CN102534799B - Preparation method of low-dimensional nano-structure sulfur group compounds - Google Patents

Abstract

The invention relates to a preparation method of a low-dimensional nanostructured chalcogenide compound, which uses salts of antimony, lead, indium, zinc or silver, and inorganic compounds of selenium, tellurium and sulfur as raw materials, and ethylene glycol or glycerine Alcohol is used as solvent to prepare precursor solution, using hydrazine or ethylenediamine as reducing agent, under the condition of 180°C to 280°C, the liquid reducing agent initially isolated from the precursor solution is evaporated into gas molecules, and gradually integrated into the precursor In the solution, the solute in the precursor solution is reduced and heat-treated to form the target product. Compared with the prior art, the invention has accurate phase, high purity and close to 100% yield. The raw materials used in the whole process are cheap and easy to obtain, and any template, surfactant and complexing agent are avoided in the reaction process. The process is simple, and it is easy to realize large-scale production. It can be used for the miniaturization and Integrated.

Description

A kind of preparation method of chalcogenide compound with low-dimensional nanostructure

technical field

The invention relates to the field of materials, in particular to a preparation method of a chalcogenide compound with a low-dimensional nanostructure.

Background technique

A series of chalcogenides including (Bi, Sb) ₂ (Se, Te, S) ₃ , PbTe, In ₂ Te ₃ , Ag ₂ Te or ZnTe, etc. and their multi-component alloys are an earlier and more important class of research Semiconductor materials, in recent years, these materials have shown great application potential in high-tech fields such as thermoelectric conversion, microelectronics, optoelectronics and laser technology. Driven by Moore's law, the integration of chips is getting higher and higher, and the running speed is getting faster and faster. The heat dissipation problem has become an important factor restricting the further development of IC design and the microelectronics industry, thus proposing the miniaturization and functional integration of devices. It is hoped that thermoelectric elements, microelectronics and optoelectronic devices will be integrated on one chip to achieve rapid heat dissipation of the chip. Thermoelectric refrigeration requires materials to have high cooling efficiency at room temperature and low temperature, and traditional thermoelectric bulk materials can no longer meet this demand. The low-dimensional nanostructures of the above-mentioned chalcogenide materials such as quantum wells, superlattices, quantum wires, and quantum dots are very likely to greatly improve the thermoelectric properties of the materials again.

At present, low-dimensional nanostructures of chalcogenides are usually prepared by chemical vapor deposition (CVD), physical vapor deposition (PVD), laser etching, arc discharge, electrochemical deposition, hydrothermal/solvothermal and other methods. Usually high temperature is required, and the cost of top-down physical methods such as laser etching is relatively high; the disadvantage of preparing chalcogenide nano-one-dimensional structures by electrochemical deposition is that conductive substrates and templates must be used, and the scope of application is narrow, and one-dimensional nanostructures The surface properties of the product are affected by the quality of the template; while wet chemical methods such as hydrothermal/solvothermal methods usually need to introduce substances such as surfactants and complexing agents, and subsequent steps such as cleaning and drying are required.

Contents of the invention

The object of the present invention is to provide a method for preparing chalcogenides with low-dimensional nanostructure with controllable composition, which has easy-to-obtain raw materials, low cost, simple and feasible operation, in order to overcome the above-mentioned defects in the prior art.

The purpose of the present invention can be achieved through the following technical solutions:

A method for preparing chalcogenides with a low-dimensional nanostructure, characterized in that the method comprises the following steps:

(1) Configuration of the flooding solution: dissolve the chalcogen compound in the solvent to obtain an acid solution of 0.01-0.1mol/L chalcogen, and dissolve the salt of antimony, lead, indium, zinc or silver in In the solvent, prepare 0.01～0.1mol/L antimony, lead, indium, zinc or silver salt solution; the above two solutions are dispersed by ultrasonic, heated, and dropwise added organic acid or inorganic acid to adjust the pH to PH=2-7 and Magnetic stirring and other means to fully dissolve until a uniform and stable precursor solution is obtained, that is, a uniform and stable precursor solution is made;

(2) Co-reduction treatment: load the precursor solution obtained in step (1) on the substrate or in the crucible, and then place it in a sealed reduction device. The temperature of the control device is from room temperature to 180 °C. The gas reduces the precursor solution for 10 to 30 minutes. The liquid reducing agent isolated from the precursor solution in the sealed reduction device is heated and evaporated, and gradually melts into the precursor solution in the form of gas molecules to participate in the reaction. Antimony, lead, Salts of indium, zinc, or silver, and compounds containing selenium, tellurium, and sulfur are reduced to corresponding active elemental atoms, which combine to form low-dimensional nanostructures with less crystallinity of the target chalcogenide;

(3) Heat treatment: under the atmosphere of reducing gas, the chalcogenide low-dimensional nanostructure with low crystallization degree obtained in step (2) is grown at a constant temperature of 180° C. to 280° C. for 0.5 to 12 hours. In the process, the cold shrinkage effect of the reaction vessel can make the solvent in the precursor solution be released from the reduction reaction device in the form of gas, so that only the dry chalcogenide low-dimensional nano-products remain on the substrate or in the crucible to obtain uniform products. Deposited on a substrate or in a crucible, it is the product.

The chalcogen compound described in step (1) is one of selenium, tellurium and sulfur oxides or acids or sulfur-containing organic compounds.

The salt of antimony, lead, indium, zinc or silver described in step (1) is one of nitrate, acetate, chloride or metal alkoxide of antimony, lead, indium, zinc or silver.

The solvent described in step (1) is selected from one or more of ethylene glycol, glycerol, deionized water, absolute ethanol, benzene, toluene or carbon tetrachloride.

The molar ratio of each element in the precursor solution described in step (1) is selected from Sb: Te is 2: 3, Sb: Se is 2: 3, Sb: S is 2: 3, Pb: Te is 1: 1 , In:Te ratio of 2:3, Ag:Te ratio of 2:1 or Zn:Te ratio of 1:1.

The substrate is single crystal silicon, quartz glass, sapphire, common glass, ceramics or organic substrate material, and its size matches the container used.

The crucible is a ceramic crucible, an ordinary crucible or a quartz glass crucible, and its size matches the container used.

The reducing gas is N ₂ H ₄ , NH ₃ , C ₂ N ₂ H ₈ , H ₂ S or CH ₂ N ₂ S.

The sealing recovery device is composed of a polytetrafluoroethylene lining and a stainless steel or copper sheath, the polytetrafluoroethylene lining is built with a polytetrafluoroethylene pillar as a bearing platform for the substrate, and the top is provided with a polytetrafluoroethylene Sealing the top cover, the stainless steel or copper sheath is arranged outside the polytetrafluoroethylene lining to seal the polytetrafluoroethylene lining inside.

Compared with the prior art, the present invention utilizes the liquid-phase chemical method to prepare the chalcogenide low-dimensional nanostructure, and the raw materials are cheap and easy to obtain, the process is simple, and the composition is controllable. It can realize the integration of micro-thermoelectric and optoelectronic devices, thereby promoting the development of thermoelectric refrigeration and microelectronics, optoelectronics, communications, lasers, superconductivity and other fields. Furthermore, the method of preparing low-dimensional nanostructures of chalcogenides by liquid phase chemistry For the first time, inorganic compounds are used as raw materials, and the gas reducing agent is gradually dissolved and diffused into the precursor solution for co-reduction, and induces the formation of low-dimensional nanostructures of chalcogenides. This method can also form nanostructured films assembled from low-dimensional chalcogenide nanostructures in situ, with controllable morphology and thickness. This kind of nanostructured film builds a bridge between nanoscale quantum effects and macroscopic easy-to-measure and easy-to-operate applications. Because of its combination of high performance, high energy density and high energy conversion speed, it will be possible in micro-electrothermal systems, on-chip thermochemistry and Micro-electro-mechanical systems and other fields have potential application prospects.

Description of drawings

Fig. 1 is the X-ray diffraction pattern that adopts the present invention to synthesize antimony selenide nanowire;

Fig. 2 is the X-ray diffraction pattern that adopts the present invention to synthesize antimony telluride nanowire;

Fig. 3 is the X-ray diffraction spectrum of the nano low-dimensional nanostructure of the synthetic tellurium selenium antimony (Sb ₂ Se ₂ Te) ternary alloy of the present invention;

Fig. 4 is a scanning electron microscope picture of antimony selenide nanowires obtained by heat treatment at 200°C in the present invention;

Figure 5 is a scanning electron microscope picture of antimony selenide nanowires obtained by heat treatment at 240°C in the present invention;

Fig. 6 is a scanning electron microscope picture of antimony selenide nanowires obtained by heat treatment at 280°C in the present invention;

Fig. 7 is the scanning electron microscope picture that adopts the present invention to synthesize antimony selenide nano-hexagonal sheet;

Fig. 8 is the scanning electron microscope picture of adopting the present invention to synthesize antimony telluride nano-hexagonal sheet;

Fig. 9 is the scanning electron microscope picture that adopts the present invention to synthesize antimony sulfide nanobelt;

Fig. 10 is a scanning electron microscope picture of a lead telluride nanowire synthesized by the present invention;

Fig. 11 is a scanning electron microscope picture of a nanostructured film woven from indium telluride nanowires synthesized by the present invention;

Figure 12 is a scanning electron microscope picture of zinc telluride nanowires synthesized by the present invention;

Figure 13 is a scanning electron microscope picture of silver telluride nanowires synthesized by the present invention;

Fig. 14 is a scanning electron microscope picture of a low-dimensional nanostructure of a tellurium-selenide-antimony ternary alloy synthesized by the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

Example 1

Synthesis of Antimony Selenide Nanorods at 200℃

1 ingredient

(1) Configuration of 0.2mol/L H ₂ SeO ₃ solution: Dissolve 0.002mol of SeO ₂ in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make H ₂ SeO with a concentration of 0.2mol/L ₃ solutions.

(2) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: dissolve 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ in ethylene glycol, add 0.4ml of nitric acid, and dilute to 10ml of solution, Stir with a stirring magnet to prepare a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Se+Sb mixed solution: Take 12ml of 0.2mol/L H ₂ SeO ₃ solution and 8ml of 0.1mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 minutes , and the product is a mixed solution of Se+Sb precursors in a stoichiometric ratio of Sb ₂ Se ₃ ; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene column platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in a stainless steel or copper sheath, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to heat up the container to 200°C, keep it warm for 12 hours, and cool it with the furnace to make a large number of one-dimensional nanorods with a diameter of 0.5-1 micron and a length of 5-10 microns accumulated on the glass substrate, and the synthesized antimony selenide nanowires The X-ray diffraction pattern is shown in Figure 1, and the scanning electron microscope picture of the antimony selenide nanowire obtained by heat treatment is shown in Figure 4.

Example 2

Synthesis of Antimony Selenide Nanowires at 240℃

1 ingredient

(1) Configuration of 0.2mol/L H ₂ SeO ₃ solution: Dissolve 0.002mol of SeO ₂ in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make H ₂ SeO with a concentration of 0.2mol/L ₃ solutions.

(2) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 10ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Se+Sb mixed solution: Take 12ml of 0.2mol/L H ₂ SeO ₃ solution and 8ml of 0.1mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 minutes , and the product is a mixed solution of Se+Sb precursors in a stoichiometric ratio of Sb ₂ Se ₃ ; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to heat up the container to 240°C, keep it warm for 12 hours, and cool it with the furnace to prepare a large number of nanowires with a diameter of 100-500 nanometers and a length of tens to hundreds of microns distributed on the glass substrate. The antimony selenide nanowires obtained by heat treatment The scanning electron microscope picture of the line is shown in Fig. 5.

Example 3

Synthesis of Antimony Selenide Nanowires at 280℃

1 ingredient

(1) Configuration of 0.2mol/LH ₂ SeO ₃ solution: Dissolve 0.002mol of SeO ₂ (0.222g) in ethylene glycol, set the volume to 10ml of solution, put in stirring magnet and stir to make the concentration 0.2mol/L H ₂ SeO ₃ solution.

(2) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 10ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Se+Sb mixed solution: Take 12ml of 0.2mol/L H ₂ SeO ₃ solution and 8ml of 0.1mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 minutes , and the product is a mixed solution of Se+Sb precursors in a stoichiometric ratio of Sb ₂ Se ₃ ; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to raise the temperature of the container to 280°C, keep it warm for 12 hours, and cool it with the furnace to produce a large number of nanopillars with a diameter of about 1 micron and a length of tens of microns distributed on the glass substrate. The scanning electron microscope of the antimony selenide nanowires obtained by heat treatment The picture is shown in Figure 6.

Example 4

Synthesis of antimony selenide nanosheets at 250°C under rapid heating conditions

1 ingredient

(1) Configuration of 0.1mol/LH ₂ SeO ₃ solution: Dissolve 0.002mol of SeO ₂ (0.222g) in ethylene glycol, set the volume to 20ml solution, put in stirring magnet and stir to make the concentration 0.1mol/L H ₂ SeO ₃ solution.

(2) Configuration of 0.05mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 20ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Se+Sb mixed solution: Take 12ml of 0.1mol/L H ₂ SeO ₃ solution and 8ml of 0.05mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 minutes , and the product is a mixed solution of Se+Sb precursors in a stoichiometric ratio of Sb ₂ Se ₃ ; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Rapidly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Immediately placed in an environment of 250°C, kept warm for 20 minutes, and cooled with the furnace, a large number of two-dimensional nanohexagonal sheets with a thickness of tens of nanometers and a size of about 1 micron distributed on the glass substrate were produced. The scanning electron microscope picture is shown in Figure 7.

Example 5

Synthesis of Antimony Telluride Nanosheets at 260℃

1 ingredient

(1) Configuration of 0.2mol/LH ₂ TeO ₃ solution: Dissolve 0.002mol of TeO ₂ (0.319g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.2mol/L H ₂ TeO ₃ solution.

(2) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 10ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Te+Sb mixed solution: Take 12ml of 0.2mol/L H ₂ TeO ₃ solution and 8ml of 0.1mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 minutes , and the product is a Te+Sb precursor mixed solution with a stoichiometric ratio of Sb ₂ Te ₃ ; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to heat up the container to 260°C, keep it warm for 10 hours, and cool it with the furnace to produce a large number of two-dimensional nanohexagonal sheets with a thickness of tens of nanometers and a size of about 1 micron distributed on the glass substrate. The X-ray diffraction pattern is shown in Figure 2 The scanning electron microscope picture is shown in Figure 8.

Example 6

Synthesis of Antimony Sulfide Nanoribbons at 250℃

1 ingredient

(1) Configuration of 0.2mol/CH ₄ N ₂ S solution: 0.002mol of CH ₄ N ₂ S (0.152g) was dissolved in ethylene glycol, and the volume was adjusted to 10ml solution, and stirred with a stirring magnet to make a concentration of 0.2mol/L CH ₄ N ₂ S solution.

(2) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 10ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of S+Sb mixed solution: take 12ml of 0.2mol/L CH ₄ N ₂ S solution and 8ml of 0.1mol/L Sb ₂ (OCH ₂ CH ₂ O) ₃ solution, mix and keep stirring for 30 Minutes, the product is Sb ₂ S ₃ S+Sb precursor mixed solution with a stoichiometric ratio; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to heat up the container to 250°C, keep it warm for 10 hours, and cool with the furnace to produce a large number of nanobelts distributed on the glass substrate with a width of several hundred nanometers to 1 micron and a length of tens of microns. The scanning electron microscope picture is shown in Figure 9. Show.

Example 7

Synthesis of lead telluride nanowires at 200°C

1 ingredient

(1) Configuration of 0.2mol/LH ₂ TeO ₃ solution: Dissolve 0.002mol of TeO ₂ (0.319g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.2mol/L H ₂ TeO ₃ solution.

(2) Configuration of 0.2mol/LPb(CH ₃ COO) ₃ solution: Dissolve 0.002mol of Pb(CH ₃ COO) ₃ ·3H ₂ O (0.758g) in ethylene glycol, add 0.4ml of nitric acid, and dilute to 10ml solution, put it into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(3) Configuration of Te+Pb mixed solution: Take 10ml of 0.2mol/L H ₂ TeO ₃ solution and 10ml of 0.2mol/L Pb(CH ₃ COO) ₃ solution, mix and keep stirring for 30 minutes to prepare The product is a Te+Pb precursor mixed solution of PbTe according to the stoichiometric ratio; it is ready for use.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to raise the temperature of the container to 200°C, keep it warm for 12 hours, and cool down with the furnace to produce a large number of nanowires with a diameter of 100-200 nm and a length of 3-6 microns distributed on the glass substrate. The scanning electron microscope picture is shown in Figure 10.

Example 8

Synthesis of Indium Telluride Nanowires at 260°C

1 ingredient

(1) Configuration of 0.1mol/LH ₂ TeO ₃ solution: Dissolve 0.001mol of TeO ₂ (0.159g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.1mol/L H ₂ TeO ₃ solution.

(2) Configuration of 0.1mol/L In(NO ₃ ) ₃ solution: 0.001mol of In(NO ₃ ) ₃ ·4.5H ₂ O (0.382g) was dissolved in ethylene glycol, 0.4ml of nitric acid was added, and the volume was adjusted to 10ml of the solution was put into a stirring magnet and stirred to prepare an In(NO ₃ ) ₃ ·4.5H ₂ O solution with a concentration of 0.1 mol/L.

(3) Configuration of Te+In mixed solution: take 12ml of 0.1mol/L H ₂ TeO ₃ solution and 8ml of 0.1mol/L In(NO ₃ ) ₃ ·4.5H ₂ O solution, mix and keep stirring for 30 Minutes, the product is In ₂ Te ₃ Te+In precursor mixed solution with a stoichiometric ratio; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to raise the temperature of the container to 260 ° C, keep it warm for 12 hours, and cool it with the furnace to prepare a nanostructured film with a diameter of about 100 nanometers and a length of about 1 micron that is deposited on the glass substrate. The scanning electron microscope picture is shown in Figure 11. shown.

Example 9

Synthesis of ZnTe Nanowires at 260°C

1 ingredient

(1) Configuration of 0.2mol/LH ₂ TeO ₃ solution: Dissolve 0.002mol of TeO ₂ (0.319g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.2mol/L H ₂ TeO ₃ solution.

(2) The configuration of 0.2mol/L Zn(CH ₃ COO) ₂ solution: 0.002mol of Zn(CH ₃ COO) ₂ ·2H ₂ O (0.439g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added, and the volume was adjusted to 10ml solution, put it into a stirring magnet and stir to make a Zn(CH ₃ COO) ₂ solution with a concentration of 0.2 mol/L.

(3) Configuration of Te+Zn mixed solution: Take 10ml of 0.2mol/L H ₂ TeO ₃ solution and 10ml of 0.2mol/L Zn(CH ₃ COO) ₂ solution, mix and keep stirring for 30 minutes to prepare The product is a Te+Zn precursor mixed solution in which ZnTe is stoichiometrically proportioned; it is ready for use.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to raise the temperature of the container to 260°C, keep it warm for 12 hours, and cool down with the furnace to prepare nanowires with a length of several microns distributed on the glass substrate. The scanning electron microscope picture is shown in Figure 12.

Example 10

Synthesis of Silver Telluride Nanowires at 260°C

1 ingredient

(1) Configuration of 0.1mol/LH ₂ TeO ₃ solution: Dissolve 0.001mol of TeO ₂ (0.159g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.1mol/L H ₂ TeO ₃ solution.

(2) Configuration of 0.1mol/L AgNO ₃ solution: Dissolve 0.001mol AgNO ₃ (0.170g) in ethylene glycol, add 0.4ml nitric acid, dilute to 10ml solution, put in stirring magnet and stir to make the concentration 0.1mol/L AgNO ₃ solution.

(3) Configuration of Te+Ag mixed solution: Take 12ml of 0.1mol/L H ₂ TeO ₃ solution and 8ml of 0.1mol/L AgNO ₃ solution, mix and keep stirring for 30 minutes to make the product Ag ₂ Te Te+Ag precursor mixed solution according to stoichiometric ratio; ready for use.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to raise the temperature of the container to 260°C, keep it warm for 12 hours, and cool down with the furnace to produce ultra-long nanowires with a diameter of about 400 nanometers and a length ranging from hundreds of microns to several millimeters. The scanning electron microscope picture is shown in Figure 13.

Example 11

Synthesis of low-dimensional nanostructures of tellurium-selenide-antimony ternary alloys

1 ingredient

(1) Configuration of 0.2mol/LH ₂ SeO ₃ solution: Dissolve 0.002mol of SeO ₂ (0.222g) in ethylene glycol, set the volume to 10ml of solution, put in stirring magnet and stir to make the concentration 0.2mol/L H ₂ SeO ₃ solution.

(2) Configuration of 0.1mol/LH ₂ TeO ₃ solution: Dissolve 0.001mol TeO ₂ (0.159g) in ethylene glycol, set the volume to 10ml solution, put in stirring magnet and stir to make the concentration 0.1mol/L H ₂ TeO ₃ solution.

(3) Configuration of 0.1mol/LSb ₂ (OCH ₂ CH ₂ O) ₃ solution: 0.001mol of Sb ₂ (OCH ₂ CH ₂ O) ₃ (0.423g) was dissolved in ethylene glycol, and 0.4ml of nitric acid was added to constant volume to 10ml of the solution, put into a stirring magnet to stir, and make a Sb ₂ (OCH ₂ CH ₂ O) ₃ solution with a concentration of 0.1 mol/L.

(4) Configuration of Te+Se+Sb mixed solution: Take 5ml of 0.1mol/L H ₂ TeO ₃ solution, 5ml of 0.2mol/L H ₂ SeO ₃ solution and 5ml of 0.1mol/L Sb ₂ ( OCH ₂ CH ₂ O) ₃ solution, mixed, and continuously stirred for 30 minutes to prepare a Te+Se+Sb precursor mixed solution of Sb ₂ Se ₂ Te in a stoichiometric ratio; set aside.

2 co-reduction reaction

Place the substrate carrying the precursor solution on the polytetrafluoroethylene columnar platform of the reaction device, inject 1ml of 85vol% hydrazine into the bottom of the polytetrafluoroethylene container, place the reaction container in an autoclave, and seal it. Slowly raise the temperature to 180°C and react for 10 minutes.

3 heat treatment

Continue to heat up the container to 240°C, keep it warm for 12 hours, and cool it with the furnace to produce a large number of nanowires with a diameter of 100-300 nanometers and a length of tens of microns distributed on the glass substrate and a large number of hexagonal sheets with a diameter of about 500 nanometers. X - The ray diffraction spectrum is shown in Figure 3, and the scanning electron microscope picture is shown in Figure 14.

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described here to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art according to the disclosure of the present invention should fall within the protection scope of the present invention.

Claims (9)

1. a preparation method of the chalcogenide of low-dimensional nanostructure, it is characterized in that, the method comprises the following steps: (1) Configuration of the flooding solution: dissolve the chalcogen compound in the solvent to obtain an acid solution of 0.01-0.1mol/L chalcogen, and dissolve the salt of antimony, lead, indium, zinc or silver in In the solvent, prepare 0.01-0.1mol/L antimony, lead, indium, zinc or silver salt solution; fully mix the above two solutions to make a uniform and stable precursor solution; (2) Co-reduction treatment: load the precursor solution obtained in step (1) on the substrate or in the crucible, and then place it in a sealed reduction device. The temperature of the control device is from room temperature to 180 °C. The gas co-reduces the precursor solution for 10 to 30 minutes to obtain a low-dimensional chalcogenide nanostructure with a low degree of crystallinity; (3) Heat treatment: under the atmosphere of reducing gas, the chalcogenide low-dimensional nanostructure with low crystallization degree obtained in step (2) is grown at a constant temperature of 180 ° C to 280 ° C for 0.5 to 12 hours, and then naturally cooled To room temperature, the obtained product is evenly deposited on the substrate or in the crucible, which is the product. 2. the preparation method of the chalcogenide of a kind of low-dimensional nanostructure according to claim 1, is characterized in that, the chalcogenide described in step (1) is the oxide or acid of selenium, tellurium and sulfur or One of the sulfur-containing organic compounds. 3. the preparation method of the chalcogenide of a kind of low-dimensional nanostructure according to claim 1 is characterized in that, the salt of antimony, lead, indium, zinc or silver described in step (1) is antimony, lead , indium, zinc or silver nitrates, acetates, chlorides or metal alkoxides. 4. the preparation method of the chalcogenide of a kind of low-dimensional nanostructure according to claim 1, is characterized in that, the solvent described in step (1) is selected from ethylene glycol, glycerol, deionized water, One or more of absolute ethanol, benzene, toluene or carbon tetrachloride. 5. the preparation method of the chalcogenide of a kind of low-dimensional nanostructure according to claim 1, is characterized in that, the mol ratio of each element in the precursor solution described in step (1) is selected from Sb:Te is 2:3﹑Sb:Se is 2:3﹑Sb:S is 2:3﹑Pb:Te is 1:1﹑In:Te is 2:3﹑Ag:Te is 2:1 or Zn:Te is 1: One of 1. 6 . The method for preparing a low-dimensional nanostructured chalcogenide according to claim 1 , wherein the substrate is monocrystalline silicon, quartz glass, sapphire, ceramics or an organic substrate material. 7. The method for preparing a low-dimensional nanostructured chalcogenide according to claim 1, wherein the crucible is a ceramic crucible or a quartz glass crucible. 8. The method for preparing a low-dimensional nanostructured chalcogenide according to claim 1, wherein the reducing gas is N ₂ H ₄ ﹑ NH ₃ ﹑ C ₂ N ₂ H ₈ ﹑ H _2S or _{CH2N2S .} 9. the preparation method of the chalcogenide of a kind of low-dimensional nanostructure according to claim 1, it is characterized in that, described sealed reducing device is made of polytetrafluoroethylene liner and stainless steel or copper cladding, and described The polytetrafluoroethylene lining has a built-in polytetrafluoroethylene pillar as the substrate bearing platform, and the top is provided with a polytetrafluoroethylene sealing top cover, and the stainless steel or copper cladding is set outside the polytetrafluoroethylene lining. Teflon liner seals inside.