JP2004268587A

JP2004268587A - Information recording medium

Info

Publication number: JP2004268587A
Application number: JP2004064974A
Authority: JP
Inventors: Akemi Hirotsune; 朱美廣常; Motoyasu Terao; 元康寺尾; Yasushi Miyauchi; 靖宮内
Original assignee: Hitachi Ltd
Current assignee: Hitachi Ltd
Priority date: 1993-06-18
Filing date: 2004-03-09
Publication date: 2004-09-30

Abstract

<P>PROBLEM TO BE SOLVED: To provide an information recording medium which enables rewriting or super-resolution readout more many times than ever before while maintaining good recording/reproduction characteristics. <P>SOLUTION: This information recording medium is characterized in that Cr and at least one element X or B, X being selected from the group of Cr, Ag, Ba, Co, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn, Ti, V, In and lanthanoid elements, are added to an Sb-Te-Ge-based or Sb-Te-In-based phase-change type recording film 3 or thin film for super-resolution readout. The information recording medium is also characterized in that a component 3b with a higher melting point than that of a phase-change component 3a is deposited in the recording film 3 or the thin film for super-resolution readout, so as to prevent the flow/segregation of the film in recording/erasing and super-resolution readout. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

この発明は、情報記録用薄膜およびその製造方法ならびに情報記録媒体に関し、さらに詳しく言えば、例えば映像や音声などのアナログ信号をＦＭ変調して得た情報や、電子計算機のデータやファクシミリ信号やディジタル・オーディオ信号などのディジタル情報をレーザ光、電子線等のエネルギービームによってリアルタイムで記録・再生することができる情報記録用薄膜または超解像読み出し用薄膜、およびその製造方法ならびに、その情報記録用薄膜または超解像読み出し用薄膜を用いた情報記録媒体に関する。 The present invention relates to an information recording thin film, a method of manufacturing the same, and an information recording medium, and more specifically, for example, information obtained by FM-modulating analog signals such as video and audio, data of a computer, facsimile signal, and digital data. An information recording thin film or super-resolution reading thin film capable of recording / reproducing digital information such as an audio signal in real time with an energy beam such as a laser beam or an electron beam, a thin film for super-resolution reading, a method of manufacturing the same, and a thin film for recording the information Alternatively, the present invention relates to an information recording medium using a super-resolution reading thin film.

レーザ光を照射して薄膜（記録膜）に情報を記録する原理は種々知られているが、そのうちで膜材料の相転移（相変化とも呼ばれる）やフォトダークニングなど、レーザ光の照射による原子配列変化を利用するものは、薄膜の変形をほとんど伴わないため、２枚のディスク部材を直接貼り合わせて両面ディスク構造の情報記録媒体が得られるという長所を持つ。また、ＧｅＳｂＴｅ系やＩｎＳｂＴｅ系の記録膜では、情報の書き換えを行なうことができる利点がある。 There are various known principles of recording information on a thin film (recording film) by irradiating a laser beam. Among them, atoms such as phase transition (also called phase change) of the film material and photodarkening are used. The method utilizing the arrangement change has an advantage that an information recording medium having a double-sided disk structure can be obtained by directly bonding two disk members, since the thin film is hardly deformed. In addition, a GeSbTe-based or InSbTe-based recording film has an advantage that information can be rewritten.

しかし、この種の記録膜では、ピットポジション記録においては１０⁵回、ピットエッジ記録においては１０⁴回を越える多数回の書き換えを行なうと、
記録膜の流動により書き換え特性が低下するため、記録膜の流動を防止する方法が研究されている。記録膜の流動は、記録時のレーザ照射により、記録膜が流動し、保護層や中間層の熱膨張による変形により、記録膜が少しずつ押されて生じる。 However, in the recording film of this kind, 10 ⁵ times in pit position recording, when in the pit edge recording is performed multiple programming exceeding 10 ⁴ times,
Since the rewriting characteristics are degraded by the flow of the recording film, methods for preventing the flow of the recording film have been studied. The flow of the recording film occurs when the recording film flows by laser irradiation at the time of recording, and is gradually pressed by the deformation due to thermal expansion of the protective layer and the intermediate layer.

例えば、特開平４−２２８１２７号公報には、記録膜のマイクロセル化により流動を防止する方法が開示され、文献 T．Ohta et al. "Optical Data Strage" '89 Proc. SPIE, 1078，27（1989）には、記録膜を薄くして熱容量を下げ且つ隣接する層との付着力の影響が大きくなるのを利用して記録膜の流動を防止する方法が開示されている。 For example, Japanese Patent Application Laid-Open No. 4-228127 discloses a method for preventing flow by making a recording film into microcells. Ohta et al. "Optical Data Strage" '89 Proc. SPIE, 1078, 27 (1989) takes advantage of the fact that the recording film is thinned to reduce the heat capacity and the effect of the adhesive force between adjacent layers is increased. A method of preventing the recording film from flowing is disclosed.

映像信号や音声信号などをＦＭ変調したアナログ情報信号や、電子計算機のデータ、ファクシミリ信号、ディジタルオーディオ信号などのディジタル情報信号を基板表面に凹凸として転写した光ディスクや、レーザ光、電子線等の記録用ビームによって信号やデータをリアルタイムで記録することが可能な情報の記録用薄膜等を有する光ディスクにおいては、信号再生分解能は、ほとんど再生光学系の光源の波長λと対物レンズの開口数ＮＡで決まり、記録マーク周期２ＮＡ／λが読み取り限界である。 Recording of analog information signals obtained by FM-modulating video signals, audio signals, etc., digital information signals such as computer data, facsimile signals, digital audio signals, etc. on the substrate surface as laser light, electron beams, etc. Signal reproduction resolution is mostly determined by the wavelength λ of the light source of the reproduction optical system and the numerical aperture NA of the objective lens on an optical disc having a thin film for recording information that can record signals and data in real time using a beam for data reproduction. , The recording mark period 2NA / λ is the reading limit.

高記録密度化のための手法としては、相変化により反射率が変化する媒体を用いて凹凸で記録されたデータを再生する方法が特開平３−２９２６３２号公報に記載され、また、相変化記録膜に記録されたデータを高密度再生するための溶融マスク層を持つ媒体が特開平５−７３９６１号公報に記載されている。 As a method for increasing the recording density, a method of reproducing data recorded with irregularities using a medium whose reflectivity changes due to a phase change is described in JP-A-3-292632. A medium having a molten mask layer for reproducing data recorded on a film at high density is described in Japanese Patent Application Laid-Open No. Hei 5-73661.

なお、本明細書では、結晶−非晶質間の相変化ばかりでなく、融解（液相への変化）と再結晶化、結晶状態−結晶状態間の相変化も含むものとして「相変化」という用語を使用する。 In this specification, “phase change” includes not only a phase change between a crystal and an amorphous phase, but also melting (change to a liquid phase) and recrystallization, and a phase change between a crystalline state and a crystalline state. Use the term

特開平４−２２８１２７号公報JP-A-4-228127

特開平３−２９２６３２号公報JP-A-3-292632 特開平５−７３９６１号公報JP-A-5-73961

従来の記録膜はいずれも、書き換え可能な相転移型の記録膜として用いる場合、ア.書き換え可能回数が十分でない、イ.書き換え可能回数を多くすると結晶化速度が遅くなる、ウ.書き換え可能回数を多くすると再生信号強度が十分でなくなる、などの問題を有している。 When any of the conventional recording films is used as a rewritable phase transition type recording film, a. The number of rewritable times is not sufficient, a. , The signal strength of the reproduced signal becomes insufficient.

そこで、この発明の目的は、良好な記録・再生特性を保持しながら従来より多数回の書き換えが可能である情報記録用薄膜およびその製造方法ならびにその薄膜を用いた情報記録媒体を提供することにある。 SUMMARY OF THE INVENTION It is an object of the present invention to provide an information recording thin film that can be rewritten more times than before while maintaining good recording / reproducing characteristics, a method of manufacturing the same, and an information recording medium using the thin film. is there.

また、特開平３−２９２６３２号公報に記載の方法は、Ｓｂ₂Ｓｅ₃ 膜を用い、読み出し光の走査スポット内で部分的に相変化させて反射率を変え、高反射率領域内のみの位相ピットを読みだす。この方法では、上記の膜の融点が高温のため、レーザの照射パワーが高く、位相ピットで情報を記録した光ディスク以外の相変化型光ディスク、光磁気ディスクなどに適用できない。さらに、多数回の読み出しを繰り返すと膜の流動、偏析が少しずつ生じ、超解像読み出し可能回数が少ない、などの欠点がある。また、特開平５−７３９６１号公報に記載の媒体は、溶融マスク層を用い、読み出し光の走査スポット内で部分的に溶融して反射率を変え、見かけ上スポットサイズを小さくする。この媒体では、融点が低い溶融マスク層を用いており、粘度が低いため、多数回の読み出しを繰り返すと膜の流動、偏析が少しずつ生じ、超解像読み出し可能回数が少ない、などの欠点がある
。 The method described in JP-A-3-292632 uses a Sb ₂ Se ₃ film and changes the reflectance by partially changing the phase within the scanning spot of the readout light to change the phase only in the high reflectance region. Read out the pit. In this method, since the melting point of the film is high, the irradiation power of the laser is high, and it cannot be applied to a phase change optical disk other than an optical disk in which information is recorded by phase pits, a magneto-optical disk, and the like. Further, when reading is repeated many times, there is a disadvantage that the film flows and segregates little by little, and the number of times of super-resolution reading is small. Further, the medium described in Japanese Patent Application Laid-Open No. Hei 5-73661 uses a fusion mask layer and partially melts the scanning spot of the readout light to change the reflectance and apparently reduce the spot size. In this medium, a melting mask layer with a low melting point is used, and the viscosity is low. Therefore, when reading is repeated many times, the flow and segregation of the film occur little by little, and the number of times that super-resolution reading is possible is small. is there.

そこで、この発明の他の目的は、上記した従来技術の欠点を解消し、映像信号や音声信号などのアナログ情報信号や、電子計算機のデータ、ファクシミリ信号、ディジタルオーディオ信号などのディジタル情報信号が凹凸により記録された光ディスクや相変化型光ディスク、光磁気ディスクなどに適用でき、流動、偏析を防止することにより、超解像読み出し可能回数を増大した超解像読み出し用薄膜を提供することにある。 Therefore, another object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to make analog information signals such as video signals and audio signals and digital information signals such as computer data, facsimile signals and digital audio signals uneven. An object of the present invention is to provide a super-resolution readout thin film which can be applied to an optical disk, a phase-change type optical disk, a magneto-optical disk, and the like recorded thereon, and which can prevent the flow and segregation, thereby increasing the number of times the super-resolution readout can be performed.

（１）この発明の第１の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、前記情報記録用薄膜の膜厚方向の平均組成が、一般式
Ｓｂ_xＴｅ_yＡ_pＢ_qＣ_r （１）
で表わされ、前記ＡはＧｅおよびＩｎからなる第１群から選ばれた少なくとも一つの元素、前記Ｂはランタノイド元素（Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，ＹｂおよびＬｕ）およびＡｇ，Ｂａ，Ｃｏ，Ｃｒ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，ＴｉおよびＶからなる第２群から選ばれた少なくとも一つの元素、前記ＣはＳｂ，Ｔｅおよび前記ＡおよびＢで表わされる元素以外の少なくとも一つの元素を表わし、前記ｘ，ｙ，ｐ，ｑおよびｒの単位はいずれも原子パーセントで、それぞれ２≦ｘ≦４１，２５≦ｙ≦７５，０．１≦ｐ≦６０，３≦ｑ≦４０，０．１≦ｒ≦３０の範囲にあることを特徴とする。
（２）この発明の第２の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、前記情報記録用薄膜の膜厚方向の平均組成が、一般式
Ｓｂ_xＴｅ_yＡ_pＢ_q （２）
で表わされ、前記ＡはＧｅおよびＩｎからなる第１群から選ばれた少なくとも一つの元素、前記Ｂはランタノイド元素およびＡｇ，Ｂａ，Ｃｏ，Ｃｒ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，ＴｉおよびＶからなる第２群から選ばれた少なくとも一つの元素を表わし、前記ｘ，ｙ，ｄおよびｅの単位はいずれも原子パーセントで、それぞれ２≦ｘ≦４１，２５≦ｙ≦７５，０．１≦ｐ≦６０，３≦ｑ≦４０の範囲にあることを特徴とする。 (1) A first thin film for information recording according to the present invention is an information recording thin film formed on a substrate directly or through a protective layer, for recording and reproducing information by a change in atomic arrangement caused by irradiation with an energy beam. In the thin film, the average composition in the thickness direction of the information recording thin film has a general formula
Sb _x T _y _Ap B _q C _r (1)
Wherein A is at least one element selected from the first group consisting of Ge and In, and B is a lanthanoid element (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy). , Ho, Er, Tm, Yb and Lu) and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, At least one element selected from the second group consisting of Cs, Ga, Pd, Bi, Sn, Ti, and V; and C represents at least one element other than Sb, Te, and the elements represented by A and B. The unit of x, y, p, q and r is atomic percent, and 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 0.1 ≦ p ≦ 60, 3 ≦ q ≦ 40, 0.1 ≦ r ≦ 30 And butterflies.
(2) A second thin film for information recording according to the present invention is an information recording thin film formed on a substrate directly or via a protective layer, for recording and reproducing information by an atomic arrangement change caused by irradiation of an energy beam. In the thin film, the average composition in the thickness direction of the information recording thin film has a general formula
Sb _x T _y _Ap B _q (2)
Wherein A is at least one element selected from the first group consisting of Ge and In, B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd. , Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn, Ti and V, at least one element selected from the group consisting of , Y, d and e are in atomic percent, and are in the ranges of 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 0.1 ≦ p ≦ 60, and 3 ≦ q ≦ 40, respectively. .

これは、前記第１の情報記録用薄膜の前記Ｃで表わされる元素を除いたものに相当する。
（３）この発明の第３の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、前記情報記録用薄膜の膜厚方向の平均組成が、一般式
Ｓｂ_xＴｅ_yＢ_qＣ_r （３）
で表わされ、前記Ｂはランタノイド元素およびＡｇ，Ｂａ，Ｃｏ，Ｃｒ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，ＴｉおよびＶからなる群から選ばれた少なくとも一つの元素、前記ＣはＳｂ，Ｔｅおよび前記Ｂで表わされる元素以外の少なくとも一つの元素を表わし、前記ｘ，ｙ，ｅおよびｆの単位はいずれも原子パーセントで、それぞれ２≦ｘ≦４１，２５≦ｙ≦７５，３≦ｑ≦４０，０．１≦ｒ≦３０の範囲にあることを特徴とする。 This corresponds to the first information recording thin film excluding the element represented by C.
(3) A third thin film for information recording according to the present invention, which is formed on a substrate directly or via a protective layer, for recording and reproducing information by a change in atomic arrangement caused by irradiation with an energy beam. In the thin film, the average composition in the thickness direction of the information recording thin film has a general formula
Sb _x T _y B _q C _r (3)
Wherein B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs , Ga, Pd, Bi, Sn, Ti and V, at least one element selected from the group consisting of Sb, Te and B, and x and y , E and f are in atomic percent, and are in the ranges of 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 3 ≦ q ≦ 40, and 0.1 ≦ r ≦ 30, respectively.

これは、前記第１の情報記録用薄膜の前記Ａで表わされる元素を除いたものに相当する。
（４）この発明の第４の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、前記情報記録用薄膜の膜厚方向の平均組成が、一般式
Ｓｂ_xＴｅ_yＢ_q （４）
で表わされ、前記Ｂはランタノイド元素およびＡｇ，Ｂａ，Ｃｏ，Ｃｒ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，ＴｉおよびＶからなる群から選ばれた少なくとも一つの元素を表わし、前記ｘ，ｙおよびｅの単位はいずれも原子パーセントで、それぞれ２≦ｘ≦４１，２５≦ｙ≦７５，３≦ｑ≦４０の範囲にあることを特徴とする。 This corresponds to the first information recording thin film except for the element represented by A.
(4) A fourth thin film for information recording according to the present invention is formed on a substrate directly or via a protective layer, for recording and reproducing information by a change in atomic arrangement caused by irradiation with an energy beam. In the thin film, the average composition in the thickness direction of the information recording thin film has a general formula
Sb _x Te _y B _q (4)
Wherein B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs , Ga, Pd, Bi, Sn, Ti and V represent at least one element selected from the group consisting of x, y, and e, each of which is an atomic percent, and 2 ≦ x ≦ 41, 25 ≦ It is characterized by being in the range of y ≦ 75, 3 ≦ q ≦ 40.

これは、前記第１の情報記録用薄膜の前記ＡおよびＣで表わされる元素を除いたものに相当する。
（５）この発明の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、
前記情報記録用薄膜の平均組成が、一般式
（Ｇｅ_aＳｂ_bＴｅ_c）_1-dＸ_d （５）
で表わされ、
前記ＸはＣｒおよびＡｇ，Ｂａ，Ｃｏ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，Ｔｉ，Ｖ，Ｉｎおよびランタノイド元素からなる少なくとも一つの元素を表わし、前記ａ，ｂ，ｃおよびｄが、それぞれ
０．０２≦ａ≦０．１９，０．０４≦ｂ≦０．４，０．５≦ｃ≦０．７５，０．０３≦ｄ≦０．３，の範囲にあることを特徴とする。
（６）この発明の情報記録用薄膜は、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、
前記情報記録用薄膜の平均組成が、一般式
（Ｇｅ_aＳｂ_bＴｅ_c）_1-dＸ_d （５）
で表わされ、
前記ＸはＣｒおよびＡｇ，Ｂａ，Ｃｏ，Ｎｉ，Ｐｔ，Ｓｉ，Ｓｒ，Ａｕ，Ｃｄ，Ｃｕ，Ｌｉ，Ｍｏ，Ｍｎ，Ｚｎ，Ａｌ，Ｆｅ，Ｐｂ，Ｎａ，Ｃｓ，Ｇａ，Ｐｄ，Ｂｉ，Ｓｎ，Ｔｉ，Ｖ，Ｉｎおよびランタノイド元素からなる少なくとも一つの元素を表わし、前記ａ，ｂ，ｃおよびｄが、それぞれ
０．２５≦ａ≦０．６５，０≦ｂ≦０．２，０．３５≦ｃ≦０．７５，０．０３≦ｄ≦０．３の範囲にあることを特徴とする。
（７）前記１〜６のいずれかに記載の情報記録用薄膜において、前記ＢまたはＸが膜厚方向において濃度勾配を有することを特徴とする。
（８）前記１〜６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、その析出物が前記Ｂまたは前記Ｘで表わされる元素を含んでいることを特徴とする。
（９）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の少なくとも一部分が、当該薄膜の光入射側に非連続膜状に平均膜厚１〜１０ｎｍの範囲で存在することを特徴とする。
（１０）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の構成元素の原子数の和が、当該薄膜の構成元素の全原子数の和に対して１０〜５０％の範囲にあることを特徴とする。
（１１）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分含有量が膜厚方向において変化することを特徴とする。
（１２）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、当該薄膜の平均組成を元素単体または化合物組成の低融点成分Ｌと元素単体または化合物組成の高融点成分Ｈにより
Ｌ_jＨ_k （６）
の式で表した時、２０≦ｋ／（ｊ＋Ｋ）≦４０（７）である組成を基準組成とし、各元素の膜中での含有量は前記式で決まる値±１０原子％の範囲内にあることを特徴とする。
（１３）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の融点が７８０゜Ｃ以上であることを特徴とする。
（１４）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の融点と当該薄膜の残成分の融点との差が１５０゜Ｃ以上であることを特徴とする。
（１５）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の析出物が、当該薄膜の内部に粒状または柱状に分布していることを特徴とする。
（１６）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の析出物の当該薄膜の膜面方向での最大外寸法が５ｎｍ以上、５０ｎｍ以下であることを特徴とする。
（１７）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の析出物が、当該薄膜の両方の界面からその膜厚方向に柱状に延びており、析出物の膜厚方向の長さが５ｎｍ以上で、当該薄膜の膜厚の（１／２）以下であることを特徴とする。
（１８）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の析出物が、当該薄膜の一方の界面からその膜厚方向に柱状に延びており、析出物の膜厚方向の長さが１０ｎｍ以上で、当該薄膜の膜厚以下である請求項９または１０に記載の情報記録用薄膜。
（１９）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、高融点成分の析出物の膜厚方向の長さが１０ｎｍ以上で、当該薄膜の膜厚以下であることを特徴とする。
（２０）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、隣接する２つの高融点成分の析出物の中心間を結ぶ直線が、当該薄膜の膜面方向でそれら析出物の間の領域を通る長さが１５ｎｍ以上、７０ｎｍ以下であることを特徴とする。
（２１）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる多孔質の析出物を含んでおり、当該残成分が前記多孔質析出物の孔内に分布していることを特徴とする。
（２２）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる多孔質の析出物を含んでおり、高融点成分の多孔質状析出物の孔の当該薄膜の膜面方向での最大孔寸法が８０ｎｍ以下であり、隣接する２つの前記孔の間の領域の当該薄膜の膜面方向での最大壁厚さが２０ｎｍ以下であることを特徴とする。
（２３）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、当該薄膜の残成分の融点が６５０゜Ｃ以下であることを特徴とする。
（２４）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、当該薄膜の残成分の融点が２５０゜Ｃ以下であることを特徴とする。
（２５）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、当該薄膜の複素屈折率の実数部および虚数部の少なくとも一方が、光の照射によって照射前のそれに対して２０％以上変化することを特徴とする。
（２６）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、その析出物が当該薄膜の残成分からなる領域内に分布していることを特徴とする。
（２７）前記２６に記載の情報記録用薄膜において、前記高融点成分の析出物の当該薄膜の膜面方向での最大外寸法が５ｎｍ以上、５０ｎｍ以下であることを特徴とする。
（２８）前記２６に記載の情報記録用薄膜において、前記高融点成分の析出物が、当該薄膜の両方の界面からその膜厚方向に柱状に延びており、前記析出物の膜厚方向の長さが５ｎｍ以上で、当該薄膜の膜厚の（１／２）以下であることを特徴とする。
（２９）前記２６に記載の情報記録用薄膜において、前記高融点成分の析出物が、当該薄膜の一方の界面からその膜厚方向に柱状に延びており、前記析出物の膜厚方向の長さが１０ｎｍ以上で、当該薄膜の膜厚以下であることを特徴とする。
（３０）前記２６に記載の情報記録用薄膜において、前記高融点成分の析出物の膜厚方向の長さが１０ｎｍ以上で、当該薄膜の膜厚以下であることを特徴とする。
（３１）前記２６に記載の情報記録用薄膜において、隣接する２つの前記高融点成分の析出物の中心間を結ぶ直線が、当該薄膜の膜面方向でそれら析出物の間の領域を通る長さが１５ｎｍ以上、７０ｎｍ以下であることを特徴とする。
（３２）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる多孔質の析出物を含んでおり、当該薄膜の残成分が前記多孔質析出物の孔内に分布していることを特徴とする情報記録用薄膜。
（３３）前記３２に記載の情報記録用薄膜において、前記高融点成分の多孔質状析出物の孔の当該薄膜の膜面方向での最大内寸法が８０ｎｍ以下であり、隣接する２つの前記孔の間の領域の当該薄膜の膜面方向での最大壁厚さが２０ｎｍ以下であることを特徴とする。
（３４）前記２６または３２に記載の情報記録用薄膜において、当該薄膜の残成分の融点が６５０゜Ｃ以下であることを特徴とする。
（３５）前記３２または３２に記載の情報記録用薄膜において、当該薄膜の残成分の融点が２５０゜Ｃ以下であることを特徴とする。
（３６）前記２６または３２のいずれかに記載の情報記録用薄膜において、当該薄膜の複素屈折率の実数部および虚数部の少なくとも一方が、光の照射によって照射前のそれに対して２０％以上変化することを特徴とする。
（３７）前記２６または３２のいずれかに記載の情報記録用薄膜において、前記高融点成分の構成元素の原子数の和が、当該薄膜の全原子数の和に対して１０〜５０％の範囲にあることを特徴とする。
（３８）前記２６または３２のいずれかに記載の情報記録用薄膜において、平均組成を元素単体または化合物組成の低融点成分Ｌと元素単体または化合物組成の高融点成分Ｈにより
Ｌ_jＨ_k （６）
の式で表した時、２０≦ｋ／（ｊ＋Ｋ）≦４０（７）である組成を基準組成とし、各元素の膜中での含有量は前記式で決まる値±１０原子％の範囲内にあることを特徴とする。
（３９）前記２６または３２のいずれかに記載の情報記録用薄膜において、前記高融点成分の融点が７８０゜Ｃ以上であることを特徴とする。
（４０）前記２６または３２のいずれかに記載の情報記録用薄膜において、前記高融点成分の融点と当該薄膜の残成分の融点との差が１５０゜Ｃ以上であることを特徴とする。
（４１）前記２，５および６のいずれかに記載の情報記録用薄膜において、当該薄膜の残成分より相対的に融点が高い高融点成分からなる析出物を含んでおり、前記Ｂまたは前記Ｘで表わされる元素がＭｏおよびＳｉ，Ｐｔ，Ｃｏ，Ｍｎ，Ｗであることが好ましく、Ｃｒであることが特に好ましい。
（４２）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜の製造方法において、
基板上に直接または保護層を介して薄膜を形成する工程と、
前記薄膜にエネルギービームを照射して前記薄膜中に高融点成分を生成または成長させる工程と
を備えてなることを特徴とする。
（４３）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜の製造方法において、基板上に直接または保護層を介して高融点成分の材料あるいは高融点成分の組成に近い組成を持つ材料を被着させて島状の種結晶を形成する工程と、前記種結晶の上に前記高融点成分と前記残成分とを含む材料を被着させ、前記高融点成分を選択的に前記種結晶上に成長させると共に、それら種結晶の間を埋めるように前記残成分を成長させる工程とを備えてなることを特徴とする。 This corresponds to the first information recording thin film excluding the elements represented by A and C.
(5) An information recording thin film according to the present invention is an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation with an energy beam.
The average composition of the information recording thin film is represented by the general formula _{_{_{(Ge a Sb b Te c)}}} 1-d X d (5)
Represented by
X is Cr and Ag, Ba, Co, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn. , Ti, V, In and at least one element consisting of lanthanoid elements, wherein a, b, c and d are respectively 0.02 ≦ a ≦ 0.19, 0.04 ≦ b ≦ 0.4, 0 0.5 ≦ c ≦ 0.75, 0.03 ≦ d ≦ 0.3.
(6) An information recording thin film according to the present invention is an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam.
The average composition of the information recording thin film is represented by the general formula _{_{_{(Ge a Sb b Te c)}}} 1-d X d (5)
Represented by
X is Cr and Ag, Ba, Co, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn. , Ti, V, In and at least one element consisting of lanthanoid elements, wherein a, b, c and d are 0.25 ≦ a ≦ 0.65, 0 ≦ b ≦ 0.2 and 0.35, respectively. ≦ c ≦ 0.75, 0.03 ≦ d ≦ 0.3.
(7) The information recording thin film according to any one of (1) to (6) above, wherein B or X has a concentration gradient in a film thickness direction.
(8) The information recording thin film according to any one of the above 1 to 6, wherein the thin film contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the precipitate is the B or It is characterized by containing the element represented by X.
(9) The information recording thin film according to any one of the above 2, 5 and 6, wherein the thin film contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and at least one of the high melting point components It is characterized in that a part of the thin film exists on the light incident side of the thin film in the form of a discontinuous film with an average thickness of 1 to 10 nm.
(10) The information recording thin film according to any one of (2), (5), and (6), further comprising a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the composition of the high melting point component. A feature is that the sum of the number of atoms of the element is in a range of 10 to 50% with respect to the sum of the total number of atoms of the constituent elements of the thin film.
(11) The information recording thin film according to any one of the above 2, 5 and 6, wherein the thin film for information recording contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and contains a high melting point component. Vary in the film thickness direction.
(12) The information recording thin film according to any one of (2), (5), and (6), wherein the thin film includes a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the average composition of the thin film With the low melting point component L of the elemental or compound composition and the high melting point component H of the elemental or compound composition
L _j H _k (6)
In the formula, a composition satisfying 20 ≦ k / (j + K) ≦ 40 is set as a reference composition, and the content of each element in the film is within a range of ± 10 atomic% determined by the above formula. There is a feature.
(13) The information recording thin film according to any one of (2), (5), and (6), wherein the thin film contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the melting point of the high melting point component Is 780 ° C. or more.
(14) The information recording thin film according to any one of (2), (5), and (6), wherein the thin film contains a precipitate composed of a high melting point component having a melting point higher than the remaining components of the thin film, and the melting point of the high melting point component And a difference between the melting point of the remaining component of the thin film and 150 ° C. or more.
(15) The information recording thin film according to any one of the above items 2, 5 and 6, further comprising a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and depositing the high melting point component. The object is characterized in that it is distributed in the form of particles or columns inside the thin film.
(16) The information recording thin film according to any one of the above items 2, 5 and 6, further comprising a deposit composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and depositing the high melting point component. The maximum outer dimension of the object in the film surface direction of the thin film is 5 nm or more and 50 nm or less.
(17) The information recording thin film according to any one of the above items 2, 5 and 6, further comprising a deposit composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and depositing the high melting point component. The substance extends in a columnar shape in the thickness direction from both interfaces of the thin film, and the length of the precipitate in the thickness direction is 5 nm or more and (1/2) or less of the thickness of the thin film. It is characterized by.
(18) The information recording thin film according to any one of the above items 2, 5 and 6, wherein the thin film for information recording contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film. 11. The article according to claim 9, wherein the substance extends from one interface of the thin film in a columnar shape in the thickness direction thereof, and the length of the precipitate in the thickness direction is 10 nm or more and not more than the thickness of the thin film. Information recording thin film.
(19) The information recording thin film according to any one of the above items 2, 5, and 6, further comprising a precipitate composed of a high melting point component having a melting point higher than the remaining components of the thin film, and depositing the high melting point component. The length of the object in the thickness direction is not less than 10 nm and not more than the thickness of the thin film.
(20) The thin film for information recording according to any one of the above items 2, 5 and 6, which contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and includes two adjacent high melting points. A straight line connecting the centers of the precipitates of the melting point component passes through a region between the precipitates in the film surface direction of the thin film, and has a length of 15 nm or more and 70 nm or less.
(21) The thin film for recording information according to any one of (2), (5), and (6), further comprising a porous precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film. It is characterized in that components are distributed in pores of the porous precipitate.
(22) The information recording thin film according to any one of the above (2), (5) and (6), comprising a porous deposit composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, The maximum pore size of the pores of the porous precipitate of the component in the film surface direction of the thin film is 80 nm or less, and the maximum wall thickness of the region between two adjacent holes in the film surface direction of the thin film. Is 20 nm or less.
(23) The information recording thin film according to any one of 2, 5, and 6, further comprising a precipitate composed of a high melting point component having a relatively higher melting point than the remaining component of the thin film, and the remaining component of the thin film. Has a melting point of 650 ° C. or less.
(24) The information recording thin film according to any one of the items 2, 5, and 6, further comprising a precipitate composed of a high melting point component having a relatively higher melting point than the remaining component of the thin film, and the remaining component of the thin film. Has a melting point of 250 ° C. or less.
(25) The information recording thin film according to any one of the above items 2, 5, and 6, which contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the complex refractive index of the thin film. At least one of the real part and the imaginary part of the ratio changes by 20% or more with respect to that before irradiation by light irradiation.
(26) An information recording thin film formed on a substrate directly or through a protective layer and recording / reproducing information by a change in atomic arrangement caused by irradiation with an energy beam, relative to the remaining components of the thin film. The thin film includes a precipitate composed of a high melting point component having a high melting point, and the precipitate is distributed in a region composed of a residual component of the thin film.
(27) In the information recording thin film described in the item (26), a maximum outer dimension of the precipitate of the high melting point component in a film surface direction of the thin film is 5 nm or more and 50 nm or less.
(28) In the information recording thin film described in (26), the precipitate of the high melting point component extends in a columnar shape in the thickness direction from both interfaces of the thin film, and the length of the precipitate in the thickness direction is long. Is not less than 5 nm and not more than (１／) the thickness of the thin film.
(29) In the information recording thin film according to the item (26), the precipitate of the high melting point component extends from one interface of the thin film in a columnar shape in the film thickness direction, and the length of the precipitate in the film thickness direction is increased. Is not less than 10 nm and not more than the thickness of the thin film.
(30) The thin film for information recording according to (26), wherein a length of the precipitate of the high melting point component in a thickness direction is 10 nm or more and not more than the thickness of the thin film.
(31) In the information recording thin film as described in 26 above, a straight line connecting the centers of two adjacent high melting point component precipitates passes through a region between the precipitates in the film surface direction of the thin film. Is not less than 15 nm and not more than 70 nm.
(32) An information recording thin film formed on a substrate directly or through a protective layer and recording / reproducing information by an atomic arrangement change caused by irradiation of an energy beam, relative to a residual component of the thin film. An information recording thin film, comprising a porous precipitate composed of a high melting point component having a high melting point, wherein residual components of the thin film are distributed in pores of the porous precipitate.
(33) In the information recording thin film according to the above (32), the maximum internal dimension of the pores of the porous precipitate of the high melting point component in the film surface direction of the thin film is 80 nm or less, and two adjacent pores are formed. Is characterized in that the maximum wall thickness in the film surface direction of the thin film in the region between is not more than 20 nm.
(34) The thin film for information recording as described in (26) or (32) above, wherein the remaining component of the thin film has a melting point of 650 ° C. or less.
(35) The thin film for information recording as described in (32) or (32) above, wherein the remaining component of the thin film has a melting point of 250 ° C. or less.
(36) In the information recording thin film according to any one of (26) and (32), at least one of a real part and an imaginary part of a complex refractive index of the thin film changes by 20% or more with respect to that before irradiation by light irradiation. It is characterized by doing.
(37) In the information recording thin film according to any one of (26) and (32), the sum of the number of atoms of the constituent elements of the high melting point component is in a range of 10 to 50% with respect to the sum of the total number of atoms of the thin film. Characterized by the following.
(38) In the information recording thin film according to any one of the above items 26 and 32, the average composition is determined by a low melting point component L of a simple element or a compound composition and a high melting point component H of a simple element or a compound composition.
L _j H _k (6)
In the formula, a composition satisfying 20 ≦ k / (j + K) ≦ 40 is set as a reference composition, and the content of each element in the film is within a range of ± 10 atomic% determined by the above formula. There is a feature.
(39) In the information recording thin film according to any one of (26) and (32), the melting point of the high melting point component is 780 ° C or more.
(40) The thin film for information recording according to any one of (26) and (32), wherein the difference between the melting point of the high melting point component and the melting point of the remaining components of the thin film is 150 ° C. or more.
(41) The information recording thin film according to any one of the items 2, 5, and 6, further comprising a precipitate composed of a high melting point component having a melting point relatively higher than the remaining components of the thin film, and the B or X The elements represented by are preferably Mo and Si, Pt, Co, Mn, W, and particularly preferably Cr.
(42) A method for manufacturing an information recording thin film, which is formed directly on a substrate or through a protective layer and records / reproduces information by an atomic arrangement change caused by irradiation of an energy beam,
Forming a thin film directly on the substrate or via a protective layer,
Irradiating the thin film with an energy beam to generate or grow a high melting point component in the thin film.
(43) In a method of manufacturing an information recording thin film, which is formed on a substrate directly or through a protective layer and records / reproduces information by a change in atomic arrangement caused by irradiation of an energy beam, a method of directly or protecting a substrate. Forming an island-shaped seed crystal by applying a material having a high melting point component or a material having a composition close to the composition of the high melting point component through a layer; and forming the high melting point component and the residue on the seed crystal. And a step of selectively growing the high melting point component on the seed crystal and growing the remaining component so as to fill the space between the seed crystals. Features.

前記島状の種結晶を形成するための膜の平均膜厚は、１ｎｍ以上、１０ｎｍ以下が好ましい。１ｎｍ未満であると高融点成分を成長させる効果が小さく、１０ｎｍを越えるとノイズ増大の原因となる。 The average film thickness of the film for forming the island-shaped seed crystal is preferably 1 nm or more and 10 nm or less. If it is less than 1 nm, the effect of growing the high melting point component is small, and if it exceeds 10 nm, noise may be increased.

この方法では、高融点成分は情報記録用薄膜の片側の界面からその内部に向かって成長しやすい。 In this method, the high melting point component tends to grow from the interface on one side of the information recording thin film toward the inside thereof.

前記第１および第２の情報記録用薄膜の製造方法では、成膜するのに真空蒸着、ガス中蒸着、スパッタリング、イオンビーム蒸着、イオンプレーティング、電子ビーム蒸着など、公知の方法を用いることができるが、スパッタリングを用いるのが好ましい。 In the first and second methods for producing a thin film for information recording, a known method such as vacuum deposition, vapor deposition in gas, sputtering, ion beam deposition, ion plating, and electron beam deposition may be used. Although it is possible, it is preferable to use sputtering.

スパッタリングの場合、記録用薄膜の組成のターゲットによってスパッタする方法では、膜中での均一性が良くノイズを低くすることができる。一方、高融点成分の組成のターゲットと残成分の組成のターゲットによる回転同時スパッタ法では、高融点成分の析出を早めることができ、書き換え可能回数を延ばすのに有効である。
（４４）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録用薄膜の製造方法において、基板上に直接または保護層を介して相変化成分と高融点成分より成る膜の形成時に高融点成分の含有量を膜厚方向に変化させる工程を備えてることを特徴とする。
（４５）前記１〜６，２６および３２のいずれかに記載の情報記録用薄膜を記録層として備えた情報記録媒体であることを特徴とする。
（４６）前記１〜６，２６および３２のいずれかに記載の情報記録用薄膜を超解像読出し用のマスク層として備えた情報記録媒体であることを特徴とする。
（４７）前記１〜６，２６および３２のいずれかに記載の情報記録用薄膜を超解像読出し用の反射層として備えた情報記録媒体であることを特徴とする。
（４８）前記高融点成分の析出後の前記残成分の融点が６５０゜Ｃ以下である、前記１〜６，２６および３２のいずれかに記載の情報記録媒体を備えた情報記録媒体であることを特徴とする。
（４９）前記１〜６，２６および３２のいずれか４７または４８に記載の情報記録用薄膜を超解像読出し用の反射層として備えた情報記録媒体において、前記反射層の反射率が６０％以上であることを特徴とする。
（５０）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録媒体において、前記１〜６，２６および３２のいずれかに記載の情報記録用薄膜を記録層または超解像読出し用のマスク層として備え、かつ反射層側にＳｉＯ₂ 層と記録膜側にＺｎＳ−ＳｉＯ₂ 層の２層構造の中間層を備えることを特徴とする。
（５１）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録媒体において、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録用薄膜を記録層または超解像読出し用のマスク層として備え、かつＳｉ−Ｓｎ、Ｓｉ−Ｇｅ，Ｓｉ−Ｉｎ化合物の少なくとも１つ、またはこれに近い組成である反射層を備えることを特徴とする。
（５２）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録媒体において、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録用薄膜を記録層または超解像読出し用のマスク層として備え、かつ反射層の膜厚が、１５０ｎｍ以上３００ｎｍ以下である特徴を持つ。
（５３）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録媒体において、基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録用薄膜を記録層または超解像読出し用のマスク層として備え、かつ光入射側にＳｉＯ₂層と記録膜側にＺｎＳ−ＳｉＯ₂層の２層構造の保護層を備えることを特徴とする。
（５４）保護層２および中間層４の材料は、ＺｎＳ−ＳｉＯ₂、Ｓｉ−Ｎ系材料，Ｓｉ−Ｏ−Ｎ系材料，ＳｉＯ₂，ＳｉＯ，Ｔａ₂Ｏ₅，ＴｉＯ₂，Ａｌ₂Ｏ₃，Ｙ₂Ｏ₃，ＣｅＯ，Ｌａ₂Ｏ₃，Ｉｎ₂Ｏ₃，ＧｅＯ，ＧｅＯ₂，ＰｂＯ，ＳｎＯ，ＳｎＯ₂，Ｂｉ₂Ｏ₃，ＴｅＯ₂ＷＯ₂，ＷＯ₃，Ｓｃ₂Ｏ₃，ＺｒＯ₂などの酸化物，ＴａＮ，ＡｌＮ，Ｓｉ₃Ｎ₄，Ａｌ−Ｓｉ−Ｎ系材料（例えばＡｌＳｉＮ₂）などの窒化物、ＺｎＳ，Ｓｂ₂Ｓ₃，ＣｄＳ，Ｉｎ₂Ｓ₃，Ｇａ₂Ｓ₃，ＧｅＳ，ＳｎＳ₂，ＰｂＳ，Ｂｉ₂Ｓ₃，などの硫化物、ＳｎＳｅ₂，Ｓｂ₂Ｓｅ₃，ＣｄＳｅ，ＺｎＳｅ，Ｉｎ₂Ｓｅ₃，Ｇａ₂Ｓｅ₃，ＧｅＳｅ，ＧｅＳｅ₂，ＳｎＳｅ，ＰｂＳｅ，Ｂｉ₂Ｓｅ₃などのセレン化物、ＣｅＦ₃，ＭｇＦ₂，ＣａＦ₂などの弗化物、あるいはＳｉ，Ｇｅ，ＴｉＢ₂，Ｂ₄Ｃ，Ｂ，Ｃ，または、上記の材料に近い組成のものを用いるのが好ましい。また、これらの混合材料の層やこれらの多重層でもよい。 In the case of sputtering, a method of sputtering with a target having a composition of a recording thin film has good uniformity in the film and can reduce noise. On the other hand, the rotation simultaneous sputtering method using the target having the composition of the high melting point component and the target having the composition of the remaining component can accelerate the deposition of the high melting point component and is effective in extending the number of rewritable times.
(44) In a method of manufacturing an information recording thin film, which is formed directly on a substrate or via a protective layer and records or reproduces information by a change in atomic arrangement caused by irradiation of an energy beam, a method of directly or protecting a substrate on a substrate. A step of changing the content of the high melting point component in the film thickness direction when forming a film composed of the phase change component and the high melting point component through the layer.
(45) An information recording medium comprising the information recording thin film according to any one of 1 to 6, 26, and 32 as a recording layer.
(46) An information recording medium comprising the information recording thin film described in any one of 1 to 6, 26, and 32 as a mask layer for super-resolution reading.
(47) An information recording medium comprising the information recording thin film described in any one of 1 to 6, 26 and 32 as a reflective layer for super-resolution reading.
(48) An information recording medium provided with the information recording medium according to any one of 1 to 6, 26 and 32, wherein the melting point of the residual component after the precipitation of the high melting point component is 650 ° C. or less. It is characterized.
(49) In an information recording medium comprising the information recording thin film according to any one of 47 to 48 of 1 to 6, 26 and 32 as a reflective layer for super-resolution reading, the reflectance of the reflective layer is 60%. It is characterized by the above.
(50) An information recording medium which is formed on a substrate directly or through a protective layer and records or reproduces information by a change in atomic arrangement caused by irradiation of an energy beam. And a mask layer for super-resolution reading, and an intermediate layer having a two-layer structure of a SiO ₂ layer on the reflective layer side and a ZnS—SiO ₂ layer on the recording film side. It is characterized by the following.
(51) An information recording medium which is formed on a substrate directly or through a protective layer and records or reproduces information by a change in atomic arrangement caused by irradiation with an energy beam. An information recording thin film for recording or reproducing information is formed as a recording layer or a mask layer for super-resolution reading by forming an atomic arrangement change caused by irradiation of an energy beam, and is formed of Si-Sn, Si-Ge, It is characterized by including a reflective layer having a composition of at least one of Si-In compounds or a composition close thereto.
(52) An information recording medium which is formed on a substrate directly or through a protective layer and records or reproduces information by a change in atomic arrangement caused by irradiation of an energy beam. A formed information recording thin film for recording or reproducing information by a change in atomic arrangement generated by irradiation with an energy beam is provided as a recording layer or a mask layer for super-resolution reading, and the thickness of the reflective layer is 150 nm. It has a feature of not less than 300 nm.
(53) An information recording medium which is formed directly on a substrate or through a protective layer and records or reproduces information by a change in atomic arrangement caused by irradiation with an energy beam. A formed information recording thin film for recording or reproducing information by a change in atomic arrangement generated by irradiation of an energy beam is provided as a recording layer or a mask layer for super-resolution reading, and a SiO ₂ layer is formed on the light incident side. On the recording film side, a protective layer having a two-layer structure of a ZnS—SiO ₂ layer is provided.
(54) the material of the protective layer 2 and the intermediate layer _{4, ZnS-SiO 2, Si-} N -based material, SiO-N based _{_{material, SiO 2, SiO, Ta 2}} O 5, TiO 2, Al 2 O 3 _{_{, Y 2 O 3, CeO,}} La 2 O 3, In 2 O 3, GeO, GeO 2, PbO, SnO, SnO 2, Bi 2 O 3, TeO 2 WO 2, WO 3, Sc 2 O 3, ZrO 2 oxides such _{as, TaN, AlN, Si 3 N} 4, Al-Si-N material (e.g., AlSiN ₂₎ nitride such _{_{as, ZnS, Sb 2 S 3,}} CdS, in 2 S 3, Ga 2 S 3, Sulfides such as GeS, SnS ₂ , PbS, Bi ₂ S ₃ , SnSe ₂ , Sb ₂ Se ₃ , CdSe, ZnSe, In ₂ Se ₃ , Ga ₂ Se ₃ , GeSe, GeSe ₂ , SnSe, PbSe, Bi ₂ selenide, such as _{_{_{Se 3, CeF 3, MgF 2}}} , CaF 2 , etc. Fluorides or _{Si,, Ge, TiB 2,} B 4 C, B, C, or, preferably used ones having a composition close to the above materials. Further, a layer of a mixed material thereof or a multilayer thereof may be used.

多重層の場合、ＺｎＳを７０モル％以上含む材料、例えばＺｎＳ−ＳｉＯ₂と、Ｓｉ，Ｇｅのうちの少なくとも一者を７０原子％以上含む材料、例えばＳｉ、あるいはＳｉの酸化物、例えばＳｉＯ₂との２層膜が好ましい。この場合、記録感度低下を防ぐため、ＺｎＳ−ＳｉＯ₂層の方を記録膜側に設け、その厚さを３ｎｍ以上とする。また、ＳｉＯ₂層の低熱膨張係数による記録膜流動抑制効果を発揮させるために、厚さ１０ｎｍ以下が好ましい。この２層膜は保護層２の代わりに設けると好ましいが、中間層４の代わりに設けてもよい。保護層２の代わりとしてはＳｉＯ₂層の厚さが５０ｎｍ以上２５０ｎｍ以下が好ましい。中間層の代わりに２層膜を設ける場合は、ＳｉＯ₂層の膜厚は１０ｎｍ以上８０ｎｍ以下が好ましい。これらの２層膜を設けることは、本発明の記録膜を用いる場合だけではなく、他の相変化記録膜を用いる場合にも好ましい。 In the case of a multi-layer, a material containing ZnS of 70 mol% or more, for example, ZnS—SiO _2, and a material containing at least one of Si and Ge of 70 atomic% or more, for example, Si, or an oxide of Si, for example, SiO ₂ Are preferred. In this case, in order to prevent a decrease in recording sensitivity, the ZnS-SiO ₂ layer is provided on the recording film side, and its thickness is set to 3 nm or more. The thickness is preferably 10 nm or less in order to exhibit the effect of suppressing the flow of the recording film due to the low thermal expansion coefficient of the SiO ₂ layer. This two-layer film is preferably provided in place of the protective layer 2, but may be provided in place of the intermediate layer 4. As a substitute for the protective layer 2, the thickness of the SiO ₂ layer is preferably 50 nm or more and 250 nm or less. When a two-layer film is provided instead of the intermediate layer, the thickness of the SiO ₂ layer is preferably from 10 nm to 80 nm. Providing these two-layer films is preferable not only when using the recording film of the present invention but also when using another phase change recording film.

中間層４の屈折率が１．７以上、２．３以下の範囲にある場合、膜厚が３ｎｍ以上、１００ｎｍ以下、および１８０ｎｍ以上、４００ｎｍ以下が好ましい。 When the refractive index of the intermediate layer 4 is in the range of 1.7 or more and 2.3 or less, the film thickness is preferably 3 nm or more, 100 nm or less, and 180 nm or more and 400 nm or less.

反射層５の材料としては、Ａｌ−Ｔｉ、Ｓｉ−Ｇｅ混合材料が、記録マーク部分の光吸収率を記録マーク以外の部分の光吸収率より小さくできるので、光吸収率差による消え残りを防止でき、さらに書き換え可能回数が低下せず、好ましい。Ｇｅの含有量は１０原子％以上８０原子％以下が書き換え可能回数が低下が生じにくく、好ましい。 As a material of the reflective layer 5, a mixed material of Al—Ti and Si—Ge can make the light absorption of the recording mark portion smaller than the light absorption of the portion other than the recording mark, so that the disappearance due to the difference in the light absorption ratio is prevented. It is preferable because the number of rewritable times does not decrease. The content of Ge is preferably 10 atomic% or more and 80 atomic% or less, because the number of rewritable times hardly decreases.

次いで、Ｓｉ−ＳｎまたはＳｉ−Ｉｎ混合材料、あるいはこれら混合材料の２種以上の混合材料でも同様の結果が得られ、好ましい。これらの反射層材料は、本発明の相変化膜ばかりでなく、他の相変化膜を用いる場合の反射層材料として用いても、従来のものに比べて、書き換え可能回数が低下しないため好ましい。 Next, a similar result is obtained with a Si-Sn or Si-In mixed material or a mixed material of two or more of these mixed materials, which is preferable. These reflective layer materials are preferable not only for the phase change film of the present invention but also for use as a reflective layer material when another phase change film is used, because the number of rewritable times is not reduced as compared with the conventional one.

さらに、Ｓｉ，Ｇｅ，Ｃ，Ａｕ，Ａｇ，Ｃｕ，Ａｌ，Ｎｉ，Ｆｅ，Ｃｏ，Ｃｒ，Ｔｉ，Ｐｄ，Ｐｔ，Ｗ，Ｔａ，Ｍｏ，Ｓｂの元素単体、またはこれらを主成分とする合金、あるいはこれら同志の合金よりなる層を用いてもよいし、それらの層よりなる多重層を用いてもよいし、これらと酸化物などの他の物質との複合層などを用いてもよい。 Further, a single element of Si, Ge, C, Au, Ag, Cu, Al, Ni, Fe, Co, Cr, Ti, Pd, Pt, W, Ta, Mo, Sb, or an alloy containing these as main components, Alternatively, a layer made of these alloys may be used, a multi-layer made of these layers may be used, or a composite layer of these and another substance such as an oxide may be used.

この実施例では、表面に直接、トラッキングガイドなどの凹凸を形成したポリカーボネート基板１を用いているが、その代わりに、ポリオレフィン、エポキシ、アクリル樹脂、紫外線硬化樹脂層を表面に形成した化学強化ガラスなどを用いてもよい。 In this embodiment, the polycarbonate substrate 1 having the surface directly formed with irregularities such as a tracking guide is used, but instead, a polyolefin, an epoxy, an acrylic resin, a chemically strengthened glass having an ultraviolet curable resin layer formed on the surface, or the like is used. May be used.

中間層４、反射層５および保護層２の一部を省略した単純積層構造、例えば基板１／保護層２／記録膜３、基板１／記録膜３／中間層４、基板１／記録膜３／反射層５などの構成でも、従来のものに比べると、多数回書き換えを行なってもノイズ上昇が少なく、良好な結果が得られ、好ましい。 Simple laminated structure in which the intermediate layer 4, the reflective layer 5, and the protective layer 2 are partially omitted, for example, substrate 1 / protective layer 2 / recording film 3, substrate 1 / recording film 3 / intermediate layer 4, substrate 1 / recording film 3. Even with the configuration such as the reflective layer 5, the noise rise is small even when rewriting is performed many times, and good results are obtained, which is preferable, compared to the conventional configuration.

以上述べたように、この実施例の情報記録用薄膜は、記録・再生・消去特性を良好に保ちながら、従来より多数回の書き換えが可能である。また、記録・消去に用いるレーザ光のパワーが低くてよいという利点もある。
（５５）超解像読み出し用ビームの照射を受けて超解像効果を生ずる本発明の超解像読み出し用薄膜は、相変化成分及び析出した高融点成分を含むことを特徴とする。超解像読み出し用薄膜は、基板上に直接もしくは無機物及び有機物のうち少なくとも一者からなる保護層を介して形成される。
（５６）相変化成分より相対的に融点が高い高融点成分は、柱状または塊状析出物として、あるいは多孔質状析出物として析出している。
（５７）超解像読み出し用薄膜の平均組成は、次の一般式で表されるものとすることができる。 As described above, the information recording thin film of this embodiment can be rewritten more times than before while maintaining good recording / reproducing / erasing characteristics. Another advantage is that the power of the laser beam used for recording / erasing may be low.
(55) The super-resolution readout thin film of the present invention which produces a super-resolution effect upon irradiation with a super-resolution readout beam is characterized by containing a phase change component and a precipitated high melting point component. The thin film for super-resolution reading is formed directly on a substrate or via a protective layer made of at least one of an inorganic substance and an organic substance.
(56) The high melting point component having a relatively higher melting point than the phase change component is deposited as a columnar or massive precipitate, or as a porous precipitate.
(57) The average composition of the super-resolution readout thin film can be represented by the following general formula.

Ｄ_eＥ_fＦ_g （８）
ここで、前記ＥはＳｎ，Ｐｂ，Ｂｉ，Ｚｎ，Ｇａ，Ｉｎから選ばれた少なくとも１つの元素、前記ＥはＡｓ，Ｂ，Ｃ，Ｎ，Ｏ，Ｓ，Ｓｅ，Ｓｉ，Ｔｅ，Ａｇ，Ａｌ，Ａｕ，Ｂａ，Ｂｅ，Ｃａ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｓ，Ｃｕ，Ｆｅ，Ｇｅ，Ｈｆ，Ｈｇ，Ｉｒ，Ｋ，Ｌｉ，Ｍｇ，Ｍｎ，Ｍｏ，Ｎａ，Ｎｂ，Ｎｉ，Ｏｓ，Ｐｄ，Ｐｔ，Ｒｂ，Ｒｅ，Ｒｈ，Ｒｕ，Ｓｂ，Ｓｃ，Ｓｒ，Ｔａ，Ｔｉ，Ｖ，Ｗ，Ｙ，Ｚｒより成る群より選ばれた少なくとも１つの元素を表し、前記Ｆは前記Ｄ及び前記Ｅで表される以外の少なくとも１つの元素を表し、例えば、Ｔｌ，Ｂｒ，Ｃｌ，Ｆ，Ｈ，Ｉ，Ｐ等とすることができる。また、前記ｅ，ｆ及びｇの単位はいずれも原子パーセントで、それぞれ３０≦ｅ≦９５、５≦ｆ≦５０、０≦ｇ≦２０の範囲にあることが好ましい。さらに、４０≦ｅ≦８７、１３≦ｆ≦４０、０≦ｇ≦１０の範囲にあることがより好ましい。 _{_{_{D e E f F g (8}}} )
Here, E is at least one element selected from Sn, Pb, Bi, Zn, Ga, and In, and E is As, B, C, N, O, S, Se, Si, Te, Ag, and Al. , Au, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ge, Hf, Hg, Ir, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Os, Pd, Pt , Rb, Re, Rh, Ru, Sb, Sc, Sr, Ta, Ti, V, W, Y, Zr, and at least one element selected from the group consisting of D and E. Represents at least one element other than that described above, and may be, for example, Tl, Br, Cl, F, H, I, P, or the like. Further, the unit of each of e, f and g is an atomic percent, and preferably ranges from 30 ≦ e ≦ 95, 5 ≦ f ≦ 50, and 0 ≦ g ≦ 20, respectively. Furthermore, it is more preferable that the range is 40 ≦ e ≦ 87, 13 ≦ f ≦ 40, and 0 ≦ g ≦ 10.

前記Ｆで表される元素は、例えば、前記Ｄ及びＥで表される元素がそれぞれＳｎ及びＴｅであれば、Ｓｎ及びＴｅ以外の元素であればよい。また、前記Ｄ、Ｄ’（前記Ｄが上記Ｓｎ，ＺｎのようにＤ，Ｄ’２元素の場合）、Ｅ、Ｆの組合せにおいて、Ｄ−Ｅ、Ｅ−Ｆ、Ｄ’−Ｅの組合せからできる高融点成分が共晶点をもたないか、共晶点をもっていてもＤ、Ｄ−Ｄ’の融点より１５０℃以上融点が高いことが好ましい。
（５８）超解像読み出し用薄膜は、また、平均組成が次の一般式で表されるものを使用することができる。 The element represented by F may be any element other than Sn and Te as long as the elements represented by D and E are Sn and Te, respectively. In the combination of D, D '(when D is D and D'2 elements such as Sn and Zn), E and F, the combination of DE, EF and D'-E It is preferable that the resulting high melting point component does not have a eutectic point, or even if it has a eutectic point, the melting point is 150 ° C. or more higher than the melting points of D and DD ′.
(58) As the super-resolution readout thin film, one having an average composition represented by the following general formula can be used.

Ｓｅ_pＭ_qＮ_rＯ_s （１１）
ここで、前記ＭはＩｎ，Ｓｂ，Ｂｉ，Ｔｅ，Ａｕ，Ｂ，Ｃｓ，Ｓｎ，Ｔｌ，Ｓ，Ｇｅ，Ｆｅ，Ｚｎから選ばれた少なくとも１つの元素、前記ＮはＡｓ，Ｃ，Ｎ，Ｏ，Ｓｉ，Ａｇ，Ａｌ，Ｂａ，Ｂｅ，Ｃａ，Ｃｄ，Ｃｏ，Ｃｒ，Ｃｕ，Ｈｆ，Ｈｇ，Ｉｒ，Ｋ，Ｌｉ，Ｍｇ，Ｍｎ，Ｍｏ，Ｎａ，Ｎｂ，Ｎｉ，Ｏｓ，Ｐｄ，Ｐｔ，Ｒｂ，Ｒｅ，Ｒｈ，Ｒｕ，Ｓｃ，Ｓｒ，Ｔａ，Ｔｉ，Ｖ，Ｗ，Ｙ，Ｚｒ，Ｐｂ，Ｇａ，Ｕ及び、Ｓｅ及び前記Ｍで表される元素以外の少なくとも１つの元素を表す。前記ＯはＳｅ及び前記Ｍ及び前記Ｎで表される以外の少なくとも１つの元素を表し、例えばＢｒ，Ｃｌ，Ｆ，Ｈ，Ｉ，Ｐとすることができる。また、前記ｐ，ｑ，ｒ及びｓの単位はいずれも原子パーセントで、それぞれ４０≦ｐ≦９５、０≦ｑ≦５５、５≦ｒ≦５０、０≦ｓ≦２０の範囲にあることが好ましく、５０≦ｐ≦８０、０≦ｑ≦４０、１０≦ｒ≦４０、０≦ｓ≦１０の範囲にあることがより好ましい。
（５９）超解像読み出し用薄膜の平均組成を、元素単体または化合物組成の低融点成分Ｌと元素単体または化合物組成の高融点成分Ｈより、次式で表すとき、
Ｌ_jＨ_k （６）
下式（７）の範囲の組成を基準組成とし、上記薄膜を構成する各元素の膜中での含有量は、式（７）で決まる値±１０原子％の範囲内にあることが好ましく、±５原子％の範囲内にあるとより好ましい。 _{_{_{_{Se p M q N r O s}}}} (11)
Here, M is at least one element selected from In, Sb, Bi, Te, Au, B, Cs, Sn, Tl, S, Ge, Fe and Zn, and N is As, C, N, O , Si, Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Hf, Hg, Ir, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Os, Pd, Pt, Rb , Re, Rh, Ru, Sc, Sr, Ta, Ti, V, W, Y, Zr, Pb, Ga, U, and at least one element other than Se and the element represented by M. O represents Se and at least one element other than M and N, and may be, for example, Br, Cl, F, H, I, or P. Further, the units of p, q, r and s are all in atomic percent, and are preferably in the ranges of 40 ≦ p ≦ 95, 0 ≦ q ≦ 55, 5 ≦ r ≦ 50 and 0 ≦ s ≦ 20, respectively. , 50 ≦ p ≦ 80, 0 ≦ q ≦ 40, 10 ≦ r ≦ 40, and 0 ≦ s ≦ 10.
(59) When the average composition of the super-resolution read-out thin film is expressed by the following formula from the low melting point component L of the elemental element or the compound composition and the high melting point component H of the elemental element or the compound composition,
L _j H _k (6)
With the composition in the range of the following formula (7) as a reference composition, the content of each element constituting the thin film in the film is preferably within a range of ± 10 atomic% determined by the formula (7), More preferably, it is within the range of ± 5 atomic%.

２０≦ｋ／（ｊ＋ｋ）≦４０（７）
例えば、超解像読み出し用膜の基準組成が（ＧｅＳｂ₂Ｔｅ₄ ）₈₀（Ｃｒ₄Ｔｅ₅ ）₂₀である場合、式（７）のＬはＧｅＳｂ₂Ｔｅ₄ 、ＨはＣｒ₄Ｔｅ₅ であって、ｋ／（ｊ＋ｋ）は２０である。ここで各元素の原子％は、それぞれ、ＬのＧｅは１１％、Ｓｂは２３％、Ｔｅは４６％、ＨのＣｒは９％、Ｔｅは１１％である。そこで、式（７）で決まる値±１０原子％の範囲はＬのＧｅは１〜２１％、Ｓｂは１３〜３３％、Ｔｅは３６〜５６％、ＨのＣｒは０〜１９％、Ｔｅは１〜２１％である。
（６０）低融点成分と高融点成分は、いずれも金属または半金属元素を５０原子％以上含むことが好ましく、６５原子％以上含むことがより好ましい。
（６１）上記式（８）および（１１）の組成は相変化記録膜としても使用でき、超解像読み出し薄膜を用いない記録媒体の相変化記録膜としても使用できる。この記録膜を使用した場合、結晶化と非晶質化で反射率差の大きな媒体を作製できる。 20 ≦ k / (j + k) ≦ 40 (7)
For example, when the reference composition of the super-resolution readout film is (GeSb ₂ Te ₄ ) ₈₀ (Cr ₄ Te ₅ ) ₂₀ , L in the formula (7) is GeSb ₂ Te ₄ and H is Cr ₄ Te _5. Thus, k / (j + k) is 20. Here, the atomic% of each element is 11% for Ge of L, 23% of Sb, 46% of Te, 9% of Cr of H, and 11% of Te, respectively. Thus, the range of the value ± 10 atomic% determined by the equation (7) is 1 to 21% for L Ge, 13 to 33% for Sb, 36 to 56% for Te, 0 to 19% for Cr of H, and Te for H. 1 to 21%.
(60) Both the low melting point component and the high melting point component preferably contain a metal or metalloid element in an amount of 50 atomic% or more, more preferably 65 atomic% or more.
(61) The compositions of the above formulas (8) and (11) can be used also as a phase change recording film, and can also be used as a phase change recording film of a recording medium not using a super-resolution readout thin film. When this recording film is used, a medium having a large difference in reflectance between crystallization and amorphization can be manufactured.

高融点成分の原子数の和は、超解像読み出し膜の構成元素の全原子数の和に対する割合で１０〜５０％の範囲であることが好ましく、２０〜４０％の範囲であることがより好ましい。
（６２）高融点成分と相変化成分の組み合わせでは、それぞれの成分中に同じ元素が３０原子％以上、８０原子％以下の範囲で存在することが好ましい。 The sum of the number of atoms of the high melting point component is preferably in the range of 10 to 50%, and more preferably in the range of 20 to 40%, relative to the sum of the total number of atoms of the constituent elements of the super-resolution readout film. preferable.
(62) In the combination of the high melting point component and the phase change component, the same element is preferably present in each component in a range of 30 at% or more and 80 at% or less.

高融点成分の融点は、析出後の残成分である相変化成分の融点より１５０℃以上高いことが好ましい。
（６３）高融点成分の平均組成は、下記のＡ群のうち少なくとも一者、もしくはこれに近い組成あるいは、融点８００℃以上の化合物とすることができる。ここで、これに近い組成とは、列挙した組成からのずれが±１０原子％の範囲内にあるものを指す（以下、同じ）。例えば、ＢａＰｄ₂ の場合、それぞれの元素の原子％は、Ｂａは３３％、Ｐｄは６７％である。そこで、組成ＢａＰｄ₂ からのずれが±１０原子％の範囲は、Ｂａは２３〜４３％、Ｐｄは５７〜７７％である。
＜Ａ群＞
ＢａＰｄ₂ ，ＢａＰｄ₅ ，ＮｄＰｄ，ＮｄＰｄ₃ ，ＮｄＰｄ₅ ，Ｎｄ₇Ｐｔ₃ ，Ｎｄ₃Ｐｔ₂ ，ＮｄＰｔ，Ｎｄ₃Ｐｔ₄ ，ＮｄＰｔ₂ ，ＮｄＰｔ₅ ，Ｂｉ₂Ｎｄ，ＢｉＮｄ，Ｂｉ₃Ｎｄ₄ ，Ｂｉ₃Ｎｄ₅ ，ＢｉＮｄ₂ ，Ｃｄ₂Ｎｄ，ＣｄＮｄ，Ｍｎ₂Ｎｄ，Ｍｎ₂₃Ｎｄ₆ ，Ｍｎ₁₂Ｎｄ，Ｎｄ₅Ｓｂ₃ ，Ｎｄ₄Ｓｂ₃ ，ＮｄＳｂ，ＮｄＳｂ₂ ，Ｆｅ₂Ｎｄ，Ｆｅ₁₇Ｎｄ₂ ，Ｃｓ₃Ｇｅ₂ ，ＣｓＧｅ，ＣｓＧｅ₄ ，Ｎｄ₅Ｓｉ₃ ，Ｎｄ₅Ｓｉ₄ ，ＮｄＳｉ，Ｎｄ₃Ｓｉ₄ ，Ｎｄ₂Ｓｉ₃，Ｎｄ₅Ｓｉ₉，Ｃｓ₂Ｔｅ，ＮｄＴｅ₃ ，Ｎｄ₂Ｔｅ₅ ，ＮｄＴｅ₂ ，Ｎｄ₄Ｔｅ₇ ，Ｎｄ₂Ｔｅ₃ ，Ｎｄ₃Ｔｅ₄ ，ＮｄＴｅ，Ｃｅ₃Ｉｒ，Ｃｅ₂Ｉｒ，Ｃｅ₅₅Ｉｒ₄₅，ＣｅＩｒ₂ ，ＣｅＩｒ₃ ，Ｃｅ₂Ｉｒ₇ ，ＣｅＩｒ₅ ，ＣａＰｄ，ＣａＰｄ₂ ，ＣａＧｅ，Ｃａ₂Ｇｅ，ＧｅＮａ₃ ，ＧｅＮａ，ＣａＳｉ₂ ，Ｃａ₂Ｓｉ，ＣａＳｉ，Ｓｅ₂Ｓｒ，Ｓｅ₃Ｓｒ₂ ，ＳｅＳｒ，ＧｅＳｒ₂ ，ＧｅＳｒ，Ｇｅ₂Ｓｒ，ＳｎＳｒ，Ｓｎ₃Ｓｒ₅ ，ＳｎＳｒ₂ ，Ｃｅ₂Ｔｌ，Ｃｅ₅Ｔｌ₃ ，ＣｅＴｌ₃ ，Ｃｅ₃Ｔｌ₅，ＣｅＴｌ，ＢａＴｌ，Ｐｄ₁₃Ｔｌ₉ ，Ｐｄ₂Ｔｌ，Ｐｄ₃Ｔｌ，Ｍｇ₂Ｓｉ，Ｍｇ₂Ｇｅ，ＢａＰｄ₂ ，ＢａＰｄ₅ ，Ｃｅ₄Ｓｅ₇ ，Ｃｅ₃Ｓｅ₄ ，Ｃｅ₂Ｓｅ₃ ，ＣｅＳｅ，Ｃｅ₅Ｇｅ₃ ，Ｃｅ₄Ｇｅ₃，Ｃｅ₅Ｇｅ₄ ，ＣｅＧｅ，Ｃｅ₃Ｇｅ₅ ，Ｃｅ₅Ｓｉ₃ ，Ｃｅ₃Ｓｉ₂ ，Ｃｅ₅Ｓｉ₄ ，ＣｅＳｉ，Ｃｅ₃Ｓｉ₅ ，ＣｅＳｉ₂，ＣｅＴｅ₃ ，Ｃｅ₂Ｔｅ₅ ，ＣｅＴｅ₂ ，Ｃｅ₄Ｔｅ₇ ，Ｃｅ₃Ｔｅ₄ ，ＣｅＴｅ，Ｌａ₃Ｓｅ₇ ，ＬａＳｅ₂ ，Ｌａ₄Ｓｅ₇ ，Ｌａ₂Ｓｅ₃ ，Ｌａ₃Ｓｅ₄ ，ＬａＳｅ，ＧｅＬａ₃ ，Ｇｅ₃Ｌａ₅ ，Ｇｅ₃Ｌａ₄ ，Ｇｅ₄Ｌａ₅ ，ＧｅＬａ，Ｇｅ₅Ｌａ₃ ，ＢａＳｅ₂，Ｂａ₂Ｓｅ₃ ，ＢａＳｅ，ＰｄＳｅ，Ｍｏ₃Ｓｅ₄ ，ＭｏＳｅ₂ ，Ｂａ₂Ｇｅ，ＢａＧｅ₂ ，ＢａＧｅ，Ｂａ₂Ｔｅ₃ ，ＢａＴｅ，Ｇｅ₂Ｐｄ₅ ，ＧｅＰｄ₂，Ｇｅ₉Ｐｄ₂₅，ＧｅＰｄ，Ｇｅ₃Ｐｔ，Ｇｅ₃Ｐｔ₂ ，ＧｅＰｔ，Ｇｅ₂Ｐｔ₃ ，ＧｅＰｔ₂ ，ＧｅＰｔ₃ ，Ｐｕ₃Ｓｎ，Ｐｕ₅Ｓｎ₃ ，Ｐｕ₅Ｓｎ₄，Ｐｕ₈Ｓｎ₇ ，Ｐｕ₇Ｓｎ₈ ，ＰｕＳｎ₂ ，ＰｕＳｎ₃ ，Ｐｔ₅Ｔｅ₄ ，Ｐｔ₄Ｔｅ₅ ，ＰｔＴｅ₂ ，ＧｅＮｉ，Ｇｅ₃Ｎｉ₅ ，Ｇｅ₂Ｎｉ₅ ，ＧｅＮｉ₃ ，ＮｉＴｅ_0.85，ＮｉＴｅ_0.775 ，Ｎｉ₃±_xＴｅ_x ，Ｃｒ₁₁Ｇｅ₁₉，ＣｒＧｅ，Ｃｒ₁₁Ｇｅ₈ ，Ｃｒ₅Ｇｅ₃ ，Ｃｒ₃Ｇｅ，ＣｒＳｉ₂ ，Ｃｒ₅Ｓｉ₃ ，Ｃｒ₃Ｓｉ，Ｃｒ₅Ｔｅ₈ ，Ｃｒ₄Ｔｅ₅ ，Ｃｒ₃Ｔｅ₄ ，Ｃｒ_1-xＴｅ，Ｇｅ₃Ｍｎ₅ ，ＧｅＭｎ₂ ，Ｍｎ₆Ｓｉ，Ｍｎ₉Ｓｉ₂ ，Ｍｎ₃Ｓｉ，Ｍｎ₅Ｓｉ₂ ，Ｍｎ₅Ｓｉ₃ ，ＭｎＳｉ，Ｍｎ₁₁Ｓｉ₁₉，Ｍｎ₂Ｓｎ，Ｍｎ_3.25Ｓｎ，ＭｎＴｅ，Ｔｅ₂Ｗ，ＦｅＧｅ₂ ，Ｆｅ₅Ｇｅ₃ ，Ｆｅ₃Ｇｅ，Ｆｅ₂Ｓｉ，Ｆｅ₅Ｓｉ₃ ，ＦｅＳｉ，ＦｅＳｉ₂ ，Ｇｅ₂Ｍｏ，Ｇｅ₄₁Ｍｏ₂₃，Ｇｅ₁₆Ｍｏ₉ ，Ｇｅ₂₃Ｍｏ₁₃，Ｇｅ₃Ｍｏ₅ ，ＧｅＭｏ₃，Ｍｏ₃Ｓｉ，Ｍｏ₅Ｓｉ₃ ，ＭｏＳｉ₂ ，ＭｏＳｎ，ＭｏＳｎ₂ ，Ｍｏ₃Ｔｅ₄，ＭｏＴｅ₂ ，Ｓｉ₂Ｔｉ，ＳｉＴｉ，Ｓｉ₄Ｔｉ₅ ，Ｓｉ₃Ｔｉ₅ ，ＳｉＴｉ₃，Ｓｎ₅Ｔｉ₆ ，Ｓｎ₃Ｔｉ₅ ，ＳｎＴｉ₂ ，ＳｎＴｉ₃ ，ＣｏＧｅ₂ ，Ｃｏ₅Ｇｅ₇ ，ＣｏＧｅ，Ｃｏ₅Ｇｅ₃ ，Ｃｏ₄Ｇｅ，Ｃｏ₃Ｔｅ₄ ，Ｇｅ₇Ｒｅ₃ ，Ｒｅ₅Ｓｉ₃ ，ＲｅＳｉ，ＲｅＳｉ₂ ，Ｒｅ₂Ｔｅ。
（６４）高融点成分の平均組成は、また、前記Ａ群及び下記のＢ群に挙げた化合物，のうち少なくとも一者、もしくはこれに近い組成あるいは、融点６００℃以上の化合物とすることができる。
＜Ｂ群＞
Ｃｓ₃Ｇｅ，Ｂａ₂Ｔｌ，ＧｅＰｄ₃ ，Ｆｅ₆Ｇｅ₅ ，ＦｅＴｅ₂ ，Ｃｏ₅Ｇｅ₂ ，Ｎｄ₃Ｐｄ，Ｃｓ₃Ｔｅ₂ ，Ｃｅ₄Ｉｒ，ＮａＰｄ，Ｃａ₉Ｐｄ，Ｃａ₃Ｐｄ₂ ，Ｃａ₂Ｇｅ，Ｓｅ₃Ｓｒ，Ｃｅ₃Ｔｌ，ＣｅＳｅ₂ ，Ｃｅ₃Ｇｅ，ＢａＳｅ₃ ，ＧｅＳｅ₂ ，ＧｅＳｅ，ＢａＴｅ₂ ，ＧｅＰｄ₅ ，Ｇｅ₈Ｍｎ₁₁，ＭｎＴｅ₂ ，Ｇｅ₃Ｗ₂ ，ＦｅＧｅ，Ｆｅ₄Ｇｅ₃ ，Ｆｅ₃Ｓｎ，Ｆｅ₃Ｓｎ₂ ，ＦｅＳｎ，ＣｏＴｅ₂。
（６５）高融点成分の平均組成は、また、前記Ｂ群及び下記Ｃ群に挙げた化合物，のうち少なくとも一者、もしくはこれに近い組成、あるいは、融点４００℃以上の化合物とすることができる。
＜Ｃ群＞
Ｂａ₄Ｔｌ，ＣｓＴｅ，Ｂａ₄Ｔｌ，Ｂａ₁₃Ｔｌ，Ｃｄ₁₁Ｎｄ，Ｃｄ₆Ｎｄ，Ｃｓ₅Ｔｅ₄ ，Ｃａ₃Ｐｄ，Ｃａ₅Ｐｄ₂ ，Ｓｎ₃Ｓｒ，Ｂａ₁₃Ｔｌ，ＰｄＴｌ₂，ＦｅＳｅ₂ ，ＦｅＳｅ，Ｃｒ₂Ｔｅ₃ ，ＣｒＴｅ₃ ，ＦｅＳｎ₂ 。
（６６）高融点成分として前記Ａ群に挙げたものを使用するとき、相変化成分の平均組成は、下記Ｄ群の組成のうち少なくとも一者、もしくはこれに近い組成あるいは、融点６５０℃以下の化合物であることが好ましい。
＜Ｄ群＞
Ｓｎ，Ｐｂ，Ｓｂ，Ｔｅ，Ｚｎ，Ｃｄ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，Ｔｌ，Ｍｇ，Ｔｌ₂Ｓｅ，ＴｌＳｅ，Ｔｌ₂Ｓｅ₃ ，Ｔｌ₃Ｔｅ₂ ，ＴｌＴｅ，ＩｎＢｉ，Ｉｎ₂Ｂｉ，ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ，Ｉｎ₃ＳｅＴｅ₂ ，ＡｇＩｎＴｅ₂ ，ＧｅＳｂ₄Ｔｅ₇ ，Ｇｅ₂Ｓｂ₂Ｔｅ₅ ，ＧｅＳｂ₂Ｔｅ₄，ＧｅＢｉ₄Ｔｅ₇ ，ＧｅＢｉ₂Ｔｅ₄ ，Ｇｅ₃Ｂｉ₂Ｔｅ₆ ，Ｓｎ₂Ｓｂ₆Ｓｅ₁₁，Ｓｎ₂Ｓｂ₂Ｓｅ₅ ，ＳｎＳｂ₂Ｔｅ₄ ，Ｐｂ₂Ｓｂ₆Ｔｅ₁₁，ＣｕＡｓＳｅ₂ ，Ｃｕ₃ＡｓＳｅ₃ ，ＣｕＳｂＳ₂ ，ＣｕＳｂＳｅ₂ ，ＩｎＳｅ，Ｓｂ₂Ｓｅ₃ ，Ｓｂ₂Ｔｅ₃ ，Ｂｉ₂Ｔｅ₃ ，ＳｎＳｂ，ＦｅＴｅ，Ｆｅ₂Ｔｅ₃ ，ＦｅＴｅ₂ ，ＺｎＳｂ，Ｚｎ₃Ｓｂ₂ ，ＶＴｅ₂ ，Ｖ₅Ｔｅ₈ ，ＡｇＩｎ₂ ，ＢｉＳｅ，ＩｎＳｂ，Ｉｎ₂Ｔｅ，Ｉｎ₂Ｔｅ₅ ，Ｂａ₄Ｔｌ，Ｃｄ₁₁Ｎｄ，Ｂａ₁₃Ｔｌ，Ｃｄ₆Ｎｄ，Ｂａ₂Ｔｌ。
（６７）高融点成分として前記Ｂ群に挙げたものを使用するとき、相変化成分の平均組成は、下記Ｅ群の組成のうち少なくとも一者、もしくはこれに近い組成あるいは、融点４５０℃以下の化合物であることが好ましい。
＜Ｅ群＞
Ｓｎ，Ｐｂ，Ｔｅ，Ｚｎ，Ｃｄ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，Ｔｌ，Ｔｌ₂Ｓｅ，ＴｌＳｅ，Ｔｌ₂Ｓｅ₃ ，Ｔｌ₃Ｔｅ₂ ，ＴｌＴｅ，ＩｎＢｉ，Ｉｎ₂Ｂｉ，ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ，Ｂａ₄Ｔｌ。
（６８）高融点成分として前記Ｃ群に挙げたものを使用するとき、相変化成分の平均組成は、下記Ｆ群の組成のうち少なくとも一者、もしくはこれに近い組成あるいは、融点２５０℃以下の化合物であることが好ましい。
＜Ｆ群＞
Ｓｎ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，ＩｎＢｉ，Ｉｎ₂Ｂｉ，ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ。
（６９）超解像読み出し用薄膜の組成または膜厚は、内周と外周において異なることが好ましく、超解像読み出し用薄膜のトラック周辺部も結晶化するのが好ましい。本発明による超解像読み出し用薄膜は、すでに情報が記録されたＲＯＭディスク及び情報を記録できるＲＡＭディスクのいずれの情報記録媒体にも適用できる。
（７０）本発明による超解像読み出し用薄膜を備える情報記録媒体の超解像読み出し用装置は、超解像読み出し用薄膜の最高温度となる領域でも膜全体は融解しないで高融点成分が固相に留まる超解像読み出しパワーにプリセットがされているか、手動または自動で設定する手段を有することが好ましい。また、超解像読み出し時の反射光強度分布の乱れを検出する手段と、上記乱れの大きさに応じてレーザパワーを調節する手段を有することが好ましい。また、超解像読み出し時のレーザパワーをオートフォーカスやトラッキングに必要なパワーに比較して２倍以上大きくする手段を有することが好ましく、３倍以上大きくする手段を有することがより好ましい。この装置は、本発明以外の媒体に用いても、超解像読み出しレーザパワー一定の場合より良好な結果が得られる。
（７１）超解像読み出しレーザ光はパルス光とし、レーザパルスの周期Ｔ、線速ｖ、スポット径（λ／ＮＡ）、パルス幅ｘが下記（９）及び（１０）の関係を満
たすことが好ましく、
０．４λ／ＮＡ≦ｖＴ≦１．５λ／ＮＡ（９）
０．３≦ｘ／Ｔ≦０．５（１０）
さらに下記（１２）及び（１０）の関係を満たすことがより好ましい。 The melting point of the high melting point component is preferably 150 ° C. or higher than the melting point of the phase change component, which is the remaining component after precipitation.
(63) The average composition of the high melting point component can be at least one of the following Group A or a composition close to this, or a compound having a melting point of 800 ° C or higher. Here, a composition close to this refers to a composition having a deviation from the listed composition within a range of ± 10 atomic% (the same applies hereinafter). For example, in the case of BaPd ₂ , the atomic% of each element is Ba for 33% and Pd for 67%. Therefore, in the range where the deviation from the composition BaPd ₂ is ± 10 atomic%, Ba is 23 to 43% and Pd is 57 to 77%.
<Group A>
_{_{BaPd 2, BaPd 5, NdPd,}} NdPd 3, NdPd 5, Nd 7 Pt 3, Nd 3 Pt 2, NdPt, Nd 3 Pt 4, NdPt 2, NdPt 5, Bi 2 Nd, BiNd, Bi 3 Nd 4, Bi 3 _{_{_{Nd 5, BiNd 2, Cd 2}}} Nd, CdNd, Mn 2 Nd, Mn 23 Nd 6, Mn 12 Nd, Nd 5 Sb 3, Nd 4 Sb 3, NdSb, NdSb 2, Fe 2 Nd, Fe 17 Nd 2, Cs _{_{_{3 Ge 2, CsGe, CsGe 4}}} , Nd 5 Si 3, Nd 5 Si 4, NdSi, Nd 3 Si 4, Nd 2 Si 3, Nd 5 Si 9, Cs 2 Te, NdTe 3, Nd 2 Te 5, NdTe 2 _{_{_{, Nd 4 Te 7, Nd 2}}} Te 3, Nd 3 Te 4, NdTe, Ce 3 Ir, Ce 2 Ir, Ce 55 Ir 45, CeIr 2, CeIr 3, Ce 2 Ir 7, CeIr 5, CaPd, CaPd 2, C _{_{Ge, Ca 2 Ge, GeNa 3}} , GeNa, CaSi 2, Ca 2 Si, CaSi, Se 2 Sr, Se 3 Sr 2, SeSr, GeSr 2, GeSr, Ge 2 Sr, SnSr, Sn 3 Sr 5, SnSr 2, Ce ₂ Tl, Ce ₅ Tl ₃ , CeTl ₃ , Ce ₃ Tl ₅ , CeTl, BaTl, Pd ₁₃ Tl ₉ , Pd ₂ Tl, Pd ₃ Tl, Mg ₂ Si, Mg ₂ Ge, BaPd ₂ , BaPd ₅ , Ce ₄ _{_{_{Se 7, Ce 3 Se 4,}}} Ce 2 Se 3, CeSe, Ce 5 Ge 3, Ce 4 Ge 3, Ce 5 Ge 4, CeGe, Ce 3 Ge 5, Ce 5 Si 3, Ce 3 Si 2, Ce 5 Si _{_{_{4, CeSi, Ce 3 Si 5}}} , CeSi 2, CeTe 3, Ce 2 Te 5, CeTe 2, Ce 4 Te 7, Ce 3 Te 4, CeTe, La 3 Se 7, LaSe 2, La 4 Se 7, La 2 Se _3, _{_{a 3 Se 4, LaSe, GeLa}} 3, Ge 3 La 5, Ge 3 La 4, Ge 4 La 5, GeLa, Ge 5 La 3, BaSe 2, Ba 2 Se 3, BaSe, PdSe, Mo 3 Se 4, MoSe ₂ , Ba ₂ Ge, BaGe ₂ , BaGe, Ba ₂ Te ₃ , BaTe, Ge ₂ Pd ₅ , GePd ₂ , Ge ₉ Pd ₂₅ , GePd, Ge ₃ Pt, Ge ₃ Pt ₂ , GePt, Ge ₂ Pt ₃ , GePt _{_{_{2, GePt 3, Pu 3 Sn}}} , Pu 5 Sn 3, Pu 5 Sn 4, Pu 8 Sn 7, Pu 7 Sn 8, PuSn 2, PuSn 3, Pt 5 Te 4, Pt 4 Te 5, PtTe 2, GeNi, _{_{_{Ge 3 Ni 5, Ge 2 Ni}}} 5, GeNi 3, NiTe 0.85, NiTe 0.775, Ni 3 ± x Te x, Cr 11 Ge 19, CrGe, Cr 11 Ge 8, Cr 5 Ge 3, Cr 3 Ge, CrSi 2, Cr ₅ Si ₃ , Cr ₃ Si, Cr ₅ Te ₈ , Cr ₄ Te ₅ , Cr ₃ Te ₄ , Cr _{1 -x} Te, Ge ₃ Mn ₅ , GeMn ₂ , Mn ₆ Si, Mn ₉ Si ₂ , Mn ₃ Si, Mn _{_{_{_{5 Si 2, Mn 5 Si 3}}}} , MnSi, Mn 11 Si 19, Mn 2 Sn, Mn 3.25 Sn, MnTe, Te 2 W, FeGe 2, Fe 5 Ge 3, Fe 3 Ge, Fe 2 Si, Fe 5 Si 3 , FeSi, FeSi ₂ , Ge ₂ Mo, Ge ₄₁ Mo ₂₃ , Ge ₁₆ Mo ₉ , Ge ₂₃ Mo ₁₃ , Ge ₃ Mo ₅ , GeMo ₃ , Mo ₃ Si, Mo ₅ Si ₃ , MoSi ₂ , MoSn, MoSn ₂ , Mo ₃ Te ₄ , MoTe ₂ , Si ₂ Ti, SiTi, Si ₄ Ti ₅ , Si ₃ Ti ₅ , SiTi ₃ , Sn ₅ Ti ₆ , Sn ₃ Ti ₅ , SnTi ₂ , SnTi ₃ , CoGe ₂ , Co ₅ Ge ₇ , CoGe, Co ₅ Ge ₃ , Co ₄ G e, Co ₃ Te ₄ , Ge ₇ Re ₃ , Re ₅ Si ₃ , ReSi, ReSi ₂ , Re ₂ Te.
(64) The average composition of the high melting point component can be at least one of the compounds listed in the above-mentioned group A and the following group B or a composition close to this, or a compound having a melting point of 600 ° C. or more. .
<Group B>
Cs ₃ Ge, Ba ₂ Tl, GePd ₃ , Fe ₆ Ge ₅ , FeTe ₂ , Co ₅ Ge ₂ , Nd ₃ Pd, Cs ₃ Te ₂ , Ce ₄ Ir, NaPd, Ca ₉ Pd, Ca ₃ Pd ₂ , Ca ₂ Ge, Se ₃ Sr, Ce ₃ Tl, CeSe ₂ , Ce ₃ Ge, BaSe ₃ , GeSe ₂ , GeSe, BaTe ₂ , GePd ₅ , Ge ₈ Mn ₁₁ , MnTe ₂ , Ge ₃ W ₂ , FeGe, Fe ₄ Ge ₃ , Fe ₃ Sn, Fe ₃ Sn ₂ , FeSn, CoTe ₂ .
(65) The average composition of the high melting point component may be at least one of the compounds listed in the above-mentioned group B and the following group C or a composition close to this, or a compound having a melting point of 400 ° C. or more. .
<Group C>
Ba ₄ Tl, CsTe, Ba ₄ Tl, Ba ₁₃ Tl, Cd ₁₁ Nd, Cd ₆ Nd, Cs ₅ Te ₄ , Ca ₃ Pd, Ca ₅ Pd ₂ , Sn ₃ Sr, Ba ₁₃ Tl, PdTl ₂ , FeSe ₂ , _{_{FeSe, Cr 2 Te 3, CrTe}} 3, FeSn 2.
(66) When the high melting point component used in the above-mentioned group A is used, the average composition of the phase change component is at least one of the following group D compositions, or a composition close to this, or a melting point of 650 ° C or less. Preferably, it is a compound.
<Group D>
Sn, Pb, Sb, Te, Zn, Cd, Se, In, Ga, S, Tl, Mg, Tl 2 Se, TlSe, Tl 2 Se 3, Tl 3 Te 2, TlTe, InBi, In 2 Bi, TeBi, Tl-Se, Tl-Te, Pb-Sn, Bi-Sn, SeTe, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In, In 3 SeTe 2, AgInTe 2, GeSb 4 _{_{_{Te 7, Ge 2 Sb 2 Te}}} 5, GeSb 2 Te 4, GeBi 4 Te 7, GeBi 2 Te 4, Ge 3 Bi 2 Te 6, Sn 2 Sb 6 Se 11, Sn 2 Sb 2 Se 5, SnSb 2 Te 4 _{_{_{, Pb 2 Sb 6 Te 11,}}} CuAsSe 2, Cu 3 AsSe 3, CuSbS 2, CuSbSe 2, InSe, Sb 2 Se 3, Sb 2 Te 3, Bi 2 Te 3, SnSb, FeTe, Fe 2 Te 3, FeTe 2 _{_{ZnSb, Zn 3 Sb 2, VTe}} 2, V 5 Te 8, AgIn 2, BiSe, InSb, In 2 Te, In 2 Te 5, Ba 4 Tl, Cd 11 Nd, Ba 13 Tl, Cd 6 Nd, Ba 2 Tl .
(67) When using those listed in Group B as the high melting point component, the average composition of the phase change component is at least one of the following Group E compositions, or a composition close to this, or a melting point of 450 ° C or lower. It is preferably a compound.
<Group E>
Sn, Pb, Te, Zn, Cd, Se, In, Ga, S, Tl, Tl 2 Se, TlSe, Tl 2 Se 3, Tl 3 Te 2, TlTe, InBi, In 2 Bi, TeBi, TlSe, Tl-Te, Pb-Sn, Bi-Sn, Se-Te, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In, Ba 4 Tl.
(68) When the high melting point component used in the group C is used, the average composition of the phase change component is at least one of the following group F compositions or a composition close to this, or the melting point is 250 ° C. or less. It is preferably a compound.
<Group F>
Sn, Se, In, Ga, S, InBi, In ₂ Bi, TeBi, Tl-Se, Tl-Te, Pb-Sn, Bi-Sn, Se-Te, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In.
(69) The composition or film thickness of the super-resolution readout thin film is preferably different between the inner periphery and the outer periphery, and it is preferable that the track periphery of the super-resolution readout thin film is also crystallized. The super-resolution readout thin film according to the present invention can be applied to any information recording medium such as a ROM disk on which information is already recorded and a RAM disk on which information can be recorded.
(70) A super-resolution readout device for an information recording medium having a super-resolution readout thin film according to the present invention is capable of solidifying a high melting point component without melting the entire film even in a region where the super-resolution readout thin film has the highest temperature. It is preferable that the super-resolution reading power remaining in the phase is preset or has means for manually or automatically setting the super-resolution reading power. Further, it is preferable to have means for detecting disturbance of the reflected light intensity distribution at the time of super-resolution reading, and means for adjusting the laser power in accordance with the magnitude of the disturbance. Further, it is preferable to have means for increasing the laser power at the time of super-resolution reading by at least twice as much as the power required for auto-focusing and tracking, and it is more preferable to have means for increasing the laser power by at least three times. Even if this apparatus is used for a medium other than the present invention, better results can be obtained than when the super-resolution reading laser power is constant.
(71) The super-resolution readout laser light is pulsed light, and the laser pulse period T, linear velocity v, spot diameter (λ / NA), and pulse width x satisfy the following relationships (9) and (10). Preferably,
0.4λ / NA ≦ vT ≦ 1.5λ / NA (9)
0.3 ≦ x / T ≦ 0.5 (10)
More preferably, the following relationships (12) and (10) are satisfied.

０．５λ／ＮＡ≦ｖＴ≦０．９λ／ＮＡ（１２）
（７２）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜において、当該薄膜を有する情報記録用媒体を用いる情報の記録再生装置または媒体初期結晶化用装置でレーザ光を繰り返し照射することにより、当該薄膜の残成分より相対的に融点が高い高融点成分が析出し、その析出物が当該薄膜の残成分からなる領域内に分布する特徴を持つ。
（７３）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用薄膜を有する情報記録用媒体を用いる情報の記録再生方法または媒体初期結晶化用方法においてレーザ光を繰り返し照射することにより、当該薄膜の残成分より相対的に融点が高い高融点成分が析出し、その析出物が当該薄膜の残成分からなる領域内に分布する特徴を持つ。
（７４）（１）から（６）に記載の情報記録用薄膜において、当該薄膜を有する情報記録用媒体を用いる情報の記録再生装置または媒体初期結晶化用装置においてレーザ光を繰り返し照射することにより、当該薄膜の残成分より相対的に融点が高い高融点成分が析出し、その析出物が当該薄膜の残成分からなる領域内に分布し、その析出物が前記ＢおよびＸの少なくとも一方で表わされる元素を含むことを特徴とする。
（７５）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用媒体の製造方法であって、
基板上に保護層、記録膜または超解像読みだし膜、中間層、反射層を形成する工程と、これに別の基板または同様にして前記各層を形成した別の基板を貼り合わせる工程と前記媒体にエネルギービームを照射して前記薄膜中に高融点成分を生成または成長させる工程とを備えてなることを特徴とする。
（７６）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録・再生する情報記録用媒体の製造方法であって、基板上に保護層を形成する工程と高融点成分の材料あるいは高融点成分の組成に近い組成を持つ材料を被着させて島状の種結晶を形成する工程と、前記種結晶の上に前記高融点成分と前記残成分とを含む材料を被着させ、前記高融点成分を選択的に前記種結晶上に成長させると共に、それら種結晶の間を埋めるように前記残成分を成長させる工程と中間層、反射層を形成する工程と、これに別の基板または同様にして前記各層を形成した別の基板を貼り合わせる工程と備えてなることを特徴とする。
（７７）基板上に直接または保護層を介して形成された、エネルギービームの照射を受けて生じる原子配列変化によって情報を記録または再生する情報記録用媒体の製造方法であって、
基板上に保護層を形成する工程と、相変化成分と高融点成分より成る膜の形成を行ないつつ高融点成分の含有量を膜厚方向に変化させる工程と、中間層、反射層を形成する工程と、これに別の基板または同様にして前記各層を形成した別の基板を貼り合わせる工程を備えてることを特徴とする。
（７８）前記高融点成分としては、例えば、
ＬａＴｅ₃，ＬａＴｅ₂，Ｌａ₂Ｔｅ₃，Ｌａ₃Ｔｅ₄，ＬａＴｅ，Ｌａ₂Ｔｅ₅，
Ｌａ₄Ｔｅ₇，Ｌａ₃Ｔｅ，Ｌａ₂Ｓｂ，Ｌａ₃Ｓｂ₂，ＬａＳｂ，ＬａＳｂ₂，
Ｌａ₃Ｇｅ，Ｌａ₅Ｇｅ₃，Ｌａ₄Ｇｅ₃，Ｌａ₅Ｇｅ₄，ＬａＧｅ，Ｌａ₃Ｇｅ₅，
Ａｇ₂Ｔｅ，Ｃｒ₃Ｔｅ₄，Ｃｒ₅Ｔｅ₈，Ｃｒ₂Ｔｅ₃，Ｃｒ₄Ｔｅ₅，ＣｒＳｂ，
Ｃｒ₃Ｇｅ，Ｃｒ₅Ｇｅ₃，Ｃｒ₁₁Ｇｅ₈，ＣｒＧｅ，Ｃｒ₁₁Ｇｅ₁₉，ＰｔＴｅ₂，Ｐｔ₄Ｔｅ₅，Ｐｔ₅Ｔｅ₄，Ｐｔ₄Ｓｂ，Ｐｔ₃Ｓｂ₂，ＰｔＳｂ，Ｐｔ₃Ｇｅ，
Ｐｔ₂Ｇｅ，Ｐｔ₃Ｇｅ₂，ＰｔＧｅ，Ｐｔ₂Ｇｅ₃，ＰｔＧｅ₃，ＮｉＴｅ，
ＮｉＴｅ_0.85，ＮｉＳｂ，Ｎｉ₃Ｇｅ，Ｎｉ₅Ｇｅ₂，Ｎｉ₅Ｇｅ₃，ＮｉＧｅ，
ＣｏＴｅ，ＣｏＴｅ₂，Ｃｏ₃Ｔｅ₄，ＣｏＳｂ，ＣｏＳｂ₂，ＣｏＳｂ₃，
Ｃｏ₅Ｇｅ₂，Ｃｏ₅Ｇｅ₃，ＣｏＧｅ，Ｃｏ₅Ｇｅ₇，ＣｏＧｅ₂，Ｓｉ₂Ｔｅ₃，
ＳｉＳｂ，ＳｉＧｅ，ＣｅＴｅ，Ｃｅ₃Ｔｅ₄，Ｃｅ₂Ｔｅ₃，Ｃｅ₄Ｔｅ₇，
ＣｅＴｅ₂，ＣｅＴｅ₃，Ｃｅ₂Ｓｂ，Ｃｅ₅Ｓｂ₃，Ｃｅ₄Ｓｂ₅，ＣｅＳｂ，
ＣｅＳｂ₂，Ｃｅ₃Ｇｅ，Ｃｅ₅Ｇｅ₃，Ｃｅ₄Ｇｅ₃，Ｃｅ₅Ｇｅ₄，ＣｅＧｅ，
Ｃｅ₃Ｇｅ₅，Ｃｅ₅Ｓｉ₃，Ｃｅ₃Ｓｉ₂，Ｃｅ₅Ｓｉ₄，ＣｅＳｉ，Ｃｅ₃Ｓｉ₅，
ＣｅＳｉ₂，Ｃｒ₃Ｓｉ，Ｃｒ₅Ｓｉ₃，ＣｒＳｉ，ＣｒＳｉ₃，ＣｒＳｉ₂，
Ｃｏ₃Ｓｉ，ＣｏＳｉ，ＣｏＳｉ₂，ＮｉＳｉ₂，ＮｉＳｉ，Ｎｉ₃Ｓｉ₂，
Ｎｉ₂Ｓｉ，Ｎｉ₅Ｓｉ₂，Ｎｉ₃Ｓｉ，Ｐｔ₅Ｓｉ₂，Ｐｔ₂Ｓｉ，ＰｔＳｉ，
ＬａＳｉ₂，Ａｇ₃Ｉｎ，Ａｇ₂Ｉｎ，Ｂｉ₂Ｃｅ，ＢｉＣｅ，Ｂｉ₃Ｃｅ₄，
Ｂｉ₃Ｃｅ₅，ＢｉＣｅ₂，Ｃｄ₁₁Ｃｅ，Ｃｄ₆Ｃｅ，Ｃｄ₅₈Ｃｅ₁₃，Ｃｄ₃Ｃｅ，Ｃｄ₂Ｃｅ，ＣｄＣｅ，Ｃｅ₃Ｉｎ，Ｃｅ₂Ｉｎ，Ｃｅ_1+xＩｎ，Ｃｅ₃Ｉｎ₅，
ＣｅＩｎ₂，ＣｅＩｎ₃，Ｃｅ₂Ｐｂ，ＣｅＰｂ，ＣｅＰｂ₃，Ｃｅ₃Ｓｎ，
Ｃｅ₅Ｓｎ₃，Ｃｅ₅Ｓｎ₄，Ｃｅ₁₁Ｓｎ₁₀，Ｃｅ₃Ｓｎ₅，Ｃｅ₃Ｓｎ₇，
Ｃｅ₂Ｓｎ₅，ＣｅＳｎ₃，ＣｅＺｎ，ＣｅＺｎ₂，ＣｅＺｎ₃，Ｃｅ₃Ｚｎ₁₁，
Ｃｅ₁₃Ｚｎ₅₈，ＣｅＺｎ₅，Ｃｅ₃Ｚｎ₂₂，Ｃｅ₂Ｚｎ₁₇，ＣｅＺｎ₁₁，
Ｃｄ₂₁Ｃｏ₅，ＣｏＧａ，ＣｏＧａ₃，ＣｏＳｎ，Ｃｒ₃Ｇａ，ＣｒＧａ，
Ｃｒ₅Ｇａ₆，ＣｒＧａ₄，Ｃｕ₉Ｇａ₄，Ｃｕ₃Ｓｎ，Ｃｕ₃Ｚｎ，Ｂｉ₂Ｌａ，
ＢｉＬａ，Ｂｉ₃Ｌａ₄，Ｂｉ₃Ｌａ₅，ＢｉＬａ₂，Ｃｄ₁₁Ｌａ，Ｃｄ₁₇Ｌａ₂，
Ｃｄ₉Ｌａ₂，Ｃｄ₂Ｌａ，ＣｄＬａ，Ｇａ₆Ｌａ，Ｇａ₂Ｌａ，ＧａＬａ，
Ｇａ₃Ｌａ₅，ＧａＬａ₃，Ｉｎ₃Ｌａ，Ｉｎ₂Ｌａ，Ｉｎ₅Ｌａ₃，Ｉｎ_xＬａ，
ＩｎＬａ，ＩｎＬａ₂，ＩｎＬａ₃，Ｌａ₅Ｐｂ₃，Ｌａ₄Ｐｂ₃，Ｌａ₁₁Ｐｂ₁₀，
Ｌａ₃Ｐｂ₄，Ｌａ₅Ｐｂ₄，ＬａＰｂ₂，ＬａＰｂ₃，ＬａＺｎ，ＬａＺｎ₂，
ＬａＺｎ₄，ＬａＺｎ₅，Ｌａ₃Ｚｎ₂₂，Ｌａ₂Ｚｎ₁₇，ＬａＺｎ₁₁，ＬａＺｎ₁₃，ＮｉＢｉ，Ｇａ₃Ｎｉ₂，ＧａＮｉ，Ｇａ₂Ｎｉ₃，Ｇａ₃Ｎｉ₅，ＧａＮｉ₃，
Ｎｉ₃Ｓｎ，Ｎｉ₃Ｓｎ₂，Ｎｉ₃Ｓｎ₄，ＮｉＺｎ，Ｎｉ₅Ｚｎ₂₁，ＰｔＢｉ，
ＰｔＢｉ₂，ＰｔＢｉ₃，ＰｔＣｄ₂，Ｐｔ₂Ｃｄ₉，Ｇａ₇Ｐｔ₃，Ｇａ₂Ｐｔ，
Ｇａ₃Ｐｔ₂，ＧａＰｔ，Ｇａ₃Ｐｔ₅，ＧａＰｔ₂，ＧａＰｔ₃，Ｉｎ₇Ｐｔ₃，
Ｉｎ₂Ｐｔ，Ｉｎ₃Ｐｔ₂，ＩｎＰｔ，Ｉｎ₅Ｐｔ₆，Ｉｎ₂Ｐｔ₃，ＩｎＰｔ₂，
ＩｎＰｔ₃，Ｐｔ₃Ｐｂ，ＰｔＰｂ，Ｐｔ₂Ｐｂ₃，Ｐｔ₃Ｓｎ，ＰｔＳｎ，
Ｐｔ₂Ｓｎ₃，ＰｔＳｎ₂，ＰｔＳｎ₄，Ｐｔ₃Ｚｎ，ＰｔＺｎ₂，ＡｌＳ，
Ａｌ₂Ｓ₃，ＢａＳ，ＢａＣ₂，ＣｄＳ，Ｃｏ₄Ｓ₃，Ｃｏ₉Ｓ₈，ＣｏＳ，ＣｏＯ，Ｃｏ₃Ｏ₄，Ｃｏ₂Ｏ₃，Ｃｒ₂Ｏ₃，Ｃｒ₃Ｏ₄，ＣｒＯ，ＣｒＳ，ＣｒＮ，
Ｃｒ₂Ｎ，Ｃｒ₂₃Ｃ₆，Ｃｒ₇Ｃ₃，Ｃｒ₃Ｃ₂，Ｃｕ₂Ｓ，Ｃｕ₉Ｓ₅，ＣｕＯ，
Ｃｕ₂Ｏ，Ｉｎ₄Ｓ₅，Ｉｎ₃Ｓ₄，Ｌａ₂Ｓ₃，Ｌａ₂Ｏ₃，Ｍｏ₂Ｃ，ＭｏＣ，
Ｍｎ₂₃Ｃ₆，Ｍｎ₄Ｃ，Ｍｎ₇Ｃ₃，ＮｉＯ，ＳｉＳ₂，ＳｉＯ₂，Ｓｉ₃Ｎ₄，
Ｃｕ₂Ｔｅ，ＣｕＴｅ，Ｃｕ₃Ｓｂ，Ｍｎ₂Ｓｂ，ＭｎＴｅ，ＭｎＴｅ₂，
Ｍｎ₅Ｇｅ₃，Ｍｎ_3.25Ｇｅ，Ｍｎ₅Ｇｅ₂，Ｍｎ₃Ｇｅ₂，Ｇｅ₃Ｗ，Ｔｅ₂Ｗ，
ＡｌＳｂ，Ａｌ₂Ｔｅ₃，Ｆｅ₂Ｇｅ，ＦｅＧｅ₂，ＦｅＳｂ₂，Ｍｏ₃Ｓｂ₇，
Ｍｏ₃Ｔｅ₄，ＭｏＴｅ₂，ＰｂＴｅ，ＧｅＰｄ₂，Ｇｅ₂Ｐｄ₅，Ｇｅ₉Ｐｄ₂₅，
ＧｅＰｄ₅，Ｐｄ₃Ｓｂ，Ｐｄ₅Ｓｂ₃，ＰｄＳｂ，ＳｎＴｅ，Ｔｉ₅Ｇｅ₃，
Ｇｅ₃₁Ｖ₁₇，Ｇｅ₈Ｖ₁₁，Ｇｅ₃Ｖ₅，ＧｅＶ₃，Ｖ₅Ｔｅ₄，Ｖ₃Ｔｅ₄，ＺｎＴｅ，Ａｇ₂Ｓｅ，Ｃｕ₂Ｓｅ，Ａｌ₂Ｓｅ₃，ＩｎＡｓ，ＣｏＳｅ，Ｍｎ₃Ｉｎ，
Ｎｉ₃Ｉｎ，ＮｉＩｎ，Ｎｉ₂Ｉｎ₃，Ｎｉ₃Ｉｎ₇，ＰｂＳｅ，
などの高融点化合物、あるいはこれらに近い組成の高融点化合物、あるいはこれらの混合物、あるいはこれらの混合組成に近い３元以上の化合物がある。 0.5λ / NA ≦ vT ≦ 0.9λ / NA (12)
(72) In an information recording thin film formed on a substrate directly or through a protective layer and recording / reproducing information by an atomic arrangement change caused by irradiation of an energy beam, an information recording medium having the thin film is used. By repeatedly irradiating a laser beam with an information recording / reproducing device or a medium initial crystallization device to be used, a high melting point component having a melting point relatively higher than the remaining component of the thin film is deposited, and the deposit is deposited on the thin film. It has the feature of being distributed in the region consisting of components.
(73) Information recording using an information recording medium having an information recording thin film formed on a substrate directly or through a protective layer and recording / reproducing information by an atomic arrangement change caused by irradiation with an energy beam. By repeatedly irradiating a laser beam in a reproducing method or a method for initial crystallization of a medium, a high melting point component having a melting point relatively higher than the remaining components of the thin film is deposited, and a region where the deposit is composed of the remaining components of the thin film. It has features that are distributed within.
(74) The information recording thin film according to any one of (1) to (6), which is repeatedly irradiated with a laser beam in an information recording / reproducing apparatus or an initial medium crystallization apparatus using an information recording medium having the thin film. A high melting point component having a relatively higher melting point than the remaining components of the thin film is precipitated, and the precipitate is distributed in a region composed of the remaining components of the thin film, and the precipitate is represented by at least one of B and X. It is characterized by containing the element which is.
(75) A method for manufacturing an information recording medium for recording / reproducing information by a change in atomic arrangement formed upon irradiation of an energy beam, which is formed directly on a substrate or via a protective layer,
A step of forming a protective layer, a recording film or a super-resolution readout film on a substrate, an intermediate layer, and a reflective layer, and a step of bonding another substrate or another substrate on which each of the layers is formed in the same manner to the above, and Irradiating a medium with an energy beam to generate or grow a high melting point component in the thin film.
(76) A method for manufacturing an information recording medium for recording / reproducing information by changing an atomic arrangement generated by irradiation of an energy beam, which is formed directly on a substrate or through a protective layer, the method comprising: Forming a layer and depositing a material having a composition close to the material of the high melting point component or the composition of the high melting point component to form an island-shaped seed crystal; and forming the high melting point component on the seed crystal. A step of depositing a material containing the residual component, selectively growing the high melting point component on the seed crystal, and growing the residual component so as to fill the space between the seed crystals; The method is characterized by comprising a step of forming a layer and a step of bonding another substrate or another substrate on which each of the layers is formed in the same manner to this.
(77) A method for producing an information recording medium for recording or reproducing information by a change in atomic arrangement formed upon irradiation with an energy beam, which is formed directly on a substrate or via a protective layer,
A step of forming a protective layer on the substrate, a step of changing the content of the high melting point component in the film thickness direction while forming a film composed of a phase change component and a high melting point component, and forming an intermediate layer and a reflective layer And a step of bonding another substrate or another substrate on which each of the layers is formed in the same manner to the above.
(78) Examples of the high melting point component include:
LaTe ₃ , LaTe ₂ , La ₂ Te ₃ , La ₃ Te ₄ , LaTe, La ₂ Te ₅ ,
La ₄ Te ₇ , La ₃ Te, La ₂ Sb, La ₃ Sb ₂ , LaSb, LaSb ₂ ,
La ₃ Ge, La ₅ Ge ₃ , La ₄ Ge ₃ , La ₅ Ge ₄ , LaGe, La ₃ Ge ₅ ,
Ag ₂ Te, Cr ₃ Te ₄ , Cr ₅ Te ₈ , Cr ₂ Te ₃ , Cr ₄ Te ₅ , CrSb,
_{_{_{Cr 3 Ge, Cr 5 Ge 3}}} , Cr 11 Ge 8, CrGe, Cr 11 Ge 19, PtTe 2, Pt 4 Te 5, Pt 5 Te 4, Pt 4 Sb, Pt 3 Sb 2, PtSb, Pt 3 Ge,
Pt ₂ Ge, Pt ₃ Ge ₂ , PtGe, Pt ₂ Ge ₃ , PtGe ₃ , NiTe,
NiTe _0.85 , NiSb, Ni ₃ Ge, Ni ₅ Ge ₂ , Ni ₅ Ge ₃ , NiGe,
CoTe, CoTe ₂ , Co ₃ Te ₄ , CoSb, CoSb ₂ , CoSb ₃ ,
_{_{_{Co 5 Ge 2, Co 5 Ge}}} 3, CoGe, Co 5 Ge 7, CoGe 2, Si 2 Te 3,
_{SiSb, SiGe, CeTe, Ce 3} Te 4, Ce 2 Te 3, Ce 4 Te 7,
CeTe ₂ , CeTe ₃ , Ce ₂ Sb, Ce ₅ Sb ₃ , Ce ₄ Sb ₅ , CeSb,
CeSb ₂ , Ce ₃ Ge, Ce ₅ Ge ₃ , Ce ₄ Ge ₃ , Ce ₅ Ge ₄ , CeGe,
Ce ₃ Ge ₅ , Ce ₅ Si ₃ , Ce ₃ Si ₂ , Ce ₅ Si ₄ , CeSi, Ce ₃ Si ₅ ,
CeSi ₂ , Cr ₃ Si, Cr ₅ Si ₃ , CrSi, CrSi ₃ , CrSi ₂ ,
Co ₃ Si, CoSi, CoSi ₂ , NiSi ₂ , NiSi, Ni ₃ Si ₂ ,
Ni ₂ Si, Ni ₅ Si ₂ , Ni ₃ Si, Pt ₅ Si ₂ , Pt ₂ Si, PtSi,
LaSi ₂ , Ag ₃ In, Ag ₂ In, Bi ₂ Ce, BiCe, Bi ₃ Ce ₄ ,
_{_{_{Bi 3 Ce 5, BiCe 2,}}} Cd 11 Ce, Cd 6 Ce, Cd 58 Ce 13, Cd 3 Ce, Cd 2 Ce, CdCe, Ce 3 In, Ce 2 In, Ce 1 + x In, Ce 3 In 5,
CeIn ₂ , CeIn ₃ , Ce ₂ Pb, CePb, CePb ₃ , Ce ₃ Sn,
_{_{_{Ce 5 Sn 3, Ce 5 Sn}}} 4, Ce 11 Sn 10, Ce 3 Sn 5, Ce 3 Sn 7,
Ce ₂ Sn ₅ , CeSn ₃ , CeZn, CeZn ₂ , CeZn ₃ , Ce ₃ Zn ₁₁ ,
Ce ₁₃ Zn ₅₈ , CeZn ₅ , Ce ₃ Zn ₂₂ , Ce ₂ Zn ₁₇ , CeZn ₁₁ ,
Cd ₂₁ Co ₅ , CoGa, CoGa ₃ , CoSn, Cr ₃ Ga, CrGa,
Cr ₅ Ga ₆ , CrGa ₄ , Cu ₉ Ga ₄ , Cu ₃ Sn, Cu ₃ Zn, Bi ₂ La,
BiLa, Bi ₃ La ₄ , Bi ₃ La ₅ , BiLa ₂ , Cd ₁₁ La, Cd ₁₇ La ₂ ,
Cd ₉ La ₂ , Cd ₂ La, CdLa, Ga ₆ La, Ga ₂ La, GaLa,
Ga ₃ La ₅ , GaLa ₃ , In ₃ La, In ₂ La, In ₅ La ₃ , In _x La,
InLa, InLa ₂ , InLa ₃ , La ₅ Pb ₃ , La ₄ Pb ₃ , La ₁₁ Pb ₁₀ ,
La ₃ Pb ₄ , La ₅ Pb ₄ , LaPb ₂ , LaPb ₃ , LaZn, LaZn ₂ ,
_{_{_{LaZn 4, LaZn 5, La 3}}} Zn 22, La 2 Zn 17, LaZn 11, LaZn 13, NiBi, Ga 3 Ni 2, GaNi, Ga 2 Ni 3, Ga 3 Ni 5, GaNi 3,
Ni ₃ Sn, Ni ₃ Sn ₂ , Ni ₃ Sn ₄ , NiZn, Ni ₅ Zn ₂₁ , PtBi,
PtBi ₂ , PtBi ₃ , PtCd ₂ , Pt ₂ Cd ₉ , Ga ₇ Pt ₃ , Ga ₂ Pt,
Ga ₃ Pt ₂ , GaPt, Ga ₃ Pt ₅ , GaPt ₂ , GaPt ₃ , In ₇ Pt ₃ ,
In ₂ Pt, In ₃ Pt ₂ , InPt, In ₅ Pt ₆ , In ₂ Pt ₃ , InPt ₂ ,
InPt ₃ , Pt ₃ Pb, PtPb, Pt ₂ Pb ₃ , Pt ₃ Sn, PtSn,
Pt ₂ Sn ₃ , PtSn ₂ , PtSn ₄ , Pt ₃ Zn, PtZn ₂ , AlS,
Al ₂ S ₃ , BaS, BaC ₂ , CdS, Co ₄ S ₃ , Co ₉ S ₈ , CoS, CoO, Co ₃ O ₄ , Co ₂ O ₃ , Cr ₂ O ₃ , Cr ₃ O ₄ , CrO, CrS, CrN,
Cr ₂ N, Cr ₂₃ C ₆ , Cr ₇ C ₃ , Cr ₃ C ₂ , Cu ₂ S, Cu ₉ S ₅ , CuO,
Cu ₂ O, In ₄ S ₅ , In ₃ S ₄ , La ₂ S ₃ , La ₂ O ₃ , Mo ₂ C, MoC,
Mn ₂₃ C ₆ , Mn ₄ C, Mn ₇ C ₃ , NiO, SiS ₂ , SiO ₂ , Si ₃ N ₄ ,
Cu ₂ Te, CuTe, Cu ₃ Sb, Mn ₂ Sb, MnTe, MnTe ₂ ,
Mn ₅ Ge ₃ , Mn _3.25 Ge, Mn ₅ Ge ₂ , Mn ₃ Ge ₂ , Ge ₃ W, Te ₂ W,
AlSb, Al ₂ Te ₃ , Fe ₂ Ge, FeGe ₂ , FeSb ₂ , Mo ₃ Sb ₇ ,
Mo ₃ Te ₄ , MoTe ₂ , PbTe, GePd ₂ , Ge ₂ Pd ₅ , Ge ₉ Pd ₂₅ ,
GePd ₅ , Pd ₃ Sb, Pd ₅ Sb ₃ , PdSb, SnTe, Ti ₅ Ge ₃ ,
Ge ₃₁ V ₁₇ , Ge ₈ V ₁₁ , Ge ₃ V ₅ , GeV ₃ , V ₅ Te ₄ , V ₃ Te ₄ , ZnTe, Ag ₂ Se, Cu ₂ Se, Al ₂ Se ₃ , InAs, CoSe, Mn ₃ In ,
Ni ₃ In, NiIn, Ni ₂ In ₃ , Ni ₃ In ₇ , PbSe,
Or a high melting point compound having a composition close to the above, or a mixture thereof, or a ternary or higher compound close to a mixture thereof.

これらの中では、
ＬａＳｂ，ＣｒＳｂ，ＣｏＳｂ，Ｃｒ₃Ｔｅ₄，Ｃｒ₂Ｔｅ₃，Ｃｒ₄Ｔｅ₅，
ＣｏＴｅ，Ｃｏ₃Ｔｅ₄，ＬａＴｅ₃，Ｃｕ₂Ｔｅ，ＣｕＴｅ，Ｃｕ₃Ｓｂ，
ＭｎＴｅ，ＭｎＴｅ₂，Ｍｎ₂Ｓｂ
のうちの少なくとも１つが特に好ましい。その理由は、屈折率が残成分に近いので、ノイズが発生しにくく融点も高いことにある。 Among these,
_{LaSb, CrSb, CoSb, Cr 3} Te 4, Cr 2 Te 3, Cr 4 Te 5,
CoTe, Co ₃ Te ₄ , LaTe ₃ , Cu ₂ Te, CuTe, Cu ₃ Sb,
MnTe, MnTe ₂ , Mn ₂ Sb
At least one of them is particularly preferred. The reason is that since the refractive index is close to the residual component, noise is hardly generated and the melting point is high.

前記高融点成分中に含まれる酸化物、硫化物、窒化物、炭化物の含有量は、前記高融点成分の全構成原子数の４０原子％未満とするのが好ましく、１０原子％未満とするのが特に好ましい。これらの含有量が４０原子％以上であると、当該薄膜の高融点成分以外の成分すなわち残成分との複素屈折率の差を小さくできなかったり、当該残成分中に酸素等が拡散して記録・再生特性を劣化させたりする問題を生じやすいからである。 The content of oxides, sulfides, nitrides, and carbides contained in the high melting point component is preferably less than 40 at% of the total number of constituent atoms of the high melting point component, and is preferably less than 10 at%. Is particularly preferred. If the content is 40 atomic% or more, the difference in the complex refractive index from the components other than the high melting point component of the thin film, that is, the residual component, cannot be reduced, or oxygen or the like diffuses into the residual component to record. -This is because a problem of deteriorating reproduction characteristics is likely to occur.

前記情報記録用薄膜では、前記高融点成分の析出物が分布した状態で情報の記録・再生・消去を行なうものであるから、前記高融点成分と、可逆的に相変化する成分との混合組成になっているのが好ましい。ここで「相変化」とは、結晶状態−非晶質状態間の相変化だけでなく、結晶状態−結晶質状態間の相変化も含む
。 In the information recording thin film, information is recorded / reproduced / erased in a state where precipitates of the high melting point component are distributed. Therefore, a mixed composition of the high melting point component and a component that reversibly changes phase is used. It is preferred that Here, the “phase change” includes not only a phase change between a crystalline state and an amorphous state but also a phase change between a crystalline state and a crystalline state.

可逆的に相変化する成分としては、既知の相変化記録材料の他、好適な相変化特性を持った材料であれば任意のものを使用することができるが、高融点成分の例として前で述べた多数の化合物の中では、Ｃｒなどの遷移金属元素を含む化合物が好ましく、且つその遷移金属元素の含有量は当該薄膜の総構成原子数の４０原子％以下が好ましく、３４原子％以下がより好ましい。この条件が満たされると、析出する高融点成分とＴｅ系またはＳｂ系の相変化成分との界面反射率を小さくする効果が大きくなるという利点がある。 As the reversibly phase-changeable component, in addition to a known phase-change recording material, any material having suitable phase-change characteristics can be used. Among the many compounds described above, a compound containing a transition metal element such as Cr is preferable, and the content of the transition metal element is preferably 40 atom% or less of the total number of constituent atoms of the thin film, and 34 atom% or less. More preferred. When this condition is satisfied, there is an advantage that the effect of reducing the interface reflectance between the precipitated high melting point component and the Te-based or Sb-based phase change component increases.

前記高融点成分の屈折率の実数部ｎ₁と虚数部ｋ₁の値は、前記高融点成分と相変化成分との界面での光散乱を防ぐ観点から、前記相変化成分の結晶状態での実数部ｎ₂と虚数部ｋ₂の値のそれぞれ±４０％以内であるのが好ましく、±２０％以内であるのがより好ましい。 The values of the real part n ₁ and the imaginary part k ₁ of the refractive index of the high melting point component are, from the viewpoint of preventing light scattering at the interface between the high melting point component and the phase change component, in the crystalline state of the phase change component. The value of each of the real part n ₂ and the imaginary part k ₂ is preferably within ± 40%, more preferably within ± 20%.

ｎ₁とｎ₂の差が±１０％以内、ｋ₁とｋ₂の差が±７０％以内であり、且つ
｜〔（ｎ₁＋ｉｋ₁）−（ｎ₂＋ｉｋ₂）〕／〔（ｎ₁＋ｉｋ₁）＋（ｎ₂＋ｉｋ₂）〕｜²で表わされる界面反射率が６％以下があるのが好ましい。また、ｎ₁とｎ₂の差が±１０％以内、ｋ₁とｋ₂の差が±７０％以内であり、且つ界面反射率が２％以下であるのがより好ましい。これらの条件を満たすことは、膜厚を厚くして再生信号レベルを大きくし、界面での光散乱を防ぐのに好ましい。 n ₁ and the difference between n ₂ is within 10% ±, the difference between k ₁ and k ₂ is not less than 70% ±, and | _{_{[(n 1 + ik 1) -}} (n 2 + ik 2) ] / [(n ₁ + Ik ₁ ) + (n ₂ + ik ₂ )] | ² is preferably 6% or less. More preferably, the difference between n ₁ and n ₂ is within ± 10%, the difference between k ₁ and k ₂ is within ± 70%, and the interface reflectance is 2% or less. It is preferable to satisfy these conditions in order to increase the reproduction signal level by increasing the film thickness and to prevent light scattering at the interface.

高融点成分の屈折率（ｎ，ｋ）の好ましい範囲は、相変化成分がＧｅ−Ｓｂ−Ｔｅ系の場合は、
５．０≦ｎ≦６．２，１．１≦ｋ≦６．１であり、
相変化成分がＩｎ−Ｓｂ−Ｔｅ系の場合は、
１．５≦ｎ≦１．８，０．６≦ｋ≦３．６である。 The preferable range of the refractive index (n, k) of the high melting point component is as follows when the phase change component is a Ge—Sb—Te system.
5.0 ≦ n ≦ 6.2, 1.1 ≦ k ≦ 6.1,
When the phase change component is an In-Sb-Te system,
1.5 ≦ n ≦ 1.8, 0.6 ≦ k ≦ 3.6.

高融点成分が前記情報記録用薄膜において、高融点成分の析出物を明確に判別できない場合は、次のように解する。すなわち、当該薄膜の平均組成から前記高融点成分以外の残成分（例えば相変化成分）の組成のいずれか一つを除くと、残部の８０％以上、より好ましくは９０％以上がこの発明の融点の条件を満たす高融点成分の組成となる場合、この発明の高融点成分が析出しているものとする。 If the high melting point component cannot clearly discriminate the precipitate of the high melting point component in the information recording thin film, the following explanation is made. That is, when one of the compositions of the remaining components (for example, phase change components) other than the high melting point component is excluded from the average composition of the thin film, 80% or more, and more preferably 90% or more of the remaining portion has a melting point of the present invention. In the case where the composition of the high melting point component satisfies the above condition, it is assumed that the high melting point component of the present invention is precipitated.

情報記録用薄膜の保護に用いる「保護層」は、有機物でもよいし無機物でもよいが、無機物の方が耐熱性の面で好ましい。しかし、機械的強度を増すために、基板とは別に形成した無機物の保護層を厚くすると、クラック発生、透過率低下、感度低下などを生じやすいので、この保護層を薄くする一方、この保護層の当該情報記録用薄膜と反対の側に厚い有機物層を密着させるのが好ましい。この有機物層は基板とは別に形成した層でもよいし、有機物の基板でもよい。これによって変形が起こり難くなる。 The “protective layer” used for protecting the information recording thin film may be an organic substance or an inorganic substance, but an inorganic substance is preferable in terms of heat resistance. However, if the thickness of the inorganic protective layer formed separately from the substrate is increased in order to increase the mechanical strength, cracks, a decrease in transmittance, a decrease in sensitivity, and the like are likely to occur. Preferably, a thick organic material layer is adhered to the side opposite to the information recording thin film. This organic layer may be a layer formed separately from the substrate, or may be an organic substrate. This makes deformation less likely to occur.

有機物の保護層は、例えばアクリル樹脂、ポリカーボネート、ポリオレフィン、エポキシ樹脂、ポリイミド、ポリアミド、ポリスチレン、ポリエチレン、ポリエチレンテレフタレ−ト、ポリ４フッ化エチレン（テフロン：登録商標）などのフッ素樹脂などにより形成することができる。ホットメルト接着剤として知られているエチレン−酢酸ビニル共重合体などや、粘着剤などでもよい。これらの樹脂の少なくとも１つを主成分とする紫外線硬化樹脂で形成してもよい。有機物の基板で保護層を兼ねてもよい。 The organic protective layer is formed of, for example, an acrylic resin, polycarbonate, polyolefin, epoxy resin, polyimide, polyamide, polystyrene, polyethylene, polyethylene terephthalate, or a fluororesin such as polytetrafluoroethylene (Teflon: registered trademark). be able to. An ethylene-vinyl acetate copolymer or the like known as a hot melt adhesive or a pressure-sensitive adhesive may be used. It may be formed of an ultraviolet curable resin containing at least one of these resins as a main component. An organic substrate may also serve as the protective layer.

無機物の保護層は、例えば酸化物、弗化物、窒化物、硫化物、セレン化物、炭化物、ホウ化物、ホウ素、炭素、あるいは金属などを主成分とする無機物などにより形成することができる。ガラス、石英、サファイア、鉄、チタン、あるいはアルミニウムを主成分とする無機物の基板で保護層を兼ねてもよい。 The inorganic protective layer can be formed of, for example, an inorganic material mainly containing an oxide, a fluoride, a nitride, a sulfide, a selenide, a carbide, a boride, boron, carbon, or a metal. An inorganic substrate containing glass, quartz, sapphire, iron, titanium, or aluminum as a main component may also serve as the protective layer.

無機物の保護層の例としては、Ｃｅ，Ｌａ，Ｓｉ，Ｉｎ，Ａｌ，Ｇｅ，Ｐｂ，Ｓｎ，Ｂｉ，Ｔｅ，Ｔａ，Ｓｃ，Ｙ，Ｔｉ，Ｚｒ，Ｖ，Ｎｂ，ＣｒおよびＷよりなる群より選ばれた少なくとも１つの元素の酸化物、Ｃｄ，Ｚｎ，Ｇａ，Ｉｎ，Ｓｂ，Ｇｅ，Ｓｎ，Ｐｂよりなる群より選ばれた少なくとも１つの元素の硫化物またはセレン化物、Ｍｇ，Ｃｅ，Ｃａなどの弗化物、Ｓｉ，Ａｌ，Ｔａ，Ｂなどの窒化物、または、ホウ素あるいは炭素より成るものであって、たとえば主成分が、ＣｅＯ₂，Ｌａ₂Ｏ₃，ＳｉＯ，ＳｉＯ₂，Ｉｎ₂Ｏ₃，Ａｌ₂Ｏ₃，ＧｅＯ，ＧｅＯ₂，ＰｂＯ，ＳｎＯ，ＳｎＯ₂，Ｂｉ₂Ｏ₃，ＴｅＯ₂，ＷＯ₂，ＷＯ₃，Ｔａ₂Ｏ₅，Ｓｃ₂Ｏ₃，Ｙ₂Ｏ₃，ＴｉＯ₂，ＺｒＯ₂，ＣｄＳ，ＺｎＳ，ＣｄＳｅ，ＺｎＳｅ，Ｉｎ₂Ｓ₃，Ｉｎ₂Ｓｅ₃，Ｓｂ₂Ｓ₃，Ｓｂ₂Ｓｅ₃，Ｇａ₂Ｓ₃，Ｇａ₂Ｓｅ₃，ＭｇＦ₂，ＣｅＦ₃，ＣａＦ₂，ＧｅＳ，ＧｅＳｅ，ＧｅＳｅ₂，ＳｎＳ，ＳｎＳ₂，ＳｎＳｅ，ＳｎＳｅ₂，ＰｂＳ，ＰｂＳｅ，Ｂｉ₂Ｓｅ₃，Ｂｉ₂Ｓ₃，ＴａＮ，Ｓｉ₃Ｎ₄，ＡｌＮ，ＡｌＳｉＮ₂，Ｓｉ，ＴｉＢ₂，Ｂ₄Ｃ，ＳｉＣ，Ｂ，Ｃのうちの１つあるいはそれに近い組成をもったもの、またはそれらの混合物がある。 Examples of the inorganic protective layer include a group consisting of Ce, La, Si, In, Al, Ge, Pb, Sn, Bi, Te, Ta, Sc, Y, Ti, Zr, V, Nb, Cr and W. Oxide of at least one selected element, sulfide or selenide of at least one element selected from the group consisting of Cd, Zn, Ga, In, Sb, Ge, Sn, Pb, Mg, Ce, Ca, etc. Of fluoride, nitride such as Si, Al, Ta, B, or boron or carbon, for example, whose main components are CeO ₂ , La ₂ O ₃ , SiO, SiO ₂ , In ₂ O ₃ _{_{, Al 2 O 3, GeO,}} GeO 2, PbO, SnO, SnO 2, Bi 2 O 3, TeO 2, WO 2, WO 3, Ta 2 O 5, Sc 2 O 3, Y 2 O 3, TiO 2, _{ZrO 2, CdS, ZnS, CdSe} , ZnS _{_{_{, In 2 S 3, In 2}}} Se 3, Sb 2 S 3, Sb 2 Se 3, Ga 2 S 3, Ga 2 Se 3, MgF 2, CeF 3, CaF 2, GeS, GeSe, GeSe 2, SnS, SnS ₂ , SnSe, SnSe ₂ , PbS, PbSe, Bi ₂ Se ₃ , Bi ₂ S ₃ , TaN, Si ₃ N ₄ , AlN, AlSiN ₂ , Si, TiB ₂ , B ₄ C, SiC, B, C There are those with one or more compositions, or mixtures thereof.

これらのうち、硫化物では、ＺｎＳまたはそれに近い組成のものが、屈折率が適当な大きさで膜が安定である点で好ましい。窒化物では、表面反射率があまり高くなく、膜が安定で強固である点で、ＴａＮ，Ｓｉ₃Ｎ₄，ＡｌＳｉＮ₂またはＡｌＮ（窒化アルミニウム）またはそれに近い組成のものが好ましい。酸化物では、膜が安定である点で、Ｙ₂Ｏ₃，Ｓｃ₂Ｏ₃，ＣｅＯ₂，ＴｉＯ₂，ＺｒＯ₂，ＳｉＯ，Ｔａ₂Ｏ₅，Ｉｎ₂Ｏ₃，Ａｌ₂Ｏ₃，ＳｎＯ₂またはＳｉＯ₂またはそれらに近い組成のものが好ましい。水素を含む非晶質Ｓｉでもよい。 Among these, sulfides having a composition close to ZnS or ZnS are preferable because the refractive index is appropriate and the film is stable. The nitride is preferably TaN, Si ₃ N ₄ , AlSiN ₂ or AlN (aluminum nitride) or a composition close to AlN because the surface reflectance is not so high and the film is stable and strong. In the case of oxides, Y ₂ O ₃ , Sc ₂ O ₃ , CeO ₂ , TiO ₂ , ZrO ₂ , SiO, Ta ₂ O ₅ , In ₂ O ₃ , Al ₂ O ₃ , SnO ₂ , because the film is stable. Alternatively, SiO ₂ or a composition close to SiO ₂ is preferable. Amorphous Si containing hydrogen may be used.

前記保護層を無機物−無機物、あるいは無機物−有機物の２層あるいは３層以上の多層構成にすれば、さらに保護効果が高まる。 If the protective layer has a multilayer structure of two layers or three or more layers of inorganic-inorganic or inorganic-organic, the protective effect is further enhanced.

前記保護層に混合物を使用すると、膜形成が容易である。例えば、厚さ５０〜５００ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀層では、保護効果、記録・消去特性、書き換え特性ともに良好であり、膜の形成も容易である。 When a mixture is used for the protective layer, film formation is easy. For example, a (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer having a thickness of 50 to 500 nm has good protection effects, recording / erasing characteristics, and rewriting characteristics, and is easy to form.

前記保護層はまた、有機物および無機物の複合材料により形成することもできる。 The protective layer can also be formed of a composite material of an organic substance and an inorganic substance.

無機物の保護層は、そのままの組成で電子ビーム蒸着、スパッタリングなどにより形成してもよいが、反応性スパッタリングあるいは、金属、半金属、半導体の少なくとも１元素よりなる膜を形成した後に酸素、硫黄、窒素のうちの少なくとも一つと反応させるようにすると、成膜が容易となる。 The inorganic protective layer may be formed by electron beam evaporation, sputtering or the like with the composition as it is, but after reactive sputtering or forming a film made of at least one element of a metal, a semimetal, and a semiconductor, oxygen, sulfur, By reacting with at least one of nitrogen, film formation is facilitated.

一般に、薄膜に光を照射すると、薄膜の表面からの反射光と薄膜の裏面からの反射光との重ね合わせにより干渉が生じる。そこで、薄膜の反射率の変化で信号を読み取る場合には、記録用薄膜に近接して光を反射する「反射層」を設けることにより、干渉の効果を大きくし、それによって再生（読出し）信号を大きくすることができる。なお、光を吸収する吸収層としてもよい。 Generally, when light is applied to a thin film, interference occurs due to superposition of light reflected from the front surface of the thin film and light reflected from the back surface of the thin film. Therefore, when a signal is read by a change in the reflectance of the thin film, the effect of interference is increased by providing a "reflection layer" that reflects light close to the thin film for recording, thereby reproducing (reading) a signal. Can be increased. Note that an absorption layer that absorbs light may be used.

干渉の効果をより大きくするためには、記録用薄膜と反射層の間に「中間層」を設けるのが好ましい。中間層は、書き換え時に記録用薄膜と反射層との間で相互拡散が起こるのを防止する作用、および反射層への熱の逃げを減少させて記録感度を高め、、消え残りを防止する作用がある。 In order to further enhance the effect of interference, it is preferable to provide an "intermediate layer" between the recording thin film and the reflective layer. The intermediate layer prevents mutual diffusion between the recording thin film and the reflective layer at the time of rewriting, and reduces the escape of heat to the reflective layer to increase the recording sensitivity and prevent the unerased portion. There is.

中間層の材質を適当に選ぶと、情報記録用薄膜の役割の少なくとも一部を担わせることもできる。例えば、中間層をセレン化物で形成すると、記録用薄膜の少なくとも一部の元素が中間層中へ拡散し、あるいは中間層中の元素と反応し、あるいは中間層の少なくとも一部の元素が記録用薄膜または反射層中へ拡散し、それによって記録用薄膜の一部の役割を果たすようになる。 By appropriately selecting the material of the intermediate layer, it is possible to play at least a part of the role of the information recording thin film. For example, when the intermediate layer is formed of selenide, at least some elements of the recording thin film diffuse into the intermediate layer, or react with the elements in the intermediate layer, or at least some elements of the intermediate layer are used for recording. It diffuses into the thin film or reflective layer, thereby serving as part of the recording thin film.

中間層の膜厚は、３ｎｍ以上、４００ｎｍ以下で、且つ、記録状態および消去状態のいずれか一方において、読み出し光の波長付近で記録用薄膜の反射率が極小値に近く、しかもその値が他方の状態において２０％付近あるいはそれ以上となるようにするのが好ましい。 The film thickness of the intermediate layer is not less than 3 nm and not more than 400 nm, and the reflectance of the recording thin film is close to the minimum value near the wavelength of the read light in one of the recording state and the erasing state, and the value is the other. It is preferable that the value be around 20% or more in the above condition.

反射層として、熱伝導率が２．０Ｗ／ｃｍ・ｄｅｇ以上の高熱伝導率材料（例えばＡｕなど）を主成分とする材料を用いると、熱拡散率が高くなり、高速で結晶化する記録用薄膜を用いても、高パワーのレーザ光を照射したときに確実に非晶質化するようになる。この場合、中間層にも、熱伝導率の高い材料（例えばＡｌ₂Ｏ₃，ＡｌＮ，Ｓｉ₃Ｎ₄，ＺｎＳなどあるいはそれに近い組成の材料）を用いるか、ＳｉＯ₂などの熱伝導率が中程度（０．０２Ｗ／ｃｍ・ｄｅｇ以上、０．１Ｗ／ｃｍ・ｄｅｇ以下）の材料を用い、中間層を薄くするのが特に好ましい。ただし、記録感度を高めるには、前記の値よりも低い熱伝導率の材料で反射層を形成するのが好ましい。 When a material having a high thermal conductivity material (for example, Au or the like) having a thermal conductivity of 2.0 W / cm · deg or more as a main component is used as the reflective layer, the thermal diffusivity becomes high and the recording layer is crystallized at high speed. Even when a thin film is used, it becomes surely amorphous when irradiated with high-power laser light. In this case, a material having high thermal conductivity (for example, Al ₂ O ₃ , AlN, Si ₃ N ₄ , ZnS, or the like or a material having a composition similar thereto) or a medium having high thermal conductivity such as SiO ₂ is also used for the intermediate layer. It is particularly preferable to use a material having a thickness of about 0.02 W / cm · deg or more and 0.1 W / cm · deg or less and make the intermediate layer thin. However, in order to increase the recording sensitivity, it is preferable to form the reflective layer with a material having a thermal conductivity lower than the above value.

反射層は、情報記録用薄膜の基板側に配置してもよいし、情報記録用薄膜の基板とは反対側に配置してもよい。 The reflective layer may be disposed on the substrate side of the information recording thin film, or may be disposed on the side opposite to the information recording thin film substrate.

反射層の中間層とは反対の側に、前記保護層に使用可能な無機物よりなる保護層（上びき層）を形成すれば、さらに好ましい。これら中間層、反射層、保護層よりなる３層構成では、全体として、単層の保護層より強固となる。 It is more preferable that a protective layer (overcoat layer) made of an inorganic substance usable for the protective layer is formed on the side of the reflective layer opposite to the intermediate layer. In the three-layer structure including the intermediate layer, the reflective layer, and the protective layer, the overall structure is stronger than a single protective layer.

前記基板、記録用薄膜、保護層、中間層および反射層の形成は、真空蒸着、ガス中蒸着、スパッタリング、イオンビーム蒸着、イオンプレーティング、電子ビーム蒸着、射出成形、キャスティング、回転塗布、プラズマ重合などの方法からいずれかを適宜選定して行なえばよい。 The formation of the substrate, the recording thin film, the protective layer, the intermediate layer, and the reflective layer is performed by vacuum evaporation, gas evaporation, sputtering, ion beam evaporation, ion plating, electron beam evaporation, injection molding, casting, spin coating, and plasma polymerization. Any of these methods may be appropriately selected and performed.

前記記録用薄膜、保護層、中間層、反射層、および反射層に隣接した保護層は、すべてスパッタリングにより形成するのが最も好ましい。 Most preferably, the recording thin film, the protective layer, the intermediate layer, the reflective layer, and the protective layer adjacent to the reflective layer are all formed by sputtering.

前記の情報記録用薄膜は、共蒸着や共スパッタリングなどによって、保護膜用に使用可能な材料として前述した酸化物、弗化物、窒化物、有機物など、あるいは炭素または炭化物の中に分散させた形態としてもよい。そうすることによって、光吸収係数を調節し再生信号強度を大きくすることができる場合がある。 The information recording thin film is formed by dispersing the above-mentioned oxide, fluoride, nitride, organic material, or the like as a material usable for the protective film by co-evaporation or co-sputtering, or in carbon or carbide. It may be. By doing so, there are cases where the light absorption coefficient can be adjusted to increase the reproduction signal intensity.

この場合、混合比率は、薄膜中で酸素、弗素、窒素、炭素が膜全体に対して占める原子数の割合が４０％以下が好ましく、２０％以下がより好ましい。 In this case, the mixing ratio is such that the ratio of the number of atoms occupied by oxygen, fluorine, nitrogen, and carbon to the whole film in the thin film is preferably 40% or less, more preferably 20% or less.

このような複合膜化を行なうことにより、結晶化の速度が低下し、感度が低下するのが普通であるが、有機物との複合膜化では感度が向上する。 The formation of such a composite film usually lowers the crystallization speed and lowers the sensitivity, but the formation of a composite film with an organic substance improves the sensitivity.

一般に、相転移（相変化）によって情報の記録を行なう場合、記録膜の全面をあらかじめ結晶化させておくのが好ましいが、基板に有機物を用いている場合には基板を高温にすることができない。そこで、それ以外の方法で結晶化させる必要がある。 Generally, when recording information by phase transition (phase change), it is preferable to crystallize the entire surface of the recording film in advance, but when an organic substance is used for the substrate, the substrate cannot be heated to a high temperature. . Therefore, it is necessary to crystallize by other methods.

この場合の好ましい結晶化法としては、例えば、スポット径が２μｍ以下となるように集束したレーザ光の照射、キセノンランプや水銀ランプなどによる紫外線照射と加熱、フラッシュランプ光の照射、高出力ガスレーザや出力１Ｗ程度の高出力半導体レーザからの大きなレーザ光スポットによる光の照射、あるいは加熱とレーザ光照射との組合せなどがある。 As a preferable crystallization method in this case, for example, irradiation of laser light focused so that the spot diameter becomes 2 μm or less, irradiation and heating of ultraviolet light by a xenon lamp or a mercury lamp, irradiation of flash lamp light, high-power gas laser, Light irradiation by a large laser light spot from a high-power semiconductor laser with an output of about 1 W, or a combination of heating and laser light irradiation is available.

スポット径を２μｍ以下まで集束したレーザ光を情報記録用薄膜に照射する場合、複数回の照射が必要となる場合が多い。このため、単一のレーザ光では、薄膜に繰り返し照射することになり、長時間を要する。これを避けるには、半導体レーザアレイを用いるか、ガスレーザのビームを複数に分割して同時に複数箇所に照射するようにするのがよい。これにより、薄膜を１回転するだけで多数回のレーザ光照射が可能となる。 When irradiating the information recording thin film with a laser beam focused to a spot diameter of 2 μm or less, it is often necessary to irradiate the laser beam a plurality of times. Therefore, a single laser beam repeatedly irradiates the thin film, which requires a long time. In order to avoid this, it is preferable to use a semiconductor laser array or divide the beam of the gas laser into a plurality of beams and irradiate a plurality of portions simultaneously. This makes it possible to irradiate the laser beam a number of times with only one rotation of the thin film.

各光スポットは、同一の記録トラック上に並列させてもよいが、２つあるいはそれ以上のトラック上に並列させてもよい。トラック上とトラック間に同時に照射するようにすれば、さらに好ましい。各スポットのレーザ光パワーは同じである必要はない。 Each light spot may be arranged on the same recording track, or may be arranged on two or more tracks. It is more preferable to irradiate simultaneously on the track and between the tracks. The laser light power of each spot does not need to be the same.

ガスレーザあるいは高出力半導体レーザからの単一ビームを照射する場合、スポット径（円形の光スポットであれば光強度が（１／２）になる位置での直径、楕円形の光スポットであれば前記位置での長径）が５μｍ以上、５ｍｍ以下とすると能率がよい。 When irradiating a single beam from a gas laser or a high-power semiconductor laser, the spot diameter (the diameter at a position where the light intensity becomes (1/2) for a circular light spot, or the above-mentioned for an elliptical light spot) The efficiency is good when the major axis at the position is 5 μm or more and 5 mm or less.

結晶化を記録トラック上のみで生じさせ、トラック間は非晶質のままとしてもよい。記録トラック間のみを結晶化させてもよい。 Crystallization may occur only on the recording tracks, and the space between the tracks may be left amorphous. Crystallization may be performed only between the recording tracks.

例えば、Ｓｂ，Ｔｅ，ＧｅおよびＣｒを主成分とする薄膜を複数の蒸発源からの回転蒸着によって形成した場合、蒸着直後にはＳｂ，Ｔｅ，ＧｅおよびＣｒの原子がうまく結合していない場合が多い。また、この薄膜をスパッタリングによって形成した場合も、原子配列が極めて乱れた状態になる。そこで、このような場合には、まず、高いパワー密度のレーザ光を記録トラック上に照射して加熱し、高融点成分を析出させるとともに、場合によっては薄膜を選択的に融解させるのがよい。その後、前記記録トラック上に低いパワー密度のレーザ光を照射して前記薄膜を結晶化させる。こうすると、トラック全周にわたって反射率が均一になりやすい利点がある。 For example, when a thin film mainly composed of Sb, Te, Ge and Cr is formed by rotary evaporation from a plurality of evaporation sources, the atoms of Sb, Te, Ge and Cr may not bond well immediately after the evaporation. Many. Also, when this thin film is formed by sputtering, the atomic arrangement is extremely disturbed. Therefore, in such a case, it is preferable to first irradiate the recording track with a laser beam having a high power density and heat it to precipitate a high melting point component, and to selectively melt the thin film in some cases. Thereafter, the recording track is irradiated with a laser beam having a low power density to crystallize the thin film. This has the advantage that the reflectance tends to be uniform over the entire circumference of the track.

レーザ光などのエネルギービームを照射する前には、情報記録用薄膜中に高融点成分が存在しない場合もあるが、以上のような結晶化処理により、その薄膜中に高融点成分を析出あるいは成長させることができる。析出あるいは成長した高融点成分は、前述したように、薄膜中にほぼ独立して粒状または柱状に分布し、あるいは、高融点成分が連続して多孔質状に分布する。前者の場合は、当該薄膜の残成分（通常は相変化成分）の中に高融点成分が分布する。後者の場合は、高融点成分の析出物の多数の孔の中に残成分が埋め込まれる。 Before irradiating an energy beam such as a laser beam, the high melting point component may not be present in the information recording thin film, but the high melting point component is deposited or grown in the thin film by the above crystallization treatment. Can be done. As described above, the precipitated or grown high melting point component is almost independently distributed in the form of particles or columns in the thin film, or the high melting point component is continuously distributed in a porous state. In the former case, the high melting point component is distributed in the remaining component (usually a phase change component) of the thin film. In the latter case, the remaining components are embedded in many pores of the precipitate of the high melting point component.

この第１の製造方法では、高融点成分は情報記録用薄膜の両側の界面からその内部に向かって成長しやすい。 In the first manufacturing method, the high melting point component tends to grow from the interfaces on both sides of the information recording thin film toward the inside thereof.

結晶化するパワーレベルと非晶質に近い状態にするパワーレベルとの間でパワー変調したレーザ光で情報を記録（オーバーライト）することは、薄膜の結晶化後の状態の如何に関わらず可能である。 It is possible to record (overwrite) information with a laser beam whose power has been modulated between the power level at which it crystallizes and the power level at which it approaches an amorphous state, regardless of the state of the thin film after crystallization. It is.

この発明の第１〜第６の情報記録用薄膜では、必ずしも非晶質状態と結晶状態の間の変化を記録に利用する必要はなく、膜の形状変化をほとんど伴わない何らかの原子配列変化によって、光学的性質の変化を起こさせれば足りる。前記高融点成分の析出物により、薄膜の流動・偏析が確実に防止される。 In the first to sixth information recording thin films of the present invention, it is not always necessary to use a change between an amorphous state and a crystalline state for recording. It is enough to cause a change in optical properties. The flow of the thin film and segregation are surely prevented by the precipitate of the high melting point component.

例えば、結晶粒径や結晶形の変化、結晶と準安定状態（π，γなど）との間の変化などでもよい。非晶質状態と結晶状態の変化でもよいし、完全な非晶質や結晶状態でなく両状態の部分が混在し、それらの比率が変化するだけでもよい。 For example, a change in crystal grain size or crystal form, a change between a crystal and a metastable state (π, γ, or the like) may be used. It may be a change between an amorphous state and a crystalline state, or it may be a state where both amorphous and crystalline states are mixed, and the ratio between them is only changed.

また、記録用薄膜と、保護層および中間層のうちの少なくとも一つとの間で、これらの層を構成する原子のうちの一部が拡散、化学反応などにより移動することにより、情報が記録されるものでもよいし、原子の移動と相変化の両方により情報が記録されるものでもよい。 In addition, information is recorded between the recording thin film and at least one of the protective layer and the intermediate layer by a part of atoms constituting these layers moving by diffusion, chemical reaction, or the like. The information may be recorded by both the movement of atoms and the phase change.

この発明の第１の情報記録媒体は、前記第１〜第６のいずれかの情報記録用薄膜を記録層として備えていることを特徴とする。 A first information recording medium according to the present invention is characterized by comprising any one of the first to sixth information recording thin films as a recording layer.

前記情報記録用薄膜の少なくとも一方の界面は、前記保護層に密着しているのが好ましい。保護層により、情報書き換え時の薄膜の変形に起因するノイズ増加を防止することができる。 It is preferable that at least one interface of the information recording thin film is in close contact with the protective layer. The protective layer can prevent an increase in noise due to deformation of the thin film when information is rewritten.

この発明の第２の情報記録媒体は、前記第１および第６の情報記録用薄膜のいずれかを、超解像読出し用のマスク層として備えていることを特徴とする。 A second information recording medium according to the present invention is characterized in that one of the first and sixth information recording thin films is provided as a mask layer for super-resolution reading.

この発明の第１〜第４の情報記録用薄膜およびそれを用いた情報記録媒体では、ＳｂおよびＴｅに前記ＢまたはＸに表される元素が添加されているので、レーザ光などの記録・再生光の照射によって融解しない高融点成分の析出物が内部に生成される。このため、高融点成分以外の残成分が前記光によって融解しても、その流動および偏析が効果的に防止され、その結果、多数回書き換えした際の流動および偏析が効果的に防止される。また、析出した高融点成分が情報記録用薄膜の膜厚の厚さまで大きい場合は上記薄膜が接している保護層や中間層の熱膨張による変形を押さえ、保護層と中間層の間隔を保つため、上記薄膜の流動防止効果がより高くなる。このため、搬送波対雑音比（Ｃ／Ｎ）が安定し、記録・再生特性を良好に保ちながら従来より多数回の書き換えあるいは読み出しが可能となる。 In the first to fourth information recording thin films and the information recording medium using the same according to the present invention, since the element represented by B or X is added to Sb and Te, recording / reproduction of laser light or the like is performed. A precipitate of a high melting point component that is not melted by light irradiation is generated inside. For this reason, even if the remaining components other than the high melting point components are melted by the light, the flow and segregation thereof are effectively prevented, and as a result, the flow and segregation when rewriting many times are effectively prevented. Further, when the deposited high melting point component is large up to the thickness of the information recording thin film, deformation of the protective layer or the intermediate layer in contact with the thin film due to thermal expansion is suppressed, and the distance between the protective layer and the intermediate layer is maintained. In addition, the effect of preventing the thin film from flowing becomes higher. As a result, the carrier-to-noise ratio (C / N) is stabilized, and rewriting or reading can be performed a larger number of times than before, while maintaining good recording / reproducing characteristics.

Ｓｂ、Ｔｅおよび前記ＢまたはＸで表わされる元素にさらに前記Ａで表わされる元素が共存すると、非晶質状態が安定に保持され、しかも記録・消去時の結晶化が高速で行なわれるようになる。また、結晶化速度が最適に制御され、搬送波対雑音比と消去比とが向上する。 When the element represented by A coexists with Sb, Te and the element represented by B or X, the amorphous state is stably maintained, and the crystallization at the time of recording / erasing is performed at high speed. . Also, the crystallization rate is optimally controlled, and the carrier-to-noise ratio and the erasure ratio are improved.

この発明の第５および第６の情報記録用薄膜およびそれを用いた情報記録媒体では、レーザ光などの記録・再生光が照射されても、内部に含まれている高融点成分の析出物は融解しない。このため、高融点成分以外の残成分が前記光によって融解しても、その流動および偏析が効果的に防止される。その結果、記録・再生特性を良好に保ちながら従来より多数回の書き換えあるいは読み出しが可能となる。 In the fifth and sixth information recording thin films of the present invention and the information recording medium using the same, even if the recording / reproducing light such as a laser beam is irradiated, the precipitate of the high melting point component contained in the thin film is contained therein. Does not melt. Therefore, even if the remaining components other than the high melting point component are melted by the light, the flow and segregation thereof are effectively prevented. As a result, rewriting or reading can be performed a larger number of times than before while maintaining good recording / reproducing characteristics.

この発明の第１の情報記録媒体では、前記第１〜第６の情報記録用薄膜を備えているので、記録・再生特性を良好に保ちながら従来より多数回の書き換えあるいは読み出しが可能となる。 Since the first information recording medium of the present invention includes the first to sixth information recording thin films, rewriting or reading can be performed more times than before, while maintaining good recording / reproducing characteristics.

この発明の第２の情報記録媒体では、前記第１〜第６の情報記録用薄膜のいずれかよりなるマスク層に光スポットが照射されると、光スポット内の高温部では、前記高融点成分以外の残成分が少なくとも融解する。高温部の屈折率の実数部または虚数部（消衰係数）は、光スポット外の低温部のそれよりも小さくなるため、前記マスク層により、光スポット径の領域の一部が部分的にマスクされ、あたかも光スポット径が減少したようになる。その結果、光スポット径よりも小さい記録マークを読み出すことができる、すなわち超解像読出しが可能となる。 In the second information recording medium of the present invention, when the light spot is irradiated on the mask layer made of any of the first to sixth information recording thin films, the high melting point component in the high temperature part in the light spot At least the remaining components are melted. Since the real part or the imaginary part (extinction coefficient) of the refractive index of the high-temperature part is smaller than that of the low-temperature part outside the light spot, a part of the light spot diameter region is partially masked by the mask layer. As a result, the light spot diameter is reduced. As a result, a recording mark smaller than the light spot diameter can be read, that is, super-resolution reading can be performed.

この発明の第３の情報記録媒体では、前記第１〜第６の情報記録用薄膜のいずれかよりなる反射層に光スポットが照射されると、光スポットの径内の高温部の屈折率の実数部または消衰係数が光スポット外の低温部のそれよりも小さくなる。このため、当該反射層の高温部に照射された光の反射光には、記録マークの読み取りに十分なコントラストが与えられなくなる。その結果、あたかも光スポット径が減少したようになるため、光スポット径より小さいピッチで形成された記録マークを読み出すことができる、すなわち超解像読出しが可能となる。 In the third information recording medium of the present invention, when the light spot is irradiated on the reflection layer formed of any of the first to sixth information recording thin films, the refractive index of the high temperature portion within the diameter of the light spot is reduced. The real part or extinction coefficient is smaller than that of the low temperature part outside the light spot. Therefore, the reflected light of the light applied to the high-temperature portion of the reflective layer does not have sufficient contrast for reading the recording mark. As a result, the light spot diameter is reduced, so that the recording marks formed at a pitch smaller than the light spot diameter can be read, that is, super-resolution reading can be performed.

また、相変化成分より相対的に融点が高い高融点成分が析出しているため、超解像読み出し時に、レーザ照射によって超解像読み出し膜が融解した際の流動及び偏析が効果的に防止される。このため、良好な超解像読み出し特性を保ちながら従来より多数回の超解像読み出しを行うことが可能となる。 In addition, since a high melting point component having a melting point relatively higher than that of the phase change component is precipitated, flow and segregation when the super resolution readout film is melted by laser irradiation during super resolution readout are effectively prevented. You. For this reason, it is possible to perform super-resolution reading a larger number of times than before, while maintaining good super-resolution reading characteristics.

超解像読み出し用薄膜の平均組成を前記一般式（８）で表されるものとするとき、式中のＡで表される元素は低温で融解するため、超解像読み出しが低温で可能となり、相変化光ディスクをはじめとする位相ピットで情報を記録した光ディスク以外の光ディスクでも超解像読み出しを行うことができる。これに前記Ｂで表される元素が共存すると、前記ＤとＥの化合物またはＥの元素またはＥの元素同士の化合物が高融点成分となり、超解像読み出し膜が融解した際の流動及び偏析を防止する効果をもつ。（１２）式中のＦとして例えばＴｌを共存させると、Ｃ／Ｎを大きくさせることができる。 When the average composition of the thin film for super-resolution reading is represented by the general formula (8), the element represented by A in the formula melts at a low temperature, so that super-resolution reading can be performed at a low temperature. In addition, super-resolution reading can be performed on an optical disk other than an optical disk on which information is recorded using phase pits, such as a phase-change optical disk. When the element represented by B coexists with this, the compound of D and E or the element of E or the compound of elements of E becomes a high melting point component, and the flow and segregation when the super-resolution readout film is melted are reduced. It has the effect of preventing. If, for example, Tl coexists as F in the equation (12), C / N can be increased.

本発明の超解像読み出し用装置では、超解像読み出し時にのみレーザパワーを大きくするため、超解像読み出し膜の劣化を防ぎ、多数回の超解像読み出しが可能となる。また、超解像読み出し時のレーザの周期Ｔ、線速ｖ、スポット径（λ／ＮＡ）、パルス幅ｘが前記（９）及び（１０）の関係を満たすことにより、超解像読み出し時のマスク領域の大きさを適当に保ち、超解像読み出し特性をよくすることができる。この装置は、本発明以外の媒体に用いても、超解像読み出しレーザパワー一定の場合より良好な結果が得られる。 In the super-resolution reading device of the present invention, the laser power is increased only during super-resolution reading, so that deterioration of the super-resolution reading film can be prevented and super-resolution reading can be performed many times. Further, the laser period T, linear velocity v, spot diameter (λ / NA), and pulse width x at the time of super-resolution reading satisfy the above-mentioned relations (9) and (10), so that the super-resolution reading can be performed. The size of the mask region can be appropriately maintained, and the super-resolution readout characteristics can be improved. Even if this apparatus is used for a medium other than the present invention, better results can be obtained than when the super-resolution reading laser power is constant.

以上説明したように、この発明の情報記録用薄膜および情報記録媒体によれば、良好な記録・再生特性を保持しながら、従来より多数回の書き換えが可能となる。 As described above, according to the information recording thin film and the information recording medium of the present invention, rewriting can be performed more times than before, while maintaining good recording / reproducing characteristics.

この発明の情報記録用薄膜の製造方法によれば、この発明の情報記録用薄膜および情報記録媒体が容易に得られる。 According to the method for manufacturing an information recording thin film of the present invention, the information recording thin film and the information recording medium of the present invention can be easily obtained.

以上説明したように、本発明によれば、多数回の超解像読み出しが可能であり、超解像読み出し特性がよい超解像読み出し用薄膜、情報記録媒体及び超解像読み出し装置を得ることができる。 As described above, according to the present invention, a super-resolution readout thin film, a super-resolution read-out thin film, an information recording medium, and a super-resolution read-out device capable of performing super-resolution readout many times and having excellent super-resolution readout characteristics are obtained. Can be.

以下、この発明を実施例によって詳細に説明する。
〔実施例１〕
（構成・製法）
図３は、この発明の第１実施例の情報記録用薄膜を用いたディスク状情報記録媒体の断面構造を示す。この媒体は次のようにして製作された。 Hereinafter, the present invention will be described in detail with reference to examples.
[Example 1]
(Structure and manufacturing method)
FIG. 3 shows a sectional structure of a disc-shaped information recording medium using the information recording thin film according to the first embodiment of the present invention. This medium was manufactured as follows.

まず、直径１３ｃｍ，厚さ１．２ｍｍで表面に断面Ｕ字形のトラッキング溝を有するポリカーボネート基板１を形成した。次に、この基板１上に薄膜を順次、形成するため、基板１をマグネトロン・スパッタリング装置内に置いた。この装置は複数のターゲットを持ち、積層膜を順次、形成することができるものである。また、形成される膜の厚さの均一性および再現性に優れている。 First, a polycarbonate substrate 1 having a diameter of 13 cm, a thickness of 1.2 mm, and a tracking groove having a U-shaped cross section on the surface was formed. Next, the substrate 1 was placed in a magnetron sputtering apparatus in order to sequentially form thin films on the substrate 1. This apparatus has a plurality of targets and can sequentially form a stacked film. Further, the thickness of the formed film is excellent in uniformity and reproducibility.

マグネトロン・スパッタリング装置により、基板１上にまず（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる保護層２を膜厚約１２５ｎｍとなるように形成した。続いて、保護層２上に、高融点成分であるＣｒ₄Ｔｅ₅膜（図示せず）を島状に平均膜厚３ｎｍまで形成した後、その上にＳｂ₁₆Ｔｅ₅₅Ｇｅ₁₆Ｃｒ₁₃、すなわち（（Ｇｅ₂Ｓｂ₂Ｔｅ₅）₇（Ｃｒ₄Ｔｅ₅）₃）の組成の記録膜３を膜厚約３０ｎｍまで形成した。この際、Ｃｒ₄Ｔｅ₅ターゲットとＧｅ₂Ｓｂ₂Ｔｅ₅ターゲットとによる回転同時スパッタ法を用いた。島状Ｃｒ₄Ｔｅ₅膜のサイズは２〜２０ｎｍ程度、島のピッチは（サイズ）×（１．５〜１０）が望ましい。 First, a protective layer 2 made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film was formed on the substrate 1 by a magnetron sputtering apparatus so as to have a thickness of about 125 nm. Subsequently, a Cr ₄ Te ₅ film (not shown), which is a high melting point component, is formed in an island shape to an average film thickness of 3 nm on the protective layer 2, and Sb ₁₆ Te ₅₅ Ge ₁₆ Cr ₁₃ , that is, A recording film 3 having a composition of ((Ge ₂ Sb ₂ Te ₅ ) ₇ (Cr ₄ Te ₅ ) ₃ ) was formed to a thickness of about 30 nm. At this time, a rotation simultaneous sputtering method using a Cr ₄ Te ₅ target and a Ge ₂ Sb ₂ Te ₅ target was used. The size of the island-like Cr ₄ Te ₅ film is preferably about 2 to 20 nm, and the pitch of the islands is preferably (size) × (1.5 to 10).

Ｃｒ₄Ｔｅ₅膜は必ずしも形成する必要はない。その場合、記録膜３中に析出する高融点成分は、後述する初期結晶化の際に生じるもののみとなる。 It is not always necessary to form the Cr ₄ Te ₅ film. In this case, only the high melting point component that precipitates in the recording film 3 is generated at the time of initial crystallization described later.

次に、記録膜３上に、（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層４を約２５ｎｍの膜厚まで形成した後、その上に同じスパッタリング装置内でＡｌ₉₇Ｔｉ₃膜よりなる反射層５を膜厚８０ｎｍまで形成した。こうして、第１のディスク部材を得た。 Next, an intermediate layer 4 made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film is formed on the recording film 3 to a thickness of about 25 nm, and then an Al ₉₇ Ti ₃ film is formed thereon in the same sputtering apparatus. The reflective layer 5 was formed to a thickness of 80 nm. Thus, a first disk member was obtained.

他方、まったく同様の方法により、第１のディスク部材と同じ構成を持つ第２のディスク部材を得た。第２のディスク部材は、直径１３ｃｍ，厚さ１．２ｍｍの基板１’上に順に積層された、膜厚約１２５ｎｍの
（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる保護層２’、平均膜厚３ｎｍの
Ｃｒ₄Ｔｅ₅膜（図示せず）、膜厚約３０ｎｍのＳｂ₁₆Ｔｅ₅₅Ｇｅ₁₆Ｃｒ₁₃、すなわち（（Ｇｅ₂Ｓｂ₂Ｔｅ₅）₇（Ｃｒ₄Ｔｅ₅）₃）の記録膜３’、膜厚約２５ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層４’、および膜厚８０ｎｍの
Ａｌ₉₇Ｔｉ₃膜よりなる反射層５’を備えている。 On the other hand, a second disk member having the same configuration as the first disk member was obtained by exactly the same method. The second disk member is composed of a protective layer 2 ′ made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 125 nm and an average film, which are sequentially laminated on a substrate 1 ′ having a diameter of 13 cm and a thickness of 1.2 mm. 3 nm thick Cr ₄ Te ₅ film (not shown), about 30 nm thick Sb ₁₆ Te ₅₅ Ge ₁₆ Cr ₁₃ , that is, ((Ge ₂ Sb ₂ Te ₅ ) ₇ (Cr ₄ Te ₅ ) ₃ ) recording film 3 ', an intermediate layer 4' made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 25 nm, and a reflective layer 5 'made of an Al ₉₇ Ti ₃ film having a thickness of 80 nm.

その後、塩化ビニル−酢酸ビニル系ホットメルト接着剤層６を介して、前記第１および第２のディスク部材の反射層５，５’同士を貼り合わせ、図３に示すディスク状情報記録媒体を得た。 Thereafter, the reflective layers 5 and 5 'of the first and second disk members are bonded together via a vinyl chloride-vinyl acetate hot melt adhesive layer 6, thereby obtaining a disk-shaped information recording medium shown in FIG. Was.

この媒体では、反射層５，５’の全面を接着すると、全面を接着しない場合に比べて書き換え可能回数を多くすることができ、また、反射層５，５’の記録領域に対応する箇所に接着剤を付けない場合、その箇所にも接着剤を付けた場合よりも少し記録感度が高くなった。
（初期結晶化）
前記のようにして製作した媒体の記録膜３、３’に、次のようにして初期結晶化を行なった。なお、記録膜３’についてもまったく同様であるから、以下の説明では記録膜３についてのみ述べることとする。 In this medium, when the entire surfaces of the reflective layers 5, 5 'are adhered, the number of rewritable times can be increased as compared with the case where the entire surfaces are not adhered. When no adhesive was applied, the recording sensitivity was slightly higher than when the adhesive was also applied to that portion.
(Initial crystallization)
Initial crystallization was performed on the recording films 3, 3 'of the medium manufactured as described above as follows. Note that the recording film 3 'is completely the same, so that only the recording film 3 will be described below.

媒体を１８００ｒｐｍで回転させ、半導体レーザ（波長８３０ｎｍ）のレーザ光パワーを記録が行なわれないレベル（約１ｍＷ）に保ち、そのレーザ光を記録ヘッド中の開口数（ＮＡ）がＯ．５５のレンズで集光し、基板１を通して記録膜３に照射した。記録膜３からの反射光を検出して、基板１のトラッキング溝の中心にレーザ光スポットの中心が常に一致するようにトラッキングを行なうと共に、記録膜３上にレーザ光の焦点が来るように、自動焦点合わせを行ないながら記録ヘッドを駆動した。 The medium is rotated at 1800 rpm, the laser light power of the semiconductor laser (wavelength 830 nm) is maintained at a level (about 1 mW) at which recording is not performed, and the laser light is emitted at a numerical aperture (NA) in the recording head of O.D. The light was condensed by 55 lenses and irradiated on the recording film 3 through the substrate 1. By detecting the reflected light from the recording film 3 and performing tracking so that the center of the laser light spot always coincides with the center of the tracking groove of the substrate 1, the focus of the laser light is brought on the recording film 3, The recording head was driven while performing automatic focusing.

まず、初期結晶化のため、記録膜５の同一記録トラック上に、パワー１２ｍＷ，１３ｍＷ，１４ｍＷの連続レーザ光をそれぞれ５００回照射した。最後に、パワー１５ｍＷの連続（ＤＣ）レーザ光を１０００回照射した。各回の照射時間（光スポット通過時間）は、約０．１μｓｅｃである。 First, for the initial crystallization, the same recording track of the recording film 5 was irradiated with continuous laser beams of 12 mW, 13 mW and 14 mW each 500 times. Finally, continuous (DC) laser light with a power of 15 mW was irradiated 1000 times. Each irradiation time (light spot passing time) is about 0.1 μsec.

続いて、パワー８ｍＷの連続レーザ光を５００回照射した。各回の照射時間（光スポット通過時間）は、約０．１μｓｅｃである。この時のレーザ光パワーは５〜９ｍＷの範囲であればよい。 Subsequently, a continuous laser beam having a power of 8 mW was irradiated 500 times. Each irradiation time (light spot passing time) is about 0.1 μsec. The laser light power at this time may be in the range of 5 to 9 mW.

前記２種類のレーザ光照射のうち、パワーの低い方（８ｍＷ）の照射は省略してもよい。 Of the two types of laser beam irradiation, the irradiation with the lower power (8 mW) may be omitted.

このように、パワーの異なるレーザ光を照射すると、初期結晶化を充分に行なうことができる。 When the laser beams having different powers are irradiated as described above, the initial crystallization can be sufficiently performed.

これらのレーザ光照射は、半導体レーザ・アレイを用いて行なうか、ガスレーザからの光ビームを複数に分割したもの、あるいは高出力ガスレーザや半導体レーザからの光ビームのスポット形状を媒体の半径方向に長い長円形にしたものを用いて行なえば、さらに好ましい。こうすると、媒体を少数回転させるだけで初期結晶化を完了することも可能となる。 Irradiation of these laser beams is performed using a semiconductor laser array, a light beam from a gas laser divided into a plurality of beams, or a spot shape of a light beam from a high-power gas laser or a semiconductor laser that is elongated in the radial direction of the medium. It is more preferable to use an oval shape. In this case, the initial crystallization can be completed only by rotating the medium a few times.

複数のレーザ光スポットを用いる場合、それらレーザ光スポットを同一の記録トラック上に配置せず、媒体の半径方向に位置を少しずつズラして配置すれば、１回の照射で広い範囲を初期化することができる、消え残りが少なくなる、などの効果が得られる。 When multiple laser light spots are used, a wide range can be initialized with a single irradiation if the laser light spots are not arranged on the same recording track but are slightly shifted in the radial direction of the medium. And the effect of reducing the disappearance is obtained.

次に、円形スポットの１２ｍＷの連続レーザ光（記録の高パワー光）を１回照射する（照射時間：約０．１μｓｅｃ）毎に、パワー１８ｍＷのパルス・レーザ光（記録用の高パワー光）を照射し、記録膜５を非晶質化して記録点を形成した。その後、その記録点を８ｍＷの連続レーザ光（初期結晶化用の低パワー光）を照射して結晶化させるために、８ｍＷの連続レーザ光を何回照射することが必要かを調査した。 Next, each time a circular spot of 12 mW continuous laser light (high-power light for recording) is irradiated (irradiation time: about 0.1 μsec), a pulsed laser light of 18 mW (high-power light for recording) is emitted. And the recording film 5 was made amorphous to form recording points. Then, it was investigated how many times the continuous laser beam of 8 mW was required to irradiate the recording point with the continuous laser beam of 8 mW (low power light for initial crystallization) for crystallization.

その結果、１２ｍＷの連続レーザ光の照射回数が５回までは、照射回数が増加するほど、結晶化に要する前記８ｍＷの連続レーザ光照射の回数は低下した。すなわち、照射回数が増加するほど結晶化しやすいことが分かった。これは、１２ｍＷの連続レーザ光の照射により、記録膜５中に高融点成分であるＣｒ₄Ｔｅ₅の微細な結晶が多数析出し、その残部（相変化する部分）の組成が高速結晶化可能なＧｅ₂Ｓｂ₂Ｔｅ₅の組成に近づいたためと推察される。 As a result, up to five continuous laser beam irradiations of 12 mW, as the number of irradiations increased, the number of continuous laser beam irradiations of 8 mW required for crystallization decreased. That is, it was found that crystallization was more likely as the number of irradiations increased. This is because a large number of fine crystals of Cr ₄ Te ₅ , which is a high melting point component, are precipitated in the recording film 5 by irradiating a continuous laser beam of 12 mW, and the composition of the remaining portion (phase change portion) can be crystallized at high speed. It is presumed that the composition approached the composition of Ge ₂ Sb ₂ Te ₅ .

なお、Ｃｒ₄Ｔｅ₅の融点は１２５２゜Ｃであり、Ｇｅ₂Ｓｂ₂Ｔｅ₅の融点は６３０゜Ｃである。
（記録・消去）
次に、以上のようにして初期結晶化が完了した記録膜３の記録領域に、前記と同様にしてトラッキングと自動焦点合わせを行ないながら、記録用レーザ光のパワーを記録すべき情報信号に従って中間パワーレベル（８ｍＷ）と高パワーレベル（１８ｍＷ）との間で変化させて情報の記録を行なった。記録すべき部分を通り過ぎると、レーザ光パワーを再生（読出し）用レーザ光の低パワーレベル（１ｍＷ）に下げるようにした。記録用レーザ光により記録領域に形成される非晶質またはそれに近い部分が、記録点となる。 The melting point of Cr ₄ Te ₅ is 1252 ° C., and the melting point of Ge ₂ Sb ₂ Te ₅ is 630 ° C.
(Record / Erase)
Next, while performing the tracking and the automatic focusing in the same manner as described above, the power of the recording laser beam is set in the recording area of the recording film 3 where the initial crystallization is completed in accordance with the information signal to be recorded. Information was recorded while changing between a power level (8 mW) and a high power level (18 mW). After passing through the portion to be recorded, the laser light power was reduced to the low power level (1 mW) of the reproduction (reading) laser light. An amorphous portion or a portion close to the amorphous portion formed in the recording area by the recording laser light is a recording point.

記録用レーザ光の高レベルと中間レベルとのパワー比は１：０．３〜１：０．８の範囲が特に好ましい。また、この他に、短時間ずつ他のパワーレベルにしてもよい。 The power ratio between the high level and the intermediate level of the recording laser beam is particularly preferably in the range of 1: 0.3 to 1: 0.8. In addition, another power level may be set for each short time.

このような記録方法では、既に情報が記録されている部分に対して直接、新たな情報を記録すれば、新たな情報に書き換えられる。すなわち、単一の円形光スポットによるオーバーライトが可能である。 In such a recording method, if new information is recorded directly on a portion in which information has already been recorded, it is rewritten with new information. That is, overwriting with a single circular light spot is possible.

しかし、書き換え時の最初の１回転または複数回転で、前記のパワー変調した記録用レーザ光の中間パワーレベル（８ｍＷ）に近いパワー（例えば９ｍＷ）の連続光を照射して、記録されている情報をいったん消去し、その後、次の１回転で再生（読出し）用レーザ光の低パワーレベル（１ｍＷ）と記録用レーザ光の高パワーレベル（１８ｍＷ）の間で、または、記録用レーザ光の中間パワーレベル（８ｍＷ）と高パワーレベル（１８ｍＷ）の間で、情報信号に従ってパワー変調したレーザ光を照射して記録するようにしてもよい。このように、情報を消去してから記録するようにすれば、前に書かれていた情報の消え残りが少なく、高い搬送波対雑音比（Ｃ／Ｎ）が得られる。 However, during the first rotation or a plurality of rotations at the time of rewriting, continuous light having a power (for example, 9 mW) close to the intermediate power level (8 mW) of the power-modulated recording laser light is irradiated to record the recorded information. Is erased once, and then between the low power level (1 mW) of the reproducing (reading) laser light and the high power level (18 mW) of the recording laser light in the next rotation, or the middle of the recording laser light. Between the power level (8 mW) and the high power level (18 mW), recording may be performed by irradiating a laser beam whose power is modulated according to the information signal. In this way, if the information is erased before recording, the previously written information is less likely to be erased and a high carrier-to-noise ratio (C / N) can be obtained.

このようにして消去後に再書込みする場合は、最初に照射する連続レーザ光のパワーレベルは、前記記録用レーザ光の高レベル（１８ｍＷ）を１としたとき、０．４〜１．１の範囲に設定するのが好ましい。この範囲であれば、良好な書き換えが行なえるからである。 When rewriting is performed after erasing in this manner, the power level of the continuous laser light to be irradiated first is in the range of 0.4 to 1.1, where the high level (18 mW) of the recording laser light is 1. It is preferable to set This is because good rewriting can be performed within this range.

この方法は、この発明の記録膜ばかりでなく他の記録膜にも有効である。 This method is effective not only for the recording film of the present invention but also for other recording films.

この実施例の情報記録媒体では、レーザ光のパワーを最適値より１５％高くした厳しい条件で、記録・消去を１０⁵回以上繰り返すことが可能であった。また、２ＭＨｚの信号を記録した時の再生信号のＣ／Ｎは、約５０ｄＢであり、極めて良好であった。 The information recording medium of this embodiment, under severe conditions 15% higher than the optimum value the power of the laser beam, the recording and erasing was possible to repeat more than 10 ⁵ times. The C / N of the reproduced signal when a 2 MHz signal was recorded was about 50 dB, which was extremely good.

この実施例の記録膜３で、書き換え可能回数を１０⁵回以上にすることができるのは、記録膜３中に析出した高融点成分により、記録膜３の残成分（相変化部分）の流動・偏析が防止されるためと解される。 The reason why the number of rewritable times in the recording film 3 of this embodiment can be increased to 10 ⁵ times or more is that the residual component (phase change portion) of the recording film 3 flows due to the high melting point component deposited in the recording film 3. -It is understood that segregation is prevented.

なお、記録膜３の上に形成されたＺｎＳ−ＳｉＯ₂の中間層４とＡｌ−Ｔｉの反射層５とを省略した場合、前記よりも１桁少ない回数の記録・消去で多少の雑音増加が起こった。
（Ｔｅ含有量ｙとの関係）
前記の（Ｇｅ₂Ｓｂ₂Ｔｅ₅）₇（Ｃｒ₄Ｔｅ₅）₃よりなる記録膜３において、他の元素の相対的比率を一定に保ちながらＴｅ含有量ｙを変化させ、記録されている情報の消去に必要なレーザ光の照射時間と、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号の搬送波対雑音比（Ｃ／Ｎ）の変化を測定した。その結果、次のようなデータが得られた。 Incidentally, if you omit the reflecting layer 5 of the intermediate layer 4 and the Al-Ti of the formed ZnS-SiO ₂ on the recording film 3, some of the noise increase in recording and erasing of an order of magnitude fewer than the Happened.
(Relationship with Te content y)
In the recording film 3 made of (Ge ₂ Sb ₂ Te ₅ ) ₇ (Cr ₄ Te ₅ ) ₃ , the recorded information is changed by changing the Te content y while keeping the relative ratio of other elements constant. and laser light irradiation time required for erasing and measure changes in carrier-to-noise ratio of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser beam power (C / N) . As a result, the following data was obtained.

消去に必要なレーザ光照射時間
ｙ＝３４０．５μｓｅｃ
ｙ＝４００．１μｓｅｃ
ｙ＝５００．１μｓｅｃ
ｙ＝６００．１μｓｅｃ
ｙ＝６７０．５μｓｅｃ
ｙ＝７０１．０μｓｅｃ
ｙ＝７５１．５μｓｅｃ
ｙ＝８０５．０μｓｅｃ
１０⁵回書換後の再生信号のＣ／Ｎ
ｙ＝２０４２ｄＢ
ｙ＝２５４６ｄＢ
ｙ＝３０４９ｄＢ
ｙ＝３４５０ｄＢ
ｙ＝４０５０ｄＢ
ｙ＝５０５０ｄＢ
ｙ＝６０５０ｄＢ
この結果より、Ｔｅ含有量ｙが２５≦ｙ≦７５の範囲において、１０⁵回という多数回の書き換えによる特性変化が少ないことが分かる。
（Ｃｒ以外の元素の組成との関係）
図６の三角相図のＧｅ₆₅Ｔｅ₂₅Ｃｒ₁₀とＳｂ₃₀Ｔｅ₆₀Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線（1）上で組成を変化させ、一定速度で昇温した場合の未記録部分の結晶化温度と、８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化を測定した。その結果、次のようなデータが得られた。 Laser light irradiation time required for erasure y = 34 0.5 μsec
y = 40 0.1 μsec
y = 50 0.1 μsec
y = 60 0.1 μsec
y = 67 0.5 μsec
y = 70 1.0 μsec
y = 75 1.5 μsec
y = 80 5.0 μsec
105 C / N of playback signal after rewriting ⁵ times
y = 20 42 dB
y = 25 46 dB
y = 30 49 dB
y = 34 50 dB
y = 40 50 dB
y = 50 50 dB
y = 60 50 dB
From this result, the range of the Te content y is 25 ≦ y ≦ 75, it can be seen characteristic change due to a number of times of rewriting of less 10 ⁵ times.
(Relationship with composition of elements other than Cr)
Unrecorded when the composition was changed on a straight line (1) connecting the Ge ₆₅ Te ₂₅ Cr ₁₀ and Sb ₃₀ Te ₆₀ Cr ₁₀ in the triangular phase diagram of FIG. 6 with a constant Cr content, and the temperature was raised at a constant rate. The crystallization temperature of the portion and the change in the bit error rate when the portion was kept at 80 ° C. and 95% relative humidity for 1000 hours were measured. As a result, the following data was obtained.

結晶化温度
Ｓｂ₃₀Ｔｅ₆₀Ｃｒ₁₀ １２０゜Ｃ
Ｓｂ₂₈Ｔｅ₅₈Ｇｅ₄Ｃｒ₁₀ １５０゜Ｃ
Ｓｂ₂₅Ｔｅ₅₅Ｇｅ₁₀Ｃｒ₁₀ １６０゜Ｃ
Ｓｂ₂₂Ｔｅ₅₁Ｇｅ₁₇Ｃｒ₁₀ １７０゜Ｃ
Ｓｂ₁₂Ｔｅ₃₈Ｇｅ₄₀Ｃｒ₁₀ １９０゜Ｃ
Ｓｂ₂Ｔｅ₂₈Ｇｅ₆₀Ｃｒ₁₀ ２２０゜Ｃ
ビット・エラーレートの変化
Ｓｂ₃₀Ｔｅ₆₀Ｃｒ₁₀ ２倍
Ｓｂ₂₈Ｔｅ₅₈Ｇｅ₄Ｃｒ₁₀ ２倍
Ｓｂ₂₅Ｔｅ₅₅Ｇｅ₁₀Ｃｒ₁₀ ２倍
Ｓｂ₂₂Ｔｅ₅₁Ｇｅ₁₇Ｃｒ₁₀ ２．５倍
Ｓｂ₁₂Ｔｅ₃₈Ｇｅ₄₀Ｃｒ₁₀ ４倍
Ｓｂ₂Ｔｅ₂₃Ｇｅ₆₀Ｃｒ₁₀ ５倍
この結果より、Ｃｒ以外の組成が変化しても、十分高い結晶化温度が得られ、高温多湿下においてもビット・エラーレートの変化があまり大きくないことが分かる。 Crystallization temperature Sb ₃₀ Te ₆₀ Cr ₁₀ 120 ° C
Sb ₂₈ Te ₅₈ Ge ₄ Cr ₁₀ 150 ° C
Sb ₂₅ Te ₅₅ Ge ₁₀ Cr ₁₀ 160 ° C
Sb ₂₂ Te ₅₁ Ge ₁₇ Cr ₁₀ 170 ° C
Sb ₁₂ Te ₃₈ Ge ₄₀ Cr ₁₀ 190 ° C
Sb ₂ Te ₂₈ Ge ₆₀ Cr ₁₀ 220 ° C
Change in bit error rate Sb ₃₀ Te ₆₀ Cr ₁₀ twice Sb ₂₈ Te ₅₈ Ge ₄ Cr ₁₀ twice Sb ₂₅ Te ₅₅ Ge ₁₀ Cr ₁₀ twice Sb ₂₂ Te ₅₁ Ge ₁₇ Cr ₁₀ 2.5 times Sb ₁₂ Te ₃₈ Ge ₄₀ Cr ₁₀ 4 times Sb ₂ Te ₂₃ Ge ₆₀ Cr ₁₀ 5 times From this result, a sufficiently high crystallization temperature can be obtained even if the composition other than Cr changes, and the bit error rate changes even under high temperature and high humidity. Is not so large.

図６の三角相図のＳｂ₄₅Ｔｅ₄₅Ｃｒ₁₀とＧｅ₁₈Ｔｅ₇₂Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線（2）上で組成を変化させ、一定速度で昇温した場合の結晶化温度と、８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化を測定した。その結果、次のようなデータが得られた。 The crystallization when the composition is changed on a straight line (2) connecting Sb ₄₅ Te ₄₅ Cr ₁₀ and Ge ₁₈ Te ₇₂ Cr ₁₀ in the triangular phase diagram of FIG. The change of the temperature and the bit error rate at 1000 ° C. in 80 ° C. and 95% relative humidity were measured. As a result, the following data was obtained.

結晶化温度
Ｓｂ₂Ｔｅ₇₁Ｇｅ₁₇Ｃｒ₁₀ ２１０゜Ｃ
Ｓｂ₄Ｔｅ₆₉Ｇｅ₁₇Ｃｒ₁₀ ２００゜Ｃ
Ｓｂ₈Ｔｅ₆₇Ｇｅ₁₅Ｃｒ₁₀ １９０゜Ｃ
Ｓｂ₂₃Ｔｅ₅₈Ｇｅ₉Ｃｒ₁₀ １７０゜Ｃ
Ｓｂ₃₀Ｔｅ₅₄Ｇｅ₆Ｃｒ₁₀ １５０゜Ｃ
Ｓｂ₃₈Ｔｅ₄₉Ｇｅ₃Ｃｒ₁₀ １３０゜Ｃ
Ｓｂ₄₁Ｔｅ₄₇Ｇｅ₂Ｃｒ₁₀ １１０゜Ｃ
ビット・エラーレートの変化
Ｓｂ₂Ｔｅ₇₁Ｇｅ₁₇Ｃｒ₁₀ ５倍
Ｓｂ₄Ｔｅ₆₉Ｇｅ₁₇Ｃｒ₁₀ ３倍
Ｓｂ₈Ｔｅ₆₇Ｇｅ₁₅Ｃｒ₁₀ ２倍
Ｓｂ₂₃Ｔｅ₅₈Ｇｅ₉Ｃｒ₁₀ １．５倍
Ｓｂ₃₀Ｔｅ₅₄Ｇｅ₆Ｃｒ₁₀ １．５倍
Ｓｂ₃₈Ｔｅ₄₉Ｇｅ₃Ｃｒ₁₀ １倍
Ｓｂ₄₁Ｔｅ₄₇Ｇｅ₂Ｃｒ₁₀ １倍
この結果より、Ｃｒ以外の組成が変化しても、十分高い結晶化温度が得られ、高温多湿下においてもビット・エラーレートの変化があまり大きくないことが分かる。 Crystallization temperature Sb ₂ Te ₇₁ Ge ₁₇ Cr ₁₀ 210 ° C
Sb ₄ Te ₆₉ Ge ₁₇ Cr ₁₀ 200 ° C
Sb ₈ Te ₆₇ Ge ₁₅ Cr ₁₀ 190 ° C
Sb ₂₃ Te ₅₈ Ge ₉ Cr ₁₀ 170 ° C
_{_{_{_{Sb 30 Te 54 Ge 6 Cr 10}}}} 150 ° C
Sb ₃₈ Te ₄₉ Ge ₃ Cr ₁₀ 130 ° C
Sb ₄₁ Te ₄₇ Ge ₂ Cr ₁₀ 110 ° C
Change in bit error rate Sb ₂ Te ₇₁ Ge ₁₇ Cr ₁₀ 5 times Sb ₄ Te ₆₉ Ge ₁₇ Cr ₁₀ 3 times Sb ₈ Te ₆₇ Ge ₁₅ Cr ₁₀ 2 times Sb ₂₃ Te ₅₈ Ge ₉ Cr ₁₀ 1.5 times Sb ₃₀ Te ₅₄ Ge ₆ Cr ₁₀ 1.5 times Sb ₃₈ Te ₄₉ Ge ₃ Cr ₁₀ 1 times Sb ₄₁ Te ₄₇ Ge ₂ Cr ₁₀ 1 times From this result, even if the composition other than Cr changes, a sufficiently high crystallization temperature can be obtained. It can be seen that the change in bit error rate is not so large even under high temperature and high humidity.

Ｇｅの含有量ｐとＳｂの含有量ｘの比（ｐ／ｘ）を変化させ、温度８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化を測定したところ、次の結果が得られた。 When the ratio (p / x) of the Ge content p and the Sb content x (p / x) was changed, and the change in the bit error rate when the device was placed at a temperature of 80 ° C. and a relative humidity of 95% for 1000 hours was measured, The following results were obtained.

ビット・エラーレートの変化
（ｐ／ｘ）＝０．１５２．０倍
（ｐ／ｘ）＝０．２５１．５倍
（ｐ／ｘ）＝０．５１．５倍
（ｐ／ｘ）＝１．０１．５倍
（ｐ／ｘ）＝２．０３．０倍
この結果より、Ｇｅの含有量ｐとＳｂの含有量ｘの比（ｐ／ｘ）が、０．２５≦（ｐ／ｘ）≦１．０の範囲であれば、ビット・エラーレートの変化が特に小さいことが分かる。 Change in bit error rate (p / x) = 0.15 2.0 times (p / x) = 0.25 1.5 times (p / x) = 0.5 1.5 times (p / x) = 1.0 1.5 times (p / x) = 2.0 3.0 times From these results, the ratio (p / x) of the Ge content p to the Sb content x is 0.25 ≦ ( It can be seen that the change of the bit error rate is particularly small in the range of (p / x) ≦ 1.0.

Ｃｒ₄Ｔｅ₅の残部であるＳｂ対Ｔｅ対Ｇｅの含有量ｘ，ｙ，ｐの比を、
ｘ：ｙ：ｐ＝２：５：２に保ってＣｒ₄Ｔｅ₅の含有量を変化させたとき、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎを測定したところ、Ｃｒの含有量ｑに関して次のような結果が得られた。 The ratio of the content x, y, p of Sb to Te to Ge, which is the balance of Cr ₄ Te ₅ , is
x: y: p = 2: 5: when varying the content of Cr ₄ Te ₅ kept at 2, regeneration of after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam When the C / N of the signal was measured, the following results were obtained for the Cr content q.

１０⁵回書換後の再生信号Ｃ／Ｎ
ｑ＝０４２ｄＢ
ｑ＝３４６ｄＢ
ｑ＝４４８ｄＢ
ｑ＝１０５０ｄＢ
ｑ＝２０５０ｄＢ
ｑ＝３４４８ｄＢ
Ｃｒの含有量ｑを変化させると、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号の「消去比」は、次のように変化した。 10 after ⁵ times of rewriting reproducing signal C / N
q = 0 42 dB
q = 346 dB
q = 4 48 dB
q = 10 50 dB
q = 20 50 dB
q = 34 48dB
Varying the content q of Cr, "erase ratio" of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam is changed as follows.

ここで「消去比」とは、すでに記録された信号の上に周波数の異なる別の信号を重ね書きしたときの、重ね書き前後の信号の比をｄＢで表したものである。 Here, the "erasing ratio" is a ratio of a signal before and after overwriting when another signal having a different frequency is overwritten on a signal already recorded, expressed in dB.

消去比
ｑ＝２２２５ｄＢ
ｑ＝３４２３ｄＢ
ｑ＝４０２０ｄＢ
ｑ＝５０１７ｄＢ
この結果より、Ｃｒの含有量ｑが増加するにつれて、消去比が低下することが分かる。 Erasure ratio q = 22 25 dB
q = 34 23dB
q = 40 20 dB
q = 50 17dB
From this result, it can be seen that the erasing ratio decreases as the Cr content q increases.

前記のＣｒを１０％添加した系で、Ｔｅの含有量ｙを一定に保ってＳｂの含有量ｘを変化させた時、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。 When the content y of Te was kept constant and the content x of Sb was changed in the system to which 10% of Cr was added, 10 ⁵ times under severe conditions in which the power of the laser beam was increased by 15% from the optimum value. The C / N of the reproduced signal after rewriting changed as follows.

１０⁵回書換後の再生信号のＣ／Ｎ
ｘ＝３８４８ｄＢ
ｘ＝３０５０ｄＢ
ｘ＝１５５０ｄＢ
ｘ＝８５０ｄＢ
ｘ＝４４８ｄＢ
ｘ＝２４６ｄＢ
ｘ＝０４５ｄＢ
この結果より、Ｓｂの含有量ｘが２％以上の範囲では、良好な再生信号のＣ／Ｎが得られることが分かる。 105 C / N of playback signal after rewriting ⁵ times
x = 38 48dB
x = 30 50 dB
x = 15 50 dB
x = 850 dB
x = 4 48 dB
x = 246 dB
x = 0 45 dB
From this result, it can be seen that when the Sb content x is 2% or more, good C / N of the reproduced signal can be obtained.

以上より、この実施例のＳｂ₁₆Ｔｅ₅₅Ｇｅ₁₆Ｃｒ₁₃、すなわち
（Ｇｅ₂Ｓｂ₂Ｔｅ₅）₇（Ｃｒ₄Ｔｅ₅）₃の記録膜３は、温度８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化は２倍以下、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎおよび消去比は、それぞれ５０ｄＢ以上および２８ｄＢ以上であり、２×１０⁵回以上の書き換えが可能で、極めて優れた特性を持つことが分かった。
（添加元素の他の例１）
Ｃｒの一部または全部に代えて、Ａｇ，Ｃｕ，Ｂａ，Ｃｏ，Ｌａ，Ｎｉ，Ｐｔ，ＳｉおよびＳｒおよびランタノイド元素のうちの少なくとも一つを添加しても、上記の場合とよく似た特性が得られる。例えば、Ｃｕを添加した場合（Ｃｕの添加量：ｑ）、下記のようなデータが得られた。 As described above, the recording film 3 of Sb ₁₆ Te ₅₅ Ge ₁₆ Cr _{13 of} this embodiment, that is, (Ge ₂ Sb ₂ Te ₅ ) ₇ (Cr ₄ Te ₅ ) ₃ , has a temperature of 80 ° C. and a relative humidity of 95%. change in bit error rate when placed 1000 hours 2 times or less, C / N and erase ratio of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam, The values were 50 dB or more and 28 dB or more, respectively, and it was found that rewriting could be performed 2 × 10 ⁵ times or more, and that it had extremely excellent characteristics.
(Other Example 1 of Additive Element)
Even if at least one of Ag, Cu, Ba, Co, La, Ni, Pt, Si, Sr, and a lanthanoid element is added instead of part or all of Cr, the characteristics are very similar to those described above. Is obtained. For example, when Cu was added (Cu addition amount: q), the following data was obtained.

書き換え可能回数
ｑ＝０５×１０⁴回
ｑ＝１．０８×１０⁴回
ｑ＝４．０１×１０⁵回
ｑ＝１０．０２×１０⁵回
ｑ＝２０．０２×１０⁵回
ｑ＝３４．０２×１０⁵回
ｑ＝４０．０１×１０⁵回
この結果より、Ｃｕを添加すると、書き換え可能回数が顕著に増加することが分かる。
（添加元素の他の例２）
Ｃｒに加えて、消去を高速化してＣ／Ｎを大きくする効果を持つＴｌ（タリウム）を添加するのが好ましい。この場合、Ｃｒのみを添加した場合よりもＣ／Ｎがさらに大きくなり、また書換可能回数も大きくなるので、より好ましい。ただし、ＣｒとＴｌの添加量の和を３０原子％以下とする方が、消え残りが大きくならず、好ましい。ＣｒとＴｌの添加量の和が０．５％以上、２０原子％以下であれば、さらに好ましい。 Number of rewritable times q = 0 5 × 10 ⁴ times q = 1.0 8 × 10 ⁴ times q = 4.0 1 × 10 ⁵ times q = 10.0 2 × 10 ⁵ times q = 20.0 2 × 10 ⁵ Times q = 34.0 2 × 10 ⁵ times q = 40.0 1 × 10 ⁵ times From this result, it can be seen that the addition of Cu significantly increases the number of rewritable times.
(Other Example 2 of Additive Element)
In addition to Cr, it is preferable to add Tl (thallium), which has the effect of speeding up erasure and increasing C / N. In this case, C / N is further increased as compared with the case where only Cr is added, and the number of rewritable times is also increased. However, it is preferable that the sum of the added amounts of Cr and Tl be 30 atom% or less, since the remaining disappearance does not increase. More preferably, the sum of the added amounts of Cr and Tl is 0.5% or more and 20% by atom or less.

例えば、Ｇｅ_8.2Ｓｂ_16.4Ｔｅ_64.4Ｔｌ_0.5Ｃｒ_10.5記録膜では、Ｃ／Ｎ５０ｄＢ、書換可能回数２×１０⁵回が得られた。 For example, the _{_{_{_{Ge 8.2 Sb 16.4 Te 64.4 Tl 0.5}}}} Cr 10.5 recording film, C / N 50 dB, the rewritable number 2 × 10 ⁵ times was obtained.

Ｔｌの一部または全部に代えて、ハロゲン元素の少なくとも一つを添加してもよく似た特性が得られる。 Similar characteristics can be obtained by adding at least one halogen element instead of part or all of Tl.

Ｔｌに代えてＮ（窒素）を添加した場合、書き換え可能回数がさらに向上する。ただし、多すぎると再生信号レベルが低下する。
（添加元素の他の例３）
この他に、Ｔｌ（タリウム）をＳｅに置換し、他の元素の相対的比率を一定に保ちながらＳｅを１原子％以上、１０原子％以下だけ添加すると、耐酸化性向上の効果がある。
（相変化成分の他の例）
この実施例の相変化成分であるＧｅ₂Ｓｂ₂Ｔｅ₅の一部を
ＧｅＳｂ₂Ｔｅ₄，ＧｅＳｂ₄Ｔｅ₇，Ｉｎ₃ＳｂＴｅ₂，Ｉｎ₃₅Ｓｂ₃₂Ｔｅ₃₃，
Ｉｎ₃₁Ｓｂ₂₆Ｔｅ₄₃、およびこれらに近い組成
のうちの少なくとも一つで置き換えても、Ｇｅの一部をＩｎに置き換えても、これに近い特性が得られる。
（高融点成分の他の例）
析出する高融点成分は、化合物でもよいし、元素単体や合金でもよい。この実施例の高融点成分であるＣｒ₄Ｔｅ₅の一部または全部を
ＬａＴｅ₂，Ｌａ₂Ｔｅ₃，Ｌａ₃Ｔｅ₄，ＬａＴｅ，Ｌａ₂Ｔｅ₅，Ｌａ₄Ｔｅ₇，
ＬａＴｅ₃，Ｌａ₃Ｔｅ，Ｌａ₂Ｓｂ，Ｌａ₃Ｓｂ₂，ＬａＳｂ，ＬａＳｂ₂，
Ｌａ₃Ｇｅ，Ｌａ₅Ｇｅ₃，Ｌａ₄Ｇｅ₃，Ｌａ₅Ｇｅ₄，ＬａＧｅ，Ｌａ₃Ｇｅ₅，
Ａｇ₂Ｔｅ，Ｃｒ₅Ｔｅ₈，Ｃｒ₂Ｔｅ₃，ＣｒＳｂ，Ｃｒ₃Ｇｅ，Ｃｒ₅Ｇｅ₃，
Ｃｒ₁₁Ｇｅ₈，ＣｒＧｅ，Ｃｒ₁₁Ｇｅ₁₉，ＰｔＴｅ₂，Ｐｔ₄Ｔｅ₅，Ｐｔ₅Ｔｅ₄，Ｐｔ₄Ｓｂ，Ｐｔ₃Ｓｂ₂，ＰｔＳｂ，Ｐｔ₃Ｇｅ，Ｐｔ₂Ｇｅ，Ｐｔ₃Ｇｅ₂，
ＰｔＧｅ，Ｐｔ₂Ｇｅ₃，ＰｔＧｅ₃，ＮｉＴｅ，ＮｉＴｅ₀．₈₅，ＮｉＳｂ，
Ｎｉ₃Ｇｅ，Ｎｉ₅Ｇｅ₂，Ｎｉ₅Ｇｅ₃，ＮｉＧｅ、ＣｏＴｅ₂，ＣｏＳｂ₂，
ＣｏＳｂ₃，Ｃｏ₅Ｇｅ₂，Ｃｏ₅Ｇｅ₃，ＣｏＧｅ，Ｃｏ₅Ｇｅ₇，ＣｏＧｅ₂，
Ｓｉ₂Ｔｅ₃，ＳｉＳｂ，ＳｉＧｅ，ＣｅＴｅ，Ｃｅ₃Ｔｅ₄，Ｃｅ₂Ｔｅ₃，
Ｃｅ₄Ｔｅ₇，ＣｅＴｅ₂，ＣｅＴｅ₃，Ｃｅ₂Ｓｂ，Ｃｅ₅Ｓｂ₃，Ｃｅ₄Ｓｂ₅，
ＣｅＳｂ，ＣｅＳｂ₂，Ｃｅ₃Ｇｅ，Ｃｅ₅Ｇｅ₃，Ｃｅ₄Ｇｅ₃，Ｃｅ₅Ｇｅ₄，
ＣｅＧｅ，Ｃｅ₃Ｇｅ₅，Ｃｅ₅Ｓｉ₃，Ｃｅ₃Ｓｉ₂，Ｃｅ₅Ｓｉ₄，ＣｅＳｉ，
Ｃｅ₃Ｓｉ₅，ＣｅＳｉ₂，Ｃｒ₃Ｓｉ，Ｃｒ₅Ｓｉ₃，ＣｒＳｉ，ＣｒＳｉ₃，
ＣｒＳｉ₂，Ｃｏ₃Ｓｉ，ＣｏＳｉ，ＣｏＳｉ₂，ＮｉＳｉ₂，ＮｉＳｉ，
Ｎｉ₃Ｓｉ₂，Ｎｉ₂Ｓｉ，Ｎｉ₅Ｓｉ₂，Ｎｉ₃Ｓｉ，Ｐｔ₅Ｓｉ₂，Ｐｔ₂Ｓｉ，
ＰｔＳｉ，ＬａＳｉ₂，Ａｇ₃Ｉｎ，Ａｇ₂Ｉｎ，Ｂｉ₂Ｃｅ，ＢｉＣｅ，
Ｂｉ₃Ｃｅ₄，Ｂｉ₃Ｃｅ₅，ＢｉＣｅ₂，Ｃｄ₁₁Ｃｅ，Ｃｄ₆Ｃｅ，Ｃｄ₅₈Ｃｅ₁₃，Ｃｄ₃Ｃｅ，Ｃｄ₂Ｃｅ，ＣｄＣｅ，Ｃｅ₃Ｉｎ，Ｃｅ₂Ｉｎ，Ｃｅ_1+xＩｎ，
Ｃｅ₃Ｉｎ₅，ＣｅＩｎ₂，ＣｅＩｎ₃，Ｃｅ₂Ｐｂ，ＣｅＰｂ，ＣｅＰｂ₃，
Ｃｅ₃Ｓｎ，Ｃｅ₅Ｓｎ₃，Ｃｅ₅Ｓｎ₄，Ｃｅ₁₁Ｓｎ₁₀，Ｃｅ₃Ｓｎ₅，
Ｃｅ₃Ｓｎ₇，Ｃｅ₂Ｓｎ₅，ＣｅＳｎ₃，ＣｅＺｎ，ＣｅＺｎ₂，ＣｅＺｎ₃，
Ｃｅ₃Ｚｎ₁₁，Ｃｅ₁₃Ｚｎ₅₈，ＣｅＺｎ₅，Ｃｅ₃Ｚｎ₂₂，Ｃｅ₂Ｚｎ₁₇，
ＣｅＺｎ₁₁，Ｃｄ₂₁Ｃｏ₅，ＣｏＧａ，ＣｏＧａ₃，ＣｏＳｎ，Ｃｒ₃Ｇａ，
ＣｒＧａ，Ｃｒ₅Ｇａ₆，ＣｒＧａ₄，Ｃｕ₉Ｇａ₄，Ｃｕ₃Ｓｎ，Ｃｕ₃Ｚｎ，
Ｂｉ₂Ｌａ，ＢｉＬａ，Ｂｉ₃Ｌａ₄，Ｂｉ₃Ｌａ₅，ＢｉＬａ₂，Ｃｄ₁₁Ｌａ，
Ｃｄ₁₇Ｌａ₂，Ｃｄ₉Ｌａ₂，Ｃｄ₂Ｌａ，ＣｄＬａ，Ｇａ₆Ｌａ，Ｇａ₂Ｌａ，
ＧａＬａ，Ｇａ₃Ｌａ₅，ＧａＬａ₃，Ｉｎ₃Ｌａ，Ｉｎ₂Ｌａ，Ｉｎ₅Ｌａ₃，
Ｉｎ_xＬａ，ＩｎＬａ，ＩｎＬａ₂，ＩｎＬａ₃，Ｌａ₅Ｐｂ₃，Ｌａ₄Ｐｂ₃，
Ｌａ₁₁Ｐｂ₁₀，Ｌａ₃Ｐｂ₄，Ｌａ₅Ｐｂ₄，ＬａＰｂ₂，ＬａＰｂ₃，ＬａＺｎ，
ＬａＺｎ₂，ＬａＺｎ₄，ＬａＺｎ₅，Ｌａ₃Ｚｎ₂₂，Ｌａ₂Ｚｎ₁₇，ＬａＺｎ₁₁，ＬａＺｎ₁₃，ＮｉＢｉ，Ｇａ₃Ｎｉ₂，ＧａＮｉ，Ｇａ₂Ｎｉ₃，Ｇａ₃Ｎｉ₅，
ＧａＮｉ₃，Ｎｉ₃Ｓｎ，Ｎｉ₃Ｓｎ₂，Ｎｉ₃Ｓｎ₄，ＮｉＺｎ，Ｎｉ₅Ｚｎ₂₁，
ＰｔＢｉ，ＰｔＢｉ₂，ＰｔＢｉ₃，ＰｔＣｄ₂，Ｐｔ₂Ｃｄ₉，Ｇａ₇Ｐｔ₃，
Ｇａ₂Ｐｔ，Ｇａ₃Ｐｔ₂，ＧａＰｔ，Ｇａ₃Ｐｔ₅，ＧａＰｔ₂，ＧａＰｔ₃，
Ｉｎ₇Ｐｔ₃，Ｉｎ₂Ｐｔ，Ｉｎ₃Ｐｔ₂，ＩｎＰｔ，Ｉｎ₅Ｐｔ₆，Ｉｎ₂Ｐｔ₃，
ＩｎＰｔ₂，ＩｎＰｔ₃，Ｐｔ₃Ｐｂ，ＰｔＰｂ，Ｐｔ₂Ｐｂ₃，Ｐｔ₃Ｓｎ，
ＰｔＳｎ，Ｐｔ₂Ｓｎ₃，ＰｔＳｎ₂，ＰｔＳｎ₄，Ｐｔ₃Ｚｎ，ＰｔＺｎ₂，
ＡｌＳ，Ａｌ₂Ｓ₃，ＢａＳ，ＢａＣ₂，ＣｄＳ，Ｃｏ₄Ｓ₃，Ｃｏ₉Ｓ₈，ＣｏＳ，ＣｏＯ，Ｃｏ₂Ｏ₄，Ｃｏ₂Ｏ₃，Ｃｒ₂Ｏ₃，Ｃｒ₃Ｏ₄，ＣｒＯ，ＣｒＳ，ＣｒＮ，Ｃｒ₂Ｎ，Ｃｒ₂₃Ｃ₆₃，Ｃｒ₇Ｃ₃，Ｃｒ₃Ｃ₂，Ｃｕ₂Ｓ，Ｃｕ₉Ｓ₅，ＣｕＯ，
Ｃｕ₂Ｏ，Ｉｎ₄Ｓ₅，Ｉｎ₃Ｓ₄，Ｌａ₂Ｓ₃，Ｌａ₂Ｏ₃，Ｍｏ₂Ｃ，ＭｏＣ，
Ｍｎ₂₃Ｃ₆，Ｍｎ₄Ｃ，Ｍｎ₇Ｃ₃，ＮｉＯ，ＳｉＳ₂，ＳｉＯ₂，Ｓｉ₃Ｎ₄，
上記高融点成分の構成元素の酸化物のうち高融点のもの、
Ｃｕ₂Ｔｅ,ＣｕＴｅ，Ｃｕ₃Ｓｂ，Ｍｎ₂Ｓｂ，ＭｎＴｅ，ＭｎＴｅ₂，
Ｍｎ₅Ｇｅ₃，Ｍｎ_3.25Ｇｅ，Ｍｎ₅Ｇｅ，Ｍｎ₃Ｇｅ₂，Ｇｅ₃Ｗ，Ｔｅ₂Ｗ，
ＡｌＳｂ，Ａｌ₂Ｔｅ₃，Ｆｅ₂Ｇｅ，ＦｅＧｅ₂，ＦｅＳｂ₂，Ｍｏ₃Ｓｂ₇，
Ｍｏ₃Ｔｅ₄，ＭｏＴｅ₂,ＰｂＴｅ，ＧｅＰｄ₂，Ｇｅ₂Ｐｄ₅，Ｇｅ₉Ｐｄ₂₅,
ＧｅＰｄ₅，Ｐｄ₃Ｓｂ，Ｐｄ₅Ｓｂ₃，ＰｄＳｂ，ＳｎＴｅ，Ｔｉ₅Ｇｅ₃，
Ｇｅ₃₁Ｖ₁₇，Ｇｅ₈Ｖ₁₁，Ｇｅ₃Ｖ₅，ＧｅＶ₃，Ｖ₅Ｔｅ₄，Ｖ₃Ｔｅ₄，ＺｎＴｅ，Ａｇ₂Ｓｅ，Ｃｕ₂Ｓｅ，Ａｌ₂Ｓｅ₃，ＩｎＡｓ，ＣｏＳｅ，Ｍｎ₃Ｉｎ，
Ｎｉ₃Ｉｎ，ＮｉＩｎ，Ｎｉ₂Ｉｎ₃，Ｎｉ₃Ｉｎ₇，ＰｂＳｅ，
などのＢ群の元素を含む高融点化合物，またはそれに近い組成のもの、あるいはこれらの混合組成や混合組成に近い３元以上の化合物のうちの少なくとも一つで置き換えても、同様な結果が得られる。 When N (nitrogen) is added instead of Tl, the number of rewritable times is further improved. However, if the amount is too large, the reproduction signal level is reduced.
(Other Example 3 of Additive Element)
In addition, when Tl (thallium) is replaced with Se and Se is added in an amount of 1 atomic% or more and 10 atomic% or less while keeping the relative ratio of other elements constant, there is an effect of improving oxidation resistance.
(Other examples of phase change components)
Part of Ge ₂ Sb ₂ Te ₅ , which is the phase change component of this embodiment, is GeSb ₂ Te ₄ , GeSb ₄ Te ₇ , In ₃ SbTe ₂ , In ₃₅ Sb ₃₂ Te ₃₃ ,
Even if it is replaced with at least one of In ₃₁ Sb ₂₆ Te ₄₃ or a composition close to them, or even if a part of Ge is replaced with In, characteristics close to this can be obtained.
(Other examples of high melting point components)
The precipitated high melting point component may be a compound, an element alone or an alloy. A part or all of Cr ₄ Te ₅ , which is a high melting point component in this embodiment, is replaced with LaTe ₂ , La ₂ Te ₃ , La ₃ Te ₄ , LaTe, La ₂ Te ₅ , La ₄ Te ₇ ,
LaTe ₃ , La ₃ Te, La ₂ Sb, La ₃ Sb ₂ , LaSb, LaSb ₂ ,
La ₃ Ge, La ₅ Ge ₃ , La ₄ Ge ₃ , La ₅ Ge ₄ , LaGe, La ₃ Ge ₅ ,
Ag ₂ Te, Cr ₅ Te ₈ , Cr ₂ Te ₃ , CrSb, Cr ₃ Ge, Cr ₅ Ge ₃ ,
Cr ₁₁ Ge ₈ , CrGe, Cr ₁₁ Ge ₁₉ , PtTe ₂ , Pt ₄ Te ₅ , Pt ₅ Te ₄ , Pt ₄ Sb, Pt ₃ Sb ₂ , PtSb, Pt ₃ Ge, Pt ₂ Ge, Pt ₃ Ge ₂ ,
PtGe, Pt ₂ Ge ₃ , PtGe ₃ , NiTe, NiTe ₀ . ₈₅ , NiSb,
_{_{_{Ni 3 Ge, Ni 5 Ge 2}}} , Ni 5 Ge 3, NiGe, CoTe 2, CoSb 2,
CoSb ₃ , Co ₅ Ge ₂ , Co ₅ Ge ₃ , CoGe, Co ₅ Ge ₇ , CoGe ₂ ,
Si ₂ Te ₃ , SiSb, SiGe, CeTe, Ce ₃ Te ₄ , Ce ₂ Te ₃ ,
Ce ₄ Te ₇ , CeTe ₂ , CeTe ₃ , Ce ₂ Sb, Ce ₅ Sb ₃ , Ce ₄ Sb ₅ ,
_{_{CeSb, CeSb 2, Ce 3 Ge}} , Ce 5 Ge 3, Ce 4 Ge 3, Ce 5 Ge 4,
CeGe, Ce ₃ Ge ₅ , Ce ₅ Si ₃ , Ce ₃ Si ₂ , Ce ₅ Si ₄ , CeSi,
Ce ₃ Si ₅ , CeSi ₂ , Cr ₃ Si, Cr ₅ Si ₃ , CrSi, CrSi ₃ ,
CrSi ₂ , Co ₃ Si, CoSi, CoSi ₂ , NiSi ₂ , NiSi,
Ni ₃ Si ₂ , Ni ₂ Si, Ni ₅ Si ₂ , Ni ₃ Si, Pt ₅ Si ₂ , Pt ₂ Si,
PtSi, LaSi ₂ , Ag ₃ In, Ag ₂ In, Bi ₂ Ce, BiCe,
_{_{_{Bi 3 Ce 4, Bi 3 Ce}}} 5, BiCe 2, Cd 11 Ce, Cd 6 Ce, Cd 58 Ce 13, Cd 3 Ce, Cd 2 Ce, CdCe, Ce 3 In, Ce 2 In, Ce 1 + x In,
Ce ₃ In ₅ , CeIn ₂ , CeIn ₃ , Ce ₂ Pb, CePb, CePb ₃ ,
Ce ₃ Sn, Ce ₅ Sn ₃ , Ce ₅ Sn ₄ , Ce ₁₁ Sn ₁₀ , Ce ₃ Sn ₅ ,
Ce ₃ Sn ₇ , Ce ₂ Sn ₅ , CeSn ₃ , CeZn, CeZn ₂ , CeZn ₃ ,
Ce ₃ Zn ₁₁ , Ce ₁₃ Zn ₅₈ , CeZn ₅ , Ce ₃ Zn ₂₂ , Ce ₂ Zn ₁₇ ,
CeZn ₁₁ , Cd ₂₁ Co ₅ , CoGa, CoGa ₃ , CoSn, Cr ₃ Ga,
_{_{CrGa, Cr 5 Ga 6, CrGa}} 4, Cu 9 Ga 4, Cu 3 Sn, Cu 3 Zn,
Bi ₂ La, BiLa, Bi ₃ La ₄ , Bi ₃ La ₅ , BiLa ₂ , Cd ₁₁ La,
Cd ₁₇ La ₂ , Cd ₉ La ₂ , Cd ₂ La, CdLa, Ga ₆ La, Ga ₂ La,
_{_{GaLa, Ga 3 La 5, GaLa}} 3, In 3 La, In 2 La, In 5 La 3,
In _x La, InLa, InLa ₂ , InLa ₃ , La ₅ Pb ₃ , La ₄ Pb ₃ ,
La ₁₁ Pb ₁₀ , La ₃ Pb ₄ , La ₅ Pb ₄ , LaPb ₂ , LaPb ₃ , LaZn,
LaZn ₂ , LaZn ₄ , LaZn ₅ , La ₃ Zn ₂₂ , La ₂ Zn ₁₇ , LaZn ₁₁ , LaZn ₁₃ , NiBi, Ga ₃ Ni ₂ , GaNi, Ga ₂ Ni ₃ , Ga ₃ Ni ₅ ,
GaNi ₃ , Ni ₃ Sn, Ni ₃ Sn ₂ , Ni ₃ Sn ₄ , NiZn, Ni ₅ Zn ₂₁ ,
PtBi, PtBi ₂ , PtBi ₃ , PtCd ₂ , Pt ₂ Cd ₉ , Ga ₇ Pt ₃ ,
Ga ₂ Pt, Ga ₃ Pt ₂ , GaPt, Ga ₃ Pt ₅ , GaPt ₂ , GaPt ₃ ,
In ₇ Pt ₃ , In ₂ Pt, In ₃ Pt ₂ , InPt, In ₅ Pt ₆ , In ₂ Pt ₃ ,
InPt ₂ , InPt ₃ , Pt ₃ Pb, PtPb, Pt ₂ Pb ₃ , Pt ₃ Sn,
_{_{PtSn, Pt 2 Sn 3, PtSn}} 2, PtSn 4, Pt 3 Zn, PtZn 2,
_{_{AlS, Al 2 S 3, BaS}} , BaC 2, CdS, Co 4 S 3, Co 9 S 8, CoS, CoO, Co 2 O 4, Co 2 O 3, Cr 2 O 3, Cr 3 O 4, CrO, _{CrS, CrN, Cr 2 N,} Cr 23 C 63, Cr 7 C 3, Cr 3 C 2, Cu 2 S, Cu 9 S 5, CuO,
Cu ₂ O, In ₄ S ₅ , In ₃ S ₄ , La ₂ S ₃ , La ₂ O ₃ , Mo ₂ C, MoC,
Mn ₂₃ C ₆ , Mn ₄ C, Mn ₇ C ₃ , NiO, SiS ₂ , SiO ₂ , Si ₃ N ₄ ,
Among the oxides of the constituent elements of the high melting point component, those having a high melting point,
Cu ₂ Te, CuTe, Cu ₃ Sb, Mn ₂ Sb, MnTe, MnTe ₂ ,
Mn ₅ Ge ₃ , Mn _3.25 Ge, Mn ₅ Ge, Mn ₃ Ge ₂ , Ge ₃ W, Te ₂ W,
AlSb, Al ₂ Te ₃ , Fe ₂ Ge, FeGe ₂ , FeSb ₂ , Mo ₃ Sb ₇ ,
Mo ₃ Te ₄ , MoTe ₂ , PbTe, GePd ₂ , Ge ₂ Pd ₅ , Ge ₉ Pd ₂₅ ,
GePd ₅ , Pd ₃ Sb, Pd ₅ Sb ₃ , PdSb, SnTe, Ti ₅ Ge ₃ ,
Ge ₃₁ V ₁₇ , Ge ₈ V ₁₁ , Ge ₃ V ₅ , GeV ₃ , V ₅ Te ₄ , V ₃ Te ₄ , ZnTe, Ag ₂ Se, Cu ₂ Se, Al ₂ Se ₃ , InAs, CoSe, Mn ₃ In ,
Ni ₃ In, NiIn, Ni ₂ In ₃ , Ni ₃ In ₇ , PbSe,
Similar results can be obtained by replacing with a high-melting point compound containing an element of group B such as, or a compound having a composition close thereto, or at least one of a mixed composition thereof and a compound having three or more elements close to the mixed composition. Can be

これらのうちで、
ＬａＳｂ，ＣｒＳｂ，ＣｏＳｂ，Ｃｒ₃Ｔｅ₄，ＬａＴｅ₃，Ｃｒ₄Ｔｅ₅，
Ｃｒ₂Ｔｅ₃，Ｃｒ₃Ｔｅ₄，ＣｏＴｅ，Ｃｏ₃Ｔｅ₄，Ｃｕ₂Ｔｅ，ＣｕＴｅ，
Ｃｕ₃Ｓｂ，ＭｎＴｅ，ＭｎＴｅ₂，Ｍｎ₂Ｓｂ
のうちの少なくとも一つが特に好ましい。少ない回数の初期結晶化で記録・消去特性が安定するためである。
（高融点成分の含有物の量）
高融点成分の析出物に含まれる酸化物、硫化物、窒化物、炭化物の含有量は、高融点成分の４０原子％未満とするのが好ましく、１０原子％未満とするのが特に好ましい。これらの含有量が多いと、相変化成分との複素屈折率の差を小さくできなかったり、相変化成分中に酸素等が拡散して記録・読み出し特性を劣化させたりする問題を生じやすい。 Of these,
_{LaSb, CrSb, CoSb, Cr 3} Te 4, LaTe 3, Cr 4 Te 5,
_{_{_{Cr 2 Te 3, Cr 3 Te}}} 4, CoTe, Co 3 Te 4, Cu 2 Te, CuTe,
Cu ₃ Sb, MnTe, MnTe ₂ , Mn ₂ Sb
At least one of them is particularly preferred. This is because the recording / erasing characteristics are stabilized by a small number of initial crystallizations.
(Amount of high melting point component)
The content of oxides, sulfides, nitrides, and carbides contained in the precipitate of the high melting point component is preferably less than 40 at% of the high melting point component, and particularly preferably less than 10 at%. If the content of these components is large, a problem that the difference between the complex refractive index and the phase change component cannot be reduced or oxygen or the like diffuses into the phase change component to deteriorate the recording / reading characteristics easily occurs.

高融点成分の例として述べた前記の多数の化合物では、遷移金属元素の含有量ｖ’が異なると、記録膜３の界面反射率は次のように変化した。 In many of the compounds described as examples of the high melting point component, when the content v 'of the transition metal element was different, the interface reflectance of the recording film 3 changed as follows.

界面反射率
ｖ’＝２５％１％
ｖ’＝３５％２％
ｖ’＝５０％６％
この結果より、遷移金属元素の含有量ｖ’が増加すると、界面反射率が増加することが分かる。
（記録用薄膜中の高融点化合物の含有量）
記録用薄膜中に含まれる高融点化合物の含有量ａ’を、その高融点化合物の構成元素の原子数の和の高融点成分の全構成元素の原子数の和に対する割合（原子％）で表わし、その含有量ａ’を変化させた場合、書き換え可能回数と、レーザパワーを１５％高くした厳しい条件で１０⁵回書き換えた後の消去比は、次のように変化した。このＣ／Ｎの変化は、主としてＣレベルの変化によるものである。 Interface reflectance v '= 25% 1%
v '= 35% 2%
v '= 50% 6%
From this result, it is understood that the interface reflectance increases as the content v ′ of the transition metal element increases.
(Content of high melting point compound in recording thin film)
The content a ′ of the high melting point compound contained in the recording thin film is expressed as a ratio (atomic%) of the sum of the number of atoms of the constituent elements of the high melting point compound to the sum of the number of atoms of all the constituent elements of the high melting point component. , when changing the content of a ', and the number of rewritable times, erase ratio after rewriting 10 ⁵ times under severe conditions higher laser power 15%, it was changed as follows. This change in C / N is mainly due to a change in C level.

書き換え可能回数
ａ’＝５原子％４×１０⁴回
ａ’＝１０原子％１×１０⁵回
ａ’＝２０原子％１．５×１０⁵回
ａ’＝３０原子％２×１０⁵回
１０⁵回書き換え後の消去比
ａ’＝３０原子％３０ｄＢ
ａ’＝４０原子％３０ｄＢ
ａ’＝５０原子％２５ｄＢ
ａ’＝６０原子％２３ｄＢ
この結果より、記録用薄膜中に含まれる高融点化合物の含有量ａ’が増加すると、書き換え可能回数は増加するが、増加し過ぎると、１０⁵回書き換え後の消去比が低下することが分かった。よって、１０原子％≦ａ’≦５０原子％の範囲が好ましいことが分かった。
（高融点成分の複素屈折率）
高融点成分の複素屈折率の実数部ｎ₁と虚数部（消衰係数）ｋ₁は、相変化成分の結晶化状態のそれらの値ｎ₂，ｋ₂との差
Δｎ＝（｜ｎ₁−ｎ₂｜／ｎ₁）×１００，
Δｋ＝（｜ｋ₁−ｋ₂｜／ｋ₁）×１００
が異なる場合、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０5回書き換えた後、再生信号のＣ／Ｎは次のように変化した。このＣ／Ｎの変化は、主としてＮレベルの変化によるものである。 Number of rewritable times a '= 5 atomic% 4 × 10 ⁴ times a' = 10 atomic% 1 × 10 ⁵ times a '= 20 atomic% 1.5 × 10 ⁵ times a' = 30 atomic% 2 × 10 ⁵ times
10 ⁵ times of rewriting erasure ratio after a '= 30 atomic% 30 dB
a '= 40 atomic% 30 dB
a '= 50 atomic% 25 dB
a '= 60 atomic% 23dB
From these results, the content a refractory compounds' increases contained in the recording thin film, although the rewritable number of times is increased, too increased, found that erasure ratio after 10 ⁵ times of rewriting is decreased Was. Therefore, it was found that the range of 10 at% ≦ a ′ ≦ 50 at% was preferable.
(Complex refractive index of high melting point component)
The real part n ₁ and the imaginary part (extinction coefficient) k ₁ of the complex refractive index of the high melting point component are the difference Δn = (| n ₁ −) between those values n ₂ and k ₂ of the crystallized state of the phase change component. n ₂ | / n ₁ ) × 100,
Δk = (| k ₁ −k ₂ | / k ₁ ) × 100
Were different, the C / N of the reproduced signal changed as follows after rewriting 105 times under severe conditions in which the power of the laser beam was 15% higher than the optimum value. This change in C / N is mainly due to a change in N level.

１０⁵回書き換え後の再生信号のＣ／Ｎ
Δｋ，Δｎ＝１０％４９ｄＢ
Δｋ，Δｎ＝２０％４８ｄＢ
Δｋ，Δｎ＝３０％４７ｄＢ
Δｋ，Δｎ＝４０％４６ｄＢ
Δｋ，Δｎ＝５０％４３ｄＢ
この結果より、複素屈折率の実数部と虚数部（消衰係数）の差Δｎ，Δｋは小さい方が好ましいことが分かった。
（高融点成分の析出物の構成・寸法）
前述したＣｒ₄Ｔｅ₅などの高融点成分は、図１（ａ）（ｂ）（ｃ）に示すような形態で記録膜３の内部に析出する。 105 C / N of playback signal after rewriting ⁵ times
Δk, Δn = 10% 49 dB
Δk, Δn = 20% 48 dB
Δk, Δn = 30% 47dB
Δk, Δn = 40% 46 dB
Δk, Δn = 50% 43 dB
From this result, it was found that it is preferable that the differences Δn and Δk between the real part and the imaginary part (extinction coefficient) of the complex refractive index are small.
(Structure and size of precipitate of high melting point component)
The high melting point component such as Cr ₄ Te ₅ described above precipitates in the recording film 3 in the form shown in FIGS. 1 (a), 1 (b) and 1 (c).

図１（ａ）では、多数の粒状の高融点成分３ｂの析出物が独立した状態で記録膜３内に分布している。記録膜３の高融点成分３ｂ以外の部分、すなわち残成分が相変化成分３ａである。高融点成分３ｂの膜面方向の長さと膜面に垂直な方向の長さとは、ほぼ同じであるか、異なっていてもそれら長さの差は小さい。ここでは、高融点成分３ｂの析出物のあるものは、記録膜３のいずれか一方の界面に接し、他のあるものはいずれの界面にも接していない。 In FIG. 1A, a large number of precipitates of the granular high melting point component 3b are distributed in the recording film 3 in an independent state. The portion other than the high melting point component 3b of the recording film 3, that is, the remaining component is the phase change component 3a. The length of the high melting point component 3b in the direction of the film surface and the length in the direction perpendicular to the film surface are substantially the same, or even if different, the difference in the lengths is small. Here, some of the precipitates of the high melting point component 3b are in contact with any one of the interfaces of the recording film 3, and others are not in contact with any of the interfaces.

図３の媒体では、高融点成分３ｂはＣｒ₄Ｔｅ₅、相変化成分３ａはＧｅ₂Ｓｂ₂Ｔｅ₅より成っている。 In the medium of FIG. 3, the high melting point component 3b is composed of Cr ₄ Te ₅ and the phase change component 3a is composed of Ge ₂ Sb ₂ Te ₅ .

図１（ｂ）では、多数の高融点成分３ｂの析出物が独立した状態で記録膜３内に分布している点は、図１（ａ）の場合と同じである。しかし、高融点成分３ｂが柱状に析出している点が異なっている。すなわち、高融点成分３ｂの膜面方向の長さよりも、膜面に垂直な方向の長さの方が大きく、膜面に垂直な断面では柱状になっている。高融点成分３ｂの析出物のあるものは、記録膜３の一方の界面に接しており、他のあるものは、記録膜３の他方の界面に接している。ここでは、両方の界面に接しているものは存在していない。 In FIG. 1B, the point that a large number of precipitates of the high melting point component 3b are distributed in the recording film 3 in an independent state is the same as in the case of FIG. 1A. However, the difference is that the high melting point component 3b is precipitated in a column shape. In other words, the length in the direction perpendicular to the film surface is larger than the length in the film surface direction of the high melting point component 3b, and the cross section perpendicular to the film surface has a columnar shape. Some of the precipitates of the high melting point component 3b are in contact with one interface of the recording film 3, and others are in contact with the other interface of the recording film 3. Here, nothing is in contact with both interfaces.

図１（ｃ）では、多数の高融点成分３ｂの析出物が互いに連結され、一体的になった状態で記録膜３内に分布している。すなわち、高融点成分３ｂが多孔質状に析出し、その高融点成分３ｂの多数の小孔の中に相変化成分３ａが埋め込まれた状態になっている。多孔質状の高融点成分３ｂは、記録膜３の両方の界面に接している。相変化成分３ａは、互いに独立した状態で記録膜３中に分布している。この状態は、図１（ａ）の場合において、相変化成分３ａと高融点成分３ｂとを置き換えたものに相当する。 In FIG. 1C, a large number of precipitates of the high melting point component 3b are connected to each other and distributed in the recording film 3 in an integrated state. That is, the high melting point component 3b is deposited in a porous state, and the phase change component 3a is embedded in many small holes of the high melting point component 3b. The porous high melting point component 3b is in contact with both interfaces of the recording film 3. The phase change components 3a are distributed in the recording film 3 independently of each other. This state corresponds to the case of FIG. 1A in which the phase change component 3a and the high melting point component 3b are replaced.

成膜条件や初期結晶化条件により、図１の（ａ）〜（ｃ）の状態のいずれかが出現するが、いずれの状態であっても、高融点成分３ｂにより、記録膜３を加熱・溶融させた場合の相変化成分３ａの流動および偏析が防止され、その結果、書き換え可能回数が向上する。 Depending on the film forming conditions and the initial crystallization conditions, one of the states shown in FIGS. 1A to 1C appears, but in any state, the recording film 3 is heated and heated by the high melting point component 3b. The flow and segregation of the phase change component 3a when melted are prevented, and as a result, the number of rewritable times is improved.

この発明においては、高融点成分３ｂの析出物の「最大外形寸法ｄ’」、「高さｈおよびｈ’」、「中心間距離」、「最大孔寸法」および「最大壁厚さ」をそれぞれ次のように定義するものとする。 In the present invention, the “maximum external dimension d ′”, “height h and h ′”, “center-to-center distance”, “maximum pore size”, and “maximum wall thickness” of the precipitate of the high melting point component 3b are respectively defined. It shall be defined as follows.

図１の（ａ）および（ｂ）のように、高融点成分３ｂの析出物が独立して分布する場合、図２（ｂ）のように、記録膜３のいずれか一方の界面から記録膜３の膜厚Ｔの（１／３）の距離だけ離れた位置で記録膜３の膜面に平行な断面（以下、第１基準断面という）を考え、その断面における各高融点成分３ｂの析出物の長さを測定する。そして、任意の方向で測定した長さの最大値を「最大外形寸法ｄ’」とする。 When precipitates of the high-melting point component 3b are independently distributed as shown in FIGS. 1A and 1B, the recording film 3 is separated from one of the interfaces of the recording film 3 as shown in FIG. A section parallel to the film surface of the recording film 3 (hereinafter referred to as a first reference section) is considered at a position separated by a distance of (１／) of the thickness T of the film thickness T, and precipitation of each high melting point component 3b in the section is considered. Measure the length of the object. The maximum value of the length measured in an arbitrary direction is defined as “maximum external dimension d ′”.

「最大外形寸法ｄ’」は、具体的には、図２（ａ）のように、第１基準断面における形状が円形または円形に近い場合は、析出物の直径を意味し、楕円形または楕円形に近い場合は、析出物の長径を意味し、多角形の場合は、析出物の最長の対角線の長さを意味する。 The “maximum outer dimension d ′” specifically refers to the diameter of the precipitate when the shape in the first reference cross section is circular or nearly circular as shown in FIG. A shape close to the shape means the major axis of the precipitate, and a polygon means the length of the longest diagonal line of the precipitate.

「高さｈ」は、記録膜３の膜面に垂直な断面（以下、第２基準断面という）を考え、その断面において、各高融点成分３ｂの析出物の記録膜３の膜面に垂直な方向の長さを測定する。こうして得られた長さを高融点成分３ｂの析出物の「高さｈ」とする。 The “height h” refers to a cross section perpendicular to the film surface of the recording film 3 (hereinafter, referred to as a second reference cross section). In the cross section, the height h is perpendicular to the film surface of the precipitate of each high melting point component 3b. Measure the length in different directions. The length thus obtained is defined as the “height h” of the precipitate of the high melting point component 3b.

この「高さｈ」は、図４（ａ）に示すように、粒状の高融点成分３ｂの析出物が分布する場合と、図４（ｂ）に示すように、柱状の高融点成分３ｂの析出物が記録膜３の両方の界面に接して分布する場合とに適用される。 This “height h” is determined when the precipitates of the granular high melting point component 3b are distributed as shown in FIG. 4 (a) and between the columnar high melting point component 3b as shown in FIG. 4 (b). This applies to the case where the precipitate is distributed in contact with both interfaces of the recording film 3.

「高さｈ’」、「高さｈ’’」は、前記「高さｈ」と同じ考え方であるが、図４（ｃ）に示すように柱状の高融点成分３ｂの析出物が記録膜３の片方の界面にのみ接して分布する場合、界面に接しない場合にそれぞれ適用される点のみが異なる。 The “height h ′” and the “height h ″” have the same concept as the “height h”. However, as shown in FIG. 4C, the columnar high melting point component 3b precipitates on the recording film. 3 is different only in that it is applied when it is distributed in contact with only one of the interfaces and when it is not in contact with the interface.

「中心間距離ｉ」は、図２（ａ）に示すように、前記第１基準断面における、隣接する２つの高融点成分３ｂの析出物の中心間の距離の平均値を意味する。 As shown in FIG. 2A, the “center-to-center distance i” means the average value of the distance between the centers of the precipitates of two adjacent high melting point components 3b in the first reference cross section.

「最大孔寸法ｐ’’」は、図１（ｃ）に示すように、多孔質の高融点成分３ｂが析出する場合に適用されるもので、前記第１基準断面における高融点成分３ｂの析出物の各孔の大きさの最大値を意味する。 The “maximum pore size p ″” is applied when the porous high melting point component 3b precipitates as shown in FIG. 1 (c). It means the maximum value of the size of each hole of an object.

この「最大孔寸法ｐ’’」は、具体的には、図５のように、第１基準断面における孔形状が円形または円形に近い場合は、孔の直径を意味し、楕円形または楕円形に近い場合は、孔の長径を意味し、多角形の場合は、孔の最長の対角線の長さを意味する。 The “maximum hole size p ″” specifically refers to the diameter of the hole when the hole shape in the first reference cross section is circular or nearly circular as shown in FIG. , Means the major axis of the hole, and polygonal means the length of the longest diagonal of the hole.

「最大壁厚さｗ」は、「最大孔寸法ｐ’’」と同様に、多孔質の高融点成分３ｂが析出する場合に適用されるもので、図５のように、前記第１基準断面において、高融点成分３ｂの析出物の隣接する２つの孔の間の壁の厚さの最大値を意味する。
（高融点成分の析出物の寸法との関係）
高融点成分３ｂの析出物の「最大外形寸法ｄ’」が異なる場合、書き換え可能回数と、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。このＣ／Ｎの変化は、主としてＮレベルの変化によるものである。 The "maximum wall thickness w" is applied when the porous high-melting point component 3b is precipitated, similarly to the "maximum pore size p". As shown in FIG. Means the maximum value of the thickness of the wall between two adjacent holes of the precipitate of the high melting point component 3b.
(Relationship with precipitate size of high melting point component)
If "Dimensions d '" of the precipitates of the high melting point component 3b are different, the number of rewritable times and a reproduction signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam C / N changed as follows. This change in C / N is mainly due to a change in N level.

書き換え可能回数
ｄ’＝５０ｎｍ２×１０⁵回
ｄ’＝３０ｎｍ２×１０⁵回
ｄ’＝１０ｎｍ２×１０⁵回
ｄ’＝５ｎｍ１．５×１０⁵回
ｄ’＝１ｎｍ４×１０⁴回
１０⁵回書き換え後の再生信号のＣ／Ｎ
ｄ’＝８０ｎｍ４６ｄＢ
ｄ’＝５０ｎｍ４７ｄＢ
ｄ’＝２０ｎｍ４９ｄＢ
ｄ’＝１５ｎｍ４９ｄＢ
ｄ’＝５ｎｍ５０ｄＢ
この結果より、５ｎｍ≦ｄ’≦５０ｎｍの範囲が好ましいことが分かった。 Number of rewritable times d ′ = 50 nm 2 × 10 ⁵ times d ′ = 30 nm 2 × 10 ⁵ times d ′ = 10 nm 2 × 10 ⁵ times d ′ = 5 nm 1.5 × 10 ⁵ times d ′ = 1 nm 4 × 10 ⁴ times
105 C / N of playback signal after rewriting ⁵ times
d '= 80 nm 46 dB
d '= 50 nm 47 dB
d '= 20 nm 49 dB
d '= 15 nm 49 dB
d '= 5 nm 50 dB
From this result, it was found that the range of 5 nm ≦ d ′ ≦ 50 nm was preferable.

図４（ｂ）のように、柱状の高融点成分３ｂが記録膜３の両側の界面より析出した場合は、析出物の「高さｈ」が異なると、書き換え可能回数は次のように変化した。 As shown in FIG. 4B, when the columnar high melting point component 3b precipitates from the interface on both sides of the recording film 3, the number of rewritable times changes as follows if the “height h” of the precipitate is different. did.

書き換え可能回数
ｈ＝３０ｎｍ２×１０⁵回
ｈ＝２０ｎｍ１．５×１０⁵回
ｈ＝１０ｎｍ１×１０⁵回
ｈ＝０ｎｍ４×１０⁴回
この結果より、１０ｎｍ≦ｈの範囲が好ましいことが分かった。 Number of rewritable times h = 30 nm 2 × 10 ⁵ times h = 20 nm 1.5 × 10 ⁵ times h = 10 nm 1 × 10 ⁵ times h = 0 nm 4 × 10 ⁴ times From this result, it is preferable that the range of 10 nm ≦ h is preferable. Do you get it.

図４（ｃ）のように、柱状の高融点成分３ｂが記録膜３の片側の界面より析出した場合、析出物の「高さｈ’」が異なると、書き換え可能回数は次のように変化した。 As shown in FIG. 4 (c), when the columnar high melting point component 3b is deposited from one interface of the recording film 3, if the "height h '" of the precipitate is different, the number of rewritable times changes as follows. did.

書き換え可能回数
ｈ’＝２０ｎｍ２×１０⁵回
ｈ’＝１０ｎｍ１．５×１０⁵回
ｈ’＝５ｎｍ１×１０⁵回
ｈ’＝１ｎｍ４×１０⁴回
柱状の高融点成分３ｂが記録膜３の界面に接していない場合、析出物の「高さｈ’’」が異なると、書き換え可能回数は次のように変化した。 Number of rewritable times h ′ = 20 nm 2 × 10 ⁵ times h ′ = 10 nm 1.5 × 10 ⁵ times h ′ = 5 nm 1 × 10 ⁵ times h ′ = 1 nm 4 × 10 ⁴ times The columnar high melting point component 3b is a recording film. When it was not in contact with the interface of No. 3, the number of rewritable times changed as follows when the “height h ″” of the precipitate was different.

書き換え可能回数
ｈ’’＝２０ｎｍ２×１０⁵回
ｈ’’＝１０ｎｍ１．５×１０⁵回
ｈ’’＝５ｎｍ１×１０⁵回
ｈ’’＝１ｎｍ４×１０⁴回
この結果より、５ｎｍ≦ｈ’、ｈ’’の範囲が好ましいことが分かった。 Number of rewritable times h ″ = 20 nm 2 × 10 ⁵ times h ″ = 10 nm 1.5 × 10 ⁵ times h ″ = 5 nm 1 × 10 ⁵ times h ″ = 1 nm 4 × 10 ⁴ times From this result, 5 nm It has been found that the range of ≦ h ′, h ″ is preferable.

「中心間距離ｉ」が異なる場合、書き換え可能回数と、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。このＣ／Ｎの変化は、主としてＣレベルの変化によるものである。 If the "center-to-center distance i" is different, the number of rewritable times and, of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam C / N is changed as follows did. This change in C / N is mainly due to a change in C level.

書き換え可能回数
ｉ＝１２０ｎｍ８×１０⁴回
ｉ＝９０ｎｍ１．５×１０⁵回
ｉ＝７０ｎｍ１．８×１０⁵回
ｉ＝６０ｎｍ２×１０⁵回
ｉ＝４０ｎｍ２×１０⁵回
ｉ＝１５ｎｍ２×１０⁵回
１０⁵回書き換え後の再生信号のＣ／Ｎ
ｉ＝７０ｎｍ５０ｄＢ
ｉ＝４０ｎｍ５０ｄＢ
ｉ＝３０ｎｍ４９ｄＢ
ｉ＝２０ｎｍ４６ｄＢ
ｉ＝１５ｎｍ４５ｄＢ
ｉ＝１０ｎｍ４４ｄＢ
ｉ＝５ｎｍ４０ｄＢ
この結果より、２０ｎｍ≦ｉ≦９０ｎｍの範囲が好ましいことが分かった。 Number of rewritable times i = 120 nm 8 × 10 ⁴ times i = 90 nm 1.5 × 10 ⁵ times i = 70 nm 1.8 × 10 ⁵ times i = 60 nm 2 × 10 ⁵ times i = 40 nm 2 × 10 ⁵ times i = 15 nm 2 × 10 ⁵ times
105 C / N of playback signal after rewriting ⁵ times
i = 70 nm 50 dB
i = 40 nm 50 dB
i = 30 nm 49 dB
i = 20 nm 46 dB
i = 15 nm 45 dB
i = 10 nm 44 dB
i = 5 nm 40 dB
From this result, it was found that the range of 20 nm ≦ i ≦ 90 nm was preferable.

図１（ｃ）のように、高融点成分３ｂが膜面方向につながって多孔質状として析出した場合、析出物の「最大孔寸法ｐ’’」が異なると、書き換え可能回数は
次のように変化した。 As shown in FIG. 1C, when the high melting point component 3b is connected in the film surface direction and deposited as a porous material, if the “maximum pore size p ″” of the precipitate is different, the number of rewritable times is as follows. Changed to

書き換え可能回数
ｐ’’＝５０ｎｍ１．５×１０⁵回
ｐ’’＝６０ｎｍ１．５×１０⁵回
ｐ’’＝８０ｎｍ１×１０⁵回
ｐ’’＝１００ｎｍ４×１０⁴回
この結果より、ｐ’’≦８０ｎｍの範囲が好ましいことが分かった。 Number of rewritable times p ″ = 50 nm 1.5 × 10 ⁵ times p ″ = 60 nm 1.5 × 10 ⁵ times p ″ = 80 nm 1 × 10 ⁵ times p ″ = 100 nm 4 × 10 ⁴ times From these results , P ″ ≦ 80 nm is preferable.

多孔質の高融点成分３ｂの「最大壁厚さｗ」が異なると、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。このＣ／Ｎの変化は、主としてＣレベルの変化によるものである。 When the "maximum wall thickness w 'of the high melting point component 3b porous differ, C / N of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser light power, the following Changed. This change in C / N is mainly due to a change in C level.

１０⁵回書き換え後の再生信号のＣ／Ｎ
ｗ＝５ｎｍ５０ｄＢ
ｗ＝１５ｎｍ４９ｄＢ
ｗ＝２０ｎｍ４６ｄＢ
ｗ＝３５ｎｍ４０ｄＢ
この結果より、ｗ≦２０ｎｍの範囲が好ましいことが分かった。
（高融点成分の融点との関係）
記録膜３中に析出する高融点成分３ｂの融点（ｍ．ｐ．）が異なると、書き換え可能回数が次のように変化することが、計算機シュミレーションにより推測できた。 105 C / N of playback signal after rewriting ⁵ times
w = 5nm 50dB
w = 15 nm 49 dB
w = 20 nm 46 dB
w = 35 nm 40 dB
From this result, it was found that the range of w ≦ 20 nm was preferable.
(Relation with melting point of high melting point component)
It was estimated by computer simulation that if the melting point (mp) of the high melting point component 3b deposited in the recording film 3 is different, the rewritable number changes as follows.

書き換え可能回数
ｍ．ｐ．＝６００゜Ｃ７×１０⁴回
ｍ．ｐ．＝７８０゜Ｃ１．５×１０⁵回
ｍ．ｐ．＝９３０゜Ｃ２×１０⁵回
この結果より、高融点成分３ｂの融点は７８０゜Ｃ以上の範囲が好ましく、９３０゜Ｃ以上の範囲がより好ましいことが分かった。 Number of rewritable times m. p. = 600 ° C 7 × 10 ⁴ times m. p. = 780 ° C 1.5 × 10 ⁵ times m. p. = From 930 ° C 2 × 10 ⁵ times this result, the melting point is preferably in the range of more than 780 ° C of the high melting point component 3b, the range of more than 930 ° C has been found more preferable.

高融点成分３ｂが析出した後の残成分（相変化成分３ａ）の融点と、高融点成分３ｂの融点との差が異なると、書き換え可能回数が次のように変化することも
、計算機シュミレーションにより推測できた。 If the difference between the melting point of the residual component (phase change component 3a) after the precipitation of the high melting point component 3b and the melting point of the high melting point component 3b is different, the number of rewritable times changes as follows. I could guess.

書き換え可能回数
ｍ．ｐ．の差＝０゜Ｃ７×１０⁴回
ｍ．ｐ．の差＝１５０゜Ｃ１．５×１０⁵回
ｍ．ｐ．の差＝３００゜Ｃ２×１０⁵回
この結果より、融点の差は１５０゜Ｃ以上の範囲が好ましく、３００゜Ｃ以上の範囲がより好ましいことが分かった。
（高融点成分と相変化分の結晶化温度の差との関係）
毎分１０゜Ｃの一定速度で昇温し、結晶化の発熱の始まる温度を測定した。その結果より、高融点成分３ｂと相変化を起こす低融点成分３ａの結晶化温度の差ｓを求めると、温度差ｓによって書き換え可能回数は次のように変化した。 Number of rewritable times m. p. Difference = 0 ° C 7 × 10 ⁴ times m. p. Difference = 150 ° C. 1.5 × 10 ⁵ times m. p. Difference = 300 ° C 2 × 10 ⁵ times result from the difference in melting point is preferably in the range of more than 150 ° C, it was found more preferable in the range of more than 300 ° C.
(Relationship between high melting point component and difference in crystallization temperature for phase change)
The temperature was raised at a constant rate of 10 ° C./min, and the temperature at which crystallization exotherm started was measured. From the result, when the difference s in the crystallization temperature between the high melting point component 3b and the low melting point component 3a that causes a phase change was determined, the number of rewritable times was changed as follows depending on the temperature difference s.

書き換え可能回数
ｓ＝５゜Ｃ４×１０⁴回
ｓ＝１０゜Ｃ１×１０⁵回
ｓ＝３０゜Ｃ１．５×１０⁵回
ｓ＝４０゜Ｃ２×１０⁵回
この結果より、融点の差は１０゜Ｃ以上の範囲が好ましく、３０゜Ｃ以上の範囲がより好ましいことが分かった。
（成膜時に被着させる高融点成分との関係）
この実施例の情報記録用薄膜を製作する際に、初期の工程で、高融点成分
Ｃｒ₄Ｔｅ₅を被着させているが、その高融点成分Ｃｒ₄Ｔｅ₅の平均膜厚ｃ’を次のように変えると、書き換え可能回数と、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。このＣ／Ｎの変化は、主としてＣレベルの変化によるものである。 Number of rewritable times s = 5 ° C 4 × 10 ⁴ times s = 10 ° C 1 × 10 ⁵ times s = 30 ° C 1.5 × 10 ⁵ times s = 40 ° C 2 × 10 ⁵ times It is found that the difference is preferably in the range of 10 ° C or more, and more preferably in the range of 30 ° C or more.
(Relationship with high melting point component to be deposited during film formation)
In manufacturing the information recording thin film of this embodiment, the high melting point component Cr ₄ Te ₅ is deposited in an initial step, and the average film thickness c ′ of the high melting point component Cr ₄ Te ₅ is set as follows. changing as, the number of rewritable times and, of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser beam C / N was changed as follows. This change in C / N is mainly due to a change in C level.

書き換え可能回数
ｃ’＝０ｎｍ５×１０⁴回
ｃ’＝１ｎｍ１×１０⁵回
ｃ’＝５ｎｍ２×１０⁵回
１０⁵回書き換え後の再生信号のＣ／Ｎ
ｃ’＝１ｎｍ４７ｄＢ
ｃ’＝５ｎｍ４７ｄＢ
ｃ’＝１０ｎｍ４６ｄＢ
ｃ’＝２０ｎｍ４０ｄＢ
この結果より、１ｎｍ≦ｃ’≦１０ｎｍの範囲が好ましいことが分かった。
（その他）
この実施例では、保護層２および中間層４をＺｎＳ−ＳｉＯ₂により形成しているが、ＺｎＳ−ＳｉＯ₂に代えて、Ｓｉ−Ｎ系材料，Ｓｉ−Ｏ−Ｎ系材料，ＳｉＯ₂，ＳｉＯ，ＴｉＯ₂，Ａｌ₂Ｏ₃，Ｙ₂Ｏ₃，ＣｅＯ，Ｌａ₂Ｏ₃，Ｉｎ₂Ｏ₃，ＧｅＯ，ＧｅＯ₂，ＰｂＯ，ＳｎＯ，ＳｎＯ₂，Ｂｉ₂Ｏ₃，ＴｅＯ₂，ＷＯ₂，ＷＯ₃，Ｓｃ₂Ｏ₃，ＺｒＯ₂などの酸化物，ＴａＮ，ＡｌＮ，Ｓｉ₃Ｎ₄，Ａｌ−Ｓｉ−Ｎ系材料（例えばＡｌＳｉＮ₂）などの窒化物、ＺｎＳ，Ｓｂ₂Ｓ₃，ＣｄＳ，Ｉｎ₂Ｓ₃，Ｇａ₂Ｓ₃，ＧｅＳ，ＳｎＳ₂，ＰｂＳ，Ｂｉ₂Ｓ₃などの硫化物、ＳｎＳｅ₂，Ｓｂ₂Ｓｅ₃，ＣｄＳｅ，ＺｎＳｅ，Ｉｎ₂Ｓｅ₃，Ｇａ₂Ｓｅ₃，ＧｅＳｅ，ＧｅＳｅ₂，ＳｎＳｅ，ＰｂＳｅ，Ｂｉ₂Ｓｅ₃などのセレン化物、ＣｅＦ₃，ＭｇＦ₂，ＣａＦ₂などの弗化物、あるいはＳｉ，Ｇｅ，ＴｉＢ₂，Ｂ₄Ｃ，Ｂ，Ｃ，または、上記の材料に近い組成のものを用いてもよい。また、これらの混合材料の層やこれらの多重層でもよい。 Number of rewritable times c ′ = 0 nm 5 × 10 ⁴ times c ′ = 1 nm 1 × 10 ⁵ times c ′ = 5 nm 2 × 10 ⁵ times
105 C / N of playback signal after rewriting ⁵ times
c ′ = 1 nm 47 dB
c ′ = 5 nm 47 dB
c ′ = 10 nm 46 dB
c ′ = 20 nm 40 dB
From this result, it was found that the range of 1 nm ≦ c ′ ≦ 10 nm was preferable.
(Other)
In this embodiment, the protective layer 2 and the intermediate layer 4 is formed by ZnS-SiO _2, instead of the ZnS-SiO _2, Si-N-based material, SiO-N based material, SiO _2, SiO _{_{_{, TiO 2, Al 2 O 3}}} , Y 2 O 3, CeO, La 2 O 3, In 2 O 3, GeO, GeO 2, PbO, SnO, SnO 2, Bi 2 O 3, TeO 2, WO 2, WO _3, Sc ₂ O _3, oxides such as _{ZrO 2, TaN, AlN, Si} 3 N 4, Al-Si-N material (e.g., AlSiN ₂₎ nitride such _{_{as, ZnS, Sb 2 S 3,}} CdS, in _{_{_{_{2 S 3, Ga 2 S 3}}}} , GeS, SnS 2, PbS, sulfides such as _{_{_{Bi 2 S 3, SnSe 2,}}} Sb 2 Se 3, CdSe, ZnSe, in 2 Se 3, Ga 2 Se 3, GeSe, GeSe ₂ , selenides such as SnSe, PbSe, Bi ₂ Se ₃ , Fluoride such as CeF ₃ , MgF ₂ , CaF ₂ , or Si, Ge, TiB ₂ , B ₄ C, B, C, or a composition close to the above materials may be used. Further, a layer of a mixed material thereof or a multilayer thereof may be used.

中間層４を省略した場合には、記録感度が約３０％低下し、消え残りも約５ｄＢ増加した。書き換え可能回数も減少した。 When the intermediate layer 4 was omitted, the recording sensitivity was reduced by about 30%, and the remaining disappearance was increased by about 5 dB. The number of rewritable times also decreased.

中間層４の屈折率が１．７以上、２．３以下の範囲にある場合、膜厚が３ｎｍ以上、１００ｎｍ以下の範囲、および１８０ｎｍ以上、４００ｎｍ以下の範囲で、それぞれ５０ｄＢ以上のＣ／Ｎが得られた。 When the refractive index of the intermediate layer 4 is in the range of 1.7 or more and 2.3 or less, the C / N of 50 dB or more in the film thickness of 3 nm or more and 100 nm or less and 180 nm or more and 400 nm or less. was gotten.

この実施例で反射層５に用いたＡｌ−Ｔｉの代わりに、Ａｕ，Ａｇ，Ｃｕ，Ａｌ，Ｎｉ，Ｆｅ，Ｃｏ，Ｃｒ，Ｔｉ，Ｐｄ，Ｐｔ，Ｗ，Ｔａ，Ｍｏ，Ｓｂの元素単体、またはこれらを主成分とする合金、あるいはこれら同志の合金よりなる層を用いてもよいし、それらの層よりなる多重層を用いてもよいし、これらと酸化物などの他の物質との複合層などを用いてもよい。 In place of Al—Ti used for the reflective layer 5 in this embodiment, Au, Ag, Cu, Al, Ni, Fe, Co, Cr, Ti, Pd, Pt, W, Ta, Mo, and Sb are used alone. Alternatively, an alloy containing these as main components or a layer made of an alloy of these may be used, a multi-layer made of those layers may be used, or a composite of these with another substance such as an oxide. A layer or the like may be used.

中間層４、反射層５および保護層２の一部を省略した単純積層構造、例えば基板１／保護層２／記録膜３、基板１／記録膜３／中間層４、基板１／記録膜３／反射層５などの構成でも、従来のものに比べると、多数回書き換えを行なってもノイズ上昇が少なく、良好な結果が得られた。 Simple laminated structure in which the intermediate layer 4, the reflective layer 5, and the protective layer 2 are partially omitted, for example, substrate 1 / protective layer 2 / recording film 3, substrate 1 / recording film 3 / intermediate layer 4, substrate 1 / recording film 3. Even with the configuration such as the reflective layer 5, the noise rise was small even when rewriting was performed many times, and good results were obtained as compared with the conventional configuration.

以上述べたように、この実施例の情報記録用薄膜は、記録・再生・消去特性を良好に保ちながら、従来より１桁以上の多数回の書き換えが可能である。また、記録・消去に用いるレーザ光のパワーが低くてよいという利点もある。
〔実施例２〕
実施例１のＳｂ−Ｔｅ−Ｇｅ−Ｃｒ系の記録膜５において、ＧｅをＩｎで全部置換したものに相当するＳｂ−Ｔｅ−Ｉｎ−Ｃｒ系のＣｒ₁₂Ｉｎ₃₅Ｓｂ₁₂Ｔｅ₄₀
、すなわち（Ｃｒ₄Ｔｅ₅）₂（Ｉｎ₃ＳｂＴｅ₂）₇により記録膜５を形成した点以外は、実施例１と同様にして、情報記録用薄膜を製作した。また、当該薄膜の初期結晶化と、その後の情報の記録・再生方法も実施例１と同様とした。
（Ｃｒ以外の元素の組成との関係）
Ｃｒ含有量を一定として、三角相図（図示せず）のＩｎ₆₅Ｔｅ₂₅Ｃｒ₁₀とＳｂ3₀Ｔｅ₆₀Ｃｒ₁₀を結ぶ直線上で他の組成を変化させると、一定速度で昇温した場合の未記録部分の結晶化温度と、８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化は、次のようになった。 As described above, the information recording thin film of this embodiment can be rewritten one or more times more than before, while maintaining good recording / reproducing / erasing characteristics. Another advantage is that the power of the laser beam used for recording / erasing may be low.
[Example 2]
In Sb-Te-Ge-Cr-based recording film 5 of the embodiment of 1, Cr ₁₂ In the Sb-Te-In-Cr system corresponding to those replaced all Ge in In ₃₅ Sb ₁₂ Te ₄₀
That is, an information recording thin film was manufactured in the same manner as in Example 1 except that the recording film 5 was formed of (Cr ₄ Te ₅ ) ₂ (In ₃ SbTe ₂ ) ₇ . The method of initial crystallization of the thin film and the subsequent recording / reproducing method of the information were the same as in the first embodiment.
(Relationship with composition of elements other than Cr)
As constant Cr content, a triangular phase diagram Varying the other composition on a straight line connecting the In ₆₅ Te ₂₅ Cr ₁₀ and Sb3 ₀ Te ₆₀ Cr ₁₀ (not shown), when the temperature was raised at a constant rate The change of the crystallization temperature of the unrecorded portion and the change of the bit error rate at 1000 ° C. in 80 ° C. and 95% relative humidity are as follows.

結晶化温度
Ｓｂ₃₀Ｔｅ₆₀Ｃｒ₁₀ １２０゜Ｃ
Ｓｂ₂₂Ｔｅ₅₁Ｉｎ₁₇Ｃｒ₁₀ １４０゜Ｃ
Ｓｂ₁₈Ｔｅ₄₇Ｉｎ₂₅Ｃｒ₁₀ １５０゜Ｃ
Ｓｂ₁₀Ｔｅ₃₅Ｉｎ₄₅Ｃｒ₁₀ １７０゜Ｃ
Ｓｂ₇Ｔｅ₃₃Ｉｎ₅₀Ｃｒ₁₀ １８０゜Ｃ
Ｓｂ₂Ｔｅ₈Ｉｎ₆₀Ｃｒ₁₀ ２２０゜Ｃ
ビット・エラーレートの変化
Ｓｂ₂₂Ｔｅ₅₁Ｉｎ₁₇Ｃｒ₁₀ ２倍
Ｓｂ₁₈Ｔｅ₄₇Ｉｎ₂₅Ｃｒ₁₀ ２倍
Ｓｂ₁₀Ｔｅ₃₅Ｉｎ₄₅Ｃｒ₁₀ ２倍
Ｓｂ₇Ｔｅ₃₃Ｉｎ₅₀Ｃｒ₁₀ ２．５倍
Ｓｂ₂Ｔｅ₈Ｉｎ₆₀Ｃｒ₁₀ ４倍
この結果より、Ｃｒ以外の組成が変化しても、十分高い結晶化温度が得られ、１０⁵回という多数回の書き換えによってもビット・エラーレートの変化があまり大きくないことが分かる。 Crystallization temperature Sb ₃₀ Te ₆₀ Cr ₁₀ 120 ° C
Sb ₂₂ Te ₅₁ In ₁₇ Cr ₁₀ 140 ° C
Sb ₁₈ Te ₄₇ In ₂₅ Cr ₁₀ 150 ° C
Sb ₁₀ Te ₃₅ In ₄₅ Cr ₁₀ 170 ° C
Sb ₇ Te ₃₃ In ₅₀ Cr ₁₀ 180 ° C
Sb ₂ Te ₈ In ₆₀ Cr ₁₀ 220 ° C
Change in bit error rate Sb ₂₂ Te ₅₁ In ₁₇ Cr ₁₀ 2 times Sb ₁₈ Te ₄₇ In ₂₅ Cr ₁₀ 2 times Sb ₁₀ Te ₃₅ In ₄₅ Cr ₁₀ 2 times Sb ₇ Te ₃₃ In ₅₀ Cr ₁₀ 2.5 times Sb ₂ from Te ₈ in ₆₀ Cr ₁₀ 4 times result, even if the change in composition other than Cr, sufficiently high crystallization temperature is obtained, it is so large change in the bit error rate by a number of times of rewrite of 10 ⁵ times I understand that there is no.

Ｃｒ含有量を一定として、同じ三角相図のＳｂ₆₅Ｔｅ₂₅Ｃｒ₁₀と
Ｉｎ₄₇Ｔｅ₄₃Ｃｒ₁₀を結ぶ直線上で組成を変化させると、一定速度で昇温した場合の結晶化温度と、８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化は、次のようになった。 When the composition is changed on a straight line connecting Sb ₆₅ Te ₂₅ Cr ₁₀ and In ₄₇ Te ₄₃ Cr ₁₀ in the same triangular phase diagram while keeping the Cr content constant, the crystallization temperature when the temperature is raised at a constant rate and the crystallization temperature are 80 The change of the bit error rate when the sample was put in the ゜ C and the relative humidity of 95% for 1000 hours was as follows.

結晶化温度
Ｓｂ₂Ｔｅ₄₂Ｉｎ₄₆Ｃｒ₁₀ ２１０゜Ｃ
Ｓｂ₄Ｔｅ₄₂Ｉｎ₄₄Ｃｒ₁₀ ２００゜Ｃ
Ｓｂ₈Ｔｅ₄₁Ｉｎ₄₁Ｃｒ₁₀ １９０゜Ｃ
Ｓｂ₁₅Ｔｅ₃₉Ｉｎ₃₆Ｃｒ₁₀ １８０゜Ｃ
Ｓｂ₃₀Ｔｅ₃₄Ｉｎ₂₆Ｃｒ₁₀ １５０゜Ｃ
Ｓｂ₃₈Ｔｅ₃₂Ｉｎ₂₀Ｃｒ₁₀ １３０゜Ｃ
Ｓｂ₄₁Ｔｅ₃₂Ｉｎ₁₇Ｃｒ₁₀ １１０゜Ｃ
ビット・エラーレートの変化
Ｓｂ₂Ｔｅ₄₂Ｉｎ₄₆Ｃｒ₁₀ ５倍
Ｓｂ₄Ｔｅ₄₂Ｉｎ₄₄Ｃｒ₁₀ ３倍
Ｓｂ₈Ｔｅ₄₁Ｉｎ₄₁Ｃｒ₁₀ ２倍
Ｓｂ₁₅Ｔｅ₃₉Ｉｎ₃₆Ｃｒ₁₀ １．５倍
Ｓｂ₃₀Ｔｅ₃₄Ｉｎ₂₆Ｃｒ₁₀ １．５倍
Ｓｂ₃₈Ｔｅ₃₂Ｉｎ₂₀Ｃｒ₁₀ １倍
Ｓｂ₄₁Ｔｅ₃₂Ｉｎ₁₇Ｃｒ₁₀ １倍
この結果より、Ｃｒ以外の組成が変化しても、十分高い結晶化温度が得られ、１０⁵回という多数回の書き換えによってもビット・エラーレートの変化があまり大きくないことが分かる。 Crystallization temperature Sb ₂ Te ₄₂ In ₄₆ Cr ₁₀ 210 ° C
Sb ₄ Te ₄₂ In ₄₄ Cr ₁₀ 200 ° C
Sb ₈ Te ₄₁ In ₄₁ Cr ₁₀ 190 ° C
Sb ₁₅ Te ₃₉ In ₃₆ Cr ₁₀ 180 ° C
Sb ₃₀ Te ₃₄ In ₂₆ Cr ₁₀ 150 ° C
Sb ₃₈ Te ₃₂ In ₂₀ Cr ₁₀ 130 ° C
Sb ₄₁ Te ₃₂ In ₁₇ Cr ₁₀ 110 ° C
Change in bit error rate Sb ₂ Te ₄₂ In ₄₆ Cr ₁₀ 5 times Sb ₄ Te ₄₂ In ₄₄ Cr ₁₀ 3 times Sb ₈ Te ₄₁ In ₄₁ Cr ₁₀ 2 times Sb ₁₅ Te ₃₉ In ₃₆ Cr ₁₀ 1.5 times Sb ₃₀ Te ₃₄ In ₂₆ Cr ₁₀ 1.5 times Sb ₃₈ Te ₃₂ In ₂₀ Cr ₁₀ 1 times Sb ₄₁ Te ₃₂ In ₁₇ Cr ₁₀ 1 times From this result, even if the composition other than Cr changes, a sufficiently high crystallization temperature can be obtained. the resulting, it is understood that is not so large change in the bit error rate by a number of times of rewrite of 10 ⁵ times.

Ｉｎの含有量ｐとＳｂの含有量ｘの比（ｐ／ｘ）を変化させると、８０゜Ｃ，相対湿度９５％中に１０００時間置いた時のビット・エラーレートの変化は、次のようになった。 When the ratio (p / x) of the content p of In and the content x of Sb is changed, the change of the bit error rate at 1000 ° C. in 80 ° C. and 95% relative humidity is as follows. Became.

ビット・エラーレートの変化
（ｐ／ｘ）＝０．５３．０倍
（ｐ／ｘ）＝１．０２．０倍
（ｐ／ｘ）＝２．０２．０倍
（ｐ／ｘ）＝３．０２．０倍
（ｐ／ｘ）＝４．０３．０倍
この結果より、Ｉｎの含有量ｐとＳｂの含有量ｘの比（ｐ／ｘ）が、
１．０≦（ｐ／ｘ）≦３．０の範囲であれば、ビット・エラーレートの変化が小さいことが分かる。 Change in bit error rate (p / x) = 0.5 3.0 times (p / x) = 1.0 2.0 times (p / x) = 2.0 2.0 times (p / x) = 3.0 2.0 times (p / x) = 4.0 3.0 times From these results, the ratio (p / x) of the In content p to the Sb content x is:
It can be seen that if the range is 1.0 ≦ (p / x) ≦ 3.0, the change in the bit error rate is small.

ＣｒをＣｕに代えたもの，すなわちＩｎ−Ｓｂ−Ｔｅ−Ｃｕ系において、同様にＩｎの含有量ｐとＳｂの含有量ｘの比（ｐ／ｘ）を変化させた場合も、同様の結果が得られた。
（相変化成分の他の例）
相変化成分であるＩｎ₃ＳｂＴｅ₂の一部を
Ｇｅ₂Ｓｂ₂Ｔｅ₅，ＧｅＳｂ₄Ｔｅ₇，ＧｅＳｂ₂Ｔｅ₄，Ｉｎ₃₅Ｓｂ₃₂Ｔｅ₃₃，
Ｉｎ₃₁Ｓｂ₂₆Ｔｅ₄₃
のうちの少なくとも一つで置き換えても、Ｉｎの一部をＧｅに置き換えても、近い特性が得られる。
（高融点成分の他の例）
高融点成分であるＣｒ₄Ｔｅ₅の一部を
ＬａＴｅ₃，ＬａＴｅ₂，Ｌａ₂Ｔｅ₃，Ｌａ₃Ｔｅ₄，ＬａＴｅ，Ｌａ₂Ｔｅ₅，
ＬａＳｂ，Ｌａ₄Ｔｅ₇，Ｌａ₃Ｔｅ，Ｌａ₂Ｓｂ，Ｌａ₃Ｓｂ₂，ＬａＳｂ₂，
Ｌａ₃Ｇｅ，Ｌａ₅Ｇｅ₃，Ｌａ₄Ｇｅ₃，Ｌａ₅Ｇｅ₄，ＬａＧｅ，Ｌａ₃Ｇｅ₅，
Ａｇ₂Ｔｅ，Ｃｒ₅Ｔｅ₈，Ｃｒ₂Ｔｅ₃，ＣｒＳｂ，Ｃｒ₃Ｇｅ，Ｃｒ₅Ｇｅ₃，
Ｃｒ₁₁Ｇｅ₈，ＣｒＧｅ，Ｃｒ₁₁Ｇｅ₁₉，ＰｔＴｅ₂，Ｐｔ₄Ｔｅ₅，Ｐｔ₅Ｔｅ₄，Ｐｔ₄Ｓｂ，Ｐｔ₃Ｓｂ₂，ＰｔＳｂ，Ｐｔ₃Ｇｅ，Ｐｔ₂Ｇｅ，Ｐｔ₃Ｇｅ₂，
ＰｔＧｅ，Ｐｔ₂Ｇｅ₃，ＰｔＧｅ₃，ＮｉＴｅ，ＮｉＴｅ_0.85，ＮｉＳｂ，
Ｎｉ₃Ｇｅ，Ｎｉ₅Ｇｅ₂，Ｎｉ₅Ｇｅ₃，ＮｉＧｅ、ＣｏＴｅ₂，ＣｏＳｂ₂，
ＣｏＳｂ₃，Ｃｏ₅Ｇｅ₂，Ｃｏ₅Ｇｅ₃，ＣｏＧｅ，Ｃｏ₅Ｇｅ₇，ＣｏＧｅ₂，
Ｓｉ₂Ｔｅ₃，ＳｉＳｂ，ＳｉＧｅ，ＣｅＴｅ，Ｃｅ₃Ｔｅ₄，Ｃｅ₂Ｔｅ₃，
Ｃｅ₄Ｔｅ₇，ＣｅＴｅ₂，ＣｅＴｅ₃，Ｃｅ₂Ｓｂ，Ｃｅ₅Ｓｂ₃，Ｃｅ₄Ｓｂ₅，
ＣｅＳｂ，ＣｅＳｂ₂，Ｃｅ₃Ｇｅ，Ｃｅ₅Ｇｅ₃，Ｃｅ₄Ｇｅ₃，Ｃｅ₅Ｇｅ₄，
ＣｅＧｅ，Ｃｅ₃Ｇｅ₅，Ｃｅ₅Ｓｉ₃，Ｃｅ₃Ｓｉ₂，Ｃｅ₅Ｓｉ₄，ＣｅＳｉ，
Ｃｅ₃Ｓｉ₅，ＣｅＳｉ₂，Ｃｒ₃Ｓｉ，Ｃｒ₅Ｓｉ₃，ＣｒＳｉ，ＣｒＳｉ₃，
ＣｒＳｉ₂，Ｃｏ₃Ｓｉ，ＣｏＳｉ，ＣｏＳｉ₂，ＮｉＳｉ₂，ＮｉＳｉ，
Ｎｉ₃Ｓｉ₂，Ｎｉ₂Ｓｉ，Ｎｉ₅Ｓｉ₂，Ｎｉ₃Ｓｉ，Ｐｔ₅Ｓｉ₂，Ｐｔ₂Ｓｉ，
ＰｔＳｉ，ＬａＳｉ₂，Ａｇ₃Ｉｎ，Ａｇ₂Ｉｎ，Ｂｉ₂Ｃｅ，ＢｉＣｅ，
Ｂｉ₃Ｃｅ₄，Ｂｉ₃Ｃｅ₅，ＢｉＣｅ₂，Ｃｄ₁₁Ｃｅ，Ｃｄ₆Ｃｅ，Ｃｄ₅₈Ｃｅ₁₃，Ｃｄ₃Ｃｅ，Ｃｄ₂Ｃｅ，ＣｄＣｅ，Ｃｅ₃Ｉｎ，Ｃｅ₂Ｉｎ，Ｃｅ_1+xＩｎ，
Ｃｅ₃Ｉｎ₅，ＣｅＩｎ₂，ＣｅＩｎ₃，Ｃｅ₂Ｐｂ，ＣｅＰｂ，ＣｅＰｂ₃，
Ｃｅ₃Ｓｎ，Ｃｅ₅Ｓｎ₃，Ｃｅ₅Ｓｎ₄，Ｃｅ₁₁Ｓｎ₁₀，Ｃｅ₃Ｓｎ₅，
Ｃｅ₃Ｓｎ₇，Ｃｅ₂Ｓｎ₅，ＣｅＳｎ₃，ＣｅＺｎ，ＣｅＺｎ₂，ＣｅＺｎ₃，
Ｃｅ₃Ｚｎ₁₁，Ｃｅ₁₃Ｚｎ₅₈，ＣｅＺｎ₅，Ｃｅ₃Ｚｎ₂₂，Ｃｅ₂Ｚｎ₁₇，
ＣｅＺｎ₁₁，Ｃｄ₂₁Ｃｏ₅，ＣｏＧａ，ＣｏＧａ₃，ＣｏＳｎ，Ｃｒ₃Ｇａ，
ＣｒＧａ，Ｃｒ₅Ｇａ₆，ＣｒＧａ₄，Ｃｕ₉Ｇａ₄，Ｃｕ₃Ｓｎ，Ｃｕ₃Ｚｎ，
Ｂｉ₂Ｌａ，ＢｉＬａ，Ｂｉ₃Ｌａ₄，Ｂｉ₃Ｌａ₅，ＢｉＬａ₂，Ｃｄ₁₁Ｌａ，
Ｃｄ₁₇Ｌａ₂，Ｃｄ₉Ｌａ₂，Ｃｄ₂Ｌａ，ＣｄＬａ，Ｇａ₆Ｌａ，Ｇａ₂Ｌａ，
ＧａＬａ，Ｇａ₃Ｌａ₅，ＧａＬａ₃，Ｉｎ₃Ｌａ，Ｉｎ₂Ｌａ，Ｉｎ₅Ｌａ₃，
Ｉｎ_xＬａ，ＩｎＬａ，ＩｎＬａ₂，ＩｎＬａ₃，Ｌａ₅Ｐｂ₃，Ｌａ₄Ｐｂ₃，
Ｌａ₁₁Ｐｂ₁₀，Ｌａ₃Ｐｂ₄，Ｌａ₅Ｐｂ₄，ＬａＰｂ₂，ＬａＰｂ₃，ＬａＺｎ，
ＬａＺｎ₂，ＬａＺｎ₄，ＬａＺｎ₅，Ｌａ₃Ｚｎ₂₂，Ｌａ₂Ｚｎ₁₇，ＬａＺｎ₁₁，ＬａＺｎ₁₃，ＮｉＢｉ，Ｇａ₃Ｎｉ₂，ＧａＮｉ，Ｇａ₂Ｎｉ₃，Ｇａ₃Ｎｉ₅，
ＧａＮｉ₃，Ｎｉ₃Ｓｎ，Ｎｉ₃Ｓｎ₂，Ｎｉ₃Ｓｎ₄，ＮｉＺｎ，Ｎｉ₅Ｚｎ₂₁，
ＰｔＢｉ，ＰｔＢｉ₂，ＰｔＢｉ₃，ＰｔＣｄ₂，Ｐｔ₂Ｃｄ₉，Ｇａ₇Ｐｔ₃，
Ｇａ₂Ｐｔ，Ｇａ₃Ｐｔ₂，ＧａＰｔ，Ｇａ₃Ｐｔ₅，ＧａＰｔ₂，ＧａＰｔ₃，
Ｉｎ₇Ｐｔ₃，Ｉｎ₂Ｐｔ，Ｉｎ₃Ｐｔ₂，ＩｎＰｔ，Ｉｎ₅Ｐｔ₆，Ｉｎ₂Ｐｔ₃，
ＩｎＰｔ₂，ＩｎＰｔ₃，Ｐｔ₃Ｐｂ，ＰｔＰｂ，Ｐｔ₂Ｐｂ₃，Ｐｔ₃Ｓｎ，
ＰｔＳｎ，Ｐｔ₂Ｓｎ₃，ＰｔＳｎ₂，ＰｔＳｎ₄，Ｐｔ₃Ｚｎ，ＰｔＺｎ₂，
ＡｌＳ，Ａｌ₂Ｓ₃，ＢａＳ，ＢａＣ₂，ＣｄＳ，Ｃｏ₄Ｓ₃，Ｃｏ₉Ｓ₈，ＣｏＳ，ＣｏＯ，Ｃｏ₂Ｏ₄，Ｃｏ₂Ｏ₃，Ｃｒ₂Ｏ₃，Ｃｒ₃Ｏ₄，ＣｒＯ，ＣｒＳ，ＣｒＮ，Ｃｒ₂Ｎ，Ｃｒ₂₃Ｃ₆₃，Ｃｒ₇Ｃ₃，Ｃｒ₃Ｃ₂，Ｃｕ₂Ｓ，Ｃｕ₉Ｓ₅，ＣｕＯ，
Ｃｕ₂Ｏ，Ｉｎ₄Ｓ₅，Ｉｎ₃Ｓ₄，Ｌａ₂Ｓ₃，Ｌａ₂Ｏ₃，Ｍｏ₂Ｃ，ＭｏＣ，
Ｍｎ₂₃Ｃ₆，Ｍｎ₄Ｃ，Ｍｎ₇Ｃ₃，ＮｉＯ，ＳｉＳ₂，ＳｉＯ₂，Ｓｉ₃Ｎ₄，
Ｃｕ₂Ｔｅ,ＣｕＴｅ，Ｃｕ₃Ｓｂ，Ｍｎ₂Ｓｂ，ＭｎＴｅ，ＭｎＴｅ₂，
Ｍｎ₅Ｇｅ₃，Ｍｎ_3.25Ｇｅ，Ｍｎ₅Ｇｅ₂，Ｍｎ₃Ｇｅ₂，Ｇｅ₃Ｗ，Ｔｅ₂Ｗ，
ＡｌＳｂ，Ａｌ₂Ｔｅ₃，Ｆｅ₂Ｇｅ，ＦｅＧｅ₂，ＦｅＳｂ₂，Ｍｏ₃Ｓｂ₇，
Ｍｏ₃Ｔｅ₄，ＭｏＴｅ₂,ＰｂＴｅ，ＧｅＰｄ₂，Ｇｅ₂Ｐｄ₅，Ｇｅ₉Ｐｄ₂₅，
ＧｅＰｄ₅,Ｐｄ₃Ｓｂ，Ｐｄ₅Ｓｂ₃，ＰｄＳｂ，ＳｎＴｅ，Ｔｉ₅Ｇｅ₃，
Ｇｅ₃₁Ｖ₁₇，Ｇｅ₈Ｖ₁₁，Ｇｅ₃Ｖ₅，ＧｅＶ₃，Ｖ₅Ｔｅ₄，Ｖ₃Ｔｅ₄，ＺｎＴｅ，Ａｇ₂Ｓｅ，Ｃｕ₂Ｓｅ，Ａｌ₂Ｓｅ₃，ＩｎＡｓ，ＣｏＳｅ，Ｍｎ₃Ｉｎ，
Ｎｉ₃Ｉｎ，ＮｉＩｎ，Ｎｉ₂Ｉｎ₃，Ｎｉ₃Ｉｎ₇，ＰｂＳｅ，
上記高融点成分の構成元素の酸化物のうち高融点のもの、
などの高融点化合物、またはそれに近い組成のもの、あるいはこれらの混合組成や混合組成に近い３元以上の化合物のうちの少なくとも一つで置き換えても、同様の結果が得られる。 In the case where Cr is replaced with Cu, that is, in the In—Sb—Te—Cu system, the same result is obtained when the ratio (p / x) of the In content p and the Sb content x is similarly changed. Obtained.
(Other examples of phase change components)
Part of In ₃ SbTe ₂ , which is a phase change component, is converted to Ge ₂ Sb ₂ Te ₅ , GeSb ₄ Te ₇ , GeSb ₂ Te ₄ , In ₃₅ Sb ₃₂ Te ₃₃ ,
In ₃₁ Sb ₂₆ Te ₄₃
Even if it is replaced with at least one of them, or if part of In is replaced with Ge, similar characteristics can be obtained.
(Other examples of high melting point components)
A part of Cr ₄ Te ₅ which is a high melting point component is converted into LaTe ₃ , LaTe ₂ , La ₂ Te ₃ , La ₃ Te ₄ , LaTe, La ₂ Te ₅ ,
LaSb, La ₄ Te ₇ , La ₃ Te, La ₂ Sb, La ₃ Sb ₂ , LaSb ₂ ,
La ₃ Ge, La ₅ Ge ₃ , La ₄ Ge ₃ , La ₅ Ge ₄ , LaGe, La ₃ Ge ₅ ,
Ag ₂ Te, Cr ₅ Te ₈ , Cr ₂ Te ₃ , CrSb, Cr ₃ Ge, Cr ₅ Ge ₃ ,
Cr ₁₁ Ge ₈ , CrGe, Cr ₁₁ Ge ₁₉ , PtTe ₂ , Pt ₄ Te ₅ , Pt ₅ Te ₄ , Pt ₄ Sb, Pt ₃ Sb ₂ , PtSb, Pt ₃ Ge, Pt ₂ Ge, Pt ₃ Ge ₂ ,
PtGe, Pt ₂ Ge ₃ , PtGe ₃ , NiTe, NiTe _0.85 , NiSb,
_{_{_{Ni 3 Ge, Ni 5 Ge 2}}} , Ni 5 Ge 3, NiGe, CoTe 2, CoSb 2,
CoSb ₃ , Co ₅ Ge ₂ , Co ₅ Ge ₃ , CoGe, Co ₅ Ge ₇ , CoGe ₂ ,
Si ₂ Te ₃ , SiSb, SiGe, CeTe, Ce ₃ Te ₄ , Ce ₂ Te ₃ ,
Ce ₄ Te ₇ , CeTe ₂ , CeTe ₃ , Ce ₂ Sb, Ce ₅ Sb ₃ , Ce ₄ Sb ₅ ,
_{_{CeSb, CeSb 2, Ce 3 Ge}} , Ce 5 Ge 3, Ce 4 Ge 3, Ce 5 Ge 4,
CeGe, Ce ₃ Ge ₅ , Ce ₅ Si ₃ , Ce ₃ Si ₂ , Ce ₅ Si ₄ , CeSi,
Ce ₃ Si ₅ , CeSi ₂ , Cr ₃ Si, Cr ₅ Si ₃ , CrSi, CrSi ₃ ,
CrSi ₂ , Co ₃ Si, CoSi, CoSi ₂ , NiSi ₂ , NiSi,
Ni ₃ Si ₂ , Ni ₂ Si, Ni ₅ Si ₂ , Ni ₃ Si, Pt ₅ Si ₂ , Pt ₂ Si,
PtSi, LaSi ₂ , Ag ₃ In, Ag ₂ In, Bi ₂ Ce, BiCe,
_{_{_{Bi 3 Ce 4, Bi 3 Ce}}} 5, BiCe 2, Cd 11 Ce, Cd 6 Ce, Cd 58 Ce 13, Cd 3 Ce, Cd 2 Ce, CdCe, Ce 3 In, Ce 2 In, Ce 1 + x In,
Ce ₃ In ₅ , CeIn ₂ , CeIn ₃ , Ce ₂ Pb, CePb, CePb ₃ ,
Ce ₃ Sn, Ce ₅ Sn ₃ , Ce ₅ Sn ₄ , Ce ₁₁ Sn ₁₀ , Ce ₃ Sn ₅ ,
Ce ₃ Sn ₇ , Ce ₂ Sn ₅ , CeSn ₃ , CeZn, CeZn ₂ , CeZn ₃ ,
Ce ₃ Zn ₁₁ , Ce ₁₃ Zn ₅₈ , CeZn ₅ , Ce ₃ Zn ₂₂ , Ce ₂ Zn ₁₇ ,
CeZn ₁₁ , Cd ₂₁ Co ₅ , CoGa, CoGa ₃ , CoSn, Cr ₃ Ga,
_{_{CrGa, Cr 5 Ga 6, CrGa}} 4, Cu 9 Ga 4, Cu 3 Sn, Cu 3 Zn,
Bi ₂ La, BiLa, Bi ₃ La ₄ , Bi ₃ La ₅ , BiLa ₂ , Cd ₁₁ La,
Cd ₁₇ La ₂ , Cd ₉ La ₂ , Cd ₂ La, CdLa, Ga ₆ La, Ga ₂ La,
_{_{GaLa, Ga 3 La 5, GaLa}} 3, In 3 La, In 2 La, In 5 La 3,
In _x La, InLa, InLa ₂ , InLa ₃ , La ₅ Pb ₃ , La ₄ Pb ₃ ,
La ₁₁ Pb ₁₀ , La ₃ Pb ₄ , La ₅ Pb ₄ , LaPb ₂ , LaPb ₃ , LaZn,
LaZn ₂ , LaZn ₄ , LaZn ₅ , La ₃ Zn ₂₂ , La ₂ Zn ₁₇ , LaZn ₁₁ , LaZn ₁₃ , NiBi, Ga ₃ Ni ₂ , GaNi, Ga ₂ Ni ₃ , Ga ₃ Ni ₅ ,
GaNi ₃ , Ni ₃ Sn, Ni ₃ Sn ₂ , Ni ₃ Sn ₄ , NiZn, Ni ₅ Zn ₂₁ ,
PtBi, PtBi ₂ , PtBi ₃ , PtCd ₂ , Pt ₂ Cd ₉ , Ga ₇ Pt ₃ ,
Ga ₂ Pt, Ga ₃ Pt ₂ , GaPt, Ga ₃ Pt ₅ , GaPt ₂ , GaPt ₃ ,
In ₇ Pt ₃ , In ₂ Pt, In ₃ Pt ₂ , InPt, In ₅ Pt ₆ , In ₂ Pt ₃ ,
InPt ₂ , InPt ₃ , Pt ₃ Pb, PtPb, Pt ₂ Pb ₃ , Pt ₃ Sn,
_{_{PtSn, Pt 2 Sn 3, PtSn}} 2, PtSn 4, Pt 3 Zn, PtZn 2,
_{_{AlS, Al 2 S 3, BaS}} , BaC 2, CdS, Co 4 S 3, Co 9 S 8, CoS, CoO, Co 2 O 4, Co 2 O 3, Cr 2 O 3, Cr 3 O 4, CrO, _{CrS, CrN, Cr 2 N,} Cr 23 C 63, Cr 7 C 3, Cr 3 C 2, Cu 2 S, Cu 9 S 5, CuO,
Cu ₂ O, In ₄ S ₅ , In ₃ S ₄ , La ₂ S ₃ , La ₂ O ₃ , Mo ₂ C, MoC,
Mn ₂₃ C ₆ , Mn ₄ C, Mn ₇ C ₃ , NiO, SiS ₂ , SiO ₂ , Si ₃ N ₄ ,
Cu ₂ Te, CuTe, Cu ₃ Sb, Mn ₂ Sb, MnTe, MnTe ₂ ,
Mn ₅ Ge ₃ , Mn _3.25 Ge, Mn ₅ Ge ₂ , Mn ₃ Ge ₂ , Ge ₃ W, Te ₂ W,
AlSb, Al ₂ Te ₃ , Fe ₂ Ge, FeGe ₂ , FeSb ₂ , Mo ₃ Sb ₇ ,
Mo ₃ Te ₄ , MoTe ₂ , PbTe, GePd ₂ , Ge ₂ Pd ₅ , Ge ₉ Pd ₂₅ ,
GePd ₅ , Pd ₃ Sb, Pd ₅ Sb ₃ , PdSb, SnTe, Ti ₅ Ge ₃ ,
Ge ₃₁ V ₁₇ , Ge ₈ V ₁₁ , Ge ₃ V ₅ , GeV ₃ , V ₅ Te ₄ , V ₃ Te ₄ , ZnTe, Ag ₂ Se, Cu ₂ Se, Al ₂ Se ₃ , InAs, CoSe, Mn ₃ In ,
Ni ₃ In, NiIn, Ni ₂ In ₃ , Ni ₃ In ₇ , PbSe,
Among the oxides of the constituent elements of the high melting point component, those having a high melting point,
Similar results can be obtained by replacing the compound with a high melting point compound such as the above, or a compound having a composition close thereto, or a mixture thereof or at least one of compounds having three or more elements close to the mixture composition.

これらのうちで、
ＬａＳｂ，Ｌａ₂Ｔｅ₃，Ｌａ₃Ｔｅ₄，ＣｒＳｂ，ＣｏＳｂ，Ｃｒ₃Ｔｅ₄，
Ｃｒ₂Ｔｅ₃，Ｃｒ₃Ｔｅ₄，ＣｏＴｅ，Ｃｏ₃Ｔｅ₄，Ｃｕ₂Ｔｅ，ＣｕＴｅ，
Ｃｕ₃Ｓｂ，ＭｎＴｅ，ＭｎＴｅ₂，Ｍｎ₂Ｓｂ，Ｃｒ₄Ｔｅ₅
のうちの少なくとも一つが特に好ましい。少ない回数の初期結晶化で記録・消去特性が安定するからである。 Of these,
_{_{LaSb, La 2 Te 3, La}} 3 Te 4, CrSb, CoSb, Cr 3 Te 4,
_{_{_{Cr 2 Te 3, Cr 3 Te}}} 4, CoTe, Co 3 Te 4, Cu 2 Te, CuTe,
Cu ₃ Sb, MnTe, MnTe ₂ , Mn ₂ Sb, Cr ₄ Te ₅
At least one of them is particularly preferred. This is because the recording / erasing characteristics are stabilized by a small number of initial crystallizations.

この実施例においても、析出する高融点成分３ｂは化合物でもよいし、元素単体や合金でもよい。
（高融点成分の含有物の量）
実施例１と同様に、高融点成分の析出物に含まれる酸化物、硫化物、窒化物、炭化物の含有量は、高融点成分の４０原子％未満とするのが好ましく、１０原子％未満とするのが特に好ましい。これらの含有量が多いと、相変化成分との複素屈折率の差を小さくできなかったり、相変化成分中に酸素等が拡散して記録・再生特性を劣化させたりする問題を生じやすい。 Also in this embodiment, the precipitated high melting point component 3b may be a compound, a simple element or an alloy.
(Amount of high melting point component)
As in Example 1, the content of oxides, sulfides, nitrides, and carbides contained in the precipitate of the high melting point component is preferably less than 40 at% of the high melting point component, and preferably less than 10 at%. It is particularly preferred to do so. If the content of these components is large, a problem that the difference in the complex refractive index from the phase change component cannot be reduced or oxygen or the like diffuses into the phase change component to deteriorate the recording / reproducing characteristics easily occurs.

なお、ここで述べていない事項は、実施例１と同様である。
〔実施例３〕
実施例１のＳｂ−Ｔｅ−Ｇｅ−Ｃｒ系の記録膜５において、前記一般式でＢまたはＸで表される元素として、Ｃｒに代えてＣｏおよびＳｉを含む
Ｓｂ₁₆Ｔｅ₃₉Ｇｅ₁₅Ｃｏ₂₂Ｓｉ₈すなわち
（Ｃｏ₃Ｓｉ）₂₇（Ｇｅ₂Ｓｂ₂Ｔｅ₅）₂₈により記録膜５を形成した点以外は、実施例１と同様にして、情報記録用薄膜を製作した。また、当該薄膜の初期結晶化と、その後の情報の記録・再生方法も実施例１と同様とした。 Note that items not described here are the same as in the first embodiment.
[Example 3]
In the Sb-Te-Ge-Cr recording film 5 of Example 1, Sb ₁₆ Te ₃₉ Ge ₁₅ Co ₂₂ Si containing Co and Si instead of Cr as the element represented by B or X in the above general formula. _8, that is, an information recording thin film was manufactured in the same manner as in Example 1 except that the recording film 5 was formed of (Co ₃ Si) ₂₇ (Ge ₂ Sb ₂ Te ₅ ) ₂₈ . The method of initial crystallization of the thin film and the subsequent recording / reproducing method of the information were the same as in the first embodiment.

この実施例では、高融点成分はＣｏ₃Ｓｉ、相変化成分はＧｅ₂Ｓｂ₂Ｔｅ₅である。 In this embodiment, the high melting point component is Co ₃ Si, and the phase change component is Ge ₂ Sb ₂ Te ₅ .

Ｓｂ対Ｔｅ対Ｇｅの含有量ｘ，ｙ，ｐの比をｘ：ｙ：ｐ＝２：５：２に保ってＣｏ₃Ｓｉの含有量ａ（実施例１のａに対応）を変化させたとき、書き換え可能回数と、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎの変化は、実施例１と同様であった。
（相変化成分の他の例）
相変化成分であるＧｅ₂Ｓｂ₂Ｔｅ₅の一部または全部を
ＧｅＳｂ₄Ｔｅ₇、ＧｅＳｂ₂Ｔｅ₄，Ｉｎ₃ＳｂＴｅ₂，Ｉｎ₃₅Ｓｂ₃₂Ｔｅ₃₃，
Ｉｎ₃₁Ｓｂ₂₆Ｔｅ₄₃
のうちの少なくとも一つで置き換えても、Ｇｅの一部または全部をＩｎに置き換えても近い特性が得られる。
（高融点成分の他の例）
高融点成分であるＣｏ₃Ｓｉの一部または全部を
Ｃｅ₅Ｓｉ₃，Ｃｅ₃Ｓｉ₂，Ｃｅ₅Ｓｉ₄，ＣｅＳｉ，Ｃｅ₃Ｓｉ₅，ＣｅＳｉ₂，
Ｃｒ₅Ｓｉ₃，ＣｒＳｉ，ＣｒＳｉ₃，ＣｒＳｉ₂，Ｃｒ₃Ｓｉ，ＣｏＳｉ，
ＣｏＳｉ₂，ＮｉＳｉ₂，ＮｉＳｉ，Ｎｉ₃Ｓｉ₂，Ｎｉ₂Ｓｉ，Ｎｉ₅Ｓｉ₂，
Ｎｉ₃Ｓｉ，Ｐｔ₅Ｓｉ₂，Ｐｔ₂Ｓｉ，ＰｔＳｉ，ＬａＳｉ₂，Ｂｉ₂Ｃｅ，
ＢｉＣｅ，Ｂｉ₃Ｃｅ₄，Ｂｉ₃Ｃｅ₅，ＢｉＣｅ₂，Ｃｄ₁₁Ｃｅ，Ｃｄ₆Ｃｅ，
Ｃｄ₅₈Ｃｅ₁₃，Ｃｄ₃Ｃｅ，Ｃｄ₂Ｃｅ，ＣｄＣｅ，Ｃｅ₂Ｐｂ，ＣｅＰｂ，
ＣｅＰｂ₃，Ｃｅ₃Ｓｎ，Ｃｅ₅Ｓｎ₃，Ｃｅ₅Ｓｎ₄，Ｃｅ₁₁Ｓｎ₁₀，Ｃｅ₃Ｓｎ₅，Ｃｅ₃Ｓｎ₇，Ｃｅ₂Ｓｎ₅，ＣｅＳｎ₃，ＣｅＺｎ，ＣｅＺｎ₂，ＣｅＺｎ₃，
Ｃｅ₃Ｚｎ₁₁，Ｃｅ₁₃Ｚｎ₅₈，ＣｅＺｎ₅，Ｃｅ₃Ｚｎ₂₂，Ｃｅ₂Ｚｎ₁₇，
ＣｅＺｎ₁₁，Ｃｄ₂₁Ｃｏ₅，ＣｏＧａ，ＣｏＧａ₃，ＣｏＳｎ，Ｃｒ₃Ｇａ，
ＣｒＧａ，Ｃｒ₅Ｇａ₆，ＣｒＧａ₄，Ｃｕ₉Ｇａ₄，Ｃｕ₃Ｓｎ，Ｃｕ₃Ｚｎ，
Ｂｉ₂Ｌａ，ＢｉＬａ，Ｂｉ₃Ｌａ₄，Ｂｉ₃Ｌａ₅，ＢｉＬａ₂，Ｃｄ₁₁Ｌａ，
Ｃｄ₁₇Ｌａ₂，Ｃｄ₉Ｌａ₂，Ｃｄ₂Ｌａ，ＣｄＬａ，Ｇａ₆Ｌａ，Ｇａ₂Ｌａ，
ＧａＬａ，Ｇａ₃Ｌａ₅，ＧａＬａ₃，Ｌａ₅Ｐｂ₃，Ｌａ₄Ｐｂ₃，Ｌａ₁₁Ｐｂ₁₀，Ｌａ₃Ｐｂ₄，Ｌａ₅Ｐｂ₄，ＬａＰｂ₂，ＬａＰｂ₃，ＬａＺｎ，ＬａＺｎ₂，
ＬａＺｎ₄，ＬａＺｎ₅，Ｌａ₃Ｚｎ₂₂，Ｌａ₂Ｚｎ₁₇，ＬａＺｎ₁₁，ＬａＺｎ₁₃，ＮｉＢｉ，Ｇａ₃Ｎｉ₂，ＧａＮｉ，Ｇａ₂Ｎｉ₃，Ｇａ₃Ｎｉ₅，ＧａＮｉ₃，
Ｎｉ₃Ｓｎ，Ｎｉ₃Ｓｎ₂，Ｎｉ₃Ｓｎ₄，ＮｉＺｎ，Ｎｉ₅Ｚｎ₂₁，ＰｔＢｉ，
ＰｔＢｉ₂，ＰｔＢｉ₃，ＰｔＣｄ₂，Ｐｔ₂Ｃｄ₉，Ｇａ₇Ｐｔ₃，Ｇａ₂Ｐｔ，
Ｇａ₃Ｐｔ₂，ＧａＰｔ，Ｇａ₃Ｐｔ₅，ＧａＰｔ₂，ＧａＰｔ₃，Ｐｔ₃Ｐｂ，
ＰｔＰｂ，Ｐｔ₂Ｐｂ₃，Ｐｔ₃Ｓｎ，ＰｔＳｎ，Ｐｔ₂Ｓｎ₃，ＰｔＳｎ₂，
ＰｔＳｎ₄，Ｐｔ₃Ｚｎ，ＰｔＺｎ₂
など、前記Ｂで表わされる元素を２以上含む高融点化合物、またはそれに近い組成のもの、あるいはこれらの混合組成や、混合組成に近い３元以上の化合物のうちの少なくとも一つで置き換えても、同様な結果が得られる。 The content a of Co ₃ Si (corresponding to a in Example 1) was changed while maintaining the ratio of Sb to Te to Ge contents x, y, p at x: y: p = 2: 5: 2. when the number of rewritable times, changes in the C / N of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value the power of the laser light was the same as in example 1.
(Other examples of phase change components)
GeSb ₄ Te ₇ some or all of Ge ₂ Sb ₂ Te ₅ is a phase change _{_{_{component, GeSb 2 Te 4, In 3}}} SbTe 2, In 35 Sb 32 Te 33,
In ₃₁ Sb ₂₆ Te ₄₃
Even if it is replaced with at least one of the above, or even if some or all of Ge is replaced with In, similar characteristics can be obtained.
(Other examples of high melting point components)
Part or all of Co ₃ Si, which is a high melting point component, is converted to Ce ₅ Si ₃ , Ce ₃ Si ₂ , Ce ₅ Si ₄ , CeSi, Ce ₃ Si ₅ , CeSi ₂ ,
Cr ₅ Si ₃ , CrSi, CrSi ₃ , CrSi ₂ , Cr ₃ Si, CoSi,
CoSi ₂ , NiSi ₂ , NiSi, Ni ₃ Si ₂ , Ni ₂ Si, Ni ₅ Si ₂ ,
Ni ₃ Si, Pt ₅ Si ₂ , Pt ₂ Si, PtSi, LaSi ₂ , Bi ₂ Ce,
_{_{BiCe, Bi 3 Ce 4, Bi}} 3 Ce 5, BiCe 2, Cd 11 Ce, Cd 6 Ce,
Cd ₅₈ Ce ₁₃ , Cd ₃ Ce, Cd ₂ Ce, CdCe, Ce ₂ Pb, CePb,
_{_{CePb 3, Ce 3 Sn, Ce}} 5 Sn 3, Ce 5 Sn 4, Ce 11 Sn 10, Ce 3 Sn 5, Ce 3 Sn 7, Ce 2 Sn 5, CeSn 3, CeZn, CeZn 2, CeZn 3,
Ce ₃ Zn ₁₁ , Ce ₁₃ Zn ₅₈ , CeZn ₅ , Ce ₃ Zn ₂₂ , Ce ₂ Zn ₁₇ ,
CeZn ₁₁ , Cd ₂₁ Co ₅ , CoGa, CoGa ₃ , CoSn, Cr ₃ Ga,
_{_{CrGa, Cr 5 Ga 6, CrGa}} 4, Cu 9 Ga 4, Cu 3 Sn, Cu 3 Zn,
Bi ₂ La, BiLa, Bi ₃ La ₄ , Bi ₃ La ₅ , BiLa ₂ , Cd ₁₁ La,
Cd ₁₇ La ₂ , Cd ₉ La ₂ , Cd ₂ La, CdLa, Ga ₆ La, Ga ₂ La,
_{_{GaLa, Ga 3 La 5, GaLa}} 3, La 5 Pb 3, La 4 Pb 3, La 11 Pb 10, La 3 Pb 4, La 5 Pb 4, LaPb 2, LaPb 3, LaZn, LaZn 2,
_{_{_{LaZn 4, LaZn 5, La 3}}} Zn 22, La 2 Zn 17, LaZn 11, LaZn 13, NiBi, Ga 3 Ni 2, GaNi, Ga 2 Ni 3, Ga 3 Ni 5, GaNi 3,
Ni ₃ Sn, Ni ₃ Sn ₂ , Ni ₃ Sn ₄ , NiZn, Ni ₅ Zn ₂₁ , PtBi,
PtBi ₂ , PtBi ₃ , PtCd ₂ , Pt ₂ Cd ₉ , Ga ₇ Pt ₃ , Ga ₂ Pt,
Ga ₃ Pt ₂ , GaPt, Ga ₃ Pt ₅ , GaPt ₂ , GaPt ₃ , Pt ₃ Pb,
_{_{PtPb, Pt 2 Pb 3, Pt}} 3 Sn, PtSn, Pt 2 Sn 3, PtSn 2,
PtSn ₄ , Pt ₃ Zn, PtZn ₂
For example, a high melting point compound containing two or more elements represented by B, or a composition close to the high melting point compound, or a mixed composition thereof, or at least one of ternary or more compounds close to the mixed composition, Similar results are obtained.

ここで述べていない事項については、実施例１と同様である。
〔実施例４〕
（構成・製法）
図３は、この発明の第１実施例の情報記録用薄膜を用いたディスク状情報記録媒体の断面構造を示す。この媒体は次のようにして製作された。 Matters not described here are the same as in the first embodiment.
[Example 4]
(Structure and manufacturing method)
FIG. 3 shows a sectional structure of a disc-shaped information recording medium using the information recording thin film according to the first embodiment of the present invention. This medium was manufactured as follows.

まず、直径１３ｃｍ，厚さ１．２ｍｍで表面に断面Ｕ字形のトラッキング溝を有するポリカーボネート基板１を形成した。次に、この基板１上に順次、薄膜を形成するため、基板１をマグネトロン・スパッタリング装置内に置いた。この装置は複数のターゲットを持ち、積層膜を順次、形成することができるものである。また、形成される膜厚の均一性および再現性に優れている。 First, a polycarbonate substrate 1 having a diameter of 13 cm, a thickness of 1.2 mm, and a tracking groove having a U-shaped cross section on the surface was formed. Next, the substrate 1 was placed in a magnetron sputtering apparatus in order to form a thin film on the substrate 1 sequentially. This apparatus has a plurality of targets and can sequentially form a stacked film. Further, the film thickness is excellent in uniformity and reproducibility.

マグネトロン・スパッタリング装置により、基板１上にまず
（ＺｎＳ）８０％・（ＳｉＯ₂）２０％、すなわち（Ｚｎ₄₀Ｓ₄₀Ｓｉ₇Ｏ₁₃）膜よりなる保護層２を膜厚約１３０ｎｍとなるように形成した。続いて、保護層２上に、高融点成分であるＣｒ₄Ｔｅ₅膜（図示せず）を島状に平均膜厚３ｎｍまで形成した後、その上にＣｒ₉Ｇｅ₇Ｓｂ₂₇Ｔｅ₅₇、すなわち（（ＧｅＳｂ₄Ｔｅ₇）₈
（Ｃｒ₄Ｔｅ₅）₂）の組成の記録膜３を膜厚約２２ｎｍまで形成した。この際、Ｃｒ₄Ｔｅ₅ターゲットとＧｅＳｂ₄Ｔｅ₇ターゲットとによる回転同時スパッタ法を用いた。 First, a protective layer 2 made of (ZnS) 80% / (SiO ₂ ) 20%, that is, a (Zn ₄₀ S ₄₀ Si ₇ O ₁₃ ) film is formed on the substrate 1 by a magnetron sputtering apparatus so as to have a film thickness of about 130 nm. Formed. Subsequently, a Cr ₄ Te ₅ film (not shown), which is a high melting point component, is formed in an island shape to an average film thickness of 3 nm on the protective layer 2, and then Cr ₉ Ge ₇ Sb ₂₇ Te ₅₇ , that is, ((GeSb ₄ Te ₇ ) ₈
A recording film 3 having a composition of (Cr ₄ Te ₅ ) ₂ ) was formed to a thickness of about 22 nm. At this time, a simultaneous rotation sputtering method using a Cr ₄ Te ₅ target and a GeSb ₄ Te ₇ target was used.

Ｃｒ₄Ｔｅ₅膜は必ずしも形成する必要はない。しかし、その場合記録膜流動がやや起こりやすくなる。Ｃｒ₄Ｔｅ₅膜を形成しない場合、記録膜３中に析出する高融点成分は、後述する初期化の際に生じるもののみとなる。 It is not always necessary to form the Cr ₄ Te ₅ film. However, in this case, the recording film flow is slightly likely to occur. When the Cr ₄ Te ₅ film is not formed, only the high melting point component precipitated in the recording film 3 is generated at the time of initialization described later.

次に、記録膜３上に、（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層４を約４０ｎｍの膜厚まで形成した後、その上に同じスパッタリング装置内で
Ａｌ₉₇Ｔｉ₃膜よりなる反射層５を膜厚２００ｎｍまで形成した。こうして、第１のディスク部材を得た。 Next, an intermediate layer 4 made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film is formed on the recording film 3 to a thickness of about 40 nm, and then an Al ₉₇ Ti ₃ film is formed thereon in the same sputtering apparatus. The reflective layer 5 was formed to a thickness of 200 nm. Thus, a first disk member was obtained.

他方、まったく同様の方法により、第１のディスク部材と同じ構成を持つ第２のディスク部材を得た。第２のディスク部材は、直径１３ｃｍ，厚さ１．２ｍｍの基板１’上に順に積層された、膜厚約１３０ｎｍの
（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる保護層２’、平均膜厚３ｎｍの
Ｃｒ₄Ｔｅ₅膜（図示せず）、膜厚約２２ｎｍのＣｒ₉Ｇｅ₇Ｓｂ₂₇Ｔｅ₅₇、すなわち（（ＧｅＳｂ₄Ｔｅ₇）₈（Ｃｒ₄Ｔｅ₅）₂）の記録膜３’、膜厚約４０ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層４’、および膜厚２００ｎｍのＡｌ₉₇Ｔｉ₃膜よりなる反射層５’を備えている。 On the other hand, a second disk member having the same configuration as the first disk member was obtained by exactly the same method. The second disk member is composed of a protective layer 2 ′ composed of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 130 nm and an average film, which are sequentially laminated on a substrate 1 ′ having a diameter of 13 cm and a thickness of 1.2 mm. 3 nm thick Cr ₄ Te ₅ film (not shown), about 22 nm thick Cr ₉ Ge ₇ Sb ₂₇ Te ₅₇ , ie, ((GeSb ₄ Te ₇ ) ₈ (Cr ₄ Te ₅ ) ₂ ) recording film 3 ′ An intermediate layer 4 'made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 40 nm, and a reflective layer 5' made of an Al ₉₇ Ti ₃ film having a thickness of 200 nm.

その後、接着剤層６を介して、前記第１および第２のディスク部材の反射層５，５’同士を貼り合わせ、図３に示すディスク状情報記録媒体を得た。 Thereafter, the reflective layers 5, 5 'of the first and second disk members were bonded together via the adhesive layer 6, to obtain a disk-shaped information recording medium shown in FIG.

この媒体では、反射層５，５’の全面を接着すると、全面を接着しない場合に比べて書き換え可能回数を多くすることができ、また、反射層５，５’の記録領域に対応する箇所に接着剤を付けない場合、その箇所にも接着剤を付けた場合よりも少し記録感度が高くなった。
（初期化）
前記のようにして製作した媒体の記録膜３、３’に、次のようにして初期化を行なった。なお、記録膜３’についてもまったく同様であるから、以下の説明では記録膜３についてのみ述べることとする。 In this medium, when the entire surfaces of the reflective layers 5, 5 'are adhered, the number of rewritable times can be increased as compared with the case where the entire surfaces are not adhered. When no adhesive was applied, the recording sensitivity was slightly higher than when the adhesive was also applied to that portion.
(Initialize)
The recording films 3, 3 'of the medium manufactured as described above were initialized as follows. Note that the recording film 3 'is completely the same, so that only the recording film 3 will be described below.

媒体を１８００ｒｐｍで回転させ、半導体レーザ（波長８３０ｎｍ）のレーザ光パワーを記録が行なわれないレベル（約１ｍＷ）に保ち、そのレーザ光を記録ヘッド中の開口数（ＮＡ）がＯ．５５のレンズで集光し、基板１を通して記録膜３に照射した。記録膜３からの反射光を検出して、基板１のトラッキング溝の中心または溝と溝の中間にレーザ光スポットの中心が常に一致するようにトラッキングを行なうと共に、記録膜３上にレーザ光の焦点が来るように、自動焦点合わせを行ないながら記録ヘッドを駆動した。 The medium is rotated at 1800 rpm, the laser light power of the semiconductor laser (wavelength 830 nm) is maintained at a level (about 1 mW) at which recording is not performed, and the laser light is emitted at a numerical aperture (NA) in the recording head of O.D. The light was condensed by 55 lenses and irradiated on the recording film 3 through the substrate 1. The reflected light from the recording film 3 is detected and tracking is performed so that the center of the laser beam spot always coincides with the center of the tracking groove of the substrate 1 or the center of the groove. The recording head was driven while performing automatic focusing so that the focus came.

まず、初期化のため、記録膜５の同一記録トラック上に、パワー１５ｍＷの連続（ＤＣ）レーザ光を２００回照射した。各回の照射時間（光スポット通過時間）は、約０．１μｓｅｃである。 First, a continuous (DC) laser beam having a power of 15 mW was irradiated 200 times on the same recording track of the recording film 5 for initialization. Each irradiation time (light spot passing time) is about 0.1 μsec.

続いて、パワー７ｍＷの連続レーザ光を５回照射した。各回の照射時間（光スポット通過時間）は、約０．１μｓｅｃである。この時のレーザ光パワーは５〜９ｍＷの範囲であればよい。 Subsequently, continuous laser light having a power of 7 mW was irradiated five times. Each irradiation time (light spot passing time) is about 0.1 μsec. The laser light power at this time may be in the range of 5 to 9 mW.

前記２種類のレーザ光照射のうち、パワーの低い方（７ｍＷ）の照射は省略してもよいが、照射した方が消去特性が良い。 Of the two types of laser light irradiation, the irradiation with the lower power (7 mW) may be omitted, but the irradiation has better erasing characteristics.

このように、パワーの異なるレーザ光を照射すると、初期化を充分に行なうことができる。 When the laser beams having different powers are irradiated as described above, the initialization can be sufficiently performed.

次に、円形スポットの１２ｍＷの連続レーザ光（初期化用の高パワー光）を１回照射する（照射時間：約０．１μｓｅｃ）毎に、パワー１５ｍＷのパルス・レーザ光（記録用の高パワー光）を照射し、記録膜５を非晶質化して記録点を形成した。その後、その記録点を７ｍＷの連続レーザ光（消去用の低パワー光）を照射して結晶化させるために、７ｍＷの連続レーザ光を何回照射することが必要かを調べた。 Next, each time a circular spot of 12 mW continuous laser light (high power light for initialization) is irradiated (irradiation time: about 0.1 μsec), a pulse laser light of 15 mW power (high power for recording) is applied. The recording film 5 was made amorphous by irradiating the recording film 5 with light (light). Then, it was examined how many times a continuous laser beam of 7 mW was required to irradiate the recording point with a continuous laser beam of 7 mW (low-power light for erasing) for crystallization.

本実施例のディスクでは、１２ｍＷの連続レーザ光の照射回数が１００回までは、照射回数が増加するほど、結晶化に要する前記７ｍＷの連続レーザ光照射の回数は低下した。すなわち、照射回数が増加するほど結晶化しやすいことが分かった。これは、１２ｍＷの連続レーザ光の照射により、記録膜５中に高融点成分であるＣｒ₄Ｔｅ₅の微細な結晶が多数析出し、その残部（相変化する部分）の組成が高速結晶化可能なＧｅＳｂ₄Ｔｅ₇の組成に近づいたためと推察される。 In the disk of this example, up to 100 continuous laser beam irradiations of 12 mW, as the number of irradiations increased, the number of continuous laser beam irradiations of 7 mW required for crystallization decreased. That is, it was found that crystallization was more likely as the number of irradiations increased. This is because a large number of fine crystals of Cr ₄ Te ₅ , which is a high melting point component, are precipitated in the recording film 5 by irradiating a continuous laser beam of 12 mW, and the composition of the remaining portion (phase change portion) can be crystallized at high speed. It is presumed that the composition approached the composition of GeSb ₄ Te ₇ .

一方、マークエッジ記録方式の信号を想定して、１６Ｔ（１Ｔは４５ｎｓ）の範囲で記録トラック上の信号書き始め位置をランダムにずらしながら２Ｔの記録マークと８Ｔのスペースの繰り返しに対応する信号Ａと、８Ｔの記録マークと２Ｔのスペースの繰り返しに対応する信号Ｂとが交互に繰り返す信号を記録する場合、信号Ａと信号Ｂとの切り変え部分ではマーク形成頻度が急に大きく変化するので、記録膜が流動すると、流動して来た記録膜材料が止められて堆積したり、後方からの流入なしに記録膜材料が流出して膜厚が薄くなったりするため、再生信号波形歪みが生ずる。記録膜中の元素が偏析する場合も、同様にその元素が対積したり不足したりする。流動や偏析はある程度起こると膜厚や濃度の勾配によって逆の流動や偏析も起こりやすくなり、ブレーキがかかる。従って、ディスクの使用前に記録領域より少し広めに高いパワー（１５ｍＷ）連続光を繰り返し照射しておくと、上記のような記録領域内での変化はある程度防止できる。従って、ディスク毎に上記の信号の多数回書き換えによる波形歪みの大きさを指標にして、上記の連続光の繰り返し照射必要回数を求めた。上記のように、結晶化速度が十分大きくなるための照射の必要回数と、波形歪みが小さくなるための照射の必要回数の大きい方がそのディスクの初期化必要回数である。本実施例のディスクでは結晶化速度が十分大きくなるための必要回数の方が大きく、１００回が必要初期化照射回数であった。 On the other hand, assuming a signal of the mark edge recording method, the signal A corresponding to the repetition of the recording mark of 2T and the space of 8T while randomly shifting the signal writing start position on the recording track within the range of 16T (1T is 45 ns). In the case of recording a signal in which a recording mark of 8T and a signal B corresponding to the repetition of a space of 2T are alternately recorded, the mark formation frequency sharply changes greatly at a switching portion between the signal A and the signal B. When the recording film flows, the flowing recording film material is stopped and deposited, or the recording film material flows out without flowing in from the rear and the film thickness becomes thin, so that a reproduced signal waveform distortion occurs. . When an element in the recording film segregates, the element accumulates or runs short. When flow and segregation occur to some extent, reverse flow and segregation are likely to occur due to the gradient of film thickness and concentration, and the brake is applied. Therefore, by repeatedly irradiating high power (15 mW) continuous light slightly wider than the recording area before using the disc, such a change in the recording area as described above can be prevented to some extent. Therefore, the required number of continuous irradiations of the continuous light was calculated using the magnitude of the waveform distortion caused by rewriting the signal many times for each disk as an index. As described above, the required number of irradiations for sufficiently increasing the crystallization speed and the larger required number of irradiations for reducing the waveform distortion are the required number of times of initialization of the disk. In the disk of the present embodiment, the required number of times for the crystallization speed to be sufficiently high was larger, and 100 times was the required number of times of the initialization irradiation.

なお、Ｃｒ₄Ｔｅ₅の融点は１２５２゜Ｃであり、ＧｅＳｂ₄Ｔｅ₇の融点は６０５゜Ｃである。
（Ｇｅ含有量ａとの関係１：−ＧｅＳｂ₄Ｔｅ₇付近）
図１０の三角相図のＧｅ₆₅Ｔｅ₂₅Ｃｒ₁₀とＳｂ₃₀Ｔｅ₆₀Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線ア．上で組成を変化させ、一定速度で昇温した場合の未記録部分の結晶化温度と、初期化のためのレーザ照射回数を測定した。その結果、次のようなデータが得られた。 The melting point of Cr ₄ Te ₅ is 1252 ° C., and the melting point of GeSb ₄ Te ₇ is 605 ° C.
(Relationship with Ge content a 1: around -GeSb ₄ Te ₇ )
Linear A was a constant Cr content connecting Ge ₆₅ Te ₂₅ Cr ₁₀ and Sb ₃₀ Te ₆₀ Cr ₁₀ of the triangular phase diagram of Figure 10. The composition was changed above, and the crystallization temperature of the unrecorded portion when the temperature was raised at a constant rate, and the number of laser irradiations for initialization were measured. As a result, the following data was obtained.

組成結晶化温度レーザ照射回数
Ｓｂ₃₀Ｔｅ₆₀Ｃｒ₁₀ １２０゜Ｃ２００回以下
Ｇｅ₂Ｓｂ₂₉Ｔｅ₅₉Ｃｒ₁₀ １３０゜Ｃ２００回以下
Ｇｅ₄Ｓｂ₂₈Ｔｅ₅₈Ｃｒ₁₀ １５０゜Ｃ２００回以下
Ｇｅ₁₀Ｓｂ₂₅Ｔｅ₅₅Ｃｒ₁₀ １６０゜Ｃ２００回以下
Ｇｅ₁₅Ｓｂ₂₃Ｔｅ₅₂Ｃｒ₁₀ １７０゜Ｃ５００回
Ｇｅ₁₇Ｓｂ₂₂Ｔｅ₅₁Ｃｒ₁₀ １７０゜Ｃ２０００回
Ｇｅ₂₅Ｓｂ₁₈Ｔｅ₄₇Ｃｒ₁₀ １８０゜Ｃ５０００回

この結果より、０．０２≦ａ≦０．１９の範囲において、適当な結晶化温度が得られ、初期化のためのレーザ照射回数を低減することができる。
（Ｓｂ含有量ｂとの関係１：−ＧｅＳｂ₄Ｔｅ₇付近）
図１０の三角相図のＳｂ₄₅Ｔｅ₄₅Ｃｒ₁₀とＧｅ₁₈Ｔｅ₇₂Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線イ．組成を変化させ、一定速度で昇温した場合の結晶化温度と、初期化のためのレーザ照射回数を測定した。その結果、次のようなデータが得られた。 Composition Crystallization temperature Laser irradiation frequency Sb ₃₀ Te ₆₀ Cr ₁₀ 120 ° C. 200 times or less Ge ₂ Sb ₂₉ Te ₅₉ Cr ₁₀ 130 ° C. 200 times or less Ge ₄ Sb ₂₈ Te ₅₈ Cr ₁₀ 150 ° C. 200 times or less Ge ₁₀ Sb Ge ₁₅ Sb ₂₃ Te ₅₂ Cr ₁₀ 170 ゜ C 500 times Ge ₁₇ Sb ₂₂ Te ₅₁ Cr ₁₀ 170 ゜ C 2000 times Ge ₂₅ Sb ₁₈ Te ₄₇ Cr ₁₀ 180 ゜ C 5000 times ₂₅ Te ₅₅ Cr ₁₀ 160 ° C. 200 times or less

From this result, an appropriate crystallization temperature can be obtained in the range of 0.02 ≦ a ≦ 0.19, and the number of laser irradiations for initialization can be reduced.
(Relationship with Sb content b 1: around -GeSb ₄ Te ₇ )
Straight it was a constant Cr content connecting Sb ₄₅ Te ₄₅ Cr ₁₀ and Ge ₁₈ Te ₇₂ Cr ₁₀ of the triangular phase diagram of Figure 10. The crystallization temperature when the composition was changed and the temperature was raised at a constant rate, and the number of laser irradiations for initialization were measured. As a result, the following data was obtained.

組成結晶化温度レーザ照射回数
Ｇｅ₁₇Ｓｂ₂Ｔｅ₇₁Ｃｒ₁₀ ２１０゜Ｃ５０００回
Ｇｅ₁₇Ｓｂ₄Ｔｅ₆₉Ｃｒ₁₀ ２００゜Ｃ１０００回
Ｇｅ₁₄Ｓｂ₁₀Ｔｅ₆₆Ｃｒ₁₀ １８０゜Ｃ５００回
Ｇｅ₁₀Ｓｂ₂₀Ｔｅ₆₀Ｃｒ₁₀ １７０゜Ｃ２００回以下
Ｇｅ₇Ｓｂ₂₆Ｔｅ₅₇Ｃｒ₁₀ １６０゜Ｃ２００回以下
Ｇｅ₅Ｓｂ₃₃Ｔｅ₅₂Ｃｒ₁₀ １５０゜Ｃ２００回以下
Ｇｅ₃Ｓｂ₃₆Ｔｅ₅₁Ｃｒ₁₀ １４０゜Ｃ２００回以下
Ｇｅ₂Ｓｂ₄₀Ｔｅ₄₈Ｃｒ₁₀ １２０゜Ｃ２００回以下

この結果より、０．０４≦ｂ≦０．４の範囲において、適当な結晶化温度が得られ、初期化のためのレーザ照射射回数を低減することができる。
（Ｔｅ含有量ｃとの関係１：−ＧｅＳｂ₄Ｔｅ₇付近）
図１０の三角相図のＳｂ₁₅Ｔｅ₇₅Ｃｒ₁₀とＧｅ₃₀Ｓｂ₆₀Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線（3）上で組成を変化させ、記録されている情報の消去に必要なレーザ光の照射時間と、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号の搬送波対雑音比（Ｃ／Ｎ）の変化を測定した。その結果、次のようなデータが得られた。 Composition Crystallization temperature Laser irradiation frequency Ge ₁₇ Sb ₂ Te ₇₁ Cr ₁₀ 210 ° C. 5000 times Ge ₁₇ Sb ₄ Te ₆₉ Cr ₁₀ 200 ° C. 1000 times Ge ₁₄ Sb ₁₀ Te ₆₆ Cr ₁₀ 180 ° C. 500 times Ge ₁₀ Sb ₂₀ Te ₆₀ Cr ₁₀ 170 ° C 200 times less _{_{_{_{Ge 7 Sb 26 Te 57 Cr 10}}}} 160 ° C 200 times less _{_{_{_{Ge 5 Sb 33 Te 52 Cr 10}}}} 150 ° C 200 times less _{_{_{_{Ge 3 Sb 36 Te 51 Cr 10}}}} 140 ° C 200 hereinafter _{_{_{_{Ge 2 Sb 40 Te 48 Cr 10}}}} 120 ° or less C 200 times times

From this result, an appropriate crystallization temperature can be obtained in the range of 0.04 ≦ b ≦ 0.4, and the number of laser irradiations for initialization can be reduced.
(The relationship between the Te content c 1: -GeSb around ₄ Te ₇₎
The Cr content connecting Sb ₁₅ Te ₇₅ Cr ₁₀ and Ge ₃₀ Sb ₆₀ Cr ₁₀ of the triangular phase diagram of Figure 10 by changing the composition on the straight line (3) which is constant, necessary for erasure of information recorded and irradiation time of the laser beam to measure a change in carrier-to-noise ratio of the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser beam power (C / N). As a result, the following data was obtained.

１０⁵回書き換えた後
組成レーザ光照射時間の再生信号のＣ／Ｎ
Ｇｅ₁₄Ｓｂ₃₆Ｔｅ₄₀Ｃｒ₁₀ ０．５μｓｅｃ４４ｄＢ
Ｇｅ₁₂Ｓｂ₃₃Ｔｅ₄₅Ｃｒ₁₀ ０．２μｓｅｃ４８ｄＢ
Ｇｅ₁₁Ｓｂ₃₁Ｔｅ₄₈Ｃｒ₁₀ ０．１μｓｅｃ５０ｄＢ
Ｇｅ₈Ｓｂ₂₇Ｔｅ₅₅Ｃｒ₁₀ ０．１μｓｅｃ５０ｄＢ
Ｇｅ₅Ｓｂ₂₂Ｔｅ₆₃Ｃｒ₁₀ ０．５μｓｅｃ５０ｄＢ
Ｇｅ₃Ｓｂ₁₉.₅Ｔｅ₆₇.₅Ｃｒ₁₀ １．０μｓｅｃ５０ｄＢ
Ｓｂ₁₅Ｔｅ₇₅Ｃｒ₁₀ ３．０μｓｅｃ５０ｄＢ
この結果より、０．５≦ｃ≦０．７５の範囲において、消去に必要なレーザ光の照射時間を少なくでき、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号の搬送波対雑音比（Ｃ／Ｎ）を良くできる。
（Ｃｒ含有量ｄとの関係１：−ＧｅＳｂ₄Ｔｅ₇付近）
Ｃｒ₄Ｔｅ₅の残部であるＧｅ対Ｓｂ対Ｔｅの含有量ａ，ｂ，ｃの比を、
ａ：ｂ：ｃ＝１：４：７に保ってＣｒ₄Ｔｅ₅の含有量を変化させたとき、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎを測定したところ、Ｃｒの含有量ｄに関して次のような結果が得られた。 After rewriting 10 ⁵ times
Composition C / N of reproduction signal of laser beam irradiation time
Ge ₁₄ Sb ₃₆ Te ₄₀ Cr ₁₀ 0.5 μsec 44 dB
Ge ₁₂ Sb ₃₃ Te ₄₅ Cr ₁₀ 0.2 μsec 48 dB
Ge ₁₁ Sb ₃₁ Te ₄₈ Cr ₁₀ 0.1 μsec 50 dB
Ge ₈ Sb ₂₇ Te ₅₅ Cr ₁₀ 0.1 μsec 50 dB
Ge ₅ Sb ₂₂ Te ₆₃ Cr ₁₀ 0.5 μsec 50 dB
_{_{_{_{Ge 3 Sb 19. 5 Te 67}}}} . 5 Cr 10 1.0μsec 50dB
Sb ₁₅ Te ₇₅ Cr ₁₀ 3.0 μsec 50 dB
From this result, in the range of 0.5 ≦ c ≦ 0.75, can reduce the irradiation time of the laser beam necessary for erasing, after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser beam power Can improve the carrier-to-noise ratio (C / N) of the reproduced signal.
(The relationship between the Cr content d 1: -GeSb around ₄ Te ₇₎
The ratio of the contents a, b, and c of Ge to Sb to Te, which is the balance of Cr ₄ Te ₅ , is
When the content of Cr ₄ Te ₅ was changed while maintaining a: b: c = 1: 4: 7, reproduction after rewriting 10 ⁵ times under severe conditions in which the power of the laser beam was 15% higher than the optimum value When the C / N of the signal was measured, the following results were obtained for the Cr content d.

１０⁵回書換後の再生信号Ｃ／Ｎ
ｄ＝０４２ｄＢ
ｄ＝３４８ｄＢ
ｄ＝１０５０ｄＢ
ｄ＝２０５０ｄＢ
ｄ＝３４４８ｄＢ
Ｃｒの含有量ｄを変化させると、レーザ光のパワーを最適値より１５％高くした厳しい条件で初期化回数を２００回として、信号を１回記録後、１回オーバーライトした時の再生信号の「消去比」は、次のように変化した。
ここで「消去比」とは、すでに記録された信号の上に周波数の異なる別の信号を重ね書きしたときの、重ね書き前後の信号の比をｄＢで表したものである。 10 after ⁵ times of rewriting reproducing signal C / N
d = 0 42 dB
d = 3 48 dB
d = 10 50 dB
d = 20 50 dB
d = 34 48 dB
When the content d of Cr is changed, the number of times of initialization is set to 200 under severe conditions in which the power of the laser beam is increased by 15% from the optimum value, and after the signal is recorded once, the reproduced signal is overwritten once. "Erase ratio" changed as follows.
Here, the "erasing ratio" is a ratio of a signal before and after overwriting when another signal having a different frequency is overwritten on a signal already recorded, expressed in dB.

信号を１回記録後、１回オーバーライト
した時の再生信号の消去比
ｄ＝１０２８ｄＢ
ｄ＝２０２５ｄＢ
ｄ＝３０２５ｄＢ
ｄ＝４０２０ｄＢ
この結果より、Ｃｒの含有量ｄが増加するにつれて、消去比が低下することが分かる。 After recording the signal once, overwriting once
Ratio of the reproduced signal at the time of d = 10 28 dB
d = 20 25 dB
d = 30 25 dB
d = 40 20 dB
From this result, it is understood that the erasing ratio decreases as the Cr content d increases.

この結果より、０．０３≦ｄ≦０．３の範囲において、消去に必要なレーザ光の照射時間を少なくでき、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号の搬送波対雑音比（Ｃ／Ｎ）を良くできる。 From this result, in the range of 0.03 ≦ d ≦ 0.3, possible to reduce the irradiation time of the laser beam necessary for erasing, after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser beam power Can improve the carrier-to-noise ratio (C / N) of the reproduced signal.

記録用薄膜の平均組成を、元素単体または化合物組成の低融点成分Ｌと元素単体または化合物組成の高融点成分Ｈにより
Ｌ_jＨ_k
の式で表わし、その含有量ｋを変化させた場合、結晶化温度とレーザパワーを１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。 The average composition of the recording thin film is determined by the low melting point component L of the elemental or compound composition and the high melting point component H of the elemental or compound composition.
L _j H _k
When represented by the formula, changing the content k of, C / N of the reproduced signal after rewriting 10 ⁵ times under severe conditions in which the crystallization temperature and the laser power increased 15%, were changed as follows .

１０⁵回書き換えた後の
組成再生信号のＣ／Ｎ結晶化温度
(GeSb₄Te₇)₉₅(Cr₄Te₅)₅ ４５ｄＢ１７０℃
(GeSb₄Te₇)₉₀(Cr₄Te₅)₁₀ ４８ｄＢ１７０℃
(GeSb₄Te₇)₈₀(Cr₄Te₅)₂₀ ５０ｄＢ１６０℃
(GeSb₄Te₇)₆₅(Cr₄Te₅)₃₅ ５０ｄＢ１５０℃
(GeSb₄Te₇)₅₀(Cr₄Te₅)₅₀ ５０ｄＢ１３０℃
(GeSb₄Te₇)₄₀(Cr₄Te₅)₆₀ ４９ｄＢ１２０℃
この結果より、２０≦ｋ／（ｊ＋ｋ）≦４０の範囲が好ましいことが分かった。
（成膜時に被着させる高融点成分との関係）
この実施例の情報記録用薄膜を製作する際に、初期の工程で、高融点成分Ｃｒ₄Ｔｅ₅を被着させているが、その高融点成分Ｃｒ₄Ｔｅ₅の平均膜厚ｚを次のように変えると、書き換え可能回数と、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎは、次のように変化した。このＣ／Ｎの変化は、主としてＣレベルの変化によるものである。 10 Composition after rewriting ⁵ times C / N crystallization temperature of reproduced signal
(GeSb ₄ Te ₇ ) ₉₅ (Cr ₄ Te ₅ ) ₅ 45 dB 170 ° C
(GeSb ₄ Te ₇ ) ₉₀ (Cr ₄ Te ₅ ) ₁₀ 48 dB 170 ° C.
(GeSb ₄ Te ₇ ) ₈₀ (Cr ₄ Te ₅ ) ₂₀ 50 dB 160 ° C.
(GeSb ₄ Te ₇ ) ₆₅ (Cr ₄ Te ₅ ) ₃₅ 50 dB 150 ° C.
(GeSb ₄ Te ₇ ) ₅₀ (Cr ₄ Te ₅ ) _{50 50} dB 130 ° C.
(GeSb ₄ Te ₇ ) ₄₀ (Cr ₄ Te ₅ ) ₆₀ 49dB 120 ° C
From these results, it was found that the range of 20 ≦ k / (j + k) ≦ 40 was preferable.
(Relationship with high melting point component to be deposited during film formation)
When manufacturing the information recording thin film of this embodiment, the high melting point component Cr ₄ Te ₅ is deposited in an initial step, and the average film thickness z of the high melting point component Cr ₄ Te ₅ is calculated as follows. in other way, C / N of the reproduced signal after rewriting 10 ⁵ times the number of rewritable times and harsh conditions 15% higher than the optimum value the power of the laser beam is changed as follows. This change in C / N is mainly due to a change in C level.

書き換え可能回数
ｚ＝０ｎｍ５×１０⁴回
ｚ＝１ｎｍ１×１０⁵回
ｚ＝５ｎｍ２×１０⁵回
１０⁵回書き換え後の再生信号のＣ／Ｎ
ｚ＝１ｎｍ４７ｄＢ
ｚ＝５ｎｍ４７ｄＢ
ｚ＝１０ｎｍ４６ｄＢ
ｚ＝２０ｎｍ４０ｄＢ
この結果より、１ｎｍ≦ｚ≦１０ｎｍの範囲が好ましいことが分かった。
（その他，保護層および中間層および反射層材質）
この実施例では、保護層２および中間層４をＺｎＳ−ＳｉＯ₂により形成しているが、ＺｎＳ−ＳｉＯ₂に代えて、Ｓｉ−Ｎ系材料，Ｓｉ−Ｏ−Ｎ系材料，ＳｉＯ₂，ＳｉＯ，ＴｉＯ₂，Ｔａ₂Ｏ₅，Ａｌ₂Ｏ₃，Ｙ₂Ｏ₃，ＣｅＯ，Ｌａ₂Ｏ₃，Ｉｎ₂Ｏ₃，ＧｅＯ，ＧｅＯ₂，ＰｂＯ，ＳｎＯ，ＳｎＯ₂，Ｂｉ₂Ｏ₃，ＴｅＯ₂，ＷＯ₂，ＷＯ₃，Ｓｃ₂Ｏ₃，ＺｒＯ₂などの酸化物，ＴａＮ，ＡｌＮ，Ｓｉ₃Ｎ₄，Ａｌ−Ｓｉ−Ｎ系材料（例えばＡｌＳｉＮ₂）などの窒化物、ＺｎＳ，Ｓｂ₂Ｓ₃，ＣｄＳ，Ｉｎ₂Ｓ₃，Ｇａ₂Ｓ₃，ＧｅＳ，ＳｎＳ₂，ＰｂＳ，Ｂｉ₂Ｓ₃，などの硫化物、ＳｎＳｅ₂，Ｓｂ₂Ｓｅ₃，ＣｄＳｅ，ＺｎＳｅ，Ｉｎ₂Ｓｅ₃，Ｇａ₂Ｓｅ₃，ＧｅＳｅ，ＧｅＳｅ₂，ＳｎＳｅ，ＰｂＳｅ，Ｂｉ₂Ｓｅ₃などのセレン化物、ＣｅＦ₃，ＭｇＦ₂，ＣａＦ₂などの弗化物、あるいはＳｉ，Ｇｅ，ＴｉＢ₂，Ｂ₄Ｃ，Ｂ，Ｃ，または、上記の材料に近い組成のものを用いてもよい。また、これらの混合材料の層やこれらの多重層でもよい。 Number of rewritable times z = 0 nm 5 × 10 ⁴ times z = 1 nm 1 × 10 ⁵ times z = 5 nm 2 × 10 ⁵ times
105 C / N of playback signal after rewriting ⁵ times
z = 1 nm 47 dB
z = 5nm 47dB
z = 10 nm 46 dB
z = 20 nm 40 dB
From this result, it was found that the range of 1 nm ≦ z ≦ 10 nm was preferable.
(Other materials for protective layer, intermediate layer and reflective layer)
In this embodiment, the protective layer 2 and the intermediate layer 4 is formed by ZnS-SiO _2, instead of the ZnS-SiO _2, Si-N-based material, SiO-N based material, SiO _2, SiO _{_{_{, TiO 2, Ta 2 O 5}}} , Al 2 O 3, Y 2 O 3, CeO, La 2 O 3, In 2 O 3, GeO, GeO 2, PbO, SnO, SnO 2, Bi 2 O 3, TeO 2 _{_{, WO 2, WO 3, Sc}} 2 O 3, oxides such as _{ZrO 2, TaN, AlN, Si} 3 N 4, Al-Si-N material (e.g., AlSiN ₂₎ nitride such as, ZnS, Sb ₂ S _{_{_{3, CdS, in 2 S 3}}} , Ga 2 S 3, GeS, SnS 2, PbS, sulfides such as _{_{_{Bi 2 S 3,, SnSe 2}}} , Sb 2 Se 3, CdSe, ZnSe, in 2 Se 3, Ga 2 _{_{Se 3, GeSe, GeSe 2,}} SnSe, PbSe, a Bi ₂ Se ₃ Selenides, CeF _3, MgF _2, fluorides such as CaF _2, or _{Si, Ge, TiB 2, B} 4 C, B, C, or may be used as a composition close to the above materials. Further, a layer of a mixed material thereof or a multilayer thereof may be used.

多重層の場合、ＺｎＳを７０モル％以上含む材料、例えば（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀と、Ｓｉ，Ｇｅのうちの少なくとも一者を７０原子％以上含む材料、例えばＳｉ、あるいはＳｉの酸化物、例えばＳｉＯ₂との２層膜が好ましい。この場合、記録感度低下を防ぐため、ＺｎＳ−ＳｉＯ₂層の方を記録膜側に設け、その厚さを３ｎｍ以上とする。また、ＳｉＯ₂などの層の低熱膨張係数による記録膜流動抑制効果を発揮させるために、厚さ１０ｎｍ以下が好ましい。この２層膜は保護層２の代わりに設けると好ましいが、中間層４の代わりに設けてもよい。保護層２の代わりとしてはＳｉＯ₂などの層の厚さが５０ｎｍ以上２５０ｎｍ以下が好ましい。中間層の代わりに２層膜を設ける場合は、ＳｉＯ₂層の膜厚は１０ｎｍ以上８０ｎｍ以下が好ましい。これらの２層膜を設けることは、本発明の記録膜を用いる場合だけではなく、他の相変化記録膜を用いる場合にも好ましい。 In the case of a multi-layer, a material containing at least 70 mol% of ZnS, for example, (ZnS) ₈₀ (SiO ₂ ) ₂₀ and a material containing at least one of Si and Ge at 70 at% or more, for example, Si, or oxidation of Si For example, a two-layer film made of a material such as SiO ₂ is preferable. In this case, in order to prevent a decrease in recording sensitivity, the ZnS-SiO ₂ layer is provided on the recording film side, and its thickness is set to 3 nm or more. Further, in order to exhibit the effect of suppressing the flow of the recording film due to the low thermal expansion coefficient of the layer such as SiO ₂ , the thickness is preferably 10 nm or less. This two-layer film is preferably provided in place of the protective layer 2, but may be provided in place of the intermediate layer 4. As a substitute for the protective layer 2, the thickness of a layer such as SiO ₂ is preferably 50 nm or more and 250 nm or less. When a two-layer film is provided instead of the intermediate layer, the thickness of the SiO ₂ layer is preferably from 10 nm to 80 nm. Providing these two-layer films is preferable not only when using the recording film of the present invention but also when using another phase change recording film.

また、ＺｎＳ−ＳｉＯ₂と基板側にＡｕ層を設けた２層膜にすると反射率決定の自由度が増すため、好ましい。このときのＡｕ層の厚さは３０ｎｍ以下が好ましい。Ａｕの代わりにたとえばＡｕ−Ｃｏ，Ａｕ−Ｃｒ、Ａｕ−Ｔｉ，Ａｕ−Ｎｉ，Ａｕ−ＡｇなどＡｕを主成分とする混合材料を用いてもよい。 Further, it is preferable to use a two-layer film in which ZnS—SiO ₂ and an Au layer are provided on the substrate side, since the degree of freedom in determining the reflectance increases. At this time, the thickness of the Au layer is preferably 30 nm or less. Instead of Au, a mixed material containing Au as a main component such as Au-Co, Au-Cr, Au-Ti, Au-Ni, or Au-Ag may be used.

この実施例で反射層５に用いたＡｌ−Ｔｉの代わりに、反射層の材料としては、Ｓｉ−Ｇｅ混合材料が、記録マーク部分の光吸収率を記録マーク以外の部分の光吸収率より小さくできるので、光吸収率差による消え残りを防止でき、さらに書き換え可能回数が低下しない。Ｇｅの含有量は１０原子％以上８０原子％以下が書き換え可能回数が低下が生じにくい。 Instead of Al—Ti used for the reflective layer 5 in this embodiment, as a material for the reflective layer, a Si—Ge mixed material is used so that the light absorptance of the recording mark portion is smaller than the light absorptance of the portion other than the recording mark. Therefore, it is possible to prevent the disappearance due to the difference in the light absorption rate, and the number of rewritable times does not decrease. When the content of Ge is 10 atomic% or more and 80 atomic% or less, the number of rewritable times hardly decreases.

次いで、Ｓｉ−ＳｎまたはＳｉ−Ｉｎ混合材料、あるいはこれら混合材料の２種以上の混合材料でも同様の結果が得られた。これらの反射層材料は、本発明の相変化膜ばかりでなく、他の相変化膜を用いる場合の反射層材料として用いても、従来の反射層材料に比べて、書き換え可能回数が低下しない。 Next, similar results were obtained with a Si-Sn or Si-In mixed material or a mixed material of two or more of these mixed materials. Even if these reflective layer materials are used as a reflective layer material when not only the phase change film of the present invention but also other phase change films are used, the number of rewritable times does not decrease as compared with a conventional reflective layer material.

以上述べたように、この実施例の情報記録用薄膜は、記録・再生・消去特性を良好に保ちながら、従来より多数回の書き換えが可能である。また、記録・消去に用いるレーザ光のパワーが低くてよいという利点もある。 As described above, the information recording thin film of this embodiment can be rewritten more times than before while maintaining good recording / reproducing / erasing characteristics. Another advantage is that the power of the laser beam used for recording / erasing may be low.

なお、ここで述べていない事項は、実施例１と同様である。
〔実施例５〕
実施例１のＧｅ−Ｓｂ−Ｔｅ−Ｃｒ系の記録膜５においてＧｅ₅₀Ｔｅ₅₀組成付近の組成Ｇｅ₄₀Ｓｂ₁₀Ｔｅ₄₀Ｃｒ₁₀により記録膜５を形成した。構造は、保護層の下に金属層を１５ｎｍ，保護層を２０ｎｍ、記録膜を２０ｎｍ、中間層を４０ｎｍ，反射層を７０ｎｍ形成した。材料は、金属層と反射層にＡｕを使用した。それ以外は、実施例１と同様にして、情報記録用薄膜を作製した。また、当該薄膜の初期化と、その後の情報の記録再生方法も実施例と同様とした。
（Ｓｂ含有量ｂとの関係−２：ＧｅＴｅ組成付近）
図１１の三角相図のＧｅ₄₅Ｔｅ₄₅Ｃｒ₁₀とＳｂ₉₀Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線（4）上で組成を変化させ、非晶質化させた時と結晶化させた時の反射率差を測定した。その結果、次のようなデータが得られた。 Note that items not described here are the same as in the first embodiment.
[Example 5]
To form a recording film 5 by the composition Ge _₄₀ Sb _₁₀ Te ₄₀ Cr ₁₀ near Ge ₅₀ Te ₅₀ composition in Ge-Sb-Te-Cr-based recording film 5 of the first embodiment. The structure was such that a metal layer was 15 nm, a protective layer was 20 nm, a recording film was 20 nm, an intermediate layer was 40 nm, and a reflective layer was 70 nm below the protective layer. Au was used for the metal layer and the reflective layer. Otherwise, in the same manner as in Example 1, an information recording thin film was produced. The method of initializing the thin film and the method of recording / reproducing information thereafter were the same as in the embodiment.
(Relationship with Sb content b-2: around GeTe composition)
The composition was changed on a straight line (4) connecting the Ge ₄₅ Te ₄₅ Cr ₁₀ and Sb ₉₀ Cr ₁₀ with a constant Cr content in the triangular phase diagram of FIG. 11 to change the composition to an amorphous state and a crystallization state. The difference in reflectance at that time was measured. As a result, the following data was obtained.

組成反射率差
Ｇｅ₄₅Ｔｅ₄₅Ｃｒ₁₀ ５０％
Ｇｅ₄₃Ｓｂ₄Ｔｅ₄₃Ｃｒ₁₀ ５１％
Ｇｅ₄₀Ｓｂ₁₀Ｔｅ₄₀Ｃｒ₁₀ ５１％
Ｇｅ₃₇Ｓｂ₁₆Ｔｅ₃₇Ｃｒ₁₀ ４４％
Ｇｅ₃₅Ｓｂ₂₀Ｔｅ₃₅Ｃｒ₁₀ ３０％
これより、ＧｅＴｅ組成付近においては、０≦ｂ≦０．２の範囲で高反射率差が得られることがわかった。Ｓｂを０．０１≦ｂ≦０．２の範囲で添加すると，６０相対湿度８０％におけるクラック発生を防止できた。しかし、Ｓｂを添加しない膜より細かい組成制御が要求される。
（Ｇｅ，Ｔｅ含有量ａ，ｃとの関係−２：ＧｅＴｅ組成付近）
図１１の三角相図のＳｂ₁₀Ｔｅ₈₀Ｃｒ₁₀とＧｅ₈₀Ｓｂ₁₀Ｃｒ₁₀を結ぶＣｒ含有量を一定とした直線（5）上で組成を変化させ、非晶質化させた時と結晶化させた時の反射率差を測定した。その結果、次のようなデータが得られた。 Composition Reflectance difference Ge ₄₅ Te ₄₅ Cr ₁₀ 50%
Ge ₄₃ Sb ₄ Te ₄₃ Cr ₁₀ 51%
Ge ₄₀ Sb ₁₀ Te ₄₀ Cr ₁₀ 51%
Ge ₃₇ Sb ₁₆ Te ₃₇ Cr ₁₀ 44%
Ge ₃₅ Sb ₂₀ Te ₃₅ Cr ₁₀ 30%
From this, it was found that a high reflectance difference was obtained in the range of 0 ≦ b ≦ 0.2 near the GeTe composition. When Sb was added in the range of 0.01 ≦ b ≦ 0.2, it was possible to prevent the occurrence of cracks at 60% relative humidity and 80%. However, finer composition control is required than a film to which Sb is not added.
(Relationship with Ge and Te contents a and c-2: Near GeTe composition)
The composition is changed on a straight line (5) connecting the Sb ₁₀ Te ₈₀ Cr ₁₀ and the Ge ₈₀ Sb ₁₀ Cr ₁₀ in the triangular phase diagram of FIG. The difference in the reflectance at that time was measured. As a result, the following data was obtained.

組成反射率差
Ｇｅ₁₅Ｓｂ₁₀Ｔｅ₆₅Ｃｒ₁₀ ３５％
Ｇｅ₂₀Ｓｂ₁₀Ｔｅ₆₀Ｃｒ₁₀ ４５％
Ｇｅ₂₈Ｓｂ₁₀Ｔｅ₅₂Ｃｒ₁₀ ５０％
Ｇｅ₄₀Ｓｂ₁₀Ｔｅ₄₀Ｃｒ₁₀ ５１％
Ｇｅ₅₂Ｓｂ₁₀Ｔｅ₂₈Ｃｒ₁₀ ４６％
Ｇｅ₆₀Ｓｂ₁₀Ｔｅ₂₀Ｃｒ₁₀ ３６％
これより、ＧｅＴｅ組成付近においては、０．２５≦ａ≦０．６５，０．３５≦ｃ≦０．７５の範囲で高反射率差が得られることがわかった。
（Ｃｒ含有量ｄとの関係−２：ＧｅＴｅ組成付近）
Ｃｒ₄Ｔｅ₅の残部であるＧｅ対Ｓｂ対Ｔｅの含有量ａ，ｂ，ｃの比を、
ａ：ｂ：ｃ＝４：１：４に保ってＣｒ₄Ｔｅ₅の含有量を変化させたとき、レーザ光のパワーを最適値より１５％高くした厳しい条件で１０⁵回書き換えた後の再生信号のＣ／Ｎを測定したところ、Ｃｒの含有量ｄに関して次のような結果が得られた。 Set formed reflectance difference _{_{_{_{Ge 15 Sb 10 Te 65 Cr 10}}}} 35%
Ge ₂₀ Sb ₁₀ Te ₆₀ Cr ₁₀ 45%
Ge ₂₈ Sb ₁₀ Te ₅₂ Cr ₁₀ 50%
Ge ₄₀ Sb ₁₀ Te ₄₀ Cr ₁₀ 51%
_{_{_{_{Ge 52 Sb 10 Te 28 Cr 10}}}} 46%
Ge ₆₀ Sb ₁₀ Te ₂₀ Cr ₁₀ 36%
From this, it was found that a high reflectance difference was obtained in the range of 0.25 ≦ a ≦ 0.65, 0.35 ≦ c ≦ 0.75 near the GeTe composition.
(Relationship with Cr content d-2: around GeTe composition)
The ratio of the contents a, b, and c of Ge to Sb to Te, which is the balance of Cr ₄ Te ₅ , is
When the content of Cr ₄ Te ₅ was changed while maintaining a: b: c = 4: 1: 4, reproduction after rewriting 10 ⁵ times under severe conditions in which the power of the laser beam was 15% higher than the optimum value When the C / N of the signal was measured, the following results were obtained for the Cr content d.

１０⁵回書換後の再生信号Ｃ／Ｎ
ｄ＝０４２ｄＢ
ｄ＝３４８ｄＢ
ｄ＝１０５０ｄＢ
ｄ＝２０５０ｄＢ
ｄ＝３４４８ｄＢ
Ｃｒの含有量ｄを変化させると、レーザ光のパワーを最適値より１５％高くした厳しい条件で初期化回数を２００回として、信号を１回記録後、１回オーバーライトした時の再生信号の「消去比」は、次のように変化した。
ここで「消去比」とはすでに記録された信号の上に周波数の異なる別の信号を重ね書きしたときの、重ね書き前後の信号の比をｄＢで表したものである。 10 after ⁵ times of rewriting reproducing signal C / N
d = 0 42 dB
d = 3 48 dB
d = 10 50 dB
d = 20 50 dB
d = 34 48 dB
When the content d of Cr is changed, the number of times of initialization is set to 200 under severe conditions in which the power of the laser beam is increased by 15% from the optimum value, and after the signal is recorded once, the reproduced signal is overwritten once. "Erase ratio" changed as follows.
Here, the "erase ratio" is a ratio of a signal before and after overwriting when another signal having a different frequency is overwritten on a signal already recorded, expressed in dB.

この結果より、０．０３≦ｄ≦０．３の範囲において、十分高い消去比が得られ、レーザ光パワーを最適値より１５％高くした厳しい条件で１０⁵回書き換え
た後の再生信号の搬送波対雑音比（Ｃ／Ｎ）を良くできる。 From this result, in the range of 0.03 ≦ d ≦ 0.3, a sufficiently high erasing ratio can be obtained, the reproduced signal after rewriting 10 ⁵ times under severe conditions 15% higher than the optimum value of the laser beam power carrier The noise-to-noise ratio (C / N) can be improved.

なお、ここで述べていない事項は、実施例１と同様である。
〔実施例６〕
実施例１の記録膜５において、前記高融点成分が膜厚方向に変化した記録膜を形成した点以外は、実施例１と同様にして情報記録用薄膜を作製した。また、その他は１実施例の用いたディスク状情報記録媒体と同様に作製した。初期化、その後の記録・再生方法も実施例１と同様にした。
（構成・製法）
前記高融点成分の含有量が膜厚方向に変化した記録膜の形成には、マグネトロン・スパッタリング装置による、Ｃｒ₄Ｔｅ₅ターゲットとＧｅＳｂ₄Ｔｅ₇ターゲットとの回転同時スパッタ法を用いた。この際、始めにＣｒ₄Ｔｅ₅膜を３ｎｍ形成しておき、その後次に示すようにＧｅＳｂ₄Ｔｅ₇ターゲットに印加する電圧を一定にし、Ｃｒ₄Ｔｅ₅ターゲットに印加する電圧を徐々に下げていった。
スパッタ時間スパッタパワー（Ｗ）光入射側からの Cr₄Te₅含有量
（秒） GeSb₄Te₇ターゲット Cr₄Te₅ターゲット記録膜膜厚（ｎｍ）（原子％）
０〜９４９１５００〜６５０
１０〜２０４９１００６〜１２４０
２１〜３３４９６５１３〜１８３０
３４〜４７４９４０１９〜２４２０
４８〜６３４９２０２４〜３０１０
この他にも、Ｃｒ₄Ｔｅ₅ターゲットに印加する電圧を一定にし、ＧｅＳｂ₄Ｔｅ₇ターゲットに印加する電圧を徐々に上げていっても、高融点成分の含有量が膜厚方向に変化した記録膜を形成できる。印加電圧は徐々に変化させた方が、記録特性が良かった。また、インラインスパッタ装置において、Ｃｒ₄Ｔｅ₅組成の面積とＧｅＳｂ₄Ｔｅ₇組成の面積を徐々に変化させたタ−ゲットを仕様し同様に作製できる。この記録膜を持つディスクを作製した。 Note that items not described here are the same as in the first embodiment.
[Example 6]
An information recording thin film was prepared in the same manner as in Example 1, except that a recording film in which the high melting point component changed in the film thickness direction was formed in the recording film 5 of Example 1. The others were manufactured in the same manner as the disk-shaped information recording medium used in the first embodiment. The initialization and the subsequent recording / reproducing method were the same as in the first embodiment.
(Structure and manufacturing method)
For the formation of the recording film in which the content of the high melting point component changed in the film thickness direction, a simultaneous rotation sputtering method of a Cr ₄ Te ₅ target and a GeSb ₄ Te ₇ target using a magnetron sputtering apparatus was used. At this time, a Cr ₄ Te ₅ film was formed to a thickness of 3 nm first, and thereafter, the voltage applied to the GeSb ₄ Te ₇ target was made constant, and the voltage applied to the Cr ₄ Te ₅ target was gradually lowered as shown below. Was.
Sputtering time Sputtering power (W) Cr ₄ Te ₅ content from light incident side (sec) GeSb ₄ Te ₇ target Cr ₄ Te ₅ target Recording film thickness (nm) (atomic%)
0-949 150 0-650
10-20 49 100 6-12 40
21-33 49 65 13-18 30
34-47 49 40 19-24 20
48-63 49 20 24-30 10
In addition, even when the voltage applied to the Cr ₄ Te ₅ target is kept constant and the voltage applied to the GeSb ₄ Te ₇ target is gradually increased, the content of the high melting point component changes in the film thickness direction. A film can be formed. The recording characteristics were better when the applied voltage was gradually changed. In an in-line sputtering apparatus, a target in which the area of the composition of Cr ₄ Te _{5 and} the area of the composition of GeSb ₄ Te ₇ are gradually changed can be similarly manufactured by using a target. A disk having this recording film was produced.

このディスクは、実施例１のように高融点成分の含有量が膜厚方向に一定の記録膜に比べ、作製が複雑になるが、初期化のためのレーザ照射回数を低減できた
。 This disc was more complicated to produce than a recording film in which the content of the high melting point component was constant in the film thickness direction as in Example 1, but the number of laser irradiations for initialization could be reduced.

ここで述べていない事項については、実施例１と同様である。
〔実施例７〕
図１２は、本発明による超解像読み出し膜を用いたディスクの構造断面図の一例を示したものである。 Matters not described here are the same as in the first embodiment.
[Example 7]
FIG. 12 shows an example of a structural sectional view of a disk using a super-resolution readout film according to the present invention.

図１２のディスクの製造にあたっては、まず、直径１３ｃｍ、厚さ１．２ｍｍの、凹凸で情報が記録されたポリカ−ボネイト基板１１を形成した。次に、この基板を複数のターゲットを備えて順次積層膜を形成でき、また、膜厚の均一性、再現性のよいマグネトロンスパッタリング装置内に取付け、この基板上に厚さ１２５ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層１２を形成した。続いて、Ｃｒ₄Ｔｅ₅ ターゲットを高周波電源で、ＧｅＳｂ₂Ｔｅ₄ ターゲットを直流電源で同時スパッタして、超解像読み出し膜である（Ｃｒ₄Ｔｅ₅ ）₂₀（ＧｅＳｂ₂Ｔｅ₄ ）₈₀膜１３を３０ｎｍ形成した。次に（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層１４を２０ｎｍ、Ａｌ₉₇Ｔｉ₃ 層１５を１００ｎｍの膜厚に順次積層した。その後、この上に接着層１６を介してポリカーボネイト基板１１’を貼りあわせた。 In manufacturing the disk shown in FIG. 12, first, a polycarbonate substrate 11 having a diameter of 13 cm and a thickness of 1.2 mm, on which information was recorded with irregularities, was formed. Next, the substrate can successively forming a laminated film provided with a plurality of targets, also, the film thickness uniformity, attached to good reproducibility magnetron sputtering in the device, (ZnS) having a thickness of 125nm on the substrate ₈₀ (SiO ₂ ) ₂₀ layer 12 was formed. Subsequently, a Cr ₄ Te ₅ target is sputtered simultaneously with a high-frequency power supply and a GeSb ₂ Te ₄ target is sputtered with a DC power supply, so that a (Cr ₄ Te ₅ ) ₂₀ (GeSb ₂ Te ₄ ) ₈₀ film 13 which is a super-resolution readout film 13 Was formed to a thickness of 30 nm. Next, a (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer 14 and an Al ₉₇ Ti ₃ layer 15 were sequentially laminated to a thickness of 20 nm and 100 nm, respectively. Thereafter, a polycarbonate substrate 11 ′ was bonded thereon via an adhesive layer 16.

一般に、薄膜に光を照射すると、薄膜の表面からの反射光と薄膜の裏面からの反射光との重ね合わせにより干渉が生じる。そこで、超解像読み出し用薄膜の反射率の変化を大きくしたい場合には、薄膜に近接して光を反射する「反射層」を設けることにより、干渉の効果を大きくすることができる。なお、光を吸収する吸収層としてもよい。図１のＡｌ₉₇Ｔｉ₃ 層１５は、この反射層の役割を果たす。 In general, when light is applied to a thin film, interference occurs due to superposition of light reflected from the front surface of the thin film and light reflected from the back surface of the thin film. Therefore, when it is desired to increase the change in the reflectance of the thin film for super-resolution reading, the effect of interference can be increased by providing a "reflection layer" that reflects light close to the thin film. Note that an absorption layer that absorbs light may be used. The Al ₉₇ Ti ₃ layer 15 in FIG. 1 plays the role of this reflection layer.

干渉の効果をより大きくするためには、超解像読み出し用薄膜と反射層の間に「中間層」を設けるのが好ましい。中間層は、超解像読み出し時に超解像読み出し用薄膜と反射層との間で相互拡散が起こるのを防止する作用、及び反射層への熱の逃げを減少させて読み出し感度を高め、また超解像読み出し後に膜を結晶化させる働きがある。図１２の（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層１４はこの中間層の作用をする。 In order to further increase the effect of interference, it is preferable to provide an "intermediate layer" between the super-resolution readout thin film and the reflective layer. The intermediate layer acts to prevent mutual diffusion between the super-resolution readout thin film and the reflective layer during super-resolution readout, and reduces readout of heat to the reflective layer to increase readout sensitivity. It functions to crystallize the film after super-resolution reading. The (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer 14 in FIG. 12 acts as this intermediate layer.

前記超解像読み出し用薄膜１３の少なくとも一方の界面は、他の物質に密着して保護されているのが好ましく、両側の界面が保護されていればさらに好ましい。この保護は、基板により行なってもよいし、基板とは別に形成した保護層により行なってもよい。「保護層」の形成により、超解像読み出し時の薄膜の変形に起因するノイズ増加を防止することができる。図１２の（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀層１２はこの保護層の作用をする。 It is preferable that at least one interface of the thin film for super-resolution reading 13 is closely adhered to another substance and protected, and it is more preferable that both interfaces are protected. This protection may be performed by a substrate or a protection layer formed separately from the substrate. By forming the “protective layer”, it is possible to prevent an increase in noise due to deformation of the thin film during super-resolution reading. The (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer 12 of FIG. 12 functions as this protective layer.

超解像読み出し膜１３の厚さは、図１３に示す結晶化状態と非晶質状態の反射率の測定結果より決定した。図２に示されるように、膜厚が３０ｎｍのとき、結晶化状態の反射率が非晶質状態より大きく、結晶化状態と非晶質状態の反射率差が最大になるため、（Ｃｒ₄Ｔｅ₅ ）₂₀（ＧｅＳｂ₂Ｔｅ₄ ）₈₀膜１３の膜厚は３０ｎｍに設定した。 The thickness of the super-resolution readout film 13 was determined from the measurement results of the reflectance in the crystallized state and the amorphous state shown in FIG. As shown in FIG. 2, when the film thickness is 30 nm, the reflectivity of the crystalline state is larger than the amorphous state, the reflectance difference between the crystalline state and the amorphous state is maximized, (Cr ₄ the film thickness of _{_{_{Te 5) 20 (GeSb 2 Te}}} 4) 80 film 13 was set to 30 nm.

上記のように作製したディスクはまず、次のようにして初期化を行なった。フラッシュ光で、予備結晶化を行なったあとディスクを１８００ｒｐｍで回転させ、半導体レーザの光強度を超解像読み出しが行なわれないレベル（約１ｍＷ）に保ち、記録ヘッド中のレンズで集光して基板１１を通して読み出し膜１３に照射し、反射率を検出することによって、トラッキング用の溝の中心に光スポットの中心が常に一致するようにヘッドを駆動した。このようにトラッキングを行いながら、さらに超解像読み出し膜上に焦点が合うように自動焦点合わせを行い、まず初期結晶化のため、同一トラック上にパワー１１ｍＷの連続レーザ光を５回照射した。この照射パワーは９〜１８ｍＷの範囲でよい。続いて６ｍＷの連続レーザ光を３回照射した。この照射パワーは４〜９ｍＷの範囲でよい。上記２種類の照射は１回以上であればよいが、パワーの高いほうの照射は２回以上がより好ましい。 The disk manufactured as described above was first initialized as follows. After pre-crystallization with flash light, the disk is rotated at 1800 rpm, the light intensity of the semiconductor laser is kept at a level at which super-resolution reading is not performed (about 1 mW), and the light is focused by a lens in the recording head. By irradiating the readout film 13 through the substrate 11 and detecting the reflectance, the head was driven so that the center of the light spot always coincided with the center of the tracking groove. While performing tracking in this manner, automatic focusing was further performed so that the super-resolution readout film was in focus. First, a continuous laser beam having a power of 11 mW was irradiated onto the same track five times for initial crystallization. This irradiation power may be in the range of 9 to 18 mW. Subsequently, a continuous laser beam of 6 mW was irradiated three times. This irradiation power may be in the range of 4 to 9 mW. The above two types of irradiation need only be performed once or more, but the irradiation with the higher power is more preferably performed twice or more.

高融点成分を含む超解像読み出し膜では、Ｃ／Ｎを良くするためには、初期結晶化を十分に行うことが重要である。このため初期結晶化は低パワーでの照射を重点的に行い、同一トラック上にパワー６ｍＷの連続レーザ光を５００回照射し、続いて１１ｍＷの連続レーザ光を３回、６ｍＷの連続レーザ光を１０回照射した。時間がかかるが、６ｍＷ５００回、１１ｍＷ３回のレーザ照射を数回繰り返すと、さらにＣ／Ｎ及び超解像読み出し可能回数が増加した。 In a super-resolution readout film containing a high melting point component, it is important to sufficiently perform initial crystallization in order to improve C / N. For this reason, the initial crystallization is performed mainly by irradiation with low power, and the same track is irradiated with continuous laser light of power 6 mW 500 times, followed by continuous laser light of 11 mW three times and continuous laser light of 6 mW. Irradiated 10 times. Although it takes time, when the laser irradiation of 6 mW 500 times and 11 mW 3 times is repeated several times, the number of times of C / N and super-resolution reading is further increased.

これらの照射は、半導体レーザアレイで行うか、ガスレーザからの光ビームを複数に分割したもの、あるいは高出力ガスレーザや半導体レーザからの光ビームをディスクの半径方向に長く整形した長円ビームで行うと、ディスクの１回転で全てのトラックに対して同時に行うことも可能である。複数の光スポットを同一トラック上に配置せず、ディスクの半径方行に位置を少しずらして配置すれば、広い範囲をイニシャライズすることができ、消え残りが少なくなるなどの効果がある。 These irradiations are performed by using a semiconductor laser array, by dividing a light beam from a gas laser into a plurality of beams, or by using an elliptical beam formed by shaping a light beam from a high-power gas laser or a semiconductor laser into a disk in the radial direction. It is also possible to perform the operation on all tracks simultaneously with one rotation of the disk. If a plurality of light spots are not arranged on the same track but are slightly shifted in the radial direction of the disc, a wide range can be initialized, and there is an effect that the unerased portion is reduced.

また、初期化の最後に、溝間にトラッキングを行いながら連続レーザ光を照射する方法で、トラック周辺部も結晶化を行うと、クロストークを２ｄＢ低減することができた。結晶化にあたっては、パワーを６ｍＷにして連続光の照射を行った。 Also, at the end of the initialization, the crosstalk could be reduced by 2 dB when the track periphery was also crystallized by irradiating continuous laser light while tracking between the grooves. For crystallization, continuous light irradiation was performed at a power of 6 mW.

超解像効果による超解像読み出しの原理は、次の通りである。図８において、３１はレーザ光などの光スポット、３２ａ，３２ｂは基板１の表面に形成された記録マークである。光スポット径は、光強度がそのピーク強度の（１／ｅ² ）になる位置での光ビームの直径として定義される。記録マークの最小ピッチは、光スポット３１のスポット径よりも小さく設定されている。 The principle of super-resolution reading by the super-resolution effect is as follows. In FIG. 8, 31 is a light spot such as a laser beam, and 32a and 32b are recording marks formed on the surface of the substrate 1. The light spot diameter is defined as the diameter of the light beam at a position where the light intensity becomes (1 / e ² ) of its peak intensity. The minimum pitch of the recording marks is set smaller than the spot diameter of the light spot 31.

光スポット内の高温領域では、超解像読み出し膜中の少なくとも相変化成分ＧｅＳｂ₂Ｔｅ₄が融解して、複素屈折率の実数部ｎまたは虚数部ｋの少なくとも一方が低下するため、反射率の低下が起こる。そこで、光スポット３１内には２つの記録マーク３２ａ，３２ｂがあるにもかかわらず、超解像読み出し層１３によって高温領域３５内にある記録マーク３２ｂが隠されるため、実際には記録マーク３２ａのみが検出される。換言すれば、実際の検出範囲３４が、図８のように、光スポット３１の円形の領域からマスクとして働く範囲３３、すなわち光スポット３１と高温領域３５の重複箇所を除いた三日月形の領域となる。こうして、光スポット径より小さい記録マークを超解像読み出しすることが可能となる。 In a high-temperature region in the light spot, at least the phase change component GeSb ₂ Te ₄ in the super-resolution readout film is melted, and at least one of the real part n or the imaginary part k of the complex refractive index is reduced. A drop occurs. Therefore, despite the presence of the two recording marks 32a and 32b in the light spot 31, the recording mark 32b in the high-temperature region 35 is hidden by the super-resolution reading layer 13, so that only the recording mark 32a is actually provided. Is detected. In other words, as shown in FIG. 8, the actual detection range 34 is a range 33 acting as a mask from the circular region of the light spot 31, that is, a crescent-shaped region excluding the overlapping portion of the light spot 31 and the high-temperature region 35. Become. In this way, it is possible to perform super-resolution reading of a recording mark smaller than the light spot diameter.

超解像読み出しを行う部分では、レーザパワーを８ｍＷにして一定に保ち、超解像読み出しを行った。このパワーは、超解像読み出し膜の融点により異なる。超解像読み出し部分を通り過ぎれば、レーザパワーを１ｍＷに下げてトラッキング及び自動焦点合わせを続けた。レーザパワーを１ｍＷに下げることは、マスク層の劣化を防ぐのに効果があった。なお、超解像読み出し中もトラッキング及び自動焦点合わせは継続される。トラッキング及び自動焦点合わせ用レーザパワーＰｔと超解像読み出し用レーザパワーＰｒの関係は次式に示される範囲内で、良好な超解像読み出し特性が得られた。 In the portion where the super-resolution reading was performed, the laser power was kept constant at 8 mW, and the super-resolution reading was performed. This power varies depending on the melting point of the super-resolution readout film. After passing the super-resolution readout, the laser power was reduced to 1 mW and tracking and autofocusing continued. Reducing the laser power to 1 mW was effective in preventing the deterioration of the mask layer. Note that tracking and automatic focusing are continued even during super-resolution reading. The relationship between the laser power Pt for tracking and automatic focusing and the laser power Pr for super-resolution reading was within the range shown by the following equation, and good super-resolution reading characteristics were obtained.

Ｐｒ／Ｐｔ≧２
超解像読み出し後、超解像読み出し膜が非晶質化したままになるディスクでは、結晶化しておく必要があった。読み出し後、再び結晶化する膜組成のディスクについては、結晶化は不要であった。 Pr / Pt ≧ 2
In a disk in which the super-resolution readout film remains amorphous after the super-resolution readout, it has to be crystallized. Crystallization was not required for disks with a film composition that crystallized again after reading.

本実施例の超解像読み出し膜を用いたディスクと超解像読み出し膜を用いないディスクで、異なるサイズのマークを超解像読み出した際のＣ／Ｎを比較したところ、次のように本実施例の超解像読み出し膜を用いたディスクにおいて微小マークの超解像効果がみられた。 A comparison between the C / N of the disc using the super-resolution readout film of the present embodiment and that of the disk without the super-resolution readout film when super-resolution readout of marks of different sizes was performed. In the disk using the super-resolution readout film of the example, the super-resolution effect of the minute mark was observed.

マークサイズ（μｍ）超解像読み出し超解像読み出し
膜あり（ｄＢ）膜なし（ｄＢ）
────────────────────────────────
０．３３０ −
０．４４３３０
０．５４７３５
０．６４９４０
０．７５０４６
０．８５０５０
保護膜、中間層のうちの少なくとも一者に用いているＺｎＳ−ＳｉＯ₂ の代わりにＳｉ−Ｎ系材料，Ｓｉ−Ｏ−Ｎ系材料，ＳｉＯ₂ ，ＳｉＯ，ＴｉＯ₂ ，Ａｌ₂Ｏ₃ ，Ｙ₂Ｏ₃ ，ＣｅＯ，Ｌａ₂Ｏ₃，Ｉｎ₂Ｏ₃，ＧｅＯ，ＧｅＯ₂，ＰｂＯ，ＳｎＯ，ＳｎＯ₂，Ｂｉ₂Ｏ₃，ＴｅＯ₂，ＷＯ₂，ＷＯ₃，Ｓｃ₂Ｏ₃，ＺｒＯ₂やＴａＮ，ＡｌＮ，ＡｌＳｉＮ₂ ，Ｓｉ₃Ｎ₄などのＡｌ−Ｓｉ−Ｎ系材料などの酸化物や窒化物、ＺｎＳ，Ｓｂ₂Ｓ₃ ，ＣｄＳ，Ｉｎ₂Ｓ₃，Ｇａ₂Ｓ₃，ＧｅＳ，ＳｎＳ₂，ＰｂＳ，Ｂｉ₂Ｓ₃，などの硫化物、ＳｎＳｅ₂ ，Ｓｂ₂Ｓｅ₃ ，ＣｄＳｅ，ＺｎＳｅ，Ｉｎ₂Ｓｅ₃，Ｇａ₂Ｓｅ₃，ＧｅＳｅ，ＧｅＳｅ₂，ＳｎＳｅ，ＰｂＳｅＢｉ₂Ｓｅ₃等のセレン化物、ＣｅＦ₃，ＭｇＦ₂，ＣａＦ₂などの弗化物、またはＳｉ，Ｇｅ，ＴｉＢ₂ ，Ｂ₄Ｃ，Ｂ，Ｃ，またはここで述べたすべての保護膜用材料に近い組成のものを用いてもよい。また、アクリル樹脂、ポリカーボネイト、ポリオレフィン、エポキシ樹脂、ポリイミド、ポリスチレン、ポリエチレン、ポリエチレンテレフタレート、ポリ４フッ化エチレン（テフロン：登録商標）、などのフッ素樹脂などにより形成することができる。ホットメルト接着剤として知られているエチレン−酢酸ビニル共重合体などや、接着剤などでもよい。これらの樹脂の少なくとも１つを主成分とする紫外線硬化樹脂で形成してもよい。有機物の基板で保護層を兼ねてもよい。あるいは、これらの混合材料層または多重層でもよい。中間層を省略した場合には、超解像読み出し感度が約３０％低下し、超解像読み出し可能回数も減少した。中間層の屈折率は、１．７以上２．３以下の範囲で、膜厚は、３ｎｍ以上４００ｎｍ以下の範囲で４８ｄＢ以上のＣ／Ｎが得られた。 Mark size (μm) Super-resolution readout Super-resolution readout
With film (dB) Without film (dB)
────────────────────────────────
0.3 30 −
0.4 43 30
0.5 47 35
0.6 49 40
0.7 50 46
0.8 50 50
Protective film, Si-N-based material instead of the ZnS-SiO ₂ is used in at least one person of the intermediate layer, SiO-N based _{_{material, SiO 2, SiO, TiO 2}} , Al 2 O 3, Y ₂ O ₃ , CeO, La ₂ O ₃ , In ₂ O ₃ , GeO, GeO ₂ , PbO, SnO, SnO ₂ , Bi ₂ O ₃ , TeO ₂ , WO ₂ , WO ₃ , Sc ₂ O ₃ , ZrO ₂ , etc. _{TaN, AlN, AlSiN 2, Si} 3 N oxides and nitrides such Al-Si-N material such as _{_{_{4, ZnS, Sb 2 S 3}}} , CdS, in 2 S 3, Ga 2 S 3, GeS, SnS Sulfides such as ₂ , PbS, Bi ₂ S ₃ , selenium such as SnSe ₂ , Sb ₂ Se ₃ , CdSe, ZnSe, In ₂ Se ₃ , Ga ₂ Se ₃ , GeSe, GeSe ₂ , SnSe, PbSeBi ₂ Se ₃ Fluoride such as CeF ₃ , MgF ₂ , CaF ₂ Alternatively, Si, Ge, TiB ₂ , B ₄ C, B, C, or a material having a composition close to all the protective film materials described herein may be used. Further, it can be formed of a fluorine resin such as acrylic resin, polycarbonate, polyolefin, epoxy resin, polyimide, polystyrene, polyethylene, polyethylene terephthalate, and polytetrafluoroethylene (Teflon: registered trademark). An ethylene-vinyl acetate copolymer known as a hot melt adhesive or an adhesive may be used. It may be formed of an ultraviolet curable resin containing at least one of these resins as a main component. An organic substrate may also serve as the protective layer. Alternatively, these may be a mixed material layer or a multilayer. When the intermediate layer was omitted, the super-resolution readout sensitivity was reduced by about 30%, and the number of super-resolution read-out times was also reduced. C / N of 48 dB or more was obtained when the refractive index of the intermediate layer was in the range of 1.7 to 2.3 and the film thickness was in the range of 3 nm to 400 nm.

反射層に用いたＡｌ−Ｔｉの代わりにＡｕ，Ａｇ，Ｃｕ，Ｃ，Ｓｉ，Ｇｅ，Ａｌ，Ｎｉ，Ｆｅ，Ｃｏ，Ｃｒ，Ｔｉ，Ｐｄ，Ｐｔ，Ｗ，Ｔａ，Ｍｏ，Ｓｂの単体、またはこれらを主成分とする合金、化合物、混合物あるいはこれら同志の合金の層、あるいは多重層、これらと酸化物などの他の物質との複合層などを用いてもよい。 Au, Ag, Cu, C, Si, Ge, Al, Ni, Fe, Co, Cr, Ti, Pd, Pt, W, Ta, Mo, Sb alone instead of Al-Ti used for the reflective layer, or Layers of alloys, compounds, mixtures or alloys containing these as main components, multilayers, composite layers of these with other substances such as oxides, and the like may be used.

基板として表面に直接トラッキングガイドなどの凹凸を形成したポリカーボネート基板の代わりに、ポリオレフィン、エポキシ、アクリル樹脂、紫外線硬化樹脂層を表面に形成した化学強化ガラスなどを用いてもよい。 Instead of a polycarbonate substrate having a surface with irregularities such as tracking guides directly formed thereon, a polyolefin, epoxy, acrylic resin, chemically strengthened glass having an ultraviolet curable resin layer formed on the surface, or the like may be used as the substrate.

なお、図１３に示した超解像読み出し膜を用いたディスクは片面構造であるが、ポリカーボネイト基板１１’の代わりに１１から１５と同じ構造を２つ作製し、接着層６を介して貼り合わせた両面構造としてもよい。
〔実施例８〕
図１に示したディスクにおいて、超解像読み出し膜の組成を次のように変化させたところ、レーザ光の照射の前後における超解像読み出し膜の消衰係数ｋの変化量△ｋ’が変化した。これらの超解像読み出し膜を備えたディスクに光スポットの直径の約２５％の長さの記録マークを形成し、それを１０⁵ 回超解像読み出した後の再生信号のＣ／Ｎを比較したところ、以下に示すような結果が得られた。 Although the disk using the super-resolution readout film shown in FIG. 13 has a single-sided structure, two identical structures as those of 11 to 15 are prepared instead of the polycarbonate substrate 11 ′, and bonded together via the adhesive layer 6. Alternatively, it may have a double-sided structure.
Example 8
In the disk shown in FIG. 1, when the composition of the super-resolution readout film was changed as follows, the change amount △ k 'of the extinction coefficient k of the super-resolution readout film before and after the irradiation of the laser beam changed. did. Forming about 25% of the recording mark having a length of a diameter of the light spot on the disc with a super-resolution readout film, compared with C / N of the reproduced signal after reading it 10 ⁵ times superresolution As a result, the following results were obtained.

膜組成消衰係数ｋの変化量１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎ
────────────────────────────────────
(Cr₄Te₅)₈₀(GeSb₂Te₄)₂₀ △ｋ’＝５％３７ｄＢ
(Cr₄Te₅)₆₀(GeSb₂Te₄)₄₀ △ｋ’＝１０％４２ｄＢ
(Cr₄Te₅)₄₀(GeSb₂Te₄)₆₀ △ｋ’＝２０％４６ｄＢ
(Cr₄Te₅)₂₀(GeSb₂Te₄)₈₀ △ｋ’＝３０％４８ｄＢ
この結果より、２０％≦△ｋ’の範囲が好ましいことが分かる。
〔実施例９〕
高融点成分を超解像読み出し膜に入れると、超解像読み出し可能回数が向上した。この時の超解像読み出し膜中の融点の差（Δｍ．ｐ＝高融点成分の融点−相変化成分の融点）による超解像読み出し可能回数の違いを調べた。ここでは相変化成分はＧｅＳｂ₂Ｔｅ₄ を用いて高融点成分を変化させた。 Film composition Change in extinction coefficient k 10 C / N of reproduced signal after ⁵ times super-resolution reading
────────────────────────────────────
(Cr ₄ Te ₅ ) ₈₀ (GeSb ₂ Te ₄ ) ₂₀ Δk ′ = 5% 37 dB
(Cr ₄ Te ₅ ) ₆₀ (GeSb ₂ Te ₄ ) ₄₀ Δk ′ = 10% 42 dB
(Cr ₄ Te ₅ ) ₄₀ (GeSb ₂ Te ₄ ) ₆₀ Δk ′ = 20% 46 dB
(Cr ₄ Te ₅ ) ₂₀ (GeSb ₂ Te ₄ ) ₈₀ Δk ′ = 30% 48 dB
From this result, it is understood that the range of 20% ≦ △ k ′ is preferable.
[Example 9]
When the high melting point component was put into the super-resolution readout film, the number of times the super-resolution readout was possible was improved. At this time, the difference in the number of times the super-resolution reading was possible due to the difference in the melting point in the super-resolution reading film (Δmp = melting point of the high melting point component−melting point of the phase change component) was examined. Here, the phase change component used GeSb ₂ Te ₄ to change the high melting point component.

高融点成分 Δｍ．ｐ（℃）超解像読み出し可能回数（回）
──────────────────────────────────
Ｐｔ₃Ｓｂ５０５×１０⁵
Ｍｏ₃Ｓｂ₇ １５０１×１０⁶
ＣｏＳｂ₃ ２００２×１０⁶
Ｃｒ₄Ｔｅ₅ ≧３００ ≧２×１０⁶
この結果より、Δｍ．ｐ≧１５０の範囲が好ましいことが分かる。
〔実施例１０〕
実施例７に記載した超解像読みだし膜において、
ＧｅＳｂ₂Ｔｅ₄ 以外の相変化成分としては、下記Ｄ群のうち少なくとも一者、もしくはこれに近い組成あるいは、融点６５０℃以下の化合物、またはそれに近い組成のもの、あるいはこれらの混合組成や混合組成に近い３元以上の化合物のうちの少なくとも一者で置き換えても同様な結果が得られる。
＜Ｄ群＞
Ｓｎ，Ｐｂ，Ｓｂ，Ｔｅ，Ｚｎ，Ｃｄ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，Ｔｌ，Ｍｇ，Ｔｌ₂Ｓｅ，ＴｌＳｅ，Ｔｌ₂Ｓｅ₃ ，Ｔｌ₃Ｔｅ₂ ，ＴｌＴｅ，ＩｎＢｉ，Ｉｎ₂Ｂ
ｉ，ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ，Ｉｎ₃ＳｅＴｅ₂ ，ＡｇＩｎＴｅ₂ ，ＧｅＳｂ₄Ｔｅ₇ ，Ｇｅ₂Ｓｂ₂Ｔｅ₅ ，ＧｅＳｂ₂Ｔｅ₄，ＧｅＢｉ₄Ｔｅ₇ ，ＧｅＢｉ₂Ｔｅ₄ ，Ｇｅ₃Ｂｉ₂Ｔｅ₆ ，Ｓｎ₂Ｓｂ₆Ｓｅ₁₁，Ｓｎ₂Ｓｂ₂Ｓｅ₅ ，ＳｎＳｂ₂Ｔｅ₄ ，Ｐｂ₂Ｓｂ₆Ｔｅ₁₁，ＣｕＡｓＳｅ₂ ，Ｃｕ₃ＡｓＳｅ₃ ，ＣｕＳｂＳ₂ ，ＣｕＳｂＳｅ₂ ，ＩｎＳｅ，Ｓｂ₂Ｓｅ₃ ，Ｓｂ₂Ｔｅ₃ ，Ｂｉ₂Ｔｅ₃ ，ＳｎＳｂ，ＦｅＴｅ，Ｆｅ₂Ｔｅ₃ ，ＦｅＴｅ₂ ，ＺｎＳｂ，Ｚｎ₃Ｓｂ₂ ，ＶＴｅ₂ ，Ｖ₅Ｔｅ₈ ，ＡｇＩｎ₂ ，ＢｉＳｅ，ＩｎＳｂ，Ｉｎ₂Ｔｅ，Ｉｎ₂Ｔｅ₅ ，Ｂａ₄Ｔｌ，Ｃｄ₁₁Ｎｄ，Ｂａ₁₃Ｔｌ，Ｃｄ₆Ｎｄ，Ｂａ₂Ｔｌ。 High melting point component Δm. p (° C) Number of times super-resolution reading is possible (times)
──────────────────────────────────
Pt ₃ Sb 50 5 × 10 ⁵
Mo ₃ Sb ₇ 150 1 × 10 ⁶
CoSb ₃ 200 2 × 10 ⁶
Cr ₄ Te ₅ ≧ 300 ≧ 2 × 10 ⁶
From this result, Δm. It is understood that the range of p ≧ 150 is preferable.
[Example 10]
In the super-resolution readout film described in Example 7,
As the phase change component other than GeSb ₂ Te ₄ , at least one of the following group D or a composition close thereto, or a compound having a melting point of 650 ° C. or lower, or a composition close thereto, or a mixed composition or a mixed composition thereof Similar results can be obtained by substituting at least one of ternary or higher compounds close to.
<Group D>
Sn, Pb, Sb, Te, Zn, Cd, Se, In, Ga, S, Tl, Mg, Tl 2 Se, TlSe, Tl 2 Se 3, Tl 3 Te 2, TlTe, InBi, In 2 B
i, TeBi, Tl-Se, Tl-Te, Pb-Sn, Bi-Sn, SeTe, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In, In 3 SeTe 2, AgInTe _{_{_{2, GeSb 4 Te 7, Ge}}} 2 Sb 2 Te 5, GeSb 2 Te 4, GeBi 4 Te 7, GeBi 2 Te 4, Ge 3 Bi 2 Te 6, Sn 2 Sb 6 Se 11, Sn 2 Sb 2 Se 5, _{_{_{SnSb 2 Te 4, Pb 2 Sb}}} 6 Te 11, CuAsSe 2, Cu 3 AsSe 3, CuSbS 2, CuSbSe 2, InSe, Sb 2 Se 3, Sb 2 Te 3, Bi 2 Te 3, SnSb, FeTe, Fe 2 Te ₃ , FeTe ₂ , ZnSb, Zn ₃ Sb ₂ , VTe ₂ , V ₅ Te ₈ , AgIn ₂ , BiSe, InSb, In ₂ Te, In ₂ Te ₅ , Ba ₄ Tl, Cd ₁₁ Nd, Ba ₁₃ Tl, Cd ₆ Nd, Ba ₂ Tl.

Ｃｒ₄Ｔｅ₅ 以外の高融点成分としては、次の化合物、合金、またはそれに近い組成のもの、あるいはこれらの混合組成や混合組成に近い３元以上の化合物のうちの少なくとも一者で置き換えても同様な結果が得られる。
（ａ）相変化成分の融点が４５０〜６５０℃の時
下記Ａ群の化合物、あるいは融点８００℃以上の化合物。
＜Ａ群＞
ＢａＰｄ₂ ，ＢａＰｄ₅ ，ＮｄＰｄ，ＮｄＰｄ₃ ，ＮｄＰｄ₅ ，Ｎｄ₇Ｐｔ₃ ，Ｎｄ₃Ｐｔ₂ ，ＮｄＰｔ，Ｎｄ₃Ｐｔ₄ ，ＮｄＰｔ₂ ，ＮｄＰｔ₅ ，Ｂｉ₂Ｎｄ，ＢｉＮｄ，Ｂｉ₃Ｎｄ₄ ，Ｂｉ₃Ｎｄ₅ ，ＢｉＮｄ₂ ，Ｃｄ₂Ｎｄ，ＣｄＮｄ，Ｍｎ₂Ｎｄ，Ｍｎ₂₃Ｎｄ₆ ，Ｍｎ₁₂Ｎｄ，Ｎｄ₅Ｓｂ₃ ，Ｎｄ₄Ｓｂ₃ ，ＮｄＳｂ，ＮｄＳｂ₂ ，Ｆｅ₂Ｎｄ，Ｆｅ₁₇Ｎｄ₂ ，Ｃｓ₃Ｇｅ₂ ，ＣｓＧｅ，ＣｓＧｅ₄ ，Ｎｄ₅Ｓｉ₃ ，Ｎｄ₅Ｓｉ₄ ，ＮｄＳｉ，Ｎｄ₃Ｓｉ₄ ，Ｎｄ₂Ｓｉ₃，Ｎｄ₅Ｓｉ₉，Ｃｓ₂Ｔｅ，ＮｄＴｅ₃ ，Ｎｄ₂Ｔｅ₅ ，ＮｄＴｅ₂ ，Ｎｄ₄Ｔｅ₇ ，Ｎｄ₂Ｔｅ₃ ，Ｎｄ₃Ｔｅ₄ ，ＮｄＴｅ，Ｃｅ₃Ｉｒ，Ｃｅ₂Ｉｒ，Ｃｅ₅₅Ｉｒ₄₅，ＣｅＩｒ₂ ，ＣｅＩｒ₃ ，Ｃｅ₂Ｉｒ₇ ，ＣｅＩｒ₅ ，ＣａＰｄ，ＣａＰｄ₂ ，ＣａＧｅ，Ｃａ₂Ｇｅ，ＧｅＮａ₃ ，ＧｅＮａ，ＣａＳｉ₂ ，Ｃａ₂Ｓｉ，ＣａＳｉ，Ｓｅ₂Ｓｒ，Ｓｅ₃Ｓｒ₂ ，ＳｅＳｒ，ＧｅＳｒ₂ ，ＧｅＳｒ，Ｇｅ₂Ｓｒ，ＳｎＳｒ，Ｓｎ₃Ｓｒ₅ ，ＳｎＳｒ₂ ，Ｃｅ₂Ｔｌ，Ｃｅ₅Ｔｌ₃ ，ＣｅＴｌ₃ ，Ｃｅ₃Ｔｌ₅，ＣｅＴｌ，ＢａＴｌ，Ｐｄ₁₃Ｔｌ₉ ，Ｐｄ₂Ｔｌ，Ｐｄ₃Ｔｌ，Ｍｇ₂Ｓｉ，Ｍｇ₂Ｇｅ，ＢａＰｄ₂ ，ＢａＰｄ₅ ，Ｃｅ₄Ｓｅ₇ ，Ｃｅ₃Ｓｅ₄ ，Ｃｅ₂Ｓｅ₃ ，ＣｅＳｅ，Ｃｅ₅Ｇｅ₃ ，Ｃｅ₄Ｇｅ₃，Ｃｅ₅Ｇｅ₄ ，ＣｅＧｅ，Ｃｅ₃Ｇｅ₅ ，Ｃｅ₅Ｓｉ₃ ，Ｃｅ₃Ｓｉ₂ ，Ｃｅ₅Ｓｉ₄ ，ＣｅＳｉ，Ｃｅ₃Ｓｉ₅ ，ＣｅＳｉ₂，ＣｅＴｅ₃ ，Ｃｅ₂Ｔｅ₅ ，ＣｅＴｅ₂ ，Ｃｅ₄Ｔｅ₇ ，Ｃｅ₃Ｔｅ₄ ，ＣｅＴｅ，Ｌａ₃Ｓｅ₇ ，ＬａＳｅ₂ ，Ｌａ₄Ｓｅ₇ ，Ｌａ₂Ｓｅ₃ ，Ｌａ₃Ｓｅ₄ ，ＬａＳｅ，ＧｅＬａ₃ ，Ｇｅ₃Ｌａ₅ ，Ｇｅ₃Ｌａ₄ ，Ｇｅ₄Ｌａ₅ ，ＧｅＬａ，Ｇｅ₅Ｌａ₃ ，ＢａＳｅ₂，Ｂａ₂Ｓｅ₃ ，ＢａＳｅ，ＰｄＳｅ，Ｍｏ₃Ｓｅ₄ ，ＭｏＳｅ₂ ，Ｂａ₂Ｇｅ，ＢａＧｅ₂ ，ＢａＧｅ，Ｂａ₂Ｔｅ₃ ，ＢａＴｅ，Ｇｅ₂Ｐｄ₅ ，ＧｅＰｄ₂，Ｇｅ₉Ｐｄ₂₅，ＧｅＰｄ，Ｇｅ₃Ｐｔ，Ｇｅ₃Ｐｔ₂ ，ＧｅＰｔ，Ｇｅ₂Ｐｔ₃ ，ＧｅＰｔ₂ ，ＧｅＰｔ₃ ，Ｐｕ₃Ｓｎ，Ｐｕ₅Ｓｎ₃ ，Ｐｕ₅Ｓｎ₄，Ｐｕ₈Ｓｎ₇ ，Ｐｕ₇Ｓｎ₈ ，ＰｕＳｎ₂ ，ＰｕＳｎ₃ ，Ｐｔ₅Ｔｅ₄ ，Ｐｔ₄Ｔｅ₅ ，ＰｔＴｅ₂ ，ＧｅＮｉ，Ｇｅ₃Ｎｉ₅ ，Ｇｅ₂Ｎｉ₅ ，ＧｅＮｉ₃ ，ＮｉＴｅ_0.85，ＮｉＴｅ_0.775，Ｎｉ₃±_xＴｅ_x ，Ｃｒ₁₁Ｇｅ₁₉，ＣｒＧｅ，Ｃｒ₁₁Ｇｅ₈ ，Ｃｒ₅Ｇｅ₃ ，Ｃｒ₃Ｇｅ，ＣｒＳｉ₂ ，Ｃｒ₅Ｓｉ₃ ，Ｃｒ₃Ｓｉ，Ｃｒ₅Ｔｅ₈ ，Ｃｒ₄Ｔｅ₅ ，Ｃｒ₃Ｔｅ₄ ，Ｃｒ_1-xＴｅ，Ｇｅ₃Ｍｎ₅ ，ＧｅＭｎ₂ ，Ｍｎ₆Ｓｉ，Ｍｎ₉Ｓｉ₂ ，Ｍｎ₃Ｓｉ，Ｍｎ₅Ｓｉ₂ ，Ｍｎ₅Ｓｉ₃ ，ＭｎＳｉ，Ｍｎ₁₁Ｓｉ₁₉，Ｍｎ₂Ｓｎ，Ｍｎ_3.25Ｓｎ，ＭｎＴｅ，Ｔｅ₂Ｗ，ＦｅＧｅ₂ ，Ｆｅ₅Ｇｅ₃ ，Ｆｅ₃Ｇｅ，Ｆｅ₂Ｓｉ，Ｆｅ₅Ｓｉ₃ ，ＦｅＳｉ，ＦｅＳｉ₂ ，Ｇｅ₂Ｍｏ，Ｇｅ₄₁Ｍｏ₂₃，Ｇｅ₁₆Ｍｏ₉ ，Ｇｅ₂₃Ｍｏ₁₃，Ｇｅ₃Ｍｏ₅ ，ＧｅＭｏ₃，Ｍｏ₃Ｓｉ，Ｍｏ₅Ｓｉ₃ ，ＭｏＳｉ₂ ，ＭｏＳｎ，ＭｏＳｎ₂ ，Ｍｏ₃Ｔｅ₄，ＭｏＴｅ₂ ，Ｓｉ₂Ｔｉ，ＳｉＴｉ，Ｓｉ₄Ｔｉ₅ ，Ｓｉ₃Ｔｉ₅ ，ＳｉＴｉ₃，Ｓｎ₅Ｔｉ₆ ，Ｓｎ₃Ｔｉ₅ ，ＳｎＴｉ₂ ，ＳｎＴｉ₃ ，ＣｏＧｅ₂ ，Ｃｏ₅Ｇｅ₇ ，ＣｏＧｅ，Ｃｏ₅Ｇｅ₃ ，Ｃｏ₄Ｇｅ，Ｃｏ₃Ｔｅ₄ ，Ｇｅ₇Ｒｅ₃ ，Ｒｅ₅Ｓｉ₃ ，ＲｅＳｉ，ＲｅＳｉ₂ ，Ｒｅ₂Ｔｅ。
（ｂ）相変化成分の融点が２５０〜４５０℃の時
前記Ａ群または下記Ｂ群の化合物、あるいは融点６００℃以上の化合物。
＜Ｂ群＞
Ｃｓ₃Ｇｅ，Ｂａ₂Ｔｌ，ＧｅＰｄ₃ ，Ｆｅ₆Ｇｅ₅ ，ＦｅＴｅ₂ ，Ｃｏ₅Ｇｅ₂ ，Ｎｄ₃Ｐｄ，Ｃｓ₃Ｔｅ₂ ，Ｃｅ₄Ｉｒ，ＮａＰｄ，Ｃａ₉Ｐｄ，Ｃａ₃Ｐｄ₂ ，Ｃａ₂Ｇｅ，Ｓｅ₃Ｓｒ，Ｃｅ₃Ｔｌ，ＣｅＳｅ₂ ，Ｃｅ₃Ｇｅ，ＢａＳｅ₃ ，ＧｅＳｅ₂ ，ＧｅＳｅ，ＢａＴｅ₂ ，ＧｅＰｄ₅ ，Ｇｅ₈Ｍｎ₁₁，ＭｎＴｅ₂ ，Ｇｅ₃Ｗ₂ ，ＦｅＧｅ，Ｆｅ₄Ｇｅ₃ ，Ｆｅ₃Ｓｎ，Ｆｅ₃Ｓｎ₂ ，ＦｅＳｎ，ＣｏＴｅ₂。
（ｃ）相変化成分の融点が２５０℃以下の時
前記Ａ群、Ｂ群または下記Ｃ群の化合物、あるいは融点４００℃以上の化合物。
＜Ｃ群＞
Ｂａ₄Ｔｌ，ＣｓＴｅ，Ｂａ₄Ｔｌ，Ｂａ₁₃Ｔｌ，Ｃｄ₁₁Ｎｄ，Ｃｄ₆Ｎｄ，Ｃｓ₅Ｔｅ₄ ，Ｃａ₃Ｐｄ，Ｃａ₅Ｐｄ₂ ，Ｓｎ₃Ｓｒ，Ｂａ₁₃Ｔｌ，ＰｄＴｌ₂，ＦｅＳｅ₂ ，ＦｅＳｅ，Ｃｒ₂Ｔｅ₃ ，ＣｒＴｅ₃ ，ＦｅＳｎ₂ 。
〔実施例１１〕
超解像読み出し膜において、上記高融点成分と上記相変化成分の組合せではＣｒ₄Ｔｅ₅ とＧｅＳｂ₂Ｔｅ₄ のように、それぞれの成分に同じ元素が存在する組みあわせが超解像読み出し特性が良好であった。ただし、同じ元素の量が多すぎると両方の成分の融点の差がでなくなるため、同じ元素の量は成分中の８０原子％以下が好ましかった。また、量が少ないとアパーチャー部分における両成分の屈折率が等しくならない場合が多く、３０原子％以上が好ましかった。
〔実施例１２〕
超解像読み出し膜中の相変化成分としてＧｅＳｂ₂Ｔｅ₄を、高融点成分としてＣｒ₄Ｔｅ₅を用い、高融点成分含有量（原子％）を変化させてＣ／Ｎと超解像読み出し可能回数を調べたところ、次のような結果が得られた。 The high melting point component other than Cr ₄ Te ₅ may be replaced by at least one of the following compounds, alloys, or a composition close thereto, or a mixed composition thereof or a ternary or higher compound close to the mixed composition. Similar results are obtained.
(A) When the melting point of the phase change component is 450 to 650 ° C. A compound of the following Group A or a compound having a melting point of 800 ° C. or more.
<Group A>
_{_{BaPd 2, BaPd 5, NdPd,}} NdPd 3, NdPd 5, Nd 7 Pt 3, Nd 3 Pt 2, NdPt, Nd 3 Pt 4, NdPt 2, NdPt 5, Bi 2 Nd, BiNd, Bi 3 Nd 4, Bi 3 _{_{_{Nd 5, BiNd 2, Cd 2}}} Nd, CdNd, Mn 2 Nd, Mn 23 Nd 6, Mn 12 Nd, Nd 5 Sb 3, Nd 4 Sb 3, NdSb, NdSb 2, Fe 2 Nd, Fe 17 Nd 2, Cs _{_{_{3 Ge 2, CsGe, CsGe 4}}} , Nd 5 Si 3, Nd 5 Si 4, NdSi, Nd 3 Si 4, Nd 2 Si 3, Nd 5 Si 9, Cs 2 Te, NdTe 3, Nd 2 Te 5, NdTe 2 _{_{_{, Nd 4 Te 7, Nd 2}}} Te 3, Nd 3 Te 4, NdTe, Ce 3 Ir, Ce 2 Ir, Ce 55 Ir 45, CeIr 2, CeIr 3, Ce 2 Ir 7, CeIr 5, CaPd, CaPd 2, C _{_{Ge, Ca 2 Ge, GeNa 3}} , GeNa, CaSi 2, Ca 2 Si, CaSi, Se 2 Sr, Se 3 Sr 2, SeSr, GeSr 2, GeSr, Ge 2 Sr, SnSr, Sn 3 Sr 5, SnSr 2, Ce ₂ Tl, Ce ₅ Tl ₃ , CeTl ₃ , Ce ₃ Tl ₅ , CeTl, BaTl, Pd ₁₃ Tl ₉ , Pd ₂ Tl, Pd ₃ Tl, Mg ₂ Si, Mg ₂ Ge, BaPd ₂ , BaPd ₅ , Ce ₄ _{_{_{Se 7, Ce 3 Se 4,}}} Ce 2 Se 3, CeSe, Ce 5 Ge 3, Ce 4 Ge 3, Ce 5 Ge 4, CeGe, Ce 3 Ge 5, Ce 5 Si 3, Ce 3 Si 2, Ce 5 Si _{_{_{4, CeSi, Ce 3 Si 5}}} , CeSi 2, CeTe 3, Ce 2 Te 5, CeTe 2, Ce 4 Te 7, Ce 3 Te 4, CeTe, La 3 Se 7, LaSe 2, La 4 Se 7, La 2 Se _3, _{_{a 3 Se 4, LaSe, GeLa}} 3, Ge 3 La 5, Ge 3 La 4, Ge 4 La 5, GeLa, Ge 5 La 3, BaSe 2, Ba 2 Se 3, BaSe, PdSe, Mo 3 Se 4, MoSe ₂ , Ba ₂ Ge, BaGe ₂ , BaGe, Ba ₂ Te ₃ , BaTe, Ge ₂ Pd ₅ , GePd ₂ , Ge ₉ Pd ₂₅ , GePd, Ge ₃ Pt, Ge ₃ Pt ₂ , GePt, Ge ₂ Pt ₃ , GePt _{_{_{2, GePt 3, Pu 3 Sn}}} , Pu 5 Sn 3, Pu 5 Sn 4, Pu 8 Sn 7, Pu 7 Sn 8, PuSn 2, PuSn 3, Pt 5 Te 4, Pt 4 Te 5, PtTe 2, GeNi, _{_{_{Ge 3 Ni 5, Ge 2 Ni}}} 5, GeNi 3, NiTe 0.85, NiTe 0.775, Ni 3 ± x Te x, Cr 11 Ge 19, CrGe, Cr 11 Ge 8, Cr 5 Ge 3, Cr 3 Ge, CrSi 2, Cr ₅ Si ₃ , Cr ₃ Si, Cr ₅ Te ₈ , Cr ₄ Te ₅ , Cr ₃ Te ₄ , Cr _{1 -x} Te, Ge ₃ Mn ₅ , GeMn ₂ , Mn ₆ Si, Mn ₉ Si ₂ , Mn ₃ Si, Mn _{_{_{_{5 Si 2, Mn 5 Si 3}}}} , MnSi, Mn 11 Si 19, Mn 2 Sn, Mn 3.25 Sn, MnTe, Te 2 W, FeGe 2, Fe 5 Ge 3, Fe 3 Ge, Fe 2 Si, Fe 5 Si 3 , FeSi, FeSi ₂ , Ge ₂ Mo, Ge ₄₁ Mo ₂₃ , Ge ₁₆ Mo ₉ , Ge ₂₃ Mo ₁₃ , Ge ₃ Mo ₅ , GeMo ₃ , Mo ₃ Si, Mo ₅ Si ₃ , MoSi ₂ , MoSn, MoSn ₂ , Mo ₃ Te ₄ , MoTe ₂ , Si ₂ Ti, SiTi, Si ₄ Ti ₅ , Si ₃ Ti ₅ , SiTi ₃ , Sn ₅ Ti ₆ , Sn ₃ Ti ₅ , SnTi ₂ , SnTi ₃ , CoGe ₂ , Co ₅ Ge ₇ , CoGe, Co ₅ Ge ₃ , Co ₄ G e, Co ₃ Te ₄ , Ge ₇ Re ₃ , Re ₅ Si ₃ , ReSi, ReSi ₂ , Re ₂ Te.
(B) When the melting point of the phase-change component is from 250 to 450 ° C. A compound of the group A or the following group B, or a compound having a melting point of 600 ° C. or higher.
<Group B>
Cs ₃ Ge, Ba ₂ Tl, GePd ₃ , Fe ₆ Ge ₅ , FeTe ₂ , Co ₅ Ge ₂ , Nd ₃ Pd, Cs ₃ Te ₂ , Ce ₄ Ir, NaPd, Ca ₉ Pd, Ca ₃ Pd ₂ , Ca ₂ Ge, Se ₃ Sr, Ce ₃ Tl, CeSe ₂ , Ce ₃ Ge, BaSe ₃ , GeSe ₂ , GeSe, BaTe ₂ , GePd ₅ , Ge ₈ Mn ₁₁ , MnTe ₂ , Ge ₃ W ₂ , FeGe, Fe ₄ Ge ₃ , Fe ₃ Sn, Fe ₃ Sn ₂ , FeSn, CoTe ₂ .
(C) When the melting point of the phase change component is 250 ° C. or lower: a compound of Group A, Group B or the following Group C, or a compound having a melting point of 400 ° C. or higher.
<Group C>
Ba ₄ Tl, CsTe, Ba ₄ Tl, Ba ₁₃ Tl, Cd ₁₁ Nd, Cd ₆ Nd, Cs ₅ Te ₄ , Ca ₃ Pd, Ca ₅ Pd ₂ , Sn ₃ Sr, Ba ₁₃ Tl, PdTl ₂ , FeSe ₂ , _{_{FeSe, Cr 2 Te 3, CrTe}} 3, FeSn 2.
[Example 11]
In the super-resolution readout film, in the combination of the high melting point component and the phase change component, the combination in which the same element exists in each component, such as Cr ₄ Te ₅ and GeSb ₂ Te ₄ , has a super-resolution readout characteristic. It was good. However, if the amount of the same element is too large, the difference in melting point between both components disappears, so the amount of the same element is preferably 80 atom% or less in the components. In addition, when the amount is small, the refractive indices of both components in the aperture portion often do not become equal, and 30 atomic% or more is preferable.
[Example 12]
Using GeSb ₂ Te ₄ as the phase change component and Cr ₄ Te ₅ as the high melting point component in the super resolution readout film, C / N and super resolution read out are possible by changing the content (atomic%) of the high melting point component. When the number of times was checked, the following results were obtained.

高融点成分含有量（原子％）超解像読み出し可能回数（回）
───────────────────────────────
５６×１０⁵
１０１×１０⁶
２０２×１０⁶
≧３０ ≧２×１０⁶
高融点成分含有量（％）Ｃ／Ｎ（ｄＢ）
─────────────────────────
≦３０ ≧４８
４０４８
５０４６
６０４２
この結果より、高融点成分含有量は１０〜５０％の範囲が好ましく、２０〜４０％の範囲がより好ましいことがわかる。 High melting point content (atomic%) Number of times super-resolution reading is possible (times)
───────────────────────────────
5 6 × 10 ⁵
10 1 × 10 ⁶
20 2 × 10 ⁶
≧ 30 ≧ 2 × 10 ⁶
High melting point component content (%) C / N (dB)
─────────────────────────
≦ 30 ≧ 48
40 48
50 46
60 42
From this result, it is understood that the content of the high melting point component is preferably in the range of 10 to 50%, and more preferably in the range of 20 to 40%.

高融点成分中で酸化物、硫化物、窒化物、炭化物の含有量は高融点成分の５０％未満とするのが好ましく、２０％未満とするのが特に好ましい。これらの含有量が多いと相変化成分との複素屈折率の差を小さくできなかったり、相変化成分中に酸素等が拡散して超解像読み出し特性を劣化させたりする問題を生じやすい。
〔実施例１３〕
超解像読み出し膜材料により、超解像読み出し膜の融点が異なるため、相変化成分の組成を変えて最適超解像読み出しパワーを調べたところ、次のようになった。高融点成分としてはＣｒ₄Ｔｅ₅を用いた。 The content of oxides, sulfides, nitrides and carbides in the high melting point component is preferably less than 50% of the high melting point component, particularly preferably less than 20%. If the content of these components is large, a problem that the difference in the complex refractive index from the phase change component cannot be reduced or oxygen or the like diffuses in the phase change component to deteriorate the super-resolution readout characteristic is likely to occur.
[Example 13]
Since the melting point of the super-resolution readout film differs depending on the material of the super-resolution readout film, the optimum super-resolution readout power was investigated by changing the composition of the phase change component. Cr ₄ Te ₅ was used as the high melting point component.

膜中の相変化成分の組成膜の融点（℃）超解像読み出しパワー（ｍＷ）
────────────────────────────────────
Ｓｎ₇₅Ｚｎ₂₅ ２５０３
Ｉｎ₂Ｔｅ₅ ４５０６
Ｇｅ₂Ｓｂ₂Ｔｅ₅ ６５０８

超解像読み出し膜の融点が低い方が、超解像読み出し時のパワーが低くて済み、好ましい。
〔実施例１４〕
回転数一定の場合、ディスクの内周と外周では線速が異なる。５インチディスクでは、線速は５．７〜１１．３ｍ／ｓまで変化するため、これに対応して内周では２０ｎｍ、外周では４０ｎｍになるように超解像読み出し膜厚を変化させたところ、光スポットのうちマスクされない領域の幅が内周ほど小さくなり、内周、外周の両方において、Ｃ／Ｎ４８ｄＢという良好な超解像読み出し特性を得た。また、内周から外周に向かってＧｅＳｂＴｅ系のＧｅＳｂ₂Ｔｅ₄ あるいはＧｅ₂Ｓｂ₂Ｔｅ₅ 組成からのずれ量を少なくしたところ、外周へいくほど結晶化速度が早くなるため、線速対応が容易になり、内周、外周の両方において、Ｃ／Ｎ４８ｄＢという良好な超解像読み出し特性を得た。
〔実施例１５〕
図１４に、超解像読み出し用装置の超解像読み出し系のブロック図を示す。超解像読み出し指令４２を受けて、光ヘッド５０からレーザ照射が行われ、光ディスク５１から戻ってきた反射光を再び光ヘッド５０で検出する。 Composition of phase change component in film Melting point of film (° C) Super-resolution read power (mW)
────────────────────────────────────
Sn ₇₅ Zn ₂₅ 250 3
In ₂ Te ₅ 450 6
Ge ₂ Sb ₂ Te ₅ 650 8

The lower the melting point of the super-resolution readout film, the lower the power required for super-resolution readout, which is preferable.
[Example 14]
When the rotation speed is constant, the linear velocity differs between the inner circumference and the outer circumference of the disk. In the case of a 5-inch disk, the linear velocity changes from 5.7 to 11.3 m / s, and accordingly, the super-resolution readout film thickness is changed to 20 nm on the inner circumference and 40 nm on the outer circumference. The width of the unmasked area of the light spot became smaller toward the inner circumference, and a good super-resolution readout characteristic of C / N of 48 dB was obtained at both the inner circumference and the outer circumference. The inner periphery was less amount of deviation from GeSb ₂ Te ₄ or Ge _₂ Sb ₂ Te ₅ composition of GeSbTe system toward the periphery from the crystallization speed toward the outer periphery becomes faster, easier linear velocity corresponding , And a good super-resolution readout characteristic of C / N of 48 dB was obtained on both the inner circumference and the outer circumference.
[Example 15]
FIG. 14 is a block diagram of a super-resolution reading system of the super-resolution reading apparatus. Upon receiving the super-resolution reading command 42, laser irradiation is performed from the optical head 50, and the reflected light returned from the optical disk 51 is detected by the optical head 50 again.

レーザ光として連続光を用いる場合は図の（ａ）の系統とし、パルス光を用いる場合にはパルス化回路４３を組み込んで（ｂ）の系統とする。パルス光の同期はアドレス部、フラグ部検出４５を通して行う。 When continuous light is used as the laser light, the system shown in FIG. 7A is used, and when pulsed light is used, the system shown in FIG. The synchronization of the pulse light is performed through the address section and the flag section detection 45.

良好な超解像読み出し特性を得るために、レーザパワー設定回路４７はトラッキング及び自動焦点合わせ用レーザパワーＰｔと超解像読み出し用レーザパワーＰｒの関係を次式のように保つ。 In order to obtain good super-resolution reading characteristics, the laser power setting circuit 47 maintains the relationship between the laser power Pt for tracking and automatic focusing and the laser power Pr for super-resolution reading as in the following equation.

Ｐｒ／Ｐｔ≧２
また、超解像読み出し用膜の最高温度となる領域でも膜全体が融解しないで高融点成分は固相に留まるようにするため、レーザパワー照射時には戻り光の反射光強度分布の乱れを光強度分布解析回路４８で検出解析し、乱れの大きさに応じてレーザパワーを調節できる回路をレーザパワー設定回路４７に組み込んだ。これにより、超解像読み出し用膜の劣化が起こりにくくなった。 Pr / Pt ≧ 2
Also, in order to ensure that the high melting point component remains in the solid phase without melting the entire film even in the region where the temperature of the super-resolution readout film reaches the maximum temperature, disturbance of the reflected light intensity distribution of the return light during laser power irradiation is reduced. A circuit capable of detecting and analyzing by the distribution analysis circuit 48 and adjusting the laser power according to the magnitude of the disturbance is incorporated in the laser power setting circuit 47. As a result, the deterioration of the super-resolution readout film is less likely to occur.

ここで、光強度分布の乱れとは、光強度分布の乱れの時間的変動、すなわち各検出器出力の比の時間的変動のことである。光強度分布の乱れは１次元的、または２次元的に配列した２個以上の検出器が記録媒体面にほぼ平行に配置されたものを用い、各検出器の出力を光強度分布解析回路４８に接続して検出した。 Here, the disturbance of the light intensity distribution refers to the temporal fluctuation of the disturbance of the light intensity distribution, that is, the temporal fluctuation of the ratio of each detector output. The light intensity distribution is disturbed by using two or more detectors arranged one-dimensionally or two-dimensionally and arranged substantially in parallel with the recording medium surface, and using the output of each detector as a light intensity distribution analysis circuit 48. Connected to and detected.

超解像読み出し用膜の劣化を防ぐため、超解像読み出しレーザ光をパルス光とした。このとき、レーザスポット径（λ／ＮＡ）とアパーチャーのトラック方向の中心部の長さａの比（ａ：λ／ＮＡ）を１／３〜１／２にでき、微小マークを持つディスクで、０．４λ／ＮＡ≦ｖＴの範囲ではスポットが３０％以上重なるため、パルス化の効果が少なく、ｖＴ≦１．５λ／ＮＡの範囲ではマークを読み飛ばしてしまうことがわかった。 In order to prevent the deterioration of the super-resolution reading film, the super-resolution reading laser light was used as pulse light. At this time, the ratio (a: λ / NA) of the laser spot diameter (λ / NA) to the length a of the center of the aperture in the track direction can be reduced to ３ to 、. In the range of 0.4λ / NA ≦ vT, the spots overlap by 30% or more, so that the effect of pulsing is small. In the range of vT ≦ 1.5λ / NA, the marks are skipped.

そこで、マークの超解像読み出しを確実に行うため、下式を満たすための回路を、図１４のパルス化回路４３に組み込んだ。 Therefore, in order to reliably perform super-resolution reading of the mark, a circuit that satisfies the following expression is incorporated in the pulse generating circuit 43 of FIG.

０．４λ／ＮＡ≦ｖＴ≦１．５λ／ＮＡ
０．３ｋ≦ｘ／Ｔ≦０．５ｋ
その結果、Ｃ／Ｎ４６ｄＢを得ることができた。ｋは比例定数で、図７の構造のディスクにおいてレーザパワー８ｍＷ，線速８ｍ／ｓの時、ｋ＝１であった。さらに、下式を満たすと、Ｃ／Ｎが２ｄＢ向上した。 0.4λ / NA ≦ vT ≦ 1.5λ / NA
0.3k ≦ x / T ≦ 0.5k
As a result, C / N of 46 dB was obtained. k is a proportional constant, and k = 1 when the laser power is 8 mW and the linear velocity is 8 m / s in the disk having the structure shown in FIG. Further, when the following expression was satisfied, the C / N was improved by 2 dB.

０．５λ／ＮＡ≦ｖＴ≦０．９λ／ＮＡ
０．３ｋ≦ｘ／Ｔ≦０．５ｋ
〔実施例１６〕
図９は、本発明の超解像読み出し膜を用いた読み書き可能ディスクの構造断面図の一例を示したものである。本実施例では、前記一般式（８）の平均組成を有する超解像読み出し膜を用いた。 0.5λ / NA ≦ vT ≦ 0.9λ / NA
0.3k ≦ x / T ≦ 0.5k
[Example 16]
FIG. 9 shows an example of a structural sectional view of a readable / writable disk using the super-resolution readout film of the present invention. In this example, a super-resolution readout film having the average composition of the general formula (8) was used.

まず、直径１３ｃｍ、厚さ１．２ｍｍのポリカーボネイト基板を形成した。次に、この基板を複数のターゲットを備え順次積層膜を形成でき、また、膜厚の均一性、再現性のよいマグネトロンスパッタリング装置内に取付け、この上に厚さ１２５ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層を形成した。続いて、（Ｓｎ₃Ｚｎ）₈₀（ＳｎＴｉ₂ ）₂₀膜を３０ｎｍ、（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層，（Ｃｒ₄Ｔｅ₅ ）₂₀（ＧｅＳｂ₂Ｔｅ₄ ）₈₀膜を３０ｎｍ形成した。次に（ＺｎＳ）₈₀（ＳｉＯ₂ ）₂₀層を２０ｎｍ、Ａｌ−Ｔｉ層を１００ｎｍ，順次積層した。その後、この上に接着層を介してポリカーボネイト基板を貼りあわせた。このディスクは片面のみ使用できるが、同じ構造のものを２つ作製し、接着層ではりあわせた両面構造としても良い。 First, a polycarbonate substrate having a diameter of 13 cm and a thickness of 1.2 mm was formed. Next, the substrate is provided with a plurality of targets, a laminated film can be formed sequentially, and the substrate is mounted in a magnetron sputtering apparatus having good uniformity and reproducibility of the film thickness, and a 125 nm-thick (ZnS) ₈₀ (SiO ₂ ) ₂₀ layers were formed. Subsequently, a (Sn ₃ Zn) ₈₀ (SnTi ₂ ) ₂₀ film was formed with a thickness of 30 nm, a (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer, and a (Cr ₄ Te ₅ ) ₂₀ (GeSb ₂ Te ₄ ) ₈₀ film with a thickness of 30 nm. Next, a (ZnS) ₈₀ (SiO ₂ ) ₂₀ layer was laminated in order of 20 nm, and an Al—Ti layer was laminated in order of 100 nm. Thereafter, a polycarbonate substrate was bonded thereon via an adhesive layer. Although this disc can be used only on one side, two discs having the same structure may be prepared and a double-sided structure may be used in which the disc is bonded with an adhesive layer.

超解像読み出しを行う部分では、レーザパワーを３ｍＷにして、超解像読み出しを行った。このパワーは、超解像読み出し膜の融点により異なる。超解像読み出し部分を通り過ぎれば、レーザパワーを１ｍＷに下げてトラッキング及び自動焦点合わせを続けた。なお、超解像読み出し中もトラッキング及び自動焦点合わせは継続される。 In the portion where the super-resolution reading was performed, the laser power was set to 3 mW, and the super-resolution reading was performed. This power varies depending on the melting point of the super-resolution readout film. After passing the super-resolution readout, the laser power was reduced to 1 mW and tracking and autofocusing continued. Note that tracking and automatic focusing are continued even during super-resolution reading.

超解像読み出し後、超解像読み出し膜は再び結晶化するため、結晶化は不要であった。
〔実施例１７〕
前記実施例１６の図９に示した（Ｓｎ₃Ｚｎ）₈₀（ＳｎＴｉ₂ ）₂₀よりなる超解像読み出し膜において、Ｚｎの含有量を一定に保ちながらＳｎとＴｉの含有量を変化させたると、超解像読み出し可能回数及び１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎは、次のように変化した。 After the super-resolution reading, the super-resolution reading film crystallized again, so that crystallization was unnecessary.
[Example 17]
In the super-resolution readout film made of (Sn ₃ Zn) ₈₀ (SnTi ₂ ) ₂₀ shown in FIG. 9 of Example 16, when the contents of Sn and Ti were changed while the Zn content was kept constant, C / N of the super-resolution readable number and 10 ⁵ times the reproduction signal after the super-resolution readout was changed as follows.

組成超解像読み出し可能回数
───────────────────────────
Ｓｎ₅₅Ｚｎ₂₀Ｔｉ₂₅ ＞２×１０⁶ 回
Ｓｎ₆₇Ｚｎ₂₀Ｔｉ₁₃ ２×１０⁶ 回
Ｓｎ₇₅Ｚｎ₂₀Ｔｉ₅ １×１０⁶ 回
Ｓｎ₈₀Ｚｎ₂₀ ５×１０⁵ 回
組成１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎ
────────────────────────────────────
Ｓｎ₂₅Ｚｎ₂₀Ｔｉ₅₅ ４４ｄＢ
Ｓｎ₃₀Ｚｎ₂₀Ｔｉ₅₀ ４６ｄＢ
Ｓｎ₄₀Ｚｎ₂₀Ｔｉ₄₀ ４８ｄＢ
Ｓｎ₅₅Ｚｎ₂₀Ｔｉ₂₅ ５０ｄＢ

これより、前記一般式（８）におけるｅ，ｆの範囲は３０≦ｅ≦９５、５≦ｆ≦５０が好ましく、４０≦ｅ≦８７、１３≦ｆ≦４０がより好ましいことがわかる。 Composition Super-resolution readout count ───────────────────────────
Sn ₅₅ Zn ₂₀ Ti ₂₅ > 2 × 10 ⁶ times Sn ₆₇ Zn ₂₀ Ti ₁₃ 2 × 10 ⁶ times Sn ₇₅ Zn ₂₀ Ti ₅ 1 × 10 ⁶ times Sn ₈₀ Zn ₂₀ 5 × 10 ⁵ times Composition 10 ⁵ times Super solution C / N of reproduction signal after image readout
────────────────────────────────────
Sn ₂₅ Zn ₂₀ Ti ₅₅ 44 dB
Sn ₃₀ Zn ₂₀ Ti ₅₀ 46dB
Sn ₄₀ Zn ₂₀ Ti ₄₀ 48 dB
Sn ₅₅ Zn ₂₀ Ti ₂₅ 50 dB

This indicates that the range of e and f in the general formula (8) is preferably 30 ≦ e ≦ 95, 5 ≦ f ≦ 50, and more preferably 40 ≦ e ≦ 87 and 13 ≦ f ≦ 40.

さらに、前記の（Ｓｎ₃Ｚｎ）₈₀（ＳｎＴｉ₂ ）₂₀よりなる超解像読み出し膜２６において、Ｓｎ，Ｚｎ，Ｔｉの含有量を一定に保ちながらＴｌを添加し、その含有量を次のように変化させた場合、１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎは、次のように変化した。 Further, in the super-resolution readout film 26 made of (Sn ₃ Zn) ₈₀ (SnTi ₂ ) _20, Tl was added while keeping the contents of Sn, Zn, and Ti constant, and the content was changed as follows. case of changing the, 10 ⁵ times C / N of the reproduced signal after superresolution readout varied as follows.

Ｔｌ含有量１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎ
──────────────────────────────────
ｇ＝０％４６ｄＢ
ｇ＝１０％４８ｄＢ
ｇ＝２０％４６ｄＢ
ｇ＝２５％４３ｄＢ
これより、前記一般式（８）におけるｇの範囲は０≦ｇ≦２０が好ましく、０≦ｇ≦１０がより好ましいことがわかる。 Tl content 105 C / N of reproduction signal after super-resolution reading ⁵ times
──────────────────────────────────
g = 0% 46 dB
g = 10% 48 dB
g = 20% 46 dB
g = 25% 43dB
This indicates that the range of g in the general formula (8) is preferably 0 ≦ g ≦ 20, and more preferably 0 ≦ g ≦ 10.

また、前記Ｄ、Ｄ’（前記Ｄが上記Ｓｎ，ＺｎのようにＤ，Ｄ’２元素の場合）、Ｅ、Ｆの組合せにおいて、Ｄ−Ｅ、Ｅ−Ｆ、Ｄ’−Ｅの組合せからできる高融点成分が共晶点をもたないか、共晶点をもっていてもＤ、Ｄ−Ｄ’の融点より１５０℃以上融点が高いのが好ましかった。
〔実施例１８〕
前記実施例１６のＳｎ−Ｚｎ−Ｔｉよりなる超解像読み出し膜を、前記一般式（８）で表される平均組成の材料、Ｐｂ−Ｓｅ，Ｐｂ−Ｃｅ，Ｐｂ−Ｌａ，Ｐｂ−Ｐｔ，Ｐｂ−Ｓｉ，Ｓｎ−Ｓｂ，Ｓｎ−Ｓｅ，Ｓｎ−Ｃｏ，Ｓｎ−Ｃｕ，Ｓｎ−Ｎｉ，Ｓｎ−Ｐｔ，Ｂｉ−Ｔｅ，Ｂｉ−Ｓｅ，Ｂｉ−Ｃｅ，Ｂｉ−Ｃｕ，Ｂｉ−Ｃｄ，Ｂｉ−Ｐｔ，Ｚｎ−Ｎｉ，Ｚｎ−Ｐｔ，Ｚｎ−Ｌａ，Ｚｎ−Ｃｅ，Ｇａ−Ｃｒ，Ｇａ−Ｃｕ，Ｇａ−Ｎｉ，Ｇａ−Ｌａ，Ｇａ−Ｐｔ，Ｇａ−Ｃｅ，Ｉｎ−Ｓｅ，Ｉｎ−Ｓｂ，Ｉｎ−Ｔｅ，Ｉｎ−Ａｓ，Ｉｎ−Ｍｎ，Ｉｎ−Ｎｉ，Ｉｎ−Ａｇ，Ｐｂ−Ｓｎ−Ｓｅ，Ｐｂ−Ｓｎ−Ｃｅ，Ｐｂ−Ｓｎ−Ｌａ，Ｐｂ−Ｓｎ−Ｐｔ，Ｐｂ−Ｓｎ−Ｓｉ，Ｐｂ−Ｓｎ−Ｓｂ，Ｐｂ−Ｓｎ−Ｃｏ，Ｐｂ−Ｓｎ−Ｃｕ，Ｐｂ−Ｓｎ−Ｎｉ，Ｓｎ−Ｂｉ−Ｓｂ，Ｓｎ−Ｂｉ−Ｓｅ，Ｓｎ−Ｂｉ−Ｃｏ，Ｓｎ−Ｂｉ−Ｃｕ，Ｓｎ−Ｂｉ−Ｎｉ，Ｓｎ−Ｂｉ−Ｐｔ，Ｓｎ−Ｂｉ−Ｔｅ，Ｓｎ−Ｂｉ−Ｃｅ，Ｓｎ−Ｂｉ−Ｃｄ，Ｚｎ−Ｓｎ−Ｓｂ，Ｚｎ−Ｓｎ−Ｓｅ，Ｚｎ−Ｓｎ−Ｃｏ，Ｚｎ−Ｓｎ−Ｃｕ，Ｚｎ−Ｓｎ−Ｎｉ，Ｚｎ−Ｓｎ−Ｐｔ，Ｚｎ−Ｓｎ−Ｎｉ，Ｚｎ−Ｓｎ−Ｌａ，Ｚｎ−Ｓｎ−Ｃｅ，Ｓｎ−Ｇａ−Ｓｂ，Ｓｎ−Ｇａ−Ｓｅ，Ｓｎ−Ｇａ−Ｃｏ，Ｓｂ−Ｇａ−Ｃｕ，Ｓｎ−Ｇａ−Ｎｉ，Ｓｎ−Ｇａ−Ｐｔ，Ｓｎ−Ｇａ−Ｃｒ，Ｓｎ−Ｇａ−Ｌａ，Ｓｎ−Ｇａ−Ｃｅ，Ｂｉ−Ｇａ−Ｔｅ，Ｂｉ−Ｇａ−Ｓｅ，Ｂｉ−Ｇａ−Ｃｕ，Ｂｉ−Ｇａ−Ｃｄ，Ｂｉ−Ｇａ−Ｐｔ，Ｂｉ−Ｇａ−Ｃｒ，Ｂｉ−Ｇａ−Ｎｉ，Ｂｉ−Ｇａ−Ｌａ，Ｂｉ−Ｇａ−Ｃｅ，Ｉｎ−Ｇａ−Ｃｒ，Ｉｎ−Ｇａ−Ｃｕ，Ｉｎ−Ｇａ−Ｎｉ，Ｉｎ−Ｇａ−Ｌａ，Ｉｎ−Ｇａ−Ｐｔ，Ｉｎ−Ｇａ−Ｃｅ，Ｉｎ−Ｇａ−Ｓｅ，Ｉｎ−Ｇａ−Ｓｂ，Ｉｎ−Ｇａ−Ｔｅ，Ｉｎ−Ｇａ−Ａｓ，Ｉｎ−Ｇａ−Ｍｎ，Ｉｎ−Ｇａ−Ａｇ，Ｉｎ−Ｂｉ−Ｔｅ，Ｉｎ−Ｂｉ−Ｓｅ，Ｉｎ−Ｂｉ−Ｃｕ，Ｉｎ−Ｂｉ−Ｃｄ，Ｉｎ−Ｂｉ−Ｐｔ，Ｉｎ−Ｂｉ−Ｓｂ，Ｉｎ−Ｂｉ−Ａｓ，Ｉｎ−Ｂｉ−Ｍｎ，Ｉｎ−Ｂｉ−Ｎｉ，Ｉｎ−Ｂｉ−Ａｇ，Ｉｎ−Ｂｉ−Ｃｅ，などに変更しても同様の結果が得られた。
〔実施例１９〕
前記実施例１６の（Ｓｎ₃Ｚｎ）₈₀（ＳｎＴｉ₂ ）₂₀よりなる超解像読み出し膜を、前記一般式（１１）で表される平均組成の材料、例えばＳｅ₅₁Ｉｎ₄₀Ｃｒ₉ （高融点成分Ｃｒ₃Ｓｅ₄；、相変化成分；ＩｎＳｅ）などに変更しても同様の結果が得られる。ただし、読み出し可能回数が２×１０⁶ 回以上、１０⁵ 回超解像読み出し後の再生信号のＣ／Ｎが４６ｄＢ以上となる前記一般式（１１）中のｐ，ｑ．ｒ，ｓの範囲は、４０≦ｐ≦９５、０≦ｑ≦５５、５≦ｒ≦５０、０≦ｓ≦２０であった。Ｃ／Ｎが４８ｄＢ以上となるより好ましい範囲は、５０≦ｐ≦８０、０≦ｑ≦４０、１０≦ｒ≦４０、０≦ｓ≦１０であった。また、この組成は、相変化記録膜２８としても使用できた。超解像読み出し膜を用いない記録媒体の相変化記録膜としても使用できる。
〔実施例２０〕
前記実施例１９のＳｅ−Ｉｎ−Ｃｒよりなる超解像読み出し膜を、前記一般式（２）で表される平均組成の材料、Ｓｅ−Ｉｎ−Ｓｉ，Ｓｅ−Ｉｎ−Ａｇ，Ｓｅ−Ｉｎ−Ａｌ，Ｓｅ−Ｉｎ−Ｂａ，Ｓｅ−Ｉｎ−Ｃａ，Ｓｅ−Ｉｎ−Ｃｄ，Ｓｅ−Ｉｎ−Ｃｏ，Ｓｅ−Ｉｎ−Ｃｕ，Ｓｅ−Ｉｎ−Ｍｇ，Ｓｅ−Ｉｎ−Ｍｎ，Ｓｅ−Ｉｎ−Ｍｏ，Ｓｅ−Ｉｎ−Ｎｉ，Ｓｅ−Ｉｎ−Ｐｄ，Ｓｅ−Ｉｎ−Ｐｔ，Ｓｅ−Ｉｎ−Ｔａ，Ｓｅ−Ｉｎ−Ｔｉ，Ｓｅ−Ｉｎ−Ｖ，Ｓｅ−Ｉｎ−Ｗ，Ｓｅ−Ｉｎ−Ｙ，Ｓｅ−Ｉｎ−Ｐｂ，Ｓｅ−Ｓｂ−Ｓｉ，Ｓｅ−Ｓｂ−Ａｇ，Ｓｅ−Ｓｂ−Ａｌ，Ｓｅ−Ｓｂ−Ｂａ，Ｓｅ−Ｓｂ−Ｃａ，Ｓｅ−Ｓｂ−Ｃｄ，Ｓｅ−Ｓｂ−Ｃｏ，Ｓｅ−Ｓｂ−Ｃｒ，Ｓｅ−Ｓｂ−Ｃｕ，Ｓｅ−Ｓｂ−Ｍｇ，Ｓｅ−Ｓｂ−Ｍｎ，Ｓｅ−Ｓｂ−Ｍｏ，Ｓｅ−Ｓｂ−Ｎｉ，Ｓｅ−Ｓｂ−Ｐｄ，Ｓｅ−Ｓｂ−Ｐｔ，Ｓｅ−Ｓｂ−Ｔａ，Ｓｅ−Ｓｂ−Ｔｉ，Ｓｅ−Ｓｂ−Ｖ，Ｓｅ−Ｓｂ−Ｗ，Ｓｅ−Ｓｂ−Ｙ，Ｓｅ−Ｓｂ−Ｐｂ，Ｓｅ−Ｂｉ−Ｓｉ，Ｓｅ−Ｂｉ−Ａｇ
，Ｓｅ−Ｂｉ−Ａｌ，Ｓｅ−Ｂｉ−Ｂａ，Ｓｅ−Ｂｉ−Ｃａ，Ｓｅ−Ｂｉ−Ｃｄ，Ｓｅ−Ｂｉ−Ｃｏ，Ｓｅ−Ｂｉ−Ｃｒ，Ｓｅ−Ｂｉ−Ｃｕ，Ｓｅ−Ｂｉ−Ｍｇ，Ｓｅ−Ｂｉ−Ｍｎ，Ｓｅ−Ｂｉ−Ｍｏ，Ｓｅ−Ｂｉ−Ｎｉ，Ｓｅ−Ｂｉ−Ｐｄ，Ｓｅ−Ｂｉ−Ｐｔ，Ｓｅ−Ｂｉ−Ｔａ，Ｓｅ−Ｂｉ−Ｔｉ，Ｓｅ−Ｂｉ−Ｖ，Ｓｅ−Ｂｉ−Ｗ，Ｓｅ−Ｂｉ−Ｙ，Ｓｅ−Ｂｉ−Ｐｂ，Ｓｅ−Ｔｅ−Ｓｉ，Ｓｅ−Ｔｅ−Ａｇ，Ｓｅ−Ｔｅ−Ａｌ，Ｓｅ−Ｔｅ−Ｂａ，Ｓｅ−Ｔｅ−Ｃａ，Ｓｅ−Ｔｅ−Ｃｄ，Ｓｅ−Ｔｅ−Ｃｏ，Ｓｅ−Ｔｅ−Ｃｒ，Ｓｅ−Ｔｅ−Ｃｕ，Ｓｅ−Ｔｅ−Ｍｇ，Ｓｅ−Ｔｅ−Ｍｎ，Ｓｅ−Ｔｅ−Ｍｏ，Ｓｅ−Ｔｅ−Ｎｉ，Ｓｅ−Ｔｅ−Ｐｄ，Ｓｅ−Ｔｅ−Ｐｔ，Ｓｅ−Ｔｅ−Ｔａ，Ｓｅ−Ｔｅ−Ｔｉ，Ｓｅ−Ｔｅ−Ｖ，Ｓｅ−Ｔｅ−Ｗ，Ｓｅ−Ｔｅ−Ｙ，Ｓｅ−Ｔｅ−Ｐｂ，Ｓｅ−Ａｕ−Ｓｉ，Ｓｅ−Ａｕ−Ａｇ，Ｓｅ−Ａｕ−Ａｌ，Ｓｅ−Ａｕ−Ｂａ，Ｓｅ−Ａｕ−Ｃａ，Ｓｅ−Ａｕ−Ｃｄ，Ｓｅ−Ａｕ−Ｃｏ，Ｓｅ−Ａｕ−Ｃｒ，Ｓｅ−Ａｕ−Ｃｕ，Ｓｅ−Ａｕ−Ｍｇ，Ｓｅ−Ａｕ−Ｍｎ，Ｓｅ−Ａｕ−Ｍｏ，Ｓｅ−Ａｕ−Ｎｉ，Ｓｅ−Ａｕ−Ｐｄ，Ｓｅ−Ａｕ−Ｐｔ，Ｓｅ−Ａｕ−Ｔａ，Ｓｅ−Ａｕ−Ｔｉ，Ｓｅ−Ａｕ−Ｖ，Ｓｅ−Ａｕ−Ｗ，Ｓｅ−Ａｕ−Ｙ，Ｓｅ−Ａｕ−Ｐｂ，Ｓｅ−Ｂ−Ｓｉ，Ｓｅ−Ｂ−Ａｇ，Ｓｅ−Ｂ−Ａｌ，Ｓｅ−Ｂ−Ｂａ，Ｓｅ−Ｂ−Ｃａ，Ｓｅ−Ｂ−Ｃｄ，Ｓｅ−Ｂ−Ｃｏ，Ｓｅ−Ｂ−Ｃｒ，Ｓｅ−Ｂ−Ｃｕ，Ｓｅ−Ｂ−Ｍｇ，Ｓｅ−Ｂ−Ｍｎ，Ｓｅ−Ｂ−Ｍｏ，Ｓｅ−Ｂ−Ｎｉ，Ｓｅ−Ｂ−Ｐｄ，Ｓｅ−Ｂ−Ｐｔ，Ｓｅ−Ｂ−Ｔａ，Ｓｅ−Ｂ−Ｔｉ，Ｓｅ−Ｂ−Ｖ，Ｓｅ−Ｂ−Ｗ，Ｓｅ−Ｂ−Ｙ，Ｓｅ−Ｂ−Ｐｂ，Ｓｅ−Ｃｓ−Ｓｉ，Ｓｅ−Ｃｓ−Ａｇ，Ｓｅ−Ｃｓ−Ａｌ，Ｓｅ−Ｃｓ−Ｂａ，Ｓｅ−Ｃｓ−Ｃａ，Ｓｅ−Ｃｓ−Ｃｄ，Ｓｅ−Ｃｓ−Ｃｏ，Ｓｅ−Ｃｓ−Ｃｒ，Ｓｅ−Ｃｓ−Ｃｕ，Ｓｅ−Ｃｓ−Ｍｇ，Ｓｅ−Ｃｓ−Ｍｎ，Ｓｅ−Ｃｓ−Ｍｏ，Ｓｅ−Ｃｓ−Ｎｉ，Ｓｅ−Ｃｓ−Ｐｄ，Ｓｅ−Ｃｓ−Ｐｔ，Ｓｅ−Ｃｓ−Ｔａ，Ｓｅ−Ｃｓ−Ｔｉ，Ｓｅ−Ｃｓ−Ｖ，Ｓｅ−Ｃｓ−Ｗ，Ｓｅ−Ｃｓ−Ｙ，Ｓｅ−Ｃｓ−Ｐｂ，Ｓｅ−Ｓｎ−Ｓｉ，Ｓｅ−Ｓｎ−Ａｇ，Ｓｅ−Ｓｎ−Ａｌ，Ｓｅ−Ｓｎ−Ｂａ，Ｓｅ−Ｓｎ−Ｃａ，Ｓｅ−Ｓｎ−Ｃｄ，Ｓｅ−Ｓｎ−Ｃｏ，Ｓｅ−Ｓｎ−Ｃｒ，Ｓｅ−Ｓｎ−Ｃｕ，Ｓｅ−Ｓｎ−Ｍｇ，Ｓｅ−Ｓｎ−Ｍｎ，Ｓｅ−Ｓｎ−Ｍｏ，Ｓｅ−Ｓｎ−Ｎｉ，Ｓｅ−Ｓｎ−Ｐｄ，Ｓｅ−Ｓｎ−Ｐｔ，Ｓｅ−Ｓｎ−Ｔａ，Ｓｅ−Ｓｎ−Ｔｉ，Ｓｅ−Ｓｎ−Ｖ，Ｓｅ−Ｓｎ−Ｗ，Ｓｅ−Ｓｎ−Ｙ，Ｓｅ−Ｓｎ−Ｐｂ，Ｓｅ−Ｔｌ−Ｓｉ，Ｓｅ−Ｔｌ−Ａｇ，Ｓｅ−Ｔｌ−Ａｌ，Ｓｅ−Ｔｌ−Ｂａ，Ｓｅ−Ｔｌ−Ｃａ，Ｓｅ−Ｔｌ−Ｃｄ，Ｓｅ−Ｔｌ−Ｃｏ，Ｓｅ−Ｔｌ−Ｃｒ，Ｓｅ−Ｔｌ−Ｃｕ，Ｓｅ−Ｔｌ−Ｍｇ，Ｓｅ−Ｔｌ−Ｍｎ，Ｓｅ−Ｔｌ−Ｍｏ，Ｓｅ−Ｔｌ−Ｎｉ，Ｓｅ−Ｔｌ−Ｐｄ，Ｓｅ−Ｔｌ−Ｐｔ，Ｓｅ−Ｔｌ−Ｔａ，Ｓｅ−Ｔｌ−Ｔｉ，Ｓｅ−Ｔｌ−Ｖ，Ｓｅ−Ｔｌ−Ｗ，Ｓｅ−Ｔｌ−Ｙ，Ｓｅ−Ｔｌ−Ｐｂ，Ｓｅ−Ｓ−Ｓｉ，Ｓｅ−Ｓ−Ａｇ，Ｓｅ−Ｓ−Ａｌ，Ｓｅ−Ｓ−Ｂａ，Ｓｅ−Ｓ−Ｃａ，Ｓｅ−Ｓ−Ｃｄ，Ｓｅ−Ｓ−Ｃｏ，Ｓｅ−Ｓ−Ｃｒ，Ｓｅ−Ｓ−Ｃｕ，Ｓｅ−Ｓ−Ｍｇ，Ｓｅ−Ｓ−Ｍｎ，Ｓｅ−Ｓ−Ｍｏ，Ｓｅ−Ｓ−Ｎｉ，Ｓｅ−Ｓ−Ｐｄ，Ｓｅ−Ｓ−Ｐｔ，Ｓｅ−Ｓ−Ｔａ，Ｓｅ−Ｓ−Ｔｉ，Ｓｅ−Ｓ−Ｖ，Ｓｅ−Ｓ−Ｗ，Ｓｅ−Ｓ−Ｙ，Ｓｅ−Ｓ−Ｐｂ，Ｓｅ−Ｇｅ−Ｓｉ，Ｓｅ−Ｇｅ−Ａｇ，Ｓｅ−Ｇｅ−Ａｌ，Ｓｅ−Ｇｅ−Ｂａ，Ｓｅ−Ｇｅ−Ｃａ，Ｓｅ−Ｇｅ−Ｃｄ，Ｓｅ−Ｇｅ−Ｃｏ，Ｓｅ−Ｇｅ−Ｃｒ，Ｓｅ−Ｇｅ−Ｃｕ，Ｓｅ−Ｇｅ−Ｍｇ，Ｓｅ−Ｇｅ−Ｍｎ，Ｓｅ−Ｇｅ−Ｍｏ，Ｓｅ−Ｇｅ−Ｎｉ，Ｓｅ−Ｇｅ−Ｐｄ，Ｓｅ−Ｇｅ−Ｐｔ，Ｓｅ−Ｇｅ−Ｔａ，Ｓｅ−Ｇｅ−Ｔｉ，Ｓｅ−Ｇｅ−Ｖ，Ｓｅ−Ｇｅ−Ｗ，Ｓｅ−Ｇｅ−Ｙ，Ｓｅ−Ｇｅ−Ｐｂ，Ｓｅ−Ｆｅ−Ｓｉ，Ｓｅ−Ｆｅ−Ａｇ，Ｓｅ−Ｆｅ−Ａｌ，Ｓｅ−Ｆｅ−Ｂａ，Ｓｅ−Ｆｅ−Ｃａ，Ｓｅ−Ｆｅ−Ｃｄ，Ｓｅ−Ｆｅ−Ｃｏ，Ｓｅ−Ｆｅ−Ｃｒ，Ｓｅ−Ｆｅ−Ｃｕ，Ｓｅ−Ｆｅ−Ｍｇ，Ｓｅ−Ｆｅ−Ｍｎ，Ｓｅ−Ｆｅ−Ｍｏ，Ｓｅ−Ｆｅ−Ｎｉ，Ｓｅ−Ｆｅ−Ｐｄ，Ｓｅ−Ｆｅ−Ｐｔ，Ｓｅ−Ｆｅ−Ｔａ，Ｓｅ−Ｆｅ−Ｔｉ，Ｓｅ−Ｆｅ−Ｖ，Ｓｅ−Ｆｅ−Ｗ，Ｓｅ−Ｆｅ−Ｙ，Ｓｅ−Ｆｅ−Ｐｂ，Ｓｅ−Ｚｎ−Ｓｉ，Ｓｅ−Ｚｎ−Ａｇ，Ｓｅ−Ｚｎ−Ａｌ，Ｓｅ−Ｚｎ−Ｂａ，Ｓｅ−Ｚｎ−Ｃａ，Ｓｅ−Ｚｎ−Ｃｄ，Ｓｅ−Ｚｎ−Ｃｏ，Ｓｅ−Ｚｎ−Ｃｒ，Ｓｅ−Ｚｎ−Ｃｕ，Ｓｅ−Ｚｎ−Ｍｇ，Ｓｅ−Ｚｎ−Ｍｎ，Ｓｅ−Ｚｎ−Ｍｏ，Ｓｅ−Ｚｎ−Ｎｉ，Ｓｅ−Ｚｎ−Ｐｄ，Ｓｅ−Ｚｎ−Ｐｔ，Ｓｅ−Ｚｎ−Ｔａ，Ｓｅ−Ｚｎ−Ｔｉ，Ｓｅ−Ｚｎ−Ｖ，Ｓｅ−Ｚｎ−Ｗ，Ｓｅ−Ｚｎ−Ｙ，Ｓｅ−Ｚｎ−Ｐｂ，などに変更しても同様の結果が得られた。
〔実施例２１〕
図７は、基板の表面に凹凸のビットで情報が刻まれた再生専用のディスク状情報記録媒体の断面を示す。 Further, in the combination of D, D ′ (when D is D, D′ 2 element like Sn and Zn), E, and F, the combination of DE, EF, and D′-E It is preferable that the resulting high melting point component has no eutectic point, or even if it has a eutectic point, the melting point is 150 ° C. or more higher than the melting points of D and DD ′.
[Example 18]
The super-resolution readout film made of Sn-Zn-Ti of Example 16 was replaced with a material having an average composition represented by the general formula (8), Pb-Se, Pb-Ce, Pb-La, Pb-Pt, Pb-Si, Sn-Sb, Sn-Se, Sn-Co, Sn-Cu, Sn-Ni, Sn-Pt, Bi-Te, Bi-Se, Bi-Ce, Bi-Cu, Bi-Cd, Bi- Pt, Zn-Ni, Zn-Pt, Zn-La, Zn-Ce, Ga-Cr, Ga-Cu, Ga-Ni, Ga-La, Ga-Pt, Ga-Ce, In-Se, In-Sb, In-Te, In-As, In-Mn, In-Ni, In-Ag, Pb-Sn-Se, Pb-Sn-Ce, Pb-Sn-La, Pb-Sn-Pt, Pb-Sn-Si, Pb-Sn-Sb, Pb-Sn-Co, Pb-Sn-Cu, Pb-Sn- i, Sn-Bi-Sb, Sn-Bi-Se, Sn-Bi-Co, Sn-Bi-Cu, Sn-Bi-Ni, Sn-Bi-Pt, Sn-Bi-Te, Sn-Bi-Ce, Sn-Bi-Cd, Zn-Sn-Sb, Zn-Sn-Se, Zn-Sn-Co, Zn-Sn-Cu, Zn-Sn-Ni, Zn-Sn-Pt, Zn-Sn-Ni, Zn- Sn-La, Zn-Sn-Ce, Sn-Ga-Sb, Sn-Ga-Se, Sn-Ga-Co, Sb-Ga-Cu, Sn-Ga-Ni, Sn-Ga-Pt, Sn-Ga- Cr, Sn-Ga-La, Sn-Ga-Ce, Bi-Ga-Te, Bi-Ga-Se, Bi-Ga-Cu, Bi-Ga-Cd, Bi-Ga-Pt, Bi-Ga-Cr, Bi-Ga-Ni, Bi-Ga-La, Bi-Ga-Ce, In-Ga- r, In-Ga-Cu, In-Ga-Ni, In-Ga-La, In-Ga-Pt, In-Ga-Ce, In-Ga-Se, In-Ga-Sb, In-Ga-Te, In-Ga-As, In-Ga-Mn, In-Ga-Ag, In-Bi-Te, In-Bi-Se, In-Bi-Cu, In-Bi-Cd, In-Bi-Pt, In- Similar results were obtained by changing to Bi-Sb, In-Bi-As, In-Bi-Mn, In-Bi-Ni, In-Bi-Ag, In-Bi-Ce, or the like.
[Example 19]
The super-resolution readout film made of (Sn ₃ Zn) ₈₀ (SnTi ₂ ) _{20 in} Example 16 was replaced with a material having an average composition represented by the general formula (11), for example, Se ₅₁ In ₄₀ Cr ₉ (high melting point). The same result can be obtained by changing the component to Cr ₃ Se ₄ ; phase change component; InSe). However, when the number of readable times is 2 × 10 ⁶ times or more and 10 ⁵ times or more, the C / N of the reproduced signal after the super-resolution reading becomes 46 dB or more, p, q. The ranges of r and s were 40 ≦ p ≦ 95, 0 ≦ q ≦ 55, 5 ≦ r ≦ 50, and 0 ≦ s ≦ 20. More preferable ranges in which C / N is 48 dB or more were 50 ≦ p ≦ 80, 0 ≦ q ≦ 40, 10 ≦ r ≦ 40, and 0 ≦ s ≦ 10. This composition could also be used as the phase change recording film 28. It can also be used as a phase change recording film of a recording medium that does not use a super-resolution readout film.
[Example 20]
The super-resolution readout film made of Se-In-Cr of Example 19 was replaced with a material having an average composition represented by the general formula (2), Se-In-Si, Se-In-Ag, and Se-In- Al, Se-In-Ba, Se-In-Ca, Se-In-Cd, Se-In-Co, Se-In-Cu, Se-In-Mg, Se-In-Mn, Se-In-Mo, Se-In-Ni, Se-In-Pd, Se-In-Pt, Se-In-Ta, Se-In-Ti, Se-In-V, Se-In-W, Se-In-Y, Se- In-Pb, Se-Sb-Si, Se-Sb-Ag, Se-Sb-Al, Se-Sb-Ba, Se-Sb-Ca, Se-Sb-Cd, Se-Sb-Co, Se-Sb- Cr, Se-Sb-Cu, Se-Sb-Mg, Se-Sb-Mn, Se-Sb- o, Se-Sb-Ni, Se-Sb-Pd, Se-Sb-Pt, Se-Sb-Ta, Se-Sb-Ti, Se-Sb-V, Se-Sb-W, Se-Sb-Y, Se-Sb-Pb, Se-Bi-Si, Se-Bi-Ag
, Se-Bi-Al, Se-Bi-Ba, Se-Bi-Ca, Se-Bi-Cd, Se-Bi-Co, Se-Bi-Cr, Se-Bi-Cu, Se-Bi-Mg, Se -Bi-Mn, Se-Bi-Mo, Se-Bi-Ni, Se-Bi-Pd, Se-Bi-Pt, Se-Bi-Ta, Se-Bi-Ti, Se-Bi-V, Se-Bi. -W, Se-Bi-Y, Se-Bi-Pb, Se-Te-Si, Se-Te-Ag, Se-Te-Al, Se-Te-Ba, Se-Te-Ca, Se-Te-Cd , Se-Te-Co, Se-Te-Cr, Se-Te-Cu, Se-Te-Mg, Se-Te-Mn, Se-Te-Mo, Se-Te-Ni, Se-Te-Pd, Se -Te-Pt, Se-Te-Ta, Se-Te-Ti, Se-Te-V, Se- e-W, Se-Te-Y, Se-Te-Pb, Se-Au-Si, Se-Au-Ag, Se-Au-Al, Se-Au-Ba, Se-Au-Ca, Se-Au- Cd, Se-Au-Co, Se-Au-Cr, Se-Au-Cu, Se-Au-Mg, Se-Au-Mn, Se-Au-Mo, Se-Au-Ni, Se-Au-Pd, Se-Au-Pt, Se-Au-Ta, Se-Au-Ti, Se-Au-V, Se-Au-W, Se-Au-Y, Se-Au-Pb, Se-B-Si, Se- B-Ag, Se-B-Al, Se-B-Ba, Se-B-Ca, Se-B-Cd, Se-B-Co, Se-B-Cr, Se-B-Cu, Se-B- Mg, Se-B-Mn, Se-B-Mo, Se-B-Ni, Se-B-Pd, Se-B-Pt, Se-B- a, Se-B-Ti, Se-BV, Se-B-W, Se-BY, Se-B-Pb, Se-Cs-Si, Se-Cs-Ag, Se-Cs-Al, Se-Cs-Ba, Se-Cs-Ca, Se-Cs-Cd, Se-Cs-Co, Se-Cs-Cr, Se-Cs-Cu, Se-Cs-Mg, Se-Cs-Mn, Se- Cs-Mo, Se-Cs-Ni, Se-Cs-Pd, Se-Cs-Pt, Se-Cs-Ta, Se-Cs-Ti, Se-Cs-V, Se-Cs-W, Se-Cs- Y, Se-Cs-Pb, Se-Sn-Si, Se-Sn-Ag, Se-Sn-Al, Se-Sn-Ba, Se-Sn-Ca, Se-Sn-Cd, Se-Sn-Co, Se-Sn-Cr, Se-Sn-Cu, Se-Sn-Mg, Se-Sn-Mn, Se-Sn-Mo, Se-Sn-Ni, Se-Sn-Pd, Se-Sn-Pt, Se-Sn-Ta, Se-Sn-Ti, Se-Sn-V, Se-Sn-W, Se-Sn-Y, Se- Sn-Pb, Se-Tl-Si, Se-Tl-Ag, Se-Tl-Al, Se-Tl-Ba, Se-Tl-Ca, Se-Tl-Cd, Se-Tl-Co, Se-Tl- Cr, Se-Tl-Cu, Se-Tl-Mg, Se-Tl-Mn, Se-Tl-Mo, Se-Tl-Ni, Se-Tl-Pd, Se-Tl-Pt, Se-Tl-Ta, Se-Tl-Ti, Se-Tl-V, Se-Tl-W, Se-Tl-Y, Se-Tl-Pb, Se-S-Si, Se-S-Ag, Se-S-Al, Se- S-Ba, Se-S-Ca, Se-S-Cd, Se-S-Co, Se-S-Cr, Se-S- u, Se-S-Mg, Se-S-Mn, Se-S-Mo, Se-S-Ni, Se-S-Pd, Se-S-Pt, Se-S-Ta, Se-S-Ti, Se-SV, Se-SW, Se-SY, Se-S-Pb, Se-Ge-Si, Se-Ge-Ag, Se-Ge-Al, Se-Ge-Ba, Se- Ge-Ca, Se-Ge-Cd, Se-Ge-Co, Se-Ge-Cr, Se-Ge-Cu, Se-Ge-Mg, Se-Ge-Mn, Se-Ge-Mo, Se-Ge- Ni, Se-Ge-Pd, Se-Ge-Pt, Se-Ge-Ta, Se-Ge-Ti, Se-Ge-V, Se-Ge-W, Se-Ge-Y, Se-Ge-Pb, Se-Fe-Si, Se-Fe-Ag, Se-Fe-Al, Se-Fe-Ba, Se-Fe-Ca, Se-Fe- d, Se-Fe-Co, Se-Fe-Cr, Se-Fe-Cu, Se-Fe-Mg, Se-Fe-Mn, Se-Fe-Mo, Se-Fe-Ni, Se-Fe-Pd, Se-Fe-Pt, Se-Fe-Ta, Se-Fe-Ti, Se-Fe-V, Se-Fe-W, Se-Fe-Y, Se-Fe-Pb, Se-Zn-Si, Se- Zn-Ag, Se-Zn-Al, Se-Zn-Ba, Se-Zn-Ca, Se-Zn-Cd, Se-Zn-Co, Se-Zn-Cr, Se-Zn-Cu, Se-Zn- Mg, Se—Zn—Mn, Se—Zn—Mo, Se—Zn—Ni, Se—Zn—Pd, Se—Zn—Pt, Se—Zn—Ta, Se—Zn—Ti, Se—Zn—V, Similar results are obtained even when the material is changed to Se-Zn-W, Se-Zn-Y, Se-Zn-Pb, or the like. was gotten.
[Example 21]
FIG. 7 shows a cross section of a read-only disc-shaped information recording medium in which information is engraved on the surface of a substrate with uneven bits.

このディスク状媒体は、基板の表面にビットが形成されていること、および記録膜をマスク層１３，１３’として用いた点が、実施例１のディスク状媒体と異なっているのみであり、他の構成は同じである。 This disk-shaped medium is different from the disk-shaped medium of Example 1 only in that bits are formed on the surface of the substrate and that the recording film is used as the mask layers 13 and 13 '. Is the same.

すなわち、表面に情報ビットを有するポリカーボネート基板１１，１１’の上に、膜厚約１２５ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる保護層１２，１２’がそれぞれ形成され、保護層１２，１２’の上には順に、平均膜厚３ｎｍの島状のＡｇ₂Ｔｅ膜（図示せず）と、膜厚約３０ｎｍの
（（Ａｇ₂Ｔｅ）₃₀（Ｓｅ₈₀−Ｔｅ₂₀）₇₀すなわちＡｇ₂₀Ｔｅ₂₄Ｓｅ₅₆の組成のマスク層１３，１３’と、膜厚約２５ｎｍの（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層１４，１４’と、膜厚８０ｎｍのＡｌ₉₇Ｔｉ₃膜よりなる反射層１５，１５’が、それぞれ形成されている。反射層１５，１５’同士は、塩化ビニル・酢酸ビニル系ホットメルト接着剤層１６によって貼り合わされている。読み出し用のレーザ光は、基板側から入射される。マスク層１３，１３’の中には、実施例１と同様の形態（図１参照）で高融点成分Ａｇ₂Ｔｅが析出しており、その残成分（図１における相変化成分３ａに相当するもの）は（Ｓｅ₈₀−Ｔｅ₂₀）である。
（高融点成分の他の例）
マスク層１３，１３’中に析出した高融点成分としては、Ａｇ₂Ｔｅ以外に、実施例１および３で述べたものを用いることができる。島状のＡｇ₂Ｔｅ膜の形成は省略してもよい。
（高融点成分析出後の残成分の他の例）
高融点成分以外の残成分であるＳｅ₈₀−Ｔｅ₂₀の一部または全部を
Ｓｎ，Ｐｂ，Ｓｂ，Ｂｉ，Ｔｅ，Ｚｎ，Ｃｄ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，Ｔｌ，
Ｍｇ，Ｔｌ₂Ｓｅ，ＴｌＳｅ，Ｔｌ₂Ｓｅ₃，Ｔｌ₃Ｔｅ₂，ＴｌＴｅ，ＩｎＢｉ，Ｉｎ₂Ｂｉ，ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，
Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ，
Ｉｎ₃ＳｅＴｅ₂，ＡｇＩｎＴｅ₂，ＧｅＳｂ₄Ｔｅ₇，Ｇｅ₂Ｓｂ₂Ｔｅ₅，
ＧｅＳｂ₂Ｔｅ₄，ＧｅＢ₄Ｔｅ₇，ＧｅＢｉ₂Ｔｅ₄，Ｇｅ₃Ｂｉ₂Ｔｅ₆，
Ｓｎ₂Ｓｂ₆Ｓｅ₁₁，Ｓｎ₂Ｓｂ₂Ｓｅ₅，ＳｎＳｂ₂Ｔｅ₄，Ｐｂ₂Ｓｂ₆Ｔｅ₁₁，
ＣｕＡｓＳｅ₂，Ｃｕ₃ＡｓＳｅ₃，ＣｕＳｂＳ₂，ＣｕＳｂＳｅ₂，ＩｎＳｅ，
Ｓｂ₂Ｓｅ₃，Ｓｂ₂Ｔｅ₃，Ｂｉ₂Ｔｅ₃，ＳｎＳｂ，ＦｅＴｅ，Ｆｅ₂Ｔｅ₃，
ＦｅＴｅ₂，ＺｎＳｂ，Ｚｎ₃Ｓｂ₂，ＶＴｅ₂，Ｖ₅Ｔｅ₈，ＡｇＩｎ₂，
ＢｉＳｅ，ＩｎＳｂ，Ｉｎ₂Ｔｅ，Ｉｎ₂Ｔｅ₅
のうちの少なくとも一者を主成分とする材料、あるいはそれに近い組成の材料で置き換えても、近い特性が得られる。 That is, on the polycarbonate substrates 11 and 11 ′ having information bits on the surface, protective layers 12 and 12 ′ each made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 125 nm are formed, respectively. On top of 12 ′, an island-shaped Ag ₂ Te film (not shown) having an average film thickness of 3 nm and ((Ag ₂ Te) ₃₀ (Se ₈₀ −Te ₂₀ ) _70, that is, Ag ₂₀ ) having a film thickness of about 30 nm are sequentially formed. From the mask layers 13 and 13 ′ having a composition of Te ₂₄ Se _56, the intermediate layers 14 and 14 ′ made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film having a thickness of about 25 nm, and the Al ₉₇ Ti ₃ film having a thickness of 80 nm The reflective layers 15 and 15 'are respectively bonded to each other by a vinyl chloride / vinyl acetate hot melt adhesive layer 16. The laser beam for reading is applied to the substrate. It is incident from the side. Among 13, 13 ', as in Example 1 embodiment (see FIG. 1) has a high melting point component Ag ₂ Te is precipitated, (corresponding to the phase change component 3a in FIG. 1) the residue component is (Se ₈₀ -Te _20).
(Other examples of high melting point components)
The high melting point component precipitated in the mask layer 13, 13 ', in addition to Ag ₂ Te, can be used those described in Examples 1 and 3. The formation of the island-shaped Ag ₂ Te film may be omitted.
(Other examples of residual components after deposition of high melting point components)
Part or all of the remaining component other than the high melting point component, Se ₈₀ -Te ₂₀ , is Sn, Pb, Sb, Bi, Te, Zn, Cd, Se, In, Ga, S, Tl,
_{Mg, Tl 2 Se, TlSe,} Tl 2 Se 3, Tl 3 Te 2, TlTe, InBi, In 2 Bi, TeBi, TlSe, TlTe, Pb-Sn, Bi-Sn,
Se-Te, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In,
In ₃ SeTe ₂ , AgInTe ₂ , GeSb ₄ Te ₇ , Ge ₂ Sb ₂ Te ₅ ,
GeSb ₂ Te ₄ , GeB ₄ Te ₇ , GeBi ₂ Te ₄ , Ge ₃ Bi ₂ Te ₆ ,
Sn ₂ Sb ₆ Se ₁₁ , Sn ₂ Sb ₂ Se ₅ , SnSb ₂ Te ₄ , Pb ₂ Sb ₆ Te ₁₁ ,
CuAsSe ₂ , Cu ₃ AsSe ₃ , CuSbS ₂ , CuSbSe ₂ , InSe,
Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ Te ₃ , SnSb, FeTe, Fe ₂ Te ₃ ,
FeTe ₂ , ZnSb, Zn ₃ Sb ₂ , VTe ₂ , V ₅ Te ₈ , AgIn ₂ ,
BiSe, InSb, In ₂ Te, In ₂ Te ₅
Even if a material having at least one of them as a main component or a material having a composition close thereto is used, similar characteristics can be obtained.

この残成分は、融点が６５０゜Ｃ以下である金属、化合物または合金が好ましい。 This residual component is preferably a metal, compound or alloy having a melting point of 650 ° C. or less.

また、超解像読みだしにおいて、各層の膜厚を変えれば、図１４とは逆に光スポット内の斜線部以外の領域だけをマスクすることもできる。 In super-resolution reading, by changing the film thickness of each layer, it is possible to mask only the region other than the hatched portion in the light spot, contrary to FIG.

残成分の融点が２５０゜Ｃ以下の場合、高融点成分の融点は４５０゜Ｃ以上であれば、これに近い特性が得られる。 When the melting point of the remaining component is 250 ° C. or less, if the melting point of the high melting point component is 450 ° C. or more, characteristics close to this can be obtained.

光スポット３１の直径の約２５％の長さの記録マークが形成されている場合、レーザ光の照射の前後におけるマスク層１３，１３’の消衰係数ｋの変化量△ｋ
’が変化すると、１０⁵回読み出した後の再生信号のＣ／Ｎは、次のように変化した。 When a recording mark having a length of about 25% of the diameter of the light spot 31 is formed, the change amount △ k of the extinction coefficient k of the mask layers 13 and 13 'before and after the irradiation of the laser beam.
When 'changes, C / N of the reproduced signal after read ¹⁰⁵ times varied as follows.

１０⁵回読み出し後の再生信号のＣ／Ｎ
△ｋ’＝５％３７ｄＢ
△ｋ’＝１０％４２ｄＢ
△ｋ’＝２０％４６ｄＢ
△ｋ’＝３０％４８ｄＢ
この結果より、２０％≦△ｋ’の範囲が好ましいことが分かった。 105 C / N of playback signal after ⁵ readings
△ k '= 5% 37dB
Δk ′ = 10% 42 dB
Δk ′ = 20% 46 dB
Δk '= 30% 48 dB
From this result, it was found that the range of 20% ≦ △ k ′ was preferable.

高融点成分の析出後の残成分の融点（ｍ．ｐ．）が変化した場合、１０⁵回読み出した後の再生信号のＣ／Ｎは、次のように変化した。 If the melting point of the remaining component after precipitation of the high melting point component (m.p) is changed, C / N of the reproduced signal after reading 10 ⁵ times, were changed as follows.

１０⁵回読み出しの後の再生信号のＣ／Ｎ
ｍ．ｐ．＝１００゜Ｃ４９ｄＢ
ｍ．ｐ．＝２５０゜Ｃ４８ｄＢ
ｍ．ｐ．＝４００゜Ｃ４７ｄＢ
ｍ．ｐ．＝６５０゜Ｃ４６ｄＢ
ｍ．ｐ．＝７００゜Ｃ４０ｄＢ
ｍ．ｐ．＝７５０゜Ｃ３３ｄＢ
この結果より、高融点成分析出後の残成分の融点は、６５０゜Ｃ以下が好ましく、２５０゜Ｃ以下がより好ましいことが分かった。
〔実施例２２〕
図９は、実施例１の相変化型の情報記録媒体に実施例４と同様のマスク層を設けることによって、情報の再生時に「超解像効果」を利用できるようにした情報記録媒体の一例である。 10 of the reproduction signal after the ^five read C / N
m. p. = 100 ゜ C 49dB
m. p. = 250 ° C 48dB
m. p. = 400 ゜ C 47dB
m. p. = 650 ° C 46dB
m. p. = 700 ° C 40dB
m. p. = 750 ° C 33dB
From this result, it was found that the melting point of the residual component after the precipitation of the high melting point component was preferably 650 ° C. or lower, more preferably 250 ° C. or lower.
[Example 22]
FIG. 9 shows an example of an information recording medium in which the "super-resolution effect" can be used when reproducing information by providing the same phase change type information recording medium of Example 1 with a mask layer as in Example 4. It is.

このディスク状媒体は、記録膜の構成が異なる以外は実施例１の情報記録媒体と同じ構成を持つ。すなわち、実施例１と同様のポリカーボネート基板１，１’の上に、（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる保護層２，２’がそれぞれ形成され、保護層２，２’の上には順に、記録膜３，３’と（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜よりなる中間層４，４’とＡｌ₉₇Ｔｉ₃膜よりなる反射層５，５’とが、それぞれ形成されている。反射層５，５’同士は、接着剤層６によって貼り合わされている。 This disk-shaped medium has the same configuration as the information recording medium of the first embodiment except that the configuration of the recording film is different. That is, protective layers 2 and 2 ′ made of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film are formed on the same polycarbonate substrates 1 and 1 ′ as in Example 1, respectively. in turn, the recording film 3, 3 and 'a (ZnS) ₈₀ (SiO ₂₎ consisting of ₂₀ film intermediate layers 4 and 4' and the Al ₉₇ Ti ₃ consisting film reflective layers 5 and 5 ', are formed respectively . The reflection layers 5 and 5 ′ are bonded together by an adhesive layer 6.

記録膜３’は、基板１’側から順に配置されたマスク層、誘電体層および記録層から構成されている。記録膜３も記録膜３’と同じ構成である。 The recording film 3 'is composed of a mask layer, a dielectric layer, and a recording layer arranged in this order from the substrate 1' side. The recording film 3 has the same configuration as the recording film 3 '.

マスク層は、実施例２１と同じ
（（Ａｇ₂Ｔｅ）₃₀（Ｓｅ₈₀−Ｔｅ₂₀）₇₀すなわちＡｇ₂₀Ｔｅ₂₄Ｓｅ₅₆の組成を持ち、実施例２１と同じマスク機能を有している。誘電体層は（ＺｎＳ）₈₀（ＳｉＯ₂）₂₀膜により形成されている。記録層としては、実施例１の記録膜３，３’と同じものの他、任意の相変化型の記録層を使用できる。 The mask layer has the same composition of ((Ag ₂ Te) ₃₀ (Se ₈₀ -Te ₂₀ ) _70, that is, Ag ₂₀ Te ₂₄ Se ₅₆ , as in Example 21, and has the same mask function as in Example 21. The body layer is formed of a (ZnS) ₈₀ (SiO ₂ ) ₂₀ film As the recording layer, any phase change type recording layer can be used in addition to the same as the recording films 3 and 3 ′ of the first embodiment. .

長さ０．４μｍの記録マークを０．８μｍ周期で形成した場合、得られた再生信号のＣ／Ｎは４６ｄＢ以上、消去比は２５ｄＢ以上であった。 When recording marks having a length of 0.4 μm were formed at a period of 0.8 μm, the C / N of the obtained reproduced signal was 46 dB or more, and the erasing ratio was 25 dB or more.

このマスク層は、この発明の情報記録用薄膜以外の従来の相変化によって記録を行な情報記録媒体や、光磁気ディスクなどの相変化以外の記録原理による情報記録媒体においても同様な効果を持つ。 This mask layer has the same effect in an information recording medium that performs recording by a conventional phase change other than the information recording thin film of the present invention, and an information recording medium such as a magneto-optical disk that uses a recording principle other than the phase change. .

この実施例で述べていない点については、実施例１と同様である。
〔実施例２３〕
この実施例のディスク状情報記録媒体は、図示していないが、実施例１の図３に示したのとほぼ同じ構成であり、実施例１のＡｌ−Ｔｉ反射層１，１’に代えて、記録膜３，３’のような高融点成分を含む層を反射層として用いている点のみが異なる。 The points not described in this embodiment are the same as in the first embodiment.
[Example 23]
Although not shown, the disc-shaped information recording medium of this embodiment has substantially the same configuration as that shown in FIG. 3 of the first embodiment, and is replaced with the Al—Ti reflective layers 1, 1 ′ of the first embodiment. The only difference is that a layer containing a high melting point component such as the recording films 3 and 3 'is used as a reflective layer.

反射層中の高融点成分については、実施例１と同様である。 The high melting point component in the reflection layer is the same as in Example 1.

反射層中の高融点成分が析出した後の残成分については、融点が６５０゜Ｃ以下である金属、化合物または合金が好ましく、且つ、複素屈折率の実数部ｎまたは虚数部（消衰係数）ｋがレーザ光の照射によって２０％以上変化し、また実数部ｎおよび虚数部ｋが高いときに反射率Ｒが６０％以上となるのが好ましい。 Regarding the remaining component after the high melting point component is precipitated in the reflective layer, a metal, a compound or an alloy having a melting point of 650 ° C. or less is preferable, and a real part n or an imaginary part (extinction coefficient) of a complex refractive index. It is preferable that k changes by 20% or more by the irradiation of the laser beam, and that the reflectance R becomes 60% or more when the real part n and the imaginary part k are high.

反射層として、膜厚８０ｎｍの（ＬａＢｉ）₃₀Ｂｉ₇₀層を用いた場合、読み出し時の超解像効果が得られ、長さ０．４μｍの記録マークを０．８μｍ周期で書いた場合、得られた再生信号のＣ／Ｎは４６ｄＢ以上、消去比は２５ｄＢ以上であった。なお、（ＬａＢｉ）₃₀Ｂｉ₇₀層では、高融点成分はＬａＢｉであり、
相変化成分はＢｉである。 When a (LaBi) ₃₀ Bi ₇₀ layer having a film thickness of 80 nm is used as the reflective layer, a super-resolution effect at the time of reading is obtained. When a recording mark having a length of 0.4 μm is written at a period of 0.8 μm, the effect is obtained. The reproduced signal had a C / N of 46 dB or more and an erasing ratio of 25 dB or more. In the (LaBi) ₃₀ Bi ₇₀ layer, the high melting point component is LaBi,
The phase change component is Bi.

超解像効果が得られる原理は、次の通りである。図８に示すように、光スポット３１内の高温領域３５では、反射層中の少なくとも相変化成分Ｂｉが融解して、複素屈折率の実数部ｎまたは虚数部ｋの少なくとも一方が低下するため、図８のマスクとして働く範囲３３での反射光が弱くなる。このため、範囲３３からの反射光は、記録膜に対して読み取りのための充分なコントラストを提供できなくなる。 The principle by which the super-resolution effect is obtained is as follows. As shown in FIG. 8, in the high temperature region 35 in the light spot 31, at least one of the real part n and the imaginary part k of the complex refractive index decreases because at least the phase change component Bi in the reflective layer is melted. The reflected light in the range 33 serving as the mask in FIG. 8 is weakened. For this reason, the reflected light from the range 33 cannot provide sufficient contrast for reading to the recording film.

一方、結晶化した固体状態の低温領域では、高温領域に比べて複素屈折率の実数部ｎまたは虚数部ｋの少なくとも一方が大きいため、読み取りのための充分なコントラストを提供できる。 On the other hand, in the crystallized solid-state low-temperature region, since at least one of the real part n and the imaginary part k of the complex refractive index is larger than in the high-temperature region, a sufficient contrast for reading can be provided.

その結果、検出範囲３４が図８のような三日月形になり、光スポット３１の直径以下の周期で高密度記録された記録マーク３２を確実に読み出すことが可能となる。 As a result, the detection range 34 has a crescent shape as shown in FIG. 8, and it is possible to reliably read the recording marks 32 recorded at a high density with a period equal to or less than the diameter of the light spot 31.

各層の膜厚を変えれば、検出範囲３４の大きさを変えることもできる。
（残成分の他の例）
高融点成分ＬａＢｉの残成分であるＢiの一部または全部を
Ｓｎ，Ｐｂ，Ｓｂ，Ｔｅ，Ｚｎ，Ｃｄ，Ｓｅ，Ｉｎ，Ｇａ，Ｓ，Ｔｌ，Ｍｇ，
Ｔｌ₂Ｓｅ，ＴｌＳｅ，Ｔｌ₂Ｓｅ₃，Ｔｌ₃Ｔｅ₂，ＴｌＴｅ，ＩｎＢｉ，
Ｉｎ₂Ｂｉ,ＴｅＢｉ，Ｔｌ−Ｓｅ，Ｔｌ−Ｔｅ，Ｐｂ−Ｓｎ，Ｂｉ−Ｓｎ，
Ｓｅ−Ｔｅ，Ｓ−Ｓｅ，Ｂｉ−Ｇａ，Ｓｎ−Ｚｎ，Ｇａ−Ｓｎ，Ｇａ−Ｉｎ，
Ｉｎ₃ＳｅＴｅ₂，ＡｇＩｎＴｅ₂，ＧｅＳｂ₄Ｔｅ₇，Ｇｅ₂Ｓｂ₂Ｔｅ₅，
ＧｅＳｂ₂Ｔｅ₄，ＧｅＢｉ₄Ｔｅ₇，ＧｅＢｉ₂Ｔｅ₄，Ｇｅ₃Ｂｉ₂Ｔｅ₆，
Ｓｎ₂Ｓｂ₆Ｓｅ₁₁，Ｓｎ₂Ｓｂ₂Ｓｅ₅，ＳｎＳｂ₂Ｔｅ₄，Ｐｂ₂Ｓｂ₆Ｔｅ₁₁，
ＣｕＡｓＳｅ₂，Ｃｕ₃ＡｓＳｅ₃，ＣｕＳｂＳ₂，ＣｕＳｂＳｅ₂，ＩｎＳｅ，
Ｓｂ₂Ｓｅ₃，Ｓｂ₂Ｔｅ₃，Ｂｉ₂Ｔｅ₃，ＳｎＳｂ，ＦｅＴｅ，Ｆｅ₂Ｔｅ₃，
ＦｅＴｅ₂，ＺｎＳｂ，Ｚｎ₃Ｓｂ₂，ＶＴｅ₂，Ｖ₅Ｔｅ₈，ＡｇＩｎ₂，
ＢｉＳｅ，ＩｎＳｂ，Ｉｎ₂Ｔｅ，Ｉｎ₂Ｔｅ₅，
などのうちの少なくとも一つを主成分とする材料で置き換えても、近い特性が得られる。 By changing the thickness of each layer, the size of the detection range 34 can be changed.
(Other examples of residual components)
Some or all of Bi, which is the remaining component of the high melting point component LaBi, is converted to Sn, Pb, Sb, Te, Zn, Cd, Se, In, Ga, S, Tl, Mg,
_{_{Tl 2 Se, TlSe, Tl 2}} Se 3, Tl 3 Te 2, TlTe, InBi,
In ₂ Bi, TeBi, Tl-Se, Tl-Te, Pb-Sn, Bi-Sn,
Se-Te, S-Se, Bi-Ga, Sn-Zn, Ga-Sn, Ga-In,
In ₃ SeTe ₂ , AgInTe ₂ , GeSb ₄ Te ₇ , Ge ₂ Sb ₂ Te ₅ ,
GeSb ₂ Te ₄ , GeBi ₄ Te ₇ , GeBi ₂ Te ₄ , Ge ₃ Bi ₂ Te ₆ ,
Sn ₂ Sb ₆ Se ₁₁ , Sn ₂ Sb ₂ Se ₅ , SnSb ₂ Te ₄ , Pb ₂ Sb ₆ Te ₁₁ ,
CuAsSe ₂ , Cu ₃ AsSe ₃ , CuSbS ₂ , CuSbSe ₂ , InSe,
Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂ Te ₃ , SnSb, FeTe, Fe ₂ Te ₃ ,
FeTe ₂ , ZnSb, Zn ₃ Sb ₂ , VTe ₂ , V ₅ Te ₈ , AgIn ₂ ,
BiSe, InSb, In ₂ Te, In ₂ Te ₅ ,
Even if a material having at least one of the above as a main component is replaced, a similar characteristic can be obtained.

残成分の融点が３５０゜Ｃ以下の場合、高融点化合物の融点は４５０゜Ｃ以上であれば、前記の場合に近い特性が得られる。
（その他）
この実施例の反射層は、本発明の記録用薄膜を用いない従来の相変化によって記録を行なう光記録媒体や、光磁気記録媒体などの他の記録原理による媒体にも適用可能である。 When the melting point of the remaining component is 350 ° C. or lower, if the melting point of the high melting point compound is 450 ° C. or higher, characteristics similar to those in the above case can be obtained.
(Other)
The reflective layer of this embodiment can be applied to a conventional optical recording medium that does not use the recording thin film for recording by a phase change or a medium based on another recording principle such as a magneto-optical recording medium.

ここで述べていない事項については、実施例１と同様である。 Matters not described here are the same as in the first embodiment.

この発明の情報記録媒体の実施例の記録用薄膜の部分断面図で、（ａ）は粒状の高融点成分が析出したもの、（ｂ）は柱状の高融点成分が析出したもの、（ｃ）は多孔質の高融点成分が析出したものを示す。FIGS. 3A and 3B are partial cross-sectional views of a recording thin film according to an embodiment of the information recording medium of the present invention, wherein FIG. 3A is a diagram in which a granular high melting point component is precipitated, FIG. Indicates that a porous high melting point component was precipitated. この発明の情報記録媒体の実施例の部分断面図で、（ａ）は（ｂ）のＤ−Ｄ線に沿った断面図、（ｂ）はその情報記録媒体の部分断面図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial cross-sectional view of an embodiment of an information recording medium according to the present invention, wherein FIG. この発明の情報記録媒体の実施例の全体断面図である。FIG. 1 is an overall sectional view of an embodiment of an information recording medium of the present invention. 記録用薄膜中に析出した高融点成分の寸法の測定法を説明する部分断面図で、（ａ）は粒状の高融点成分について、（ｂ）（ｃ）は柱状の高融点成分について示している。FIGS. 3A and 3B are partial cross-sectional views illustrating a method for measuring the size of a high melting point component deposited in a recording thin film, wherein FIG. 2A illustrates a granular high melting point component, and FIGS. . この発明の情報記録媒体の実施例を示す、図２（ａ）と同様の部分断面図である。FIG. 3 is a partial sectional view similar to FIG. 2A and showing an embodiment of the information recording medium of the present invention. この発明の情報記録用薄膜の記録層の実施例の三角相図である。1 is a triangular phase diagram of an embodiment of a recording layer of a thin film for information recording according to the present invention. この発明の情報記録媒体の他の実施例の全体断面図である。FIG. 6 is an overall sectional view of another embodiment of the information recording medium of the present invention. 超解像効果の原理を説明するための図である。It is a figure for explaining the principle of the super-resolution effect. この発明の情報記録媒体のさらに他の実施例の全体断面図である。FIG. 11 is an overall sectional view of still another embodiment of the information recording medium of the present invention. この発明の情報記録用薄膜の記録層の実施例４の三角相図である。FIG. 11 is a triangular phase diagram of Example 4 of a recording layer of an information recording thin film according to the present invention. この発明の情報記録用薄膜の記録層の実施例５の三角相図である。It is a triangular phase diagram of Example 5 of the recording layer of the thin film for information recording of the present invention. 本発明による超解像読み出しディスクの断面構造の一例を示す図。FIG. 1 is a diagram showing an example of a cross-sectional structure of a super-resolution read disk according to the present invention. 超解像読み出し膜の膜厚と反射率の関係を示す図。FIG. 5 is a diagram showing a relationship between the thickness of a super-resolution readout film and the reflectance. 超解像読み出し装置のブロック図。FIG. 2 is a block diagram of a super-resolution reading device.

Explanation of reference numerals

１，１’…基板、２，２’…保護層、３，３’…記録膜、３ａ…相変化成分、３ｂ…高融点成分、４，４’…中間層、５，５’…反射層、６…接着剤層、１１，１１’…基板、１２，１２’…保護層、１３，１３’…記録膜、１４，１４’…中間層、１５，１５’…反射層、１６…接着剤層、３２ａ，３２ｂ…記録マーク、３３…マスクとして働く範囲、３４…検出範囲、３５…高温領域。 1, 1 ': substrate, 2, 2': protective layer, 3, 3 ': recording film, 3a: phase change component, 3b: high melting point component, 4, 4': intermediate layer, 5, 5 ': reflective layer , 6 ... adhesive layer, 11, 11 '... substrate, 12, 12' ... protective layer, 13, 13 '... recording film, 14, 14' ... intermediate layer, 15, 15 '... reflective layer, 16 ... adhesive Layers 32a, 32b: recording mark, 33: range acting as a mask, 34: detection range, 35: high temperature region.

Claims

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
The average composition in the thickness direction of the information recording thin film is represented by the general formula: Sb _x Te _y _Ap B _q _Cr (1)
Represented by
A is at least one element selected from the first group consisting of Ge and In; B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, At least one element selected from the second group consisting of Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn, Ti and V, wherein C is Sb, Te and A And at least one element other than the elements represented by B,
Each of the units x, y, p, q and r is atomic percent, and 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 0.1 ≦ p ≦ 60, 3 ≦ q ≦ 40,
An information recording thin film characterized by the range of 0.1 ≦ r ≦ 30.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
The average composition in the thickness direction of the information recording thin film is represented by the general formula: Sb _x Te _y _Ap B _q (2)
Represented by
A is at least one element selected from the first group consisting of Ge and In; B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Represents at least one element selected from the second group consisting of Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn, Ti and V;
The unit of x, y, p and q is atomic percent, and is in the range of 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 0.1 ≦ p ≦ 60, and 3 ≦ q ≦ 40, respectively. Information recording thin film.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
The average composition in the thickness direction of the information recording thin film is represented by the general formula: Sb _x Te _y B _q _Cr (3)
Represented by
B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, At least one element selected from the group consisting of Bi, Sn, Ti and V, and C represents at least one element other than Sb, Te and the element represented by B;
The unit of x, y, p and q is atomic percent, and is in the range of 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, 3 ≦ q ≦ 40, and 0.1 ≦ r ≦ 30, respectively. Information recording thin film.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
The average composition in the thickness direction of the information recording thin film is represented by the general formula: Sb _x Te _y B _q (4)
Represented by
B is a lanthanoid element and Ag, Ba, Co, Cr, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Represents at least one element selected from the group consisting of Bi, Sn, Ti and V;
The unit for x, y, and q is an atomic percent, and is in the range of 2 ≦ x ≦ 41, 25 ≦ y ≦ 75, and 3 ≦ q ≦ 40, respectively.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
Average composition in the film thickness direction of the information recording thin film is represented by the general formula _{_{_{(Ge a Sb b Te c)}}} 1-d X d (5)
Represented by
X is Cr and Ag, Ba, Co, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn. , Ti, V, In, W, Zn and at least one of the lanthanoid elements, wherein a, b, c and d are respectively 0.02 ≦ a ≦ 0.19, 0.04 ≦ b ≦ 0 4. An information recording thin film, wherein the thickness is in the range of 4, 0.5 ≦ c ≦ 0.75, 0.03 ≦ d ≦ 0.3.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
Average composition in the film thickness direction of the information recording thin film is represented by the general formula _{_{_{(Ge a Sb b Te c)}}} 1-d X d (5)
Represented by
X is Cr and Ag, Ba, Co, Ni, Pt, Si, Sr, Au, Cd, Cu, Li, Mo, Mn, Zn, Al, Fe, Pb, Na, Cs, Ga, Pd, Bi, Sn. , Ti, V, In, W, Zn and at least one of lanthanoid elements, wherein a, b, c and d are respectively 0.25 ≦ a ≦ 0.65, 0 ≦ b ≦ 0.2, An information recording thin film having a range of 0.35 ≦ c ≦ 0.75, 0.03 ≦ d ≦ 0.3.

7. The information recording thin film according to claim 1, wherein at least one of B and X has a concentration gradient in a film thickness direction.

7. The thin film according to claim 1, further comprising a precipitate composed of a high melting point component having a relatively higher melting point than the remaining component of the thin film, wherein the precipitate contains an element represented by at least one of B and X. A thin film for information recording according to the present invention.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and at least a part of the high melting point component has a mean film thickness of 1 to 10 nm in a discontinuous film shape on the light incident side of the thin film. The information recording thin film according to any one of claims 1, 2, 5, and 6, wherein the information recording thin film exists in the range of:

Contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and the sum of the number of atoms of the constituent elements of the high melting point component is greater than the sum of the total number of atoms of the constituent elements of the thin film. The information recording thin film according to any one of claims 1, 2, 5, and 6, wherein the thickness is in the range of 10 to 50%.

7. The thin film according to claim 1, further comprising a precipitate composed of a high melting point component having a melting point higher than the remaining component of the thin film, wherein the content of the high melting point component changes in the film thickness direction. The information recording thin film according to any one of the above.

The thin film contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film. The average composition of the thin film is defined as a low melting point component L of a simple element or a compound and a high melting point of a simple element or a compound. With component H
L _j H _k (6)
20 ≦ k / (j + k) ≦ 40 (7)
2. A composition as a reference composition, wherein the content of each element constituting the information recording thin film in the film is within a range of ± 10 atomic% determined by the above equation.
7. The information recording thin film according to any one of claims 1, 2, 5 and 6.

7. The thin film according to claim 1, further comprising a precipitate composed of a high melting point component having a melting point relatively higher than the remaining component of the thin film, wherein the melting point of the high melting point component is 780 ° C. or more. Information recording thin film.

2. A deposit comprising a high melting point component having a melting point relatively higher than the remaining component of the thin film, wherein a difference between the melting point of the high melting point component and the melting point of the remaining component of the thin film is 150 ° C. or more. 7. The information recording thin film according to any one of claims 1, 2, 5 and 6.

3. A deposit comprising a high melting point component having a melting point relatively higher than the remaining component of the thin film, wherein the precipitate of the high melting point component is distributed in the form of particles or columns inside the thin film. 7. The information recording thin film according to any one of claims 5, 5 and 6.

It contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining component of the thin film, and the maximum outer dimension of the precipitate of the high melting point component in the film surface direction of the thin film is 5 nm or more and 50 nm or less. An information recording thin film according to any one of claims 1, 2, 5, and 6.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and the precipitate of the high melting point component extends in a columnar direction in the film thickness direction from both interfaces of the thin film, 7. The information recording thin film according to claim 1, wherein the length of the precipitate in the thickness direction is 5 nm or more and (1/2) or less of the thickness of the thin film.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining component of the thin film, and the precipitate of the high melting point component extends in a columnar direction in the thickness direction from one interface of the thin film, 7. The information recording thin film according to claim 1, wherein the length of the precipitate in the thickness direction is 10 nm or more and not more than the thickness of the thin film.

It contains a precipitate composed of a high melting point component having a melting point relatively higher than the remaining component of the thin film, and the length of the precipitate of the high melting point component in the thickness direction is 10 nm or more and not more than the thickness of the thin film. An information recording thin film according to any one of claims 1, 2, 5, and 6.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining component of the thin film, and a straight line connecting the centers of two adjacent precipitates of the high melting point component is formed in the direction of the film surface of the thin film. 7. The information recording thin film according to claim 1, wherein a length passing through a region between the precipitates is not less than 20 nm and not more than 90 nm.

3. A porous deposit comprising a high melting point component having a relatively higher melting point than a residual component of the thin film, wherein the residual component is distributed in pores of the porous deposit. 7. The information recording thin film according to any one of 5 and 6.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and the maximum pore size of the pores of the porous precipitate of the high melting point component in the film surface direction of the thin film is 80 nm or less. 7. The information recording thin film according to claim 1, wherein a maximum wall thickness in a film surface direction of the thin film in a region between two adjacent holes is 20 nm or less. .

7. The method according to claim 1, further comprising a deposit comprising a high melting point component having a relatively higher melting point than the remaining component of the thin film, wherein the melting point of the remaining component of the thin film is 650 ° C. or less. 2. The information recording thin film according to 1.

7. The thin film according to claim 1, further comprising a precipitate composed of a high melting point component having a melting point relatively higher than the remaining component of the thin film, wherein the melting point of the remaining component of the thin film is 250 ° C. or less. The information recording thin film according to 1.

It contains a precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and at least one of the real part and the imaginary part of the complex refractive index of the thin film is compared with that before irradiation by light irradiation. The information recording thin film according to any one of claims 1, 2, 5, and 6, which varies by at least 20%.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
An information recording medium comprising a precipitate composed of a high melting point component having a relatively higher melting point than the residual component of the thin film, and the precipitate being distributed in a region composed of the residual component of the thin film. Thin film.

27. The information recording thin film according to claim 26, wherein a maximum outer dimension of the precipitate of the high melting point component in a film surface direction of the thin film is 5 nm or more and 50 nm or less.

The precipitate of the high melting point component extends in a columnar manner in the film thickness direction from both interfaces of the thin film, and the length of the precipitate in the film thickness direction is 5 nm or more, and (1) (2) The information recording thin film according to claim 26, wherein

The precipitate of the high melting point component extends in a columnar shape from one interface of the thin film in the thickness direction thereof, and the length of the precipitate in the thickness direction is 10 nm or more and not more than the thickness of the thin film. An information recording thin film according to claim 26.

27. The information recording thin film according to claim 26, wherein a length of the precipitate of the high melting point component in a thickness direction is 10 nm or more and not more than the thickness of the thin film.

The length of a straight line connecting the centers of two adjacent precipitates of the high melting point component passing through a region between the precipitates in the film surface direction of the thin film is 20 nm or more and 90 nm or less. Information recording thin film.

In an information recording thin film formed on a substrate directly or via a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation of an energy beam,
It contains a porous precipitate composed of a high melting point component having a relatively higher melting point than the remaining components of the thin film, and the remaining components of the thin film are distributed in pores of the porous precipitate. Information recording thin film.

The maximum internal dimension of the pores of the porous precipitate of the high melting point component in the film surface direction of the thin film is 80 nm or less, and the maximum size of the region between two adjacent holes in the film surface direction of the thin film. 33. The information recording thin film according to claim 32, wherein the wall thickness is 20 nm or less.

33. The information recording thin film according to claim 26 or 32, wherein the melting point of the remaining components of the thin film is 650 ° C or less.

33. The information recording thin film according to claim 26, wherein the melting point of the remaining component of the thin film is 250 ° C. or less.

33. The information recording thin film according to claim 26, wherein at least one of a real part and an imaginary part of a complex refractive index of the thin film changes by 20% or more with respect to that before irradiation by light irradiation.

33. The information recording thin film according to claim 26, wherein the sum of the number of atoms of the constituent elements of the high melting point component is in a range of 10 to 50% of the sum of the total number of atoms of the thin film.

The average composition is determined by the low melting point component L of the elemental or compound composition and the high melting point component H of the elemental or compound composition.
L _j H _k (6)
In the formula, a composition satisfying 20 ≦ k / (j + k) ≦ 40 is set as a reference composition, and the content of each element constituting the information recording thin film in the film is determined by the above formula. 33. The information recording thin film according to claim 26, wherein the thickness is within a range of ± 10 at%.

33. The information recording thin film according to claim 26, wherein the melting point of the high melting point component is 780 ° C. or higher.

33. The information recording thin film according to claim 26, wherein a difference between a melting point of the high melting point component and a melting point of a remaining component of the thin film is 150 ° C. or more.

7. The information recording thin film according to claim 1, wherein the element represented by at least one of B and X is Cr.

7. The information recording thin film according to claim 1, wherein the element represented by at least one of B and X is Mo and Si, Pt, Co, Mn, W.

A method for manufacturing an information recording thin film for recording / reproducing information by changing an atomic arrangement caused by irradiation of an energy beam, which is formed directly on a substrate or through a protective layer,
Forming a thin film directly on the substrate or via a protective layer,
Irradiating the thin film with an energy beam to generate or grow a high melting point component in the thin film.

A method for manufacturing an information recording thin film for recording / reproducing information by changing an atomic arrangement caused by irradiation of an energy beam, which is formed directly on a substrate or through a protective layer,
A step of forming an island-shaped seed crystal by applying a material having a high melting point component or a material having a composition close to the composition of the high melting point component directly or through a protective layer on the substrate,
A material containing the high melting point component and the remaining component is deposited on the seed crystal, and the high melting point component is selectively grown on the seed crystal and the space between the seed crystals is filled. And a step of growing a residual component.

A method for manufacturing an information recording thin film for recording or reproducing information by changing the atomic arrangement caused by irradiation with an energy beam, which is formed directly on a substrate or via a protective layer,
A step of changing the content of the high melting point component in the film thickness direction at the time of forming a film composed of a phase change component and a high melting point component directly or via a protective layer on the substrate. Manufacturing method.

An information recording medium comprising the information recording thin film according to any one of claims 1 to 6, 26, and 32 as a recording layer.

An information recording medium comprising the information recording thin film according to any one of claims 1 to 6, 26 and 32 as a mask layer for super-resolution reading.

An information recording medium comprising the information recording thin film according to any one of claims 1 to 6, 26, and 32 as a reflective layer for super-resolution reading.

An information recording medium comprising the information recording thin film according to any one of claims 1 to 6, 26 and 32, wherein the melting point of the remaining component after the deposition of the high melting point component is 650 ° C or less.

33. An information recording medium comprising the information recording thin film according to claim 1, wherein the reflectance of the reflective layer is 60% or more.

An information recording thin film according to any one of claims 1 to 6, 26 and 32, wherein the information recording thin film is provided as a recording layer or a super-resolution readout mask layer, and the reflective layer side contains Si and the recording film side contains ZnS. An information recording medium comprising an intermediate layer having a two-layer structure of a layer as a main component.

An information recording thin film, which is formed directly on the substrate or through a protective layer and records or reproduces information by an atomic arrangement change caused by irradiation with an energy beam, is provided as a recording layer or a mask layer for super-resolution reading. And an information recording medium comprising a reflective layer having a composition of at least one of Si-Sn, Si-Ge, and Si-In compounds or a composition close thereto.

An information recording thin film, which is formed directly on the substrate or through a protective layer and records or reproduces information by an atomic arrangement change caused by irradiation with an energy beam, is provided as a recording layer or a mask layer for super-resolution reading. And an information recording medium characterized in that the thickness of the reflective layer is 150 nm or more and 300 nm or less.

An information recording thin film, which is formed directly on the substrate or through a protective layer and records or reproduces information by an atomic arrangement change caused by irradiation with an energy beam, is provided as a recording layer or a mask layer for super-resolution reading. An information recording medium comprising a protective layer having a two-layer structure of a SiO ₂ layer on the light incident side and a ZnS—SiO ₂ layer on the recording film side.

A super-resolution readout thin film formed on a substrate directly or through a protective layer and receiving a read-out beam to produce a super-resolution effect, wherein at least a phase-change component and a high melting point higher than the phase-change component are used. A super-resolution readout thin film comprising a melting point component, wherein a high melting point component is precipitated.

56. The super-resolution readout thin film according to claim 55, wherein the high melting point component is precipitated as columnar or massive precipitates.

The thin film for super-resolution reading according to claim 55, wherein said high melting point component is deposited as a porous precipitate.

A super-resolution readout thin film that is formed on a substrate directly or through a protective layer and receives a read-out beam to produce a super-resolution effect, and has an average composition represented by a general formula
_De E _f F _g
Wherein D is at least one element selected from Sn, Pb, Bi, Zn, Ga and In, and E is As, B, C, N, O, S, Se, Si, Te, Ag, Al, Au, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ge, Hf, Hg, Ir, K, Li, Mg, Mn, Mo, Na, Nb, Ni, Os, Pd, At least one element selected from the group consisting of Pt, Rb, Re, Rh, Ru, Sb, Sc, Sr, Ta, Ti, V, W, Y, and Zr, wherein F is represented by D and E; And the unit of e, f, and g is an atomic percentage, and is in the range of 30 ≦ e ≦ 95, 5 ≦ f ≦ 50, and 0 ≦ g ≦ 20, respectively. The thin film for super-resolution reading according to claim 55.

The average composition is determined by the low melting point component L of the elemental or compound composition and the high melting point component H of the elemental or compound composition.
L _j H _k (6)
In the formula, a composition satisfying 20 ≦ k / (j + k) ≦ 40 is defined as a reference composition, and the content of each element in the film is within a range of ± 10 atomic% determined by the formula. 56. The thin film for super-resolution reading according to claim 55.

56. The super-resolution reading thin film according to claim 55, wherein both the low melting point component and the high melting point component contain at least 50 atomic% of a metal or metalloid element.

56. An information recording medium, comprising: a super-resolution reading thin film according to claim 55 provided on a transparent substrate on which information is recorded by unevenness, and a reflective layer provided thereon.

56. An information recording medium, comprising a protective layer provided between a transparent substrate on which information is recorded by unevenness and the super-resolution reading thin film according to claim 55.

56. An information recording medium, comprising an intermediate layer provided between the super-resolution reading thin film according to claim 55 and a reflective layer.

56. An information recording medium, comprising: the thin film for super-resolution reading according to claim 55 provided on a transparent substrate; an information recording film provided thereon; and a reflective layer provided thereon.

56. An information recording medium comprising a protective layer provided between a transparent substrate and the super-resolution reading thin film according to claim 55.

56. An information recording medium comprising an intermediate layer provided between the super-resolution reading thin film according to claim 55 and an information recording film and at least one between an information recording film and a reflective layer.

An information recording medium including the super-resolution reading thin film according to claim 55, and a super-resolution reading apparatus including an optical head that irradiates the information recording medium with laser light and detects reflected light. An apparatus for super-resolution reading, comprising: means for detecting disturbance in the intensity distribution of reflected light during super-resolution reading; and means for adjusting laser power according to the magnitude of the disturbance.

An information recording medium including the super-resolution reading thin film according to claim 55, and a super-resolution reading apparatus including an optical head that irradiates the information recording medium with laser light and detects reflected light.
The laser light is pulse light, and the relationship among the laser pulse period T, linear velocity v, spot diameter (λ / NA), and pulse width x is
0.4λ / NA ≦ vT ≦ 1.5λ / NA (9)
And 0.3 ≦ x / T ≦ 0.5 (10)
A super-resolution readout device characterized by satisfying the following.

56. A super-resolution reading apparatus comprising: an information recording medium including the super-resolution reading thin film according to claim 55; and an optical head that irradiates the information recording medium with laser light and detects reflected light. An apparatus for super-resolution reading, comprising means for setting the light output to an output that does not melt the entire film even in a region where the temperature of the thin film for super-resolution reading is the highest.

In an information recording thin film formed on a substrate directly or through a protective layer, which records and reproduces information by a change in atomic arrangement caused by irradiation with an energy beam, the information is recorded using an information recording medium having the thin film. By repeatedly irradiating a laser beam in a recording / reproducing device or a device for initial crystallization of a medium, a high melting point component having a relatively higher melting point than the remaining components of the thin film is deposited, and the deposit is composed of the remaining components of the thin film. An information recording thin film which is distributed in a region.

An information recording / reproducing method using an information recording medium having an information recording thin film for recording / reproducing information by an atomic arrangement change caused by irradiation of an energy beam formed directly or through a protective layer on a substrate or By repeatedly irradiating a laser beam in the method for initial crystallization of a medium, a high melting point component having a relatively higher melting point than the remaining components of the thin film is deposited, and the precipitate is distributed in a region composed of the remaining components of the thin film. Recording and reproducing information.

By repeatedly irradiating the thin film with a laser beam in an information recording / reproducing apparatus using an information recording medium having the thin film or a medium initial crystallization apparatus, a high melting point having a melting point relatively higher than the remaining components of the thin film is obtained. 7. The component according to claim 1, wherein the component is deposited, and the precipitate is distributed in a region composed of the remaining component of the thin film, and the precipitate contains the element represented by at least one of B and X. An information recording thin film according to any one of the above.

A method for producing an information recording medium for recording / reproducing information by a change in atomic arrangement generated by irradiation of an energy beam, formed directly on a substrate or through a protective layer, comprising the steps of: A step of forming a film or a super-resolution reading film, an intermediate layer, a reflective layer, a step of bonding another substrate or another substrate on which each of the layers is formed in the same manner, and irradiating the medium with an energy beam. Producing or growing a high-melting point component in the thin film.

A method for manufacturing an information recording medium for recording / reproducing information by an atomic arrangement change caused by irradiation of an energy beam formed directly on a substrate or through a protective layer, wherein the protective layer is formed on the substrate. Forming an island-shaped seed crystal by applying a material having a high melting point component or a material having a composition close to the composition of the high melting point component; and forming the high melting point component and the residual component on the seed crystal. And a step of growing the high-melting-point component selectively on the seed crystal and growing the remaining component so as to fill between the seed crystals, and forming an intermediate layer and a reflective layer. And a step of bonding another substrate or another substrate on which each of the layers has been formed in the same manner as described above.

A method for manufacturing an information recording medium for recording or reproducing information by a change in atomic arrangement caused by irradiation of an energy beam formed directly on a substrate or through a protective layer, wherein the protective layer is formed on the substrate. A step of changing the content of the high melting point component in the film thickness direction while forming a film composed of a phase change component and a high melting point component; a step of forming an intermediate layer and a reflective layer; A method for manufacturing an information recording medium, comprising a step of bonding a substrate or another substrate on which each of the layers is formed in a similar manner.