JP4111931B2 - Electrically conductive complex oxide crystal compound and production method thereof. - Google Patents

Description

The present invention has the formula _{12Ca 1-X Sr X O ·} 7Al 2 O 3 (x = 0~1) composition represented by or a transparent glass having a composition obtained by adding a specific cationic elements in the composition (hereinafter, "C"
a-Sr—Al—O-based transparent glass ”. The present invention relates to a compound oxide crystal compound having a composition approximately equal to that of the glass and crystallizing electrical conductivity and a method for producing the same.

In 1970, H.C. B. Bartl et al., 12CaO ·, an alumina-calcium compound.
7Al ₂ O ₃ (hereinafter referred to as “C12A7” where appropriate) is in a unit cell containing two molecules 66
It has been shown that there is a peculiar feature that two of the oxygen atoms are included as “free oxygen” in the space in the cage existing in the crystal (Non-patent Document 1). Thereafter, it was clarified that this free oxygen can be replaced by various anions.

Hosono, one of the present inventors, made 12CaO · 7Al ₂ O ₃ synthesized by a solid-phase reaction at a temperature of 1200 ° C. in the air using CaCO ₃ and Al ₂ O ₃ or Al (OH) ₃ as raw materials.
By measuring the electron spin resonance of the crystal, it was discovered that O ₂ ^{− of} about 1 × 10 ¹⁹ atoms / cm ³ was included in the crystal, and a part of free oxygen was in the form of O ₂ ⁻ . Proposed a model in the cage (Non-patent Document 2).

Hosono et al., One of the present inventors, newly found that this free oxygen can be substituted with various anions such as O ₂ ⁻ , O ⁻ , and OH ⁻ , and the compound or its isomorphic compound itself,
A patent application was filed for an invention relating to the production method and use of the compound (Patent Documents 1 to 4).

Furthermore, Hosono et al., H the C12A7 powder or isomorphic compound is mayenite type compound ^- After inclusion and by irradiating ultraviolet light thereto, by inclusion of the electrons in the cages, the compounds Was found to be able to impart electrical conductivity, and a patent application was filed for an invention relating to the compound itself, a production method thereof, and an application of the compound (Patent Document 5).

In the manufacturing method in which H ⁻ is included in the crystal and irradiated with ultraviolet rays, electrons are generated only in the portion of the crystal irradiated with ultraviolet light, the electrons are included in the cage, and the electrons move in the cage. This causes electrical conduction. However, the electrons could not be included up to the inside of the powder or crystal in the ultraviolet non-irradiated region.

Hosono et al. Developed a method for producing a C12A7 single crystal (see Patent Document 6), and by exposing the crystal to an alkali metal vapor, electrons can be included in the cage to impart conductivity to the crystal. And applied for a patent on the compound itself, its production method, and an invention relating to the use of the compound (Patent Document 7).

In this production method, a free oxygen abstraction reaction from the C12A7 crystal that is in a solid state is used, and in this reaction, diffusion of oxygen inside the solid becomes a rate-limiting process,
It takes a long time to include a sufficient amount of electrons.

On the other hand, in the melt state of C12A7 at a high temperature, the present inventors do not have a diffusion-determining process of oxygen inside the solid in the drawing-out reaction of free oxygen, and compared with the solid state,
He had the knowledge that a rapid free oxygen extraction reaction would proceed.

However, usually, under an oxygen-free atmosphere, a 3CaO.Al ₂ O ₃ (hereinafter referred to as C3A) phase and a CaO · Al ₂ O ₃ (hereinafter referred to as CA phase), which are decomposition products, from the melt of C12A7 composition. It was known that C12A7 crystals were not generated (Non-patent Document 3).

In contrast, Hosono et al., One of the inventors of the present invention, is a reaction that occurs on the surface by reducing the surface area of the starting material by using a hydrostatic press that has a dense structure compared to powder. Melting the hydrostatic press of C12A7 powder in a reducing atmosphere under the knowledge that the oxygen extraction reaction in a certain sublimation process can be moderated and the formation of decomposition products can be suppressed, and further cooled and solidified in the atmosphere Thus, a method for producing a C12A7 compound in which oxygen in the cage is replaced with electrons has been invented and a patent application has been filed (Patent Document 8). In addition, the present inventors have found that C12A7 or its isomorphic compound thin film can be implanted with inert gas ions, and that free oxygen can be replaced with electrons by the knock-on effect, and a patent application has been filed (Patent Document 8).

Furthermore, the present inventors clarified the conditions for producing the conductor C12A7 compound or its isomorphic compound from the melt state, and have filed a patent application regarding the production method (Patent Document 9). C12A
A compound in which all free oxygen in the cage of 7 and its isomorphic compound is substituted with electrons is called an electride compound because the electrons play the role of anions.

Electride compounds are described in J. Org. L. The concept first proposed by Dye was first realized with a compound in which crown ether was used as a cation and electrons as an anion (Non-Patent Document 4). It is known that electride exhibits electrical conductivity by hopping of electrons contained as anions. Subsequently, several organic compound electrides were found, but these compounds are all stable compounds only at a low temperature of about 100K or less and are unstable compounds that react with air and water. C12A7 electride is the first electride compound that is stable at room temperature and has been found to be applicable as a cold electron emitter, a reducing agent, etc., and a patent application has been filed for an invention related thereto (Patent Document 8).

Moreover, Hosono et al., One of the present inventors, uses CaCO ₃ and Al (OH) ₃ as raw materials, and SiO 2
₂ was melted in an alumina crucible at a temperature of 1200 ° C. to 1450 ° C., and C
An a-Al-O-based glass was prepared and found to have photosensitivity by ultraviolet rays (Non-Patent Document 5).
). Furthermore, Hosono et al., One of the present inventors, held Ca—Al—O glass containing no silicon in a carbon crucible at 1550 ° C. for 4 hours, and then rapidly cooled to 800 ° C. to produce a transparent glass. It has been found that it exhibits photochromic properties (Non-Patent Document 6). Further, a patent application has been filed for finding that Tb ³⁺ is added to the glass to function as an afterglow material. (Patent Document 10)

Japanese Patent Laid-Open No. 2002-3218 JP 2002-316867 A JP 2003-128415 A JP 2003-238149 A WO03 / 089373 JP 2003-40697 A JP 2004-26608 A Japanese Patent Application No. 2003-183605 (PCT / JP04 / 001507) Japanese Patent Application No. 2004-37203 Japanese Laid-Open Patent Publication No. 2000-63245 H.B.Bartl and T.Scheller, Neuses Jarhrb. Mineral, Monatsh. 1970, 547 H. Hosono and Y. Abe, Inorg. Chem., 26, 1193, (1987) P.P.Williams, Acta Crystallogr., Sec. B, 29, 1550 (1973) F.J.Tehan, B.L.Barrett, J.L.Dye, J.Am.Chem.Soc., 96,7203-7208 (1974) H. Hosono, K. Yamazaki, and Y. Abe, J. Am. Ceram. Soc. 70, 867 (1987) H. Hosono, N. Asada, and Y. Abe, J. Appl. Phys. 67, 2840 (1990)

Conventionally, CaO and / or SrO typified by an alumina-calcium compound and Al ₂ O
_In the solid solution system ₃ , it was difficult to obtain a compound having high electrical conductivity at room temperature. However, recently, as mentioned above, (1) 12CaO · 7A that includes hydrogen anions
l ₂ O ₃ or H to the isomorphic compounds ^- ions was inclusion, a method of irradiating ultraviolet rays, (1) a method of the single-crystal sample of the compound is heat-treated with an alkali metal vapor and (3) the thin film sample of the compound (4) cooling the melt of the compound in a reducing atmosphere;
It was shown that C12A7 or its isomorphic compound having permanent electrical conductivity can be produced by the solidification method.

However, the method (1) has a great advantage in that it is possible to write a patterned electric conduction region using ultraviolet rays, but ultraviolet irradiation is necessary, and the temperature exceeds the temperature at which the inclusion hydrogen anion is released from the solid. When the sample is exposed, there is a drawback that the electrical conductivity is lost. Also,(
The method 2) is characterized in that an electride in which free oxygen is completely substituted with electrons can be produced, but on the other hand, it requires a single crystal and has a drawback that it takes a long time to produce. Further, the method (3) has an advantage that an electric conduction pattern can be written on a thin film, but it can be applied only to a thin film sample, and there is a disadvantage that an expensive ion implantation apparatus is required. The method (4) has the advantage that it can be mass-produced, but it is difficult to control the atmosphere in the melt state, the temperature and the temperature control in the cooling process, and produces an electrically conductive compound in a high yield. Has the disadvantage of being difficult.

As a result of repeated research on a method for producing an electrically conductive compound having a compound composition obtained by adding impurities to C12A7 or an isomorphous compound thereof, and further adding an impurity to the compound,
Discovered that high-efficiency compounds with high electrical conductivity exceeding 1 S / cm can be produced by a process of producing transparent glass from a molten state in a carbon crucible and crystallizing the glass in an oxygen-free atmosphere. did.

From the analysis of the light absorption spectrum, Raman spectrum, X-ray diffraction spectrum and the like of the compound, it was found that the obtained conductive compound was a crystal of C12A7 or an isomorphous compound thereof. In addition, from the electrical conductivity and light absorption spectrum, the cage in the crystal has 10 ²⁰ cm.
^It was found that a high concentration of electrons ^{exceeding -3} was included.

Furthermore, 12Ca _x Sr _{1-x, which} is difficult to produce by solid phase reaction using the process.
_{· 7Al 2 O 3 (x =} 1~0) compounds could be synthesized in high yield. In addition, Mg, Ba, rare earth metals, transition metals, Si, and Ge ions, which are difficult to add in the solid phase reaction, could be easily added.

That is, this invention consists of the following.
₍₁₎ in _{12Ca 1-X Sr X O ·} 7Al 2 O 3 compound having a composition represented by (x = 0 to 1) or _{12Ca 1-X Sr X O ·} 7Al 2 O 3 (x = 0~1) An electrically conductive composite oxide crystal compound obtained by crystallizing a composite metal oxide transparent glass obtained by melting and solidifying a mixture of two or more compounds mixed so as to have an average composition corresponding to the compound shown.
(2) The electrically conductive composite oxide crystalline compound according to (1) above, wherein the composite metal oxide transparent glass contains at least one element of Mg and Ba.
(3) The electrically conductive composite oxide crystal compound according to (1) above, wherein the composite metal oxide transparent glass contains at least one element selected from a rare earth metal element and a transition metal element. .
(4) The electrically conductive composite oxide crystal compound according to (1) above, wherein the composite metal oxide transparent glass contains at least one element of Si and Ge.

(5) 12Ca _1-X Sr _X O.7Al ₂ O ₃ (x = 0 to 1) or 12Ca _1-X Sr _X O.7Al ₂ O ₃ (x = 0 to 1) The raw material is either a fine powder of two or more compound mixtures mixed so as to have an average composition corresponding to the compound shown, as it is, a hydrostatic press-molded body of the fine powder, or a sintered body of the fine powder. As described above, in a container composed of a carbon member, after maintaining and melting at a temperature of more than 1470 ° C. and less than 1650 ° C., cooling to form a glass phase state to produce a composite metal oxide transparent glass, The composite metal oxidation
In a vacuum atmosphere of less than 1.5 Pa or in a dry inert gas atmosphere,
Electric conduction characterized in that it is crystallized while being kept in a temperature range of 950 ° C to 1470 ° C.
For producing a crystalline composite oxide crystal compound .

(6) to the raw material, Mg, Ba, rare earth metals, transition metals, Si, or Ge among the cationic elements of electrically conductive double above (5), characterized in that the addition of at least one element
A method for producing a compound oxide crystal compound .

The starting material for the (Ca, Sr) -Al-O-based transparent glass is represented by the formula 12Ca _1- XS
a compound having a composition represented by _{r X O · 7Al 2 O 3} (x = 0~1). That is,
Besides pure C12A7 compound with x = 0, pure S12A7 compound with x = 1, or Ca and S
A compound having a crystal structure equivalent to that of the C12A7 compound, such as a mixed crystal in which the mixing ratio of r is freely changed (these are abbreviated as “isomorphic compounds” in the present specification).

The starting material may be a mixture of two or more compounds mixed so as to have an average composition corresponding to a compound represented by 12Ca _1-X Sr _X O.7Al ₂ O ₃ (x = 0 to 1). That is, a compound mixture containing the amount of calcium (Ca) and the total amount of aluminum (Al) and strontium (Sr) at an atomic equivalent ratio of 12:14 may be used. Typical examples of the mixture are calcium carbonate and / or strontium carbonate and aluminum oxide.

Furthermore, the form of the starting material may be either the powder of the above compound or compound mixture as it is, a hydrostatic press-molded body of powder, or a polycrystalline sintered body. The amount of OH- ions that are initially included in these starting materials does not significantly affect the free oxygen extraction and substitution effect with electrons.

The Ca ²⁺ ions and Sr ²⁺ ions in the (Ca, Sr) -Al—O-based transparent glass are 1
Up to about 0 atomic% can be substituted with a plus divalent metal ion. Examples of metal ions include Mg ²⁺ , Ba ²⁺ , divalent rare earth metal ions, and transition metal ions. A
l ³⁺ ions are trivalent rare earth metal ions, transition metal ions, Si ⁴⁺ ions, or Ge
It can be partially substituted with ⁴⁺ ions. Mg, Ba, rare earth metal, transition metal, G
When e or Si is added, an oxide or simple substance of Mg, Ba, rare earth metal, transition metal, Ge or Si may be added to the above compound or compound mixture of the starting material.

Mg and / or Ba replace Ca or Sr, and as a result of the substitution, the lattice constant of the conductive compound finally obtained, that is, the size of the lattice changes, and the electric resistance changes through the change in electron mobility. To do. Addition of Ge and / or Si is expected to have an effect of easily forming a glass state, and the range of the glass composition can be expanded. Ge and / or Si also replaces Al ions and emits one electron per atom, which is trapped in the cage. Since the number of empty cages is 4 per 12Ca _1-X Sr _X O · 7Al ₂ O ₃ (x = 0 to 1),
The addition amount of Ge and Si was 14 in 12Ca _1-X Sr _X O.7Al ₂ O ₃ (x = 0 to 1).
It must be 4 or less for each Al ion. That is, a compound in which four Al ions out of 14 Al ions are replaced by Ge and / or becomes an electride in which electrons are contained in all cages.

In addition, rare earth metal ions and transition metal ions have a magnetic moment, and in a conductive crystal compound containing these magnetic ions, electric conduction is caused by an external magnetic field through the interaction between the magnetic moment and inclusion electrons. Can be controlled. As rare earth metals, Ce, Pr, N
Examples thereof include at least one element selected from the group consisting of d, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. In order to increase the magnetic moment, it is desirable that the addition amount is large. However, if the substitution amount for metal ions is 10 atomic% or more, a single crystal phase cannot be obtained. Therefore, the addition amount must be less than 10 atomic%. Don't be. Transition metals include Ti, V, and Cr
, Mn, Fe, Co, Ni, Cu, at least one element selected from the group.
In order to increase the magnetic moment, it is desirable that the addition amount is large. However, if the substitution amount for metal ions is 10 atomic% or more, a single crystal phase cannot be obtained. Don't be.

The (Ca, Sr) -Al-O-based transparent glass was obtained by adding at least one ion of Mg, Ba, rare earth metal, transition metal, Ge, and Si to the compound and compound mixture obtained as described above. A compound or compound mixture as a raw material is melted in a container composed of a carbon member and held until the composition becomes uniform, and then a glass phase state forming temperature, that is, about 8
It can be obtained by quenching to 00 ° C. or lower at a rate exceeding 500 ° C./min. As a container composed of a carbon member, any shape can be used, but a carbon crucible with a lid is simple. If the lid is not used, the exchange of air is intense, and if a large amount of oxygen is supplied, the concentration of electrons in the final product may not be increased. Alternatively, an alumina container with a lid may be used, and a carbon raw material may be added to the starting raw material and melted in an inert gas atmosphere.

In the (Ca, Sr) —Al—O-based transparent glass thus produced, a part of O ²⁻ is substituted and C ₂ ²⁻ and hydrogen are dissolved as negative ions (H− ions). The carbon ions are those in which a part of the carbon crucible is dissolved, and the hydrogen ions are those in which hydrogen ions contained as impurities in the carbon member or hydrogen gas contained in a trace amount in the atmosphere are dissolved.

C ₂ ²⁻ is an ion in which two hydrogen atoms are removed from acetylene (HCCH) having a triple bond between carbons, and the content is less than the amount of free oxygen in the crystallized compound, that is, 2/64 atoms. Less than equivalent. Further, the content of hydride ions (H-ions) is about the same as the content of C ₂ ²⁻ .

The melting temperature is preferably more than 1470 ° C. and less than 1650 ° C. At 1470 ° C. or lower, the compound does not melt, and at 1650 ° C. or higher, some components of the melt evaporate, resulting in different glass compositions. The retention time of the melt is preferably more than 1 minute and less than 2 hours. In less than a minute,
A glass having a uniform composition cannot be obtained, and C ₂ ²⁻ and hydride ions (H− ions) are not sufficiently absorbed. If the molten liquid is held at a high temperature for 2 hours or more, the carbon crucible is broken and the molten liquid cannot be held. If the rapid cooling rate is not more than 500 ° C./min, a glass phase state cannot be obtained and crystallization occurs. Preferably, the quench rate is greater than 800 ° C / min. Further, once the glass phase state is formed, crystallization does not occur at less than about 800 ° C.
Just cool down.

The obtained (Ca, Sr) -Al-O-based transparent glass is found to be an amorphous phase by X-ray diffraction. Moreover, it can confirm that it is an insulator which does not show electrical conductivity in a glass phase state. Further, it is confirmed from the Raman spectrum that C ₂ ²⁻ is dissolved in the glass produced in the carbon crucible.

Moreover, as a result of investigating the crystallization temperature of the obtained transparent glass by the differential thermal analysis method, as shown in FIG. 3, crystallization of the (Ca, Sr) -Al—O-based transparent glass starts from 950 ° C. I understood. Near the crystallization temperature, a gas is released and its main component mass is 2, 18, and 2
It was shown that H2 gas, water vapor and CO gas were released. Therefore,
The (Ca, Sr) —Al—O transparent glass obtained as described above can be crystallized by heating to 950 ° C. or higher in vacuum. (Ca, Sr) -Al-O-based transparent glass is 147
Since it melts above 0 ° C, the upper limit of the heating temperature is 1470 ° C. The heating time is preferably more than 1 minute and less than 1 hour. When the heating time is 1 minute or less, the temperature of the transparent glass is not uniform. Moreover, if it heats for 1 hour or more, a carbon member will be damaged.

Any method may be used to obtain a vacuum atmosphere during the crystallization treatment, but there is a method in which transparent glass is sealed in a thermally evacuated, chemically durable container such as quartz that has been evacuated. Convenient. In order to increase productivity, a method using a vacuum furnace is suitable. The oxygen partial pressure in the atmosphere needs to be less than 1 Pa. For this reason, the degree of vacuum in the atmosphere is 1.5 P.
It may be less than a.

It is confirmed by X-ray diffraction that the glass is crystallized by the heat treatment. It can also be confirmed from the X-ray diffraction pattern that the structure of the crystalline compound is a C12A7 compound or an isomorphous compound thereof. The inclusion of electrons in crystallized glass means that 1S /
This can be confirmed from the fact that it exhibits an electrical conductivity of more than cm and the presence of an absorption band having a peak at 2.8 eV in the light absorption spectrum. This light absorption band makes the crystal dark green.

In the crystallization process, a cage structure is formed with O ²⁻ and C ₂ ²⁻ contained in the glass as nuclei, and the C12A7 compound or its isomorphous compound is crystallized. As soon as the crystal is formed, O ²⁻ in the cage reacts with H ⁻ and C ₂ ²⁻ to form electrons with H ₂ O and CO. H ₂ O and CO are released to the outside from the crystal, leaving only electrons in the cage, resulting in the formation of conductive C12A7 or its isomorphic compound. The release of H ₂ O and CO gas near the crystallization temperature is confirmed from the mass analysis spectrum of the released gas. When crystallization is performed in an atmosphere containing oxygen, oxygen is taken into the crystal and reacts with electrons to become O ²⁻ , so that an electrically conductive compound cannot be obtained.

Hereinafter, the contents of the present invention will be specifically described by way of examples.
Fine powder of mixed crystal compound of C12A7 compound and Sr12A7 compound is 300 kg / cm ^2.
Then, the molded body additionally molded by a hydrostatic pressure press of 2000 kg / cm ² was used as a starting material for the (Ca, Sr) -Al—O-based transparent glass. The molded body is put in a carbon crucible with a lid, heated to 1600 ° C. at a heating rate of 1600 ° C./1 hour in the atmosphere, held for 1 hour, and then lowered to 800 ° C. at a cooling rate of 800 ° C./1 minute. Quenched and further cooled to room temperature.

As shown in FIG. 1A, the obtained compound is transparent in the visible light region, shows a typical amorphous X-ray diffraction pattern as shown in FIG. 2A, and has a crystal structure of C12A7. (Ca, Sr) -Al-O based transparent glass was confirmed. Further, the spectrum of C12A7 crystal was not shown from the Raman spectrum, and it was confirmed to be a glass phase. In the Raman spectrum, a Raman band is observed in the vicinity of 1870 cm ⁻¹ , and C ₂ ^2
- it was shown to have been included. These (Ca, Sr) -Al-O-based transparent glasses were insulators having no electrical conductivity.

Next, the (Ca, Sr) —Al—O-based transparent glass obtained as described above is put into a quartz tube having thermal durability and chemical durability, and sealed at a vacuum degree of 1 Pa, and 200 ° C. The temperature was raised to 1000 ° C. at a temperature rising rate of / 1 hour, held for 30 minutes, and cooled to room temperature at a temperature lowering rate of 200 ° C./1 hour. As a result, as shown in FIG. 1B, a dark green compound was obtained.

From the result of X-ray diffraction of the compound, it was shown that the obtained compound was a mixed crystal of C12A7 and Sr12A7, which are the same type of alumina / calcium compound. From the light diffuse reflection and electrical conductivity, it was found that the number of electrons included in the cage was 1 × 10 ²⁰ / cm ³ or more. FIG. 4 shows the temperature dependence of the electrical conductivity of the C12A7 / Sr12A7 mixed crystal compound. It exhibited an electrical conductivity of about 2 S / cm at room temperature, and showed the characteristics of a semiconductor that decreased with decreasing temperature.

The same experiment was repeated 5 times. In each case, a dark green C12A7 / Sr12A7 mixed crystal compound having an electric conductivity of about 2 S / cm at room temperature was obtained.

Comparative Example 1
A mixed crystal of C12A7 and Sr12A7 was produced under the same conditions as in Example 1 except that an alumina crucible was used instead of the carbon crucible used in Example 1. The crystal was white and was an electrical insulator.

Comparative Example 2
Instead of enclosing (Ca, Sr) -Al-O-based transparent glass in a quartz tube having thermal durability and chemical durability as in Example 1 and enclosing it at a vacuum of 1 Pa, air A mixed crystal of C12A7 and Sr12A7 was produced under the same conditions as in Example 1 except that the crystallization heat treatment was performed in the above. As a result, a white compound was obtained. The resulting compound was an electrical insulator.

When the electrically conductive complex oxide crystal compound of the present invention is made into a thin film, it is transparent at a film thickness of 1 μm or less and can be used as a transparent electrode. In addition, since the compound has localized electrons and is loosely coupled to the lattice, it can be easily extracted by applying an electric field from the outside and can be used as a cold electron emitter. Also, because it takes in oxygen easily,
It can be used as a reducing agent.

It is a drawing substitute optical photograph of the sample which crystallized (A) C12A7 system transparent glass and (B) this transparent glass. It is an X-ray diffraction pattern of (A) C12A7 series transparent glass and (B) the sample which crystallized this transparent glass. It is a graph which shows the crystallization temperature calculated | required from the differential thermal analysis method of C12A7 type | system | group transparent glass. It is a graph which shows the temperature change of the electrical conduction of the crystallized glass which crystallized C12A7 type | system | group transparent glass of the insulator.

Claims (6)

_{12Ca 1-X Sr X O ·} 7Al 2 O 3 compound having a composition represented by (x = 0 to 1) or _12Ca compound represented by _{1-X Sr X O · 7Al} 2 O 3 (x = 0~1) An electrically conductive composite oxide crystal compound obtained by crystallizing a composite metal oxide transparent glass obtained by melting and solidifying a mixture of two or more compounds mixed so as to have an average composition corresponding to. 2. The electrically conductive complex oxide crystal compound according to claim 1, wherein the complex metal oxide transparent glass contains at least one element of Mg and Ba. 2. The electrically conductive composite oxide crystal compound according to claim 1, wherein the composite metal oxide transparent glass contains at least one element selected from a rare earth metal element and a transition metal element. 2. The electrically conductive complex oxide crystal compound according to claim 1, wherein the complex metal oxide transparent glass contains at least one element of Si and Ge. _{12Ca 1-X Sr X O ·} 7Al 2 O 3 compound having a composition represented by (x = 0 to 1) or _12Ca compound represented by _{1-X Sr X O · 7Al} 2 O 3 (x = 0~1) Using as a raw material either a fine powder of a mixture of two or more compounds mixed so as to have an average composition corresponding to the above, a hydrostatic press-molded body of the fine powder, or a sintered body of the fine powder. A composite metal oxide transparent glass is manufactured by holding and melting at a temperature of more than 1470 ° C. and less than 1650 ° C. in a container composed of members to form a glass phase state by cooling the composite metal Oxide transparent
In a vacuum atmosphere of less than 1.5 Pa or in a dry inert gas atmosphere, the glass is 950
° C. and held at a temperature range of 1470 ° C. from and wherein Rukoto crystallized, electrically conductive composite
A method for producing an oxide crystal compound . 6. The electrically conductive complex acid according to claim 5, wherein at least one element of Mg, Ba, rare earth metal, transition metal, Si, or Ge cation element is added to the raw material.
A method for producing a chemical compound .