CN110504371B - Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof - Google Patents

Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof Download PDF

Info

Publication number
CN110504371B
CN110504371B CN201910805173.3A CN201910805173A CN110504371B CN 110504371 B CN110504371 B CN 110504371B CN 201910805173 A CN201910805173 A CN 201910805173A CN 110504371 B CN110504371 B CN 110504371B
Authority
CN
China
Prior art keywords
layer
itic
pbdb
buffer layer
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910805173.3A
Other languages
Chinese (zh)
Other versions
CN110504371A (en
Inventor
于军胜
张大勇
杨根杰
王子君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN201910805173.3A priority Critical patent/CN110504371B/en
Publication of CN110504371A publication Critical patent/CN110504371A/en
Application granted granted Critical
Publication of CN110504371B publication Critical patent/CN110504371B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to the field of organic semiconductor thin-film solar cells, and particularly discloses a spin coating-based methodThe organic solar cell with the centrifugal auxiliary light active layer layered and the preparation method thereof comprise the following steps: s1: cleaning a substrate consisting of the transparent substrate and the ITO transparent conductive cathode layer, and drying the substrate by using nitrogen after cleaning; s2: and (3) rotationally coating, printing or spraying PEDOT on the surface of the ITO transparent conductive cathode layer: preparing an anode buffer layer by using a PSS precursor solution, and baking the formed film at a low temperature; s3: preparing PBDB-T on the anode buffer layer by adopting a spin coating process: an ITIC photoactive layer; s4: spin-coated PBDB-T: adhering the substrate of the ITIC optical active layer to the vertical side wall for rotary centrifugation; s5: in the glove box for PBDB-T: carrying out thermal annealing treatment on the ITIC photoactive layer; s6: at a vacuum degree of 3 x 103In the condition of Pa, the ratio of PBDB-T: evaporating LiF on the surface of the ITIC photoactive layer to prepare a cathode buffer layer; s7: and evaporating a metal cathode layer on the cathode buffer layer. Finally, the purpose of improving all aspects of performance parameters of the organic solar cell is achieved.

Description

Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof
Technical Field
The invention belongs to the technical field of organic semiconductor thin-film solar cells, and particularly relates to a centrifugal auxiliary light active layer layered organic solar cell based on a spin coating process and a preparation method thereof.
Background
With the rapid development of the world economy and the gradual change of the scientific technology, the demand of people for energy is increasing, and meanwhile, the problems of environmental pollution caused by the gradual reduction of the traditional fossil energy and the overuse of the traditional fossil energy are also becoming more serious, so that the development and utilization of new energy are considered as a key project of the 21 st century. Under the background, solar energy is a renewable green energy source, and is widely concerned by researchers due to the characteristics of huge reserves, wide distribution, greenness, harmlessness and the like. Solar cells have been paid attention to researchers as a means for directly converting solar energy into electrical energy and effectively developing and utilizing the solar energy. Photoactive layer materials can be classified into inorganic semiconductor materials and organic semiconductor materials according to the properties of the photoactive layer materials of the solar cell. The inorganic semiconductor material is developed early and researched widely, and is currently applied to commercial batteries, but the complex preparation process of the inorganic semiconductor material limits the further development of the inorganic semiconductor material due to the harsh requirements on raw materials, high cost, environmental pollution and other factors. Compared with inorganic semiconductor materials, the organic solar cell prepared based on the organic semiconductor materials not only has the highest theoretical photoelectric conversion efficiency which is the same as that of the inorganic solar cell, but also has a series of advantages of simple process, wide material source, capability of being prepared based on a flexible substrate, capability of large-area production, environmental friendliness, no pollution, light weight, low cost and the like, so that the organic solar cell is expected to solve the energy crisis.
Solution-processed fullerene-based organic solar cells have been the main subject of research in the field of organic solar cells for over the past 10 years, and their power conversion efficiency has been promoted from < 1% to > 10% in the early stages under extensive research, however, absorption in the long wavelength range is weak, electronic characteristic tuning capability is poor, and expensive purification processes limit further development of fullerene-based solar cells. At this time, the non-fullerene acceptor material receives more and more attention due to its inherent advantages including tunability of the highest occupied molecular orbital and the lowest unoccupied molecular orbital levels, higher absorption capability in the long wavelength range, and different compatibility with the polymer donor, and becomes the leading system in the research field of organic solar cells at present.
However, in a system using non-fullerene materials, although the photoelectric conversion efficiency of a single-junction organic solar cell exceeds 15% and reaches the performance standard (> 15%) which can be commercialized, the average photoelectric conversion efficiency (> 20%) of the non-fullerene organic solar cell is still to be improved compared with the average photoelectric conversion efficiency of a traditional inorganic solar cell, and meanwhile, in recent 3 years, a large amount of researchers of the non-fullerene materials are synthesized for the organic solar cell, but compared with the traditional fullerene organic solar cell, the non-fullerene organic solar cell has poor phase separation in the photoactive layer and poor contact with the buffer layer, so that the separation, transmission and interfacial transfer efficiency of photogenerated carriers is low, and the device has a large interface contact resistance and a high carrier recombination probability.
Disclosure of Invention
Aiming at the defects that the phase separation in the non-fullerene photoactive layer is poor and the contact with the buffer layer is poor, the invention aims to provide a centrifugal auxiliary photoactive layer layered organic solar cell based on a spin coating process and a preparation method thereof.
A preparation method of an organic solar cell with a centrifugal auxiliary photoactive layer layered based on a spin coating process comprises the following steps:
s1: cleaning a substrate consisting of the transparent substrate and the ITO transparent conductive cathode layer, and drying the substrate by using nitrogen after cleaning;
s2: rotationally coating, printing or spraying PEDOT (Poly ethylene terephthalate) (PSS) precursor solution on the surface of the ITO transparent conductive cathode layer to prepare an anode buffer layer, and baking the formed film at low temperature;
s3, preparing a PBDB-T (heterojunction with intrinsic stability) -ITIC (intrinsic thin film) optical active layer on the anode buffer layer by adopting a spin coating process;
s4, pasting the substrate with the PBDB-T and ITIC optical active layer on the vertical side wall for rotary centrifugation;
s5: carrying out thermal annealing treatment on the PBDB-T and ITIC photoactive layer in a glove box;
s6: at a vacuum degree of 3 x 103Evaporating LiF on the surface of PBDB-T, namely the surface of the ITIC optical active layer under the Pa condition to prepare a cathode buffer layer;
s7: and evaporating a metal cathode layer on the cathode buffer layer.
In the technical scheme of the application, a PBDB-T is prepared on an anode buffer layer by adopting a spin coating process, an ITIC optical activity layer is prepared on the anode buffer layer, then a vertical side wall is fixed on the side of a turntable of a spin coater, a substrate which is just subjected to the spin coating process and is subjected to the spin coating process is placed on the substrate, the spin coater is started again, the centrifugal force generated during high-speed rotation is utilized to promote the optical activity layer to form a mixed phase state of vertical layering of a donor/acceptor, so that the charge separation and transmission capacity in the optical activity layer is improved, the contact between the optical activity layer and a cathode/anode buffer layer is promoted to form ohmic contact, the contact resistance formed between interfaces is reduced, the charge transmission capacity between different functional layers is further improved, meanwhile, in the centrifugal rotation process, the surface of the substrate is influenced by the force in the horizontal direction of rotation, a slight horizontal direction removing effect can be exerted on a non-fullerene layer on the upper layer, the method further improves the charge transmission capability and the interface contact condition between the active layer and the LiF cathode buffer layer, finally achieves the purpose of improving various performance parameters of the organic solar cell device, and solves the defects of poor phase separation in the non-fullerene system photoactive layer and poor contact with the buffer layer.
Preferably, in S1, the substrate is made of glass or transparent polymer.
More preferably, the transparent polymer material is one or more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide, vinyl chloride, or polyacrylic acid.
Preferably, in S2, the low-temperature baking temperature is 100 ℃ and the time is 20 min.
Preferably, in S2, the spin coating speed is 3000rpm and the time is 60S.
Preferably, the PBDB-T/ITIC photoactive layer in S3 is prepared from a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1: 6-6: 1, and the concentration of the mixed solution is 8-30 mg/ml.
Preferably, in S4, the rotation speed of the spin centrifugation is 5000-7000rpm, and the time is 1-5 min.
Preferably, in S5, the temperature of the thermal annealing treatment is 100-160 ℃, and the time is 10-35 min.
Preferably, in step S5, the PBDB-T/ITIC photoactive layer is placed in a glove box for 10min at room temperature.
Preferably, in S7, the material of the metal cathode layer is one or more of Ag, Al, or Au.
The organic solar cell comprises a transparent substrate, an IITO transparent conductive cathode layer, a PEDOT (power system stabilizer) anode buffer layer, a photoactive layer, a cathode buffer layer and a metal cathode layer from bottom to top in sequence.
Preferably, the spin-coating process-based organic solar cell with the centrifugation-assisted photoactive layer lamination comprises 20-50nm of anode buffer layer of PEDOT and 50-300nm of photoactive layer, 2nm of cathode buffer layer and 100-200nm of metal cathode layer.
More preferably, the spin-coating process-based organic solar cell with the centrifugation-assisted photoactive layer lamination comprises a PEDOT/PSS anode buffer layer with the thickness of 30nm, a photoactive layer with the thickness of 175nm, a cathode buffer layer with the thickness of 2nm and a metal cathode layer with the thickness of 150 nm.
In the technical scheme of the application, the PEDOT PSS precursor solution is commercially available.
Compared with the prior art, the invention has the following beneficial effects:
(1) preparing PBDB-T on an anode buffer layer by adopting a spin coating process, preparing an ITIC photoactive layer, fixing a vertical side wall on the side of a turntable of a spin coater, placing a substrate which is just subjected to the spin coating process and is subjected to an active layer on the substrate, starting the spin coater again, promoting the photoactive layer to form a mixed phase state of vertical layering of a donor/acceptor by utilizing centrifugal force generated during high-speed rotation, thereby improving the charge separation and transmission capacity in the photoactive layer, promoting the photoactive layer to form ohmic contact by improving the contact between the photoactive layer and a cathode/anode buffer layer, reducing the contact resistance formed between interfaces, further improving the charge transmission capacity between different functional layers, and simultaneously playing a slight horizontal direction-moving role on an upper non-fullerene layer by the influence of force in the horizontal direction of rotation on the surface of the substrate in the centrifugal rotation process so as to further improve the interface contact condition between the charge transmission capacity and the active layer/LiF cathode buffer layer Finally, the purpose of improving all aspects of performance parameters of the organic solar cell device is achieved;
(2) vertical layering of a non-fullerene organic solar cell photoactive layer is realized by using a simple rotary centrifugal process, and the separation condition of donor/acceptor phases in the photoactive layer is effectively optimized, so that photoproduction excitons in the photoactive layer are more effectively separated and transmitted;
(3) the layered photoactive layer prepared by the rotary centrifugal process is used for a positive organic solar cell system, so that ohmic contact is effectively formed between a PSS anode buffer layer and a photoactive layer lower layer (a PBDB-T-rich part) and between a photoactive layer upper layer (an ITIC-rich part) and a LiF cathode buffer layer, so that the contact resistance between different functional layers is reduced, and the charge transmission capability between different functional layers is effectively improved;
(4) by using a rotary centrifugal process, the upper layer (an ITIC-rich part) of the photoactive layer of the organic solar cell is optimized, a horizontal arrangement mode is formed, and the ITIC can be promoted to form a pi-pi accumulation mode in the photoactive layer, so that the electron mobility in the photoactive layer is effectively improved, the surface morphology of the photoactive layer is further optimized, and the contact condition of the photoactive layer and a cathode buffer layer is improved.
Description of the drawings:
the present invention will be described in further detail with reference to the accompanying drawings and examples.
FIG. 1 is a schematic structural diagram of an ultraviolet absorbing organic molecule doped ternary solar cell of the present invention;
FIG. 2 is a schematic structural view of a centrifugal assisted spin coating apparatus according to the present invention;
FIG. 3 is a graph comparing the internal phase distribution of a layered photoactive layer after centrifugation using a spin-coating process according to the present invention.
Reference numerals: 1-transparent substrate, 2-ITO transparent conductive cathode layer, 3-PEDOT, PSS anode buffer layer, 4-photoactive layer, 5-cathode buffer layer, 6-metal cathode layer, 7-glue homogenizing machine objective table, 8-substrate adsorption port, 9-transverse plate, 10-fixing screw, 11-vertical side wall, and 12-double faced adhesive tape for substrate fixing.
In FIG. 3, A is the distribution of the active layer phase without centrifugation, B is the distribution of chain material PBDB-T concentrated in the lower half, and the material ITIC concentrated in the upper half and has a certain horizontal orientation after centrifugation; a is the phase morphology of polymer PBDB-T, and b is the phase morphology of non-fullerene material ITIC.
Detailed Description
The invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present application.
Example 1
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:6, and the concentration of the mixed solution is 10 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 1 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 100 ℃ and the time is 35 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the material of the metal cathode layer 6 is Al, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.83V, the short-circuit current (JSC) was measured to be 17.82mA/cm2, the Fill Factor (FF) was measured to be 0.69, and the Photoelectric Conversion Efficiency (PCE) was measured to be 10.20%.
Example 2
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:1, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 2 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 100 ℃, and the time is 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Ag, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.85V, the short-circuit current (JSC) was measured to be 18.32mA/cm2, the Fill Factor (FF) was measured to be 0.72, and the Photoelectric Conversion Efficiency (PCE) was measured to be 11.21%.
Comparative example 1
Step S4 in the embodiment is eliminated, and the rest of the steps are the same as those in embodiment 2.
In this comparative example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.82V, the short-circuit current (JSC) was measured to be 17.52mA/cm2, the Fill Factor (FF) was measured to be 0.66, and the Photoelectric Conversion Efficiency (PCE) was measured to be 9.48%.
Example 3
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 6:1, and the concentration of the mixed solution is 20 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate with the PBDB-T and ITIC photoactive layer 4 spin-coated on the vertical side wall 11 for spin centrifugation at 7000rpm for 2 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 160 ℃ and the time is 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Ag, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.82V, the short-circuit current (JSC) was measured to be 16.14mA/cm2, the Fill Factor (FF) was measured to be 0.68, and the Photoelectric Conversion Efficiency (PCE) was measured to be 8.99%.
Example 4
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:2, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 6000rpm for 3 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 130 ℃ and the time is 25 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Ag, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.80V, the short-circuit current (JSC) was measured to be 15.35mA/cm2, the Fill Factor (FF) was measured to be 0.63, and the Photoelectric Conversion Efficiency (PCE) was measured to be 7.73%.
Example 5
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:1, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 2 min;
s5: PBDB-T at room temperature, namely the ITIC photoactive layer 4 is placed in a glove box for 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Ag, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.80V, the short-circuit current (JSC) was measured to be 17.21mA/cm2, the Fill Factor (FF) was measured to be 0.65, and the Photoelectric Conversion Efficiency (PCE) was measured to be 8.95%.
Comparative example 2
Step S4 in example 5 is eliminated, and the rest of the steps are the same as in example 5.
In this comparative example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.78V, the short-circuit current (JSC) was measured to be 16.15mA/cm2, the Fill Factor (FF) was measured to be 0.62, and the Photoelectric Conversion Efficiency (PCE) was measured to be 7.81%.
Example 6
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:1, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 3 min;
s5: PBDB-T at room temperature, namely the ITIC photoactive layer 4 is placed in a glove box for 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Au, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.78V, the short-circuit current (JSC) was measured to be 16.02mA/cm2, the Fill Factor (FF) was measured to be 0.64, and the Photoelectric Conversion Efficiency (PCE) was measured to be 7.99%.
Example 7
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:1, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 2 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 100 ℃, and the time is 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the material of the metal cathode layer 6 is Al, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.82V, the short-circuit current (JSC) was measured to be 18.76mA/cm2, the Fill Factor (FF) was measured to be 0.69, and the Photoelectric Conversion Efficiency (PCE) was measured to be 10.61%.
Example 8
A preparation method of a centrifugal auxiliary photoactive layer 4 layered organic solar cell based on a spin coating process comprises the following steps:
s1: cleaning a base plate with the surface roughness less than 1nm and consisting of a transparent substrate 1 and a transparent conductive anode ITO, and drying by using nitrogen after cleaning;
s2: PSS is coated on the surface of the transparent conductive cathode ITO in a rotating mode, the rotating speed of the rotating coating is 3000rpm, the time is 60s, an anode buffer layer is prepared, the formed film is baked at low temperature, the temperature of the low-temperature baking is 100 ℃, the time is 20min, and the thickness of the anode buffer layer is 30 nm;
s3, preparing a PBDB-T/ITIC photoactive layer 4 on the anode buffer layer by adopting a spin coating process, wherein the PBDB-T/ITIC photoactive layer 4 is prepared by a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1:1, and the concentration of the mixed solution is 8 mg/ml; the rotating speed of the spin coating process is 2000rpm, the spin coating time is 40s, and the thickness of the optical active layer 4 is 110 nm;
s4, adhering the substrate coated with PBDB-T and ITIC photoactive layer 4 to the vertical side wall 11 for spin centrifugation at 5000rpm for 3 min;
s5: carrying out thermal annealing treatment on the PBDB-T and the ITIC photoactive layer 4 in a glove box, wherein the temperature of the thermal annealing treatment is 100 ℃, and the time is 10 min;
s6, evaporating LiF on the surface of the PBDB-T, namely the ITIC photoactive layer 4 under the condition that the vacuum degree is 3 x 103Pa to prepare a cathode buffer layer 5, wherein the thickness of the cathode buffer layer 5 is 2 nm;
s7: and evaporating a metal cathode layer 6 on the cathode buffer layer 5, wherein the metal cathode layer 6 is made of Ag, and the thickness of the metal cathode layer 6 is 100 nm.
In this example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.80V, the short-circuit current (JSC) was measured to be 18.06mA/cm2, the Fill Factor (FF) was measured to be 0.70, and the Photoelectric Conversion Efficiency (PCE) was measured to be 10.11%.
Comparative example 3
Step S4 in example 8 is eliminated and the rest of the steps are the same as those described in example 8.
In this comparative example, under standard test conditions: AM 1.5,100mW/cm2, the open-circuit Voltage (VOC) of the device was measured to be 0.80V, the short-circuit current (JSC) was measured to be 17.92mA/cm2, the Fill Factor (FF) was measured to be 0.61, and the Photoelectric Conversion Efficiency (PCE) was measured to be 8.74%.
By comparing example 2 with comparative example 1, example 5 with comparative example 2, and example 8 with comparative example 3, it can be seen that the organic solar cells prepared by the method of introducing the centrifugal auxiliary photoactive layer 4 for delamination (i.e., the organic solar cells prepared in examples 2, 5, and 8) have higher short-circuit current density, higher fill factor, and higher open-circuit voltage than the organic solar cells prepared without modification (i.e., the organic solar cells prepared in comparative examples 1, 2, and 3). After the non-fullerene-based photoactive layer 4 is coated in a rotating manner, the donor and acceptor components in the photoactive layer 4 are still in the process of converting from liquid to solid, solid crystals are not formed yet, and the inside is soft and loose, at the moment, the photoactive layer 4 is processed by a centrifugal auxiliary method, the photoactive layer 4 can be layered by using a centrifugal force generated by high rotating speed, and a donor and acceptor semi-layered form as shown in fig. 3 is formed, wherein the form is favorable for separating and transmitting photogenerated charges in the photoactive layer 4, meanwhile, the ratio difference of the upper and lower components in the photoactive layer 4 is large (the upper layer is rich in ITIC, and the lower layer is rich in PBDB-T), the photoactive layer 4 is favorable for forming good ohmic contact with a cathode and anode buffer layer, the interfacial resistance in an organic solar cell device is effectively reduced, and the charges at different interfaces (electrons at a photoactive layer 4/electron buffer layer interface, hole transmission capacity at the interface of the photoactive layer 4/hole buffer layer), the charge recombination probability between the interfaces is reduced; meanwhile, as shown in a diagram B in fig. 3, in the process of rotational centrifugation, the surface of the photoactive layer 4 is affected by horizontal resistance parallel to the rotational direction, which may play a role in horizontal disorientation of the upper layer (ITIC-rich portion) of the photoactive layer 4, and further, due to interaction between molecules, the horizontal orientation of the surface may slightly affect the arrangement of molecules in the photoactive layer 4, thereby promoting the ITIC formation-accumulation form inside the photoactive layer 4, effectively improving the electron mobility inside the photoactive layer 4, further optimizing the surface morphology of the photoactive layer 4, and improving the contact condition between the photoactive layer 4 and the cathode buffer layer 5.
Example 9
The spin-coating process-based organic solar cell with the layered optically active layer 4 assisted centrifugally prepared by the method of the above embodiment 1-8 sequentially comprises, from bottom to top, a transparent substrate 1, an ITO transparent conductive cathode layer 2, a PEDOT: PSS anode buffer layer 3, an optically active layer 4, a cathode buffer layer 5, and a metal cathode layer 6, wherein the PEDOT: PSS anode buffer layer 3 has a thickness of 20nm, the optically active layer 4 has a thickness of 50nm, the cathode buffer layer 5 has a thickness of 2nm, and the metal cathode layer 6 has a thickness of 100 nm.
Example 10
PSS Anode buffer layer 3, PEDOT, has a thickness of 30nm, photoactive layer 4, cathode buffer layer 5, and metal cathode layer 6, respectively, have a thickness of 175nm, 2nm, and 150nm, respectively, based on example 9.
Example 11
PSS Anode buffer layer 3 is 50nm thick, photoactive layer 4 is 300nm thick, cathode buffer layer 5 is 2nm thick and metal cathode layer 6 is 200nm thick, based on example 9.
Example 12
The centrifugal auxiliary spin coating device comprises a spin coater object table 7 and a transverse plate 9 fixed on one side of the surface of the spin coater object table 7, wherein a vertical side wall 11 is arranged on the transverse plate 9, the transverse plate 9 and the side wall are integrally formed to form an L-shaped structure, at least 1 double-sided adhesive tape 12 for fixing substrates is arranged on one side of the vertical side wall 11 close to the spin coater object table 7, a substrate adsorption port 8 is further arranged on the spin coater object table 7, and the transverse plate 9 is fixed on the spin coater object table 7 through a fixing screw 10.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.

Claims (10)

1. A preparation method of an organic solar cell with a centrifugal auxiliary photoactive layer layered based on a spin coating process is characterized by comprising the following steps:
s1: cleaning a substrate consisting of the transparent substrate and the ITO transparent conductive cathode layer, and drying the substrate by using nitrogen after cleaning;
s2: rotationally coating, printing or spraying a PEDOT (Poly ethylene terephthalate) (PSS) precursor solution on the surface of the ITO transparent conductive cathode layer to prepare an anode buffer layer, and baking the formed film at a low temperature of 100 ℃;
s3, preparing a PBDB-T (heterojunction with intrinsic stability) -ITIC (intrinsic thin film) optical active layer on the anode buffer layer by adopting a spin coating process;
s4, pasting the substrate with the PBDB-T and ITIC optical active layer on the vertical side wall for rotary centrifugation;
s5: carrying out thermal annealing treatment on the PBDB-T and ITIC photoactive layer in a glove box;
s6: at a vacuum degree of 3 x 103Evaporating LiF on the surface of PBDB-T, namely the surface of the ITIC optical active layer under the Pa condition to prepare a cathode buffer layer;
s7: and evaporating a metal cathode layer on the cathode buffer layer.
2. The method of claim 1, wherein: in S1, the substrate is made of glass or transparent polymer.
3. The method of claim 1, wherein: in S2, the low-temperature baking temperature is 100 ℃, and the time is 20 min.
4. The method of claim 1, wherein: in S2, the spin coating speed was 3000rpm for 60 seconds.
5. The method of claim 1, wherein: the PBDB-T/ITIC photoactive layer in the S3 is prepared from a mixed solution of an electron donor material PBDB-T and an acceptor non-fullerene material ITIC, the mass percentage of the PBDB-T and the ITIC in the mixed solution is 1: 6-6: 1, and the concentration of the mixed solution is 8-30 mg/ml.
6. The method of claim 1, wherein: in S4, the rotation speed of the spin centrifugation is 5000-7000rpm, and the time is 1-5 min.
7. The method of claim 1, wherein: in S5, the temperature of the thermal annealing treatment is 100-160 ℃, and the time is 10-35 min.
8. The method of claim 1, wherein: in S7, the metal cathode layer is made of one or more of Ag, Al, and Au.
9. The organic solar cell based on centrifugal assisted photoactive layer delamination by spin coating process prepared by the preparation method according to any one of claims 1 to 8, wherein: the organic solar cell sequentially comprises a transparent substrate, an ITO transparent conductive cathode layer, PEDOT, a PSS anode buffer layer, an optical active layer, a cathode buffer layer and a metal cathode layer from bottom to top.
10. The spin-on process based centrifugally assisted photoactive layer layered organic solar cell of claim 9, wherein: the thickness of the PEDOT/PSS anode buffer layer is 20-50nm, the thickness of the optical active layer is 50-300nm, the thickness of the cathode buffer layer is 2nm, and the thickness of the metal cathode layer is 100-200 nm.
CN201910805173.3A 2019-08-28 2019-08-28 Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof Active CN110504371B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910805173.3A CN110504371B (en) 2019-08-28 2019-08-28 Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910805173.3A CN110504371B (en) 2019-08-28 2019-08-28 Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110504371A CN110504371A (en) 2019-11-26
CN110504371B true CN110504371B (en) 2021-11-02

Family

ID=68590234

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910805173.3A Active CN110504371B (en) 2019-08-28 2019-08-28 Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110504371B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110982047B (en) * 2019-12-19 2020-11-24 河南大学 Indacarbazine difuranyl organic solar cell donor material, and preparation method and application thereof
CN111162176B (en) * 2019-12-30 2021-09-07 电子科技大学 Preparation method for preparing organic solar cell with vertical phase gradient distribution photoactive layer by oscillation-assisted spin coating process
CN111682111B (en) * 2020-05-20 2022-03-29 华南理工大学 PBDB-T ITIC alpha-In2Se3Organic solar cell as active layer and method for manufacturing the same
CN111883661A (en) * 2020-08-28 2020-11-03 电子科技大学 Thick-film large-area organic photovoltaic device and preparation method thereof
CN112133834A (en) * 2020-11-03 2020-12-25 上海大学 Ultraviolet-stable solar cell based on composite dimension flexible transparent electrode
CN113629193A (en) * 2021-07-28 2021-11-09 电子科技大学 Organic solar cell with sandwich-configuration active layer and preparation method thereof
CN114695678B (en) * 2022-02-28 2023-04-25 电子科技大学 Method for effectively inhibiting dark current in organic photoelectric detector with inverted structure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101304074A (en) * 2008-06-30 2008-11-12 南开大学 Organic photovoltaic battery using single layer graphite material as active material and based on the active material
CN106025084B (en) * 2016-07-13 2018-07-03 电子科技大学 Organic solar batteries and preparation method based on ZnO nano particulate cathodic buffer layer
CN108666423A (en) * 2017-03-31 2018-10-16 中国科学院化学研究所 A kind of translucent organic solar batteries
CN107805254B (en) * 2017-09-18 2020-08-18 华南理工大学 Porphyrin micromolecular perovskite cathode buffer layer material and preparation method and application thereof
CN109637970A (en) * 2018-12-07 2019-04-16 北京理工大学 A kind of centering type vacuum aided spin coating vertical long hole inner wall insulation layer manufacturing method thereof

Also Published As

Publication number Publication date
CN110504371A (en) 2019-11-26

Similar Documents

Publication Publication Date Title
CN110504371B (en) Organic solar cell with centrifugal auxiliary light active layer layering based on spin coating process and preparation method thereof
CN111180587B (en) Special doped perovskite solar cell and preparation method thereof
CN112542549B (en) Wide-bandgap perovskite solar cell and preparation and application thereof
CN111883662B (en) Organic solar cell based on rotary annealing process and preparation method thereof
Shahiduzzaman et al. Enhanced photovoltaic performance of perovskite solar cells via modification of surface characteristics using a fullerene interlayer
CN111430544A (en) Perovskite solar cell based on organic material mixed doping and preparation method thereof
CN111081883B (en) Efficient and stable planar heterojunction perovskite solar cell and preparation method
CN106410037A (en) Small organic molecule donor material based double-junction solar cell device and preparation method thereof
CN111162176B (en) Preparation method for preparing organic solar cell with vertical phase gradient distribution photoactive layer by oscillation-assisted spin coating process
CN101728487B (en) Method for preparing manganese phthalocyanine bisphenol A epoxy derivative organic solar batteries
CN116322253A (en) Flexible electrode, preparation method and application thereof, flexible organic solar cell and preparation method thereof
CN108807696B (en) Method for improving interface modification of organic solar cell
CN116056469A (en) Perovskite solar cell based on ionic liquid interface modification
CN103400941B (en) Based on the organic solar batteries and preparation method thereof of heteropoly acid anode modification layer
CN105720199A (en) Large-area organic thin-film solar battery and preparation method thereof
CN111180588B (en) Thick-film organic solar cell based on continuous blade coating double-body heterojunction and preparation method thereof
CN113611800A (en) All-small-molecule organic solar cell based on novel additive and preparation method thereof
CN112563421A (en) Interface passivation layer perovskite solar cell based on DNT-Ph-Br and preparation method thereof
CN112635677B (en) Double-layer anode buffer layer polymer solar cell based on BCF modification and preparation method thereof
CN110993802A (en) Polymer solar cell based on surface modified cathode buffer layer
CN111653669A (en) Small-molecule organic solar cell and preparation method thereof
CN111628085B (en) Organic solar cell based on double electron transport layers and preparation method thereof
CN113690373B (en) Based on HfS 2 Organic solar cell as hole transport layer and method for manufacturing the same
CN113193119B (en) Perovskite solar cell based on spiro-OMeTAD doped body heterojunction and preparation method thereof
CN102945926B (en) Anode modifying material of polymer solar battery and modifying method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant