JPH04130019A - Electrically conductive oxide - Google Patents
Electrically conductive oxideInfo
- Publication number
- JPH04130019A JPH04130019A JP2246753A JP24675390A JPH04130019A JP H04130019 A JPH04130019 A JP H04130019A JP 2246753 A JP2246753 A JP 2246753A JP 24675390 A JP24675390 A JP 24675390A JP H04130019 A JPH04130019 A JP H04130019A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- electrically conductive
- conductive oxide
- formula
- carbonate
- 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.)
- Pending
Links
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002887 superconductor Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- -1 NiO Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的コ
（産業上の利用分野）
本発明は、ニッケルを含有する電気伝導性酸化物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention (Industrial Application Field) The present invention relates to an electrically conductive oxide containing nickel.
（従来の技術）
近年、銅を含むペロブスカイト構造の酸化物が、高い臨
界温度を示す超電導体となることが分って以来、各所で
銅を含む酸化物超電導体の研究が活発に行われている。(Prior art) In recent years, since it has been discovered that perovskite-structured oxides containing copper can be superconductors with high critical temperatures, research on oxide superconductors containing copper has been actively conducted in various places. There is.
このような銅を含む酸化物が高い臨界温度を示す理由に
ついては、まだ完全には明らかにはされていないか、銅
と酸素とが形成する ２次元面とＣｕ２“のもつ大きさ
１／２のスピンとが、超電導機構と密接に関係している
のものと推測されている。The reason why such copper-containing oxides exhibit a high critical temperature is not yet completely clear, or the two-dimensional plane formed by copper and oxygen is 1/2 the size of Cu It is speculated that the spin of the superconductor is closely related to the superconducting mechanism.
一方、ニッケルを含む酸化物のうち、いくつかのものは
、電気伝導性を示すことが知られており、各種電極材料
や配線材料等への応用が期待されている。また、 ３価
のＮｉ （Ｎｉ”）もＣｕ２＋と同様に、大きさ１／２
のスピンをもつ可能性があるため、上記した銅を含む酸
化物が超電導性を示す理由に基づくと、Ｎｉを含む酸化
物も超電導体となる可能性があることから、超電導材料
としての実用化も期待されている。On the other hand, some oxides containing nickel are known to exhibit electrical conductivity, and are expected to be applied to various electrode materials, wiring materials, and the like. Also, like Cu2+, trivalent Ni (Ni”) has a size of 1/2
Based on the above-mentioned reason why copper-containing oxides exhibit superconductivity, there is a possibility that Ni-containing oxides may also become superconductors. is also expected.
上述したような３価のＮｉを含み、低次元面を有する結
晶構造をとる酸化物として、Ｂ１Ｎ１（ｈが最近見出だ
されており、上述したような理由から興味ある特性を示
すことが期待されている。B1N1 (h) has recently been discovered as an oxide that contains trivalent Ni as described above and has a crystal structure with low-dimensional planes, and is expected to exhibit interesting properties for the reasons described above. has been done.
（発明が解決しようとする課題）
しかしながら、上述したＢ１Ｎｉ０３で表される酸化物
は、７０気圧以上というような高圧酸素下でしか合成で
きず、またこのような条件下で合成したとしても、室温
における電気抵抗か高く、電極材料や配線材料等として
実用化するには有用とは言いかたい。また、金属−絶縁
体転移や磁気転移、超電導転移も見出だされていない。(Problem to be Solved by the Invention) However, the above-mentioned oxide represented by B1Ni03 can only be synthesized under high pressure oxygen such as 70 atmospheres or more, and even if it is synthesized under such conditions, it can be synthesized at room temperature. Its electrical resistance is high, and it cannot be said that it is useful for practical use as an electrode material or wiring material. Furthermore, metal-insulator transition, magnetic transition, and superconducting transition have not been found.
本発明は、このような課題に対処するためになされたも
のであり、ニッケルと酸素との低次元面を有すると共に
、電気伝導性に優れ、勝つ容易に得ることが可能なニッ
ケルを含む電気伝導性酸化物を提供することを目的とす
るものである。The present invention has been made to address these problems, and uses an electrically conductive material containing nickel, which has a low-dimensional surface of nickel and oxygen, has excellent electrical conductivity, and can be easily obtained. The purpose is to provide a chemical oxide.
［発明の構成］
（課題を解決するための手段）
本発明の電気伝導性酸化物は、旧およびＮｉを含有し、
層状ペロブスカイト構造を有する酸化物であって、Ａ２
元素（ＡＥはＢａ、 ＣａおよびＳｒから選ばれた少な
くとも １種の元素を示す）を含有することを特徴とす
るものである。[Structure of the Invention] (Means for Solving the Problems) The electrically conductive oxide of the present invention contains Ni and Ni,
An oxide having a layered perovskite structure, wherein A2
It is characterized by containing an element (AE represents at least one element selected from Ba, Ca, and Sr).
すなわち本発明の電気伝導性酸化物は、前述したＢ１Ｎ
１（ｈのＢｉの一部をアルカリ土類元素で置換すること
によって、キャリア濃度を制御し、金属導電性の向上ひ
いては超電導性の発現をもたらすと共に、結晶構造の安
定化を図り、合成時の熱処理条件を緩和したものである
。That is, the electrically conductive oxide of the present invention has the above-mentioned B1N
By substituting a part of Bi in 1(h) with an alkaline earth element, the carrier concentration is controlled and the metal conductivity is improved, which leads to the expression of superconductivity. At the same time, the crystal structure is stabilized, and the The heat treatment conditions are relaxed.
本発明の電気伝導性酸化物の具体例としては、以下の式
で実質的に表される組成か例示される。Specific examples of the electrically conductive oxide of the present invention include compositions substantially represented by the following formula.
Ｂｊ＋−−ＡＥ−Ｎｌ ０３ −− （
１）（式中、Ｘは０．０１＜ Ｘ＜ １を満足する
数を示す）上記（Ｉ）式で表される酸化物は、ＡＢＯ３
と表記される層状ペロブスカイト構造を有するものであ
る。ここで、ＢｉはＡサイトと Ｂサイトの両方に入る
ことができるが、ＮｉはＢサイトにしか入らない。この
ことを考慮すると、上記（Ｉ）式の酸化物は、実質的に
は下記の（ＩＩ）式で表される。Bj+--AE-Nl 03 -- (
1) (In the formula, X represents a number satisfying 0.01<X<1) The oxide represented by the above formula (I) is ABO3
It has a layered perovskite structure expressed as . Here, Bi can enter both A site and B site, but Ni can only enter B site. Considering this, the oxide of formula (I) above is substantially represented by formula (II) below.
Ｂｉ＋−ＡＥｘＢ１＋−ｙ Ｎｌｙ ０３ −
− （ＩＩ）（式中、ｙは０．０１＜ ｙ＜ １を
満足する数を示す）上記（Ｉ）式および（ＩＩ）式にお
けるＸの値が０．０１以下ではキャリア濃度調整の効果
か十分に得られず、また１以上では結晶構造を保てない
。また、上記（ＩＩ）式におけるｙの値か０．０１以下
では高圧酸素下でしか合成できず、また１以上では結晶
構造を保てない。Bi+-AExB1+-y Nly 03-
- (II) (In the formula, y represents a number satisfying 0.01 < y < 1) If the value of If the number is 1 or more, the crystal structure cannot be maintained. Further, if the value of y in the above formula (II) is less than 0.01, it can only be synthesized under high pressure oxygen, and if it is more than 1, the crystal structure cannot be maintained.
また、Ｘで表されるＡＥによる置換量は、上記範囲内で
あれば本発明の効果か得られるが、例えばＸを０．２〜
０，５の範囲とすることによって、超電導性を付与する
ことができる。Further, the effects of the present invention can be obtained if the amount of substitution by AE represented by X is within the above range, but for example, if X is 0.2 to
By setting it in the range of 0.5, superconductivity can be imparted.
本発明の電気伝導性酸化物は、例えば以下に示す製造方
法により得ることができる。The electrically conductive oxide of the present invention can be obtained, for example, by the manufacturing method shown below.
まず、電気伝導性酸化物の構成金属元素である、Ｂ］Ｓ
ＡＥ元素、Ｎ１の単体または化合物を充分に混合する。First, B]S is a constituent metal element of the electrically conductive oxide.
Thoroughly mix the AE element and N1 alone or as a compound.
この構成元素の化合物としては、Ｂｉ２Ｏ３、ＳｒＣＯ
３、ＮｉＯ等の酸化物や炭酸塩の他に、焼成後に酸化物
に転化する、硝酸塩、水酸化物等の化合物や有機酸塩、
有機性金属等を用いてもよい。上述したような各出発原
料は、基本的には上記（Ｉ）式の原子比を満足するよう
に混合するが、製造条件等との関係で１０％程度ずれて
いても差支えない。Compounds of this constituent element include Bi2O3, SrCO
3. In addition to oxides and carbonates such as NiO, compounds such as nitrates and hydroxides and organic acid salts that are converted to oxides after firing,
Organic metals and the like may also be used. The above-mentioned starting materials are basically mixed so as to satisfy the atomic ratio of formula (I) above, but it may deviate by about 10% depending on the manufacturing conditions and the like.
次いで、この混合粉末を７００℃〜８００℃程度の温度
で仮焼して結晶化させる。この後、仮焼物を粉砕し、プ
レス成形法等によって所望の形状に成形した後、８５０
℃〜１０００℃程度の温度で焼成し、目的とする電気伝
導性酸化物を得る。なお、上記仮焼は必ずしも必要では
ない。Next, this mixed powder is calcined at a temperature of about 700°C to 800°C to crystallize it. After that, the calcined product is crushed and molded into a desired shape using a press molding method, etc., and then
The desired electrically conductive oxide is obtained by firing at a temperature of about 1000°C to 1000°C. Note that the above-mentioned calcination is not necessarily necessary.
上記仮焼工程および焼結工程は、大気中や１気圧程度の
酸素中で行っても、十分に上記（Ｉ）式または（ＩＩ）
式で表される結晶を合成することができる。Even if the above calcination step and sintering step are performed in the atmosphere or in oxygen at about 1 atm, the formula (I) or (II)
A crystal represented by the formula can be synthesized.
（作 用）
本発明の電気伝導性酸化物においては、＋３価のＢｉの
一部を＋２価のＡ２元素で置換することにより、ホール
をキャリアとして導入している。これにより、系内のキ
ャリア濃度が増加し、金属的な伝導を容易に付与するこ
とが可能となると共に、電気伝導性の向上が図れる。ま
た、上記した置換は結晶構造の安定化をもたらすため、
その合成か容易となる。(Function) In the electrically conductive oxide of the present invention, holes are introduced as carriers by replacing a portion of +3-valent Bi with +2-valent A2 element. This increases the carrier concentration within the system, making it possible to easily provide metallic conduction and improving electrical conductivity. In addition, since the above substitutions stabilize the crystal structure,
Its synthesis becomes easy.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
実施例
まず、Ｂｉ２Ｏ３粉末、ＳｒＣＯ３粉末およびＮｉＯ粉
末を、原子比てＢｉ：Ｓｒ：ＮｉＪ、５：０．５：１と
なるように所定量計量し、充分に混合した後、この混合
粉を大気中において８００°Ｃ×２４時間の条件で仮焼
した。Example First, predetermined amounts of Bi2O3 powder, SrCO3 powder, and NiO powder were weighed so that the atomic ratio was Bi:Sr:NiJ, 5:0.5:1, and after thoroughly mixing, this mixed powder was exposed to the atmosphere. It was calcined at 800°C for 24 hours.
次に、この仮焼物を粉砕し、この粉末を用いてプレス成
形法によってペレット状の成形体を作製した。次いで、
上記成形体を１気圧の酸素中にて９００℃×２４時間の
条件で焼成し、Ｂｉｏ、 ｓ Ｓｒｏ、 ｓ Ｎｉ０３
て表される酸化物の焼結体を得た。Next, this calcined product was pulverized, and a pellet-like molded body was produced using this powder by a press molding method. Then,
The above molded body was fired in oxygen at 1 atm at 900°C for 24 hours to obtain Bio, s Sro, s Ni03
A sintered body of the oxide represented by was obtained.
このようにして得た酸化物焼結体の電気抵抗および磁化
率の測定を行った。電気抵抗は室温おいて４Ｘ１０−’
Ωｃｍと良好な値を示し、また温度の低下と共に減少し
、金属的伝導を示した。そして、低温で急激に減少して
約５にで消失した。また、磁化率の測定においては、低
温（約５Ｋ）で反磁性を示した。The electrical resistance and magnetic susceptibility of the oxide sintered body thus obtained were measured. Electrical resistance is 4X10-' at room temperature
It showed a good value of Ωcm, and decreased as the temperature decreased, indicating metallic conduction. Then, it decreased rapidly at low temperatures and disappeared at about 5 ℃. Furthermore, in the measurement of magnetic susceptibility, it showed diamagnetic properties at low temperatures (approximately 5K).
比較例
Ｂｉ旧帆で表される酸化物の焼結体を上記実施例と同様
にして作製し、電気抵抗を測定したところ、室温おける
抵抗率は２０Ω印で、温度を低下させるにつれて抵抗率
は増加した。また、磁化率の測定においては、低温（約
５Ｋ）としても反磁性を示さなかった。Comparative Example A sintered body of an oxide represented by Bi old sail was prepared in the same manner as in the above example, and its electrical resistance was measured.The resistivity at room temperature was 20Ω, and as the temperature was lowered, the resistivity decreased. increased. Furthermore, in the measurement of magnetic susceptibility, no diamagnetic property was exhibited even at low temperatures (approximately 5K).
なお、上記実施例においては、ＡＥ元素としてＳｒを用
いた例について述べたが、他のＢａおよびＣａを用いた
場合においても、同様な効果か得られた。In the above example, an example was described in which Sr was used as the AE element, but similar effects were obtained when other Ba and Ca were used.
［発明の効果］
以上説明したように、本発明による電気伝導性酸化物は
、金属的伝導を示すと共に電気伝導性に優れ、よって配
線材料等として有用である。[Effects of the Invention] As explained above, the electrically conductive oxide according to the present invention exhibits metallic conductivity and has excellent electrical conductivity, and is therefore useful as a wiring material and the like.
出願人 株式会社 東芝Applicant: Toshiba Corporation
Claims (1)
およびＳｒから選ばれた少なくとも１種の元素を示す）
を構成成分とし、層状ペロブスカイト構造を有すること
を特徴とする電気伝導性酸化物。(1) Bi and Ni and AE elements (AE is Ba, Ca
and at least one element selected from Sr)
An electrically conductive oxide characterized by having a layered perovskite structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246753A JPH04130019A (en) | 1990-09-17 | 1990-09-17 | Electrically conductive oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246753A JPH04130019A (en) | 1990-09-17 | 1990-09-17 | Electrically conductive oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04130019A true JPH04130019A (en) | 1992-05-01 |
Family
ID=17153147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2246753A Pending JPH04130019A (en) | 1990-09-17 | 1990-09-17 | Electrically conductive oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04130019A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023210673A1 (en) * | 2022-04-28 | 2023-11-02 | 国立大学法人東北大学 | Crystal, phase change memory, method for producing crystal, and method for producing phase change memory |
-
1990
- 1990-09-17 JP JP2246753A patent/JPH04130019A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023210673A1 (en) * | 2022-04-28 | 2023-11-02 | 国立大学法人東北大学 | Crystal, phase change memory, method for producing crystal, and method for producing phase change memory |
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