JPH0444812B2 - - Google Patents
Info
- Publication number
- JPH0444812B2 JPH0444812B2 JP59264130A JP26413084A JPH0444812B2 JP H0444812 B2 JPH0444812 B2 JP H0444812B2 JP 59264130 A JP59264130 A JP 59264130A JP 26413084 A JP26413084 A JP 26413084A JP H0444812 B2 JPH0444812 B2 JP H0444812B2
- Authority
- JP
- Japan
- Prior art keywords
- tellurium
- film
- layer
- substrate
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910052714 tellurium Inorganic materials 0.000 claims description 46
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000010408 film Substances 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000004770 chalcogenides Chemical class 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は光記録媒体、特に光による記録および
消去可能なカルコゲナイド系酸化物からなる光記
録媒体に関するものであり、長期間にわたつて光
記録特性が保持される安定性に優れた光記録媒体
に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an optical recording medium, particularly an optical recording medium made of a chalcogenide oxide that can be recorded and erased by light, and which has been used for optical recording for a long period of time. The present invention relates to an optical recording medium that maintains its properties and has excellent stability.
光記録媒体には、レーザー光の熱エネルギーに
よつて小孔あるいは泡を形成する方式のもの及び
膜の光学的特性を変化する方式のものとが知られ
ている。前者は記録の際に、記録膜層に凹凸の形
状変化を生ずるため、記録膜や基板が経時的に変
質、腐蝕を受けやすく、通常二枚の記録媒体をエ
アサンドイツチ構造にして使用されていた。しか
し後者はこの必要はなく、単に二枚の記録媒体を
接着させて使用できるため製造行程が大巾に簡略
できる利点があつた。後者に使用される材料のう
ち、感度の高いもの、即ち一定の入射光強度に対
して光学的特性の変化の大きい材料としてカルコ
ゲナイド系低酸化物、特にテルル酸化物TeOxが
知られており、Ｘは０＜Ｘ＜2.0のものが用いら
れる。
There are known optical recording media that use the thermal energy of laser light to form small pores or bubbles, and those that change the optical properties of the film. In the former case, the recording film layer undergoes uneven shape changes during recording, so the recording film and substrate are susceptible to deterioration and corrosion over time, so two recording media are usually used in an air sandwich structure. was. However, the latter does not require this, and has the advantage that the manufacturing process can be greatly simplified because two recording media can be simply glued together. Among the materials used for the latter, chalcogenide-based low oxides, especially tellurium oxide TeOx, are known as materials with high sensitivity, that is, materials with large changes in optical properties for a constant incident light intensity. 0<X<2.0 is used.
テルル酸化物薄膜の製造法としては、TeO2の
粉末をＷまたはMoのポート型ヒーターにのせ、
ヒーターを通電加熱してTeO2を一部還元しなが
ら真空蒸着する方法、TeO2粉末と各種の還元金
属の混合物を石英るつぼに入れ、これを真空中で
加熱蒸着する方法、TeO2と金属Teとをそれぞれ
に別の蒸発源として用い、同時に蒸着する方法等
が知られている。 The method for producing a tellurium oxide thin film is to place TeO 2 powder on a W or Mo port heater,
A method in which TeO 2 is partially reduced by vacuum evaporation by heating with a heater, a method in which a mixture of TeO 2 powder and various reduced metals is placed in a quartz crucible, and the mixture is heated and evaporated in a vacuum, TeO 2 and metal Te A method is known in which both are used as separate evaporation sources and are simultaneously evaporated.
しかし、これらの方法のうち、前の２者は簡便
な方法ではあるが、蒸着中にボートあるいは還元
金属の還元力が変化するため、蒸着された膜の膜
厚方向の組成の不規則な変化が生じ易いという欠
点がある。
However, although the first two methods are simple, the reducing power of the boat or reducing metal changes during deposition, resulting in irregular changes in the composition of the deposited film in the thickness direction. The disadvantage is that it tends to occur.
２つの蒸発源を用いる方法は組成が膜厚方向で
変化せず、均一な膜を得ることができる。この方
法によつて製作されたTeOxのＸが１未満の膜
は、黒化開始温度が低く、また感度が高いという
利点を有する。しかるに該膜は黒化開始温度以下
の比較的高温下に放置された場合、及び高湿度下
に放置された場合の透過率の変化が著るしい。こ
のため、主として膜の安定性の点から、感度は劣
るもののＸが１以上の範囲のTeOxが一般的に使
用されている。 In the method using two evaporation sources, the composition does not change in the film thickness direction, and a uniform film can be obtained. A TeOx film produced by this method in which X is less than 1 has the advantage of a low blackening initiation temperature and high sensitivity. However, when this film is left at a relatively high temperature below the blackening initiation temperature or when left under high humidity, the transmittance changes significantly. For this reason, mainly from the viewpoint of film stability, TeOx in which X is 1 or more is generally used, although its sensitivity is inferior.
又、基板材料としてアクリル板、ポリカーボネ
ート板等のプラスチツク材料を用いる場合、これ
らは気体透過率が比較的大きいため、経時的に水
蒸気や酸素等が侵入し、カルコゲナイド系低酸化
物を酸化し感度を低下させるという問題があつ
た。 Furthermore, when using plastic materials such as acrylic plates and polycarbonate plates as substrate materials, these have relatively high gas permeability, so water vapor, oxygen, etc. can penetrate over time, oxidizing chalcogenide-based low oxides and reducing sensitivity. There was a problem with lowering it.
このような、カルコゲナイド系記録媒体の長期
間にわたる安定性向上に関してはすでに多くの技
術が開示されており、例えば耐蝕性の良い金属中
に分散させるもの（特開昭58−164037）、有機物
質でコーテイングするもの（特開昭56−21892、
特開昭58−125248、特開昭58−203643）、無機物
質でコーテイングするもの（特開昭58−199449）、
表面を強制的に酸化するもの（特開昭56−3442、
特開昭58−94144、特開昭58−189850、特開昭59
−2245）等を例示することができるが、操作が繁
雑になつたり、かならずしも効果が十分ではない
場合が多かつた。 Many techniques have already been disclosed for improving the long-term stability of chalcogenide-based recording media, such as dispersing it in a metal with good corrosion resistance (Japanese Patent Application Laid-open No. 164037/1982), and dispersing it in an organic material. Items to be coated (JP-A-56-21892,
JP-A-58-125248, JP-A-58-203643), those coated with inorganic substances (JP-A-58-199449),
A device that forcibly oxidizes the surface (Japanese Patent Application Laid-Open No. 56-3442,
JP-A-58-94144, JP-A-58-189850, JP-A-59
-2245), but the operations were often complicated and the effects were not always sufficient.
本発明は長期にわたる安定性が向上した光記録
媒体を提供することを目的とする。 An object of the present invention is to provide an optical recording medium with improved long-term stability.
かかる本発明の目的は基板上に高周波電力によ
つてプラズマ化された不活性ガス及び／又は酸素
ガスを通過する金属テルル蒸気から式TeOxで示
されるテルル又はその酸化物からなる層を形成
し、厚さ方向に層中の酸素成分の割合Ｘが０から
２まで変化するように成膜してなる光記録媒体に
よつて達成された。
The object of the present invention is to form a layer of tellurium or its oxide represented by the formula TeOx on a substrate from metallic tellurium vapor passing through an inert gas and/or oxygen gas that is turned into plasma by high-frequency power, This was achieved using an optical recording medium formed by forming a film such that the ratio X of oxygen components in the layer varies from 0 to 2 in the thickness direction.
以下図面を参照して詳細に説明する。 A detailed explanation will be given below with reference to the drawings.
この発明においては、不活性ガス又は酸素ガス
と不活性ガスの混合ガス雰囲気中で金属テルルが
イオンプレーテイング法によつて基板上に蒸着さ
れる。 In this invention, metallic tellurium is deposited on a substrate by an ion plating method in an atmosphere of an inert gas or a mixed gas of oxygen gas and an inert gas.
すなわち、第２図にその概念図を示すように、
製造装置は真空槽３内に設けられた金属テルル１
をのせた加熱ポート２、これに対向して基板７を
保持する基板保持具８及びこの間に配設された高
周波励起コイル４からなる。 In other words, as shown in the conceptual diagram in Figure 2,
The manufacturing equipment is a metal tellurium 1 installed in a vacuum chamber 3.
It consists of a heating port 2 on which a substrate is placed, a substrate holder 8 that holds a substrate 7 opposite thereto, and a high frequency excitation coil 4 disposed between them.
製造に際して真空槽３内はまず酸素ガス、不活
性ガス又はそれらの混合ガス（以下これらを総称
して単にガスということがある）で充填される。
この際、安定なテルル又はテルル低酸化物からな
る膜を得るためには真空槽内をまず１×10-5
Torr程度以上の高真空とした後、高純度酸素ガ
ス、不活性ガス又はそれらの混合ガスを導入し、
槽内の真空度を１×10-4〜９×10-3Torr、好ま
しくは２×10-4〜５×10-3Torrに保つのがよい。
なお、不活性ガスとしてアルゴンガス、ヘリウム
ガス、窒素ガス等を例示することが可能である。 During manufacturing, the inside of the vacuum chamber 3 is first filled with oxygen gas, inert gas, or a mixed gas thereof (hereinafter these may be collectively referred to simply as gas).
At this time, in order to obtain a film made of stable tellurium or tellurium low oxide, the inside of the vacuum chamber must first be heated to 1×10 -5
After creating a high vacuum of about Torr or more, high purity oxygen gas, inert gas or a mixture thereof is introduced,
The degree of vacuum in the tank is preferably maintained at 1 x 10 -4 to 9 x 10 -3 Torr, preferably 2 x 10 -4 to 5 x 10 -3 Torr.
In addition, it is possible to illustrate argon gas, helium gas, nitrogen gas, etc. as an inert gas.
この状態でスパイラルコイル状の高周波励起コ
イル４に50〜500ワツトの電圧を印加し、高周波
電界をつくり、ガスを励起してプラズマを生成さ
せる。生成されるプラズマは、コイル形状、大き
さ、電界の強さ及び真空度によつて制御される
が、その制御は容易であり、高精度の制御が可能
である。 In this state, a voltage of 50 to 500 watts is applied to the spiral coil-shaped high-frequency excitation coil 4 to create a high-frequency electric field and excite the gas to generate plasma. The generated plasma is controlled by the shape and size of the coil, the strength of the electric field, and the degree of vacuum, and the control is easy and can be controlled with high precision.
プラズマ生成後、加熱ポート２に通電し、金属
テルル１を加熱・融解して蒸発させる。加熱温度
及び真空槽３内の圧力によつてテルルの蒸気圧が
定まり、さらにポート開口部面積によつてテルル
の蒸発量が規定される。そして、プラズマ内を通
過したテルルの蒸発粒子は、第２図中に模式的に
示したように、プラズマ内の酸素イオンやラジカ
ルの衝撃によりその一部が酸化され、酸化されな
かつた蒸発粒子と共に基板面上に沈着する。第２
図中５，５′は酸化したテルルの蒸発粒子を、６，
６′は酸化されなかつた蒸発粒子を示す。ここで
基板としてはガラス又はアクリル板、ポリカーボ
ネート板をはじめとする各種プラスチツクを使用
することができる。 After plasma generation, electricity is applied to the heating port 2 to heat and melt the metal tellurium 1 and evaporate it. The vapor pressure of tellurium is determined by the heating temperature and the pressure inside the vacuum chamber 3, and the amount of tellurium evaporated is further determined by the port opening area. As shown schematically in Figure 2, the tellurium evaporated particles that have passed through the plasma are partially oxidized by the bombardment of oxygen ions and radicals in the plasma, and together with the evaporated particles that have not been oxidized. Deposit on the substrate surface. Second
In the figure, 5, 5' are oxidized tellurium evaporated particles, 6,
6' indicates evaporated particles that were not oxidized. Here, as the substrate, various types of plastics such as glass or acrylic plates and polycarbonate plates can be used.
テルル酸化物の組成（Ｘの値）はスパイラルコ
イル状の高周波励起コイル４に印加する電力の大
きさ、酸素ガスの分圧Po及び／又は金属テルル
の蒸発速度を変化させることにより０から２の間
で自由に制御できる。例えば、ガス分圧Poを大
きくしたり、印加電力を大きくしたり、金属テル
ルの蒸発速度を小さくすることによつてＸを大き
くすることができる。本発明の一例ではまず高周
波電力、ガス分圧及び／又は金属テルルの蒸発速
度を選択してテルルまたはテルル低酸化物
（TeOx、ここでＸは１未満）からなる層を形成
し、次いで直ちに同一蒸着装置、同一蒸発源を用
いて高周波電力、ガス分圧、金属テルルの蒸発速
度の少なくともいずれかひとつ以上の条件（以下
成膜条件という）を連続的に又は段階的に変える
ことによつて膜中の酸素成分の割合（Ｘの値）を
増していき、最表面でＸが１以上、好ましくは２
（TeO2）になるように成膜することにより、基板
面から厚さ方向にＸが０から２まで変化した光記
録媒体を得ることができる（第１図）。該記録媒
体は耐蝕性のある層を表面に形成し感度の高い層
を基板に近いところに形成しうるため、光記録膜
自体の厚さが薄くできるという利点がある。また
本発明の他の例では、まず高周波電力、ガス分圧
及び／又は金属テルルの蒸発速度を選択して
TeO2層を形成し、次いで直ちに同一蒸着装置、
同一蒸発源を用いて前記成膜条件の少なくともひ
とつ以上の条件を連続的又は段階的に変えること
によつて、膜中の酸素成分の割合（Ｘの値）を１
未満、好ましくは0.1以下に減少させていき、記
録に十分な厚さの記録層を形成する。次いで成膜
条件の少なくともひとつ以上の条件を連続的に又
は段階的に変えることによりＸの値を増してい
き、最終面でTeO2になるように成膜することに
より、基板面から表層に向つてＸの値が減少し、
次いで増大した光記録媒体を得ることができる。
該記録媒体は、高感度のテルル又はテルル低酸化
物からなる層が安定なテルル低酸化物（１＜Ｘ≦
２）層で保護されるので高感度且つ安定性の優れ
るという利点がある。 The composition of the tellurium oxide (the value of can be freely controlled between For example, X can be increased by increasing the gas partial pressure Po, increasing the applied power, or decreasing the evaporation rate of metallic tellurium. In one example of the invention, a layer of tellurium or tellurium low oxide (TeOx, where The film can be formed by continuously or stepwise changing at least one of the following conditions (hereinafter referred to as film-forming conditions): high-frequency power, gas partial pressure, and metal tellurium evaporation rate using a vapor deposition apparatus and the same evaporation source. The ratio of oxygen component (value of X) inside is increased until X is 1 or more, preferably 2
(TeO 2 ), it is possible to obtain an optical recording medium in which X changes from 0 to 2 in the thickness direction from the substrate surface (FIG. 1). The recording medium has the advantage that the thickness of the optical recording film itself can be reduced because a corrosion-resistant layer can be formed on the surface and a highly sensitive layer can be formed close to the substrate. In another example of the invention, the radio frequency power, gas partial pressure and/or evaporation rate of the tellurium metal are first selected.
Form two layers of TeO, then immediately use the same deposition equipment,
By continuously or stepwise changing at least one of the film forming conditions using the same evaporation source, the proportion of oxygen components in the film (value of X) can be reduced to 1.
The thickness of the recording layer is decreased to less than 0.1, preferably 0.1 or less, to form a recording layer having a thickness sufficient for recording. Next, the value of As a result, the value of X decreases,
An enlarged optical recording medium can then be obtained.
In the recording medium, the layer consisting of highly sensitive tellurium or tellurium low oxide is a stable tellurium low oxide (1<X≦
2) Since it is protected by a layer, it has the advantage of high sensitivity and excellent stability.
本発明の記録媒体は上記方法に従えば連続して
成膜できるので製造が簡易で且つ安価であるとい
う利点を有する。 The recording medium of the present invention has the advantage that it is easy to manufacture and inexpensive because it can be formed continuously by following the above method.
本発明では必要に応じて、透明性の良い高分子
膜、無機質膜等を任意の位置に設けて、さらに安
定性を向上させることも可能である。また本発明
では、必要に応じてテルル酸化物層及び／又はテ
ルル層には上記の効果を損わない範囲で他の物
質、例えば増感剤や安定剤を含有せしめることが
できる。 In the present invention, it is also possible to further improve stability by providing a highly transparent polymer film, inorganic film, etc. at any position as required. Further, in the present invention, the tellurium oxide layer and/or the tellurium layer may contain other substances, such as sensitizers and stabilizers, as long as the above-mentioned effects are not impaired, if necessary.
次に実施例をもつて本発明を詳細に説明する。 Next, the present invention will be explained in detail with reference to Examples.
実施例 １
第１図に示した装置により、初期圧力Ｐが１×
10-5Torrとなるまで排気し、アルゴンガスを４
×10-4Torrまで導入する。これに周波数13.56M
Hz，100ワツトの高周波電力を印加してプラズマ
を発生させる。そして純度99.99％の金属テルル
を450〜550℃に保つて融解、蒸発させ、約４Å／
sec、の蒸着速度でガラス製基板及びPMMA製基
板上に沈着させた。このとき形成された薄膜の厚
さは0.05μｍ、膜組成はオージエ電子分光法によ
りＸ＝０、つまりTe膜が形成されていた。次に
導入するガスを高純度酸素ガスに変えて、真空度
を４×10-4Torrとして高周波電力を除々に増加
しながら金属テルルを融解、蒸発して成膜し、高
周波電力が400ワツトに達するまで続けた。最表
面の膜組成はＸ＝2.0、つまりTeO2膜が形成され
ていた。さらに膜内部の組成は、基板面に近いと
ころでのＸ＝０の組成から最表面層におけるＸ＝
2.0の組成まで、連続的に変化しているのが確認
された。又、対比のために金属テルルと二酸化テ
ルルを別々の蒸発源とする装置を用いて、まず金
属テルルの蒸発源のみ加熱しテルルを溶融蒸発さ
せて基板上にテルル層を形成した。次に二酸化テ
ルルの蒸発源のみ加熱し該テルル層の上に二酸化
テルル層を形成し、基板／Te／TeO2.0からなる
記録媒体を得た（これを比較例Ａ）とする。Example 1 Using the device shown in Fig. 1, the initial pressure P is 1×
Evacuate to 10 -5 Torr and add 4 argon gas.
Introduce up to ×10 -4 Torr. This has a frequency of 13.56M
Plasma is generated by applying high frequency power of Hz and 100 watts. Then, tellurium metal with a purity of 99.99% is kept at 450 to 550°C to melt and evaporate it to approximately 4 Å/
The samples were deposited on glass and PMMA substrates at a deposition rate of 100 sec. The thickness of the thin film formed at this time was 0.05 μm, and the film composition was determined by Auger electron spectroscopy to be X=0, that is, a Te film was formed. Next, the gas introduced was changed to high-purity oxygen gas, the degree of vacuum was set to 4 × 10 -4 Torr, and the high-frequency power was gradually increased to melt and evaporate the metal tellurium to form a film, and the high-frequency power reached 400 Watts. I continued until I reached it. The film composition on the outermost surface was X=2.0, that is, a TeO 2 film was formed. Furthermore, the composition inside the film varies from the composition of X=0 near the substrate surface to the composition of X=0 in the outermost layer.
It was confirmed that the composition changes continuously up to the composition of 2.0. For comparison, using an apparatus that uses tellurium metal and tellurium dioxide as separate evaporation sources, first, only the evaporation source of metal tellurium was heated to melt and evaporate the tellurium to form a tellurium layer on the substrate. Next, only the tellurium dioxide evaporation source was heated to form a tellurium dioxide layer on the tellurium layer to obtain a recording medium consisting of substrate/Te/TeO 2.0 (this is referred to as Comparative Example A).
これら二種類の記録媒体に対して波長830nmの
半導体レーザーで記録と再生を行なつたところ良
好な記録、再生特性を示した。次に温度40℃、相
対湿度90％の恒温恒湿槽に入れ、30日経過後で
は、比較例Ａでは正常な記録を行なうのに増大し
たレーザ出力を要し、明らかに特性の劣化を示し
た。しかし本発明に基づく実施例では成膜直後と
何ら変化はなく、安定性向上に有効であることを
示している。 When recording and reproduction were performed on these two types of recording media using a semiconductor laser with a wavelength of 830 nm, good recording and reproduction characteristics were shown. Next, it was placed in a constant temperature and humidity chamber at a temperature of 40°C and a relative humidity of 90%, and after 30 days, Comparative Example A required increased laser output to perform normal recording, and the characteristics clearly deteriorated. . However, in the examples based on the present invention, there was no change from immediately after film formation, indicating that it is effective in improving stability.
又、膜面に鋭い刃物で１mm方眼の刻み目を100
個つけて、これにセロテープを貼り付けて90°引
き起こす剥離試験の結果では、実施例では膜面と
基板面の剥離は全くなく、実用上十分な強さの膜
が得られたが、比較例Ａでは完全に剥離してしま
い、単なる真空蒸着法では強固な膜は形成しえな
いことを示している。 Also, make 100 incisions of 1 mm grid on the membrane surface with a sharp knife.
In the results of a peel test by attaching cellophane tape to the film and holding it at a 90° angle, there was no peeling between the film surface and the substrate surface in the example, and a film with sufficient strength for practical use was obtained, but in the comparative example In A, the film completely peeled off, indicating that a strong film cannot be formed by simple vacuum deposition.
実施例 ２
第１図に示した装置により、初期圧力Ｐが１×
10-5Torrとまるまで排気し、高純度酸素ガスを
４×10-4Torrまで導入する。これに周波数
13.56MHz，400ワツトの高周波電力を印加してプ
ラズマを発生させる。そして純度99.99％の金属
テルルを450〜550℃に保つて融解、蒸発させ、約
４Å／sec、の蒸着速度でガラス製基板及び
PMMA製基板上に沈着させた。このとき形成さ
れた薄膜の厚さは0.05μｍ、膜組成はオージエ電
子分光法によりＸ＝２、つまりTeO2膜が形成さ
れていた。次に高周波電力を除々に減少しながら
金属テルルを融解、蒸発して成膜し、高周波電力
が50ワツトに達するまで続けた。次に高周波電力
を除々に増加しながら金属テルルを融解、蒸発し
て成膜し、高周波電力が400ワツトに達するまで
続けた。最表面の膜組成はＸ＝2.0、つまりTeO2
膜が形成されていた。さらに膜内部の組成は、膜
中心部に近いところでのＸ＝０の組成から基板層
または最表面層におけるＸ＝2.0の組成まで、連
続的に変化しているのが確認された。Example 2 Using the device shown in Fig. 1, the initial pressure P is 1×
Exhaust until the pressure stops at 10 -5 Torr, and introduce high-purity oxygen gas to 4 x 10 -4 Torr. This frequency
Plasma is generated by applying high-frequency power of 13.56 MHz and 400 watts. Metal tellurium with a purity of 99.99% is then melted and evaporated at 450 to 550°C, and deposited on glass substrates at a deposition rate of about 4 Å/sec.
Deposited on a PMMA substrate. The thickness of the thin film formed at this time was 0.05 μm, and the film composition was determined by Auger electron spectroscopy to be X=2, that is, a TeO 2 film was formed. Next, metal tellurium was melted and evaporated to form a film while gradually decreasing the high-frequency power until the high-frequency power reached 50 Watts. Next, the metal tellurium was melted and evaporated to form a film while gradually increasing the high-frequency power until the high-frequency power reached 400 watts. The film composition on the outermost surface is X=2.0, that is, TeO 2
A film was formed. Furthermore, it was confirmed that the composition inside the film changed continuously from the composition where X=0 near the center of the film to the composition where X=2.0 in the substrate layer or the outermost layer.
この記録媒体に対して波長830nmの半導体レー
ザで記録を行なつたところ良好な記録、再生特性
を示した。さらに温度40℃、相対湿度90％の恒温
恒湿槽に30日間入れたのち、同様の試験を行なつ
たところ記録、再生特性に差はなく優れた安定性
を示した。又、膜面に鋭い刃物で１mm方眼の刻み
目を100個つけて、これにセロテープを貼り付け
て90°引き起こす剥離試験では全く剥離が起こら
ず実用上十分な強さの膜が得られた。 When recording was performed on this recording medium using a semiconductor laser with a wavelength of 830 nm, it showed good recording and reproducing characteristics. Furthermore, after placing it in a constant temperature and humidity chamber at a temperature of 40°C and a relative humidity of 90% for 30 days, a similar test was performed, and there was no difference in recording or playback characteristics, indicating excellent stability. In addition, in a peel test in which 100 1 mm square notches were made on the membrane surface with a sharp knife, cellophane tape was attached to the membrane, and the membrane was rotated at a 90° angle, no peeling occurred at all, and a membrane with sufficient strength for practical use was obtained.
（発明の効果）
この発明によれば、真空槽内で蒸発したテルル
粒子が、酸素又は混合ガスプラズマ内を通過する
過程で活性化され、一部は酸化されて基板上に沈
着する。このため、はく離しにくい、環境による
影響を受け難い丈夫な安定したテルル又はテルル
酸化物からなる層が形成出来る。(Effects of the Invention) According to the present invention, tellurium particles evaporated in a vacuum chamber are activated in the process of passing through oxygen or mixed gas plasma, and some of them are oxidized and deposited on the substrate. Therefore, it is possible to form a strong and stable layer of tellurium or tellurium oxide that is difficult to peel off and is not easily affected by the environment.
更に本発明に従えば厚さ方向に膜組成Ｘが変化
したテルル又はテルル酸化物からなる層が同一の
装置内で同一の蒸発源により形成されるのでその
膜内に異物が混入せず、従つて、密着性が極めて
優れている。 Furthermore, according to the present invention, a layer made of tellurium or tellurium oxide whose film composition X changes in the thickness direction is formed in the same device and by the same evaporation source, so that no foreign matter gets mixed into the film, and Therefore, the adhesion is extremely excellent.
従つて、従来安定性を欠き実用化に不適と思わ
れていた高感度領域のテルル又はテルル低酸化物
からなる層を含む記録媒体が極めて経済的に、し
かも高い安定性を備えたものとして実現出来ると
いう顕著な効果を奏する。 Therefore, a recording medium containing a layer made of tellurium or low tellurium oxide in the high-sensitivity region, which was conventionally thought to lack stability and be unsuitable for practical use, has been realized as an extremely economical and highly stable recording medium. It has a remarkable effect.
第１図は本発明に基づく光記録媒体の一例の構
成図を示し、第２図は本発明を実施するイオンプ
レーテイング装置の模式図を示す。
図中、１は金属テルル、２は蒸発ボート、３は
真空槽、４は高周波コイル、７は基板、８は基板
保持具、９はテルル層、１０はテルル低酸化物層
および１１は二酸化テルル層である。
FIG. 1 shows a configuration diagram of an example of an optical recording medium based on the present invention, and FIG. 2 shows a schematic diagram of an ion plating apparatus implementing the present invention. In the figure, 1 is metal tellurium, 2 is an evaporation boat, 3 is a vacuum chamber, 4 is a high frequency coil, 7 is a substrate, 8 is a substrate holder, 9 is a tellurium layer, 10 is a tellurium low oxide layer, and 11 is tellurium dioxide It is a layer.
Claims (1)
れた不活性ガス、酸素ガス又はそれらの混合ガス
を通過する金属テルル蒸気から式TeOxで示され
るテルル又はその酸化物からなる層を形成し、厚
さ方向に層中の酸素成分の割合Ｘが０から２まで
連続的に又は段階的に変化するように成膜してな
る光記録媒体。1. A layer made of tellurium or its oxide represented by the formula TeOx is formed on the substrate from metallic tellurium vapor that is passed through an inert gas, oxygen gas, or a mixture thereof that is made into plasma by high-frequency power, and An optical recording medium formed by forming a film such that the ratio X of oxygen components in the layer changes continuously or stepwise from 0 to 2 in the horizontal direction.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59264130A JPS61142541A (en) | 1984-12-13 | 1984-12-13 | Optical recording medium consisting of chalcogenide oxide |
| EP85309089A EP0188100B1 (en) | 1984-12-13 | 1985-12-13 | Optical recording medium formed of chalcogen oxide and method for producing same |
| DE8585309089T DE3582149D1 (en) | 1984-12-13 | 1985-12-13 | OPTICAL RECORDING MEDIUM FORMED FROM CHALCOGENOXIDE AND METHOD FOR THE PRODUCTION THEREOF. |
| US07/082,909 US4786538A (en) | 1984-12-13 | 1987-08-10 | Optical recording medium formed of chalcogenide oxide and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59264130A JPS61142541A (en) | 1984-12-13 | 1984-12-13 | Optical recording medium consisting of chalcogenide oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61142541A JPS61142541A (en) | 1986-06-30 |
| JPH0444812B2 true JPH0444812B2 (en) | 1992-07-22 |
Family
ID=17398879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59264130A Granted JPS61142541A (en) | 1984-12-13 | 1984-12-13 | Optical recording medium consisting of chalcogenide oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61142541A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6323235A (en) * | 1986-07-16 | 1988-01-30 | Matsushita Electric Ind Co Ltd | optical information recording carrier |
| JP2794467B2 (en) * | 1989-10-04 | 1998-09-03 | 同和鉱業株式会社 | Optical disk and method of manufacturing the same |
| US20070105055A1 (en) * | 2003-12-01 | 2007-05-10 | Sony Corporation | Manufacturing method of master disc for optical disc, and master disc for optical disc |
-
1984
- 1984-12-13 JP JP59264130A patent/JPS61142541A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61142541A (en) | 1986-06-30 |
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