JP2583552B2 - Method for producing oxide superconducting thin film - Google Patents
Method for producing oxide superconducting thin filmInfo
- Publication number
- JP2583552B2 JP2583552B2 JP63025192A JP2519288A JP2583552B2 JP 2583552 B2 JP2583552 B2 JP 2583552B2 JP 63025192 A JP63025192 A JP 63025192A JP 2519288 A JP2519288 A JP 2519288A JP 2583552 B2 JP2583552 B2 JP 2583552B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- superconducting thin
- substrate
- oxide superconducting
- heating
- 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
- 239000010409 thin film Substances 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000758 substrate Substances 0.000 claims description 50
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 description 32
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 239000010408 film Substances 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- -1 oxygen ions Chemical class 0.000 description 7
- 239000002887 superconductor Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000001451 molecular beam epitaxy Methods 0.000 description 4
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (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、ジョセフソン素子、超電導記憶素子等の超
電導デバイスあるいは超電導導体などとして適用可能な
酸化物超電導薄膜の製造方法に関する。The present invention relates to a method for producing a superconducting oxide thin film applicable as a superconducting device such as a Josephson device or a superconducting memory device, or a superconducting conductor.
「従来の技術」 近年、常電導状態から超電導状態に転位する臨界温度
（Tc）が液体窒素温度を超える高い値を示す酸化物系の
超電導体が発見されている。[Background Art] In recent years, oxide-based superconductors have been discovered in which a critical temperature (Tc) at which a transition from a normal conducting state to a superconducting state is higher than the temperature of liquid nitrogen is high.
従来、この種の酸化物超電導体からなる薄膜を製造す
る方法として、例えば、真空蒸着法、スパッタリング
法、MBE（分子線エピタキー）法、CVD（化学気相成長）
法、IVD（イオン気相成長）法などの各種の成膜法が知
られている。そして、このような成膜法は、いずれも1T
orr以下の低圧下において行なわれ、しかも、薄膜中に
酸素を補給することを目的として、その雰囲気を酸素ガ
ス雰囲気、あるいは、酸素ガスと不活性ガス雰囲気など
の混合ガス雰囲気としている。Conventionally, as a method of manufacturing a thin film made of this kind of oxide superconductor, for example, a vacuum deposition method, a sputtering method, an MBE (molecular beam epitaxy) method, and a CVD (chemical vapor deposition)
Various film forming methods such as an ion vapor deposition (IVD) method and an ion vapor deposition (IVD) method are known. And, such a film formation method is 1T
The process is performed under a low pressure of orr or less, and the atmosphere is an oxygen gas atmosphere or a mixed gas atmosphere such as an oxygen gas and an inert gas atmosphere for the purpose of supplying oxygen to the thin film.
ところが前述の従来方法においては、雰囲気中の酸素
の分圧が低いことから、基体上に形成される膜体の結晶
中に所望量の酸素が導入されにくく、その結晶組成が化
学量論組成からずれてしまう問題があり、臨界電流密度
などの超電導特性が低い膜体が生成される傾向があっ
た。However, in the above-mentioned conventional method, since the partial pressure of oxygen in the atmosphere is low, it is difficult to introduce a desired amount of oxygen into the crystal of the film formed on the substrate, and the crystal composition is changed from the stoichiometric composition. There is a problem of deviation, and a film body having low superconducting characteristics such as critical current density tends to be generated.
そこで従来、成膜時あるいは成膜後において、膜体を
酸素雰囲気中において600〜1000℃程度に加熱する熱処
理を施して膜体の結晶構造を整え、酸素濃度を調節して
膜体の超電導特性を向上させる処理を行うようにしてい
る。Therefore, conventionally, at the time of film formation or after film formation, the film body is subjected to a heat treatment of heating to about 600 to 1000 ° C. in an oxygen atmosphere to adjust the crystal structure of the film body, and adjust the oxygen concentration to adjust the superconductivity of the film body. Is performed.
前述の加熱処理を行うには、例えば第３図に示すよう
に、スパッタリングターゲット１に対向して配置された
基板ホルダ２の内部に加熱ヒータ３を設け、基板ホルダ
２に装着した基板４を加熱できるように構成し、この加
熱ヒータ３により基板４を介して膜体を加熱するように
している。In order to perform the above-described heat treatment, for example, as shown in FIG. 3, a heater 3 is provided inside a substrate holder 2 arranged opposite to a sputtering target 1 and a substrate 4 mounted on the substrate holder 2 is heated. The heater 3 heats the film body through the substrate 4.
また、前述の加熱処理を行う他の方法として、真空チ
ャンバの内部に基板を設置し、この基板上の膜体に対
し、真空チャンバに設けた透明窓を通して真空チャンバ
の外部から赤外線を照射して膜体を加熱する方法、ある
いは、真空チャンバの内部に赤外線ランプを設け、この
赤外線ランプにより膜体を加熱する方法などが知られて
いる。As another method for performing the above-described heat treatment, a substrate is placed inside a vacuum chamber, and a film on the substrate is irradiated with infrared rays from outside the vacuum chamber through a transparent window provided in the vacuum chamber. There are known a method of heating a film, a method of providing an infrared lamp inside a vacuum chamber, and heating the film by the infrared lamp.
「発明が解決しようとする課題」 前記加熱ヒータ３を用いて行う従来方法においては、
酸素の存在する雰囲気で加熱ヒータ３を使用するために
加熱ヒータ３の寿命が短くなる問題がある。また、基板
を十分高温に加熱するためには、熱容量の大きな加熱ヒ
ータ３を使用する必要があるが、加熱ヒータ３の熱容量
が大きい場合、加熱後に超電導薄膜を急冷する際に、通
電を停止したにもかかわらず加熱ヒータ３が余熱を発散
させるために、冷却速度を高めることができない問題が
あり、成膜後に超電導特性が劣化する傾向があった。こ
のため従来、超電導薄膜を形成した後に別工程で超電導
薄膜に熱処理を施し、超電導薄膜の結晶構造を整え、酸
素濃度を調整する必要があった。更に加熱ヒータ３を用
いて加熱した場合、加熱ヒータ３の構成材料の一部が加
熱中に蒸発し、基板４上の超電導薄膜に不純物として混
入し、超電導薄膜の超電導特性を劣化させる問題があっ
た。“Problem to be Solved by the Invention” In the conventional method performed using the heater 3,
Since the heater 3 is used in an atmosphere where oxygen is present, there is a problem that the life of the heater 3 is shortened. Further, in order to heat the substrate to a sufficiently high temperature, it is necessary to use the heater 3 having a large heat capacity. However, when the heat capacity of the heater 3 is large, the power supply is stopped when the superconducting thin film is rapidly cooled after heating. Nevertheless, there is a problem that the cooling rate cannot be increased because the heater 3 dissipates residual heat, and the superconductivity tends to deteriorate after film formation. For this reason, conventionally, it has been necessary to heat-treat the superconducting thin film in a separate step after forming the superconducting thin film, adjust the crystal structure of the superconducting thin film, and adjust the oxygen concentration. Further, when heating is performed using the heater 3, a part of the constituent material of the heater 3 evaporates during the heating and mixes as an impurity into the superconducting thin film on the substrate 4, thereby deteriorating the superconducting characteristics of the superconducting thin film. Was.
一方、赤外線を用いて加熱を行う従来方法において
は、真空チャンバに形成した透明窓を介して膜体に赤外
線を照射する関係から、透明窓の寸法によって照射範囲
の制限を受けるために、膜体の温度を十分高温に加熱す
ることが困難になり、特に、赤外線の照射範囲が狭い場
合には、均一な加熱ができなくなる問題がある。更に、
真空チャンバに透明窓を形成する関係から真空チャンバ
の内部の真空度を上げることができず、場合によっては
透明窓が原因となって真空チャンバの真空度が低下する
問題がある。On the other hand, in the conventional method of heating using infrared light, the irradiation range is limited by the size of the transparent window because the film is irradiated with infrared light through the transparent window formed in the vacuum chamber. Is difficult to heat to a sufficiently high temperature, and in particular, when the irradiation range of infrared rays is narrow, there is a problem that uniform heating cannot be performed. Furthermore,
Due to the formation of the transparent window in the vacuum chamber, the degree of vacuum inside the vacuum chamber cannot be increased, and in some cases, the degree of vacuum in the vacuum chamber is reduced due to the transparent window.
なお、真空チャンバの内部に赤外線ランプを設けて加
熱する場合、真空チャンバの内部スペースに限度がある
ために設置可能な赤外線ランプの大きさに限界を生じ、
これが原因となって加熱できる最高温度に限界を生じ、
所望の温度に加熱できない問題がある。When an infrared lamp is provided inside the vacuum chamber and heating is performed, the size of the infrared lamp that can be installed is limited due to the limitation of the internal space of the vacuum chamber,
This limits the maximum temperature that can be heated,
There is a problem that it cannot be heated to a desired temperature.
本発明は、前記課題を解決するためになされたもの
で、結晶の形を整えて超電導特性の向上が可能な程度の
高温度に加熱することができ、温度制御も容易で急冷処
理も可能であって、不純物の混入などを生じることもな
い酸化物超電導薄膜の製造方法の提供を目的とする。The present invention has been made in order to solve the above-mentioned problems, and can be heated to a temperature high enough to improve the superconducting properties by adjusting the crystal shape, and it is also easy to control the temperature and to perform a rapid cooling process. Accordingly, it is an object of the present invention to provide a method for manufacturing an oxide superconducting thin film without mixing impurities.
「課題を解決するための手段」 第１の発明は前記課題を解決するために、少なくとも
一部が通電により発熱する導電材料からなる基材を用
い、この基材に通電して基材を加熱した状態で基材上に
酸化物超電導薄膜を形成し、酸化物超電導薄膜の形成後
に基材への通電を停止して基材を冷却するものである。Means for Solving the Problems In order to solve the above-mentioned problems, the first invention uses a base material made of a conductive material that generates heat when energized at least in part, and heats the base material by energizing the base material. In this state, an oxide superconducting thin film is formed on the substrate, and after the oxide superconducting thin film is formed, the power supply to the substrate is stopped to cool the substrate.
第２の発明は前記課題を解決するために、少なくとも
一部が通電により発熱する導電材料からなる基材を用
い、この基材上に酸化物超電導薄膜を形成するととも
に、この後に基材に通電して基材を発熱させて酸化物超
電導薄膜を加熱し、所要時間加熱した後に基材に対する
通電を停止して基材を冷却するものである。According to a second aspect of the present invention, in order to solve the above-described problems, at least a part of a base material made of a conductive material that generates heat when energized is used, an oxide superconducting thin film is formed on the base material, and then the base material is energized Then, the substrate is heated to heat the oxide superconducting thin film, and after heating for a required time, energization to the substrate is stopped to cool the substrate.
「作用」 基材を通電加熱することにより超電導薄膜の加熱処理
を行い、超電導薄膜の結晶構造を整え、超電導薄膜中の
酸素量を調節する。また、基材自身を発熱させるため
に、基材の近傍に熱容量の大きな加熱ヒータを設ける必
要がなくなり、加熱後に超電導薄膜を急冷することが可
能になる。更に、基材の近傍に加熱ヒータを設ける必要
がなくなるために超電導薄膜に対する不純物の混入もな
くなる。[Function] Heating of the superconducting thin film is carried out by heating the base material by electric current, the crystal structure of the superconducting thin film is adjusted, and the amount of oxygen in the superconducting thin film is adjusted. Further, it is not necessary to provide a heater having a large heat capacity in the vicinity of the substrate in order to generate heat in the substrate itself, and the superconducting thin film can be rapidly cooled after heating. Furthermore, since there is no need to provide a heater near the base material, impurities do not enter the superconducting thin film.
以下に本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.
第１図は、イオン源を用いたスパッタリング法を適用
して本発明を実施し、酸化物超電導薄膜を形成する場合
に用いられる装置の一例を示すもので、図中11は酸化物
超電導薄膜が形成される板状の基材を示している。FIG. 1 shows an example of an apparatus used for forming an oxide superconducting thin film by applying the sputtering method using an ion source to form an oxide superconducting thin film. 2 shows a plate-like base material to be formed.
この基材11は、第２図に示すように、ステンレス、ハ
ステロイ、スーパーアロイ等のニッケル基合金などの金
属材料からなる板状の本体部12とこの本体部12の上面に
形成されたMgO,ZrO,BaTiO3などからなる被覆層13とから
構成されている。なお、被覆層13の構成材料は、後述す
るように基材１上に形成される酸化物超電導薄膜の構成
元素と反応性が低く、化学的に安定な材料が選択され、
被覆層13は、高周波マグネトロンスパッタリング法など
の成膜法により本体部12の上面に形成されている。ま
た、前記本体部12と被覆層13の少なくとも一方は、通電
可能であって、しかも通電により発熱する材料から構成
されている。なお、基材11の形状は板状に限るものでは
なく、線状、テープ状、筒状など任意の形状を用いるこ
とができる。As shown in FIG. 2, the base material 11 includes a plate-shaped main body 12 made of a metal material such as a nickel-based alloy such as stainless steel, Hastelloy, and superalloy, and MgO formed on the upper surface of the main body 12. And a coating layer 13 made of ZrO, BaTiO 3 or the like. As a constituent material of the coating layer 13, a chemically stable material having low reactivity with constituent elements of the oxide superconducting thin film formed on the base material 1 as described later is selected.
The coating layer 13 is formed on the upper surface of the main body 12 by a film forming method such as a high-frequency magnetron sputtering method. At least one of the main body 12 and the coating layer 13 is made of a material that can be energized and generates heat when energized. The shape of the base material 11 is not limited to a plate shape, but may be any shape such as a linear shape, a tape shape, and a tubular shape.
一方、前記基材11上に形成される酸化物超電導薄膜
は、具体的にはＡ−Ｂ−Ｃ−Ｄ（ただしＡは、Sc,Y,La,
Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu等の周期
律表III a族元素のうち、１種以上を示し、ＢはSr,Ba,C
a,Be,Mg,Raなどの周期律表II a族元素のうち、１種以上
を示し、ＣはCu,Ag,Auなどの周期律表I b族元素とNbの
うち、CuあるいはCuを含む２種以上の元素を示し、Ｄ
は、O,S,Se,Te,Poなどの周期律表VI b族元素およびF,B
r,I,Atなどの周期律表VII b族元素のうち、Ｏあるいは
Ｏを含む２種以上の元素を示す。）系のものが用いられ
る。そして、この酸化物系超電導薄体の各構成元素の組
成比は、例えばＹ−Ba−Cu−Ｏ系超電導体の場合、Y:B
a:Cu:O＝1:（２〜３）：（３〜４）：（７−δ）が好ま
しく、δは０〜５の範囲が好ましい。On the other hand, the oxide superconducting thin film formed on the base material 11 is specifically ABCD (where A is Sc, Y, La,
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc. , C
a, Be, Mg, Ra, etc., from the Periodic Table II a group elements such as Cu, Ag, Au, etc. Containing two or more elements,
Is a group VIb element of the periodic table such as O, S, Se, Te, Po and F, B
Among the group VIIb elements of the periodic table VII such as r, I, At, etc., O or two or more elements containing O are shown. ) System. The composition ratio of each constituent element of this oxide-based superconducting thin body is, for example, Y: B in the case of a Y-Ba-Cu-O-based superconductor.
a: Cu: O = 1: (2-3) :( 3-4) :( 7-δ) is preferred, and δ is preferably in the range of 0-5.
なお、前記基板11に超電導薄膜を形成する手段として
は、真空蒸着法、スパッタリング法、MBE（分子線エピ
タキシー）法、CVD（化学気相成長）法、IVD（イオン気
相成長）法、クラスタイオンビーム法などの種々の成膜
法を適用することができるが、この例においてはイオン
源を用いたスパッタリング法を行う。Means for forming a superconducting thin film on the substrate 11 include vacuum deposition, sputtering, MBE (molecular beam epitaxy), CVD (chemical vapor deposition), IVD (ion vapor deposition), and cluster ion deposition. Various film formation methods such as a beam method can be applied. In this example, a sputtering method using an ion source is performed.
第１図に示す装置は、真空容器の内部に、基材11とタ
ーゲット15が対向状態で配置され、基材11の側方にター
ゲット15に対向するように第１イオン源16が設けられ、
ターゲット15の側方に基材11に対向するように第２イオ
ン源17が設けられ、更に、基材11に電源18が接続され、
基材11に通電できるように構成されている。In the apparatus shown in FIG. 1, a substrate 11 and a target 15 are arranged in a vacuum vessel in a state of facing each other, and a first ion source 16 is provided on a side of the substrate 11 so as to face the target 15;
A second ion source 17 is provided on the side of the target 15 so as to face the substrate 11, and a power source 18 is connected to the substrate 11,
It is configured so that the base 11 can be energized.
前記ターゲット15は、前述の酸化物超電導体を構成す
る元素を含む材料が用いられる。従ってＡ−Ｂ−Ｃ−Ｄ
系の各元素を含む混合粉末を仮焼し、焼結して製造され
るＡ−Ｂ−Ｃ−Ｄ系の超電導体からなるターゲット、あ
るいは、Ａ元素とＢ元素とＣ元素とＤ元素を所定の比率
で含有させた酸化物ターゲットなどを用いることができ
る。The target 15 is made of a material containing an element constituting the above-described oxide superconductor. Therefore, ABCD
A target composed of an ABCD-based superconductor produced by calcining and sintering a mixed powder containing each element of the system, or a target consisting of A, B, C and D , Etc. can be used.
前記第１イオン源16は、ターゲット15に対して加速さ
れたイオンを照射してターゲット15の構成原子を叩き出
し、基材11上に成膜させるための装置である。また、第
２イオン源17は、酸素をイオン、原子状、分子状などに
して基材11に照射する装置である。なお、これらのイオ
ン源16,17はイオン発生機とイオンの引出電極を具備し
て構成され、イオン発生機で発生させたイオンを引出電
極で加速して照射できるように構成されている。The first ion source 16 is a device for irradiating the target 15 with accelerated ions to strike out constituent atoms of the target 15 and form a film on the substrate 11. The second ion source 17 is a device that irradiates the substrate 11 with oxygen in the form of ions, atoms, molecules, or the like. These ion sources 16 and 17 are provided with an ion generator and an ion extraction electrode, and are configured so that ions generated by the ion generator can be accelerated and irradiated by the extraction electrode.
次に第１図に示す装置を用いて酸化物超電導薄膜を製
造する場合について説明する。Next, a case of manufacturing an oxide superconducting thin film using the apparatus shown in FIG. 1 will be described.
第１図に示す装置を用いて酸化物超電導薄膜を製造す
るには、まず、基材11とターゲット15を真空容器の内部
の所定位置にセットし、真空容器の内部を真空引きして
所定の圧力にした後に、イオン源16,17を作動させる。
また、電源18から基材11に通電して基材11の温度を600
〜1000℃程度に加熱する。In order to manufacture an oxide superconducting thin film using the apparatus shown in FIG. 1, first, the base material 11 and the target 15 are set at predetermined positions inside a vacuum container, and the inside of the vacuum container is evacuated to a predetermined position. After the pressure is increased, the ion sources 16 and 17 are operated.
In addition, power is supplied from the power source 18 to the
Heat to ~ 1000 ° C.
以上の操作によってイオン源16はターゲット15にイオ
ンを照射してスパッタリングを行い、基材11上にＡ−Ｂ
−Ｃ−Ｄ系の酸化物超電導体からなる膜体を生成させ
る。また、前記スパッタリングと同時にイオン源17を作
動させて基材11に酸素イオンを照射する。この酸素イオ
ン照射によって前記超電導薄膜に十分な量の酸素を供給
することができ、酸化物超電導薄膜を生成させることが
できる。By the above operation, the ion source 16 irradiates the target 15 with ions to perform sputtering, and AB on the substrate 11.
-A film body made of a CD-based oxide superconductor is generated. At the same time as the sputtering, the ion source 17 is operated to irradiate the substrate 11 with oxygen ions. By the irradiation of oxygen ions, a sufficient amount of oxygen can be supplied to the superconducting thin film, and an oxide superconducting thin film can be generated.
基材11上に所定の厚さの薄膜が生成されたならば、イ
オン源16,17によるイオン照射を停止するとともに、成
膜直後、あるいは、所定時間経過後に基材11に対する通
電加熱を停止して基材11を冷却する。When a thin film of a predetermined thickness is formed on the base material 11, the ion irradiation by the ion sources 16 and 17 is stopped, and immediately after the film formation or after a predetermined time has elapsed, the heating of the base material 11 is stopped. To cool the substrate 11.
なお、酸素イオン源17からの酸素イオンの照射を行わ
ない場合、生成された薄膜の結晶の内部に酸素が不足し
て目的の化学量論組成からずれた薄膜が生成されるおそ
れがある。このように酸素が不足した薄膜は超電導特性
に劣る欠点がある。この点においてイオン源17から酸素
イオンを供給するならば、化学量論組成に合致した目的
の組成の特性の優れた薄膜を得ることができる。If the irradiation of oxygen ions from the oxygen ion source 17 is not performed, there is a possibility that a thin film deviating from a target stoichiometric composition may be generated due to lack of oxygen inside the crystal of the generated thin film. Such a thin film lacking oxygen has a disadvantage that the superconductivity is inferior. At this point, if oxygen ions are supplied from the ion source 17, it is possible to obtain a thin film excellent in characteristics of a target composition that matches the stoichiometric composition.
また、基材11に対する通電加熱を行いつつ酸化物超電
導薄膜を形成するために、超電導薄膜を十分高温に加熱
できる効果がある。更に、通電加熱後に超電導薄膜を冷
却する場合、熱容量の大きな加熱ヒータで加熱していた
従来方法に比較して、基材11の近傍に熱容量の大きな部
材がないために、基材11を容易に急冷することができ
る。従って、形成した超電導薄膜の結晶構造を整えるこ
とができるとともに結晶中の酸素の割合を所望の値にす
ることができるので臨界温度の高い特性の優れた酸化物
超電導薄膜を製造できる効果がある。更にまた、従来方
法で用いられていた加熱ヒータを用いる必要がないため
に、超電導薄膜に不純物が混入することもなくなる。な
お、超電導薄膜の加熱のために赤外線を用いる必要がな
いために真空容器の外壁に赤外線透過用の透明窓を設け
る必要がなくなり真空容器の真空度が低下することもな
い。In addition, since the oxide superconducting thin film is formed while applying electric current to the substrate 11, the superconducting thin film can be heated to a sufficiently high temperature. Further, when the superconducting thin film is cooled after the heating by energization, the base material 11 can be easily formed because there is no member having a large heat capacity in the vicinity of the base material 11, as compared with the conventional method in which the superconducting thin film is heated by a heater having a large heat capacity. Can be quenched. Therefore, the crystal structure of the formed superconducting thin film can be adjusted, and the ratio of oxygen in the crystal can be set to a desired value, so that there is an effect that an oxide superconducting thin film having high critical temperature and excellent characteristics can be manufactured. Furthermore, since there is no need to use a heater used in the conventional method, impurities do not enter the superconducting thin film. Since it is not necessary to use infrared rays for heating the superconducting thin film, it is not necessary to provide a transparent window for transmitting infrared rays on the outer wall of the vacuum vessel, and the degree of vacuum of the vacuum vessel does not decrease.
一方、第２の発明では、超電導薄膜Ｈを形成した後
に、通電加熱によって基材11を加熱して目的を達成す
る。On the other hand, in the second invention, after forming the superconducting thin film H, the base material 11 is heated by electric heating to achieve the object.
即ち、通電加熱を停止した状態において、赤外線ラン
プなどの加熱装置で基材11を所要の温度に加熱した状態
で超電導薄膜Ｈを形成し、超電導薄膜Ｈを形成し、超電
導薄膜Ｈの形成後に赤外線ランプなどによる加熱を停止
し、次いで、基材11を所要の温度に通電加熱して超電導
薄膜Ｈの結晶構造を整え、酸素含有量を調節することが
できる。That is, in a state where the heating is stopped, the superconducting thin film H is formed while the base material 11 is heated to a required temperature by a heating device such as an infrared lamp, the superconducting thin film H is formed, and after the formation of the superconducting thin film H, The heating by the lamp or the like is stopped, and then the base material 11 is heated to a required temperature by electric current to adjust the crystal structure of the superconducting thin film H and adjust the oxygen content.
なお、前述の例において、真空容器に超電導薄膜の予
熱用の赤外線ランプなどを設けることは自由であり、真
空容器の内部全体の温度を調節する温度制御装置などを
設けても良いのは勿論である。In the above-described example, it is free to provide an infrared lamp or the like for preheating the superconducting thin film in the vacuum container. Needless to say, a temperature control device or the like for adjusting the temperature of the entire inside of the vacuum container may be provided. is there.
「実施例」 第１図に示す構成の装置を用い、ステンレス製の幅10
mm、厚さ0.5mmのテープ状の本体部に、厚さ１μｍの被
膜層を形成してなるテープ状の基材を用意するととも
に、この基材上に、イオン源を用いたスパッタリング法
によりＹ−Ba−Cu−Ｏで示される酸化物超電導体を構成
する元素をスパッタリングし、同時に酸素イオンを照射
するとともに、基板に25Vの電圧を印加して基板を700℃
に加熱し、超電導薄膜を形成した。この際、イオン源の
イオン加速電圧を1000V、イオン電流を100mA、雰囲気の
真空度を５×10-1Paとした。"Example" An apparatus having the structure shown in FIG.
A tape-shaped substrate having a 1 μm-thick coating layer formed on a tape-shaped main body having a thickness of 0.5 mm and a thickness of 0.5 mm was prepared, and Y was formed on the substrate by sputtering using an ion source. The elements constituting the oxide superconductor represented by -Ba-Cu-O are sputtered and simultaneously irradiated with oxygen ions, and a voltage of 25 V is applied to the substrate to 700 ° C.
To form a superconducting thin film. At this time, the ion acceleration voltage of the ion source was 1000 V, the ion current was 100 mA, and the degree of vacuum in the atmosphere was 5 × 10 -1 Pa.
前述の条件でスパッタリングを４時間行ったならば、
スパッタリングと通電を停止し、基板を冷却して超電導
薄膜を得た。この場合、基板温度を700℃から100℃まで
下降させるために必要な時間と、形成された超電導薄膜
の臨界温度（Tc）を測定し、後記する第１表に示した。After sputtering for 4 hours under the above conditions,
The sputtering and energization were stopped, and the substrate was cooled to obtain a superconducting thin film. In this case, the time required for lowering the substrate temperature from 700 ° C. to 100 ° C. and the critical temperature (Tc) of the formed superconducting thin film were measured and are shown in Table 1 below.
また、第３図に示す構成の従来装置にイオン源を付加
して構成した装置を用い、Ｙ−Ba−Cu−Ｏ系のスパッタ
リングターゲットを使用するとともに基板を加熱ヒータ
によって700℃に加熱し、先の例と同等の条件でイオン
スパッタリングと酸素イオン照射を同時に行って酸化物
超電導薄膜を形成し、成膜後に加熱ヒータへの通電を停
止して基板を冷却して酸化物超電導薄膜を得た。Further, using an apparatus configured by adding an ion source to the conventional apparatus having the configuration shown in FIG. 3, using a Y-Ba-Cu-O-based sputtering target and heating the substrate to 700 ° C. with a heater, Under the same conditions as in the previous example, ion sputtering and oxygen ion irradiation were simultaneously performed to form an oxide superconducting thin film, and after film formation, power to the heater was stopped and the substrate was cooled to obtain an oxide superconducting thin film. .
この場合、基板の温度を700℃から100℃まで低下させ
るために必要な時間と、形成された酸化物超電導薄膜の
臨界温度を測定し、第１表に示した。In this case, the time required for lowering the temperature of the substrate from 700 ° C. to 100 ° C. and the critical temperature of the formed oxide superconducting thin film were measured and are shown in Table 1.
第１表から明らかなように、基板に通電加熱を行って
加熱した場合は、加熱ヒータを用いて加熱した場合に比
較して冷却時間を大幅に短縮でき、急冷処理が可能であ
ることが判明した。なお、冷却時間を大幅に短縮できる
ために、超電導薄膜の製造効率が向上することも明らか
になった。また、通電加熱によって加熱した後に急冷し
て製造された酸化物超電導薄膜は臨界温度が高いことが
判明した。 As is evident from Table 1, when the substrate is heated by applying electric current, the cooling time can be significantly reduced as compared with the case where the substrate is heated by using a heater, and it has been found that rapid cooling can be performed. did. In addition, it was also found that the manufacturing time of the superconducting thin film was improved because the cooling time could be significantly reduced. In addition, it has been found that the critical temperature is high in the oxide superconducting thin film manufactured by heating and quenching by the electric current heating.
「発明の効果」 以上説明したように本発明は、基材に対する通電加熱
によって酸化物超電導薄膜を加熱するために、超電導薄
膜を十分高温に加熱することができるとともに、加熱後
に冷却する場合、熱容量の大きな加熱ヒータで加熱して
いた従来方法に比較して、基材の近傍に熱容量の大きな
部材がないために、基材を急冷することができる。従っ
て、酸化物超電導薄膜の結晶の形を整え、結晶中の酸素
量を調節することができるので臨界温度の高い特性の優
れた酸化物超電導薄膜を製造できる効果がある。また、
加熱ヒータを用いる必要がないために、超電導薄膜に雰
囲気中から不純物元素が混入することもなくなる。更
に、超電導薄膜の加熱のために赤外線を用いる必要がな
いために、真空容器の外壁に透明窓を設ける必要がなく
なり、真空容器の真空度が低下することもなく、所要の
圧力で成膜できる効果がある。[Effects of the Invention] As described above, the present invention can heat the oxide superconducting thin film by heating the base material by applying electric current, so that the superconducting thin film can be heated to a sufficiently high temperature. The substrate can be rapidly cooled because there is no member having a large heat capacity in the vicinity of the substrate as compared with the conventional method of heating with a large heater. Therefore, since the crystal shape of the oxide superconducting thin film can be adjusted and the amount of oxygen in the crystal can be adjusted, there is an effect that an oxide superconducting thin film having a high critical temperature and excellent characteristics can be manufactured. Also,
Since there is no need to use a heater, no impurity element is mixed into the superconducting thin film from the atmosphere. Furthermore, since it is not necessary to use infrared rays for heating the superconducting thin film, it is not necessary to provide a transparent window on the outer wall of the vacuum vessel, and the film can be formed at a required pressure without lowering the degree of vacuum of the vacuum vessel. effective.
第１図は、本発明方法を実施するために用いる装置の一
例を示す構成図、第２図は本発明方法の実施に用いる基
板の一例を示す断面図、第３図は、従来方法を説明する
ための構成図である。 11……基材、12……本体部、13……被覆層、15……ター
ゲット、16……第１イオン源、17……第２イオン源、18
……電源、Ｈ……超電導薄膜。FIG. 1 is a block diagram showing an example of an apparatus used for carrying out the method of the present invention, FIG. 2 is a cross-sectional view showing an example of a substrate used for carrying out the method of the present invention, and FIG. FIG. 11 ... base material, 12 ... body part, 13 ... coating layer, 15 ... target, 16 ... first ion source, 17 ... second ion source, 18
...... Power supply, H ... Superconducting thin film.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 39/24 Ｈ０１Ｌ 39/24 Ｂ Continued on the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location H01L 39/24 H01L 39/24 B
Claims (2)
材料から形成された基材を用い、この基材に通電して基
材を加熱した状態で基材上に酸化物超電導薄膜を形成
し、酸化物超電導薄膜の形成後に基材への通電を停止し
て基材を冷却することを特徴とする酸化物超電導薄膜の
製造方法。1. A substrate formed at least in part from a conductive material that generates heat when energized, forming an oxide superconducting thin film on the substrate while energizing the substrate and heating the substrate. A method for producing an oxide superconducting thin film, comprising stopping power supply to a substrate after forming the oxide superconducting thin film and cooling the substrate.
材料から形成された基材を用い、この基材上に酸化物超
電導薄膜を形成するとともに、この後に基材に通電して
基材を発熱させて酸化物超電導薄膜を加熱し、所要時間
加熱した後に基材に対する通電を停止して基材を冷却す
ることを特徴とする酸化物超電導薄膜の製造方法。2. A base material formed at least in part from a conductive material that generates heat when energized, forms an oxide superconducting thin film on the base material, and thereafter, energizes the base material to generate heat. Heating the oxide superconducting thin film, heating the substrate for a required time, and then stopping current supply to the substrate to cool the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63025192A JP2583552B2 (en) | 1988-02-05 | 1988-02-05 | Method for producing oxide superconducting thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63025192A JP2583552B2 (en) | 1988-02-05 | 1988-02-05 | Method for producing oxide superconducting thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01201008A JPH01201008A (en) | 1989-08-14 |
| JP2583552B2 true JP2583552B2 (en) | 1997-02-19 |
Family
ID=12159101
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244012A (en) * | 1988-08-03 | 1990-02-14 | Dowa Mining Co Ltd | Method for forming superconducting thin film |
| FR2684371A1 (en) * | 1991-11-29 | 1993-06-04 | Alsthom Cge Alcatel | PROCESS FOR THE TREATMENT OF A SUPERCONDUCTIVE CERAMIC PART OF TYPE (LN) 1BA2CU307-DELTA. |
| CN116102951A (en) * | 2022-12-26 | 2023-05-12 | 苏州微介面材料科技有限公司 | Antistatic nonflammable water-based epoxy coating |
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1988
- 1988-02-05 JP JP63025192A patent/JP2583552B2/en not_active Expired - Fee Related
Also Published As
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