JPH0462556B2 - - Google Patents
Info
- Publication number
- JPH0462556B2 JPH0462556B2 JP62013650A JP1365087A JPH0462556B2 JP H0462556 B2 JPH0462556 B2 JP H0462556B2 JP 62013650 A JP62013650 A JP 62013650A JP 1365087 A JP1365087 A JP 1365087A JP H0462556 B2 JPH0462556 B2 JP H0462556B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- substrate
- deposited film
- recording medium
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000758 substrate Substances 0.000 claims description 24
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- 229910052714 tellurium Inorganic materials 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 14
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 239000010408 film Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 29
- 239000011669 selenium Substances 0.000 description 24
- 230000035945 sensitivity Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000007733 ion plating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005546 reactive sputtering Methods 0.000 description 4
- -1 chalcogen fluoride Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- XVKFQTALPDUTNS-UHFFFAOYSA-N 2-chloro-1,3,4,4,5,6,6,7,8,8,8-undecafluoro-3-(trifluoromethyl)oct-1-ene Chemical compound FC(C(F)(F)F)C(C(C(C(C(F)(F)F)(C(=CF)Cl)F)(F)F)F)(F)F XVKFQTALPDUTNS-UHFFFAOYSA-N 0.000 description 1
- ABQLAMJAQZFPJI-UHFFFAOYSA-N 3-heptyloxolan-2-one Chemical compound CCCCCCCC1CCOC1=O ABQLAMJAQZFPJI-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VMTCKFAPVIWNOF-UHFFFAOYSA-N methane tetrahydrofluoride Chemical compound C.F.F.F.F VMTCKFAPVIWNOF-UHFFFAOYSA-N 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- LMDVZDMBPZVAIV-UHFFFAOYSA-N selenium hexafluoride Chemical compound F[Se](F)(F)(F)(F)F LMDVZDMBPZVAIV-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- NNCGPRGCYAWTAF-UHFFFAOYSA-N tellurium hexafluoride Chemical compound F[Te](F)(F)(F)(F)F NNCGPRGCYAWTAF-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- PPMWWXLUCOODDK-UHFFFAOYSA-N tetrafluorogermane Chemical compound F[Ge](F)(F)F PPMWWXLUCOODDK-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/257—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
- G11B7/2572—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers consisting essentially of organic materials
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24302—Metals or metalloids
- G11B2007/24316—Metals or metalloids group 16 elements (i.e. chalcogenides, Se, Te)
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/243—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising inorganic materials only, e.g. ablative layers
- G11B2007/24318—Non-metallic elements
- G11B2007/24326—Halides (F, CI, Br...)
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2531—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising glass
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2532—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising metals
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
- G11B7/266—Sputtering or spin-coating layers
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は光学的記録用媒体に関する。詳しく
は、レーザービームを照射して局部的に加熱し、
その加熱部に穴もしくは変形部を形成することに
よつて記録する光学的記録用媒体に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an optical recording medium. In detail, by irradiating a laser beam and heating locally,
The present invention relates to an optical recording medium in which recording is performed by forming holes or deformed parts in the heating part.
（従来の技術及びその問題点）
基板上に形成された薄膜にレーザービームを照
射して、穴もしくは変形部（ピツト）を形成する
ようにした光学的記録用媒体として、従来より
Teを使用することが知られている。Teは光吸収
係数が大きく低融点、低熱伝導度であるために上
記方法による記録において高い感度を示す。しか
し、Teは酸化され易く酸化されると光吸収の効
率が悪化し、記録感度が低下するという問題があ
る。(Prior art and its problems) As an optical recording medium, a thin film formed on a substrate is irradiated with a laser beam to form holes or deformed parts (pits).
It is known to use Te. Since Te has a large optical absorption coefficient, low melting point, and low thermal conductivity, it exhibits high sensitivity in recording by the above method. However, there is a problem that Te is easily oxidized, and when it is oxidized, the light absorption efficiency deteriorates and the recording sensitivity decreases.
上記問題点を改良したものとして、Teの他に
Seを含ませ合金化したもの、Teの低酸化物、Te
を有機物重合膜中に分散させたもの等がある。
（例えば、特開昭53−31104号公報、特開昭58−
54338号公報、特開昭57−98394号公報）
上記記録媒体は、真空蒸着法、イオンプレーテ
イング法、スパツタリング法により作製が可能で
ある。 In addition to Te, as an improvement on the above problems,
Alloyed with Se, low oxide of Te, Te
There are those in which the organic material is dispersed in an organic polymer film.
(For example, JP-A-53-31104, JP-A-58-
(No. 54338, Japanese Unexamined Patent Publication No. 57-98394) The above-mentioned recording medium can be produced by a vacuum evaporation method, an ion plating method, or a sputtering method.
本発明者らは、TeまたはTeを含む金属を薄膜
化したTe系記録媒体について検討した結果、こ
れらの媒体には基板上の膜全面において数千Åか
ら数μmの大きさの結晶グレインが発生しやすい
ことがＸ線及び電子線回折、さらには透過電子顕
微鏡像によつて確認され、これゆえに膜の平滑
性、ピツト形状、記録感度が悪く、レーザー光に
よる信号再生時のノイズが高いことを見い出し
た。また、上記結晶グレインを有する堆積膜の反
射率は温度65℃、相対湿度80％の加速試験におい
て24時間以内に、初期反射率の1.3倍近くにまで
増加し、経時安定性が極めて悪いことも明らかに
なつた。 As a result of studying Te-based recording media made of thin films of Te or metals containing Te, the inventors found that crystal grains ranging in size from several thousand Å to several μm occur in these media over the entire surface of the film on the substrate. This has been confirmed by X-ray and electron diffraction as well as transmission electron microscopy images, indicating that the smoothness of the film, pit shape, and recording sensitivity are poor, and the noise during signal reproduction by laser light is high. I found it. Furthermore, in an accelerated test at a temperature of 65°C and a relative humidity of 80%, the reflectance of the deposited film containing the above-mentioned crystal grains increased to nearly 1.3 times the initial reflectance within 24 hours, indicating extremely poor stability over time. It became clear.
（問題を解決するための手段）
本発明者らは、この様な結果をふまえて更に
種々検討した結果、イオンプレーテイング法又は
反応性スパツタリング法により基板上に結晶粒及
び結晶粒界がなく、従つて感度、ピツト形状共に
良好で場所による記録感度のむらがなく、しかも
経時安定性の優れた光学的記録媒体が得られる事
を見出し本発明に到達した。(Means for Solving the Problem) Based on these results, the present inventors further conducted various studies, and found that by using an ion plating method or a reactive sputtering method, there are no crystal grains or grain boundaries on the substrate. Therefore, the present inventors have discovered that it is possible to obtain an optical recording medium that has good sensitivity and pit shape, has no unevenness in recording sensitivity depending on location, and has excellent stability over time.
すなわち、本発明の要旨は基板上に記録膜を形
成し、記録膜にレーザー光ビームを照射し穴もし
くは変形部を形成して情報を記録する光学的記録
用媒体において、前記記録膜が少なくともTe，
Se及びＦを含む特定組成の記録膜であることに
ある。 That is, the gist of the present invention is an optical recording medium in which a recording film is formed on a substrate, and information is recorded by irradiating the recording film with a laser beam to form holes or deformed parts. ，
The recording film has a specific composition containing Se and F.
（発明の構成） 以下、本発明を詳細に説明する。(Structure of the invention) The present invention will be explained in detail below.
まず本発明に係る記録媒体の基板としては、ア
クリル樹脂、ポリカーボネート樹脂等のプラスチ
ツク、アルミニウム等の金属又はガラスさらには
これら基板上に熱硬化性あるいは光硬化性樹脂を
塗布したもの等が挙げられる。 First, the substrate of the recording medium according to the present invention includes plastics such as acrylic resin and polycarbonate resin, metals such as aluminum, or glass, as well as substrates coated with thermosetting or photocurable resins.
本発明においては、この基板上に反応性イオン
プレーテイング法又は反応性スパツタリング法に
より、少なくともTe，Se及びＦの３元素を含む
堆積膜を形成させる。 In the present invention, a deposited film containing at least three elements, Te, Se, and F, is formed on this substrate by a reactive ion plating method or a reactive sputtering method.
反応性イオンプレーテイング法においては、フ
ツ化物ガスあるいはフツ化物ガスとArガスとの
混合ガスからなる反応性ガスを導入した真空容器
中でグロー放電プラズマを発生させ、該プラズマ
中にTe及びSeを含む合金を蒸発させ、Te，Se及
びＦを含む堆積膜を形成する。グロー放電の発生
方法としては、コイル状電極を用いた誘導結合高
周波放電が一般的である。 In the reactive ion plating method, a glow discharge plasma is generated in a vacuum chamber into which a reactive gas consisting of fluoride gas or a mixed gas of fluoride gas and Ar gas is introduced, and Te and Se are added to the plasma. The alloy containing Te, Se, and F is evaporated to form a deposited film containing Te, Se, and F. A common method for generating glow discharge is inductively coupled high-frequency discharge using a coiled electrode.
一方反応性スパツタリング法においては、Te
及びSeを含む金属をターゲツト材としてフツ化
物ガスとArガスとの混合ガスを導入した真空容
器中でグロー放電を行なう事により基板上にTe，
Se及びＦを含む堆積膜を形成する。放電に際し
ては、平行平板型電極を用い、高周波法又は直流
法の常法を用いることができる。 On the other hand, in the reactive sputtering method, Te
By performing glow discharge in a vacuum chamber into which a mixed gas of fluoride gas and Ar gas is introduced, using a metal containing Se as a target material, Te and Se are deposited on the substrate.
A deposited film containing Se and F is formed. For discharging, parallel plate type electrodes can be used and conventional methods such as a high frequency method or a direct current method can be used.
また、上記フツ化物ガスとして、フツ化セレン
ガスを用いれば、蒸着源あるいはターゲツト材と
して、Te金属あるいはSeを含まないTe系合金を
用いることもできる。 Furthermore, if selenium fluoride gas is used as the fluoride gas, Te metal or a Te-based alloy not containing Se can also be used as the vapor deposition source or target material.
蒸着源あるいは、ターゲツト材としては、Te
又はTe及びSeを母材としてPb，Bi，Sb，Sn，
Ge，As等を含む金属合金が挙げられる。該金属
がTe，Se及びＦを含む堆積膜中に含まれること
により、該堆積膜の結晶性、結晶化温度、表面張
力あるいは粘度を制御することができる。 Te is used as a deposition source or target material.
Or Pb, Bi, Sb, Sn, using Te and Se as base materials
Examples include metal alloys containing Ge, As, etc. By including the metal in the deposited film containing Te, Se, and F, the crystallinity, crystallization temperature, surface tension, or viscosity of the deposited film can be controlled.
フツ化物ガスとしては例えば四フツ化メタン、
四フツ化エチレン、クロロトリフルオロエチレ
ン、三フツ化エチレン、六フツ化プロプレン、フ
ツ化ビニル、フツ化ビニリデンなどのフツ化炭素
ガス、フツ化炭化水素ガス、フツ化塩化炭素ガス
あるいは六フツ化硫黄、六フツ化セレン、六フツ
化テルルなどのフツ化カルコゲンガス、三フツ化
窒素などのフツ化窒素ガス、四フツ化シリコン、
四フツ化ゲルマニウム等のフツ化金属ガス、さら
にはフツ素ガスが用いられる。 Examples of fluoride gas include methane tetrafluoride,
Fluorinated carbon gas such as tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, fluorinated hydrocarbon gas, fluorinated chloride gas, or sulfur hexafluoride , chalcogen fluoride gases such as selenium hexafluoride and tellurium hexafluoride, nitrogen fluoride gases such as nitrogen trifluoride, silicon tetrafluoride,
A metal fluoride gas such as germanium tetrafluoride, or even a fluorine gas is used.
上記反応性ガスの導入量は得られる堆積膜が非
晶質となり、かつ、基板に多大なダメージを与え
ないように選ばれる。 The amount of the reactive gas introduced is selected so that the resulting deposited film will be amorphous and will not cause significant damage to the substrate.
結果として、堆積膜中に５〜25原子％のSe原
子及び１〜40原子％のＦ原子を含んでいることが
望ましい。堆積膜を後工程で60〜130℃でアニー
ルするとＦが抜け0.1〜30原子％程度となる。 As a result, it is desirable that the deposited film contains 5 to 25 at.% of Se atoms and 1 to 40 at.% of F atoms. When the deposited film is annealed at 60 to 130° C. in a post-process, F is eliminated to a concentration of about 0.1 to 30 atomic percent.
Se含有量が５原子％未満では、該堆積膜の耐
酸化性が弱く、経時安定性が悪くなる。また、25
原子％を越えると穴もしくは変形部を生じさせる
に必要なエネルギーが大きくなる。すなわち、記
録感度が悪くなる。 If the Se content is less than 5 at %, the oxidation resistance of the deposited film will be weak and the stability over time will be poor. Also, 25
If the amount exceeds atomic %, the energy required to create a hole or a deformed portion increases. That is, recording sensitivity deteriorates.
一方、Ｆ含有量が１原子％未満では、該堆積膜
は非晶質とならず、40原子％を越えると、基板に
ダメージを与えやすく、また、記録感度が悪くな
る。 On the other hand, if the F content is less than 1 atomic %, the deposited film will not become amorphous, and if it exceeds 40 atomic %, the substrate will be easily damaged and the recording sensitivity will deteriorate.
本発明において、上記Te，Se及びＦを含む堆
積膜の厚みは十分な光学的特性（反射率あるいは
透過率）が得られ、かつ、記録感度とピツト形状
を劣化させない範囲に選ばれ、通常50Å〜1μm、
望ましくは200〜1000Åとする。 In the present invention, the thickness of the deposited film containing Te, Se, and F is selected within a range that provides sufficient optical properties (reflectance or transmittance) and does not deteriorate recording sensitivity and pit shape, and is usually 50 Å. ~1μm,
The thickness is preferably 200 to 1000 Å.
本発明における堆積膜はＸ線及び電子線回折法
により一様な非晶質構造であることが確認され
た。単なる蒸着法あるいはArガスのみによるス
パツタリング法による堆積膜は多結晶となるのに
対し本発明における堆積膜が一様な非晶質となる
理由は必ずしも明らかではないが、本発明におけ
る反応性ガス分子がフツ素原子を含むために、グ
ロー放電プラズマ中においてフツ素イオン及びフ
ツ素ラジカルさらには、Se及びTeのフツ化物が
生成し、基板上においてTe及びSe原子の他に、
これらのフツ化物が堆積され、また同時にエツチ
ングが行なわれるため、結晶粒の成長が妨げられ
るためと考えられる。 The deposited film in the present invention was confirmed to have a uniform amorphous structure by X-ray and electron diffraction methods. The reason why the deposited film in the present invention is uniformly amorphous, whereas the deposited film by simple evaporation method or sputtering method using only Ar gas is polycrystalline, is not necessarily clear, but the reactive gas molecules in the present invention contains fluorine atoms, fluorine ions and fluorine radicals as well as Se and Te fluorides are generated in the glow discharge plasma, and on the substrate, in addition to Te and Se atoms,
This is thought to be because these fluorides are deposited and etched at the same time, which hinders the growth of crystal grains.
さらに、上述のフツ素イオン又はフツ素ラジカ
ルによる基板表面の軽いエツチングには基板と堆
積膜との間の付着力を均一化する効果もある。 Furthermore, the above-mentioned light etching of the substrate surface by fluorine ions or fluorine radicals has the effect of making the adhesion between the substrate and the deposited film uniform.
該非晶質性堆積膜では結晶粒及び結晶粒界が殆
んど存在しないため、これを記録媒体として用い
れば、記録感度及びピツト形状を均一化でき、さ
らに、レーザー光による再生時の反射率ムラがな
く、ノイズを低くおさえることができ従つて、高
Ｃ／Ｎ比（carrier to noise ratio）を達成する
ことができる。 Since there are almost no crystal grains or grain boundaries in the amorphous deposited film, if it is used as a recording medium, recording sensitivity and pit shape can be made uniform, and reflectance unevenness during reproduction by laser light can be made uniform. Since there is no noise, noise can be kept low and a high C/N ratio (carrier to noise ratio) can be achieved.
また、Seを含有することによりTe単独では不
可能な耐酸化性が得られ、経時安定性が大幅に改
善される。 Furthermore, by containing Se, oxidation resistance that is not possible with Te alone can be obtained, and stability over time is significantly improved.
本発明に係る記録媒体は上記のように基板上に
Te，Se及びＦを含む金属化合物の堆積膜を形成
させているが、さらに基板と該堆積膜との間に記
録感度の向上、ピツト形状の改善等のために下引
き層を設けることもでき、さらには、記録媒体保
護のために該記録媒体上に保護膜を設けることも
できる。 The recording medium according to the present invention is arranged on a substrate as described above.
A deposited film of a metal compound containing Te, Se, and F is formed, but an undercoat layer can also be provided between the substrate and the deposited film in order to improve recording sensitivity and pit shape. Furthermore, a protective film can be provided on the recording medium to protect the recording medium.
以下実施例をもつて詳細に説明を行う。 A detailed explanation will be given below using examples.
（実施例 １）
第１図は反応性スパツタリング法による光学的
記録媒体の製造のための装置の一例である。図中
１は真空容器、２は電極、３はTe又はTe，Seを
含む合金ターゲツト、４は基板、５はガス導入
口、６はシヤツター、７は排気口である。まず真
空容器１を10-6Torr台まで排気した後、Arガス
を導入口５より導入し、真空容器１の内圧を５×
10-3Torrとする。引き続き電極２の間に高周波
電圧を印加し放電を起こさせる。この状態を10分
間程度保持しターゲツト３表面を清浄にする。そ
の後真空気内を再び10-6台まで排気し、Arガス
と体積比で５％のNF3ガスを混合して導入口５よ
り導入し、全圧を５×1-3Torrとし、基板側電極
４とターゲツト側電極３間に13.56MHz、100Wの
高周波電力を印加してグロー放電を生じせしめス
パツタリングを行なつた。ターゲツトには、原子
比Te85％、Se15％の合金を用い、基板上に40nm
のスパツタ膜を堆積させた。該堆積膜中のSe含
有量は13原子％、Ｆ含有量は15原子％であつた。
ついで、この光学的記録媒体に波長830nmの
GaAs半導体レーザーで記録と再生を行なつたと
ころ、感度３ｍＷ、Ｃ／Ｎ比（carrier to noise
ratio）52dBが得られた。(Example 1) FIG. 1 is an example of an apparatus for manufacturing an optical recording medium by a reactive sputtering method. In the figure, 1 is a vacuum vessel, 2 is an electrode, 3 is Te or an alloy target containing Te and Se, 4 is a substrate, 5 is a gas inlet, 6 is a shutter, and 7 is an exhaust port. First, after evacuating the vacuum container 1 to 10 -6 Torr level, Ar gas is introduced from the inlet 5 to increase the internal pressure of the vacuum container 1 by 5×.
10 -3 Torr. Subsequently, a high frequency voltage is applied between the electrodes 2 to cause discharge. Maintain this state for about 10 minutes to clean the surface of target 3. After that, the vacuum was evacuated again to 10 -6 units, Ar gas and 5% NF 3 gas by volume were mixed and introduced from inlet 5, the total pressure was set to 5 × 1 -3 Torr, and the substrate side A high frequency power of 13.56 MHz and 100 W was applied between the electrode 4 and the target side electrode 3 to generate glow discharge and perform sputtering. The target is an alloy with an atomic ratio of 85% Te and 15% Se, and a 40nm layer is placed on the substrate.
A sputter film of 100% was deposited. The Se content in the deposited film was 13 at%, and the F content was 15 at%.
Next, this optical recording medium is exposed to a wavelength of 830 nm.
When recording and reproducing with a GaAs semiconductor laser, the sensitivity was 3 mW and the C/N ratio (carrier to noise
ratio) 52dB was obtained.
（実施例 ２）
第２図は反応性イオンプレーテイング法による
光学記録媒体製造のための装置の一例であり図中
１は反応容器、２はガス導入口、３は基板、４は
高周波コイル、５は蒸着用抵抗加熱器、６は膜厚
モニター、７はシヤツター、８は排気口である。
まず真空容器を２×10-5Torrまで排気した後、
SeF6ガスを導入し、コイル状の電極に13.56MHz
の高周波電圧を印加してグロー放電を行なう。
SeF6ガス流量10sccm、ガス圧５×10-4Torr、放
電電力200Wでグロー放電をおこすと同時に、Te
を抵抗加熱で蒸発させ、基板上に30nmの堆積膜
を形成した。該堆積膜中のSe含有量は７原子％、
Ｆ含有量は10原子％であつた。実施例１と同様
に、半導体レーザーによる記録再生を行なつたと
ころ感度３ｍＷ、Ｃ／Ｎ比50dBを得た。(Example 2) Fig. 2 shows an example of an apparatus for producing an optical recording medium by the reactive ion plating method. In the figure, 1 is a reaction vessel, 2 is a gas inlet, 3 is a substrate, 4 is a high frequency coil, 5 is a resistance heater for vapor deposition, 6 is a film thickness monitor, 7 is a shutter, and 8 is an exhaust port.
First, after evacuating the vacuum container to 2×10 -5 Torr,
Introducing SeF 6 gas to the coiled electrode at 13.56MHz
Glow discharge is performed by applying a high frequency voltage of .
At the same time, a glow discharge was generated at a SeF 6 gas flow rate of 10 sccm, a gas pressure of 5×10 -4 Torr, and a discharge power of 200 W.
was evaporated by resistance heating to form a 30 nm deposited film on the substrate. The Se content in the deposited film is 7 at%,
The F content was 10 at.%. As in Example 1, recording and reproducing using a semiconductor laser resulted in a sensitivity of 3 mW and a C/N ratio of 50 dB.
上記実施例１及び実施例２の堆積膜は比晶質で
あり、加速試験において酸化による光学的特性及
びＣ／Ｎの劣化はほとんど見られなかつた。 The deposited films of Examples 1 and 2 were specific crystalline, and almost no deterioration in optical properties and C/N due to oxidation was observed in accelerated tests.
（比較例）
真空容器を３×10-6Torrまで排気した後、Ar
ガスを５×10-3Torrまで導入し、13.56MHzの高
周波電力50Wで基板とターゲツトの間にグロー放
電を起こす。(Comparative example) After evacuating the vacuum container to 3×10 -6 Torr, Ar
Gas is introduced to 5×10 -3 Torr, and a glow discharge is generated between the substrate and target using 50 W of high frequency power at 13.56 MHz.
ターゲツトに原子比Te85％、Se15％の合金を
用い、基板上に40nmのTeSe堆積膜を形成させ
た。得られた光学的記録媒体は多結晶であり半導
体レーザーによる記録読み出し試験を行なつたと
ころＣ／Ｎ比45dBであつた。 Using an alloy with an atomic ratio of 85% Te and 15% Se as a target, a 40 nm TeSe deposited film was formed on the substrate. The obtained optical recording medium was polycrystalline, and a recording/reading test using a semiconductor laser was conducted, and the C/N ratio was 45 dB.
（発明の効果）
本発明によれば経時安定性、Ｃ／Ｎ比
（carrier to noise ratio）、ピツト形状を更に向
上しえた記録媒体を得ることができる。(Effects of the Invention) According to the present invention, it is possible to obtain a recording medium with further improved stability over time, C/N ratio (carrier to noise ratio), and pit shape.
第１図及び第２図は本発明の記録用媒体を製造
するに用いる装置の一例の概略図である。
図中、１は真空容器、２は電極、３はターゲツ
ト、４は基板をそれぞれ示す。
FIGS. 1 and 2 are schematic diagrams of an example of an apparatus used for manufacturing the recording medium of the present invention. In the figure, 1 is a vacuum vessel, 2 is an electrode, 3 is a target, and 4 is a substrate.
Claims (1)
ビームを照射し穴もしくは変形部を形成して情報
を記録する光学的記録用媒体において、前記記録
膜が少なくともTe，Se及びＦを含むものであつ
て、その含有量がTe35〜94.9原子％、Se5〜25原
子％、F0.1〜40原子％であることを特徴とする光
学的記録用媒体。1. An optical recording medium in which information is recorded by forming a recording film on a substrate and irradiating the recording film with a laser beam to form holes or deformed parts, where the recording film contains at least Te, Se, and F. An optical recording medium characterized in that the content thereof is 35 to 94.9 atomic % Te, 5 to 25 atomic % Se, and 0.1 to 40 atomic % F.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62013650A JPS63182188A (en) | 1987-01-23 | 1987-01-23 | optical recording medium |
| KR1019870000966A KR910009072B1 (en) | 1986-04-24 | 1987-02-05 | Optical recording carrier and manufacturing process therefor |
| EP87301046A EP0242942B1 (en) | 1986-04-24 | 1987-02-05 | Optical recording medium and process for producing the same |
| DE8787301046T DE3776386D1 (en) | 1986-04-24 | 1987-02-05 | OPTICAL RECORDING MEDIUM AND METHOD FOR THE PRODUCTION THEREOF. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62013650A JPS63182188A (en) | 1987-01-23 | 1987-01-23 | optical recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63182188A JPS63182188A (en) | 1988-07-27 |
| JPH0462556B2 true JPH0462556B2 (en) | 1992-10-06 |
Family
ID=11839100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62013650A Granted JPS63182188A (en) | 1986-04-24 | 1987-01-23 | optical recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63182188A (en) |
-
1987
- 1987-01-23 JP JP62013650A patent/JPS63182188A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63182188A (en) | 1988-07-27 |
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