CN109473551B - Solar cell based on dual-source evaporation and preparation method thereof - Google Patents
Solar cell based on dual-source evaporation and preparation method thereof Download PDFInfo
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- 238000001704 evaporation Methods 0.000 title claims abstract description 72
- 230000008020 evaporation Effects 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000010408 film Substances 0.000 claims abstract description 81
- 229910052959 stibnite Inorganic materials 0.000 claims abstract description 78
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000010549 co-Evaporation Methods 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 238000005516 engineering process Methods 0.000 claims abstract description 14
- 230000005525 hole transport Effects 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000007740 vapor deposition Methods 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 9
- 238000007738 vacuum evaporation Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims 1
- 230000009977 dual effect Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 238000000151 deposition Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 8
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000000224 chemical solution deposition Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- KYUIIGJSSHTWDW-UHFFFAOYSA-N 2,3-dimethoxy-n-phenylaniline Chemical compound COC1=CC=CC(NC=2C=CC=CC=2)=C1OC KYUIIGJSSHTWDW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005516 deep trap Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- 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
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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
- C23C14/0623—Sulfides, selenides or tellurides
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- 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
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- 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
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Abstract
The invention discloses a solar cell based on dual-source evaporation and a preparation method thereof, wherein the method comprises the following steps: providing a substrate comprising a cathode; forming an electron transport layer on the substrate; forming Sb on the electron transport layer2S3A film; wherein said Sb2S3And (3) forming a thin film: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb was allowed to react in a vacuum atmosphere2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film; in the Sb2S3Forming a hole transport layer on the film; an anode is formed on the hole transport layer. The invention adopts a vacuum double-source co-evaporation deposition technology and uses Sb2S5And Sb2S3Preparation of Sb by double-source coevaporation as precursor material2S3A film. High quality Sb is realized by precisely controlling evaporation and deposition parameters2S3The preparation of the film is beneficial to the improvement of the efficiency of the solar cell.
Description
Technical Field
The invention relates to the field of novel thin-film solar cell photoelectric functional materials, in particular to a solar cell based on double-source evaporation and a preparation method thereof.
Background
Sb2S3The thin film has a high absorption coefficient in the visible region, approaching the optimal band gap for solar cell applications. In addition, Sb2S3The thin-film solar cell still has good photovoltaic performance under the condition of weak light irradiation, and can realize high-efficiency photoelectric conversion in cloudy weather, indoor conditions and building walls. Therefore, for Sb2S3The research of the thin-film solar cell has high value for the next generation of photovoltaic cells. To promote Sb2S3The development of thin film solar cells has carried out the optimization of device structure design and film quality. It is well known that the absorber layer plays an important role in the photovoltaic performance of the device. Therefore, many methods have been introduced in recent years to optimize Sb2S3The quality of the film. One method for preparing Sb by adopting water-soluble Chemical Bath Deposition (CBD)2S3Film using a solution mixture of antimony chloride and sodium thiosulfate as Sb3+And S2-A low temperature precursor source of ions. However, oxidation of antimony sulfide is hardly avoided using the CBD method, and thus the formed antimony oxide generates a deep trap defect on the surface, resulting in severe recombination of photo-excited charge carriers. After thioacetamide treatment is introduced in the later period, the defect of deep oxide is eliminated, and the photoelectric conversion efficiency reaches 7.5 percent, but the CBD method still faces mesoporous TiO2Long time required for Sb formation on thin film2S3To a problem of (a). Other methods, including atomic layer deposition and precise thickness deposition, are also applicable to planar Sb2S3However, these methods have complicated preparation processes and do not meet the requirements of the existing industrialization. Therefore, the preparation method based on the vacuum evaporation deposition technology which is beneficial to large-scale industrialization obtains wide attention. Wherein Sb is prepared by adopting a vacuum single-source thermal evaporation method2S3Film, process of direct evaporation of Sb2S3Precursor powder material, deposition of Sb on a substrate2S3A method for preparing a film. However, direct single source thermally evaporated Sb2S3The film experiences sulfur loss during evaporation and post-annealing, and the composition is prone to deviation from stoichiometryThe ratio directly results in a reduction in film quality and reproducibility, which severely compromises film quality and device performance.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention is directed to a solar cell based on dual-source evaporation and a method for preparing the same, and the present invention is directed to solving the problem of single-source thermal evaporation of Sb2S3The film experiences sulfur loss during evaporation and post-annealing, which can seriously compromise film quality and device performance issues.
The technical scheme of the invention is as follows:
a preparation method of a solar cell based on dual-source evaporation comprises the following steps:
providing a substrate comprising a cathode;
forming an electron transport layer on the substrate;
forming Sb on the electron transport layer2S3A film; wherein said Sb2S3And (3) forming a thin film: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb was allowed to react in a vacuum atmosphere2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film;
in the Sb2S3Forming a hole transport layer on the film;
an anode is formed on the hole transport layer.
The preparation method of the solar cell based on the dual-source evaporation, wherein the Sb2S3The film forming process specifically includes: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb2S5And Sb2S3Respectively putting the two evaporation boats into a co-evaporation device, vacuumizing a vacuum cavity, and carrying out vacuum evaporation on the Sb2S5And Sb2S3Is controlled so that Sb is evaporated2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film.
The preparation method of the solar cell based on the dual-source evaporation comprises the following steps of: 1 to 1: 0.01, adding said Sb2S5And Sb2S3Respectively put into two evaporation boats of a co-evaporation device.
The preparation method of the solar cell based on the double-source evaporation comprises the steps of vacuumizing a vacuum cavity until the vacuum degree in the cavity is 1.0 × 10-3Pa or less.
The preparation method of the solar cell based on the dual-source evaporation comprises the step of forming Sb on the electron transport layer2S3After the film is formed, in said Sb2S3Before forming the hole transport layer on the film, the method further comprises the following steps: sb after being taken out2S3And annealing the film.
The preparation method of the solar cell based on the dual-source evaporation, wherein the temperature of the annealing treatment is 240-400 ℃.
The preparation method of the solar cell based on the dual-source evaporation comprises the step of annealing for 2-30 minutes.
A solar cell based on dual-source evaporation comprises a substrate containing a cathode, an electron transport layer and Sb from bottom to top in sequence2S3The solar cell is prepared by the preparation method based on the dual-source evaporation.
The solar cell based on the dual-source evaporation, wherein the Sb2S3The thickness of the film is 50-1000 nm.
Has the advantages that: the invention provides a method for preparing Sb by simple operation and repeatability, which adopts a vacuum double-source coevaporation deposition technology2S5And Sb2S3Dual source co-evaporation preparation as precursor materialSb2S3A film. By precise control of Sb2S5And Sb2S3The evaporation and deposition parameters of (1) realize the in-situ completion of high-quality Sb in the same vacuum environment2S3The preparation of the film will be directly advantageous for Sb-based films2S3The efficiency of the thin film solar cell is improved.
Drawings
FIG. 1 shows the preparation of Sb by vacuum double-source co-evaporation in examples 1 to 32S3Schematic representation of the film.
FIG. 2 is a Sb-based alloy prepared in example 12S3J-V plot of thin film solar cells.
Detailed Description
The invention provides a solar cell based on dual-source evaporation and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a solar cell based on double-source evaporation, which comprises the following steps:
providing a substrate comprising a cathode;
forming an electron transport layer on the substrate;
forming Sb on the electron transport layer2S3A film; wherein said Sb2S3And (3) forming a thin film: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb was allowed to react in a vacuum atmosphere2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film;
in the Sb2S3Forming a hole transport layer on the film;
an anode is formed on the hole transport layer.
Compared with the prior art, the main improvements of the embodiment are as follows:adopts a vacuum double-source co-evaporation deposition technology and uses Sb respectively2S5And Sb2S3Preparation of Sb by double-source coevaporation as precursor material2S3A film. By precise control of Sb2S5And Sb2S3Evaporation deposition parameters of (1), preparation of Sb2S3A film. Sb2S5The precursor has high sulfur content, can provide sulfur-rich atmosphere in the evaporation process, inhibit the formation of sulfur vacancy in the film and Sb2S3When the double sources are evaporated together, the two can realize the balance of the sulfur vacancy and the film crystallization, and realize the in-situ completion of high-quality Sb in a high vacuum environment2S3And the preparation of the film improves the conversion efficiency of the battery and meets the industrialization requirement of large-area devices.
In a preferred embodiment, the Sb is2S3The film forming process specifically includes: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb2S5And Sb2S3Respectively putting the two evaporation boats into a co-evaporation device, vacuumizing a vacuum cavity, and carrying out vacuum evaporation on the Sb2S5And Sb2S3Is controlled so that Sb is evaporated2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film.
Further in a preferred embodiment, the weight ratio of 0.01: 1 to 1: 0.01, adding said Sb2S5And Sb2S3Respectively put into two evaporation boats of a co-evaporation device.
Further in a preferred embodiment, the vacuum chamber is evacuated until the vacuum level in the chamber is 1.0 × 10-3Pa or less.
In a preferred embodiment, Sb is formed on the electron transport layer2S3After the film is formed, in said Sb2S3Before forming the hole transport layer on the film, the method further comprises the following steps: sb after being taken out2S3And annealing the film.
Further in a preferred embodiment, the temperature of the annealing treatment is 240-400 ℃, and the time of the annealing treatment is 2-30 minutes.
Compared with the prior art, the embodiment Sb2S3The preparation method of the film has the following advantages:
1. adopts the vacuum double-source co-evaporation deposition technology, has mature process, simple operation and repeatable preparation, improves Sb2S3The film quality and the yield are improved, the utilization rate of raw materials is improved, and the large-area industrialization requirement is met;
2. in the film forming process, the evaporation rates of two evaporation source materials can be accurately controlled, so that the evaporation pressure is changed, and Sb with high component purity and uniform distribution of the film can be prepared by double-source co-evaporation2S3A film;
3. by precise control of Sb2S5And Sb2S3Evaporation current, voltage, power, substrate heating program setting and in-situ annealing conditions of the evaporation source are set, so that the required film thickness and the adjustable film microstructure performance can be obtained easily according to requirements.
The invention also provides a solar cell based on the dual-source evaporation, which sequentially comprises a substrate containing a cathode, an electron transport layer and Sb from bottom to top2S3A thin film, a hole transport layer and an anode, wherein the Sb is2S3The solar cell is prepared by the preparation method of the solar cell based on the dual-source evaporation.
In a preferred embodiment, the Sb is2S3The thickness of the film is 50-1000 nm. Visible light can be well absorbed in the thickness range, and photon-generated carrier separation is formed.
The present invention will be described in detail below with reference to examples.
Example 1
Preparation of Sb in solar cell by vacuum double-source co-evaporation method2S3Thin films, using flat panel solar cell structures such as: FTO/c-TiO2/ Sb2S3First, the FTO substrate is cleaned and dense titanium dioxide (c-TiO) is added2) Spin coating on an FTO substrate (3000 r/30 s), and sintering in a high-temperature sintering furnace at 450 ℃ for 4 hours; then transferring the substrate into a vacuum chamber, and preparing Sb which is compact, uniform, pinhole-free, high in crystallinity and in accordance with an ideal stoichiometric ratio by adopting a vacuum double-source coevaporation method2S3A film; in particular to Sb2S5And Sb2S3Respectively put into two evaporation boats as shown in figure 1, and Sb is precisely controlled2S5And Sb2S3Evaporation rate of (2) Sb2S5And Sb2S3Simultaneous vapor deposition of Sb on a substrate2S3A film. More specifically, 0.2 g of Sb was weighed respectively2S3And Sb2S5Powder, the powder is respectively put into two evaporation boats, the distance between a substrate and an evaporation source is 25cm, the substrate does not need to be heated, the rotating speed of a substrate is 40r/min, a vacuum cavity is vacuumized, and the vacuum degree is pumped to 1.0 × 10-3After Pa, turning on an evaporation power supply, rapidly increasing the working current of the two evaporation boats from 0A to 100A simultaneously, and then opening a baffle plate for deposition until the two powders are completely evaporated to generate Sb with the thickness of about 300nm2S3The film slowly adjusts the evaporation current to 0A, and the molecular pump and the mechanical pump are sequentially closed; finally, filling nitrogen into the vacuum cavity and taking out Sb2S3Film samples. The taken out film is put into a glove box for heat treatment at 300 ℃ for 10 minutes and then is put into Sb2S3The layer is spin-coated with a spiro-OMeTAD (2, 2 ', 7, 7' -tetra- (dimethoxydiphenylamine) -spirofluorene) hole transport layer (3000 r/30 s), and finally an Ag electrode is evaporated to form the device structure of FTO/c-TiO2/ Sb2S3a/spiro-OMeTAD/Ag solar cell. The solar cell prepared in this example had the following properties:
1. under the condition of AM1.5 simulated sunlight, the solar cell measured in the room temperature environment presents obvious photovoltaic effect;
2. as shown in the J-V graph of the solar cell of fig. 2: preparation ofThe open-circuit voltage of the solar cell is 0.56V, and the short-circuit current density is 12.44mA/cm2The fill factor was 41.76%, and the photoelectric conversion efficiency was 2.9%.
Example 2
Preparation of Sb in solar cell by vacuum double-source co-evaporation method2S3The film adopts a mesoporous solar cell structure as follows: FTO/c-TiO2/meso-TiO2/ Sb2S3First, the FTO substrate is cleaned and dense titanium dioxide (c-TiO) is added2) Spin coating on an FTO substrate (3000 r/30 s), and sintering in a high-temperature sintering furnace at 450 ℃ for 1 hour; after cooling, spin-coating a mesoporous titanium dioxide layer (meso-TiO) at 4000rpm2) Sintering at 500 deg.c for 1 hr, cooling, transferring the substrate into vacuum chamber, and vacuum double-source coevaporation to prepare Sb product with high density, homogeneity, no pinhole, high crystallinity and ideal stoichiometric ratio2S3A film; in particular to Sb2S5And Sb2S3Respectively put into two evaporation boats as shown in figure 1, and Sb is precisely controlled2S5And Sb2S3Evaporation rate of (2) Sb2S5And Sb2S3Simultaneous vapor deposition of Sb on a substrate2S3A film. More specifically, 0.1 g of Sb was weighed respectively2S3And 0.3 g Sb2S5Powder, the powder is respectively put into two evaporation boats, the distance between a substrate and an evaporation source is 25cm, the substrate does not need to be heated, the rotating speed of a substrate is 40r/min, a vacuum cavity is vacuumized, and the vacuum degree is pumped to 1.0 × 10-3After Pa, turning on an evaporation power supply, rapidly increasing the working current of the two evaporation boats from 0A to 100A simultaneously, and then opening a baffle plate for deposition until the two powders are completely evaporated to generate Sb with the thickness of about 300nm2S3The film slowly adjusts the evaporation current to 0A, and the molecular pump and the mechanical pump are sequentially closed; finally, filling nitrogen into the vacuum cavity and taking out Sb2S3Film samples. The taken out film is put into a glove box for heat treatment at 320 ℃ for 10 minutes and then is put into Sb2S3Spin-coated spiro-OMeTAD hole transportTransferring the layer (3000 r/30 s), and finally evaporating an Ag electrode to form the FTO/c-TiO device structure2/ Sb2S3a/spiro-OMeTAD/Ag solar cell. The solar cell prepared in this example had the following properties:
1. under the condition of AM1.5 simulated sunlight, the solar cell measured in the room temperature environment presents obvious photovoltaic effect;
2. the prepared solar cell has the open-circuit voltage of 0.55V and the short-circuit current density of 11.35mA/cm2The fill factor was 43.6%, and the photoelectric conversion efficiency was 2.72%.
Example 3
Preparation of Sb in solar cell by vacuum double-source co-evaporation method2S3The film adopts a mesoporous solar cell structure as follows: FTO/c-TiO2/meso-TiO2/ Sb2S3First, the FTO substrate is cleaned and dense titanium dioxide (c-TiO) is added2) Spin coating on an FTO substrate (3000 r/30 s), and sintering in a high-temperature sintering furnace at 450 ℃ for 1 hour; after cooling, spin-coating a mesoporous titanium dioxide layer (meso-TiO) at 4000rpm2) Sintering at 500 deg.c for 1 hr, cooling, transferring the substrate into vacuum chamber, and vacuum double-source coevaporation to prepare Sb product with high density, homogeneity, no pinhole, high crystallinity and ideal stoichiometric ratio2S3A film; sb2S5And Sb2S3Respectively put into two evaporation boats as shown in figure 1, and Sb is precisely controlled2S5And Sb2S3Evaporation rate of (2) Sb2S5And Sb2S3Simultaneous vapor deposition of Sb on a substrate2S3A film. More specifically, 0.3 g of Sb was weighed respectively2S3And 0.1 g Sb2S5Powder, the powder is respectively put into two evaporation boats, the distance between a substrate and an evaporation source is 25cm, the substrate does not need to be heated, the rotating speed of a substrate is 20r/min, a vacuum cavity is vacuumized, and the vacuum degree is pumped to 1.0 × 10-3After Pa, turning on an evaporation power supply, rapidly increasing the working current of the two evaporation boats from 0A to 100A simultaneously and then turning onThe baffle is opened for deposition until the two powders are completely evaporated to form Sb with the thickness of about 300nm2S3The film slowly adjusts the evaporation current to 0A, and the molecular pump and the mechanical pump are sequentially closed; finally, filling nitrogen into the vacuum cavity and taking out Sb2S3Film samples. The taken out film is put into a glove box for heat treatment at 280 ℃ for 10 minutes and then is put into Sb2S3Spin-coating a spiro-OMeTAD hole transport layer (3000 r/30 s), and finally evaporating an Ag electrode to form a device structure of FTO/c-TiO2/ Sb2S3a/spiro-OMeTAD/Ag solar cell. The solar cell prepared in this example had the following properties:
1. under the condition of AM1.5 simulated sunlight, the solar cell measured in the room temperature environment presents obvious photovoltaic effect;
2. the prepared solar cell has the open-circuit voltage of 0.57V and the short-circuit current density of 12.04 mA/cm2The fill factor was 40.3%, and the photoelectric conversion efficiency was 2.76%.
In summary, the invention provides a solar cell based on dual-source evaporation and a preparation method thereof, and the solar cell adopts a vacuum dual-source co-evaporation deposition technology and uses Sb2S5And Sb2S3Co-evaporation of Sb as precursor material2S3A film. Compared with the prior art, the Sb of the invention2S3The preparation method of the film has the following advantages: 1. adopts the vacuum double-source co-evaporation deposition technology, has mature process, simple operation and repeatable preparation, improves Sb2S3The film quality and the yield are improved, the utilization rate of raw materials is improved, and the large-area industrialization requirement is met; 2. in the film forming process, the evaporation rates of two evaporation source materials can be accurately controlled, so that the evaporation pressure is changed, and Sb with high component purity and uniform distribution of the film can be prepared by double-source co-evaporation2S3A film; 3. by precise control of Sb2S5And Sb2S3Evaporation current, voltage, power, substrate heating program setting and in-situ annealing conditions of the evaporation source are set, so that the required film thickness and the adjustable film microstructure performance can be obtained easily according to requirements.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of a solar cell based on dual-source evaporation is characterized by comprising the following steps:
providing a substrate comprising a cathode;
forming an electron transport layer on the substrate;
forming Sb on the electron transport layer2S3A film; wherein said Sb2S3And (3) forming a thin film: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, the mass ratio of 0.01: 1 to 1: 0.01, adding said Sb2S5And Sb2S3Respectively putting the two evaporation boats into a co-evaporation device, and enabling Sb to be in a vacuum environment2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3Film of Sb after taking out2S3Annealing the film;
in the Sb2S3Forming a hole transport layer on the film;
an anode is formed on the hole transport layer.
2. The method according to claim 1, wherein the Sb is used for preparing a solar cell by dual-source evaporation2S3The film forming process specifically includes: adopts a vacuum double-source co-evaporation deposition technology with Sb2S5And Sb2S3As a precursor material, Sb2S5And Sb2S3Respectively putting the two evaporation boats into a co-evaporation device, vacuumizing a vacuum cavity, and carrying out vacuum evaporation on the Sb2S5And Sb2S3OfThe transmission rate is controlled so that Sb2S5And Sb2S3Simultaneous vapor deposition of Sb on the electron transport layer2S3A film.
3. The method for preparing the solar cell based on the dual-source evaporation as claimed in claim 2, wherein the vacuum chamber is evacuated until the degree of vacuum in the chamber is 1.0 × 10-3Pa or less.
4. The method as claimed in claim 1, wherein the annealing temperature is about 240-400 ℃.
5. The method according to claim 1, wherein the annealing is performed for 2-30 minutes.
6. A solar cell based on dual-source evaporation comprises a substrate containing a cathode, an electron transport layer and Sb from bottom to top in sequence2S3The thin film, the hole transport layer and the anode are characterized in that the solar cell is prepared by the preparation method of the solar cell based on the dual-source evaporation as claimed in any one of claims 1 to 5.
7. The solar cell based on dual source evaporation according to claim 6, wherein the Sb is2S3The thickness of the film is 50-1000 nm.
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