JPS6161556B2 - - Google Patents
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- Publication number
- JPS6161556B2 JPS6161556B2 JP55012027A JP1202780A JPS6161556B2 JP S6161556 B2 JPS6161556 B2 JP S6161556B2 JP 55012027 A JP55012027 A JP 55012027A JP 1202780 A JP1202780 A JP 1202780A JP S6161556 B2 JPS6161556 B2 JP S6161556B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- bapb
- oxygen
- torr
- heat
- 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
Links
- 239000010409 thin film Substances 0.000 claims description 31
- 229910016063 BaPb Inorganic materials 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明は酸化物超伝導薄膜、特に素子化を目的
とするBaPb1-xBixO3超伝導薄膜の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an oxide superconducting thin film, particularly a BaPb 1-x Bi x O 3 superconducting thin film intended for device production.
BaPb1-xBixO3はx=0.3でTc=13Kの高い転移温
度を有する酸化物超伝導材料であり、酸化性雰囲
気においても高温まで安定で、ジヨセフソン素子
等の超伝導素子に適用する場合には、信頼性の高
い素子が期待できる。BaPb 1-x Bi x O 3 is an oxide superconducting material with a high transition temperature of Tc = 13K at x = 0.3, and is stable up to high temperatures even in an oxidizing atmosphere, making it suitable for superconducting devices such as Josephson devices. In some cases, highly reliable devices can be expected.
しかし、BaPb1-xBixO3はペロヴスカイト製造
を有する酸化物固溶体であり、4種類の元素で構
成されているために、蒸着法等の普通の薄膜形成
法でこの材料の薄膜を形成することは至難であ
る。また多元素系材料の薄膜形成に有利とされて
いる通常のスパツタ法では表面が粗くなり、良質
な薄膜が得られず、かつの膜は非晶質である。こ
の非晶質膜を結晶化温度以上の温度で熱処理する
と薄膜構成元素の大半は蒸発したり、他の鉛酸化
物になるか、あるいは基板と反応したりするので
BaPb1-xBixO3となるのは一部であり、膜の均一
性、平坦性等は非常に悪く、素子化のための薄膜
化はまだ未検討の段階で、素子に必要な薄膜はま
だ得られていないのが現状である。 However, since BaPb 1-x Bi x O 3 is an oxide solid solution with perovskite formation and is composed of four types of elements, it is difficult to form thin films of this material using ordinary thin film forming methods such as vapor deposition. That is extremely difficult. In addition, the conventional sputtering method, which is said to be advantageous for forming thin films of multi-element materials, results in a rough surface, making it impossible to obtain a good quality thin film, and the film is amorphous. If this amorphous film is heat-treated at a temperature higher than the crystallization temperature, most of the thin film's constituent elements will evaporate, become other lead oxides, or react with the substrate.
Only a portion of BaPb 1-x Bi x O 3 is formed, and the uniformity and flatness of the film are very poor, and thinning the film for device production has not yet been considered. The current situation is that it has not yet been obtained.
本発明の目的は、したがつて、ジヨセフソン素
子等の微細構造を有する素子の作製を可能にする
ような、均一で、かつ平坦な酸化物超伝導薄膜の
製造方法を提供することである。 The object of the present invention is therefore to provide a method for producing a uniform and flat oxide superconducting thin film, which makes it possible to produce devices with fine structures such as Josephson devices.
上記目的を達成するために、本発明による酸化
物超伝導薄膜の製造方法はBaPb1-xBixO3(x=
0.05〜0.35)磁器をターゲツトとし、酸素の割合
を10〜50%とするアルゴン、酸素混合雰囲気中
で、雰囲気圧力を4〜10×10-2Torrにおいて陽
極電圧1〜2kV印加の下での高周波スパツタによ
つてBaPb1-xBixO3の薄膜を形成する工程と、そ
のようにして得られるBaPb1-xBixO3薄膜を酸化
性雰囲気において500〜550℃で熱処理する工程と
から成ることを要旨とする。 In order to achieve the above object, the method for manufacturing an oxide superconducting thin film according to the present invention is based on BaPb 1-x Bi x O 3 (x=
0.05~0.35) High frequency with porcelain as a target in an argon/oxygen mixed atmosphere with an oxygen content of 10~50%, an atmospheric pressure of 4~10×10 -2 Torr, and an anode voltage of 1~2 kV applied. A step of forming a BaPb 1-x Bi x O 3 thin film by sputtering, and a step of heat-treating the BaPb 1-x Bi x O 3 thin film thus obtained at 500 to 550°C in an oxidizing atmosphere. The main point is to become.
以下本発明を実施例を用いて一層詳しく説明す
るが、それは例示であつて、本発明の枠を越える
ことなく、いろいろな変形や改良があり得ること
は勿論である。 The present invention will be described in more detail below using examples, but these are merely illustrative, and it goes without saying that various modifications and improvements can be made without going beyond the scope of the present invention.
ターゲツトを次の様に作製する。BaCO3,
PbO2,Bi2O3所定の組成に調合し、酸素雰囲気中
で800℃、2時間加熱して反応させる。こうして
得られた粉末をターゲツト形状の円板に成形プレ
スし、880℃で8時間、酸素雰囲気中で焼結して
ターゲツトを得る。このターゲツトを用い、アル
ゴン酸素混合雰囲気(酸素50%)中で陽極電圧
1.6kV、圧力6×10-2Torrの条件でスパツタする
とBaPb1-xBixO3結晶薄膜が得られる。堆積速度
は8〜10nm/minである。アルゴン酸素混合雰
囲気の圧力が高すぎる場合には非晶質となり、ま
た圧力が低い場合には結晶性が非常に悪くなる。
第1図はいろいろのアルゴン酸素混合雰囲気の圧
力でスパツタして得られる薄膜のCuKαを用い
たX線回折図形を示す。図中A,B,Cはそれぞ
れ10×10-2Torr,6×10-2Torr,2×10-2Torr
の圧力において得られた膜で、300nm、680nm、
890nmの厚さを有していた。Aは非晶質であり、
Bは(200)方向に配向性を持つ良い結晶性を示
し、CはBに比較すると結晶性の劣るのがわか
る。Bで得られた薄膜を500℃で12時間、空気中
で熱処理すると、立方晶系格子定数が439pmから
429pmまで減少し、結晶性はさらに良くなる。A
またはCの薄膜を熱処理すると、BaPb1-xBixO3
のピークと共に他の鉛酸化物のピークも現れる。
第2図は第1図中のBを熱処理して得られた薄膜
の比抵抗の温度特性で、超伝導状態への転移の様
子を示している。 Create a target as follows. BaCO3 ,
PbO 2 and Bi 2 O 3 are mixed into a predetermined composition and heated at 800° C. for 2 hours in an oxygen atmosphere to react. The powder thus obtained is pressed into a target-shaped disc and sintered at 880° C. for 8 hours in an oxygen atmosphere to obtain a target. Using this target, the anode voltage was measured in an argon-oxygen mixed atmosphere (50% oxygen).
A BaPb 1-x Bi x O 3 crystal thin film is obtained by sputtering under the conditions of 1.6 kV and a pressure of 6 x 10 -2 Torr. The deposition rate is 8-10 nm/min. If the pressure of the argon/oxygen mixed atmosphere is too high, it becomes amorphous, and if the pressure is low, the crystallinity becomes very poor.
Figure 1 shows X-ray diffraction patterns using CuKα of thin films obtained by sputtering under various pressures in mixed argon and oxygen atmospheres. In the figure, A, B, and C are respectively 10×10 -2 Torr, 6×10 -2 Torr, and 2×10 -2 Torr.
Films obtained at pressures of 300nm, 680nm,
It had a thickness of 890 nm. A is amorphous;
It can be seen that B exhibits good crystallinity with orientation in the (200) direction, while C has inferior crystallinity compared to B. When the thin film obtained in B was heat treated in air at 500℃ for 12 hours, the cubic lattice constant changed from 439pm to
It decreases to 429pm, and the crystallinity becomes even better. A
Or when a thin film of C is heat treated, BaPb 1-x Bi x O 3
Along with this peak, other lead oxide peaks also appear.
FIG. 2 shows the temperature characteristics of the resistivity of a thin film obtained by heat-treating B in FIG. 1, and shows the transition to a superconducting state.
アルゴン酸素混合雰囲気で酸素が10%の場合に
同じ特徴が確認されたが、この場合、良い結晶性
の膜を得るためには8〜10×10-2Torr程度のよ
り高い雰囲気圧力が必要である。 The same characteristics were observed in an argon-oxygen mixed atmosphere with 10% oxygen, but in this case a higher atmospheric pressure of around 8-10×10 -2 Torr is required to obtain a good crystalline film. be.
一般に雰囲気圧力は4〜10×10-2Torrの範囲
にあるのが好ましい。これよりも低い圧力では得
られる薄膜の表面があれ、これよりも高い圧力で
は薄膜の堆積速度が小さ過ぎて、実用的でなくな
る。 Generally, it is preferred that the atmospheric pressure is in the range of 4 to 10 x 10 -2 Torr. At a pressure lower than this, the surface of the thin film may be obtained, but at a pressure higher than this, the deposition rate of the thin film is too low to be practical.
薄膜形成後の熱処理は500〜550℃の範囲にある
温度で行なうのが適切である。500℃以下の熱処
理温度では良好な超伝導特性が得られず、この温
度が550℃を越えると、薄膜の表面があれる。 The heat treatment after forming the thin film is suitably carried out at a temperature in the range of 500 to 550°C. Good superconducting properties cannot be obtained at heat treatment temperatures below 500°C, and when this temperature exceeds 550°C, the surface of the thin film cracks.
高周波スパツタの際の陽極電圧は、余り低いと
放電が得られず、高過ぎると単位面積当りの電力
が大きくなり過ぎてターゲツトが破壊されるので
1〜2kVが適切で、約60〜120℃の基板温度で良
好な性質を持つたBaPb1-xBixO3の結晶薄膜が得
られることが確認された。 The appropriate anode voltage for high-frequency sputtering is 1 to 2 kV, as if it is too low, no discharge will be obtained, and if it is too high, the power per unit area will be too large and the target will be destroyed. It was confirmed that a crystal thin film of BaPb 1-x Bi x O 3 with good properties could be obtained at the substrate temperature.
以上述べた通り、本発明によれば、基板温度が
60〜120℃と低いために、レジスト材料を損うこ
となくBaPb1-xBixO3の結晶化薄膜を得ることが
でき、微細加工が可能となる。スパツタして得た
薄膜は転移温度が極めて低いがこれを約500℃で
熱処理すると、Tcは約10Kになり、転移も急峻
になる。しかも特筆すべきことはあらかじめ結晶
化している薄膜を熱処理した場合には膜の均一
性、平坦性が損なわれず。全てBaPb1-xBixO3に
なるということである。そのため、感光性樹脂等
による微細加工した細い線幅の薄膜も熱処理をす
ることによつて損なわれることが殆んどないとい
う点で、本発明による方法は素子化に非常に適し
ている。 As described above, according to the present invention, the substrate temperature is
Because the temperature is as low as 60 to 120°C, a crystallized thin film of BaPb 1-x Bi x O 3 can be obtained without damaging the resist material, making microfabrication possible. The thin film obtained by sputtering has an extremely low transition temperature, but when it is heat-treated at about 500°C, the Tc becomes about 10K and the transition becomes steeper. Moreover, what is noteworthy is that when a thin film that has already been crystallized is heat-treated, the uniformity and flatness of the film are not impaired. This means that everything becomes BaPb 1-x Bi x O 3 . Therefore, the method according to the present invention is very suitable for device fabrication in that even a finely processed thin film with a narrow line width made of photosensitive resin or the like is hardly damaged by heat treatment.
このように、本発明によれば、配向性が強く、
単結晶に近い良質のBaPb1-xBixO3超伝導薄膜を
作製することが可能になるばかりでなく、スパツ
タ中の温度が60〜120℃と低いために感光性樹脂
の使用が可能になり、リフトオフ工程等の微細加
工も可能のになる等の利点がある。 As described above, according to the present invention, the orientation is strong;
Not only is it possible to produce a high-quality BaPb 1-x Bi x O 3 superconducting thin film that is close to a single crystal, but the temperature during sputtering is low at 60 to 120°C, making it possible to use photosensitive resins. This has the advantage that microfabrication such as a lift-off process becomes possible.
第1図はいろいろのアルゴン酸素混合雰囲気の
圧力でスパツタして得られる薄膜のX線回折図
形、第2図は本発明の方法によつて得られる
BaPb1-xBixO3薄膜の比抵抗の温度特性を示す図
である。
Figure 1 shows the X-ray diffraction patterns of thin films obtained by sputtering under various pressures of mixed argon and oxygen atmospheres, and Figure 2 shows the X-ray diffraction patterns obtained by the method of the present invention.
FIG. 3 is a diagram showing the temperature characteristics of specific resistance of a BaPb 1-x Bi x O 3 thin film.
Claims (1)
ゲツトとし、酸素の割合を10〜50%とするアルゴ
ン・酸素混合雰囲気中で、雰囲気圧力を4〜10×
10-2Torrにおいて陽極電圧1〜2kV印加の下での
高周波スパツタによつて BaPb1-xBixO3の薄膜を形成する工程と、そのよ
うにして得られるBaPb1-xBixO3薄膜を酸化性雰
囲気において500〜550℃で熱処理する工程とから
なることを特徴とする酸化物超伝導薄膜の製造方
法。[Claims] 1 BaPb 1-x Bi x O 3 (x = 0.05 to 0.35) The target is porcelain, and the atmospheric pressure is 4 to 4 in an argon/oxygen mixed atmosphere with an oxygen content of 10 to 50%. 10×
Forming a thin film of BaPb 1-x Bi x O 3 by high-frequency sputtering under an anodic voltage of 1-2 kV at 10 -2 Torr and the BaPb 1-x Bi x O 3 thus obtained A method for producing an oxide superconducting thin film, comprising the step of heat-treating the thin film at 500 to 550°C in an oxidizing atmosphere.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1202780A JPS56109824A (en) | 1980-02-05 | 1980-02-05 | Manufacture of oxide superconductive thin film |
US06/202,640 US4316785A (en) | 1979-11-05 | 1980-10-31 | Oxide superconductor Josephson junction and fabrication method therefor |
FR8023545A FR2469005A1 (en) | 1979-11-05 | 1980-11-04 | JOSEPHSON JUNCTION OF OXIDE-BASED SUPRACONDUCTORS AND ITS MANUFACTURING PROCESS |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1202780A JPS56109824A (en) | 1980-02-05 | 1980-02-05 | Manufacture of oxide superconductive thin film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS56109824A JPS56109824A (en) | 1981-08-31 |
JPS6161556B2 true JPS6161556B2 (en) | 1986-12-26 |
Family
ID=11794114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1202780A Granted JPS56109824A (en) | 1979-11-05 | 1980-02-05 | Manufacture of oxide superconductive thin film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS56109824A (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61168530A (en) * | 1985-01-21 | 1986-07-30 | Nippon Telegr & Teleph Corp <Ntt> | Superconductive oxide material and production thereof |
JPS6465003A (en) * | 1987-01-30 | 1989-03-10 | Agency Ind Science Techn | Superconductive material and production thereof |
DE3886429T2 (en) * | 1987-02-05 | 1994-07-28 | Sumitomo Electric Industries | Process for producing a superconducting thin film. |
KR910002311B1 (en) * | 1987-02-27 | 1991-04-11 | 가부시기가이샤 히다찌세이사꾸쇼 | A superconductor device |
AU598113B2 (en) * | 1987-03-14 | 1990-06-14 | Sumitomo Electric Industries, Ltd. | Process for depositing a superconducting thin film |
DE3850800T2 (en) * | 1987-04-13 | 1994-11-17 | Hitachi Ltd | Superconducting material and process for its production. |
CA1336566C (en) * | 1987-05-31 | 1995-08-08 | Naoji Fujimori | Superconducting thin film |
DE3855246T2 (en) * | 1987-07-06 | 1996-12-05 | Sumitomo Electric Industries | Superconducting thin film and process for its production |
JPS6460925A (en) * | 1987-08-31 | 1989-03-08 | Semiconductor Energy Lab | Fabricating method for superconductive material |
JPS6467824A (en) * | 1987-09-07 | 1989-03-14 | Semiconductor Energy Lab | Forming device for oxide superconducting material |
JPS6467823A (en) * | 1987-09-07 | 1989-03-14 | Semiconductor Energy Lab | Formation of oxide superconducting film |
JPS6476903A (en) * | 1987-09-16 | 1989-03-23 | Semiconductor Energy Lab | Apparatus for producing oxide superconducting material |
-
1980
- 1980-02-05 JP JP1202780A patent/JPS56109824A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS56109824A (en) | 1981-08-31 |
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