JPWO2019013098A1 - Crystal-containing glass and method for producing the same - Google Patents

Abstract

A layered crystal of a transition metal chalcogenide can be easily obtained at low cost. The present invention is a crystal-containing glass, which is characterized in that it contains a transition metal chalcogenide layered crystal.

Description

  The present invention relates to a crystal-containing glass and a method for manufacturing the glass.

  In recent years, layered crystals such as transition metal chalcogenides have attracted attention as next-generation semiconductor materials. These layered crystals are easy to process into thin films because each layer is bonded by Van der Waals force, and because they are also excellent in surface roughness, they are extremely useful for miniaturization and high performance of electronic devices. Contribute. Further, these crystals exhibit various functions such as metal, superconductor, etc. as well as semiconductors, and are expected to be applied to optoelectronic devices with flexibility and transparency and electronic devices with ultra-low energy consumption. There is.

`` Synthesis of Colloidal 2D 3D MoS2 Nanostructures by Pilsed Laser Ablation in an Organic Liquid Environment '' Sci. Technol. Adv. Mater., 2013, 14, 043501-043513., Y. Zhao et al. `` Molybdenumu (IV) speciation in sulfidic waters Stability and Labilityof thiomolybdates '' Geochimica et Cosmochimica Acta, 2000, 64, 1149-1158., G. Helz and B. Erickson. `` The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets '' Nature Chemistry., 2013, 5, 263-275., M. Chhowalla et al.

Among the transition metal chalcogenides, layered crystals contained in natural ore such as MoS ₂ (molybdenum disulfide) can be obtained by separating and purifying from natural ore. However, this method is not suitable for applications requiring purity such as semiconductor applications because three-dimensional crystals and other components may be mixed in addition to the layered crystals.

  Therefore, various efforts have been made to obtain high-purity transition metal chalcogenide layered crystals. In order to obtain a transition metal chalcogenide layered crystal, the oxidized transition metal material is reduced and the chalcogen element is further modified.However, depending on the production conditions, crystals other than the layered crystal are also generated, so during the production, the reaction atmosphere It is necessary to strictly control the oxidation-reduction state and reaction temperature of the above, which requires a great deal of labor and cost.

For example, Non-Patent Document 1 discloses a method of synthesizing MoS ₂ which is a layered crystal by laser irradiation. Further, Non-Patent Document 2 discloses a method in which thiomolybdate (MoO _[n] S _[4-n] ) is first obtained and then crystals are generated by a liquid-gas reaction. Furthermore, Non-Patent Document 3 discloses a method of producing a transition metal chalcogenide layered crystal by a gas-gas reaction. However, in order to obtain a transition metal chalcogenide layered crystal, manufacturing cost and labor are required in each case, so it is very difficult to obtain it at low cost.

  As a result of intensive experiments based on the knowledge and experience of researching glass for many years, the present inventor has surprisingly been able to deposit a transition metal chalcogenide layered crystal in glass, and from this glass, a transition metal chalcogenide layered crystal is easy. The present invention has been found to be obtained, and is proposed as the present invention. That is, the present invention is a crystal-containing glass, which is characterized by containing a transition metal chalcogenide layered crystal.

  In the present invention, the crystal-containing glass of the present invention can be obtained by precipitating a transition metal chalcogenide crystal in the process of producing glass. In the crystal-containing glass, the crystal inside can be easily purified by separating the glass by, for example, acid treatment. Therefore, a highly pure transition metal chalcogenide layered crystal can be easily obtained at low cost without requiring special equipment or labor.

  Further, in the crystal-containing glass of the present invention, the transition metal chalcogenide layered crystal is preferably 0.01% by mass or more of the entire crystal-containing glass. By doing so, it becomes possible to efficiently obtain a transition metal chalcogenide layered crystal.

The crystal-containing glass of the present invention preferably contains M _x O _y (M is any of transition metal atoms) and Z (Z is any of S, Se, Te, and Po) as a glass composition. ..

Here, M _x O _y is an oxide of a transition metal converted into an oxide, M is a transition metal atom, and O is an oxygen atom. Moreover, _{X and Y} show the number of each atom. Examples of M (transition metal atom) include Mo, Hf, W, Re, Hf, W, Re, Ge, Nb, Pb, Sn, Ta, Ti, Ga, In, and Zr.

  Z is a chalcogen atom and is any of S, Se, Te and Po.

Further, the crystal-containing glass of the present invention has a glass composition of, by mass%, SiO ₂ 60 to 80%, Al ₂ O _{30 to} 10%, B ₂ O ₃ 0 to 5%, R ₂ O (Li ₂ O + Na). ₂ O + K ₂ O) 5 to 25%, and further contains M _x O _y (M is any of transition metal atoms) and Z (Z is any of S, Se, Te, and Po). preferable. By doing so, the transition metal chalcogenide layered crystal is more likely to be precipitated in the glass.

In the crystal-containing glass of the present invention, the transition metal chalcogenide layered crystal is preferably MoS ₂ . The layered crystal of MoS ₂ can be obtained by adding the Mo raw material and the S raw material to the glass raw material.

  Further, the method for producing a crystal-containing glass of the present invention, the glass raw material is prepared so as to contain a transition metal atom and a chalcogen atom, then the glass raw material is melted, and held in the glass at a temperature lower than the melting temperature. It is preferred to deposit the transition metal chalcogenide layered crystals. By doing so, the crystal-containing glass in which the transition metal chalcogenide layered crystal is precipitated in the glass can be easily obtained at low cost.

  Further, the method for producing a transition metal chalcogenide layered crystal of the present invention is characterized in that the glass and the transition metal chalcogenide layered crystal are separated from the crystal-containing glass to obtain a transition metal chalcogenide layered crystal.

  Further, in the method for producing a transition metal chalcogenide layered crystal of the present invention, it is preferable to separate the glass and the transition metal chalcogenide layered crystal with an acid. In this case, the glass is dissolved by the acid, whereas the transition metal chalcogenide crystal is not dissolved in the acid, and as a result, the crystal can be taken out from the crystal-containing glass. The separation method may be used in combination with pulverization or sieving.

  Since the crystal-containing glass of the present invention contains a transition metal chalcogenide layered crystal, it is possible to obtain a crystal from the glass. Further, since the transition metal chalcogenide layered crystal is contained in high purity, the crystal can be used for a highly functional member such as a semiconductor if separated from glass. Furthermore, it is possible to obtain a next-generation composite material having the characteristics of glass materials such as barrier resistance and translucency and the transition metal chalcogenide layered crystals.

  Further, the crystal-containing glass manufacturing method of the present invention requires a special manufacturing facility or material, because in addition to the general glass melting method, only a crystallization step of maintaining the temperature lower than the melting temperature is provided. Therefore, the manufacturing cost and labor can be reduced.

  Furthermore, in the method for producing a transition metal chalcogenide layered crystal of the present invention, the transition metal chalcogenide layered crystal is dissolved, for example, by treating the obtained crystal-containing glass with a chemical agent such as an acid, and collecting the crystal. Therefore, it is possible to reduce manufacturing cost and labor without requiring special manufacturing equipment and materials. Further, since the glass phase is easily removed by chemical treatment, there is little risk that other components will be mixed, and a highly pure transition metal chalcogenide layered crystal can be obtained at low cost.

  An electronic device of the present invention is characterized by including the above-mentioned crystal-containing glass. The transition metal chalcogenide layered crystal of the present invention has a high carrier mobility and an ultraviolet to near-infrared energy band gap, and thus can be applied to transistors, diodes, amplifiers, switches and the like. It can also be applied to photoelectric conversion elements, LEDs, and the like.

In addition to this, the electronic element of the present invention can be applied to a relay, a fuse, a thermistor, etc., and can be an electronic element having flexibility and transparency. Further, since the electronic element of the present invention can have a function as a superconductor, it can be used as an element with ultra-low energy consumption applied to a quantum computer or as a next-generation member showing a Meissner effect and applied to a linear motor car or the like. Expected to be used.

It is a graph which shows an example of the relationship between the crystal structure (amorphous form) and the temperature of the crystal-containing glass of the present invention. It is a graph which shows an example of the relationship between the crystal structure (triangle) and temperature of the crystal-containing glass of the present invention. The microscope observation image of the amorphous layered crystal of MoS ₂ obtained by the present invention is shown. The microscope observation image of the triangular layered crystal of MoS ₂ obtained by the present invention is shown.

  Hereinafter, the crystal-containing glass of the present invention will be described in detail below. In the following description, unless otherwise specified, the percentage notation indicates “mass%”.

  An example of the crystal-containing glass of the present invention will be shown below, but it is clear from the gist of the present application that the glass composition is not limited to this as long as it is a glass composition capable of precipitating a transition metal chalcogenide layered crystal. For example, quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass, non-alkali glass, E glass, A glass, etc. are also applicable.

The crystal-containing glass of the present invention has a glass composition of, by mass%, SiO ₂ 60 to 80%, Al ₂ O _{3 to} 10%, B ₂ O ₃ 0 to 5%, R ₂ O (Li ₂ O + Na ₂ O + K). _The total amount of ₂ O) 5 to 25%, and M _x O _y (M is any of transition metal atoms) and Z (Z is any of S, Se, Te, and Po) are preferably contained.

SiO ₂ is a component that constitutes a glass network, and is an important component for the crystal-containing glass of the present invention. The content of SiO ₂ is 60 to 80%, preferably 65 to 75%. When the content of SiO ₂ is too small, it becomes difficult to vitrify, and as a result, crystals other than the transition metal chalcogenide layered crystals are likely to precipitate as devitrified substances. On the other hand, if the content of SiO ₂ is too large, when the crystal is separated from the crystal-containing glass, the glass component becomes difficult to dissolve with an acid such as hydrofluoric acid, and the glass and the transition metal chalcogenide layered crystal are separated. Takes time and cost.

Al ₂ O ₃ has the effect of improving the chemical resistance of glass, but if added too much, the meltability and workability of glass will deteriorate. The content of Al ₂ O ₃ is 0 to 10%, 0 to 5%, 1 to 5%, preferably 1 to 4%.

B ₂ O ₃ has the effect of lowering the viscosity of the glass and improving the meltability. The content of B ₂ O ₃ is preferably 0 to 5%, more preferably 0 to 3%. On the other hand, from the environmental aspect, it is desirable not to contain it if possible. Not containing B ₂ O ₃ means that B ₂ O ₃ is not intentionally added, and unavoidable impurities are not excluded. More specifically, it means that the content of B ₂ O ₃ is 0.05% or less by mass.

The alkali metal oxides Li ₂ O, Na ₂ O and K ₂ O have the effect of reducing the viscosity of the glass. It is also effective when a large amount of the crystal forming element raw material is contained in the glass raw material. R ₂ O (the total content of Li ₂ O, Na ₂ O and K ₂ O) is preferably 5 to 25%, more preferably 7 to 24%, and particularly preferably 8 to 23%. On the other hand, if the total amount of these components is too small, the meltability deteriorates.

The content of Li ₂ O is 0 to 5%, preferably 0 to 3%. When the content of Li ₂ O increases, the raw material cost increases. Further, the content of Na ₂ O is 3 to 13%, preferably 3 to 10%. If the amount of Na ₂ O is too small, the viscosity of the glass increases and the meltability deteriorates. Further, the content of K ₂ O is 2 to 10%, preferably 2 to 6%. If the content of K ₂ O is too large, the water resistance of the glass deteriorates.

  MgO, CaO, SrO and BaO are effective in lowering the viscosity of the glass and making the glass raw material contain a large amount of the crystal forming element raw material. RO (the total content of MgO, CaO, SrO and BaO) is preferably 0 to 20%. When the total amount of these components is large, it causes devitrification, and crystals other than the intended transition metal chalcogenide layered crystals are precipitated, which is not preferable.

  The content of MgO is 0 to 5%, preferably 0 to 3%. If the content of MgO is too large, the raw material cost becomes high. The content of CaO is 0 to 5%, preferably 0 to 4%. When the content of CaO is too large, it causes devitrification. The SrO content is 0 to 12%, preferably 0 to 8%. If the content of SrO is too large, Sr-based crystals such as strontium feldspar tend to precipitate, and the glass devitrifies. Further, the content of BaO is 0 to 5%. When the content of BaO is too large, Ba-based crystals such as barium feldspar tend to precipitate in the glass, and the glass devitrifies. In addition, it is preferable that the content of BaO is as small as possible from the viewpoint of the environment.

Further, in the present invention, one or more kinds of polyvalent oxides such as Sb ₂ O ₃ , As ₂ O ₃ and SnO ₂ , halogens such as F and Cl, SO _{3 and the} like may be contained as a fining agent. In this case, the standard content of the fining agent is 5% or less in total, preferably 1% or less, more preferably 0.5% or less.

In addition to the above, the crystal-containing glass of the present invention contains a transition metal chalcogenide layered crystal as an essential component. Examples of transition metal chalcogenide layered crystals include MoS ₂ , HfS ₂ , WS ₂ , ReS ₂ , GeS, MoReS ₂ , MoSSe, MoWS ₂ , NbReS ₂ , NbReSe ₂ , PbSnS ₂ , ReMoS ₂ , ReNbS ₂ , ReS ₂ . 1T-TaS ₂ , 2H-TaS ₂ , TiGaS ₂ , TiInS ₂ , WSSe, ZrS ₂ , TiS _{2 and the} like.

In the crystal-containing glass of the present invention, the content of M _x O _y (M is any of transition metal atoms) in terms of oxide is SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , R ₂ O or RO. When the total is taken as 100%, it is externally applied, preferably 0.05 to 40%, 0.1 to 40%, 0.5 to 40%, 1 to 40%, 3 to 35%, 5 to 30. %, 10 to 30%, especially 20 to 30%. The higher the content of M _x O _y (M is any of transition metal atoms), the more transition metal chalcogenide layered crystals can be obtained. On the other hand, if the content is too large, it becomes difficult to melt and mold the glass raw material.

Furthermore, in the crystal-containing glass of the present invention, the content of Z (Z is any of S, Se, Te, and Po) is the total of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , R ₂ O, and RO. Is 100%, preferably 0.1-40%, 0.2-40%, 1-40%, 3-40%, 5-35%, 10-30%, 20-30%. As the content of Z (Z is any one of S, Se, Te, and Po) is larger, more transition metal chalcogenide layered crystals can be obtained. On the other hand, if the content is too large, it becomes difficult to melt and mold the glass raw material.

  Regarding the raw material used in the present invention, for example, the raw material form and the timing of addition may be such as addition as a fining agent or reducing agent as in the case of S (sulfur) raw material, or addition as a chalcogen element raw material as described later. Include in the content of different raw materials.

In the crystal-containing glass of the present invention, the transition metal chalcogenide layered crystal is preferably MoS ₂ . In order to precipitate the MoS ₂ layered crystal, Mo and S may be added in the form of simple substance, oxide or compound.

  The crystal size is preferably 10 μm or more, more preferably 30 μm or more, 50 μm or more, and particularly preferably 100 μm or more. The larger the crystal size, the easier the processing when incorporated in an electronic device or the like, which is preferable. Further, in the present invention, a transition metal chalcogenide layer crystal having a desired shape, size, and thickness can be obtained by adjusting the temperature and time of the crystal precipitation step and the crystal growth step in the crystallization step.

  Next, the method for producing the crystal-containing glass of the present invention will be described below.

  First, glass raw materials are prepared so as to have a desired composition to prepare a glass batch.

A predetermined amount of a transition metal source material and a chalcogen source material (hereinafter referred to as a crystal forming element material) are added to the glass material. Alternatively, or instead of these, a compound of a transition metal and a chalcogen can be used. For example, as a raw material to be a transition metal source, there are MoO ₃ , MoF ₆ , WO ₃ , Nb ₂ O _{5 and the} like, and as a raw material to be a chalcogen source, S, SeO ₂ , SeF ₆ , SCl ₂ , TeO _2, etc. Furthermore, as the compound of the transition metal and chalcogen, there are MoS ₃ , RuS ₃ , TaS _{3 and the} like.

  As the amount of the crystal forming element raw material added increases, the content of the transition metal chalcogenide layered crystal in the crystal-containing glass increases. Therefore, the amount of addition of the crystal forming element raw material is preferably 0.05% or more, 0.1% or more, 0.2% or more, 0.3%, respectively, when the other materials are set to 100%. As described above, 0.5% or more, 1% or more, 3% or more, 5% or more, 10% or more, 20% or more are preferable. In this way, many transition metal chalcogenide layered crystals can be obtained. The larger the amount of the crystal forming element raw material added, the easier the crystallization, and as a result, the transition metal chalcogen lamellar crystal can be precipitated in the glass without providing the crystallization step.

  However, on the other hand, when the amount of the crystal forming element raw material added is increased, it becomes difficult to melt and mold the glass raw material. Therefore, the addition amount of the crystal forming element raw material is preferably 40% or less, more preferably 30% or less, and particularly preferably 25% or less.

In the case of precipitating the MoS ₂ layered crystal, the crystal forming element raw material includes, for example, MoO ₃ and S, and the addition amounts of each are preferably 0.05% or more, 0.1% or more, 0.2% or more. As described above, 0.5% or more, 1% or more, 3% or more, 5% or more, particularly preferably 10% or more. The larger the amount added, the easier the crystallization, and as a result, MoS ₂ layered crystals can be precipitated in the glass without providing a crystallization step.

  Next, this glass batch is put into a melting furnace at 800 to 1500 ° C. and melted.

Further, the melting step is preferably performed in a reducing atmosphere. When melted in a reducing atmosphere, transition metal chalcogenide layered crystals are likely to precipitate in the subsequent crystallization step. In order to efficiently obtain the transition metal chalcogenide layered crystal, it is preferable to use a reducing agent as a raw material and to carry out the melting and crystallization steps in a reducing atmosphere with a low O ₂ partial pressure.

  When using a reducing agent, C, S, Al, and Si are preferable, and in order to efficiently obtain a transition metal chalcogenide layered crystal, it is preferable to add 0.01% or more by mass of these in total.

  Incidentally, in the case of ordinary glass production, a clarification step is generally performed after this, but this may be omitted for the purpose of collecting crystals.

  Next, a crystallization step of maintaining the temperature lower than the melting temperature is performed. Thereby, the transition metal chalcogenide layered crystal is deposited in the glass.

  As the crystallization step, it is preferable to perform the crystal precipitation step and the crystal growth step at the same time. By doing so, crystals can be efficiently deposited and grown. The holding temperature in the crystallization step is preferably 700 to 1100 ° C, preferably 750 to 1100 ° C, 800 to 1000 ° C, and particularly preferably 800 to 900 ° C. The holding temperature and holding time in the crystallization step can be changed according to the desired number of crystals and crystal seeds, but if you want to obtain a large number of crystals or grow the crystals large, you can increase the holding time. Good. The holding time is 0.5 hours or more, 1 hour or more, 3 hours or more, 5 hours or more, 10 hours or more, and particularly 20 hours or more. Of course, it is also possible to perform the crystal precipitation step and the crystal growth step as separate steps.

  1 and 2 show the relationship between the crystal structure in glass and the temperature in the crystallization step when Mo and S are used as the crystal forming element raw materials. FIG. 1 shows the case where the obtained crystal is an amorphous crystal, and FIG. 2 shows the case where it is a triangular crystal. In addition, in the crystallization process, ▪ is a crystal precipitation process, and ● is a crystal growth process.

  As described above, the holding temperature and the holding time can be changed according to the desired size of the crystal and the crystal seed. However, in the shaded region of FIGS. 1 and 2, the crystal precipitation and the crystal growth are performed simultaneously. You can proceed. Therefore, if held in this region, crystals can be efficiently precipitated and grown.

  Subsequently, the glass is molded. The molding may be performed by any molding method as long as the crystals are collected later. For example, in addition to the overflow downdraw method, the float method, the rollout method, the pressing method, the Danner method, the containerless method and the like, various methods such as water granulation can be used. The shape after molding can also take various forms such as a thick plate shape, a thin plate shape, a tubular shape, a granulated shape, a fiber shape, and a flake shape.

  Further, as another method of producing the crystal-containing glass of the present invention, for example, a method of forming a molten glass in which crystals are not precipitated and then providing a crystallization step can be adopted.

  Further, as another method for producing the crystal-containing glass of the present invention, a glass raw material to which a three-dimensional crystal serving as a precursor of a transition metal chalcogen lamellar crystal is added, melted, and a chalcogen element is desorbed from the three-dimensional crystal. It is also possible to adopt a method in which the transition metal chalcogen layer crystals are reduced.

  Then, the manufacturing method of the transition metal chalcogenide layered crystal of the present invention is explained below.

  In the method for producing a transition metal chalcogenide layered crystal of the present invention, it is preferable that at least the transition metal chalcogenide layered crystal is taken out by melting the glass in the crystal-containing glass.

  In the method for producing a transition metal chalcogenide layered crystal of the present invention, any chemical agent or separation method may be used as long as the glass in the crystal-containing glass can be preferentially melted to obtain the transition metal chalcogenide layered crystal.

  Examples of the drug capable of dissolving glass in the crystal-containing glass include acids such as hydrofluoric acid, nitric acid, hydrochloric acid, and sulfuric acid, and mixed solutions thereof, and any concentration can be used with respect to its concentration and use conditions.

  Hereinafter, the present invention will be described based on examples.

  Table 1 is an example of the crystal-containing glass of the present invention.

The glasses in Table 1 were prepared as follows. 300 g of glass raw material was prepared so as to have the composition in the table, 0.06% of MoO ₃ and 0.8% of S were further added as raw material of the crystal forming element, and a predetermined amount of C was used as a reducing component. Add and mix for 20 minutes on a muller. Next, the glass raw material was placed in an alumina magnetic crucible and melted at 1450 ° C. for 1 hour to obtain a molten glass, which was then held at 1000 ° C. for 15.5 hours to carry out crystal precipitation to obtain a crystal-containing glass.

  Next, in order to prevent damage during processing, it was annealed at 540 ° C for 30 minutes and then gradually cooled to room temperature at 3 ° C / minute.

  Next, the obtained crystal-containing glass was placed in a clean Teflon (registered trademark) container, and the acid mixed solution (40% HF: 2N-HCl = 1: 9) was filled to the extent that the sample was completely covered. The Teflon (registered trademark) container containing the sample and the mixed solution was ultrasonically vibrated for 30 minutes.

  Then, using a Teflon (registered trademark) funnel and a membrane filter (5C 100CIRCLES 125 mm manufactured by ADVANTEC), the mixed solution was transferred to another clean Teflon (registered trademark) container, and Teflon (registered trademark) funnel was used using ion-exchanged water. And the membrane filter was washed 10 times.

  The obtained crystal is observed under a microscope and EPMA (JEOL Ltd., JXA-8900M), and further component analysis is performed with EPMA (JEOL Ltd., JXA-8900M), and an X-ray diffractometer (RIGAKU, The crystal diffraction peak was confirmed by SmartLab), and the crystal was identified as a molybdenum disulfide crystal. Images observed by a microscope are shown in FIGS. 1 and 2. The amorphous crystal in FIG. 3 and the triangular crystal in FIG. 4 were both layered crystals. Also. All the obtained crystals were molybdenum disulfide layered crystals.

  Table 2 is another example of the crystal-containing glass of the present invention.

  No. 300 g of glass raw materials were blended so that the glasses 1 to 13 had the proportions shown in Table 2, and further the crystal forming element raw materials were added at the proportions shown in Table 2 and an appropriate amount of C as a reducing component was added. And mixed for 20 minutes to obtain a glass raw material. Next, the glass raw material was put into an alumina magnetic crucible and melted and crystallized under the conditions shown in Table 2 to obtain glass containing crystals.

  Then, crystals were separated and identified from the obtained crystal-containing glass by the same method as in Example 1, and the crystals shown in Table 2 were obtained. The crystals obtained from each sample were all transition metal chalcogen lamellar crystals.

  Thus, by using the present invention, it is possible to obtain a composite material combining a transition metal chalcogen layered crystal and glass useful as a next-generation material. It can be easily obtained at low cost.

  A layered crystal of transition metal chalcogen can exhibit various functions such as a semiconductor, a metal, and a superconductor by combining a large number of transition metal atoms and chalcogen atoms. Therefore, the composite material in which the transition metal chalcogenide layered crystal and glass are combined and the transition metal chalcogenide layered crystal can be expected to be applied to optoelectronic devices having flexibility and transparency and electronic devices with ultra-low energy consumption.

Claims (9)

  A crystal-containing glass, comprising a transition metal chalcogenide layered crystal.   The crystal-containing glass according to claim 1, wherein the transition metal chalcogenide layered crystal is 0.01% by mass or more of the entire crystal-containing glass. The glass composition containing M _x O _y (M is any of transition metal atoms) and Z (Z is any of S, Se, Te, and Po), The glass composition according to claim 1 or 2, Crystal-containing glass. As a glass composition, in _{mass%, SiO 2 60~80%, Al} 2 O 3 0~10%, B 2 O 3 0~5%, R 2 O (Li 2 O + Na 2 O + K 2 O in total amount) 5 25%, further containing M _x O _y (M is any of transition metal atoms) and Z (Z is any of S, Se, Te and Po), and any of claims 1 to 3 characterized by the above-mentioned. The crystal-containing glass as described in 1. The crystal-containing glass according to any one of claims 1 to 4, wherein the transition metal chalcogenide layered crystal is MoS ₂ .   A glass raw material is prepared so as to contain a transition metal atom and a chalcogen atom, then the glass raw material is melted, and a transition metal chalcogenide layered crystal is precipitated in the glass by holding the glass raw material at a temperature lower than the melting temperature. Method for producing crystal-containing glass.   A method for producing a transition metal chalcogenide layered crystal, comprising separating the glass and the transition metal chalcogenide layered crystal from the crystal-containing glass according to any one of claims 1 to 5 to obtain a transition metal chalcogenide layered crystal.   The method for producing a transition metal chalcogenide layered crystal according to claim 7, wherein the glass and the transition metal chalcogenide layered crystal are separated with an acid.   An electronic device comprising the crystal-containing glass according to claim 1.

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