CN110257873B - Cu-doped SnSe semiconductor film and electrochemical preparation method thereof - Google Patents

Cu-doped SnSe semiconductor film and electrochemical preparation method thereof Download PDF

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CN110257873B
CN110257873B CN201910665929.9A CN201910665929A CN110257873B CN 110257873 B CN110257873 B CN 110257873B CN 201910665929 A CN201910665929 A CN 201910665929A CN 110257873 B CN110257873 B CN 110257873B
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李志林
王峰
曹凯
刘景军
吉静
张正平
窦美玲
宋夜
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Abstract

The invention relates to a Cu-doped SnSe semiconductor film and an electrochemical preparation method thereof, wherein copper chloride, stannous chloride and sodium selenite are selected as copper, tin and selenium sources, disodium ethylene diamine tetraacetate is taken as a complexing agent, urea and sodium dodecyl sulfate are taken as additives to prepare an electrolyte, the pH value of the electrolyte is adjusted to be 1.5-5, then electrodeposition is carried out at room temperature to obtain the Cu-doped SnSe predeposited film, and then the SnSe predeposited film is annealed to obtain the Cu-doped SnSe semiconductor film. The method can prepare the Cu-doped SnSe semiconductor film without impurity phase, and the film has high carrier concentration, mobility and conductivity, thereby being beneficial to improving the thermoelectric property of the film. The preparation method can regulate and control the chemical components and the electric transmission performance of the electrolyte through the components of the electrolyte, the deposition process and the annealing method, has the characteristics of strong controllability and good repeatability, and is suitable for large-area preparation.

Description

Cu-doped SnSe semiconductor film and electrochemical preparation method thereof
Technical Field
The invention belongs to the field of thermoelectric materials, and particularly relates to a Cu-doped SnSe semiconductor film and an electrochemical preparation method thereof.
Background
Thermoelectric materials can directly convert heat energy into electric energy, and have wide research and application in the fields of waste heat utilization, power generation devices, temperature measurement and the like. Early thermoelectric materials mainly comprise metal materials, but the limitations of the metal materials are very obvious, the Seebeck coefficient of the material is low, the thermal conductivity is often high, the thermoelectric figure of merit is low, and the requirement of the industry on the thermoelectric materials is difficult to meet. Abram Ioffe discovered that semiconductor materials have significantly superior thermoelectric conversion effects compared to metallic materials at the end of the 1950 s, and therefore more and more researchers have been invested in the search for semiconductor thermoelectric materials.
Thermoelectric figure of merit ZT of the thermoelectric material can best measure the thermoelectric performance, and the ZT expression is as follows:
Figure 394999DEST_PATH_IMAGE001
wherein: alpha is a Seebeck coefficient with the unit of mu V/K; sigma is the conductivity, and the unit is S/m; t is the absolute temperature in K; kappa is the thermal conductivity in W/m K. The higher the ZT value, the higher the thermoelectric conversion efficiency of the material. In the expression of ZT, α2σ is also known as Power Factor (PF), PF is proportional to ZT, so the higher the PF, the higher the thermoelectric performance of the material. As the Seebeck coefficient of the material is relatively stable, the conductivity sigma in the PF is a key factor, and the improvement of the conductivity can obviously improve the thermoelectric performance of the material.
The SnSe has simple structure and stable property. In recent years, SnSe is found to have very good thermoelectric properties. Due to the special crystal structure, the single crystal SnSe has the highest ZT value of 2.6 in the b-axis direction, so that the SnSe is regarded as a thermoelectric material with extremely high potential. Sn and Se are elements of groups IV and VI respectively. PbTe, which is also composed of group IV-VI elements and excellent in thermoelectric properties, has been industrially used. Compared with Pb and Te, Sn and Se are abundant on the earth, so that the price is relatively low, and the industrialization cost of the thermoelectric material can be reduced. Pb element in PbTe is an important source of heavy metal pollution, and SnSe also has the property of environmental friendliness, thereby meeting the social development requirement of current green development. Undoped SnSe semiconductors have been found to be p-type semiconductors. In the temperature range of 300-800K, the SnSe structure is an orthogonal layered structure, and Sn-Se bonds are stronger in the b and c directions and weaker in the a direction, so that the SnSe structure is easy to cleave along the (100) plane. The SnSe structure contains SnSe7The coordination polyhedron, the special crystal structure and the like enable the material to have strong anisotropy, so that the SnSe has extremely low lattice thermal conductivity relative to other thermoelectric materials in a special orientation, and therefore has higher thermoelectric performance.
However, the growth conditions of single crystal SnSe are severe, preparation is expensive, and large-scale industrial production is not facilitated. And the mechanical property is poor, the brittleness is large, and the processing and the application are not facilitated. Although the polycrystalline SnSe is easy to prepare and has better mechanical property than single crystal, the thermoelectric property is not outstanding (ZT is less than or equal to 1.1). Thus, industrial application of either single crystal or polycrystalline SnSe as a thermoelectric material is limited.
The preparation process of the polycrystalline SnSe by adopting the electrodeposition method can be obviously simplified. The reduction of thermoelectric performance caused by polycrystal can be compensated by adding doping elements to increase the carrier concentration and further increase the conductivity. Therefore, the preparation of the doped SnSe polycrystalline film by the electrodeposition method can be developed into an effective way for realizing the practicability of the SnSe semiconductor as the thermoelectric material. In addition, the electrical properties of the SnSe crystal structure are obviously changed in different orientations due to the anisotropy of the SnSe crystal structure, and the thermoelectric property of the polycrystalline SnSe material can be further improved through orientation adjustment. Therefore, the thermoelectric property of the SnSe film with specific preferred orientation can be further improved by preparing the SnSe film with specific preferred orientation.
The thermoelectric film prepared by adopting electrochemical deposition also has the following advantages:
(1) by controlling the corresponding electrodeposition parameters, such as deposition potential, deposition current, concentration of each component of electrolyte, deposition temperature, deposition time and the like, the structure, the form and the chemical element ratio of the generated film can be accurately controlled, and the grain size and the porosity of the film are easy to control.
(2) Can be operated at normal temperature and normal pressure, and is more energy-saving and simple.
(3) Can be prepared in large quantities, and has higher economical efficiency and productivity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a Cu-doped SnSe semiconductor film and an electrochemical preparation method thereof. The thin film has high carrier concentration, mobility and conductivity, and is beneficial to improving the thermoelectric performance of the thin film. The preparation method can regulate and control the chemical components and the electric transmission performance of the electrolyte through the components of the electrolyte, the deposition process and the annealing method, has the characteristics of strong controllability and good repeatability, and is suitable for large-area preparation.
The invention specifically adopts the following technical scheme that an electrochemical preparation method of a Cu-doped SnSe semiconductor film comprises the steps of respectively taking copper chloride, stannous chloride and sodium selenite as copper, tin and selenium sources, taking ethylene diamine tetraacetic acid as a complexing agent to prepare electrolyte, adjusting the pH value of the electrolyte to be 1.5-5, then carrying out electrodeposition at room temperature to obtain a Cu-doped SnSe pre-deposited film, and finally annealing the SnSe pre-deposited film at the temperature of 600 ℃ for 10 minutes-10 hours under the protection of inert atmosphere to obtain the Cu-doped SnSe semiconductor film.
In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:
(1) preparing an electrolyte: in the electrolyte: cu2+、Sn2+、SeO3 2-The molar ratio of the ethylene diamine tetraacetic acid disodium is (1-10) to (50-150) to (10-50) to (50-150);
(2) electro-deposition: after the step (1) is finished, performing electrodeposition by using the prepared solution, wherein the deposition potential is between-0.7V and-1.5V relative to a saturated calomel electrode, the electrodeposition temperature is between 5 and 95 ℃, and the electrodeposition is performed without stirring at room temperature to obtain a Cu-doped SnSe pre-deposited film;
(3) annealing treatment: and (3) placing the Cu-doped SnSe pre-deposited film obtained in the step (2) under the protection of inert atmosphere, and annealing at the temperature of 150-600 ℃ for 10 minutes to 10 hours.
In a preferred embodiment of the invention, the electrolyte of step (1) is adjusted in pH with dilute hydrochloric acid.
In a preferred embodiment of the invention, urea is added as an additive to prepare an electrolyte, after the pH value of the plating solution is adjusted to be 1.5-5, electrodeposition is carried out at room temperature to obtain a Cu-doped SnSe pre-deposited film, and finally the SnSe pre-deposited film is kept at the temperature of 150 ℃ and 600 ℃ for 10 minutes to 10 hours under the protection of inert atmosphere to obtain an edgebA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
In the preferred embodiment of the invention, sodium dodecyl sulfate is added as an additive to prepare electrolyte, the pH value of the plating solution is adjusted to be 1.5-5, then electrodeposition is carried out at room temperature to obtain a Cu-doped SnSe pre-deposited film, and finally the SnSe pre-deposited film is subjected toPreserving the heat for 10 minutes to 10 hours at the temperature of between 150 and 600 ℃ under the protection of inert atmosphere to obtain the edgecA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
In a preferred embodiment of the invention, the concentration of urea in the electrolyte is 5-50 mg/L.
In a preferred embodiment of the present invention, the concentration of sodium dodecylsulfate in the electrolyte is 5 to 50 mg/L.
The invention also protects the Cu-doped SnSe semiconductor film prepared by the preparation method, the obtained Cu-doped SnSe semiconductor film is a polycrystalline p-type semiconductor, the range of (Sn + Cu)/Se is 0.5-2.5, and the ratio of Cu/(Cu + Sn + Se) is 0.01% -5.0%.
In a preferred embodiment of the invention, the resulting film has a thickness of 1015cm-3-1019cm-3Carrier concentration of (1 cm)2/V·s-100cm2A carrier mobility of/V.s, and an electrical conductivity of 0.01S/cm to 50S/cm.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) complexing agent disodium ethylene diamine tetraacetate and Cu added into electrolyte2+、Sn2+Form stable complex, inhibit Sn2+The co-deposition of Sn, Se and Cu is realized.
(2) The electrodeposition plating solution used in the invention is clear, can be kept stable for a long time, is simple and easy to operate, and is suitable for large-scale industrial production.
(3) The addition of urea can lead the Cu-doped SnSe film to be onbThe axes have preferred orientation, and the addition of the sodium dodecyl sulfate can lead the Cu-doped SnSe film to be oncThe axes have a preferred orientation.
(4) By adjusting the deposition potential and the pH, the metal atom ratio can be accurately controlled, and the ratio of (Sn + Cu)/Se is 0.5-2.5; the ratio of Cu/(Cu + Sn + Se) is 0.01-5.0%.
(5) The Cu-doped SnSe film prepared by the method is a continuous, uniform and compact film in the micro-morphology, and cracks and holes are avoided.
(6) Cu doping prepared by the inventionThe SnSe film has high carrier concentration and carrier mobility, determines high conductivity and is beneficial to power factorPFAnd thermoelectric figure of meritZTIs improved.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is XRD patterns of thin films obtained in examples one, two, three and comparative example one;
FIG. 2 is a SEM image of films obtained in examples I, II, III and comparative example I;
wherein (a) the film of embodiment one; (b) the film of example two; (c) the film of example three; (d) the film of comparative example one.
Detailed Description
The present invention will be described in detail with reference to specific embodiments so that the objects, technical solutions and advantages of the present invention can be clearly understood, and it should be noted that the specific embodiments are only used for better explaining the present invention and do not limit the present invention.
Pretreating the ITO glass: the working electrode is made of ITO glass (2cm multiplied by 4cm), an area of 2cm multiplied by 2cm is reserved for an electrodeposition test after being shielded by an insulating tape strip, ultrasonic cleaning is sequentially carried out by deionized water, acetone, ethanol and deionized water, each step is carried out for 30 minutes, and finally the cleaned ITO glass is placed in an oven at 60 ℃ to be dried for standby.
Example one
(1) Preparing an electrodeposition solution: 0.90g of disodium ethylene diamine tetraacetate and 0.45g of SnCl are weighed in sequence2·2H2O、0.13g Na2SeO3·5H2O、CuCl2·5H2Dissolving the product in 200ml of de-ionized water after oxygen removal, uniformly stirring, and adjusting the pH value to 2.6 by using 0.1M dilute hydrochloric acid.
(2) Electro-deposition: taking the solution prepared in the step (1) as an electrolyte, taking pretreated ITO glass as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum sheet as an auxiliary electrode, connecting the three electrodes to corresponding end buttons of a potentiostat by leads, ensuring that the distance between the working electrode and the platinum sheet is 3cm, ensuring that the temperature of the electrolyte is 15-40 ℃, and the deposition time is 20-60 min to obtain a Cu-doped SnSe pre-deposited film, and testing the chemical composition of the film by an Oxford INCA-Penta-FET-X3 type X-ray energy dispersion spectrometer, wherein the results are shown in Table 1. The atomic ratio of (Sn + Cu)/Se is controlled to be 1.02, and the ratio is close to the stoichiometric ratio of 1: 1, the Cu doping proportion Cu/(Cu + Sn + Se) is controlled to be 0.031.
(3) Annealing treatment: and placing the pre-deposited film in a quartz boat, then placing the quartz boat in a tubular furnace, annealing the quartz boat at 300 ℃ for 30min under the protection of Ar gas, and cooling the quartz boat to room temperature along with the furnace to obtain the Cu-doped SnSe semiconductor film.
Example two
(1) Preparing an electrodeposition solution: 0.90g of disodium ethylene diamine tetraacetate and 0.45g of SnCl are weighed in sequence2·2H2O、0.13g Na2SeO3·5H2O、CuCl2·5H2O, the addition of urea is 10mg/L, the urea is dissolved in 200ml of de-ionized water after oxygen removal and evenly stirred, and the pH value is adjusted to 2.6 by 0.1M dilute hydrochloric acid.
(2) Electro-deposition: taking the solution prepared in the step (1) as an electrolyte, taking pretreated ITO glass as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum sheet as an auxiliary electrode, connecting the three electrodes to corresponding end buttons of a potentiostat by leads, ensuring that the distance between the working electrode and the platinum sheet is 3cm, ensuring that the temperature of the electrolyte is 15-40 ℃, and the deposition time is 20-60 min to obtain a Cu-doped SnSe pre-deposited film, and testing the chemical composition of the film by an Oxford INCA-Penta-FET-X3 type X-ray energy dispersion spectrometer, wherein the results are shown in Table 1. The atomic ratio of (Sn + Cu)/Se is controlled to be 1.04, and the atomic ratio is close to the stoichiometric ratio of 1: 1, the Cu doping proportion Cu/(Cu + Sn + Se) is controlled to be 0.031.
(3) Annealing treatment: placing the pre-deposited film in a quartz boat, placing in a tube furnace, annealing at 300 deg.C for 30min under Ar gas protection, cooling to room temperature to obtain edgebA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
EXAMPLE III
(1) Preparing an electrodeposition solution: 0.90g of disodium ethylene diamine tetraacetate and 0g of disodium ethylene diamine tetraacetate are weighed in sequence.45g SnCl2·2H2O、0.13g Na2SeO3·5H2O、CuCl2·5H2O, the addition amount of sodium dodecyl sulfate is 10mg/L, the sodium dodecyl sulfate is dissolved in 200ml of deionized water after oxygen removal and is uniformly stirred, and the pH value is adjusted to 2.6 by 0.1M dilute hydrochloric acid.
(2) Electro-deposition: taking the solution prepared in the step (1) as an electrolyte, taking pretreated ITO glass as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum sheet as an auxiliary electrode, connecting the three electrodes to corresponding end buttons of a potentiostat by leads, ensuring that the distance between the working electrode and the platinum sheet is 3cm, ensuring that the temperature of the electrolyte is 15-40 ℃, and the deposition time is 20-60 min to obtain a Cu-doped SnSe pre-deposited film, and testing the chemical composition of the film by an Oxford INCA-Penta-FET-X3 type X-ray energy dispersion spectrometer, wherein the results are shown in Table 1. The atomic ratio of (Sn + Cu)/Se is controlled to be 1.05, and the atomic ratio is close to the stoichiometric ratio of 1: 1, the Cu doping ratio Cu/(Cu + Sn + Se) is controlled to be 0.032.
(3) Annealing treatment: placing the pre-deposited film in a quartz boat, placing in a tube furnace, annealing at 300 deg.C for 30min under Ar gas protection, cooling to room temperature to obtain edgecA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
Comparative example 1
(1) Preparing an electrodeposition solution: 0.90g of disodium ethylene diamine tetraacetate and 0.45g of SnCl are weighed in sequence2·2H2O、0.13g Na2SeO3·5H2Dissolving the product in 200ml of de-ionized water after oxygen removal, uniformly stirring, and adjusting the pH value to 2.5 by using 0.1M dilute hydrochloric acid.
(2) Electro-deposition: taking the solution prepared in the step (1) as an electrolyte, taking pretreated ITO glass as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum sheet as an auxiliary electrode, connecting the three electrodes to corresponding end buttons of a potentiostat by leads, ensuring that the distance between the working electrode and the platinum sheet is 3cm, ensuring that the temperature of the electrolyte is 15-40 ℃, and the deposition time is 20-60 min, obtaining an undoped polycrystalline SnSe pre-deposited film, and testing the chemical composition of the film by an Oxford INCA-Penta-FET-X3 type X-ray energy dispersion spectrometer, wherein the results are shown in Table 1. The undoped Cu element, namely Sn/Se atomic ratio, is controlled to be 0.99, and is close to the stoichiometric ratio of 1: 1.
(3) annealing treatment: and placing the pre-deposited film in a quartz boat, then placing the quartz boat in a tube furnace, annealing the quartz boat at 300 ℃ for 30min under the protection of Ar gas, and cooling the quartz boat to room temperature along with the furnace to obtain the undoped polycrystalline SnSe semiconductor film.
The X-ray diffraction pattern of the film was measured by an X-ray diffractometer type RINT 2200V/PC. CuKa radiation is adopted, the tube voltage is 40kV, the current is 40mA, and the scanning speed is 4 degrees/minute. And testing the morphology of the film by using a JEOLFE-JSM-6701F scanning electron microscope.
The X-ray diffraction spectra of the Cu-doped SnSe thin film prepared in the first, second, and third examples of the present invention and the undoped SnSe thin film prepared in the first comparative example are given in fig. 1, and the spectra only include the diffraction peaks of the ITO and SnSe or (Cu, Sn) Se of the substrate, and have no other diffraction peaks, indicating that the crystal structure of the thin film is an orthogonal SnSe pure phase structure, and no other impurity phase occurs. This is because the atomic ratio of (Sn + Cu)/Se during electrodeposition is controlled to be 1: around 1, the proper atomic ratio ensures that the structure is thermodynamically stable. The pure SnSe structure can ensure the characteristics of high and low electrical conductivity of the Cu-doped SnSe film. From the X-ray diffraction results of example two, it can also be seen that the film has a distinct (020) crystal face, i.e., after the additive urea is addedbThe axes are preferentially oriented. From the X-ray diffraction results of example III, it can be seen that the film has a distinct (002) crystal face, i.e., a crystal face of the film, after the addition of the additive sodium dodecyl sulfatecThe axes are preferentially oriented. Indicating that the preferred orientation of the film can be controlled by additives.
Scanning electron micrographs of the Cu-doped SnSe thin film prepared in examples one, two, and three and the undoped SnSe thin film prepared in comparative example one are given in fig. 2, and it can be seen that the thin films are continuous, uniform, and dense in the micro-morphology. This dense structure is a reliable guarantee of the excellent electrical transmission properties of the thin film.
The electrical transmission performance of the obtained film was measured by a hall analyzer of type RH2030, and the results are shown in table 2. It can be seen that the carrier types of the Cu-doped SnSe thin films obtained in the first, second and third embodiments are all p-type, and the carrier concentrations are all increased by one order of magnitude compared with the undoped thin film in the first comparative embodiment. Although the carrier mobility is reduced to a certain degree after doping, the conductivity of the film is improved by more than 3 times compared with that of an undoped SnSe film. After the additives of urea and sodium dodecyl sulfate are added, the conductivity is further improved, which shows that the special preferred orientation is favorable for further improving the electric transmission performance. The method for regulating and controlling preferred orientation by using the additive can improve the electric transmission performance of the Cu-doped SnSe thin film.
Table 1 test results of atomic ratio of films obtained in examples one, two, three and comparative example one
Figure 659146DEST_PATH_IMAGE002
TABLE 2 results of Hall Effect testing of thin films obtained in examples one, two, and three and comparative example one
Figure 124762DEST_PATH_IMAGE003
The above specific embodiments describe the basic principles and main features of the present invention. It will be appreciated by those skilled in the art that the scope of the present invention is not limited to the embodiments described above, and any changes or substitutions which are not thought of through the inventive work should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.

Claims (6)

1. An electrochemical preparation method of a Cu-doped SnSe semiconductor film is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparing an electrolyte: copper chloride, stannous chloride and sodium selenite are respectively used as copper, tin and selenium sources, disodium ethylene diamine tetraacetate is used as a complexing agent to prepare electrolyte, and the electrolyte comprises the following components in percentage by weight: cu2+、Sn2+、SeO3 2-The molar ratio of the ethylene diamine tetraacetic acid disodium is(1-10): 50-150): 10-50): 50-150); adding urea as an additive to prepare electrolyte, and performing electrodeposition after adjusting the pH value of the plating solution to 1.5-5;
(2) electro-deposition: after the step (1) is finished, performing electrodeposition by using the prepared solution, wherein the deposition potential of the solution is within-0.7V to-1.5V relative to a saturated calomel electrode, and performing stir-free electrodeposition at room temperature to obtain a Cu-doped SnSe pre-deposited film;
(3) annealing treatment: placing the Cu-doped SnSe pre-deposited film obtained in the step (2) under the protection of inert atmosphere, and annealing at the temperature of 150-600 ℃ for 10 minutes to 10 hours to obtain an edgebA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
2. An electrochemical preparation method of a Cu-doped SnSe semiconductor film is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparing an electrolyte: copper chloride, stannous chloride and sodium selenite are respectively used as copper, tin and selenium sources, disodium ethylene diamine tetraacetate is used as a complexing agent to prepare electrolyte, and the electrolyte comprises the following components in percentage by weight: cu2+、Sn2+、SeO3 2-The molar ratio of the ethylene diamine tetraacetic acid disodium is (1-10) to (50-150) to (10-50) to (50-150); adding sodium dodecyl sulfate as additive to prepare electrolyte, regulating pH value of the electrolyte to 1.5-5, and performing electrodeposition;
(2) electro-deposition: after the step (1) is finished, performing electrodeposition by using the prepared solution, wherein the deposition potential of the solution is within-0.7V to-1.5V relative to a saturated calomel electrode, and performing stir-free electrodeposition at room temperature to obtain a Cu-doped SnSe pre-deposited film;
(3) annealing treatment: placing the Cu-doped SnSe pre-deposited film obtained in the step (2) under the protection of inert atmosphere, and annealing at the temperature of 150-600 ℃ for 10 minutes to 10 hours to obtain an edgecA Cu-doped SnSe semiconductor film with a preferred orientation of the axis.
3. The method according to claim 1 or 2, wherein the electrolyte of step (1) is adjusted in pH with dilute hydrochloric acid.
4. The method according to claim 1, wherein the concentration of urea in the electrolyte is 5 to 50 mg/L.
5. The method of claim 2, wherein the electrolyte has a concentration of sodium dodecyl sulfate of 5 to 50 mg/L.
6. The Cu-doped SnSe semiconductor film obtained by the preparation method according to any one of claims 1 to 5, wherein the obtained film has a thickness of 1015cm-3-1019cm-3Carrier concentration of (1 cm)2/V·s-100cm2A carrier mobility of/V.s, and an electrical conductivity of 0.01S/cm to 50S/cm.
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CN115838934A (en) * 2022-11-25 2023-03-24 昆明理工大学 Photoelectrochemical semiconductor element extraction method for improving conductivity and deposition rate
CN115915895B (en) * 2023-02-09 2023-10-03 北京航空航天大学 Preparation method of thermoelectric refrigeration material based on P-type SnSe crystal

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