JPH0218320B2 - - Google Patents
Info
- Publication number
- JPH0218320B2 JPH0218320B2 JP58202815A JP20281583A JPH0218320B2 JP H0218320 B2 JPH0218320 B2 JP H0218320B2 JP 58202815 A JP58202815 A JP 58202815A JP 20281583 A JP20281583 A JP 20281583A JP H0218320 B2 JPH0218320 B2 JP H0218320B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- bpb
- substrate
- producing
- bapb
- 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
- 239000010409 thin film Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 14
- 229910016063 BaPb Inorganic materials 0.000 claims description 6
- 239000002887 superconductor Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910010252 TiO3 Inorganic materials 0.000 claims description 4
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 description 11
- 239000010980 sapphire Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 229910002367 SrTiO Inorganic materials 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- -1 KTaO3 Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
Description
【発明の詳細な説明】
〔技術分野〕
本発明は酸化物超伝導体薄膜の製造方法に関
し、特に酸化物BaPb1-xBixO3（0.05＜ｘ＜0.30）
（以下BPBと略記する）の結晶性薄膜のエピタキ
シヤル成長方法に関するものである。[Detailed Description of the Invention] [Technical Field] The present invention relates to a method for producing an oxide superconductor thin film, and in particular, to a method for producing an oxide superconductor thin film, particularly an oxide BaPb 1-x Bi x O 3 (0.05<x<0.30).
(hereinafter abbreviated as BPB) relates to a method for epitaxial growth of a crystalline thin film.
高周波（r.f.）マグネトロンスパツタリングに
よつてBPB薄膜を作製するにあたつて、従来は、
基板として比較的安価で容易に入手でき、かつ物
理的および化学的に安定なサフアイア単結晶を用
いていた。このサフアイア基板上に得られた薄膜
は、BPBと基板との間の格子定数のミスマツチ
および結晶の対称性の相違に起因して、基板との
界面付近に格子不整を生じ、結晶性の低いものと
なる。
Conventionally, when producing BPB thin films by radio frequency (RF) magnetron sputtering,
As a substrate, sapphire single crystal, which is relatively inexpensive, easily available, and physically and chemically stable, was used. The thin film obtained on this sapphire substrate has a lattice mismatch near the interface with the substrate due to a mismatch in lattice constants and a difference in crystal symmetry between BPB and the substrate, and has low crystallinity. becomes.
これらの膜、例えばサフアイア単結晶（Ｒ面）
基板上に形成したBPB薄膜に対して酸素と酸化
鉛との混合ガス雰囲気中で550℃で熱処理するこ
とによつて形成したBaPb0.7Bi0.3O3薄膜の場合に
は、第１図に示すように、膜厚3200Å以下では、
結晶性の低下により、膜厚の減少とともに超伝導
転移温度Tcの低下が見られた。 These films, such as sapphire single crystal (R plane)
In the case of a BaPb 0.7 Bi 0.3 O 3 thin film formed by heat-treating a BPB thin film formed on a substrate at 550°C in a mixed gas atmosphere of oxygen and lead oxide, as shown in Figure 1, However, at a film thickness of 3200Å or less,
Due to the decrease in crystallinity, a decrease in the superconducting transition temperature Tc was observed as well as a decrease in the film thickness.
そこで、本発明の目的は、上記欠点を解決する
ために、BPBと同じペロブスカイト構造を有す
る酸化物薄膜をサフアイア単結晶基板上にエピタ
キシヤル成長させたものを新たに基板として、そ
の上に結晶性の良いBPB単結晶薄膜をエピタキ
シヤル成長させる方法を提供することにある。
Therefore, in order to solve the above-mentioned drawbacks, the purpose of the present invention is to epitaxially grow an oxide thin film having the same perovskite structure as BPB on a sapphire single crystal substrate as a new substrate, and to develop crystalline The purpose of this invention is to provide a method for epitaxially growing a good BPB single crystal thin film.
このような目的を達成するために、すなわち、
サフアイア単結晶の基板としての物理的および化
学的安定性を損うことなく、BPB単結晶のエピ
タキシヤル成長を行なわしめるために、本発明で
は、サフアイア基板の上にBPBに近い格子定数
および結晶の対称性を持つペロブスカイト型酸化
物、例えばSrTiO3、BaTiO3、KTaO3、（Sr、
Ba）TiO3、（Ca、Sr）TiO3、MgOなど薄膜を形
成した積層型複合基板を用い、その複合基板上に
BPBのエピタキシヤル薄膜を形成する。
In order to achieve such objectives, i.e.
In order to epitaxially grow a BPB single crystal without impairing the physical and chemical stability of the sapphire single crystal as a substrate, in the present invention, a sapphire substrate with a lattice constant close to that of BPB and a crystal structure Perovskite oxides with symmetry, such as SrTiO 3 , BaTiO 3 , KTaO 3 , (Sr,
Using a laminated composite substrate on which thin films such as Ba) TiO 3 , (Ca, Sr) TiO 3 , MgO, etc. are formed,
Form an epitaxial thin film of BPB.
本発明により得られたBPB薄膜は膜厚3200Å
以下でも高い超伝導転移温度を示しており、直接
サフアイア基板上に作製したBPB薄膜に較べ良
質のBPB薄膜が得られる。 The BPB thin film obtained by the present invention has a thickness of 3200 Å.
It shows a high superconducting transition temperature even below, and a BPB thin film of better quality can be obtained compared to a BPB thin film fabricated directly on a sapphire substrate.
以下に図面を参照して本発明を詳細に説明す
る。
The present invention will be described in detail below with reference to the drawings.
先ず、r.f.マグネトロンスパツタリングによつ
てサフアイア基板（α−Al2O3）Ｃ面上に、基板
と垂直方向に１１１方向が揃つた膜厚を3000〜
4000Åの範囲で種々変えて単結晶SrTiO3薄膜を
形成した。この場合のスパツタリング条件は、ア
ルゴン51％と酸素49％の混合ガスを雰囲気ガスと
し、ガス圧6Pa、基板温度830℃、印加電圧
2.4KVで130Å／minの堆積速度であつた。 First, by RF magnetron sputtering, a film thickness of 3000 ~ 3000 was formed on the C surface of a sapphire substrate (α-Al 2 O 3 ) with 111 directions aligned perpendicular to the substrate.
Single-crystal SrTiO 3 thin films were formed with various thicknesses within the range of 4000 Å. The sputtering conditions in this case are a mixed gas of 51% argon and 49% oxygen as the atmospheric gas, gas pressure 6Pa, substrate temperature 830℃, and applied voltage.
The deposition rate was 130 Å/min at 2.4 KV.
これによつて得られたSrTiO3／α−Al2O3積層
型の複合基板の上に、さらに、r.f.マグネトロン
スパツタリングによつてBPBを膜厚850〜4500Å
程度に堆積させた。その際のBPBのスパツタリ
ング条件は、アルゴン50％と酸素50％との混合ガ
スを雰囲気ガスとし、ガス圧５×10-3Torr、基
板温度240℃、印加電圧1.8KV、堆積温度300Å／
minであつた。このようにして得られた
SrTiO3／α−Al2O3積層型の複合基板上のBPB
薄膜はSrTiO3の配向に強く影響され、第２図に
おいて点線１で示されるＸ線回折パターンに見ら
れるように、いわゆるas−deposit状態の場合に
もほぼ１１１方向に配向している。さらに、かか
るBPB薄膜を酸素と酸化鉛との混合ガス雰囲気
中で560℃で約12時間にわたつて熱処理すること
により、第２図に実線２で示すように完全に１１
１配向した（2θ＝77.38゜）BPB薄膜が得られた。
このようにして得られたBPB薄膜については、
超伝導転移温度Tcの膜厚に対する変化は第３図
の実線３に示すようになる。第３図において、点
線で示す曲線４は従来のBPB薄膜の場合を示す。
従つて、この第３図からもわかるように、同じ膜
厚でも、本発明によれば、従来の場合より超伝導
転移温度Tcが高く、従つて、結晶性の良好な薄
膜が得られることが確められた。SrTiO3の代わ
りに、KTaO3、BaTiO3、Sr0.6Ba0.4TiO3、Ca0.4
Sr0.6TiO3をサフアイア基板の上に形成した積層
型の複合基板上にBPB薄膜を堆装積させた場合
についても同様に結晶配向の揃つた単結晶性薄膜
を形成することができた。 On the thus obtained SrTiO 3 /α-Al 2 O 3 laminated composite substrate, BPB was further deposited to a thickness of 850 to 4500 Å by RF magnetron sputtering.
It was deposited to a certain extent. The BPB sputtering conditions at that time were as follows: a mixed gas of 50% argon and 50% oxygen was used as the atmospheric gas, gas pressure was 5×10 -3 Torr, substrate temperature was 240℃, applied voltage was 1.8KV, and deposition temperature was 300Å/3.
It was min. obtained in this way
BPB on SrTiO 3 / α-Al 2 O 3 stacked composite substrate
The thin film is strongly influenced by the orientation of SrTiO 3 and is oriented in approximately the 111 direction even in the so-called as-deposit state, as seen in the X-ray diffraction pattern indicated by the dotted line 1 in FIG. Furthermore, by heat-treating the BPB thin film at 560°C for about 12 hours in a mixed gas atmosphere of oxygen and lead oxide, it completely becomes
A BPB thin film with mono-orientation (2θ=77.38°) was obtained.
Regarding the BPB thin film obtained in this way,
The change in the superconducting transition temperature Tc with respect to the film thickness is as shown by the solid line 3 in FIG. In FIG. 3, curve 4 shown by a dotted line shows the case of a conventional BPB thin film.
Therefore, as can be seen from FIG. 3, even with the same film thickness, according to the present invention, the superconducting transition temperature Tc is higher than in the conventional case, and therefore a thin film with good crystallinity can be obtained. Confirmed. Instead of SrTiO3 , KTaO3 , BaTiO3 , Sr0.6 Ba0.4 TiO3 , Ca0.4
Similarly, when a BPB thin film was deposited on a laminated composite substrate made of Sr 0.6 TiO 3 formed on a sapphire substrate, a single crystal thin film with uniform crystal orientation could be formed.
以上説明したように、本発明によれば、サフア
イア基板上に、BPBと同じペロブスカイト型結
晶構造をもつSrTiO3、BaTiO3、KTaO3、（Sr、
Ba）TiO3、（Ca、Sr）TiO3、MgOなどの酸化物
の単結晶性薄膜を中間層として堆積させ、その上
にBPB薄膜を形成することにより、基板とBPB
との格子定数および結晶の対称性が近ずくので、
堆積初期から結晶性が良く電気的特性の良好な単
結晶性BPB薄膜が得られる利点がある。
As explained above, according to the present invention, SrTiO 3 , BaTiO 3 , KTaO 3 , (Sr,
By depositing a single-crystalline thin film of oxides such as Ba) TiO3 , (Ca,Sr) TiO3 , and MgO as an intermediate layer, and forming a BPB thin film on top of it, the substrate and BPB
Since the lattice constant and crystal symmetry approach that of
This method has the advantage that a single-crystalline BPB thin film with good crystallinity and good electrical properties can be obtained from the initial stage of deposition.
第１図は従来のサフアイア単結晶（Ｒ面）上に
作製したBPB薄膜の膜厚による超伝導転移温度
Tcの変化を示す特性曲線図、第２図は本発明に
よりサフアイアＣ面上に中間膜としてSrTiO3を
作製し、次いでその上にr.f.マグネトロンスパツ
タリングによつて作製したas−depositおよび熱
処理後の各BPB薄膜のＸ線回折パターンの説明
用線図、第３図は本発明により製造したBPB薄
膜の膜厚に対する超伝導転移温度Tcの変化を従
来のサフアイア基板上に直接に作製したBPB薄
膜の膜厚に対する超伝導転移温度Tcの変化と対
比して示す特性曲線図である。
１…as−depositのＸ線回折パターン、２…完
全に１１１配向したＸ線回折パターン、３…本発
明によるBPB薄膜、４…従来のBPB薄膜。
Figure 1 shows the superconducting transition temperature depending on the film thickness of a BPB thin film fabricated on a conventional sapphire single crystal (R-plane).
Figure 2 is a characteristic curve diagram showing changes in Tc. SrTiO 3 was produced as an interlayer film on the sapphire C surface according to the present invention, and then as-deposited and heat-treated were produced on it by RF magnetron sputtering. Fig. 3 is an explanatory diagram of the X-ray diffraction pattern of each BPB thin film produced according to the present invention, and Fig. 3 shows the change in the superconducting transition temperature Tc with respect to the film thickness of the BPB thin film produced according to the present invention. FIG. 3 is a characteristic curve diagram showing a comparison of changes in superconducting transition temperature Tc with respect to film thickness. 1. As-deposit X-ray diffraction pattern, 2. Completely 111-oriented X-ray diffraction pattern, 3. BPB thin film according to the present invention, 4. Conventional BPB thin film.
Claims (1)
化物超伝導体BaPb1-xBixO3（0.05＜ｘ＜0.30）薄
膜を作製するにあたつて、サフアイア単結晶上に
BaPb1-xBixO3と同じペロブスカイト型結晶構造
を有し、その格子定数がBaPb1-xBixO3と近い値
を持つ酸化物の薄膜を成長させ、得られた複合基
板上にBaPb1-xBixO3をエピタキシヤル成長させ
ることを特徴とする酸化物超伝導体薄膜の製造方
法。 ２ 特許請求の範囲第１項記載の酸化物超伝導体
薄膜の製造方法において、前記酸化物は、
SrTiO3、BaTiO3、KTaO3、（Sr、Ba）TiO3、
（Ca、Sr）TiO3またはMgOであることを特徴と
する酸化物超伝導体薄膜の製造方法。[Claims] 1. When producing an oxide superconductor BaPb 1-x Bi x O 3 (0.05<x<0.30) thin film by high-frequency magnetron sputtering,
A thin film of an oxide with the same perovskite crystal structure as BaPb 1-x Bi x O 3 and a lattice constant close to that of BaPb 1-x Bi x O 3 is grown, and a thin film is grown on the resulting composite substrate. A method for producing an oxide superconductor thin film, which comprises epitaxially growing BaPb 1-x Bi x O 3 . 2. In the method for producing an oxide superconductor thin film according to claim 1, the oxide comprises:
SrTiO3 , BaTiO3 , KTaO3 , (Sr,Ba) TiO3 ,
A method for producing an oxide superconductor thin film characterized by being (Ca, Sr) TiO 3 or MgO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58202815A JPS6096599A (en) | 1983-10-31 | 1983-10-31 | Production of superconductive thin film of oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58202815A JPS6096599A (en) | 1983-10-31 | 1983-10-31 | Production of superconductive thin film of oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6096599A JPS6096599A (en) | 1985-05-30 |
| JPH0218320B2 true JPH0218320B2 (en) | 1990-04-25 |
Family
ID=16463654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58202815A Granted JPS6096599A (en) | 1983-10-31 | 1983-10-31 | Production of superconductive thin film of oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6096599A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1339019C (en) * | 1987-02-05 | 1997-03-25 | Sumitomo Electric Industries, Ltd. | Process for preparing a superconducting thin film |
| KR0132061B1 (en) * | 1987-03-14 | 1998-04-24 | 나까하라 쯔네오 | Process for depositing a superconducting thin film |
| JPH0724338B2 (en) * | 1987-03-18 | 1995-03-15 | 株式会社日立製作所 | Electronic device |
| JP2644223B2 (en) * | 1987-03-24 | 1997-08-25 | 古河電気工業株式会社 | Superconducting wire manufacturing method |
| JPS6487763A (en) * | 1987-05-26 | 1989-03-31 | Sumitomo Electric Industries | Superconducting material |
| JPS6460925A (en) * | 1987-08-31 | 1989-03-08 | Semiconductor Energy Lab | Fabricating method for superconductive material |
| EP0344352B1 (en) * | 1988-06-03 | 1994-09-28 | International Business Machines Corporation | Method for making artificial layered high-Tc superconductors |
| JP2757257B2 (en) * | 1988-05-16 | 1998-05-25 | 日本電信電話株式会社 | Method for forming oxide superconducting thin film |
| JPH02258700A (en) * | 1989-03-30 | 1990-10-19 | Res Inst For Prod Dev | Ferroelectric thin film and production thereof |
| US5358927A (en) * | 1990-05-31 | 1994-10-25 | Bell Communications Research, Inc. | Growth of a,b-axis oriented pervoskite thin films |
-
1983
- 1983-10-31 JP JP58202815A patent/JPS6096599A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6096599A (en) | 1985-05-30 |
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