JPS63151490A - Information recording medium - Google Patents
Information recording mediumInfo
- Publication number
- JPS63151490A JPS63151490A JP61298769A JP29876986A JPS63151490A JP S63151490 A JPS63151490 A JP S63151490A JP 61298769 A JP61298769 A JP 61298769A JP 29876986 A JP29876986 A JP 29876986A JP S63151490 A JPS63151490 A JP S63151490A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous
- recording film
- recording
- recording medium
- fine particles
- 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
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000010419 fine particle Substances 0.000 claims abstract description 13
- 239000005416 organic matter Substances 0.000 claims description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002923 metal particle Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005324 grain boundary diffusion Methods 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 59
- 239000007789 gas Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BLBNEWYCYZMDEK-UHFFFAOYSA-N $l^{1}-indiganyloxyindium Chemical compound [In]O[In] BLBNEWYCYZMDEK-UHFFFAOYSA-N 0.000 description 1
- 241000981595 Zoysia japonica Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24302—Metals or metalloids
- G11B2007/2431—Metals or metalloids group 13 elements (B, Al, Ga, In)
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
- G11B7/0045—Recording
- G11B7/00452—Recording involving bubble or bump forming
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
- G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/254—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers
- G11B7/2548—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of protective topcoat layers consisting essentially of inorganic materials
Abstract
Description
【発明の詳細な説明】
工発明の目的〕 ゛
（産業上の利用分野）′
本発明はレーザビームの照射により光学的に情報の記録
再生を行なう情報記録媒体、特に記録膜に***変形部（
バブル）を形成して配録を行なうタイプの情報記録媒体
に関す木。DETAILED DESCRIPTION OF THE INVENTION OBJECTS OF THE INVENTION (Industrial Field of Application) The present invention relates to an information recording medium in which information is optically recorded and reproduced by laser beam irradiation, and in particular, a recording film having a raised deformed portion (
A tree related to a type of information recording medium that performs recording by forming a bubble.
（従来の技術） 光学的に書込み可能な情報記録媒体として。(Conventional technology) As an optically writable information recording medium.
基板上に形成式れた記録膜に、記録すべき情報に対応し
たパルス変調レーザビームを照射して局部的に加熱を行
なうことにより、ピットｉ称される孔部を形成する情報
記録媒体は公知である。しかしながら、このようなピッ
トを形成する情報記録媒体では、形成されたビットの周
辺に記録膜の肉盛シ（リムと称される）が残ることは避
けられない。このリム形状は必ずしも一様なものでなく
、録媒膜の材料が不均一に凝固して小球状に付着したり
Ｘムが形成されることも知られている。このようなリム
の形成は、再生信号のＣＮＲ（キャリア・ノイズ比）の
劣化の要因となる。There is a well-known information recording medium in which a recording film formed on a substrate is irradiated with a pulse modulated laser beam corresponding to the information to be recorded and locally heated to form holes called pits. It is. However, in an information recording medium in which such pits are formed, it is inevitable that an overlay (referred to as a rim) of the recording film remains around the formed bits. This rim shape is not necessarily uniform, and it is known that the material of the recording medium solidifies non-uniformly and adheres to the rim in the form of small spheres or forms X-rays. The formation of such a rim causes deterioration of the CNR (carrier-to-noise ratio) of the reproduced signal.
−芳、記録膜にピットを形成せず、逆にレーザビームの
照射によシバプルと称される***変形部を形成して情報
の記録を行なう、いわゆるバブルモード情報記録媒体が
、例えば特開昭５６−１２７９３７号公報（文献■）、
特開ｍ５ａ−６５３４１号公報等（文献■）によシ提案
されている。これらの情報記録媒体では、ビットを形成
する媒体における前記の問題は本質的に存在しない。と
ころが、文献■に記載された媒体は、基板上に透明な有
機物中間層、金属質光吸収層を積層して構成され、金属
質光吸収層の局部加熱によシ間接的に有機物中間層を加
熱し、該中間層から発生するガスによって金属質光吸収
層を***−変形させてパズルを形成するものであるため
、光利用効率が著しく劣シ。-Yoshi, for example, a so-called bubble mode information recording medium, which records information by forming raised deformed parts called Shiba pulls by laser beam irradiation without forming pits in the recording film, was developed in Japanese Patent Laid-Open No. Publication No. 56-127937 (Reference ■),
This is proposed in Japanese Patent Application Laid-Open No. M5A-65341 (Reference ■). In these information recording media, the problems described above in media forming bits essentially do not exist. However, the medium described in document (■) is constructed by laminating a transparent organic intermediate layer and a metallic light absorbing layer on a substrate, and the organic intermediate layer is indirectly formed by local heating of the metallic light absorbing layer. Since the metal light absorbing layer is heated and the gas generated from the intermediate layer bulges and deforms to form a puzzle, the light utilization efficiency is extremely poor.
ｄビ録のために極めて大きいエネルギーを必要とする欠
点がある。また、文献■に記載された媒体は。It has the disadvantage that extremely large amounts of energy are required for recording. Also, the media described in document ■.
基板上に金属質光反射層、光透過層および金属質光吸収
層を積ノーシて構成され、光吸収層の局部加熱により光
透過層を間接的に加熱し、光透過層から発生するガスで
光吸収層を***Φ変形させてバブルを形成するものであ
り、基板上に光反射層が形成されていることから文献■
に比べて光の利用効率が高い利点がある。しかし、この
媒体は３層構造であるために製造工程が著しく複雑化し
、歩留りが悪く、製造コストが上昇するという大きな問
題がある。しかも実際に記録感度の向上を図るためには
、光透過層、光吸収層の厚さをそれぞれの層の屈折率、
使用レーザビームの波長に応じて光の利用効率が最大と
なるように厳密に制御する必要があシ、この要請も製造
を困難にする要因となっている。It consists of a metallic light-reflecting layer, a light-transmitting layer, and a metallic light-absorbing layer on a substrate, and the light-transmitting layer is indirectly heated by local heating of the light-absorbing layer, and the gas generated from the light-transmitting layer is heated. The bubble is formed by deforming the light absorbing layer into a raised Φ shape, and since the light reflecting layer is formed on the substrate, the literature
It has the advantage of higher light utilization efficiency compared to . However, since this medium has a three-layer structure, there are major problems in that the manufacturing process is significantly complicated, the yield is low, and the manufacturing cost is increased. Moreover, in order to actually improve the recording sensitivity, the thickness of the light-transmitting layer and the light-absorbing layer must be adjusted according to the refractive index of each layer.
It is necessary to strictly control the wavelength of the laser beam used so that the light utilization efficiency is maximized, and this requirement also becomes a factor that makes manufacturing difficult.
そこで、文献■、■にみられるような欠点を除いたバブ
ルモード情報記録媒体として、本発明者らは光吸収性と
ガス放出性を兼備えた記録膜を基板上に形成して構成さ
れる媒体を特開昭５８−１５８０３６号公報（文献■）
、特開昭５８−１５８０５２号公報（文献■）等で提案
している。これらの媒体は記録膜が単層であるため製造
上格段に有利であシ、またレーザビームの照射によシ加
熱された膜自身が光を吸収し、かつガスを放出して***
・変形するため、記録感度が高いという利点があもしか
しながら、これらの媒体における記録膜はガス放出性を
有する有機物中に、光吸収性を有する金属１例えばＴｅ
を含有させた構成であシ、レーザビームのエネルギーに
よりガス放出量が大きく変化するので、所望のバブルを
形成するためにはレーザビームのエネルギーを極めて厳
密に制御する必要がある。この制御が適切でないと、ガ
ス放出量が不十分でバブルが形成されなかったシ、逆に
ガス放出量が多過ぎて記録膜が破裂しビットを形成して
しまうこともあり、記録の安定性という点で問題がある
。Therefore, in order to create a bubble mode information recording medium that eliminates the drawbacks seen in documents The medium is JP-A-58-158036 (Reference ■)
, JP-A-58-158052 (Reference ■), etc. These media have a single-layer recording film, which is extremely advantageous in terms of manufacturing, and when the film is heated by laser beam irradiation, the film itself absorbs light and emits gas, causing it to bulge and deform. Therefore, the recording film of these media may have the advantage of high recording sensitivity, but the recording film of these media contains a metal 1 that has a light absorbing property, such as Te, in an organic substance that has a gas releasing property.
However, since the amount of gas released varies greatly depending on the energy of the laser beam, it is necessary to control the energy of the laser beam extremely strictly in order to form the desired bubble. If this control is not appropriate, the amount of gas released may be insufficient and no bubbles will be formed, or on the other hand, the amount of gas released may be too large and the recording film may burst and form bits, resulting in poor recording stability. There is a problem in this respect.
かかる問題点に関し、本発明者らは記録膜が単層であり
ながら安定した記録の可能なバブルモード情報記録媒体
を特願昭５９−２２８５０６として提案した。特願昭５
９−２２８５０６の情報記録媒体は熱的に安定である金
属微粒子と、加熱によりガスを放出する作用を有する有
機物を分散させた構造であるため、金属微粒子の含有量
を制御することによりレーザビームの照射に対する光吸
収率を容易に制御することができ、それによって光吸収
率を向上させ高い記録感度を得ることが可能となる。In order to solve this problem, the present inventors proposed a bubble mode information recording medium that is capable of stable recording even though the recording film is a single layer in Japanese Patent Application No. 59-228506. Special request 1977
The information recording medium No. 9-228506 has a structure in which thermally stable metal particles and organic matter that releases gas when heated are dispersed, so by controlling the content of metal particles, the laser beam can be controlled. The light absorption rate with respect to irradiation can be easily controlled, thereby making it possible to improve the light absorption rate and obtain high recording sensitivity.
また、特開昭５８−１５８０３６号等の単層宿造の記録
膜によるバブルモード情報記録媒体が有機物のマトリク
ス中に金属を含有させた構成でめったのに対し、特願昭
５９−２２８５０６号では有機物が金属酸化物マトリク
ス中に分散した形となっているので、有機物の含有量を
制御することによシ、レーザビームの照射により金属微
粒子を介して加見られる熱で放出するガスのｉｔを制御
することが容易である。従って、予め有機物の含有量を
適切にしておくことで、バブルを安定に形成することが
でき、ビットを形成することなくバブル形態を維持する
ためにレーザビームのエネルギーヲ制御しなければなら
ないという従来技術の煩雑さが解消される。即ち、レー
ザビームのエネルギーの変動等に対して、常に安定にバ
ブルモードの記録を行なうことが可能である。In addition, while bubble mode information recording media using a single layered recording film such as Japanese Patent Application Laid-Open No. 58-158036 had a structure in which metal was contained in an organic matrix, Japanese Patent Application No. 59-228506 Since the organic matter is dispersed in the metal oxide matrix, by controlling the content of the organic matter, it is possible to reduce the amount of gas released by the heat generated through the metal particles by laser beam irradiation. Easy to control. Therefore, by adjusting the content of organic matter in advance, bubbles can be formed stably, whereas conventional methods require controlling the energy of the laser beam in order to maintain the bubble shape without forming bits. Technology complexity is eliminated. That is, it is possible to always stably record the bubble mode despite fluctuations in the energy of the laser beam.
しかし、特願昭５９−２２８５０６として開示した情報
記録媒体には、大気中に保存した場合の安定性、即ち、
寿命特性が必ずしも常に良好とは限らないという問題点
があった。However, the information recording medium disclosed in Japanese Patent Application No. 59-228506 has stability when stored in the atmosphere, that is,
There was a problem that the life characteristics were not always good.
（発明が解決しようとする問題点）
本発明が解決しようとする問題点は、特願昭５９−２２
８５０６の寿命特性である。即ち、特願昭５９−２２８
５０６の低価格（単層）％高感度、記録の安定性と云っ
た長所を保有しながら、石らに、長寿命という特性をも
併わせもつ新規↑ｌｆｌ記報媒体を提供することが発明
の目的でおる。(Problems to be solved by the invention) The problems to be solved by the present invention are as follows:
These are the life characteristics of 8506. That is, the patent application No. 59-228
The invention is to provide a new ↑lfl recording medium that has the advantages of low cost (single layer) %506, high sensitivity and recording stability, but also has the characteristics of long life. I am here for the purpose of
（問題点を解決するための手段）
本発明は、上述した寿命特性の改良を、記録膜の主要構
成成分であるＩｎ２Ｏ５マトリクスおよびＩｎ微粒子を
いずれも非晶質状態で記録膜中に含ませることによシ行
なう。(Means for Solving the Problems) The present invention improves the above-mentioned life characteristics by including In2O5 matrix and In fine particles, which are the main components of the recording film, in an amorphous state. Let's do good.
本発明による記録膜はｂ Ｉｎターゲットを少くともα
４と０２とを含む混合ガスでスパッタ替ングして形成で
きる。記録膜中に含まれるＩｎ２Ｏ３マトリクスおよび
Ｉｎ微粒子を非晶質化するのは１Ｍ形成時のプロセスパ
ラメータを変化させて行なう。プロセスパラメータとは
ガス組成（ＣＨ４／Ｑ２比）、印加電力、放電圧力、基
板温度他である。The recording film according to the present invention has a b In target of at least α
It can be formed by sputtering using a mixed gas containing 4 and 02. The In2O3 matrix and In fine particles contained in the recording film are made amorphous by changing the process parameters during 1M formation. Process parameters include gas composition (CH4/Q2 ratio), applied power, discharge pressure, substrate temperature, etc.
（作 用）
本発明による情報記録媒体の基板上、に形成する記録膜
は、王として非晶質Ｉｎ２Ｏ５からなるマトリクス中に
、光吸収作用を有する非晶質Ｉｎ微粒子とガス放出作用
を有する有機物とが分散する構造をもっている。(Function) The recording film formed on the substrate of the information recording medium according to the present invention consists of amorphous In fine particles having a light absorption function and an organic substance having a gas release function in a matrix mainly composed of amorphous In2O5. It has a distributed structure.
一般に、酸化物等の誘電体マトリクス中に金属粒子の分
散する複合構造の薄膜の劣化は、分散会゛属粒子が大気
中の水分、酸素と反応して水酸化物、酸化物に変化する
過程即ち、腐蝕反応として進行する。今少し、ミクロに
見ると、大気中の水分、酸素は、記録膜表面よυマトリ
クスである酸化物粒子の結晶粒界を拡散して内部へ浸入
する。その結果、金属粒子の腐蝕反応が進行する訳であ
る。In general, the deterioration of thin films with a composite structure in which metal particles are dispersed in a dielectric matrix such as an oxide occurs due to the process in which the dispersed particles react with moisture and oxygen in the atmosphere and change into hydroxides and oxides. That is, it proceeds as a corrosion reaction. If we look at it a little more microscopically, moisture and oxygen in the atmosphere diffuse through the crystal grain boundaries of the oxide particles, which are the υ matrix, from the surface of the recording film and penetrate into the inside. As a result, the corrosion reaction of the metal particles progresses.
また、金属粒子が多結晶体である場合、金属粒子の腐蝕
反応は粒子表面よシ開始され、水分、酸素が結晶粒界を
拡散する過程を経過して粒子内部へ進行する。最終的に
は粒子全体が水酸化物、酸化物等へ腐蝕生成物に変化す
る。Further, when the metal particles are polycrystalline, the corrosion reaction of the metal particles starts from the surface of the particles and progresses into the interior of the particles through a process in which moisture and oxygen diffuse through the grain boundaries. Eventually, the entire particle transforms into corrosion products such as hydroxides and oxides.
以上述べたマトリクスおよび分散金属粒子が多結晶体で
ある薄膜の劣化機構から首肯されるように１本発明の記
録膜のマトリクスは非晶質Ｉｎ２Ｏ３分散金属粒子は非
晶質Ｉｎ微粒子であって、結晶粒界が存在しないため、
多結晶体に見られるような粒界拡散による劣化、腐蝕反
応の進行が著しく抑有機構である。有機物は本来の性質
として水分に対して不活性でろって、金属に見られるよ
うな酸化還元反応による腐蝕は進行しない。As can be seen from the above-mentioned deterioration mechanism of a thin film in which the matrix and the dispersed metal particles are polycrystalline, in the matrix of the recording film of the present invention, the amorphous In2O3 dispersed metal particles are amorphous In fine particles, Since there are no grain boundaries,
Deterioration due to grain boundary diffusion and progression of corrosion reactions, as seen in polycrystalline materials, are a significant suppressive mechanism. Organic substances are naturally inert to moisture, and corrosion due to redox reactions that occur with metals does not proceed.
（実施例）
第１図は本発明の一実施例に係る情報記録媒体の配置状
Ｕ％即ち、バブル形成後の状態を模式的に示す断面図で
ある。基板ｌＯは、例えばＰＣ基板で１Ｌこの基板１０
上に非晶質Ｉｎ２Ｏ３マトリクス中に非晶質Ｉｎ微粒子
および有機物を分゛散させてなる記録膜１２が形成され
ている。第１図中２０で示したものがバブルである。(Example) FIG. 1 is a sectional view schematically showing the arrangement U% of an information recording medium according to an example of the present invention, that is, the state after bubble formation. The board 10 is, for example, a PC board with a capacity of 1L.
A recording film 12 is formed thereon by dispersing amorphous In fine particles and organic matter in an amorphous In2O3 matrix. What is indicated by 20 in FIG. 1 is a bubble.
第２図は本発明の情報記録媒体の記録膜１２の構造を模
式的に示す断面図である。記録膜１２は、非晶質Ｉｎ２
Ｏ３マトリクス１４中に非晶質Ｉｎ微粒子１６と有機物
１８とが分散された構造である。FIG. 2 is a cross-sectional view schematically showing the structure of the recording film 12 of the information recording medium of the present invention. The recording film 12 is made of amorphous In2
It has a structure in which amorphous In fine particles 16 and organic substances 18 are dispersed in an O3 matrix 14.
第１図におけるバブル２０は、記録用レーザビーム（図
示していない）の照射に対して、非晶質Ｉｎ微粒子１６
がその光吸収作用で熱を発生し、これによシ間接的に加
熱された有、機構がガス放出を行ない、その圧力が記録
膜１２と基板１０との界面に作用した結果、形成された
ものである。第１図中２２は、記録膜が***変形したた
めに形成された空洞である。The bubble 20 in FIG.
generates heat due to its light absorption action, which causes the gas to be indirectly heated.The mechanism releases gas, and the pressure acts on the interface between the recording film 12 and the substrate 10, resulting in the formation of a gas. It is something. Reference numeral 22 in FIG. 1 indicates a cavity formed due to the upheaval deformation of the recording film.
ζうして情報がバブル２０の形で記録された情報記録媒
体からの再生は、記録時に使用したレーザビームの１１
５〜ｌ／１０程度の強度の再生用レーザビームを記録膜
１２に照射し、その反射光または透過光を光検出器で検
出することによって行なう、即ち、記録膜１２のうちバ
ブル２ｏの形成された領域は、照射された再生用レーザ
ビームがバブル２０の形状に応じて回折を受けるため、
パルプ２０の形成されていない領域（平担部）と比較し
て、その反射光または透過光の強度が著しく異なる。従
って、この反射または透過光の強度を検出してバブル２
０の有無に対応した再生出方を取出せば、ＣＮＨの極め
て高い良好な再生を行なうことができる。ζReproduction from an information recording medium on which information is recorded in the form of bubbles 20 is performed using the laser beam 11 of the laser beam used during recording.
This is done by irradiating the recording film 12 with a reproduction laser beam with an intensity of about 5 to 1/10, and detecting the reflected light or transmitted light with a photodetector. The irradiated reproduction laser beam is diffracted in the area according to the shape of the bubble 20, so
The intensity of the reflected light or transmitted light is significantly different from that of the area (flat area) where the pulp 20 is not formed. Therefore, by detecting the intensity of this reflected or transmitted light, the bubble 2
If the regeneration method corresponding to the presence or absence of 0 is determined, good regeneration with extremely high CNH can be performed.
次に１本発明のより具体的な実施例について説明する。Next, a more specific embodiment of the present invention will be described.
実施例−１
直径５インチのＩｎターゲットを備えたＤＣマグネトロ
ンスパッタ装置を用いて記録膜の形成を行なった。基板
には厚さ１．２鰭のポリカーボネート基板（ＰＣ基板）
を用いた。スパッタリングはＣＨ４と０２との混合ガス
であり、混合比は体積に換算してＣＨ４１０２＝ ７０
／３０ トした。−ｑ スフ ａ−メ−／ テ測定した
ガス流量はＣＨ４が２１ ＳＣＣＭ、 ０２が９Ｓαχ
である。スパッタリングは５ ｍＴｏｒｒの圧力（電離
真空計による）、３００Ｗの印加電力（ＤＣ）として、
約４分間の放電により、厚さ８０ｎｍの記録膜が基板上
に堆積した。Example 1 A recording film was formed using a DC magnetron sputtering device equipped with an In target having a diameter of 5 inches. The board is a polycarbonate board (PC board) with a thickness of 1.2 fins.
was used. Sputtering is a mixed gas of CH4 and 02, and the mixing ratio is CH4102 = 70 in terms of volume.
/30. -q Step a-me/te The measured gas flow rate is 21 SCCM for CH4, 9Sαχ for 02
It is. Sputtering was performed at a pressure of 5 mTorr (according to an ionization vacuum gauge) and an applied power (DC) of 300 W.
By discharging for about 4 minutes, a recording film with a thickness of 80 nm was deposited on the substrate.
次に、こうして製作された情報記録媒体を線速１．２ｍ
／ｓｅｅの速度で回転させ、記録用レーザビームとして
、スポットサイズ１．５μｍに集束させた出力８ｍＷ、
パルス幅０．６９ μｓｅｃ 、 ２．５５ ／Ｊ ｓ
ｅｄのＣＤフォーマットにＫｙ４されたＧａＡＪＡｓレ
ーザビームを基板面から照射して記録を行なった。次に
、再生用レーザビームとして出力０．５ｒｎＷの連続ビ
ームを照射し、反射光を検出したところ、再生信号の侶
は５０ ｄＢという良好な値を示した。また、記録後の
記録膜を光学顕微鏡で観察したところ、形状良好なバブ
ルの形成されていることが確認できた。Next, the information recording medium produced in this way was
/see, and output 8 mW focused to a spot size of 1.5 μm as a recording laser beam.
Pulse width 0.69 μsec, 2.55/J s
Recording was performed by irradiating the substrate surface with a GaAJAs laser beam Ky4-formatted to the ED CD format. Next, when a continuous beam with an output of 0.5 rnW was irradiated as a reproduction laser beam and the reflected light was detected, the amplitude of the reproduction signal showed a good value of 50 dB. Furthermore, when the recording film after recording was observed with an optical microscope, it was confirmed that bubbles with good shape were formed.
この様な良好な記録再生特性を示す情報記録媒体の寿命
特性と記録膜の結晶性との関係を調べるため以下のよう
な実験を行なった。ＣＨ４１０２＝７０／３０圧力５ｍ
Ｔｏｒｒ一定として、印加電力を２００Ｗ、３００Ｗ、
４００Ｗ、５００Ｗと変化させた情報記録媒体を４種製
作した。膜厚は２００ｎｍ、基板はガラス基板とした。In order to investigate the relationship between the life characteristics of an information recording medium exhibiting such good recording and reproducing characteristics and the crystallinity of the recording film, the following experiment was conducted. CH4102=70/30 pressure 5m
Assuming that Torr is constant, the applied power is 200W, 300W,
We produced four types of information recording media with varying power levels of 400W and 500W. The film thickness was 200 nm, and the substrate was a glass substrate.
この４種媒体の記録膜の結晶状態をＸ線回折の手法で調
べたところ、記録膜中の結晶質成分は、記録膜形成時の
印加電力が２００Ｗの場合Ｉｎ２Ｏ５、５００Ｗの場合
Ｉｎであって、 ３００Ｗおよび４００Ｗで形成した
記録膜は非晶、質であった。When the crystalline state of the recording films of these four types of media was investigated using the X-ray diffraction method, the crystalline components in the recording films were In2O5 when the power applied during recording film formation was 200W, and In when the power was 500W. The recording films formed at 300 W and 400 W were amorphous and of poor quality.
次に、この４種媒体を７０°Ｑ、８５％ＲＨの条件に設
定された恒温恒湿槽に５日間放置して寿命特性を調べた
。この加速劣化テスト前後の分光反射率変化（波長８３
０ ｎｍ ）で媒体の寿命特性を評価したところ（テス
ト前の分光反射率を１に規格化）、印加電力２００Ｗの
媒体においては０．５３，５００Ｗでは０．６１という
大きい変化を示したのに対し、３００Ｗでは０．８４，
４００Ｗでは０．８８という小さな変化を示した。記録
媒体の寿命特性としては、本実施例の加速劣化テスト条
件の場合、分光反射率変化として０．８以内の小さの変
化が実用化に必要である。Next, these four types of media were left in a constant temperature and humidity chamber set at 70° Q and 85% RH for 5 days to examine their life characteristics. Spectral reflectance change before and after this accelerated deterioration test (wavelength 83
When the lifetime characteristics of the media were evaluated at 0 nm) (the spectral reflectance before the test was normalized to 1), the media with an applied power of 200 W showed a large change of 0.53, and with 500 W it showed a large change of 0.61. On the other hand, at 300W, it is 0.84,
At 400W, it showed a small change of 0.88. Regarding the life characteristics of the recording medium, in the case of the accelerated deterioration test conditions of this example, a small change of 0.8 or less in spectral reflectance is required for practical use.
従って、記録膜が非晶質でありた印加電力３００Ｗ 。Therefore, the applied power was 300 W when the recording film was amorphous.
４００Ｗで製作した情報記録媒体の寿命特性は良好と言
うことができる。またｂ ＣＨ４１０２比、圧力を一定
としても印加電力を変化させることによって即ち、形成
条件によって記録膜の結晶性を変化させられることも判
る。It can be said that the life characteristics of the information recording medium manufactured at 400W are good. It is also seen that even if the bCH4102 ratio and pressure are constant, the crystallinity of the recording film can be changed by changing the applied power, that is, by changing the formation conditions.
印加電力を３００Ｗ 、圧力を５ｍＴｏｒｒ一定として
、ＣＨ４１０２比を９０／１０，８０／２０，７０／３
０，６０／４０と変化させた情報記録媒体を上記の方法
に準じて４種製作した。膜厚は２００ｎｍ ＋基板はガ
ラス基板とした。この４種媒体の記録膜の結晶状態をＸ
線回折の手法で調べたところ、記録膜中の結晶質成分は
、記録膜形成時のＣＨ４１０２が９０／ｌ ＯのときＩ
ｎ、６０／４０のときＩｎ２Ｏ３であって、８０／２０
および７０／３０で形成した記録膜はいずれも非晶質で
あった。この４種媒体の寿命特性を上記した方法と同様
に（７０℃、８５％ＲＨ，５日間）調べたところ、分光
反射率の変化は、ＣＨ４１０２＝９０／１０のとき０．
７１，６０／４０のとき０．６１という比較的大きい値
を示したのに対し、ＣＨ４１０２＝ ８０／２０のとき
０．８６，７０／３０のとき０．８３という小さい変化
であった。従って、この実験からも記録膜が非晶質であ
れば情報記録媒体の寿命特性は良好であると言うことが
できる。The applied power was 300W, the pressure was constant at 5mTorr, and the CH4102 ratio was 90/10, 80/20, 70/3.
Four types of information recording media with different ratios of 0 and 60/40 were manufactured according to the above method. The film thickness was 200 nm and the substrate was a glass substrate. The crystalline state of the recording film of these four types of media is
When investigated using a linear diffraction method, the crystalline component in the recording film was found to be I
In2O3 when n, 60/40, and 80/20
Both of the recording films formed with 70/30 and 70/30 were amorphous. When the lifetime characteristics of these four types of media were investigated in the same manner as described above (70°C, 85% RH, 5 days), the change in spectral reflectance was 0.0% when CH4102 = 90/10.
When CH4102=80/20, it showed a relatively large value of 0.61, while when CH4102=80/20, it showed a small change of 0.86, and when CH4102=70/30, it showed a small value of 0.83. Therefore, it can be said from this experiment that the life characteristics of the information recording medium are good if the recording film is amorphous.
第３図は記録膜形成時の印加電力とガス組成とをパラメ
ータとして形成された記録膜が結晶質であるか非晶質で
あるかを示すダイアダラムである。FIG. 3 is a diagram showing whether the recording film formed is crystalline or amorphous using the applied power and gas composition during recording film formation as parameters.
ＱＣＨ４１ＱＯ２はそれぞれＣＨ４１０２の流量を示す
。第３図において、直線ＡＢは本実施例に用いたスパッ
タ装置の印加電力の上限である。約５００Ｗの限界値を
超えると放電が不安定になった。直線ＡＢと曲線ＣＤと
Ｙ軸とで囲まれた領域が結晶質Ｉｎが検出（Ｘ線回折）
される領域でめり、曲ＱＥ Ｆ （！：Ｘ軸とＱＯ２／
（Ｑ （！Ｈ４＋ＱＯ２） ＝ ０．５ ｔＤ直！１
１−１’囲ルル領域がＸ線回折で結晶質Ｉｎ２Ｏ３の検
出される領域である。曲線ＣＤ、曲線ＥＦで囲まれる斜
線の領域が非晶質となる領域である。ただし、第３図に
示したダイアグラムは本実施例に用いたスパッタ装置に
個有のものであって１本発明が第３図に示した印加電力
、ガス組成の値に限定されるものではない。QCH41QO2 each indicates the flow rate of CH4102. In FIG. 3, straight line AB is the upper limit of the applied power of the sputtering apparatus used in this example. When the limit value of about 500W was exceeded, the discharge became unstable. Crystalline In is detected in the area surrounded by straight line AB, curve CD, and Y axis (X-ray diffraction)
The song QE F (!: X axis and QO2/
(Q (!H4+QO2) = 0.5 tD direct!1
The area surrounded by 1-1' is the area where crystalline In2O3 is detected by X-ray diffraction. The shaded area surrounded by curve CD and curve EF is an amorphous area. However, the diagram shown in FIG. 3 is specific to the sputtering apparatus used in this example, and the present invention is not limited to the values of applied power and gas composition shown in FIG. .
ところで、第３図に斜線で示した領域の記録膜の構造、
を説明する。印加電力３０ ＧＷ 、 ＣＨａ１０２＝
７０／３０で形成した記録膜をＡｒ気流中で３００℃。By the way, the structure of the recording film in the shaded area in FIG.
Explain. Applied power 30 GW, CHa102=
A recording film formed with a 70/30 ratio was heated at 300°C in an Ar air flow.
１０分間熱処理した。基板は単結晶Ｓ１．膜厚は２００
ｎｍである。Ｘ線回折で結晶性を調べたところ、結晶
質Ｉｎ２Ｏ３と結晶質Ｉｎの回折ピークが明瞭に認めら
れた。この結果は熱処理を行なわない記録膜中に非晶質
Ｉｎ２Ｏ３と非晶質Ｉｎとが含まれていることを示して
いる０次に、同一条件で形成した記録膜を８１基板よシ
はく離して１、粉末とした。この粉末についてＴＧＡ、
ＤＴＡを測定した。雰囲気は同じ＜ Ａｒ気流中とした
。ＴＧＡでは、２００〜２３０℃にわたる約６ｔＩｂの
重量減少が認められた。この結果は記録膜中にＩｎ２Ｏ
３＠ Ｉｎ以外に揮発性の成分の含まれていることを示
している。 ＤＴＡでは、１５７℃に吸熱ピーク、２３
０〜２４０ ’０にかけて発熱ピークが認められた。１
５７℃はＩｎの融点１５６℃に極めて近（、Ｉｎのメル
トに伴なう吸熱反応、。Heat treatment was performed for 10 minutes. The substrate is single crystal S1. Film thickness is 200
It is nm. When the crystallinity was examined by X-ray diffraction, the diffraction peaks of crystalline In2O3 and crystalline In were clearly observed. This result shows that amorphous In2O3 and amorphous In are contained in the recording film without heat treatment.Next, the recording film formed under the same conditions was peeled off from the 81 substrate. 1. Made into powder. Regarding this powder, TGA,
DTA was measured. The atmosphere was the same < Ar airflow. TGA showed a weight loss of approximately 6 tIb over 200-230°C. This result shows that In2O is present in the recording film.
3@ Indicates that volatile components other than In are included. In DTA, there is an endothermic peak at 157°C, 23
An exothermic peak was observed from 0 to 240'0. 1
57°C is extremely close to the melting point of In, 156°C (an endothermic reaction accompanying the melting of In).
であることは明らかである。揮発性の成分が何であるか
を調べるため、同一の粉末についてＧＣ７ＭＳを測定し
たところ、２００℃附近から炭化水素の放出されること
が確認できた。以上から第３図の斜線で示した領域の記
録膜は、非晶質ＩｎｚＯｓ％非晶質Ｉｎ、有機物とから
構成されることが判る。It is clear that In order to investigate the volatile components, GC7MS was performed on the same powder, and it was confirmed that hydrocarbons were released from around 200°C. From the above, it can be seen that the recording film in the shaded area in FIG. 3 is composed of amorphous InzOs% amorphous In and organic matter.
実施例−２
実施例−１と同一のスパッタ装置を用いて記録膜の形成
を行なりた。スパッタリングガスはＣＨ４と０２とＮ２
とが混合ガ不であシ、４ガス流量はＣＨ４が２１ ＳＣ
ＣＭ 、 ０２が９ ＳＣＣＭ 、 Ｎ２が５ＳＣＣＭ
とし九。Example 2 A recording film was formed using the same sputtering apparatus as in Example 1. Sputtering gas is CH4, 02 and N2
There is no mixing gas, and the 4 gas flow rate is 21 SC for CH4.
CM, 02 is 9 SCCM, N2 is 5 SCCM
Toshiku.
スパッタリングは圧力５ｍＴｏｒｒ一定とし、印加電力
を２００Ｗ、３００Ｗ、４００Ｗ、５００Ｗと変化させ
た。記録再生特性の測定用にはＰＣ基板を用い、膜厚は
９０ｎｍとした。結晶性評価用および加速劣化テスト用
にはガラス基板を用い、膜厚は２００ ｎｍとした。The sputtering was performed at a constant pressure of 5 mTorr, and the applied power was changed to 200W, 300W, 400W, and 500W. A PC board was used to measure the recording and reproducing characteristics, and the film thickness was 90 nm. A glass substrate was used for crystallinity evaluation and accelerated deterioration test, and the film thickness was 200 nm.
こうして製作した４種の情報記録媒体の記録再生特性を
、実施例−１と同様の方法で調べたところ、４種の媒体
いずれも８〜ｌｏｍＷの記録）（ワーに対し、再生信号
ＣＮＲとして４０ｄＢ以上の良好な値が得られた。When the recording and reproducing characteristics of the four types of information recording media manufactured in this way were investigated in the same manner as in Example-1, it was found that all four types of media had a recording power of 8 to lomW (with respect to power, the reproduction signal CNR was 40 dB The above good values were obtained.
次に、Ｘ線回折で記録膜の結晶性を調べたところ、４種
とも非晶質であって、結晶質Ｉｎ２Ｏ３＃ ＠晶質Ｉｎ
の回折ピークは認められなかりた。引続き、この媒体を
７０℃、８５ＳＲＨの恒温恒湿槽に５日間放置して、放
置前後の分光反射率の変化を調べたところ、いずれの媒
体も０．８以内の小さな変化を示した。Next, when the crystallinity of the recording film was examined by X-ray diffraction, all four types were amorphous, and crystalline In2O3# @crystalline In
No diffraction peak was observed. Subsequently, this medium was left in a constant temperature and humidity chamber at 70° C. and 85 SRH for 5 days, and changes in spectral reflectance before and after being left were examined, and all mediums showed small changes within 0.8.
以上、実施例から明らかなように本発明の情報記録媒体
は、非晶質ＩｎｚＯ３を主な構成成分とするマトリクス
中に非晶質Ｉｎ微粒子と有機物とを分散させた構造の記
録膜を用いるため、以下の効果がある。As is clear from the examples above, the information recording medium of the present invention uses a recording film having a structure in which amorphous In fine particles and organic matter are dispersed in a matrix whose main constituent is amorphous InzO3. , has the following effects.
■長寿命である。■Long lifespan.
■記録膜が単層である。即ち、低価格である。■The recording film is a single layer. That is, the price is low.
■広い範囲のレーザビーム照射条件に対して安定にバブ
ルが形成できる。即ち、使い勝手が良い。■Bubbles can be stably formed under a wide range of laser beam irradiation conditions. In other words, it is easy to use.
■高感度である。■High sensitivity.
第１図は本発明に係る情報記録媒体の記録状態、即ち、
バブル形成後の状態を模式的に示す断面図、編２図は本
発明に係る情報記録媒体の記録膜の構造を模式的に示す
断面図、第３図は本発明に係る情報記録媒体の記録膜の
結晶状態を４膜形成時の印加電力、ガス組成をパラメー
タと、して示すダイアグラムである。
ｌＯ・・・基板
１２・・・記録膜
１４・・・非晶質Ｉｎ２Ｏ３マトリクス１６・・・非晶
質Ｉｎ微粒子
１８・・・有機物
２０・・・バブル
２２・・・空洞FIG. 1 shows the recording state of the information recording medium according to the present invention, that is,
FIG. 2 is a cross-sectional view schematically showing the structure of the recording film of the information recording medium according to the present invention, and FIG. 3 is a cross-sectional view schematically showing the state after bubble formation. 4 is a diagram showing the crystalline state of a film using applied power and gas composition during film formation as parameters. lO...Substrate 12...Recording film 14...Amorphous In2O3 matrix 16...Amorphous In fine particles 18...Organic substance 20...Bubble 22...Cavity
Claims (1)
記録する記録膜を基板上に形成してなる情報記録媒体に
おいて、前記記録膜は非晶質Ｉｎ＿２Ｏ＿３を主な構成
成分とするマトリクス中に非晶質Ｉｎ微粒子と有機物と
を分散させた構造であることを特徴とする情報記録媒体
。In an information recording medium in which a recording film is formed on a substrate to record information by forming raised deformed portions by irradiation with a laser beam, the recording film has non-crystalline parts in a matrix whose main component is amorphous In_2O_3. An information recording medium characterized by having a structure in which crystalline In fine particles and organic matter are dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61298769A JPS63151490A (en) | 1986-12-17 | 1986-12-17 | Information recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61298769A JPS63151490A (en) | 1986-12-17 | 1986-12-17 | Information recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63151490A true JPS63151490A (en) | 1988-06-24 |
Family
ID=17863978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61298769A Pending JPS63151490A (en) | 1986-12-17 | 1986-12-17 | Information recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63151490A (en) |
-
1986
- 1986-12-17 JP JP61298769A patent/JPS63151490A/en active Pending
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