CN102655217A - Inorganic-organic heterojunction all solid solar battery - Google Patents

Inorganic-organic heterojunction all solid solar battery Download PDF

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CN102655217A
CN102655217A CN2012101506859A CN201210150685A CN102655217A CN 102655217 A CN102655217 A CN 102655217A CN 2012101506859 A CN2012101506859 A CN 2012101506859A CN 201210150685 A CN201210150685 A CN 201210150685A CN 102655217 A CN102655217 A CN 102655217A
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inorganic
solar cell
solid state
organic heterojunction
crystal semiconductor
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马廷丽
郭薇
翁韬
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Dalian University of Technology
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Dalian University of Technology
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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
    • Y02E10/549—Organic PV cells
    • 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
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    • 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 provides an inorganic-organic heterojunction all solid solar battery, comprising a substrate, a conductive oxide layer, a nanocrystalline semiconductor layer, a photosensitizer, a hole transport layer, a counter electrode and a package back plate, wherein the substrate has the characteristic of photopermeability; the conductive oxide layer is arranged on the substrate; the nanocrystalline semiconductor layer is arranged on the conductive oxide layer; the photosensitizer is coated on the nanocrystalline semiconductor layer; the hole transport layer is soaked in the nanocrystalline semiconductor layer; and the counter electrode is arranged on the hole transport layer. According to the inorganic-organic heterojunction all solid solar battery, the transparent conductive oxide layer is etched into a first transparent conductive oxide layer and a second transparent conductive oxide layer, the counter electrode is electrically connected with the first transparent conductive oxide layer by a conducting wire, and an inorganic semiconductor is taken as the photosensitizer, so that the absorption spectrum of the inorganic-organic heterojunction all solid solar battery can be expanded, an all solid structure can be realized, the manufacture cost of the battery can be reduced, and the battery is simple in manufacture and package technology, thereby being applicable to the large-area coating and the industrialized production.

Description

The all solid state solar cell of inorganic-organic heterojunction
Technical field
The present invention relates to technical field of solar batteries, relate in particular to a kind of inorganic-all solid state solar cell of organic heterojunction.
Background technology
In recent years, dye-sensitized solar cells more and more receives the extensive concern of scientific research institution and energy industry circle as emerging energy.Through the research of recent two decades, dye-sensitized solar cells has been obtained bigger progress.But still there is following defective in said conventional dyes sensitization solar battery: (1) conventional dyes sensitization solar cell is low to the effective rate of utilization of solar spectrum.Conventional dyes sensitization battery adopts the ruthenium based dye as sensitising agent usually, and its spectral absorption narrow range only limits to the visible-range of 400～750nm.That is, the near infrared light that accounts for solar spectrum 48% can not get effective utilization, and then has influenced the lifting of cell photoelectric conversion efficiency.Simultaneously, the ruthenium element of said ruthenium based dye costs an arm and a leg, and reserves are limited, and processes such as exploitation are prone to cause environmental pollution; (2) electrolyte solution of conventional dyes sensitization battery and elemental iodine are easy to volatilization, and said electrolyte solution causes erosion to encapsulating material, and then cause electrolyte solution to be revealed, and reduce the durability and the stability of battery; (3) the light anode of conventional dyes sensitization battery and too high to the electrode manufacturing cost.The light anode of conventional dyes sensitization battery and electrode is all adopted the glass with transparent conductive oxide is substrate; Because the vacuum film formation technology of transparent conductive oxide and in solar cell to the specific (special) requirements of glass transmission etc.; Cause its cost too high relatively, reach 50～60% of entire cell manufacturing cost than other part of conventional dyes sensitization battery; (4) conventional dyes sensitization cell making process is complicated, is difficult to adapt to large tracts of land production and industrialization demand.Above-mentioned defective has restricted the improved efficiency of conventional dyes sensitization solar cell, and has limited its large-scale production, is that those skilled in the art need badly and deal with problems.
On the other hand, the inorganic-organic heterojunction thin-film solar cells as the novel organic film battery of the third generation comprises: the light anode, i.e. and electron donor, said smooth anode is through the film preparation of inorganic semiconductor photosensitizer sensitization semiconductor film; Hole transmission layer, said hole transmission layer are high molecular polymer; To electrode, the said metal preparation that electrodes use is had high work function.Though the highest energy conversion efficiency of said traditional inorganic-organic heterojunction thin-film solar cells has reached 6%, and has very big room for promotion.But the semiconductor equalizing of said traditional inorganic-organic heterojunction thin-film solar cells is the sulfide that cadmium, antimony, lead etc. form, and said semiconductive thin film contains heavy metal element, and toxicity is big, and reserves are limited, and cost is higher, should not extensively promote.Simultaneously, the preparation technology of the hole transmission layer of said traditional inorganic-organic heterojunction thin-film solar cells requires height, must under the anhydrous high vacuum condition of anaerobic, carry out, and could guarantee that battery has higher photoelectric properties.Therefore, use low cost, reserves are abundant; Nontoxic inorganic semiconductor sensitising agent; And the inorganic-organic heterojunction solar cell of the manufacture craft that is simple and easy to realize making, further improve the solar cell energy conversion efficiency, have important science and social effect.
So to the problem that prior art exists, this case designer relies on the industry experience for many years of being engaged in, the active research improvement is so there has been all solid state solar cell of the inorganic-organic heterojunction of invention.
Summary of the invention
The present invention be directed in the prior art; Traditional DSSC photoelectric conversion efficiency is low, complex process, manufacturing cost high; And traditional related element reserves of inorganic-organic heterojunction thin-film solar cells are limited, toxicity is big, be inappropriate for defectives such as extensive popularization provide a kind of inorganic-all solid state solar cell of organic heterojunction.
In order to address the above problem, the present invention provide a kind of inorganic-all solid state solar cell of organic heterojunction, comprise substrate, said substrate is glass, PEN, PET or the plastics with light transmission features; Conductive oxide layer, said conductive oxide layer are arranged on the said substrate; The nano crystal semiconductor layer, said nano crystal semiconductor layer forms film layer structure by the nano crystal semiconductor particle, and is arranged on the said conductive oxide layer; Sensitising agent, said sensitising agent are coated on the said nano crystal semiconductor layer, and after optical excitation, produce electron-hole pair; Hole transmission layer, said hole transmission layer soaks in said nano crystal semiconductor layer; To electrode, said electrode is arranged on the said hole transmission layer, and is used to collect said hole; And, the encapsulation backboard, said encapsulation backboard is arranged on a said side that differs from hole transmission layer to electrode, and be used to prevent said inorganic-all solid state solar cell of organic heterojunction receives external environmental.
Optional; Said conductive oxide layer etching forms first conductive oxide layer and second conductive oxide layer; Said first oxide skin(coating) and said second oxide skin(coating) also are arranged on the said substrate at interval, and said first conductive oxide layer is connected electrode electricity with said.
Optional, said substrate has the visible light transmissivity greater than 55%.
Optional, said conductive oxide layer is ITO, FTO or AZO.
Optional, the nano crystal semiconductor particle of said formation nano crystal semiconductor layer is a titanium dioxide, zinc oxide, and tin oxide, IV B, II B group 4 transition metal or element doping band gap are a kind of in the oxide of 3.0 ~ 3.6eV or several kinds of formations wherein.
Optional, the said nano crystal semiconductor particle that is used to form the nano crystal semiconductor layer is nano particle, nanotube, microballoon, nano wire, nanometer rods.
Optional, the nano crystal semiconductor particle grain size of said nano crystal semiconductor layer is 2 ~ 2000nm.
Optional, the said nano crystal semiconductor particle that is used to form the nano crystal semiconductor layer is the TiO of 2 ~ 40nm 2The TiO of particle or 20 ~ 2000nm 2Microballoon.
Optional, said sensitising agent is the inorganic semiconductor sensitising agent.
Optional, said sensitising agent is CdS, SnS, Ag 2S, Sb 2S 3, one or more formations in the polynary semiconductor sulfuration thing of PbS, ZnS, InS, CuZnSnS (Se) or the selenides.
Optional, the particle diameter of said sensitising agent is 2 ~ 10nm preferably.
Optional, said hole transmission layer is one or several the combination that has among polythiophene class polymeric material, TPD, NPB, TTB or the HTM2 of hole transport function.
Optional, said polythiophene class polymeric material is for gathering the 3-hexyl thiophene.
Optional, said is that workfunction range is the metal electrode of 4～5.6eV to electrode.
Optional, said is a kind of among Al, Au, the Ag to electrode.
In sum; The present invention is inorganic-and all solid state solar cell of organic heterojunction is etched into first including transparent conducting oxide layer and second including transparent conducting oxide layer with said including transparent conducting oxide layer; With said electrode is electrically connected with said first including transparent conducting oxide layer; And adopt inorganic semiconductor not only to expand the absorption spectrum of inorganic-organic heterojunction solar cell as sensitising agent, realize full consolidated structures, and reduce its manufacturing cost; And simplify making, packaging technology, be applicable to large tracts of land coating and industrialization production.
Description of drawings
Shown in Figure 1 for the sectional structure sketch map of the present invention's first inorganic-all solid state solar cell of organic heterojunction;
Shown in Figure 2 for the sectional structure sketch map of the present invention's second inorganic-all solid state solar cell of organic heterojunction.
Embodiment
By the technology contents, the structural feature that specify the invention, reached purpose and effect, will combine embodiment and conjunction with figs. to specify below.
First execution mode
See also Fig. 1, shown in Figure 1 for the sectional structure sketch map of all solid state solar cell 1 of the present invention's first inorganic-organic heterojunction.The all solid state solar cell 1 of said first inorganic-organic heterojunction comprises substrate 10, and said substrate 10 is for having glass, PEN, PET or the plastics of certain light transmission features; Conductive oxide layer 11, said conductive oxide layer 11 are arranged on the said substrate 10; Nano crystal semiconductor layer 12, said nano crystal semiconductor layer 12 forms film layer structure by the nano crystal semiconductor particle, and is arranged on the said conductive oxide layer 11; Sensitising agent 13, said sensitising agent 13 is coated on the said nano crystal semiconductor layer 12, and after optical excitation, produces electron-hole pair; Hole transmission layer 14, said hole transmission layer 14 soaks in said nano crystal semiconductor layer 12; To electrode 15, said electrode 15 is arranged on the said hole transmission layer 14, and is used to collect said hole; And, encapsulation backboard 16, said encapsulation backboard 16 is arranged on a said side that differs from hole transmission layer 14 to electrode 15, and is used to prevent that all solid state solar cell 1 of said first inorganic-organic heterojunction from receiving external environmental.
In the present invention, preferably, said substrate 10 has the visible light transmissivity greater than 55%.Said conductive oxide layer 11 is ITO, FTO or AZO.The said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is the wide bandgap semiconductor oxide; Include but not limited to titanium dioxide; Zinc oxide, tin oxide, IV B, II B group 4 transition metal or element doping band gap are a kind of in the oxide of 3.0 ~ 3.6eV or several kinds of formations wherein.The said nano crystal semiconductor particle grain size that is used to form nano crystal semiconductor layer 12 is 2 ~ 2000nm.Further, the said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is the TiO of 2 ~ 40nm 2The TiO of particle or 20 ~ 2000nm 2Microballoon.
Said sensitising agent 13 is the inorganic semiconductor sensitising agent, includes but not limited to CdS, SnS, Ag 2S, Sb 2S 3, PbS, ZnS, InS, and polynary semiconductor sulfuration thing of CuZnSnS (Se) or selenides.The particle diameter of said sensitising agent 13 is 2 ~ 10nm preferably.The spectral absorption scope of said sensitising agent 13 can be controlled through the particle of synthetic different-grain diameter.In the according to the invention first organic-inorganic heterogeneous solar cell 1, adopt inorganic semiconductor sensitising agent 13; And utilize its quantum size effect; Through changing synthesis condition and method control size; And then the spectral absorption of realization relative broad range, and said inorganic semiconductor sensitising agent 13 is cheap, and reserves are abundant, environmental friendliness.
Said hole transmission layer 14 is one or several the combination among the polythiophene class polymeric material, TPD, NPB, TTB or the HTM2 that include but not limited to have the hole transport function.In the present invention; The hole transmission layer 14 that adopts said polythiophene class polymeric material to prepare can be realized all solid state design of all solid state solar cell 1 of said first inorganic-organic heterojunction; And can reduce requirement to encapsulating material; Its preparation technology is easy, is applicable to large tracts of land coating and industrialization production.For better implement the present invention, to be convenient to said hole transmission layer 14 and to soak into completely with said nano crystal semiconductor layer 11, said hole transmission layer 14 preferably gathers 3-hexyl thiophene (P3HT).The said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is a nanostructure, includes but not limited to nano pore structures such as nano particle, nanotube, microballoon, nano wire, nanometer rods.
Said to electrode 15 for workfunction range is the metal electrode of 4～5.6eV, include but not limited to Al, Au, Ag.Saidly can adopt conventional silk screen print method to electrode 15, knife coating, hot vapour deposition method are deposited on the said hole transmission layer 14, are used to collect said hole.
Second execution mode
Said second execution mode adopts identical numeral number to set forth with the said first execution mode components identical.Said second execution mode with shown in the difference of first execution mode be; The all solid state solar cell 2 of second inorganic-organic heterojunction of said second execution mode further adopts the necessary circuit design to realize the board-like solar battery structure of one pole, further reduces the manufacturing cost of all solid state solar cell 2 of said second inorganic-organic heterojunction.Specifically will combine embodiment and conjunction with figs. to specify, same section repeats no more.
See also Fig. 2, and combine to consult Fig. 1, shown in Figure 2 is the sectional structure sketch map of all solid state solar cell 2 of the present invention's second inorganic-organic heterojunction.The all solid state solar cell 2 of said second inorganic-organic heterojunction comprises substrate 10, and said substrate 10 is for having glass, PEN, PET or the plastics of certain light transmission features; Conductive oxide layer 11, said conductive oxide layer 11 etchings form first conductive oxide layer 111 and second conductive oxide layer 112, and are arranged on the said substrate 10 at interval; Nano crystal semiconductor layer 12, said nano crystal semiconductor layer 12 forms film layer structure by the nano crystal semiconductor particle, and is arranged on said second conductive oxide layer 112; Sensitising agent 13, said sensitising agent 13 is coated on the said nano crystal semiconductor layer 12, and after optical excitation, produces electron-hole pair; Hole transmission layer 14, said hole transmission layer 14 soaks in said nano crystal semiconductor layer 12; To electrode 15, be arranged on the said hole transmission layer 14, be used to collect said hole, and be electrically connected through lead 17 with said first conductive oxide layer 111; And, encapsulation backboard 16, said encapsulation backboard 16 is arranged on a said side that differs from hole transmission layer 14 to electrode 15, and is used to prevent that all solid state solar cell 1 of said first inorganic-organic heterojunction from receiving external environmental.
In the present invention, preferably, said substrate 10 has the visible light transmissivity greater than 55%.Said conductive oxide layer 11 is ITO, FTO or AZO.The said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is the wide bandgap semiconductor oxide; Include but not limited to titanium dioxide; Zinc oxide, tin oxide, IV B, II B group 4 transition metal or element doping band gap are a kind of in the oxide of 3.0 ~ 3.6eV or several kinds of formations wherein.The said nano crystal semiconductor particle grain size that is used to form nano crystal semiconductor layer 12 is 10 ~ 2000nm.Further, the said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is the TiO of 2 ~ 40nm 2The TiO of particle or 20 ~ 2000nm 2Microballoon.
Said sensitising agent 13 is the inorganic semiconductor sensitising agent, includes but not limited to CdS, SnS, Ag 2S, Sb 2S 3, PbS, ZnS, polynary semiconductor sulfuration thing of InS and CuZnSnS (Se) or selenides.The particle diameter of said sensitising agent 13 is 2 ~ 10nm preferably.The spectral absorption scope of said sensitising agent 13 can be controlled through the particle of synthetic different-grain diameter.In the according to the invention second organic-inorganic heterogeneous solar cell 2, adopt inorganic semiconductor sensitising agent 13; And utilize its quantum size effect; Through changing synthesis condition and method control size; And then the spectral absorption of realization relative broad range, and said inorganic semiconductor sensitising agent 13 is cheap, and reserves are abundant, environmental friendliness.
Said hole transmission layer 14 is one or several the combination among the polythiophene class polymeric material, TPD, NPB, TTB or the HTM2 that include but not limited to have the hole transport function.In the present invention; The hole transmission layer 14 that adopts said polythiophene class polymeric material to prepare can be realized all solid state design of all solid state solar cell 2 of said second inorganic-organic heterojunction; And can reduce requirement to encapsulating material; Its preparation technology is easy, is applicable to large tracts of land coating and industrialization production.For better implement the present invention, to be convenient to said hole transmission layer 14 and to soak into completely with said nano crystal semiconductor layer 11, said hole transmission layer 14 preferably gathers 3-hexyl thiophene (P3HT).The said nano crystal semiconductor particle that is used to form nano crystal semiconductor layer 12 is a nanostructure, includes but not limited to nano pore structures such as nano particle, nanotube, microballoon, nano wire, nanometer rods.
Said to electrode 15 for workfunction range is the metal electrode of 4～5.6eV, include but not limited to Al, Au, Ag.Saidly can adopt conventional silk screen print method to electrode 15, knife coating, hot vapour deposition method are deposited on the said hole transmission layer 14, are used to collect said hole.
The all solid state solar cell 2 of according to the invention second inorganic-organic heterojunction adopts said including transparent conducting oxide layer 11 is etched into first including transparent conducting oxide layer 111 and second including transparent conducting oxide layer 112; And electrode 15 is electrically connected with said first including transparent conducting oxide layer 111 said; To form the board-like solar cell of one pole; Realize the separation of both positive and negative polarity; And further reduced the consumption of substrate 10 and including transparent conducting oxide layer 11, reduced the manufacturing cost of second inorganic-organic heterojunction all solid state solar cell 2.
Following non-limitative experiment can make those of ordinary skill in the art more comprehensively understand the present invention, but is not regarded as limitation of the present invention.
Experiment 1
The structure of all solid state solar cell 2 of said second inorganic-organic heterojunction specifically comprises:
Substrate 10 is a glass;
Conductive oxide layer 11 is an ito thin film;
Nano crystal semiconductor layer 12 adopts silk screen printing method for producing to become film for particle diameter is the TiO 2 particles composition of 2～20nm;
Sensitising agent 13 is SnS, through conventional CBD method film forming, specifically is Xi Yuan with the stannic chloride, and thioacetamide is the sulphur source, wherein, mol ratio Sn: S=1: 1～1: 1.6, be mixed with SnS solution, nano crystal semiconductor layer 12 is immersed in the said sensitising agent 13 soak then;
Hole transmission layer 14 specifically uses spin-coating method to make under vacuum condition for gathering 3-hexyl thiophene (P3HT);
To electrode 15 is Ag;
Encapsulation backboard 16 is a glass.
After the SnS of said sensitising agent 13 receives optical excitation, can effectively produce light induced electron and be injected in the conduction band of nano-crystalline titanium dioxide of nano crystal semiconductor layer 12, and then transfer to external circuit (not shown) through second conductive oxide layer 112.After the SnS of said sensitising agent 13 received optical excitation, the hole that is produced transferred to external circuit after transferring to first conductive oxide layer 111 through hole transmission layer 14 via lead 17.Apparently, the energy level of metal sulfide is suitable for all solid state solar cell 2 of according to the invention second inorganic-organic heterojunction.Similarly, CuZnSnS (Se) low-cost polynary chalcogenide semiconductor of class or selenides also can be suitable for all solid state solar cell 2 of according to the invention second inorganic-organic heterojunction.
The photoelectric properties parameter testing condition of above-mentioned battery is following: solar simulator Peccell L-15, Keithley digital source table 2601, linear volt-ampere scanning, voltage range 0.8～0V, AM1.5.Its photoelectric properties parameter is asked for an interview table 1.
Table 1. is inorganic-parameter of organic heterojunction solar cell
Figure BDA00001641210600091
Experiment 2
The structure of all solid state solar cell 2 of said second inorganic-organic heterojunction is specially:
Substrate 10 is a glass;
Conductive oxide layer 11 is an ito thin film;
Nano crystal semiconductor layer 12 is the TiO of 20～2000nm for particle diameter 2Microballoon is formed, said TiO 2Microballoon is to pile up the spherical micrometer structure form that forms by nano particle;
Sensitising agent 13 is SnS, through conventional CBD method film forming, specifically is Xi Yuan with the stannic chloride, and thioacetamide is the sulphur source, wherein, mol ratio Sn: S=1: 1～1: 1.6, be mixed with SnS solution, nano crystal semiconductor layer 12 is immersed in the said sensitising agent 13 soak then;
Hole transmission layer 14 specifically uses spin-coating method to make under vacuum condition for gathering 3-hexyl thiophene (P3HT);
To electrode 15 is Ag;
Encapsulation backboard 16 is a glass.
The manufacture method of said second inorganic-organic heterojunction solar cell 2 is with experiment 1, and the photoelectric properties parameter testing condition of battery is with experiment 1, and the photoelectric properties parameter is asked for an interview table 2.
Table 2. is inorganic-parameter of organic heterojunction solar cell
Experiment 3
The structure of all solid state solar cell 2 of said second inorganic-organic heterojunction is specially:
Substrate 10 is a glass;
Conductive oxide layer 11 is an ito thin film;
Nano crystal semiconductor layer 12 is the TiO of 20～2000nm for particle diameter 2Microballoon is formed, said TiO 2Microballoon is to pile up the spherical micrometer structure form that forms by nano particle;
Sensitising agent 13 is SnS, through conventional CBD method film forming, specifically is Xi Yuan with the stannic chloride, and thioacetamide is the sulphur source, wherein, mol ratio Sn: S=1: 1～1: 1.6, be mixed with SnS solution, nano crystal semiconductor layer 12 is immersed in the said sensitising agent 13 soak then;
Hole transmission layer 14 specifically uses spin-coating method to make under non-vacuum condition for gathering 3-hexyl thiophene (P3HT);
To electrode 15 is Ag;
Encapsulation backboard 16 is a glass.
The manufacture method of said second inorganic-organic heterojunction solar cell 2 is with experiment 1, and the photoelectric properties parameter testing condition of battery is with experiment 1, and the photoelectric properties parameter is asked for an interview table 3.
Data are provable in the table, and the present invention is prepared states second inorganic-organic heterojunction solar cell 2, can be under antivacuum natural conditions, realize that the whole soln method makes, and technology is easy, is applicable to large tracts of land coating and industrialization production.Simultaneously, hole transmission layer 14 also can use hot vapour deposition method to make, and the solar cell of producing can obtain photovoltaic performance preferably equally.
Table 3. is inorganic-parameter of organic heterojunction solar cell
Experiment 4
The structure of all solid state solar cell 2 of said second inorganic-organic heterojunction is specially:
Substrate 10 is a glass;
Conductive oxide layer 11 is an ito thin film;
Nano crystal semiconductor layer 12 is the TiO of 20～2000nm for particle diameter 2Microballoon is formed, said TiO 2Microballoon is to pile up the spherical micrometer structure form that forms by nano particle;
Sensitising agent 13 is SnS, through conventional CBD method film forming, specifically is Xi Yuan with the stannic chloride, and thioacetamide is the sulphur source, wherein, mol ratio Sn: S=1: 1～1: 1.6, be mixed with SnS solution, nano crystal semiconductor layer 12 is immersed in the said sensitising agent 13 soak then;
Hole transmission layer 14 specifically uses spin-coating method to make under vacuum condition for gathering 3-hexyl thiophene (P3HT);
To electrode 15 is Al, adopts hot vapour deposition method to be deposited on the hole mobile material, reaches the effect of collecting the hole;
Encapsulation backboard 16 is a glass.
The manufacture method of said second inorganic-organic heterojunction solar cell 2 is with experiment 1, and the photoelectric properties parameter testing condition of battery is with experiment 1, and the photoelectric properties parameter is asked for an interview table 4.
Table 4.Al is inorganic-parameter of organic heterojunction solar cell
Figure BDA00001641210600121
Experiment 5
The structure of all solid state solar cell 2 of said second inorganic-organic heterojunction is specially:
Substrate 10 is a glass;
Conductive oxide layer 11 is an ito thin film;
Nano crystal semiconductor layer 12 is the TiO of 20～2000nm for particle diameter 2Microballoon is formed, said TiO 2Microballoon is to pile up the spherical micrometer structure form that forms by nano particle;
Sensitising agent 13 is SnS, through conventional CBD method film forming, specifically is Xi Yuan with the stannic chloride, and thioacetamide is the sulphur source, wherein, mol ratio Sn: S=1: 1～1: 1.6, be mixed with SnS solution, nano crystal semiconductor layer 12 is immersed in the said sensitising agent 13 soak then;
Hole transmission layer 4 specifically uses spin-coating method to make under vacuum condition for gathering 3-hexyl thiophene (P3HT);
To electrode 15 is Al, adopts hot vapour deposition method to be deposited on the hole mobile material, reaches the effect of collecting the hole;
Encapsulation backboard 16 is the high molecular polymer film of flexibility or rigid glass substrate.
The manufacture method of said second inorganic-organic heterojunction solar cell 2 is with experiment 1, and the photoelectric properties parameter is asked for an interview table 5.
Table 5. is inorganic-parameter of organic heterojunction solar cell
Battery structure Open circuit voltage (mV) Short circuit current (mA/cm -2) Fill factor, curve factor (%) Conversion efficiency (%)
To the electrode high molecular polymer 0.46 0.14 0.40 0.025
To glass electrode substrate 0.46 0.14 0.40 0.025
In sum; The present invention is inorganic-and all solid state solar cell of organic heterojunction adopts said including transparent conducting oxide layer is etched into first including transparent conducting oxide layer and second including transparent conducting oxide layer; And with the said technical scheme that electrode is electrically connected with said first including transparent conducting oxide layer; And adopt inorganic semiconductor not only to expand the absorption spectrum of inorganic-organic heterojunction solar cell as sensitising agent, realize full consolidated structures, and reduce its manufacturing cost; And simplify making, packaging technology, be applicable to large tracts of land coating and industrialization production.
Those skilled in the art all should be appreciated that, under the situation that does not break away from the spirit or scope of the present invention, can carry out various modifications and modification to the present invention.Thereby, if when any modification or modification fall in the protection range of appended claims and equivalent, think that the present invention contains these modifications and modification.

Claims (15)

1. all solid state solar cell of inorganic-organic heterojunction comprises,
Substrate;
Conductive oxide layer, said conductive oxide layer are arranged on the said substrate;
The nano crystal semiconductor layer, said nano crystal semiconductor layer forms film layer structure by the nano crystal semiconductor particle, and is arranged on the said conductive oxide layer;
Sensitising agent, said sensitising agent are coated on the said nano crystal semiconductor layer, and after optical excitation, produce electron-hole pair;
Hole transmission layer, said hole transmission layer soaks in said nano crystal semiconductor layer;
To electrode, said electrode is arranged on the said hole transmission layer, and is used to collect said hole; And,
The encapsulation backboard, said encapsulation backboard is arranged on a said side that differs from hole transmission layer to electrode, and be used to prevent said inorganic-all solid state solar cell of organic heterojunction receives external environmental.
2. as claimed in claim 1 inorganic-all solid state solar cell of organic heterojunction; It is characterized in that; The further etching of said conductive oxide layer forms first conductive oxide layer and second conductive oxide layer; Said first oxide skin(coating) and said second oxide skin(coating) also are arranged on the said substrate at interval, and said first conductive oxide layer is connected electrode electricity with said.
3. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said substrate has the visible light transmissivity greater than 55%.
4. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said conductive oxide layer is ITO, FTO or AZO.
5. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction; It is characterized in that; The nano crystal semiconductor particle of said formation nano crystal semiconductor layer is a titanium dioxide; Zinc oxide, tin oxide, IV B, II B group 4 transition metal or element doping band gap are a kind of in the oxide of 3.0 ~ 3.6eV or several kinds of formations wherein.
6. as claimed in claim 5 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that the said nano crystal semiconductor particle that is used to form the nano crystal semiconductor layer is nano particle, nanotube, microballoon, nano wire, nanometer rods.
7. as claimed in claim 5 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that the nano crystal semiconductor particle grain size of said nano crystal semiconductor layer is 2 ~ 2000nm.
8. as claimed in claim 7 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that the said nano crystal semiconductor particle that is used to form the nano crystal semiconductor layer is the TiO of 2 ~ 40nm 2The TiO of particle or 20 ~ 2000nm 2Microballoon.
9. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said sensitising agent is the inorganic semiconductor sensitising agent.
10. as claimed in claim 9 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said sensitising agent is CdS, SnS, Ag 2S, Sb 2S 3, one or more formations in the polynary semiconductor sulfuration thing of PbS, ZnS, InS, CuZnSnS (Se) or the selenides.
11. as claimed in claim 10 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that the particle diameter of said sensitising agent is 2 ~ 10nm.
12. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction; It is characterized in that said hole transmission layer is one or several the combination that has among polythiophene class polymeric material, TPD, NPB, TTB or the HTM2 of hole transport function.
13. as claimed in claim 12 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said polythiophene class polymeric material is for gathering the 3-hexyl thiophene.
14. as claimed in claim 2 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said is that workfunction range is the metal electrode of 4～5.6eV to electrode.
15. as claimed in claim 14 inorganic-all solid state solar cell of organic heterojunction, it is characterized in that said is a kind of among Al, Au, the Ag to electrode.
CN2012101506859A 2012-05-15 2012-05-15 Inorganic-organic heterojunction all solid solar battery Pending CN102655217A (en)

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