JPH0816024B2 - Manufacturing method of superconducting material - Google Patents
Manufacturing method of superconducting materialInfo
- Publication number
- JPH0816024B2 JPH0816024B2 JP62214445A JP21444587A JPH0816024B2 JP H0816024 B2 JPH0816024 B2 JP H0816024B2 JP 62214445 A JP62214445 A JP 62214445A JP 21444587 A JP21444587 A JP 21444587A JP H0816024 B2 JPH0816024 B2 JP H0816024B2
- Authority
- JP
- Japan
- Prior art keywords
- superconducting material
- producing
- material according
- item
- sintering
- 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
- 239000000463 material Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000843 powder Substances 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 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
- 230000000737 periodic effect Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910002367 SrTiO Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims 3
- 229910052742 iron Inorganic materials 0.000 claims 3
- 229910052759 nickel Inorganic materials 0.000 claims 3
- 229910052709 silver Inorganic materials 0.000 claims 3
- 229910052725 zinc Inorganic materials 0.000 claims 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000002887 superconductor Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 9
- 238000001451 molecular beam epitaxy Methods 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- 229910002480 Cu-O Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium 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
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (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 本発明は超電導材料の製造方法に関する。より詳細に
は、高い超電導臨界温度を有する超電導材料の新規な製
造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a superconducting material. More specifically, it relates to a novel method for producing a superconducting material having a high superconducting critical temperature.
従来の技術 Ba−La−Cu−Ｏ系、Sr−La−Cu−Ｏ系、Ba−Ｙ−Cu−
Ｏ系等の複合酸化物超電導体は、高臨界温度を示すこと
で注目されている。これらの複合酸化物超電導体を用い
て、各種の電気、電子材料を製造する場合、バルクのも
のは炉を使用して焼結により形成し、薄膜はスパッタリ
ング、MBE（分子ビームエピタキシー）等により製造す
るのが一般的である。Conventional technology Ba-La-Cu-O system, Sr-La-Cu-O system, Ba-Y-Cu-
O-based composite oxide superconductors have been attracting attention because of their high critical temperature. When manufacturing various electrical and electronic materials using these complex oxide superconductors, bulk materials are formed by sintering in a furnace, and thin films are manufactured by sputtering, MBE (molecular beam epitaxy), etc. It is common to do.
発明が解決しようとする問題点 上記のように、複合酸化物超電導体は、炉を使用した
焼結、またはスパッタリング、MBE等で製造されるた
め、大面積の薄膜や数10から数100μｍの厚さの厚膜を
形成することが困難であった。Problems to be Solved by the Invention As described above, since the complex oxide superconductor is manufactured by sintering using a furnace, or sputtering, MBE, etc., it is a thin film having a large area or a thickness of several tens to several 100 μm. It was difficult to form a thick film.
すなわち、スパッタリングやMBE等で、大面積の超電
導体薄膜を形成しようとすると、厚さ、組成等が不均一
になる。That is, when it is attempted to form a large-area superconductor thin film by sputtering, MBE, etc., the thickness, composition, etc. become non-uniform.
また、数10から数100μｍの厚みをもつ超電導体厚膜
を炉を用いた焼結により作製しようとすると、ポーラス
な不均一のものとなり、スパッタリングやMBE等で作製
しようとすると大変時間がかかるとともに、均一性が保
たれなくなる。Moreover, if a superconductor thick film having a thickness of several tens to several hundreds of μm is attempted to be produced by sintering using a furnace, it becomes porous and non-uniform, and it takes much time to produce it by sputtering or MBE. , Uniformity cannot be maintained.
従って、本発明の目的は上記の問題を解決し、大面積
の薄膜および任意の厚さの厚膜等の超電導材料を製造す
る方法を提供することにある。Therefore, an object of the present invention is to solve the above problems and provide a method for producing a superconducting material such as a thin film having a large area and a thick film having an arbitrary thickness.
問題点を解決するための手段 本発明に従うと、周期律表II a族元素から選択された
少なくとも１種の元素α、周期律表III a族元素から選
択された少なくとも１種の元素βおよび周期律表I b、I
I b、III b、IV a、VIII a族元素から選択された少なく
とも１種の元素γを含有する窒化物、酸化物、水酸化
物、炭酸塩、硫酸塩、シュウ酸塩または硝酸塩の粉末を
混合、予備焼成し、焼成体を粉砕して、粉末焼成体を
得、該粉末焼成体を高圧気体中でレーザービームにより
焼結することを特徴とする超電導材料の製造方法が提供
される。Means for Solving the Problems According to the present invention, at least one element α selected from the group IIa elements of the periodic table, at least one element β selected from the group IIIa elements of the periodic table, and the period Ib, I
Powders of nitrides, oxides, hydroxides, carbonates, sulfates, oxalates or nitrates containing at least one element γ selected from Group I b, III b, IV a and VIII a elements Provided is a method for producing a superconducting material, which comprises mixing, pre-firing, pulverizing a fired body to obtain a powder fired body, and sintering the powder fired body with a laser beam in a high-pressure gas.
本発明に用いる超電導材料は、 一般式：（α1-xβｘ）γyOz （但し、α、β、γは、上記定義の元素であり、ｘはα
＋βに対するβの原子比で、0.1≦ｘ≦0.9であり、ｙお
よびｚは（α1-xβｘ）を１とした場合に0.4≦ｙ≦3.
0、１≦ｚ≦５となる原子比である） で表される組成の複合酸化物であることが好ましい。こ
れらの複合酸化物はペロブスカイト型または擬似ペロブ
スカイト型酸化物を主体としたものと考えられる。The superconducting material used in the present invention has the general formula: (α 1-x β x ) γ y O z (where α, β and γ are the elements defined above, and x is α
The atomic ratio of β to + β is 0.1 ≦ x ≦ 0.9, and y and z are 0.4 ≦ y ≦ 3 when (α 1−x β x ) is 1.
It is preferable that the composite oxide has a composition represented by: 0, 1 ≦ z ≦ 5. It is considered that these complex oxides are mainly composed of perovskite type or pseudo perovskite type oxides.
上記周期律表II a族元素αとしては、Ba、Sr、Ca、M
g、Be等が好ましく、例えば、Ba、Srを挙げることがで
き、この元素αの10〜80％をMg、Ca、Srから選択された
１種または２種の元素で置換することもできる。また上
記周期律表III a族元素βはとしては、Ｙ、La、Sc、C
e、Gd、Ho、Er、Tm、Yb、Lu等が好ましく、例えばＹ、L
aとすることができ、この元素βのうち、10〜80％をSc
またはLa以外のランタノイド元素から選択された１種ま
たは２種の元素で置換することもできる。前記元素γは
一般にCuであるが、その一部を周期律表I b、II b、III
b、IV aおよびVIII族から選択される他の元素、例え
ば、Ti、Ｖ等で置換することもできる。The Group IIa element α of the periodic table includes Ba, Sr, Ca, and M.
g, Be and the like are preferable, and examples thereof include Ba and Sr, and 10 to 80% of the element α can be replaced with one or two elements selected from Mg, Ca and Sr. The group IIIa element β in the periodic table is Y, La, Sc, C
e, Gd, Ho, Er, Tm, Yb, Lu and the like are preferable, for example Y, L
a, and 10 to 80% of this element β is Sc
Alternatively, it may be substituted with one or two elements selected from lanthanoid elements other than La. The element γ is generally Cu, a part of which is the periodic table I b, II b, III.
It can also be replaced by other elements selected from groups b, IVa and VIII, for example Ti, V and the like.
本発明に従うと、上記焼結時の圧力は、１〜100気圧
であることが好ましく、焼結雰囲気の酸素分圧は全圧の
10％以上であることが好ましい。また、上記の予備焼成
は、酸素分圧が0.1気圧乃至150気圧のO2含有雰囲気下で
行い、予備焼成温度は700〜1000℃であることが好まし
い。According to the present invention, the pressure during sintering is preferably 1 to 100 atm, and the oxygen partial pressure of the sintering atmosphere is less than the total pressure.
It is preferably 10% or more. The pre-baking is preferably performed in an O 2 -containing atmosphere having an oxygen partial pressure of 0.1 atm to 150 atm, and the pre-baking temperature is preferably 700 to 1000 ° C.
さらに、上記粉末焼成体を基板上で焼成することが好
ましく、基板としてはSrTiO3またはMgOの単結晶を用
い、成膜面を｛100｝とすることが好ましい。Further, it is preferable that the powder fired body is fired on a substrate, and as the substrate, a single crystal of SrTiO 3 or MgO is used, and the film formation surface is preferably {100}.
作用 本発明による超電導材料の製造方法は、周期律表II a
族元素から選択された少なくとも１種の元素α、周期律
表III a族元素から選択された少なくとも１種の元素β
および周期律表I b、II b、III b、IV b、VIII a族元素
から選択された少なくとも１種の元素γを含有する窒化
物、酸化物、水酸化物、炭酸塩、硫酸塩、シュウ酸塩ま
たは硝酸塩の粉末を混合、予備焼成し、焼成体を粉砕し
て、粉末焼成体を得、該粉末焼成体を高圧気体中でレー
ザービームにより焼結することを主要な特徴とする。Action The method for producing a superconducting material according to the present invention is described in Periodic Table IIa.
At least one element α selected from group elements, at least one element β selected from group IIIa elements of the periodic table
And nitrides, oxides, hydroxides, carbonates, sulphates, shu which contain at least one element γ selected from the group Ib, IIb, IIIb, IVb and VIIIa elements of the periodic table. The main feature is that powders of acid salts or nitrates are mixed and pre-fired, the fired body is crushed to obtain a powder fired body, and the powder fired body is sintered by a laser beam in a high-pressure gas.
従来、Ba−La−Cu−Ｏ系、Sr−La−Cu−Ｏ系、Ba−Ｙ
−Cu−Ｏ系等の複合酸化物超電導体は、炉を使用する焼
結、スパッタリング、MBE等で製造していた。すなわ
ち、大きな形状のものは炉を用いて焼結で製造し、薄膜
等はスパッタリング、MBE等で製造するのが一般的であ
った。Conventionally, Ba-La-Cu-O system, Sr-La-Cu-O system, Ba-Y
The complex oxide superconductor such as —Cu—O system was manufactured by sintering using a furnace, sputtering, MBE and the like. That is, it is general that large-sized ones are manufactured by sintering in a furnace, and thin films and the like are manufactured by sputtering, MBE and the like.
しかしながら、炉を用いる焼結では、厚さ1mm程度も
のまでしか製造することができない。その理由は、上記
の複合酸化物超電導体を焼結によって製造する場合、原
料粉末を予備焼成し、焼成体を粉砕して得た粉末焼成体
を成形、焼結に付すが、成形の際、バインダー、水等を
混合すると超電導特性に悪影響を与える。従って、乾燥
状態で粉末焼成体を成形しなければならないからで、こ
のため成形可能な形状は制限される。さらに、成形方法
を改善しても、炉を用いた焼結により得られる超電導体
は空孔が多いポーラスなものであり、十分な厚さを持た
ないものは特に、均一性に問題がある。However, sintering using a furnace can produce only a thickness of about 1 mm. The reason is that, when the above-mentioned composite oxide superconductor is manufactured by sintering, the raw material powder is pre-fired, and the powder fired body obtained by crushing the fired body is molded and subjected to sintering. Mixing a binder, water, etc. adversely affects the superconducting properties. Therefore, the powder fired body must be molded in a dry state, which limits the shape that can be molded. Further, even if the molding method is improved, the superconductor obtained by sintering using a furnace is porous with many pores, and the one that does not have a sufficient thickness has a problem in uniformity.
一方、スパッタリング、MBE等で超電導体薄膜を製造
する際の成膜速度は、10分の１Å／秒程度のオーダーで
あり、1mm近い厚さのものを製造するには極めて時間が
かかる。さらにこれらの方法では、薄膜は優れた質のも
のが得られるが1mm近い超電導体は均質にならない。ま
た、スパッタリング、MBE等では大きな面積のものは製
造することが困難である。On the other hand, the film formation rate when producing a superconductor thin film by sputtering, MBE, etc. is on the order of about 1/10 Å / sec, and it takes a very long time to produce a film having a thickness close to 1 mm. In addition, these methods produce excellent thin films, but do not make the superconductor close to 1 mm homogeneous. Further, it is difficult to manufacture a large area by sputtering or MBE.
本発明の方法では、高圧気体中でレーザービームを用
いて上記の粉末焼成体を焼結する。レーザービームが照
射された部分の粒界には液相が生じるが、高圧気体中で
焼結しているため液相が粒界を十分に満たし、得られる
焼結体は気孔を持たない。また、本発明の方法では基板
上で粉末焼成体を焼結するため、厚さ等における制限も
一般の焼結に較べ大幅に緩やかになる。In the method of the present invention, the powder fired body is sintered using a laser beam in a high pressure gas. A liquid phase is generated at the grain boundary of the portion irradiated with the laser beam, but the liquid phase sufficiently fills the grain boundary because it is sintered in a high pressure gas, and the obtained sintered body has no pores. Further, in the method of the present invention, since the powder fired body is sintered on the substrate, the restrictions on the thickness and the like are considerably loosened as compared with general sintering.
本発明において、レーザービームを用いる理由は、上
記の粉末焼成体を局所的に加熱、焼結することが可能に
なるからであり、レーザービームを照射、加熱された粒
界に生じた液相には高圧力が全方向から等方的にかか
り、焼結体の間隙を充填する。このため、本発明に用い
るレーザービームは、ある程度細いことが好ましく、集
光することも好ましい。In the present invention, the reason why the laser beam is used is that it becomes possible to locally heat and sinter the above-mentioned powder fired body. Is isotropically applied with high pressure from all directions to fill the gaps in the sintered body. Therefore, the laser beam used in the present invention is preferably thin to some extent, and it is also preferable to focus it.
本発明の方法に用いるレーザーは赤外線レーザーであ
ることが好ましいが、焼結に必要なエネルギーが供給で
きるレーザーであれば、赤外線レーザーに規定されるも
のではない。The laser used in the method of the present invention is preferably an infrared laser, but is not limited to an infrared laser as long as it can supply the energy required for sintering.
本発明の方法では、上記の焼結を高圧気体中で行う。
焼結雰囲気は、10％以上酸素を含んでいる不活性ガス雰
囲気または同様な窒素ガス雰囲気が好ましい。複合酸化
物超電導体の超電導特性には、結晶中の酸素欠陥が大き
く影響している。このような雰囲気下で焼結することに
より結晶中の酸素欠陥は適当となり、得られる超電導材
料は優れた超電導特性を有するものとなる。In the method of the present invention, the above sintering is performed in a high pressure gas.
The sintering atmosphere is preferably an inert gas atmosphere containing 10% or more oxygen or a similar nitrogen gas atmosphere. Oxygen defects in the crystal have a great influence on the superconducting properties of the composite oxide superconductor. By sintering in such an atmosphere, oxygen defects in the crystal become appropriate, and the obtained superconducting material has excellent superconducting properties.
また、本発明の好ましい態様に従うと、基板としてSr
TiO3単結晶またはMgO単結晶を用い、成膜面を｛100｝と
する。該基板成膜面上に形成された超電導体はａ軸およ
びｂ軸が基板成膜面と平行になり、ｃ軸が基板成膜面に
垂直あるいは垂直に近い角度で揃うｃ軸配向性を持ち、
特に臨界電流密度Jcが向上する。According to a preferred embodiment of the present invention, Sr is used as the substrate.
TiO 3 single crystal or MgO single crystal is used, and the film formation surface is {100}. The superconductor formed on the substrate film-forming surface has a c-axis orientation in which the a-axis and the b-axis are parallel to the substrate film-forming surface, and the c-axis is perpendicular or nearly perpendicular to the substrate film-forming surface. ,
Especially, the critical current density Jc is improved.
また、上記の複合酸化物超電導体は、焼結体の結晶粒
径が小さい方が超電導臨界温度の高い物質が形成され易
いようである。従って、最終的な焼結体の結晶粒径が小
さくなるように考慮すべきである。Further, in the above complex oxide superconductor, it seems that a substance having a higher superconducting critical temperature is more likely to be formed when the crystal grain size of the sintered body is smaller. Therefore, it should be taken into consideration that the crystal grain size of the final sintered body becomes small.
そこで、まず、原料粉末の平均粒系は各々20μｍ以下
であることが好ましく、特に予備焼成後の焼結体粉末
は、10μｍ以下に粉砕することが好ましい。即ち、焼結
に付す原料粉末の粒径が大きくなると、得られる焼結体
の結晶粒径は忽ち大きくなる。しかしながら、粉砕工程
を過剰に行うことは作業時間が増加して効率上好ましく
ないので、本発明の目的とする超電導特性を持つ超電導
材料を得るには上記範囲を満たせば十分である。Therefore, first, the average grain size of the raw material powder is preferably 20 μm or less, and particularly, the sintered powder after pre-firing is preferably pulverized to 10 μm or less. That is, as the particle size of the raw material powder subjected to sintering increases, the crystal grain size of the obtained sintered body immediately increases. However, it is not preferable to perform the pulverization step excessively because the working time increases, and therefore it is sufficient to satisfy the above range in order to obtain the superconducting material having the superconducting properties which is the object of the present invention.
本発明の好ましい態様に従うと、焼結時の基板温度は
400〜1000℃とすることが好ましい。基板温度をこの範
囲に保つことにより、得られる超電導材料の結晶構造、
酸素欠陥等がより好ましいものとなり、特にTcが向上す
る。According to a preferred embodiment of the present invention, the substrate temperature during sintering is
The temperature is preferably 400 to 1000 ° C. By keeping the substrate temperature in this range, the crystal structure of the resulting superconducting material,
Oxygen defects are more preferable, and Tc is particularly improved.
また、焼結後の超電導体を酸素含有雰囲気で熱処理す
ることが好ましい。この熱処理は、300〜1500℃の範囲
の温度に加熱後100℃／分以下の冷却速度で徐冷する過
程を含むことが好ましい。Further, it is preferable to heat-treat the sintered superconductor in an oxygen-containing atmosphere. This heat treatment preferably includes a process of heating to a temperature in the range of 300 to 1500 ° C. and then gradually cooling at a cooling rate of 100 ° C./min or less.
実施例 以下に本発明を実施例により、さらに詳しく説明する
が、以下に記述するものは本発明の１実施例に過ぎず、
本発明の技術的範囲を制限するものではない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, what is described below is only one example of the present invention.
It does not limit the technical scope of the present invention.
純度3N以上、平均粒径５μｍ以下のBaCO3と純度3N以
上、平均粒径５μｍ以下のY2O3粉末および純度3N以上、
平均粒径３μｍ以下のCuO粉末とを原子比がY:Ba:Cu＝1:
2:3となるように混合した。この原料混合物粉末を900℃
で24時間焼成した。得られた焼成体を100メッシュ以下
の粉末に粉砕後、SrTiO3単結晶基板の（100）面に厚さ
0.5mmで加圧成形した。BaCO 3 having a purity of 3N or more and an average particle size of 5 μm or less and Y 2 O 3 powder having a purity of 3N or more and an average particle size of 5 μm or less and a purity of 3N or more,
CuO powder with an average particle size of 3 μm or less has an atomic ratio of Y: Ba: Cu = 1:
Mixed to be 2: 3. This raw material mixture powder is 900 ℃
It was baked for 24 hours. After crushing the obtained fired body into powder of 100 mesh or less, the thickness on the (100) plane of the SrTiO 3 single crystal substrate
It was pressure molded at 0.5 mm.
この基板をチャンバ内に入れ、真空に排気した後、20
気圧のArガスと30気圧の酸素ガスを導入した。ヒータで
基板温度を730℃とし、出力500WのCO2レーザーを照射し
た。レーザービーム照射中に基板温度が変化しないよう
にヒータを調整した。焼結終了後、チャンバ内を大気圧
まで減圧し、さらに酸素雰囲気とした。その後、基板温
度を７℃／分の冷却速度で室温まで冷却した。Place this substrate in the chamber, evacuate it to 20
Ar gas at atmospheric pressure and oxygen gas at 30 atmospheric pressure were introduced. The substrate temperature was set to 730 ° C with a heater and a CO 2 laser with an output of 500 W was irradiated. The heater was adjusted so that the substrate temperature did not change during laser beam irradiation. After the completion of sintering, the pressure in the chamber was reduced to atmospheric pressure, and an oxygen atmosphere was created. Then, the substrate temperature was cooled to room temperature at a cooling rate of 7 ° C./min.
得られた超電導材料は、厚さ0.3mmの膜状であった。
超電導特性を以下に示す。The obtained superconducting material was in the form of a film having a thickness of 0.3 mm.
The superconducting properties are shown below.
超電導臨界温度（オンセット） 97K 超電導臨界温度（抵抗０） 81K 臨界電流 ３×105A/cm2 この結果本発明の方法が、優れた超電導特性を有する
超電導材料を製造するのに有効であることが立証され
た。Superconducting critical temperature (onset) 97K Superconducting critical temperature (resistance 0) 81K Critical current 3 × 10 5 A / cm 2 As a result, the method of the present invention is effective for producing a superconducting material having excellent superconducting properties. It was proved.
発明の効果 本発明の方法に従うと、従来の方法では製造できなか
った厚さ、面積の複合酸化物超電導体膜が製造可能とな
る。これは、本発明に独特なレーザービームを用いた焼
結により、可能となった。EFFECTS OF THE INVENTION According to the method of the present invention, a composite oxide superconductor film having a thickness and area which cannot be produced by the conventional method can be produced. This is made possible by the sintering using a laser beam unique to the present invention.
また、本発明の方法で製造された超電導材料はその超
電導特性も優れたものとなる。本発明は集積回路パッケ
ージ、回路基板等の配線材料に応用すると効果的であ
る。In addition, the superconducting material produced by the method of the present invention also has excellent superconducting properties. The present invention is effective when applied to wiring materials such as integrated circuit packages and circuit boards.
───────────────────────────────────────────────────── 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 Ｈ０１Ｂ 13/00 ５６５ Ｚ Ｈ０１Ｌ 39/12 ＺＡＡ Ｃ // Ｈ０１Ｂ 12/00 ＺＡＡ (56)参考文献 特開 昭57−160975（ＪＰ，Ａ) 特開 昭57−20486（ＪＰ，Ａ) 特開 昭63−288940（ＪＰ，Ａ) 特開 昭63−292531（ＪＰ，Ａ) 特開 昭64−27117（ＪＰ，Ａ) 特開 昭64−45023（ＪＰ，Ａ) Ｐｈｙｓｉｃａｌ Ｒｅｖｉｅｗ Ｌｅ ｔｔｅｒｓ Ｖｏｌ．58 ｐ．908〜912 Ｊａｐｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｖｏ ｌ．26 ｐ．Ｌ454〜Ｌ455 Ｊａｐｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｖｏ ｌ．26 ｐ．Ｌ665〜Ｌ667 Ｊａｐｎｅｓｅ Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｈｙｓｉｃｓ Ｖｏ ｌ．26 ｐ．Ｌ815〜Ｌ817 Ｐｈｙｓｉｃａｌ Ｒｅｖｉｅｗ Ｂ Ｖｏｌ．35 ｐ．8782〜8784─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location H01B 13/00 565 Z H01L 39/12 ZAA C // H01B 12/00 ZAA (56) References Special Kai 57-160975 (JP, A) JP 57-20486 (JP, A) JP 63-288940 (JP, A) JP 63-292531 (JP, A) JP 64-27117 ( JP, A) JP 64-45023 (JP, A) Physical Review Letters Vol. 58 p. 908 to 912 Japan Journal of Applied Physics Vol. 26 p. L454 to L455 Japan Journal of Applied Physics Vol. 26 p. L665 to L667 Japan Journal of Applied Physics Vol. 26 p. L815 to L817 Physical Review B Vol. 35 p. 8782 ~ 8784
Claims (13)
とも１種の元素α、周期律表III a族元素から選択され
た少なくとも１種の元素βおよび周期律表I b、II b、I
II b、IV a、VIII a族元素から選択された少なくとも１
種の元素γを含有する窒化物、酸化物、水酸化物、炭酸
塩、硫酸塩、シュウ酸塩または硝酸塩の粉末を混合、予
備焼成し、焼成体を粉砕して、粉末焼成体を得、該粉末
焼成体を、全圧が１気圧より高く、酸素分圧が全圧の10
％以上であり、酸素以外の気体を含む混合気体中でレー
ザービームにより焼結することを特徴とする超電導材料
の製造方法。1. At least one element α selected from Group IIa elements of the Periodic Table, at least one element β selected from Group IIIa elements of the Periodic Table and Periodic Tables Ib, IIb, I
At least 1 selected from II b, IV a, and VIII a group elements
Mixing powder of nitride, oxide, hydroxide, carbonate, sulfate, oxalate or nitrate containing seed element γ, pre-baking, grinding the fired body, to obtain a powder fired body, The powder fired body had a total pressure higher than 1 atm and an oxygen partial pressure of 10
% Or more, and sintering with a laser beam in a mixed gas containing a gas other than oxygen. A method for producing a superconducting material.
＋βに対するβの原子比で、0.1≦ｘ≦0.9であり、ｙお
よびｚは（α1-xβｘ）を１とした場合に0.4≦ｙ≦3.
0、１≦ｚ≦５となる原子比である） で表される組成の複合酸化物であることを特徴とする特
許請求の範囲第１項に記載の超電導材料の製造方法。2. The oxide superconducting material has a general formula: (α 1-x β x ) γ y O z (where α, β and γ are elements defined above, and x is α
The atomic ratio of β to + β is 0.1 ≦ x ≦ 0.9, and y and z are 0.4 ≦ y ≦ 3 when (α 1−x β x ) is 1.
The atomic ratio of 0 ≦ 1 ≦ z ≦ 5) is a complex oxide having a composition represented by the formula: The method for manufacturing a superconducting material according to claim 1.
であり、γがAl、Fe、Co、Ni、Zn、Cu、AgおよびTiで構
成される群から選択された少なくとも１種の元素である
ことを特徴とする特許請求の範囲第１項または第２項に
記載の超電導材料の製造方法。3. In the above general formula, α is Ba and β is Y
And γ is at least one element selected from the group consisting of Al, Fe, Co, Ni, Zn, Cu, Ag and Ti. Item 3. A method for producing a superconducting material according to item 2.
であり、γがAl、Fe、Co、Ni、Zn、Cu、AgおよびTiで構
成される群から選択された少なくとも１種の元素である
ことを特徴とする特許請求の範囲第１項または第２項に
記載の超電導材料の製造方法。4. In the above general formula, α is Ba, and β is La
And γ is at least one element selected from the group consisting of Al, Fe, Co, Ni, Zn, Cu, Ag and Ti. Item 3. A method for producing a superconducting material according to item 2.
であり、γがAl、Fe、Co、Ni、Zn、Cu、AgおよびTiで構
成される群から選択された少なくとも１種の元素である
ことを特徴とする特許請求の範囲第１項または第２項に
記載の超電導材料の製造方法。5. In the general formula, α is Sr and β is La
And γ is at least one element selected from the group consisting of Al, Fe, Co, Ni, Zn, Cu, Ag and Ti. Item 3. A method for producing a superconducting material according to item 2.
物、水酸化物、炭酸塩、硫酸塩、シュウ酸塩または硝酸
塩の粉末が、各々平均粒径20μｍ以下であることを特徴
とする特許請求の範囲第１項乃至第５項のいずれか１項
に記載の超電導材料の製造方法。6. The powder of the nitride, oxide, hydroxide, carbonate, sulfate, oxalate or nitrate of the elements α, β and γ each has an average particle size of 20 μm or less. The method for producing a superconducting material according to any one of claims 1 to 5.
とを特徴とする特許請求の範囲第１項乃至第６項のいず
れか１項に記載の超電導材料の製造方法。7. The method for producing a superconducting material according to claim 1, wherein sintering of the powder fired body is performed on a substrate.
晶であることを特徴とする特許請求の範囲第７項に記載
の超電導材料の製造方法。8. The method for producing a superconducting material according to claim 7, wherein the substrate is MgO single crystal or SrTiO 3 single crystal.
を特徴とする特許請求の範囲第８項に記載の超電導材料
の製造方法。9. The method for producing a superconducting material according to claim 8, wherein sintering is performed on the {100} plane of the substrate.
0気圧以下であることを特徴とする特許請求の範囲第１
項乃至第９項に記載の超電導材料の製造方法。10. The pressure during sintering is higher than 1 atm.
Claim 1 characterized in that it is 0 atm or less
Item 10. A method for manufacturing a superconducting material according to items 9.
度で実施することを特徴とする特許請求の範囲第１項乃
至第10項のいずれか１項に記載の超電導材料の製造方
法。11. The method for producing a superconducting material according to claim 1, wherein the pre-baking is carried out at a temperature in the range of 700 to 1000 ° C.
下に粉砕することを特徴とする特許請求の範囲第１項乃
至第11項のいずれか１項に記載の超電導材料の製造方
法。12. The method for producing a superconducting material according to any one of claims 1 to 11, wherein the fired body after the preliminary firing is pulverized to have an average particle size of 10 μm or less.
気圧のO2含有雰囲気下で行うことを特徴とする特許請求
の範囲第１項乃至第12項のいずれか１項に記載の超電導
材料の製造方法。13. Pre-baking is carried out at an oxygen partial pressure of 0.1 atm to 150 atm.
13. The method for producing a superconducting material according to claim 1, wherein the superconducting material is produced in an atmosphere containing O 2 at atmospheric pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62214445A JPH0816024B2 (en) | 1987-08-28 | 1987-08-28 | Manufacturing method of superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62214445A JPH0816024B2 (en) | 1987-08-28 | 1987-08-28 | Manufacturing method of superconducting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6456359A JPS6456359A (en) | 1989-03-03 |
| JPH0816024B2 true JPH0816024B2 (en) | 1996-02-21 |
Family
ID=16655886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62214445A Expired - Lifetime JPH0816024B2 (en) | 1987-08-28 | 1987-08-28 | Manufacturing method of superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816024B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2603482B2 (en) * | 1987-09-30 | 1997-04-23 | 株式会社豊田中央研究所 | Superconductor manufacturing method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5845194B2 (en) * | 1980-07-11 | 1983-10-07 | 日本電信電話株式会社 | Superconducting integrated circuit and its manufacturing method |
| JPS57160975A (en) * | 1981-03-27 | 1982-10-04 | Katsuya Okabe | Ceramics sintering method |
| JPH0613429B2 (en) * | 1987-05-21 | 1994-02-23 | 科学技術庁金属材料技術研究所長 | Method for manufacturing oxide superconductor |
| JPS63292531A (en) * | 1987-05-26 | 1988-11-29 | Toshiba Corp | Manufacture of superconductive wire of compound |
| JPS6427117A (en) * | 1987-07-21 | 1989-01-30 | Toshiba Corp | Superconductor device |
| JPS6445023A (en) * | 1987-08-14 | 1989-02-17 | Univ Tokai | Heat treatment method for superconductive film |
-
1987
- 1987-08-28 JP JP62214445A patent/JPH0816024B2/en not_active Expired - Lifetime
Non-Patent Citations (5)
| Title |
|---|
| ＪａｐｎｅｓｅＪｏｕｒｎａｌｏｆＡｐｐｌｉｅｄＰｈｙｓｉｃｓＶｏｌ．２６ｐ．Ｌ４５４〜Ｌ４５５ |
| ＪａｐｎｅｓｅＪｏｕｒｎａｌｏｆＡｐｐｌｉｅｄＰｈｙｓｉｃｓＶｏｌ．２６ｐ．Ｌ６６５〜Ｌ６６７ |
| ＪａｐｎｅｓｅＪｏｕｒｎａｌｏｆＡｐｐｌｉｅｄＰｈｙｓｉｃｓＶｏｌ．２６ｐ．Ｌ８１５〜Ｌ８１７ |
| ＰｈｙｓｉｃａｌＲｅｖｉｅｗＢＶｏｌ．３５ｐ．８７８２〜８７８４ |
| ＰｈｙｓｉｃａｌＲｅｖｉｅｗＬｅｔｔｅｒｓＶｏｌ．５８ｐ．９０８〜９１２ |
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|---|---|
| JPS6456359A (en) | 1989-03-03 |
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