FR2641530A2 - NOVEL COMPOSITE MATERIAL, MANUFACTURING METHOD AND APPLICATION - Google Patents

NOVEL COMPOSITE MATERIAL, MANUFACTURING METHOD AND APPLICATION Download PDF

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FR2641530A2
FR2641530A2 FR8900156A FR8900156A FR2641530A2 FR 2641530 A2 FR2641530 A2 FR 2641530A2 FR 8900156 A FR8900156 A FR 8900156A FR 8900156 A FR8900156 A FR 8900156A FR 2641530 A2 FR2641530 A2 FR 2641530A2
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composite material
copper oxide
alkaline earth
mixed valence
oxygen
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FR2641530B2 (en
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Bernard Mercey
Hugues Murray
Gilles Poullain
Bernard Raveau
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Centre National de la Recherche Scientifique CNRS
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Priority claimed from FR8801059A external-priority patent/FR2626569A1/en
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Priority to FR898900156A priority Critical patent/FR2641530B2/en
Priority to EP89901861A priority patent/EP0397743A1/en
Priority to JP1501727A priority patent/JPH03503157A/en
Priority to PCT/FR1989/000028 priority patent/WO1989007344A1/en
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Abstract

New composite material comprising a petrowskite-type, mixed-valency copper oxide phase deficient in oxygen, in contact with a nitride phase. Application to electrical and electronic circuits.

Description

La présente invention concerne des oxydes de cuivre à valence mixte de type perovskite. The present invention relates to mixed valence copper oxides of the perovskite type.

Elle a plus particulièrement trait à une sous famille de ce type d'oxyde et à un perfectionnement à la demande de brevet- français n0 88 01059. It relates more particularly to a subfamily of this type of oxide and to an improvement at French patent application No. 88 01 059.

Au cours du dernier lustre, les structures du type perovskite, c'est-à-dire dérivé de la structure de la perovskite elle-même (CaTiO3) ont fait l'objet de très nombreuses études. En particulier, les recherches ont beaucoup porté sur les oxydes de cuivre à valence mixte qui dérivaient de la perovskite. During the last chandelier, structures of the perovskite type, that is to say derived from the structure of perovskite itself (CaTiO3) have been the subject of very numerous studies. In particular, much research has been done on mixed valence copper oxides derived from perovskite.

Ces structures ont des propriétés intéressantes de divers ordres. These structures have interesting properties of various orders.

Toutefois, c'est leur propriété supraconductrice qui a été le moteur de ces recherches.However, it is their superconducting property that has been the driving force behind this research.

il est extrêmement difficile de donner une formule générale de ces dérivés des perovskites ; en effet, de très nombreuses sortes de substitution ont été réalisées, et un très grand nombre de composés ont déjà été synthétisés ou sont sur le point de l'être. it is extremely difficult to give a general formula for these derivatives of perovskites; indeed, many kinds of substitution have been made, and a very large number of compounds have already been synthesized or are about to be.

A titre indicatif, et sans que cela soit en rien limitatif, on peut donner l'allure générale de la formule des oxydes de cuivre à valence mixte dérivés de la perovskite (dans la suite de la description, ce type d'oxyde de cuivre à valence mixte de type perovskite sera indifféremment appelé oxyde de cuivre ou perovskite) TX(iNlAT)yCU2O(2 + 3x/2 +y |ss avec ou x et y sont des nombres choisis dans l'intervalle fermé O et 4 avec la contrainte x + y = 4. De préférence, x est au moins égal à I
T représente un élément dont la valence la plus élevée est 3 et présent à cette dernière valence dans la structure ; de préférence, le numéro atomique de cet élément est supérieur à 20.Les éléments donnant les meilleurs résultats sont ceux de l'ancien groupe des terres rares, c'est-à-dire les lanthanides (à l'exception du cérium) l'yttrium et le scandium, aUxquels on ajoute le bismuth, le thallium et leurs mélanges
MAT représente un métal divalent et est dans son état de valence le plus élevé quand il y en a plusieurs. En particulier, les alcalino-terreux auxquels on ajoute les éléments qui leur sont voisins et le cuivre ainsi que leur mélange. Les alcalino-terreux préférés sont le baryum, le strontium et le calcium ; lorsque MAT représente le cuivre, d'une part cet élément n'est pas seul, et d'autre part, il intervient rarement pour une valeur supérieure à 1 dans la valeur de y
6 est l'excédent d'oxygène par rapport à la stoechiométrie.As an indication, and without this being in any way limiting, one can give the general appearance of the formula of copper oxides with mixed valence derived from perovskite (in the following description, this type of copper oxide with mixed valence of perovskite type will be indifferently called copper oxide or perovskite) TX (iNlAT) yCU2O (2 + 3x / 2 + y | ss with or x and y are numbers chosen in the closed interval O and 4 with the constraint x + y = 4. Preferably, x is at least equal to I
T represents an element whose highest valence is 3 and present at this latter valence in the structure; preferably, the atomic number of this element is greater than 20. The elements giving the best results are those of the old group of rare earths, that is to say the lanthanides (with the exception of cerium) l yttrium and scandium, to which bismuth, thallium and their mixtures are added
MAT represents a divalent metal and is in its highest valence state when there are several. In particular, the alkaline earths to which the elements which are adjacent to them and copper and their mixture are added. The preferred alkaline earths are barium, strontium and calcium; when MAT represents copper, on the one hand this element is not alone, and on the other hand, it rarely intervenes for a value greater than 1 in the value of y
6 is the excess oxygen relative to the stoichiometry.

Il est parfois égal à zéro.Sometimes it is zero.

En effet, les structures de type spécifié ci-dessus sont des structures dont le réseau est déficitaire en oxygène. Pour pallier ce déficit, ces structures cristallines absorbent un excédent d'oxygène par rapport à la stoechiométrie, c'est cet excédent qui donnerait aux structures leur propriété supraconductrice. Indeed, the structures of the type specified above are structures whose network is deficient in oxygen. To overcome this deficit, these crystal structures absorb an excess of oxygen compared to stoichiometry, it is this excess which would give the structures their superconductive property.

L'oxygène ainsi fixé, bien qu'il soit fortement ancré dans le réseau cristallin, peut jouer un râle d'oxydant vis-à-vis de matériau ou de milieux réducteurs. Par exemple, il peut être absorbé par des substrats réducteurs du type silicium ou être relargué lentement en atmosphère de vide très poussé. The oxygen thus fixed, although it is strongly anchored in the crystal lattice, can play a rattle of oxidant with respect to material or reducing media. For example, it can be absorbed by reducing substrates of the silicon type or be released slowly in a very high vacuum atmosphere.

Pour pallier ces difficultés selon la demande de brevet principal, il a été proposé de recouvrir les éléments perovskites d'une couche de nitrure d'épaisseur convenable. To overcome these difficulties according to the main patent application, it has been proposed to cover the perovskite elements with a layer of nitride of suitable thickness.

Cette technique, qui a un caractère très général, peut s'appliquer aussi bien aux perovskites pures qu'aux perovskites dans lesquelles l'oxygène a été partiellement substitué par de l'azote, et peut permettre de protéger les perovskites qui ne sont pas supraconductrices, pour d'autres emplois qui ne sont pas impliqués par cette propriété, permet d'obtenir selon la revendication 1 de la demande de brevet principal "un matériau composite caractérisé par le fait qu'il comporte une phase oxyde de cuivre à valence mixte du type perovskite déficitaire en oxygène, en contact avec une phase nitrure".  This technique, which is very general in nature, can be applied to both pure perovskites and perovskites in which oxygen has been partially substituted by nitrogen, and can protect perovskites which are not superconductive , for other uses which are not involved in this property, makes it possible to obtain according to claim 1 of the main patent application "a composite material characterized in that it comprises a copper oxide phase with mixed valence of perovskite type deficient in oxygen, in contact with a nitride phase ".

Parmi les perovskites qui présentent un intérêt particulier, il convient de citer celles dont la formule générale est
I3i2(MAT)n+îCunO#n+#+ b où MAT est un métal alcalino-terreux ou un mélange de métaux alcalino-terreux et n un entier choisi entre 1 et 2.Among the perovskites which are of particular interest, mention should be made of those whose general formula is
I3i2 (MAT) n + îCunO # n + # + b where MAT is an alkaline earth metal or a mixture of alkaline earth metals and n an integer chosen between 1 and 2.

De préférence, ledit métal alcalino-terreux est choisi dans le groupe constitué par le strontium, le calcium et le baryum et leur mélange. Preferably, said alkaline earth metal is chosen from the group consisting of strontium, calcium and barium and their mixture.

Parmi cette famille de composés, celle qui correspond à la structure
Bi2Sr2CuO6 + , et celle a pour formule Bi2Sr2CaCu208 +6
L'application de la technique décrite et revendiquée dans la demande de brevet principal a conduit a des matériaux composites satisfaisant. Toutefois, on a constaté que les meilleurs résultats étaient obtenus lorsque la température du traitement thermique c) était de p#référence inférieure à 800 C. Among this family of compounds, that which corresponds to the structure
Bi2Sr2CuO6 +, and that has the formula Bi2Sr2CaCu208 +6
The application of the technique described and claimed in the main patent application has led to satisfactory composite materials. However, it has been found that the best results are obtained when the temperature of the heat treatment c) is at p # reference less than 800 C.

Si l'on désire toutefois maintenir une température plus élevée, qui devra toutefois rester compatible avec la résistance des nitrures, il convient alors de procéder le traitement thermique en deux étapes, une première étape que l'on pourra qualifier d'homogénéisation par diffusion à une température qui pourra être plus élevée de 8000C, suivie par une deuxième étape de recuit à température nettement inférieure 8000C et ce, sous une pression de préférence élevée d'oxygène, par exemple une pression partielle d'oxygène comprise entre 10 et 1000 kPa, de préférence entre 100 et 1000 kPa. If, however, it is desired to maintain a higher temperature, which must nevertheless remain compatible with the resistance of the nitrides, it is then necessary to carry out the heat treatment in two stages, a first stage which can be described as homogenization by diffusion at a temperature which may be higher by 8000C, followed by a second annealing step at a much lower temperature 8000C and this, under a preferably high oxygen pressure, for example a partial oxygen pressure of between 10 and 1000 kPa, preferably between 100 and 1000 kPa.

Selon le présent perfectionnement, on a également trouvé qu'il était souhaitable de chauffer la phase dérivée de la perovskite de manière directe et non au travers du support et du porte-échantillon. Pour ce faire, l'on peut faire appel aux techniques de chauffage par laser, balayant la surface de la couche de perovskite déposée après l'étape b).  According to the present improvement, it has also been found that it is desirable to heat the phase derived from perovskite directly and not through the support and the sample holder. To do this, we can use laser heating techniques, scanning the surface of the perovskite layer deposited after step b).

Cette technique permet de déposer des perovskites pour lesquelles la température préférée de traitement thermique est supérieure à la température de résistance des nitrures et/ou du substrat. Il s'établit en effet un gradient de température entre la perovskite et le porte-échantillon qui permet à la couche de nitrure de résister tout en ayant une
température convenable pour le traitement thermique de ladite perovskite. This technique makes it possible to deposit perovskites for which the preferred heat treatment temperature is higher than the resistance temperature of the nitrides and / or of the substrate. A temperature gradient is established between the perovskite and the sample holder which allows the nitride layer to resist while having a
temperature suitable for the heat treatment of said perovskite.

Claims (4)

REVENDICATIONS fi est l'excédent d'oxygène par rapport à la stoechiométrie, et n est un entier choisi entre 1 et 2. fi is the excess oxygen over the stoichiometry, and n is an integer chosen between 1 and 2. B#2(MAT)n+I S ou MAT est un métal alcalino-terreux ou un mélange de métaux alcalino-terreux B # 2 (MAT) n + I S or MAT is an alkaline earth metal or a mixture of alkaline earth metals 1. Matériau composite selon l'une des revendications 1 à 6 prises séparément du brevet principal, caractérisé par le fait que ladite phase oxyde de cuivre à valence mixte du type pérowskite déficitaire en oxygène correspond à la formule générale  1. Composite material according to one of claims 1 to 6 taken separately from the main patent, characterized in that the said copper oxide phase with mixed valence of the oxygen-deficient perowskite type corresponds to the general formula 2. Matériau composite selon la revendication I, caractérisé par le fiat que ledit métal alcalino-terreux est choisi dans le groupe constitué par le strontium, le calcium et le baryum. 2. Composite material according to claim I, characterized by the fact that said alkaline earth metal is chosen from the group consisting of strontium, calcium and barium. 3. Matériau composite selon les revendications 1 et 2 prises séparément, caractérisé par le fait que ledit oxyde de cuivre à valence mixte répond à la formule  3. Composite material according to claims 1 and 2 taken separately, characterized in that said copper oxide with mixed valence corresponds to the formula Bi2 Sr2 CuO6 + Bi2 Sr2 CuO6 + 4. Matériaux selon les revendications 1 et 2, prises séparément, caractérisé par le fait que ledit oxyde de cuivre à valence mixte a polir formule  4. Materials according to claims 1 and 2, taken separately, characterized in that said copper oxide with mixed valence to polish formula Bi2 Sr2 Cal Cu2O8 +  Bi2 Sr2 Cal Cu2O8 +
FR898900156A 1988-01-29 1989-01-09 NOVEL COMPOSITE MATERIAL, MANUFACTURING METHOD AND APPLICATION Expired - Lifetime FR2641530B2 (en)

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FR898900156A FR2641530B2 (en) 1988-01-29 1989-01-09 NOVEL COMPOSITE MATERIAL, MANUFACTURING METHOD AND APPLICATION
EP89901861A EP0397743A1 (en) 1988-01-29 1989-01-27 New composite material comprising a perowskite-type phase and a nitride phase, process for producing it and electrical assemblies containing it
JP1501727A JPH03503157A (en) 1988-01-29 1989-01-27 A novel composite material having a perovskite phase and a nitride phase, its manufacturing method, and electrical components containing the same
PCT/FR1989/000028 WO1989007344A1 (en) 1988-01-29 1989-01-27 New composite material comprising a perowskite-type phase and a nitride phase, process for producing it and electrical assemblies containing it

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FR8801059A FR2626569A1 (en) 1988-01-29 1988-01-29 New composite material comprising a phase of perovskite type and a nitride phase, process of manufacture and electrical systems containing it
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WO1988010009A1 (en) * 1987-06-09 1988-12-15 E.I. Du Pont De Nemours And Company Improved process for making superconductors

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US3600218A (en) * 1968-05-15 1971-08-17 Ibm Method for depositing insulating films of silicon nitride and aluminum nitride
AU599223B2 (en) * 1987-04-15 1990-07-12 Semiconductor Energy Laboratory Co. Ltd. Superconducting ceramic pattern and its manufacturing method
CA1326976C (en) * 1987-05-26 1994-02-15 Satoshi Takano Superconducting member
FR2617645B1 (en) * 1987-07-03 1989-10-20 Thomson Csf DEVICE IN SUPERCONDUCTING MATERIAL AND METHOD FOR PRODUCING THE SAME

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WO1988010009A1 (en) * 1987-06-09 1988-12-15 E.I. Du Pont De Nemours And Company Improved process for making superconductors

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CHEMICAL ABSTRACTS, vol. 109, no. 26, 26 décembre 1988, page 766, résumé no. 242016w, Columbus, Ohio, US; C.M. SUNG et al.: "Microstructure of the superconducting phase (85 K) in bismuth strontium calcium copper oxide", & PROC. - ANNU. MEET., ELECTRON MICROSC. SOC. AM. 1988, 46th, 876-7 *
JOURNAL OF THE LESS-COMMON METALS, vol. 144, 1988, pages L1-L3, Elsevier Sequoia, Lausanne, CH; S. KEMMLER-SACK et al.: "Neuer Hoch-Tc-supraleiter im system Bi-Pb-Sr-Ca-Cu-O" *
MATERIALS LETTERS, vol. 6, nos. 11,12, juillet 1988, pages 438-443, Elsevier Science Publishers B.V., Amsterdam, NL; L.M. FALTER et al.: "Thermal processing of ceramic superconductors in the system Bi-Ca-Sr-Cu-O" *
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JPH03503157A (en) 1991-07-18

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