CN102709348B - A kind of Nanocrystalline/quandot dot sensitive silicon substrate battery piece and preparation method thereof - Google Patents
A kind of Nanocrystalline/quandot dot sensitive silicon substrate battery piece and preparation method thereof Download PDFInfo
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- CN102709348B CN102709348B CN201210189397.4A CN201210189397A CN102709348B CN 102709348 B CN102709348 B CN 102709348B CN 201210189397 A CN201210189397 A CN 201210189397A CN 102709348 B CN102709348 B CN 102709348B
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Abstract
The invention discloses a kind of nanocrystalline/quantum dot sensitized silicon chip solar cell and preparation method thereof, by method coated with nano crystalline substance/quantum dots on silicon based cells sheet such as spraying, spin coating, printings.Nanocrystalline/quantum dot sensitized silicon chip solar cell provided by the invention has the absorptivity of sunlight and electricity conversion is high, reflectivity is low advantage, compared with former silicon based cells sheet, open circuit voltage increases 5% ~ 15%, and density of photocurrent and photoelectric conversion efficiency increase about 10 ~ 60%; Nanocrystalline in the present invention/quantum dot can replace SiN as passivation and antireflection layer and reduce costs in addition, has simple process, the advantage that the reaction time is short, easy large-scale production and application simultaneously.
Description
Technical field
The present invention relates to semiconductor nano/quantum dot light electric material and solar cell, be specifically related to a kind of Nanocrystalline/quandot dot sensitive silicon substrate battery piece and preparation method thereof.
Background technology
Solar energy will become following important energy sources.To 21 century Mo, regenerative resource will account for more than 80% in energy resource structure, and solar power generation will account for more than 60%.
Monocrystaline silicon solar cell is called first generation photovoltaic device, and the highest theoretical conversion efficiencies is about 31-33%, and the most high conversion efficiency in laboratory is about 25%.On market, mass-produced single crystal silicon solar cell average efficiency is about 15%, is that current conversion efficiency is the highest, the photovoltaic device that technology is the most ripe.Dominate in large-scale application and industrial production, occupies more than 90% of current world photovoltaic market.
Although crystal silicon solar batteries has higher photoelectric conversion efficiency, still have a certain distance from theoretical value, there is very large development space.The energy gap of crystalline silicon is 1.12eV, solar photon higher than energy gap is absorbed rear generation hot electron and hole, by Phonon emission subsequently, these hot carriers cooled rapidly before their energy is captured, cause a large amount of solar energies with the form loss of " hot electron ", limit device efficiency.In addition, cell panel has certain reflex, also loses part solar energy.
Battery manufacturers adopts the technology such as surface-texturing, surface etching, emitter region passivation, subregion doping to process to cell panel, improves the photoelectric conversion efficiency of photovoltaic device, reduces light reflection loss; Although the light abstraction width of battery is expanded to some extent, the absorption of solar energy and conversion efficiency are not significantly improved; On crystal silicon material, evaporation SiN antireflective passivating coating also increases production cost greatly.
Nanocrystalline/quantum dot has following features: (1) quantum size effect (2) macro quanta tunnel effect (3) Dielectric confinement effect; And create energy gap modulation by these effects, high extinction coefficient, a lot of characteristic such as large intrinsic dipole moment.These characteristics allow it be considered to photovoltaic device critical material of future generation as light absorber and to cause great concern.So the quantum dot sensitized crystal-silicon battery slice of Appropriate application effectively can increase its absorption to light, reduces reflection, increase density of photocurrent and electricity conversion.
In research process, we pass through coated with nano crystalline substance/quantum dot on a silicon substrate, can reach antireflective, the effect of passivation and sensitization silicon wafer, promote the photoelectric conversion efficiency of cell piece, thus reduce the application cost of silion cell.Secondly, nanocrystalline/quantum dot itself has antireflecting effect, and this technology can replace antireflective coating, reaches good anti-reflective effect, thus can save cost from technique.
The advantage of crystal silicon solar batteries: technical maturity, has good conversion efficiency.The advantage of nanocrystalline/quantum dot with existing silicon wafer solar cell is combined, the conversion efficiency of solar cell can be improved further, and quantum dot can replace silicon nitride and makes antireflective coating in theory, not only antireflective can be reached but also promote the double action of conversion efficiency.
Summary of the invention
The present invention utilizes quantum dot energy gap to modulate, high extinction coefficient, a lot of characteristic such as large intrinsic dipole moment, on the industrial basis of existing crystal silicon solar batteries, growing nano-crystal/quantum dot on silicon based cells sheet, prepare high to the absorption efficiency of solar spectrum, reflectivity is low, density of photocurrent and the high silicon based cells sheet of electricity conversion.
The present invention is achieved by following technical proposals:
A kind of nanocrystalline/quantum dot sensitized silica-based solar cell sheet, by silicon based cells sheet and nanocrystalline/quantum dot coat, described nanocrystalline/growth of quantum dot coat dense uniform ground is on described silicon based cells surface, thickness is between 50 ~ 200nm, nanocrystalline/quantum dot and silicon based cells sheet can form heterojunction, thus effectively transmit wide raw charge carrier and electric charge that nanocrystalline/quantum dot produces.
Described nanocrystalline/quantum dot is one in nano semiconductor material copper sulfide, vulcanized lead, artificial gold, zinc sulphide, molybdenum sulfide, iron sulfide, antimony trisulfide, cadmium sulfide, silver sulfide, nickel sulfide, cadmium selenide and lead selenide, particle diameter is at 5-50nm.
Described silicon based cells sheet is monocrystalline silicon, polysilicon, amorphous silicon or microcrystalline silicon solar cell sheet.
The preparation method of above-mentioned Nanocrystalline/quandot dot sensitive silicon substrate battery piece comprises the following steps:
(1) synthesis of nanocrystalline/quantum dot: the preparation source metal solution of 0.01-0.5mol/L and the sulphur source solution of 0.01-0.5mol/L, according to source metal: the mol ratio in sulphur source is that sulphur source dropwise joins in source metal solution by 1:1-1:3, centrifugation, washing gained solid matter, obtains nanocrystalline/quantum dot; Source metal is the acetate of copper, lead, tin, zinc, molybdenum, iron, antimony, bismuth, cadmium, silver, nickel or cobalt, sulfate, nitrate or hydrochloride, and sulphur source comprises vulcanized sodium, thioacetamide, thiocarbamide and sodium thiosulfate;
(2) nanocrystalline/quantum dot is coated on silicon based cells sheet: by above-mentioned nanocrystalline/quantum dot is dispersed in ethanol, water or acetone soln, and silicon based cells sheet applies 1 ~ 10 layer, often applies after one deck, dry in 60 ~ 80 DEG C of baking ovens;
(3) heat treatment: after having applied, by the silicon based cells sheet heat treatment 3 ~ 10Min in 100 ~ 300 DEG C of baking ovens after nanocrystalline/quantum dot sensitized, grows on silicon based cells surface with making nanocrystalline/quantum dot dense uniform.
Described painting method comprises spraying, spin coating, printing, drips painting and roller coating.
Described silicon based cells sheet is through preliminary treatment:
1) silicon based cells sheet is put into ethanol, acetone or aqueous solvent supersound washing 1 ~ 15min, rinse with water;
2) under 20 ~ 60 DEG C of conditions, with distilled water, H
2o
2with the mixed solution cleaning 5 ~ 15Min of ammoniacal liquor;
3) put into the hydrofluoric acid solution of mass concentration 5% ~ 30%, ultrasonic erosion 2 ~ 15Min, uses ultrapure water.
For regulating the speed of reaction and controlling the pattern of nanocrystalline/quantum dot, surfactant or complexing agent can also be added in source metal solution after adding sulphur source in step (1), such as triethanolamine, EDTA etc., the molar concentration rate of source metal and surfactant is between 1:1 ~ 1:3.
Distilled water, H in step (2)
2o
2be according to distilled water with the mixed solution of ammoniacal liquor: mass fraction is the H of 30%
2o
2: the volume ratio of the ammoniacal liquor of mass fraction 25% ~ 28% is that 2:1:1-9:1:1 joins.
Pass through technique scheme, the invention provides a kind of silicon based cells sheet that absorptivity and electricity conversion are high, reflectivity is low of sunlight, compared with former silicon based cells sheet, open circuit voltage increases 5% ~ 15%, and density of photocurrent and photoelectric conversion efficiency increase about 10 ~ 60%; Nanocrystalline in the present invention/quantum dot can replace SiN as passivation and antireflection layer and reduce costs in addition, has simple process, the advantage that the reaction time is short, easy large-scale production and application simultaneously.
Accompanying drawing explanation
Fig. 1 Nanocrystalline/quandot dot sensitive silicon substrate battery piece structural representation, in figure, 1 is comb electrode, and 2 is quantum dot layer, and 3 is N-type layer, and 4 is P-N junction, and 5 is P-type layer, and 6 is back electrode.
Fig. 2 is embodiment 1 nanocrystalline/quantum dot sensitized crystal-silicon battery slice current-voltage curve figure.
Fig. 3 is embodiment 1 nanocrystalline/quantum dot sensitized crystal-silicon battery slice photoelectric respone power diagram.
Specific embodiments
Pure raw material is analyzed in the raw materials used employing of the present invention.
Embodiment 1
(1) preliminary treatment of silicon chip
First silicon chip vertically being put into absolute ethyl alcohol supersound washing 5min, after rinsing, at room temperature, is the distilled water of 4:1:1: H by volume ratio with water
2o
2(mass concentration 30%): ammoniacal liquor (mass concentration 25%) mixed solution cleaning 5Min, and then the hydrofluoric acid solution vertically put into ethanol is diluted to 30% corrodes, and ultrasonic 5Min, after taking-up, with ultrapure water;
(2) synthesis of nanocrystalline/quantum dot
Compound concentration is that the Schweinfurt green ethanolic solution of 0.05mol/L and the thioacetamide ethanolic solution of 0.05mol/L are as source metal and sulphur source respectively, according to the volume ratio of 1:1,30mL thioacetyl amine aqueous solution is joined in 30mL Schweinfurt green solution with the rate of addition of 20 droplets/minute, add EDTA1.5mmol, reaction 100min, obtain copper sulphide nano crystalline substance/quantum dot solution, centrifugation, gained solid matter water and ethanol replace washing 5 times, obtain pure copper sulphide nano crystalline substance/quantum dot;
(3) coating of nanocrystalline/quantum dot
The copper sulphide nano of above-mentioned synthesis crystalline substance/quantum dot is dispersed in ethanolic solution, on silicon based cells sheet, 5 layers are applied by dripping the method be coated with, often apply one deck dry in 60 DEG C of baking ovens, after having applied, the silicon based cells sheet after nanocrystalline/quantum dot sensitized is processed 5Min in 200 DEG C of baking ovens.
With power be the xenon lamp simulated solar irradiation of 500W as light source, survey its I-V curve with electrochemical workstation, and be converted into photoelectric respone power diagram.As can be seen from accompanying drawing 2, relative to former silicon chip, its open circuit voltage (Voc) is increased to 0.60V from 0.57V, and open circuit voltage adds about 5%.
As can be seen from accompanying drawing 3, relative to former silicon chip, peak power is from 0.019 (mw/cm
2) be increased to 0.025 (mw/cm
2), peak photoelectric respone power adds about 32%, illustrates that the silica-based solar cell photoelectric properties after the quanta point material sensitization of dripping and being coated with significantly improve.
Embodiment 2
The difference of the present embodiment and embodiment 1 is that source metal solution and sulphur source solution in step (2) are respectively the thioacetamide alcoholic solution of lead acetate solution into 0.05mol/L and 0.15M; Coating 5 layers in step (3).
Embodiment 3
The synthesis of a, nanocrystalline/quantum dot
Compound concentration is that the cadmium sulfate solution of 0.05mol/L and the sodium sulfide solution of 0.05M are as source metal and sulphur source respectively, the volume ratio of thioacetyl amine aqueous solution according to 1:1 is slowly joined in cadmium sulfate solution, control the rate of addition of 20/min, CdS nanocrystal/the quantum dot obtained, centrifugation, alternately wash for several times with water and ethanol, obtain CdS nanocrystal/quantum dot.
The preliminary treatment of b, silicon based cells sheet
Silicon based cells sheet vertically being put into absolute ethyl alcohol supersound washing 2-10min, after rinsing, at ambient temperature, is the distilled water of 4:1:1 by ratio: the H of mass fraction 30% with water
2o
2: the ammoniacal liquor mixed solution cleaning 2-10Min of mass fraction 25%, and then the hydrofluoric acid solution vertically put into ethanol is diluted to 30% corrodes, ultrasonic 2-10Min, after taking-up, uses ultrapure water.
C, the coating of nanocrystalline/quantum dot on silicon based cells sheet
CdS nanocrystal/the quantum dot of synthesis is dispersed in ethanolic solution, on silicon based cells sheet, 10 layers are applied by dripping the method be coated with, often apply one deck dry in 60 DEG C of baking ovens, after having applied, the silicon chip after cadmiumsulfide quantum dot sensitized is processed 2-10Min in 200 DEG C of baking ovens.
Embodiment 4
The synthesis of a, nanocrystalline/quantum dot
Compound concentration is that the butter of tin/ethanolic solution of 0.05mol/L and the thioacetamide/ethanolic solution of 0.15M are as source metal and sulphur source respectively, thioacetyl amine aqueous solution is slowly joined in butter of tin solution according to the volume ratio of 1:3, control the rate of addition of 20/min, the artificial gold obtained is nanocrystalline/quantum dot, centrifugation, washing for several times, obtain artificial gold nanocrystalline/quantum dot.
The preliminary treatment of b, silicon based cells sheet
Silicon based cells sheet vertically being put into absolute ethyl alcohol supersound washing 10min, after rinsing, under 50 DEG C of conditions, is the distilled water of 4:1:1 by ratio: the H of mass fraction 30% with water
2o
2: the ammoniacal liquor mixed solution cleaning 10Min of mass fraction 25%, and then the hydrofluoric acid solution vertically put into ethanol is diluted to 30% corrodes, ultrasonic 10Min, after taking-up, uses ultrapure water.
C, the coating of nanocrystalline/quantum dot on silicon based cells sheet
Nanocrystalline for the artificial gold of synthesis/quantum dot is dispersed in ethanolic solution, on silica-based, 5 layers are applied by dripping the method be coated with, often apply one deck dry in 60 DEG C of baking ovens, after having applied, the silicon chip after artificial gold is quantum dot sensitized processes 10Min in 200 DEG C of baking ovens.
Embodiment 5
The synthesis of a, nanocrystalline/quantum dot
Compound concentration is that the zinc acetate solution of 0.05mol/L and the thiourea solution of 0.05M are as source metal and sulphur source respectively, the volume ratio of thiourea solution according to 1:1 is slowly joined in zinc acetate solution, control the rate of addition of 20/min, zinc sulfide nano-crystalline/the quantum dot obtained, centrifugation, washing for several times, obtains ZnS quantum dots.
The preliminary treatment of b, silicon based cells sheet
Silicon based cells sheet vertically being put into absolute ethyl alcohol supersound washing 2-10min, after rinsing, under 50 DEG C of conditions, is the distilled water of 4:1:1 by ratio: the H of mass fraction 30% with water
2o
2: the ammoniacal liquor mixed solution cleaning 2Min of mass fraction 25%, and then the hydrofluoric acid solution vertically put into ethanol is diluted to 30% corrodes, ultrasonic 2Min, after taking-up, uses ultrapure water.
C, the coating of nanocrystalline/quantum dot on silicon based cells sheet
The quantum dot of synthesis being dispersed in ethanolic solution, on silica-based, applying 1 layer by dripping the method be coated with, dry in 60 DEG C of baking ovens, after having applied, the silicon chip after quantum dot sensitized is processed 2Min in 200 DEG C of baking ovens.
Just the present invention will be further described for above embodiment, and be not used to limit patent of the present invention, allly implements for the present invention's equivalence, within the right that all should be contained in patent of the present invention.
Claims (1)
1. the preparation method of a Nanocrystalline/quandot dot sensitive silicon substrate battery piece, described nanocrystalline/quantum dot sensitized silica-based solar cell sheet comprises by silicon based cells sheet and nanocrystalline/quantum dot coat, described nanocrystalline/growth of quantum dot coat dense uniform ground on described silicon based cells surface, thickness is between 50 ~ 200nm; Described nanocrystalline/quantum dot is one in nano semiconductor material copper sulfide, vulcanized lead, artificial gold, zinc sulphide, molybdenum sulfide, iron sulfide, antimony trisulfide, cadmium sulfide, silver sulfide, nickel sulfide, cadmium selenide and lead selenide, particle diameter is at 5-50nm; Described silicon based cells sheet is monocrystalline silicon, polysilicon, amorphous silicon or microcrystalline silicon solar cell sheet; It is characterized in that, described preparation method comprises the following steps:
(1) synthesis of nanocrystalline/quantum dot: the preparation source metal solution of 0.01-0.5mol/L and the sulphur source solution of 0.01-0.5mol/L, according to source metal: the mol ratio in sulphur source is that sulphur source dropwise joins in source metal solution by 1:1-1:3, surfactant is added, source metal: the molar concentration rate of surfactant is 1:1-1:3 after adding sulphur source; Centrifugation, washing gained solid matter, obtains nanocrystalline/quantum dot; Source metal is the acetate of copper, lead, tin, zinc, molybdenum, iron, antimony, bismuth, cadmium, silver, nickel or cobalt, sulfate, nitrate or hydrochloride, and sulphur source comprises vulcanized sodium, thioacetamide, thiocarbamide and sodium thiosulfate;
(2) nanocrystalline/quantum dot is coated on silicon based cells sheet: by above-mentioned nanocrystalline/quantum dot is dispersed in ethanol, water or acetone soln, and silicon based cells sheet applies 1 ~ 10 layer, often applies after one deck, dry in 60 ~ 80 DEG C of baking ovens; Described painting method comprises spraying, spin coating, printing, drips painting and roller coating; Described silicon based cells sheet is through preliminary treatment: silicon based cells sheet is put into ethanol, acetone or aqueous solvent supersound washing 1 ~ 15min, rinse with water; Under 20 ~ 60 DEG C of conditions, with distilled water, H
2o
2with the mixed solution cleaning 5 ~ 15Min of ammoniacal liquor; Distilled water, H
2o
2be according to distilled water with the mixed solution of ammoniacal liquor: mass fraction is the H of 30%
2o
2: the volume ratio of the ammoniacal liquor of mass fraction 25% ~ 28% is that 2:1:1-9:1:1 joins; Put into the hydrofluoric acid solution of mass concentration 5% ~ 30%, ultrasonic erosion 2 ~ 15Min, with ultrapure water;
(3) heat treatment: after having applied, by the silicon based cells sheet heat treatment 3 ~ 10Min in 100 ~ 300 DEG C of baking ovens after nanocrystalline/quantum dot sensitized, grows on silicon based cells surface with making nanocrystalline/quantum dot dense uniform.
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| CN103178126B (en) * | 2013-04-03 | 2016-07-06 | 上海师范大学 | A kind of preparation method of Colloidal Quantum Dots sensitization silica-based solar cell sheet |
| CN103903867B (en) * | 2013-12-19 | 2017-04-12 | 山东精工电子科技有限公司 | Method for preparing CdSe quantum dot sensitization polycrystalline silicon solar cell material |
| CN104538291A (en) * | 2014-12-24 | 2015-04-22 | 上海师范大学 | Method for preparing direct broad-band-gap semiconductor nanocrystalline/Si heterojunction composite crystal silicon wafer |
| CN104600154A (en) * | 2014-12-24 | 2015-05-06 | 上海师范大学 | Preparation method of QDs/Si heterojunction composite crystalline silicon wafer having high quantum efficiency |
| CN106064093B (en) * | 2016-05-20 | 2018-09-07 | 辽宁石油化工大学 | A kind of preparation method of fabricated in situ CuS/WO3 heterojunction photocatalysts |
| WO2021072637A1 (en) * | 2019-10-15 | 2021-04-22 | 诸暨易联众创企业管理服务有限公司 | Silver nanocrystalline/semiconductor quantum dot composite nanomaterial |
| CN114572941B (en) * | 2022-03-01 | 2023-07-21 | 北京师范大学 | Method for preparing copper chalcogenide heterojunction nano-material with excellent LSPR absorption intensity and spectral stability |
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