JPH0859296A - Production of ultrafine particle-dispersed glass-like material - Google Patents

Abstract

PURPOSE: To obtain a glassy material prevented from growing grains without mutually aggregating ultrafine particles and incapable of freely crystallizing M-O (M is a metal) around the ultrafine particles because of mutual action with ultrafine particles by dissolving a mixture of ultrafine particle dispersion with an organometallic compound into an organic solvent, applying the solution to a substrate, preparing dried film and baking the film. CONSTITUTION: This method for producing ultrafine particle dispersed glass-like material is to dissolve an ultrafine particle dispersion obtained by separately dispersing ultrafine particles of a metal (e.g. Au having 10nm particle diameter) into a solvent (e.g. terpineol) and an organometallic compound (e.g. an metal alkoxide, an organometallic complex, or an organic acid metal salt) into an organic solvent, mix these dispersions, apply the mixture to a substrate such as glass plate, remove the organic solvent from the mixture at 60-120 deg.C for 10min in the air or degass and dry the mixture in a hermetically sealed vessel, prepare a flat film and carry out baking of the film at 300-800 deg.C. The resultant ultrafine particle-dispersed glass-like material does not cause aggregation because of its mutual action with a metal oxide such as AlO or TiO.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art It is well known that ultrafine particles having a size of a metal smaller than several tens of nanometers have characteristics completely different from those of bulk metals in terms of electronic structure, lattice specific heat, spin susceptibility and the like. Among these metals, gold, silver and CdS _x
It is known as a colored glass or a filter glass as a dispersion of a semiconductor composed of Se _{1 -x} ultrafine particles 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, metal colloid particles are added to and dispersed in a liquid silica sol obtained by hydrolyzing a metal alkoxide, which is then poured into a container for gelation and drying, Sol to be sintered
Gel method, or semiconductor fine particles such as Si dispersed in an alkoxide sol and dried to gelate the alkoxide, and then sintered, and obtained by coating the surface with oxide glass, and SiCl ₄ , GeCl ₄ , a sol-gel-combustion method in which hydrogen and oxygen are introduced into a glass raw material such as PCl ₃ and glass fine particles produced by combustion are mixed and fired,
Further, a precipitation method of precipitating fine particles in the glass by cooling and holding a glass melt containing CdSe or the like to a temperature not lower than the flowing temperature and not lower than the deformation temperature, and at least one of Cd source, S source, Se source and Te source powder. Powder and low melting point glass powder are mixed and sintered to produce a composite glass, and the composite glass is used as a target to obtain a fine particle-dispersed glass by the sputtering method, and a metal accelerated at high speed on a glass substrate. An ion implantation method is known, in which ions are collided and implanted, and then the grain size is controlled by heat treatment.

[0004]

However, in general, the sol-
The gel method not only takes a very long time to obtain the fine particle-dispersed glass, but it is difficult to prevent the aggregation of the metal colloid particles, and the more serious problem is that the concentration of the metal fine particles is limited, It was difficult to adjust the concentration. Further, it was difficult to increase the content concentration of the metal fine particles even by the sol-gel-combustion method. Furthermore, not only is it difficult to control the particle size of the fine metal particles by the precipitation method and the sputtering method, but it is also difficult to increase the content concentration of the fine metal particles. In the ion implantation method, the apparatus is large and not suitable for mass production, and it is difficult to increase the content concentration of the metal fine particles.

In addition, recently, there are various problems as described above.
As a method for solving the above, Japanese Patent Laid-Open No. 6-115973
As disclosed in US Pat.
Of polymer composites and organometallic compounds dispersed in water
Is dissolved in an organic solvent, coated on a substrate and dried.
After the formation of the film
Manufacturing methods are known. However, ultrafine particle dispersed glass
When preparing a product, a polymer composite and an organometallic compound
In order to mix it evenly with the skeleton-forming components,
Polymer in compound and organometallic compound or skeleton-forming component
A solvent with good compatibility with is required. However,
Because the polymers in the compound are limited, organometallic compounds
Alternatively, there is a problem that the skeleton-forming component is naturally limited.
It was The present invention solves these problems.
Independently disperse ultrafine metal particles
Increase the concentration of ultrafine particles, and
Ultrafine particle dispersion that is not restricted by the species of the skeleton-forming component
A method for manufacturing a glass-like material is provided.

[0006]

That is, a feature of the present invention is that a mixture of an ultrafine particle dispersion liquid in which ultrafine particles of metal are independently dispersed in a solvent and an organic metal compound are dissolved in an organic solvent. This is a method for producing an ultrafine particle-dispersed glass-like material, which comprises coating this on a substrate to form a dried film, and then sintering the film. In the present invention, the organometallic compound is selected from metal alkoxides, organometallic complexes, and organic acid metal salts. Furthermore, the present invention provides a mixture of an ultrafine particle dispersion liquid in which ultrafine metal particles are independently dispersed in a solvent, and an organometallic compound, M ′.
A third component forming a glass skeleton, which is an organic compound containing an element represented by (M ′ is an element selected from Si, B, and P), may be mixed.

The ultrafine particle dispersion liquid in which ultrafine metal particles are independently dispersed in the solvent used in the present invention is at least Au, Pt, Pd, having a particle size of 10 nm or less, independently dispersed in a solvent such as α-terpineol, toluene. Ultrafine particles of precious metal selected from Rh and Ag, or Ti, V, Cr, Mn,
Fe, Ni, Cu, Zn, Cd, Y, W, Sn, Ge,
It contains ultrafine particles of a metal selected from In and Ga.

The ultrafine particles are described in, for example, Japanese Patent Laid-Open No. 3-342.
It is produced by a method called an in-gas evaporation method as disclosed in Japanese Patent Laid-Open No. 11. That is, it is obtained by introducing helium inert gas into the chamber to evaporate the metal, and cooling and condensing by collision with the inert gas. In this case, the organic solvent is used in the stage where the particles immediately after generation are in an isolated state. Is introduced to coat the surface of the particles. The amount of the metal ultrafine particles added can be selected according to the desired transmittance and is not particularly limited.

Subsequently, an organometallic compound selected from metal alkoxides, organometallic complexes, and organic acid metal salts is prepared, and this is treated with metacresol, dimethylformamide,
An organic metal compound such as cyclohexane, formic acid, α-terpineol, toluene, xylene and carbitol is dissolved in a soluble organic solvent, and this is mixed with the ultrafine particle dispersion. It is preferable to use the same solvent as the ultrafine particle dispersion liquid. Of course, in the case of the present invention, the mixture of the ultrafine particle dispersion liquid and the organometallic compound can be simultaneously dissolved in the organic solvent.

[0010] Metal alkoxide of the above organic metal compound is displayed in the general formula _{M- (O-C n H 2n} + 1) m, tetraethoxy titanium Specifically, triethoxy aluminum, triethoxy antimony, tetraethoxygermanium , 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. still,
M is an amphoteric element selected from Al, Ge, Sn, Sb, Ga, Pb or Ti, Fe, Co, Ni, Cu,
It is a metal element selected from Nb, Ta, Cd, In, Cr and Mn. Further, the organometallic complex of the organometallic compound includes ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl acetate),
There are aluminum oxine complexes and the like. Examples of organic acid metal salts of organic metal compounds include aluminum benzoate, iron naphthenate, copper octylate, and titanium stearate.

Further, in the present invention, together with the ultrafine particle dispersion liquid in which the ultrafine particles of the above metal are independently dispersed and the organometallic compound, the third component is represented by the general formula M '(M' is selected from Si, B and P). An organic compound containing an element forming a glass skeleton represented by (which is an element) can also be used, and thereby the strength of the formed film can be improved. 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 of an ultrafine particle dispersion in which the ultrafine particles of the metal thus prepared are independently dispersed and an organic metal compound are dissolved in an organic solvent, or the above dispersion, the organic metal compound and an organic compound forming a glass skeleton. After thoroughly stirring the mixture of and in an organic solvent, apply it to a substrate such as a glass plate, remove the organic solvent by drying in an air at 60 to 120 ° C for 10 minutes, or degas in a closed container. While drying, a flat film is prepared. The firing conditions are 300-
It is 800 ° C, preferably 300 to 600 ° C. Since the firing conditions are relatively mild, the soda glass can be used without damaging the substrate, for example, inexpensive soda glass. In addition, the firing is performed in the atmosphere because a glassy oxide is formed around the fixed ultrafine particles.

In the obtained ultrafine particle-dispersed glassy material, the ultrafine particles do not aggregate due to the interaction with the metal oxide such as Al-O- or Ti-O-, and the ultrafine particles grow large. Without being fixed in the membrane. The surrounding Al-O- or Ti-O- cannot crystallize freely due to the interaction with the ultrafine particles, forms amorphous glass, becomes the main component of the film, and transmits light well. It will be possible.

The composition of the above-mentioned ultrafine particle-dispersed glassy material is such that ultrafine particles of metal and MO _x (M is Al, Ge, Sn, Sb,
Amphoteric element selected from Ga and Pb or Ti and F
e, Co, Ni, Cu, Nb, Ta, Cd, In, C
Metal element selected from r and Mn, x is 0.1 to 3)
The amorphous ultrafine particles are composed of two components, and the content of the ultrafine particles is 90 mol% at maximum. The composition of the three-component glassy material is composed of ultrafine metal particles, MO _X , and M′O _y which is the third component forming the glass skeleton,
The content of the ultrafine particles is 90 mol% at the maximum.

[0015]

In the present invention, since the solvent of the ultrafine particle dispersion liquid in which the ultrafine particles of metal are independently dispersed can be freely selected,
There is no limitation on the kind of the third component forming the organometallic compound or the glass skeleton, and it is not necessary to finish the paste-like material in which each component is melted. Also, the ultrafine particles are M-
Due to the interaction with O- (M is an amphoteric element or a metal element), ultrafine particles are fixed in each other without agglomeration and large grain growth, and the surrounding M-O- with ultrafine particles. It cannot crystallize freely due to the interaction and forms an amorphous glass. Therefore, the concentration of ultrafine particles can be increased in the product, and a material having excellent nonlinear optical characteristics can be obtained. Further, in the present invention, since the firing temperature can be made relatively low, the substrate is not damaged.

[0016]

Next, the present invention will be described in more detail with reference to specific examples. The evaluation method for the glassy material used in this example is as follows. 1. Chemical state of ultrafine particles in glassy material The chemical state of ultrafine metal particles in glassy material is measured by X-ray diffractometry since the metal is a crystal. This X-ray diffractometer is RIGAKU's RI equipped with a thin film attachment.
The compound is determined by obtaining an X-ray diffraction pattern by the 2θ method with an incident fixed angle of 1 ° on NT1200.

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 obtaining the full width at half maximum of the main peak of the noble metal seen in the X-ray diffraction pattern obtained in 1 and calculating the size of the crystal body from Scherrer's equation.

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 UVIDEC-650 type spectrophotometer (manufactured by JASCO Corporation). The result is shown in FIG.

Example 1 An ultrafine particle dispersion liquid was prepared in which 50% by weight of ultrafine particles of gold were dispersed in α-terpineol. Tetra i-propoxy titanium / Ti as the dispersion liquid and the organometallic compound
(I-OC ₃ H ₇ ) ₃ was dissolved in α-terpineol in a predetermined weight ratio and stirred well, and this was coated on a soda glass substrate and then placed in a closed container, which was then placed at 120 ° C.
At 10 minutes, the solvent was removed and dried while degassing with a rotary pump. This sample is placed in a furnace at 500 °
C, firing was performed for 10 minutes to remove organic substances, and sintering was performed to obtain a film-like glass-like substance. Table 1 shows the properties of glassy materials
Shown in

[0022]

[Table 1]

As a result, the ultrafine gold particles of the glassy material maintain the same particle size as the ultrafine gold particles of the polymer composite after the heat treatment, and are fixed in the Ti—O—glass as they are. I understand that. Further, since the color tone of the film shows a colloidal color different from the red color of gold colloid, gold and Ti-O
It is presumed that − interacted. This interaction hinders the aggregation and grain growth of the ultrafine particles and fixes the ultrafine particles in the glass.

Further, X of the glass-like material according to Example 1-3
According to the line diffraction pattern, since the diffraction peak of gold was broad, it was revealed that the crystallite size was small and the particles were fixed as they were. In addition, since no diffraction peaks other than gold are seen, it can be seen that TiO _x has an amorphous structure. Further, according to the optical absorption spectrum of the glassy material according to Example 1-3, the absorption peak at about 530 nm found in the ultrafine particles of the dispersion liquid as the raw material is said to be due to the resonance absorption of the surface plasmon, It has a golden red color. In Example 1-3, the absorption peak moved to the long wavelength side near 620 nm. This phenomenon suggests that the plasmon band of Au was changed because Ti—O surrounding the Au ultrafine particles interacted with the surface plasmon of Au.

Example 2 The ultrafine particle dispersion liquid used in Example 1 and an aluminum oxine complex / Al (C ₉ H ₆ NO) ₃ as an organometallic compound.
Was dissolved in meta-cresol at a predetermined weight ratio and stirred well, and this was coated on a soda glass substrate and then placed in a closed container, which was degassed with a rotary pump at 120 ° C for 10 minutes. The solvent was removed and dried. This sample was baked in a furnace at 500 ° C. for 10 minutes to remove organic substances, and was sintered to obtain a film-like glass-like substance. Table 2 shows the properties of the obtained glassy material.

[0026]

[Table 2]

Further, the glassy material X according to Example 2-3 is used.
The line diffraction pattern shows that the diffraction peak of gold is broad, so that the crystallite size is small and the particles are fixed as they are. Further, since no diffraction peaks other than gold are seen, it is understood that AlO _x has an amorphous structure. Further, according to the light absorption spectrum of the glassy material according to Example 2-3, the absorption peak is 5 in this example.
The phenomenon extends widely from 30 nm to the long wavelength side, and this phenomenon suggests that the plasmon band of Au has changed because Al—O surrounding the ultrafine Au particles interacted with the surface plasmon of Au.

Example 3 Tetra i-propoxysilane / Si was added as a third component to the ultrafine particle dispersion liquid and the organometallic compound obtained in Example 1.
(I-OC ₃ H ₇ ) ₄ was dissolved in α-terpineol and stirred well, and this was coated on a soda glass substrate and then placed in a closed container, which was kept at 120 ° C. for 10 minutes.
The solvent was removed and dried while degassing with a rotary pump. This sample was dried in a furnace at 500 ° C. for 10 minutes to remove organic substances, and was sintered to obtain a film-like glass-like substance. The characteristics of the obtained glassy material are shown in Table 3.

[0029]

[Table 3]

6 mol% of Ti-O (Example 3-3),
Even when Al-O was as small as 12 mol% (Example 3-4), Au / T containing fixed gold ultrafine particles at a high concentration.
A three-component glass composed of i-O / Si-O or Au / Al-O / Si-O can be produced, and the strength of the obtained film can be increased and the chemical durability can be improved.

In addition, in the measurement results of the ultrafine particle-dispersed glassy materials according to the above-mentioned examples, (1) the resonance absorption due to the surface plasmon peculiar to the ultrafine particles appears, (2)
That only specific MO _X blocks grain growth of ultrafine particles,
(3) Change of plasmon band by transmitting light,
(4) M has a chemical structure close to its maximum oxidation state,
The results show that O _x is amorphous and (5) the content of ultrafine particles is 90 mol% at the maximum. Thus, ultrafine particles dispersed glassy material ultrafine particles and MO _X is,
It can be seen that M-O and the plasmons of the ultrafine particles electrostatically interact with each other at the interface of the ultrafine particles to form a glass-like substance containing 90 mol% of the ultrafine particles.

Comparative Example 1 The ultrafine particle dispersion liquid used in Example 1 alone was coated on a soda glass substrate and then placed in a closed container, which was then placed at 120 °.
The solvent was removed and dried while degassing with a rotary pump at C for 10 minutes. 500 samples of this sample in the furnace
The organic substance was removed by drying at ° C for 10 minutes and was sintered to obtain a film-like glass-like substance. Further, the X-ray diffraction pattern of the glassy material according to Comparative Example 1 suggests that this sample has a sharp peak, a large crystallite size, and grain growth.

Comparative Example 2 The ultrafine particle dispersion liquid used in Example 1 and the organometallic compound (M
-R) is dissolved in α-terpineol in a predetermined weight ratio and well stirred, and this is coated on a soda glass substrate and then placed in a closed container, which is kept at 120 ° C for 10 minutes.
The solvent was removed and dried while degassing with a rotary pump. This sample was dried in a furnace at 500 ° C. for 10 minutes to remove organic substances, and was sintered to obtain a film-like glass-like substance. Si as a non-metal element as M of M-R
Was used. Table 4 shows the properties of the obtained glassy material.

[0034]

[Table 4]

As a result, in the film obtained in Comparative Example 1, the ultrafine gold particles aggregated and grew during the heat treatment to form a gold-colored film. Further, in Comparative Example 2, when the organometallic compound (M = Si) that does not interact with the ultrafine particles was used, the aggregation of the ultrafine particles could not be prevented.

[0036]

As described above, in the present invention, the solvent of the ultrafine particle dispersion liquid in which the ultrafine particles of the metal are independently dispersed can be freely selected, and is limited to the species of the organometallic compound or the third component forming the glass skeleton. There is no need to finish it into a paste-like product in which each component is melted. Further, the ultrafine particles do not aggregate with each other, grain growth is prevented, and the surrounding M-O- cannot crystallize freely due to the interaction with the ultrafine particles and form a glassy material. In the product, the concentration of ultrafine particles can be increased, and a material having excellent nonlinear optical characteristics can be obtained. In addition to the mixture of the dispersion liquid and the organometallic compound, if a component forming the glass skeleton, which is an organic compound containing M ′ which is an element selected from Si, B, and P, is mixed as the third component, In addition to the strength of the obtained film, the chemical durability is also improved.

Claims (3)

[Claims] 1. A mixture of an ultrafine particle dispersion liquid in which ultrafine particles of metal are independently dispersed in a solvent and an organic metal compound is dissolved in an organic solvent, and this is applied onto a substrate to form a dried film. A method for producing an ultrafine particle-dispersed glassy material, which is characterized by comprising sintering. 2. The method for producing an ultrafine particle-dispersed glassy material according to claim 2, wherein the organometallic compound is selected from a metal alkoxide, an organometallic complex, and an organic acid metal salt. 3. A mixture of an ultrafine particle dispersion in which ultrafine particles of a metal are independently dispersed in a solvent and an organometallic compound are added to M ′.
The ultrafine particle-dispersed glass according to claim 1, wherein a third component forming a glass skeleton, which is an organic compound containing an element represented by (M 'is an element selected from Si, B, and P), is mixed. Method for manufacturing a shaped article.