CN117790623A - Back interface modification method for improving photovoltaic performance of Sb2Se3 thin film solar cell - Google Patents
Back interface modification method for improving photovoltaic performance of Sb2Se3 thin film solar cell Download PDFInfo
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- CN117790623A CN117790623A CN202311746986.2A CN202311746986A CN117790623A CN 117790623 A CN117790623 A CN 117790623A CN 202311746986 A CN202311746986 A CN 202311746986A CN 117790623 A CN117790623 A CN 117790623A
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- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 238000002715 modification method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 230000001105 regulatory effect Effects 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000003599 detergent Substances 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims description 64
- 239000010408 film Substances 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 238000012512 characterization method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 229910016001 MoSe Inorganic materials 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000011056 performance test Methods 0.000 abstract 1
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a back interface modification method for improving the photovoltaic performance of an Sb2Se3 thin film solar cell, which is used for preparing Sb at first 2 Se 3 Mo substrates of thin film solar cell devices were first washed with ethanol, detergent and deionized water. The cleaned Mo substrate was annealed in an air flow in a furnace to grow MoO 2 And a regulating layer. In addition, the solar cell prepared by using an unannealed Mo substrate is used as a control group, and finally, through a series of device performance tests, the MoSe is effectively reduced 2 Interfacial layer thickness and back contact barrier. The invention adopts the air annealing process to treat the Mo substrate of the solar cell device and modify Mo/Sb in the cell device 2 Se 3 Contact characteristics of back interface are improved based on Sb of substrate structure 2 Se 3 Thin film solar cellPhotoelectric conversion efficiency.
Description
Technical Field
The invention relates to the technical field of semiconductor materials and semiconductor devices, in particular to a back interface modification method for improving the photovoltaic performance of an Sb2Se3 thin film solar cell.
Background
Solar energy is expected to be a carbon-free energy source for meeting the energy demand of people, and one of ways to realize the effective utilization of solar energy is a solar cell device. Antimony selenide (Sb) 2 Se 3 ) Is a solar cell film material with proper band gap, high absorption coefficient and good conductivity, and the theoretical photoelectric conversion efficiency of the solar cell device can exceed 30 percent, therefore, sb 2 Se 3 Solar cell devices have shown great research potential in a number of new solar cell devices. However, sb based on the underlying structure 2 Se 3 Film solar cell (Mo/Sb) 2 Se 3 The highest efficiency (10%) of/CdS/ITO/Ag) is far lower than the theoretical photoelectric conversion efficiency, and a large gap is left from practical application. To further improve Sb 2 Se 3 The invention designs a novel back interface modification method for improving the photovoltaic performance of the Sb2Se3 thin film solar cell to solve the problems.
Disclosure of Invention
The invention aims to provide a back interface modification method for improving the photovoltaic performance of an Sb2Se3 thin film solar cell, which aims to solve at least one technical problem in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a back interface modification method for improving photovoltaic performance of an Sb2Se3 thin film solar cell comprises the following steps:
step S1, moO 2 Preparing a regulating layer;
(a1) For preparing Sb 2 Se 3 The Mo substrate of the thin film solar cell device is firstly washed by ethanol, a detergent and deionized water;
(b1) The cleaned Mo substrate was annealed in an air flow in a furnace toGrowth of MoO 2 A regulation layer;
step S2, sb in a Battery device 2 Se 3 Preparing an absorption layer;
preparing Sb precursor films on various Mo substrates by a radio frequency magnetron sputtering process method, and placing the Sb precursor films prepared on the Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer;
step S3, sb 2 Se 3 Preparing a thin film solar cell;
(a3) Respectively preparing CdS buffer layers on a plurality of samples by a chemical water bath method;
(b3) Drying the film after preparing CdS;
(c3) Sb is made of 2 Se 3 Annealing the CdS heterojunction in a vacuum state;
(d3) Preparing an ITO layer on CdS by adopting a magnetron sputtering method;
(e3) Preparing a front electrode of the solar cell device by using a thermal evaporation method;
step S4, sb 2 Se 3 Performance characterization of the thin film solar cell device;
and testing J-V curves, J-V curves with variable temperature dark states, CV-DLCP and admittance spectrums of the prepared devices, and carrying out characterization of relevant performances.
Preferably, the step S1, (b 1) performs the steps of: blowing the cleaned Mo substrate surface by a nitrogen gun, placing in a heat treatment furnace, introducing air to directly anneal at 300 and 400 ℃ for 15 minutes to obtain the MoO with the thickness of 80nm and 800nm 2 A control layer, in addition, a Mo substrate which is not treated by an air annealing process is used as a control group to respectively prepare Sb on the three Mo substrates 2 Se 3 A solar cell device.
Preferably, the step S2 performs the following steps: the Sb precursor film is prepared on the three Mo substrates by a radio frequency magnetron sputtering process method, and the background air pressure is 5 multiplied by 10 -4 Pa, sputtering time of 40min, sputtering air pressure of the film1Pa, then, placing the Sb precursor films prepared on the three Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer, selenium particles are placed on two sides of the sample, and the total mass of the selenium particles is 0.4g; ar gas is always introduced in the selenizing treatment process, so that the air pressure is maintained to be 7 multiplied by 10 4 Pa, selenizing temperature 410 ℃, heating rate 20 ℃/min, sample selenizing time 15 min, and sample respectively marked as S Mo1 ,S Mo2 S and S Mo3 。
Preferably, the step S3, (a 3) performs the steps of: the multiple samples are S Mo1 ,S Mo2 S and S Mo3, at Three samples S Mo1 ,S Mo2 S and S Mo3 Respectively preparing CdS buffer layers by a chemical water bath method, wherein the solution for preparing CdS is prepared from CdSO 4 Ammonia water and thiourea, the temperature of the chemical water bath method is 85 ℃, and the deposition time is 9 minutes.
Preferably, the step S3, (c 3) performs the steps of: the treatment temperature of the annealing treatment is 325 ℃, and the annealing time is 5min.
Preferably, the step S3, (d 3) performs the steps of: the ITO layer is prepared on CdS by adopting a magnetron sputtering method, and the sputtering power, time and air pressure of the ITO layer are 120W,25min and 0.4Pa respectively.
Compared with the prior art, the back interface modification method for improving the photovoltaic performance of the Sb2Se3 thin film solar cell has the following beneficial effects:
the invention adopts the air annealing process to prepare MoO on the Mo substrate 2 The preparation process is simple and direct. In addition, in contrast to other regulatory layers, moO 2 The regulating layer can effectively reduce Mo/Sb 2 Se 3 Inter MoSe 2 The thickness of the interfacial layer can also effectively promote Sb 2 Se 3 The absorption layer is to ideal [ hk1 ]]Oriented growth of Sb 2 Se 3 The characteristics of the/CdS heterojunction front interface are also further optimized.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 shows MoO 2 Regulatory layer and no MoO 2 Sb of regulatory layer 2 Se 3 Comparing the performance of the thin film solar cell device;
FIG. 3 is a temperature change J-V curve of the device;
FIG. 4 is a device Sb 2 Se 3 Performance characterization at the CdS heterojunction interface;
FIG. 5 is a device Sb 2 Se 3 And (3) compounding characterization of a CdS heterojunction interface.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
In the description of the present invention, it should be understood that the terms "upper," "lower," "front," "rear," "left," "right," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the present invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
Referring to fig. 1-5, moSe is shown for influencing transport of photogenerated carriers at the back interface 2 The existence of interface layer and higher back contact barrier, the oxidation modification of Mo/Sb of Mo substrate is proposed 2 Se 3 The back interface method comprises the following specific steps: step S1, moO 2 Preparing a regulating layer;
(a1) For preparing Sb 2 Se 3 The Mo substrate of the thin film solar cell device is firstly washed by ethanol, a detergent and deionized water;
(b1) The cleaned Mo substrate was annealed in an air flow in a furnace to grow MoO 2 A regulation layer;
the step S1, (b 1) performs the steps of: blow-drying the cleaned Mo substrate surface by a nitrogen gun, placing the Mo substrate surface in a heat treatment furnace, and introducing airDirectly annealing at 300 and 400 deg.C for 15 min to obtain MoO with thickness of 80nm and 800nm 2 A control layer, in addition, a Mo substrate which is not treated by an air annealing process is used as a control group to respectively prepare Sb on the three Mo substrates 2 Se 3 A solar cell device.
Step S2, sb in a Battery device 2 Se 3 Preparing an absorption layer;
preparing Sb precursor films on various Mo substrates by a radio frequency magnetron sputtering process method, and placing the Sb precursor films prepared on the Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer;
the step S2 performs the following steps: the Sb precursor film is prepared on the three Mo substrates by a radio frequency magnetron sputtering process method, and the background air pressure is 5 multiplied by 10 -4 Pa, sputtering time of 40min, sputtering air pressure of 1Pa, and then placing the Sb precursor film prepared on the three Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer, selenium particles are placed on two sides of the sample, and the total mass of the selenium particles is 0.4g; ar gas is always introduced in the selenizing treatment process, so that the air pressure is maintained to be 7 multiplied by 10 4 Pa, selenizing temperature 410 ℃, heating rate 20 ℃/min, sample selenizing time 15 min, and sample respectively marked as S Mo1 ,S Mo2 S and S Mo3 。
Step S3, sb 2 Se 3 Preparing a thin film solar cell;
(a3) Respectively preparing CdS buffer layers on a plurality of samples by a chemical water bath method;
(b3) Drying the film after preparing CdS;
(c3) Sb is made of 2 Se 3 Annealing the CdS heterojunction in a vacuum state;
the step S3, (c 3) performs the steps of: the treatment temperature of the annealing treatment is 325 ℃, and the annealing time is 5min.
(d3) Preparing an ITO layer on CdS by adopting a magnetron sputtering method;
the step S3, (d 3) performs the steps of: the ITO layer is prepared on CdS by adopting a magnetron sputtering method, and the sputtering power, time and air pressure of the ITO layer are 120W,25min and 0.4Pa respectively.
(e3) Preparing a front electrode of the solar cell device by using a thermal evaporation method;
step S4, sb 2 Se 3 Performance characterization of the thin film solar cell device;
and testing J-V curves, J-V curves with variable temperature dark states, CV-DLCP and admittance spectrums of the prepared devices, and carrying out characterization of relevant performances.
FIG. 2 shows MoO 2 Regulatory layer and no MoO 2 Sb of regulatory layer 2 Se 3 Performance contrast of thin film solar cell device, moO with proper thickness 2 The control layer (80 nm) can promote Sb 2 Se 3 The absorber layer grows in the (211) orientation such that Sb 2 Se 3 Grain growth of the absorption layer, inhibition of MoSe 2 Generating an interface layer; and have no MoO 2 Sb of regulatory layer 2 Se 3 Device performance comparison, moO 2 The regulating layer can improve the efficiency of the device from 5.75% to 8.14%, and the back contact barrier of the device is also reduced.
FIG. 3 shows the results of a further measurement of the temperature change J-V curve of the device, from which it is known that there is no MoO 2 Device of control layer was compared in Mo/Sb 2 Se 3 MoO is added at the back interface 2 After the regulating layer, the back contact barrier can be effectively reduced from 217meV to 73.9meV, and Sb can be caused 2 Se 3 Recombination at the/CdS heterojunction interface is also reduced; moO (MoO) 2 The regulating layer not only can modify Mo/Sb 2 Se 3 Back interface contact characteristics can also improve Sb 2 Se 3 Performance of the/CdS heterojunction.
Further illustrated in FIG. 4, mo/Sb in a battery device 2 Se 3 Adding MoO 2 The regulating layer can reduce Sb 2 Se 3 Defects of the heterojunction interface of/CdS and increase Sb 2 Se 3 The built-in potential of the/CdS heterojunction promotes the transportation of photo-generated carriers at the heterojunction interface. And as can be seen from the admittance spectrum test of the device, moO 2 The regulating layer can lead to Sb 2 Se 3 The Se vacancy defect of the absorption layer is reduced, and the device performance is further improved.
FIG. 5 illustrates the presence of Mo/Sb 2 Se 3 After the back interface is modified, sb can be simultaneously made 2 Se 3 The recombination rate at the/CdS heterojunction interface is reduced, and Sb is optimized 2 Se 3 The performance of the/CdS heterojunction interface further demonstrates MoO 2 The regulating layer can effectively inhibit MoSe 2 The generation of interface layer reduces back contact potential barrier and can optimize Sb 2 Se 3 a/CdS heterojunction interface.
In conclusion, the invention adopts the air annealing process to treat the Mo substrate of the solar cell device and modify Mo/Sb in the cell device 2 Se 3 Contact characteristics of back interface are improved based on Sb of substrate structure 2 Se 3 Photoelectric conversion efficiency of the thin film solar cell;
compared with other back interface regulation and control processes of solar cell devices, the air annealing process is adopted to prepare MoO on the Mo substrate 2 The preparation process is simple and direct. In addition, in contrast to other regulatory layers, moO 2 The regulating layer can effectively reduce Mo/Sb 2 Se 3 Inter MoSe 2 The thickness of the interfacial layer can also effectively promote Sb 2 Se 3 The absorption layer is to ideal [ hk1 ]]Oriented growth of Sb 2 Se 3 The characteristics of the/CdS heterojunction front interface are also further optimized.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The back interface modification method for improving the photovoltaic performance of the Sb2Se3 thin film solar cell is characterized by comprising the following steps of:
step S1, moO 2 Preparing a regulating layer;
(a1) For preparing Sb 2 Se 3 The Mo substrate of the thin film solar cell device is firstly washed by ethanol, a detergent and deionized water;
(b1) The cleaned Mo substrate was annealed in an air flow in a furnace to grow MoO 2 A regulation layer;
step S2, sb in a Battery device 2 Se 3 Preparing an absorption layer;
preparing Sb precursor films on various Mo substrates by a radio frequency magnetron sputtering process method, and placing the Sb precursor films prepared on the Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer;
step S3, sb 2 Se 3 Preparing a thin film solar cell;
(a3) Respectively preparing CdS buffer layers on a plurality of samples by a chemical water bath method;
(b3) Drying the film after preparing CdS;
(c3) Sb is made of 2 Se 3 Annealing the CdS heterojunction in a vacuum state;
(d3) Preparing an ITO layer on CdS by adopting a magnetron sputtering method;
(e3) Preparing a front electrode of the solar cell device by using a thermal evaporation method;
step S4, sb 2 Se 3 Performance characterization of the thin film solar cell device;
and testing J-V curves, J-V curves with variable temperature dark states, CV-DLCP and admittance spectrums of the prepared devices, and carrying out characterization of relevant performances.
2. The back interface modification method for improving photovoltaic performance of Sb2Se3 thin film solar cell according to claim 1, wherein step S1, (b 1) performs the following steps: blow-drying the cleaned Mo substrate surface with a nitrogen gun, placing in a heat treatment furnace, introducing air to directly anneal at 300 and 400 ℃ for 15 minutesTo a thickness of 80nm and 800nm 2 A control layer, in addition, a Mo substrate which is not treated by an air annealing process is used as a control group to respectively prepare Sb on the three Mo substrates 2 Se 3 A solar cell device.
3. The back interface modification method for improving photovoltaic performance of the Sb2Se3 thin film solar cell, which is characterized by comprising the following steps of: the step S2 performs the following steps: the Sb precursor film is prepared on the three Mo substrates by a radio frequency magnetron sputtering process method, and the background air pressure is 5 multiplied by 10 -4 Pa, sputtering time of 40min, sputtering air pressure of 1Pa, and then placing the Sb precursor film prepared on the three Mo substrates in a heat treatment furnace for selenizing treatment to prepare Sb 2 Se 3 An absorption layer, selenium particles are placed on two sides of the sample, and the total mass of the selenium particles is 0.4g; ar gas is always introduced in the selenizing treatment process, so that the air pressure is maintained to be 7 multiplied by 10 4 Pa, selenizing temperature 410 ℃, heating rate 20 ℃/min, sample selenizing time 15 min, and sample respectively marked as S Mo1 ,S Mo2 S and S Mo3 。
4. The back interface modification method for improving photovoltaic performance of the Sb2Se3 thin film solar cell, which is characterized by comprising the following steps of: the step S3, (a 3) performs the steps of: the multiple samples are S Mo1 ,S Mo2 S and S Mo3, at Three samples S Mo1 ,S Mo2 S and S Mo3 Respectively preparing CdS buffer layers by a chemical water bath method, wherein the solution for preparing CdS is prepared from CdSO 4 Ammonia water and thiourea, the temperature of the chemical water bath method is 85 ℃, and the deposition time is 9 minutes.
5. The back interface modification method for improving photovoltaic performance of the Sb2Se3 thin film solar cell, which is disclosed in claim 4, is characterized in that: the step S3, (c 3) performs the steps of: the treatment temperature of the annealing treatment is 325 ℃, and the annealing time is 5min.
6. The back interface modification method for improving photovoltaic performance of the Sb2Se3 thin film solar cell, which is disclosed in claim 5, is characterized in that: the step S3, (d 3) performs the steps of: the ITO layer is prepared on CdS by adopting a magnetron sputtering method, and the sputtering power, time and air pressure of the ITO layer are 120W,25min and 0.4Pa respectively.
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| CN202311746986.2A CN117790623A (en) | 2023-12-19 | 2023-12-19 | Back interface modification method for improving photovoltaic performance of Sb2Se3 thin film solar cell |
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| CN202311746986.2A CN117790623A (en) | 2023-12-19 | 2023-12-19 | Back interface modification method for improving photovoltaic performance of Sb2Se3 thin film solar cell |
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