AU2021100535A4 - Spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film - Google Patents
Spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 54
- 238000005118 spray pyrolysis Methods 0.000 title claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000002243 precursor Substances 0.000 claims abstract description 45
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 53
- 239000012159 carrier gas Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000019994 cava Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 101100499944 Arabidopsis thaliana POL2A gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
of Specification
The present invention discloses a spray pyrolysis preparation method of gradient self-doping
multi metal oxide AXBYOz semiconductor thin film. The liquid feeding flow rate gradual
change controller precisely controls the liquid feeding flow rate of the precursor solutions of
metal A and B, and regulates the ratio of metal ions in the coating process by adjusting the
initial liquid feeding flow rate and the gradual change rate of the liquid ffeeding low rate, and
on the premise of inhibiting the precipitation of heterophase in monobasic metal oxide, the
metal ion A/B ratio gradient between the bottom and the top of the thin film with different
thicknesses can be controlled, and the gradient self-doping AxByOz semiconductor film with
controllable A/B ratio gradient and thickness from the bottom to the top of the thin film can
be prepared. This technology does not depend on the controllable metal ion A/B ratio gradient
formed by high temperature thermal diffusion and can avoid the problems of uncontrollable
A/B ratio gradient and phase separation of heterophase in monobasic metal oxide of A or B
easily happened in the high temperature thermal assisted spray pyrolysis preparation method.
8
10Care
a
11 1
14 1
Fig. 1
1/2
Description
a 10Care
11 1
14 1
Fig. 1
1/2
Spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film
Technical field:
The present invention relates to a spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film.
Background technology:
Multi metal oxide semiconductor thin film is one of the widely used functional thin film materials, and the low photoelectric separation efficiency is the most critical factor restricting its development. Gradient self-doping can create a built-in electric field throughout the photoelectric electrode thin film, which is an effective way to promote its photoelectric separation and enhance its photocatalytic performance. Gradient self-doping is a new semiconductor modification technology that first proposed by Wang et al in the world in 2017. It has been proved that it can effectively improve the photoelectric properties of semiconductor thin film. However, the existing gradient self-doping technology is achieved by thermal diffusion assisted spray pyrolysis preparation method. The preparation method has the following defects: (1) the A/B concentration gradient is formed by thermal diffusion assistance, but as it is controlled by the thermal diffusivity of A and B, only thin film with thickness of less than 550 nm can be produced, which is difficult to control the A/B concentration gradient, the bottom and top of the thin film are easy to phase separate, which will form carrier recombination center and reduce the efficiency of carrier photoelectric separation; (2) the thermal diffusion assistance inevitably needs to react at a high temperature; the above defects seriously restrict the development and application of the existing gradient self-doping technology.
Invention summary:
The aim of the present invention is to provide a spray pyrolysis preparation method of gradient self-doping multi metal oxide AxByOz semiconductor thin film. The liquid feeding flow rate gradual change controller precisely controls the liquid feeding flow rate of the precursor solutions of metal A and B, and regulates the ratio of metal ions in the coating process by adjusting the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate, and on the premise of inhibiting the precipitation of heterophase in monobasic metal oxide, the metal ion A/B ratio gradient between the bottom and the top of the thin film with different thicknesses can be controlled, and the gradient self-doping AxByOz semiconductor thin film with controllable A/B ratio gradient and thicknesses from the bottom to the top of the thin film can be prepared. This technology does not depend on the controllable metal ion A/B ratio gradient formed by thermal diffusion at a high temperature and can avoid the problems of uncontrollable A/B ratio gradient and phase separation of heterophase in monobasic metal oxide of A or B easily happened in the high temperature thermal assisted spray pyrolysis preparation method.
The present invention is realized by the following technical solution:
The spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film, by precisely controlling the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate of the precursor solutions of metal A and B, the ratio of metal ions in the spray pyrolysis deposition process on the substrate surface at 100-550°C is controlled to prepare the gradient self-doping multi metal oxide (AxByOz is an oxide with the ratio of the chemical dose of metal A, metal B, oxygen atom 0 is x:y:z) thin film. The gradient change of metal ion A/B ratio is formed from the bottom of the film to the top of the thin film.
By precisely controlling the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate of the precursor solutions of metal A and B, the metal salt solution of metal A and B is as the precursor solution, the initial liquid feeding flow rate (0.1 ~ 10 L/min)
and the gradual change rate (0.01 -10L/min)of the liquid feeding flow rate of the precursor solutions of the metal A and B in the spray pyrolysis deposition process are set by the gradual change controller. The liquid feeding flow rate is gradually changed according to the set parameters during the coating process, spray pyrolysis deposition is carried out at 100-550°C,
and the gradient change of metal ion A/B ratio is formed from the bottom of the thin film to the top of the thin film.
Among which the initial liquid feeding flow rate of the precursor solution of the metal A and B in the spray pyrolysis deposition process is 0.1 -1OL/min, and the gradual change rate of the liquid feeding flow rate is 0.01 -10L/min 2 .
The metal salt of the precursor solution of the metal A and B includes but is not limited to nitrates, acetate and chloride of metal A and B; the solvent includes but is not limited to acetic acid, methyl alcohol, ethanol, acetone and water.
Preferably, by adding stabilizer into the precursor solutions of metal A and B, and the stabilizer includes but is not limited to polyethylene glycol and trimethyl orthoformate.
The icon concentration CA, CB of metal ion A and B in the precursor solutions of metal A and B are 1-1000mM respectively.
Preferably, the multi metal oxide is AxByOz, VA and V3 which are the liquid feeding rates of the precursor solutions of metal A and B are required to meet0<VA10L/min, 0<VBl10 L/min, and 0.5x(x:y) <CBVB/ CAVA < 2x(x:y).
The distance between the ultrasonic atomizer nozzle and the substrate in the spray pyrolysis deposition process is 1~-00cm, the pressure of carrier gas is 0.1 - 10 Bar.
The thickness of the oxide thin film is controlled atl0nm10m.
The spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film includes the following steps:
1) The precursor solutions for preparing metal A and B are respectively placed in the liquid storage tank A and B;
2) The parameter setting of the precursor solution: the initial flow rate VAlnitial and final flow rate VAFinal of metal A precursor solution flowing into the mixing vessel are set by gradual change controller A, the initial flow rate VBlnitial and final flow rate VBFinal of metal B precursor solution flowing into the mixing vessel and the coating time T are set by gradient controller B, the ultrasonic atomization power is set to 50 - 500 W, the pressure of carrier gas is 0.1 - 10 Bar, the distance between the ultrasonic atomizer nozzle and the substrate is 1 100cm and the heating temperature of sample stage is 100 - 550°C;
3) After the sample stage is heated to the specified temperature and stays stable, the carrier gas begins to spray, and the precursor solutions of metal A and B begins to flow into the mixing vessel according to the set initial liquid flow rate and gradual change rate of the liquid feeding flow rate. After being mixed evenly, the solution is sprayed on the substrate is sprayed on the substrate fixed on the sample stage by the ultrasonic atomization with the carrier gas to be deposited; and the liquid feeding flow rate of A and B is changed respectively according to the set gradual change rate (VAFinal - VAInitial )/T, (VBFinal
VBInitial )/T during the spray process to precisely control the ratio of A and B of the mixing solution in the ultrasonic atomizer so that to realize the controllable construction of the A/B ratio gradient from the bottom of the thin film (t=0) to the top of the thin film (t=T); the coating is ended when the time t is T, the carrier gas and heating are turned off and the samples are collected after they are cooled to room temperature.
In particular, the ultrasonic atomizer nozzle is provided with a fairing which enables the atomized micro droplets are evenly sprayed out at a certain speed by use of the carrier gas.
The carrier gas includes but is not limited to one or more kind of gas, including compressed air, oxygen, nitrogen and argon.
The beneficial effects of the present invention are as follows:
(1) the present invention realizes the gradient change of A/B ratio between the bottom and the top of the thin film through the gradual change of the liquid feeding flow rate of A and B, solves the problem that the metal A/B ratio gradient formed by thermal assistance in the thermal diffusion assisted spray pyrolysis preparation method is controlled by the thermal diffusivity of metal A and B, and can not regulate the metal A/B ratio gradient, for the thin film with different thicknesses (10 nm ~ 10 m level), the precisely controllable metal A/B ratio gradient can be created from bottom to top on the premise of avoiding heterophase precipitation.
(2) In the present invention, the thermal diffusion of metal A and B does not need to be heated at a high temperature, but only needs an appropriate temperature to make the metal salt form oxide.
(3) With a wide range of applications, the thermal diffusion assisted spray pyrolysis preparation method is suitable for the preparation of binary metal oxide thin film. This method can be used for the preparation of gradient self-doping multi metal oxide thin film.
In a word, the present invention has a wide range of application. For the thin film with different thicknesses (10 nm ~ 10 m level), the precisely controllable metal A/B ratio gradient can be created from bottom to top on the premise of avoiding heterophase precipitation. It does not depend on the controllable metal ion A/B ratio gradient formed by high temperature thermal diffusion and can avoid the problems of uncontrollable A/B ratio gradient and phase separation of heterophase in monobasic metal oxide of A or B easily happened in the high temperature thermal assisted spray pyrolysis.
Description of the figure:
Fig. 1 is a structural diagram of a solution controllable blending gradient self-doping multi metal oxide semiconductor thin film preparation device in the embodiments of the present invention;
Among them, 1. liquid storage tank A; 2. liquid storage tank B; 3. liquid feeding flow rate gradual change controller A; 4. liquid feeding flow rate gradual change controller B; 5. flow rate controller A; 6. flow rate controller B; 7. mixing vessel; 8. ultrasonic nebulizer; 9. ultrasonic power controller; 10. fairing; 11. spray area; 12. gradient self-doping AxByOz thin film; 13. substrate; 14. sample stage; 15. temperature controller.
Fig. 2 is the sample result diagram of embodiment 1, in which, (a) scanning electron microscope (SEM) picture; (b) glow discharge emission spectrometry (GDOS) test results, in which the molar ratio of ordinate for A is A/(A+B), for B is B/(A+B), and the molar ratio A/B of A and B is the GDOS test result, Depth is the distance to the top of the thin film, scatter diagram is the test experimental result, full line is the linear fitting; (c) X-ray diffraction (XRD) of gradient self-doping AxByOz.
Detailed Description of Embodiments:
The following is a further description of the present invention rather than a limitation of the present invention.
Embodiment 1:
As shown in the Fig.1, the solution controllable blending gradient self-doping multi metal oxide semiconductor film preparation device, the device includes a spray area, a heatable sample stage provided in the spray area, the sample stage was used for fixing the substrate after being cleaned, the temperature of the sample stage was controlled by a temperature controller, a mixing vessel, an ultrasonic atomizer and a fairing were arranged directly above the sample stage, the device also includes a liquid storage tank A, a liquid storage tank B, ultrasonic power controller, liquid feeding flow rate gradual change controller, flow rate controller, liquid storage tank A and liquid storage tank B were respectively filled with precursor solutions of metal A and B, the precursor solutions of metal A and B flowed into the mixing vessel under the control of the flow rate controller, and atomized into fine droplets in the ultrasonic atomizer, after being sprayed out from the nozzle through the fairing with the carrier gas, the spray was deposited on the substrate fixed on the sample stage of the spray area; both of the initial liquid feeding flow rate of precursor solutions of metal A and B and the gradual change rate of the liquid feeding flow rate in the sputtering process could be set by the corresponding liquid feeding flow rate gradual change controller A and B, which were realized by controlling the flow rate controller; the ultrasonic power controller was used to control the power of the ultrasonic atomizer, the distance between the nozzle of the ultrasonic atomizer and the substrate was 1 ~ 100cm.
The spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film includes the following steps:
1) The precursor solutions of metal A and B with ion concentration CA andCB respectively were placed in the liquid storage tanks A and B respectively; the solute includes but was not limited to nitrate, acetate and chloride of A and B; the solvent includes but were not limited to acetic acid, methanol, ethanol, acetone and water.
2) The parameter setting of the precursor solution: the initial flow rate VAlnitial and final flow rate VAFinal of metal A precursor solution flowing into the mixing vessel were set by the gradual change controller A, the initial flow rate VBlnitial and final flow rate VBFinal of metal B precursor solution flowing into the mixing vessel were set by the gradient controller B and the coating time T, the ultrasonic atomization power was set to 50 ~ 500 W, the pressure of carrier gas was set to 0.1 ~ 10 Bar, the distance between the ultrasonic atomizer nozzle and the substrate was 1 ~ 100cm and the heating temperature of sample stage was 100 ~ 550°C;
3) After the sample stage was heated to the specified temperature and stays stable, the carrier gas began to spray, the precursor solutions of metal A and B began to flow into the mixing vessel according to the set initial liquid flow rate VAInitial, VBlnitial, after being mixed evenly, the solution was atomized into fine droplets in the ultrasonic atomizer and sprayed out with the carrier gas from the nozzle on the substrate fixed on the sample stage to be deposited; and the liquid feeding flow rate of A and B was changed respectively according to the set gradual change rate (VAFinal - VAInitial )/T, (VBFinal - VBlnitial)/T during the spray process to precisely control the ratio of A and B of the mixing solution in the ultrasonic atomizer so that to realize the controllable construction of the A/B ratio gradient from the bottom of the thin film (t=0) to the top of the thin film (t=T); when the time t was T, the rates of A and B were gradually changed to VAFinal, VBFinal respectively, and the coating was ended, the carrier gas and heating were turned off and the samples were collected after they were cooled to room temperature.
Embodiment 1: Take the gradient self-doping ABO4 with stoichiometric ratio x:y:z =1:1:4 as an example
Referring to the specific embodiment, the initial flow rate of the precursor solution (metal A ion concentration 20 mM) of metal A was 12 ml/min, and the initial flow rate of the precursor solution of metal B (metal B ion concentration 20 mM) was 8 ml/min, the precursor solution of metal A was based on the initial flow rate, the liquid feeding flow rate gradually decreased at a gradual rate of 0.4mL/min 2, the precursor solution of metal B was based on the initial 2 flow rate, the liquid feeding flow rate gradually increased at a gradual rate of 0.4ml/min2, and the coating time was 10mmin. The ultrasonic power was 100W, the distance between atomizer nozzle and the substrate is 20cm, the pressure of carrier gas was 0.6 bar and the heating temperature of sample stage was 300°C.
Embodiment 2: Referring to embodiment 1, the difference was that the precursor solution of metal A was based on the initial liquid feeding flow rate, the liquid feeding flow rate gradually decreased (or increased) at a gradual change rate of 0.1 ~ 1mL/min 2, the precursor solution of metal B was based on the initial liquid feeding flow rate, and the liquid feeding flow rate did not change.
Embodiment 3:
Referring to embodiment 1, the difference was that the ion concentration of metal A and B in the precursor solutions of metal A and B was 2010OOmM.
Embodiment 4:
Referring to embodiment 1, the difference was that the power of the ultrasonic atomizer was 100 ~ 500W.
Embodiment 5: referring to embodiment 1, the difference was that the distance between the nozzle of the ultrasonic atomizer and the substrate was 2050cm.
Embodiment 6: referring to embodiment 1, the difference was that the carrier gas pressure was 0.6 ~ 1OBar.
Embodiment 7: referring to embodiment 1, the difference was that the heating temperature of the sample stage was 300 ~ 550°C.
Claims (10)
1. The spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film, characterized in that, by precisely controlling the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate of the precursor solutions of metal A and B, the ratio of metal ions in the spray pyrolysis deposition process on the substrate surface at 100-550°C is controlled to prepare the gradient self-doping multi metal oxide thin film. The gradient change of metal ion A/B ratio is formed from the bottom of the thin film to the top of the thin film; the thickness of the oxide thin film is controlled at l0nm-10tm; and the multi metal oxide is AxByOz, among which A is metal A, B is metal B, o is oxygen atom, x, y and z are the chemical dose of metal A, metal B and oxygen atom 0.
2. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1, characterized in that, by precisely controlling the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate, the metal salt solutions of metal A and B are as the precursor solutions, the initial liquid feeding flow rate and the gradual change rate of the liquid feeding flow rate of the precursor solutions of metal A and B in the spray pyrolysis deposition process are set by the gradual change controller. The liquid feeding flow rate is gradually changed according to the set parameters during the coating process, spray pyrolysis deposition is carried out at 100-550 C, and the gradient change of metal ion A/B ratio is formed from the bottom of the thin film to the top of the thin film.
3. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 2, characterized in that, the initial liquid feeding flow rate of the precursor solution of metal A and B in the spray pyrolysis deposition process is 0.1 -1L/min, and the gradual change rate of the liquid feeding flow rate is 0.01 1OL/min2
4. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 2, characterized in that, the metal salt of the precursor solution of metal A and B includes any of nitrates, acetate and chloride of A, B; the solvent
includes any of acetic acid, methyl alcohol, ethanol, acetone and water.
5. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1 or claim 2, characterized in that, by adding stabilizer into the precursor solutions of metal A and B, and the stabilizer includes polyethylene glycol and trimethyl orthoformate.
6. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1 or claim 2, characterized in that, the icon concentration of metal A and B in the precursor solutions of metal A and B is 1-1000mM respectively.
7. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1 or claim 2, characterized in that, VA and VB which are the liquid feeding flow rates of the precursor solutions of metal A and B are required to meet O<VA 10L/min, O<VB10 L/min, and 0.5x (x:y) <CBVB/ CAVA < 2x(x:y). CA and CB are the icon concentration of metal A and B in the precursor solutions respectively.
8, According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1 or claim 2, characterized in that, the distance between the ultrasonic atomizer nozzle and the substrate in the spray pyrolysis deposition process is 1-100cm.
9. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 1 or claim 2, characterized in that, it includes the following steps:
1) The precursor solutions of metal A and B with icon concentration CA and CB of A and B respectively are placed in the liquid storage tank A and B respectively;
2) The parameter setting of the precursor solution: the initial flow rate VAlnitial and final flow rate VAFinal of metal A precursor solution flowing into the mixing vessel are set by the gradual change controller A, the initial flow rate VBlnitial and final flow rate VBFinal of metal B precursor solution flowing into the mixing vessel and the coating time T are set by the gradient controller B, the ultrasonic atomization power is set to 50 ~ 500 W, the pressure of carrier gas is set to 0.1 ~ 10 Bar, the distance between the ultrasonic atomizer nozzle and the substrate is 1 ~ 100cm and the heating temperature of sample stage is 100 ~ 550°C;
3) After the sample stage is heated to the specified temperature and stays stable, the carrier gas begins to spray, the precursor solutions of metal A and B begin to flow into the mixing vessel according to the set initial liquid flow rate and gradual change rate of the liquid feeding flow rate. After being mixed evenly, the solution is sprayed on the substrate fixed on the sample stage by the ultrasonic atomization with the carrier gas to be deposited; and the liquid feeding flow rates of A and B are changed respectively according to the set gradual change rate (VAFinal - VAInitial )/T, (VBFinal - VBlnitial )/T during the spray process to precisely control the ratio of A and B of the mixing solution in the ultrasonic atomizer so that to realize the controllable construction of the A/B ratio gradient from the bottom of the thin film (t=O) to the top of the thin film (t=T); the coating is ended when the time t is T, the carrier gas and heating are turned off and the samples are collected after they are cooled to room temperature.
10. According to the spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film of claim 9, characterized in that, the ultrasonic atomizer nozzle is provided with a fairing, the carrier gas includes one or more kind of gas, including compressed air, oxygen, nitrogen and argon, and the carrier gas pressure is 0.1-10bar.
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| PCT/CN2019/083188 WO2020191837A1 (en) | 2019-03-28 | 2019-04-18 | Spray pyrolysis preparation method for gradient self-doping multi-element metal oxide semiconductor film |
| AU2021100535A AU2021100535A4 (en) | 2019-03-28 | 2021-01-28 | Spray pyrolysis preparation method of gradient self-doping multi metal oxide semiconductor thin film |
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