CN107546289A - A kind of antimony selenide thin-film solar cells and preparation method thereof - Google Patents
A kind of antimony selenide thin-film solar cells and preparation method thereof Download PDFInfo
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- CN107546289A CN107546289A CN201710649458.3A CN201710649458A CN107546289A CN 107546289 A CN107546289 A CN 107546289A CN 201710649458 A CN201710649458 A CN 201710649458A CN 107546289 A CN107546289 A CN 107546289A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of antimony selenide thin-film solar cells and preparation method thereof, wherein battery includes:Conductive substrates, n-layer, p-type layer and electrode, the n-layer are SnO 2 thin film, and the p-type layer is selenizing Sb film.Compared to traditional n-layer cadmium sulfide, the tin oxide that the present invention uses is green non-poisonous, can be used to construct green non-poisonous new antimony selenide thin-film solar cells.And tin oxide energy gap is big, chemical property is stable, can improve extinction of the battery in short-wave band, increases the photoelectric current of battery, and obtain higher device stability.This method is hopeful to obtain efficient green non-poisonous antimony selenide thin-film solar cells.
Description
Technical field
It is thin more particularly, to a kind of antimony selenide the invention belongs to photoelectric material and thin-film solar cells preparation field
Film solar cell and preparation method thereof.
Background technology
Due to current energy shortage and problem of environmental pollution getting worse, people increasingly pay close attention to it is other on the earth can be again
The development and utilization of the raw energy.And in numerous regenerative resources, and it is most with prospects with solar energy, according to statistics, the earth
The solar energy that air, ocean and land absorb is about 3.85 × 10 every year24J, the just generation more complete than 2002 of the solar energy of one hour
The energy summation that boundary uses is more.Electricity can be converted solar energy into based on the solar cell that photovoltaic effect is prepared
Can, and this mode for producing electric energy will not cause environmental pollution in conversion process, and it is very green.At present, silicon substrate
Solar cell occupies most of market share of photovoltaic industry, but silica-based solar with its higher electricity conversion advantage
Energy consumption is larger in process of production for battery, and raw material availability is not high, and can not realize flexibility, is unfavorable for long-run development.
Therefore, we developed a kind of new thin-film solar cells using antimony selenide as light-absorption layer.Antimony selenide
It is a kind of novel photovoltaic material, possesses suitable energy gap 1.17eV, absorptivity is more than 105cm-1, green non-poisonous, valency
Lattice are cheap, and just there is manufacturer production the country.At present, the report about antimony selenide thin-film solar cells is concentrated mainly on cadmium sulfide
Highest electricity conversion on the superstrate structure device of n-layer, to have reported is 5.6%.But cadmium sulfide is a kind of Toxic
Matter, environmental pollution is likely to result in actual use, be detrimental to health, and found during practical study, cadmium
Antimony selenide layer is readily diffused into, causes device performance unstable.
As can be seen here, the stable material of a kind of green non-poisonous and chemical property is found as antimony selenide thin-film solar cells
N-layer the problem of being a urgent need to resolve.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of antimony selenide thin-film solar cells
And preparation method thereof, environmental pollution can be caused by thus solving existing n-layer, be detrimental to health and device performance is unstable
Technical problem.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of antimony selenide thin-film solar cells, bag
Include:Conductive substrates, n-layer, p-type layer and electrode, the n-layer are SnO 2 thin film, and the p-type layer is selenizing Sb film.
Tin oxide is a kind of common compound, possesses suitable position of energy band, larger energy gap (~3.6eV),
Higher carrier mobility, foundation photovoltaic effect principle, there is the possibility of the n-layer as antimony selenide thin-film solar cells
Property, but the relevant report applied it in antimony selenide thin-film solar cells is had no before this.It is green non-poisonous compared to other
Common semiconductor material, such as titanium oxide and zinc oxide, according to relevant report and our existing researchs, titanium oxide is in ultraviolet lighting bar
Property is unstable under part, and zinc oxide is easily and acid reaction, and their energy gap is respectively less than tin oxide, by contrast,
Tin oxide energy gap is bigger and chemical property is stable, is good as one of antimony selenide thin-film solar cells n-layer
Selection.
Further, conductive substrates are transparent conducting glass FTO or ITO electro-conductive glass.
Preferably, conductive substrates are transparent conducting glass FTO.
Further, electrode is carbon electrode or gold electrode.
Preferably, electrode is gold electrode.
It is another aspect of this invention to provide that a kind of preparation method of antimony selenide thin-film solar cells is provided, including:
(1) the stannous chloride aqueous solution is prepared, the hydrochloric acid that 5 to 10 drop mass fractions are 36%~38% is instilled after preparing, is obtained
To precursor solution;
(2) SnO 2 thin film is prepared based on precursor solution, one layer of selenizing Sb film is deposited on SnO 2 thin film, in selenium
Change Sb film and the surface electrode evaporation of conductive substrates.
Due to stannous chloride, facile hydrolysis produces flocculent deposit in water, therefore need to add acid reagent and suppress precipitation generation.For
Avoid introducing other impurity, we have selected hydrochloric acid.
Further, step (2) includes:
(2-1) is based on precursor solution, and it is thin to prepare tin oxide using sol-gal process, sputtering method or spray pyrolysis method
Film;
(2-2) deposits one using thermal evaporation, gas phase transfer sedimentation or quick thermal evaporation on SnO 2 thin film
Layer selenizing Sb film, gold electrode is deposited on the surface of selenizing Sb film and conductive substrates using thermal evaporation.
Step (2-1) is preferably:
SnO 2 thin film is prepared using spray pyrolysis method, thermal station heating-up temperature is 380 DEG C~530 DEG C, the heat time is 5~
15min, after precursor solution loading spray gun is sprayed, made annealing treatment, annealing temperature is 380 DEG C~530 DEG C, annealing
Time is 20~40min.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect:
(1) present invention has been firstly introduced n-layer of the tin oxide as antimony selenide thin-film solar cells, obtains green nothing
Malicious and high stability battery device, environmental pollution can be caused by thus solving existing cadmium sulfide n-layer, be detrimental to health
And cause the unstable technical problem of device performance.Tin oxide possesses suitable position of energy band, can form type I with antimony selenide
Type pn-junction;Larger energy gap (~3.6eV), it is less in the extinction of short wavelength's section compared to cadmium sulfide, it can thus improve electricity
The photoelectric current in pond;Higher carrier mobility (> 10cm2V-1s-1), be advantageous to the transmission of carrier;And than cadmium sulfide more
Stable chemical property, the stability of device can be improved.The invention provides the preparation method of a set of SnO 2 thin film, using this
The SnO 2 thin film that method is prepared can be as the n-layer of antimony selenide thin-film solar cells.The present invention is finally obtained efficiency
The antimony selenide thin-film solar cells using tin oxide as the non-toxic stable of cushion more than 3%.
(2) preferably, SnO 2 thin film is prepared using spray pyrolysis method, thermal station heating-up temperature is 380 DEG C~530 DEG C, is added
The hot time is 5~15min, after precursor solution loading spray gun is sprayed, is made annealing treatment, annealing temperature is 380 DEG C
~530 DEG C, annealing time is 20~40min, thus film quality battery that is good, and then preparing that the present invention prepares
Device performance stability is good and photoelectric transformation efficiency is high.
Brief description of the drawings
Fig. 1 is a kind of device junction composition for antimony selenide thin-film solar cells that the embodiment of the present invention 1 provides;
Fig. 2 is the X ray diffracting spectrum for the SnO 2 thin film that the embodiment of the present invention 1 provides;
Fig. 3 is the surface pattern for the SnO 2 thin film that the embodiment of the present invention 1 provides;
Fig. 4 (a) is that the combination that the embodiment of the present invention 1 provides can be in the X ray of the SnO 2 thin film of 480eV-500eV scopes
Photoelectron spectroscopy;
Fig. 4 (b) is that the combination that the embodiment of the present invention 1 provides can be in the X ray of the SnO 2 thin film of 528eV-534eV scopes
Photoelectron spectroscopy;
Fig. 5 is the cross section pattern for the battery device that the embodiment of the present invention 1 provides;
Fig. 6 is that the Current density-voltage for the antimony selenide thin-film solar cells that the embodiment of the present invention 1 provides is efficiency song
Line;
Fig. 7 is storage stability of the unencapsulated battery of the offer of the embodiment of the present invention 1 under dark condition;
Fig. 8 is the battery and device of the conventional batteries under lasting AM 1.5G illumination conditions that the embodiment of the present invention 1 provides
The comparison diagram of stability.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
As shown in figure 1, a kind of antimony selenide thin-film solar cells, including:Conductive substrates, n-layer, p-type layer and electrode, institute
It is SnO 2 thin film to state n-layer, and the p-type layer is selenizing Sb film.
Tin oxide is a kind of common compound, possesses suitable position of energy band, larger energy gap (~3.6eV),
Higher carrier mobility, foundation photovoltaic effect principle, there is the possibility of the n-layer as antimony selenide thin-film solar cells
Property, but the relevant report applied it in antimony selenide thin-film solar cells is had no before this.It is green non-poisonous compared to other
Common semiconductor material, such as titanium oxide and zinc oxide, according to relevant report and our existing researchs, titanium oxide is in ultraviolet lighting bar
Property is unstable under part, and zinc oxide is easily and acid reaction, and their energy gap is respectively less than tin oxide, by contrast,
Tin oxide energy gap is bigger and chemical property is stable, is good as one of antimony selenide thin-film solar cells n-layer
Selection.
The present invention has been firstly introduced n-layer of the tin oxide as antimony selenide thin-film solar cells, obtains green non-poisonous
And the battery device that stability is high, environmental pollution can be caused by thus solving existing cadmium sulfide n-layer, be detrimental to health and
Cause the technical problem that device performance is unstable.The invention provides the preparation method of a set of SnO 2 thin film, using this method
The SnO 2 thin film prepared can be as the n-layer of antimony selenide thin-film solar cells.
Conductive substrates are transparent conducting glass FTO or ITO electro-conductive glass.Preferably, conductive substrates are electrically conducting transparent glass
Glass FTO.
Electrode is carbon electrode, platinum electrode or gold electrode.Preferably, electrode is gold electrode.
Embodiment 1
The first step, using be cleaned by ultrasonic method, in accordance with the following steps be cleaned by ultrasonic ITO or FTO glass, each step 30min,
Heating-up temperature is 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, nitrogen is used
Drying.
Second step, SnO 2 thin film is prepared using spray pyrolysis method.0.285g stannous chlorides are weighed, it is molten to arrive 20mL deionizations
In water, then the hydrochloric acid that 5 drop mass fractions are 36% is instilled, rocking makes its uniform dissolution, by 5cm × 5cm of wash clean FTO glass
Glass is put into thermal station, and regulation thermal station temperature to 400 DEG C and preheats 10min, and precursor solution loading spray gun is sprayed, sprayed
After the completion of, it is 480 DEG C constant to keep thermal station temperature, carries out 30min annealing, closes thermal station afterwards, makes its natural cooling.
3rd step, selenizing Sb film is deposited using quick thermal evaporation.The antimony selenide powder for weighing 0.38g is positioned over evaporation
Source, it is that 30s rises to 300 DEG C from room temperature to set evaporation procedure, 550 DEG C is warming up in 300 DEG C of insulations 900s, 30s, 550 DEG C of depositions
35s, device can be taken out by being cooled to less than 180 DEG C.
4th step, using thermal evaporation, gold electrode is deposited on antimony selenide surface and FTO.
The X ray diffracting spectrum for the SnO 2 thin film that the embodiment of the present invention 1 obtains is as shown in Fig. 2 surface pattern such as Fig. 3 institutes
Show, x-ray photoelectron power spectrum is as shown in Figure 4.The cross section for the solar cell that embodiment 1 obtains is as shown in figure 5, wherein selenizing
Antimony layer is about 612nm thickness, and stannic oxide layer is about 60nm thickness, and performance test is carried out to it, the current density voltage curve that measures and
Parameters as shown in fig. 6, storage stability result under dark condition of unencapsulated battery as shown in fig. 7, with it is traditional
Using the comparing result of device stability of the cadmium sulfide as the selenizing antimony battery of n-layer under lasting AM 1.5G illumination conditions such as
Shown in Fig. 8, as seen from the figure, compared to traditional selenizing antimony battery using cadmium sulfide as n-layer, the selenium using tin oxide as n-layer
It is more preferable to change stability of the antimony battery under illumination condition.
Embodiment 2
The first step, using method is cleaned by ultrasonic, it is cleaned by ultrasonic FTO glass, each step 30min, heating temperature in accordance with the following steps
Spend for 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, dried up with nitrogen.
Second step, SnO 2 thin film is prepared using spray pyrolysis method.0.285g stannous chlorides are weighed, it is molten to arrive 20mL deionizations
In water, then the hydrochloric acid that 7 drop mass fractions are 37% is instilled, rocking makes its uniform dissolution, by clean 5cm × 5cm FTO glass
It is put into thermal station, regulation thermal station temperature to 430 DEG C and preheats 9min, and precursor solution loading spray gun is sprayed, sprayed
Cheng Hou, it is 430 DEG C constant to keep thermal station temperature, carries out 25min annealing, closes thermal station afterwards, makes its natural cooling.
3rd step, selenizing Sb film is deposited using quick thermal evaporation.The antimony selenide powder for weighing 0.38g is positioned over evaporation
Source, it is that 30s rises to 300 DEG C from room temperature to set evaporation procedure, 550 DEG C is warming up in 300 DEG C of insulations 900s, 30s, 550 DEG C of depositions
35s, device can be taken out by being cooled to less than 180 DEG C.
4th step, using thermal evaporation, gold electrode is deposited on antimony selenide surface and FTO.
Embodiment 3
The first step, using be cleaned by ultrasonic method, in accordance with the following steps be cleaned by ultrasonic ITO or FTO glass, each step 30min,
Heating-up temperature is 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, nitrogen is used
Drying.
Second step, SnO 2 thin film is prepared using spray pyrolysis method.0.285g stannous chlorides are weighed, it is molten to arrive 20mL deionizations
In water, then the hydrochloric acid that 10 drop mass fractions are 38% is instilled, rocking makes its uniform dissolution, by 5cm × 5cm of wash clean FTO
Glass is put into thermal station, and regulation thermal station temperature to 380 DEG C and preheats 15min, and precursor solution loading spray gun is sprayed, sprayed
After the completion of painting, it is 380 DEG C constant to keep thermal station temperature, carries out 40min annealing, closes thermal station afterwards, makes it naturally cold
But.
3rd step, selenizing Sb film is deposited using quick thermal evaporation.The antimony selenide powder for weighing 0.38g is positioned over evaporation
Source, it is that 30s rises to 300 DEG C from room temperature to set evaporation procedure, 550 DEG C is warming up in 300 DEG C of insulations 900s, 30s, 550 DEG C of depositions
35s, device can be taken out by being cooled to less than 180 DEG C.
4th step, using thermal evaporation, gold electrode is deposited on antimony selenide surface and FTO.
Embodiment 4
The first step, using be cleaned by ultrasonic method, in accordance with the following steps be cleaned by ultrasonic ITO or FTO glass, each step 30min,
Heating-up temperature is 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, nitrogen is used
Drying.
Second step, SnO 2 thin film is prepared using spray pyrolysis method.0.285g stannous chlorides are weighed, it is molten to arrive 20mL deionizations
In water, then the hydrochloric acid that 5 drop mass fractions are 36% is instilled, rocking makes its uniform dissolution, by 5cm × 5cm of wash clean FTO glass
Glass is put into thermal station, and regulation thermal station temperature to 530 DEG C and preheats 5min, and precursor solution loading spray gun is sprayed, sprayed
After the completion of, it is 530 DEG C constant to keep thermal station temperature, carries out 20min annealing, closes thermal station afterwards, makes its natural cooling.
3rd step, selenizing Sb film is deposited using quick thermal evaporation.The antimony selenide powder for weighing 0.38g is positioned over evaporation
Source, it is that 30s rises to 300 DEG C from room temperature to set evaporation procedure, 550 DEG C is warming up in 300 DEG C of insulations 900s, 30s, 550 DEG C of depositions
35s, device can be taken out by being cooled to less than 180 DEG C.
4th step, using thermal evaporation, gold electrode is deposited on antimony selenide surface and FTO.
Embodiment 5
The first step, using be cleaned by ultrasonic method, in accordance with the following steps be cleaned by ultrasonic ITO or FTO glass, each step 30min,
Heating-up temperature is 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, nitrogen is used
Drying.
Second step, based on precursor solution, SnO 2 thin film is prepared using sol-gal process;Aoxidized using thermal evaporation
One layer of selenizing Sb film is deposited on tin thin film, using thermal evaporation in selenizing Sb film and the surface gold evaporation electricity of conductive substrates
Pole.
Embodiment 6
The first step, using be cleaned by ultrasonic method, in accordance with the following steps be cleaned by ultrasonic ITO or FTO glass, each step 30min,
Heating-up temperature is 20-50 DEG C:Liquid detergent+deionized water, acetone, isopropanol, ethanol, deionized water.After cleaning, nitrogen is used
Drying.
Second step, based on precursor solution, SnO 2 thin film is prepared using sputtering method;Sedimentation is shifted in oxygen using gas phase
Change and one layer of selenizing Sb film is deposited on tin thin film, using thermal evaporation in selenizing Sb film and the surface gold evaporation electricity of conductive substrates
Pole.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (8)
- A kind of 1. antimony selenide thin-film solar cells, it is characterised in that including:Conductive substrates (1), n-layer (2), p-type layer (3) With electrode (4), the n-layer (2) is SnO 2 thin film, and the p-type layer (3) is selenizing Sb film.
- 2. a kind of antimony selenide thin-film solar cells as claimed in claim 1, it is characterised in that the conductive substrates (1) are Transparent conducting glass FTO or ITO electro-conductive glass.
- 3. a kind of antimony selenide thin-film solar cells as claimed in claim 2, it is characterised in that the conductive substrates (1) are Transparent conducting glass FTO.
- 4. a kind of antimony selenide thin-film solar cells as claimed in claim 1, it is characterised in that the electrode (4) is carbon electricity Pole or gold electrode.
- 5. a kind of antimony selenide thin-film solar cells as claimed in claim 4, it is characterised in that the electrode (4) is gold electricity Pole.
- A kind of 6. preparation method of antimony selenide thin-film solar cells described in claim 1-5 any one, it is characterised in that Including:(1) the stannous chloride aqueous solution is prepared, the hydrochloric acid that 5 to 10 drop mass fractions are 36%~38% is instilled after preparing, before obtaining Drive liquid solution;(2) SnO 2 thin film is prepared based on precursor solution, one layer of selenizing Sb film is deposited on SnO 2 thin film, in antimony selenide The surface electrode evaporation of film and conductive substrates.
- A kind of 7. preparation method of antimony selenide thin-film solar cells as claimed in claim 6, it is characterised in that the step (2) include:(2-1) is based on precursor solution, and SnO 2 thin film is prepared using sol-gal process, sputtering method or spray pyrolysis method;(2-2) deposits one layer of selenium using thermal evaporation, gas phase transfer sedimentation or quick thermal evaporation on SnO 2 thin film Change Sb film, gold electrode is deposited on the surface of selenizing Sb film and conductive substrates using thermal evaporation.
- A kind of 8. preparation method of antimony selenide thin-film solar cells as claimed in claim 7, it is characterised in that the step (2-1) is preferably:SnO 2 thin film is prepared using spray pyrolysis method, thermal station heating-up temperature is 380 DEG C~530 DEG C, the heat time is 5~ 15min, after precursor solution loading spray gun is sprayed, made annealing treatment, annealing temperature is 380 DEG C~530 DEG C, annealing Time is 20~40min.
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CN113013286A (en) * | 2021-01-27 | 2021-06-22 | 西北工业大学深圳研究院 | Antimony selenide film with high (hk1) crystal face abundance, antimony selenide film solar cell and preparation method thereof |
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CN109671848B (en) * | 2018-12-12 | 2020-05-19 | 华中科技大学 | CuPbSbS3Novel thin-film solar cell and preparation method thereof |
CN110137272A (en) * | 2019-05-14 | 2019-08-16 | 西北工业大学深圳研究院 | A kind of preparation method of the solar battery of alcohol steam after annealing processing antimony trisulfide base film |
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