CN103055774A - Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent - Google Patents
Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent Download PDFInfo
- Publication number
- CN103055774A CN103055774A CN2013100453740A CN201310045374A CN103055774A CN 103055774 A CN103055774 A CN 103055774A CN 2013100453740 A CN2013100453740 A CN 2013100453740A CN 201310045374 A CN201310045374 A CN 201310045374A CN 103055774 A CN103055774 A CN 103055774A
- Authority
- CN
- China
- Prior art keywords
- zns
- sns
- source
- reaction
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for forming a ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of a normal pressure solvent. Reaction raw materials are dispersed in the solvent to form a raw material solution; and then the reaction raw material solution is added to a three-necked flask step by steps; and the thermosynthesis reaction of the normal pressure solvent is completed by heating in a magnetic stirring oil bath. The synthesis speed of the thermosynthesis reaction of the normal pressure solvent is increased through magnetic stirring; and the thermodynamic and dynamic conditions for generating a product are achieved through stirring while heating so that the target product ZnS/SnS/CuA core-shell structure composite powder is synthesized. The method provided by the invention has the advantages of low cost, simple reaction device, high reaction process controllability and the like, and is capable of controlling the whole reaction synthesis process quite flexibly, thereby forming specific structure and specific composition.
Description
Technical field
The present invention relates to a kind of method of Solvent at Atmospheric Pressure thermal synthesis ZnS/SnS/CuA three-layer nuclear shell structure semi-conducting material composite granule, wherein A is one or both among S and the Se, and this semi-conducting material can be used for the technical fields such as solar cell, photovoltage device.
Background technology
ZnS/SnS/Cu (S and/or Se) semi-conducting material can be used for preparation and the relative photo power conversion device Development and Production of thin film solar cell presoma; Generally, the condition of the synthetic above-mentioned composite of solvent heat is comparatively harsh, and reaction speed is also slower, even will just can carry out through long-time insulation under the sealing high pressure; This synthesis mode flexibility is also relatively poor, and can not intervene the reaction pilot process under the enclosed environment, is difficult to finish the controlledly synthesis of the ad hoc structures such as nucleocapsid.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Solvent at Atmospheric Pressure thermal synthesis ZnS/SnS/Cu (S and/or Se) three-layer nuclear shell structure semi-conducting material composite granule.
Concrete steps are:
(1) by a mole proportioning Zn:Sn:S:Cu:(S+Se)=1:1:2 ~ 3:1.5 ~ 2.5:2 ~ 3 take by weighing zinc source, Xi Yuan, sulphur source, copper source and sulphur selenium source and are dissolved in respectively organic solvent, make zinc source solution, tin source solution, sulphur source solution, copper source solution and sulphur selenium source solution, sulphur source and selenium source mix with arbitrary proportion in the described sulphur selenium source.
(2) the zinc source solution that step (1) is made and interior mixing of sulphur source solution adding there-necked flask, described there-necked flask places the magnetic agitation oil bath, and three bottlenecks insert respectively sealing plug, condenser pipe and thermometer, heat while stirring,, naturally cool to room temperature and make the solution that contains the ZnS nano powder after 0.5 ~ 5 hour 80 ~ 150 ℃ of lower insulations.
(3) in the solution that contains the ZnS nano powder that the tin source solution adding step (2) that step (1) is made makes, 160 ~ 190 ℃ of insulation reaction 1 ~ 5 hour, then naturally cool to room temperature and make the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule or take out product and use respectively deionized water and absolute ethyl alcohol centrifuge washing 3 ~ 4 times and obtained the ZnS/SnS composite powder in 6 ~ 8 hours 60 ~ 80 ℃ of vacuum drying, more ultrasonic being scattered in of ZnS/SnS composite powder obtained ZnS/SnS composite powder suspension in the ethylene glycol.
(4) the copper source solution that step (1) is made and sulphur selenium source solution join in the solution or ZnS/SnS composite powder suspension that contain the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule that step (3) makes, 60 ~ 140 ℃ of insulation reaction 1 ~ 5 hour, then naturally cool to and take out product after the room temperature and use respectively deionized water and absolute ethyl alcohol centrifuge washing 3 ~ 4 times, products therefrom namely made ZnS/SnS/CuA three-layer nuclear shell structure composite granule in 6 ~ 8 hours 60 ~ 80 ℃ of vacuum drying, and wherein A is one or both among S and the Se.
Described zinc source is a kind of in zinc acetate, zinc chloride and the zinc nitrate.
Described Xi Yuan is stannous chloride or butter of tin.
Described copper source is a kind of in copper chloride, copper nitrate and the copper acetate.
Described sulphur source is a kind of in thiocarbamide, sulphur powder and the thioacetamide.
Described selenium source is selenium powder or selenous acid.
Described organic solvent is one or more in ethylenediamine, hydrazine hydrate and the ethylene glycol, when being multiple, the solvent that uses with arbitrary volume than mixing.
The present invention adopts the normal pressure open system to synthesize ZnS/SnS/CuA nucleocapsid structure composite powder material, controls the degree of carrying out of reaction by control reaction temperature and reaction time; Control the target product stoichiometric proportion by control raw material proportioning; The synthetic nuclear material of technique leading portion can be synthetic with regard to directly entering next step without centrifugation and washing, namely realizes finishing in the same reaction system the synthetic of three-layer nuclear shell structure.
Substep addition sequence and the elementary reaction temperature and time of the temperature-rise period growth pattern of controlling product of the present invention by adjusting the course of reaction Raw obtains the composite granule of different structure and pattern.
The present invention adopts magnetic agitation to accelerate the aggregate velocity of Solvent at Atmospheric Pressure thermal response, in the course of reaction by heating while stirring to reach the thermodynamics and dynamics condition that product generates.
Compare with the synthetic composite granule technique of common high pressure solvent heat, the advantages such as the present invention has that cost is low, reaction unit is simple, the course of reaction controllability is strong, thus and can control more flexibly whole reaction building-up process and form specific structure and specific composition combination.
Description of drawings:
Fig. 1 is synthesis process flow diagram of the present invention.
Fig. 2 is the SEM shape appearance figure of the synthetic ZnS/SnS/CuSe three-layer nuclear shell structure composite granule of the embodiment of the invention 1.
Fig. 3 is the XRD diffraction pattern of the synthetic ZnS/SnS/CuSe three-layer nuclear shell structure composite granule of the embodiment of the invention 1.
Fig. 4 is the FESEM photo of the synthetic powder of the embodiment of the invention 2 steps (2), step (3) and step (4), wherein a figure is the synthetic ZnS nano powder FESEM photo of step (2), b figure is the synthetic two-layer nucleocapsid structure semi-conducting material of the ZnS/SnS composite granule FESEM photo of step (3), and c figure is the synthetic ZnS/SnS/CuSe three-layer nuclear shell structure composite granule FESEM photo of step (4).
Fig. 5 is the XRD diffracting spectrum of the synthetic ZnS/SnS/CuS three-layer nuclear shell structure composite granule of the embodiment of the invention 2.
Fig. 6 is the FESEM photo of the synthetic ZnS/SnS/CuS three-layer nuclear shell structure composite granule of the embodiment of the invention 3.
The specific embodiment
Embodiment 1:
(1) takes by weighing 2.7375 gram zinc acetates, 2.8206 gram stannous chlorides, 2.8549 gram thiocarbamides, 4.9913 gram copper acetates and 2.961 gram selenium powders by mole proportioning Zn:Sn:S:Cu:Se=1:1:3:2:3, wherein zinc acetate, stannous chloride, thiocarbamide and copper acetate are dissolved in respectively ethylene glycol and make solution, and selenium powder is dissolved in hydrazine hydrate and makes solution.
The ethylene glycol solution of the zinc acetate that (2) step (1) is made and interior mixing of the ethylene glycol solution of thiocarbamide adding there-necked flask, add again 5 milliliters of ethylenediamines, described there-necked flask places the magnetic agitation oil bath, and three bottlenecks insert respectively sealing plug, condenser pipe and thermometer, heat while stirring,, naturally cool to room temperature and make the solution that contains the ZnS nano powder after 1 hour 150 ℃ of lower insulations.
In the solution that contains the ZnS nano powder that the ethylene glycol solution adding step (2) of the stannous chloride that (3) step (1) is made makes, 180 ℃ of insulation reaction 1 hour, then naturally cool to room temperature and make the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule.
The ethylene glycol solution of the copper acetate that (4) step (1) is made and the hydrazine hydrate solution of selenium join in the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule that step (3) makes, 100 ℃ of insulation reaction 1 hour, then naturally cool to and take out product after the room temperature and use respectively deionized water and absolute ethyl alcohol centrifuge washing 4 times, products therefrom namely made target powder in 8 hours 80 ℃ of vacuum drying.
Target powder is ZnS/SnS/CuSe three-layer nuclear shell structure composite granule (seeing accompanying drawing 3) through XRD analysis; Through scanning electron microscope analysis, product is mainly the nucleocapsid structure of graininess and rod-shaped powder, and approximately 1 ~ 5 micron of the particle size of graininess powder can be found out by the picture that amplifies, and the graininess powder is reunited by many little irregular tablets and formed (seeing accompanying drawing 2).
Embodiment 2:
(1) takes by weighing 0.5488 gram zinc acetate, 0.5641 gram stannous chloride, 0.3806 gram thiocarbamide, 0.9983 gram copper acetate and 0.3806 gram thiocarbamide by mole proportioning Zn:Sn:S:Cu:S=1:1:2:2:2, wherein zinc acetate, stannous chloride, copper acetate and two parts of thiocarbamides are dissolved in respectively ethylene glycol and make solution, and the ethylene glycol solution of two parts of thiocarbamides is label a (containing 0.3806 gram thiocarbamide), b (containing 0.3806 gram thiocarbamide) respectively.
The ethylene glycol solution of the zinc acetate that (2) step (1) is made and interior mixing of the ethylene glycol solution of a thiocarbamide adding there-necked flask, described there-necked flask places the magnetic agitation oil bath, and three bottlenecks insert respectively sealing plug, condenser pipe and thermometer, heat while stirring,, naturally cool to room temperature and make the solution that contains the ZnS nano powder after 1 hour 150 ℃ of lower insulations.
In the solution that contains the ZnS nano powder that the ethylene glycol solution adding step (2) of the stannous chloride that (3) step (1) is made makes, 190 ℃ of insulation reaction 1 hour, insulation naturally cools to room temperature after finishing, take out product, respectively product is carried out centrifuge washing 4 times with distilled water and absolute ethyl alcohol, the 60 ℃ of lower vacuum drying in vacuum drying chamber of product behind the centrifuge washing are obtained the two-layer nucleocapsid structure composite powder of ZnS/SnS in 6 hours, more ultrasonic being scattered in of ZnS/SnS composite powder obtained ZnS/SnS composite powder suspension in the ethylene glycol.
The ethylene glycol solution of the copper acetate that (4) step (1) is made and the ethylene glycol solution of b thiocarbamide join in the ZnS/SnS composite powder suspension that step (3) makes, 130 ℃ of insulation reaction 1 hour, then naturally cool to and take out product after the room temperature and use respectively deionized water and absolute ethyl alcohol centrifuge washing 4 times, products therefrom namely made target powder in 6 hours 60 ℃ of vacuum drying.
Target powder is ZnS/SnS/CuSe three-layer nuclear shell structure composite granule (seeing accompanying drawing 5) through XRD analysis; The product of step (2) takes out and carries out centrifuge washing 4 times with distilled water and absolute ethyl alcohol respectively and place in the vacuum drying chamber obtaining the ZnS nano powder in 6 hours 60 ℃ of lower dryings, the emission electromicroscopic photograph can find out that ZnS is smooth spheric granules through the field, and grain diameter is about 1 micron; It is outer that the two-layer nucleocapsid structure composite powder of the ZnS/SnS that step (3) makes can find out that through field emission electromicroscopic photograph the SnS of sheet is wrapped in spherical ZnS; The target powder of step (4) can find out that through field emission electromicroscopic photograph outermost layer CuS is the granule (seeing accompanying drawing 4) that is attached on the SnS lamella.
Embodiment 3
(1) takes by weighing 0.5488 gram zinc acetate, 0.5641 gram stannous chloride, 0.5709 gram thiocarbamide, 0.9983 gram copper acetate and 0.5709 gram thiocarbamide by mole proportioning Zn:Sn:S:Cu:S=1:1:3:2:3, wherein zinc acetate, stannous chloride, copper acetate and two parts of thiocarbamides are dissolved in respectively ethylene glycol and make solution, and the ethylene glycol solution of two parts of thiocarbamides is label a (containing 0.5709 gram thiocarbamide), b (containing 0.5709 gram thiocarbamide) respectively.
The ethylene glycol solution of the zinc acetate that (2) step (1) is made and interior mixing of the ethylene glycol solution of a thiocarbamide adding there-necked flask, described there-necked flask places the magnetic agitation oil bath, and three bottlenecks insert respectively sealing plug, condenser pipe and thermometer, heat while stirring,, naturally cool to room temperature and make the solution that contains the ZnS nano powder after 1 hour 150 ℃ of lower insulations.
In the solution that contains the ZnS nano powder that the ethylene glycol solution adding step (2) of the stannous chloride that (3) step (1) is made makes, 180 ℃ of insulation reaction 1 hour, then naturally cool to room temperature and make the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule.
The ethylene glycol solution of the copper acetate that (4) step (1) is made and the ethylene glycol solution of b thiocarbamide join in the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule that step (3) makes, 130 ℃ of insulation reaction 1 hour, then naturally cool to and take out product after the room temperature and use respectively deionized water and absolute ethyl alcohol centrifuge washing 4 times, products therefrom namely made target powder in 6 hours 60 ℃ of vacuum drying.
Target powder is ZnS/SnS/CuSe three-layer nuclear shell structure composite granule through XRD analysis; The emission electromicroscopic photograph can be found out powder shape, not of uniform size through the field, and the ZnS of some spherical shape is exposed outside, and the particle that superscribes is all larger, and closely knit (seeing accompanying drawing 6).
Claims (4)
1. the method for a Solvent at Atmospheric Pressure thermal synthesis ZnS/SnS/CuA nucleocapsid structure composite granule is characterized in that concrete steps are:
(1) by a mole proportioning Zn:Sn:S:Cu:(S+Se)=1:1:2 ~ 3:1.5 ~ 2.5:2 ~ 3 take by weighing zinc source, Xi Yuan, sulphur source, copper source and sulphur selenium source and are dissolved in respectively organic solvent, make zinc source solution, tin source solution, sulphur source solution, copper source solution and sulphur selenium source solution, sulphur source and selenium source mix with arbitrary proportion in the described sulphur selenium source;
(2) the zinc source solution that step (1) is made and interior mixing of sulphur source solution adding there-necked flask, described there-necked flask places the magnetic agitation oil bath, and three bottlenecks insert respectively sealing plug, condenser pipe and thermometer, heat while stirring,, naturally cool to room temperature and make the solution that contains the ZnS nano powder after 0.5 ~ 5 hour 80 ~ 150 ℃ of lower insulations;
(3) in the solution that contains the ZnS nano powder that the tin source solution adding step (2) that step (1) is made makes, 160 ~ 190 ℃ of insulation reaction 1 ~ 5 hour, then naturally cool to room temperature and make the solution that contains the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule or take out product and use respectively deionized water and absolute ethyl alcohol centrifuge washing 3 ~ 4 times and obtained the ZnS/SnS composite powder in 6 ~ 8 hours 60 ~ 80 ℃ of vacuum drying, more ultrasonic being scattered in of ZnS/SnS composite powder obtained ZnS/SnS composite powder suspension in the ethylene glycol;
(4) the copper source solution that step (1) is made and sulphur selenium source solution join in the solution or ZnS/SnS composite powder suspension that contain the two-layer nucleocapsid structure semi-conducting material of ZnS/SnS composite granule that step (3) makes, 60 ~ 140 ℃ of insulation reaction 1 ~ 5 hour, then naturally cool to and take out product after the room temperature and use respectively deionized water and absolute ethyl alcohol centrifuge washing 3 ~ 4 times, products therefrom namely made ZnS/SnS/CuA three-layer nuclear shell structure composite granule in 6 ~ 8 hours 60 ~ 80 ℃ of vacuum drying, and wherein A is one or both among S and the Se;
Described zinc source is a kind of in zinc acetate, zinc chloride and the zinc nitrate;
Described Xi Yuan is stannous chloride or butter of tin;
Described copper source is a kind of in copper chloride, copper nitrate and the copper acetate;
Described sulphur source is a kind of in thiocarbamide, sulphur powder and the thioacetamide;
Described selenium source is selenium powder or selenous acid;
Described organic solvent is one or more in ethylenediamine, hydrazine hydrate and the ethylene glycol, when being multiple, the solvent that uses with arbitrary volume than mixing.
2. synthetic method according to claim 1 is characterized in that: adopt the synthetic ZnS/SnS/CuA nucleocapsid structure composite powder material of normal pressure open system, control the degree of carrying out of reaction by control reaction temperature and reaction time; Control the target product stoichiometric proportion by control raw material proportioning; The synthetic nuclear material of technique leading portion can be synthetic with regard to directly entering next step without centrifugation and washing, namely realizes finishing in the same reaction system the synthetic of three-layer nuclear shell structure.
3. synthetic method according to claim 1 and 2, it is characterized in that: the substep addition sequence by adjusting the course of reaction Raw and the elementary reaction temperature and time of temperature-rise period are controlled the growth pattern of product, obtain the composite granule of different structure and pattern.
4. synthetic method according to claim 1 and 2 is characterized in that: adopt magnetic agitation to accelerate the aggregate velocity of Solvent at Atmospheric Pressure thermal response, in the course of reaction by heating while stirring to reach the thermodynamics and dynamics condition that product generates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100453740A CN103055774A (en) | 2013-02-06 | 2013-02-06 | Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100453740A CN103055774A (en) | 2013-02-06 | 2013-02-06 | Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103055774A true CN103055774A (en) | 2013-04-24 |
Family
ID=48098842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100453740A Pending CN103055774A (en) | 2013-02-06 | 2013-02-06 | Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055774A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105308758A (en) * | 2013-08-01 | 2016-02-03 | 株式会社Lg化学 | Three-layer core-shell nanoparticle for manufacture of light-absorbing layer for solar cell and method for preparing same |
| CN105324852A (en) * | 2013-08-01 | 2016-02-10 | 株式会社Lg化学 | Metal chalcogenide nanoparticles for preparing light absorption layer of solar cell, and preparation method therefor |
| CN107469834A (en) * | 2017-08-25 | 2017-12-15 | 内江师范学院 | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541415A (en) * | 2006-11-14 | 2009-09-23 | 巴斯夫欧洲公司 | Method for production of a mini suspoemulsion or suspension of sub-micron core/shell particles |
| US20110081451A1 (en) * | 2009-10-01 | 2011-04-07 | Symrise Ag | Spherical core-shell-particle |
-
2013
- 2013-02-06 CN CN2013100453740A patent/CN103055774A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101541415A (en) * | 2006-11-14 | 2009-09-23 | 巴斯夫欧洲公司 | Method for production of a mini suspoemulsion or suspension of sub-micron core/shell particles |
| US20110081451A1 (en) * | 2009-10-01 | 2011-04-07 | Symrise Ag | Spherical core-shell-particle |
Non-Patent Citations (2)
| Title |
|---|
| PETER REISS ET AL.: "Core/Shell Semiconductor Nanocrystals", 《SMALL》 * |
| 高洁 等: "溶剂热法合成In2S3/CuSe核壳结构粉体", 《无机化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105308758A (en) * | 2013-08-01 | 2016-02-03 | 株式会社Lg化学 | Three-layer core-shell nanoparticle for manufacture of light-absorbing layer for solar cell and method for preparing same |
| CN105324852A (en) * | 2013-08-01 | 2016-02-10 | 株式会社Lg化学 | Metal chalcogenide nanoparticles for preparing light absorption layer of solar cell, and preparation method therefor |
| US9478684B2 (en) | 2013-08-01 | 2016-10-25 | Lg Chem, Ltd. | Three-layer core-shell nanoparticles for manufacturing solar cell light absorption layer and method of manufacturing the same |
| EP2996159A4 (en) * | 2013-08-01 | 2017-01-18 | LG Chem, Ltd. | Three-layer core-shell nanoparticle for manufacture of light-absorbing layer for solar cell and method for preparing same |
| CN105308758B (en) * | 2013-08-01 | 2017-02-15 | 株式会社Lg化学 | Three-layer core-shell nanoparticle for manufacture of light-absorbing layer for solar cell and method for preparing same |
| CN105324852B (en) * | 2013-08-01 | 2018-02-23 | 株式会社Lg化学 | Metal chalcogenide compound nano particle of light absorbing layer for preparing solar cell and preparation method thereof |
| EP3029742B1 (en) * | 2013-08-01 | 2020-01-15 | LG Chem, Ltd. | Metal chalcogenide nanoparticles for preparing light absorption layer of solar cell, and preparation method therefor |
| CN107469834A (en) * | 2017-08-25 | 2017-12-15 | 内江师范学院 | A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method |
| CN107469834B (en) * | 2017-08-25 | 2020-07-07 | 内江师范学院 | Preparation method of ZnS/CuS nanosheet composite photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055774A (en) | Method for forming ZnS/SnS/CuA core-shell structure composite powder through thermosynthesis of normal pressure solvent | |
| CN102060273A (en) | Method for preparing I-III-VI group semiconductor material through solvothermal synthesis in constant pressure open system | |
| CN102642818B (en) | Method for preparing CZTS (Copper Zinc Tin Sulfide) (Se) series nanometer powder by low-temperature mechanical alloying | |
| CN103145175B (en) | Preparation method of small-size nano-zinc oxide powder | |
| CN108373164B (en) | A kind of C cladding Cu2The synthetic method of O cuboctahedron core-shell structure | |
| CN102557117A (en) | Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves | |
| CN104724756B (en) | A kind of one-step method prepares that size is controlled, the method for ad hoc structure barium oxide | |
| CN106542579A (en) | A kind of preparation method of flower ball-shaped calcium molybdate | |
| CN104891553A (en) | Preparation method of ZnO semispherical micro-nanostructure and obtained product | |
| CN102351238A (en) | Method for preparing hollow copper sulphide crystal with nano-twin structure | |
| CN102874863B (en) | Synthetic method for zinc oxide nano-particles | |
| CN105036175B (en) | Method of preparing copper sulfide-zinc sulfide heterojunction three-dimensional nanostructure by using solid phase method | |
| CN102249199A (en) | Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder | |
| CN104016708B (en) | A kind of preparation method of high breaking strength earthenware supporter | |
| CN109371263A (en) | Preparation method of copper-gallium alloy and silver-gallium alloy | |
| CN103466688B (en) | A kind of method for preparing ZnS nanosheet | |
| CN105036192B (en) | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof | |
| CN103922421A (en) | Method for preparing alpha-Fe2O3 | |
| CN104402705A (en) | Spherical calcium citrate, and preparation method and application thereof | |
| CN106328916B (en) | A kind of lithium vanadate Li3VO4The microwave radiation preparation of nano-hollow ball | |
| CN105271125A (en) | Spherical potassium perchlorate production technology | |
| CN110776020A (en) | NiMnO of stick equipment 3Method for synthesizing nanoflower | |
| CN102627315A (en) | Preparation method of wurtzite structure CZTS (Se) system powder | |
| CN103613115A (en) | Method for synthesizing ZnO/ZnSe (zinc oxide/zinc selenide) coaxial nano structure through gas-phase anion exchange | |
| CN102623552A (en) | Method for preparing core-shell-structured metal sulfoselenide semi-conductor composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130424 |