CN105470392B - A kind of organic inorganic hybridization solar cell and preparation method thereof - Google Patents
A kind of organic inorganic hybridization solar cell and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of organic inorganic hybridization solar cell and preparation method thereof, the structure of the solar cell sequentially consists of cathode electrode, n-type nano-silicon piece substrate, organic conjugate material hole transmission layer and anode electrode, doped with silane coupler in the hole transmission layer, the anode electrode is the silver electrode of grid line shape, the cathode electrode is aluminium electrode, and the surface texture of the n-type nano-silicon piece substrate is irregular inverted pyramid structure.This method comprises the steps：The silicon chip of nanostructured is obtained by wet etching；In PEDOT：Silane coupler is adulterated in PSS mixed solution；By doped with the PEDOT of silane coupler:PSS mixed solutions are spun on nanostructured silicon chip by spin-coating method, and are made annealing treatment；In hole transmission layer PEDOT:Anode electrode Ag is deposited on PSS；In the non-burnishing surface evaporation cathode electrode A l of silicon chip.The organic inorganic hybridization solar cell prepared by this method can lift open-circuit voltage, be advantageous to the separation and collection of electric charge.
Description
Technical field
The present invention relates to photoelectric device technical field, more particularly to a kind of organic inorganic hybridization solar cell and its preparation
Method.
Background technology
With the increase year by year of global energy requirements amount, energy problem has become the head that countries in the world economic development runs into
Want problem.Solar energy is inexhaustible as a kind of green energy resource, is the following optimal energy mode in the whole world.Mesh
Before, silica-based solar cell account for more than the 90% of the solar cell market share, but monocrystalline silicon battery is to the high-purity of silicon chip
Degree requires that (six more than nine) cause such devices cost of material high, in addition, complicated production technology, energy loss are excessively serious
The problems such as all limit the large-scale practical application of such battery, by contrast, using silicon chip and organic conjugate transmission material as base
For the hybrid inorganic-organic solar cell of plinth because its unique excellent performance is increasingly subject to pay attention to, being expected to turn into has development latent
The solar powered technology of energy, its Heterosis are：Hybrid inorganic-organic solar cell processing course is relatively easy, manufacture
Temperature is relatively low, and energy expenditure is small, and element manufacturing cost is low, and large area manufacture etc. can be achieved.
In recent years, in order to improve the photoelectric transformation efficiency of organic inorganic hybridization solar cell, many researchers are from each
Aspect is studied it, and the effective ways of one of them are by obtaining miscellaneous nanometer to the etching of silicon chip surface
Structure, 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, so as to improve the overall efficiency of battery.But the organic inorganic hybridization sun using nanostructured silicon chip as substrate
Problems with generally be present in energy battery：(1) silicon chip surface can not be penetrated into due to the presence of nanostructured, organic material completely
In the gap of nanostructured, cause to contact with nanometer silicon chip by the film that spin-coating method is formed poor, it is impossible to it is good to form quality
Schottky junction, so as to cause the relatively low open-circuit voltage of device；(2) the nanostructured silicon chip surface obtained by etching is present very
Defect modes, the presence of these defect states have a strong impact on the recombination-rate surface of device, so as to influence the separation of electric charge and transmission.
In view of it is above-mentioned the defects of, the design people, be actively subject to research and innovation, to found a kind of organic inorganic hybridization too
Positive energy battery and preparation method thereof, makes it with more the value in industry.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of organic inorganic hybridization solar cell and its system
Preparation Method, open-circuit voltage can be lifted, reduce the recombination-rate surface of solar cell, be advantageous to the separation and collection of electric charge.
A kind of organic inorganic hybridization solar cell proposed by the present invention, it is characterised in that：The structure of the solar cell
Cathode electrode, n-type nano-silicon piece substrate, organic conjugate material hole transmission layer and anode electrode are sequentially consisted of, it is described
Doped with silane coupler in hole transmission layer, the anode electrode is the silver electrode of grid line shape, and the cathode electrode is aluminium electricity
Pole, the surface texture of the n-type nano-silicon piece substrate is irregular inverted pyramid structure,
As a further improvement on the present invention, the anode electrode is deposited on hole transmission layer, thickness 200nm, institute
State cathode electrode to be deposited on the lower surface of n-type nano-silicon piece basalis, thickness 200nm.
As a further improvement on the present invention, the organic conjugate material hole transmission layer is the poly- of doping silane coupler
(3,4- ethene dioxythiophenes)-polystyrolsulfon acid PEDOT：PSS films, thickness 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), VTES (A-151), γ-methyl
Acryloxypropyl trimethoxy silane (KH-570), vinyltri-t-butylperoxy silane (VTPS), the second of vinyl three
TMOS (A-151), γ-chloropropyl triethoxysilane this it is several in one kind or several combination.
A kind of preparation method of organic inorganic hybridization solar cell proposed by the present invention, it is characterised in that：Including following
Step：
(1) silicon chip of nanostructured is obtained by wet etching；
(2) in PEDOT：Silane coupler is adulterated in PSS mixed solution；
(3) by doped with the PEDOT of silane coupler:PSS mixed solutions are spun on nanostructured silicon chip by spin-coating method
On, and made annealing treatment；
(4) in hole transmission layer PEDOT:Anode electrode Ag is deposited on PSS；
(5) in the non-burnishing surface evaporation cathode electrode A l 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/L AgNO3With etch 5min in 4.8mol/L HF mixed solution, clear water is removed in silicon chip after rinsing with concentrated nitric acid
Silver ion, after taking-up cleaning drying be positioned over the silicon oxide layer that surface is removed in HF solution, be subsequently placed in volumetric concentration as 1%
TMAH (TMAH) solution in etch 1min.
As the further improvement of the inventive method, PEDOT described in step (2)：PSS mixed solution includes PEDOT:
PSS, DMSO and Triton solution, three is with 100:5:1 ratio mixing, the silane coupler of doping account for mixed liquor volume
0.003。
As the further improvement of the inventive method, the spin coating rotating speed of spin-coating method described in step (3) is 4000r/min,
Time is 1min, and annealing temperature is 125 DEG C, annealing time 30min.
As the further improvement of the inventive method, the evaporation mode in step (4) and (5) is that vacuum temperature film steams
Plating.
By such scheme, beneficial effects of the present invention are：The present invention is by adulterating silane coupler in PEDOT:PSS is molten
Spin-coating film in liquid, compared to the PEDOT undoped with silane coupler:PSS spin coatings into film, there is advantages below：(1) utilize
Silane coupler can significantly improve silicon chip substrate in PEDOT:The characteristic of PSS contact force, form the second best in quality Schottky
Knot, so as to lift the open-circuit voltage of device；(2) silane coupler hydrolysis can form one layer of passivation in nanostructured silicon chip surface
Layer, reduces the recombination-rate surface of solar cell, is more beneficial for the separation and collection of electric charge.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with embodiments of the invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the structural representation of organic inorganic hybridization solar cell of the present invention；
Fig. 2 is the organic inorganic hybridization solar cell ESEM sectional view of present invention doping silane coupler；
Fig. 3 is the J-V curves 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 curves 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 the solar cell of present invention doping silane coupler and the existing solar energy undoped with silane coupler
Battery peeling force comparison diagram.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail, implemented below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
A kind of organic inorganic hybridization solar cell, the structure of the solar cell sequentially consist of cathode electrode 1,
N-type nano-silicon piece substrate 2, organic conjugate material hole transmission layer 3 and anode electrode 4, doped with silicon in the hole transmission layer
Alkane coupling agent, the anode electrode are the silver electrode of grid line shape, and the cathode electrode is aluminium electrode, the n-type nano-silicon chip base
The surface texture at bottom is irregular inverted pyramid structure,
The anode electrode is deposited on hole transmission layer, and thickness 200nm, the cathode electrode is deposited in n-type nanometer
On the lower surface of silicon chip basalis, thickness 200nm.
The organic conjugate material hole transmission layer is poly- (3,4- the ethene dioxythiophenes)-polyphenyl of doping silane coupler
Vinyl sulfonic acid PEDOT：PSS films, thickness 70nm.
Described silane coupler is gamma-aminopropyl-triethoxy-silane (KH-550), γ-(2,3- glycidoxy) third
Base trimethoxy silane (GOPS), γ-glycidoxypropyltrime,hoxysilane (KH-560), (the beta-methoxy second of vinyl three
Epoxide) silane (A-172), VTES (A-151), γ-methacryloxypropyl trimethoxy silane
(KH-570), vinyltri-t-butylperoxy silane (VTPS), VTES (A-151), γ-chloropropyl three
Ethoxysilane this it is several in one kind or several combination.
A kind of preparation method of organic inorganic hybridization solar cell, comprises the steps：
(1) silicon chip of nanostructured is obtained by wet etching；
(2) in PEDOT：Silane coupler is adulterated in PSS mixed solution；
(3) by doped with the PEDOT of silane coupler:PSS mixed solutions are spun on nanostructured silicon chip by spin-coating method
On, and made annealing treatment；
(4) in hole transmission layer PEDOT:Anode electrode Ag is deposited on PSS；
(5) in the non-burnishing surface evaporation cathode electrode A l of silicon chip.
Wet etching mode in step (1) is：Silicon chip is dipped in 0.2mol/L AgNO3With 4.8mol/L HF mixing
Etch 5min in solution, clear water removes the silver ion in silicon chip with concentrated nitric acid after rinsing, drying is cleaned after taking-up, and to be positioned over HF molten
The silicon oxide layer on surface is removed in liquid, is subsequently placed in TMAH (TMAH) solution that volumetric concentration is 1% and etches
1min。
PEDOT described in step (2)：PSS mixed solution includes PEDOT:PSS, DMSO and Triton solution, three with
100:5:1 ratio mixing, the silane coupler of doping account for the 0.003 of mixed liquor volume.
The spin coating rotating speed of spin-coating method described in step (3) is 4000r/min, and time 1min, annealing temperature is 125 DEG C,
Annealing time is 30min.
Evaporation mode in step (4) and (5) is vacuum temperature film evaporation.
Silane coupler is introduced in the present invention as additive, is doped in organic conjugate material, by spin coating into
Device is made in film, you can to realize the lifting of device efficiency.The organic conjugate transmission material that the present invention uses is poly- (3,4- ethene
Dioxy thiophene)-polystyrolsulfon acid (PEDOT:PSS).Silane coupler hydrolyzes in acid condition, what one end hydrolyzed to form
With-OH keys and PEDOT:PSS-OSO3For H groups by hydrogen bond phase separation, the other end hydrolysis generation Si-O keys of chemical formula should
Key sloughs a molecule with being reacted by the Si -- H bond and Si-OH that etch the nanostructured silicon chip surface obtained under annealing conditions
Water forms Si-O-Si, turns into a fine and close network, so as to improve PEDOT:The contact force of PSS films and nanometer silicon chip, and then
The quality of the formed schottky junction of lifting.Furthermore silane coupler hydrolysis generation group is attached to the surface of structure silicon chip, energy
Enough to play passivation to silicon chip, the surface for effectively reducing solar cell meets speed, is more beneficial for separation and the receipts of electronics
Collection.
Embodiment one：
The silicon chip that institutional framework is 0.05-0.1 Ω/cm is cleaned by ultrasonic 20min, nitrogen with acetone, ethanol, deionized water successively
With concentrated sulfuric acid hydrogen peroxide mixed solution processing 30min after air-blowing is dry.Silicon chip is dipped in 0.2mol/L AgNO3With 4.8mol/L HF
Mixed solution in etch 5min, clear water removes the silver ion in silicon chip with concentrated nitric acid after rinsing, after taking-up cleaning drying place
The silicon oxide layer on surface is removed in HF solution, is subsequently placed in the TMAH solution that volumetric concentration is 1% and etches 1min.Will
PEDOT:PSS, DMSO and Triton are with 100:5:1 ratio mixing after, addition volume ratio be 0.003 silane coupler γ-
(2,3- glycidoxy) propyl trimethoxy silicane (GOPS), stirs, using spin-coating method by PEDOT:PSS is spun on knot
The surface of structure silicon chip, rotating speed 4000r/min, time 1min, Vacuum Heat is utilized after annealing 30min under conditions of 125 DEG C
Spend the Al electrodes and Ag electrodes that film evaporation thickness is about 200nm.Device under room temperature environment, measures the J-V of device without encapsulation
Curve and external quantum efficiency curve have following characteristics as shown in Figure 3 and Figure 4, using device made from the above method：
(1) short circuit current is 0.630V, open-circuit voltage 30.34mA/cm2, fill factor, curve factor 0.72, electricity conversion
For 13.74%；
(2) device highest open-circuit voltage can reach 0.640V；
(3) external quantum efficiency>90%.
Embodiment two：
The silicon chip that institutional framework is 0.05-0.1 Ω/cm is cleaned by ultrasonic 20min, nitrogen with acetone, ethanol, deionized water successively
With concentrated sulfuric acid hydrogen peroxide mixed solution processing 30min after air-blowing is dry.Silicon chip is dipped in 0.2mol/L AgNO3With 4.8mol/L HF
Mixed solution in etch 5min, clear water removes the silver ion in silicon chip with concentrated nitric acid after rinsing, above-mentioned steps are repeated
Perform etching the damage for removing non-burnishing surface to the non-burnishing surface of silicon chip, cleaning drying, which is positioned in HF solution, after silicon chip extracting removes
The silicon oxide layer on surface, it is subsequently placed in the TMAH solution that volumetric concentration is 1% and etches 1min.By PEDOT:PSS, DMSO and
Triton is with 100:5:After 1 ratio mixing, silane coupler γ-(2, the 3- glycidoxy) that volume ratio is 0.003 is added
Propyl trimethoxy silicane (GOPS), stirs, using spin-coating method by PEDOT:PSS is spun on the surface of structure silicon chip, turns
Speed is 4000r/min, time 1min, is about using vacuum temperature film evaporation thickness after the 30min that annealed under conditions of 125 DEG C
200nm Al electrodes and Ag electrodes.Device under room temperature environment, measures the J-V curves and external quantum efficiency of device without encapsulation
Curve such as Fig. 5 and Fig. 6, there are following characteristics using device made from the above method：
(1) short circuit current is 0.632V, open-circuit voltage 31.65mA/cm2, fill factor, curve factor 0.71, electricity conversion
For 14.20%；
(2) device highest open-circuit voltage can reach 0.640V；
(3) external quantum efficiency>90%.
J-V curves in embodiment one and two are in 100mW/cm2AM1.5 solar simulators irradiation under measure
Obtain.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (6)
- A kind of 1. preparation method of organic inorganic hybridization solar cell, it is characterised in that：Comprise the steps：(1) silicon chip of nanostructured is obtained by wet etching；(2) in PEDOT：Silane coupler is adulterated in PSS mixed solution；(3) by doped with the PEDOT of silane coupler:PSS mixed solutions are spun on nanostructured silicon chip by spin-coating method, and Made annealing treatment；(4) in hole transmission layer PEDOT:Anode electrode Ag is deposited on PSS；(5) in the non-burnishing surface evaporation cathode electrode A l of silicon chip；The structure of solar cell prepared by this method sequentially consists of cathode electrode, n-type nano-silicon piece substrate, organic common Conjugated material hole transmission layer and anode electrode, doped with silane coupler in the hole transmission layer, the anode electrode is grid The silver electrode of wire, the cathode electrode are aluminium electrode, and the surface texture of the n-type nano-silicon piece substrate is irregular gold Word tower structure；Wet etching mode in step (1) is：Silicon chip is dipped in 0.2mol/L AgNO3With 4.8mol/L HF mixed solution Middle etching 5min, clear water remove the silver ion in silicon chip with concentrated nitric acid after rinsing, drying is cleaned after taking-up and is positioned in HF solution The silicon oxide layer on surface is removed, is subsequently placed in TMAH (TMAH) solution that volumetric concentration is 1% and etches 1min；PEDOT described in step (2)：PSS mixed solution includes PEDOT:PSS, DMSO and Triton solution, three is with 100: 5:1 volume ratio mixing, the silane coupler of doping account for the 0.003 of mixed liquor volume.
- A kind of 2. preparation method of organic inorganic hybridization solar cell according to claim 1, it is characterised in that：It is described Anode electrode is deposited on hole transmission layer, and thickness 200nm, the cathode electrode is deposited in n-type nano-silicon piece basalis On lower surface, thickness 200nm.
- A kind of 3. preparation method of organic inorganic hybridization solar cell according to claim 2, it is characterised in that：It is described Organic conjugate material hole transmission layer is poly- (3,4- the ethene dioxythiophenes)-polystyrolsulfon acid of doping silane coupler PEDOT：PSS films, thickness 70nm.
- A kind of 4. preparation method of organic inorganic hybridization solar cell according to claim 3, it is characterised in that：It is described Silane coupler be gamma-aminopropyl-triethoxy-silane (KH-550), γ-(2,3- glycidoxy) propyl trimethoxy silicon Alkane (GOPS), γ-glycidoxypropyltrime,hoxysilane (KH-560), vinyl three (beta-methoxy ethyoxyl) silane (A- 172), VTES (A-151), γ-methacryloxypropyl trimethoxy silane (KH-570), ethene Base tri-t-butylperoxy silane (VTPS), VTES (A-151), γ-chloropropyl triethoxysilane this One kind or several combination in several.
- A kind of 5. preparation method of organic inorganic hybridization solar cell according to claim 1, it is characterised in that：Step (3) the spin coating rotating speed of spin-coating method described in is 4000r/min, and time 1min, annealing temperature is 125 DEG C, and annealing time is 30min。
- A kind of 6. preparation method of organic inorganic hybridization solar cell according to claim 5, it is characterised in that：Step (4) the evaporation mode and in (5) is Vacuum Heat plated film evaporation.
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| CN106784042B (en) * | 2016-12-01 | 2018-07-24 | 西北工业大学 | A kind of preparation method of hybrid solar cell |
| CN106559029A (en) * | 2016-12-06 | 2017-04-05 | 庄爱芹 | Hollow type photovoltaic glass curtain wall and preparation method thereof |
| CN107863410A (en) * | 2017-10-13 | 2018-03-30 | 南昌大学 | A kind of preparation method of solar battery |
| CN110299429B (en) * | 2019-05-23 | 2020-11-10 | 云南大学 | Novel silicon-organic hybrid solar cell and preparation method thereof |
| 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 |
| WO2024198647A1 (en) * | 2023-03-28 | 2024-10-03 | 隆基绿能科技股份有限公司 | Silane coupling agent, linking method therefor, and solar cell |
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