JP2001355065A - Sputtering target for depositing optical recording medium protective film exhibiting excellent cracking-off resistance under direct current sputtering condition - Google Patents
Sputtering target for depositing optical recording medium protective film exhibiting excellent cracking-off resistance under direct current sputtering conditionInfo
- Publication number
- JP2001355065A JP2001355065A JP2000176458A JP2000176458A JP2001355065A JP 2001355065 A JP2001355065 A JP 2001355065A JP 2000176458 A JP2000176458 A JP 2000176458A JP 2000176458 A JP2000176458 A JP 2000176458A JP 2001355065 A JP2001355065 A JP 2001355065A
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- optical recording
- sputtering
- recording medium
- zinc sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Optical Record Carriers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、半導体レーザー
などの光ビームを用いて情報の記録・再生・消去を行う
ことのできる光ディスクなど光記録媒体の保護膜を、直
流スパッタリング法、特に高出力直流スパッタリング法
にて形成するために用いるスパッタリングターゲット
（以下、ターゲットと云う）に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a DC sputtering method, particularly a high-output DC method, for forming a protective film on an optical recording medium such as an optical disk capable of recording, reproducing and erasing information using a light beam such as a semiconductor laser. The present invention relates to a sputtering target (hereinafter, referred to as a target) used for forming by a sputtering method.
【０００２】[0002]
【従来の技術】一般に、光ディスクなどの光記録媒体
は、基本的には例えばポリカーボネイトの基板の表面に
下部保護膜、記録膜、上部保護膜、反射膜および紫外線
硬化樹脂膜などの膜を形成した構成を有することが知ら
れており、前記光記録媒体の下部保護膜および上部保護
膜の各膜は、例えば特開平６−６５７２５号公報に記載
の質量％で（以下、％は質量％を示す）、酸化ケイ素：
４〜２０％、硫化亜鉛：残りからなる配合組成を有する
混合粉末のホットプレス焼結体で構成されたターゲット
を用い、これを高周波マグネトロンスパッタリング装置
にセットして形成されることも知られている。硫化亜鉛
は、光記録媒体保護膜に要求される高い光屈折率と光透
過率、さらに耐熱性を具備することから、光記録媒体保
護膜の主要成分として用いられている。反面、硫化亜鉛
単独で例えば光ディスクの保護膜を形成した場合、内部
応力の高い保護膜となってしまい、この状態で前記光デ
ィスクに記録のためのレーザー照射を行うと、前記レー
ザー照射に伴う急熱・急冷によって前記保護膜に割れが
発生し易いものとなる。そこで、光記録媒体保護膜では
硫化亜鉛に酸化ケイ素を配合して、保護膜中の残留内部
応力を低減するようにしている。2. Description of the Related Art Generally, an optical recording medium such as an optical disk basically has a film such as a lower protective film, a recording film, an upper protective film, a reflective film, and an ultraviolet curable resin film formed on the surface of a polycarbonate substrate. It is known that each of the lower protective film and the upper protective film of the optical recording medium has a mass% described in, for example, JP-A-6-65725 (hereinafter,% indicates mass%). ), Silicon oxide:
It is also known that a target formed of a hot-press sintered body of a mixed powder having a composition of 4 to 20% zinc sulfide: the remainder is used, and the target is set in a high-frequency magnetron sputtering apparatus. . Zinc sulfide is used as a main component of the optical recording medium protective film because it has high optical refractive index and light transmittance required for the optical recording medium protective film and further has heat resistance. On the other hand, for example, when a protective film of an optical disk is formed by zinc sulfide alone, the protective film has a high internal stress. When laser irradiation for recording is performed on the optical disk in this state, rapid heating caused by the laser irradiation is performed. -The rapid cooling causes the protective film to be easily cracked. Therefore, in the optical recording medium protection film, zinc oxide is mixed with zinc sulfide to reduce the residual internal stress in the protection film.
【０００３】近年、光記録媒体の値下げ要求は一層厳し
くなり、一層低コストで光記録保護膜を成膜することが
求められている。しかし、従来の光記録保護膜形成用ス
パッタリングターゲットを用い高周波スパッタリングに
より光記録保護膜を形成する方法ではコスト削減に限界
がある。その理由として高周波スパッタリング装置は高
周波電力を制御するための装置の値段が高いところか
ら、高周波スパッタリング装置自体が高価なものとな
り、また、高周波電力損失による電力消費も無視できな
いほど大きくなって電力効率も低いからである。そのた
め、高周波スパッタリング装置に比べて成膜速度が速
く、スパッタリング効率が良く、しかも制御が容易でさ
らに価格の安い直流スパッタリング装置を使用して光記
録保護膜を成膜する研究がなされている。In recent years, the demand for lowering the price of an optical recording medium has become more severe, and there has been a demand for forming an optical recording protective film at lower cost. However, there is a limit in cost reduction in the conventional method of forming an optical recording protective film by high frequency sputtering using a sputtering target for forming an optical recording protective film. The reason is that the high-frequency sputtering device itself is expensive because the price of the device for controlling the high-frequency power is high, and the power consumption due to the high-frequency power loss is so large that the power efficiency cannot be ignored. Because it is low. For this reason, studies have been made on forming an optical recording protection film using a DC sputtering device which has a higher film forming rate, higher sputtering efficiency, easier control, and lower cost than a high frequency sputtering device.
【０００４】かかる直流スパッタリングが可能な光記録
媒体保護膜形成用スパッタリングターゲットとして、例
えば、特開２０００−６４０３５号公報には、カルコゲ
ン化物とガラスからなるターゲットの主要マトリックス
に、低抵抗化材として酸素欠損または酸素欠陥をもつ酸
化亜鉛、または酸化硼素および／または酸化アルミニウ
ムをドープした酸化亜鉛を用い、不活性ガス雰囲気中ま
たは真空中で加圧燒結して得られたターゲットが開示さ
れている。As a sputtering target for forming a protective film for an optical recording medium capable of performing DC sputtering, for example, Japanese Patent Application Laid-Open No. 2000-64035 discloses that a main matrix of a target made of chalcogenide and glass is used. A target obtained by sintering under pressure in an inert gas atmosphere or in a vacuum using zinc oxide doped with deficiency or oxygen vacancy, or boron oxide and / or aluminum oxide is disclosed.
【０００５】[0005]
【発明が解決しようとする課題】しかし、前記酸素欠損
または酸素欠陥をもつ酸化亜鉛、または酸化硼素および
／または酸化アルミニウムをドープした酸化亜鉛を用い
た光記録保護膜形成用スパッタリングターゲットは、直
流スパッタリングは可能であるものの、高出力の直流ス
パッタを行なうと、割れが発生するために成膜速度を上
げることができない。However, the sputtering target for forming an optical recording protective film using zinc oxide having oxygen deficiency or oxygen deficiency, or zinc oxide doped with boron oxide and / or aluminum oxide, is a direct current sputtering target. However, when high-output DC sputtering is performed, cracks occur, so that the film formation rate cannot be increased.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明者らは,
上述の観点から、高出力直流スパッタ条件下において優
れた耐割損性を発揮する光記録媒体保護膜形成用スパッ
タリングターゲットを得るべく研究を行った結果、
（ａ）光記録媒体保護膜形成用スパッタリングターゲッ
トの素地となる硫化亜鉛に銅を固溶させると、導電性が
付与されて、直流スパッタ条件下において、ターゲット
表面に滞留するＡｒイオンからプラス電荷をすばやく電
源側に還流する、（ｂ）酸化インジウムを混合すると、
スパッタ衝撃に対する耐割損性を向上させ、直流スパッ
タ放電を安定化させる、（ｃ）直流スパッタを行うと、
Ａｒイオンのプラス電荷が絶縁体である酸化ケイ素上に
残り、プラス電荷を有する酸化ケイ素粒子に向かってプ
ラズマ中の電子が衝突し、それによって著しい異常放電
が発生し、酸化ケイ素粒子の溶融・凝固が発生して割れ
の起点が形成されるが、酸化ケイ素内部に酸化チタンを
分散させると、酸化チタンは酸化ケイ素上のプラス電荷
の素地への導通路を形成するので異常放電による割れが
防止できる、という研究結果が得られ、これら研究をさ
らに推進した結果、銅：０．１〜３％、酸化ケイ素：２
〜１０％、酸化チタン：２〜１０％、酸化インジウム：
２０〜４０％、硫化亜鉛：残りからなる組成を有し、前
記銅は一部または全部が硫化亜鉛に固溶し、さらに前記
酸化チタンは酸化ケイ素により結合した複合粒子となっ
て含まれているホットプレス焼結体で構成したスパッタ
リングターゲットは、これを用いて直流スパッタリン
グ、特に高出力直流スパッタリングを行ったところ、優
れた耐割損性を発揮し、このスパッタリングターゲット
を用いて形成した光記録媒体保護膜は、前記従来ターゲ
ットを用いて形成した光記録媒体保護膜の示す光屈折率
および光透過率と同等の光屈折率と光透過率を示す、と
いう研究結果が得られたのである。Means for Solving the Problems Therefore, the present inventors have proposed:
In view of the above, as a result of conducting research to obtain a sputtering target for forming an optical recording medium protective film that exhibits excellent crack resistance under high-power DC sputtering conditions,
(A) When copper is solid-dissolved in zinc sulfide, which is a base of a sputtering target for forming an optical recording medium protective film, conductivity is imparted, and a positive charge is generated from Ar ions staying on the target surface under DC sputtering conditions. When (b) indium oxide is mixed, which quickly returns to the power supply side,
(C) DC sputtering is performed to improve the resistance to spatter impact and to stabilize DC sputtering discharge.
The positive charges of Ar ions remain on the silicon oxide, which is an insulator, and electrons in the plasma collide with the silicon oxide particles having the positive charges, thereby causing a remarkable abnormal discharge and melting and coagulation of the silicon oxide particles. When the titanium oxide is dispersed inside the silicon oxide, the titanium oxide forms a conduction path to the base of the positive charge on the silicon oxide, so that the crack due to the abnormal discharge can be prevented. As a result of further promoting these studies, copper: 0.1 to 3%, silicon oxide: 2
-10%, titanium oxide: 2-10%, indium oxide:
20-40%, zinc sulfide: has a composition consisting of the remainder, the copper is partly or wholly dissolved in zinc sulfide, and the titanium oxide is contained as composite particles bonded by silicon oxide. The sputtering target composed of the hot-pressed sintered body, when subjected to DC sputtering, particularly high-power DC sputtering, exhibits excellent split resistance, and an optical recording medium formed using this sputtering target. Research results have shown that the protective film has the same light refractive index and light transmittance as the light refractive index and light transmittance of the optical recording medium protective film formed using the conventional target.
【０００７】この発明は、前記の研究結果に基づいてな
されたものであって、（１）銅：０．１〜３％、酸化ケ
イ素：２〜１０％、酸化チタン：２〜１０％、酸化イン
ジウム：２０〜４０％、硫化亜鉛：残りからなる組成を
有するホットプレス焼結体で構成した直流スパッタ条件
下で優れた耐割損性を発揮する光記録媒体保護膜形成用
スパッタリングターゲット、（２）銅：０．１〜３％、
酸化ケイ素：２〜１０％、酸化チタン：２〜１０％、酸
化インジウム：２０〜４０％、硫化亜鉛：残りからなる
組成を有し、前記銅の一部または全部が硫化亜鉛に固溶
しており、さらに前記酸化チタンは連続相である酸化ケ
イ素により接合した複合粒子として素地中に分散してい
る組織を有するホットプレス焼結体で構成した直流スパ
ッタ条件下で優れた耐割損性を発揮する光記録媒体保護
膜形成用スパッタリングターゲット、に特徴を有するも
のである。The present invention has been made on the basis of the above-mentioned research results. (1) Copper: 0.1 to 3%, silicon oxide: 2 to 10%, titanium oxide: 2 to 10%, oxide Indium: 20 to 40%, zinc sulfide: a sputtering target for forming an optical recording medium protective film, which exhibits excellent split resistance under DC sputtering conditions and is composed of a hot-pressed sintered body having the composition of (2) ) Copper: 0.1-3%,
Silicon oxide: 2 to 10%, Titanium oxide: 2 to 10%, Indium oxide: 20 to 40%, Zinc sulfide: Remaining, and a part or all of the copper is dissolved in zinc sulfide. In addition, the titanium oxide exhibits excellent breakage resistance under DC sputtering conditions composed of a hot-press sintered body having a structure dispersed in a matrix as composite particles bonded by a continuous phase of silicon oxide. And a sputtering target for forming an optical recording medium protective film.
【０００８】前記直流スパッタ条件下で優れた耐割損性
を発揮する光記録媒体保護膜形成用スパッタリングター
ゲットは、原料粉末として、銅が硫化亜鉛に固溶してい
る銅固溶硫化亜鉛粉末、および酸化チタンを連続相であ
る酸化ケイ素で結合してなる酸化チタンと酸化ケイ素の
複合粉末を使用し、これら粉末を含む混合粉末をホット
プレスすることにより得られる。したがって、この発明
は、（３）原料粉末を所定の組成となるように配合し混
合して得られた混合粉末をホットプレスすることにより
スパッタリングターゲットを製造する方法において、原
料粉末として、銅が硫化亜鉛に固溶している銅固溶硫化
亜鉛粉末、および酸化チタン分散相を酸化ケイ素連続相
で結合してなる酸化チタンと酸化ケイ素の複合粉末を使
用する直流スパッタ条件下で優れた耐割損性を発揮する
光記録媒体保護膜形成用スパッタリングターゲットの製
造方法、に特徴を有するものである。[0008] The sputtering target for forming an optical recording medium protective film exhibiting excellent breakage resistance under the above-mentioned direct current sputtering conditions comprises a copper solid solution zinc sulfide powder in which copper is dissolved in zinc sulfide as a raw material powder; And a composite powder of titanium oxide and silicon oxide obtained by bonding titanium oxide with silicon oxide as a continuous phase, and hot-pressing a mixed powder containing these powders. Therefore, the present invention provides (3) a method of manufacturing a sputtering target by hot-pressing a mixed powder obtained by mixing and mixing raw material powders to have a predetermined composition, wherein copper is used as a raw material powder; Excellent cracking resistance under DC sputtering conditions using copper-dissolved zinc sulfide powder solid-dissolved in zinc and titanium oxide-silicon oxide composite powder obtained by combining titanium oxide dispersed phase with silicon oxide continuous phase And a method of manufacturing a sputtering target for forming an optical recording medium protective film exhibiting the property.
【０００９】この発明の光記録媒体保護膜形成用ターゲ
ットを構成するホットプレス焼結体の配合組成を前記の
通りに限定した理由を説明する。 （ａ）酸化ケイ素 酸化ケイ素は硫化亜鉛に配合してホットプレス焼結体を
作製し、このホットプレス焼結体をターゲットとしスパ
ッタリングして得られた保護膜の残留内部応力を低減す
る作用を有するが、ホットプレス焼結体における酸化ケ
イ素の含有量が２％未満では、前記保護膜における内部
応力の発生を抑制する作用が不充分であり、一方その含
有量が１０％を超えると、直流スパッタ条件下における
異常放電の抑制が困難に成ることから、その含有割合を
２〜１０％、望ましくは２〜７％と定めた。The reason why the composition of the hot-pressed sintered body constituting the target for forming an optical recording medium protective film of the present invention is limited as described above will be described. (A) Silicon oxide Silicon oxide is mixed with zinc sulfide to produce a hot-press sintered body, and has an action of reducing residual internal stress of a protective film obtained by sputtering using the hot-press sintered body as a target. However, when the content of silicon oxide in the hot-pressed sintered body is less than 2%, the effect of suppressing the generation of internal stress in the protective film is insufficient. On the other hand, when the content exceeds 10%, DC sputtering is performed. Since it becomes difficult to suppress abnormal discharge under the conditions, the content ratio is set to 2 to 10%, preferably 2 to 7%.
【００１０】（ｂ）銅 銅は、硫化亜鉛に固溶して素地を強化し、スパッタ衝撃
による割れの発生を抑制する効果があるが、耐割損性向
上効果を十分に発揮させるためには、０．１％未満では
不十分であり、一方、その含有量が３％を越えると、例
えば光ディスクの保護膜とした場合にレーザー光の吸収
が大きくなるなど光学的特性の劣化が避けられなくなる
ことから、その含有量を０．１〜３％に定めた。一層望
ましい範囲は０．５〜２．５％である。(B) Copper Copper has the effect of forming a solid solution in zinc sulfide to reinforce the base and to suppress the occurrence of cracks due to sputter impact. However, in order to sufficiently exhibit the effect of improving the breakage resistance, If the content is less than 0.1%, the content exceeds 3%. On the other hand, if the content is more than 3%, deterioration of optical characteristics such as increased absorption of laser light when used as a protective film of an optical disk is inevitable. Therefore, the content was set to 0.1 to 3%. A more desirable range is 0.5-2.5%.
【００１１】（ｃ）酸化チタン 直流スパッタ条件下では、Ａｒイオンがターゲットをス
パッタする際に、プラスの電荷が酸化ケイ素上に滞留す
るが、酸化チタンを酸化ケイ素粒子内に分散させること
により、このプラス電荷をすばやく素地に移行して異常
放電を抑制し、直流スパッタ条件下における著しい異常
放電に伴う割れの発生を防止する。したがってこの耐割
損性を十分に発揮させるためには、その含有量が２％未
満では不充分であり、一方その含有量が１０％を越える
と、例えば光ディスクの保護膜とした場合に、レーザー
光の吸収が大きくなるなどの光学特性の劣化が避けられ
なくなることから、その配合割合を２〜１０％、望まし
くは２〜７％と定めた。(C) Titanium oxide Under DC sputtering conditions, when Ar ions are sputtered on a target, a positive charge stays on silicon oxide. However, by dispersing titanium oxide in silicon oxide particles, A positive charge is quickly transferred to the substrate to suppress abnormal discharge and prevent the occurrence of cracks associated with a remarkable abnormal discharge under DC sputtering conditions. Therefore, if the content is less than 2%, it is not sufficient to sufficiently exhibit the splitting resistance, while if the content exceeds 10%, for example, when the protective film of an optical disc is used as a laser, Since the deterioration of optical characteristics such as an increase in light absorption is inevitable, the mixing ratio is set to 2 to 10%, preferably 2 to 7%.
【００１２】（ｄ）酸化インジウム 酸化インジウムは、素地を形成する硫化亜鉛粒子間およ
び／または硫化亜鉛粒子と酸化ケイ素粒子との粒子間に
存在し、硫化亜鉛同士および／または硫化亜鉛粒子と酸
化ケイ素粒子との結合力を高め、耐割損性の向上に効果
を発揮するので添加するが、その含有量が２０％未満で
は耐割損性を十分に発揮することができず、一方、その
含有量が４０％を越えると、レーザー光の吸収が大きく
なるなど光学的特性の劣化が避けられなくなることか
ら、その含有量を２０〜４０％に定めた。一層望ましい
範囲は２５〜３５％である。(D) Indium oxide Indium oxide exists between the zinc sulfide particles forming the matrix and / or between the zinc sulfide particles and the silicon oxide particles. It is added because it increases the bonding force with the particles and is effective in improving the cracking resistance. However, if the content is less than 20%, the cracking resistance cannot be sufficiently exerted. If the amount exceeds 40%, deterioration of optical characteristics such as increase in absorption of laser light is unavoidable. Therefore, the content is set to 20 to 40%. A more desirable range is 25-35%.
【００１３】[0013]
【発明の実施の態様】つぎに、この発明の光記録媒体保
護膜形成用ターゲットを実施例により具体的に説明す
る。原料粉末として、表１に示される割合のＣｕをＺｎ
Ｓに固溶した平均粒径：３μｍのＣｕ固溶ＺｎＳ粉末
（以下、固溶粉末という）ａ〜ｊ、表１に示される割合
のＴｉＯ2をＳｉＯ2で結合した平均粒径：５μｍの複合
粉末（以下、複合粉末という）Ａ〜Ｄを用意し、さらに
いずれも市販の平均粒径：０．３μｍを有する純度：９
９．９％以上のＩｎ2Ｏ3粉末を用意し、さらに純度：９
９．９９％以上を有し平均粒径：３μｍを有するＺｎＳ
粉末、純度：９９．９％以上を有し平均粒径：５μｍを
有するＳｉＯ2粉末、および平均粒径：５μｍを有する
Ｂ2Ｏ3粉末を１％ドープしたＺｎＯ粉末も用意した。こ
れら固溶粉末、複合粉末、Ｉｎ2Ｏ3粉末、ＺｎＳ粉末、
ＳｉＯ2粉末、およびＢ2Ｏ3粉末を１％ドープしたＺｎ
Ｏ粉末などの原料粉末を表２に示される配合組成に配合
し、ボールミルで８時間混合した後、この混合粉末を黒
鉛型に充填した状態で、ホットプレス装置に装入し、雰
囲気：１．３Ｐａ以下の真空雰囲気、温度：１２２３
Ｋ、圧力：３４．３ＭＰａ、保持時間：３時間の条件で
ホットプレスしてホットプレス焼結体とすることによ
り、表３に示される組成を有し、直径：１２５ｍｍ×厚
さ：５ｍｍの寸法をもった本発明ターゲット１〜１０お
よび従来ターゲット１〜２をそれぞれ製造した。Next, the target for forming an optical recording medium protective film of the present invention will be described in detail with reference to examples. As a raw material powder, Cu in a ratio shown in Table 1 was changed to Zn
Average particle size of solid solution in S: 3 μm Cu solid solution ZnS powder (hereinafter referred to as solid solution powder) a to j, TiO 2 in the ratio shown in Table 1 bonded by SiO 2 , composite of 5 μm Powders (hereinafter, referred to as composite powders) A to D are prepared, and all have a commercially available average particle diameter: 0.3 μm and a purity: 9
An In 2 O 3 powder of 9.9% or more was prepared.
ZnS having 9.99% or more and having an average particle size of 3 μm
Powder, SiO 2 powder having a purity of 99.9% or more and having an average particle diameter of 5 μm, and ZnO powder doped with 1% of B 2 O 3 powder having an average particle diameter of 5 μm were also prepared. These solid solution powder, composite powder, In 2 O 3 powder, ZnS powder,
Zn doped with 1% SiO 2 powder and B 2 O 3 powder
Raw powders such as O powder were blended in the blending composition shown in Table 2 and mixed by a ball mill for 8 hours. Then, the mixed powder was charged into a graphite mold and charged into a hot press, and the atmosphere was 1. Vacuum atmosphere of 3 Pa or less, temperature: 1223
K, pressure: 34.3 MPa, holding time: 3 hours, hot-pressed to obtain a hot-pressed sintered body, having the composition shown in Table 3, having a diameter of 125 mm and a thickness of 5 mm Inventive targets 1 to 10 and conventional targets 1 and 2 having the following were produced.
【００１４】前記の本発明ターゲット１〜１０および従
来ターゲット２のそれぞれを無酸素銅製の水冷バッキン
グプレートにハンダ付けした状態で、通常の直流マグネ
トロンスパッタリング装置に装着し、まず装置内を真空
排気装置にて６．７×１０-6Ｐａの真空雰囲気とした
後、Ａｒガスを導入して装置内雰囲気を０．２Ｐａのス
パッタガス圧とし、引き続いて直流電源よりターゲット
に５００Ｗのスパッタ電力を印加して、前記ターゲット
と対向し、かつ５ｃｍの間隔を設けて平行配置した直
径：３ｃｍ×厚さ：０．５ｍｍのガラス基板と前記ター
ゲットの間にグロー放電を発生させ、グロー放電を形成
するプラズマ中のＡｒイオンを前記ターゲットの表面に
衝突させて前記ターゲットをスパッタし、スパッタ粒子
を前記基板表面に蒸着することにより厚さ：９０ｎｍの
光記録媒体保護膜を形成した。また、前述の従来ターゲ
ットにおいては、これがいずれも絶縁体からなるので、
直流マグネトロンスパッタリング装置での保護膜形成は
不可能であることから、これを通常の高周波マグネトロ
ンスパッタリング装置に装着し、ターゲットへのスパッ
タ電力の印加を高周波電源よりマッチングボックスを介
して行なう以外は上記の直流マグネトロンスパッタリン
グ装置での保護膜形成条件と同一の条件で保護膜を形成
した。この結果形成された光記録媒体保護膜に含まれる
ＣｕおよびＴｉＯ2の光屈折率および光透過率に及ぼす
影響を調べること、並びに光記録媒体保護膜の光屈折率
および光透過率を評価することを目的として、波長：７
８０ｎｍのレーザーを用い、光記録媒体保護膜の屈折率
および消衰係数を測定し、この測定結果を表３に示し
た。Each of the targets 1 to 10 of the present invention and the conventional target 2 is mounted on a normal DC magnetron sputtering apparatus while being soldered to a water-cooled backing plate made of oxygen-free copper. After a vacuum atmosphere of 6.7 × 10 −6 Pa was applied, Ar gas was introduced to set the atmosphere in the apparatus to a sputtering gas pressure of 0.2 Pa, and then a sputtering power of 500 W was applied to the target from a DC power supply. A glow discharge is generated between the glass substrate having a diameter of 3 cm × thickness: 0.5 mm, which is opposed to the target and is arranged in parallel with a space of 5 cm, and a glow discharge in the plasma for forming a glow discharge. The target is sputtered by colliding Ar ions on the surface of the target, and sputter particles are deposited on the substrate surface Thickness by Rukoto: forming an optical recording medium protecting film of 90 nm. In addition, in the above-mentioned conventional target, since each of them is made of an insulator,
Since it is impossible to form a protective film with a DC magnetron sputtering device, the above is attached to a normal high-frequency magnetron sputtering device, except that the application of sputtering power to the target is performed from a high-frequency power source via a matching box. The protective film was formed under the same conditions as those for forming the protective film in the DC magnetron sputtering apparatus. To examine the effects of Cu and TiO 2 contained in the optical recording medium protective film formed as a result on the optical refractive index and the optical transmittance, and to evaluate the optical refractive index and optical transmittance of the optical recording medium protective film. Wavelength: 7
Using a laser of 80 nm, the refractive index and the extinction coefficient of the optical recording medium protective film were measured, and the measurement results are shown in Table 3.
【００１５】ついで、前記の各種ターゲットの耐割損性
を評価する目的で、ターゲットへのスパッタ電力の印加
条件を、前記の５００Ｗから１００Ｗづつ上げて行き、
この間上昇スパッタ電力毎に１分間保持する条件とする
以外は、前記の光記録媒体保護膜形成条件と同一の条件
でスパッタを行い、前記ターゲット材に割れが発生した
時点の印加スパッタ電力（割れ発生臨界スパッタ電力）
を測定した。この測定結果を表３に示した。Next, in order to evaluate the cracking resistance of the various targets, the conditions for applying the sputtering power to the targets were increased by 100 W from the above 500 W,
Sputtering was performed under the same conditions as those for forming the optical recording medium protective film described above, except that the conditions were maintained for one minute for each increased sputter power during this time. Critical sputtering power)
Was measured. Table 3 shows the measurement results.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】[0018]
【表３】 [Table 3]
【００１９】[0019]
【発明の効果】表３に示される結果から、本発明ターゲ
ット１〜１０は、従来ターゲット１〜２に比して著しく
高い割れ発生臨界スパッタ電力を示し、このことは高出
力直流スパッタに対して優れた耐割損性を示すものであ
り、さらに本発明ターゲット１〜１０は従来ターゲット
１〜２によって形成された保護膜の屈折率および消衰係
数の比較から、光記録媒体保護膜の屈折率および消衰係
数にほとんど変化が見られないことが明らかである。上
述のように、この発明のターゲットは、高出力の直流ス
パッタの負荷によっても割れの発生が抑制され、優れた
耐割損性を示すことから、従来光記録媒体保護膜と同等
の特性を具備した保護膜の高速成膜を可能とし、生産性
の向上に寄与するものである。From the results shown in Table 3, the targets 1 to 10 of the present invention show a remarkably higher cracking critical sputtering power than the conventional targets 1 and 2, which indicates that The targets 1 to 10 of the present invention show excellent splitting resistance, and the refractive indices of the protective films of the optical recording media are determined by comparing the refractive indices and extinction coefficients of the protective films formed by the conventional targets 1 and 2. It is clear that there is almost no change in the extinction coefficient. As described above, the target of the present invention suppresses the generation of cracks even under the load of high-power DC sputtering, and exhibits excellent splitting resistance. This enables high-speed film formation of the protective film, thereby contributing to an improvement in productivity.
フロントページの続き (72)発明者 森 理恵 埼玉県大宮市北袋町１−297 三菱マテリ アル株式会社総合研究所内 (72)発明者 姜 仁鎬 兵庫県三田市テクノパ−ク12−６ 三菱マ テリアル株式会社三田工場内 (72)発明者 小田 淳一 兵庫県三田市テクノパ−ク12−６ 三菱マ テリアル株式会社三田工場内 Ｆターム(参考） 4G030 AA16 AA31 AA34 AA37 AA56 BA14 BA18 CA01 GA29 4K029 BA43 BA51 BA64 BD12 CA05 DC05 DC09 DC34 5D121 AA04 EE03 EE09 EE13 Continued on the front page (72) Inventor Rie Mori 1-297 Kitabukuro-cho, Omiya-shi, Saitama Prefecture Mitsubishi Materials Co., Ltd. (72) Inventor Jin-ho Kang 12-6 Technopark, Mita-shi, Hyogo Mitsubishi Materials Corporation (72) Inventor Junichi Oda 12-6 Technopark, Mita City, Hyogo Prefecture Mitsubishi Materials Corporation Mita Plant F term (reference) 4G030 AA16 AA31 AA34 AA37 AA56 BA14 BA18 CA01 GA29 4K029 BA43 BA51 BA64 BD12 CA05 DC05 DC09 DC34 5D121 AA04 EE03 EE09 EE13
Claims (3)
銅：０．１〜３％、酸化ケイ素：２〜１０％、酸化チタ
ン：２〜１０％、酸化インジウム：２０〜４０％、硫化
亜鉛：残りからなる組成を有するホットプレス焼結体で
構成したことを特徴とする、直流スパッタ条件下で優れ
た耐割損性を発揮する光記録媒体保護膜形成用スパッタ
リングターゲット。(1) In% by mass (hereinafter,% indicates mass%)
Copper: 0.1 to 3%, silicon oxide: 2 to 10%, titanium oxide: 2 to 10%, indium oxide: 20 to 40%, zinc sulfide: a hot press sintered body having a composition consisting of the remainder. A sputtering target for forming an optical recording medium protective film, which exhibits excellent crack resistance under DC sputtering conditions.
０％、酸化チタン：２〜１０％、酸化インジウム：２０
〜４０％、硫化亜鉛：残りからなる組成を有し、前記銅
の一部または全部が硫化亜鉛に固溶しており、さらに前
記酸化チタンは連続相である酸化ケイ素により結合した
複合粒子として素地中に分散している組織を有するホッ
トプレス焼結体で構成したことを特徴とする、直流スパ
ッタ条件下で優れた耐割損性を発揮する光記録媒体保護
膜形成用スパッタリングターゲット。2. Copper: 0.1-3%, silicon oxide: 2-1
0%, titanium oxide: 2 to 10%, indium oxide: 20
４０40%, zinc sulfide: having a composition consisting of the remainder, a part or all of the copper is dissolved in zinc sulfide, and the titanium oxide is a base particle as composite particles bonded by a continuous phase, silicon oxide. A sputtering target for forming a protective film for an optical recording medium exhibiting excellent splitting resistance under DC sputtering conditions, comprising a hot press sintered body having a structure dispersed therein.
混合して得られた混合粉末をホットプレスすることによ
りスパッタリングターゲットを製造する方法において、 原料粉末として、銅が硫化亜鉛に固溶している銅固溶硫
化亜鉛粉末、並びに酸化チタンが分散相となり酸化ケイ
素が連続相となって酸化チタンと酸化ケイ素が結合して
なる複合粉末を使用することを特徴とする直流スパッタ
条件下で優れた耐割損性を発揮する光記録媒体保護膜形
成用スパッタリングターゲットの製造方法。3. A method for producing a sputtering target by hot-pressing a mixed powder obtained by blending and mixing raw material powders to have a predetermined composition, wherein copper is dissolved in zinc sulfide as the raw material powder. Under a DC sputtering condition, a composite powder comprising copper solid solution zinc sulfide powder, and titanium oxide and silicon oxide combined with titanium oxide as a dispersed phase and silicon oxide as a continuous phase is used. A method for producing a sputtering target for forming an optical recording medium protective film exhibiting excellent crack resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000176458A JP2001355065A (en) | 2000-06-13 | 2000-06-13 | Sputtering target for depositing optical recording medium protective film exhibiting excellent cracking-off resistance under direct current sputtering condition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000176458A JP2001355065A (en) | 2000-06-13 | 2000-06-13 | Sputtering target for depositing optical recording medium protective film exhibiting excellent cracking-off resistance under direct current sputtering condition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001355065A true JP2001355065A (en) | 2001-12-25 |
Family
ID=18678183
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000176458A Withdrawn JP2001355065A (en) | 2000-06-13 | 2000-06-13 | Sputtering target for depositing optical recording medium protective film exhibiting excellent cracking-off resistance under direct current sputtering condition |
Country Status (1)
| Country | Link |
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| JP (1) | JP2001355065A (en) |
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|---|---|---|---|---|
| WO2003069612A1 (en) * | 2002-02-14 | 2003-08-21 | Nikko Materials Company, Limited | Sputtering target containing zinc sulfide as major component, optical recording medium on which phase change optical disk protective film containing zinc sulfide as major component is formed by using the target, and method for manufacturing the sputtering target |
| JP2006299307A (en) * | 2005-04-18 | 2006-11-02 | Mitsubishi Materials Corp | Sputtering target for forming protective film of optical recording medium |
| JP2008159242A (en) * | 2007-11-30 | 2008-07-10 | Nikko Kinzoku Kk | Optical recording medium with phase-change type optical disk protective film composed essentially of zinc sulfide formed by using sputtering target composed essentially of zinc sulfide |
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| EP2395124A1 (en) * | 2009-02-05 | 2011-12-14 | JX Nippon Mining & Metals Corporation | Thin film comprising titanium oxide as major component and sintered sputtering target comprising titanium oxide as major component |
| CN102912293A (en) * | 2012-11-13 | 2013-02-06 | 中国航天科技集团公司第五研究院第五一0研究所 | Multi-spectrum protective film and preparation method thereof |
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|---|---|---|---|---|
| WO2003069612A1 (en) * | 2002-02-14 | 2003-08-21 | Nikko Materials Company, Limited | Sputtering target containing zinc sulfide as major component, optical recording medium on which phase change optical disk protective film containing zinc sulfide as major component is formed by using the target, and method for manufacturing the sputtering target |
| CN1296924C (en) * | 2002-02-14 | 2007-01-24 | 日矿金属株式会社 | Sputtering target containing zinc sulfide as major component, optical recording medium on which phase change optical disk protective film containing zinc sulfide as major component is formed by using |
| US7279211B2 (en) | 2002-02-14 | 2007-10-09 | Nippon Mining & Metals Co., Ltd. | Sputtering target containing zinc sulfide as major component, optical recording medium on which phase change optical disk protective film containing zinc sulfide as major component is formed by using the target, and method for manufacturing the sputtering target |
| US7601481B2 (en) * | 2004-03-19 | 2009-10-13 | Ricoh Company, Ltd. | Multilayer phase-change information recording medium, and method for recording and reproducing using the same |
| JP2006299307A (en) * | 2005-04-18 | 2006-11-02 | Mitsubishi Materials Corp | Sputtering target for forming protective film of optical recording medium |
| JP4697404B2 (en) * | 2005-04-18 | 2011-06-08 | 三菱マテリアル株式会社 | Sputtering target for forming an optical recording medium protective film |
| JP4642833B2 (en) * | 2007-11-30 | 2011-03-02 | Ｊｘ日鉱日石金属株式会社 | Optical recording medium having a phase change optical disc protective film mainly composed of zinc sulfide formed using a sputtering target composed mainly of zinc sulfide |
| JP2008159242A (en) * | 2007-11-30 | 2008-07-10 | Nikko Kinzoku Kk | Optical recording medium with phase-change type optical disk protective film composed essentially of zinc sulfide formed by using sputtering target composed essentially of zinc sulfide |
| EP2395124A1 (en) * | 2009-02-05 | 2011-12-14 | JX Nippon Mining & Metals Corporation | Thin film comprising titanium oxide as major component and sintered sputtering target comprising titanium oxide as major component |
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| CN102912293A (en) * | 2012-11-13 | 2013-02-06 | 中国航天科技集团公司第五研究院第五一0研究所 | Multi-spectrum protective film and preparation method thereof |
| WO2020044796A1 (en) * | 2018-08-28 | 2020-03-05 | 三菱マテリアル株式会社 | Sputtering target and method for producing sputtering target |
| JP2020033583A (en) * | 2018-08-28 | 2020-03-05 | 三菱マテリアル株式会社 | Sputtering target and method for manufacturing the same |
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| JP7081394B2 (en) | 2018-08-28 | 2022-06-07 | 三菱マテリアル株式会社 | Sputtering target and manufacturing method of sputtering target |
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