JPH0788204B2 - Protective film for oxide superconductor and method of forming the same - Google Patents
Protective film for oxide superconductor and method of forming the sameInfo
- Publication number
- JPH0788204B2 JPH0788204B2 JP63310040A JP31004088A JPH0788204B2 JP H0788204 B2 JPH0788204 B2 JP H0788204B2 JP 63310040 A JP63310040 A JP 63310040A JP 31004088 A JP31004088 A JP 31004088A JP H0788204 B2 JPH0788204 B2 JP H0788204B2
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- film
- hydrogen
- oxide superconductor
- oxide
- 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 - Fee Related
Links
- 230000001681 protective effect Effects 0.000 title claims description 45
- 239000002887 superconductor Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000010408 film Substances 0.000 description 71
- 239000008188 pellet Substances 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 3
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OSOKRZIXBNTTJX-UHFFFAOYSA-N [O].[Ca].[Cu].[Sr].[Bi] Chemical compound [O].[Ca].[Cu].[Sr].[Bi] OSOKRZIXBNTTJX-UHFFFAOYSA-N 0.000 description 1
- CNEWPRQQHICZBP-UHFFFAOYSA-N [O].[Cu].[Ba].[La] Chemical compound [O].[Cu].[Ba].[La] CNEWPRQQHICZBP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- UZFMKSXYXFSTAP-UHFFFAOYSA-N barium yttrium Chemical compound [Y].[Ba] UZFMKSXYXFSTAP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、酸化物超電導体用の保護膜に係り、特に耐
湿，耐炭酸化特性に優れた高強度の酸化物超電導体用保
護膜に関する。Description: TECHNICAL FIELD The present invention relates to a protective film for an oxide superconductor, and more particularly to a high-strength protective film for an oxide superconductor excellent in moisture resistance and carbonation resistance. .
1986年初めにランタン・バリウム・銅の酸化物超電導体
がベドノルツとミユラーによつて発見されて以来、酸化
物超電導体に関する研究活動が活発化した。1987年春に
は90K級の転移温度を有するイツトリウム・バリウム・
銅の酸化物（Ｙ−Ba−Cu−Ｏと略称する）が米国ヒユー
ストン大学のチユーらによつて、1988年初めには105K級
の転移温度を有するビスマス・ストロンチウム・カルシ
ウム・銅の酸化物（Bi−Sr−Ca−Cu−Ｏと略称する）が
金材技研の前田らによつて、120K級の転移温度を有する
タリウム・バリウム・カルシウム・銅の酸化物（Tl−Ba
−Ca−Cu−Ｏと略称する）がアーカンサス（Arkansas）
大のハーマンらによつて発見された。これら酸化物系超
電導体は、臨界温度が液体窒素の沸点である77Kを大き
く上まわつており、高価な液体ヘリウムを用いなくても
安価な液体窒素で超電導状態が得られるため注目されて
いる。これら酸化物超電導体は、特にＹ−Ba−Cu−Ｏ系
のものは大気中に存在する水分と反応して分解したり、
炭酸ガスと反応して炭酸塩となり超電導体が壊れる。こ
のため、酸化物超電導材料を用いた線材やデバイス等へ
の応用に当つては、大気中の水分や炭酸ガスとの接触を
さけるための保護膜の形成が必須の条件となる。Since the discovery of lanthanum-barium-copper oxide superconductors by Bednorz and Müller in early 1986, research activities on oxide superconductors have become active. In the spring of 1987, yttrium barium, which has a transition temperature of 90K,
An oxide of copper (abbreviated as Y-Ba-Cu-O) is a bismuth-strontium-calcium-copper oxide having a transition temperature of 105 K class in early 1988 by Chou et al. Bi-Sr-Ca-Cu-O) is an oxide of thallium / barium / calcium / copper (Tl-Ba) having a transition temperature of 120K grade according to Maeda et al.
-Ca-Cu-O) is Arkansas
It was discovered by the great Harmans. These oxide-based superconductors have a critical temperature well above the boiling point of liquid nitrogen, 77K, and are attracting attention because they can obtain a superconducting state with inexpensive liquid nitrogen without using expensive liquid helium. These oxide superconductors, especially those of the Y-Ba-Cu-O system, decompose with reaction with water present in the atmosphere,
It reacts with carbon dioxide to form carbonate, which destroys the superconductor. Therefore, in application to a wire or device using an oxide superconducting material, formation of a protective film for avoiding contact with moisture and carbon dioxide in the atmosphere is an essential condition.
かかる保護膜として、第35回応用物理学関係連合講演会
予稿集P151,31P−Ｙ−２に見られるフツ化ビニルのプラ
ズマ重合膜がある。この膜はフツ素を含有しているため
疎水性が強く大気中の水分に対して安定であり、酸化物
超電導体を保護することができる。As such a protective film, there is a plasma polymerized film of vinyl fluoride, which is found in Proceedings of the 35th Joint Lecture on Applied Physics, P151, 31P-Y-2. Since this film contains fluorine, it is highly hydrophobic and stable to moisture in the atmosphere, and can protect the oxide superconductor.
しかし、前記予稿集には、保護膜の硬度や強度，原料ガ
スの公害性の点については充分配慮されていない。すな
わち、一般のプラズマ重合膜は硬度，強度が小さいため
プラズマ重合膜をコートした線材やデバイスでは取扱い
時に傷がつき易く、原料ガスフルオロエチレンは大気圏
のオゾン層破壊のもとになるフツ素を含有しているため
使用が好ましくない。However, the above-mentioned proceedings do not sufficiently consider the hardness and strength of the protective film and the pollution of the source gas. That is, since a general plasma polymerized film has low hardness and strength, a wire or device coated with the plasma polymerized film is easily scratched during handling, and the raw material gas fluoroethylene contains fluorine, which causes ozone layer depletion in the atmosphere. Therefore, it is not preferable to use.
本発明の目的は、硬度及び強度が大きく、耐水及び耐炭
酸化特性に優れた酸化物超電導体用の保護膜を提供する
にある。他の目的は前記保護膜を形成する方法を提供す
るにある。An object of the present invention is to provide a protective film for an oxide superconductor which has high hardness and strength and is excellent in water resistance and carbonation resistance. Another object is to provide a method of forming the protective film.
炭化水素１〜2vol％と水素99〜98vol％との混合ガスを
基板温度600〜1000℃の条件下でプラズマ分解して得ら
れる膜は、ダイヤモンド、又はダイヤモンド状炭素膜と
称せられ、硬度が非常に大きい疎水性膜であるが脆いた
め酸化物超電導体用の保護膜としては適しない。この膜
は水素の含有率が小さく、水素と炭素との原子数比（H/
C）は0.05以下程度である。一方、炭化水素と水素との
混合ガスを基板温度200℃以下の低温条件下でプラズマ
分解して得られる膜（プラズマ重合膜）は、密着力に富
んでいるが硬度が小さく傷つき易い。また、疎水性も前
記ダイヤモンド状炭素膜に比べかなり小さい。この膜の
H/Cは１ないし２以上で水素の含有率が大きい。A film obtained by plasma decomposition of a mixed gas of 1 to 2 vol% of hydrocarbons and 99 to 98 vol% of hydrogen under the condition of a substrate temperature of 600 to 1000 ° C is called a diamond or diamond-like carbon film and has an extremely high hardness. Although it is a very large hydrophobic film, it is not suitable as a protective film for oxide superconductors because it is brittle. This film has a low hydrogen content, and the atomic ratio of hydrogen to carbon (H /
C) is about 0.05 or less. On the other hand, a film (plasma polymerized film) obtained by plasma decomposition of a mixed gas of hydrocarbon and hydrogen under a low temperature condition of a substrate temperature of 200 ° C. or less has a high adhesion, but has a small hardness and is easily scratched. Also, the hydrophobicity is considerably smaller than that of the diamond-like carbon film. Of this membrane
H / C is 1 to 2 or more, and the hydrogen content is large.
発明者らは、炭化水素と水素との混合比，基板温度，基
板とプラズマとの位置など成膜条件を種種変化させて膜
形成を行ない、得られた膜の特性を評価した。その結
果、膜中のH/Cを0.33を越え1.0未満とすれば、密着力，
硬度及び疎水性に優れた膜が形成できることを実験的に
見い出し本発明に至つた。The inventors performed film formation by changing the film formation conditions such as the mixing ratio of hydrocarbon and hydrogen, the substrate temperature, the position of the substrate and plasma, and evaluated the characteristics of the obtained film. As a result, if the H / C in the film exceeds 0.33 and is less than 1.0, the adhesion,
The inventors have found experimentally that a film excellent in hardness and hydrophobicity can be formed, and completed the present invention.
〔作用〕 前記炭化水素としては、メタン，エタン，エチレン，ア
セチレン，プロパン等の脂肪族炭化水素及びベンゼン，
トルエン等の芳香族炭化水素を用いることができるが、
常温・常圧下でガス状の炭化水素がプラズマ反応器への
供給等の点で便利である。炭化水素と水素との混合ガス
のプラズマを形成する手段としては、マイクロ波，高周
波等の電磁波エネルギーを使用することができる。保護
膜を形成したい酸化物超電導体は、炭化水素と水素との
混合ガスプラズマのアフターグロー部を置くのがよい。
これは、プラズマ密度の高い位置に置くと酸化物超電導
体の表面がエツチングされたり、原子状水素によつて還
元されたりするのをさけるためである。酸化物超電導体
の保護膜形成時における加熱温度は、400〜600℃がよ
い。これは、加熱温度を上げ過ぎるとH/Cが小さくなつ
てダイヤモンドライクとなり、低く過ぎるとプラズマ重
合膜的になるためである。炭化水素と水素ガスとの混合
比は、炭化水素の種類によつても変わるがおおむね炭化
水素の濃度10〜50％がよい。また、本発明になる保護膜
は、Ｙ−Ba−Cu−Ｏ系に限らず、Bi−Sr−Ca−Cu−Ｏ及
びTl−Ca−Ba−Cu−Ｏ系超電導体のいずれにも用いるこ
とができる。[Action] Examples of the hydrocarbon include aliphatic hydrocarbons such as methane, ethane, ethylene, acetylene and propane, and benzene,
Although aromatic hydrocarbons such as toluene can be used,
Gaseous hydrocarbons at room temperature and atmospheric pressure are convenient in terms of supplying them to the plasma reactor. Electromagnetic energy such as microwave or high frequency can be used as a means for forming plasma of a mixed gas of hydrocarbon and hydrogen. The oxide superconductor for which the protective film is desired to be formed preferably has an afterglow part of plasma of a mixed gas of hydrocarbon and hydrogen.
This is to prevent the surface of the oxide superconductor from being etched or reduced by atomic hydrogen when placed in a position where the plasma density is high. The heating temperature for forming the protective film of the oxide superconductor is preferably 400 to 600 ° C. This is because if the heating temperature is too high, the H / C becomes small and becomes diamond-like, and if it is too low, it becomes a plasma polymerized film. The mixing ratio of hydrocarbon and hydrogen gas varies depending on the type of hydrocarbon, but the concentration of hydrocarbon is generally 10 to 50%. Further, the protective film according to the present invention is not limited to the Y-Ba-Cu-O system, but may be used for any of the Bi-Sr-Ca-Cu-O and Tl-Ca-Ba-Cu-O system superconductors. You can
以下、本発明を具体的実施例を用いてさらに詳細に説明
する。第１図は本発明になる保護膜を形成する装置の概
略構成図を示したものである。炭化水素と水素との混合
ガス１は減圧にされた反応器２に供給される。この混合
ガスにRF電源３からの高周波を誘導コイル４を通して印
加し、プラズマ５を形成する。このプラズマのアフタグ
ロー部に酸化物超電導ペレツト６を置き、必要に応じて
電気炉７により加熱し、ペレツトを炭素と水素とから成
る保護膜でコーテイングする。ペレツトに前記保護膜が
均一に付着するよう、ペレツトは時折り裏がえしにす
る。排ガス８は真空ポンプにより排気する。Hereinafter, the present invention will be described in more detail with reference to specific examples. FIG. 1 is a schematic configuration diagram of an apparatus for forming a protective film according to the present invention. A mixed gas 1 of hydrocarbon and hydrogen is supplied to a reactor 2 whose pressure is reduced. A high frequency from the RF power source 3 is applied to this mixed gas through the induction coil 4 to form plasma 5. An oxide superconducting pellet 6 is placed in the afterglow portion of this plasma, heated by an electric furnace 7 if necessary, and the pellet is coated with a protective film made of carbon and hydrogen. The pellets are occasionally turned upside down so that the protective film is evenly attached to the pellets. The exhaust gas 8 is exhausted by a vacuum pump.
［実施例１］ 第１図に概略構成を示した実験装置を用い、表１に示す
条件下でＹ−Ba−Cu−Ｏペレツトの表面コーテイングを
行なつた。Ｙ−Ba−Cu−Ｏペレツトの設定位置はプラズ
マ発光部下流側数cmとした。[Example 1] Using the experimental apparatus whose schematic configuration is shown in Fig. 1, surface coating of Y-Ba-Cu-O pellets was performed under the conditions shown in Table 1. The Y-Ba-Cu-O pellet was set at a position several cm downstream of the plasma emission part.
膜厚は約２μｍであつた。この膜のH/Cは約0.5,ビツカ
ース硬度は80であつた。保護膜を形成したペレツトと形
成しないペレツトについて次に耐候試験を行なつた。耐
候試験条件は、40℃の飽和湿度，炭酸ガス濃度１％の雰
囲気中で５時間放置とした。放置後のペレツトの抵抗率
の温度依存性を第２図に示した。保護膜を被覆してペレ
ツトの耐候試験後の抵抗率の温度依存性ａは、耐候試験
前の抵抗率の温度依存性ｂとほぼ同じであつたのに対
し、保護膜を被覆しないペレツトの耐候試験後の抵抗率
の温度依存性ｃは大きく変化し、全く超電導性を失なつ
ている。以上の結果より炭素と水素とから成る保護膜を
被覆することによつて酸化物超電導体の耐候性は著しく
改善されることがわかる。 The film thickness was about 2 μm. The H / C of this film was about 0.5, and the Vickers hardness was 80. Next, a weathering test was performed on the pellets with and without the protective film. The weather resistance test conditions were that the sample was left for 5 hours in an atmosphere of saturated humidity of 40 ° C. and carbon dioxide concentration of 1%. The temperature dependence of the resistivity of the pellet after standing is shown in FIG. The temperature dependence a of the resistivity of the pellet coated with the protective film after the weathering test was almost the same as the temperature dependency b of the resistance before the weathering test, while the weathering resistance of the pellet not coated with the protective film was measured. The temperature dependence c of the resistivity after the test changed greatly, and the superconductivity was completely lost. From the above results, it is understood that the weather resistance of the oxide superconductor is remarkably improved by coating the protective film made of carbon and hydrogen.
［実施例２］ 実施例１と同じ装置を用い、酸化物超電導体のペレツト
をプラズマ中に固定して実施例１と同じ条件下で保護膜
の形成を行なつた後、保護膜を機械的に剥離し抵抗率の
温度依存性を測定した。結果を第３図に示したが超電導
特性がかなり劣化していた。ｄは保護膜を被覆しない耐
候試験後のペレツト、ｅは保護膜を被覆した耐候試験後
のペレツトを示す。次にMgO基板上にＹ−Ba−Cu−Ｏの
薄膜をスパツタ法により形成した試料をプラズマ中呼び
アフターグロー部に置いて、前記した方法と同様にして
保護膜の形成を行ない、SIMSによつて膜厚さ方向の酸素
分析を行なつた。その結果、アフターグロー部に置いた
試料では酸素濃度の分布が膜厚さ方向でほぼ均一であつ
たのに対し、プラズマ中で保護膜を形成した試料では、
膜表面層で酸素の不足が認められた。これは、プラズマ
中では解離した原子状の水素濃度が高いため保護膜形成
の初期において酸化物超電導体の表面が還元されたこと
を意味する。以上の結果より、保護膜を形成する位置は
プラズマ中よりアフターグロー部が好ましいと言える。Example 2 Using the same apparatus as in Example 1, the pellet of the oxide superconductor was fixed in plasma to form a protective film under the same conditions as in Example 1, and then the protective film was mechanically formed. It was peeled off and the temperature dependence of the resistivity was measured. The results are shown in Fig. 3, but the superconducting properties were considerably deteriorated. d is a pellet after the weather resistance test in which the protective film is not coated, and e is a pellet after the weather resistance test in which the protective film is coated. Next, a sample in which a thin film of Y-Ba-Cu-O was formed on the MgO substrate by the sputtering method was placed in the afterglow part in the plasma, and the protective film was formed in the same manner as described above. Then, oxygen analysis in the film thickness direction was performed. As a result, in the sample placed in the afterglow part, the oxygen concentration distribution was almost uniform in the film thickness direction, whereas in the sample with the protective film formed in plasma,
A lack of oxygen was observed in the film surface layer. This means that the surface of the oxide superconductor was reduced in the initial stage of forming the protective film because the dissociated atomic hydrogen concentration was high in the plasma. From the above results, it can be said that the position where the protective film is formed is preferably in the afterglow part rather than in the plasma.
［実施例３］ 実施例１と同じ装置を用い種々のプロパンと水素との濃
度比の条件下で保護膜の形成を行ない、膜の水素と炭素
の比（H/C）と膜のビツカース硬度及び膜の密着力を評
価した。膜の密着力は、酸化物超電導体ペレツトの表面
を2mm間隔で切り込みを入れて保護膜を形成したのち、
保護膜にスコツチテープをはり、はがした時の剥離頻度
で評価（ピール試験）した。実験結果を第４図と第５図
に示した。第４図の結果より、通常の取扱いで傷がつか
ない硬度50kg/mm2以上を得るにはH/Cを1.0未満にする必
要のあることがわかる。また、第５図の結果より、通常
の取扱いで剥離しないピール試験残存率50％以上を得る
ためにはH/Cを0.33を越える必要のあることがわかる。
以上２つの結果より、H/Cは0.33を越え1.0未満にするこ
とが好ましいと言える。Example 3 A protective film was formed using the same apparatus as in Example 1 under various concentration ratios of propane and hydrogen, and the hydrogen / carbon ratio (H / C) of the film and the Vickers hardness of the film. And the adhesion of the film was evaluated. The adhesion of the film is measured by cutting the surface of the oxide superconductor pellet at intervals of 2 mm to form a protective film.
A Scottish tape was adhered to the protective film, and the peeling frequency when peeled off was evaluated (peel test). The experimental results are shown in FIGS. 4 and 5. From the results shown in FIG. 4, it can be seen that H / C needs to be less than 1.0 in order to obtain a hardness of 50 kg / mm 2 or more that is not scratched by ordinary handling. Further, from the results shown in FIG. 5, it is understood that the H / C needs to exceed 0.33 in order to obtain a peel test residual rate of 50% or more which does not peel in normal handling.
From the above two results, it can be said that H / C is preferably more than 0.33 and less than 1.0.
また、以上の結果から、酸化物超電導体側に硬度は小さ
くなるが密着力の大きい相対的に水素含有率の多い膜を
形成し、反対側に密着力は小さいが硬度の大きい相対的
に水素含有率の小さい膜を形成し、二層構造とすればさ
らに特性の向上が期待できることがわかる。Also, from the above results, a film with a relatively high hydrogen content was formed on the oxide superconductor side with a small hardness but a large adhesion, and a film with a relatively high hydrogen content was formed on the opposite side with a relatively high hydrogen content and a relatively high hydrogen content. It can be seen that further improvement in characteristics can be expected by forming a film having a low rate and forming a two-layer structure.
［実施例４］ 実施例１と同じ装置を用い、実施例１と同じ条件下で種
々の膜厚の炭素と水素とからなる保護膜を形成し、実施
例１と同じ条件下で耐候試験を実施した。試験の結果、
保護膜の膜厚が0.01μｍ以下では酸化物超電導体の超電
導特性が全く消失した。0.01μｍ〜0.05μｍ膜厚では超
電導特性を示したが劣化は大きかつた。0.05μｍ以上の
膜厚ではほとんど劣化は認められなかつた。以上の結果
より、保護膜の膜厚は0.05μｍ以上が好適となる。Example 4 Using the same apparatus as in Example 1, protective films made of carbon and hydrogen having various thicknesses were formed under the same conditions as in Example 1, and a weather resistance test was performed under the same conditions as in Example 1. Carried out. Test results,
When the thickness of the protective film was 0.01 μm or less, the superconducting properties of the oxide superconductor disappeared at all. Although the superconducting property was exhibited at the film thickness of 0.01 μm to 0.05 μm, the deterioration was large. Almost no deterioration was observed at a film thickness of 0.05 μm or more. From the above results, the thickness of the protective film is preferably 0.05 μm or more.
以上の実験では、いずれもＹ−Ba−Cu−Ｏ系の超電導酸
化物を用いて行なつたが、Bi−Sr−Ca−Cu−Ｏ及びTl−
Ba−Ca−Cu−Ｏ系でも保護膜の保護作用がピンホールフ
リーと疎水性にもとづく大気中の水分及び炭酸ガスと超
電導酸化物との接触防止にあるため適用可能である。In each of the above experiments, Y-Ba-Cu-O-based superconducting oxide was used, but Bi-Sr-Ca-Cu-O and Tl-
Even a Ba-Ca-Cu-O system can be applied because the protective function of the protective film is to prevent contact between the superconducting oxide and moisture and carbon dioxide in the atmosphere based on the pinhole-free property and hydrophobicity.
本発明によれば、硬度が大きく密着性に富んだ疎水性の
大きい膜を酸化物超電導体の表面に形成できるので、大
気中の水分及び炭酸ガスと酸化物超電導体の反応による
劣化が防止でき寿命を著しく延長することができる。ま
た、接触等による傷がつきにくくなるので取扱いが容易
となる。さらに、原料ガスがフツ素を含有していないの
で大気中にフツ素系のガスを排気することがなく、大気
圏オゾン層破壊などの公害の心配もない。According to the present invention, since a film having high hardness and high adhesion and high hydrophobicity can be formed on the surface of the oxide superconductor, deterioration due to the reaction between the oxide superconductor and moisture and carbon dioxide in the atmosphere can be prevented. The life can be significantly extended. In addition, since it is less likely to be scratched by contact or the like, it is easy to handle. Further, since the raw material gas does not contain fluorine, fluorine-based gas is not discharged into the atmosphere, and there is no concern about pollution such as ozone depletion in the atmosphere.
第１図は、本発明になる保護膜を形成するため一装置概
略図、第２図は、本発明になる保護膜の保護性能を示す
特性図、第３図は、プラズマ中で保護膜を形成すると超
電導特性が劣化することを示す特性図、第４図は、保護
膜のH/Cと膜のビツカース硬度との関係を示す特性図、
第５図は、保護膜のH/Cと膜の密着力との関係を示す特
性図である。 １……炭化水素−水素混合ガス、２……反応管、３……
RF電源、５……プラズマ、６……酸化物超電導ペレツ
ト。FIG. 1 is a schematic view of an apparatus for forming a protective film according to the present invention, FIG. 2 is a characteristic diagram showing protective performance of the protective film according to the present invention, and FIG. FIG. 4 is a characteristic diagram showing that the superconducting property is deteriorated when formed, and FIG. 4 is a characteristic diagram showing the relationship between H / C of the protective film and Vickers hardness of the film,
FIG. 5 is a characteristic diagram showing the relationship between the H / C of the protective film and the adhesive force of the film. 1 ... Hydrocarbon-hydrogen mixed gas, 2 ... Reaction tube, 3 ...
RF power source, 5 ... Plasma, 6 ... Oxide superconducting pellet.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加茂 友一 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 松田 臣平 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (56)参考文献 特開 昭63−281316（ＪＰ，Ａ) 特開 昭63−299008（ＪＰ，Ａ) 特開 昭64−45011（ＪＰ，Ａ) 特開 平１−197308（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuichi Kamo 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory Ltd. (72) Inheihei Matsuda 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Japan Hitachi, Ltd. (56) Reference JP 63-281316 (JP, A) JP 63-299008 (JP, A) JP 64-45011 (JP, A) JP 1-197308 ( JP, A)
Claims (4)
体用保護膜において、水素と炭素との原子数比（H/C）
が0.33を越え１未満の範囲であることを特徴とする酸化
物超電導体用保護膜。1. A protective film for an oxide superconductor composed of carbon and hydrogen, wherein the atomic ratio of hydrogen to carbon (H / C).
Is in the range of more than 0.33 and less than 1, which is a protective film for an oxide superconductor.
厚が0.05μｍ以上であることを特徴とする酸化物超電導
体用保護膜。2. The protective film according to claim 1, wherein the protective film has a thickness of 0.05 μm or more.
いて、炭化水素と水素混合ガスプラズマのアフターグロ
ー部で形成することを特徴とする酸化物超電導体用保護
膜の形成法。3. A method of forming a protective film for an oxide superconductor according to claim 1, wherein the protective film is formed in an afterglow part of a hydrocarbon / hydrogen mixed gas plasma.
電導体に接触する側を相対的に水素を多くし、反対側を
水素の含有率を小さくしたことを特徴とする酸化物超電
導体用保護膜。4. The oxide superconducting film according to claim 1, wherein the side in contact with the superconductor has a relatively large amount of hydrogen and the opposite side has a small hydrogen content. Body protection film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63310040A JPH0788204B2 (en) | 1988-12-09 | 1988-12-09 | Protective film for oxide superconductor and method of forming the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63310040A JPH0788204B2 (en) | 1988-12-09 | 1988-12-09 | Protective film for oxide superconductor and method of forming the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02243502A JPH02243502A (en) | 1990-09-27 |
| JPH0788204B2 true JPH0788204B2 (en) | 1995-09-27 |
Family
ID=18000437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63310040A Expired - Fee Related JPH0788204B2 (en) | 1988-12-09 | 1988-12-09 | Protective film for oxide superconductor and method of forming the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788204B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140086500A (en) * | 2012-12-28 | 2014-07-08 | 엘지디스플레이 주식회사 | Organic Light Emitting Device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10044841B4 (en) * | 2000-09-11 | 2006-11-30 | Osram Opto Semiconductors Gmbh | Plasma encapsulation for electronic and microelectronic components such as OLEDs and method for its production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01197308A (en) * | 1988-02-01 | 1989-08-09 | Semiconductor Energy Lab Co Ltd | Oxide superconductor protected with carbon film and production thereof |
| JPS63281316A (en) * | 1987-05-13 | 1988-11-17 | Sumitomo Electric Ind Ltd | Superconductive cable |
| JPS63299008A (en) * | 1987-05-29 | 1988-12-06 | Hitachi Cable Ltd | current control wire |
| JPS6445011A (en) * | 1987-08-13 | 1989-02-17 | Tdk Corp | Superconductive oxide ceramic material |
-
1988
- 1988-12-09 JP JP63310040A patent/JPH0788204B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140086500A (en) * | 2012-12-28 | 2014-07-08 | 엘지디스플레이 주식회사 | Organic Light Emitting Device |
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| Publication number | Publication date |
|---|---|
| JPH02243502A (en) | 1990-09-27 |
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