JP2002104842A - Glass composition containing ultra-fine particle of semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new glass composition having characteristics such as photoabsorption/emission, high refractive index, excellent transparency, etc., preferably utilizable as a material for a photo-emitter of a display and an illumination utensil or a material for optical parts such as an optical guide. SOLUTION: This glass composition comprises an amorphous matrix mainly composed of metal element to oxygen bond in which ultra-fine particles of a semiconductor are uniformly dispersed, the heat loss in air being 10 to 80 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass composition in which ultrafine semiconductor particles are uniformly dispersed. The semiconductor ultrafine particles contained in the glass composition of the present invention have characteristics such as a light emitting ability with a narrow half bandwidth of a light emitting band and a high refractive index. Therefore, since the glass composition of the present invention retains such characteristics, when it is formed into a thin film or a fibrous molded product, it can be used for optical applications such as an optical waveguide or a luminous body such as a display or a lighting fixture.

[0002]

2. Description of the Related Art Inorganic glass represented by quartz glass includes:
A functional optical glass in which various optical functional materials are dispersed is provided. Moreover, as compared with amorphous resins represented by styrene resins, acrylic resins, or aromatic polycarbonate resins, they have excellent characteristics such as excellent heat resistance and solvent resistance, or a low coefficient of linear expansion. . However, since such glass molding generally requires melting at a high temperature, there is a disadvantage in that, for example, productivity in obtaining a thin film-shaped molded body is poor.

[0003] As a method for synthesizing a glass mainly containing a metal element-oxygen bond which can disperse a photofunctional organic substance while improving such disadvantages, there is known a so-called sol-gel method for hydrolytic condensation of metal alkoxide. Have been.
Commonly used metal alkoxides in the sol-gel method are alkoxysilanes. Then, the raw material solution of the sol-gel method or the raw material solution which has been subjected to oligomerization to such an extent that fluidity is not lost is applied to a desired substrate and then vitrified to easily form a thin film under mild conditions. You can get the body.

On the other hand, semiconductor ultrafine particles have absorption / emission characteristics due to the quantum effect of a semiconductor crystal as a main component thereof.
Industrial application as a new optical functional material is expected. Ultrafine particles having such properties include colloid particles, nanocrystals, and nanoparticle (Nancrystal).
Optics, or Quantum Dots (Quan)
Tum dot) or the like. In particular, the excellent light emitting characteristics of semiconductor ultrafine particles having an organic ligand such as phosphine oxides bonded thereto are described in, for example, E. FIG. B. Kat
ari et al; Phys. Chem. , 98, 410
9-4117 (1994). But,
Even if it is attempted to dissolve such conventional semiconductor ultrafine particles bound with an organic ligand in the sol-gel method raw material solution,
Since the raw material solution is usually a hydroalcoholic solution, sufficient solubility cannot be obtained, and the vitrified glass composition becomes cloudy, so that it has been difficult to apply it to optical applications.

In US Pat. No. 5,990,479 (1999), for example, a coordinating alkoxysilane such as 3-mercaptopropyltrimethoxysilane is first allowed to act on the surface of a semiconductor nanocrystal mainly composed of CdSe. Then, an alkoxysilane having a functional group useful for imparting hydrophilicity or biological interaction (hereinafter referred to as a biofunctional group) such as trimethoxysilylpropylurea or aminopropyltrimethoxysilane is allowed to act under alkaline conditions. Discloses a method of introducing the biofunctional group by promoting the sol-gel reaction on the semiconductor crystal surface. However, since the purpose of this technique is to introduce the biofunctional group onto the surface of the semiconductor nanocrystal by the sol-gel method, the biofunctional group is formed to avoid the formation of a glass matrix by the sol-gel method. The reaction concentration of silanes in water-containing methanol is 0.1
It is assumed to be extremely dilute to about 0.01% by volume. Therefore, with the technology disclosed herein, it was practically impossible to prepare a glass composition in which semiconductor ultrafine particles were dispersed.

Further, a method called an ion implantation method in which a semiconductor material is absorbed into a glass matrix to form semiconductor ultrafine particles in the matrix is disclosed in, for example, A.I. Meldrum et al .; Mater. Res. So
c. Symp. Proc., 536, 317-322.
(1999). However, in this method, the ions of the semiconductor raw material are implanted from the surface of a glass matrix such as quartz glass formed in advance, so that there is a limit in controlling the concentration of the semiconductor ultrafine particles in the depth direction from the surface and the control of the particle size. there were.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to form semiconductor ultrafine particles uniformly in an amorphous matrix and to form them under mild conditions. And a molded product thereof.

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies on glass synthesis by a sol-gel method and on ultrafine semiconductor particles having solubility in a sol-gel reaction system. As a result, the use of semiconductor ultrafine particles combined with an organic ligand containing a polyethylene glycol residue, such as triethylene glycol monomethyl ether, achieves highly uniform dispersion of semiconductor ultrafine particles in an amorphous matrix. This has led to the present invention.

That is, a first gist of the present invention is that ultrafine semiconductor particles are uniformly dispersed in an amorphous matrix mainly composed of a metal element and an oxygen bond, and the heat loss in air is 10 to 8%.
0% by weight of the glass composition. Further, a second gist of the present invention is a method for producing the glass composition, comprising a step of performing a hydrolysis-condensation reaction of a metal alkoxide mainly composed of alkoxysilanes in the presence of semiconductor ultrafine particles bonded with an organic ligand, Exists.

A third aspect of the present invention resides in a thin-film or fiber-shaped molded product of the above-mentioned glass composition. Further, a fourth gist of the present invention resides in an optical waveguide using any one of the molded bodies.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Glass Composition] The glass composition of the present invention is obtained by uniformly dispersing semiconductor ultrafine particles to be described later in an amorphous matrix mainly composed of a metal element-oxygen bond. The heating loss in air is 10 to 80% by weight. The non-crystalline matrix mainly composed of a metal element-oxygen bond is exemplified most typically as a composition mainly composed of silica (SiO ₂ ).
“Amorphous” in the present invention means a structure that does not clearly show a diffraction peak due to an ordered structure by X-ray scattering measurement (XRD). "Matrix" in the present invention
Means a continuous phase containing a dispersed phase such as semiconductor ultrafine particles.

The expression "mainly composed of a metal element and an oxygen bond" means that the maximum proportion of all the chemical bonds constituting the amorphous matrix is a metal element-oxygen bond. Oxygen bond ratio is usually 30 to 95
%, Preferably 40 to 90%, more preferably 50 to 8%
5%, most preferably 55-80%. If the ratio is less than 40%, the mechanical strength and the coefficient of linear expansion of the glass composition may be extremely reduced. There is.

The glass composition of the present invention contains semiconductor ultrafine particles uniformly dispersed in the amorphous matrix.
The condition of uniform dispersion as referred to herein means a state in which any of the following two kinds of measured physical property fluctuation ranges in an arbitrary place of the glass composition is satisfied, and the two kinds of measured physical property fluctuation ranges are: One is a refractive index n _d ²⁵ (a refractive index measured at 25 ° C. using a sodium D line as a light source; for example, AST
(Measured in accordance with the MD542 standard) is within ± 0.05 (the fluctuation range is preferably within 0.03, most preferably within 0.01), and the other is 1 mm
Absorbance (wavelength is arbitrarily selected) calculated in proportion to the thickness of the sample is within ± 0.1.
5 or less, and most preferably 0.01 or less). In a uniform dispersion state of the glass composition of the present invention, when observed by a transmission electron microscope (TEM),
Aggregation of the semiconductor crystal, which will be described later, which is the main component of the semiconductor ultrafine particles contained therein is not usually observed, and of course, neither aggregation nor turbidity is visually observed.

The above-mentioned loss on heating in air specifically means the loss on heating when the temperature is raised from 30 ° C. to 550 to 600 ° C. The heating loss here is a heating loss measured by, for example, thermogravimetric analysis (TG) under air flow. Such heating is performed, for example, in a range of 30 ° C. to 550 to 600 ° C. for a sample of about 10 mg. 5 to 2 per minute
If the temperature is raised at a temperature rising rate of about 0 ° C. and the temperature is kept in the range of 550 to 600 ° C. for 90 minutes or more, a measured value of weight loss with sufficient reproducibility is usually given. Such a heat loss is caused by the residual solvent, the organic structure such as an alkoxy group in an amorphous matrix or a hydroxyl group, or the organic structure such as an organic ligand contained in the semiconductor ultrafine particles being evaporated, thermally decomposed, or condensed. This is considered to be caused by loss due to elimination of the group. Such a heating loss is preferably as small as possible in terms of an increase in the elastic modulus of the glass composition and a decrease in the coefficient of linear expansion.
If the amount is less than 0% by weight, the homogeneity of the glass composition as a molded article may be reduced. On the other hand, when it is desired to provide the glass composition with appropriate toughness (impact resistance and flexibility), it is preferable to control the elastic modulus to an appropriate range.
Such control of the elastic modulus can be performed, for example, in a method for producing a glass composition of the present invention by a sol-gel method described below, in which a metal alkoxide which is a matrix material has a non-hydrolyzable substituent such as an alkyl group or a phenyl group. Or by controlling the degree of progress of the hydrolysis-condensation reaction. Therefore, the suitable range of the heating loss varies depending on the purpose. For example, when it is used as a thin film or a fibrous formed body as described below, it is preferably 15 to 70% by weight, more preferably 20 to 60% by weight,
Most preferably, it is about 25 to 55% by weight.

[Physical Properties of Glass Composition] The glass composition of the present invention preferably has transparency at any wavelength in the visible region. The above refractive index n _d of the glass composition of the present invention.
²⁵ is usually in the range of about 1.5 to 2.7, but for the purpose of increasing the refractive index, the lower limit of the refractive index is preferably 1.
55, more preferably 1.6, most preferably 1.7, and considering the balance of mechanical properties and moldability, the upper limit of the refractive index is preferably 2.5, more preferably 2.4, most preferably 2.4. 2.3. The refractive index is controlled by the content of the semiconductor ultrafine particles described later and the composition of the amorphous matrix. The semiconductor ultrafine particles described below usually have a function of imparting a high refractive index to the glass composition of the present invention, and the main factor is that the semiconductor crystal constituting the semiconductor ultrafine particles occupies a space in the glass composition, There is an effect that a high refractive index contributes.

In order to obtain a sufficient effect of increasing the refractive index, the glass composition of the present invention contains 5% by volume or more, preferably 10% by volume or more, and more preferably 10% by volume or more of semiconductor ultra-fine particles as the main semiconductor crystal. 15% by volume or more, most preferably 20% by volume or more, while the content is usually 70% by volume or less, preferably 60% by volume or less, in terms of mechanical properties, moldability or specific gravity of the glass composition. Preferably it is 50% by volume or less, most preferably 40% by volume or less. Such quantification of the semiconductor crystal content is possible by observing a semiconductor crystal image by a transmission electron microscope (TEM) (information on elemental analysis of an image by a technique such as EDX is also obtained in addition to the particle size). Semiconductors determined by any elemental analysis such as various emission analysis such as fluorescence X-ray analysis of the glass composition obtained or by dissolving the glass composition in a suitable liquid such as strong alkaline water or hydrofluoric acid. It can be estimated from the content weight of the composition and the crystal specific gravity of the semiconductor composition.

The transparency of the glass composition of the present invention is determined by the fact that the light transmittance at a wavelength in the visible region outside the absorption wavelength region of the ultrafine semiconductor particles contained is usually 7 in terms of a proportional conversion of an optical path length of 3 mm.
0% or more, preferably 80% or more, more preferably 85% or more.
%, Most preferably 90% or more. Such a measurement can be performed, for example, using ASTM D-1003 (3
(mm thickness). Here, the visible region means a wavelength region of 400 to 650 nm.
However, as described below, properties not depending on the transparency in the visible region wavelength of the glass composition of the present invention, for example,
When utilizing the property of shielding high energy electromagnetic waves such as X-rays and gamma rays, elementary rays such as electron beams and neutron rays, and low molecular rays such as α rays, such transparency may not be required.

The glass composition of the present invention has a light absorption or light emission (hereinafter, referred to as absorption and emission) ability by a quantum effect of a semiconductor crystal constituting semiconductor ultrafine particles contained therein, and the absorption according to the particle diameter of the semiconductor crystal. In some cases, the composition has a function as a luminescent glass composition having a controllable emission wavelength. There is no particular limitation on the composition of the semiconductor crystal imparting such light-absorbing ability, but a particularly preferable semiconductor crystal composition is a II-VI compound semiconductor or a III-V compound semiconductor described later.

An optional additive may be added to the glass composition of the present invention.
For example, antioxidants, heat stabilizers, or stabilizers such as light stabilizers, glass fibers, glass beads, mica, talc,
Fillers such as kaolin, clay minerals, carbon fibers, carbon black, graphite, metal fibers, metal powders, additives such as antistatic agents, plasticizers, ultraviolet absorbers, and coloring agents such as pigments and dyes are required. It is also possible to mix optional additives accordingly.

The metal element Configuration composition of the amorphous matrix] constituting subject of the amorphous matrix - if a specific example of the oxygen bond as the composition formula of the corresponding metal oxides, lithium oxide (Li ₂ O ), Sodium oxide (Na ₂ O),
Potassium oxide (K ₂ O), rubidium oxide (Rb ₂ O),
Alkali metal oxides such as cesium oxide (Cs ₂ O), magnesium oxide (MgO), calcium oxide (Ca
O), alkaline earth metal oxides such as strontium oxide (SrO) and barium oxide (BaO), boron oxide (B ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), phosphorus oxide (P ₂ O ₅ ), titanium oxide (Ti
O ₂ ), zinc oxide (ZnO), gallium oxide (Ga
₂ O ₃ ), germanium oxide (GeO ₂ ), zirconium oxide (ZrO ₂ ), cadmium oxide (CdO), tellurium oxide (TeO ₂ ), barium oxide (BaO), tungsten oxide (WO ₃ ), tantalum oxide (Ta ₂₎ O _5), lead oxide (PbO), bismuth oxide (Bi ₂ O _{3) 2-valent,} etc. 6
Examples thereof include oxides of valent elements, and a part of these metal elements can be replaced with lanthanoid cations.
Of these, preferred are B ₂ O ₃ , Al ₂ O ₃ , SiO ₂ ,
Oxides of trivalent to pentavalent elements such as P ₂ O ₅ , TiO ₂ , GeO ₂ , and ZrO ₂ , among which aluminum oxide Al ₂ O ₃ ,
SiO ₂ , TiO ₂ , ZrO _{2, and the} like are suitably formed by a sol-gel method described later, and particularly, SiO ₂ and TiO ₂ are optimal.

The above-mentioned amorphous matrix is composed of such a metal acid.
May contain an inorganic glass composition other than the oxide composition
Specifically, lithium fluoride (LiF), sodium fluoride
Thorium (NaF), potassium fluoride (KF), fluoride
Such as rubidium (RbF) and cesium fluoride (CsF)
Alkali metal fluoride, beryllium fluoride (Be
F_Two), Magnesium fluoride (MgF_Two), Aluminum fluoride
Um (AlF_Three), Calcium fluoride (CaF_Two)
Scandium (ScF)_Three), Manganese fluoride (Mn)
F _Two), Iron fluoride (FeF_Two, FeF_Three) Cobalt fluoride
(CoF_Two), Nickel fluoride (NiF_Two), Zinc fluoride
(ZnF_Two), Gallium fluoride (GaF_Three), Fluoride strike
Ronium (SrF_Two), Yttrium fluoride (Y
F_Three), Zirconium fluoride (ZrF_Four), Cadmium fluoride
Um (CdF_Two), Indium fluoride (InF_Three)
Barium (BaF)_Two), Lanthanum fluoride (LaF_Three),
Neodymium fluoride (NdF_Three), Ytterbium fluoride
(YbF_Three), Lead fluoride (PbF_Two), Thorium fluoride
(ThF_Four), Etc., fluorides of divalent to tetravalent elements, gallium
(Ga), germanium (Ge), phosphorus (P), arsenic
(As), antimony (Sb), etc.
Element, sulfur (S), selenium (Se), tellurium (Te), etc.
Examples include elements of Group 16 of the periodic table.

Any combination of these inorganic glass raw material compositions
A very wide range of inorganic glass compositions is known
Constituent composition of the amorphous matrix of the glass composition of the present invention and
Can be used, for example, TeO_Two-BaO-Z
nO, TeO_Two-WO_Three-Ta_TwoO_Five, TeO_Two-WO_Three-B
i_TwoO_Three, TeO_Two-BaO-PbO, CaO-Al
_TwoO_Three, CaO-Al_TwoO_Three-BaO, CaO-Al_TwoO_Three−
Na_TwoO, CaO-Al_TwoO_Three-K_TwoO, CaO-Al_TwoO_Three
-SiO_Two, PbO-Bi_TwoO_Three-BaO, PbO-Bi_Two
O_Three-ZnO, PbO-Bi_TwoO_Three, PbO-Bi_TwoO_Three−
BaO-ZnO, PbO-Bi_TwoO_Three-CdO-Al
_TwoO_Three, PbO-Bi_TwoO_Three-GeO_Two, PbO-Bi_TwoO_Three
-GeO_Two−Tl_TwoO, BaO-PbO-Bi_TwoO_Three, Ba
O-PbO-Bi_TwoO _Three-ZnO, Bi_TwoO_Three-Ga_TwoO_Three−
PbO, Bi_TwoO_Three-Ga_TwoO_Three-CdO, Bi_TwoO_Three-Ga
_TwoO_Three-Oxide glass such as (Pb, Cd) O, ZrF_Four
-BaF_Two, ZrF_Four-ThF_Four, ZrF_Four-BaF_Two-N
aF, ZrF_Four-BaF_Two-ThF_Four, ZrF_Four-BaF_Two
-LaF_Three, ZrF_Four-BaF_Two-MFn-AlF_Three(However,
Here, MFn is LiF, NaF, CaF_Two, Y, F_Three, G
aF_Three, LaF_Three, NdF_Three, ThF_FourEtc.), ZrF
_Four-BaF_Two-LaF_Three-AlF_Three-NaF (commonly known as ZBLA)
Zirconium fluoride glass such as N), AlF_Three-Pb
F_Two-SrF_Two-MgF_Two, AlF_Three-BaF_Two-YF_Three-T
hF_Four, AlF_Three-YF_Three-BaF_Two-CaF_Two, AlF_Three−
CdF_Two-LiF-PbF_TwoAluminum fluoride glass such as
System, PbF_Two-MF_Two-XF_Three, AF-MF_Two-XF
_Three(Where A is an alkali metal, M and X are independently iron,
Transition metals such as cobalt and nickel), I
nF_Three-BaF_Two-YF_ThreeTrifluoride glass etc.
System, As-S, Ge-S, Ge-PS, As-Se,
As-Ge-Se, Ge-Se, Ge-As-Se, L
a-Ga-Ge-Se, Ge-Sb-Se, Ge-Se
-Te, As-Ge-Se-Te, As-Se-Te, etc.
Chalcogenide glass system, TeCl_Four, TeBr_Four, T
eI_FourSuch as chalcohalide glass, boron nitride (B
N) glass and the like.

In any of the inorganic glass compositions exemplified above,
When lanthanoid cations such as Er ³⁺ , Pr ³⁺ , Eu ³⁺ , and Tb ³⁺ are contained, useful energy can be transferred by transferring energy between the lanthanoid cation and the semiconductor ultrafine particles contained in the glass composition of the present invention. Absorption and emission may be obtained in some cases. [Semiconductor ultrafine particles] The semiconductor ultrafine particles, which are components of the glass composition of the present invention, are mainly composed of a semiconductor crystal as described below, and usually bind an organic ligand to the surface of the semiconductor crystal.

The semiconductor crystal may be either a semiconductor single crystal, a mixed crystal in which a plurality of semiconductor crystal compositions are phase-separated, or a mixed semiconductor crystal in which phase separation is not observed, and may have a core-shell structure described later. . The particle size of such a semiconductor crystal is usually 0.5 to 20 nm as a weight average particle size, and preferably 1 to 15 n in terms of electromagnetic characteristics such as light-absorbing and emitting ability.
m, more preferably 2 to 12 nm, most preferably 2 to
It is set to 10 nm. The absorption and emission characteristics of the semiconductor crystal due to the quantum effect are controlled by such a particle size, which can usually be determined by observing the glass composition with a transmission electron microscope (TEM). When the atomic number of an element contained in a semiconductor crystal is small and it is difficult to obtain a contrast by an electron beam, it can be estimated by light scattering or neutron scattering measurement of the composition.

Although there is no limitation on the particle size distribution of the semiconductor crystal,
In the case of utilizing the light emission characteristics due to the quantum effect of a semiconductor crystal,
By changing the distribution, the required emission wavelength width can be changed. In the case where the wavelength width needs to be narrowed, the particle size distribution is narrowed, but the standard deviation is usually within ± 40%, preferably within ± 30%, more preferably within ± 20%, and most preferably. Is within ± 10%. In the case of a particle size distribution exceeding the standard deviation range, it is difficult to sufficiently achieve the purpose of narrowing the emission band wavelength width due to the quantum effect.

The glass composition of the present invention may contain a plurality of types of semiconductor ultrafine particles, or even if the semiconductor ultrafine particles made of the same type of semiconductor crystal have a particle size distribution such as a two-peak distribution, arbitrarily. You can change it. The semiconductor ultrafine particles contained in the resin composition of the present invention may be bonded with any ligand other than the above-mentioned radically copolymerized phosphorus atom-containing ligand.

[Composition of semiconductor crystal] The above semiconductor ultrafine particles
There is no particular limitation on the composition of the semiconductor crystal contained in the semiconductor.
Examples of physical compositions include carbon, silicon, germanium,
Simple substance of element of group 14 of the periodic table such as tin, phosphorus (black phosphorus)
Periodic Table of the Periodic Elements of Group 15 Elements, Selenium, Tellurium, etc.
A simple substance of group 16 elements, and a plurality of elements such as silicon carbide (SiC)
A compound composed of an element of Group 14 of the periodic table, tin (IV) oxide (S
nO_Two), Tin sulfide (II, IV) (Sn (II) Sn (IV) S_Three),
Tin (IV) sulfide (SnS_Two), Tin (II) sulfide (SnS),
Tin (II) selenide (SnSe), Tin (II) telluride (S
nTe), lead (II) sulfide (PbS), lead (II) selenide
(PbSe), lead (II) telluride (PbTe), etc.
Compound of group 14 element and periodic table group 16 element, nitriding
Boron (BN), boron phosphide (BP), boron arsenide
(BAs), Aluminum nitride (AlN), Al phosphide
Minium (AlP), aluminum arsenide (AlAs),
Aluminum antimonide (AlSb), gallium nitride
(GaN), gallium phosphide (GaP), gallium arsenide
(GaAs), gallium antimonide (GaSb), nitrogen
Indium phosphide (InN), Indium phosphide (InN)
P), indium arsenide (InAs), indium antimonide
Group 13 elements such as indium (InSb) and Periodic Table
Compounds with Group 15 elements (or III-V compounds)
Body), aluminum sulfide (Al_TwoS_Three), Aluminum selenide
Ni (Al_TwoSe_Three), Gallium sulfide (Ga_TwoS_Three),
Gallium lenide (Ga_TwoSe_Three), Gallium telluride (G
a_TwoTe_Three), Indium oxide (In) _TwoO_Three), Sulfide
Um (In_TwoS_Three), Indium selenide (In)_TwoS
e_Three), Indium telluride (In)_TwoTe_Three) And other periodic tables
Compounds of Group 13 elements and Group 16 elements of the periodic table;
Lithium (I) (TlCl), thallium (I) bromide (Tl
Br), thallium (I) iodide (TlI), etc.
Compound of group 13 element and group 17 element of the periodic table, zinc oxide
(ZnO), zinc sulfide (ZnS), zinc selenide (Zn
Se), zinc telluride (ZnTe), cadmium oxide
(CdO), cadmium sulfide (CdS), cadmium selenide
CdSe, Cadmium Telluride (CdT)
e), mercury sulfide (HgS), mercury selenide (HgS)
e), mercury telluride (HgTe), etc.
Compound of element and element of group 16 of the periodic table (or group II-VI
Compound semiconductor), arsenic sulfide (III) (As_TwoS_Three), Sele
Arsenic (III) (As_TwoSe_Three), Arsenic (III) telluride
(As_TwoTe_Three), Antimony (III) sulfide (Sb
_TwoS_Three), Antimony (III) selenide (Sb_TwoSe_Three),
Antimony (III) telluride (Sb_TwoTe_Three), Bis sulfide
Trout (III) (Bi_TwoS_Three), Bismuth (III) selenide
(Bi_TwoSe_Three), Bismuth (III) telluride (Bi)_TwoTe
_Three) And other elements of the Periodic Table Group 16 and the Periodic Table Group 16
Compound, copper (I) oxide (Cu_TwoO), copper (I) selenide
(Cu_TwoSe) and other elements of Periodic Table 11 and Periodic Table 16
Compounds with group III elements, copper (I) chloride (CuCl), copper bromide
(I) (CuBr), copper (I) iodide (CuI), chloride
Periodic Table 11 of silver (AgCl), silver bromide (AgBr), etc.
Compound of group 17 element and group 17 element of the periodic table, nickel oxide
(II) Periodic Table Group 10 elements such as (NiO) and Periodic Table 1
Compounds with Group 6 elements, cobalt (II) oxide (CoO),
Group 9 elements of the periodic table such as cobalt (II) sulfide (CoS)
Compounds with Group 16 elements of the periodic table, triiron tetroxide (Fe
_ThreeO_Four), Periodic table group 8 elements such as iron (II) (FeS)
Of manganese with Group 16 element of the periodic table, manganese oxide (II)
(MnO) and other Group 7 elements of the Periodic Table and Group 16 elements
With molybdenum (IV) sulfide (MoS_Two), Oxidation
Tungsten (IV) (WO_Two) And other elements of Group 6 of the periodic table
Compound with Group 16 element of the periodic table, vanadium (II) oxide
(VO), vanadium (IV) oxide (VO _Two), Tan oxide
Tal (V) (Ta_TwoO_Five) And other periodic table elements
Compounds with Group 16 elements, titanium oxide (TiO 2_Two, Ti_Two
O_Five, Ti_TwoO_Three, Ti_FiveO₉And other elements of the Periodic Table 4
Compound with Group 16 element of the periodic table, magnesium sulfide (M
gS), periodic table of magnesium selenide (MgSe), etc.
Compound of group 2 element and group 16 element of the periodic table, cadmium oxide
Medium (II) Chromium (III) (CdCr_TwoO_Four),selenium
Cadmium (II) chromium (III) (CdCr_TwoS
e_Four), Copper (II) chromium (III) (CuCr)_TwoS_Four),
Mercury (II) selenide chromium (III) (HgCr_TwoSe_Four)
Such as chalcogen spinels, barium titanate (Ba)
TiO_Three) And the like. G. Schmid
Adv. Mater. , 4, p. 494 (199
Reported in 1) (BN)₇₅(BF_Two)_FifteenF_FifteenAnd
D. Fenske et al .; Angew. Chem. Int.
Ed. Engl. 29, 1452 (1990).
Reported Cu₁₄₆Se₇₃(Triethyl phosphite
N)_{twenty two}Semiconductor cluster with a fixed structure like
Are similarly exemplified.

Of these, in terms of high refractive index and luminous power,
Preferred and suitable for the method for producing semiconductor ultrafine particles described below
The practically important ones represented by the composition formula are, for example, Sn
S_Two, SnS, SnSe, SnTe, PbS, PbS
e, PbTe, and other periodic table group 14 elements and periodic table group 16
Compound with element, GaN, GaP, GaAs, GaS
III-V such as b, InN, InP, InAs, InSb, etc.
Group compound semiconductor, Ga_TwoO_Three, Ga_TwoS_Three, Ga_TwoSe_Three, G
a_TwoTe_Three, In_TwoO_Three, In_TwoS_Three, In_TwoSe_Three, In _TwoT
e_ThreeOf group 13 elements of the periodic table and group 16 elements of the periodic table
Compound, ZnO, ZnS, ZnSe, ZnTe, Cd
O, CdS, CdSe, CdTe, HgO, HgS, H
II-VI compound semiconductors such as gSe and HgTe, As
_TwoO_Three, As_TwoS_Three, As _TwoSe_Three, As_TwoTe_Three, Sb_TwoO_Three,
Sb_TwoS_Three, Sb_TwoSe_Three, Sb_TwoTe_Three, Bi_TwoO_Three, Bi_Two
S_Three, Bi_TwoSe_Three, Bi_TwoTe_ThreeGroup 15 elements of the periodic table
And compounds of Group 16 elements of the periodic table, MgS, MgSe, etc.
Compound of Group 2 of the periodic table and Group 16 of the periodic table
Yes, among them, GaN, GaP, InN, InP, Ga
_TwoO_Three, Ga _TwoS_Three, In_TwoO_Three, In_TwoS_Three, ZnO, Zn
S, CdO, CdS, etc. do not contain highly toxic negative elements
Therefore, it is preferable in terms of environmental pollution resistance and safety to organisms.
From the viewpoint of, ZnO and ZnS are more preferable, high refractive index,
ZnS is most preferable in terms of safety, economy of raw materials, and the like.
In addition, CdSe and ZnSe are extremely stable in terms of light emission stability.
preferable.

The semiconductor crystal which is the main component of the semiconductor ultrafine particles used in the present invention is, for example, A.I. R. Kortan et al .;
J. Am. Chem. Soc. 112, p. 1327 (1990) or U.S. Pat. No. 5,985,173 (1999), a so-called semiconductor comprising a core and an outer shell for the purpose of improving the emission characteristics of the semiconductor crystal. When the core-shell structure is used, the light emitting ability due to the quantum effect of the semiconductor crystal forming the core may be improved in some cases, so that the glass composition of the present invention is preferably used for applications utilizing the light emitting ability. is there. In this case, a semiconductor crystal structure having a larger band gap energy than the semiconductor crystal structure of the core is used as a shell, so that energy loss via a surface level or a crystal lattice defect level that attenuates the luminous efficiency of the core crystal is achieved. In some cases can be prevented. A semiconductor crystal structure suitably used for such a shell has a bandgap in a bulk state of 2.0 electron volts or more at a temperature of 300 K, such as boron nitride (BN), depending on the bandgap energy of the core semiconductor crystal. , Boron arsenide (BAs), gallium nitride (GaN), gallium phosphide (GaP) and other compounds of the periodic table group 13 and the periodic table group 15 (III-V compound semiconductors), zinc oxide (ZnO) ), Zinc sulfide (ZnS), zinc selenide (ZnS)
Se), zinc telluride (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), etc.
A compound of a group 2 element and a group 16 element of the periodic table (II-VI compound semiconductor), magnesium sulfide (MgS), magnesium selenide (MgSe), etc .; And the like are preferably used. Among these, a semiconductor crystal composition that is a more preferable shell is:
III-V compound semiconductor such as BN, BAs, GaN, Z
1. The band gap of a bulk state of a II-VI compound semiconductor such as nO, ZnS, ZnSe, and CdS, and a compound of a group 2 element and a group 16 element of the periodic table such as MgS and MgSe at a temperature of 300 K is 2. 3 eV or more, most preferably BN, BAs, GaN, Zn
The band gap of a bulk state of O, ZnS, ZnSe, MgS, MgSe, etc. is 2.5 eV or more at a temperature of 300K.

The semiconductor ultrafine particles used in the glass composition of the present invention may cause a photodegradation reaction such as decomposition or alteration of an organic substance such as an organic ligand close to the surface by a photocatalytic action of the semiconductor surface. is there. Such a photodegradation reaction causes a decrease in light resistance of the glass composition. Since such photocatalysis is caused by the absorption of semiconductor crystals, which are the main components of the semiconductor ultrafine particles, when the glass composition of the present invention is applied to optical applications, it does not have a light absorbing ability in a wavelength region of a light source in the application. Selection of the semiconductor crystal composition may be preferred. Therefore, in the case of application to a normal optical device using a visible or near-ultraviolet wavelength region, the wavelength at the long wavelength end of the absorption spectrum of the semiconductor ultrafine particles to be contained in the glass composition of the present invention is usually 450 nm or less, the visible region. In view of the colorlessness in the above, the thickness is preferably 400 nm or less, more preferably 360 nm or less, and most preferably 330 nm or less. Preferred semiconductor crystal seeds for this purpose are ZnO and ZnS
And ZnS is particularly preferable.

In any of the semiconductor crystal compositions exemplified above, if necessary, for example, Al, Mn, Cu, Zn, A
Elements such as g, Cl, Ce, Eu, Tb, and Er may be added. The addition of such a doping substance may greatly improve the light emitting characteristics of the semiconductor crystal. Examples of semiconductor crystal seeds that exhibit a favorable effect by the addition of such a doping substance include ZnO and ZnS, and ZnS is particularly preferable in this respect. A particularly preferred doping system is ZnS doped with Mn ²⁺ as described in the aforementioned US Pat. No. 5,985,173.

Since the glass composition of the present invention contains a very well dispersed and non-aggregated semiconductor crystal, the absorption and emission of the semiconductor crystal due to the quantum effect may have nonlinearity. It is also useful as an optical material. [Organic ligand] The organic ligand in which the semiconductor ultrafine particles are usually bonded to the surface of the semiconductor crystal, which is the main component thereof, shields desirable physical properties of the semiconductor crystal, such as light absorption and emission properties, from adverse effects from the outside. It is desirable that the glass composition has an effect and has compatibility with the amorphous matrix of the glass composition of the present invention. Such an organic ligand has a coordination functional group to be described later, and thereby binds to the semiconductor crystal surface.

As a coordination functional group in such an organic ligand,
Normally use a functional group containing a Group 15 or 16 element in the periodic table
I have. As a specific example, a primary amino group (—N
H_Two) A secondary amino group (-NHR; wherein R is a methyl group,
Carbon such as ethyl group, propyl group, butyl group and phenyl group
A hydrocarbon group of the number 6 or less; the same applies hereinafter), tertiary amino
Group (-NR¹R^Two; However, R¹And R^TwoIs independently a methyl group,
Carbon number of tyl group, propyl group, butyl group, phenyl group, etc.
6 or less; the same applies to the following), a nitrile group,
A functional group having a nitrogen-containing multiple bond such as an isocyanate group,
Nitrogen-containing nitrogen-containing aromatic rings such as pyridine and triazine rings
Functional group, primary phosphine group (-PH_Two) Secondary phosph
Infin group (-PHR), Tertiary phosphine group (-PR
¹R^Two) Primary phosphine oxide group (-PH_Two= O),
Secondary phosphine oxide group (-PHR = O), tertiary phosphine
Fin oxide group (-PR¹R^Two= 0) primary phosphine
Selenide group (-PH_Two= Se) Secondary phosphine seleni
Group (-PHR = Se), tertiary phosphine selenide group
(-PR¹R^Two= Periodic table of phosphorus-containing functional groups such as Se)
Functional group containing group 15 element, hydroxyl group (-OH), methyl
Ruether group (-OCH_Three), Phenyl ether group (-
OC₆H_Five), Carboxyl group (-COOH)
Functional group, mercapto group (also called thiol group; -S
H), a methylsulfide group (-SCH_Three), Ethylsul
Fido group (-SCH_TwoCH_Three), Phenyl sulfide group
(-SC₆H_Five), Methyl disulfide group (—S—S—C
H_Three), A phenyl disulfide group (—S—S—C
₆H_Five), Thioacid group (—COSH), dithioacid group (—CS
SH), xanthate group, xanthate group, isothio
Cyanate group, thiocarbamate group, thiophene ring, etc.
Sulfur-containing functional groups, similarly -SeH, -SeCH_Three, -S
eC₆H_FiveSelenium-containing functional groups such as -TeH, -T
eCH_Three, -TeC₆H _FivePeriod of tellurium-containing functional groups such as
Examples include functional groups containing Group 16 elements. this
Among them, nitrogen is preferably used such as a pyridine ring.
Containing functional group, tertiary phosphine group, tertiary phosphineoxy
And tertiary phosphine selenide groups and other phosphorus-containing functional groups
Functional groups containing elements of group 15 of the periodic table, mercapto
Periodic Table of Sulfur-Containing Functional Groups such as Groups and Methyl Sulfides
A functional group containing a Group 16 element,
Phosphorus-containing functionalities such as fin groups and tertiary phosphine oxide groups
Group or a sulfur-containing functional group such as a mercapto group
Preferably used, tertiary phosphine oxide groups and merka
The ptto group is most preferably used.

Although the specific coordination chemical structure of an organic ligand for a semiconductor crystal typified by a semiconductor nanocrystal has not been sufficiently elucidated, the surface of the semiconductor ultrafine particles used in the present invention is exemplified above. The coordinating functional group does not necessarily have to keep the same structure. For example, in the case of a mercapto group (SH), a structure in which a covalent bond is formed with a metal element M (for example, zinc or cadmium in a II-VI compound semiconductor, gallium or indium in a III-V compound semiconductor) existing at the terminal of a semiconductor crystal. (For example, SM
Phosphine oxide group (P = O)
In the case of, a change to a structure in which a covalent bond with the metal element M is formed (for example, a structure of POM) may be considered.

[Preferred Structure of Organic Ligands] The above-mentioned organic ligands have an effect of shielding desirable physical properties such as a light-absorbing / emitting ability of a semiconductor crystal, which is a main component of semiconductor ultrafine particles, from an adverse influence from the outside (hereinafter referred to as “the organic ligand”). It is desirable that the glass composition of the present invention has compatibility with an amorphous matrix (hereinafter, referred to as “matrix compatibility”).

From the viewpoint of the above-mentioned shielding effect, the organic ligand preferably has a methylene group chain having 6 or more carbon atoms. When the semiconductor ultrafine particles are placed in the external environment (in some cases, acidic or alkaline) of a water-containing system as in a production method, the effect is remarkably exhibited. this is,
In such a water-containing system (particularly in an acidic system), a chemical change such as elution of a transition metal element from the surface of the semiconductor crystal due to a protonic acid is liable to occur, but an organic ligand having a methylene group chain having 6 or more carbon atoms is used. When bonded to the semiconductor crystal surface, it forms a kind of hydrophobic barrier due to its hydrophobicity,
This is presumed to be due to a mechanism of preventing a protic solvent molecule such as water, methanol, or ethanol, or a protonic acid from approaching the semiconductor crystal surface. By using such an organic ligand having a methylene group chain having 6 or more carbon atoms, specifically, an effect of retaining or stabilizing the luminous ability of the semiconductor ultrafine particles is often observed. The number of carbon atoms in this methylene group chain is usually about 6 to 20, preferably about 8 to 16, and most preferably about 9 to 12.

In terms of the above matrix compatibility, the organic ligand is polyethylene glycol (hereinafter abbreviated as PEG).
It is preferably a compound containing a residue, and the effect is particularly remarkable in the method for producing the glass composition of the present invention (usually a water-containing lower alcohol solvent system) by a sol-gel method described later. This is presumed to be due not only to the solubility of the PEG chain in the water-containing lower alcohol solvent system, but also to the excellent compatibility with the above-mentioned inorganic glass amorphous matrix (for example, SiO ₂ ). Such a PEG residue is a residue represented by the following general formula (2).

[0038]

## STR2 ##-(CH ₂ CH ₂ O) _n —R (2) In the general formula (2), R is a hydrogen atom and has 1 to 1 carbon atoms.
A structure arbitrarily selected from the group consisting of an alkyl group having 7 carbon atoms and an aryl group having 10 or less carbon atoms, and n represents a natural number of 50 or less.

A hydrogen atom is preferably used as R in the general formula (2). Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, tert-butyl group, n
-A pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a benzyl group and the like, and preferably alkyl having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group and an isopropyl group in terms of hydrophilicity. Groups are used, most preferably methyl groups. Specific examples of the aryl group used for R include a phenyl group, a toluyl group (monomethylphenyl group), a dimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, a 4-tert-butylphenyl group, a pyridyl group, and a monomethylpyridyl group. Group,
Examples thereof include a dimethylpyridyl group, and a phenyl group or a pyridyl group is preferably used in terms of hydrophilicity.

The natural number n in the general formula (2) is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and most preferably 10 or less. If the value of n is too large, the content of PEG residues in the glass composition becomes unnecessarily large, and undesired effects such as a decrease in mechanical strength such as rigidity and an increase in coefficient of linear expansion may occur.
However, conversely, it can be said that mechanical property control (for example, balance between rigidity and toughness by elastic modulus control) of the glass composition is possible by controlling the numerical value of n. As a preferable structure of the general formula (2), an ethylene glycol residue (n
= 2) and a triethylene glycol residue (n = 3). More preferred in terms of compatibility with an amorphous matrix is a triethylene glycol residue, which is most preferred in terms of chemical stability. Is a triethylene glycol monomethyl ether (hereinafter abbreviated as MTEG) residue in which R is a methyl group.

As an organic ligand that is very preferably used in the present invention in view of the above-mentioned shielding effect, matrix compatibility, and ease of chemical synthesis, ω- represented by the following general formula (1):
MTEG esters of mercapto fatty acids are mentioned.

[0042]

Embedded image HS (CH ₂ ) _n COO (CH ₂ CH ₂ O) ₃ CH ₃ (1) In the general formula (1), n represents a natural number having 6 to 11 carbon atoms. As a particularly preferred specific compound, 11-mercaptoundecanoic acid MTEG ester corresponding to n = 10 in the general formula (1) is exemplified. A compound in which the terminal methyl group of the MTEG ester is a hydrogen atom is also suitable.

The MTEG ester of the general formula (1) is
For example, a method of subjecting an ω-mercapto fatty acid such as 11-mercaptoundecanoic acid and an excess equivalent of MTEG to dehydration esterification in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid (equilibration reaction by heating or dehydration under reduced pressure if necessary) Is accelerated) or transesterification using MTEG in an excess equivalent.

The same effect may be obtained by using a polyalkylene glycol residue obtained by copolymerizing an arbitrary alkylene oxide such as propylene oxide with ethylene oxide instead of the PEG residue. However, PEG residues are usually best. [Manufacturing Method of Semiconductor Crystal] The semiconductor crystal may be formed by an arbitrary method such as a conventional semiconductor crystal manufacturing method described below. (A) High vacuum process such as molecular beam epitaxy or CVD. By this method, high-purity semiconductor ultrafine particles whose composition is highly controlled can be obtained, but toxic gases such as phosphine and arsine may be used as raw materials, and expensive production equipment is required. There are restrictions on the above usage. (B) A method in which a raw material aqueous solution is present as reverse micelles in a nonpolar organic solvent and crystals are grown in the reverse micelle phase (hereinafter referred to as reverse micelle method). S. Zou
Int. J. Quant. Chem. , 72, 4
39 (1999). A well-known reverse micelle stabilization technique can be used in a general-purpose reactor, relatively inexpensive and chemically stable salts can be used as raw materials, and the reaction is performed at a relatively low temperature that does not exceed the boiling point of water. It is a suitable method for production. However, the light emission characteristics may be inferior to those of the following hot soap method. (C) A method of injecting a thermally decomposable raw material into a high-temperature liquid-phase organic medium to grow crystals (hereinafter referred to as a hot soap method). B. This is a method reported in a document by Murray et al. As compared with the reverse micelle method, a semiconductor crystal having excellent particle size distribution and purity can be obtained, and the product has excellent light emission characteristics and is generally soluble in an organic solvent. For the purpose of desirably controlling the reaction rate during the crystal growth process in the liquid phase in the hot soap method, a coordinating organic compound having an appropriate coordinating power for a semiconductor constituent element is used as a liquid phase component (also serves as a solvent and a ligand). ). Examples of such coordinating organic compounds include trialkyl phosphines such as tributyl phosphine, trihexyl phosphine, and trioctyl phosphine, and trialkyl phosphines such as tributyl phosphine oxide, trihexyl phosphine oxide, trioctyl phosphine oxide, and tridecyl phosphine oxide. Phosphine oxides, octylamine, decylamine,
Ω-aminoalkanes such as dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
And dialkyl sulfoxides such as dimethyl sulfoxide and dibutyl sulfoxide. Of these,
Trialkyl phosphine oxides such as tributyl phosphine oxide and trioctyl phosphine oxide, and ω-aminoalkanes having 12 or more carbon atoms such as dodecylamine, hexadecylamine, and octadecylamine are preferable, among which trioctyl phosphine oxide and the like are preferable. Most preferred are trialkylphosphine oxides and ω-aminoalkanes having 16 or more carbon atoms, such as hexadecylamine. (D) A solution reaction involving semiconductor crystal growth similar to the hot soap method described above, but a method in which an acid-base reaction is performed at a relatively low temperature as a driving force has been known for a long time (for example, PA Jackson). J. Cryst. Growth
h, 3-4, 395 (1968)). Recently, Diaz et al .; Phys. Chem. B, 103
Vol., Page 9854 (1999) illustrates the synthesis of cadmium sulfide (CdS) nanocrystals using cadmium (II) carboxylate and sodium sulfide as raw materials and dimethyl sulfoxide (DMSO) as a solvent.

The semiconductor raw materials usable in the liquid phase production method include a substance containing a positive element selected from Groups 2 to 15 of the periodic table and a negative element selected from Groups 15 to 17 of the periodic table. Substances. It is known that the Group 15 element of the periodic table also constitutes a semiconductor as a trivalent positive element, for example, bismuth sulfide or bismuth telluride described in the Dictionary of Physical and Chemical Sciences (4th edition, Iwanami Shoten, 1987). ing.

When there are a plurality of semiconductor raw materials, these may be mixed in advance, or may be individually injected into the reaction liquid phase. These raw materials may be used as a solution using an appropriate diluting solvent. [Binding of Desired Organic Ligand to Semiconductor Crystal Surface] A semiconductor crystal obtained by any of the manufacturing methods exemplified above is added to the preferred organic ligand (hereinafter simply referred to as “organic ligand”). ) Is exemplified. (A) Method by Ligand Exchange Reaction The organic solvent-soluble semiconductor ultrafine particles synthesized by the hot soap method or the like are dissolved in a relatively weakly coordinating organic solvent such as toluene, methylene chloride, or pyridine. The reaction is performed by adding a desired organic ligand (preferably having a strongly coordinating functional group such as a phosphine oxide group or a mercapto group). As a result, ligand exchange in which the added organic ligand replaces the originally existing ligand proceeds, but the coordination force of these ligands is adjusted to leave the desired organic ligand. There is a need to. When pyridine is used as a solvent, pyridine is a weak but coordinating solvent molecule, so that ligand exchange proceeds first, and then ligand exchange by the added desired organic ligand proceeds. It may be. (B) Addition of organic ligand to reaction liquid phase of hot soap method This is a method of adding a desired organic ligand to the reaction liquid phase of the hot soap method. Organic ligands suitable for such a method are organic ligands having a strongly coordinating functional group such as a phosphine group, a phosphine oxide group, or a mercapto group, and particularly those having a phosphine oxide group are optimal. . The addition of the coordinating organic ligand to the reaction liquid phase of the hot soap method is preferably carried out at a later stage of the hot soap method reaction. The reason is that after a semiconductor crystal having a desired size is generated, a coordinating organic ligand is coordinated on the surface thereof. The timing of the addition of the desired organic ligand is
The choice is made according to the particle size of the semiconductor crystal determined by the desired absorption / emission ability. (C) Addition of organic ligand to reaction liquid phase of reverse micelle method This is a method of adding a desired organic ligand to the reaction liquid phase of the reverse micelle method. Organic ligands suitable for such a method are those having a phosphine group or a phosphine oxide group, or organic ligands having a strongly coordinating functional group such as a mercapto group, and especially the PEG having hydrophilicity. Organic ligands with residues are optimal.

[Method for Producing Glass Composition] The method for producing the glass composition of the present invention is not limited, but the above-mentioned sol-gel method is preferably used. More specifically, this is a method in which the semiconductor ultrafine particles are added in advance to a raw material solution of a sol-gel method. Specifically, a first step of obtaining a raw material solution by mixing semiconductor ultrafine particles with a solution mainly composed of a metal alkoxide, and a second step of performing a hydrolytic condensation reaction of a metal alkoxide or the like in the raw material solution. This is a method including at least one step.

The first step is a step of mixing the ultrafine semiconductor particles and the amorphous matrix raw material. The amorphous matrix raw material is a compound that forms the above-mentioned various inorganic glass compositions via an oxygen atom or a nitrogen atom by a hydrolysis reaction and a condensation reaction, and the structure thereof is not particularly limited. The metal alkoxide represented by (3) is exemplified.

[0049]

Embedded image MR _m Z _n (3) where the above general formula (3), M is a metal atom, R represents an alkoxy group having 6 or less carbon atoms, Z is a hydrogen atom, a hydroxyl group or having 10 or less carbon, Represents either an alkyl group or an aryl group, respectively. M + n is a natural number equal to the valence number of the metal atom M, m is a natural number, n
Represents an integer of zero or more.

Specific examples of the metal alkoxide represented by the general formula (3) will be described below using preferred examples of alkoxysilanes. That is, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane (commonly known as TEOS), tetra-n-propyloxysilane, tetraisopropyloxysilane, and tetra-n-butoxysilane;
Monoalkyl trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propyloxysilane, ethyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, 4-
Chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-aminophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4
Monoaryl trialkoxysilanes such as -methylphenyltriethoxysilane, 4-hydroxyphenyltriethoxysilane, phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane , 4-aminophenyloxytriethoxysilane, 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane,
Monoaryloxy trialkoxysilanes such as 4-hydroxyphenyloxytriethoxysilane, monohydroxytrialkoxysilanes such as monohydroxytrimethoxysilane, monohydroxytriethoxysilane, monohydroxytri-n-propyloxysilane, dimethyldimethoxy Dialkyl dialkoxy silanes such as silane, dimethyl diethoxy silane, dimethyl di-n-propyloxy silane, methyl (ethyl) diethoxy silane, methyl (cyclohexyl) diethoxy silane, and monoalkyl mono such as methyl (phenyl) diethoxy silane Aryl dialkoxy silanes, diaryl dialkoxy silanes such as diphenyl diethoxy silane, dihydroxy dimethoxy silane, dihydroxy such as dihydroxy diethoxy silane Alkoxysilanes, methyl (hydroxymethyl) monoalkyl monohydroxy dialkoxysilane such as dimethoxysilane, phenyl (hydroxy)
Monoarylmonohydroxydialkoxysilanes such as dimethoxysilane, trialkylmonoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, dimethyl (ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane, and dimethyl (phenyl) ethoxysilane Dialkylmonoarylmonoalkoxysilanes, monoalkyldiarylmonoalkoxysilanes such as methyl (diphenyl) ethoxysilane, trihydroxymonoalkoxysilanes such as trihydroxymethoxysilane and trihydroxyethoxysilane and tetramethoxysilane Oligomers of the above-mentioned alkoxysilanes such as pentamers and the like can be mentioned.

Further examples of the metal alkoxide represented by the general formula (3) for various metal elements M include diethoxyberyllium, triethoxyboron, diethoxymagnesium, triethoxyaluminum, tetraethoxytitanium, tetra-n-butoxy. Titanium, diethoxy zinc,
Triethoxygallium, tetraethoxygermanium,
Tetraethoxyzirconium, diethoxycadmium,
Triethoxyindium, diethoxy lead, tetramethoxy lead and the like can be mentioned.

These metal alkoxides may be used in combination with the following metal halides. That is,
As halogenosilanes, tetrahalogenosilanes such as tetrachlorosilane, monoalkyltrihalogenosilanes such as methyltrichlorosilane, monoaryltrihalogenosilanes such as phenyltrichlorosilane, monoalkoxytrihalogenosilanes such as methoxytrichlorosilane, Dialkyldihalogenosilanes such as dimethyldichlorosilane, monoalkylmonoaryldihalogenosilanes such as methyl (phenyl) dichlorosilane, diaryldihalogenosilanes such as diphenyldichlorosilane,
Trialkoxydihalogenosilanes such as diethoxydichlorosilane, monoalkylmonoalkoxydichlorosilanes such as methyl (ethoxy) dichlorosilane, monoarylmonoethoxydichlorosilanes such as phenyl (ethoxy) dichlorosilane, and trimethylchlorosilane Alkyl monohalogenosilanes, dialkyl monoaryl monohalogenosilanes such as dimethyl (phenyl) chlorosilane, monoalkyl diaryl monohalogenosilanes such as methyl (diphenyl) chlorosilane, triethoxy monohalogenosilanes such as triethoxychlorosilane, and tetra Oligomers of the above-mentioned halogenosilanes such as dimer to pentamer of chlorosilane and the like can be mentioned. As the metal halides other than the silanes, various halides in the example of the positive element-containing substance serving as the semiconductor raw material described above are also exemplified. Such metal halides are
It is particularly preferably used when a small amount of metal element is to be contained in the molecular chains of the amorphous matrix.

Compounds in which various positive elements represented by silicon, such as hexamethyldisilazane, are bonded to nitrogen atoms can also be used as a raw material for an amorphous matrix. Among these exemplified amorphous matrix raw materials, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and monoalkyl trialkoxysilanes such as methyltriethoxysilane, ethyltriethoxysilane and n-butyltriethoxysilane , Trialkoxyaluminums such as triethoxyaluminum, tetraalkoxytitaniums such as tetraethoxytitanium, tetrahalogenosilanes such as tetrachlorosilane, trihalogenoaluminums such as trichloroaluminum, and tetrahalogenotitaniums such as tetrachlorotitanium. Preferably used,
More preferably, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, trialkoxyaluminums such as triethoxyaluminum, tetrahalogenosilanes such as tetrachlorosilane, and most preferably tetraalkoxysilane such as tetraethoxysilane Kind is used. Note that any of these exemplified amorphous matrix raw materials may be used in combination with an arbitrary composition.

In the first step, the amorphous matrix raw material includes lower alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol and t-butyl alcohol, ethylene glycol and glycerin. , Lower ketones such as acetone and methyl ethyl ketone, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, aliphatic linear ethers such as diethyl ether, methyl cellosolve and ethyl cellosolve, acetonitrile and acrylonitrile and the like. Nitriles, esters of lower fatty acids such as methyl acetate and ethyl acetate, N, N
-Dimethylacetamide, N, N-dimethylformamide (commonly known as DMF), N-methylpyrrolidone (commonly known as NM
P) and a water-soluble solvent (including an appropriate amount of water) such as sulfoxides such as dimethyl sulfoxide (DMSO), and the semiconductor ultrafine particles are mixed therein. There is no limitation on the order and time of the mixing, and stirring may be appropriately added. Further, the inside of the mixing container may be an inert gas atmosphere such as nitrogen or argon. The temperature in the mixing is not limited as long as the solution does not condense, but is usually in the range of -50 to 100 ° C, preferably 0 to 70 ° C, and most preferably about 20 to 50 ° C. Pressure may be applied. Since these water-soluble solvents are usually removed in a later step, those having a relatively low boiling point such as methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and tetrahydrofuran are preferable, and the solubility of the amorphous matrix raw material is low. From the viewpoint, lower alcohols such as methanol, ethanol, n-propanol and isopropyl alcohol are more preferable, and ethanol is most preferable.

The mixing ratio of the semiconductor ultrafine particles to the amorphous matrix raw material in the first step is adjusted according to the content of the semiconductor crystals in the glass composition of the present invention described above.
The water contained in the water-soluble solvent is essential for the hydrolysis-condensation reaction in the second step, and the amount of water added is the total number of moles of the reactive groups (alkoxy groups and halogen atoms) of the amorphous matrix material. To 0.1 to 1000 equivalents, preferably 0.5 to 500 equivalents, more preferably 0.8 to 100 equivalents, most preferably, in terms of hydrolysis reactivity and solubility of the amorphous matrix raw material and the like. Is about 1 to 50 equivalents. Further, the concentration of the amorphous matrix raw material in the raw material solution obtained in the first step is adjusted according to the applicability of the reaction solution and the rate of the sol-gel reaction in the production of a thin film or fibrous molded article described later. However, it is usually about 0.01 to 50% by weight, preferably about 0.1 to 30% by weight, and most preferably about 1 to 20% by weight.

The second step is a hydrolysis-condensation reaction step of the amorphous matrix material, and is usually carried out with an acid catalyst (for example, a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, etc.).
Organic acids such as trifluoroacetic acid and trifluoromethanesulfonic acid, acidic ion exchange resins and the like; or base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing aromatic compounds such as pyridine) , Basic ion exchange resins, hydroxides such as sodium hydroxide, carbonates such as potassium carbonate, carboxylate salts such as sodium acetate, etc.)
And then the hydrolysis and condensation reactions are allowed to proceed. The amount of the catalyst added varies depending on the desired reaction rate, but is usually 0.001 to 1000 meq / L as the equivalent of a protonic acid or a proton base, and is preferably 0.1 to 1 in terms of the reaction rate and the stability of the semiconductor ultrafine particles. 01-100
It is set to about milliequivalent / L, most preferably about 0.005 to 50 milliequivalent / L. A plurality of such catalysts may be used in combination. The reaction in the second step may be appropriately stirred.
The inside of the reaction vessel may be an atmosphere of an inert gas such as nitrogen or argon.

The temperature of the hydrolysis-condensation reaction of the amorphous matrix raw material in the second step is not limited as long as the reaction mixture does not condense. Is usually -20 to 150
° C, preferably from 10 to 100 ° C, most preferably from 30 to 100 ° C.
The temperature may be in the range of about 80 ° C., and may be appropriately pressurized, for example, to avoid boiling. The reaction temperature may be appropriately changed according to the degree of progress of the reaction.
In some cases, it is preferable to use a relatively low temperature of about 0 to 40 ° C. and a relatively high temperature of about 50 to 100 ° C. as the polymer chains of the amorphous matrix are formed and thickened. Also,
In the production of a thin film or fibrous shaped body described below, the temperature may be higher than the boiling point of the solvent at a later stage of the reaction in order to remove the water-soluble solvent.

Usually, when the molecular weight of the amorphous matrix is increased to a high molecular weight by the reaction in the second step, the fluidity of the reaction solution is rapidly decreased, and it is difficult to extract the product from the reactor. Therefore, it is necessary to control the reaction time of the second step. Usually, the reaction solution is withdrawn from the reactor before gelation of the entire reaction solution occurs, and the process proceeds to a step of forming a thin film or a fiber-shaped molded body, which will be described later. The reaction time from the addition of the catalyst to the extraction is not limited, but is usually from 10 minutes to 720 hours, preferably from 0.5 to 360 hours, most preferably from 1 to 180 hours from the viewpoint of the progress of the reaction and the productivity. Degree.

In the production of the glass composition of the present invention by the above-mentioned sol-gel method, a mixture of plural kinds of raw material solutions, a mixture of plural kinds of hydrolytic condensation reaction liquids, Improvements may be made by any combination of necessary components such as addition of an arbitrary raw material solution, addition of semiconductor ultrafine particles to the reaction solution in which the hydrolysis and condensation reaction has progressed, and the like.

[Applications of Glass Composition] The glass composition of the present invention usually contains semiconductor crystals dispersed to 20 nm or less. Since the material has extremely reduced scattering, it is suitably used for various optical applications described below that require high light transmittance. In particular, it is suitably used as a thin-film or fire-bar-shaped molded product by utilizing features such as a high refractive index and an ability to absorb and emit light.

Specific examples of the thin film-shaped molded body include an optical waveguide such as a thin film waveguide and an optical amplifier, a luminous body of a display, and a coating layer such as an antireflection or light absorption. Of these, the high refractive index is preferably used for a thin film waveguide or an antireflection coating layer of a display, and the luminous ability is used for an optical amplifier or a luminous body of a display. What is used is a light-absorbing coating layer for ultraviolet rays or the like (used for lenses of displays and glasses). An optical waveguide such as an optical fiber or an optical amplifier is exemplified as the fiber-shaped molded body. In addition, the glass composition of the present invention can be used as a light refraction member, specifically, a material for a lens, a prism, and the like.

Further, since a semiconductor crystal usually contains a high concentration of an element having a high atomic number, a high-energy electromagnetic wave such as an ultraviolet ray such as an X-ray or a gamma ray, an elementary particle beam such as an electron beam or a neutron beam, or an α-ray. High ability to absorb or scatter low molecular beam. Therefore, the glass composition of the present invention can be used as a molded product such as a building material that shields the high-energy electromagnetic wave, elementary particle beam, or low-molecular beam. In this case, the glass composition does not necessarily need to have visual transparency.

The glass composition of the present invention has a coefficient of linear expansion relatively close to that of general-purpose inorganic glass such as quartz glass, or has good adhesiveness with such inorganic glass. Since it has application moldability, it is used as a useful glassware coating material. [Thin-film shaped body] The method for obtaining the thin-film shaped body is not particularly limited, but is preferably applied to the reaction solution or the raw material solution in the method for producing a glass composition of the present invention by the sol-gel method reaction. Usually, such a liquid is applied to a substrate, the amorphous matrix of the glass composition is polymerized to a desired degree, and a volatile component such as a solvent is heated or depressurized during or after the polymerization. To remove. There is no particular limitation on the substrate used in such a coating method, for example, metal, metal oxide, ceramics,
Inorganic substances such as compound semiconductors, quartz and silica glass, organic substances such as various polymers and paper, or liquid surfaces such as organic liquids and mercury can be used. Among them, it is preferable to use an inorganic substance such as a metal, a metal oxide, ceramics, quartz, and silica glass from the viewpoint of the stability of the obtained thin film. As a method for applying to the substrate, a general method such as a spin coating method, a dip coating method, a wetting film method, a spray coating method, and a die coating method can be used.

The film thickness, size, shape, and surface properties (eg, flat, spherical, curved, concave, convex, porous surface, smoothness, or thickness distribution) of the thin-film molded article thus obtained Is not particularly limited, for example, the film thickness is
Usually, 1 to 100,000 nm, preferably 1 to 10,
000 nm, more preferably about 1 to 1,000 nm.

[Fibrous Molded Article] The method for obtaining the above-mentioned fibrous molded article is not particularly limited, but the spinning of the reaction solution in the method for producing the glass composition of the present invention by the above-mentioned sol-gel reaction is preferred. It is molding, and it is necessary that such a reaction solution is allowed to advance the reaction to such an extent that it has a spinnable viscosity and sol solution elasticity.

During or after the spinning step, volatile components such as a solvent are removed by heating or reducing the pressure. The surface of the fibrous formed body obtained in the spinning step may be coated with a synthetic resin solution or another sol-gel method reaction solution as necessary. There are no particular restrictions on the thickness, thickness distribution, or cross-sectional shape of the fibrous formed body thus obtained.
1 to 10,000 μm, preferably 1 to 1,000 μm
m, more preferably about 5 to 500 μm.

[0067]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.
The raw material reagents are Aldric unless otherwise specified.
The product of Company h was used without purification. However, the purified toluene was washed with concentrated sulfuric acid, water, saturated aqueous sodium hydrogen carbonate, and water in that order, dried over anhydrous magnesium sulfate, and then filtered through filter paper.
Obtained by distillation from diphosphorus pentaoxide (P ₂ O _5), dried with purified methylene chloride phosphorus pentoxide (P ₂ O _5), was obtained by direct distillation at atmospheric pressure from here. In addition, methanol and n-butanol used in the synthesis example of the semiconductor ultrafine particles were both anhydrous grade (99.
8%).

[Measurement Apparatus and Conditions, etc.] (1) Infrared absorption spectrum (FT-IR): FT / IR-8000 type FT-IR manufactured by JASCO Corporation. Measured at 23 ° C. (2) X-ray diffraction (XRD) spectrum: RINT 1500 manufactured by Rigaku Corporation (X-ray source: copper Kα ray, wavelength 1.541)
8Å). Measured at 23 ° C. (3) Transmission electron microscope (TEM) observation: H-9000UHR transmission electron microscope manufactured by Hitachi, Ltd. (acceleration voltage: 300 kV, degree of vacuum during observation: about 7.6 × 10 ⁻⁹ Torr)
r). (4) Photoexcitation light emission (PL) spectrum: F-2500 type spectrofluorimeter manufactured by Hitachi, Ltd., scan speed 60 nm / min, excitation side slit 5 nm, fluorescence side slit 5 nm, photomultiplier voltage 400 V The measurement was performed using a quartz cell having an optical path length of 1 cm. (5) Thermogravimetric analysis (TG): Using TG / DTA320 manufactured by Seiko Instruments Inc., place about 10 mg of a sample in an aluminum pan, and set at 30 ° C. to 550 ° C. in an air stream of 200 mL / min. The measured temperature immediately below was 562 to 563 ° C.) at a rate of 20 ° C. per minute, and after reaching the set temperature, the heating loss was calculated from the weight when the sample was kept at the set temperature for 120 minutes and the initial weight. .

Synthesis Example 1 [11-Mercaptoundecanoic acid
Synthesis of MTEG ester] 11-mercaptoundecanoic acid (1.70 g) and Tokyo Chemical
Triethylene glycol monomer supplied by Seisei Co., Ltd.
Tyl ether (hereinafter abbreviated as MTEG: 50 mL), and
Add concentrated sulfuric acid (Kokusan Chemical Co., Ltd .; 5 drops) to a dry nitrogen atmosphere.
Mix in Lasco, 30mmHg while stirring at 60 ° C
The dehydration under reduced pressure at the following pressure was performed for a total of about 36 hours. reaction
A precipitate obtained by gradually adding the liquid to a large amount of ice water with stirring
Is mixed solvent of n-hexane / ethyl acetate (5/1 volume ratio)
And wash the organic phase with saturated aqueous sodium bicarbonate and then water
The extract was dried over sodium sulfate, filtered and concentrated. this
The product is 1730 cm in the IR spectrum^-1To d
Stell group, and 2870cm ^-1Peak and 2820cm
^-1Broad from 3050 to 2650 including shoulder
Assigned to TEGMME-derived hydrocarbon structures
11-mercaptoun
Decanoic acid MTEG ester (hereinafter abbreviated as 11-MTEG)
Generation) was confirmed.

Synthesis Example 2 [Synthesis of CdSe Ultrafine Particles] Trioctylphosphine oxide (hereinafter referred to as TOPO) was placed in a colorless and transparent Pyrex glass three-necked flask equipped with an air-cooled Liebig reflux tube and a thermocouple for controlling the reaction temperature.
4 g) and heated to 360 ° C. in a dry argon gas atmosphere while stirring with a magnetic stirrer. Separately, in a glove box in a dry nitrogen atmosphere, dimethyl cadmium (Strem Chemi) is further added to a liquid in which selenium (simple black powder; 0.1 g) is dissolved in tributylphosphine (hereinafter abbreviated as TBP; 6.014 g).
Cal .; 97%; 0.216 g) was mixed and dissolved to prepare a glass bottle which was sealed with a rubber stopper (septum supplied from Aldrich), wrapped tightly with aluminum foil, and shielded from light. A part (2.0 mL) of the raw material solution A was injected into the flask containing the TOPO at once with a syringe, and this time was regarded as the reaction start time. Twenty minutes after the start of the reaction, the heat source was removed, and when cooled to about 50 ° C., purified toluene (2 mL) was added with a syringe to dilute the mixture, and methanol (10 mL) was injected to generate insolubles. This insoluble material is centrifuged (3000 rpm),
The supernatant was removed by decantation and separated, followed by vacuum drying at room temperature for about 14 hours to obtain a solid powder.

In the XRD spectrum of this solid powder, the 002 face and the 1st face of Wurtzite type CdSe crystal
From the observation of diffraction peaks belonging to 10 planes, Cd
Generation of Se nanocrystals was confirmed. The average particle size of the CdSe nanocrystals was about 4 nm according to TEM observation. This CdSe nanocrystal gave a red emission band (peak wavelength: 595 nm, half width: 43 nm) when irradiated with excitation light having a wavelength of 366 nm in a purified toluene solution.

Synthesis Example 3 [CdSe having ZnS shell]
Synthesis of semiconductor ultrafine particles mainly composed of nanocrystals] B. O. Dabbousi et al .; Phys. Che
m. B, 101, 9463 (1997). This will be described below. TOPO in a brown glass three-necked flask in a dry argon gas atmosphere
(15 g) was added, and the mixture was stirred under reduced pressure at a temperature of 130 to 150 ° C. in a molten state for about 2 hours. During this time, an operation of returning to atmospheric pressure with dry argon gas was performed several times in order to replace the remaining air and moisture. Approx. 1 with the temperature set to 100 ° C
After a lapse of time, the solid powder of CdSe nanocrystals obtained in Synthesis Example 2 (0.094 g) of trioctylphosphine (1.5
g, hereinafter abbreviated as TOP) solution to obtain a transparent solution containing CdSe nanocrystals. This was further stirred for about 80 minutes under reduced pressure of 100 ° C., and then the temperature was set to 180 ° C. and the pressure was restored to the atmospheric pressure with dry argon gas. Separately, in a dry nitrogen atmosphere glove box, 1N concentration of diethyl zinc n-
Hexane solution (1.34 mL; 1.34 mmol) and bis (trimethylsilyl) sulfide (0.239 g;
1.34 mmol) in TOP (9 mL) was prepared in a glass bottle sealed with a septum used in Synthesis Example 2, wrapped tightly with aluminum foil, and shielded from light. This raw material solution B was mixed with the above 180
The solution was dropped into a transparent solution containing CdSe nanocrystals at 20 ° C. over 20 minutes. After the temperature was lowered to 90 ° C., stirring was continued for about 1 hour. After allowing to stand at room temperature for about 14 hours, the mixture was again heated and stirred at 90 ° C. for 3 hours. The heat source was removed and n-butanol (8 mL) was added to the reaction and cooled to room temperature to give a clear red solution.

This red solution did not have the odor of the sulfur compound such as bis (trimethylsilyl) sulfide as the raw material, but instead had the leek-like odor peculiar to selenium. Since the solution of the CdSe nanocrystal obtained in Synthesis Example 2 did not have such selenium odor, the selenium atom due to the sulfur atom on the nanocrystal surface was increased with the progress of the intended sulfide generation reaction on the CdSe nanocrystal surface. It is presumed that selenium was liberated by some mechanism such as the substitution reaction of selenium, and it was considered that semiconductor ultrafine particles mainly composed of CdSe nanocrystals having a ZnS shell were generated as described in the above-mentioned literature (hereinafter referred to as CdSe). / ZnS-TOPO).

A part (8 mL) of this red solution was added dropwise to methanol (16 mL) at room temperature under a stream of dry nitrogen to obtain a solution.
A red insoluble substance was obtained by a precipitation operation in which stirring was continued for 0 minutes. This red insoluble matter was separated by centrifugation and decantation in the same manner as in Synthesis Example 2, and purified toluene (14 mL)
Was re-dissolved. Using this re-dissolved toluene solution, a similar series of purification operations including precipitation, centrifugation, and decantation was performed again to obtain a solid product. This solid product was washed by shaking with 1 mL of purified methanol, and then separated by decantation. This solid product gives a clear red purified toluene solution, which is irradiated with excitation light having a wavelength of 468 nm to emit an orange emission band (having a peak wavelength of 59 nm).
7 nm, half width at 41 nm). This luminescence was apparently higher in luminescence intensity than in the case of the CdSe nanocrystal obtained in Synthesis Example 2 at the same solution concentration.
It was considered that the conversion to the CdSe nanocrystal having a ZnS shell and the contribution of the non-light emitting process via the surface state and the like were suppressed.

Synthesis Example 4 [Synthesis of Ultrafine Semiconductor Particles Containing 11-MTEG as Ligand] CdSe / ZnS-TOPO obtained in Synthesis Example 3 (about 0.5
g) in a glass container protected from light by wrapping it in an aluminum foil without any gap under a dry nitrogen atmosphere under a purified methylene chloride (6 m
L). While stirring the mixture at room temperature, a homogeneous solution obtained by adding 11-MTEG (0.4 g) obtained in Synthesis Example 1 was left under light-shielding conditions at room temperature for about 18 hours. After the reaction solution was concentrated, ethanol (8 mL) was added, and the mixture was heated and refluxed at atmospheric pressure for 15 minutes while stirring, whereby a uniform ethanol solution was obtained. CdSe / ZnS-T obtained in Synthesis Example 3
Since OPO is substantially insoluble in ethanol, it was concluded that TOPO, which is considered to be the main constituent of the organic ligand, was replaced by 11-MTEG, and thus became ethanol-soluble. Hereinafter, this ethanol solution is referred to as CdSe / ZnS
-Referred to as MTEG solution. This solution exhibited the same luminous ability as CdSe / ZnS-TOPO obtained in Synthesis Example 3.

Example 1 [Preparation of glass composition] The CdSe / ZnS-MTEG solution obtained in Synthesis Example 4 (0.
5 mL), ethanol (2 mL), tetraethoxysilane (0.307 g, 2.13 mmol), and water (0.1 mL).
2 g, 11 mmol) at room temperature in the atmosphere to form a homogeneous solution.
g) was added and shaken to obtain a uniform solution. This solution was left sealed for 1 week at room temperature in a light-tight stopper, but no thickening was observed. Then, the solution was heated at 60 ° C. for a total of 21 hours under open conditions in the atmosphere, and gradually thickened, and finally a red transparent glassy solid I got The Cd obtained in Synthesis Example 3
It showed the same luminous ability as Se / ZnS-TOPO. The loss on heating of this glass composition in air was 34% by weight, calculated from the results of the TG measurement conditions described above.

Example 2 [Thin Film Form of Glass Composition] In the operation of Example 1, the reaction liquid was immediately heated at 60 ° C. under the condition of opening to the atmosphere in the air without leaving the light-tight stopper at room temperature for one week. When the thickening becomes remarkable, it is applied on a clean quartz plate, and heating at 60 ° C. in the atmosphere is continued. As a result, a red-transparent thin-film molded product having the same luminous ability as that of CdSe / ZnS-TOPO obtained in Synthesis Example 3 is obtained. A general-purpose mercury lamp (power consumption 9 watts) is emitted on the surface of this thin film-shaped molded product 3
When ultraviolet light having a wavelength of 65 nm is irradiated, high-luminance orange light emission is observed not only from the front and back surfaces of the thin film-shaped molded product but also from the end surfaces. Therefore, such a thin film-shaped molded article is useful as a light-emitting body for a display or a lighting fixture, or as an optical waveguide.

Example 3 [Fiber-like molded product of glass composition] At the point where the thickening of the reaction solution of Example 2 progresses and it starts to show a gel state, the reaction solution is stretched while sucking with a glass pipette having a suction port of about 1 mm in diameter. Heating at 60 ° C. in the atmosphere is continued to obtain a gel keeping the fiber shape. As a result, a red and transparent fibrous molded product having the same luminous ability as that of CdSe / ZnS-TOPO obtained in Synthesis Example 3 is obtained. When the fibrous formed body is irradiated with the ultraviolet light used in Example 2, high-brightness orange light emission is observed from the end face of the fibrous formed body. Therefore, such a fiber-shaped molded article is useful as an optical waveguide. When a nitrogen laser pulse (wavelength: 337 nm, pulse width: 5 nanoseconds, frequency: 10 Hz) is incident on one end face of such a fibrous formed body, a high-brightness orange emission pulse is observed from the other end face. Nd: YAG as laser light
When a laser second harmonic pulse (wavelength 532 nm, pulse width 5 nanoseconds, frequency 10 Hz) is incident, a high-luminance orange light-emitting pulse is similarly observed from the other end face. Therefore, such a fiber-shaped molded product is useful as an optical waveguide, and is used for light emission and light transmission in a wide wavelength range according to the absorption / emission characteristics of the ultrafine semiconductor particles contained therein. Further, since the fiber has a higher refractive index than general-purpose quartz glass, it is useful as a core of an optical fiber.

[0079]

The glass composition provided by the present invention, in which semiconductor ultrafine particles are uniformly dispersed, has characteristics such as light-absorbing ability, high refractive index, and excellent transparency. Since it is produced by a solution reaction, it can be easily formed by applying or spinning such a solution. Accordingly, when this is formed into a thin film or fiber shaped molded body, it is used as a material for a light emitting body such as a display or a lighting fixture, or a material for an optical member such as an optical waveguide.

The glass composition of the present invention has a coefficient of linear expansion relatively close to that of general-purpose inorganic glass such as quartz glass, or has good adhesion to such inorganic glass, and is therefore used as a useful glass product coating material. . Glass composition of the present invention, high energy electromagnetic waves such as X-rays and gamma rays, elementary particles such as electron beams and neutron beams, or α
Since it has the effect of shielding low molecular beams such as radiation, it is also used as a coating material for shielding such radiation.

Claims (12)

[Claims] 1. A glass characterized in that semiconductor ultrafine particles are uniformly dispersed in an amorphous matrix mainly composed of a metal element-oxygen bond, and a loss on heating in air is 10 to 80% by weight. Composition. 2. The glass composition according to claim 1, wherein the amorphous matrix is mainly composed of silicon-oxygen bonds. 3. The glass composition according to claim 1, wherein the semiconductor ultrafine particles are formed by bonding an organic ligand. 4. The glass composition according to claim 3, wherein the organic ligand is a phosphine oxide or a thiol. 5. The glass composition according to claim 3, wherein the organic ligand has a methylene group chain having 6 or more carbon atoms. 6. The glass composition according to claim 3, wherein the organic ligand contains a polyethylene glycol residue. 7. The glass composition according to claim 6, wherein the organic ligand is represented by the following general formula (1). Embedded image HS (CH ₂ ) _n COO (CH ₂ CH ₂ O) ₃ CH ₃ (1) (However, in the general formula (1), n represents a natural number having 6 to 11 carbon atoms.) 8. The semiconductor ultrafine particles mainly comprising a semiconductor crystal containing zinc or cadmium.
8. The glass composition according to any one of 7. 9. The method according to claim 1, further comprising a step of performing a hydrolysis-condensation reaction of a metal alkoxide mainly composed of alkoxysilanes in the presence of semiconductor ultrafine particles having an organic ligand bonded thereto. A method for producing a glass composition according to any one of the above. 10. A thin film-shaped molded article of the glass composition according to claim 1. 11. A fibrous molded article of the glass composition according to claim 1. 12. An optical waveguide using the molded product according to claim 10.