JP2535303B2 - Ultra fine particle dispersed glass and its manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrafine particle-dispersed glass material and a method for producing the same, and more particularly to an infrared transmission filter glass, a colored glass, an optical device such as a coloring agent for glass, etc., which utilizes a nonlinear optical effect The present invention relates to an ultrafine particle-dispersed glassy material applicable to optical and electronic materials and a method for producing the same.

[0002]

2. Description of the Related Art It is well known that ultrafine particles having a size of metal smaller than several tens of nanometers have properties which are completely different from those of bulk metal, such as structure, lattice specific heat and spin susceptibility. Among these, there are colored glass and filter glass as a dispersion of ultrafine particles of gold or silver metal or CdS _x Se _1-x semiconductor in glass. It is also known that a colored glass filter, which is a colored glass of this type, exhibits a non-linear optical characteristic, and is attracting attention as a material applicable to electronic materials for optical switches and optical computers. The reason why the colored glass has the nonlinear optical property is that the energy band is discretized due to the quantum confinement effect, and it is interpreted that the third-order nonlinear property is increased due to the band filling effect or the exciton confinement effect.

As a method for producing such fine particle-dispersed glass, generally known are a sol-gel method, a dissolution precipitation method, a sputtering method and an ion implantation method.

[0004]

However, in general, the sol-
The gel method not only takes a very long time to obtain fine particle-dispersed glass, but it is difficult to prevent the aggregation of metal or semiconductor colloidal particles, and a further serious problem is that the concentration of fine particles is limited. It was difficult to obtain a high concentration. Further, it is difficult to increase the content concentration of fine particles even by the sol-gel-combustion method. Furthermore, not only is it difficult to control the particle size of the fine particles by the precipitation method and the sputtering method, but it is also difficult to increase the content concentration of the fine particles. And in the ion implantation method,
The device was large and not suitable for mass production, and it was difficult to increase the concentration of fine particles. Moreover, Cu ₂
A method for obtaining a glass in which O fine particles are deposited has not yet been put into practical use, and a glass in which Cu ₂ O fine particles are deposited has not been proposed.

As described above, in the conventional method, since the content concentration of the metal or semiconductor fine particles is low, the material has a small third-order nonlinear susceptibility χ ⁽³⁾ . Generally, for materials with a large third-order nonlinear susceptibility χ ⁽³⁾ , the incident light intensity required to induce an optical bistable response can be small,
It is said that not only high integration is possible, but also fast response switches are possible. For this reason, attention is focused on particles having a high concentration of fine particles and a large third-order nonlinear susceptibility χ ⁽³⁾ .

In addition, in the ultrafine particles of semiconductor, non-linearity
The trapped excitons, which are said to have a large effect on
It only exists in a space that is 3-4 times the Bohr radius.
Yes. A well-studied semiconductor is the ultrafine particle size.
CdS-CdSe with a diameter of several tens of nm has a Bohr radius
Since it is about several nanometers, you can take full advantage of the advantages of ultrafine particles.
Not available. To maximize the use of ultrafine particles,
Or to get more excitons, Bohr radius
Is desired to be small. Therefore, the Bohr radius is small
CuBr (1.25 nm), CuCl (0.7 nm)
Has been recently noticed and studied. Similarly, Bohr radius
Cu as a small semiconductor₂O (0.7 nm) is the spotlight
Although it is bathed, since Cu easily reacts in glass, C
uO, Cu²⁺, Cu⁺, Cu, etc.
Degree Cu₂Glass with ultrafine O particles deposited and dispersed
I haven't been able to get it. The present invention has such problems
Of Cu, especially Cu₂O ultrafine particles
Concentrate these ultrafine particles while standing and dispersing
Particle Dispersion Glass with Nonlinear Optical Properties
A strip and a method for producing the same are provided.

[0007]

That is, a feature of the present invention is that in an ultrafine particle-dispersed glassy material comprising ultrafine particles of metal oxide and MO _x , the ultrafine particles have a particle size of 1 to 50 nm. Cu ₂ O, and each of the ultrafine particles is M
O _x (M is an amphoteric element selected from Al, Ge, Sn, Sb, Ga, Pb or Ti, Fe, Nb, Ta,
Metal element selected from Cd, In , Cr and Mn , x
Is 0.1 to 3) and is surrounded by an amorphous inorganic substance, and the content of the ultrafine particles is 90 mol% at the maximum.

The present invention also provides ultrafine particles of metal oxide,
In an ultrafine particle-dispersed glassy material comprising MO _x and M′O _y which is a third component forming a glass skeleton, the ultrafine particles are Cu ₂ O having a particle size of 1 to 50 nm, and each of the ultrafine particles is MO _x (M is Al, Ge, Sn, Sb,
Amphoteric element selected from Ga and Pb or Ti and F
e, Nb, Ta, Cd, In , Cr, Mn, an amorphous inorganic substance composed of a metal element, x is 0.1 to 3 and M′O _y (M ′). Is selected from Si, B, P
It is an element , and y is 0.1 to 3), and includes the ultrafine particle-dispersed glassy material in which the content of the ultrafine particles is 90 mol% at the maximum. In addition, the present invention provides ultrafine particles of C
A mixture of a polymer composite obtained by dispersing u ₂ O in a polymer without agglomerating it and an organometallic compound is dissolved in an organic solvent, applied on a substrate, and dried to form a film. The method also includes a method for producing a glassy material in which ultrafine particles are dispersed after sintering.

In addition, the polymer composite forms a thermodynamically metastable polymer layer obtained by evaporating and solidifying a melted polymer or super-quenching, and copper is formed on the surface of the polymer layer. After the layers are brought into close contact with each other, the polymer layer is heated at a temperature not higher than the melting temperature to stabilize the polymer layer, whereby Cu ₂ O which is made into ultrafine particles from the copper layer is dispersed in the polymer without agglomeration. It was obtained. Then, M'is added to the mixture of the polymer composite and the organometallic compound.
A third component forming a glass skeleton represented by (M ′ is an element selected from Si, B and P) may be mixed.

In the method for producing a glassy material in which ultrafine particles are dispersed according to the present invention, a step of obtaining a polymer composite in which ultrafine particles of Cu ₂ O are evenly dispersed in a polymer and a mixture thereof with an organometallic compound Is dissolved in an organic solvent, coated on a substrate to form a dried film, and then sintered. First, in obtaining a polymer composite, the first is to form the polymer layer into a thermodynamically metastable state. Specifically, this is a vacuum evaporation method in which a polymer is heated in a vacuum to melt and evaporate to solidify a polymer layer on a substrate, and the polymer is melted at a melting temperature or higher and immediately kept in this state. A method of melting and quenching by pouring into liquid nitrogen or the like to rapidly cool and then depositing a polymer layer on the substrate, or dissolving the polymer in a solvent (concentration 60% or less, preferably 20% or less) and coating it on the substrate Later, while maintaining a constant temperature in a closed container,
High-speed desolvation method to remove solvent by degassing at high speed (240 l / min or more) and freezing to remove solvent by degassing at low temperature (20 ° C or less, preferably 0 ° C or less) at high speed There is a drying method. In this high-speed solvent removal method and freeze-drying method,
As the amount of solvent decreases, the polymer tries to return to a stable structure, but if the desolvation rate is high, it cannot return to a stable structure, and thermodynamically metastable molding is possible.

In the case of the vacuum deposition method, a vacuum degree of 10 ⁻⁴ to 10 ⁻⁶ Torr and a deposition rate of 0.1 to 100 μm / min, preferably 0.
At 5 to 5 μm / min, a polymer layer can be obtained on a substrate such as glass. In the melt-quenching and solidification method, a polymer is melted and cooled at a rate equal to or higher than a critical cooling rate specific to the polymer,
Obtain a polymer layer. The resulting polymer layer is placed in thermodynamically metastable <br/> state, shifts over time to a stable state.

The polymer used in the present invention is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET),
Polyvinyl alcohol, polyphenylene sulfide (P
PS), polystyrene (PS), polycarbonate, polymethylmethacrylate, etc., and those having a molecular cohesive energy of 2000 cal / mol or more are preferable. This polymer includes a crystalline polymer and an amorphous polymer which are usually called. Regarding the molecular cohesive energy, the Chemical Handbook, edited by the Chemical Society of Japan (edited in 1974)
890, page 890.

Subsequently, the thermodynamically metastable polymer layer is transferred to the step of bringing a copper layer into close contact with the surface of the polymer layer. In this step, copper is vapor-deposited on the polymer layer by a vacuum vapor deposition apparatus, or the copper layer is laminated on the polymer layer by a method of directly adhering a copper plate to the polymer layer.

The composite in which the copper layer and the polymer layer are in close contact is heated at a temperature not lower than the glass transition point of the polymer and not higher than the melting temperature to bring the polymer layer into a stable state. as a result,
Copper is 100 nm or less and becomes Cu ₂ O ultrafine particles having a maximum particle size distribution in the range of 1 to 10 nm and diffuses and permeates into the polymer layer. This state is maintained until the polymer layer is completely relaxed. Subsequently, the copper layer adhering to the polymer layer also decreases in thickness and eventually disappears. The ultrafine particles are distributed in the polymer layer without being aggregated.

The obtained polymer composite is mixed and dissolved in a solvent consisting of an organic solvent such as metacresol, dimethylformamide, dichloromethane, formic acid and the like, and an ultrafine particle dispersion paste in which ultrafine particles of Cu ₂ O are uniformly dispersed To Since the ultrafine particles have a small particle size and have an interaction with the polymer, separation, precipitation and aggregation of the ultrafine particles do not occur in the paste. In this case, the content of Cu ₂ O ultrafine particles is 0.01 to 80% by weight.

Subsequently, an organometallic compound selected from metal alkoxides , organometallic complexes, and organic acid metal salts is prepared, and metacresol, dimethylformamide,
Dissolve in an organic solvent such as dichloromethane or formic acid, and add C
mixing the u 2 _O ultrafine particles dispersed paste. Of course,
In the case of the present invention, the mixture of the polymer composite and the organometallic compound may be simultaneously dissolved in the organic solvent.

[0017] Metal alkoxide <br/> of the organic metal compound is displayed in the general formula _{M- (O-C n H 2n} + 1) m, tetraethoxy titanium Specifically, triethoxy aluminum, triethoxy antimony, tetra There are ethoxy germanium, tetraethoxy tantalum, diethoxy tin, tetra i-propoxy titanium, tri i-propoxy aluminum, tri i-butoxy aluminum, penta n-butoxy tantalum, tetra i-aminoxy tin and the like. Examples of the organometallic complex of the organometallic compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetylacetate), and aluminum oxine complex. Examples of organic acid metal salts of organic metal compounds include aluminum benzoate and iron naphthenate.

In addition, in the present invention, an organic compound containing an element represented by M ′ as a third component (where M ′ is Si, B,
It is also possible to use an element selected from P, which is an element that forms a glass skeleton), and this can improve the strength of the produced film. Specifically, tetra i-propoxysilane, triethyl borate, tristearyl borate, triphenyl borate, tricresyl phosphate, triphenyl phosphate, iproniazide phosphate, diphenyl phosphate, phosphonoacetic acid, phosphoramidon, di n-butyl phosphate. , Triethyl phosphate, tri-n-amyl phosphate and the like. The third component not only increases the strength of the film, but also improves the chemical durability. This addition amount is 0.1 to 90 mol%.

A mixture obtained by dissolving the polymer composite thus prepared and an organometallic compound in an organic solvent or a mixture obtained by dissolving the polymer composite, the organometallic compound and the organic compound forming the glass skeleton in an organic solvent Was thoroughly stirred and then applied to a substrate such as a glass plate and dried by removing the organic solvent in the air at 60 to 120 ° C. for 10 minutes, or dried in a closed container while degassing. Subsequently, the sample thus obtained was sintered by three methods.

The first is a method in which the sample is sintered at once in a weakly oxidizing atmosphere. Specifically, an inert gas such as N ₂ , CO ₂ , Ar or the like and an oxygen concentration of 0.01 to 1.0% are used. This is a method of sintering at a temperature of 300 ° C. or higher in an atmosphere consisting of O ₂ and the Cu ₂ O fine particles are fixed to the glass matrix by one firing.

Secondly, the sample containing Cu ₂ O is added with N ₂ ,
300 ° in an atmosphere consisting of an inert gas such as CO ₂ and Ar and O ₂ with an oxygen concentration of 0.01% or less, or under reduced pressure.
Cu fine particles reduced by heating at a temperature of C or higher are fixed and baked in a glass matrix, and then this sample is heat-treated at a temperature of 100 to 300 ° C. in an oxidizing atmosphere to convert Cu fine particles into Cu ₂ O fine particles. It is a method of oxidizing.

Thirdly, the sample containing Cu ₂ O is added with N ₂ ,
Inert gas such as CO ₂ and Ar and oxygen concentration of 1.0% or more,
Alternatively, by sintering in air at a temperature of 300 ° C. or higher, organic components are decomposed and removed to oxidize Cu ₂ O fine particles into CuO fine particles, which are fixed and baked in a glass matrix, and then this sample is N ₂ , Heat treatment is performed at a temperature of 100 to 300 ° C. in a mixed gas of H ₂ or CH ₄ or CO having a concentration of 0.01% or more as a reducing gas such as an inert gas such as CO ₂ or Ar,
This is a method of reducing CuO fine particles to Cu ₂ O fine particles.

In the obtained ultrafine particle-dispersed glassy material,
The ultrafine particles of Cu ₂ O are fixed in the film without causing agglomeration of the ultrafine particles due to the interaction with Al-O- or Ti-O-, and causing large grain growth. Surrounding Al-O
-Or-Ti-O-cannot be crystallized freely due to the interaction with ultrafine particles and forms amorphous glass. That is, the composition of the ultrafine particle-dispersed glassy material is such that each of the Cu ₂ O ultrafine particles has MO _x (M is Al, Ge, Sn, Sb, G).
Amphoteric element selected from a and Pb or Ti and F
e, Nb, Ta, Cd, In , Cr, Mn , x is 0.1 to 3) surrounded by an amorphous inorganic material, Content rate is 1 to 90
Mol%. Further, in the case of three components, Cu ₂ O ultrafine particles, MO _x , and M′O _y (M ′ is an element selected from Si, B, and P, which is the third component forming the glass skeleton And y is 0.1 to 3), and the Cu ₂ O ultrafine particle content is 1 to 90 mol%.

[0024]

In the present invention, since the mixture of the polymer composite obtained by dispersing the Cu ₂ O ultrafine particles and the organometallic compound is fired, the ultrafine particles are MO- (M is an amphoteric element). Alternatively, the ultrafine particles do not agglomerate due to the interaction with the metal element) and are fixed therein without large grain growth, and the surrounding M-O- is due to the existence of the ultrafine particles and their interaction. As a result, it cannot be crystallized freely, and an amorphous glass is produced. Therefore, in the fired product, the concentration of ultrafine particles can be increased, and a material having a high nonlinear susceptibility can be obtained. Further, in the present invention, since the firing temperature can be made relatively low, the substrate is not damaged.

[0025]

Next, the present invention will be described in more detail with reference to specific examples. The evaluation method in this example is as follows.

1. Chemical state of ultrafine particles in glassy material The chemical state of ultrafine particles in glassy material was measured with Cu ₂ O.
The X-ray diffraction method is used because the ultrafine particles of are crystalline. This X-ray diffractometer is a RINT 1200 manufactured by Rigaku Corporation equipped with a thin film attachment, and the compound is determined by obtaining an X-ray diffraction pattern by the 2θ method at an incident fixed angle of 1 °.

2. Ultrafine particles, product content This was calculated from the mixture of raw materials in terms of mol%. All organic components were decomposed and removed during the sintering process, and all inorganic components were not vaporized or lost.

3. Particle size This is a value obtained by calculating the full width at half maximum of the main peak of the compound seen in the X-ray diffraction pattern obtained in 1 and calculating the size of the crystal body from Scherrer's formula.

4. Based on the X-ray diffraction pattern obtained in Structure 1 of glassy component, it was determined whether or not there were diffraction peaks other than ultrafine particles. When there is no diffraction peak or when a broad halo is observed, it is assumed to have an amorphous structure.

5. Optical characteristics The optical absorption spectrum of the sample formed on the soda glass substrate was evaluated using a U3300 type spectrophotometer (manufactured by Hitachi, Ltd.).

Example 1 and Comparative Example 1 Using a vacuum vapor deposition apparatus, 5 g of polymer pellets of nylon 11 were placed in a tungsten board and 10 ⁻⁶ Torr.
Depressurize to. Then, a voltage is applied to heat the tungsten board in a vacuum to melt the polymer, and the polymer is melted on the substrate (glass plate) placed on the top of the tungsten board.
A polymer layer of a vapor deposited film having a thickness of about 5 μm was obtained at a rate of about 1 μm / min at a degree of vacuum of ⁻⁴ to 10 ⁻⁶ Torr. The molecular weight of this polymer layer is about 1/2 to 1/10 of that of the polymer pellet.

Further, the copper chip was put in a tungsten board, heated and melted, and vapor deposition was performed at a vacuum degree of 10 ⁻⁴ to 10 ⁻⁶ Torr to deposit a copper vapor deposition film on the polymer layer. This was taken out from the vacuum vapor deposition apparatus and left in a constant temperature bath kept at 120 ° C. for 10 minutes to obtain a composite. As a result, this polymer composite contained about 6 Cu ₂ O ultrafine particles.
The content was 0% by weight, and the size was 4 to 8 nm.

The tetra i- propoxytitanium (Example) As the polymer composite and an organometallic compound, well stirred tetra profile <br/> Pokishishiran (Comparative Example) was dissolved in meta-cresol at a predetermined weight ratio After applying this on a soda glass substrate, it was placed in a closed container, and this was dried at 120 ° C for 10 minutes while degassing with a rotary pump to remove the solvent.

Then, as Method 1, the sample is fired in N ₂ gas having an O ₂ concentration of 0.05% at 500 ° C. for 20 minutes. As Method 2, first, the mixture was baked under reduced pressure of 10 ⁻⁵ Torr at 300 ° C. for 20 minutes under reduced pressure, fixed in a glass matrix with Cu fine particles to remove organic components, and then at 150 ° C. in the atmosphere. , Heat treatment for 60 minutes, Cu
To Cu ₂ O. Then, as Method 3, first, the above sample was fired in the atmosphere at 500 ° C. for 20 minutes to form Cu.
After fixing in a glass matrix with fine particles in the state of O to remove organic components, heat treatment was performed at 150 ° C. for 10 minutes in an N ₂ atmosphere having a H ₂ concentration of 0.1% to convert CuO to Cu ₂
Reduce to O. The properties of the glassy material thus obtained are shown in Table 1.

[0035]

[Table 1]

FIG. 1 shows the X-ray diffraction patterns of the fired films of Example 1-2 and Comparative Example 1-2. Example 1-2 and Comparative Example 1
-2, the diffraction peak of Cu (111) is seen in each of
It shows that Cu ₂ O was reduced to Cu. Furthermore,
In Comparative Example 1-2, the Cu (111) peak became sharp, which indicates that the reduced Cu particles grew and could not be fixed in the glass matrix in the state of ultrafine particles. On the other hand, in Example 1-2, it is found that the Cu (111) peak is broad and is fixed in the glass matrix while maintaining the ultrafine particle state even after firing. Since no diffraction peaks attributed to oxides of Si and Ti are seen in FIG. 1, these oxides are considered to have an amorphous structure.

FIG. 2 shows X-ray diffraction patterns before and after the low temperature oxidation treatment of the fired film in Example 1-2. In this fired film, Cu is fixed in the glass matrix in the form of ultrafine particles. By heat treatment in air at 150 ° C for 60 minutes,
Cu is oxidized to Cu ₂ O and still maintains an ultrafine particle state. Also, be extended processing time up to 15 hours, changes in the diffraction pattern is not observed, Cu from Cu ₂ O
Oxidation to O and aggregation of ultrafine particles did not occur.

FIG. 3 shows the optical absorption spectra of the fired films of Example 1-2 and Comparative Example 1-2. In the fired film of Comparative Example 1-2, Cu ₂ O grains grow and the polymer composites are formed. 6 on the long wavelength side
The rising shoulder (arrow in the figure) also shifts to the long wavelength side from around 00 nm. This is similar to the absorption spectrum of bulk Cu ₂ O thin films. Then, in Example 1-2 in which the Cu ₂ O ultrafine particles could be fixed in the glass matrix, the shoulder (arrow in the figure) was the same as that of the polymer composite, and absorption on the long wavelength side was gradually decreased. , Shows that the redness increases as the absorbance on the long wavelength side increases. This change is considered to be due to the interaction between Cu ₂ O microcrystals and the oxide surrounding them.

Example 2 A film-like glassy material was obtained by the method 2 in which the compounding amount of the polymer composite obtained in Example 1 was changed and the baking method was used. The properties of the glassy material thus obtained are shown in Table 2 .

[0040]

[Table 2]

As a result, in this example, it is understood that Cu ₂ O fine particles can be fixed in the glass matrix at a high concentration.

[0042]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, by firing a mixture of a polymer composite obtained by dispersing ultrafine particles of Cu ₂ O and an organometallic compound, the ultrafine particles are converted into MO particles.
_The ultrafine particles are surrounded by an amorphous inorganic substance composed of _X and do not aggregate due to the interaction with MO-, and are fixed in the ultrafine particles while keeping the particle size at the time of the raw material. Where M-
O-cannot be crystallized freely due to the presence of ultrafine particles and the interaction with them, and forms amorphous glass. Therefore, in the fired product, the concentration of ultrafine particles can be increased, and a material having a large nonlinear susceptibility can be easily obtained in an extremely short time.

[Brief description of drawings]

FIG. 1 shows X-ray diffraction patterns of fired films of Example 1-2 and Comparative example 1-2.

FIG. 2 shows X-ray diffraction patterns of a fired film in Example 1-2 before and after low temperature oxidation treatment.

FIG. 3 shows light absorption spectra of fired films of Example 1-2 and Comparative example 1-2.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, adult, 4-11-807, Sumiyoshidai, Higashinada-ku, Kobe City Jin Misaki, Examiner (56) Reference JP-A-5-270861 (JP, A)

Claims (6)

(57) [Claims] 1. An ultrafine particle-dispersed glassy material comprising ultrafine particles of metal oxide and MO _x , wherein the ultrafine particles are Cu ₂ O having a particle size of 1 to 50 nm, and each of the ultrafine particles has MO _x ( M is an amphoteric element selected from Al, Ge, Sn, Sb, Ga, Pb or Ti, Fe, Nb, T
a, Cd, In , Cr, Mn , x is 0.1 to 3) surrounded by an amorphous inorganic substance, and the content of the ultrafine particles is 90 mol% at maximum. An ultrafine particle-dispersed glassy material characterized by being present. 2. An ultrafine particle-dispersed glassy material comprising ultrafine particles of metal oxide, MO _x , and M′O _y which is a third component forming a glass skeleton, wherein the ultrafine particles have a particle size of 1 to 50 nm. Cu ₂ O, and each of the ultrafine particles is M
O _x (M is Al, Ge, Sn, Sb, Ga, Pb, C
Amphoteric element selected from r and Mn or Ti and F
e, Nb, Ta, Cd, In, an amorphous inorganic substance made of a metal element, x is 0.1 to 3, and M′O _y (M ′ is selected from Si, B and P). And y is 0.1 to 3), and the content of the ultrafine particles is 90 mol% at maximum. 3. A polymer composite obtained by dispersing ultrafine particles of Cu ₂ O in a polymer without aggregating,
A method for producing an ultrafine particle-dispersed glassy material, which comprises dissolving a mixture with an organometallic compound in an organic solvent, coating the solution on a substrate, drying the film to produce a film, and then sintering the film. 4. The method for producing an ultrafine particle-dispersed glassy material according to claim 3, wherein the organometallic compound is selected from metal alkoxides , organometallic complexes, and organic acid metal salts. 5. A polymer composite forms a thermodynamically unstable polymer layer obtained by evaporating and solidifying a melted polymer or super-quenching, and copper is formed on the surface of the polymer layer. After the layers are brought into close contact with each other, the polymer layer is heated at a temperature not higher than the melting temperature to stabilize the polymer layer, whereby Cu ₂ O which is made into ultrafine particles from the copper layer is dispersed in the polymer without agglomeration. The method for producing an ultrafine particle-dispersed glassy material according to claim 3, which is obtained. 6. A glass skeleton represented by M ′ (M ′ is an element selected from Si, B and P) is formed in the mixture of the polymer composite and the organometallic compound. 4. The method for producing an ultrafine particle-dispersed glassy material according to claim 3, wherein the third component is mixed.