CN118055627A - Double-donor alloy phase ternary organic photovoltaic cell and preparation method thereof - Google Patents
Double-donor alloy phase ternary organic photovoltaic cell and preparation method thereof Download PDFInfo
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- 238000013086 organic photovoltaic Methods 0.000 title claims abstract description 71
- 229910000905 alloy phase Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 58
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- 238000012986 modification Methods 0.000 claims description 51
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- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 17
- KZDTZHQLABJVLE-UHFFFAOYSA-N 1,8-diiodooctane Chemical group ICCCCCCCCI KZDTZHQLABJVLE-UHFFFAOYSA-N 0.000 claims description 16
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229910003472 fullerene Inorganic materials 0.000 claims description 5
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 4
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 11
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- 230000000694 effects Effects 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
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- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 2
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a double-donor alloy phase ternary organic photovoltaic cell and a preparation method thereof, and belongs to the technical field of photoelectric materials; the active layer is a composite film formed by two electron donors and one electron acceptor, the electron donors are D18 and BTR, and the electron acceptor is Y6. The BTR and D18 can form a small-degree alloy phase, so that not only the original crystallinity and molecular orientation of a host and guest donor are reserved, but also the compatibility with Y6 is realized, the ACQ effect of a receptor is inhibited, and the smaller non-radiative recombination loss is realized. And the D18:BTR:Y6 ternary system shows higher CT state energy level and smaller CT-LE state difference, so that the ternary system shows smaller recombination energy, thereby reducing radiation recombination loss under band gap. The ternary organic photovoltaic cell has excellent photovoltaic performance.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a double-donor alloy phase ternary organic photovoltaic cell and a preparation method thereof.
Background
Organic photovoltaic cells have been rapidly developed with efficient material development and device engineering. The multi-strategy is always an effective way for realizing the performance breakthrough of the organic photovoltaic device, wherein spectrum complementation, energy level regulation and shape optimization are main consideration factors of multi-strategy material combination and effective device construction. However, the traditional multi-element material combination factors are only considered, and the breakthrough of the higher performance of the organic photovoltaic device cannot be met. The efficiency limiting bottleneck of organic photovoltaic devices is quite clear compared to inorganic photovoltaic devices, namely the low open circuit voltage (nat. Common.2023,14,5079;Joule 2022,6,662) caused by the large energy loss, wherein radiative recombination losses below the band gap and non-radiative recombination losses occupy the main loss fractions, these energy losses mainly occur during the exciton to charge transition state, due to the discontinuous energy level characteristics of the organic semiconductor, and the interface changes caused by the mixed material system, the exciton and charge state of the organic photovoltaic system are greatly changed (Nat.Common.2022, 13,3256;Angew.Chem.Int.Ed.2023,62,e202304931). In particular, the energy level and interface changes due to the diversity of the material components of the multi-component system complicate this factor. The energy loss of organic photovoltaic systems, especially of multi-element systems, the energy level structure change formed by material combinations, and the phase distribution of multi-element combinations are not negligible (Nat. Energy 2023,8,978-988).
The Chinese patent document with publication number CN116367556A discloses a high-efficiency quaternary organic photovoltaic cell and a preparation method thereof, an active layer of the quaternary organic photovoltaic cell is a blend film of an electron donor PM6 and three non-fullerene receptors L8-BO, BTP-S8 and BTP-S2, and the quaternary organic photovoltaic cell shows PCE of which the maximum content is 19.19 percent by utilizing complementation of absorption of the PM6, L8-BO, BTP-S8 and BTP-S2 and optimization of the morphology of the active layer by the L8-BO.
The Chinese patent document with publication number CN115785126A discloses a ternary organic solar cell based on conjugated organic molecules, in particular, the conjugated organic molecules adopt dithienobenzothiadiazole as a central electron-withdrawing unit, a condensed ring thiophene unit is introduced as pi bridge, and a rhodanine or cyanoacetate derivative is taken as a terminal group unit, the conjugated organic molecules belong to A-pi-A' -pi-A conjugated organic molecules, and the conjugated organic molecules are taken as a third component material, can be matched with the energy levels of a polymer donor material PM6 and a non-fullerene acceptor material Y6, can remarkably improve the performance of the organic solar cell, and the photovoltaic efficiency of the solar cell exceeds 17 percent.
In prior art studies, multiple combinations of multiple acceptors and donors are typically employed to form a particular phase distribution pattern (parallel phases or alloy equality). In order to improve the device efficiency of organic photovoltaic cells, it is necessary to explore energy loss mechanisms of a dual donor system and a multi-element system with different phase distributions, and develop novel efficient organic photovoltaic cells.
Disclosure of Invention
The invention provides a ternary organic photovoltaic cell with a double-donor alloy phase, which is based on a ternary system D18:BTR:Y6 of a donor alloy phase mode and can reach 19.4% of photovoltaic efficiency.
The technical scheme adopted is as follows:
A dual-donor alloy phase ternary organic photovoltaic cell comprises a substrate, an anode modification layer, an active layer based on a dual-donor/acceptor system, a cathode modification layer and a cathode which are sequentially laminated; the active layer is a composite film formed by two electron donors and an electron acceptor, the electron donors are a polymer donor D18 and a liquid crystal small molecule donor BTR, and the electron acceptor is a non-fullerene acceptor Y6.
Specifically, the active layer is a blend film of two electron donors and one electron acceptor, or a composite film comprising a mixed electron donor film and an electron acceptor film which are laminated; the thickness of the active layer is 50-150 nm.
The invention forms a small-degree alloy phase by utilizing a molecular framework of the liquid crystal small molecular donor BTR similar to the polymer donor D18, not only can keep the original crystallinity and molecular orientation of a host and guest donor, but also can realize larger compatibility with Y6, and reduces the aggregation of Y6, thereby inhibiting the receptor ACQ effect and realizing smaller non-radiative composite loss. In addition, the D18:BTR:Y6 ternary system shows higher CT state energy level and smaller CT-LE state difference, so that the ternary system shows smaller recombination energy, and the radiation recombination loss under the band gap is reduced. Thus, the ternary system based on d18:btr:y6 shows reduced energy loss and high open circuit voltage, synergistically excellent exciton and carrier behavior, ultimately showing excellent photovoltaic performance, and photovoltaic efficiency up to 19.4% in the dual donor ternary system based on Y6.
The structural formula of the polymer donor D18 is:
the structural formula of the liquid crystal small molecule donor BTR is as follows:
the non-fullerene acceptor Y6 has the structural formula:
In the above formula, R 1 is 2-ethylhexyl and R 2 is 2-butyloctyl.
Preferably, when the active layer is a blend film of two electron donors and one electron acceptor, the mass ratio of electron donor to electron acceptor is 1:0.5 to 1.5.
Preferably, in the active layer, the mass ratio of the polymer donor D18 to the liquid crystal small molecule donor BTR is 1:0.05 to 0.5.
Preferably, the active layer further comprises an additive, wherein the additive is 1, 8-diiodooctane or 3, 5-dichloro bromobenzene.
Preferably, the substrate is glass; the anode is ITO; the anode modification layer is PEDOT: PSS; the cathode modification layer is PDINN; the cathode is Ag.
The invention also provides a preparation method of the double-donor alloy phase ternary organic photovoltaic cell, which comprises the following steps:
(1) Preparing an anode modification layer on an anode on one side surface of a substrate;
(2) Coating the mixed solution of D18, BTR and Y6 on the anode modification Layer, or coating the mixed solution of D18 and BTR on the anode modification Layer first and then coating the Y6 solution (Layer-by-Layer, lbL); annealing treatment is carried out after coating is finished, so that the active layer is formed;
(3) And (3) sequentially preparing a cathode buffer layer and a cathode layer on the active layer prepared in the step (2) to obtain the double-donor alloy phase ternary organic photovoltaic cell.
Preferably, the total concentration of electron donor and electron acceptor in the mixed solution of D18, BTR and Y6 is 4.5-19 mg/mL.
Preferably, when preparing the active layer, the mixed solution of D18 and BTR is coated on the anode modification layer, then the Y6 solution is coated, and annealing treatment is carried out after the coating is finished, so that the active layer is formed. Experimental results prove that the energy conversion efficiency of the dual-donor alloy phase ternary organic photovoltaic cell prepared by adopting the gradual deposition method is higher and is better than that of a ternary organic photovoltaic cell based on a bulk heterojunction (bulk heterojunction, BHJ) structure formed by coating a mixed solution of D18, BTR and Y6.
Further preferably, the total concentration of the electron donor in the mixed solution of D18 and BTR is 3 to 7.5mg/mL, and the concentration of the Y6 solution is 1.5 to 11.25mg/mL.
It is further preferred that the mixed solution of D18, BTR and Y6 or the Y6 solution further comprises an additive, wherein the additive is 1, 8-diiodooctane or 3, 5-dibromobenzene. The additive can increase the solubility of the receptor to perform the morphology optimization function of the active layer.
Illustratively, the volume of the additive is 0.2-2% of the volume of the mixed solution of D18, BTR and Y6, or 0.2-2% of the volume of the Y6 solution.
Preferably, the annealing temperature is 80-200 ℃ and the annealing time is 5-30 min.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts a ternary strategy, utilizes BDT (benzodithiophene) structures similar to D18 and BTR to form alloy phases, and causes different compatibility between a donor alloy phase and a receptor, thereby showing different phase distribution and phase purity and exciton state energy distribution difference. The research shows that in a ternary system D18:BTR:Y6 of a smaller degree donor alloy phase mode, not only can the crystallinity and molecular accumulation of the original donor be maintained, but also the better compatibility of an alloy phase and a receptor can be realized, the phase purity of the receptor is improved, and the coordination of the crystallinity and the compatibility is realized. More importantly, the appropriate donor alloy phase mode can reduce the aggregation of the receptor (reduce ACQ effect) so as to reduce non-radiative recombination loss, and meanwhile, the alloy phase is beneficial to improving the energy level of a CT state, shortening the energy level difference between the CT state and an LE state, thereby reducing the recombination energy of a system, realizing the alleviation of the radiative recombination loss below a band gap and finally realizing the reduction of energy loss. The invention further prepares the ternary organic photovoltaic cell by adopting a step-by-step deposition method (Layer-by-Layer, lbL), adding a solid additive and the like, eliminates the influence of a receptor and the liquid additive on a donor alloy phase, maintains the purity of the alloy phase, again proves that a D18 ternary system with a smaller alloy phase has lower energy loss, and can realize higher open-circuit voltage. Finally, low energy loss, synergistically optimized crystallinity and component compatibility, D18-based ternary systems achieve photovoltaic efficiencies up to 19.4%, one of the highest photovoltaic efficiencies based on the Y6 receptor system.
Drawings
Fig. 1 is an EQE spectrum of the conventional BHJ type organic photovoltaic cell in comparative examples 1 to 4 and example 1.
Fig. 2 is an EQE spectrum of the organic photovoltaic cells prepared by the LbL method in comparative examples 5-7 and examples 2-3.
Fig. 3 is a current-voltage curve under light of the conventional BHJ type organic photovoltaic cells of comparative examples 1 to 4 and example 1.
Fig. 4 is a current-voltage curve under light for organic photovoltaic cells prepared by the LbL method of comparative examples 5-7 and examples 2-3.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
Comparative example 1
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) PM6 and Y6 are added into chloroform according to the mass ratio of 1:1.2 to prepare a mixed solution with the total concentration of 16.5mg/mL, 1, 8-Diiodooctane (DIO) is added, the addition amount of 1, 8-diiodooctane is 0.25 percent of the volume of the mixed solution, an active layer solution is obtained, the active layer solution is coated by rotating at 2500rpm for 30 seconds, and then annealing is carried out at 100 ℃ for 10 minutes to form an active layer with the thickness of about 100 nm;
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under the AM1.5 simulated sunlight irradiation with the illumination intensity of 100mW/cm 2, the open circuit voltage of the organic photovoltaic cell was measured to be 0.835V, the short circuit current density was measured to be 27.47mA/cm 2, the filling factor was measured to be 77.68%, the PCE was measured to be 17.84%, the external quantum efficiency curve of the organic photovoltaic cell was shown in fig. 1, and the current-voltage curve was shown in fig. 3.
Comparative example 2
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Adding BTR and Y6 to chloroform at a mass ratio of 1.6:1 to prepare a mixed solution (active layer solution) with a total concentration of 16.5mg/mL, spin-coating the active layer solution at 1500rpm for 30s, and annealing at 100deg.C for 10 minutes to form an active layer of about 100 nm;
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under AM1.5 simulated sunlight with an illumination intensity of 100mW/cm 2, and the open circuit voltage of the organic photovoltaic cell was measured to be 0.864V, the short circuit current density was measured to be 17.82mA/cm 2, the fill factor was 52.02%, and the PCE was measured to be 8.01%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 1, and the current-voltage curve is shown in fig. 3.
Comparative example 3
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Adding PM6, BTR and Y6 into chloroform to prepare a mixed solution with the total concentration of 16.5mg/mL, wherein the mass ratio of electron donor to electron acceptor is 1:1.2, the mass ratio of PM6 to BTR is 0.95:0.05, adding 1, 8-Diiodooctane (DIO) with the addition amount of 0.25 percent of the volume of the mixed solution to obtain an active layer solution, spin-coating the active layer solution for 30s at 2500rpm, and annealing at 100 ℃ for 10 minutes to form an active layer of about 100 nm;
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, and the open circuit voltage of the organic photovoltaic cell was measured to be 0.835V, the short circuit current density was measured to be 28.18mA/cm 2, the fill factor was 78.17%, and the PCE was measured to be 18.40%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 1, and the current-voltage curve is shown in fig. 3.
Comparative example 4
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Adding D18 and Y6 into chloroform according to a mass ratio of 1:1.2 to prepare a mixed solution with a total concentration of 16.5mg/mL, adding 1, 8-Diiodooctane (DIO) with an addition amount of 0.25% of the volume of the mixed solution to obtain an active layer solution, spin-coating the active layer solution at 2500rpm for 30s, and annealing at 100 ℃ for 10min to form an active layer of about 100 nm;
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, and the open circuit voltage of the organic photovoltaic cell was measured to be 0.843V, the short circuit current density was measured to be 27.15mA/cm 2, the fill factor was 79.82%, and the PCE was measured to be 18.24%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 1, and the current-voltage curve is shown in fig. 3.
Example 1
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Adding D18, BTR and Y6 into chloroform to prepare a mixed solution with the total concentration of 16.5mg/mL, wherein the mass ratio of an electron donor to an electron acceptor is 1:1.2, the mass ratio of D18 to BTR is 0.95:0.5, adding 1, 8-Diiodooctane (DIO) with the addition amount of 0.25 percent of the volume of the mixed solution to obtain an active layer solution, spin-coating the active layer solution for 30s at 2500rpm, and annealing at 100 ℃ for 10 minutes to form an active layer of about 100 nm;
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, and the open-circuit voltage of the organic photovoltaic cell was measured to be 0.851V, the short-circuit current density was measured to be 27.82mA/cm 2, the fill factor was 79.14%, and the PCE was measured to be 18.75%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 1, and the current-voltage curve is shown in fig. 3.
Comparative example 5
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Firstly, preparing 7mg/mL of PM6 chloroform solution and 8mg/mL of Y6 chloroform solution, wherein 1, 8-diiodooctane is added into the Y6 chloroform solution, the addition amount of the 1, 8-diiodooctane is 0.25% of the volume of the Y6 chloroform solution, and firstly, spin-coating the 7mg/mL of PM6 chloroform solution onto an anode modification layer at a rotating speed of 2000rpm for 30 seconds to form an electron donor film; subsequently spin-coating the Y6 chloroform solution added with DIO onto the electron donor film at 2000rpm for 30 seconds, and then annealing at 100 ℃ for 10 minutes to form an active layer of about 110nm (thickness ratio of electron donor film to electron acceptor film about 65nm:45 nm);
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under the AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2, the open-circuit voltage of the organic photovoltaic cell was 0.831V, the short-circuit current density was 27.85mA/cm 2, the filling factor was 76.80%, and the PCE was 17.79%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 2, and the current-voltage curve is shown in fig. 4.
Comparative example 6
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Firstly, preparing a mixed chloroform solution of PM6 and BTR with the total concentration of 7mg/mL (the mass ratio of PM6 to BTR is 0.95:0.05) and a Y6 chloroform solution with the concentration of 8mg/mL, wherein 1, 8-diiodooctane is added into the Y6 chloroform solution, the addition amount of 1, 8-diiodooctane is 0.25 percent of the volume of the Y6 chloroform solution, and firstly, spin-coating the mixed chloroform solution of PM6 and BTR with the concentration of 7mg/mL on an anode modification layer at a rotating speed of 2000rpm for 30 seconds to form a mixed electron donor film; spin-coating Y6 chloroform solution added with DIO onto the mixed electron donor film at 2000rpm for 30 seconds, and annealing at 100deg.C for 10 minutes to form an active layer of about 110nm (thickness ratio of mixed electron donor film to electron acceptor film about 65nm:45 nm);
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under the AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2, the open-circuit voltage of the organic photovoltaic cell was 0.831V, the short-circuit current density was 28.70mA/cm 2, the filling factor was 77.78%, and the PCE was 18.55%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 2, and the current-voltage curve is shown in fig. 4.
Comparative example 7
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Firstly, preparing 4.5mg/mL of D18 chloroform solution and 8mg/mL of Y6 chloroform solution, wherein 1, 8-diiodooctane is added into the Y6 chloroform solution, the addition amount of the 1, 8-diiodooctane is 0.25% of the volume of the Y6 chloroform solution, and firstly, spin-coating the 4.5mg/mL of D18 chloroform solution onto an anode modification layer at a rotating speed of 2000rpm for 30 seconds to form an electron donor film; subsequently spin-coating the Y6 chloroform solution added with DIO onto the electron donor film at 2000rpm for 30 seconds, and then annealing at 100 ℃ for 10 minutes to form an active layer of about 110nm (thickness ratio of electron donor film to electron acceptor film about 65nm:45 nm);
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, and the open circuit voltage of the organic photovoltaic cell was measured to be 0.838V, the short circuit current density was measured to be 28.36mA/cm 2, the fill factor was 76.44%, and the PCE was measured to be 18.17%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 2, and the current-voltage curve is shown in fig. 4.
Example 2
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Firstly, preparing a mixed chloroform solution of D18 and BTR with the total concentration of 4.5mg/mL (the mass ratio of the D18 to the BTR is 0.95:0.05) and a Y6 chloroform solution with the concentration of 8mg/mL, wherein 1, 8-diiodooctane is added into the Y6 chloroform solution, the addition amount of the 1, 8-diiodooctane is 0.25 percent of the volume of the Y6 chloroform solution, and firstly, spin-coating the mixed chloroform solution of D18 and BTR with the concentration of 4.5mg/mL onto an anode modification layer at the rotating speed of 2000rpm for 30 seconds to form a mixed electron donor film; spin-coating Y6 chloroform solution added with DIO onto the mixed electron donor film at 2000rpm for 30 seconds, and annealing at 100deg.C for 10 minutes to form an active layer of about 110nm (thickness ratio of mixed electron donor film to electron acceptor film about 65nm:45 nm);
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under the AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2, and the open-circuit voltage of the organic photovoltaic cell was measured to be 0.851V, the short-circuit current density was measured to be 27.89mA/cm 2, the filling factor was 80.28%, and the PCE was measured to be 19.08%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 2, and the current-voltage curve is shown in fig. 4.
Example 3
(1) Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, treating by using ultraviolet ozone for 15 minutes, then rotationally coating a layer of 10 nm-thick PEDOT (PSS) (batch number is Baytron P AI 4083) at 4000rpm, and baking the PEDOT in air at 150 ℃ for 20 minutes to obtain an anode modification layer;
(2) Firstly, preparing a mixed chloroform solution of D18 and BTR with the total concentration of 4.5mg/mL (the mass ratio of the D18 to the BTR is 0.95:0.05) and a Y6 chloroform solution, wherein 3, 5-Dichlorobenzene (DCBB) is added into the Y6 chloroform solution, the concentration of Y6 is 8.0mg/mL and the concentration of DCBB is 10mg/mL in the Y6 chloroform solution added with DCBB; first, 4.5mg/mL of a mixed chloroform solution of D18 and BTR is spin-coated on an anode modification layer at a rotating speed of 2000rpm for 30 seconds to form a mixed electron donor film; subsequently spin-coating the Y6 chloroform solution added with DCBB onto the mixed electron donor film at 2000rpm for 30 seconds, and then annealing at 100 ℃ for 10 minutes to form an active layer of about 110nm (thickness ratio of mixed electron donor film to electron acceptor film about 65nm:45 nm);
(3) 1.0mg/mL PDINN methanol solution is spin-coated on the active layer at 4000rpm for 40s to form a cathode modification layer, an Ag (100 nm) electrode is deposited on the cathode modification layer through thermal evaporation, and the BHJ type organic photovoltaic cell with the active area of 6mm 2 and the test aperture area of 4.73mm 2 is prepared.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, and the open circuit voltage of the organic photovoltaic cell was measured to be 0.859V, the short circuit current density was measured to be 27.83mA/cm 2, the fill factor was 81.16%, and the PCE was 19.41%. The external quantum efficiency curve of the organic photovoltaic cell is shown in fig. 2, and the current-voltage curve is shown in fig. 4.
As seen from the External Quantum Efficiency (EQE) spectra of binary and ternary batteries (FIGS. 1-2), the higher EQE values of PM6: BTR: Y6 in the 400-580nm and 680-780nm wavelength ranges and D18: BTR: Y6 in the 500-660nm and 700-860nm wavelength ranges may result from an alloy-like donor phase having a fine morphology, resulting in an increase in J SC, as compared to the corresponding binary device. Because of the good compatibility between D18 and Y6, the formation of excessive alloy forms of BTR and D18 is prevented, and the balance of compatibility and crystallinity is realized, and the D18:BTR:Y6 has finer morphology, so that slight red shift occurs at the edge of EQE. The ternary organic photovoltaic cell prepared by the method has lower energy loss and obviously improved open circuit voltage, proper short circuit current density and high level of filling factor, and the PCE of the ternary organic photovoltaic cell (D18: BTR/Y6, DCBB) of the embodiment 3 reaches 19.41 percent and is obviously superior to the binary organic light Fu Yang cell (D18/Y6, 18.17 percent) prepared by the corresponding progressive deposition method, and the ternary organic photovoltaic cell (D18: BTR: Y6, 18.75 percent) based on the bulk heterojunction (bulk heterojunction, BHJ) structure of the embodiment 1.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The double-donor alloy phase ternary organic photovoltaic cell is characterized by comprising a substrate, an anode modification layer, an active layer based on a double-donor/acceptor system, a cathode modification layer and a cathode which are sequentially laminated; the active layer is a composite film formed by two electron donors and an electron acceptor, the electron donors are a polymer donor D18 and a liquid crystal small molecule donor BTR, and the electron acceptor is a non-fullerene acceptor Y6.
2. The two-donor alloy phase ternary organic photovoltaic cell of claim 1, wherein the active layer is a blend film of two electron donors and one electron acceptor, or a composite film comprising a mixed electron donor film and an electron acceptor film in a layered arrangement; the thickness of the active layer is 50-150 nm.
3. The bi-donor alloy phase ternary organic photovoltaic cell of claim 2 wherein when the active layer is a blend film of two electron donors and one electron acceptor, the mass ratio of electron donor to electron acceptor is 1:0.5 to 1.5.
4. The dual-donor alloy phase ternary organic photovoltaic cell according to claim 1, wherein the mass ratio of the polymer donor D18 to the liquid crystal small molecule donor BTR in the active layer is 1:0.05 to 0.5.
5. The bi-donor alloy phase ternary organic photovoltaic cell of claim 1 wherein the substrate is glass; the anode is ITO; the anode modification layer is PEDOT: PSS; the cathode modification layer is PDINN; the cathode is Ag.
6. The method for preparing a dual-donor alloy phase ternary organic photovoltaic cell according to any one of claims 1 to 5, comprising the steps of:
(1) Preparing an anode modification layer on an anode on one side surface of a substrate;
(2) Coating the mixed solution of D18, BTR and Y6 on the anode modification layer, or coating the mixed solution of D18 and BTR on the anode modification layer first, and then coating the Y6 solution; annealing treatment is carried out after coating is finished, so that the active layer is formed;
(3) And (3) sequentially preparing a cathode buffer layer and a cathode layer on the active layer prepared in the step (2) to obtain the double-donor alloy phase ternary organic photovoltaic cell.
7. The method for producing a two-donor alloy phase ternary organic photovoltaic cell according to claim 6, wherein the total concentration of electron donor and electron acceptor in the mixed solution of D18, BTR and Y6 is 4.5-19 mg/mL.
8. The method for producing a ternary organic photovoltaic cell of a double-donor alloy phase according to claim 6, wherein the total concentration of electron donors in the mixed solution of D18 and BTR is 3-7.5 mg/mL and the concentration of Y6 solution is 1.5-11.25 mg/mL.
9. The method for preparing the dual-donor alloy phase ternary organic photovoltaic cell according to claim 6, wherein the mixed solution of D18, BTR and Y6 or the Y6 solution further comprises an additive, and the additive is 1, 8-diiodooctane or 3, 5-dibromobenzene.
10. The method for preparing a dual-donor alloy phase ternary organic photovoltaic cell according to claim 6, wherein the annealing temperature is 80-200 ℃ and the annealing time is 5-30 min.
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