CN115432671A - Novel semiconductor material and synthesis method thereof - Google Patents
Novel semiconductor material and synthesis method thereof Download PDFInfo
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- CN115432671A CN115432671A CN202210981049.4A CN202210981049A CN115432671A CN 115432671 A CN115432671 A CN 115432671A CN 202210981049 A CN202210981049 A CN 202210981049A CN 115432671 A CN115432671 A CN 115432671A
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- 239000000463 material Substances 0.000 title claims abstract description 109
- 239000004065 semiconductor Substances 0.000 title claims abstract description 75
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000002490 spark plasma sintering Methods 0.000 claims description 7
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- 230000001681 protective effect Effects 0.000 claims description 6
- 238000005551 mechanical alloying Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 3
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
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- 125000000129 anionic group Chemical group 0.000 description 2
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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Abstract
The invention belongs to the field of novel semiconductor materials, and discloses a novel semiconductor material and a synthesis method thereof, wherein the diamond semiconductor material is Cu 3‑x Ag x InSnSe 5 The semiconductor material is characterized in that x is more than or equal to 0 and less than or equal to 1. The lattice structure is a square structure, and the space group is
The invention improves the composition and structure of the material to prepare Cu 2 SnSe 3 With CuInSe 2 (or AgInSe) 2 ) The tetrahedral units of these different diamond-like compounds are rearranged to obtain a plurality of Cu 3‑x Ag x InSnSe 5 Diamond-like semiconductor material having a tetragonal structure
In addition, the preparation method has low cost and can be popularized and applied in a large scale.
Description
Technical Field
The invention belongs to the field of novel semiconductor materials, and particularly relates to a novel semiconductor material and a synthesis method thereof.
Background
The numerous diamond-like compounds have various structures, are widely used for manufacturing semiconductor devices, have the advantages of environmental friendliness, high abundance and the like, and are widely applied to the fields of optical materials, infrared detection materials, thermoelectric materials, solar energy and the like, so that the diamond-like compounds have very important significance for the research work of the diamond-like compounds. However, with the rapid development of diamond-like compounds in various fields, many diamond-like compounds cannot meet the demand for higher performance (e.g., highly tunable band gap, combined high electrical conductivity and low thermal conductivity, etc.). The polynary diamond-like compound has more complex components and can meet different application scenes, so that the exploration of the novel polynary diamond-like compound is necessary. However, the number of the polynary diamond-like compounds is known to be small, so that the search for novel polynary diamond-like compounds with stable components has important research significance.
One important approach in finding polytropic diamond-like compounds is to form solid solutions for alloying. The identity of the crystal structure is a prerequisite for the formation of an infinite solid solution between the components, whereas for components of non-identical structure the mutual solubility is generally limited. Thus, it is very challenging to form a solid solution with greater solubility or to form a stable single phase for two diamond-like compound components of different structures.
In the family of diamond-like compounds, there are two compounds with different crystal structures, I-III-VI respectively 2 Forms I and I 2 -IV-VI 3 Type (iii) however, both compounds have a relatively similar atomic arrangement from the point of view of the bonding. In I-III-VI 2 (e.g., cuInSe 2 ，CuInTe 2 ，AgGaSe 2 ，CuInS 2 ) In the family of compounds, cations tend to occupy anionic componentsHas a coordination number of 4 to form tetrahedra [ I-VI ] 4 ]And tetrahedrons [ III-VI 4 ]E.g. [ CuSe ] 4 ]And [ InSe ] 4 ]，[CuTe 4 ]And [ InTe ] 4 ]，[AgSe 4 ]And [ GaSe ] 4 ][CuS 4 ]And [ InS ] 4 ]The tetrahedral structures are arranged in a vertex-sharing manner, and the tetrahedral proportion is [ I-VI 4 ]:[III-VI 4 ]=1:1, forming a chalcopyrite-structured compound with a crystal structure of
The symmetry is high. Similarly, in I 2 -IV-VI 3 (e.g. Cu) 2 GeSe 3 ，Cu 2 SnSe 3 ，Ag 2 SnSe 3 ) In the compound family, the basic units are tetrahedra [ II-VI ] 4 ]And tetrahedron [ IV-VI 4 ]E.g. [ CuSe ] 4 ]And [ GeSe ] 4 ]，[CuSe 4 ]And [ SnSe ] 4 ]，[AgSe 4 ]And [ SnSe ] 4 ]The tetrahedral structures are arranged in a vertex-sharing manner, and the tetrahedral proportion is [ II-VI 4 ]:[IV-VI 4 ]=2:1, a monoclinic structure compound is formed, the crystal structure is Cc (9), and the symmetry is low. Deriving new stable single phases from the two diamondoid compounds with different crystal structures is very challenging work.
On the other hand, for the above two ternary diamond-like compounds, the common synthesis method is high-temperature melting combined with long-time annealing and solvothermal synthesis. The main disadvantages of high-temperature smelting combined with long-time annealing are that the proportion is difficult to control accurately and the synthesis period is long. Se element is extremely volatile at high temperature, the boiling point is 684.9 ℃, therefore, long-time annealing is generally carried out after high-temperature smelting so as to realize the proportion as accurate as possible, otherwise, the proportion of the Se element is difficult to accurately control. The main disadvantage of the solvothermal synthesis method is high synthesis cost and difficult large-scale production. Certain soluble cationic and anionic salts are expensive, difficult to obtain, and the synthetic products are susceptible to reaction conditions including pressure, temperature, time, and ph. In addition, it is difficult to obtain the product by conventional high-temperature smelting and solvent thermal synthesis methodGo to square structure
Pure phase of (2).
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention aims to provide a novel semiconductor material and a synthesis method thereof, wherein Cu is modified by improving the composition and structure of the material 2 SnSe 3 With CuInSe 2 (or AgInSe) 2 ) The tetrahedral units of these different diamond-like compounds are rearranged to obtain a plurality of Cu 3- x Ag x InSnSe 5 Diamond-like semiconductor material having a tetragonal structure
In addition, the preparation method has low cost and can be popularized and applied in a large scale.
To achieve the above object, according to one aspect of the present invention, there is provided a diamond-like semiconductor material characterized in that the semiconductor material is specifically Cu 3-x Ag x InSnSe 5 The single-phase semiconductor material is characterized in that x is more than or equal to 0 and less than or equal to 1.
As a further preferred aspect of the present invention, the Cu 3-x Ag x InSnSe 5 The lattice structure of the semiconductor material is a square structure, and the space group is
As a further preference of the present invention, the semiconductor material is specifically Cu 3 InSnSe 5 The unit cell parameters of the semiconductor material are a =0.572 plus or minus 0.0008nm, b =0.572 plus or minus 0.0008nm, c =1.147 plus or minus 0.0004nm, and alpha = beta = gamma =90 degrees.
As a further preference of the present invention, the semiconductor material is specifically Cu 2 AgInSnSe 5 Semiconductor material, unit cell parameters a =0.581 ± 0.0005nm, b =0.581 ± 0.0005nm, c =1.161 ± 0.0006nm, α = β = γ =90 °.
As the inventionIn a further preferred embodiment, the semiconductor material is specifically Cu 3 InSnSe 5 Semiconductor material or Cu 2 AgInSnSe 5 Semiconductor material of, wherein Cu 3 InSnSe 5 The band gap of the semiconductor material is 1.07eV 2 AgInSnSe 5 The bandgap of the semiconductor material is 0.95eV.
According to another aspect of the present invention, there is provided a method for preparing the diamond-like semiconductor material, comprising the steps of:
(1) Preparing raw material powder: in a protective atmosphere environment according to the chemical formula Cu 3-x Ag x InSnSe 5 Weighing simple substance material powder corresponding to each element according to the nominal chemical dose ratio;
(2) Powder mixing: fully mixing the various powders obtained in the step (1), putting the powders into a high-energy ball milling tank in a glove box, and sealing; wherein, O in the glove box 2 The concentration of (2) is not higher than 0.2vol.%, and the ball-material ratio satisfies the mass ratio of 15;
(3) Mechanical alloying: mounting the ball milling tank obtained in the step (2) on a high-energy ball mill, and performing ball milling at a rotating speed of not less than 580r/min for 180-600 minutes; collecting the ball-milled powder to obtain Cu 3- x Ag x InSnSe 5 And (3) material powder.
As a further preferred of the present invention, the method further comprises the steps of:
(4) And (3) spark plasma sintering: cu obtained in the step (3) 3-x Ag x InSnSe 5 Filling the material powder into a graphite die, and then performing discharge plasma sintering to obtain Cu 3-x Ag x InSnSe 5 A block of material; wherein the spark plasma sintering satisfies: the vacuum degree of the furnace chamber is less than 8Pa, the axial pressure is 50-70MPa, the sintering temperature is 480-500 ℃, and the sintering time is not higher than 20min; and after the discharge plasma sintering is finished, cooling the room temperature along with the furnace and gradually removing the pressure.
In a further preferred embodiment of the present invention, in the step (1), the protective atmosphere is an argon atmosphere.
According to a further aspect of the invention, the invention provides the use of a diamond-like semiconductor material as described above as a thermoelectric semiconductor material.
As a further preference of the present invention, the semiconductor material is specifically Cu 3 InSnSe 5 The thermoelectric figure of merit of the semiconductor material at 500 ℃ is 1.08.
Through the technical scheme, compared with the prior art, the method obtains the multi-element diamond-like compound Cu by utilizing the arrangement of tetrahedral elements in the diamond-like compound 3-x Ag x InSnSe 5 Is under the influence of
The space group has an optical band gap of about 1eV, and can be used as a thermoelectric material.
The prior art forms composite materials containing two phases, which are difficult to tune the crystal structure and the energy band structure of the materials, and only can compromise the physical properties, for example, a material with low electrical conductivity is compounded with a material with high electrical conductivity to improve the electrical conductivity of a matrix, and a material with high thermal conductivity is compounded with a material with low thermal conductivity to reduce the thermal conductivity of the materials. In contrast thereto, the present invention gives Cu 3- x Ag x InSnSe 5 Single phase (e.g. Cu) 3 InSnSe 5 And Cu 2 AgInSnSe 5 ) It has specific space group structure and phase parameters, and is a novel polynary diamond-like compound. The invention can be regarded as that two kinds of diamond-like compounds (CuInSe) with different structures exist 2 -Cu 2 SnSe 3 Or AgInSe 2 -Cu 2 SnSe 3 ) With tetrahedral units of Cu 3 InSnSe 5 For example, it is composed of [ CuSe4 ]]、[SnSe4]And [ InSe4 ]]Three tetrahedrons are randomly arranged in a vertex-sharing manner, the ratio of the tetrahedrons is 3 3 InSnSe 5 A compound; with Cu 2 AgInSnSe 5 For example, it is composed of [ CuSe4 ]]、[AgSe4]、[SnSe4]And [ InSe4 ]]Four tetrahedrons are randomly arranged in a vertex-sharing manner, the tetrahedron ratio is 2 2 AgInSnSe 5 A compound is provided. Moreover, the compounds obtained by the invention all belong to diamond-like compound Cu with a tetragonal structure 3-x Ag x InSnSe 5 。
In addition, the synthesis method has low cost, and a powder initial product can be obtained through mechanical alloying treatment of high-energy ball milling; and can further combine the plasma fast sintering technology to obtain bulk crystals. The composition of the synthesized sample is uniform, the actual proportion of each element of the generated semiconductor material is close to the nominal proportion, and the difference between the measured value and the nominal value is basically negligible. The mechanical alloying method can avoid the volatilization of Se element, can synthesize powder samples rapidly in large scale, has low synthesis cost and uniform components of the synthesized samples; and the plasma rapid sintering technology can be further combined, so that the proportion of the final compact semiconductor material is ensured to be close to the nominal proportion (without annealing treatment) to the maximum extent.
The invention makes various attempts in the research and development process, and finds that many diamond-like materials are difficult to synthesize single-phase substances like Cu 2 SnSe 3 And MnSe, cuInSe 2 And ZnSe, etc., and finally CuInSe was found 2 And Cu 2 SnSe 3 ，AgInSe 2 And Cu 2 SnSe 3 The two groups are capable of forming a single phase composition.
Specifically, the present invention can achieve the following advantageous effects:
(1) The invention realizes the construction of novel polynary diamond-like compounds, the principle lies in rearranging tetrahedral elements, which is a new strategy and is different from the forming principle of infinite solid solution.
(2) The invention overcomes the problem of low solubility between components with different crystal structures and forms stable Cu 3- x Ag x InSnSe 5 Single phase (e.g. Cu) 3 InSnSe 5 And Cu 2 AgInSnSe 5 )。
(3) The preparation method adopts quick and low-cost mechanical alloying treatment, can be preferably matched with discharge plasma sintering, and can quickly obtain large-scale compactCu 3-x Ag x InSnSe 5 The semiconductor material avoids the defects of high-temperature smelting with long period of the diamond-like compound and the traditional synthesis scheme of solvent thermal synthesis with high cost and severe conditions, and also avoids the problem of hot-pressing sintering with long period in the traditional method. The invention adopts discharge plasma sintering, the sintering time is not more than 20min, and the invention has the characteristic of rapidness.
(4) Cu obtained by the invention 3-x Ag x InSnSe 5 The intrinsic thermoelectric figure of merit of the material is close to 1, and the material can be used as a thermoelectric material.
Drawings
FIG. 1 shows diamond-like material Cu 2 SnSe 3 、CuInSe 2 And Cu 3 InSnSe 5 Schematic structural diagram of (1). Corresponding to Cu from left to right in the figure 2 SnSe 3 、CuInSe 2 、Cu 3 InSnSe 5 。
FIG. 2 is Cu 3-x Ag x InSnSe 5 (X =0,1) X-ray diffraction results of semiconductor materials before and after SPS sintering.
FIG. 3 is Cu 3-x Ag x InSnSe 5 (x =0,1) a Scanning Electron Microscope (SEM) backscattered electron image of the polished face of the semiconductor material; the scale in FIG. 3 represents 200 μm, 20 μm, 50 μm, and 20 μm in this order from left to right and from top to bottom; in addition, the table shown in the lower right of the figure is a corresponding region (i.e., cu) 3 InSnSe 5 Corresponding Spot 1 region, cu 2 AgInSnSe 5 Corresponding Spot 2 region) energy spectral analysis (EDS) of the matrix composition.
FIG. 4 is Cu 3-x Ag x InSnSe 5 (x =0,1) results of absorbance testing of semiconductor materials.
FIG. 5 shows Cu 3 InSnSe 5 Resistivity, thermal conductivity, and thermoelectric figure of merit versus temperature curve for semiconductor materials.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A method for producing a diamond-like semiconductor includes the steps of:
(1) In a glove box, under the protection atmosphere of argon, elemental elements of copper, indium, tin and selenium powder are weighed. Elemental mass in terms of Cu 3 InSnSe 5 The formula nominal dose proportioning weights (i.e., such that the atomic stoichiometric ratio of the powder as a whole satisfies Cu: in: sn: se = 3. The error range of the weighing balance used in this example was. + -. 0.0005g.
(2) The initially weighed powders were thoroughly mixed by hand in a mortar for 35min and sealed after being charged into a high energy ball mill pot in a glove box under the condition that the oxygen concentration was less than 0.2 vol.%.
(3) Placing the ball milling tank on a high-energy ball mill for ball milling at a rotating speed of 580r/min, wherein ball milling beads are made of stainless steel, the ball-material mass ratio is 15 3 InSnSe 5 And (3) powder.
(4) The collected powder was filled into a graphite mold, and then discharge Plasma Sintering (SPS) was performed. The sintering conditions are as follows: the vacuum degree of the furnace chamber is less than 8Pa, the axial pressure is 70MPa, the temperature is rapidly raised to 500 ℃, the temperature is slowly cooled to the room temperature subsequently, the cooling rate is 10 ℃/min, and in the process, the pressure is reduced to 10MPa from 70MPa after 6 min. Finally, the mold is demoulded by applying axial pressure, and the compact block Cu can be obtained 3 InSnSe 5 A semiconductor material.
Diamond-like compound Cu 2 SnSe 3 ，CuInSe 2 The crystal structure of the semiconductor material is known as shown in fig. 1. The material obtained in the above example is refined by polycrystalline powder XRD and combined with TEM spindle electron diffraction analysis chart to determine Cu 3 InSnSe 5 Semiconductor materialThe crystal structure of the material is shown in figure 1. Cu was confirmed by marking the transmission electron diffraction pattern 3 InSnSe 5 The lattice structure is a square structure and the space group is
Through XRD powder diffraction fine trimming, cu can be determined 3 InSnSe 5 Specific unit cell parameters are a =0.572 ± 0.0008nm, b =0.572 ± 0.0008nm, c =1.147 ± 0.0004nm, α = β = γ =90 °.
XRD detection is carried out on the materials obtained in the step (3) and the step (4) respectively, and the results show that the diamond-like compound Cu 3 InSnSe 5 Semiconductor material, remaining before and after sintering
As shown in fig. 2.
SEM and EDS tests are carried out on the material obtained in the step (4), and the result shows that the diamond-like compound Cu 3 InSnSe 5 Semiconductor material, the elements are uniformly distributed, and the actual atomic ratio is very close to the nominal atomic ratio, as shown in fig. 3.
Carrying out an absorbance test on the material obtained in the step (4), wherein the result shows that the diamond-like compound Cu 3 InSnSe 5 The bandgap of the semiconductor material is at 1.07eV, as shown in fig. 4.
The material obtained in the step (4) is tested for Seebeck coefficient, resistivity and thermal conductivity at different temperatures, and the result shows that the diamond-like compound Cu 3 InSnSe 5 The thermoelectric figure of merit of the semiconductor material was 1.08 at 500 deg.C, as shown in FIG. 5.
Example 2
A method for producing a diamond-like semiconductor includes the steps of:
(1) In a glove box, argon is used as protective atmosphere, and elemental elements of copper, silver, indium, tin and selenium powder are weighed. Elemental mass in terms of Cu 2 AgInSnSe 5 Formula (iv) nominal dose-proportioning weighing (i.e. such that the atomic stoichiometric ratio of the powder as a whole satisfies Cu: ag: in: sn: se = 2.The balance error range is +/-0.0005 g.
(2) Fully mixing the initially weighed powder in a planetary ball mill under the protective atmosphere, wherein the ball milling parameters are that the rotating speed is 150r/min, the time length is 2 hours, and under the condition that the oxygen concentration is less than 0.2vol.%, a high-energy ball milling tank is filled in a glove box and then sealed.
(3) Placing the ball milling tank on a high-energy ball mill, performing ball milling at a rotating speed of 580r/min, wherein ball milling beads are made of stainless steel, the ball material mass ratio is 30 2 AgInSnSe 5 And (3) powder.
(4) The collected powder was filled into a graphite mold, and then spark plasma sintering was performed. The sintering conditions are as follows: the vacuum degree of the furnace chamber is less than 8Pa, the axial pressure is 50MPa, the temperature is rapidly increased to 480 ℃, the temperature is slowly cooled to the room temperature subsequently, the cooling rate is 10 ℃/min, and in the process, the pressure is reduced to 10MPa from 50MPa after 6 min. Finally, the mold is demoulded by applying axial pressure, and the compact block Cu can be obtained 2 AgInSnSe 5 A semiconductor material.
Prepared Cu 2 AgInSnSe 5 The semiconductor material can be determined to be a square structure through the calibration of transmission electron diffraction patterns, and the space group is
Specific unit cell parameters can be determined by XRD powder diffraction refinement as a =0.581 ± 0.0005nm, b =0.581 ± 0.0005nm, c =1.161 ± 0.0006nm, α = β = γ =90 °.
XRD detection is carried out on the materials obtained in the step (3) and the step (4), and the results show that the diamond-like compound Cu 2 AgInSnSe 5 Semiconductor material, remaining before and after sintering
As shown in fig. 2.
SEM and EDS tests are carried out on the material obtained in the step (4), and the result shows that the diamond-like compound Cu 2 AgInSnSe 5 Semiconductor materialThe material, the elements are evenly distributed, and the actual atomic ratio is very close to the nominal atomic ratio, as shown in fig. 3.
Carrying out an absorbance test on the material obtained in the step (4), wherein the result shows that the diamond-like compound Cu 2 AgInSnSe 5 The bandgap of the semiconductor material is at 0.95eV as shown in figure 4.
Example 3
The procedure of example 1 was followed. Only changing the mixing mode in the step (2) into 'full mixing in a planetary ball mill, wherein the ball milling parameters are that the rotating speed is 150r/min, the time length is 2 h', and changing the ball milling time in the step (3) into 300min. To obtain diamond-like compound Cu 3 InSnSe 5 A semiconductor material.
Example 4
The procedure was followed in example 2. Except that the mixing manner in the step (2) was changed to "thorough mixing in a mortar by hand for 35min", and the ball milling time in the step (3) was changed to 180min. To obtain diamond-like compound Cu 2 AgInSnSe 5 A semiconductor material.
The above examples are merely illustrative, and the raw material powders used are commercially available.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A diamond-like semiconductor material, characterized in that the semiconductor material is specifically Cu 3-x Ag x InSnSe 5 The single-phase semiconductor material is characterized in that x is more than or equal to 0 and less than or equal to 1.
2. The diamond-like semiconductor material of claim 1, wherein the Cu 3-x Ag x InSnSe 5 The lattice structure of the semiconductor material is a square structure, and the space group is
3. Diamond-like semiconductor material according to claim 2, characterised in that the semiconductor material is in particular Cu 3 InSnSe 5 The unit cell parameters of the semiconductor material are a =0.572 plus or minus 0.0008nm, b =0.572 plus or minus 0.0008nm, c =1.147 plus or minus 0.0004nm, and alpha = beta = gamma =90 degrees.
4. Diamond-like semiconductor material according to claim 2, characterized in that said semiconductor material is in particular Cu 2 AgInSnSe 5 Semiconductor material with unit cell parameters a =0.581 ± 0.0005nm, b =0.581 ± 0.0005nm, c =1.161 ± 0.0006nm, α = β = γ =90 °.
5. Diamond-like semiconductor material according to claim 1, characterised in that the semiconductor material is in particular Cu 3 InSnSe 5 Semiconductor material or Cu 2 AgInSnSe 5 Semiconductor material of, wherein Cu 3 InSnSe 5 The band gap of the semiconductor material is 1.07eV 2 AgInSnSe 5 The bandgap of the semiconductor material is 0.95eV.
6. A method for the preparation of a diamond-like semiconductor material according to any of the claims 1-5, characterized in that it comprises the following steps:
(1) Preparing raw material powder: in a protective atmosphere environment according to the chemical formula Cu 3-x Ag x InSnSe 5 Weighing simple substance material powder corresponding to each element according to the nominal chemical dose ratio;
(2) Powder mixing: fully mixing the various powders obtained in the step (1), putting the powders into a high-energy ball milling tank in a glove box, and sealing; wherein, O in the glove box 2 The concentration of (2) is not higher than 0.2vol.%, and the ball-material ratio satisfies the mass ratio of 15;
(3) Mechanical alloying: installing the ball milling tank obtained in the step (2) on a high-energy ball mill,ball milling is carried out at a rotating speed of not less than 580r/min for 180-600 minutes; collecting the ball-milled powder to obtain Cu 3-x Ag x InSnSe 5 And (3) material powder.
7. The method of claim 5, further comprising the steps of:
(4) And (3) spark plasma sintering: cu obtained in the step (3) 3-x Ag x InSnSe 5 Filling the material powder into a graphite die, and then performing discharge plasma sintering to obtain Cu 3-x Ag x InSnSe 5 A block of material; wherein the spark plasma sintering satisfies: the vacuum degree of the furnace chamber is less than 8Pa, the axial pressure is 50-70MPa, the sintering temperature is 480-500 ℃, and the sintering time is not higher than 20min; and after the discharge plasma sintering is finished, cooling the room temperature along with the furnace and gradually removing the pressure.
8. The method according to claim 5, wherein in the step (1), the protective atmosphere is an argon atmosphere.
9. Use of a diamond-like semiconductor material according to any of claims 1-5 as a thermoelectric semiconductor material.
10. Use according to claim 9, wherein the semiconductor material is in particular Cu 3 InSnSe 5 The thermoelectric figure of merit of the semiconductor material at 500 ℃ is 1.08.
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| CN101723669A (en) * | 2008-10-31 | 2010-06-09 | 中国科学院上海硅酸盐研究所 | Compound capable of being used for thermoelectric material and preparation method thereof |
| CN103606573A (en) * | 2013-11-27 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Intermediate band absorbing material of chalcopyrite structure and preparing method thereof |
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| CN103606573A (en) * | 2013-11-27 | 2014-02-26 | 中国科学院上海硅酸盐研究所 | Intermediate band absorbing material of chalcopyrite structure and preparing method thereof |
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