CN112210755A - p-type transparent conductive SnO2Semiconductor film, preparation method and application thereof - Google Patents

p-type transparent conductive SnO2Semiconductor film, preparation method and application thereof Download PDF

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CN112210755A
CN112210755A CN202010934605.3A CN202010934605A CN112210755A CN 112210755 A CN112210755 A CN 112210755A CN 202010934605 A CN202010934605 A CN 202010934605A CN 112210755 A CN112210755 A CN 112210755A
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film
transparent conductive
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CN112210755B (en
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何云斌
黎明锴
付旺
叶盼
刘博涵
肖兴林
魏浩然
尹魏玲
卢寅梅
常钢
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Wuhan Ruilian Zhichuang Photoelectric Co ltd
Hubei University
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Wuhan Ruilian Zhichuang Photoelectric Co ltd
Hubei University
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

Abstract

The invention provides a p-type transparent conductive SnO2Semiconductor film, preparation method and application thereof, and p-type transparent conductive SnO2A method for producing a semiconductor thin film, comprising: preparation of Mg-doped SnO2A ceramic target material; providing a substrate, SnO doped with Mg2Ceramic target material, Mg-doped SnO prepared on the surface of the substrate2A film; SnO for doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film. The p-type transparent conductive SnO of the invention2Method for producing semiconductor thin film using Mg2+The energy required for entering the displacement position and the gap position is different, and the gap Mg is annealed under the condition of proper temperature and oxygen enrichment2+Migration to a displaced positionFurther improving the carrier concentration and obtaining high-quality p-type transparent conductive SnO2An ultra-wide bandgap semiconductor film.

Description

p-type transparent conductive SnO2Semiconductor film, preparation method and application thereof
Technical Field
The invention relates to the technical field of p-type transparent conductive films, in particular to p-type transparent conductive SnO2Semiconductor film and its preparation method and application.
Background
At present, the application of Transparent Conductive Oxide (TCO) in photoelectric devices, green energy devices and intelligent sensors has attracted people's attention. However, up to now, active functions based on p-n junctions have not been put to practical use, since most existing transparent conductor oxides are n-type and few suitable high quality p-type epitaxial TCOs are available. In recent years, great efforts have been made to obtain suitable p-type TCOs. p-type ZnO is the most famous case reported in large numbers in recent years, but p-type ZnO rapidly fails due to its complex defect behavior.
Tin oxide (SnO)2) The TCO material is one of the most important TCO materials, and has wide application in modern technologies such as photoelectric detectors, solar cells, light-emitting diodes and gas sensors due to excellent physical and photoelectric properties such as wide band gap (3.6eV), good conductivity and optical transmittance. However, SnO2Due to the presence of oxygen vacancies and interstitial Sn4+Iso-shallow donor defects leading to unintentional doping of SnO2Are all n-type conductive. So far, only a few documents report the progress of doping tin dioxide p-type, wherein p-type SnO2The doping elements of (A) are mainly Al, Ga, In, Sb, Zn and other elements. And techniques such as magnetron sputtering, sol-gel and spray pyrolysis are used. However, the above reports all have the disadvantages of low film carrier concentration, poor crystal quality, uncontrollable thickness, difficulty in preparing epitaxial films and the like, and the practical application of the epitaxial films in photoelectric devices is severely limited.
Disclosure of Invention
In view of the above, the present invention provides a p-type transparent conductive SnO2A semiconductor film, a preparation method and an application thereof are provided to solve the technical problems in the prior art.
In a first aspect, the present invention provides a p-type transparent conductive SnO2A method for producing a semiconductor thin film, comprising:
preparation of Mg-doped SnO2A ceramic target material;
providing a substrate, SnO doped with Mg2A ceramic target material, Mg-doped SnO is prepared on the surface of the substrate2A film;
SnO for doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film.
Optionally, the p-type transparent conductive SnO2Method for preparing semiconductor thin film, SnO doped with Mg2Ceramic target material, growing Mg-doped SnO on the surface of the substrate2The film specifically includes: placing the substrate in a vacuum cavity of a pulsed laser deposition system, and vacuumizing until the air pressure is lower than 10-4Pa, heating the substrate to 650-700 ℃, then introducing oxygen into the vacuum cavity to ensure that the air pressure is 2-5 Pa, controlling the Pulse laser energy to be 200-210 mJ/Pulse and the Pulse frequency to be 4-8 Hz, and utilizing Mg-doped SnO2The ceramic target material is Mg-doped SnO prepared on the surface of the substrate2A film.
Alternatively to this, the first and second parts may,the preparation method of the p-type transparent conductive SnO2 semiconductor film comprises the step of preparing the Mg-doped SnO2The preparation method of the ceramic target comprises the following steps:
mixing MgO powder and SnO2Mixing the powder and then carrying out ball milling to obtain mixed powder;
pressing the mixed powder into a ceramic green sheet;
sintering the ceramic blank sheet at 1000-1200 ℃ for 3-4 h to obtain Mg-doped SnO2A ceramic target material.
Optionally, the p-type transparent conductive SnO2Preparation method of semiconductor film, Mg-doped SnO2Placing the film in a tube furnace, vacuumizing, introducing oxygen until the pressure is 0.1-0.2 Mpa, and then doping Mg SnO at 600-800 DEG C2And annealing the film.
Optionally, the p-type transparent conductive SnO2The preparation method of the semiconductor film comprises the step of pressing the mixed powder into a ceramic blank sheet with the thickness of 2-3 mm under the pressure of 4-6 MPa.
Optionally, the p-type transparent conductive SnO2The preparation method of the semiconductor film comprises the step of cleaning the substrate by acetone, absolute ethyl alcohol and deionized water in sequence before the step of placing the substrate in a vacuum cavity of a pulse laser deposition system.
Optionally, the p-type transparent conductive SnO2The preparation method of the semiconductor film comprises the step of preparing a substrate comprising a c-plane sapphire substrate.
Optionally, the p-type transparent conductive SnO2Method for producing semiconductor thin film, MgO powder and SnO2The powder molar ratio is 4: 95-100.
In a second aspect, the invention also provides p-type transparent conductive SnO2The semiconductor film is prepared by the preparation method.
In a third aspect, the invention also provides the p-type transparent conductive SnO2Use of a semiconductor thin film in an optoelectronic device.
The invention relates to p-type transparent conductive SnO2The preparation method of the semiconductor film has the advantages over the prior artThe following beneficial effects:
(1) the p-type transparent conductive SnO of the invention2Method for producing semiconductor thin film using Mg2+The energy required for entering the displacement position and the gap position is different, and the gap Mg is annealed under the condition of oxygen enrichment2+The carrier concentration is further improved by moving to a displacement position, and high-quality p-type transparent conductive SnO is obtained2An ultra-wide bandgap semiconductor film;
(2) the p-type transparent conductive SnO of the invention2The preparation method of the semiconductor film has the advantages of simple operation process, cheap and easily-obtained raw materials, no need of preparation at a higher temperature, and low production cost, meets the condition of large-scale industrial production, requires low energy consumption, and conforms to the concept of low energy and environmental protection.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing a p-type transparent conductive SnO2 semiconductor thin film according to the invention;
FIG. 2 is an XRD diffraction pattern of the thin films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2;
FIG. 3 is a (200) plane rocking curve of the films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2;
FIG. 4 is a graph showing the variation of the full width at half maximum of the (200) plane rocking curve with annealing temperature of the films prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention;
FIG. 5 is a transmitted light spectrum of the films prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention;
FIG. 6 shows absorption spectra of films prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention;
FIG. 7 is a graph showing the electrical properties of films prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
P-type transparent conductive SnO2The preparation method of the semiconductor film, as shown in fig. 1, comprises the following steps:
s1 preparation of Mg doped SnO2A ceramic target material;
s2, providing a substrate and doping SnO with Mg2A ceramic target material, Mg-doped SnO is prepared on the surface of the substrate2A film;
s3, and SnO doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film.
In the embodiment of the present application, the substrate includes a c-plane sapphire substrate or a glass substrate, a silicon or quartz glass substrate, a GaN/sapphire (silicon) substrate, or the like; sapphire substrate whose main component is alumina (Al)2O3)，c-Al2O3C-plane sapphire; in the implementation of the application, the substrate is a c-plane sapphire substrate.
In the embodiment of the application, Mg-doped SnO is prepared on the surface of the c-plane sapphire substrate by adopting methods such as a pulse laser method, a magnetron sputtering method or an electron beam evaporation method2Thin films, in particular Mg-doped SnO prepared by a pulsed laser method2The specific method of the film is as follows:
sequentially ultrasonically cleaning a c-surface sapphire substrate by using acetone, absolute ethyl alcohol and deionized water, wherein each cleaning process is 15min, drying the cleaned c-surface sapphire substrate by using nitrogen; then placing the c-surface sapphire substrate in a vacuum cavity of a pulse laser deposition system, and vacuumizing until the air pressure is lower than 10-4Pa, heating the substrate to 700 ℃, then introducing oxygen into the vacuum cavity to ensure that the air pressure is 2Pa, controlling the Pulse laser energy to be 210mJ/Pulse and the Pulse frequency to be 5Hz, setting the time of laser deposition of the film to be 60min, and utilizing Mg-doped SnO2The ceramic target material is Mg-doped SnO prepared on the surface of the c-plane sapphire substrate2A film.
In particular, Mg-doped SnO in the examples of the application2The preparation method of the ceramic target comprises the following steps: in a molar ratio of MgO to SnO20.1097g MgO powder and 9.8903g SnO were weighed in a ratio of 4:962Mixing the powder, adding 20g of deionized water, then placing the mixture into a planetary ball milling tank (zirconia ceramic balls are used as a ball milling medium), and carrying out ball milling for 8 hours to obtain mixed powder; then placing the mixed powder in a drying box, drying for 10 hours at 110 ℃, taking out and cooling to room temperature, screening out zirconia balls, adding 1g of ethanol, fully and uniformly grinding by using a bowl mill, pressing into ceramic blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 5MPa, then placing the ceramic blank sheets in a crucible of a tube furnace, heating the tube furnace to 1200 ℃ under the air atmosphere and preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain Mg-doped SnO2A ceramic target material.
Specifically, in the embodiment of the application, the prepared Mg-doped SnO2Placing the film into a tube furnace, and vacuumizing until the air pressure is lower than 10-2Pa; then introducing high-purity oxygen, controlling the pressure to be 0.13Mpa, adjusting the annealing temperature to be 600 ℃, preserving the heat for 30min, and then naturally cooling to room temperature to finish Mg-doped SnO2Annealing the film to obtain p-type transparent conductive SnO2A semiconductor thin film.
In the examples of the present application, Mg2+
Figure RE-GDA0002788256590000051
And Sn4+
Figure RE-GDA0002788256590000052
With similar ionic radii therebetween. Thus, theoretically, the substitution of magnesium at the tin site should result in the formation of two "hole" states above the valence band top (VBM). Thereby forming p-type SnO2. The Pulse Laser Deposition (PLD) has the advantages of high growth rate, high film crystallization quality, controllable film thickness and capability of realizing epitaxial film growth at low temperature. Therefore, the invention prepares Mg-doped SnO on the c-plane sapphire substrate by the Pulsed Laser Deposition (PLD) technology2A film. But in practice due to Mg2+Into SnO2Then exists in two forms of interstitial site and substitutional site, wherein Mg in the interstitial site2+Will provide free electrons to disfavor the formation of p-type material, substitutional Mg2+Holes are provided to favor the formation of p-type material, thus utilizing Mg2+The energy required for entering the displacement position and the gap position is different, and the gap Mg is annealed under the condition of oxygen enrichment2+The carrier concentration is further improved by moving to a displacement position, and high-quality p-type transparent conductive SnO is obtained2An ultra-wide bandgap semiconductor film.
In the examples of the present application, Mg is doped into SnO2The middle formed shallow level acceptor provides holes to compensate SnO2Higher background carrier concentration. Deposition by adopting a pulse laser method is favorable for obtaining Mg-doped SnO with high crystallization quality2A film. And doping Mg with SnO at a series of annealing temperatures2Annealing the film to obtain the optimal annealing condition, and greatly increasing Mg-doped SnO2Carrier concentration of the thin film. In addition, the preparation of high-quality p-type conductive SnO provided by the embodiment of the application2The method for extending the film has the advantages of simple operation process, cheap and easily obtained raw materials, no need of preparation at a higher temperature, and low production cost, meets the conditions of large-scale industrial production, requires low energy consumption, and conforms to the concept of low energy and environmental protection. Therefore, the high-quality p-type conductive SnO provided by the invention2The epitaxial film preparation method has better practical application prospect.
Based on the same inventive concept, the applicationEmbodiments also provide a p-type transparent conductive SnO2The semiconductor film is prepared by the preparation method, and the thickness of the film is 390 nm.
Based on the same inventive concept, the embodiment of the application also provides the p-type transparent conductive SnO2Use of a semiconductor thin film in an opto-electronic device.
Example 2
P-type transparent conductive SnO2The preparation method of the semiconductor film, as shown in fig. 1, comprises the following steps:
s1 preparation of Mg doped SnO2A ceramic target material;
s2, providing a substrate and doping SnO with Mg2A ceramic target material, Mg-doped SnO is prepared on the surface of the substrate2A film;
s3, and SnO doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film.
In the embodiments of the present application, the substrate includes a c-plane sapphire substrate or a glass substrate, a silicon or quartz glass substrate, a GaN/sapphire (silicon) substrate, or the like; sapphire substrate whose main component is alumina (Al)2O3)，c-Al2O3C-plane sapphire; in the implementation of the application, the substrate is a c-plane sapphire substrate.
In the embodiment of the application, Mg-doped SnO is prepared on the surface of the c-plane sapphire substrate by adopting methods such as a pulse laser method, a magnetron sputtering method or an electron beam evaporation method2Thin films, in particular Mg-doped SnO prepared by a pulsed laser method2The specific method of the film is as follows:
ultrasonically cleaning the c-surface sapphire substrate by using acetone, absolute ethyl alcohol and deionized water in sequence, wherein each cleaning process is 15min, and drying the cleaned c-surface sapphire substrate by using nitrogen; then placing the c-surface sapphire substrate in a vacuum cavity of a pulse laser deposition system, and vacuumizing until the air pressure is lower than 10-4Pa, heating the substrate to 700 deg.C, introducing oxygen gas into the vacuum chamber to make the pressure at 2Pa, and controlling pulseThe laser energy is 210mJ/Pulse, the Pulse frequency is 5Hz, the time for depositing the film by the laser is set to be 60min, and Mg-doped SnO is utilized2The ceramic target material is Mg-doped SnO prepared on the surface of the c-plane sapphire substrate2A film.
In particular, Mg-doped SnO in the examples of the application2The preparation method of the ceramic target comprises the following steps: in a molar ratio of MgO to SnO20.1097g MgO powder and 9.8903g SnO were weighed in a ratio of 4:962Mixing the powder, adding 20g of deionized water, then placing the mixture into a planetary ball milling tank (zirconia ceramic balls are used as a ball milling medium), and carrying out ball milling for 8 hours to obtain mixed powder; then placing the mixed powder in a drying box, drying for 10 hours at 110 ℃, taking out and cooling to room temperature, screening out zirconia balls, adding 1g of ethanol, fully and uniformly grinding by using a bowl mill, pressing into ceramic blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 5MPa, then placing the ceramic blank sheets in a crucible of a tube furnace, heating the tube furnace to 1200 ℃ under the air atmosphere and preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain Mg-doped SnO2A ceramic target material.
Specifically, in the embodiment of the application, the prepared Mg-doped SnO2Placing the film into a tube furnace, and vacuumizing until the air pressure is lower than 10-2Pa; then introducing high-purity oxygen, controlling the pressure to be 0.13Mpa, adjusting the annealing temperature to be 700 ℃, preserving the heat for 30min, and then naturally cooling to room temperature to finish Mg-doped SnO2Annealing the film to obtain p-type transparent conductive SnO2A semiconductor thin film.
Based on the same inventive concept, the embodiment of the application also provides p-type transparent conductive SnO2The semiconductor film is prepared by the preparation method, and the thickness of the film is 390 nm.
Based on the same inventive concept, the embodiment of the application also provides the p-type transparent conductive SnO2Use of a semiconductor thin film in an opto-electronic device.
Example 3
P-type transparent conductive SnO2The method for preparing a semiconductor thin film, as shown in FIG. 1, comprises the following stepsThe method comprises the following steps:
s1 preparation of Mg doped SnO2A ceramic target material;
s2, providing a substrate and doping SnO with Mg2A ceramic target material, Mg-doped SnO is prepared on the surface of the substrate2A film;
s3, and SnO doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film.
In the embodiments of the present application, the substrate includes a c-plane sapphire substrate or a glass substrate, a silicon or quartz glass substrate, a GaN/sapphire (silicon) substrate, or the like; sapphire substrate whose main component is alumina (Al)2O3)，c-Al2O3C-plane sapphire; in the implementation of the application, the substrate is a c-plane sapphire substrate.
In the embodiment of the application, Mg-doped SnO is prepared on the surface of the c-plane sapphire substrate by adopting methods such as a pulse laser method, a magnetron sputtering method or an electron beam evaporation method2Thin films, in particular Mg-doped SnO prepared by a pulsed laser method2The specific method of the film is as follows:
ultrasonically cleaning the c-surface sapphire substrate by using acetone, absolute ethyl alcohol and deionized water in sequence, wherein each cleaning process is 15min, and drying the cleaned c-surface sapphire substrate by using nitrogen; then placing the c-surface sapphire substrate in a vacuum cavity of a pulse laser deposition system, and vacuumizing until the air pressure is lower than 10-4Pa, heating the substrate to 700 ℃, then introducing oxygen into the vacuum cavity to ensure that the air pressure is 2Pa, controlling the Pulse laser energy to be 210mJ/Pulse and the Pulse frequency to be 5Hz, setting the time of laser deposition of the film to be 60min, and utilizing Mg-doped SnO2The ceramic target material is Mg-doped SnO prepared on the surface of the c-plane sapphire substrate2A film.
In particular, Mg-doped SnO in the examples of the application2The preparation method of the ceramic target comprises the following steps: in a molar ratio of MgO to SnO20.1097g MgO powder and 9.8903g SnO were weighed in a ratio of 4:962The powders were mixed, 20g of deionized water was added, followed by planetary ball millingBall milling for 8 hours in a tank (the ball milling medium is zirconia ceramic balls) to obtain mixed powder; then placing the mixed powder in a drying box, drying for 10 hours at 110 ℃, taking out and cooling to room temperature, screening out zirconia balls, adding 1g of ethanol, fully and uniformly grinding by using a bowl mill, pressing into ceramic blank sheets with the diameter of 27.5mm and the thickness of 2mm by using a tablet press under the pressure of 5MPa, then placing the ceramic blank sheets in a crucible of a tube furnace, heating the tube furnace to 1200 ℃ under the air atmosphere and preserving the temperature for 3 hours, and naturally cooling to room temperature to obtain Mg-doped SnO2A ceramic target material.
Specifically, in the embodiment of the application, the prepared Mg-doped SnO2Placing the film into a tube furnace, and vacuumizing until the air pressure is lower than 10-2Pa; then introducing high-purity oxygen, controlling the pressure to be 0.13Mpa, adjusting the annealing temperature to be 800 ℃, preserving the heat for 30min, and then naturally cooling to room temperature to finish Mg-doped SnO2Annealing the film to obtain p-type transparent conductive SnO2A semiconductor thin film.
Based on the same inventive concept, the embodiment of the application also provides p-type transparent conductive SnO2The semiconductor film is prepared by the preparation method, and the thickness of the film is 390 nm.
Based on the same inventive concept, the embodiment of the application also provides the p-type transparent conductive SnO2Use of a semiconductor thin film in an opto-electronic device.
Comparative example 1
The same as example 1 except that the annealing temperature was 500 ℃.
Comparative example 2
Same as example 1, except that SnO was prepared2The semiconductor film is not subjected to an annealing process.
XRD diffraction patterns of the films prepared in the examples 1-3 and the comparative examples 1-2 are tested, and the results are shown in figure 2. In FIG. 2, Ann-600 is the film obtained in example 1 (annealing temperature 600 ℃ C.), Ann-700 is the film obtained in example 2 (annealing temperature 700 ℃ C.), Ann-800 is the film obtained in example 3 (annealing temperature 800 ℃ C.), Ann-500 is a comparative example1 (annealing temperature 500 ℃) and As-growth is the film prepared in comparative example 2, and it can be seen from FIG. 2 that distinct diffraction peaks appear at about 38 DEG and 80 DEG in addition to the characteristic peak of c-plane sapphire of the film substrate appearing at about 41 DEG, and the two peaks are respectively SnO determined by the precise comparison of PDF (No.41-1445) cards2The diffraction peaks of (200) and (400) planes of (A) and (B) and no diffraction peaks of other hetero phases are observed, so that it can be concluded that Mg is present2+Successfully incorporate SnO2Within the crystal lattice of (a).
The (200) plane rocking curves of the films prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in FIG. 3. As can be seen from FIG. 3, SnO gradually increases with increasing annealing temperature2The full width at half maximum of the rocking curve of the film (200) face increases rapidly, indicating that the crystalline quality of the film decreases significantly with decreasing annealing temperature.
The results of testing the (200) plane rocking curve full width at half maximum of the films prepared in examples 1 to 3 and comparative examples 1 to 2 are shown in FIG. 4. As can be seen from FIG. 4, SnO increases with increasing annealing temperature from 500 ℃ to 800 ℃2The full width at half maximum of the rocking curve of the film (200) face is rapidly increased from 0.032 DEG to 0.171 DEG, wherein the full width at half maximum is narrower at annealing temperatures of 500 ℃ and 600 ℃, and the out-of-plane order of the crystal is good.
The transmission spectra of the films prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in FIG. 5. As can be seen from fig. 5, it can be seen from fig. 5 that the film has good transmittance to visible light at room temperature, the transmittance is about 90%, and the annealing temperature change has no significant influence on the visible light transmittance of the film, and the film has good optical thermal stability.
The absorption spectra of the films prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in FIG. 6. SnO2The film is a direct band gap semiconductor material, so the optical band gap can be obtained by extrapolating the linear part of the curve to the abscissa intercept with the ordinate being zero according to the Tuac relational expression by a linear extrapolation method, and the optical band gap Eg of the film is obtained. As can be seen from FIG. 6, the present invention was preparedThe band gaps of the obtained film are all 4.13eV, the optical band gap Eg of the film is not changed along with the change of annealing temperature, and the film has good optical thermal stability.
The electrical properties of the films prepared in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in FIG. 7 (where the abscissa is the annealing temperature). In FIG. 7, unannealed SnO is shown2Thin films and Mg-SnO annealed at different temperatures2Carrier concentration, carrier mobility and resistivity of the thin film. Since the effective mass of holes is relatively heavy, the mobility of holes is lower than that of electrons, when the conductive type of the film is p-type, the majority of carriers in the film are holes, so that the mobility is lower, and when the concentration of holes is reduced, the mobility is increased. The resistivity varies with carrier concentration, and decreases as carrier concentration increases. Non-annealed SnO2The conductivity type of the film is p type, but the hole concentration is only 5X 1015cm-3. After annealing at 500 ℃ for 30 minutes, since in SnO2The coexistence of interstitial Mg atoms and substitutional Mg atoms in the lattice results in the transition of the conductivity type of the thin film from weak p-type to an electron concentration of 7X 1015cm-3The mobility and the resistivity have small change range. Subsequently, the annealing temperature was increased to 600 ℃ at the same annealing time of 30 minutes, and we obtained a hole concentration of 1.44X 1017cm-3Having a mobility of 4cm2V-1s-1And p-type SnO having resistivity reaching a minimum value of 10.412. omega. cm due to high hole concentration2A film. The pair of epitaxial p-type Mg-SnO2The thin film has great application potential in the aspects of manufacturing pn junction or field effect transistor and the like. For higher annealing temperatures, not only interstitial Mg atoms are removed, but also substitutional Mg atoms are removed due to excessive annealing temperatures. The hole concentration decreases at an annealing temperature of 700 c and the conductivity type even becomes intrinsic at an annealing temperature of 800 c, while the mobility correspondingly increases stepwise and the resistivity increases gradually.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. P-type transparent conductive SnO2A method for producing a semiconductor thin film, comprising:
preparation of Mg-doped SnO2A ceramic target material;
providing a substrate, SnO doped with Mg2A ceramic target material, Mg-doped SnO is prepared on the surface of the substrate2A film;
SnO for doping Mg at 600-800 ℃ in oxygen atmosphere2Annealing the film to obtain the p-type transparent conductive SnO2A semiconductor thin film.
2. The p-type transparent conductive SnO as claimed in claim 12The preparation method of the semiconductor film is characterized in that the Mg-doped SnO2 film growing on the surface of the substrate by using the Mg-doped SnO2 ceramic target specifically comprises the following steps: placing the substrate in a vacuum cavity of a pulsed laser deposition system, and vacuumizing until the air pressure is lower than 10-4Pa, heating the substrate to 650-700 ℃, then introducing oxygen into the vacuum cavity to enable the air pressure to be 2-5 Pa, controlling the Pulse laser energy to be 200-210 mJ/Pulse and the Pulse frequency to be 4-8 Hz, and preparing the Mg-doped SnO2 film on the surface of the substrate by utilizing a Mg-doped SnO2 ceramic target.
3. The p-type transparent conductive SnO as claimed in claim 12A method for producing a semiconductor thin film, characterized in that the Mg-doped SnO2The preparation method of the ceramic target comprises the following steps:
mixing MgO powder and SnO2Mixing the powder and then carrying out ball milling to obtain mixed powder;
pressing the mixed powder into a ceramic green sheet;
sintering the ceramic blank sheet at 1000-1200 ℃ for 3-4 h to obtain Mg-doped SnO2A ceramic target material.
4. The p-type transparent conductive SnO as claimed in claim 12A process for producing a semiconductor thin film, characterized in that Mg-doped SnO2Placing the film in a tube furnace, vacuumizing, introducing oxygen until the pressure is 0.1-0.2 Mpa, and then doping Mg SnO at 600-800 DEG C2And annealing the film.
5. The p-type transparent conductive SnO as claimed in claim 32The preparation method of the semiconductor film is characterized in that the mixed powder is pressed into a ceramic green sheet with the thickness of 2-3 mm under the pressure of 4-6 MPa.
6. The p-type transparent conductive SnO as claimed in claim 32The preparation method of the semiconductor film is characterized by also comprising the step of sequentially cleaning the substrate with acetone, absolute ethyl alcohol and deionized water before placing the substrate in a vacuum cavity of a pulse laser deposition system.
7. The p-type transparent conductive SnO as claimed in claim 12The preparation method of the semiconductor film is characterized in that the substrate comprises a c-plane sapphire substrate.
8. The p-type transparent conductive SnO as claimed in claim 32A method for producing a semiconductor thin film, characterized in that MgO powder and SnO2The powder molar ratio is 4: 95-100.
9. P-type transparent conductive SnO2A semiconductor thin film produced by the production method according to any one of claims 1 to 8.
10. The p-type transparent conductive SnO as claimed in claim 92Use of a semiconductor thin film in an optoelectronic device.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134569A (en) * 2021-11-30 2022-03-04 湖北大学 SnO2(Cu) single crystal film, and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAIYING HE 等: "Novel p-type conductivity in SnO2 thin films by Mg doping", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
SHIHUI YU 等: "Transparent conducting Sb-doped SnO2 thin films grown by pulsed laser deposition", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 *
张兵临 等: "SnO2薄膜的脉冲激光沉积", 《光电子·激光》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134569A (en) * 2021-11-30 2022-03-04 湖北大学 SnO2(Cu) single crystal film, and preparation method and application thereof

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