CN106067514A - A kind of translucent organic solar batteries and preparation method thereof - Google Patents
A kind of translucent organic solar batteries and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of translucent organic solar batteries, including substrate and organic solar cell element, organic solar cell element comprises transparent anode, hole transmission layer, active layer, electron transfer layer and transparent cathode successively；The thickness of described electron transfer layer is 5～30nm, and electron transfer layer is PF3N 2TNDI.Present invention also offers the preparation method of above-mentioned translucent organic solar batteries.The characteristic that the present invention utilizes described electric transmission layer thickness to change flexibly carries out optics regulation and control, can optimize the photoelectric transformation efficiency of described active layer；Meanwhile, the light transmission of device can realize by regulating and controlling the thickness of described transparent cathode.Translucent organic solar batteries prepared by the present invention has the feature that energy conversion efficiency is high, transmitance is high, color rendering properties is good simultaneously, is expected to realize the application of BIPV.
Description
Technical field
The present invention relates to organic electro-optic device technical field, particularly to a kind of translucent organic solar batteries and system thereof
Preparation Method.
Background technology
Increasingly serious along with global energy crisis and environmental problem, solar energy as a kind of green renewable new forms of energy,
Become the focus of research both at home and abroad.Solaode is the main Land use systems of solar energy, with traditional inorganic solar-electricity
Pond is compared, and organic solar batteries has low cost, light weight, solution processable, is particularly prone to advantage prepared by large area,
Thus there is research and using value more widely.At present, the highest energy conversion efficiency of single-unit organic solar batteries is
More than 11% (Advanced Materials, 2016, DOI:10.1002/adma.201600281).Meanwhile, organic light-absorption layer
It is discontinuous that material has absorption spectrum, is easily formed in the characteristic of the translucent solar cell device of visible light wave range.Therefore, half
Transparent organic solar batteries can be applied in the manufacture of building colour window and vehicle glass, has huge business and dives
Energy.
At present, realize higher energy conversion efficiency, light transmittance and color developing be simultaneously still faced with bigger challenge.Right
In the selection of device active layers material, usually narrow band gap polymeric donor (such as: PBDTT-DPP, PTB7, PIDT-PhanQ,
PCDTBT and PBDTTT-C-T) with the mixture of fullerene acceptor, by further optimised devices structure or reduce semi-transparent funerary objects
The light loss that in part, the introducing of transparency electrode brings, when mean transmissivity is 20% and 30%, its device efficiency respectively up to
6.55% (Scientific reports, 2016, DOI:10.1038/srep12161) and 5.6% (Nature Photonics
2013,7,995).But, in translucent battery, the thickness of active layer is usually 80～100nm, because thinner active layer can drop
The short-circuit current density of low device, thus cause the reduction of device efficiency；And according to Lambert-beer's law, the thinnest active layer,
Its light transmittance is the highest.Therefore, the method finding raising device efficiency based on relatively thin active layer thickness further is non-the normally off key
's.From the angle of raising light transmittance, preparation high-quality transparent top electrode is key point.It is generally selected super thin metal (such as silver) thin film
As transparent top electrode, because it has easily processing, good conductivity, the advantage of depth of penetration length.But, metal (such as calcium)/silver
Double-decker electrode is generally also more difficult to get the Ag films that light transmission is good, electric conductivity is high, surface is smooth, this severely limits semi-transparent
The energy conversion efficiency of bright organic solar batteries and the further raising of mean transmissivity.
Summary of the invention
In order to overcome the disadvantages mentioned above of prior art with not enough, it is an object of the invention to provide a kind of translucent organic too
Sun energy battery, significantly improves the energy conversion efficiency of device, concurrently facilitates formation transparent cathode, thus improve the average of device
Transmitance, and this translucent organic solar batteries has good color developing.
Another object of the present invention is to provide the preparation method of above-mentioned translucent organic solar batteries.
The purpose of the present invention is achieved through the following technical solutions:
A kind of translucent organic solar batteries, including substrate and organic solar cell element, organic solar batteries
Element comprises transparent anode, hole transmission layer, active layer, electron transfer layer and transparent cathode successively；
The thickness of described electron transfer layer is 5～30nm, and electron transfer layer is PF3N-2TNDI, has a following structural formula:
Wherein n is the natural number of 0～10000.
Described hole transmission layer is PEDOT:PSS, and thickness is 30～50nm.
Active layer be mass ratio be 1:(1.5～1.6) PTB7-Th and PC71The mixture of BM, thickness is 50～100nm.
Described substrate is glass.
Described transparent anode is ITO layer, is coated on substrate.
Described transparent cathode is Ag, and thickness is 10～20nm.
The thickness of described electron transfer layer is 15nm, and the thickness of described transparent cathode is 14nm.
A kind of translucent organic solar batteries preparation method, comprises the following steps:
(1) cleaning is coated with the glass substrate of ITO layer and is dried；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000～3500rpm, thick
Degree is about 40nm；Then 140～160 DEG C of thermal anneal process 15～20min；
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5～1.6, molten
In chlorobenzene solvent, it is configured to mixed solution, 50～55 DEG C of stirrings 10～14h；Then mixed solution is spun on PEDOT:PSS
On hole transmission layer, obtain the active layer that thickness is 50～100nm；
(4) PF3N-2TNDI is dissolved in solvent, is configured to solution；Then solution is spun on PTB7-Th:PC71BM lives
On property layer, form the electron transfer layer that thickness is 5～30nm；
(5) on PF3N-2TNDI electron transfer layer, evaporation thickness is the Ag transparent cathode of 10～20nm.
Step (4) is described to be dissolved in PF3N-2TNDI in solvent, is configured to solution；Then solution is spun on PTB7-Th:
PC71On BM active layer, particularly as follows:
Being dissolved in the mixed solvent being made up of acetic acid and methanol by PF3N-2TNDI, being configured to concentration is 0.5～5mg mL-1
Solution；Then solution is spun on PTB7-Th:PC71On BM active layer, spin coating speed is 2000～2200rpm；
In described mixed solvent, the volume ratio of acetic acid and methanol is 3:97～5:95.
Step (3) described spin coating, specifically, spin coating speed is 1000～3500rpm.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the translucent organic solar batteries in the present invention, has higher energy conversion efficiency and mean transmissivity,
And this translucent organic solar batteries shows good color developing.
(2) characteristic that the present invention can change flexibly according to electric transmission layer thickness innovatively carries out optics regulation and control, thus
Optimize the energy conversion efficiency of active layer.
(3) electron transfer layer that the present invention uses is conducive to even compact, good conductivity, transparent the moon that transparency is high simultaneously
The formation of pole, thus it is effectively increased the mean transmissivity of device.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the translucent organic solar batteries device of embodiments of the invention.Wherein, 1 is substrate, 2
For transparent anode, 3 is hole transmission layer, and 4 is active layer, and 5 is electron transfer layer, and 6 is transparent cathode.
Fig. 2 (a)～(d) are respectively electron transfer layer in the translucent organic solar batteries of embodiments of the invention
(15nm) upper thickness be respectively 10,12,14, the atomic force microscope figure of the silver electrode of 20nm.
Fig. 3 be embodiments of the invention translucent organic solar batteries device in silver electrode thickness when being 14nm, electricity
Sub-transport layer thickness is respectively Current density-voltage characteristic curve when 5 and 15nm.
Fig. 4 be embodiments of the invention translucent organic solar batteries device in silver electrode thickness when being 14nm, electricity
Transmitance distribution curve when sub-transport layer thickness is respectively 5 and 15nm.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) glass substrate of ITO layer it is coated with successively with acetone, micron order quasiconductor special purpose detergent, deionized water, different
Propanol ultrasonic cleaning, drying nitrogen dry up be placed in culture dish standby；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000rpm, and thickness is
40nm；Then 140 DEG C of thermal anneal process 20min；
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5, is dissolved in volume
Ratio is that in the DIO/ chlorobenzene solvent of 3/97, being configured to concentration is 20mg mL-1Mixed solution, 50 DEG C stirring 12h；Then will be mixed
Closing solution to be spun on PEDOT:PSS hole transmission layer, spin coating speed is 3500rpm, obtains the active layer that thickness is 50nm；
(4) PF3N-2TNDI is dissolved in acetic acid/methanol solvate that volume ratio is 5/95, is configured to concentration and is respectively 0.5,2
With 4.5mg mL-1Solution；Then the solution of variable concentrations is spun on PTB7-Th:PC71On BM active layer, spin coating speed is
2000rpm, forms thickness and is respectively the electron transfer layer of 5,15 and 30nm；
The preparation process of the PF3N-2TNDI of the present embodiment is as follows:
By bromo-for monomer 2,7-bis-N, N '-two (2-ethyl hexane)-1,7-two thiophene-tetracarboxylic acid diimide
(0.5mmol), 2,7-bis-(4,4,5,5-tetramethyl-1,3,2-dioxaborinate base)-9,9 '-two (6-(N, N-diethylamide
Base-propyl group) fluorine) (0.5mmol) and 5mg tetra-(Phenylphosphine) palladium be dissolved in the mixed solvent of 5mL toluene and 2mL oxolane, add
Enter the wet chemical of 2mL/2M.Under the protection of nitrogen, 95 DEG C of heated and stirred 3 hours.Question response solution is cooled to room temperature,
It is precipitated in acetone and obtains crude product, be dissolved in toluene, and with organic membrane filtration of 0.45 micron, concentrate, will
This solution precipitates in methanol and obtains polymer beads, is finally dried 24 hours at 45 DEG C in vacuum drying oven, obtains black-and-blue
Polymer solids.The molecular weight recorded with GPC is Mn=12.3kg/mol, PDI=1.70.
The bromo-N of monomer 2,7-bis-, N '-two (2-ethyl hexane)-1,7-two thiophene-tetracarboxylic acid diimide is according to literary composition
Prepared by (Chem.Mater.2011,23,4563) open method of offering.Monomer 2,7-bis-(4,4,5,5-tetramethyl-1,3,2-dioxy
Miscellaneous boryl)-9,9 '-two (6-(N, N-diethyl amido-propyl group) fluorine) be according to document (J.Am.Chem.Soc.2004,
126,9845) prepared by open method.
(5) on PF3N-2TNDI electron transfer layer, evaporation thickness is that the silver electrode of 100nm is as negative electrode.
The translucent organic solar batteries device architecture that the present embodiment obtains is as shown in Figure 1.
For the effect of further comparative illustration electron transfer layer, being prepared for structure is ITO/PEDOT:PSS/PTB7-Th:
PC71The device of BM/Ca/Al, the detailed preparation process of device is as follows:
(1) glass substrate of ITO layer it is coated with successively with acetone, micron order quasiconductor special purpose detergent, deionized water, different
Propanol ultrasonic cleaning, drying nitrogen dry up be placed in culture dish standby；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000rpm, and thickness is
40nm；Then 140 DEG C of thermal anneal process 20min；
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5, is dissolved in volume
Ratio is that in the DIO/ chlorobenzene solvent of 3/97, being configured to concentration is 20mg mL-1Mixed solution, 50 DEG C stirring 12h；Then will be mixed
Closing solution to be spun on PEDOT:PSS hole transmission layer, spin coating speed is 3500rpm, obtains the active layer that thickness is 50nm；
(4) at PTB7-Th:PC71On BM active layer, evaporation thickness is that the silver electrode of the calcium of 10nm and 100nm is as the moon successively
Pole.
The organic solar batteries of two kinds of different structures described in embodiment 1 is carried out photoelectric device performance test, and visits
Study carefully the impact on device performance of the different electric transmission layer thickness, the results are shown in Table 1.
Table 1 different structure and the solar cell device performance indications of different electric transmission layer thickness
As shown in Table 1, the organic solar batteries that prepared by the present invention can be by introducing new electron transfer layer PF3N-
2TNDI improves the performance of device, and can be by changing the thickness of electron transfer layer, the performance of flexible modulation device.Work as electronics
When transport layer thickness is 15nm, device performance is optimal, and short-circuit current density increases to 16.07mA cm from 12.96-2, energy is changed
Efficiency increases to 9.07% from 6.64%, increases about 37%.
Embodiment 2
(1) glass substrate of ITO layer it is coated with successively with acetone, micron order quasiconductor special purpose detergent, deionized water, different
Propanol ultrasonic cleaning, drying nitrogen dry up be placed in culture dish standby；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000rpm, and thickness is about
40nm；Then 140 DEG C of thermal anneal process 20min；
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5, is dissolved in volume
Ratio is that in the DIO/ chlorobenzene solvent of 3/97, being configured to concentration is 20mg mL-1Mixed solution, 50 DEG C stirring 12h；Then will be mixed
Closing solution to be spun on PEDOT:PSS hole transmission layer, spin coating speed is 3500rpm, obtains the active layer that thickness is 50nm；
(4) PF3N-2TNDI being dissolved in acetic acid/methanol solvate that volume ratio is 5/95, being configured to concentration is 2mg mL-1's
Solution；Then the solution of variable concentrations is spun on PTB7-Th/PC71On BM active layer, spin coating speed is 2000rpm, forms thickness
Degree is the electron transfer layer of 15nm；
(5) on PF3N-2TNDI electron transfer layer, evaporation thickness is 10,12,14 or the silver-colored transparent cathode of 20nm.
Atomic force microscopy for the silver electrode at the upper different-thickness (10,12,14 or 20nm) of electron transfer layer (15nm)
Mirror morphology characterization, result such as Fig. 2, its rms surface roughness is followed successively by 3.90,2.67,2.90 and 1.94nm.Meanwhile, four probe
Method records its surface resistance RsIt is followed successively by 16.4,9.5,7.4 and 2.9 Ω/sq.When being 15nm for electric transmission layer thickness, no
With the solar cell device performance parameter under silver transparency electrode thickness and light transmittance parameter testing, the results are shown in Table 2.Work as silver electrode
When thickness is 12～20nm, preferable short-circuit current density can be obtained, illustrate the most to be formed even compact, good conductivity saturating
Bright negative electrode.When silver electrode thickness is 14nm, mean transmissivity, up to 24%, the most also can obtain higher energy conversion efficiency
(6.3%).
Solar cell device performance parameter under table 2 different silver transparency electrode thickness and light transmittance parameter
Embodiment 3
(1) glass substrate of ITO layer it is coated with successively with acetone, micron order quasiconductor special purpose detergent, deionized water, different
Propanol ultrasonic cleaning, drying nitrogen dry up be placed in culture dish standby；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000rpm, and thickness is about
40nm；Then 140 DEG C of thermal anneal process 20min.
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5, is dissolved in volume
Ratio is that in the DIO/ chlorobenzene solvent of 3/97, being configured to concentration is 20mg mL-1Mixed solution, 50 DEG C stirring 12h；Then will be mixed
Closing solution to be spun on PEDOT:PSS hole transmission layer, spin coating speed is 3500rpm, obtains the active layer that thickness is 50nm；
(4) PF3N-2TNDI being dissolved in acetic acid/methanol solvate that volume ratio is 5/95, being configured to concentration is 0.5mg mL-1
Solution；Then the solution of variable concentrations is spun on PTB7-Th:PC71On BM active layer, spin coating speed is 2000rpm, is formed
Thickness is respectively the electron transfer layer of 5nm, 15nm；
(5) on PF3N-2TNDI electron transfer layer, evaporation thickness is the silver-colored transparent cathode of 14nm.
From Fig. 3～4, when the thickness of silver transparency electrode is 14nm, electric transmission layer thickness is the device of 5nm
The mean transmissivity device higher than 15nm, about 30%, now efficiency still may be up to 6%, and has excellent color developing, meter
Calculation obtains its chromaticity coordinates, and (x, y) is (0.326,0.328), and color rendering index is 96.6%.
From embodiment 1～3, the present invention, by introducing a kind of effective electron transport layer materials, can prepare same
Time there is the translucent solar cell of higher energy conversion efficiency, mean transmissivity and color rendering index.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a translucent organic solar batteries, including substrate and organic solar cell element, it is characterised in that You Jitai
Sun can comprise transparent anode, hole transmission layer, active layer, electron transfer layer and transparent cathode by cell device successively；
The thickness of described electron transfer layer is 5～30nm, and electron transfer layer is PF3N-2TNDI, has a following structural formula:
Wherein n is the natural number of 0～10000.
Translucent organic solar batteries the most according to claim 1, it is characterised in that described hole transmission layer is
PEDOT:PSS, thickness is 30～50nm.
Translucent organic solar batteries the most according to claim 1, it is characterised in that active layer be mass ratio be 1:
PTB7-Th and PC of (1.5～1.6)71The mixture of BM, thickness is 50～100nm.
Translucent organic solar batteries the most according to claim 1, it is characterised in that described substrate is glass.
5. according to the translucent organic solar batteries described in claim 1 or 4, it is characterised in that described transparent anode is ITO
Layer, is coated on substrate.
Translucent organic solar batteries the most according to claim 1, it is characterised in that described transparent cathode is Ag is thick
Degree is 10～20nm.
Translucent organic solar batteries the most according to claim 6, it is characterised in that the thickness of described electron transfer layer
For 15nm, the thickness of described transparent cathode is 14nm.
8. a translucent organic solar batteries preparation method, it is characterised in that comprise the following steps:
(1) cleaning is coated with the glass substrate of ITO layer and is dried；
(2) being spun in ITO layer by PEDOT:PSS solution as hole transmission layer, rotating speed is 3000～3500rpm, and thickness is about
For 40nm；Then 140～160 DEG C of thermal anneal process 15～20min；
(3) by donor material PTB7-Th and acceptor material PC71BM mixes according to the mass ratio of 1:1.5～1.6, is dissolved in chlorine
In benzene solvent, it is configured to mixed solution, 50～55 DEG C of stirrings 10～14h；Then mixed solution is spun on PEDOT:PSS hole
In transport layer, obtain the active layer that thickness is 50～100nm；
(4) PF3N-2TNDI is dissolved in solvent, is configured to solution；Then solution is spun on PTB7-Th:PC71BM active layer
On, form the electron transfer layer that thickness is 5～30nm；
(5) on PF3N-2TNDI electron transfer layer, evaporation thickness is the Ag transparent cathode of 10～20nm.
Translucent organic solar batteries preparation method the most according to claim 8, it is characterised in that step (4) is described
PF3N-2TNDI is dissolved in solvent, is configured to solution；Then solution is spun on PTB7-Th:PC71On BM active layer, specifically
For:
Being dissolved in the mixed solvent being made up of acetic acid and methanol by PF3N-2TNDI, being configured to concentration is 0.5～5mg mL-1Molten
Liquid；Then solution is spun on PTB7-Th:PC71On BM active layer, spin coating speed is 2000～2200rpm；
In described mixed solvent, the volume ratio of acetic acid and methanol is 3:97～5:95.
Translucent organic solar batteries preparation method the most according to claim 8, it is characterised in that step (3) is described
Spin coating, specifically, spin coating speed is 1000～3500rpm.
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| CN106876594A (en) * | 2017-03-31 | 2017-06-20 | 华南理工大学 | A kind of translucent solar cell device and application |
| CN109935700A (en) * | 2017-12-19 | 2019-06-25 | 国家纳米科学中心 | Organic solar batteries and preparation method thereof comprising polyaminoacid electronics collecting layer |
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