JPH03127033A - Production of glass dispersed with fine particle of semiconductor - Google Patents

Abstract

PURPOSE:To uniformly disperse the fine particles of a semiconductor in glass by gelatinizing a sol which is formed by previously adding a soluble cation source and sulfur compd. in the dispersion medium of the sol and heat treating the gel, thereby dispersing the fine particles of the semiconductor. CONSTITUTION:The sol which is previously added with the water- or alcohol- soluble cation source and sulfur compd. is gelatinized and the resulted gel is heat treated to disperse the fine particles of the semiconductor, by which the glass dispersed with the fine particles of the semiconductor is produced. The sol previously added with the cation source and sulfur source is gelatinized and the resulted gel is heat treated, by which the compsn. is uniformized and the glass dispersed with the fine particles of the semiconductor having the form of a thin film, bulk, fiber, etc., is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing semiconductor fine particle dispersed glass, which forms the basis of an optical device that utilizes nonlinear optical effects. salt & 1
The method for producing CdS-containing silica glass by the sol-gel method, as described on page 336 of the abstracts of the 989 Annual Conference, is based on silicon alkoxide (Si(OCaHs).
)4) Cd dissolved in methanol
Add (CHsCOO)12HaO and stir. Add the mixed solution of slightly aqueous ethanol/k ammonia water and continue stirring. Transfer this solution to a petri dish and make a gel plate. It can also be placed in an atmosphere containing hydrogen sulfide (Has) gas to create a CdS-containing glass by a sulfidation reaction.J, Appl, Phys, 63(3), 9571
CdS fine particle doped thin film glass as disclosed in No. 988 is manufactured by using Corning's 7095 glass as a target and CdS by high frequency magnetron sputtering method.
Problems to be Solved by the Invention The above method for manufacturing semiconductor fine particle dispersed glass can be used to disperse S in an amount of 2 to 4% by weight.
There are the following two issues: 1) In the case of the sol-gel method: Place the gel body in a hydrogen sulfide atmosphere to create a CdS-containing glass through a sulfurization reaction. Distribute CdS uniformly inside the gel body. When using the sputtering method: The equipment is expensive and it takes time to form a glass thin film (especially when forming glass with a low sputtering speed of 5 inches).
An object of the present invention is to provide a method for manufacturing glass in which semiconductor fine particles are homogeneously dispersed.Means for Solving the ProblemsIn order to solve the above problems, the present invention (Top: In the process of creating semiconductor fine particle dispersed glass using the sol-gel method,
A sol to which a water or alcohol-soluble cation source and a sulfur compound have been added in advance is gelled, and the resulting gel is heat-treated to disperse semiconductor particles, thereby producing a semiconductor particle-dispersed glass. In the manufacturing method of semiconductor fine particle dispersed glass, in the process of creating semiconductor fine particle dispersed glass by the sol-gel method, a sol to which a cation source and a sulfur source have been added in advance is gelled, and the resulting gel is heat-treated. Although the composition can be made uniform, it is possible to obtain a glass in which semiconductor fine particles are dispersed in the form of a thin film, fiber or the like. A cation source and a sulfur compound that are soluble in the solvent are preferable because the salt produced can be dispersed more uniformly.Epsilon water or methanol is used as the dispersion medium for the sol.
Alcohols such as ethanol are used exclusively, but cation sources include cadmium, selenium, molybdenum, etc. Among them, cadmium, zinc, and lead compounds (because they easily react uniformly with sulfur compounds to form semiconductors) The preferred cadmium compound is
For example, CdC1a, CdCO5, Cd(NOs)*,
Cd(CHsCOO)*, Cd(HCOO)a
As a zinc compound (for example, ZnC1*,
Zn(CHCOO)at* As a lead compound!
For example, PbC1,, PbC0*, Pb(NOs
)*, Pb(CHsCOO)a, etc. are listed as sulfur compounds (for example, Na5a (NH
a) *a 8C (NHa), etc. If Rare 4 Below, we will explain the embodiments of the present invention.Example 1 A Cd8-doped 5ide glass was prototyped through the steps shown in Figure 1, and the results are shown in Table 1. The following Cd source and sulfur compound (S source) were added to the sol so that the CdS to be doped with the 5ift glass was 3% by weight, i.e., methanol. Cd(HCOO)* dissolved in methanol was added to the sol with stirring, and then 5C(N
Ha)* was then added and heated at 80 t to gel the sol.1. Furthermore, it was heated at 350 tons to burn off the organic matter remaining in the gel body (bulk).
In order to control the crystal grain size of CdS, heat treatment was performed at 500 t for 2 hours. The grain size of the CdS obtained at this time was 50 to 80 A, indicating that fine particles of CdS were dispersed within 5 ins. The optical properties are shown in Figure 2. 4Q was also used instead of Cd(HCOO)* dissolved in methanol as a Cd source.
CdC1a, CdCO5, Cd(NOs)a and Cd(CHsCOO)2 were mixed with Na instead of 5C(NHs)*, which was dissolved in methanol as a sulfur compound.
By using 5H and (NH4)*S, almost the same characteristics as shown in Figure 2 can be obtained. .

Furthermore, using the same method, we were able to fabricate a fibrous CdS-doped 5ide glass with a diameter of 0.5 m and a length of 20 cm. We made a prototype of SiO2 glass and made a sol using the raw materials shown in Table 1.
The following Zn sources and sulfur compounds were added to the sol so that the ZnS doped with 2 glasses was 3% by weight. That is, the Zn (CH3
Coo )2 was added to the sol with stirring, and then SC(NHe)a dissolved in methanol was added and heated at 80°C to gel the sol.
The organic matter remaining in the bulk (bulk) was heated at 350°C to burn;
After heating for 2 hours at .degree. C., the particle size of the ZnS obtained at this time was 60 to 80 A.

Also, ZnCII as a Zn source! , Na5H to the sulfur compound
, (NH4)23, a ZnS-doped glass similar to that of Example 2 could be obtained.Example 3 A PbS-doped 5i (h glass) was prototyped through the same process as in Example 1, and t was also shown in Table 1. A sol was prepared using the raw materials shown in .The following Pb sources and S sources were added to the SiO2 glass so that the PbS to be doped was 3% by weight.In other words, Pb dissolved in methanol ( CHsCOO)2
was added to the sol with stirring. Then, 5C(NH2)2 dissolved in methanol was added and heated at 80℃ to gel the sol. Furthermore, the organic matter remaining in the gel body (bulk) was burned. Heat at 350℃ for
In order to control the crystal grain size of PBS, it was heated at 500°C for 2 hours, and the grain size of PbS obtained at this time was 60 to 100A, and
Also, PbC1a, PbC0a and Pb(N
Os)a is converted into a sulfur compound by adding Na5H and (N
H4) Example 4 A PbS-doped glass similar to Example 3 could be obtained using 2S. Through the same process as Example 1, boron alkoxide or titanium alkoxide was added in addition to silicon alkoxide. Experimental production of LACdS-doped 5iO2-BaO3 or CdS-doped Si0g-TiO2 glass Example 5 A semiconductor-doped glass with almost the same optical properties as Example 1 was obtained Using the sol shown in Example 1 Then, on a quartz glass substrate with a thickness of 0.5 mm, a 5iCh glass thin film with a thickness of 2.5 μm containing 5% CdS by weight was formed by the briping method, and an optical bistable device was fabricated. Laser light (N2 light excited dye laser light) with a wavelength of 530 nm is incident from the quartz glass substrate side with a spot diameter of 5 μm.
Example 6 Examples 6 Example 6 shown in Example 2 shown in Fig. 3 measured in Fig. 3 L:, ZnS is 5% by weight
A 5-ins glass thin film with a thickness of 2.8 μm was formed using a briping method to fabricate an optically bistable device, and a laser beam with a wavelength of 530 nm (
N2 photoexcited dye laser light) was incident with a spot diameter of 5 μm, and then the relationship between the intensity of the incident light and the intensity of the output light was measured at room temperature (25°C).
), it showed almost the same bistable characteristics as shown in Figure 3.According to the method of the present invention, Mo5a dispersion glass can be prototyped using an alcohol-soluble substance, such as (NH4)MO34. Effects of the Invention Invention Q According to the method for producing semiconductor fine particle dispersed glass, the sol is gelled by adding a soluble cation source and a sulfur compound to the dispersion medium of the sol in advance, and the resulting gel is heat-treated. It is possible to obtain a homogeneous semiconductor particle-dispersed glass having a thin film or fiber-like morphology.As an application of this method, it is possible to produce optical bistable devices, etc.

[Brief explanation of the drawing]

Figure 1 shows the manufacturing process of semiconductor-doped glass using the sol-gel method of the present invention. Figure 2 shows the optical properties of semiconductor-doped glass. Figure 3 shows the optical bistability characteristics.

Claims (3)

[Claims] (1) In the process of creating semiconductor fine particle dispersed glass using the sol-gel method, a sol is gelled by adding a soluble cation source and a sulfur compound to the dispersion medium of the sol in advance, and the resulting gel is heat-treated. A method for producing semiconductor fine particle dispersed glass, characterized by dispersing semiconductor fine particles. (2) The method for producing semiconductor fine particle dispersed glass according to claim 1, wherein the cation source is one of a cadmium compound, a zinc compound, or a lead compound. (3) The method for producing a semiconductor particle-dispersed glass according to claim 1 or 2, wherein the semiconductor particle-dispersed glass is in the form of a bulk, a film, or a fiber.