JPH0770746A - Target material for forming carbon coating film - Google Patents
Target material for forming carbon coating filmInfo
- Publication number
- JPH0770746A JPH0770746A JP5246283A JP24628393A JPH0770746A JP H0770746 A JPH0770746 A JP H0770746A JP 5246283 A JP5246283 A JP 5246283A JP 24628393 A JP24628393 A JP 24628393A JP H0770746 A JPH0770746 A JP H0770746A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- pores
- bulk density
- carbon coating
- target material
- 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.)
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Links
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- Carbon And Carbon Compounds (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種基材面にスパッタ
リングにより炭素被膜を形成する際に炭素源として用い
るターゲット材、特に磁気記録装置の磁気ディスク等に
均質で優れた硬度の炭素膜を被着するために好適な炭素
被膜形成用ターゲット材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a target material used as a carbon source for forming a carbon film on a surface of various substrates by sputtering, particularly a carbon film having a uniform and excellent hardness for a magnetic disk of a magnetic recording device. The present invention relates to a carbon coating-forming target material suitable for deposition.
【０００２】[0002]
【従来の技術】磁気記録装置のハードディスクは常に磁
気ヘッドと摺接しながら使用されるため、摺動面に損傷
を受け易い。したがって、磁気ヘッドや記録媒体の磁性
層を保護する目的でその表面に摩擦抵抗の少ない炭素被
膜が形成されている。この炭素被膜は、通常、高周波ス
パッタリングまたは直流スパッタリングにより炭素源を
基材面に衝突させて形成されるが、炭素源となるターゲ
ット材としては従来から黒鉛材料が用いられている。2. Description of the Related Art Since a hard disk of a magnetic recording device is always used in sliding contact with a magnetic head, its sliding surface is easily damaged. Therefore, for the purpose of protecting the magnetic layer of the magnetic head or the recording medium, a carbon coating having a low frictional resistance is formed on the surface thereof. This carbon film is usually formed by colliding a carbon source with the surface of a substrate by high frequency sputtering or direct current sputtering, and a graphite material has been conventionally used as a target material serving as a carbon source.
【０００３】ところが、形成される炭素被膜にブリスタ
ー（花咲き現象と呼ばれる膨れ）が発生して、製品歩留
りを減退させることがある。これは装置面の問題のほか
に、スパッタリング操作過程でターゲット材である黒鉛
材料の灰分あるいは組織内から脱離した炭素粒子、組織
ポア内の煤状物などが飛散して生じた異物パーティクル
が炭素被膜中に混入することが原因と考えられている。However, a blister (a swelling called a flower bloom phenomenon) may occur in the formed carbon film, which may reduce the product yield. This is not only a problem of the equipment, but also the ash content of the graphite material that is the target material during the sputtering operation or the carbon particles desorbed from the tissue, and the foreign particles generated by the soot-like substances in the tissue pores scattering. It is thought that the cause is mixing in the coating.
【０００４】[0004]
【発明が解決しようとする課題】近時、磁気ディスクの
高集積化に伴って磁気ヘッドがフェライト系から材質硬
度の高い薄膜ヘッドに移行しており、加えてディスクと
ヘッドとの接触機構も変化していることから、従来の炭
素被膜では耐摩耗性の点で保護膜としての性能が不十分
になってきている。Recently, as the magnetic disk has been highly integrated, the magnetic head has been changed from a ferrite type to a thin film head having a high material hardness, and in addition, the contact mechanism between the disk and the head has changed. Therefore, the conventional carbon coating has become insufficient in performance as a protective film in terms of wear resistance.
【０００５】本発明者は、ブリスターを発生させずに耐
摩耗性に優れる炭素被膜の形成化につきターゲット材の
面から多角的に検討をおこなった結果、特定範囲にある
物性を備えるガラス状カーボンが極めて好適であること
を確認した。The present inventor conducted a multifaceted study from the viewpoint of the target material to form a carbon coating film having excellent wear resistance without generating blisters, and as a result, glassy carbon having physical properties within a specific range was found. It was confirmed to be extremely suitable.
【０００６】本発明は上記の知見に基づいて開発された
もので、その目的は、スパッタリングにより常に均質で
高硬度の炭素被膜を歩留りよく形成することができる炭
素被膜形成用ターゲット材を提供することにある。The present invention was developed on the basis of the above findings, and an object thereof is to provide a target material for forming a carbon coating, which can always form a uniform and high hardness carbon coating with good yield by sputtering. It is in.
【０００７】[0007]
【課題を解決するための手段】上記の目的を達成するた
めの本発明による炭素被膜形成用ターゲット材は、嵩密
度１．４７g/cc以上、組織気孔のポア径が１０μm 以下
でポア含有率が５％以下の均質緻密性状を有し、かつ総
灰分が１０ppm 以下の高純度特性を備えるガラス状カー
ボンからなることを構成上の特徴とする。The carbon coating forming target material according to the present invention for achieving the above object has a bulk density of 1.47 g / cc or more, a pore diameter of tissue pores of 10 μm or less, and a pore content rate of 10 μm or less. The structural feature is that it is made of glassy carbon having a homogeneous denseness of 5% or less and a high purity characteristic of total ash content of 10 ppm or less.
【０００８】上記構成において特定したガラス状カーボ
ンの各材質性状の値は、嵩密度および総灰分については
ＪＩＳ Ｒ7222−1979「高純度黒鉛素材の物理試験方
法」、組織気孔のポア径は光学顕微鏡あるいは走査型電
子顕微鏡観察によって測定した最大ポア径、ポア含有率
（気孔率）は真比重と比重からの算出値である。The values of the respective material properties of the glassy carbon specified in the above constitution are JIS R7222-1979 "Physical test method for high purity graphite material" for bulk density and total ash content, and the pore diameter of tissue pores is determined by an optical microscope or The maximum pore diameter and pore content (porosity) measured by scanning electron microscope observation are values calculated from true specific gravity and specific gravity.
【０００９】ガラス状カーボンは、黒鉛材料などの一般
炭素質物のようにガーボン粒子が集合した組織構造体と
は異なり、無定形ガラス状の連続緻密組織を呈する特異
な炭素構造体であるため、スパッタリングによってター
ゲット材が消耗する過程で粒子脱離によるパーティクル
の発生を伴うことがない。しかし、ガラス状カーボンの
組織には製造時に不可避的に形成される微小なポアが内
在しており、ポアの内面には熱分解生成物が煤状に沈着
している。このため、組織がスパッタリングの衝撃によ
って表面から消耗して内在ポアが露出するようになる
と、前記の微細な煤状物が飛散してブリスターの発生原
因となる。Unlike a general carbonaceous material such as a graphite material and the like, in which glassy carbon is an aggregate structure of garbon particles, glassy carbon is a peculiar carbon structure having an amorphous glassy continuous dense structure. Therefore, particles are not generated due to particle detachment in the process of exhausting the target material. However, the microstructure of glassy carbon internally contains minute pores that are inevitably formed during production, and thermal decomposition products are deposited in the form of soot on the inner surface of the pores. For this reason, when the structure is consumed from the surface by the impact of sputtering and the internal pores are exposed, the fine soot-like material is scattered and causes blisters.
【００１０】本発明で特定した嵩密度１．４７g/cc以上
の組織は内在ポアの少ない組織緻密性を保有しており、
この組織性状がポア露出時における煤状物の放出を少な
くする機能を営む。この機能は、組織気孔として内在す
るポア径が１０μm 以下で、そのポア含有率が５％以下
であると一層効果が助長される。一方、総灰分が１０５
ppm 以下の純度特性も、煤状物の発生を抑制してパーテ
ィクルによる悪影響を防止する機能要件となる。これら
の組織性状および純度特性は同時に満たす必要があり、
例えば嵩密度が１．４７g/cc以下であっても、総灰分が
１０ppm を越えるような場合には、ブリスターのない正
常な炭素被膜を形成することができなくなる。The structure having a bulk density of 1.47 g / cc or more specified in the present invention has the structure compactness with few internal pores,
This texture has the function of reducing the release of soot when the pores are exposed. The effect of this function is further promoted when the pore diameter inherent in the tissue pores is 10 μm or less and the pore content is 5% or less. On the other hand, the total ash content is 105
Purity characteristics below ppm are also functional requirements for suppressing the generation of soot and preventing the adverse effects of particles. These texture and purity characteristics must be met at the same time,
For example, even if the bulk density is 1.47 g / cc or less, if the total ash content exceeds 10 ppm, a normal carbon film without blisters cannot be formed.
【００１１】本発明で特定された材質性状のガラス状カ
ーボン材は、従来プロセスによる製造技術において各工
程の条件を適宜に調整することによって得ることができ
る。まず、材質の高密度化を図るために、原料となる熱
硬化性樹脂として残炭率が少なくとも４０％のフェノー
ル系、フラン系またはポリイミド系の樹脂を選択使用す
る。通常、原料樹脂の形態は粉状もしくは液状である
が、その形態に応じてモールド成形、射出成形、注型成
形、多重成形等から最も好適な成形手段を選定し、炭素
被膜形成装置の支持体に適合する板状形体に成形し、１
００〜１８０℃の温度範囲で硬化処理を施す。この際、
原料樹脂の選択、成形および硬化の条件を制御すること
によって目的とする嵩密度、ポア径、ポア含有率を確保
する。The glassy carbonaceous material having the material properties specified in the present invention can be obtained by appropriately adjusting the conditions of each step in the manufacturing technique by the conventional process. First, in order to increase the density of the material, a phenol-based, furan-based, or polyimide-based resin having a residual carbon rate of at least 40% is selectively used as a raw thermosetting resin. Usually, the form of the raw material resin is powdery or liquid, but depending on the form, the most suitable forming means is selected from mold forming, injection molding, cast molding, multiple forming, etc. 1)
Curing treatment is performed in the temperature range of 00 to 180 ° C. On this occasion,
The target bulk density, pore diameter, and pore content rate are secured by controlling the raw material resin selection, molding, and curing conditions.
【００１２】焼成炭化処理は、硬化した樹脂成形体を黒
鉛坩堝に詰め、または黒鉛板で挟持した状態で、窒素、
アルゴン等の不活性ガスで置換された電気炉中で加熱す
るか、燃焼ガス加熱方式のリードハンマー炉中に炭素質
パッキングで被包充填して加熱する方法でおこなう。処
理温度は、通常８００〜１５００℃程度であるが、必要
に応じて２０００℃以上の高温で黒鉛化処理する。The firing and carbonization treatment is carried out by filling the cured resin molded body in a graphite crucible or sandwiching it between graphite plates with nitrogen,
It is carried out by heating in an electric furnace which is replaced with an inert gas such as argon, or by encapsulating and heating in a lead gas furnace of a combustion gas heating system with carbonaceous packing. The treatment temperature is usually about 800 to 1500 ° C., but if necessary, graphitization treatment is performed at a high temperature of 2000 ° C. or higher.
【００１３】総灰分が１０ppm 以下の高純度特性を確保
するには、特別に製造された有機質以外の成分を含有し
ない高純度の原料樹脂を外部からの不純物汚染のない環
境下で硬化、焼成を施す方法、常法に従って製造したガ
ラス状カーボン材をハロゲン系ガス雰囲気中で加熱する
二次的な精製処理を施す方法、あるいはこれら両者を組
み合わせて適用する手段が用いられる。高純度の原料樹
脂は、予め吸着分離あるいは高純度蒸留、クロマトグラ
フィー等の手段で不純物を除去したのち、外部からの環
境汚染を防止するためにクリーンルームまたはこれに準
じた環境中で合成する。硬化および焼成時の不純物汚染
を防止するには、処理環境を外部から遮断し、半導体製
造時に使用されるような超高純度のアルゴン、窒素ガス
等の不活性ガスに置換しておこなう。In order to ensure high purity characteristics of total ash content of 10 ppm or less, a specially produced high purity raw material resin containing no components other than organic substances is cured and baked in an environment free from external impurity contamination. A method of applying, a method of applying a secondary refining treatment of heating a glassy carbon material manufactured according to a conventional method in a halogen-based gas atmosphere, or a means of applying both in combination is used. The high-purity raw material resin is preliminarily subjected to adsorption separation, high-purity distillation, chromatography or the like to remove impurities, and then synthesized in a clean room or an environment equivalent thereto in order to prevent environmental pollution from the outside. In order to prevent contamination of impurities during curing and baking, the processing environment is shielded from the outside and replaced with an inert gas such as ultra-high purity argon or nitrogen gas used in semiconductor manufacturing.
【００１４】[0014]
【作用】上記のような特定性状のガラス状カーボンから
なる本発明のターゲット材は、スパッタリングによる消
耗過程における微細な煤状物の発生を抑制してブリスタ
ー現象を効果的に防止する。そのうえ、ガラス状カーボ
ンを構成するＣ−Ｃ結合エネルギーは黒鉛組織のそれよ
りも低い関係で、スパッタリングにより形成される炭素
被膜中に占めるダイヤモンドライクカーボン(DLC) の生
成比率が相対的に高くなる。このため、黒鉛ターゲット
材に比べて炭素被膜の硬度が著しく増大し、耐摩耗性に
優れる被膜形成が可能となる。The target material of the present invention, which is made of glassy carbon having the above-mentioned specific characteristics, suppresses the generation of fine soot-like substances during the consumption process by sputtering and effectively prevents the blister phenomenon. In addition, since the C—C bond energy constituting the glassy carbon is lower than that of the graphite structure, the production ratio of diamond-like carbon (DLC) in the carbon coating formed by sputtering is relatively high. Therefore, the hardness of the carbon coating is remarkably increased as compared with the graphite target material, and it becomes possible to form a coating having excellent wear resistance.
【００１５】このような作用が相俟って、ブリスターの
発生がない状態で優れた硬度の均質性状を備える炭素被
膜を常に歩留りよく得ることがことができるから、特に
高性能磁気ディスクを対象とする保護被膜を形成するた
めのターゲット材として有用となる。In combination with such an action, a carbon coating having excellent homogeneity of hardness can be always obtained in a good yield without the occurrence of blisters, and therefore, especially for a high performance magnetic disk. It is useful as a target material for forming a protective film that protects against heat.
【００１６】[0016]
【実施例】以下、本発明の実施例を比較例と対比して具
体的に説明する。EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples.
【００１７】実施例１〜３、比較例１〜５ 減圧蒸留により精製したフェノールおよびホルマリンを
原料とし、常法に従い付加縮合反応させてフェノール樹
脂初期縮合物（液状樹脂）を調製した。該フェノール樹
脂初期縮合物をポリプロピレン製のバットに流し込んで
真空デシケータに入れ、１０torr以下の減圧下で脱気処
理をおこなったのち、電気オーブンに移し１００℃の温
度で硬化して板状体に成形した。この際、減圧度および
脱気時間を制御して嵩密度および組織気孔のポア状態を
調整した。Examples 1 to 3 and Comparative Examples 1 to 5 Phenol and formalin purified by vacuum distillation were used as raw materials, and addition condensation reaction was carried out according to a conventional method to prepare a phenol resin initial condensate (liquid resin). The phenol resin initial condensate is poured into a polypropylene vat, placed in a vacuum desiccator, deaerated under a reduced pressure of 10 torr or less, then transferred to an electric oven and cured at a temperature of 100 ° C. to form a plate. did. At this time, the degree of pressure reduction and the deaeration time were controlled to adjust the bulk density and the pore state of the tissue pores.
【００１８】ついで、成形された板状体を不純物５ppm
未満の高純度黒鉛板〔東海カーボン（株）製、G347SS〕
で挟み付け、同じく高純度黒鉛製の発熱体を設置した加
熱炉〔東海高熱工業（株）製、TP150 〕にセットした。
この加熱炉の内部を不純物１０ppm 未満の高純度アルゴ
ンガス雰囲気で保持しながら１０００℃に加熱して焼成
炭化処理を施した。得られたガラス状カーボン板の一部
につき、塩素ガスによる脱灰精製処理をおこなった。Then, the molded plate-like body is treated with impurities of 5 ppm.
High-purity graphite plate of less than [Tokai Carbon Co., Ltd., G347SS]
It was then sandwiched between and set in a heating furnace [TP150 manufactured by Tokai High Heat Industrial Co., Ltd.] in which a heating element made of high-purity graphite was also installed.
The inside of this heating furnace was heated to 1000 ° C. while being maintained in an atmosphere of high-purity argon gas containing less than 10 ppm of impurities to perform calcination carbonization treatment. A part of the glassy carbon plate thus obtained was subjected to deashing purification treatment with chlorine gas.
【００１９】このようにして製造した嵩密度、ポア径、
ポア含有率および総灰分の異なるガラス状カーボン板
を、クリーンルーム内で直径１５０mm、厚さ６mmの円盤
形状に加工した。各ガラス状カーボン円盤をターゲット
材として高周波スパッタリング装置の陰極に配置し、対
極にディスク基材を装着して装置内を所定の真空度に保
持したのち、３〜７×１０-3Torrの圧力で高純度アルゴ
ンガス（不純物５ppm 未満）を導入しながらスパッタリ
ング操作をおこなって基材面に炭素被膜を形成した。形
成された炭素被膜のビッカース硬度とディスク基材の歩
留をターゲット材としたガラス状カーボンの性状と対比
させて表１に示した。なお、比較のために従来の黒鉛タ
ーゲット材を用いて同様に試験した結果を表１に併載し
た（比較例５）。The bulk density, pore diameter, and
Glassy carbon plates having different pore contents and total ash content were processed into a disk shape having a diameter of 150 mm and a thickness of 6 mm in a clean room. Each glassy carbon disk was placed as a target material on the cathode of the high frequency sputtering device, a disk substrate was attached to the counter electrode and the inside of the device was maintained at a predetermined degree of vacuum, then at a pressure of 3 to 7 × 10 -3 Torr A carbon coating was formed on the surface of the base material by carrying out a sputtering operation while introducing high-purity argon gas (impurities of less than 5 ppm). Table 1 shows the Vickers hardness of the formed carbon coating and the yield of the disc substrate in comparison with the properties of the glassy carbon used as the target material. For comparison, the results of the same test using a conventional graphite target material are also shown in Table 1 (Comparative Example 5).
【００２０】[0020]
【表１】 〔表注〕(1) 実施例および比較例１〜４はガラス状カー
ボンのターゲット材、比較例５は黒鉛ターゲット材。 (2) ディスク基材の歩留は、試験数２０に対する製品合
格率。[Table 1] [Table Note] (1) Examples and Comparative Examples 1 to 4 are glassy carbon target materials, and Comparative Example 5 is a graphite target material. (2) The yield of the disk substrate is the product pass rate for 20 tests.
【００２１】表１の結果から、本発明の実施例は本発明
の材質性状要件を外れるガラス状カーボンをターゲット
材とした比較例１〜４および従来の黒鉛材をターゲット
材とした比較例５に比べ、形成された炭素被膜のパーテ
ィクル混入によるブリスター発生が効果的に抑制され、
歩留りが向上していることが認められる。また、実施例
による被膜の硬度は黒鉛ターゲット材適用時に比較して
著しく増大しており、耐摩耗性が改善されていることも
判る。From the results shown in Table 1, the examples of the present invention are comparative examples 1 to 4 in which glassy carbon that does not meet the material property requirements of the present invention is used as the target material and comparative example 5 in which the conventional graphite material is used as the target material. In comparison, the occurrence of blisters due to the inclusion of particles in the formed carbon coating is effectively suppressed,
It is recognized that the yield is improved. Also, it can be seen that the hardness of the coating film according to the example is remarkably increased as compared to when the graphite target material is applied, and the wear resistance is improved.
【００２２】[0022]
【発明の効果】以上のとおり、本発明によればブリスタ
ーの発生を伴うことなしに常に均質で優れた硬度を有す
る炭素被膜を歩留りよく形成し得る炭素被膜形成用のタ
ーゲット材を提供することができる。したがって、特に
過酷な条件下で使用される高性能磁気記録装置の磁気デ
ィスクを対象とする保護膜形成用として有用性が期待さ
れる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to provide a target material for forming a carbon coating, which is capable of forming a carbon coating having a uniform and excellent hardness at all times without generating blister. it can. Therefore, it is expected to be useful as a protective film for a magnetic disk of a high-performance magnetic recording device used under particularly severe conditions.
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【手続補正書】[Procedure amendment]
【提出日】平成５年１１月１２日[Submission date] November 12, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】本発明で特定した嵩密度１．４７ｇ／ｃｃ
以上の組織は内在ポアの少ない組織緻密性を保有してお
り、この組織性状がポア露出時における煤状物の放出を
少なくする機能を営む。この機能は、組織気孔として内
在するポア径が１０μｍ以下で、そのポア含有率が５％
以下であると一層効果が助長される。一方、総灰分が１
０ｐｐｍ以下の純度特性も、煤状物の発生を抑制してパ
ーティクルによる悪影響を防止する機能要件となる。こ
れらの組織性状および純度特性は同時に満たす必要があ
り、例えば嵩密度が１．４７ｇ／ｃｃ以下であっても、
総灰分が１０ｐｐｍを越えるような場合には、ブリスタ
ーのない正常な炭素被膜を形成することができなくな
る。Bulk density 1.47 g / cc specified in the present invention
The above tissue possesses a tissue compaction with few internal pores, and this tissue property functions to reduce the release of soot-like substances when the pore is exposed. This function has a pore diameter of 10 μm or less that is intrinsic as tissue pores, and the pore content is 5%.
The effect is further promoted if it is the following. On the other hand, the total ash content is 1
Purity characteristics of 0 ppm or less are also functional requirements for suppressing the generation of soot-like substances and preventing the adverse effects of particles. It is necessary to satisfy these texture properties and purity characteristics at the same time. For example, even if the bulk density is 1.47 g / cc or less,
If the total ash content exceeds 10 ppm, a normal carbon film without blisters cannot be formed.
Claims (1)
ア径が１０μm 以下でポア含有率が５％以下の均質緻密
性状を有し、かつ総灰分が１０ppm 以下の高純度特性を
備えるガラス状カーボンからなることを特徴とする炭素
被膜形成用ターゲット材。1. A high-purity property having a bulk density of 1.47 g / cc or more, a pore diameter of tissue pores of 10 μm or less, a pore content of 5% or less, and a total ash content of 10 ppm or less. A target material for forming a carbon coating, which is made of glassy carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246283A JPH0770746A (en) | 1993-09-06 | 1993-09-06 | Target material for forming carbon coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5246283A JPH0770746A (en) | 1993-09-06 | 1993-09-06 | Target material for forming carbon coating film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0770746A true JPH0770746A (en) | 1995-03-14 |
Family
ID=17146245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5246283A Pending JPH0770746A (en) | 1993-09-06 | 1993-09-06 | Target material for forming carbon coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0770746A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009283107A (en) * | 2008-05-26 | 2009-12-03 | Fuji Electric Device Technology Co Ltd | Protection film mainly including tetrahedral amorphous carbon film and magnetic recording medium having the same |
-
1993
- 1993-09-06 JP JP5246283A patent/JPH0770746A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009283107A (en) * | 2008-05-26 | 2009-12-03 | Fuji Electric Device Technology Co Ltd | Protection film mainly including tetrahedral amorphous carbon film and magnetic recording medium having the same |
| US8888966B2 (en) | 2008-05-26 | 2014-11-18 | Fuji Electric Co., Ltd. | Protective film mainly composed of a tetrahedral amorphous carbon film and a magnetic recording medium having the protective film |
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