JPH03296026A - Nonlinear optical material and production thereof - Google Patents

Abstract

PURPOSE:To obtain the bistable characteristics excellent in moisture resistance and heat resistance and as well as good nonlinear optical characteristics by forming a coating layer of SiO2 glass on the surface of glass formed by dispersing the fine particles of a semiconductor into low melting lead glass. CONSTITUTION:The coating layer 2 consisting of any of the SiO2 glass, TiO2-SiO2 glass or ZrO2-SiO2 glass is formed on the surface of the glass 1 formed by dispersing the fine particles of the semiconductor into the low melting lead glass essentially consisting of PbO, B2O3 and SiO2. The fine particles of the semiconductor can, therefore, be dispersed uniformly at a high concn. into the low melting lead glass matrix and the elution of the lead from the semiconductor dispersed glass is prevented. The nonlinear optical material which exhibits not only the bistable characteristics excellent in the moisture resistance and heat resistance but the good nonlinear optical characteristics as well is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a glass nonlinear optical material in which fine semiconductor particles are dispersed, which forms the basis of an optical device utilizing a nonlinear optical effect, and a method for manufacturing the same.

Conventional technology Conventional technology includes, for example, Journal of Optical Society of America, Vol. 73, p. 647 (
J,Opt,Soc,Am,, Vol, 73.1983
), a cut-off filter glass in which Cd5XSe+-x is dispersed in borosilicate glass is used as a nonlinear optical material.

This cut-off filter glass is manufactured by placing CdSxSe and borosilicate glass materials in a platinum crucible and melting them at a high temperature of about 1600°C.

In addition, those using low melting point lead-based glass have also been manufactured.

This low-melting point lead-based glass is widely used mainly for bonding electronic parts (hermetic seals, etc.).

Problems to be Solved by the Invention Conventional semiconductor fine particle dispersed glass and its manufacturing method have the following problems.

That is, Cd5XSe+-x is added to borosilicate glass by 2
It is difficult to uniformly disperse more than 4 wt %, and it cannot be produced unless melted at a high temperature of 1600° C. or higher, making it extremely difficult to control the glass composition and semiconductor composition.

On the other hand, low-melting lead glass has a softening point of 600° C. or lower and can be used at low temperatures, but it is inferior in moisture resistance and heat resistance compared to borosilicate glass. In particular, there is a problem in that lead is leached out under high temperature conditions.

The present invention aims to provide a nonlinear optical material in which fine semiconductor particles are uniformly dispersed at a high concentration and exhibits good nonlinear optical properties including bistable properties with excellent moisture resistance and heat resistance, and a method for producing the same. purpose.

Means for Solving the Problems The first invention of the present application is a low-melting point lead-based glass containing pbo, B2O3, and SiO□ as main components with semiconductor fine particles dispersed therein. 5iOz
The present invention relates to a nonlinear optical material characterized in that a coating layer made of either Zr0z-based glass or Zr0z-5in2-based glass is formed.

In the second invention of the present application, a glass thin film in which semiconductor fine particles are dispersed in a low melting point lead-based glass mainly composed of pbo, B2O3, S]02 is formed on a SiO□ substrate, and a SiO□-based glass is formed on the surface of the thin film. It is characterized in that a coating layer made of glass, TiO2-5i02 glass, or Zr0z 5iOz glass is formed.

The third invention of the present application is a method for manufacturing the nonlinear optical material of the first invention, which comprises dispersing SiO on the surface of semiconductor fine particle dispersed glass.
□-based glass, TiO2SiO□-based glass or Zr02
- A coating layer made of either SiO2-based glass is formed using a sputtering method or a sol-gel method.

A fourth invention of the present application is a method for manufacturing the nonlinear optical material according to the second invention, in which a semiconductor fine particle dispersed glass thin film is formed on a 5i02 substrate by a sputtering method, and then 5iOz glass, TiO2- 5inz
The coating layer is formed by sputtering or sol-gel method.

Function The nonlinear optical material of the present invention comprises semiconductor fine particles such as PbO, B
It can be highly concentrated and uniformly dispersed in a low melting point lead-based glass matrix containing 2O3, SiOtu3, and SiO2 as main components. Then, on the surface of this semiconductor dispersion glass, 5
i02 series glass, TiO□-5iOz series glass or Z
By forming a coating layer made of either rO□-3in2 type glass, lead elution can be prevented,
It is possible to provide a nonlinear optical material that exhibits good nonlinear optical properties including bistable properties with excellent moisture resistance and heat resistance. Furthermore, by using a sputtering method or a sol-gel method, the above-mentioned nonlinear optical material can be rationally manufactured.

Example The glass matrix of the present invention is preferably a low-melting point glass. Particularly, to form a composite glass of a semiconductor material and a low-melting point glass, a lead-based glass containing Pb0-BzO+-SiO2 as a main component is used, since the semiconductor material is It is preferable because it has good dispersibility.

The semiconductor fine particles dispersed in the glass matrix contain C.
I-■ group compound semiconductors such as uCl, CdS, CdSe,
CdO, CdTe5ZnSe, ZnO, ZnTe,
■-■ group compound semiconductors such as HgTe, Cd5Se,
Mixed crystal 1l-Vl group compound semiconductors such as HgCdTe, Ga
As, GaN, GaP, GaSb, InAs,
Ink, InSb, GaAlAs, InAlA
Preferred are m-v group compound semiconductors such as S, or group II raw conductors such as Si and Ge.

Specific examples of the present invention will be described below.

Example 1 PbO-BzOs-SiO having the composition shown in Table 1
2-based glass raw materials and CuC1 or Pb O-Bg
O:+-5iOz-based glass raw materials and cdsxse+-x
(X=0.1) was placed in a platinum crucible and melted at 900°C, then poured onto an iron plate heated to 300°C to a thickness of ll1l.
It was made of ffi sheet glass. The glass that had been further cooled to room temperature was heated again in an electric furnace at 300°C for 1 hour.
Crystals of CuC1 or CdSxSe I ->1 were grown. The amount of CuC1 dispersed in this glass is 10wt%
The particle size was 30-60. Also Cd5)I
The dispersion amount of Se+-x is 12-1% and the particle size is 60-
There were 100 people. As shown in FIG. 1, a SiO□ coating layer 2 having a thickness of 1 micron was formed on both sides of the semiconductor dispersion glass 1 by sputtering using SiO□ glass as a target. In the lead-based glass plate having the composition shown in Table 1, some lead was eluted in the boiling test, but when a SiO□ coating layer is formed on the surface of the lead-based glass as in this example, lead elution is prevented. It was found to be stable and not visible at all. Furthermore, the band gaps obtained from the absorption spectra of the semiconductor-dispersed glass on which the two types of 5iOz coating layers were formed are 0.9e compared to the bulk semiconductor.
ν, 0.7 eV blue shift, indicating that the semiconductor was a quantum dot. Furthermore, glasses A and D in Table 1 were able to obtain particularly uniform semiconductor-dispersed glasses. In addition to the above semiconductors, PbO4z03-SiO2 glass also uses CdS, CdSe, and Cd02CdT.
e, Zn5e, ZnO, ZnTe, HgTe, H
gCdTe could also be dispersed.

Table 1 Example 2 Pb O-BgO3-5iO having the composition shown in Table 1
Z-based glass raw materials and CuCL or PbO-B20s
-5iOz glass raw material and CdSxSe+-x (X=
0.1) was placed in a platinum crucible and melted at 900°C, then poured onto an iron plate heated to 300°C to a thickness of 1IIIl.
It was made into a sheet glass. The glass, which had been further cooled to room temperature, was heated again in an electric furnace at 300°C for 1 hour, and CuC1
Alternatively, crystals of CdS, Se, , -, were grown.

The amount of CuC1 dispersed in this glass was 10evt%, and the particle size was 30-60%. Also Cd5) ISe+
-The dispersion amount of x is 12wt% and the particle size is 60-100
It was a person. 5 by the sol-gel method on both sides of the above glass.
An iOz coating layer was formed. The SiO2 coating layer was formed by repeating three times the steps of spin-coding a sol composed of the raw materials shown in Table 2 onto the surface of the semiconductor-dispersed glass, drying it, and then firing it at 350°C. Obtained S
The thickness of the iO2 coating layer was 1.3 microns. The glass in which the SiO□ coating layer was formed on the surface of the lead-based glass of this example was found to be stable with no lead elution observed in the boiling test. Furthermore, the above two types of SiO
□The band gap obtained from the absorption spectrum of the semiconductor-dispersed glass on which the coating layer was formed was blue-shifted by 0.9 eV and 0.7 eV compared to the bulk semiconductor, respectively, indicating that the semiconductor was a quantum dot. Ta. Furthermore, glasses A and D in Table 1 were able to obtain particularly uniform semiconductor-dispersed glasses. Furthermore, 10% of Ti(OCJs)a or zr(OczosL) was added to the sol solution in Table 2.
TiO
When the surface of the semiconductor-dispersed glass was coated with 2-510z series or Zr(h-5i02 series glass), it was possible to obtain the same effect as the SiO□ coating layer.Pb 0-BzOz
-5iOz glass contains CdS, C in addition to the above semiconductors.
dSe, Cd01CdTe, Zn5e, ZnO1
ZnTe, HgTe, and HgCdTe could also be dispersed.

Table 2 Example 3 Pb0-Bz[1x-5i having the composition shown in Table 1
After synthesizing and pulverizing Oz-based glass, 40
-500° in a platinum crucible after mixing t% of CuC1
Pb 0-BzO: +-5iOz, CuCl
A composite glass (diameter: 80 mm, thickness: 5 mm) was synthesized. CdSxSe I −x (χ=o,
A composite glass containing 40 wt% of 1) was produced. The glass plate thus produced was made into a thin film using a high-frequency magnetron sputtering device using a targen membrane. Sputtering was performed under an argon gas atmosphere. As shown in Figure 2, the film thickness is 200 mm.
After forming a micron semiconductor dispersion and thin film glass 1 on a silica glass substrate (0.3 mm) 3, it was heated in an electric furnace at 300°C for 1 hour to form CuCl or CdS.

A crystal of Se+-8 was grown. CuC in this glass
The dispersion amount of No. 1 was 31 wt%, and the particle size was 40-60%. In addition, the dispersion amount of CdSxSe+-x is 28-t%
The particle size was 50-90. Furthermore, using SiO□ glass as a target on the surface of the above-mentioned glass, a SiO□ glass having a thickness of 1 μU was prepared using a sputtering method.
Covering layer 2 was formed as shown in FIG.

In the case of the glass thin film without a coating layer, some lead elution was observed in the boiling test, or in the case of the glass thin film with the 5iOz coating layer of this example, no lead elution was observed and it was stable. Understood. The hand gaps obtained from the absorption spectra of the glass in which the above two types of semiconductors are dispersed are 1.1 eν and 0.9 eν, respectively, compared to the bulk semiconductor.
It was found that the semiconductor was a quantum dot because of the e-si blue shift.

Example 4 Pb0-BzO having the composition shown in Table 1: +-3i
After synthesizing and crushing 02 series glass, 40
-500° in a platinum crucible after mixing t% of CuCl.
A Pb 0-BzO3-5iOz, CuC1 composite glass (diameter 80+am, thickness 5 mm) was synthesized by sintering with C. A composite glass was prepared by adding 40-t% of CdSxSe+-x (X=0.1) to a similar glass. Using the glass plate thus produced as a target, the glass was made into a thin film using a high frequency magnetron sputtering device. Sputtering was performed under an argon gas atmosphere. After forming a thin film glass with a film thickness of 200 microns on a silica glass base vi (0,3+n+n),
CuC1 or CdSxS was heated for 1 h in an electric furnace at °C.
A crystal of e+-x was grown. CuCl in this glass
The dispersion amount was 31-t% and the particle size was 40-60%. In addition, the dispersion amount of Cd5ySe+-x is 28wt%
The particle size was 50-90. Further, a 5i02 coating layer having a thickness of 1.4 μm was formed on both sides of the glass by a sol-gel method in the same manner as in Example 2. The glass in which the SiO□ coating layer was formed on the surface of the lead-based glass of this example was found to be stable with no lead elution observed in the boiling test. Furthermore, the hand gaps obtained from the absorption spectra of the glasses on which the two types of SiO□ coating layers were formed are 0.9 eL and 0.7 e compared to the bulk semiconductor, respectively.
The V blue shift indicates that the semiconductor is a quantum dot.

Furthermore, using the raw material obtained by adding 10 wtX of Ti(OCz)Is)4 or Zr (OCJ5) to the sol solution shown in Table 2, the surface of the semiconductor-dispersed glass was coated with TiO□-5iOz-based or Zr07SiOz-based glass by the above method. As a result, it was possible to obtain an effect equivalent to that of the SiO□ coating layer.

Example 5 CdS, 5e1-, produced by the method shown in Example 1
An optical bistable laser was fabricated using a thin film of ×(×·0.1) dispersion glass plate.

Laser light (N2 light-excited dye laser light) with a wavelength of 530 nm was applied to the device from the quartz glass substrate side with a spot diameter of 5 μm.

Next, we will calculate the relationship between the intensity of the incident light and the intensity of the emitted light at room temperature (25°
When measured in C), the glass of Example 1 had the third
It exhibited bistable characteristics as shown in the figure.

Effects of the Invention According to the present invention, it is possible to disperse semiconductor fine particles uniformly at a high concentration, and also to prevent the elution of lead even at high temperatures. It is possible to provide a nonlinear optical material that exhibits good nonlinear optical properties such as the above characteristics. Furthermore, according to the method of the present invention, the above-mentioned nonlinear optical material can be rationally manufactured.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of a semiconductor dispersion glass coated with a SiO□-based glass glass, which is an embodiment of the present invention, and FIG. 2 is a semiconductor dispersion glass coated with a 5iO7-based glass glass, which is another embodiment of the present invention. FIG. 3 is a diagram showing the optical bistable characteristics of a bistable element using the semiconductor dispersion glass.

Claims (4)

[Claims] (1) SiO_2-based glass, TiO_2-Si
A nonlinear optical material characterized in that a coating layer made of either O_2-based glass or ZrO_2-SiO_2-based glass is formed. (2) A thin film of glass in which semiconductor fine particles are dispersed in low melting point lead-based glass mainly composed of PbO, B_2O_3, and SiO_2 is formed on the SiO_2 substrate, and the surface of the thin film is coated with SiO_2-based glass and TiO_2-SiO_2-based glass. or ZrO_2-SiO_2 glass. (3) A method for manufacturing the nonlinear optical material according to claim 1, wherein SiO_2-based glass, TiO_2-SiO_2
A method for manufacturing a nonlinear optical material, characterized in that a coating layer made of either ZrO_2-SiO_2-based glass or ZrO_2-SiO_2-based glass is formed using a sputtering method or a sol-gel method. (4) A method for manufacturing the nonlinear optical material according to claim 2, wherein after forming a semiconductor fine particle-dispersed glass thin film on a SiO_2 substrate by sputtering, the surface of this thin film is further coated with SiO_2-based glass, TiO_2-SiO_2-based glass, etc. Glass or ZrO_
A method for producing a nonlinear optical material, characterized in that a coating layer made of either 2-SiO_2-based glass is formed by a sputtering method or a sol-gel method.