JP2012167191A - Inorganic composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic composition including a rare earth metal or/and a transition metal in the fourth period dispersed in an inorganic matrix having long-term light resistance and heat resistance with high concentration and uniformity, and a process for producing them at a low temperature and with easy moldability.SOLUTION: The inorganic composition includes at least one rare earth metal or/and a transition metal in the fourth period dispersed in the inorganic matrix, wherein a dispersed phase including the rare earth metal or/and the transition metal in the fourth period, to which another metal species is coordinated via oxygen, is formed.

Description

  The present invention controls the transmission, refraction, reflection, polarization plane rotation, and the like of incident light, and exhibits optical function application fields or magnetic functions that are excited by incident light and exhibit functions such as light emission (fluorescence) and amplification. The present invention relates to an inorganic composition containing a rare earth metal and / or a fourth periodic transition metal used in a magnetic functional application field, and further relates to a method for producing the inorganic composition.

  Rare earth elements have various applications in the fields of optical functions and magnetic functions, and are an essential element group for current science and technology. Since the application of cerium to gas lamp light-emitting materials at the end of the 19th century, red phosphors for television receivers CRT (europium, yttrium), scintillators for medical diagnostic X-ray CT (gadolinium, praseodymium), light control glass (neodymium, cerium) , Solid lasers (yttrium, neodymium), capacitors (yttrium, gadolinium), optical fiber amplifiers (erbium, praseodymium, terbium, dysprosium), magneto-optical disks (terbium, gadolinium), etc. ing. On the other hand, the fourth periodic transition metal is used as a fluorescent material for fluorescent lamps, mercury lamps, and cathode ray tubes, as is the case with rare earth metals. Moreover, it is used as various inorganic pigments by the absorption characteristic. Furthermore, many applications have been made as magnetic materials.

  The rare earth metal or / and the fourth periodic transition metal are often doped in the host material in the form of a rare earth ion or / and a fourth periodic transition metal ion, a rare earth oxide or / and a fourth periodic transition metal oxide, or the like. The As such a host material, glass, garnet crystal (YAG, YIG), or transparent ceramic material (YAG, yttria, zirconia, etc.) is used.

When used as a light emitting material, the rare earth metal and / or the fourth periodic transition metal are aggregated or extremely close to each other when the rare earth metal and / or the fourth periodic transition metal is doped at a high concentration. For this reason, such a method has a problem that it is difficult to dope at a high concentration because a phenomenon called “quenching” in which the light emission (fluorescence) ability is lowered occurs. In practice, the concentration of rare earth metal and / or the fourth period transition metal is substantially reduced. As a matter of fact, the concentration is only about 100 ppm at most. In addition, the doping to the inorganic host requires a high-temperature process such as molten glass, pulling a single crystal from the melt, or creating a high-density sintered body.
If it becomes possible to low-temperature-dope inorganic materials such as glass with rare earth metals and / or fourth-period transition metals used in various optical function application fields and magnetic function fields, doping glass on various substrates New applications with performance such as formation and economy will be possible.

As an example of dispersing high-concentration rare earth metal and / or fourth period transition metal in the field of optical function application, other metal species are coordinated to rare earth metal or / and fourth period transition metal via oxygen. Although compounding with an organic material using an inorganic dispersed phase is shown (Patent Document 1), it is essentially impossible to ensure light resistance and heat resistance over a long period of time because an organic material is used as a matrix. is there. Moreover, in the inorganic dispersed phase currently disperse | distributed to the organic polymer by patent document 1, the dispersed phase precursor as described in patent document 1 containing a rare earth metal or / and a 4th period transition metal (refer FIG. 1 of patent document 1). In the case where the substituent (R) is an alkylcarbonyl group such as an alkyl group or an acetyl group, the substituent (R) bonded to the coordination metal atom is dispersed in the organic polymer while being retained. It is a composite that contains organic substances in the dispersed phase.
If the dispersed phase precursor described in Patent Document 1 containing rare earth metal and / or the fourth period transition metal (see FIG. 1 of Patent Document 1) can be dispersed in the inorganic matrix, it is considered that the desired characteristics can be expressed. -It is difficult to disperse the dispersed phase precursor described in Patent Document 1 containing rare earth metal and / or fourth period transition metal in an inorganic matrix efficiently and at a high concentration by a combination of conventional techniques represented by the gel method. there were.

  In addition, the conventional glass and ceramics process requires heat treatment at a high temperature, and the target rare earth metal and / or the fourth period transition metal is not highly agglomerated by thermal diffusion of the constituent elements accompanying the heat treatment. It is difficult to disperse at a concentration.

  Therefore, development of a material capable of efficiently dispersing the rare earth metal and / or the fourth period transition metal in the inorganic matrix and a process having a low temperature and easy moldability is required.

International Publication WO2006 / 004187

It is difficult to maintain environmental stability such as light resistance, water resistance and heat resistance over a long period of time with a composite material in which a dispersed phase, which is a conventional technique, is dispersed in an organic polymer.
Further, the dispersed phase precursor described in Patent Document 1 (see FIG. 1 of Patent Document 1) containing the rare earth metal and / or the fourth period transition metal of Patent Document 1 is a substituent bonded to a coordination metal atom. (R) may contain an alkylcarbonyl group such as an alkyl group or an acetyl group, and there is a problem that if it is simply mixed in a medium, the composition contains an organic substance.
An object of the present invention is to provide an inorganic composition in which a rare earth metal and / or a fourth period transition metal is uniformly dispersed in an inorganic matrix having excellent environmental stability instead.
Another object of the present invention is to provide a manufacturing process having low temperature and easy moldability, which has been difficult to achieve with the conventional glass and ceramics processes.

The inventors of the present invention have made extensive studies in order to achieve the above object, and as a result, an inorganic composition in which at least one rare earth metal and / or a fourth periodic transition metal is dispersed in an inorganic medium, The present inventors have found that an inorganic composition in which a dispersed phase formed by coordinating another metal element with oxygen via a metal or / and a fourth period transition metal is effective, and has completed the invention.
That is, the present invention is characterized by having the following configuration.

[1] An inorganic composition in which at least one rare earth metal and / or a fourth periodic transition metal is dispersed in an inorganic medium, wherein the rare earth metal or / and the fourth periodic transition metal is at least one kind An inorganic composition, wherein a dispersed phase formed by coordinating a rare earth metal and / or a fourth periodic transition metal with another metal element via oxygen forms a dispersed phase in an inorganic medium.
[2] The inorganic composition as described in [1] above, wherein the dispersed phase has an average diameter of 0.1 to 50 nm.
[3] The metal element coordinated to the rare earth metal and / or the fourth period transition metal via oxygen is one or more metals selected from Group 3B, Group 4A, Group 5A, and Group 6A metals. The inorganic composition as described in [1] or [2] above, which is an element.
[4] Molar ratio (M2 / M1) of the rare earth metal or / and the fourth periodic transition metal (M1) and the metal element (M2) coordinated to the rare earth metal or / and the fourth periodic transition metal via oxygen ) Is 1 to 4, the inorganic composition according to any one of [1] to [3] above.
[5] The inorganic composition as described in any one of [1] to [4], wherein the inorganic medium is an inorganic amorphous medium derived from an inorganic polymer.
[6] The inorganic composition as described in [5] above, wherein the inorganic polymer is a silicon-containing polymer, a borazine polymer, or a borazine silicon polymer.
[7] The inorganic composition as described in [6] above, wherein the silicon-containing polymer is polysilazane.

According to the present invention, a rare earth metal and / or a fourth periodic transition metal in an inorganic matrix applicable to an optical function application field having sufficient transparency, long-term light resistance, moisture resistance and heat resistance, and a magnetic function field. Can be provided. Furthermore, it becomes possible to manufacture at a significantly lower temperature than conventional ceramics and glass. In addition, it is possible to form an inorganic composition in which a rare earth metal and / or a fourth period transition metal is dispersed in an inorganic matrix on various substrates including a resin substrate.
Compared with the case where it is dispersed in an organic polymer, a composite material having high environmental stability such as light resistance, moisture resistance and heat resistance can be formed. In addition, since the silica matrix is inherently superior in transparency compared to the organic polymer, it is very advantageous in an application utilizing light transmission.

The schematic diagram of the disperse phase precursor concerning this invention.

The emission spectrum of the inorganic composition film of Example 1 containing 0.5% by weight of Eu. (In the figure, x indicates noise caused by the device)

The excitation spectrum of the inorganic composition film of Example 1 containing 0.5% by weight of Eu. In the figure, chart (2) shows a partially enlarged view of chart (1). The arrow in the chart (1) indicates a peak due to the oxygen coordination field, and the arrow in the chart (2) indicates a peak due to the Eu ion. (In the figure, x indicates noise caused by the device)

  The inorganic composition of the present invention is an inorganic composition in which at least one rare earth metal and / or a fourth periodic transition metal is dispersed in an inorganic medium, wherein the rare earth metal or / and the fourth periodic transition metal is An inorganic phase characterized in that a dispersed phase formed by coordinating at least one kind of rare earth metal and / or a fourth periodic transition metal with another metal element via oxygen forms a dispersed phase in an inorganic medium. It is a composition.

  The amount of the rare earth metal and / or the fourth period transition metal in the inorganic composition is determined according to the purpose and is not particularly limited, but is preferably 100 ppm to 20%. According to the present invention, in a commonly used inorganic medium such as glass, single crystal, ceramics, etc., the upper limit of the doping amount is about 1000 ppm to suppress the aggregation of the doped metal, while the aggregation is suppressed. Can be added up to 20%.

  The average diameter of the dispersed phase in the inorganic composition is preferably 0.1 to 50 nm. When the inorganic composition according to the present invention is used for an optical material or the like, it is desirably optically transparent (transmissible). If the size of the dispersed phase exceeds 50 nm, it is not preferable because the decrease in transmittance due to scattering becomes remarkable. More preferably, it is 20 nm or less. Considering application as a bulk having a long optical amplification and light guide length, 10 nm or less is preferable.

  The metal element coordinated to the rare earth metal or / and the fourth period transition metal in the dispersed phase of the inorganic composition via oxygen is not particularly limited, but is preferably selected from Group 3B, Group 4A, Group 5A, and Group 6A metals. One or more metal elements.

In the present invention, the rare earth metal and / or the fourth periodic transition metal is coordinated through oxygen bonded to other metal atoms.
The dispersed phase of the present invention can be formed in an inorganic medium using a dispersed phase precursor schematically shown in FIG. The inorganic composition of the present invention comprises a rare earth metal or / and a fourth periodic transition metal (1) formed from a dispersed phase precursor shown in the figure and coordinated with other metal species (2) via oxygen. ) And a complex containing an inorganic medium (not shown). Here, what is important in the dispersed phase precursor is to reduce as much as possible the presence of the same kind of rare earth metal and / or the fourth period transition metal at adjacent positions via oxygen. Accordingly, the number and atoms of ligands composed of oxygen and other metal atoms are not fixed and are not strictly limited to the molecular structure as shown in FIG. 1 in terms of stoichiometry.
In addition, the inorganic composition of the present invention can have an association structure as long as the presence of the same kind of rare earth metal can be reduced as much as possible in an adjacent position through oxygen.

  The functional group R of the dispersed phase precursor shown in FIG. 1 is not particularly limited and is selected depending on the type of inorganic medium to be combined. It is possible to select for the purpose of improving the compatibility or reactivity with the inorganic medium. For example, R includes hydrogen, alkyl groups, alkylcarbonyl groups such as acetyl groups, and the like.

  It is preferable that the molar ratio (M2 / M1) of the rare earth metal or / and the fourth period transition metal (M1) and the coordination metal element (M2) in the dispersed phase of the inorganic composition is 1 to 4. When the molar ratio (M2 / M1) is less than 1, the dispersion effect of the rare earth metal and / or the fourth period transition metal (M1) cannot be maintained, and the aggregation of (M1) proceeds. The upper limit of the molar ratio (M2 / M1) is not particularly limited, but even if it is greater than 4, the effect does not change, and 4 or less is sufficient.

  The inorganic medium of the inorganic composition is not particularly limited as long as it can maintain transparency, can be formed at low temperature and can be easily molded. For example, an inorganic amorphous medium derived from an inorganic polymer such as a silicon-containing polymer, a borazine polymer, or a borazine silicon polymer is used.

Examples of the inorganic amorphous medium derived from an inorganic polymer include silicon nitride compositions derived from borazine polymers such as silicon oxide compositions derived from silicon-containing polymers, silicon carbide compositions, silicon oxycarbide compositions, Examples include silicon boron nitride compositions derived from borazine silicon polymers.
Preferably, a silicon-based composition derived from a silicon-containing polymer is used.

Polysilazane, polycarbosilane, polysiloxane polysilazane and the like are used as the silicon-containing polymer for inducing the silicon-based composition. Preferably, polysilazane is used. Polysilazane reacts with oxygen and moisture in the atmosphere and is converted to silicon oxide. In general, alkoxysilane and its polymer used in the sol-gel method are accompanied by large volume shrinkage when converted to silicon oxide by dehydration condensation reaction (Reaction Formula 1), whereas polysilazane is a nitrogen element in the molecule. By replacing oxygen with oxygen, conversion to silicon oxide (reaction formulas 2 and 3) proceeds, so that silicon oxide can be formed without volume shrinkage.
Si (OR) ₄ + 2H ₂ O → SiO ₂ + 4ROH (1)
_{- (SiH 2 NH) - +} 2H 2 O → SiO 2 + NH 3 ↑ + 2H 2 ↑ (2)
_{- (SiH 2 NH) - +} O 2 → SiO 2 + NH 3 ↑ (3)

  In the inorganic composition of the present invention, a solution containing a dispersed phase precursor obtained by coordinating an inorganic polymer and a rare earth metal or / and a fourth periodic transition metal with other metal species via oxygen is applied onto a substrate. It is manufactured by.

  The method for forming the dispersed phase precursor is not particularly limited as long as the metal coordination via oxygen to the target rare earth metal and / or the fourth period transition metal can be formed. For example, a method of mixing a rare earth metal or / and a fourth period transition metal raw material and a coordinating metal raw material, followed by heat treatment and pulverization (starting raw materials include metal salts, hydroxides, oxides, etc. ), A method of dissolving a rare earth metal or / and a metal salt capable of coordinating with the 4th period transition metal salt in a solvent, and then precipitating by precipitation, a rare earth metal or / and a 4th period transition metal salt in an organic solvent And a metal alkoxide capable of coordination.

  In order to obtain a nanometer-sized dispersed phase precursor, a method of reacting a rare earth metal or / and a fourth period transition metal salt with a metal alkoxide capable of coordination in an organic solvent is preferably used. The solvent used is not particularly limited, and any final product that forms a coordination structure can be dispersed in an inorganic medium, and any compound that can induce the inorganic medium is soluble and non-reactive. It may be used.

An aprotic solvent having no active hydrogen is preferred. Examples of such solvents include ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, ethylene glycol dimethyl ether and propylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran and dioxane; methyl acetate, ethyl acetate and propyl acetate. Esters; glycol derivatives such as 2-methoxyethyl acetate, propylene glycol 1-monomethyl ether 2-acetate; aromatic compounds such as benzene, toluene, xylene; hydrocarbon compounds such as pentane, hexane, heptane, cyclohexane; acetonitrile, etc. Is used.

  When polysilazane is used as a silicon-containing polymer, it is essential to use not only the polysilazane solvent but also the dispersed phase precursor solvent as an aprotic solvent. When a solvent having active protons is used, the active proton part in the solvent reacts with polysilazane, and the polymerization of polysilazane proceeds, so that a desired uniform coating solution capable of forming a film cannot be prepared.

  In order to form the dispersed phase precursor, it is possible to use a method of heating to the reflux temperature of the solvent, which is an effective means because it can often accelerate the reaction rate. It is also possible to control the size of the dispersed phase precursor by adding water to the resulting coordination product and hydrolyzing it.

As starting materials for rare earth metals and / or fourth period transition metals, mineral salts such as nitrates, sulfates, carbonates, chlorides, organic acid salts such as formates, acetates, oxalates, alkoxides, etc. are used. It is done. Considering the reduction of anionic impurities, it is preferable to use organic acid salts such as formate, acetate and oxalate and alkoxides. More preferably, acetate or alkoxide is used.
The acetate usually contains water of crystallization and can be used as it is depending on the type of metal to be coordinated, but it is preferable to perform a dehydration treatment before the reaction.

  The obtained dispersed phase precursor is mixed with an inorganic polymer solution that can be guided to an inorganic medium to produce the inorganic composition-forming liquid of the present invention.

By the mixing, the dispersed phase precursor and the inorganic polymer react, and the dispersed phase formed by coordination of the rare earth metal and / or the fourth period transition metal with other metal elements via oxygen forms the dispersed phase in the inorganic medium. An inorganic composition is produced.
In the case of the dispersed phase precursor shown in FIG. 1, the substituent represented by R in the figure is removed by reaction with the inorganic polymer, and an inorganic composition that is an inorganic substance having no substituent R is generated.
When the silicon-containing polymer is an inorganic polymer, the substituent R is separated from the rare earth metal and / or another metal element (M2) coordinated to the fourth periodic transition metal via oxygen. Bonding with silicon (Si) and bonding [-(M2) -O-Si-] can be performed, and an inorganic composition containing no organic compound group (R group) can be generated.

  When a dispersed phase precursor containing an alkoxide is used as a starting material, the reaction between the terminal alkoxyl group and the polysilazane proceeds very quickly, and therefore, rapid mixing may cause precipitation of the polymer. It is preferable to use a technique such as dropping a solution. When the reaction scale becomes large, it is also preferable to add dropwise while cooling the reaction vessel.

  After applying the mixed solution onto the substrate, the mixed solution is dried at a temperature at which the solvent can be removed to obtain an inorganic composition in which at least one rare earth metal and / or fourth period transition metal is dispersed in an inorganic medium.

  According to the method of the present invention, a reaction at a high temperature such as glass, single crystal, ceramics or the like that is usually used as an inorganic medium is unnecessary, so that it can be formed on a plastic substrate, a highly reactive glass substrate, or a silicon substrate. It becomes possible. When using an inorganic substrate such as glass or silicon that is usually used, heating at a temperature of about 500 ° C. is possible to promote the conversion of an inorganic polymer into an inorganic medium (in the case of polysilazane, conversion to silicon oxide). is there.

  By drying at a temperature at which the solvent can be removed, reaction by-products (hydrogen, ammonia, products containing the substituent R, etc.) can usually be removed together with the solvent.

  The method for applying the inorganic composition to the substrate is not particularly limited as long as it is generally used in a liquid phase method. For example, spin coating, dip coating, roll coating, screen printing, inkjet printing, etc. are used. It is done.

[Example 1]
<Preparation of dispersed phase precursor>
As a result of adding europium acetate dehydrated in toluene at 110 ° C. for 1 hour and tri-s-butoxyaluminum (Eu / Al = 3 mol, total oxide equivalent concentration of Eu and Al of 5% by weight) and refluxing for 12 hours, A colorless and transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic light scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 2 nm. In addition, the coordination of Al via oxygen to Eu was confirmed by the change in 27Al-NMR spectrum before and after the reaction of tri-s-butoxyaluminum.

<Preparation of inorganic composition>
As a silicon-containing polymer, “AQUAMICA” (20% xylene solution, manufactured by AZ Electronic Materials) was used. A toluene solution of the EuAl-containing dispersed phase precursor prepared by the above method was dropped into the silicon-containing polymer and stirred at room temperature for 2 hours to obtain a precursor liquid for forming an inorganic composition. The mixing ratio was adjusted so that the proportion of europium in the inorganic composition was 5% and 0.5% by weight with respect to the total solid content.
The obtained precursor liquid was deposited on Vycor glass (manufactured by Corning) by spin coating, and then dried and coined at 100 ° C. to form a colorless and transparent coating film. The film thickness was made in the range of 2 to 50 μm by changing the rotation speed of the spin coat. It was confirmed that the optical transparency was almost the same as the transmittance of the silicon-containing polymer.

<Fluorescence intensity measurement>
The fluorescence spectrum and the excitation spectrum were measured using a fluorimeter of the Eu-containing inorganic composition. By setting the excitation light to 380 nm, emission peaks attributed to Eu ions were observed at 590 nm and 613 nm (FIG. 2). In addition, in the excitation spectrum for the 614 nm peak, a broad peak attributed to the oxygen coordination field having a peak at 273 nm corresponding to the absorption of Eu ions was observed in the range of 350 to 450 nm (FIG. 3). . From this result, it was confirmed that even when doped with europium ions at a high concentration, quenching was suppressed and the emission process of europium was expressed.

<Environmental stability test>
The obtained inorganic composition was kept at 200 ° C. for 24 hours, and then a transmission spectrum and an emission spectrum were measured. No clear change was observed with the transmission spectrum and emission spectrum.

(Comparative Example 1)
An example in which environmental stability is compared with the organic-inorganic composite described in Patent Document 1 is shown as Comparative Example 1.

Europium acetate dehydrated under reduced pressure at 110 ° C. for 1 hour in propylene glycol α-monomethyl ether and tri-s-butoxyaluminum (Eu / Al = 3 mol, total oxide equivalent concentration of Eu and Al of 5% by weight) were added. The mixture was refluxed for a time to obtain a colorless and transparent solution. The particle size of the obtained reaction product was measured by a dynamic scattering method, and it was confirmed that the peak top of the particle size distribution was an inorganic dispersion material having a wavelength of 1.5 nm. Further, the coordination of Al via oxygen to Eu was confirmed from the change in 27Al-NMR spectrum before and after the reaction of tri-s-butoxyaluminum.
Hydroxypropyl cellulose (Nippon Soda Co., Ltd.) was used as the transparent organic polymer. This organic polymer and Eu-Al-containing composite nanoparticles prepared by the above method were mixed in ethyl cellosolve and stirred at room temperature for 2 hours to obtain a mixed solution. The mixing ratio was adjusted so that the ratio of Eu in the composite composition was 8% by weight with respect to the total solid content.
The obtained precursor liquid was formed into a film on Vycor glass (manufactured by Corning) by spin coating, and then dried at 100 ° C. to form a colorless and transparent coating film having a thickness of 10 μm. It was confirmed that the optical transparency was almost the same as the transmittance of the base polymer.

  The fluorescence spectrum and excitation spectrum of the obtained Eu-containing organic-inorganic composite were measured. The same emission and excitation spectra as in Example 1 were observed. When the obtained composite was kept at 200 ° C. for 24 hours, slight yellowing was confirmed. In the emission spectrum, formation of a broad emission band centering on 400 to 500 nm was confirmed.

  It was confirmed that Example 1, which is the inorganic composition of the present invention, is superior in environmental stability to Comparative Example 1. Therefore, the inorganic composition of the present invention can exert a particularly remarkable effect in applications in devices driven in harsh environments such as light emitting elements such as LEDs and solar cells.

[Example 2]
A composite film containing Eu was prepared by changing to tetra-i-propoxytitanium instead of tri-s-butoxyaluminum in the same manner as in Example 1, and a colorless transparent film was formed.
By measurement with a fluorimeter, emission peaks attributed to Eu ions were observed at 590 nm and 613 nm as in Example 1.

Example 3
<Preparation of inorganic dispersed phase>
As a result of adding terbium acetate dehydrated in toluene at 110 ° C. for 1 hour and tri-s-butoxyaluminum (Tb / Al = 3 mol, total oxide equivalent concentration of Eu and Al of 5% by weight) and refluxing for 12 hours, A colorless and transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic light scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 2.1 nm.
<Preparation of composite of inorganic dispersed phase and silicon-containing polymer>
As a silicon-containing polymer, “AQUAMICA” (20% xylene solution, manufactured by AZ Electronic Materials) was used. A toluene solution of a TbAl-containing inorganic dispersed phase prepared by the above method was dropped into the silicon-containing polymer and stirred at room temperature for 2 hours to obtain a precursor liquid for forming a complex. The mixing ratio was adjusted so that the proportion of terbium in the composite composition was 5% by weight with respect to the total solid content.
The obtained precursor liquid was deposited on Vycor glass (manufactured by Corning) by spin coating, and then dried and coined at 100 ° C. to form a colorless and transparent coating film. It was confirmed that the obtained coating film was almost equivalent to the transmittance of the silicon-containing polymer and ensured optical transparency.
<Fluorescence intensity measurement>
The fluorescence spectrum and excitation spectrum of the Eu-containing inorganic composite were measured using a fluorometer. By setting the excitation light to 380 nm, emission peaks attributed to Tb ions were observed at 489 nm and 543 nm.

Example 4
<Preparation of inorganic dispersed phase>
As a result of adding erbium acetate dehydrated in toluene at 110 ° C. for 1 hour and tri-s-butoxyaluminum (Er / Al = 3 mol, total oxide equivalent concentration of Eu and Al of 5% by weight) and refluxing for 12 hours, A red-purple transparent solution was obtained. The particle size of the obtained reaction product was measured by a dynamic light scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 1.8 nm.
<Preparation of composite of inorganic dispersed phase and silicon-containing polymer>
As a silicon-containing polymer, “AQUAMICA” (20% xylene solution, manufactured by AZ Electronic Materials) was used. A toluene solution of an ErAl-containing inorganic dispersed phase prepared by the above method was added dropwise to this silicon-containing polymer and stirred at room temperature for 2 hours to obtain a precursor liquid for forming a complex. The mixing ratio was adjusted so that the ratio of erbium in the composite composition was 0.5% by weight with respect to the total solid content.
The obtained precursor liquid was formed into a film on Vycor glass (manufactured by Corning) by spin coating, and then dried and coined at 100 ° C. to form a red-purple transparent coating film. It was confirmed that the obtained coating film was almost equivalent to the transmittance of the silicon-containing polymer and ensured optical transparency.
<Fluorescence intensity measurement>
The emission spectrum was measured at 1.54 μm by irradiating the Er-containing inorganic composite with excitation light of 514.5 nm.

Example 5
<Preparation of inorganic dispersed phase>
As a result of adding nickel acetate dehydrated in toluene at 110 ° C. for 1 hour and tri-s-butoxyaluminum (Ni / Al = 2 mol, total oxide equivalent concentration of Ni and Al of 5% by weight) and refluxing for 12 hours, A green clear solution was obtained. The particle size of the obtained reaction product was measured by a dynamic light scattering method, and it was confirmed that the peak top of the particle size distribution was a composite nanoparticle of 2.8 nm.
<Preparation of composite of inorganic dispersed phase and silicon-containing polymer>
As a silicon-containing polymer, “AQUAMICA” (20% xylene solution, manufactured by AZ Electronic Materials) was used. A toluene solution of the NiAl-containing inorganic dispersed phase prepared by the above method was dropped into the silicon-containing polymer and stirred at room temperature for 2 hours to obtain a precursor solution for forming a complex. The mixing ratio was adjusted so that the proportion of nickel in the composite composition was 5% by weight with respect to the total solid content.
The obtained precursor liquid was formed into a film on Vycor glass (manufactured by Corning) by spin coating, and then dried and coined at 100 ° C. to form a transparent coating film having a greenish color. Absorption of ions corresponding to Ni ions was confirmed by measurement of the transmission spectrum.

Example 6
A composite film containing Ni was prepared in the same manner as in Example 5 using nickel acetate and pentaethoxyniobium as starting materials (Ni / Nb = 2 mol, the total oxide equivalent concentration of Ni and Nb being 5% by weight). . A greenish transparent film was formed, and absorption of ions corresponding to Ni ions was confirmed by measurement of the transmission spectrum.

INDUSTRIAL APPLICABILITY The present invention can be used as an optical functional material that controls the transmission, refraction, reflection, polarization plane rotation, and the like of incident light and is excited by incident light to exhibit functions such as light emission (fluorescence) and amplification. It can be used in various optical application fields using materials.
Examples of specific applications of the inorganic composition of the present invention include light control optical elements such as optical amplifiers, lenses, contrast-enhancing glass, and optical filters, light-emitting devices, solar cells, and the like.
In addition, the inorganic composition of the present invention can be used as a material in a magnetic function application field that exhibits a magnetic function.

DESCRIPTION OF SYMBOLS 1 Rare earth metal or 4th period transition metal 2 Other metal element coordinated to rare earth metal or 4th period transition metal through oxygen

Claims (7)

  An inorganic composition in which at least one rare earth metal and / or a fourth periodic transition metal is dispersed in an inorganic medium, wherein the rare earth metal or / and the fourth periodic transition metal are at least one rare earth metal or An inorganic composition characterized in that a dispersed phase formed by coordinating other metal elements with oxygen through the fourth period transition metal forms a dispersed phase in an inorganic medium.   The inorganic composition according to claim 1, wherein the dispersed phase has an average diameter of 0.1 to 50 nm.   The metal element coordinated to the rare earth metal and / or the fourth periodic transition metal via oxygen is one or more metal elements selected from Group 3B, 4A, 5A, and 6A metals. The inorganic composition according to claim 1 or 2, characterized in that   The molar ratio (M2 / M1) of the rare earth metal or / and the fourth periodic transition metal (M1) and the metal element (M2) coordinated to the rare earth metal or / and the fourth periodic transition metal via oxygen is: It is 1 to 4, The inorganic composition in any one of Claims 1-3 characterized by the above-mentioned.   The inorganic composition according to any one of claims 1 to 4, wherein the inorganic medium is an inorganic amorphous medium derived from an inorganic polymer.   The inorganic composition according to claim 5, wherein the inorganic polymer is a silicon-containing polymer, a borazine polymer, or a borazine silicon polymer. The inorganic composition according to claim 6, wherein the silicon-containing polymer is polysilazane.

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