CN105470392A - Organic-inorganic hybrid solar cell and manufacturing method therefor - Google Patents
Organic-inorganic hybrid solar cell and manufacturing method therefor Download PDFInfo
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Abstract
The invention relates to an organic-inorganic hybrid solar cell and a manufacturing method therefor. The solar cell structurally comprises a negative electrode, an n-type nano silicon wafer substrate, an organic conjugate material hole transport layer and a positive electrode from bottom to top, wherein the hole transport layer is doped with a silane coupling agent; the positive electrode is a gate-line-shaped silver electrode; the negative electrode is an aluminum electrode; and the surface structure of the n-type nano silicon wafer substrate is an irregular inverted pyramid structure. The method comprises the following steps of: obtaining a nanostructure silicon wafer with wet etching; doping a PEDOT:PSS mixed solution of with the silane coupling agent; coating the nanostructure silicon wafer with the PEDOT:PSS mixed solution doped with the silane coupling agent in a spin-coating manner, and performing annealing treatment; plating the hole transport layer PEDOT:PSS with the positive electrode Ag in an evaporation manner; and plating an unpolished surface of the silicon wafer with the negative electrode Al. The organic-inorganic hybrid solar cell prepared with the method can increase open circuit voltage, thereby facilitating charge separation and collection.
Description
Technical field
The present invention relates to photoelectric device technical field, particularly relate to a kind of organic inorganic hybridization solar cell and preparation method thereof.
Background technology
Along with the increase year by year of global energy requirements amount, energy problem has become the matter of utmost importance that countries in the world economic development runs into.Solar energy is as a kind of green energy resource, inexhaustible, is following global optimal energy mode.At present, silica-based solar cell account for more than 90% of the solar cell market share, but to the high-purity of silicon chip, monocrystalline silicon battery requires that (six more than nine) cause such devices cost of material high, in addition, complicated production technology, the problems such as energy loss is too serious all limit the large-scale practical application of this type of battery, by contrast, hybrid inorganic-organic solar cell based on silicon chip and organic conjugate transferring material comes into one's own day by day because of its unique excellent performance, be expected to become the solar powered technology with development potentiality, its Heterosis is: hybrid inorganic-organic solar cell processing course is relatively simple, manufacture temperature lower, energy ezpenditure is little, element manufacturing cost is low, large area manufacture etc. can be realized.
In recent years, in order to improve the photoelectric conversion efficiency of organic inorganic hybridization solar cell, many researchers are studied it in all its bearings, the effective ways of one of them are namely by obtaining nanostructure miscellaneous to the etching of silicon chip surface, such as: silicon nanowires, silicon nanorods, inverted pyramid structure etc., these structures can significantly improve the absorption of light, reduce the reflection of silicon chip, thus improve the overall efficiency of battery.But, usually there is following problem in the organic inorganic hybridization solar cell being substrate with nanostructure silicon chip: (1) silicon chip surface is due to the existence of nanostructure, organic material can not penetrate in the gap of nanostructure completely, the film resulting through spin-coating method formation contacts poor with nanometer silicon chip, the second best in quality schottky junction can not be formed, thus the open circuit voltage causing device lower; (2) there is a lot of defect state in the nanostructure silicon chip surface obtained by etching, the existence of these defect states has a strong impact on the recombination-rate surface of device, thus affects separation and the transmission of electric charge.
Because above-mentioned defect, the design people, actively in addition research and innovation, to founding a kind of organic inorganic hybridization solar cell and preparation method thereof, make it have more value in industry.
Summary of the invention
For solving the problems of the technologies described above, the object of this invention is to provide a kind of organic inorganic hybridization solar cell and preparation method thereof, can open circuit voltage be promoted, reduce the recombination-rate surface of solar cell, be conducive to separation and the collection of electric charge.
A kind of organic inorganic hybridization solar cell that the present invention proposes, it is characterized in that: the structure of this solar cell is followed successively by cathode electrode, the substrate of N-shaped nanometer silicon chip, organic conjugate material hole transmission layer and anode electrode from bottom to up, doped with silane coupler in described hole transmission layer, described anode electrode is the silver electrode of grid line shape, described cathode electrode is aluminium electrode, the surface texture of described N-shaped nanometer silicon chip substrate is irregular inverted pyramid structure
As a further improvement on the present invention, described anode electrode evaporation is on hole transmission layer, and thickness is 200nm, and described cathode electrode evaporation is on the lower surface of N-shaped nanometer silicon chip basalis, and thickness is 200nm.
As a further improvement on the present invention, described organic conjugate material hole transmission layer is poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS film of doping silane coupler, and thickness is 70nm.
As a further improvement on the present invention, described silane coupler is gamma-aminopropyl-triethoxy-silane (KH-550), γ-(2, 3-glycidoxy) propyl trimethoxy silicane (GOPS), γ-glycidoxypropyltrime,hoxysilane (KH-560), vinyl three (beta-methoxy-ethyoxyl) silane (A-172), vinyltriethoxysilane (A-151), γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltri-t-butylperoxy silane (VTPS), vinyltriethoxysilane (A-151), γ-chloropropyl triethoxysilane this several in one or several combination.
The preparation method of a kind of organic inorganic hybridization solar cell that the present invention proposes, is characterized in that: comprise the steps:
(1) silicon chip of nanostructure is obtained by wet etching;
(2) adulterate silane coupler in the mixed solution of PEDOT:PSS;
(3) the PEDOT:PSS mixed solution doped with silane coupler is spun on nanostructure silicon chip by spin-coating method, and carries out annealing in process;
(4) evaporation anode electrode Ag on hole transmission layer PEDOT:PSS;
(5) at the non-burnishing surface evaporation cathode electrode Al of silicon chip.
As the further improvement of the inventive method, the wet etching mode in step (1) is: silicon chip is dipped in 0.2mol/LAgNO
35min is etched with in the mixed solution of 4.8mol/LHF, remove the silver ion in silicon chip with red fuming nitric acid (RFNA) after clear water rinses, take out after cleaning dry up be positioned in HF solution removes surface silicon oxide layer, be then placed in volumetric concentration be 1% TMAH (Tetramethylammonium hydroxide) solution etch 1min.
As the further improvement of the inventive method, described in step (2), the mixed solution of PEDOT:PSS comprises PEDOT:PSS, DMSO and Triton solution, three mixes with the ratio of 100:5:1, and the silane coupler of doping accounts for 0.003 of mixed liquor volume.
As the further improvement of the inventive method, described in step (3), the spin coating rotating speed of spin-coating method is 4000r/min, and the time is 1min, and annealing temperature is 125 DEG C, and annealing time is 30min.
As the further improvement of the inventive method, the evaporation mode in step (4) and (5) is vacuum temperature film evaporation.
By such scheme, beneficial effect of the present invention is: the present invention is by doping silane coupler spin-coating film in PEDOT:PSS solution, compared to the film that the PEDOT:PSS spin coating of undoped silicon alkane coupling agent becomes, have the following advantages: (1) utilizes silane coupler can significantly improve at the bottom of silicon wafer-based in the characteristic of the contact force of PEDOT:PSS, form the second best in quality schottky junction, thus the open circuit voltage of boost device; (2) silane coupler hydrolysis can form one deck passivation layer at nanostructure silicon chip surface, reduces the recombination-rate surface of solar cell, is more conducive to separation and the collection of electric charge.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of specification, coordinates accompanying drawing to be described in detail as follows below with embodiments of the invention.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic inorganic hybridization solar cell of the present invention;
Fig. 2 is that the present invention adulterates the organic inorganic hybridization solar cell ESEM sectional view of silane coupler;
Fig. 3 is the J-V curve of organic inorganic hybridization solar cell in the embodiment of the present invention one;
Fig. 4 is the external quantum efficiency curve of organic inorganic hybridization solar cell in the embodiment of the present invention one;
Fig. 5 is the J-V curve of organic inorganic hybridization solar cell in the embodiment of the present invention two,
Fig. 6 is the external quantum efficiency curve of organic inorganic hybridization solar cell in the embodiment of the present invention two;
Fig. 7 is that the present invention adulterates the solar cell of silane coupler and the solar cell peeling force comparison diagram of existing undoped silicon alkane coupling agent.
Embodiment
Below in conjunction with drawings and Examples, be described in further detail the specific embodiment of the present invention, following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
A kind of organic inorganic hybridization solar cell, the structure of this solar cell is followed successively by cathode electrode 1, N-shaped nanometer silicon chip substrate 2, organic conjugate material hole transmission layer 3 and anode electrode 4 from bottom to up, doped with silane coupler in described hole transmission layer, described anode electrode is the silver electrode of grid line shape, described cathode electrode is aluminium electrode, the surface texture of described N-shaped nanometer silicon chip substrate is irregular inverted pyramid structure
Described anode electrode evaporation is on hole transmission layer, and thickness is 200nm, and described cathode electrode evaporation is on the lower surface of N-shaped nanometer silicon chip basalis, and thickness is 200nm.
Described organic conjugate material hole transmission layer is poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS film of doping silane coupler, and thickness is 70nm.
Described silane coupler is gamma-aminopropyl-triethoxy-silane (KH-550), γ-(2, 3-glycidoxy) propyl trimethoxy silicane (GOPS), γ-glycidoxypropyltrime,hoxysilane (KH-560), vinyl three (beta-methoxy-ethyoxyl) silane (A-172), vinyltriethoxysilane (A-151), γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltri-t-butylperoxy silane (VTPS), vinyltriethoxysilane (A-151), γ-chloropropyl triethoxysilane this several in one or several combination.
A preparation method for organic inorganic hybridization solar cell, comprises the steps:
(1) silicon chip of nanostructure is obtained by wet etching;
(2) adulterate silane coupler in the mixed solution of PEDOT:PSS;
(3) the PEDOT:PSS mixed solution doped with silane coupler is spun on nanostructure silicon chip by spin-coating method, and carries out annealing in process;
(4) evaporation anode electrode Ag on hole transmission layer PEDOT:PSS;
(5) at the non-burnishing surface evaporation cathode electrode Al of silicon chip.
Wet etching mode in step (1) is: silicon chip is dipped in 0.2mol/LAgNO
35min is etched with in the mixed solution of 4.8mol/LHF, remove the silver ion in silicon chip with red fuming nitric acid (RFNA) after clear water rinses, take out after cleaning dry up be positioned in HF solution removes surface silicon oxide layer, be then placed in volumetric concentration be 1% TMAH (Tetramethylammonium hydroxide) solution etch 1min.
Described in step (2), the mixed solution of PEDOT:PSS comprises PEDOT:PSS, DMSO and Triton solution, and three mixes with the ratio of 100:5:1, and the silane coupler of doping accounts for 0.003 of mixed liquor volume.
Described in step (3), the spin coating rotating speed of spin-coating method is 4000r/min, and the time is 1min, and annealing temperature is 125 DEG C, and annealing time is 30min.
Evaporation mode in step (4) and (5) is vacuum temperature film evaporation.
Introduce silane coupler in the present invention as additive, be doped in organic conjugate material, obtain device by spin-coating film, namely can realize the lifting of device efficiency.The organic conjugate transferring material that the present invention adopts is poly-(3,4-rthylene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS).Silane coupler is hydrolyzed in acid condition, one end hydrolysis formed with-the OSO of-OH key and PEDOT:PSS
3h group is acted on mutually by hydrogen bond, the other end hydrolysis of chemical formula generates Si-O key, this key reacts with the Si-H key and Si-OH by etching the nanostructure silicon chip surface obtained, under annealing conditions, slough a part water form Si-O-Si, become a fine and close network, thus improve the contact force of PEDOT:PSS film and nanometer silicon chip, and then promote the quality of the schottky junction formed.Moreover silane coupler hydrolysis generates the surface that group is attached to structure silicon chip, can play passivation to silicon chip, and the surface effectively reducing solar cell meets speed, is more conducive to separation and the collection of electronics.
Embodiment one:
Institutional framework is that the silicon chip of 0.05-0.1 Ω/cm uses acetone, ethanol, deionized water ultrasonic cleaning 20min successively, and nitrogen dries up rear concentrated sulfuric acid hydrogen peroxide mixed solution process 30min.Silicon chip is dipped in 0.2mol/LAgNO
35min is etched with in the mixed solution of 4.8mol/LHF, remove the silver ion in silicon chip with red fuming nitric acid (RFNA) after clear water rinses, take out after cleaning dry up be positioned in HF solution removes surface silicon oxide layer, be then placed in volumetric concentration be 1% TMAH solution etch 1min.By PEDOT:PSS, DMSO and Triton is with after the mixing of the ratio of 100:5:1, add the silane coupler γ-(2 that volume ratio is 0.003,3-glycidoxy) propyl trimethoxy silicane (GOPS), stir, adopt spin-coating method PEDOT:PSS to be spun on the surface of structure silicon chip, rotating speed is 4000r/min, time is 1min, utilizes vacuum temperature film evaporation thickness to be about Al electrode and the Ag electrode of 200nm under the condition of 125 DEG C after the 30min that anneals.Device, without the need to encapsulation, under room temperature environment, records the J-V curve of device and external quantum efficiency curve as shown in Figure 3 and Figure 4, utilizes the obtained device of said method to have following characteristics:
(1) short circuit current is 0.630V, and open circuit voltage is 30.34mA/cm
2, fill factor, curve factor is 0.72, and electricity conversion is 13.74%;
(2) the most high open circuit voltage of device can reach 0.640V;
(3) external quantum efficiency >90%.
Embodiment two:
Institutional framework is that the silicon chip of 0.05-0.1 Ω/cm uses acetone, ethanol, deionized water ultrasonic cleaning 20min successively, and nitrogen dries up rear concentrated sulfuric acid hydrogen peroxide mixed solution process 30min.Silicon chip is dipped in 0.2mol/LAgNO
35min is etched with in the mixed solution of 4.8mol/LHF, remove the silver ion in silicon chip with red fuming nitric acid (RFNA) after clear water rinses, above-mentioned steps is carried out repeat to etch the damage of removing non-burnishing surface to the non-burnishing surface of silicon chip, after silicon chip extracting cleaning dry up be positioned in HF solution remove surface silicon oxide layer, be then placed in volumetric concentration be 1% TMAH solution etch 1min.By PEDOT:PSS, DMSO and Triton is with after the mixing of the ratio of 100:5:1, add the silane coupler γ-(2 that volume ratio is 0.003,3-glycidoxy) propyl trimethoxy silicane (GOPS), stir, adopt spin-coating method PEDOT:PSS to be spun on the surface of structure silicon chip, rotating speed is 4000r/min, time is 1min, utilizes vacuum temperature film evaporation thickness to be about Al electrode and the Ag electrode of 200nm under the condition of 125 DEG C after the 30min that anneals.Device, without the need to encapsulation, under room temperature environment, records the J-V curve of device and external quantum efficiency curve as Fig. 5 and Fig. 6, utilizes the obtained device of said method to have following characteristics:
(1) short circuit current is 0.632V, and open circuit voltage is 31.65mA/cm
2, fill factor, curve factor is 0.71, and electricity conversion is 14.20%;
(2) the most high open circuit voltage of device can reach 0.640V;
(3) external quantum efficiency >90%.
J-V curve in embodiment one and two is all at 100mW/cm
2aM1.5 solar simulator irradiation under measure and obtain.
The above is only the preferred embodiment of the present invention; be not limited to the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (9)
1. an organic inorganic hybridization solar cell, it is characterized in that: the structure of this solar cell is followed successively by cathode electrode, the substrate of N-shaped nanometer silicon chip, organic conjugate material hole transmission layer and anode electrode from bottom to up, doped with silane coupler in described hole transmission layer, described anode electrode is the silver electrode of grid line shape, described cathode electrode is aluminium electrode, and the surface texture of described N-shaped nanometer silicon chip substrate is irregular inverted pyramid structure.
2. a kind of organic inorganic hybridization solar cell according to claim 1, it is characterized in that: described anode electrode evaporation is on hole transmission layer, thickness is 200nm, and described cathode electrode evaporation is on the lower surface of N-shaped nanometer silicon chip basalis, and thickness is 200nm.
3. a kind of organic inorganic hybridization solar cell according to claim 2, it is characterized in that: described organic conjugate material hole transmission layer is poly-(3 of doping silane coupler, 4-ethene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS film, thickness is 70nm.
4. a kind of organic inorganic hybridization solar cell according to claim 3, it is characterized in that: described silane coupler is gamma-aminopropyl-triethoxy-silane (KH-550), γ-(2, 3-glycidoxy) propyl trimethoxy silicane (GOPS), γ-glycidoxypropyltrime,hoxysilane (KH-560), vinyl three (beta-methoxy-ethyoxyl) silane (A-172), vinyltriethoxysilane (A-151), γ-methacryloxypropyl trimethoxy silane (KH-570), vinyltri-t-butylperoxy silane (VTPS), vinyltriethoxysilane (A-151), γ-chloropropyl triethoxysilane this several in one or several combination.
5. a preparation method for organic inorganic hybridization solar cell, is characterized in that: comprise the steps:
(1) silicon chip of nanostructure is obtained by wet etching;
(2) adulterate silane coupler in the mixed solution of PEDOT:PSS;
(3) the PEDOT:PSS mixed solution doped with silane coupler is spun on nanostructure silicon chip by spin-coating method, and carries out annealing in process;
(4) evaporation anode electrode Ag on hole transmission layer PEDOT:PSS;
(5) at the non-burnishing surface evaporation cathode electrode Al of silicon chip.
6. the preparation method of a kind of organic inorganic hybridization solar cell according to claim 5, is characterized in that: the wet etching mode in step (1) is: silicon chip is dipped in 0.2mol/LAgNO
35min is etched with in the mixed solution of 4.8mol/LHF, remove the silver ion in silicon chip with red fuming nitric acid (RFNA) after clear water rinses, take out after cleaning dry up be positioned in HF solution removes surface silicon oxide layer, be then placed in volumetric concentration be 1% TMAH (Tetramethylammonium hydroxide) solution etch 1min.
7. the preparation method of a kind of organic inorganic hybridization solar cell according to claim 6, it is characterized in that: described in step (2), the mixed solution of PEDOT:PSS comprises PEDOT:PSS, DMSO and Triton solution, three mixes with the ratio of 100:5:1, and the silane coupler of doping accounts for 0.003 of mixed liquor volume.
8. the preparation method of a kind of organic inorganic hybridization solar cell according to claim 7, it is characterized in that: described in step (3), the spin coating rotating speed of spin-coating method is 4000r/min, time is 1min, and annealing temperature is 125 DEG C, and annealing time is 30min.
9. the preparation method of a kind of organic inorganic hybridization solar cell according to claim 8, is characterized in that: the evaporation mode in step (4) and (5) is vacuum temperature film evaporation.
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| CN111653638A (en) * | 2020-07-02 | 2020-09-11 | 河北大学 | Multi-interface junction solar cell and preparation method thereof |
| CN111916672A (en) * | 2020-07-31 | 2020-11-10 | 上海交通大学 | Chemical coupling silicon-conductive polymer composite electrode with stable interface and preparation method thereof |
| CN114813881A (en) * | 2022-05-09 | 2022-07-29 | 西安交通大学 | Biosensor based on organic electrochemical transistor and detection method |
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