JPH04503501A - Small particle semiconductor in hard matrix - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Small particle semiconductor in hard matrix field of invention The present invention relates to small particle semiconductors immobilized in the pores of a glass matrix.

Background of the invention It is well known that the electrical and optical properties of semiconductors depend on the dimensions of the semiconductor particles. It is being For example, particles can be is the minimum dimension that a polymer cluster must exceed (before it becomes a semiconductor). It is. Signs of the bulk semiconducting nature of CdS occur in particles with diameters greater than 60 mm. It is estimated that. In PbS, the bandgap is the semiconductor cluster size As it decreases, it moves to a higher energy side and finally exists at the beginning of the PbS molecule. The bulk semiconductor properties are focused on the transition energy of the state, and the bulk semiconductor properties are formed by particles with a diameter of more than 150 μm. Appears as a child.

The preparation of small-particle semiconductors is based on the electrical or optical properties of these materials compared to bulk semiconductors. Attempts are being made to utilize any of the properties of However, very small particles Preparation of child semiconductors is often difficult and applies to a wide range of semiconductor composites.

Some semiconductors are produced in the gas phase, low-temperature matrix, converted micelles, surfactant bubbles, and bilayer liquid films. , clay, prepared as a colloidal suspension in a solvent containing various surfactants to maintain dispersion. or has been experimented with. However, small particle semiconductors prepared by these methods body is inherently unstable as an aggregate or coupled with electrical or optical devices It may be difficult to do so. For useful devices, small particle semiconductors are Solid, preferably transparent solid and can be modified by standard fabrication techniques , in a medium capable of providing an inert or protective environment for reactive semiconductor materials. Should be combined.

One approach is to add Cd, S, and Se to the standard components of common glasses. CdS or CdSxSe1-w glass cutoff by standard melting procedure Prepare the filter.

This type of glass is well known as a long wavelength bass optical filter with a large amount of X. It is something. Nonlinear optical effects have been reported for these glasses; The high temperatures and strong oxidizing conditions used to prepare the lath may lead to other semiconductor composites. severely restricting the applicability of the technique.

Mah 1 e r1 Inorganic Chemistry, Vol, 27, No 3.1988.435-4 Page 36 includes metathesis of microemulsions, gas-solid reactions on high surface area silica, and perfluorocarbons. -Synthesis within the channels of the bonesulfonic acid film, semiconductor particles within the polymer film A method of preparation is disclosed that includes the production of. In particular, ethylene-15% methacrylic acid Copolymer (E-MAA) provides good mechanical and optical properties, nanometer It has been shown to provide high dynamic stability on semiconductor particles of this size.

Rajh et al., Chemical Physics Letters SVol 1 43, NO63, 1988, pp. 305-307, aqueous colloidal dispersion of semiconductors. was mixed in tetramethoxysilane (7MO8) and silane was added by adding NH4OH. By accelerating the polymerization of recon alkoxide and drying the resulting gel for several months, A method of bonding quantized colloidal semiconductor particles to transparent silicate glass using is disclosed.

They are first bound with metal ions and then dried to an initial mass of about 172. After passing through gaseous H, S or H2Se, a suitable anionic acid is added to precipitate the particles. A method of producing colloidal glass by adding a colloid is also disclosed.

Roy et al., “Better Ceramics Thr.

ugh Chemistry”, Materials Res, Soc, Sym p,, Vol, 32, Ed, J, C, Brjnker, D, E, C1ark, D , RlUl rich.

Elseviers 1984 uses a tetraethoxysilane/ethanol solution. CdS and into a sol-gel unit by mixing with an aqueous solution of metal ions. and AgX (X-CLBr, I).

Kuczynski et al., J. Phys. Chem., V.

1.89.1985, pages 2720-2722 describes how cleaned porous glass is soaking in dC12 solution, drying the glass under vacuum, then pouring By immersing the sample in a sodium sulfate solution, porous Vycorga discloses the preparation of CdS in laths.

Nonlinear optical properties of semiconductors such as degenerate four-wave mixing, optical bistability and phase changes has been reported (Rustagi et al., 0ptics Letters V ol, 9. No. 8 (1984), pp. 344-346). Ru Stagi et al. for measuring degenerate four-wave mixing of discernible radiation in silicated glasses. An experimental sequence is described.

materials provided by prior art, i.e., small particles embedded in porous glass or polymeric membranes. Particle semiconductors are unsuitable for many electrical and optical applications. porous glass Glass composites are brittle and cannot be machined or polished using techniques used for standard optical glasses. cannot be polished. Generally, the polymer/semiconductor composite is thermally stable or electrically stable. Lacks the high optical properties most needed for optical and optical applications. For example, It is difficult to produce high performance optical fibers from semiconductor/semiconductor composites.

The object of the present invention is to provide chemical and mechanical provides a stable dispersion of small semiconductor particles. Such materials, compared to bulk semiconductors, It is expected to have more agile optical nonlinearity. Wavelength tuning depends on the dimensions and This can be easily achieved by controlling the concentration of semiconductor particles. present invention Another object of the invention is to provide a material that produces third-order nonlinear optical effects.

Summary of the invention These purposes include substantially porous glass, semiconductors contained in the pores of said glass, and This is achieved by the present invention which provides an article of manufacture comprising a polymer and a polymer. The present invention Also provided are materials that produce nonlinear optical effects.

Details of the invention Suitable porous glasses have sizes between 10 and 500, interconnected pores and chamfers. an amorphous matrix material with channels, and the material is an easily replaceable organic matrix material. or optionally filled with inorganic compounds such as organic solvents, water, inorganic salts. Appropriate polyester Porous glass is available under the trade name Vycor (Corning Glass Co., Corning, N, Y, This glass is commercially available as ”).

A suitable porous glass is produced by hydrolysis of the precursor material followed by drying of the resulting gel. It can be prepared by The pore size of the sol-gel derived glass is: It can be controlled by the choice of solvent and the pH of the hydrolysis conditions. appropriate Single glass is Sioz, Ge0z% Ti0z, Y20m and Zr Contains O. A suitable multi-component glass is 5iO2-Baos 5io2 B20s , 5iOz -B20s Na2O, S iO, -Na20.5iQ2-20 ．． 5i02-GeOz, 5io2 AlzOi, 5iOz Ti0z, 5iOi -Y203, A1203-GeOz, A1203 Z to2, Tie, - ZrOz, Zr02-sto, PbO-La2O3Zr0z TiO2 including. Preparation of these single and multicomponent porous glasses by sol-gel technique , is conventionally well known. Porous glass is highly sensitive to colloidal silica at high pH (pH 9). For gelation of lyca (e.g. DuPont's Radox) and subsequent drying of the resulting gel. Therefore, it may be prepared. A preferred glass is SiO2.

The expression "semiconductor material" used here refers to an intermediate between an insulator and a metal as an electrical conductor; or refer to a bulk material with a bandgap between approximately 0.2 and 4v. Main departure Semiconductor materials suitable in the art are well known in the art. The semiconductor material is S-2 , 5e-2, 0-2, ■-2, p-3, sbzu and A s-3. Cd'', Zn+2, Pb'' combined with at least one anion selected from , Cu+2, Ga+3, In'' and Ti+3. It will be revealed. Preferably, the semiconductor is Cd55CdSeSZnS, Zn5e, Pb S, Pb5e.

Pb12, Ti’o2, In203 + gallium, copper or indium sulfides; gallium, copper or indium selenides; cadmium, tin or zinc; Phosphides of lead; arsenides of cadmium, tin or zinc. Cd5 as described above 5CdSe.

Zn5SZnSe, Pb5SPbSeSPb 12, TiCh and In, 0 3 Semiconductors exist predominately as single-phase materials, and as a result, the stoichiometry does not change, and the original Qualitatively, for example, it is written as 1:1.1:2 or 2:3. Other semiconductors , exist in one or more phases, and as a result the stoichiometry changes with sample preparation and processing Maybe. However, these compounds are Ga2s3, CuS, In2 S3, Ga2 Se3, Cu5eS Inz Se3, Cd3 P2, Pb3 P2, Zn3 P2, Cd3 As, Pb3 As2 and Zn 3 As, generally limited by the prevailing stoichiometry. These different stoichiometric semiconductors are limited by the dominant stoichiometry as described above. . Semiconductor materials are compounds derived from two or more cations as described above. Thione mixtures or solid solutions can be included. Glass/Semiconductor/Polymer Semiconductor concentration in the composite is determined by the amount of metal salt bound to the glass/semiconductor composite range of 0.01 to 20 wt% based on the ratio of semiconductor to glass. It is surrounded. A preferred concentration is 0.1-5 wt%.

The bandgap energy of the semiconductor particles in the porous glass is determined by the method of preparing the particles. The annealing time is controlled by the temperature and depends on the particle size. in general , the formation of small particles is performed using a sol-gel technique (more fully explained in “Method 1” below). The use of short-term, low-temperature annealing is recommended. Preferably half The particles of conductive material have a diameter of about 500 Å or less, more preferably about 200 Å or less . The composites of the present invention exhibit minimal light scattering and can be used as optical filters and third-order nonlinear optical filters. It is useful for generating scientific effects.

The bubble-filled polymers of these composites are capable of diffusing or capillary action into porous glass. either induced by polymerization of appropriate monomers that are adsorbed. suitable monomer Inject the semiconductor into the bubble space of the glass by breaking the glass or injecting the semiconductor particles into the bubble space of the glass. Small enough to diffuse and fill without dissolving or reacting soot. good Suitable monomers can be polymerized by the use of suitable priming agents, heating, radiation, It can be controlled by treatment of monomer-saturated glasses with light or electron beams.

Particularly suitable monomers are methacrylate esters; acrylate esters; vinyl acetate; acrylonitrile; methacrylonitrile; formula CH2=C (X) a vinylidene halide of 2, where X is independently C1 or F; CH2”’C(R)C(R)=CH2 substituted butadiene, where each R is independently 01-CIO alkyl, CI or F; formula CH2-CHC ON (R) Acrylamide derivative of 2, where each R is an independent hydrogen or 01~Cl　O alkyl; formula CH2-C(CH3)　CON　(R ) methacrylamide derivatives of 2, where each R is independently hydrogen or C1 ~C1o alkyl; and mixtures thereof. methacrylate esthetics and styrene are most preferred. Methacrylate esters useful in the present invention is a branched alkyl or n-alkyl ester of Cl-12 alcohol and methacrylic acid. esters, such as methyl and ethyl methacrylate. Methyl methacrylate is most preferred.

One known type of azo polymerization initiator is a soot that reacts with or dissolves semiconductors. It has the property of being easily soluble in the monomer mixture without oxidation, and has a unique half-life at the polymerization temperature. Therefore, it is served appropriately. The “specific half-life” used here is approximately 1 to 4 hours. The half-life is between Examples of such detonators include azocumene, 2.2--azobi (isobutylnitrile), 2.2-1azobis(2-methyl)butanenitrile , and 2-(t-butylazo)-2-cyanopropane. unique Other soluble non-azo initiators with half-lives of Includes benzoyl peroxide and lauroyl peroxide.

The glass/semiconductor composite is partially immersed in molten organic material and inserted into the glass hole. An inert organic material with a high melting point and specific dimensions is added to the glass/half by The bubble space of the conductor composite can be filled. This method involves machining or polishing A mechanically strong composite can be provided which can be Poor thermal stability and solvent leaching resistance compared to molecularly packed composites.

In certain instances, articles of manufacture of the present invention include pH-adjusted solutions of silicate glass precursors. is added to an aqueous solution of metal salts, mixed to form a gel, and the gel is dried to form a metal salt. forming an ion-implanted glass and exposing the dried gel to gaseous H2S or H2Se. to form semiconductor particles in the porous glass, and fill the remaining air bubble spaces in the glass with monomers. and polymerize the monomer to form the glass/polymer/semiconductor composite of the present invention. prepared by forming a compound. In addition, porous glass pieces are free of metal ions. The solution-saturated glass can be partially immersed in the solution, and then the solution-saturated glass is injected with metal ions. It is dried to give a glass. After the aforementioned gas treatment, the pores are monomerized. and the monomer is polymerized as described above. In a third different way The metal ion-implanted glass is exposed to a unique anion solution to form a porous glass. forming semiconductor particles inside.

Glass/semiconductor composites can be manufactured using the three methods mentioned above except for monomer injection and priming. It can be prepared by several methods. However, the appearance of the present invention These chipped materials can be easily injected into wet atmospheres and unopened holes. Very sensitive to liquids, resulting in clouding and cracking. these things The texture is very brittle and can only be polished by hand using dry techniques. these are , also exhibits poor optical properties.

In contrast, the glass/semiconductor/polymer composite of the present invention is similar to ordinary silicate glass. It has similar mechanical properties. The composite can be cut, machined and standard ceramic Can be polished by wet polishing technique. The optical properties of these composites are It is equivalent to that of standard optical glass. These composites are suitable for use in wet atmospheres or Not attacked by polar or non-polar organic solvents. However, the embedded Prolonged exposure to known solvents that dissolve polymers may cause some of the polymers to leach out. It may cause it to come out. Similarly, exposure to strong bases can cause silicate glass composites to Some glass may exude from the compound. These are embedded high It is thermally stable at the post-mixing point of the molecules.

The glass/semiconductor/polymer composite of the present invention can be formed into a variety of shapes. . Disks, plates, rods, etc. can be made using sol-gel moldings of special shapes. glass/semiconductor/polymer composites are often cut into Cut or polish. The fibers are solge-treated before drying and polymer injection. can be extracted from the file.

The manufactured article according to the present invention is a narrow frequency band bass filter, a UV cutoff filter, etc. and is useful as an optical filter such as a long wavelength pass filter. Generally, The lath matrix creates the desired shape for the filter, and the semiconductor materials and polymers are It is added for the purpose of The glass is then made into a filter with the desired optical properties. Polished to obtain. The use of such filters is well known in the art.

The invention is further illustrated in the following examples, all parts and percentages are by weight: All temperatures are in °C. The particle size in the example is determined by the nematode shape of the X-ray diffraction pattern. It was decided that In some cases, the minimum particle size can be determined from band gap energy measurements. Estimated. The amount of bandgap energy is compared to that of the provided Norku material. A large size indicates the presence of particles with a diameter of about 500 Å or less.

Example Method 1: Tetraalkyl orthosilicate (0.1 mol) is dissolved in methanol (0.1 mol). 75 mol) and/or formaldehyde (0,256 mol).

The use of methanol/formaldehyde mixtures may cause migration to large pore glasses. However, the drying time increases considerably. If desired, the resulting solvent can be used to control the pore size of the final glass. May be acidified with nitric acid to reduce oxidation. This mixture is diluted with dilution water (1 mol. desired amount of M(NO3)x (M-Cd, Pb, ZnSCuS) dissolved in It is added to a stirred solution containing In, Ga, Ti; x-2, 3). Generate The mixture is fluid at this stage if the pH is <10 and is poured into a bottle to form a gel. Become. The bottle may be made of any inert material (e.g. glass, polyethylene, polystyrene). polymers or polymerization temperatures are preferred because the This is because glass sticks to the glass bottle, causing it to shrink and close. Said Bottle is capped and heated at about 60°C for about 8 hours or until a hard firm gel product forms. heated up to. The bottle is capped and the gel is stored in the bottle at about 60°C for about 24 hours. It is dried in flowing air or until it shrinks to about 1/2 of its initial volume.

The partially dried gel is removed from the bottle and subjected to a slow lamp heating process. The gel is thoroughly dried at a high flow rate (200 cc/min) of oxygen or is heated in air at 450-500°C for 24-48 hours.

A colorless disk of highly porous glass is formed when the glass is M-Cu or In. They are obtained except in cases where they turn pale blue-green and pale yellow, respectively. glass at this stage is a metal ion (M=Cd) uniformly dispersed inside a highly porous and brittle skeleton.

It is pure silica containing Pb, Zn5CLJ% Ga). M=Ti or In At this stage, the metal oxides present in the glass, namely TiO□ and In2O , are themselves semiconductors. Typically, other semiconductor components are placed in high vacuum systems using glass. gaseous reagent (H2S, SH) while heating the glass in a tube furnace. 2S e SP H3, A s H3, S I M e 31) prepared from those glasses. Semiconductor cluster dimensions and color of said glass The temperature is determined either during the reaction with the gaseous reagent or by the annealing temperature after the reaction. is controlled.

To protect the semiconductor clusters and maintain dispersion, the pores of the glass are It is extinguished by filling the entire effective residual milk amount. This is an inert atmosphere The glass/semiconductor composite was added to lwt% of VAZO-64 (trade name manufactured by DuPont). ) to completely fill the pores of the glass. This is done by wicking with the monomer until the end. injected gas The lath was removed from the MMA/VAZO and kept at about 60°C in an inert atmosphere for about 8 hours. Heating causes the polymer of MMA to ooze out to deliver PMMA to the glass pores.

The use of other monomers may result in the use of different priming agents or polymerization conditions as described in the prior art. may request.

The dense glass/semiconductor/PMMA composite is made from a piece of ordinary silica glass. Cut and polished as if it had been cut and polished, with no residual pores.

Method 2: Porous sol prepared as described in Method 1 (with the exception of omitting the metal nitrate) Rugel glass or commercially available porous glass is made from the desired metal ion salts (nitric acid or is partially immersed in a solution (preferably a highly mobile organic solvent) of acetic acid). . The solution is fitted into the glass until the pores are completely filled. ck up). The solution-loaded glass is then wet-dried in Method 1. Dry slowly using the described protocol. Solvents and anions are removed by drying. removed during the process, leaving metal oxide species in the pores of the glass.

However, the distribution of metal species is not uniform, similar to that obtained with method 1. drying The glass is then exposed to a gaseous reagent as described in Method 1, causing the pore space to become highly concentrated. filled with children.

Nonlinear optical properties of composites For a substance to have third-order nonlinearity, the refractive index (n) measures the linear magnitude of the light intensity (1). It is a nonlinear refractive index. Generally, the unit used for n2 in MKS units is cm’/ It is KW.

Other parameters often used to characterize third-order nonlinearity are Yes, it is usually cut in cgs units like esu (“0ptical B15t ability: Controlling light with light ”, H, M, GibbsSAcademic PressSNew York, (see 1987) The third-order nonlinearity of materials is further classified into resonance and non-resonance. Resonance is the absorption of matter. Convergence, for example, refers to the overlap of laser wavelengths in the light absorption of a material, and non-resonance refers to the opposite. means. In the case of resonant nonlinearity, the absorption rate (α) of the material depends on the laser intensity, and α =α0+α2I (4) or This is the nonlinear absorption rate, which measures the magnitude of the nonlinearity. Both Δα and Δn are -Related based on Mars-Kronig's relation: Here, C is the speed of light, h is the blank constant, E is the optical frequency, and P is the Cauchy theory. Integral amount: Experimentally, either Δα or Δn can be measured, and based on equations (1) to (7), the total The third-order nonlinear parameter, α, is necessary in the case of resonant nonlinearity.

This is because nonlinearity depends on or is limited by the absorption rate of the material under the laser wavelength. be. Therefore, in the case of resonant nonlinearity, α2/αO”2/−b technique is used to calculate Δα. to measure and express either α2/α0 or Δα/α0 as nonlinear. Therefore, nonlinearity can be characterized.

If the material has significant n or α2, optical bistability and phase change (degeneracy) A number of third-order nonlinear optical phenomena, such as four-wave mixing (four-wave mixing), can be demonstrated. phase Variation experiments (described in the next section) are recognized for some of the materials of the invention.

The phase change efficiency defined as the intensity ratio of the phase change beam and the probe beam is , which is also a nonlinear measurement. It is shared by both n and α2, and is expressed as is proportional to: where λ is the laser wavelength and ■ is the pump beam intensity. phase change effect The rate depends on the crystal structure of the optical configuration, the spatial properties of the laser beam and the optical properties of the sample. Depends on. The phase change efficiency is therefore a good choice for configuring the material's intrinsic nonlinearity. It is not a universal parameter.

Laser-induced absorption changes. The change in sample conduction as a function of guided laser power (11) is , measured by absorption changes using the Ponbou probe technique. laser induced conduction The changes measure the magnitude and speed of the optical nonlinearity. The result is Δ0D10D.

where OD is defined as -1og(I/IO) is the optical density and ΔOD is the induced change in optical density.

The sample prepared for evaluation was irradiated with a dye laser using the optical arrangement depicted in Figure 1. irradiated by. As shown in Figure 1, a 10/90 beam splitter (B SI) splits the dye laser pulse into two parts. Some parts are strong pump beams. , a mirror (Ml), an attenuator and another mirror (M4). weak point The other part, which is a pump beam, passes through a filter (F) and then passes through a 50150 beam beam. Head to Pritsuta (BS2). Some signals from BS2 are reversed through BS2 It goes to the mirror (M2) that sends the side signal and goes to the detector that gives the reference signal. B The other probe beam from S2 is directed to mirror (M3). Pon from M4 The probe beam from M3 and M3 are directed towards the sample and empty at the sample. Intermittently and temporarily overlap. The intensity of the probe beam conducted through the sample (■ 1) is measured by the signal detector, and the signal strength from the reference detector is measured by the boxcar integrator. distributed along with the power to correct for laser intensity fluctuations. The output dependence of ΔOD is as a function of the pump beam intensity, where the beam intensity is adjusted by an attenuator. is obtained by measuring the changes in the intensity of a conducted beam.

was irradiated. 10/90 beam splitter (BSI) as shown in Figure 2. splits the dye laser pulse into two parts. Some of the low signals from BSI , 50150 beam splitter (BS2), and perform reference detection of the reference beam. (D), and sends the probe beam (IP) to the mirror (Ml).

The other signal from the BSI goes to the 50/50 beam splitter (BS3).

A part of this beam, the forward pump beam (■1), is sent to the attenuator and mirror (M2). I am headed. Forward and aft pump beams from M2 and M3 and pump beams from Ml. A lobe beam is directed towards the sample and overlaps spatially and temporally with the sample.

The phase change beam (I) returns to BS2 and is detected by D. It will be done. ■ The size of test S C Measure optical nonlinearity of materials. ■ is distributed by the signal from the reference detector and correct for laser intensity fluctuations. Nonlinear output dependence adjusts the intensity of 11 with an attenuator It is measured by The nonlinear time dependence means that the arrival time of Ib can be measured on the delay path. It is measured by adjusting the

In the samples evaluated in these experiments, the dominant contribution to the nonlinearity was the laser This is due to induced absorption bleaching and related changes in the refractive index. pump probe experiment measures the sample absorption changes, and the changes related to the refractive index can be obtained based on analysis. Large absorption changes from Ponbu probe experiments The observation of can be correlated to the observation of strong phase change signals from DFWM experiments.

warm Cadmium-loaded glass disks were prepared using 1,0 Og nitric acid dissolved in 18 ml of water. Cadmium, tetramethyl orthosilicate (15ml), methanol (25ml) ml) and nitric acid (2 ml)) as described in Method 1. Generate The solution was thoroughly mixed and poured into a 25 ml polyethylene bottle to a depth of about 1/4 inch. Approximately 3 ml of water was injected. After heating and drying, the resulting definite cadmium One of the loaded glass disks (approximately 0.35 g) was placed under high vacuum (10-3 t o r r) and exposed to H2S at 200 torr. The disk is Heated at 100°C for 15 minutes in an H2S atmosphere of 00 torr, then heated under vacuum. It will be processed for another 15 minutes. After cooling to room temperature, the yellow disc should be placed in a glove box. 1% V of methyl methacrylate (MMA) It is immersed in azo-64 (trade name of DuPont) solution. MMA saturation disc , placed in a tightly capped jar and heated in a vacuum oven at 60° C. overnight. M MA is polymerized into a dense glass/CdS/polymethyl methacrylate (PM MA) Obtain the composite. The X-ray pattern of the composite shows the presence of crystalline CdS with particle size 40. Indicates presence.

The Cd:S ratio obtained from elemental analysis of CdS-containing composites is probably 1°0 to 1.7 as a result of incomplete conversion to CdS.

Examples 2-21 The procedure essentially as described in Example 1 can be applied to other glasses/semiconductors as shown in Table 1. /PMMA composites. In all cases, the color of the glass I admit that the tone is very uniform.

The weight of metal salt given is the addition of the formulation given in Example 1 above.

Table 1 Glass/semiconductor/PMMA composite Example Semiconductor (Wt, investigated range) Anion source (range) I CclS Cd CNOs, ) 2.1.0g H2S Yellow (colorless (0,025-1. 0g) - yellow) 2 PbS' Pb CN0s)y, H, S (brown-4 colors) (0,025~ 1.0g) 3 ZnS Zn (Nov) i, O, Ig Hx S None Color 4 CuS C ttCNOs)z, o, 1g IbS Green brown 5 Ga2 s3 Ga (NO 3, H, S, no color (0,025-0.75g) 6　1n2　Sx　In　CNOs　)s, H,S Yellow color (0,025~1 ．． 0g) → Red) 8 Pb5e pb CN0s) 2, H, Se Black color (0,025-0.5g) 9ZnSe Zn (No,) 2.0.1g H2Se Yellow Color 10CuSe C u(NOx) 2.0.1g HxSe brown-black 11 Ga2Sel Ga( NO))s, HzSe yellow (0,025-0.75g) 12 In2Se, In(No,)z, HxSe (Orange-(0,025~ 1. 0g) m red) 13 Cds P2 Cd, (Not) 2, PH, (Colorless = (0,025-1.0g) black) 14 pb3p2 Pb (NOs) 2.0.025g PHx R color 15 Zn s P-x Zn (NOs)z, 0. Ig PH, None Color table 1 (continued) Metal salt 8 color 5 17 Pbs AS2 Pb (Not) 2.0. Ig ASHs black color 18 Z113AS2 Zn(NOx)-x, 0. Ig AsH3 Yellow Color 19 Pb 12 Pb (Not) 2.0.1g MeSil Yellow Color 20 TiO2Ti (i-QC, H,) 4 None Color a, used in the specific examples mentioned The amount of metal salt is immediately given as follows: Numbers in parentheses are used for other preparations. The weight ranges for the metal salts used are shown, and the same is true for glass/semiconductor/PMMA composites. child These numbers represent only the substantial amounts used and are not meant to be limiting.

b, Colors in parentheses indicate practical observations of samples with different metal loading and annealing conditions. color. These colors serve as an indication only and are not meant to be limiting. stomach.

c, P b: S = 1. Os determined by, for example, elemental analysis.

c3. Cd: 5e-1,3, determined for example by elemental analysis.

Vycol/CdS/PMMA composite was prepared by the procedure mentioned in Method 2. Ta. Vycor glass pieces (1/2 inch removed and oxygen passed to capture organic matter) It was fired at 500°C. Clean and cooled glass is Cd(NOi)2 The pores of the glass were filled with the aqueous solution (containing 1.0g in 10ml). Partially immersed until cooked. The glass was heated at -60°C while air was flowing through it. It was dried day and night and then at 450° C. for 24 hours. cooled cadmium The filler glass was treated with H2S and MMA as described in Example 1. resulting in The composite is non-uniformly colored and contains a non-uniform semiconductor (CdS) distribution. There tends to be.

Examples 23-25 This procedure is applicable to other Vycol/semiconductor/PMMA composites as shown in Table 2. Used in preparation.

Vycol/Semiconductor/PMMA composite Example Semiconductor (Wt, investigated range) Anion source (range) 22 CdS Cd (NOv) 2.1. 0g H2S Yellow color (0,025-1 ．． 0g) 23 PbS Pb (Now) 2, H, S Black color (0,025-1.0 g) 24 CdSe Cd CNOs) x, H, Se Red-orange (0,025~ 1.0g) 25 Pb5e Pb CNOs) x, HzSe Black color (0,025~) ,,Og) a. The amount of metal salt used in the particular example given is immediately given by the following salt: . Numbers in parentheses indicate weight ranges of metal salts used in other preparations, glass/semiconductor The same is true for body/PMMA composites. These numbers only reflect the substantial amount used. represents and is not meant to be limited.

b, Colors in parentheses indicate practical observations of samples with different metal loading and annealing conditions. Indicates the colored color. These colors serve as an indication only and are meant to be limited. do not have.

Examples 26-29 Table 3 shows the resonance X(3) properties of selected glass/semiconductor/polymer composites.

In general, the nonlinearities of Examples 26-28 are the same as those of the reference material, Cd x S e H-x It has long been well known that it is one of the substances compared to doped glass. There is.

relative absorption change PbS 27 625nm IMW/am’-6,3%n2S3 in sol-gel 28 540nm in sol-gel 3.2MW/cm2 +5%In, Se x 570nm 1.9MW/cm' +2.6%625nm 1.0MW/c m'-5.7%29 450nm in sol-gel 2.8MW/cm'- 22%dS Comparison *Corning BMW/cm' -29% 3-69 filter 500nm *Corning 3 69 (Cd-S es-) doped glass parameters are: Albright et al, Opt.

Excerpted from Letters, Dan, 41.3 (1987).

Example 30 A degenerate four-wave mixing experiment (optical phase change) is performed using the configuration shown in Figure 2 in a sol-gel thin film. Executed on CdS. The phase change efficiency is 1.3X10-3 of the probe beam, Specifically, the phase change signal intensity was 0.13% of the probe beam.

FIG.1 FIG.2 international search report

Claims (10)

[Claims] 1. Substantially porous glass, polymeric and semiconducting materials contained in the pores of said glass The semiconductor material is Cd+2, Zn+2, Pb+2, Cu+2, Ga+ 3, at least one cation selected from the group consisting of In+3 and Ti+3 and S-2, Se-2, O-2, I-2, P-3, Sb-3 and As-3. and at least one anion selected from the group Manufactured articles. 2. The article of manufacture according to claim 1, wherein the semiconductor is CdS, Cd Se, ZnS, ZnSe, PbS, PbSe, PbI2, CuS, CuSe, T iO2, In2O3, Ga2S3, In2S3, Ga2Se3, Cd3As2, Pb3P2, Zn3P2, Cd3P2, Pb3As2, Zn3As2 and In selected from the group consisting of 2Se3, Ga2Se3, Ga2S3, In2S3 , Ga2Se3 and all phosphides plus arsenides. 3. The article of manufacture according to claim 1, wherein the polymer is methacrylate. ester; acrylate ester; styrene; vinyl acetate; acrylate Nitrile; methacrylonitrile; vinylidene halide of formula CH2=C(X)2 , where each X is C1 or F; the formula CH2=C(R)C(R)=C H2-substituted butadiene, where each R is an independent C1-C10 alkyl Cl, C1 or F; an acrylamide derivative of the formula CH2=CHCON(R)2 a conductor, where each R is independently hydrogen or C1-C10 alkyl; A methacrylamide derivative of the formula CH2=C(CH3)CON(R)2, where it Each R is independently selected from the group consisting of hydrogen or C1-C10 alkyl. It is prepared from at least one monomer. 4. The article of manufacture according to claim 1, wherein the glass comprises SiO2, GeO2, TiO2, Y2O3, ZrO2, SiO2-BaO, SiO2-B2 O3, SiO2-B2O3-Na2O, SiO2-Na2O, SiO2-K2O , SiO2-A12O3, SiO2-GeO2, SiO2-TiO2, SiO2 -Y2O3, Al2O3-GeO7, Al2O3-ZrO2, TiO2-ZrO 2. Group consisting of ZrO2-SiO2, PbO-La2O3-ZrO2-TiO2 selected from. 5. In the article of manufacture of claim 4, the preferred glass is SiO2 It is. 6. In the article of manufacture according to claim 1, the preferred monomer is methacrylate. rate esters and styrene. 7. In the article of manufacture according to claim 6, the preferred monomer is methylmethane. It is tacrylate. 8. The article of manufacture according to claim 1, wherein the cation concentration in the glass is The concentration is about 0.01 wt% to about 20 wt%. 9. The article of manufacture of claim 8, wherein the concentration is about 0.1 wt%. ~5wt%. 10. An article of manufacture comprising the article of claim 1 and a source of coherent electromagnetic radiation. A device for generating a third-order nonlinear optical effect, characterized in that: