CN102208461A - Solar cell and preparation method thereof - Google Patents

Solar cell and preparation method thereof Download PDF

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Publication number
CN102208461A
CN102208461A CN2010101383243A CN201010138324A CN102208461A CN 102208461 A CN102208461 A CN 102208461A CN 2010101383243 A CN2010101383243 A CN 2010101383243A CN 201010138324 A CN201010138324 A CN 201010138324A CN 102208461 A CN102208461 A CN 102208461A
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transition zone
solar cell
electrode
semi
layer
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CN102208461B (en
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周明杰
黄杰
汪磊
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a solar cell and a preparation method thereof. The solar cell comprises a substrate, a first electrode, a first transitional layer, an optical activity layer, a second transitional layer and a second electrode which are arranged in sequence, wherein the first transitional layer and the second transitional layer are semiconductor layers in which carriers with different properties are transmitted; the optical activity layer comprises a substrate layer and columns arranged on the substrate layer in the form of an array; and the second transitional layer is filled between the cylinders and provided with a surface layer which is higher than the end surfaces of the cylinders. The solar cell is obtained by preparing each layer of material on the substrate. In the invention, because a two-dimensional photonic crystal structure is formed on the solar cell, the absorption of sunlight is enhanced and the photoelectric conversion efficiency is improved without increasing optical activity thickness. The preparation method disclosed by the invention has the advantages of simple process and no pollution and is beneficial for industrial production.

Description

Solar cell and preparation method thereof
Technical field
The present invention relates to energy technology field, relate in particular to a kind of solar cell and preparation method thereof.
Background technology
Along with the development of society, environmental pollution is more and more serious, and the energy demand of countries in the world is in rapid increase.Under these circumstances, the clean energy technology of economical and efficient receives much concern.Solar energy is regarded as one of energy of the most promising reproducible utilization, and is comparatively ripe based on the solar battery technology of semiconductors such as silicon, but the cost of these solar cells is still higher at present, can only use in more among a small circle.Make solar energy obtain large-scale promotion, just must develop more cheap solar cell material and technology, reduce the cost of solar cell.
Compare with the inorganic silicon solar cell, organic solar batteries has plurality of advantages, and it is all better that the synthetic cost of organic material is low on the one hand, function is easy to modulation, pliability and film forming; The manufacturing process of organic solar batteries does not need to relate to thin-film technique and expensive physics or chemical process means such as inorganic matter sputter, chemical vapour deposition (CVD), high purity silicon crystal growth preparation, doping on the other hand, can realize the large tracts of land manufacturing by film techniques such as spin coating or inkjet printings, process is simple relatively, can use flexible substrate, environmental friendliness, light portable, cost of manufacture are also lower.
Though organic solar batteries has above advantage, low the remaining of its photoelectric conversion efficiency realized business-like a great problem.The thickness of photoactive layer increases in the organic solar batteries, just can increase the propagation path of sunlight in photoactive layer, increases the absorption to light, thereby improves photoelectric conversion efficiency.But after photoactive layer thickness increased, the The built-in electric field can diminish, and causes the exciton in the photoactive layer to be difficult to be separated into free carrier, and free carrier is reduced, and reduced the photoelectric conversion efficiency of solar cell.Therefore, how under the condition that does not increase photoactive layer thickness, to strengthen the absorption of solar cell, thereby improve photoelectric conversion efficiency, just become a problem demanding prompt solution sunlight.
Summary of the invention
The technical problem to be solved in the present invention is, at the above-mentioned defective of prior art, providing a kind of does not increase photoactive layer thickness and strengthen the solar cell that sunlight is absorbed.
The technical problem that the present invention further will solve is, a kind of preparation method of solar cell also is provided.
In order to reach above-mentioned purpose, according to the present invention, a kind of solar cell is provided, comprise the substrate, first electrode, first transition zone, photoactive layer, second transition zone, second electrode that set gradually, described first transition zone and second transition zone are the semiconductor layer of transmission charge carrier different in kind, described photoactive layer comprises basalis and the cylinder of the array arrangement that forms on described basalis, described second transition zone is filled between the described cylinder and has the superficial layer that exceeds described cylinder end face.
In solar cell of the present invention, preferably, described photoactive layer is mixed and made into by electron donor material and electron acceptor material.
In solar cell of the present invention, described ground, described first transition zone and second transition zone are the semiconductor layer of transmission charge carrier different in kind, when described first transition zone is when having the material of cavity transmission ability, described second transition zone is the material with electron transport ability, when described first transition zone is when having the material of electron transport ability, described second transition zone is the material with cavity transmission ability.
In solar cell of the present invention, preferably, described second electrode is the metal film electrode that Ag or Au make, and described first transition zone is by TiO x, Cs 2CO 3, ZnO or SnO 2Make, described second transition zone is by PEDOT:PSS, NiO, MoO 3, V 2O 5, WO 3Or the poly-wolframic acid of peroxide is made.
In solar cell of the present invention, preferably, described second electrode is the metal film electrode that Al, Ca or Ba make, and described first transition zone is by PEDOT:PSS, NiO, MoO 3, V 2O 5, WO 3Or the poly-wolframic acid of peroxide makes, and described second transition zone is by TiO x, Cs 2CO 3, ZnO or SnO 2Make.
In solar cell of the present invention, preferably, described first electrode is FTO or ito thin film electrode.
In solar cell of the present invention, preferably, described substrate is a transparent substrates.
In order to reach above-mentioned purpose, according to the present invention, also provide a kind of preparation method of solar cell, may further comprise the steps:
1. with light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms first electrode, cleans oven dry;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on first electrode cools off as first transition zone;
3. on first transition zone mixed layer of spin coating one deck electron donor material and electron acceptor material as the basalis of photoactive layer, and utilize PRINT (Pattern Replication In Non-wettingTemplates) method on basalis, to prepare the cylinder of the array arrangement of photoactive layer, the formation photoactive layer that is heating and curing, cooling;
4. the semi-conducting material that utilizes sol-gel process will have electric transmission or cavity transmission ability is filled in the space between the cylinder of array arrangement, and the semi-conducting material that preparation one deck has electric transmission or cavity transmission ability above cylinder, be heating and curing and form second transition zone, cooling, when described first transition zone is when having the semi-conducting material of cavity transmission ability, described second transition zone is the semi-conducting material with electron transport ability, when described first transition zone is when having the semi-conducting material of electron transport ability, described second transition zone is the semi-conducting material with cavity transmission ability;
5. the evaporation metal membrane electrode is as second electrode on second transition zone, and annealing obtains solar cell.
In the solar cell of the present invention, the photoactive layer and second transition zone are alternately distributed, and have formed two-dimensional photon crystal structure.2 D photon crystal is a kind of structure that is formed by the different two media alternate cycle arrangement of refractive index, and its energy gap is main relevant with the refringence of two media.Under the constant situation of other condition, the medium refraction rate variance that changes photonic crystal can change its energy gap.When difference diminished, the width of forbidden photon band can reduce.When difference increased, the width of forbidden photon band also can increase.Because the existence of photonic crystal band, the light that frequency drops in the forbidden band can not be propagated therein, will be reflected back.Therefore, this structure can make that part of light that has little time to be absorbed by photoactive layer repeatedly reflex to again in the photoactive layer, increases the absorption to sunlight, improves photoelectric conversion efficiency.The two-dimensional photon crystal structure that the present invention forms by the photoactive layer and second transition zone, can realize specific band even all band sun reflection of light, under the situation that does not increase photoactive layer thickness, strengthen it to the absorbing of sunlight, thereby improve the photoelectric conversion efficiency of solar cell.
In the solar cell of the present invention, first transition zone and second transition zone have played the effect of transmission charge carrier, are beneficial to the free carrier that produces in the photoactive layer and are transferred in the electrode apace by it, and have the function that stops exciton.
The preparation method of solar cell of the present invention, technology is simple, with low cost, pollution-free, is beneficial to suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the structural representation of solar cell of the present invention;
Fig. 2 is the structural representation of the photoactive layer of solar cell of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further described in detail below in conjunction with drawings and Examples.
Fig. 1 is the structural representation of solar cell of the present invention.As shown in Figure 1, solar cell of the present invention comprises substrate 10, first electrode 20, second electrode 30, first transition zone 40, second transition zone 50 and photoactive layer 60.First electrode 20 is positioned on the substrate 10, is first transition zone 40 above it, is photoactive layer 60 then, and the photoactive layer 60 and second transition zone 50 form two-dimensional photon crystal structure, are second electrode 30 on second transition zone 50.Draw lead connection electrical equipment respectively from first electrode 20 and second electrode 30, under irradiation of sunlight, solar cell of the present invention can make its work to the electrical equipment output voltage.
Substrate 10 is a transparent substrates, so long as light transmissive material make all can, as glass, metal, silicon, plastics or organic synthesis material etc.
The 20 preferred uses of first electrode can make the transparency electrode of light transmission, and as the electrode that conducting metal oxides such as FTO, ITO are made, its male or female as solar cell uses.
Second electrode 30 uses metal film electrodes, and its male or female as solar cell uses, and constitutes the two poles of the earth of solar cell with first electrode 20.Second electrode 30 is divided into two classes according to the height of its material work function, and a class is the metal with high work function, and as Ag, Au etc., another kind of is the metal with low work function, as Al, Ca, Ba etc.
First transition zone 40 and second transition zone 50 have the effect of transmission charge carrier, can make the free carrier that produces in the photoactive layer be transferred to electrode one end fast by it, and can partly stop exciton.First transition zone 40 and second transition zone, 50 employed materials are different according to transmission charge carrier character, are divided into two classes, and the I class has electron transport ability, as TiO x, Cs 2CO 3, ZnO, SnO 2Deng, the II class has cavity transmission ability, as PEDOT:PSS, NiO, MoO 3, V 2O 5, WO 3, the poly-wolframic acid of peroxide etc.First transition zone, the 40 preferred materials that use with good light transmittance.The different in kind of first transition zone 40 and second transition zone, 50 transmission charge carriers, even the I class material of first transition zone 40 for having electron transport ability, then the II class material of second transition zone 50 for having cavity transmission ability; Otherwise, if the II class material of first transition zone 40 for having cavity transmission ability, then the I class material of second transition zone 50 for having electron transport ability.
When second electrode 30 had the metal of high work function for the first kind, first transition zone 40 was an I class material, and second transition zone 50 is an II class material; When second electrode 30 is second class when having the metal of low work function, first transition zone 40 is an II class material, and second transition zone 50 is an I class material.
Photoactive layer 60 is that solar cell absorbs the main region that sunlight produces photoelectric current and photovoltage, mix in proportion by electron donor material and electron acceptor material, electron donor material can have the donor material of the electronic capability of providing for phthalocyanine dye, pentacene, porphyrin compound, cyanine dyes etc., and electron acceptor material can be PTCDA, C 60, C 70, acceptor material with the electronic capability accepted such as perylene and derivative thereof.
Fig. 2 is the structural representation of the photoactive layer of solar cell of the present invention.As shown in Figure 2, photoactive layer 60 comprises a basalis (not shown) and the cylinder of the array arrangement that forms on the surface of basalis, the cycle of the column structure of array arrangement (distance between the axis of adjacent two cylinders) is d, and the bottom surface diameter of cylinder is r, and the height of cylinder is h.Second transition zone 50 is filled in the space between the cylinder of array arrangement, and the height h that exceeds cylinder forms plane superficial layer above the cylinder of array arrangement.Second transition zone 50 and active layer 60 are alternately arranged, and form the two-dimensional photon crystal structure with periodic structure, reflect light to the absorption that strengthens 60 pairs of sunlights of photoactive layer in the active layer 60, have improved the photoelectric conversion efficiency of solar cell.
Preparation method's step of solar cell of the present invention is as follows:
1. with light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms first electrode, cleans oven dry;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on first electrode cools off as first transition zone;
3. the mixed layer of spin coating one deck electron donor material and electron acceptor material and utilizes the PRINT method to prepare the cylinder of the array arrangement of photoactive layer on basalis as the basalis of photoactive layer on first transition zone, the formation photoactive layer that is heating and curing, cooling;
4. the semi-conducting material that utilizes sol-gel process will have electric transmission or cavity transmission ability is filled in the space between the cylinder of array arrangement, and the semi-conducting material that preparation one deck has electric transmission or cavity transmission ability above cylinder, be heating and curing and form second transition zone, cooling, when described first transition zone is when having the semi-conducting material of cavity transmission ability, described second transition zone is the semi-conducting material with electron transport ability, when described first transition zone is when having the semi-conducting material of electron transport ability, described second transition zone is the semi-conducting material with cavity transmission ability;
5. the evaporation metal membrane electrode is as second electrode on second transition zone, and annealing obtains solar cell.
Embodiment 1
1. the quartz glass that with thickness is 1.1mm plates the ito thin film that a layer thickness is 150nm as substrate in a side of substrate, and square resistance is 15 Ω/sides, and is etched into needed stripe,, cleans oven dry as first electrode;
2. the thick TiO of spin coating one deck 60nm on first electrode that cleans up xLayer and is transferred in the glove box as first transition zone, in 150 ℃ of heating 30min, cooling;
3. spin coating one layer thickness is the photoactive layer basalis of 40nm on first transition zone, photoactive layer solution is the toluene solution of the P3HT:PCBM of 18mg/mL, wherein, the quality of PCBM is 44% of a gross mass, utilizing PRINT method continuation manufacturing cycle d on the photoactive layer basalis then is that 180nm, height h are the cylindrical-array of the periodic arrangement of 150nm for 350nm, bottom surface diameter r, and in 120 ℃ of heating 25min, cooling;
4. utilize sol-gel process that the poly-wolframic acid of peroxide is filled in the space of cylindrical-array, and the peroxide of spin coating one deck 50nm gathers wolframic acid above cylinder, form second transition zone, cooling in 180 ℃ of heating 30min;
5. deposit thickness is the Ag film of 70nm on second transition zone, as second electrode, and at 120 ℃ of annealing in process 5min.
In the present embodiment, with ito thin film is first electrode (negative electrode), the Ag film is second electrode (anode), photoactive layer and transition zone are clipped between two electrodes, owing to use torpescence metal A g as electrode, electrode is stable, and airborne oxygen, steam etc. also are difficult to enter photoactive layer, have improved the stability of solar cell device.
Embodiment 2
1. the quartz glass that with thickness is 1.1mm plates the ito thin film that a layer thickness is 15nm as substrate in a side of substrate, and square resistance is 15 Ω/sides, and is etched into needed stripe,, cleans oven dry as first electrode (negative electrode);
2. the PEDOT:PSS conducting polymer thin film that spin coating one deck 50nm is thick on first electrode that cleans up is as first transition zone, and is transferred in the glove box, in 150 ℃ of heating 30min, cooling;
3. spin coating one layer thickness is the photoactive layer basalis of 35nm on first transition zone, photoactive layer solution is the toluene solution of the P3HT:PCBM of 20mg/mL, wherein, the quality of PCBM is 50% of a gross mass, utilizing PRINT method continuation manufacturing cycle d on the photoactive layer basalis then is that 150nm, height h are the cylindrical-array of the periodic arrangement of 100nm for 400nm, bottom surface diameter r, and in 120 ℃ of heating 20min, cooling;
4. utilize sol-gel process that the poly-wolframic acid of peroxide is filled in the space of cylindrical-array, and above cylinder the ZnO film of spin coating one deck 50nm, form second transition zones for 20 ℃ in 180 ℃ of heating, cooling;
5. deposit thickness is the Al film of 100nm on second transition zone, as second electrode, and at 120 ℃ of annealing in process 10min.
The above only is representative embodiment of the present invention, does not limit the present invention in any way, and all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces or improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. solar cell, it is characterized in that, comprise the substrate, first electrode, first transition zone, photoactive layer, second transition zone, second electrode that set gradually, described first transition zone and second transition zone are the semiconductor layer of transmission charge carrier different in kind, described photoactive layer comprises basalis and the cylinder of the array arrangement that forms on described basalis, described second transition zone is filled between the described cylinder and has the superficial layer that exceeds described cylinder end face.
2. solar cell according to claim 1 is characterized in that described photoactive layer is mixed and made into by electron donor material and electron acceptor material.
3. solar cell according to claim 1, it is characterized in that, when described first transition zone is when having the semi-conducting material of cavity transmission ability, described second transition zone is the semi-conducting material with electron transport ability, when described first transition zone is when having the semi-conducting material of electron transport ability, described second transition zone is the semi-conducting material with cavity transmission ability.
4. solar cell according to claim 3 is characterized in that, described second electrode is the metal film electrode that Ag or Au make.
5. solar cell according to claim 4 is characterized in that, described first transition zone is by TiO x, Cs 2CO 3, ZnO or SnO 2Make, affiliated second transition zone is by PEDOT:PSS, NiO, MoO3, V2O5, WO 3Or the poly-wolframic acid of peroxide is made.
6. solar cell according to claim 3 is characterized in that, described second electrode is the metal film electrode that Al, Ca or Ba make.
7. solar cell according to claim 6 is characterized in that, described first transition zone is by PEDOT:PSS, NiO, MoO 3, V 2O 5, WO 3Or the poly-wolframic acid of peroxide makes, and described second transition zone is by TiO x, Cs 2CO 3, ZnO or SnO 2Make.
8. solar cell according to claim 1 is characterized in that, described first electrode is FTO or ito thin film electrode.
9. solar cell according to claim 1 is characterized in that, described substrate is a transparent substrates.
10. the preparation method of a solar cell is characterized in that, may further comprise the steps:
1. with light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms first electrode, cleans oven dry;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on first electrode cools off as first transition zone;
3. the mixed layer of spin coating one deck electron donor material and electron acceptor material and utilizes the PRINT method to prepare the cylinder of the array arrangement of photoactive layer on basalis as the basalis of photoactive layer on first transition zone, the formation photoactive layer that is heating and curing, cooling;
4. the semi-conducting material that utilizes sol-gel process will have electric transmission or cavity transmission ability is filled in the space between the cylinder of array arrangement, and the semi-conducting material that preparation one deck has electric transmission or cavity transmission ability above cylinder, be heating and curing and form second transition zone, cooling, when described first transition zone is when having the semi-conducting material of cavity transmission ability, described second transition zone is the semi-conducting material with electron transport ability, when described first transition zone is when having the semi-conducting material of electron transport ability, described second transition zone is the semi-conducting material with cavity transmission ability;
5. the evaporation metal membrane electrode is as second electrode on second transition zone, and annealing obtains solar cell.
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Cited By (4)

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WO2013078581A1 (en) * 2011-11-28 2013-06-06 海洋王照明科技股份有限公司 Polymer solar cell device and method for preparing same
CN104051657A (en) * 2013-03-12 2014-09-17 海洋王照明科技股份有限公司 Composite anode and preparation method thereof, and organic light-emitting device and preparation method thereof
CN106471687A (en) * 2014-02-28 2017-03-01 国立研究开发法人科学技术振兴机构 Heat radiation light source and 2 D photon crystal used in this light source
CN108899432A (en) * 2018-07-09 2018-11-27 上海大学 A kind of preparation method of organic electroluminescent and integrated photovoltaic device

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013078581A1 (en) * 2011-11-28 2013-06-06 海洋王照明科技股份有限公司 Polymer solar cell device and method for preparing same
CN104011892A (en) * 2011-11-28 2014-08-27 海洋王照明科技股份有限公司 Polymer solar cell device and method for preparing same
CN104011892B (en) * 2011-11-28 2016-08-24 海洋王照明科技股份有限公司 High polymer solar cell device and preparation method thereof
CN104051657A (en) * 2013-03-12 2014-09-17 海洋王照明科技股份有限公司 Composite anode and preparation method thereof, and organic light-emitting device and preparation method thereof
CN106471687A (en) * 2014-02-28 2017-03-01 国立研究开发法人科学技术振兴机构 Heat radiation light source and 2 D photon crystal used in this light source
CN106471687B (en) * 2014-02-28 2019-02-19 国立研究开发法人科学技术振兴机构 Heat radiation light source and the 2 D photon crystal used in the light source
CN108899432A (en) * 2018-07-09 2018-11-27 上海大学 A kind of preparation method of organic electroluminescent and integrated photovoltaic device

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