JPH08267925A - Optical recording medium and production thereof - Google Patents
Optical recording medium and production thereofInfo
- Publication number
- JPH08267925A JPH08267925A JP7099944A JP9994495A JPH08267925A JP H08267925 A JPH08267925 A JP H08267925A JP 7099944 A JP7099944 A JP 7099944A JP 9994495 A JP9994495 A JP 9994495A JP H08267925 A JPH08267925 A JP H08267925A
- Authority
- JP
- Japan
- Prior art keywords
- recording layer
- layer
- recording
- recording medium
- optical recording
- 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.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000004544 sputter deposition Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- 230000000704 physical effect Effects 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 238000002310 reflectometry Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 82
- 239000010408 film Substances 0.000 description 15
- 239000011241 protective layer Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001947 vapour-phase growth Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- 229910003564 SiAlON Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Optical Record Carriers And Manufacture Thereof (AREA)
- Manufacturing Optical Record Carriers (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、追記型の光記録媒体
と、その製造方法とに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a write-once type optical recording medium and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】大容量情報記録媒体として、光記録ディ
スク等の光記録媒体が注目されている。光記録媒体とし
ては、相変化型光記録媒体や光磁気記録媒体等の書き換
え可能タイプ、あるいはピット形成型光記録媒体等の追
記タイプなどがある。2. Description of the Related Art As a large-capacity information recording medium, an optical recording medium such as an optical recording disk is drawing attention. The optical recording medium includes a rewritable type such as a phase change type optical recording medium and a magneto-optical recording medium, and a write-once type such as a pit formation type optical recording medium.
【０００３】近年、コンパクトディスク（以下、ＣＤと
略称する）規格に対応して追記を行なうことのできる光
記録ディスクが実用化されている。この光記録ディスク
は、透明樹脂基板上に、色素層、Ａｕ反射層および保護
膜をこの順に設層して形成され、ＣＤ規格に対応した７
０％以上の反射率を示すものである。In recent years, an optical recording disc has been put into practical use, which enables additional recording in conformity with the compact disc (hereinafter abbreviated as CD) standard. This optical recording disc was formed by forming a dye layer, an Au reflecting layer and a protective film in this order on a transparent resin substrate, and was formed in compliance with the CD standard.
It shows a reflectance of 0% or more.
【０００４】しかし、この光記録ディスクは波長選択性
が強く、現在のＣＤプレーヤで使用されている７８０nm
付近以外の波長域では７０％以上の反射率を得ることが
できない。このため、７００nmを下回るような短波長の
レーザ光を用いる高密度記録対応の装置で使用すること
が難しい。However, this optical recording disk has a strong wavelength selectivity, and is 780 nm used in the present CD player.
It is not possible to obtain a reflectance of 70% or more in wavelength regions other than the vicinity. For this reason, it is difficult to use it in an apparatus compatible with high-density recording using a laser beam having a short wavelength of less than 700 nm.
【０００５】ところで、追記型の記録層材料としてＳｂ
2 Ｓ3 を用いることが提案されている（特開平３−２４
１５３７号公報、同３−２４０５８９号公報、同３−２
４８８８４号公報、同４−１０５２２６号公報）。これ
らの提案における光情報記録媒体では、Ｓｂ2 Ｓ3 の熱
伝導率の低さを利用して記録レーザ光照射部で蓄熱によ
り温度を上昇させ、これにより基板を変形させて記録ピ
ットを形成する。しかし、これらの提案において、７８
０nmより短い波長域で７０％以上の反射率を実現した実
施例はない。By the way, Sb is used as a write-once recording layer material.
It has been proposed to use 2 S 3 (Japanese Patent Laid-Open No. 3-24).
No. 1537, No. 3-240589, No. 3-2
48884 and 4-105226). In the optical information recording media in these proposals, the low thermal conductivity of Sb 2 S 3 is used to increase the temperature by heat storage in the recording laser light irradiation section, thereby deforming the substrate to form a recording pit. . However, in these proposals, 78
There is no example in which a reflectance of 70% or more is realized in a wavelength range shorter than 0 nm.
【０００６】上記特開平３−２４０５８９号公報では、
Ａｒ＋Ｎ2 雰囲気中でスパッタすることによりＳｂ2 Ｓ
3 膜中へＮ2 をトラップし、これによりＳｂ2 Ｓ3 膜の
屈折率、消衰係数を小さくしている。同公報では、Ｎ2
トラップによりＳｂ2 Ｓ3 膜を熱的に安定な非晶質とし
て相変化による影響をなくし、記録特性および耐候性を
改善したとしている。しかし、本発明者らの実験によれ
ば、Ａｒ＋Ｎ2 雰囲気中でスパッタしても、Ｓｂ2 Ｓ3
膜中へのＮ2 トラップは認められなかった。In the above-mentioned Japanese Laid-Open Patent Publication No. 3-240589,
Sb 2 S by sputtering in Ar + N 2 atmosphere
The N 2 trap to 3 film, thereby Sb 2 S 3 film refractive index of, and reduce the extinction coefficient. In this publication, N 2
It is said that the trap makes the Sb 2 S 3 film a thermally stable amorphous material to eliminate the influence of the phase change and improve the recording characteristics and weather resistance. However, according to the experiments conducted by the present inventors, even if sputtering is performed in an Ar + N 2 atmosphere, Sb 2 S 3
No N 2 trap was found in the film.
【０００７】また、上記特開平３−２４８８８４号公報
では、Ｓｂ2 Ｓ3 膜の形成に蒸着法を用いることにより
複素屈折率を制御し、７０％以上の反射率を得ている。
同公報には、スパッタ法を用いると反射率７０％以上は
実現できない旨の記載がある。しかし、同公報において
７０％以上の反射率を確認しているのは波長７８０nmに
おいてだけである。同公報の実施例では、厚さ１１０nm
の記録層を蒸着法により形成しているが、蒸着法は精密
な膜厚制御が難しいので、均質性の高い膜をこのように
薄く形成することは、生産工程上は困難である。Further, in the above-mentioned Japanese Patent Laid-Open No. 3-248884, the complex refractive index is controlled by using the vapor deposition method to form the Sb 2 S 3 film, and the reflectance of 70% or more is obtained.
The publication describes that a reflectance of 70% or more cannot be realized by using the sputtering method. However, in the publication, the reflectance of 70% or more is confirmed only at the wavelength of 780 nm. In the example of the publication, the thickness is 110 nm.
The recording layer of No. 1 is formed by the vapor deposition method. However, since it is difficult to precisely control the film thickness by the vapor deposition method, it is difficult in the production process to form such a thin film having high homogeneity.
【０００８】媒体の反射率や記録感度などの各種特性の
制御のためには、図１に示すように記録層３上に誘電体
層４と反射層５とを積層する構成とすることが好まし
い。この場合、反射率は、各層の物性や厚さなどを適宜
設定することにより制御し、記録感度、変調度、ジッタ
ー、クロストーク等の各種特性も、媒体の熱的設計、す
なわち各層の材質や厚さなどを適宜設定することにより
制御する。このとき、記録層の物性制御の範囲が狭い
と、反射率とそれ以外の各種特性とを両立させることが
難しくなる。上述したように特開平３−２４８８８４号
公報では、Ｓｂ2 Ｓ3 膜の複素屈折率を所望の値とする
ために蒸着法を用いているが、広範囲にわたって複素屈
折率を制御できる蒸着法は開示されていない。In order to control various characteristics such as the reflectivity and recording sensitivity of the medium, it is preferable that the dielectric layer 4 and the reflective layer 5 are laminated on the recording layer 3 as shown in FIG. . In this case, the reflectance is controlled by appropriately setting the physical properties and thickness of each layer, and various characteristics such as recording sensitivity, modulation degree, jitter, and crosstalk are also determined by the thermal design of the medium, that is, the material of each layer and It is controlled by appropriately setting the thickness and the like. At this time, if the control range of the physical properties of the recording layer is narrow, it becomes difficult to achieve both reflectance and various other properties. As described above, in Japanese Patent Laid-Open No. 3-248884, the vapor deposition method is used to set the complex refractive index of the Sb 2 S 3 film to a desired value, but a vapor deposition method capable of controlling the complex refractive index over a wide range is disclosed. It has not been.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、長波
長域から短波長域にわたって高反射率が得られ、また、
記録層の物性が容易かつ広範囲に制御可能な追記型の光
記録媒体を提供することである。The object of the present invention is to obtain a high reflectance from a long wavelength region to a short wavelength region, and
An object of the present invention is to provide a write-once type optical recording medium in which the physical properties of the recording layer can be easily controlled in a wide range.
【００１０】[0010]
【課題を解決するための手段】このような目的は下記
（１）〜（３）のいずれかの構成によって達成される。 （１）基板表面に、記録層および反射層をこの順で有
し、記録層がＳｂの硫化物と金属状態のＳｂとを含有
し、記録層中において全Ｓｂに対する金属状態のＳｂの
比率が２０〜５０原子％である光記録媒体。 （２）記録層が実質的に窒素を含有しない上記（１）の
光記録媒体。 （３）基板表面に、記録層および反射層をこの順で有す
る光記録媒体を製造する方法であって、ターゲットとし
て硫化アンチモンを用い、ＡｒおよびＮ2 を含む雰囲気
中でスパッタ法により記録層を形成する工程を有し、こ
の工程における雰囲気中の分圧比Ｎ2 ／Ａｒが５％超２
０％以下である光記録媒体の製造方法。Such an object is achieved by any of the following constitutions (1) to (3). (1) The substrate surface has a recording layer and a reflective layer in this order, the recording layer contains a sulfide of Sb and Sb in a metallic state, and the ratio of Sb in the metallic state to all Sb in the recording layer is An optical recording medium of 20 to 50 atomic%. (2) The optical recording medium according to (1) above, wherein the recording layer does not substantially contain nitrogen. (3) A method for manufacturing an optical recording medium having a recording layer and a reflective layer in this order on the surface of a substrate, wherein antimony sulfide is used as a target, and the recording layer is formed by a sputtering method in an atmosphere containing Ar and N 2. And a partial pressure ratio N 2 / Ar in the atmosphere in this step is more than 5% 2
A method for producing an optical recording medium, which is 0% or less.
【００１１】[0011]
【作用および効果】図１に示されるように、本発明の光
記録媒体は、基板２の表面に、記録層３および反射層５
を有する。As shown in FIG. 1, the optical recording medium of the present invention has the recording layer 3 and the reflective layer 5 on the surface of the substrate 2.
Have.
【００１２】記録時には、基板２の裏面側から基板２を
通して記録レーザ光が照射され、記録層３が加熱され
る。記録層はＳｂの硫化物と金属状態のＳｂとを含有
し、熱伝導率が低いので、記録レーザ光照射部は蓄熱に
より温度が上昇し、基板が変形する。また、相変化等の
膜質の変化が生じることもある。これらにより照射部の
多重反射条件が変化し、反射率が変化して記録ピットと
なる。このようにして生じる光反射率の変化は不可逆的
であるので、追記型の光記録媒体として使用することが
できる。At the time of recording, a recording laser beam is irradiated from the back side of the substrate 2 through the substrate 2 to heat the recording layer 3. Since the recording layer contains sulfide of Sb and Sb in a metallic state and has a low thermal conductivity, the temperature of the recording laser light irradiation portion rises due to heat storage, and the substrate is deformed. Moreover, a change in film quality such as a phase change may occur. As a result, the multiple reflection condition of the irradiation portion changes, and the reflectance changes to form a recording pit. Since the change of the light reflectance thus generated is irreversible, it can be used as a write-once type optical recording medium.
【００１３】本発明では、記録層中において全Ｓｂに対
する金属状態のＳｂの比率を所定範囲に制御するので、
ＣＤに対して用いられている７８０nm近傍での光の反射
率を未記録部で７０％以上とすることが可能であり、ま
た、変調度を３０％以上とすることができるので、ＣＤ
プレーヤで再生可能な追記型光記録ディスクとしての使
用が可能である。そして、７００nm以下、特に６００〜
７００nmの短波長域においてもこのような反射率を得る
ことが可能なので、短波長レーザ光を用いる高密度記録
にも対応することができる。しかも、金属状態のＳｂの
比率の制御により記録層の複素屈折率を広範囲に変更で
きるため、媒体設計の自由度が高くなり、高反射率と適
度な記録感度とが共に得られ、また、同時に、高変調
度、低ジッター、低クロストークも実現可能である。In the present invention, the ratio of metallic Sb to total Sb in the recording layer is controlled within a predetermined range.
Since the reflectance of light near 780 nm, which is used for CD, can be 70% or more in the unrecorded portion, and the modulation degree can be 30% or more, the CD
It can be used as a write-once type optical recording disk which can be reproduced by a player. And 700 nm or less, especially 600 ~
Since such a reflectance can be obtained even in a short wavelength region of 700 nm, it is possible to support high density recording using short wavelength laser light. Moreover, since the complex refractive index of the recording layer can be changed over a wide range by controlling the ratio of Sb in the metallic state, the degree of freedom in medium design is increased, and high reflectance and appropriate recording sensitivity can be obtained at the same time. High modulation, low jitter, and low crosstalk are also possible.
【００１４】[0014]
【具体的構成】以下、本発明の具体的構成について詳細
に説明する。Specific Structure The specific structure of the present invention will be described in detail below.
【００１５】図１に本発明の光記録媒体の構成例を示
す。この光記録媒体は、基板２の表面に、記録層３、誘
電体層４および反射層５をこの順で有し、反射層５上に
は保護層６が設けられている。FIG. 1 shows an example of the structure of the optical recording medium of the present invention. This optical recording medium has a recording layer 3, a dielectric layer 4, and a reflective layer 5 in this order on the surface of a substrate 2, and a protective layer 6 is provided on the reflective layer 5.
【００１６】＜基板２＞光記録媒体１では、基板２を通
して記録層３に記録光および再生光が照射されるので、
基板２はこれらの光に対して実質的に透明である必要が
ある。また、基板２は、記録層３の温度上昇により変形
する必要があるので、基板２の材質としては樹脂が好ま
しい。具体的には、アクリル樹脂、ポリカーボネート樹
脂、エポキシ樹脂、ポリオレフィン樹脂等の各種樹脂を
用いればよい。ただし、基板にガラスを用い、基板と記
録層との間に樹脂膜を形成して、この樹脂膜を変形させ
る構成としてもよい。<Substrate 2> In the optical recording medium 1, since the recording layer 3 is irradiated with the recording light and the reproducing light through the substrate 2,
The substrate 2 needs to be substantially transparent to these lights. Further, since the substrate 2 needs to be deformed due to the temperature rise of the recording layer 3, the material of the substrate 2 is preferably resin. Specifically, various resins such as acrylic resin, polycarbonate resin, epoxy resin, and polyolefin resin may be used. However, glass may be used for the substrate, a resin film may be formed between the substrate and the recording layer, and the resin film may be deformed.
【００１７】基板２の形状および寸法は特に限定されな
いが、通常、ディスク状であり、その厚さは、通常、
０．５〜３mm程度、直径は５０〜３６０mm程度である。The shape and size of the substrate 2 are not particularly limited, but are usually disk-shaped, and their thickness is usually
The diameter is about 0.5 to 3 mm and the diameter is about 50 to 360 mm.
【００１８】基板２の表面には、トラッキング用やアド
レス用等のために、グルーブ等の所定のパターンが必要
に応じて設けられる。例えば、図示例の光記録媒体には
グルーブが設けられており、記録光は、通常、グルーブ
内に照射される。A predetermined pattern such as a groove is provided on the surface of the substrate 2 for tracking, addressing, etc., if necessary. For example, the optical recording medium of the illustrated example is provided with a groove, and the recording light is normally applied to the inside of the groove.
【００１９】＜記録層３＞記録層３は、Ｓｂの硫化物と
金属状態のＳｂとを含有する。記録層中において、全Ｓ
ｂに対する金属状態のＳｂの比率は、２０〜５０原子
％、好ましくは２５〜４５原子％である。金属状態のＳ
ｂの比率が低すぎると、消衰係数（複素屈折率の虚部）
ｋが零に近づくため感度が低くなってしまい、一方、金
属状態のＳｂの比率が高すぎると、消衰係数ｋが大きく
なりすぎて高反射率が得られなくなるので、いずれの場
合も高反射率と適度な記録感度との両立が難しくなる。
なお、波長７８０nmにおける記録層の消衰係数ｋは、好
ましくは０．１０〜０．３０であり、より好ましくは
０．１５〜０．２５である。また、波長７８０nmにおけ
る記録層の屈折率（複素屈折率の実部）ｎは、好ましく
は３．０〜３．３程度である。<Recording Layer 3> The recording layer 3 contains a sulfide of Sb and Sb in a metallic state. All S in the recording layer
The ratio of metallic Sb to b is 20 to 50 atom%, preferably 25 to 45 atom%. S in metallic state
If the ratio of b is too low, the extinction coefficient (imaginary part of complex refractive index)
Since k approaches zero, the sensitivity becomes low. On the other hand, if the ratio of Sb in the metallic state is too high, the extinction coefficient k becomes too large and high reflectance cannot be obtained. It becomes difficult to achieve both high rate and appropriate recording sensitivity.
The extinction coefficient k of the recording layer at a wavelength of 780 nm is preferably 0.10 to 0.30, more preferably 0.15 to 0.25. The refractive index (real part of complex refractive index) n of the recording layer at a wavelength of 780 nm is preferably about 3.0 to 3.3.
【００２０】本発明では、このように金属状態のＳｂの
比率を制御することにより、記録層のｋ、ｎを制御でき
るので、媒体の熱的設計を最適化するために記録層や誘
電体層の厚さを大きく変更した場合でも、高い反射率を
得ることが可能である。In the present invention, since the k and n of the recording layer can be controlled by controlling the ratio of Sb in the metal state as described above, the recording layer and the dielectric layer can be optimized to optimize the thermal design of the medium. It is possible to obtain a high reflectance even when the thickness of is significantly changed.
【００２１】Ｓｂの硫化物および金属状態のＳｂの量
は、ＥＳＣＡなどにより測定することができる。ＥＳＣ
Ａでの測定に際しては、まず、Ａｒスパッタイオン銃で
０．５〜３kV程度にて表面吸着炭素や酸化層等を除去し
た後、Ｍｇ−ＫαやＡｌ−Ｋαのアノードを用いたＸ線
銃でＳｂ3d5/2 のＥＳＣＡスペクトルを測定し、ケミカ
ルシフトの違いから金属状態のＳｂの比率を求める。具
体的には、Ｓｂ3d5/2 のスペクトルにおいて、直線を用
いてバックグラウンドを除き、半値幅の等価な２つのガ
ウシアンのピーク値を１．０〜１．５eVの間隔に保って
カーブフィッティングし、得られた両者の積分強度から
原子百分率を求める。このとき、高エネルギー側のピー
クがＳｂ硫化物で、低エネルギー側のピークが金属Ｓｂ
である。The amount of Sb sulfide and Sb in the metallic state can be measured by ESCA or the like. ESC
At the time of measurement at A, first, after removing the surface adsorbed carbon and oxide layers with an Ar sputter ion gun at about 0.5 to 3 kV, with an X-ray gun using Mg-Kα or Al-Kα anodes. The ESCA spectrum of Sb3d5 / 2 is measured, and the ratio of Sb in the metallic state is obtained from the difference in chemical shift. Specifically, in the Sb3d5 / 2 spectrum, a straight line was used to remove the background, and curve fitting was performed by keeping the peak values of two Gaussians having an equivalent half-value width at intervals of 1.0 to 1.5 eV. The atomic percentage is calculated from the integrated intensities of the two obtained. At this time, the peak on the high energy side is Sb sulfide, and the peak on the low energy side is metal Sb.
Is.
【００２２】記録層の厚さは、記録層の物性、誘電体層
の物性およびその厚さに応じて適宜決定するが、好まし
くは１０〜３００nm、より好ましくは３０〜２００nmと
する。記録層が薄すぎると変調度を大きくすることが困
難となり、厚すぎると記録層での光吸収のために反射率
が不十分となる。The thickness of the recording layer is appropriately determined according to the physical properties of the recording layer, the physical properties of the dielectric layer and the thickness thereof, but is preferably 10 to 300 nm, more preferably 30 to 200 nm. If the recording layer is too thin, it becomes difficult to increase the degree of modulation, and if it is too thick, the reflectance is insufficient due to light absorption in the recording layer.
【００２３】記録層３は、スパッタ法や蒸着法などの気
相成長法により形成することが好ましく、特に、ターゲ
ットとしてＳｂ2 Ｓ3 等の硫化アンチモンを用い、Ａｒ
およびＮ2 を含む雰囲気中でスパッタ法により形成する
ことが好ましい。この方法では、雰囲気中の分圧比Ｎ2
／Ａｒを、好ましくは５％超２０％以下、より好ましく
は７〜１５％とする。この分圧比が低すぎると金属状態
のＳｂの比率が高くなりすぎる傾向があり、この分圧比
が高すぎると金属状態のＳｂの比率が低くなりすぎる傾
向がある。The recording layer 3 is preferably formed by a vapor phase growth method such as a sputtering method or a vapor deposition method. In particular, antimony sulfide such as Sb 2 S 3 is used as a target and Ar is used.
It is preferably formed by a sputtering method in an atmosphere containing N 2 and N 2 . In this method, the partial pressure ratio N 2 in the atmosphere is
/ Ar is preferably more than 5% and 20% or less, more preferably 7 to 15%. If this partial pressure ratio is too low, the ratio of Sb in the metallic state tends to be too high, and if this partial pressure ratio is too high, the ratio of Sb in the metallic state tends to be too low.
【００２４】ターゲットとして硫化アンチモンを用い、
Ａｒ中で放電を行なうと、Ｓｂに対し軽元素であるＳは
スパッタ膜中に入りづらいため、スパッタ膜はターゲッ
ト組成に対しＳｂリッチとなり、膜中には金属状態のＳ
ｂが存在することになる。スパッタ雰囲気中にＡｒ以外
の不活性ガス（Ｎ2 、Ｘｅ、Ｋｒ等）を加えれば、金属
状態のＳｂの比率が減少し、膜の光学定数を変化させる
ことができる。本発明では、Ａｒ＋Ｎ2 雰囲気中でＮ2
の分圧比を上記のように制御することにより、最適な光
学定数をもつ記録層を形成することができる。なお、上
記した記録層が形成できるのであれば、Ｎ2 以外の不活
性ガスを用いてもよい。また、ターゲットの硫化アンチ
モンとしては、通常、Ｓｂ2 Ｓ3 を用いるが、化学量論
組成からはずれたものを用いてもよい。さらに、化学量
論組成からはずれたターゲットを用いることにより、Ａ
ｒ以外の不活性ガスを用いないで上記記録層を形成して
もよい。Using antimony sulfide as a target,
When discharged in Ar, S, which is a light element with respect to Sb, is hard to enter into the sputtered film, so the sputtered film becomes rich in Sb with respect to the target composition, and S in the metallic state is contained in the film.
b will exist. If an inert gas other than Ar (N 2 , Xe, Kr, etc.) is added to the sputtering atmosphere, the ratio of Sb in the metallic state is reduced, and the optical constant of the film can be changed. In the present invention, N 2 in Ar + N 2 atmosphere
By controlling the partial pressure ratio of the above as described above, a recording layer having an optimum optical constant can be formed. An inert gas other than N 2 may be used as long as the recording layer described above can be formed. Further, as the target antimony sulfide, Sb 2 S 3 is usually used, but those deviating from the stoichiometric composition may be used. Furthermore, by using a target out of the stoichiometric composition, A
The recording layer may be formed without using an inert gas other than r.
【００２５】なお、スパッタ時の雰囲気圧力は、通常、
０．１〜１０Pa程度とすることが好ましい。The atmospheric pressure during sputtering is usually
It is preferably about 0.1 to 10 Pa.
【００２６】このようにして形成された記録層は非晶質
であり、Ｓｂの硫化物と金属状態のＳｂとが混在してい
ると考えられる。The recording layer thus formed is amorphous, and it is considered that Sb sulfide and metallic Sb are mixed.
【００２７】Ｓｂの硫化物をＳｂ2 Ｓx で表わしたと
き、ｘは、通常、３〜５程度であることが好ましいが、
ｘ＜３の硫化物が存在していてもよい。When the sulfide of Sb is represented by Sb 2 S x , x is usually preferably about 3 to 5,
Sulfides with x <3 may be present.
【００２８】記録層中には、単体のＳが含まれていても
よい。また、記録層中には、ＳｂおよびＳの他、例えば
Ｓｅ、Ｔｅ、Ａｓ、Ｓｉ、Ｇｅ等の１種以上が含まれて
いてもよいが、これらの元素の合計は２０原子％以下で
あることが好ましい。A single S may be contained in the recording layer. The recording layer may contain one or more of Se, Te, As, Si, Ge, etc. in addition to Sb and S, but the total of these elements is 20 atomic% or less. It is preferable.
【００２９】なお、Ａｒ＋Ｎ2 雰囲気中でスパッタを行
なっても、通常、記録層中の窒素はＥＳＣＡの検出限界
以下であり、実質的に認められない。Even when sputtering is performed in an Ar + N 2 atmosphere, nitrogen in the recording layer is usually below the detection limit of ESCA and is not substantially recognized.
【００３０】＜誘電体層４＞誘電体層４は、各種誘電体
から構成される。用いる誘電体は特に限定されず、透明
な各種セラミックスや各種ガラスなどを用いればよく、
例えば、酸化ケイ素、窒化ケイ素、硫化亜鉛等の各種酸
化物、窒化物、硫化物やこれらの混合物、あるいは、Ｌ
ａ、Ｓｉ、ＯおよびＮを含有するいわゆるLaSiON、Ｓ
ｉ、Ａｌ、ＯおよびＮを含有するいわゆるSiAlON、ある
いはＹを含有するSiAlON等を用いればよい。<Dielectric Layer 4> The dielectric layer 4 is made of various dielectrics. The dielectric used is not particularly limited, and various transparent ceramics or various glasses may be used,
For example, various oxides such as silicon oxide, silicon nitride and zinc sulfide, nitrides, sulfides and mixtures thereof, or L
So-called LaSiON, S containing a, Si, O and N
So-called SiAlON containing i, Al, O and N, or SiAlON containing Y may be used.
【００３１】誘電体層４の厚さは、用いる誘電体の物性
や記録層の物性および厚さなどに応じ、必要とされる波
長範囲において高反射率および最適な記録感度が得られ
るように適宜設定すればよいが、通常、２０〜５００n
m、特に３０〜３００nmの範囲から選択することが好ま
しい。The thickness of the dielectric layer 4 depends on the physical properties of the dielectric used, the physical properties and thickness of the recording layer, etc., so that high reflectance and optimum recording sensitivity can be obtained in the required wavelength range. It can be set, but usually 20-500n
It is preferable to select m, especially in the range of 30 to 300 nm.
【００３２】誘電体層４は、スパッタ法や蒸着法等の気
相成長法により形成されることが好ましい。The dielectric layer 4 is preferably formed by a vapor phase growth method such as a sputtering method or a vapor deposition method.
【００３３】＜反射層５＞反射層５は、高反射率の金属
や合金から構成することが好ましく、例えば、Ａｇ、Ａ
ｌ、Ａｕ、Ｐｔ、Ｃｕ等の１種、またはこれらを少なく
とも１種含む合金などから適宜選択すればよい。<Reflective Layer 5> The reflective layer 5 is preferably made of a metal or alloy having a high reflectance, for example, Ag or A.
It may be appropriately selected from one kind such as 1, Au, Pt, and Cu, or an alloy containing at least one of these.
【００３４】反射層５の厚さは、３０〜１５０nmとする
ことが好ましい。厚さが前記範囲未満であると十分な反
射率が得にくくなる。また、前記範囲を超えても反射率
の向上は小さく、コスト的に不利になる。The thickness of the reflective layer 5 is preferably 30 to 150 nm. If the thickness is less than the above range, it becomes difficult to obtain sufficient reflectance. Further, even if it exceeds the above range, the improvement in reflectance is small, which is disadvantageous in terms of cost.
【００３５】反射層５は、スパッタ法や蒸着法等の気相
成長法により形成することが好ましい。The reflective layer 5 is preferably formed by a vapor phase growth method such as a sputtering method or a vapor deposition method.
【００３６】＜保護層６＞保護層６は、耐擦傷性や耐食
性の向上のために設けるものであり、種々の有機系の物
質から構成することが好ましいが、特に、放射線硬化型
化合物やその組成物を、電子線、紫外線等の放射線によ
り硬化させた物質から構成することが好ましい。<Protective Layer 6> The protective layer 6 is provided to improve scratch resistance and corrosion resistance, and is preferably composed of various organic substances, and particularly, the radiation curable compound and its compound. The composition is preferably composed of a substance cured by radiation such as electron beam or ultraviolet ray.
【００３７】保護層６の厚さは、通常、０．１〜１００
μm 程度であり、スピンコート、グラビア塗布、スプレ
ーコート、ディッピング等、通常の方法により形成すれ
ばよい。The thickness of the protective layer 6 is usually 0.1-100.
It is about μm, and it may be formed by a usual method such as spin coating, gravure coating, spray coating, or dipping.
【００３８】＜媒体構造＞以上では、本発明を片面記録
型の光記録媒体に適用する場合について説明したが、本
発明は両面記録型の光記録媒体にも適用可能である。両
面記録型の光記録媒体に適用する場合、一対の基板２、
２を、記録層３が内封されるように接着する。また、片
面記録型であって、保護層６上に保護板を接着した構成
とすることもできる。この場合の保護板としては、通
常、基板２と同質のものを用いればよいが、透明である
必要はなく、その他の材質も用いることができる。<Medium Structure> The case where the present invention is applied to a single-sided recording type optical recording medium has been described above, but the present invention is also applicable to a double-sided recording type optical recording medium. When applied to a double-sided recording type optical recording medium, a pair of substrates 2,
2 is adhered so that the recording layer 3 is enclosed. It is also possible to adopt a single-sided recording type in which a protective plate is bonded onto the protective layer 6. In this case, the protective plate may be made of the same material as the substrate 2, but it does not have to be transparent, and other materials can be used.
【００３９】[0039]
【実施例】以下、本発明の具体的実施例を挙げ、本発明
をさらに詳細に説明する。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the present invention.
【００４０】＜実施例１＞基板２の表面に、記録層３、
誘電体層４、反射層５および保護層６を形成し、図１に
示される構成の光記録ディスクサンプルを作製した。<Example 1> On the surface of the substrate 2, the recording layer 3,
The dielectric layer 4, the reflective layer 5, and the protective layer 6 were formed, and an optical recording disk sample having the structure shown in FIG. 1 was produced.
【００４１】基板２には、射出成形によりグルーブを同
時形成した直径１２０mm、厚さ１．２mmのディスク状ポ
リカーボネート樹脂を用いた。For the substrate 2, a disc-shaped polycarbonate resin having a diameter of 120 mm and a thickness of 1.2 mm in which grooves were simultaneously formed by injection molding was used.
【００４２】記録層３は、Ｓｂ2 Ｓ3 ターゲットを使用
し、ＡｒおよびＮ2 からなる雰囲気中で分圧比Ｎ2 ／Ａ
ｒを０．１０として、スパッタ法により形成した。記録
層３の厚さは１５０nmとした。この記録層中の全Ｓｂに
対する金属状態のＳｂの比率を調べたところ、３８％で
あった。なお、金属状態のＳｂの比率は、前述した方法
にしたがってＥＳＣＡにより測定した。ＥＳＣＡの条件
は、 Ｘ線：Ｍｇ−Ｋα １２ kV −２０ mA 、 静電レンズ：２mmφ、 ＰＥ：４０eV、 カウフマン型イオン銃：０．５ kV −３０ mA とした。The recording layer 3 uses a Sb 2 S 3 target and has a partial pressure ratio N 2 / A in an atmosphere consisting of Ar and N 2.
It was formed by a sputtering method with r set to 0.10. The thickness of the recording layer 3 was 150 nm. When the ratio of metallic Sb to all Sb in this recording layer was examined, it was 38%. The ratio of Sb in the metallic state was measured by ESCA according to the method described above. The ESCA conditions were X-ray: Mg-Kα 12 kV -20 mA, electrostatic lens: 2 mmφ, PE: 40 eV, Kauffman type ion gun: 0.5 kV -30 mA.
【００４３】誘電体層４は、ＺｎＳおよびＳｉＯ2 をタ
ーゲットとしてスパッタ法により形成した。ＺｎＳ：Ｓ
ｉＯ2 （モル比）は８５：１５とし、厚さは１８０nmと
した。The dielectric layer 4 was formed by sputtering using ZnS and SiO 2 as targets. ZnS: S
The iO 2 (molar ratio) was 85:15 and the thickness was 180 nm.
【００４４】反射層５は、Ａｕをターゲットとしてスパ
ッタ法により１００nmの厚さに形成した。The reflective layer 5 was formed to a thickness of 100 nm by a sputtering method using Au as a target.
【００４５】保護層６は、紫外線硬化型樹脂をスピンコ
ート法により塗布後、紫外線照射により硬化して形成し
た。硬化後の厚さは５μm であった。The protective layer 6 was formed by applying a UV-curable resin by spin coating and then curing it by irradiating it with UV light. The thickness after curing was 5 μm.
【００４６】このようにして作製したサンプルに、記録
パワー８．５mWでＥＦＭ信号を記録した。このサンプル
の未記録部における反射率は、波長７８０nmで７５％、
波長６３５nmで７０％であり、また、７８０nmおよび６
３５nmでの３Ｔ信号の変調度はいずれも３０％以上であ
った。An EFM signal was recorded on the sample thus manufactured with a recording power of 8.5 mW. The reflectance of the unrecorded portion of this sample is 75% at a wavelength of 780 nm,
70% at a wavelength of 635 nm, and 780 nm and 6
The degree of modulation of the 3T signal at 35 nm was 30% or more.
【００４７】なお、このサンプルの記録層の消衰係数は
０．１８、複素屈折率は３．２０であった。The extinction coefficient of the recording layer of this sample was 0.18 and the complex refractive index was 3.20.
【００４８】＜実施例２＞実施例１と同様にして、基板
上に記録層を形成した。この実施例では、記録層形成時
の雰囲気中の分圧比Ｎ2 ／Ａｒを変更し、記録層中の全
Ｓｂに対する金属状態のＳｂの比率を調べた。また、記
録層の消衰係数ｋおよび屈折率ｎを、波長７８０nmにて
測定した。結果を表１に示す。<Example 2> In the same manner as in Example 1, a recording layer was formed on the substrate. In this example, the partial pressure ratio N 2 / Ar in the atmosphere during formation of the recording layer was changed, and the ratio of Sb in the metal state to the total Sb in the recording layer was investigated. The extinction coefficient k and the refractive index n of the recording layer were measured at a wavelength of 780 nm. The results are shown in Table 1.
【００４９】[0049]
【表１】 [Table 1]
【００５０】表１から、Ｎ2 ／Ａｒを制御することによ
り、記録層中の金属状態のＳｂの比率を広範囲にわたっ
て変更できることがわかる。It can be seen from Table 1 that the ratio of Sb in the metal state in the recording layer can be changed over a wide range by controlling N 2 / Ar.
【００５１】なお、ＥＳＣＡによる分析では、上記実施
例で形成した記録層中に窒素は検出されなかった。In the analysis by ESCA, nitrogen was not detected in the recording layer formed in the above example.
【図１】本発明の光記録媒体の構成例を示す部分断面図
である。FIG. 1 is a partial cross-sectional view showing a configuration example of an optical recording medium of the present invention.
２ 基板 ３ 記録層 ４ 誘電体層 ５ 反射層 ６ 保護層 2 substrate 3 recording layer 4 dielectric layer 5 reflective layer 6 protective layer
Claims (3)
順で有し、記録層がＳｂの硫化物と金属状態のＳｂとを
含有し、記録層中において全Ｓｂに対する金属状態のＳ
ｂの比率が２０〜５０原子％である光記録媒体。1. A recording layer and a reflective layer are provided in this order on a surface of a substrate, the recording layer contains a sulfide of Sb and Sb in a metallic state, and S in a metallic state for all Sb in the recording layer.
An optical recording medium in which the ratio of b is 20 to 50 atomic%.
項１の光記録媒体。2. The optical recording medium according to claim 1, wherein the recording layer contains substantially no nitrogen.
順で有する光記録媒体を製造する方法であって、ターゲ
ットとして硫化アンチモンを用い、ＡｒおよびＮ2 を含
む雰囲気中でスパッタ法により記録層を形成する工程を
有し、この工程における雰囲気中の分圧比Ｎ2 ／Ａｒが
５％超２０％以下である光記録媒体の製造方法。3. A method for manufacturing an optical recording medium having a recording layer and a reflective layer in this order on a substrate surface, wherein antimony sulfide is used as a target, and recording is performed by a sputtering method in an atmosphere containing Ar and N 2. A method for producing an optical recording medium, which has a step of forming a layer, and in which the partial pressure ratio N 2 / Ar in the atmosphere is more than 5% and 20% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7099944A JPH08267925A (en) | 1995-03-31 | 1995-03-31 | Optical recording medium and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7099944A JPH08267925A (en) | 1995-03-31 | 1995-03-31 | Optical recording medium and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08267925A true JPH08267925A (en) | 1996-10-15 |
Family
ID=14260826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7099944A Pending JPH08267925A (en) | 1995-03-31 | 1995-03-31 | Optical recording medium and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08267925A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008096680A1 (en) * | 2007-02-09 | 2008-08-14 | Panasonic Corporation | Information recording medium, process for producing the information recording medium, sputtering target, and film forming apparatus |
-
1995
- 1995-03-31 JP JP7099944A patent/JPH08267925A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008096680A1 (en) * | 2007-02-09 | 2008-08-14 | Panasonic Corporation | Information recording medium, process for producing the information recording medium, sputtering target, and film forming apparatus |
| US8273438B2 (en) | 2007-02-09 | 2012-09-25 | Panasonic Corporation | Information recording medium, process for producing the information recording medium, sputtering target and film forming apparatus |
| JP5226537B2 (en) * | 2007-02-09 | 2013-07-03 | パナソニック株式会社 | Information recording medium, method for manufacturing the same, sputtering target, and film forming apparatus |
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