CN102208461B - Solar cell and preparation method thereof - Google Patents
Solar cell and preparation method thereof Download PDFInfo
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- CN102208461B CN102208461B CN201010138324.3A CN201010138324A CN102208461B CN 102208461 B CN102208461 B CN 102208461B CN 201010138324 A CN201010138324 A CN 201010138324A CN 102208461 B CN102208461 B CN 102208461B
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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
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 social development, environmental pollution is more and more serious, and the energy demand of countries in the world is sharply increasing.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 comparatively ripe as basic solar battery technology take semiconductors such as silicon, but the cost of these solar cells is still higher at present, can only in more among a small circle, use.Make solar energy obtain large-scale promotion, just must develop more cheap solar cell material and technology, reduce the cost of solar cell.
Compared with 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 the 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 large area manufacture by film techniques such as spin coating or inkjet printings, process is relatively simple, can use flexible substrate, environmental friendliness, light portable, cost of manufacture are also lower.
Although organic solar batteries has above advantage, low the remaining of its photoelectric conversion efficiency realized business-like a great problem.In organic solar batteries, the thickness of photoactive layer increases, and 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 increases, its internal electric field can diminish, and causes the exciton in photoactive layer to be difficult to be separated into free carrier, free carrier is reduced, reduce 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 to sunlight, thereby improve photoelectric conversion efficiency, just become a problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention is, for the above-mentioned defect 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 is also provided.
In order to reach above-mentioned purpose, according to the present invention, a kind of solar cell is provided, comprise the substrate, the first electrode, First Transition layer, photoactive layer, the second transition zone, the second electrode that set gradually, described First Transition layer and the 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, and described the second transition zone is filled between 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 by electron donor material and electron acceptor material.
In solar cell of the present invention, described ground, described First Transition layer and the second transition zone are the semiconductor layer of transmission charge carrier different in kind, when described First Transition layer is while having the material of cavity transmission ability, described the second transition zone is the material with electron transport ability, when described First Transition layer is while having the material of electron transport ability, described the second transition zone is the material with cavity transmission ability.
In solar cell of the present invention, preferably, described the second electrode is the metal film electrode that Ag or Au make, and described First Transition layer is by TiO
x, Cs
2cO
3, ZnO or SnO
2make, described the 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 the second electrode is the metal film electrode that Al, Ca or Ba make, and described First Transition layer is by PEDOT:PSS, NiO, MoO
3, V
2o
5, WO
3or the poly-wolframic acid of peroxide makes, described the second transition zone is by TiO
x, Cs
2cO
3, ZnO or SnO
2make.
In solar cell of the present invention, preferably, described the first electrode is FTO or ito thin film electrode.
In solar cell of the present invention, preferably, described substrate is transparent substrates.
In order to reach above-mentioned purpose, according to the present invention, also provide a kind of preparation method of solar cell, comprise the following steps:
1. using light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms the first electrode, cleans, and dries;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on the first electrode is as First Transition layer, cooling;
3. on First Transition layer the 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. utilize sol-gel process the semi-conducting material with electric transmission or cavity transmission ability to be filled in to the space between the cylinder of array arrangement, and above cylinder, prepare one deck and have the semi-conducting material of electric transmission or cavity transmission ability, be heating and curing and form the second transition zone, cooling, when described First Transition layer is while having the semi-conducting material of cavity transmission ability, described the second transition zone is the semi-conducting material with electron transport ability, when described First Transition layer is while having the semi-conducting material of electron transport ability, described the second transition zone is the semi-conducting material with cavity transmission ability,
5. on the second transition zone, evaporation metal membrane electrode is as the second electrode, and annealing, obtains solar cell.
In solar cell of the present invention, photoactive layer and the second transition zone are alternately distributed, and have formed two-dimensional photon crystal structure.2 D photon crystal is to arrange by the different two media alternate cycle of refractive index a kind of structure forming, and its energy gap is main relevant with the refringence of two media.In the situation that other condition is constant, the medium refraction rate variance that changes photonic crystal can change its energy gap.When difference diminishes, the width of forbidden photon band can reduce.When difference increases, the width of forbidden photon band also can increase.Due to the existence of photonic crystal band, the light that frequency drops in forbidden band can not be propagated therein, will be reflected back.Therefore, this structure can make the part light that has little time to be absorbed by photoactive layer again multiple reflections in photoactive layer, increase the absorption to sunlight, improve photoelectric conversion efficiency.The two-dimensional photon crystal structure that the present invention forms by photoactive layer and the second transition zone, can realize even all band sun reflection of light of specific band, in the situation that not increasing photoactive layer thickness, strengthen it to the absorbing of sunlight, thereby improve the photoelectric conversion efficiency of solar cell.
In solar cell of the present invention, First Transition layer and the second transition zone have played the effect of transmission charge carrier, are beneficial to the free carrier producing in photoactive layer and are transferred in electrode rapidly by it, and have the function that stops exciton.
The preparation method of solar cell of the present invention, technique is simple, with low cost, pollution-free, is beneficial to suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in 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 object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is described in further detail.
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, the first electrode 20, the second electrode 30, First Transition layer 40, the second transition zone 50 and photoactive layer 60.The first electrode 20 is positioned on substrate 10, is First Transition layer 40 above it, is then photoactive layer 60, and photoactive layer 60 and the second transition zone 50 form two-dimensional photon crystal structure, is the second electrode 30 on the second transition zone 50.From the first electrode 20 and the second electrode 30, draw respectively wire connection electrical equipment, under the irradiation of sunlight, solar cell of the present invention can make its work to electrical equipment output voltage.
Substrate 10 is transparent substrates, as long as light transmissive material make all can, as glass, metal, silicon, plastics or organic synthesis material etc.
The preferred use of the first electrode 20 can make the transparency electrode of light transmission, and as the electrode that the conducting metal oxides such as FTO, ITO are made, its male or female as solar cell is used.
The second electrode 30 is used metal film electrode, and its male or female as solar cell is used, and forms the two poles of the earth of solar cell together with the first electrode 20.The 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 layer 40 and the second transition zone 50 have the effect of transmission charge carrier, can make the free carrier producing in photoactive layer pass through its fast transport to electrode one end, and can partly stop exciton.The material that First Transition layer 40 is used from the second transition zone 50 is different according to transmission charge carrier character, is divided into two classes, and I class has electron transport ability, as TiO
x, Cs
2cO
3, ZnO, SnO
2deng, 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 layer 40 is preferably used the material with good light transmittance.First Transition layer 40 and the second transition zone 50 transmit the different in kind of charge carrier, and even First Transition layer 40 is for having the I class material of electron transport ability, and the second transition zone 50 is for having the II class material of cavity transmission ability; Otherwise if First Transition layer 40 is for having the II class material of cavity transmission ability, the second transition zone 50 is for having the I class material of electron transport ability.
When the second electrode 30 has the metal of high work function for the first kind, First Transition layer 40 is I class material, and the second transition zone 50 is II class material; When the second electrode 30 has the metal of low work function for Equations of The Second Kind, First Transition layer 40 is II class material, and the second transition zone 50 is I class material.
Photoactive layer 60 is main region that solar cell absorbs sunlight generation photoelectric current and photovoltage, by electron donor material and electron acceptor material, mixed in proportion, electron donor material can have for phthalocyanine dye, pentacene, porphyrin compound, cyanine dyes etc. the donor material of the electronic capability of providing, and electron acceptor material can be PTCDA, C
60, C
70, perylene and derivative thereof etc. have the acceptor material of the electronic capability accepted.
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 (distance between the axis of adjacent two cylinders) of the column structure of array arrangement is d, the bottom surface diameter of cylinder is r, and the height of cylinder is h.The 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.The second transition zone 50 and active layer 60 alternative arrangements, form the two-dimensional photon crystal structure with periodic structure, reflects light in active layer 60 and strengthen the absorption of photoactive layer 60 to sunlight, improved the photoelectric conversion efficiency of solar cell.
Preparation method's step of solar cell of the present invention is as follows:
1. using light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms the first electrode, cleans, and dries;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on the first electrode is as First Transition layer, cooling;
3. on First Transition layer, the mixed layer of spin coating one deck electron donor material and electron acceptor material, as the basalis of photoactive layer, and utilizes PRINT method on basalis, to prepare the cylinder of the array arrangement of photoactive layer, and the formation photoactive layer that is heating and curing is cooling;
4. utilize sol-gel process the semi-conducting material with electric transmission or cavity transmission ability to be filled in to the space between the cylinder of array arrangement, and above cylinder, prepare one deck and have the semi-conducting material of electric transmission or cavity transmission ability, be heating and curing and form the second transition zone, cooling, when described First Transition layer is while having the semi-conducting material of cavity transmission ability, described the second transition zone is the semi-conducting material with electron transport ability, when described First Transition layer is while having the semi-conducting material of electron transport ability, described the second transition zone is the semi-conducting material with cavity transmission ability,
5. on the second transition zone, evaporation metal membrane electrode is as the second electrode, and annealing, obtains solar cell.
Embodiment 1
1. the quartz glass using thickness as 1.1mm, as substrate, plates in a side of substrate the ito thin film that a layer thickness is 150nm, and square resistance is 15 Ω/sides, and is etched into needed stripe, as the first electrode, cleans, and dries;
2. the thick TiO of spin coating one deck 60nm on the first electrode cleaning up
xlayer, as First Transition layer, and is transferred in glove box, at 150 ℃ of heating 30min, cooling;
3. the photoactive layer basalis that spin coating a layer thickness is 40nm on First Transition layer, photoactive layer solution is the toluene solution of the P3HT:PCBM of 18mg/mL, wherein, the quality of PCBM is 44% of gross mass, then utilize PRINT method continue on photoactive layer basalis manufacturing cycle d for 350nm, bottom surface diameter r be the cylindrical-array of 180nm, the height h periodic arrangement that is 150nm, and in 120 ℃ of heating 25min, cooling;
4. utilize sol-gel process that poly-peroxide wolframic acid is filled in the space of cylindrical-array, and the peroxide of spin coating one deck 50nm gathers wolframic acid above cylinder, in 180 ℃ of heating 30min, form the second transition zone, cooling;
5. the Ag film that deposit thickness is 70nm on the second transition zone, as the second electrode, and at 120 ℃ of annealing in process 5min.
In the present embodiment, take ito thin film as the first electrode (negative electrode), Ag film is the second electrode (anode), photoactive layer and transition zone are clipped between two electrodes, owing to using torpescence metal A g as electrode, electrode is stable, and airborne oxygen, steam etc. are also difficult to enter photoactive layer, have improved the stability of solar cell device.
Embodiment 2
1. the quartz glass using thickness as 1.1mm, as substrate, plates in a side of substrate the ito thin film that a layer thickness is 15nm, and square resistance is 15 Ω/sides, and is etched into needed stripe, as the first electrode (negative electrode), cleans, and dries;
2. the PEDOT:PSS conducting polymer thin film that spin coating one deck 50nm is thick on the first electrode cleaning up is as First Transition layer, and is transferred in glove box, at 150 ℃ of heating 30min, cooling;
3. the photoactive layer basalis that spin coating a layer thickness is 35nm on First Transition layer, photoactive layer solution is the toluene solution of the P3HT:PCBM of 20mg/mL, wherein, the quality of PCBM is 50% of gross mass, then utilize PRINT method continue on photoactive layer basalis manufacturing cycle d for 400nm, bottom surface diameter r be the cylindrical-array of 150nm, the height h periodic arrangement that is 100nm, and in 120 ℃ of heating 20min, cooling;
4. utilize sol-gel process that poly-peroxide wolframic acid is filled in the space of cylindrical-array, and above cylinder the ZnO film of spin coating one deck 50nm, in 20 ℃ of 180 ℃ of heating, form the second transition zones, cooling;
5. the Al film that deposit thickness is 100nm on the second transition zone, as the second electrode, and at 120 ℃ of annealing in process 10min.
The foregoing is only representative embodiment of the present invention, do not limit the present invention in any way, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace or improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a solar cell, it is characterized in that, comprise the substrate setting gradually, the first electrode, First Transition layer, photoactive layer, the second transition zone, the second electrode, described First Transition layer and the second transition zone are the semiconductor layer of transmission charge carrier different in kind, described photoactive layer comprises a basalis and the cylinder of the array arrangement that forms on the surface of described basalis, the cycle of the column structure of described array arrangement is d, the bottom surface diameter of cylinder is r, the height of cylinder is h, wherein, d is the distance between the axis of adjacent two cylinders, when d is 350nm, r is 180nm, h is 150nm or when d is 400nm, r is 150nm, h is 100nm, described the second transition zone is filled between described cylinder and has the superficial layer that exceeds described cylinder end face, and described the second transition zone and photoactive layer alternative arrangement form the two-dimensional photon crystal structure with periodic structure, described the first electrode is FTO or ito thin film electrode, the male or female that described the first electrode is solar cell, described the second electrode is the metal film electrode that the metal film electrode made of Ag or Au or Ca or Ba make, when described the second electrode be Ag or Au make metal film electrode time, described First Transition layer is by TiO
x, Cs
2cO
3, ZnO or SnO
2make, described the second transition zone is by PEDOT:PSS, NiO, MoO
3, V
2o
5, WO
3or the poly-wolframic acid of peroxide is made, when described the second electrode be Ca or Ba make metal film electrode time, described First Transition layer is by PEDOT:PSS, NiO, MoO
3, V
2o
5, WO
3or the poly-wolframic acid of peroxide makes, described the second transition zone is by TiO
x, Cs
2cO
3, ZnO or SnO
2make.
2. solar cell according to claim 1, is characterized in that, described photoactive layer is mixed by electron donor material and electron acceptor material.
3. solar cell according to claim 1, it is characterized in that, when described First Transition layer is while having the semi-conducting material of cavity transmission ability, described the second transition zone is the semi-conducting material with electron transport ability, when described First Transition layer is while having the semi-conducting material of electron transport ability, described the second transition zone is the semi-conducting material with cavity transmission ability.
4. solar cell according to claim 1, is characterized in that, described substrate is transparent substrates.
5. a preparation method for the solar cell as described in claim 1～4 any one, is characterized in that, comprises the following steps:
1. using light transmissive material as substrate, at substrate one side plating layer of metal oxide, etching forms the first electrode, cleans, and dries;
2. the semi-conducting material that spin coating or evaporation one deck have hole transport or electron transport ability on the first electrode is as First Transition layer, cooling;
3. on First Transition layer, the mixed layer of spin coating one deck electron donor material and electron acceptor material, as the basalis of photoactive layer, and utilizes PRINT method on basalis, to prepare the cylinder of the array arrangement of photoactive layer, and the formation photoactive layer that is heating and curing is cooling;
4. utilize sol-gel process the semi-conducting material with electric transmission or cavity transmission ability to be filled in to the space between the cylinder of array arrangement, and above cylinder, prepare one deck and have the semi-conducting material of electric transmission or cavity transmission ability, be heating and curing and form the second transition zone, cooling, when described First Transition layer is while having the semi-conducting material of cavity transmission ability, described the second transition zone is the semi-conducting material with electron transport ability, when described First Transition layer is while having the semi-conducting material of electron transport ability, described the second transition zone is the semi-conducting material with cavity transmission ability,
5. on the second transition zone, evaporation metal membrane electrode is as the second electrode, and annealing, obtains solar cell.
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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 |
| EP3113304B1 (en) * | 2014-02-28 | 2022-04-13 | Japan Science and Technology Agency | Thermal-radiation light source and two-dimensional photonic crystal used therein |
| 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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