CN108110142A - A kind of cathode interface layer material and preparation method thereof and a kind of trans solar cell and preparation method thereof - Google Patents
A kind of cathode interface layer material and preparation method thereof and a kind of trans solar cell and preparation method thereof Download PDFInfo
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- CN108110142A CN108110142A CN201711350066.3A CN201711350066A CN108110142A CN 108110142 A CN108110142 A CN 108110142A CN 201711350066 A CN201711350066 A CN 201711350066A CN 108110142 A CN108110142 A CN 108110142A
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Abstract
The present invention provides a kind of cathode interface layer material and preparation method thereof, which coats vacant multi-metal oxygen cluster compound for surfactant, can be used as the cathode interface layer material of solar cell.The present invention provides a kind of trans solar cells, include cathode, cathode interface layer, active layer, anode interface layer and the anode for sequentially contacting setting；The cathode interface layer is K2[(CnH2n+1)4N]5[PW11O39] or K3[(CnH2n+1)4N]5[SiW11O39], n 4,6,8 or 10.The open-circuit voltage of the trans solar cell is 0.4~0.85V, and short circuit current flow is 9.53~15.93mAcm‑2, fill factor, curve factor is 53.2~67%, and photoelectric conversion efficiency is 4.42~8%.The present invention provides the preparation methods of trans solar cell, can obtain cathode interface layer at normal temperatures.
Description
Technical field
The present invention relates to technical field of solar batteries more particularly to a kind of cathode interface layer material and preparation method thereof and
A kind of trans solar cell and preparation method thereof.
Background technology
Polymer solar battery (PSCs) because material source is wide, property is easily adjusted, can be achieved flexibility, large area, it is low into
Originally, outstanding advantages of whole soln processing, international hot research field is had become in recent years.By people's more than ten years not
There is being breakthrough progress in slack effort, PSCs fields in recent years.
Under normal conditions, PSCs is made of the yin, yang electrode of active layer and both sides.According to the role of the electrode of light incidence
(cathode or anode), PSCs can be divided into two kinds of structures：When the electrode of light incidence is cathode, PSCs is trans device (I-
PSCs)；When the electrode of light incidence is anode, PSCs is formal device.And trans polymer solar battery has height because of it
Efficiency and long-life, more formal polymer solar battery have better application prospect.
In the prior art, the metal oxide of solution processing, such as zinc oxide (ZnO), titanium oxide (TiO2) commonly use and do cathode
Boundary layer.But high-temperature heating treatment is needed in such metal oxide cathode boundary layer membrane-film preparation process, waste is substantial amounts of
Resource.So far, surfactant is coated into vacant multi-metal oxygen cluster compound there has been no technical staff and is applied to trans gather
It closes in object solar cell.
The content of the invention
It is an object of the invention to provide a kind of trans solar cell, which is lacked with surfactant cladding
Position multi-metal oxygen cluster compound is as cathode interface layer material.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The present invention provides a kind of cathode interface layer materials, and the substance of chemical composition is formed as shown in Formulas I or Formula II：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；
K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
The present invention also provides the preparation methods of the cathode interface layer material, comprise the following steps：
Surfactant solution is added dropwise in multi-metal oxygen cluster solution, precipitation reaction obtains cathode interface layer material；Institute
It is (0.8~0.9) to state the ratio between total electrical charge number of surfactant base and multi-metal oxygen cluster raw material in preparation process:1；
In the preparation process, the selection of multi-metal oxygen cluster raw material is as follows：
When in the cathode interface layer material molecule, the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster it
Than for 0.7 when, the surfactant base be (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K7PW11O39；
When in the cathode interface layer material molecule, the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster it
Than for 0.6 when, the surfactant base be (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K8SiW11O39。
The present invention provides a kind of using the material as the solar cell of cathode interface layer, set comprising sequentially contact
Cathode, cathode interface layer, active layer, anode interface layer and anode, which is characterized in that the cathode interface layer by with Formulas I or
The substance of chemical composition shown in Formula II is formed：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
Preferably, the active layer is any one in polyphenyl 1,4-Dithiapentalene derivative and polycarbazole analog derivative and richness
Strangle the mixture of vinyl derivative.
Preferably, when the active layer is the mixture of polyphenyl 1,4-Dithiapentalene derivative and fullerene derivative, institute
The mass ratio for stating polyphenyl 1,4-Dithiapentalene derivative and fullerene derivative is 1:(1~2)；
When the active layer is the mixture of polycarbazole analog derivative and fullerene derivative, the polycarbazole class is spread out
The mass ratio of biology and fullerene derivative is 1:(3~5).
Preferably, the thickness of the cathode is 160~200nm；
The thickness of the cathode interface layer is 1~5nm；
The thickness of the active layer is 60~120nm；
The thickness of the anode interface layer is 8~12nm；
The thickness of the anode is 90~110nm.
Preferably, the anode interface layer is molybdenum trioxide；
The anode is silver or aluminium；
The cathode is tin indium oxide.
The present invention also provides a kind of preparation methods of the solar cell, comprise the following steps：
(1) in the cathode surface after the single side surface coated cathode boundary material methanol solution of cathode, solvent volatilization
Form cathode interface layer；The cathode interface material has chemical composition shown in Formulas I or Formula II；
(2) active layer material solution is coated in the cathode interface layer surface, in the cathode interface layer after solvent volatilization
Surface forms active layer；
(3) in the active layer surface vapor deposition anodic interface material, anode interface layer is formed；
(4) anode is deposited in the anodic interface layer surface, obtains solar cell.
Preferably, the concentration of the cathode interface material methanol solution is 0.5~1.5mg/mL；
The concentration of the active layer material solution is 18~35mg/mL.
Preferably, the speed of vapor deposition is in the step (3)
The speed of vapor deposition is in the step (4)
The present invention provides a kind of cathode interface layer material and preparation method thereof, which is surface-active
The vacant multi-metal oxygen cluster compound of agent cladding, can use as the cathode interface layer material of trans solar cell.
The present invention provides a kind of trans solar cells, include the cathode, cathode interface layer, activity for sequentially contacting setting
Layer, anode interface layer and anode；Cathode interface layer substance of chemical composition as shown in Formulas I or Formula II is formed：K2
[(CnH2n+1)4N]5[PW11O39] Formulas I；K3[(CnH2n+1)4N]5[SiW11O39] Formula II；In Formulas I and Formula II n independently be 4,6,8 or
10.The composition material of trans solar cell cathode interface layer provided by the invention is vacant for the surfactant cladding of alcohol-soluble
Multi-metal oxygen cluster compound includes organic radical moiety ((CnH2n+1)4N]5) and inorganic group part (PW11O39Or SiW11O39),
According to similar compatibility principle, inorganic group part can be good at and cathode contacts, and organic radical moiety can reduce cathode
Surface polarity, while be conducive to the adherency of active layer, reduce the contact resistance between active layer and cathode；Meanwhile cathode circle
The vacant position of multi-metal oxygen cluster is oxygen-enriched state in surface material, can effectively make up the anoxic trap on cathode material surface,
So as to improve the electric property of trans solar cell.From the experimental result of embodiment, it is provided by the invention it is trans too
The open-circuit voltage of positive energy battery is 0.4~0.85V, and short circuit current flow is 9.53~15.93mAcm-2, fill factor, curve factor for 53.2~
67%, photoelectric conversion efficiency is 4.42~8%.
The present invention also provides the preparation methods of the trans solar cell, and the moon is coated successively in the single side surface of cathode
Pole interlayer materials solution, coating active layer material solution, vapor deposition anode interface layer and vapor deposition anode, obtain trans solar-electricity
Pond.Preparation method provided by the invention can obtain cathode interface layer at normal temperatures, can save substantial amounts of resource.
Description of the drawings
Fig. 1 is the Current density-voltage performance chart for the trans solar cell that embodiment 5 obtains；
Fig. 2 is the Current density-voltage performance chart for the trans solar cell that embodiment 8 obtains；
Fig. 3 is the Current density-voltage performance chart for the trans solar cell that embodiment 16 obtains.
Specific embodiment
The present invention provides a kind of cathode interface layer materials, and the substance of chemical composition is formed as shown in Formulas I or Formula II：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；
K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
The present invention also provides the preparation methods of the cathode interface layer material, comprise the following steps：
Surfactant solution is added dropwise in multi-metal oxygen cluster solution, precipitation reaction obtains cathode interface layer material；Institute
It is (0.8~0.9) to state the ratio between total electrical charge number of surfactant base and multi-metal oxygen cluster raw material in preparation process:1；
Selection in the preparation process on multi-metal oxygen cluster raw material is as follows：
When in the cathode interface layer material molecule, the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster it
Than for 0.7 when, the surfactant base be (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K7PW11O39；
When in the cathode interface layer material molecule, the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster it
Than for 0.6 when, the surfactant base be (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K8SiW11O39。
In the present invention, the solvent of the surfactant solution and multi-metal oxygen cluster solution independently be methanol and/or
Ethyl alcohol.In the present invention, the concentration of the surfactant solution is preferably 5~20mg/mL, more preferably 8~18mg/mL,
Most preferably 10~15mg/mL；The concentration of the multi-metal oxygen cluster solution is preferably 15~20mg/mL, more preferably 16~
19mg/mL is most preferably 17~18mg/mL.In the present invention, surfactant base and multi-metal oxygen in the preparation process
The ratio between total electrical charge number of cluster raw material is (0.8~0.9):1, be preferably (0.83~0.85):1.In the present invention, the surface is lived
Property agent raw material is
(CnH2n+1)4NBr；The multi-metal oxygen cluster raw material is K7PW11O39Or K8SiW11O39。
In the present invention, the precipitation reaction carries out at room temperature, without any additional heating and cooling down operation；By institute
State surfactant solution be added dropwise in multi-metal oxygen cluster solution after start generate white precipitate, if precipitation generation rate compared with
Slowly, suitable water can be added to promote the precipitation of precipitation.The present invention does not have the specific time of the precipitation reaction special want
It asks, can be adjusted according to actual technology requirement.In the specific embodiment of the invention, the precipitation reaction drips table from first
Face activator solution starts to calculate when adding in, reaction time 2h.
In the present invention, when in the cathode interface layer material molecule, the total electrical charge and multi-metal oxygen cluster of quaternary ammonium salt group
The ratio between total electrical charge number when being 0.7, the surfactant base is (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are
K7PW11O39, corresponding product is cathode interface layer material shown in Formulas I；When in the cathode interface layer material molecule, quaternary ammonium salt
When the ratio between the total electrical charge of group and the total electrical charge number of multi-metal oxygen cluster are 0.6, the surfactant base is (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K8SiW11O39, corresponding product is cathode interface layer material shown in Formula II.
The present invention also provides a kind of trans solar cells, include the cathode, cathode interface layer, work for sequentially contacting setting
Property layer, anode interface layer and anode；Cathode interface layer substance of chemical composition as shown in Formulas I or Formula II is formed：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
Trans solar cell provided by the invention includes cathode.In the present invention, the cathode is preferably tin indium oxide
(ITO)；The thickness of the cathode is preferably 160~200nm, more preferably 170~190nm, is most preferably 180nm.The present invention
There is no any particular/special requirement to the source of the cathode, it will using the present techniques well-known to those skilled in the art that meet
The cathode asked.
Trans solar cell provided by the invention includes the cathode interface layer for being arranged on one side surface of cathode.In the present invention
In, cathode interface layer substance of chemical composition as shown in Formulas I or Formula II is formed：K2[(CnH2n+1)4N]5[PW11O39]
Formulas I；K3[(CnH2n+1)4N]5[SiW11O39] Formula II；N independently is 4,6,8 or 10 in Formulas I and Formula II；The group of the cathode interface layer
It is the vacant multi-metal oxygen cluster compound of surfactant cladding of alcohol-soluble into material, includes organic radical moiety and inorganic group
Part, according to similar compatibility principle, inorganic group part can be good at and cathode contacts, and organic radical moiety can be reduced
The surface polarity of cathode, while be conducive to the adherency of active layer, reduce the contact resistance between active layer and cathode.In the present invention
In, the thickness of the cathode interface layer is preferably 1~5nm, more preferably 2~4nm, is most preferably 3nm.
Trans solar cell provided by the invention includes the active layer for being arranged on cathode interface layer surface.In the present invention
In, the active layer is preferably that any one and fullerene in polyphenyl 1,4-Dithiapentalene derivative and polycarbazole analog derivative spread out
The mixture of biology.In the present invention, the polyphenyl 1,4-Dithiapentalene derivative is preferably purchased from 1-Material companies of Canada
PTB7 (poly- { double [(2- ethylhexyls) oxygroup] benzo [1,2-b of 4,8-：4,5-b'] Dithiophene -2,6- diyls-alternating -3-
Fluoro- 2- [(2- ethylhexyls) carbonyl] thieno [3,4-b] thiophene -4,6- diyl }), PTB7-Th (poly- [4,8- double (5- (2- second
Base hexyl) thiophene -2- bases) benzo [1,2-b：4,5-b'] Dithiophene -2,6- diyls-alternating-(4- (2- ethylhexyls) -3- fluorine
Thieno [3,4-b] thiophene -) -2- Ethyl formate -2-6 diyls)]), the polycarbazole analog derivative is preferably purchased from Canada
1-Material companies PCDTBT (it is poly- [[9- (1- octyl groups nonyl) -9H- carbazole -2,7- diyls] -2,5- thiophene diyl -2,1,
3- diazosulfide -4,7- diyl -2,5- thiophene diyl]), the fullerene derivative is preferably purchased from U.S. American
The PC of Dye Source, Inc companies71BM ([6,6]-phenyl-carbon 71- methyl butyrates) or PC61BM ([6,6]-phenyl-carbon 61-
Methyl butyrate).
In the present invention, the structural formula of each substance is as follows in the active layer：
In the present invention, when the active layer is polyphenyl 1,4-Dithiapentalene derivative and the mixture of fullerene derivative
When, the mass ratio of the polyphenyl 1,4-Dithiapentalene derivative and fullerene derivative is preferably 1:(1~2), more preferably 1:
1.5；When the active layer is the mixture of polycarbazole analog derivative and fullerene derivative, the polycarbazole analog derivative
Mass ratio with fullerene derivative is preferably 1:(3~5), more preferably 1:4.In the present invention, the polyphenyl and two thiophenes
The thickness of fen derivatives active layer is preferably 80~120nm, more preferably 90~110nm, is most preferably 100nm；The poly- click
The thickness of azole derivative active layer is preferably 60~90nm, more preferably 65~85nm, is most preferably 70nm.
Trans solar cell provided by the invention includes the anode interface layer for being arranged on active layer surface.In the present invention
In, the anode interface layer is preferably molybdenum trioxide；The thickness of the anode interface layer is preferably 8~12nm, more preferably 9~
11nm is most preferably 10nm.
Trans solar cell provided by the invention includes the anode for being arranged on anodic interface layer surface.In the present invention,
The anode is preferably silver or aluminium；The thickness of the anode is preferably 90~110nm, more preferably 95~105nm, is most preferably
100nm。
The present invention also provides the preparation methods of trans solar cell described in above-mentioned technical proposal, comprise the following steps：
(1) in the cathode surface after the single side surface coated cathode boundary material methanol solution of cathode, solvent volatilization
Form cathode interface layer；The cathode interface material has chemical composition shown in Formulas I or Formula II；
(2) active layer material solution is coated in the cathode interface layer surface, in the cathode interface layer after solvent volatilization
Surface forms active layer；
(3) in the active layer surface vapor deposition anodic interface material, anode interface layer is formed；
(4) anode is deposited in the anodic interface layer surface, obtains trans solar cell.
The present invention cathode single side surface coated cathode boundary material methanol solution, solvent volatilization after in the cathode table
Face forms cathode interface layer.In the present invention, the cathode interface material has chemical composition shown in Formulas I or Formula II, herein not
It is repeated again.In the present invention, the concentration of the cathode interface material methanol solution is preferably 0.5~1.5mg/mL, more excellent
Elect 1mg/mL as.
The present invention does not have the embodiment of the coating any particular/special requirement, can be molten by cathode interface material methanol
Liquid is homogeneously applied to cathode surface.In the present invention, the coating is specifically the spin coating carried out using spin coating instrument,
The rotating speed of the spin coating is preferably 1400~1600r/min, more preferably 1500r/min；The time of the spin coating is preferably 1~
3min can be specifically 1min, 2min or 3min.In the present invention, the coating thickness tool of cathode interface material methanol solution
Body carries out experience setting according to the thickness of cathode interface layer.The present invention does not have the mode that the solvent volatilizees any
Particular/special requirement can make solvent volatilization totally obtain solid cathode interface layer.The present invention specifically makes institute at room temperature
Solvent is stated to volatilize naturally.
After obtaining being arranged at the cathode interface layer on cathode, the present invention coats active layer material in the cathode interface layer surface
Expect solution, active layer is formed in the cathode interface layer surface after solvent volatilization.In the present invention, the active layer material solution
Solvent be preferably volume ratio be 97:3 chlorobenzene and 1, the mixture of 8 diiodo-octanes or be that volume ratio is 1:3 chlorobenzene and
The mixture of dichloro-benzenes；The active layer material is any one in polyphenyl 1,4-Dithiapentalene derivative and polycarbazole analog derivative
With the mixture of fullerene derivative, no longer repeated herein.In the present invention, the concentration of the active layer material solution
Preferably 18~35mg/mL, more preferably 25~30mg/mL.The present invention is same to the technology requirement of the coating and solvent volatilization
Described in technical solution above, no longer repeated herein.
After obtaining the active layer being arranged on cathode interface layer, the present invention is in the active layer surface vapor deposition anodic interface material
Material forms anode interface layer.The present invention does not have the method for the vapor deposition any particular/special requirement, using those skilled in the art
The common method of institute is deposited.In the present invention, the vapor deposition is preferably using molybdenum trioxide powder as raw material, the vapor deposition
Speed is preferablyMore preferablyMost preferablyThe vacuum degree of the vapor deposition
Preferably 1.7~1.9 × 10-4Pa, more preferably 1.8 × 10-4Pa；The electric current of the vapor deposition is preferably 25~33A, more preferably
For 29~30A；The voltage of the vapor deposition is preferably 1~2V, more preferably 1.5V；The temperature of the substrate is preferably 28~33
DEG C, more preferably 30 DEG C.The present invention does not have particular/special requirement to the grain size of the molybdenum trioxide powder, using those skilled in the art
Known commercially available vapor deposition molybdenum trioxide powder.
After obtaining being arranged at the anode interface layer on active layer, anode is deposited in the anodic interface layer surface in the present invention,
Obtain trans solar cell.The present invention does not have the method for the vapor deposition any particular/special requirement, using people in the art
The common method of member institute is deposited.In the present invention, the vapor deposition is preferably with aluminium or silver-colored for raw material, the speed of the vapor deposition
Degree is preferablyMore preferablyMost preferablyThe vacuum degree of the vapor deposition is preferably 1.7
~1.9 × 10-4Pa, more preferably 1.8 × 10-4Pa；The electric current of the vapor deposition is preferably 32~40A, more preferably 34~37A；
The voltage of the vapor deposition is preferably 1~2V, more preferably 1.5~1.7V；The temperature of the substrate is preferably 28~33 DEG C, more excellent
Elect 30 DEG C as.The present invention does not have particular/special requirement to the form of the aluminium and silver, using well-known to those skilled in the art commercially available
Vapor deposition aluminium (powder, item, piece and block etc.) and silver-colored (powder, item, piece and block etc.).
With reference to embodiment to cathode interface layer material provided by the invention and preparation method thereof and solar cell and
Its preparation method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Compound K2[(C8H17)4N]5[PW11O39] preparation
By 0.10g (C8H17)4NBr is dissolved in 15mL methanol, 0.86g K7PW11O39It is dissolved in 15mL methanol, controls
(C8H17)4NBr and K7PW11O39Molar ratio be 2.5:1 (charge ratio be 2.5:3).It is stirred at room temperature under state, by (C8H17)4NBr methanol solutions are added drop-wise to K dropwise7PW11O39Methanol solution in, with (C8H17)4The instillation of NBr, solution turned cloudy have
White precipitate generates.Room temperature continues after stirring 2h, and the precipitation of generation is filtered out, and deionization is washed 3 times, each 30mL, is finally obtained
To white solid sample, room temperature in vacuo drying obtains compound K2[(C8H17)4N]5[PW11O39]。
Elemental analysis (%), theoretical value { K2[C32H68N]5[PW11O39], 5089.88g mol-1}：C37.76,H 6.73,
N 1.38；Experiment value：C 38.57,H 6.77,N 1.33.
Embodiment 2
Compound K3[(C8H17)4N]5[SiW11O39] preparation
By 0.10g (C8H17)4NBr is dissolved in 15mL methanol, 0.96g K8SiW11O39It is dissolved in 15mL methanol, controls
(C8H17)4NBr and K8SiW11O39Molar ratio be 2.5:1 (charge ratio be 2.5:3).It is stirred at room temperature under state, by (C8H17)4NBr methanol solutions are added drop-wise to K dropwise8SiW11O39Methanol solution in, with (C8H17)4The instillation of NBr, solution turned cloudy have
White precipitate generates.Room temperature continues after stirring 2h, and the precipitation of generation is filtered out, and deionization is washed 3 times, each 30mL, is finally obtained
To white solid sample, room temperature in vacuo drying obtains compound K3[(C8H17)4N]5[SiW11O39]。
Elemental analysis (%), theoretical value { K3[C32H68N]5[SiW11O39], 5126.09g mol-1}：C37.49,H 6.69,
N 1.37；Experiment value：C 39.11,H 6.83,N 1.35.
Embodiment 3
ITO/K2[(C4H9)4N]5[PW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 160nm thickness ITO cathodes is coated with-1K2[(C4H9)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C4H9)4N]5
[PW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml's concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM (matter
Amount is than being 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer MoO3,
Thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage is
0.725V, short-circuit current density 14.95mAcm-2, fill factor, curve factor 64.2%, it is 6.96% to be computed electricity conversion.
Embodiment 4
ITO/K2[(C6H13)4N]5[PW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 170nm thickness ito anodes is coated with-1K2[(C6H13)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C6H13)4N]5
[PW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml's concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM (matter
Amount is than being 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer MoO3,
Thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage is
0.735V, short-circuit current density 15.32mAcm-2, fill factor, curve factor 64.8%, it is 7.30% to be computed electricity conversion.
Embodiment 5
ITO/K2[(C8H17)4N]5[PW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 180nm thickness ito anodes is coated with-1K2[(C8H17)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C8H17)4N]5
[PW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml's concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM (matter
Amount is than being 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer MoO3,
Thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results are shown in Figure 1.Since 1 can
It is 0.750V, short-circuit current density 15.93mAcm to know the device open-circuit voltage-2, fill factor, curve factor 67.0%, be computed power turn
It is 8.00% to change efficiency.
Embodiment 6
ITO/K2[(C10H21)4N]5[PW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 190nm thickness ito anodes is coated with-1K2[(C10H21)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C10H21)4N]5
[PW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml's concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM (matter
Amount is than being 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer MoO3,
Thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.745V, short-circuit current density 15.56mAcm-2, fill factor, curve factor 65.7%, it is 7.62% to be computed electricity conversion.
Embodiment 7
ITO/K2[(C8H17)4N]5[PW11O39]/PTB7:PC71BM/MoO3/Ag
It is 1.0mg mL concentration on the glass substrate of 200nm thickness ito anodes is coated with-1K2[(C8H17)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C8H17)4N]5
[PW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml's concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM (matter
Amount is than being 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer MoO3,
Thickness is about 10nm；WithSpeed vapor deposition Ag anodes, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.750V, short-circuit current density 15.83mAcm-2, fill factor, curve factor 65.2%, it is 7.74% to be computed electricity conversion.
Embodiment 8
ITO/K2[(C8H17)4N]5[PW11O39]/PCDTBT:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 165nm thickness ito anodes is coated with-1K2[(C8H17)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C8H17)4N]5
[PW11O39], thickness is about 3nm；With dichloro-benzenes：Chlorobenzene (3：1, v%) it is 35mg/ml's concentration as mixed solvent
PCDTBT and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PCDTBT:
PC71BM (mass ratioes 1:4), thickness is about 70nm；Then in storehouse is deposited successively withSpeed vapor deposition anodic interface
Layer MoO3, thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results are shown in Figure 1.It can by Fig. 2
It is 0.85V, short-circuit current density 10.75mAcm to know the device open-circuit voltage-2, fill factor, curve factor 62.5%, be computed photoelectricity turn
It is 5.71% to change efficiency.
Embodiment 9
ITO/K2[(C8H17)4N]5[PW11O39]/PCDTBT:PC71BM/MoO3/Ag
It is 1.0mg mL concentration on the glass substrate of 175nm thickness ito anodes is coated with-1K2[(C8H17)4N]5
[PW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K2[(C8H17)4N]5
[PW11O39], thickness is about 3nm；With dichloro-benzenes：Chlorobenzene (3：1, v%) it is 35mg/ml's concentration as mixed solvent
PCDTBT and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PCDTBT:
PC71BM (mass ratioes 1:4), thickness is about 70nm；Then in storehouse is deposited successively withSpeed vapor deposition anodic interface
Layer MoO3, thickness is about 10nm；WithSpeed vapor deposition Ag anodes, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.835V, short-circuit current density 10.15mAcm-2, fill factor, curve factor 61.3%, it is 5.20% to be computed electricity conversion.
Embodiment 10
ITO/K3[(C4H9)4N]5[SiW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 185nm thickness ito anodes is coated with-1K3[(C4H9)4N]5
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C4H9)4N]5
[SiW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM
(mass ratio 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer
MoO3, thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.700V, short-circuit current density 15.32mAcm-2, fill factor, curve factor 53.2%, it is 5.70% to be computed electricity conversion.
Embodiment 11
ITO/K3[(C6H13)4N]5[SiW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 195nm thickness ito anodes is coated with-1K3[(C6H13)4N]5
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C6H13)4N]5
[SiW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml concentration
PTB7 and PC71The mixed solution of BM rotates 1min spin coatings under the rotating speed of 1500r/min and obtains active layer PTB7:PC71BM
(mass ratio 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer
MoO3, thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.710V, short-circuit current density 15.00mAcm-2, fill factor, curve factor 55.7%, it is 5.93% to be computed electricity conversion.
Embodiment 12
ITO/K3[(C8H17)4N]5[SiW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 180nm thickness ito anodes is coated with-1K3[(C8H17)4N]5
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C8H17)4N]5
[SiW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM
(mass ratio 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer
MoO3, thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.725V, short-circuit current density 15.29mAcm-2, fill factor, curve factor 57.6%, it is 6.38% to be computed electricity conversion.
Embodiment 13
ITO/K3[(C8H17)5N]4[SiW11O39]/PTB7:PC71BM/MoO3/Ag
It is 1.0mg mL concentration on the glass substrate of 190nm thickness ito anodes is coated with-1K3[(C8H17)5N]4
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C8H17)4N]5
[SiW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM
(mass ratio 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer
MoO3, thickness is about 10nm；WithSpeed vapor deposition Ag anodes, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.720V, short-circuit current density 15.11mAcm-2, fill factor, curve factor 56.2%, it is 6.11% to be computed electricity conversion.
Embodiment 14
ITO/K3[(C8H17)5N]4[SiW11O39]/PCDTBT:PC71BM/MoO3/Ag
It is 1.0mg mL concentration on the glass substrate of 170nm thickness ito anodes is coated with-1K3[(C8H17)5N]4
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C8H17)4N]5
[SiW11O39], thickness is about 3nm；With dichloro-benzenes：Chlorobenzene (3：1, v%) it is 35mg/ml's concentration as mixed solvent
PCDTBT and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PCDTBT:
PC71BM (mass ratioes 1:4), thickness is about 70nm；Then in storehouse is deposited successively withSpeed vapor deposition anodic interface
Layer MoO3, thickness is about 10nm；WithSpeed vapor deposition Ag anodes, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.825V, short-circuit current density 9.53mAcm-2, fill factor, curve factor 56.2%, it is 4.42% to be computed electricity conversion.
Embodiment 15
ITO/K3[(C10H21)4N]5[SiW11O39]/PTB7:PC71BM/MoO3/Al
It is 1.0mg mL concentration on the glass substrate of 180nm thickness ito anodes is coated with-1K3[(C10H21)4N]5
[SiW11O39] methanol solution 1min is rotated under the rotating speed of 1500r/min, spin coating obtains cathode interface layer K3[(C10H21)4N]5
[SiW11O39], thickness is about 3nm；With chlorobenzene：1,8 diiodo-octane (97：3, v%) it is mixed solvent, is 25mg/ml concentration
PTB7 and PC71The mixed solution of BM rotates 1min under the rotating speed of 1500r/min, and spin coating obtains active layer PTB7:PC71BM
(mass ratio 1:1.5), thickness is about 90nm；Then in storehouse is deposited successively withSpeed vapor deposition anode interface layer
MoO3, thickness is about 10nm；WithSpeed evaporating Al anode, thickness is about 100nm.
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.715V, short-circuit current density 14.64mAcm-2, fill factor, curve factor 56.5%, it is 5.91% to be computed electricity conversion.
Embodiment 16
[ITO/K2[(C8H17)4N]5[PW11O39]/PTB7-Th:PC71BM/MoO3/Al]
The spin coating embellishing cathode interface layer K successively on the glass substrate of ito anode for being coated with 180nm thickness2[(C8H17)4N]5
[PW11O39] (preparation method：It is 1.0mg mL concentration using spin coating instrument-1K2[(C8H17)4N]5[PW11O39] methanol
Solution rotates 1min under the rotating speed of 2000r/min), thickness is about 3nm；Active layer PTB7-Th:PC71BM, thickness are about
100nm；Then positive anodic interface decorative layer MoO is deposited successively in the vapor deposition storehouse of high vacuum3, thickness is about 10nm；Al anodes,
Thickness is about 100nm, wherein MoO3Evaporation rate be aboutThe evaporation rate of Al is
The trans solar cell device that the present embodiment obtains is tested for the property, the results are shown in Figure 3.It can by Fig. 3
Know, which is 0.80V, short-circuit current density 15.01mAcm-2, fill factor, curve factor 50.9%, be computed photoelectricity turn
It is 6.15% to change efficiency.
Embodiment 17
[ITO/K3[(C8H17)4N]5[SiW11O39]/PTB7-Th:PC71BM/MoO3/Al]
The spin coating embellishing cathode interface layer K successively on the glass substrate of ito anode for being coated with 180nm thickness3[(C8H17)4N]5
[SiW11O39] (preparation method：It is 1.0mg mL concentration using spin coating instrument-1K3[(C8H17)4N]5[SiW11O39] alcohol
Solution rotates 1min under the rotating speed of 2000r/min), thickness is about 3nm；Active layer PTB7-Th:PC71BM, thickness are about
100nm；Then positive anodic interface decorative layer MoO is deposited successively in the vapor deposition storehouse of high vacuum3, thickness is about 10nm；Al anodes,
Thickness is about 100nm, wherein MoO3Evaporation rate be aboutThe evaporation rate of Al is
The trans solar cell device that the present embodiment obtains is tested for the property, the results show device open-circuit voltage
For 0.80V, short-circuit current density 12.83mAcm-2, fill factor, curve factor 50.2%, it is 5.12% to be computed electricity conversion.
As seen from the above embodiment, the present invention provides a kind of trans solar cell, the moon for sequentially contacting setting is included
Pole, cathode interface layer, active layer, anode interface layer and anode；Cathode interface layer chemical group as shown in Formulas I or Formula II
Into substance formed：K2[(CnH2n+1)4N]5[PW11O39] Formulas I；K3[(CnH2n+1)4N]5[SiW11O39] Formula II；N in Formulas I and Formula II
It independently is 4,6,8 or 10；The active layer is any one in polyphenyl 1,4-Dithiapentalene derivative and polycarbazole analog derivative
With the mixture of fullerene derivative.The composition material of trans solar cell cathode interface layer provided by the invention is molten for alcohol
Property N-type semiconductor, i.e. the vacant multi-metal oxygen cluster compound of surfactant cladding includes organic radical moiety ((CnH2n+1)4N]5) and inorganic group part (PW11O39Or SiW11O39), according to similar compatibility principle, inorganic group part can be good at
And cathode contacts, organic radical moiety can reduce the surface polarity of cathode, while be conducive to the adherency of active layer, reduce activity
Contact resistance between layer and cathode；Meanwhile in cathode interface layer material multi-metal oxygen cluster vacant position for oxygen-enriched state, energy
Enough anoxic traps for effectively making up cathode material surface, so as to improve the electric property of trans solar cell.By embodiment
Experimental result understand that the open-circuit voltage of trans solar cell provided by the invention is 0.4~0.85V, short circuit current flow is
9.53~15.93mAcm-2, fill factor, curve factor is 53.2~67%, and photoelectric conversion efficiency is 4.42~8%.
The present invention also provides the preparation methods of the trans solar cell, and the moon is coated successively in the single side surface of cathode
Pole boundary material solution, coating active layer material solution, vapor deposition anode interface layer and vapor deposition anode, obtain trans solar-electricity
Pond.Preparation method provided by the invention can obtain cathode interface layer at normal temperatures, can save substantial amounts of resource.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of cathode interface layer material, the substance of chemical composition is formed as shown in Formulas I or Formula II：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；
K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
2. the preparation method of cathode interface layer material, comprises the following steps described in claim 1：
Surfactant solution is added dropwise in multi-metal oxygen cluster solution, precipitation reaction obtains cathode interface layer material；The system
The ratio between total electrical charge number of surfactant base and multi-metal oxygen cluster raw material is (0.8~0.9) during standby:1；
In the preparation process, the selection of multi-metal oxygen cluster raw material is as follows：
When in the cathode interface layer material molecule, the ratio between the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster are
When 0.7, the surfactant base is (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K7PW11O39；
When in the cathode interface layer material molecule, the ratio between the total electrical charge of quaternary ammonium salt group and the total electrical charge number of multi-metal oxygen cluster are
When 0.6, the surfactant base is (CnH2n+1)4NBr, the multi-metal oxygen cluster raw material are K8SiW11O39。
3. it is a kind of using material described in claim 1 as the trans solar cell of cathode interface layer, it is set comprising sequentially contact
Cathode, cathode interface layer, active layer, anode interface layer and anode, which is characterized in that the cathode interface layer by with Formulas I or
The substance of chemical composition shown in Formula II is formed：
K2[(CnH2n+1)4N]5[PW11O39] Formulas I；
K3[(CnH2n+1)4N]5[SiW11O39] Formula II；
N independently is 4,6,8 or 10 in Formulas I and Formula II.
4. trans solar cell according to claim 3, which is characterized in that the active layer spreads out for polyphenyl 1,4-Dithiapentalene
Biology and any one in polycarbazole analog derivative and the mixture of fullerene derivative.
5. trans solar cell according to claim 3, which is characterized in that when the active layer is polyphenyl 1,4-Dithiapentalene
During the mixture of derivative and fullerene derivative, the quality of the polyphenyl 1,4-Dithiapentalene derivative and fullerene derivative
Than for 1:(1~2)；
When the active layer is the mixture of polycarbazole analog derivative and fullerene derivative, the polycarbazole analog derivative
Mass ratio with fullerene derivative is 1:(3~5).
6. the trans solar cell according to claim 3~5 any one, which is characterized in that the thickness of the cathode
For 160~200nm；
The thickness of the cathode interface layer is 1~5nm；
The thickness of the active layer is 60~120nm；
The thickness of the anode interface layer is 8~12nm；
The thickness of the anode is 90~110nm.
7. trans solar cell according to claim 6, which is characterized in that the anode interface layer is molybdenum trioxide；
The anode is silver or aluminium；
The cathode is tin indium oxide.
8. the preparation method of trans solar cell, comprises the following steps described in claim 3~7 any one：
(1) formed after the single side surface coated cathode boundary material methanol solution of cathode, solvent volatilization in the cathode surface
Cathode interface layer；The cathode interface material has chemical composition shown in Formulas I or Formula II；
(2) active layer material solution is coated in the cathode interface layer surface, in the cathode interface layer surface after solvent volatilization
Form active layer；
(3) in the active layer surface vapor deposition anodic interface material, anode interface layer is formed；
(4) anode is deposited in the anodic interface layer surface, obtains trans solar cell.
9. preparation method according to claim 8, which is characterized in that the concentration of the cathode interface material methanol solution is
0.5~1.5mg/mL；
The concentration of the active layer material solution is 18~35mg/mL.
10. preparation method according to claim 8, which is characterized in that the speed of vapor deposition is in the step (3)
The speed of vapor deposition is in the step (4)
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