JPH03168728A - Nonlinear optical material and its production - Google Patents

Abstract

PURPOSE:To obtain a thin film in which a tellurium-based glass material is uniformly doped with semiconductor fine particles in high density by dispersing the fine particles in the matrix. CONSTITUTION:Since the melting temp. of the tellurium-based glass as a matrix is >=1,000 deg.C, the semiconductor fine particles are hardly decomposed or sublimated, hence the fine particles are dispersed in the glass in large quantities, and the glass composition and kind of the semiconductor can be freely changed. Consequently, the composite glass of the semiconductor and tellurium-based glass is used as a target, and a thin film in which the glass matrix is uniformly doped with the semiconductor fine particles in large quantities is easily obtained by sputtering method.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a glass nonlinear optical material doped with semiconductor particles, which forms the basis of an optical device that utilizes nonlinear optical effects, and a method for manufacturing the same. For example, a) J, Opt. Soc. Am,,73,647(1
There is a type of sharp-cut filter glass that is used as a nonlinear optical material, which is a borosilicate glass (this becomes the glass matrix) doped with CdSxSe1-11 described in 983).This glass is used for CdO, CdS.
, CdSe, S, Ss, etc. and borosilicate glass are placed in a platinum crucible and melted at a high temperature of about 1600°C. Phys. , 63(3
). C as described in 957 (-1988)
A thin film glass doped with dS fine particles is used.This thin film glass uses Corning 7059 glass as a target with CdS placed on it. Problems to be Solved by the Invention The conventional method for manufacturing glass doped with semiconductor fine particles has the following problems. , b) In the case of sharp-cut filter glass, it is necessary to melt it at a high temperature of 1600°C or higher, so semiconductor fine particles easily sublimate. Therefore, it is difficult to disperse more than a few percent of CdSx Se1-κ in borosilicate glass. In particular, when using the sputtering method, it was difficult to assemble the glass, and it was also difficult to freely change the type of semiconductor particles.
In the case of glass containing a large amount of silicon dioxide (Si(h)) such as No. 59, the sputtering rate is low, so it takes time to form a thin film, and the conventional method using a target does not allow a large amount of semiconductor particles to be uniformly distributed in the glass matrix. Means for solving the problem that it was difficult to obtain a thin film doped with A method for manufacturing a nonlinear optical material having a structure in which semiconductor fine particles are uniformly doped in large amounts is provided.

Function: The nonlinear optical material of the present invention has a structure in which the tellurium-based glass used as the matrix has a melting temperature of 1000°C or lower.Semiconductor fine particles are less likely to sublimate, and therefore can be dispersed in large quantities in the glass. In addition, the type of glass bonding point semiconductor can be changed freely. Furthermore, by using a sputtering method using a composite glass of semiconductor and tellurium glass as a target, it is easy to produce a thin film in which a glass matrix is uniformly doped with a large amount of semiconductor fine particles.

Examples Tellurium-based glass is preferable for the glass matrix of the present invention, and in particular, considering the stability of the glass, the ease of melting, the risk of decomposition of semiconductor particles, and the dispersibility, at least CdO
, B20s. Glass containing Tent as the main component is preferable (1. Here, the fine particles include I-VI such as CuC1.CuBr).
Group I metal chloride 'aL CdS, CdSe, CdO, C
I of dTe, ZnSe, ZnO, ZnTe, HgTe, etc.
I-VI group compound semiconductor Mixed crystal II-VI compound semiconductor such as CdSSe, HgCdTe 4IFSGaAs, G
aN, GaP, Garb, InAs, InP,
II of InSb, GaAIAs, InAIAs, etc.
IV group compound semiconductor or IV such as Si, Ge, etc.
Preferred are semiconductors from the group L~. Examples of the present invention will be described in detail below (Example 1) CdO, B2 0s . Ten
Glass raw materials containing T as the main component and CuC
dSi+Se+-x (X=0.1) was placed in a platinum or gold crucible and stirred at 850°C, then poured into a mold heated to 300°C to form a sheet glass with a thickness of 1 mm.The glass was further cooled to room temperature. was heated again at 300℃ for 1 hour to form CuCl or CdS*Se+-x
The doping amount of CuC1 in this glass is 10 wt% and the particle size is 30 to 60. (ix) The band gaps obtained from the absorption spectra of glasses doped with the above two types of semiconductors are 0.0. 9eV
, 0. It was found that the semiconductor was a quantum dot because of the 7 eV blue shift.In addition to the above semiconductors, CuBr, CdS, and CdS
e, CdO, CdTe, ZnSe, ZnO,
ZnTe, HgTe, and HgCdTe can also be doped, and a tellurium-based glass having the composition shown in Table 1 and Table 1 B was combined, crushed, and mixed with 40 wt% CuC1.The diameter was 80 m.
It was shaped to a thickness of 5 mm and sintered at 500°C to produce a composite glass plate. Similarly, CdSxSe+-x (X-0.
A composite glass plate containing 40 wt% of 1) was prepared and
Using the glass plate prepared in this way as a target, this glass was made into a thin film using a high-frequency sputtering device. Sputtering was performed in an Ar gas atmosphere. A thin film of glass with a thickness of 200 μm was placed on a quartz glass substrate (thickness: 0.3 mm). The CuC 1 doping amount in this glass was 31wt by heating at 300℃ for 1 hour to elongate the CuCl or CdSxSe+-x crystals.
%, and the particle size is 40 to 60 people. The band gaps obtained from the spectra are 1. 1e
V, 0. The fact that there is a 9 eV pull shift indicates that the semiconductor is a quantum dot.9 In addition to the above semiconductors, there are also CuBr, CdS, and CdS.
e, CdO, CdTe, ZnSe, ZnO,
ZnTe, HgTe, HgCdTe in glass
Composite glass containing ~40 wt% mixture could be produced (Example 3) An optical bistable device was fabricated using the CuC 1 doped glass thin film and the CdSxSe+-i+ (X=0.1) doped glass thin film produced by the method of Example 2. A laser beam with a wavelength of 350 nm (N2 light-excited dye laser beam) was incident on the quartz glass substrate side of this device with a spot diameter of 5 μm.Next, the relationship between the intensity of the incident light and the intensity of the emitted light was determined at 25°C.
The bistability shown in Figure 1 was measured using a circle (Example 4).
l-doped glass thin film and CdSxSe+-x(X-
0. 1) A wavelength of 350 nm from the quartz glass substrate side of an optically bistable device fabricated using a doped glass thin film.
Laser light (N2 light excited dye laser light) with a spot diameter of 5
When the relationship between the intensity of the incident light and the intensity of the emitted light was measured at 25°C, it showed bistability as shown in Figure 2. Alternatively, by targeting a composite glass of a semiconductor and tellurium glass and using a sputtering method to create a thin film in which a tellurium glass matrix is uniformly doped with semiconductor fine particles at a high concentration, a glass material with large nonlinear optical properties can be obtained. It is possible to create optical bistable devices as an application of this technology.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are diagrams showing the optical bistable characteristics of a bistable device using the semiconductor-doped glass of the present invention, respectively.

Claims (4)

[Claims] (1) A nonlinear optical material characterized in that semiconductor fine particles are dispersed in a tellurium-based glass matrix. (2) The tellurium-based glass matrix is at least CdO
, B_2O_3, and TeO_2 as main components. (3) A method for manufacturing a nonlinear optical material, which comprises manufacturing a semiconductor-doped tellurium glass in which semiconductor particles are dispersed in a tellurium-based glass matrix by mixing and melting a semiconductor and tellurium-based glass. (4) A method for producing a nonlinear optical material, which comprises producing a semiconductor-doped tellurium glass thin film in which semiconductor fine particles are dispersed in a tellurium-based glass matrix using a sputtering method using a composite glass of a semiconductor and tellurium-based glass as a target. .