JP2919748B2 - Method for producing ultrafine particle-dispersed glassy material - Google Patents

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 glass-like material, and more particularly to a method for producing an infrared-transmitting filter glass, a colored glass, a color forming agent for glass, a light-emitting device, etc. The present invention relates to 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, when ultrafine particles having a metal size smaller than several tens of nanometers, characteristics completely different from those of bulk metals appear in electronic structure, lattice specific heat, spin susceptibility and the like. Among such metals, gold, silver and CdS _k
Colored glass and filter glass are known as semiconductors made of ultrafine Se1 _-x particles dispersed in glass. It is also known that a colored glass filter, which is a colored glass of this kind, exhibits non-linear optical characteristics, and is attracting attention as being applicable to electronic materials of optical switches and optical computers. As a cause of the colored glass having nonlinear optical characteristics, discretization of an energy band due to a quantum confinement effect is observed, and it is interpreted that the third-order nonlinear characteristic increases due to a band filling effect or an exciton confinement effect.

[0003] As a method for producing such a fine particle-dispersed glass, a metal colloid particle is added to a liquid silica sol obtained by hydrolyzing a metal alkoxide, dispersed, poured into a container, gelled, and dried. Sol to be sintered
Gel method, semiconductor fine particles such as Si are dispersed in an alkoxide sol, dried, gelled alkoxide, sintered, and covered with oxide glass to obtain semiconductor fine particles, SiCl ₄ , GeCl ₄ , a sol-gel-burning method in which hydrogen and oxygen are introduced into glass raw materials such as PCl ₃ and mixed with glass fine particles generated by burning, followed by firing.
Further, a precipitation method in which a glass melt containing CdSe or the like is cooled to a temperature equal to or lower than a flowing temperature and equal to or higher than a yield temperature to precipitate fine particles in glass, and at least one of Cd source, S source, Se source, and Te source powder Powder and low-melting 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 using a sputtering method. There is known an ion implantation method in which ion implantation is performed by bombarding ions and then controlling the particle size by heat treatment.

[0004]

However, in general, sol-
The gel method not only requires a very long time to obtain fine particle-dispersed glass, but also has difficulty in preventing the aggregation of metal colloid particles. It was difficult to make the concentration. Also, it has been difficult to increase the concentration of metal fine particles even by the sol-gel-burning method. Furthermore, it is difficult not only to control the particle size of the metal fine particles but also to increase the content concentration of the metal fine particles by the deposition method and the sputtering method. In the ion implantation method, the apparatus is large and unsuitable for mass production, and it is difficult to increase the concentration of fine metal particles.

Recently, there have been various problems as described above.
As a method for solving the problem, JP-A-6-115973
As disclosed in U.S. Pat.
Of polymer composites and organometallic compounds dispersed in water
In an organic solvent, apply it on a substrate and dry it.
After forming a film, the ultrafine particle dispersed glass
Manufacturing methods are known. However, ultra-fine particle dispersion glass
When preparing a solid, a polymer composite and an organometallic compound
Or a polymer compound to uniformly mix
Polymer and organometallic compound or skeleton forming component in compound
Therefore, a solvent having good compatibility is required. However, polymer
Because the polymer in the compound is limited, organometallic compounds
Alternatively, there is a problem that the skeleton-forming components are naturally limited.
Was. The present invention solves such a problem.
And disperse the metal ultrafine particles independently.
Increase the concentration of these ultrafine particles, and
Ultrafine particle dispersion that is not restricted by species of skeletal or skeletal components
Provided is a method for producing a glassy material.

[0006]

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

The ultrafine particle dispersion in which ultrafine metal particles are independently dispersed in a solvent used in the present invention is at least Au, Pt, Pd, and 10 nm or less independently dispersed in a solvent such as α-terpineol or toluene. Selected from Rh, Ag
Ultra-fine particles of noble metal 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 disclosed in, for example, JP-A-3-342.
It is manufactured by a method called a gas evaporation method as disclosed in Japanese Patent Publication No. That is, helium inert gas is introduced into the chamber to evaporate the metal, and the metal is cooled and condensed by collision with the inert gas. In this case, the organic solvent is obtained at a stage where the particles immediately after generation are in an isolated state. Is applied to coat the particle surface. The amount of the ultrafine metal particles to be added can be selected according to the desired transmittance, and is not particularly limited.

Subsequently, an organometallic compound selected from a metal alkoxide, an organometallic complex, and an organic acid metal salt is prepared, and this is treated with meta-cresol, dimethylformamide,
An organic metal compound such as cyclohexane, formic acid, α-terpineol, toluene, xylene, carbitol or the like is dissolved in an organic solvent in which it is soluble, and this is mixed with the ultrafine particle dispersion. Preferably, the same solvent as the ultrafine particle dispersion is used. Of course, in the case of the present invention, the mixture of the ultrafine particle dispersion 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, and Pb, or Ti, Fe, Co, Ni, Cu,
It is a metal element selected from Nb, Ta, Cd, In, Cr, and Mn. In addition, organometallic complexes of organometallic compounds include ethyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl acetate),
Aluminum oxine complex and the like. Examples of the organic acid metal salt of an organic metal compound include aluminum benzoate, iron naphthenate, copper octylate, and titanium stearate.

In the present invention, together with an organometallic compound and an ultrafine particle dispersion in which ultrafine particles of the above metal are independently dispersed, the general formula M ′ (M ′ is selected from Si, B, and P) as the third component . An organic compound containing an element that forms a glass skeleton represented by the formula (I) can also be used, and the strength of the film thus formed can be improved. Specifically, tetra i-propoxysilane, triethyl borate, tristearyl borate, triphenyl borate, tricresyl phosphate, triphenyl phosphate, iproniazide phosphate, diphenyl phosphate, phosphonoacetic acid, phosphoramidone, 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 prepared by dissolving an organic metal compound and an ultrafine particle dispersion obtained by independently dispersing the metal ultrafine particles prepared as described above or an organic metal compound or an organic compound forming a glass skeleton. After thoroughly stirring a mixture obtained by dissolving and in an organic solvent, the mixture is applied to a substrate such as a glass plate, and the organic solvent is removed in the air at 60 to 120 ° C. for 10 minutes and dried, or deaerated in a closed container. While drying, a flat film is produced. The firing conditions are 300 ~
The temperature is 800 ° C, preferably 300 to 600 ° C. The firing conditions are relatively mild, so that the substrate is not hindered. For example, inexpensive soda glass can be used. The firing is performed in the air to generate a glassy oxide around the fixed ultrafine particles.

In the obtained ultrafine particle-dispersed glassy material, the ultrafine particles do not agglomerate due to the interaction with a 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 freely crystallize due to the interaction with the ultrafine particles, generates amorphous glass, becomes a main component of the film, and transmits light well. It becomes possible.

The composition of the ultrafine particle-dispersed glass material is as follows: metal ultrafine particles and MOX (M is Al, Ge, Sn, Sb,
Amphoteric element selected from Ga, Pb or Ti, F
e, Co, Ni, Cu, Nb, Ta, Cd, In, C
a metal element selected from r and Mn, x is 0.1 to 3)
And the content of the ultrafine particles is at most 90 mol%. The composition of the three-component glassy material is composed of ultrafine metal particles, MOX, and M'Oy, which is a third component forming a glass skeleton.
The content of the ultrafine particles is at most 90 mol%.

[0015]

In the present invention, the solvent of the ultrafine particle dispersion in which metal ultrafine particles are independently dispersed can be freely selected.
There is no restriction on the species of the third component forming the organometallic compound or the glass skeleton, and there is no need to finish the paste into which each component is dissolved. In addition, the ultrafine particles are M-
Due to the interaction with O- (M is an amphoteric element or a metal element), the ultrafine particles are fixed in the ultrafine particles without agglomeration and large grain growth, and the surrounding MO- The crystals cannot freely crystallize due to the interaction and produce an amorphous glass. Therefore, the concentration of the ultrafine particles in the product can be increased, and a material having excellent nonlinear optical characteristics can be obtained. Further, in the present invention, the firing temperature can be made relatively low, so that the substrate is not damaged.

[0016]

Next, the present invention will be described in more detail with reference to specific examples. In addition, the evaluation method of the glassy substance used in the present example is as follows. 1. Chemical state of ultrafine particles in glassy substance The chemical state of ultrafine metal particles in a glassy substance is measured by an X-ray diffraction method because the metal is a crystalline substance. This X-ray diffractometer is manufactured by Rigaku Corporation with a thin film attachment, RI
In NT1200, the compound is determined by obtaining an X-ray diffraction pattern by the 2θ method at a fixed incident angle of 1 °.

2. Content of ultrafine particles and product This was determined by converting the mixture of raw materials into mol%. During the sintering process, all organic components were decomposed and removed, and all inorganic components did not vaporize or disappear.

3. This is a value obtained by determining the half-width of the main peak of the noble metal in the X-ray diffraction pattern obtained in 1 and calculating the size of the crystal from Scherrer's formula.

4. From the X-ray diffraction pattern obtained in the structure 1 of the vitreous component, it was determined whether or not there was a diffraction peak other than the ultrafine particles. When there was no diffraction peak or when a broad halo was observed, it was regarded as having an amorphous structure.

[5] Optical characteristics The light absorption spectrum of a sample formed on a soda glass substrate was evaluated using a UVIDEC-650 spectrophotometer (manufactured by JASCO Corporation). The result is shown in FIG.

Example 1 An ultrafine particle dispersion in which 50% by weight of ultrafine gold particles were dispersed in α-terpineol was prepared. The above dispersion and tetra-i-propoxytitanium / Ti as an organometallic compound
(I-OC ₃ H ₇ ) ₃ was dissolved in α-terpineol at a predetermined weight ratio, stirred well, applied to a soda glass substrate, placed in a closed container, and placed at 120 ° C.
The solvent was removed while drying with a rotary pump for 10 minutes while drying. 500 ° in a furnace
C: Baking for 10 minutes to remove organic substances and sintering to obtain a film-like glassy substance. Table 1 shows the properties of glassy materials.
Shown in

[0022]

[Table 1]

As a result, the ultrafine gold particles in the form of glass maintain almost the same particle diameter as the ultrafine gold particles in the polymer composite after the heat treatment, and are fixed as they are in the Ti-O-vitreous material. You can see that it is. Further, since the color of the film shows a colloid color different from the red color of gold colloid, gold and Ti-O
-Are presumed to have interacted. This interaction prevents aggregation and grain growth of the ultrafine particles, and fixes the ultrafine particles in the glass.

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

Example 2 Ultrafine particle dispersion used in Example 1 and 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 the mixture was stirred well. This was applied on a soda glass substrate, and then placed in a closed container. This was deaerated with a rotary pump at 120 ° C. for 10 minutes while being deaerated. The solvent was removed and dried. This sample was baked in a furnace at 500 ° C. for 10 minutes to remove organic substances and sintered to obtain a film-like glassy substance. Table 2 shows the properties of the obtained glassy material.

[0026]

[Table 2]

Further, X of the glassy material according to Example 2-3 was
According to the line diffraction pattern, since the diffraction peak of gold is broad, the crystallite size is small, indicating that the particles are fixed as fine particles. Further, since no diffraction peak is observed except for gold, it can be seen that AlO _x has an amorphous structure. Also, according to the light absorption spectrum of the glassy material according to Example 2-3, the absorption peak was 5 in this example.
The plasmon broadly extends from 30 nm to the longer wavelength side, and this phenomenon suggests that the plasmon band of Au has changed because Al—O surrounding the Au ultrafine particles interacted with the surface plasmon of Au.

Example 3 The dispersion of the ultrafine particles obtained in Example 1 and the organometallic compound were mixed with tetra-i-propoxysilane / Si as a third component.
(I-OC ₃ H ₇ ) ₄ was dissolved in α-terpineol and stirred well. This was applied on a soda glass substrate, then placed in a closed container, and placed at 120 ° C. for 10 minutes.
The solvent was removed while degassing with a rotary pump and drying was performed. This sample was dried in a furnace at 500 ° C. for 10 minutes to remove organic substances, and sintered to obtain a film-like glassy substance. Table 3 shows the properties of the obtained glassy material.

[0029]

[Table 3]

6 mol% of Ti—O (Example 3-3),
Au / T containing high concentration of immobilized ultrafine gold particles even when Al-O content is as small as 12 mol% (Example 3-4).
A three-component glass consisting of i-O / Si-O or Au / Al-O / Si-O can be manufactured, and the strength of the obtained film can be increased and the chemical durability can be improved.

The measurement results of the ultrafine particle-dispersed glassy material according to the above-described examples show that (1) resonance absorption due to surface plasmon peculiar to the ultrafine particles appears, and (2)
That only certain MO _X prevents the grain growth of ultrafine particles,
(3) transmitting the light and changing the plasmon band;
(4) M has a chemical structure close to its maximum oxidation state,
It O _X is amorphous, it has been obtained results such that (5) the content of the ultrafine particles is up to 90 mol%. Thus, ultrafine particles dispersed glassy material ultrafine particles and MO _X is,
It can be seen that the plasmon of the MO and the ultrafine particles interacts electrostatically at the interface between the ultrafine particles, and that the glass is a glass containing up to 90 mol% of the ultrafine particles.

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

Comparative Example 2 The ultrafine particle dispersion used in Example 1 and an organometallic compound (M
-R) is dissolved in α-terpineol in a predetermined weight ratio and stirred well, and the mixture is applied on a soda glass substrate, and then placed in a closed container.
The solvent was removed while degassing with a rotary pump and drying was performed. This sample was dried in a furnace at 500 ° C. for 10 minutes to remove organic substances, and sintered to obtain a film-like glassy substance. Si as a nonmetallic element as M in MR
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 golden film. In Comparative Example 2, when an organometallic compound (M = Si) that did not interact with the ultrafine particles was used, 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 metal ultrafine particles are independently dispersed can be freely selected, and is limited to the kind of the organometallic compound or the third component forming the glass skeleton. It does not need to be finished, and it is not necessary to finish each component into a paste. In addition, the ultrafine particles do not agglomerate and the grain growth is prevented, and the surrounding MO- cannot be freely crystallized due to the interaction with the ultrafine particles, thereby producing a glassy substance. In the product, the concentration of the ultrafine particles can be increased, and a material having excellent nonlinear optical characteristics can be obtained. In addition to the mixture of the dispersion and the organometallic compound, the third component is selected from Si, B, and P.
If a component that forms a glass skeleton, which is an organic compound containing the element M ′, is mixed, the chemical durability as well as the strength of the obtained film is improved.

Continuation of the front page (56) References JP-A-5-270842 (JP, A) JP-A-7-53239 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C03B 8 / 02 C03C 14/00

Claims (3)

(57) [Claims] A mixture of an ultrafine particle dispersion in which metal ultrafine particles are independently dispersed in a solvent and an organic metal compound is dissolved in an organic solvent, and the mixture is applied on a substrate to produce a dried film. Thereafter, sintering is performed. 2. The method 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 metal ultrafine particles are independently dispersed in a solvent and an organometallic compound,
The ultrafine particle dispersed glass according to claim 1, further comprising 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). Manufacturing method of the product.