CN106098946B - Solar battery and preparation method thereof - Google Patents
Solar battery and preparation method thereof Download PDFInfo
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- CN106098946B CN106098946B CN201610712637.2A CN201610712637A CN106098946B CN 106098946 B CN106098946 B CN 106098946B CN 201610712637 A CN201610712637 A CN 201610712637A CN 106098946 B CN106098946 B CN 106098946B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
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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
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- 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
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Abstract
The invention discloses a kind of solar battery and preparation method thereof, the solar battery includes: glass substrate；Cathode layer, the cathode layer are located on the surface of the glass substrate；Electron transfer layer, the electron transfer layer are located on the surface of the cathode layer；Light-absorption layer, the light-absorption layer are located on the surface of the electron transfer layer；Hole transmission layer, the hole transmission layer are located on the surface of the light-absorption layer；Anode layer, the anode layer are located on the surface of the hole transmission layer, and are electrically connected between the cathode layer and the anode layer, wherein the hole transmission layer is formed by prestox modified metal complex phthalocyanine.Solar battery energy conversion efficiency with higher and stability.
Description
Technical field
The invention belongs to energy technology fields, specifically, the present invention relates to a kind of solar batteries and preparation method thereof.
Background technique
The use of hole mobile material has important role in perovskite solar cell, transmits as holoe carrier
Channel, can not only reduce Carrier recombination rate, improve device photoelectric transfer efficiency, and perovskite activity material can be completely cut off
Material is contacted with water oxygen, improves device stability and service life.But reported in high-performance perovskite solar cell at present, routinely make
Hole mobile material spiro-OMeTAD is (5 times or more of gold) at high price since synthesis is complicated, and exists and stablize
Property difference disadvantage, seriously affected the popularization and application and industrialization of perovskite solar cell.The hole transport material of current high performance
The developmental research of material seriously lags behind the development of perovskite solar cell, carries out perovskite solar cell research, more particularly to
The research and development of core hole mobile material promote the upgrading of solar cell technology for seizing the first chance of solar cell industry development
The replacement is of great significance.
The perovskite solar battery researched and developed at present is mainly with inorganic, metal oxide, organic polymer semiconductor material
And Organic micromolecular semiconductor material is hole transmission layer.For the above two inorganic hole transporter electron energy level difficulty tune
Control, it is more difficult to realize high-performance solar cell device；High molecular material synthesizes complicated purification difficult since molecular weight is big, therefore criticizes
Secondary large production is not easy, and is unfavorable for reducing cost and industrialized development from now on.The design of small organic molecule structure is simple, and synthesis mentions
It is pure simple, it can be film-made using hot evaporation or liquid phase spin coating, the concern by more and more Research Teams.Current small molecule hole
The research of transmission material is concentrated mainly on benzidine and thiophene molecule, and the pi-conjugated metal of the big ring of important organic semiconducting materials is matched
It closes object and is substantially at blank in the research of perovskite solar cell hole transport.Organometallic complex synthesis is simple, has good
Good heat, chemical stability and excellent photoelectric properties, the concern by vast researcher.As important organic metal
Complex, phthalocyanine (Pc) are the important types of macrocyclic complex, have height Pi-conjugated systems.It is sky with metal complex phthalocyanine
Hole transport materials are conducive to improve the working life of perovskite solar battery, reduce device cost.Metal phthalocyanine was forming a film
Conjugation accumulation from beginning to end easy to form, is conducive to transistor application, but being unsuitable for diode component includes the sun in journey
Energy battery, the application such as Organic Light Emitting Diode.And the face face accumulation thin film-forming method of metal phthalocyanine is conducive to organic diode device
Carrier transport, improve conductive capability and device performance.Although with template inducing metal phthalocyanine film forming forming face face heap
It accumulates and realizes the raising of organic photovoltaic devices it has been reported that still designing by Phthalocyanine structure, realize the accumulation of phthalocyanine face face
And it is applied to the hole transport application of perovskite solar battery, the correlative study for reaching raising photoelectric conversion efficiency yet there are no report
Road.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of solar battery and preparation method thereof, solar battery energy conversion efficiency with higher
And stability.
In one aspect of the invention, the invention proposes a kind of solar batteries.According to an embodiment of the invention, described
Solar battery includes:
Glass substrate；
Cathode layer, the cathode layer are located on the surface of the glass substrate；
Electron transfer layer, the electron transfer layer are located on the surface of the cathode layer；
Light-absorption layer, the light-absorption layer are located on the surface of the electron transfer layer；
Hole transmission layer, the hole transmission layer are located on the surface of the light-absorption layer；
Anode layer, the anode layer are located on the surface of the hole transmission layer, and the cathode layer and the anode
It is electrically connected between layer,
Wherein, the hole transmission layer is formed by prestox modified metal complex phthalocyanine.
Solar battery according to an embodiment of the present invention is by using by prestox modified metal complex phthalocyanine shape as a result,
At hole transmission layer so that hole transmission layer is conducive to diode photoelectric device in forming process forming face face packed structures
Carrier transport, so as to significantly improve device photoelectric transfer efficiency, while the introducing of methyl can significantly improve phthalocyanine
Hydrophobicity enhances its property stable in the air, and plays passivation and protective effect to light-absorption layer, to significantly improve too
The stability of positive energy battery.
In addition, solar battery according to the above embodiment of the present invention can also have the following additional technical features:
In some embodiments of the invention, the prestox modified metal complex phthalocyanine is to modify copper selected from prestox
Phthalocyanine, prestox modification ZnPc, prestox modification aluminium phthalocyanine, prestox modification palladium phthalocyanine, prestox modify titanium phthalocyanines and eight
Methyl modifies at least one of vanadyl phthalocyanine.Thus, it is possible to significantly improve the energy conversion efficiency and stability of the solar battery.
In some embodiments of the invention, the hole transmission layer with a thickness of 30~80nm, preferably 60nm.As a result,
It can be further improved the energy conversion efficiency and stability of the solar battery.
In some embodiments of the invention, the electron transfer layer includes TiO2、SnO2, C60 and C60 derivative PCBM
At least one of；It is optional, the electron transfer layer with a thickness of 30~55nm, preferably 45nm.
In some embodiments of the invention, the light-absorption layer is by ABXmY3-mOne or more materials of type crystal structure
It is formed, wherein A CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, m 1,
2 or 3.
In some embodiments of the invention, the light-absorption layer with a thickness of 100~800nm, preferably 150~500nm.
In some embodiments of the invention, the hole transmission layer is by prestox modified metal complex phthalocyanine
Vapor deposition is carried out to be formed on the surface of the light-absorption layer.Thus, it is possible to significantly improve hole transmission layer film forming, it is suitable for big
Area preparation, so as to reduce the preparation cost of solar battery.
In some embodiments of the invention, the cathode layer is ITO or FTO cathode layer, optional, the cathode layer
With a thickness of 100~150nm, preferably 120nm；Optional, the anode layer is gold, silver, aluminium or graphene composite material anode layer；
It is optional, the anode layer with a thickness of 80~120nm, preferably 100nm.
In another aspect of the invention, the invention proposes a kind of methods for preparing above-mentioned solar battery.According to this
The embodiment of invention, this method comprises:
(1) glass substrate is provided；
(2) cathode layer is formed in the glass baseplate surface；
(3) electron transfer layer is formed in the cathode layer surface；
(4) light-absorption layer is formed in the electron-transport layer surface；
(5) hole transmission layer is formed in the extinction layer surface；
(6) anode layer is formed in the hole transport layer surface, and the cathode layer is electrically connected with the anode layer.
The method according to an embodiment of the present invention for preparing solar battery can be prepared above-mentioned with higher as a result,
The solar battery of energy conversion efficiency and stability.
In addition, the method according to the above embodiment of the present invention for preparing solar battery can also have following additional skill
Art feature:
In some embodiments of the invention, in step (2), forming cathode layer in the glass baseplate surface is to pass through
FTO or ITO are sputtered on the glass substrate, then the FTO film or ito film of formation are etched.
In some embodiments of the invention, in step (3), the electron transfer layer is that institute is formed in by rubbing method
State cathode layer surface.
In some embodiments of the invention, in step (4), it is logical for forming light-absorption layer in the electron-transport layer surface
ABX will be contained by crossingmY3-mThe one or more precursor solution of type crystal structure is spin-coated on the electron-transport layer surface after annealing
It obtains, wherein A CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, and m is
1,2 or 3.
In some embodiments of the invention, in step (5), it is logical for forming hole transmission layer in the extinction layer surface
It crosses and prestox modified metal complex phthalocyanine is deposited；Optional, the prestox modified metal complex phthalein
Cyanines be selected from prestox modify copper phthalocyanine, prestox modify ZnPc, prestox modify aluminium phthalocyanine, prestox modify palladium phthalocyanine,
Prestox modifies at least one of titanium phthalocyanines and prestox modification vanadyl phthalocyanine.Gained solar energy can be not only significantly improved as a result,
The energy conversion efficiency and stability of battery, and hole transmission layer film forming can be significantly improved, it is suitable for large area and prepares,
So as to reduce the preparation cost of solar battery.
In some embodiments of the invention, in step (6), it is logical for forming anode layer in the hole transport layer surface
Cross what vacuum thermal evaporation mode obtained.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures
Obviously and it is readily appreciated that, in which:
Fig. 1 is the structural schematic diagram of solar battery according to an embodiment of the invention；
Fig. 2 is the method flow schematic diagram according to an embodiment of the invention for preparing solar battery；
Fig. 3 (a) is the photoelectric conversion efficiency I-V curve figure of solar battery obtained by embodiment and comparative example；
Fig. 3 (b) is the photoelectric conversion efficiency quantum yield EQE figure of solar battery obtained by embodiment and comparative example；
Fig. 4 (a) be in solar battery obtained by embodiment and comparative example hole mobile material device photoelectric transfer efficiency with
Working time variation diagram；
Fig. 4 (b) be in solar battery obtained by embodiment and comparative example hole mobile material device open-circuit voltage with work
Time variation diagram；
Fig. 4 (c) be in solar battery obtained by embodiment and comparative example hole mobile material shorted devices electric current with work
Time variation diagram；
Fig. 4 (d) be in solar battery obtained by embodiment and comparative example hole mobile material device fill factor with work
Time variation diagram；
Fig. 5 (a) is perovskite active layer atomic force microscopy diagram (1 micron of scale)；
Fig. 5 (b) is perovskite active layer atomic force microscopy diagram (100 nanometers of scale)；
Fig. 5 (c) is solar battery hole-transporting layer atomic force microscopy diagram (1 micron of scale) obtained by comparative example；
Fig. 5 (d) be solar battery hole-transporting layer atomic force microscopy diagram (100 nanometers of scale) obtained by comparative example and
Contact angle side view；
Fig. 5 (e) is solar battery hole-transporting layer atomic force microscopy diagram (1 micron of scale) obtained by embodiment；
Fig. 5 (f) be solar battery hole-transporting layer atomic force microscopy diagram (100 nanometers of scale) obtained by embodiment and
Contact angle side view；
Fig. 6 (a) is perovskite active layer water oxygen stability uv-vis spectra test spectrogram；
Fig. 6 (b) is the test spectrogram of hole transmission layer water oxygen stability uv-vis spectra obtained by comparative example；
Fig. 6 (c) is the test spectrogram of hole transmission layer water oxygen stability uv-vis spectra obtained by embodiment；
Fig. 7 (a) is the phthalocyanine hole transmission layer XRD spectrum (3-10 ° of scanning angle) being deposited in FTO；
Fig. 7 (b) is the phthalocyanine hole transmission layer XRD spectrum (25-27 ° of scanning angle) being deposited in FTO；
Fig. 7 (c) is the phthalocyanine hole transmission layer XRD spectrum (3-10 ° of scanning angle) being deposited in calcium titanium ore bed；
Fig. 7 (d) is the phthalocyanine hole transmission layer XRD spectrum (25-27 ° of scanning angle) being deposited in calcium titanium ore bed.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
In the description of the present invention, it is to be understood that, term " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outside", " up time
The orientation or positional relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be orientation based on the figure or
Positional relationship is merely for convenience of description of the present invention and simplification of the description, rather than the device or element of indication or suggestion meaning must
There must be specific orientation, be constructed and operated in a specific orientation, therefore be not considered as limiting the invention.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements, unless otherwise restricted clearly.For those of ordinary skill in the art
For, the specific meanings of the above terms in the present invention can be understood according to specific conditions.
In the present invention unless specifically defined or limited otherwise, fisrt feature in the second feature " on " or " down " can be with
It is that the first and second features directly contact or the first and second features pass through intermediary mediate contact.Moreover, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature be directly above or diagonally above the second feature, or be merely representative of
First feature horizontal height is higher than second feature.Fisrt feature can be under the second feature " below ", " below " and " below "
One feature is directly under or diagonally below the second feature, or is merely representative of first feature horizontal height less than second feature.
In one aspect of the invention, the invention proposes a kind of solar batteries.According to an embodiment of the invention, with reference to
Fig. 1, the solar battery include: glass substrate 100, cathode layer 200, electron transfer layer 300, light-absorption layer 400, hole transmission layer
500 and anode layer 600.
According to an embodiment of the invention, those skilled in the art can be according to actual needs to the specific material of glass substrate
It is selected with shape.
According to an embodiment of the invention, cathode layer 200 can be located on the surface of glass substrate 100, it is according to the present invention
One specific embodiment, cathode layer 200 can be FTO or ITO cathode layer.Specifically, forming cathode layer in glass baseplate surface
It is by the way that the FTO film or ito film of formation on the glass substrate, are then etched into required cathode layer figure by FTO or ITO sputtering
Case then successively distinguishes the FTO etched or ito glass in detergent, deionized water, dehydrated alcohol, acetone, isopropanol
Ultrasonic 15min is put into baking oven and dries at 120 DEG C after cleaning up, then UV/ozone handles 30min.It should be noted that
Those skilled in the art the concrete type to the concrete shape of cathode layer pattern and detergent can carry out according to actual needs
Selection.
According to one embodiment of present invention, the thickness of cathode layer is not particularly restricted, and those skilled in the art can be with
It being selected according to actual needs, a specific embodiment according to the present invention, the thickness of cathode layer can be 100~150nm,
It is preferred that 120nm.Inventors have found that if thickness is too low can not to form effective film covering, and thickness is excessively high easy to form connects greatly very much
Electric shock resistance, is unfavorable for device performance.
According to an embodiment of the invention, electron transfer layer 300 can be located on the surface of cathode layer 200.
According to one embodiment of present invention, the concrete type of electron transfer layer 300 is not particularly restricted, this field skill
Art personnel can select according to actual needs, a specific embodiment according to the present invention, and electron transfer layer 300 includes
TiO2、SnO2, at least one of C60 and C60 derivative PCBM.Inventors have found that such electron transport material carrier mobility
Rate is high, can liquid phase process film, so as to significantly reduce device preparation cost.
The thickness of still another embodiment in accordance with the present invention, electron transfer layer 300 is not particularly restricted, art technology
Personnel can select according to actual needs, and a specific embodiment according to the present invention, the thickness of electron transfer layer 300 can
Think 30~55nm, preferably 45nm.Inventors have found that if the too low effective film that can not be formed of electron transport layer thickness covers, and
If the excessively high too big contact resistance easy to form of thickness, is unfavorable for device performance.
According to still another embodiment of the invention, electron transfer layer 300 can be formed in cathode layer 200 by rubbing method
On surface.Specifically, being coated with using rubbing method on 200 surface of cathode layer so that electron transfer layer includes C60 derivative PCBM as an example
PCBM solution, then in 80 DEG C of annealing 10min, to form electron transfer layer 300 on the surface of cathode layer 200.It needs
Bright, those skilled in the art can according to actual needs select the concrete type for being coated with solution.
According to an embodiment of the invention, light-absorption layer 400 can be located on the surface of electron transfer layer 300.
According to one embodiment of present invention, the concrete type of light-absorption layer 400 is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, and a specific embodiment according to the present invention, light-absorption layer 400 can be by ABXmY3-m
One or more materials of type crystal structure are formed, wherein A CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, X, Y
It is separately Cl, Br or I, m 1,2 or 3.Inventors have found that perovskite material carrier mobility rate is high, exciton diffusion
It is long to pass journey, there is hypersorption 400-800 nanometers of visible light regions, by adjusting different ligands component ratio, absorption can be expanded
It is extremely 900 nanometers infrared, solar photon can be used, sufficiently so as to significantly improve the performance of solar battery.
The thickness of still another embodiment in accordance with the present invention, light-absorption layer 400 is not particularly restricted, those skilled in the art
It can be selected according to actual needs, a specific embodiment according to the present invention, the thickness of light-absorption layer 400 can be 100
~800nm, preferably 150~500nm.Inventors have found that if perovskite light-absorption layer thickness is too low can not to form effective film covering,
And if the excessively high too big contact resistance easy to form of thickness, be unfavorable for device performance.
According to still another embodiment of the invention, forming light-absorption layer 400 on 300 surface of electron transfer layer is by that will contain
ABXmY3The one or more precursor solution of-m type crystal structure is spin-coated on what electron-transport layer surface after annealing obtained.Specifically
, it is CH with A3NH3, B Pb, X and Y are I, for m is 2, under nitrogen protection, by the PbI of equimolar amounts2And CH3NH3I
Co-dissolve forms the precursor solution that concentration is 40wt%, then the spin coating 30s at revolving speed 3000rpm in DMF solution,
Then the heating anneal 45min at 100 DEG C, formation contain CH3NH3PbI3Light-absorption layer.
According to an embodiment of the invention, hole transmission layer 500 can be located on the surface of light-absorption layer 400, and hole passes
Defeated layer 500 is formed by prestox modified metal complex phthalocyanine.Inventors have found that by using with prestox modified metal
The hole transmission layer that object phthalocyanine is formed, so that hole transmission layer is conducive to diode in forming process forming face face packed structures
Photoelectric device carrier transport, so as to significantly improve device photoelectric transfer efficiency, while the introducing of methyl can be mentioned significantly
The hydrophobicity of high phthalocyanine enhances its property stable in the air, and plays passivation and protective effect to light-absorption layer, thus significantly
Improve the stability of solar battery.
According to one embodiment of present invention, the concrete type of prestox modified metal complex phthalocyanine is not limited especially
System, those skilled in the art can select according to actual needs, and a specific embodiment according to the present invention, prestox is repaired
Gilding metal complex phthalocyanine can for selected from prestox modify copper phthalocyanine, prestox modify ZnPc, prestox modify aluminium phthalocyanine,
Prestox modifies at least one of palladium phthalocyanine, prestox modification titanium phthalocyanines and prestox modification vanadyl phthalocyanine.Inventors have found that such
The synthesis of prestox modified metal complex phthalocyanine is simple, can be with by the modification of functionalization group and central metal ion effect
Change the properties such as its work content, absorption, so as to significantly improve the energy conversion efficiency of gained solar battery.
The thickness of still another embodiment in accordance with the present invention, hole transmission layer 500 is not particularly restricted, art technology
Personnel can select according to actual needs, and a specific embodiment according to the present invention, the thickness of hole transmission layer 500 can
Think 30~80nm, preferably 60nm.Inventors have found that if the too low effective film that can not be formed of thickness of hole transport layer covers, and
If the excessively high too big contact resistance easy to form of thickness, is unfavorable for device performance.
According to still another embodiment of the invention, hole transmission layer 500 can be by prestox modified metal complex
Phthalocyanine carries out vapor deposition and is formed on the surface of light-absorption layer 400.Specifically, by taking prestox modifies copper phthalocyanine as an example, 1 × 10- 6Under Pa vacuum degree, prestox modification copper phthalocyanine is deposited, prestox is formed in extinction layer surface and modifies the conduct of copper phthalocyanine film
Hole transmission layer.Inventors have found that hole transmission layer film forming can be significantly improved by forming hole transmission layer by using vapor deposition,
It is prepared suitable for large area, so as to reduce the preparation cost of solar battery.
According to an embodiment of the invention, anode layer 600 can be located on the surface of hole transmission layer 500, and anode layer
It is electrically connected between 600 and cathode layer 200.
According to one embodiment of present invention, the concrete type of anode layer 600 is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, and a specific embodiment according to the present invention, anode layer 600 can be gold, silver, aluminium
Or graphene composite material anode layer.Specifically, being formed so that anode layer is gold anode layer as an example on 500 surface of hole transmission layer
Anode layer 600 is 1 × 10-6By carrying out vacuum thermal evaporation to gold under Pa vacuum degree, thus in 500 surface shape of hole transmission layer
At gold thin film, that is, gold anode layer.
The thickness of still another embodiment in accordance with the present invention, anode layer 600 is not particularly restricted, those skilled in the art
Can be selected according to actual needs, a specific embodiment according to the present invention, the thickness of anode layer 600 can for 80~
120nm, preferably 100nm.Inventors have found that if anode layer thickness is too low can not to form effective film covering, and if thickness is excessively high
Device cost can be obviously increased.
Solar battery according to an embodiment of the present invention is by using by prestox modified metal complex phthalocyanine shape as a result,
At hole transmission layer so that hole transmission layer is conducive to diode photoelectric device in forming process forming face face packed structures
Carrier transport, so as to significantly improve device photoelectric transfer efficiency, while the introducing of methyl can significantly improve phthalocyanine
Hydrophobicity enhances its property stable in the air, and plays passivation and protective effect to light-absorption layer, to significantly improve too
The stability of positive energy battery.
In another aspect of the invention, the invention proposes a kind of methods for preparing above-mentioned solar battery.According to this
The embodiment of invention, with reference to Fig. 2, this method comprises:
S100: glass substrate is provided
In the step, those skilled in the art the specific material and shape to glass substrate can carry out according to actual needs
Selection.
S200: cathode layer is formed in glass baseplate surface
In the step, forming cathode layer in glass baseplate surface is by sputtering on the glass substrate, so FTO or ITO
The FTO film or ito film of formation are etched into required cathode layer pattern afterwards, then successively washing the FTO etched or ito glass
Agent, deionized water, dehydrated alcohol, acetone, ultrasound 15min respectively in isopropanol are washed, baking oven is put into after cleaning up in 120 DEG C of bakings
Dry, then UV/ozone handles 30min, can form FTO or ITO cathode layer in glass baseplate surface.It should be noted that
Those skilled in the art the concrete shape of cathode layer pattern and the concrete type of detergent can select according to actual needs
It selects.
According to one embodiment of present invention, the thickness of cathode layer is not particularly restricted, and those skilled in the art can be with
It being selected according to actual needs, a specific embodiment according to the present invention, the thickness of cathode layer can be 100~150nm,
It is preferred that 120nm.Inventors have found that if thickness is too low can not to form effective film covering, and thickness is excessively high easy to form connects greatly very much
Electric shock resistance, is unfavorable for device performance.
S300: electron transfer layer is formed in cathode layer surface
In the step, electron transfer layer can be formed in cathode layer surface by rubbing method.
According to one embodiment of present invention, the concrete type of electron transfer layer is not particularly restricted, art technology
Personnel can select according to actual needs, and a specific embodiment according to the present invention, electron transfer layer includes TiO2、
SnO2, at least one of C60 and C60 derivative PCBM.Inventors have found that such electron transport material carrier mobility rate
Height, can liquid phase process film, so as to significantly reduce device preparation cost.
The thickness of still another embodiment in accordance with the present invention, electron transfer layer is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, a specific embodiment according to the present invention, and the thickness of electron transfer layer can be
30~55nm, preferably 45nm.Inventors have found that if electron transport layer thickness is too low can not to form effective film covering, and if thick
High too big contact resistance easy to form is spent, device performance is unfavorable for.
Specifically, being coated with using rubbing method in anode layer surface so that electron transfer layer includes C60 derivative PCBM as an example
PCBM solution, then in 80 DEG C of annealing 10min, to form electron transfer layer on the surface of anode layer.It should be noted that
Those skilled in the art can according to actual needs select the concrete type for being coated with solution.
S400: light-absorption layer is formed in electron-transport layer surface
According to one embodiment of present invention, the concrete type of light-absorption layer is not particularly restricted, those skilled in the art
It can be selected according to actual needs, a specific embodiment according to the present invention, light-absorption layer can be by ABXmY3-mType crystal
One or more materials of structure are formed, wherein A CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y difference are only
It is on the spot Cl, Br or I, m 1,2 or 3.Inventors have found that perovskite material carrier mobility rate is high, exciton diffusion passes journey
It is long, there is hypersorption 400-800 nanometers of visible light regions, by adjusting different ligands component ratio, absorption can be expanded to red
Outer 900 nanometers, solar photon can be used, sufficiently so as to significantly improve the performance of solar battery.
The thickness of still another embodiment in accordance with the present invention, light-absorption layer is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, a specific embodiment according to the present invention, the thickness of light-absorption layer can for 100~
800nm, preferably 150~500nm.Inventors have found that if the too low effective film that can not be formed of perovskite light-absorption layer thickness covers, and
If the excessively high too big contact resistance easy to form of thickness, is unfavorable for device performance.
In the step, forming light-absorption layer in electron-transport layer surface is by that will contain ABXmY3-mType crystal structure is a kind of
Or a variety of precursor solutions is spin-coated on what electron-transport layer surface after annealing obtained.Specifically, being CH with A3NH3, B Pb, X
It is I with Y, for m is 2, under nitrogen protection, by the PbI of equimolar amounts2And CH3NH3I co-dissolve is in DMF solution, shape
The precursor solution for being 40wt% at concentration, then the spin coating 30s at revolving speed 3000rpm, the then heating anneal at 100 DEG C
45min, formation contain CH3NH3PbI3Light-absorption layer.
S500: hole transmission layer is formed in extinction layer surface
In the step, hole transmission layer can be formed in suction by carrying out vapor deposition to prestox modified metal complex phthalocyanine
On the surface of photosphere.Inventors have found that by using the hole transmission layer formed by prestox modified metal complex phthalocyanine,
So that hole transmission layer is conducive to diode photoelectric device carrier transport in forming process forming face face packed structures, thus
Device photoelectric transfer efficiency can be significantly improved, while the introducing of methyl can significantly improve the hydrophobicity of phthalocyanine, enhance its
Stability in air, and passivation and protective effect are played to light-absorption layer, to significantly improve the stabilization of solar battery
Property, in addition, hole transmission layer film forming can be significantly improved by forming hole transmission layer by using vapor deposition, it is suitable for large area system
It is standby, so as to reduce the preparation cost of solar battery.
According to one embodiment of present invention, the concrete type of prestox modified metal complex phthalocyanine is not limited especially
System, those skilled in the art can select according to actual needs, and a specific embodiment according to the present invention, prestox is repaired
Gilding metal complex phthalocyanine can for selected from prestox modify copper phthalocyanine, prestox modify ZnPc, prestox modify aluminium phthalocyanine,
Prestox modifies at least one of palladium phthalocyanine, prestox modification titanium phthalocyanines and prestox modification vanadyl phthalocyanine.Inventors have found that such
The synthesis of prestox modified metal complex phthalocyanine is simple, can be with by the modification of functionalization group and central metal ion effect
Change the properties such as its work content, absorption, so as to significantly improve the energy conversion efficiency of gained solar battery.
The thickness of still another embodiment in accordance with the present invention, hole transmission layer is not particularly restricted, those skilled in the art
Member can be selected according to actual needs, a specific embodiment according to the present invention, and the thickness of hole transmission layer can be
30~80nm, preferably 60nm.Inventors have found that if thickness of hole transport layer is too low can not to form effective film covering, and if thick
High too big contact resistance easy to form is spent, device performance is unfavorable for.
Specifically, by taking prestox modifies copper phthalocyanine as an example, 1 × 10-6Under Pa vacuum degree, to prestox modify copper phthalocyanine into
Row vapor deposition forms prestox modification copper phthalocyanine film as hole transmission layer in extinction layer surface.
S600: anode layer is formed in hole transport layer surface, and cathode layer is electrically connected with anode layer
According to one embodiment of present invention, the concrete type of anode layer is not particularly restricted, those skilled in the art
It can be selected according to actual needs, a specific embodiment according to the present invention, anode layer can be gold, silver, aluminium or stone
Black alkene composite material anode layer.Specifically, forming anode layer gold in hole transport layer surface so that anode layer is gold anode layer as an example
It is 1 × 10-6By carrying out vacuum thermal evaporation to gold under Pa vacuum degree, so that forming gold thin film in hole transport layer surface is gold
Anode layer.
The thickness of still another embodiment in accordance with the present invention, anode layer is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, a specific embodiment according to the present invention, the thickness of anode layer can for 80~
120nm, preferably 100nm.Inventors have found that if anode layer thickness is too low can not to form effective film covering, and if thickness is excessively high
Device cost can be obviously increased.
The method according to an embodiment of the present invention for preparing solar battery is matched by using by prestox modified metal as a result,
The hole transmission layer that object phthalocyanine is formed is closed, so that hole transmission layer is conducive to two poles in forming process forming face face packed structures
Pipe photoelectric device carrier transport, so as to significantly improve device photoelectric transfer efficiency, while the introducing of methyl can be significant
The hydrophobicity for improving phthalocyanine, enhances its property stable in the air, and play passivation and protective effect to light-absorption layer, thus aobvious
The stability for improving solar battery is write, is passed in addition, forming hole transmission layer by using vapor deposition and can significantly improve hole
Defeated layer film forming is suitable for large area and prepares, so as to reduce the preparation cost of solar battery.On it should be noted that
It states and is equally applicable to the method for preparing solar battery for feature and advantage described in solar battery, it is no longer superfluous herein
It states.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment
First on the glass substrate by FTO sputtering, the FTO film of formation is then etched into required cathode layer pattern, then
The FTO glass etched is successively cleaned by ultrasonic in detergent, deionized water, dehydrated alcohol, acetone, isopropanol respectively
15min is put into baking oven and dries at 120 DEG C after cleaning up, then UV/ozone handles 30min, so as in glass baseplate surface
Upper formation is then coated with PCBM solution in FTO cathode layer surface using rubbing method, then exists with a thickness of the FTO cathode layer of 120nm
80 DEG C of annealing 10min, so that the electron transfer layer of 45nm is formed on the surface of FTO cathode layer, it then under nitrogen protection, will
The PbI of equimolar amounts2And CH3NH3I co-dissolve forms the precursor solution that concentration is 40wt%, then exists in DMF solution
Spin coating 30s under revolving speed 3000rpm, then the heating anneal 45min at 100 DEG C, to form 200nm in electron-transport layer surface
Contain CH3NH3PbI3Light-absorption layer, then 1 × 10-6Under Pa vacuum degree, prestox modification copper phthalocyanine is deposited,
Extinction layer surface forms the prestox modification copper phthalocyanine film of 60nm as hole transmission layer, finally 1 × 10-6Lead under Pa vacuum degree
Cross to gold carry out vacuum thermal evaporation, hole transport layer surface formed 100nm gold thin film, that is, gold anode layer, and anode layer and
Cathode layer electrical connection.
Comparative example
First on the glass substrate by FTO sputtering, the FTO film of formation is then etched into required cathode layer pattern, then
The FTO glass etched is successively cleaned by ultrasonic in detergent, deionized water, dehydrated alcohol, acetone, isopropanol respectively
15min is put into baking oven and dries at 120 DEG C after cleaning up, then UV/ozone handles 30min, so as in glass baseplate surface
Upper formation is then coated with PCBM solution in FTO cathode layer surface using rubbing method, then exists with a thickness of the FTO cathode layer of 120nm
80 DEG C of annealing 10min, so that the electron transfer layer of 45nm is formed on the surface of FTO cathode layer, it then under nitrogen protection, will
The PbI of equimolar amounts2And CH3NH3I co-dissolve forms the precursor solution that concentration is 40wt%, then exists in DMF solution
Spin coating 30s under revolving speed 3000rpm, then the heating anneal 45min at 100 DEG C, to form 200nm in electron-transport layer surface
Contain CH3NH3PbI3Light-absorption layer, then 1 × 10-6Under Pa vacuum degree, native copper phthalocyanine is deposited, in light-absorption layer
Surface forms the native copper phthalocyanine film of 60nm as hole transmission layer, finally 1 × 10-6By carrying out vacuum to gold under Pa vacuum degree
Hot evaporation forms gold thin film, that is, gold anode layer of 100nm, and anode layer and cathode layer electrical connection in hole transport layer surface.
Evaluation:
1, the photoelectric conversion efficiency for the solar battery that embodiment and comparative example is obtained respectively, hole mobile material device
Stability, the surface texture of hole transmission layer, water oxygen stability and hole transmission layer molecular structure tested；
2, evaluation index and test method:
Photoelectric conversion efficiency test condition: spatial distribution AM1.5G, intensity of illumination 1000/m2, AAA solar simulator
(Beijing stand upright Han Guang company), I-V curve is measured with Keithly2400 type digital sourcemeter, and all devices are not necessarily to special envelope
Dress, test normally measure in atmospheric environment, and 25 DEG C of temperature, humidity 65% is tested map such as Fig. 3 (a) (I-V curve figure) and 3
(b) shown in (quantum yield EQE figure)；Under same test condition, using embodiment prestox copper phthalocyanine as the device of hole transmission layer
Part has higher short-circuit current density and fill factor than comparative example native copper phthalocyanine, at 300 nanometers to 800 nanometer wavelength ranges
Has higher quantum yield, prestox copper phthalocyanine device photoelectric transfer efficiency is 10%, much higher than the 7.6% of native copper phthalocyanine.
Hole mobile material device performance stability test condition: 25 DEG C of test condition temperature, humidity 65% tests map
As (hole mobile material device photoelectric transfer efficiency is with the working time in solar battery obtained by embodiment and comparative example by Fig. 4 (a)
Variation diagram), 4 (b) (hole mobile material device open-circuit voltage is with the working time in solar battery obtained by embodiment and comparative example
Variation diagram), 4 (c) (hole mobile material shorted devices electric current is with the working time in solar battery obtained by embodiment and comparative example
Variation diagram) and 4 (d) (when hole mobile material device fill factor is with work in solar battery obtained by embodiment and comparative example
Between variation diagram) shown in；Known to: it is defeated that embodiment prestox copper phthalocyanine device has more excellent stabilization open-circuit voltage and short circuit current
Out, photoelectric conversion efficiency and fill factor, which change over time reduction amplitude, will also be far below comparative example native copper phthalocyanine device.
The surface texture test condition of hole transmission layer: test map such as Fig. 5 (a) (perovskite active layer atomic force microscopy
Mirror figure (1 micron of scale)), 5 (b) (perovskite active layer atomic force microscopy diagram (100 nanometers of scales)), 5 (c) (comparative example institutes
Solar battery hole-transporting layer atomic force microscopy diagram (1 micron of scale)), 5 (d) (solar batteries obtained by comparative example
Hole-transporting layer atomic force microscopy diagram (100 nanometers of scale) and contact angle side view), 5 (e) (solar energy obtained by embodiment
Battery hole-transporting layer atomic force microscopy diagram (1 micron of scale)), 5 (f) (hole passes in solar battery obtained by embodiment
Defeated layer atomic force microscopy diagram (100 nanometers of scale) and contact angle side view) shown in.Fig. 5 (a) and (b) display preparation gained calcium
Titanium ore forms large particle crystal shape, and for size in 300-400 ran, grain structure is loose, there is larger gap；Fig. 5 (c) and
(d) display comparative example native copper phthalocyanine vapor deposition forms ghost body in calcium titanium ore bed, and 100 ran of size is loosely organized, together
It is 81.2 ° that Shi Yuantong phthalocyanine layer hydrophobicity, which tests contact angle,；Fig. 5 (e) and (f) show embodiment prestox copper phthalocyanine vapor deposition in calcium
Titanium ore layer forms compacted particulate crystallization, and for size in 20 rans, it is 119.6 ° that hydrophobicity, which tests contact angle, can be to calcium titanium
Mine plays preferably isolation water oxygen protective effect.
Water oxygen stability test condition: test condition is 25 DEG C of room temperature, and humidity 65% tests map such as Fig. 6 (a) (calcium titanium
Mine active layer water oxygen stability uv-vis spectra tests spectrogram), 6 (b) (hole transmission layer water oxygen stability obtained by comparative example is purple
Outer visible spectrum tests spectrogram) and 6 (c) (hole transmission layer water oxygen stability uv-vis spectra obtained by embodiment tests spectrogram)
Shown, as shown in Fig. 6 (a), perovskite active layer is influenced quickly in the case where not there is hole transmission layer coverage condition by water oxygen in air
Degradation, its film ultravioletvisible absorption intensity declines by day at any time；Fig. 6 (b) can be found that comparative example native copper phthalocyanine to calcium titanium
Ore bed has certain protective effect, and the degradation speed of perovskite active layer is reduced on certain depth；Fig. 6 (c) shows to implement
Example prestox copper phthalocyanine has very good protective effect to calcium titanium ore bed, and in test in 10 days, perovskite active layer is several
It remains unchanged.
The molecular structure test condition of hole transmission layer: test condition is 25 DEG C of room temperature, and humidity 65%, test map is as schemed
(the phthalocyanine sky in FTO is deposited in 7 (a) (vapor deposition is in the phthalocyanine hole transmission layer XRD spectrums (3-10 ° of scanning angle) of FTO), 7 (b)
Cave transport layer XRD spectrum (25-27 ° of scanning angle)), 7 (c) (vapor deposition in the phthalocyanine hole transmission layer XRD spectrum of calcium titanium ore bed
(3-10 ° of scanning angle)) and 7 (d) (vapor deposition in phthalocyanine hole transmission layer XRD spectrum (the scanning angle 25- of calcium titanium ore bed
27 °)), Fig. 7 (a) display is when vapor deposition is when on FTO, comparative example native copper phthalocyanine and embodiment prestox copper phthalocyanine x-ray diffraction peak
Respectively 6.8 ° and 5.8 °, correspondence d value is material molecule height；Both Fig. 7 (b) displays do not go out to spread out in 25-27 ° of scanning range
Signal is penetrated, shows the two vapor deposition when FTO, molecule all erects arrangement and FTO, forms (edge-to-edge) from beginning to end arrangement
Mode；When comparative example native copper phthalocyanine vapor deposition is when calcium titanium ore bed, x-ray diffraction peak is 6.8 ° for Fig. 7 (c) display, is remained unchanged,
Native copper Phthalocyanine keeps (edge-to-edge) pattern of rows and columns from beginning to end on calcium titanium ore bed, and embodiment prestox copper phthalein
Cyanines do not have diffracted signal in 3-10 ° of sweep interval；Fig. 7 (d) display scale native copper phthalocyanine vapor deposition is when calcium titanium ore bed at 25-27 °
Section does not have diffracted signal, and embodiment prestox copper phthalocyanine x-ray diffraction peak is 26.1 °, and corresponding d value is the accumulation of molecule face face
(face-to-face) distanceAfter showing that prestox copper phthalocyanine is vaporized on perovskite, become from original setting arrangement mode
Couch arrangement mode, is more conducive to solar cell device hole transport.
Conclusion: MOLECULE DESIGN is carried out by former Phthalocyanine, 8 methyl groups is introduced, prepares prestox modified metal phthalein
Cyanines, the material are conducive to form the accumulation of molecule face face when vapor deposition, improve material carrier migration rate, form dense film, mention
High thin-film hydrophobic enhances and protects to the water oxygen of perovskite, which can more efficiently be applied to perovskite solar-electricity
Pond hole transport improves device photoelectric transfer efficiency and stability.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (16)
1. a kind of perovskite solar battery, comprising:
Glass substrate；
Cathode layer, the cathode layer are located on the surface of the glass substrate；
Electron transfer layer, the electron transfer layer are located on the surface of the cathode layer；
Light-absorption layer, the light-absorption layer are located on the surface of the electron transfer layer；
Hole transmission layer, the hole transmission layer are located on the surface of the light-absorption layer；
Anode layer, the anode layer are located on the surface of the hole transmission layer, and the cathode layer and the anode layer it
Between be electrically connected,
Wherein, the hole transmission layer is formed by prestox modified metal complex phthalocyanine,
The light-absorption layer is by ABXmY3-mOne or more materials of type crystal structure are formed, wherein A CH3NH3、C4H9NH3Or
NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, m 1,2 or 3；
The hole transmission layer with a thickness of 30~80nm.
2. perovskite solar battery according to claim 1, which is characterized in that the prestox modified metal complex
Phthalocyanine is to modify copper phthalocyanine, prestox modification ZnPc, prestox selected from prestox to modify aluminium phthalocyanine, prestox modification palladium phthalein
At least one of cyanines, prestox modification titanium phthalocyanines and prestox modification vanadyl phthalocyanine.
3. perovskite solar battery according to claim 1 or 2, which is characterized in that the thickness of the hole transmission layer
For 60nm.
4. perovskite solar battery according to claim 1, which is characterized in that the electron transfer layer includes TiO2、
SnO2, at least one of C60 and C60 derivative PCBM；
The electron transfer layer with a thickness of 30~55nm.
5. perovskite solar battery according to claim 1, which is characterized in that the electron transfer layer with a thickness of
45nm。
6. perovskite solar battery according to claim 1, which is characterized in that the light-absorption layer with a thickness of 100~
800nm。
7. perovskite solar battery according to claim 1, which is characterized in that the light-absorption layer with a thickness of 150~
500nm。
8. perovskite solar battery according to claim 1, which is characterized in that the hole transmission layer is by eight
Methyl modified metal complex phthalocyanine carries out vapor deposition and is formed on the surface of the light-absorption layer.
9. perovskite solar battery according to claim 1, which is characterized in that the cathode layer is ITO or FTO cathode
Layer,
The cathode layer with a thickness of 100~150nm；
The anode layer is gold, silver, aluminium or graphene composite material anode layer；
The anode layer with a thickness of 80~120nm.
10. perovskite solar battery according to claim 1, which is characterized in that the cathode layer with a thickness of
120nm；
The anode layer with a thickness of 100nm.
11. a kind of method for preparing perovskite solar battery of any of claims 1-10, which is characterized in that packet
It includes:
(1) glass substrate is provided；
(2) cathode layer is formed in the glass baseplate surface；
(3) electron transfer layer is formed in the cathode layer surface；
(4) light-absorption layer is formed in the electron-transport layer surface；
(5) hole transmission layer is formed in the extinction layer surface；
(6) anode layer is formed in the hole transport layer surface, and the cathode layer is electrically connected with the anode layer.
12. according to the method for claim 11, which is characterized in that in step (2), formed in the glass baseplate surface
Cathode layer is then to etch to obtain to the FTO film or ito film of formation by sputtering at FTO or ITO on the glass substrate
's.
13. method according to claim 11 or 12, which is characterized in that in step (3), the electron transfer layer is logical
It crosses rubbing method and is formed in the cathode layer surface.
14. according to the method for claim 11, which is characterized in that in step (4), in the electron-transport layer surface shape
It is by the way that ABX will be contained at light-absorption layermY3-mThe one or more precursor solution of type crystal structure is spin-coated on the electron-transport
Layer surface after annealing obtains,
Wherein, A CH3NH3、C4H9NH3Or NH2=CHNH2, B is Pb or Sn, and X, Y are separately Cl, Br or I, m 1,2
Or 3.
15. according to the method for claim 11, which is characterized in that in step (5), form sky in the extinction layer surface
Cave transport layer is by the way that prestox modified metal complex phthalocyanine is deposited；
The prestox modified metal complex phthalocyanine is that copper phthalocyanine, prestox modification ZnPc, eight first are modified selected from prestox
Base modifies at least one of aluminium phthalocyanine, prestox modification palladium phthalocyanine, prestox modification titanium phthalocyanines and prestox modification vanadyl phthalocyanine.
16. according to the method for claim 11, which is characterized in that in step (6), in the hole transport layer surface shape
It at anode layer is obtained by vacuum thermal evaporation mode.
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