、後述する比較例に比べて、成膜サンプルの透過率、屈折率、非晶質の安定性が、いずれも良好な値を示した。
As a result, the sputtering target of Example 1-7 reached a relative density of 90 or more, and stable RF sputtering was possible.
Further, the transmittance of the sputtered film reaches 95 to 98% (405 nm), the refractive index is 1.8 to 2.1, no specific crystal peak is observed, and stable amorphous nature (1 0.0-1.1).
Furthermore, since the target of this example does not use ZnS, the characteristic deterioration of the optical information recording medium due to sulfur diffusion / contamination does not occur. Moreover, compared with the comparative example mentioned later, all of the transmittance | permeability, refractive index, and amorphous stability of the film-forming sample showed the favorable value.
（比較例１−６）
表１に示すように、本願発明の条件とは異なる原料粉の成分及び組成比の材料、特に比較例４においてはＺｎＳ原料粉を準備し、これを実施例と同様の条件で、ターゲットを作製し、かつこのターゲットを用いてスパッタ膜を形成した。
この結果を、同様に表１に示す。
(Comparative Example 1-6)
As shown in Table 1, a raw material component and composition ratio material different from the conditions of the present invention, in particular, Comparative Example 4 is prepared ZnS raw material powder, and a target is produced under the same conditions as in the examples. And a sputtered film was formed using this target.
The results are also shown in Table 1.
本発明の組成比から逸脱する比較例の成分・組成、例えば比較例１については、ガラス形成酸化物が全く含有されていないため、非晶質性が１．９と悪い結果となった。
比較例２は、Ｓｉ酸化物量が多いために、屈折率が基準よりも低下した。比較例３については、Ｓｉ酸化物量が多いために、屈折率が基準よりも低下した。また、特に比較例４は、ＺｎＳが多く含有されており、透過率が８０％と低く、また硫黄による汚染の危険のある材料であった。
The component / composition of the comparative example deviating from the composition ratio of the present invention, for example, comparative example 1, did not contain any glass-forming oxide, and thus the amorphousness was 1.9, which was a bad result.
In Comparative Example 2, since the amount of Si oxide was large, the refractive index was lower than the standard. In Comparative Example 3, since the amount of Si oxide was large, the refractive index was lower than the standard. In particular, Comparative Example 4 was a material that contained a large amount of ZnS, had a low transmittance of 80%, and had a risk of contamination with sulfur.
本発明のスパッタリングターゲットを使用して形成された薄膜は、光情報記録媒体の構造の一部を形成し、ＺｎＳを使用していないので、記録層材への硫黄成分の拡散がなくなり、これによる記録層の劣化がなくなるという著しい効果がある。また、隣接する高反射率で高熱伝導特性を有する純ＡｇまたはＡｇ合金を反射層に用いた場合には、該反射層への硫黄成分の拡散も無くなり、反射層が腐食劣化して特性劣化を引き起こす原因が一掃されるという優れた効果を有する。
さらに、非晶質性が安定化するとともにターゲットに導電性が付与され、相対密度を９０％以上の高密度化によって、安定したＲＦスパッタ成膜を可能とする。そして、スパッタの制御性を容易にし、スパッタリング効率を向上させることができるという著しい効果がある。さらにまた、成膜の際にスパッタ時に発生するパーティクル（発塵）やノジュールを低減し、品質のばらつきが少なく量産性を向上させることができ、光ディスク保護膜をもつ光記録媒体を低コストで安定して製造できるという著しい効果がある。
The thin film formed using the sputtering target of the present invention forms part of the structure of the optical information recording medium and does not use ZnS, so that there is no diffusion of the sulfur component into the recording layer material. There is a remarkable effect that the recording layer is not deteriorated. In addition, when pure Ag or Ag alloy having high heat conductivity and adjacent reflectivity is used for the reflection layer, diffusion of sulfur component to the reflection layer is eliminated, and the reflection layer is deteriorated due to corrosion deterioration. It has an excellent effect of causing the cause to be wiped out.
Further, the amorphousness is stabilized and the target is provided with conductivity, and the relative density is increased to 90% or more, thereby enabling stable RF sputtering film formation. And there exists a remarkable effect that the controllability of sputtering can be facilitated and the sputtering efficiency can be improved. Furthermore, particles (dust generation) and nodules generated during sputtering during film formation can be reduced, quality variations can be reduced, and mass productivity can be improved. Optical recording media with an optical disc protective film can be stably manufactured at low cost. There is a remarkable effect that it can be manufactured.
Claims (7)
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