CN105603532B - A kind of preparation method of antimony selenide micron single crystal grain - Google Patents
A kind of preparation method of antimony selenide micron single crystal grain Download PDFInfo
- Publication number
- CN105603532B CN105603532B CN201610168330.0A CN201610168330A CN105603532B CN 105603532 B CN105603532 B CN 105603532B CN 201610168330 A CN201610168330 A CN 201610168330A CN 105603532 B CN105603532 B CN 105603532B
- Authority
- CN
- China
- Prior art keywords
- single crystal
- crystal grain
- preparation
- reaction container
- quartz reaction
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
Abstract
The invention discloses a kind of preparation methods of antimony selenide micron single crystal grain, and with simple substance antimony, elemental selenium and fluxing agent ground and mixed, Vacuum Package keeps 48~120h in quartz reaction container at 600~750 DEG C, to quartz reaction container fast cooling；Sample is taken out, up to antimony selenide single crystal grain after washing, drying；The size of prepared single crystal grain can be regulated and controled using recrystallization temperature and time, the ingredient of particle can effectively be allocated within the specific limits by the molar ratio of each element in presoma, preparation-obtained single crystal grain is uniform, size is controllable, and performance is better than the single crystal grain that conventional method is prepared.
Description
Technical field
The present invention relates to photoelectric semiconductor material and device arts, more particularly, to a kind of antimony selenide micron list
The preparation method of brilliant particle.
Background technology
Solar cell is all a research hotspot all the time, and current compound film battery mainly has cadmium telluride
（CdTe）And copper indium gallium selenide（CIGS）Solar cell, both batteries are because contained Partial Elements have severe toxicity and also have Partial Elements
Scarcity of resources, it is expensive, it is difficult to application on a large scale；And the copper-zinc-tin-sulfur risen in recent years（CZTS）Based solar battery profit
The In in CIGS is replaced with large storage capacity, cheap Zn and Sn, and achieves 12.7% photoelectric conversion efficiency record, but
CZTS is all multicomponent system as CIGS, and Thermodynamically stable section is small, and the control of component and lattice defect is excessively complicated, causes
Impurity and defect are excessive in material, and the further of efficiency promotes difficulty.Compared to above-mentioned different materials, antimony selenide（Sb2Se3）It is
A kind of binary single-phase compounds, since its raw material large storage capacity, toxicity are low, cheap, bandwidth is suitable（~1.15eV）, inhale
Backscatter extinction logarithmic ratio is big（>105cm-1）, crystal growth temperature is low, is very suitable for making the solar cell of novel low-cost low toxicity.
At present, Sb has all been related to both at home and abroad2Se3Application of the material in terms of solar cell, Sb2Se3Preparation
Mainly there are the techniques such as solution heat note method, solvent-thermal method, hydro-thermal method, electrodeposition process, hot spray process, and to prepare nanotube, nanometer
Based on line and nano thin-film, and Sb2Se3Large-particle monocrystal preparation be still technical barrier；When preparing solar cell,
The performance of single crystal battery is again more preferable than the performance of hull cell, still, traditional Crystal Growth Technique（Gas phase transmission technology melts
Melt technology）It is difficult to grow the large size single crystal for meeting solar battery obsorbing layer performance requirement.
The content of the invention
The technical problems to be solved by the invention are to overcome existing preparation large scale Sb2Se3It is above-mentioned scarce present in particle
It falls into, a kind of Sb is provided2Se3The preparation method of micron single crystal grain.
Second object of the present invention is to provide the Sb that above-mentioned preparation method obtains2Se3Micron single crystal grain.
Third object of the present invention is to provide containing above-mentioned Sb2Se3The solar cell of single crystal grain.
Fourth object of the present invention is to provide above-mentioned Sb2Se3Application of the single crystal grain in terms of solar cell is prepared.
The purpose of the present invention is what is be achieved by the following technical programs：
1. a kind of preparation method of antimony selenide micron single crystal grain, comprises the following steps：
S1. reaction raw materials simple substance antimony, elemental selenium are mixed in a certain ratio, add in fluxing agent, ground and mixed is uniformly prepared
Into presoma；
S2. presoma is fitted into quartz reaction container, vacuumizes or be passed through after inert gas and seals quartz reaction appearance
Device；
S3. the quartz reaction container after sealing is kept into 48~120h at 600~750 DEG C, it is fast to quartz reaction container
Prompt drop warms to room temperature, and the sample in quartz reaction container is taken out, up to antimony selenide single crystal grain after washing, drying；Wherein, S1 institutes
It is 1 to state simple substance antimony and elemental selenium molar ratio：1.5~3.
The present invention is by simple substance antimony（Sb）, elemental selenium（Se）It is mixed according to designed ratio, and adds in fluxing agent, fully ground
Mill is mixed and made into presoma, the crystallization generation Sb under high temperature fused state2Se3Single crystal grain；Crystal grain is flat in fused salt
It is grown under weighing apparatus state, when grain shape and size reach requirement, fast cooling is carried out to reaction vessel, is inhibited in temperature-fall period
The nonequilibrium state growth of crystal, so as to control the pattern of single crystal grain；The ingredient of single crystal grain can be by first in presoma
The molar ratio of element is effectively allocated within the specific limits, and the size of single crystal grain can be regulated and controled using crystallization temperature and time.
For different elements, different structure compositions needs the parameter controlled, such as element ratio, crystallization temperature, knot
Brilliant time, inventor need constantly to grope in this process, so as to which satisfactory single crystal grain be made.
It can make each single crystal grain shape due to preparing solar cell energy using pattern rule, the uniform single crystal grain of component
Into a battery unit, the influence for absorbing layer defects and interface impurity to device performance is effectively reduced, and single crystal grain is formed
Matte can effectively improve the utilization rate of incident light, have advanced optical characteristics, theoretically can significantly promote Sb2Se3Battery
Transfer efficiency, therefore, single crystal grain have performance more superior than thin-film material and obtained the extensive concern of people.It is existing
The pattern that technology prepares single crystal grain using molten-salt growth method is uncontrollable, and component is uneven, and the time for forming single crystal grain is too long, no
Beneficial to industrial production, reaction raw materials and fluxing agent are ground by the invention, pass through vacuum sealing, high temperature melting molten bonding
Crystalline substance obtains morphology controllable, the controllable single crystal grain of component.
In fact, prepare meet solar battery obsorbing layer single crystal grain it is extremely difficult, be only control element composition,
Raw material proportioning or the growth technique for only controlling monocrystalline are likely to that single crystal grain is caused to prepare failure；It to combine and be actually subjected to
Element composition, the growth technique of raw material proportioning and monocrystalline of the single crystal grain of preparation, can just finally obtain qualified monocrystalline
Grain.The present invention is using molten-salt growth method as prototype, by the way that reaction raw materials and fluxing agent are ground uniform vacuum-pumping density according to a certain percentage
Envelope, reacts certain time at a certain temperature by it, when the preferable size pattern of reaction generation, is pressed down by fast cooling
The further growth of combinations body, timely cooling and suitable temperature can effectively prepare the micron monocrystalline of ideal dimensions size
Particle.
It is brilliant in this period when, it is necessary to cool down to quartz reaction container, being cooled to 450 DEG C first after completion of the reaction
Body growth course remains at equilibrium state growth, advantageously reduces the surface defect of crystal, then carries out fast cooling, is to press down
The nonequilibrium state growth of combinations body, and effectively prevent the generation of other impurities phase.
It has a certain impact in addition, fluxing agent species and dosage prepare tool to single crystal grain, suitable fused salt species and molten
Suitable fluxing agent dosage contributes to the growth of molten salt system crystal in salt system, it is preferable that fluxing agent described in S1 for KI,
One or more in CsCl, CsI.
Preferably, the mixing molar ratio of the fluxing agent and reaction raw materials is 1~10：1.
Preferably, it is 10~10 that the vacuum degree in rear quartz reaction container is vacuumized described in S22 Pa。
The present invention also provides the antimony selenide micron single crystal grains that any one method obtains.
Solar cell containing the single crystal grain is provided simultaneously.
Additionally provide application of the single crystal grain in terms of solar cell is prepared.
Compared with prior art, the invention has the advantages that：
The present invention provides a kind of preparation method of antimony selenide micron single crystal grain, i.e., according to the formula hybrid reaction of design
Raw material, then addition fluxing agent, which is fully ground, is mixed with presoma, by precursor powder Vacuum Package in quartz reaction container
In, melting recrystallization generates Sb at a temperature of setting2Se3Single crystal grain；The size of prepared single crystal grain can be utilized and tied again
Brilliant temperature and time regulates and controls, and the ingredient of particle can be effective within the specific limits by the molar ratio of each element in presoma
Allotment, preparation-obtained single crystal grain ingredient uniformly, regular shape, size it is controllable, performance is prepared into better than conventional method
The single crystal grain arrived, specific advantage are as follows：
（1）High-temperature fusion crystallization can obtain the uniform single crystal grain of component, and fast cooling inhibits single in temperature-fall period
Brilliant nonequilibrium state growth, so as to control the pattern of single crystal grain and component.
（2）Different fused salt combinations and proportioning can in single crystal growth process by the phase mutual friction of crystal grain and crystal grain with
The phase mutual friction of fused salt effectively eliminates the crystal face corner angle of grain surface, so as to control the form of grain surface, obtains surface more
Bright and clean single crystal grain.
（3）Reaction raw materials used are resourceful, cheap, Preparation equipment is simple, pollute small in preparation process, are easy to
Industrialized production.
Description of the drawings
Fig. 1 is the Sb that in embodiment 1 prepared by molten-salt growth method2Se3Single crystal grain.
Fig. 2 is the surface topography of the sample prepared in comparative example 1.
Fig. 3 is the surface topography of the sample prepared in comparative example 2.
Specific embodiment
With reference to the content that Figure of description and specific embodiment further illustrate the present invention, but should not be construed as to this
The limitation of invention.Without departing from the spirit and substance of the case in the present invention, the method for the present invention, step or condition are made simple
Modifications or substitutions all belong to the scope of the present invention；Unless otherwise specified, technological means used in embodiment is art technology
Conventional means known to personnel.
Embodiment 1
2 mmol Sb of reaction raw materials, 3 mmol Se and 10 mmol CsCl of fluxing agent are weighed, presoma is obtained after mixing,
Presoma is fully ground, is uniformly mixed it；Mixed sample is fitted into quartzy bottle, is taken out using vacuum pump assembly
Vacuum reaches 10~102Pa（It can also blanketing with inert gas）, so as to exclude the influence that air reacts fused salt, use oxyhydrogen flame
By quartzy bottle closure；The quartzy bottle that biased sample is housed after sealing is placed in common heating furnace from room temperature and is heated to 700 DEG C of guarantors
72h is held, 450 DEG C is then cooled to and takes out quartzy bottles and fast cooling is to room temperature（Into the water）；Finally by the sample in quartzy bottle
Product take out, and ultrasound washing repeatedly removes fluxing agent CsCl, and sample is placed in 80 DEG C of 2 h of drying of drying box afterwards, obtain surface tool
There is the micron-scale Sb of crystal gloss2Se3Single crystal grain, about 55 microns.
To the Sb of acquisition2Se3Single crystal grain carries out performance detection, the results showed that, the Sb of embodiment 12Se3Single crystal grain is equal
In rice-shaped strip, resistance value is 3.22K Ω, and band gap width is about 1.27eV.
Embodiment 2
2 mmol Sb of reaction raw materials, 4 mmol Se and fluxing agent 30mmol CsI are weighed, presoma is obtained after mixing, it is right
Presoma is fully ground, and is uniformly mixed it；Mixed sample is fitted into quartzy bottle, is taken out using vacuum pump assembly true
Sky reaches 10~102Pa（It can also blanketing with inert gas）, will with oxyhydrogen flame so as to exclude the influence that air reacts fused salt
Quartzy bottle closure；The quartzy bottle that biased sample is housed after sealing is placed in common heating furnace from room temperature and is heated to 650 DEG C of holdings
Then 96h cools to 450 DEG C and takes out quartzy bottles and fast cooling is to room temperature（Into the water）；Finally by the sample in quartzy bottle
It takes out, ultrasound washing repeatedly removes fluxing agent CsI, and sample is placed in 80 DEG C of 2 h of drying of drying box afterwards, and obtaining surface has crystalline substance
The micron-scale Sb of body gloss2Se3Single crystal grain, about 60 microns.
To the Sb of acquisition2Se3Single crystal grain carries out performance detection, the results showed that, the Sb of embodiment 22Se3Single crystal grain is equal
In rice-shaped strip, resistance value is 3.02 K Ω, and band gap width is about 1.21eV.
Embodiment 3
2 mmol Sb of reaction raw materials, 6 mmol Se and 64 mmol KI of fluxing agent are weighed, presoma is obtained after mixing, it is right
Presoma is fully ground, and is uniformly mixed it；Mixed sample is fitted into quartzy bottle, is taken out using vacuum pump assembly true
Sky reaches 10~102Pa（It can also blanketing with inert gas）, will with oxyhydrogen flame so as to exclude the influence that air reacts fused salt
Quartzy bottle closure；The quartzy bottle that biased sample is housed after sealing is placed in common heating furnace from room temperature and is heated to 600 DEG C of holdings
Then 120h cools to 450 DEG C and takes out quartzy bottles and fast cooling is to room temperature（Into the water）；Finally by the sample in quartzy bottle
It takes out, ultrasound washing repeatedly removes fluxing agent KI, and sample is placed in 80 DEG C of 2 h of drying of drying box afterwards, and obtaining surface has crystalline substance
The micron-scale Sb of body gloss2Se3Single crystal grain, about 50 microns.
To the Sb of acquisition2Se3Single crystal grain carries out performance detection, the results showed that, the Sb of embodiment 32Se3Single crystal grain is equal
In rice-shaped strip, resistance value is 3.54K Ω, and band gap width is about 1.31eV.
Comparative example 1
Experimental method is with embodiment 1, and uniquely the difference is that, reaction raw materials are free of fluxing agent, to the Sb finally obtained2Se3It is single
Brilliant particle carries out nature examination, the results showed that：Pattern rule, the uniform Sb of component can not be prepared2Se3Micron single crystal grain.
Comparative example 2
Experimental method with embodiment 1, it is unique unlike, presoma is directly placed into quartzy bottle and reacted without grinding,
To the Sb finally obtained2Se3Single crystal grain carries out nature examination, the results showed that：Obtained sample composition is uneven, grain shape
Irregularly, the particle of micron-scale is less.
Comparative example 3
The quartzy bottle that biased sample is housed after sealing uniquely the difference is that, is placed on common liter by experimental method with embodiment 1
900 DEG C of holding 96h are heated to from room temperature in warm stove, the quartzy bottle of 650 DEG C of taking-ups is then cooled to and fast cooling is to room temperature, to most
The particle obtained eventually carries out nature examination, the results showed that：Particle surface finish is poor, and there are apparent simple substance Se, simple substance Sb
Cluster body does not meet the absorption layer material as solar cell.
Claims (7)
1. a kind of preparation method of antimony selenide micron single crystal grain, which is characterized in that comprise the following steps：
S1. reaction raw materials simple substance antimony, elemental selenium are mixed in a certain ratio, fluxing agent are added in, before ground and mixed is uniformly configured to
Drive body；
S2. presoma is fitted into quartz reaction container, vacuumizes or be passed through after inert gas and seals quartz reaction container；
S3. the quartz reaction container after sealing is kept into 48~120h at 600~750 DEG C, to the fast prompt drop of quartz reaction container
It warms to room temperature, the sample in quartz reaction container is taken out, up to antimony selenide single crystal grain after washing, drying；Wherein, it is single described in S1
Matter antimony and elemental selenium molar ratio are 1：Fluxing agent described in 1.5~3, S1 is the one or more in KI, CsCl or CsI.
2. preparation method according to claim 1, which is characterized in that S3 is first cooled to quartz reaction container 450 DEG C, then
Fast cooling is to room temperature.
3. preparation method according to claim 1, which is characterized in that the mixing molar ratio of the fluxing agent and reaction raw materials
For 1~10：1.
4. preparation method according to claim 1, which is characterized in that vacuumized described in S2 true in rear quartz reaction container
Reciprocal of duty cycle is 10~102Pa。
5. the antimony selenide micron single crystal grain that any one of Claims 1-4 preparation method obtains.
6. the solar cell containing single crystal grain described in claim 5.
7. application of the single crystal grain described in claim 5 in terms of solar cell is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168330.0A CN105603532B (en) | 2016-03-23 | 2016-03-23 | A kind of preparation method of antimony selenide micron single crystal grain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610168330.0A CN105603532B (en) | 2016-03-23 | 2016-03-23 | A kind of preparation method of antimony selenide micron single crystal grain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105603532A CN105603532A (en) | 2016-05-25 |
| CN105603532B true CN105603532B (en) | 2018-05-22 |
Family
ID=55983858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610168330.0A Active CN105603532B (en) | 2016-03-23 | 2016-03-23 | A kind of preparation method of antimony selenide micron single crystal grain |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105603532B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477534B (en) * | 2016-09-29 | 2018-08-31 | 广东先导稀材股份有限公司 | A kind of preparation method of selenium arsenic alloy |
| CN113235166B (en) * | 2021-05-13 | 2022-05-27 | 重庆文理学院 | Preparation method of large-size antimony selenide single crystal material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101217178A (en) * | 2007-12-26 | 2008-07-09 | 中国科学院上海硅酸盐研究所 | A preparation method for antimonide molybdenum base thermoelectric material |
| CN101643938A (en) * | 2009-09-08 | 2010-02-10 | 南京大学 | Method for preparing submicron grade square pipe-shaped Sb2Se3 |
| CN102583272A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Vermicular Sb2Se3 hydrogen storage material and preparation method thereof |
| CN104846428A (en) * | 2015-04-13 | 2015-08-19 | 山东大学 | Method used for growth of transition metal chalcogenide crystals via metal fluxing agent method |
| CN104952979A (en) * | 2015-06-11 | 2015-09-30 | 岭南师范学院 | Micron-sized spherical copper-zinc-tin-sulfur monocrystal particle preparation method |
| CN104979429A (en) * | 2015-06-11 | 2015-10-14 | 岭南师范学院 | Preparation method for micron-sized spherical CZTSSe monocrystalline particles |
| CN105161555A (en) * | 2015-08-19 | 2015-12-16 | 岭南师范学院 | Single-crystal particle film and preparation method of substrate-free flexible solar cell employing single-crystal particle film |
-
2016
- 2016-03-23 CN CN201610168330.0A patent/CN105603532B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101217178A (en) * | 2007-12-26 | 2008-07-09 | 中国科学院上海硅酸盐研究所 | A preparation method for antimonide molybdenum base thermoelectric material |
| CN101643938A (en) * | 2009-09-08 | 2010-02-10 | 南京大学 | Method for preparing submicron grade square pipe-shaped Sb2Se3 |
| CN102583272A (en) * | 2012-01-21 | 2012-07-18 | 哈尔滨工业大学 | Vermicular Sb2Se3 hydrogen storage material and preparation method thereof |
| CN104846428A (en) * | 2015-04-13 | 2015-08-19 | 山东大学 | Method used for growth of transition metal chalcogenide crystals via metal fluxing agent method |
| CN104952979A (en) * | 2015-06-11 | 2015-09-30 | 岭南师范学院 | Micron-sized spherical copper-zinc-tin-sulfur monocrystal particle preparation method |
| CN104979429A (en) * | 2015-06-11 | 2015-10-14 | 岭南师范学院 | Preparation method for micron-sized spherical CZTSSe monocrystalline particles |
| CN105161555A (en) * | 2015-08-19 | 2015-12-16 | 岭南师范学院 | Single-crystal particle film and preparation method of substrate-free flexible solar cell employing single-crystal particle film |
Non-Patent Citations (4)
| Title |
|---|
| Microwave-assisted synthesis of Sb2Se3 submicron tetragonal tubular and spherical crystals;Lei Guo，等;《Nanotechnology》;20091207;第21卷;035606-1至7 * |
| OPTICAL, PHOTOELECTRIC AND ELECTRIC PROPERTIES OF SINGLE-CRYSTALLINE Sb2Se3;F. KOSEK，等;《Czech. J. Phys. B》;19781231;第28卷;标题，2.Experimental部分 * |
| Sb2Se3热电材料的真空熔炼合成及微结构研究;胡孔刚，等;《铸造技术》;20121130;第33卷(第11期);I 试验材料与方法第1段，2.1XRD衍射分析第1段，图2 * |
| Single Crystal Growth and Magnetic Properties of Mn-doped Bi2Se3 and Sb2Se3;Jeongyong Choi,等;《Journal of Magnetics》;20041231;第9卷(第4期);125-127 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105603532A (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nagaoka et al. | Preparation of Cu2ZnSnS4 single crystals from Sn solutions | |
| CN102107905B (en) | Method for preparing Cu2ZnSnS4 solar battery material | |
| Nagaoka et al. | Growth of Cu2ZnSnS4 single crystal by traveling heater method | |
| WO2019085678A1 (en) | Multinary alloy compound, ink and thin-film absorption layer thereof, and preparation methods therefor | |
| CN103361724A (en) | Boron-gallium co-doped efficient polycrystalline silicon and preparation method thereof | |
| CN113372012A (en) | Metal element doped inorganic lead-free CsSnI3Method for perovskite stabilization | |
| CN111490148A (en) | Preparation method of polycrystalline SnSe-based thermoelectric material | |
| CN105603532B (en) | A kind of preparation method of antimony selenide micron single crystal grain | |
| CN104952979B (en) | The preparation method of a kind of micron-size spherical copper-zinc-tin-sulfur single crystal grain and single crystal grain thereof and application | |
| WO2014002574A1 (en) | Semiconductor film manufacturing method | |
| CN104979429B (en) | A kind of preparation method of micron-size spherical copper zinc tin sulfur selenium single crystal grain | |
| CN109706525B (en) | Bismuth-based topological insulator material and preparation method thereof | |
| Nagaoka et al. | Na-doped Cu2ZnSnS4 single crystal grown by traveling-heater method | |
| Das et al. | Growth and characterization of kesterite Cu2ZnSn (SxSe1− x) 4 crystals for photovoltaic applications | |
| CN102390856B (en) | Method for preparing high-stability gamma-phase nanometer lanthanum sulfide powder in low temperature | |
| Muska et al. | Influence of compositional deviations on the properties of Cu2ZnSnSe4 monograin powders | |
| CN105742385B (en) | A kind of copper and iron zinc-tin sulfur micron single crystal grain and preparation method thereof and the application in terms of preparing solaode | |
| CN110808335B (en) | Preparation method and application of tin-lead binary perovskite film with preferred orientation growth | |
| CN106206841B (en) | Gallium arsenide substrate material preparation method | |
| Kim et al. | Solvothermal synthesis and characterization of a CuInTe2 absorber for thin-film photovoltaics | |
| Kotani et al. | Composition‐ratio control of CZTS films deposited by PLD | |
| Durán et al. | Growth, structural characterization, and optical band gap of Cu (In1− xGax) 5Se8 alloys | |
| KR101269848B1 (en) | Manufacturing method of single phased cigs nanopowder | |
| JP5660004B2 (en) | Method for producing ZnMgO film | |
| CN108217732A (en) | A kind of preparation method nanocrystalline buergerite CMTS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |