CN114420845A - Ternary-assistance-based full-polymer organic photovoltaic device adopting step-by-step solution deposition and preparation method thereof - Google Patents

Ternary-assistance-based full-polymer organic photovoltaic device adopting step-by-step solution deposition and preparation method thereof Download PDF

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CN114420845A
CN114420845A CN202210013296.5A CN202210013296A CN114420845A CN 114420845 A CN114420845 A CN 114420845A CN 202210013296 A CN202210013296 A CN 202210013296A CN 114420845 A CN114420845 A CN 114420845A
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殷航
崔风哲
郝晓涛
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Shandong University
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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Abstract

The invention relates to a ternary-assisted stepwise solution deposition-based all-polymer organic photovoltaic device and a preparation method thereof, belonging to the technical field of organic photovoltaic device preparation. In addition, a polymer receptor PDI-2T is selected as a third component to modify the exciton diffusion behavior in the intrinsic receptor material PY-IT. The ternary (1+2) assisted stepwise solution deposition strategy adopts a preparation method that 1 donor (PBDB-T-2F) is deposited first and then 2 blended receptors (PY-IT: PDI-2T) are deposited to form films in sequence. The method not only realizes the regulation effect of the sequential deposition strategy on the ideal vertical phase distribution form, but also successfully reserves the regulation effect of the ternary strategy on the exciton diffusion behavior.

Description

Ternary-assistance-based full-polymer organic photovoltaic device adopting step-by-step solution deposition and preparation method thereof
Technical Field
The invention relates to preparation and application of a high-efficiency all-polymer system solar cell device, in particular to an all-polymer organic photovoltaic device based on ternary-assisted stepwise solution deposition and a preparation method thereof, and belongs to the technical field of organic photovoltaic device preparation.
Background
Under the background of global energy structure transformation and low-carbon development consensus, organic solar cells are becoming important branch directions for promoting clean renewable energy and green environmental protection industries. The organic solar cell prepared based on the solution processing method has the advantages of lightness, thinness, flexibility, translucency, wearability, roll-to-roll printing and the like which cannot be achieved by an inorganic semiconductor photovoltaic cell. In recent years, the power conversion efficiency of organic photovoltaic devices based on small molecule receptors has risen to more than 19%, but there is still a gap in efficiency of approximately 26% compared with conventional silicon-based solar cells. In addition, the organic photovoltaic cell still has a lot of promotion spaces compared with the traditional crystal silicon photovoltaic industry in the aspects of long-term operation stability of devices, large-area device preparation for commercialization, cost control and the like. By focusing on the specific properties of organic photovoltaics, the organic semiconductor technology is taken as the advantage of the organic photovoltaics to promote the industrialization of the organic photovoltaics, so that the development of a high-efficiency and stable all-polymer organic photovoltaic system becomes a hot spot field in recent years. The all-polymer solar cell mainly comprises a polymer donor material and a polymer acceptor material, and the organic photovoltaic cell with the small molecular-based acceptor has irreplaceable advantages in the aspects of device thermal stability, bending stability, donor-acceptor ratio tolerance, device operation life and the like, and the organic photovoltaic cell is benefited by the excellent mechanical flexibility and in-chain carrier transport property of the polymer material. In the last three years, with the exploration and development of the technology for the high molecular weight of small molecular receptors, the efficiency of all-polymer solar cells has exceeded 15%. From the related research results that have been published on a global scale, the power conversion efficiency of all-polymer solar cells has a certain improved space compared with organic solar cells based on small molecule receptors, which is caused by the non-ideal vertical component distribution caused by the blending behavior of the polymer donor and the polymer receptor in the active layer.
The vertical distribution form of the donor and acceptor components in the active layer can adjust the actions of exciton diffusion and dissociation, carrier transport and extraction and the like, and further has certain influence on the comprehensive performance of the photovoltaic device. The ideal morphology of the vertical phase distribution is one in which the donor material is more distributed in the anode region and the acceptor material is more distributed in the cathode region, thereby forming a gradient of the donor-acceptor ratio along the depth of the film. The binary solution step-by-step deposition is a preparation technical means that a layer of pure donor or acceptor film is firstly deposited on a substrate and then a layer of pure acceptor or donor film is deposited in the preparation process of an active layer. This has the advantage that a good proportional distribution gradient of the donor and acceptor materials can be formed, but this can result in a degree of oversizing of the crystal size of the donor and acceptor phases and separation too far to favour exciton dissociation and charge transfer processes. The ternary strategy is to add a third component which can be an acceptor or a donor into a binary donor-acceptor blending solution to achieve the purpose of optimizing exciton diffusion and carrier kinetics, but the ternary strategy is difficult to generate an ideal optimization effect on the vertical phase distribution of a main donor-acceptor component. The two optimization means are common technical means for optimizing the high-efficiency organic solar cell at present, and the regulation and control and the physical mechanism on the details of the two optimization means are widely and deeply researched, but the methods for combining the two optimization means and respectively taking the advantages are rarely artificial.
Disclosure of Invention
Aiming at the non-ideal vertical phase distribution form in the existing all-polymer solar cell, the invention provides an all-polymer organic photovoltaic device based on ternary-assisted stepwise solution deposition and a preparation method thereof to overcome the defects, and the method has simple operation process and certain universality.
The invention selects a full polymer system with higher photoelectric conversion efficiency as an intrinsic system, wherein the polymer donor material is PBDB-T-2F, and the polymer receptor material is PY-IT. In addition, a polymer receptor PDI-2T is selected as a third component to modify the exciton diffusion behavior in the intrinsic receptor material PY-IT. The ternary (1+2) assisted stepwise solution deposition strategy adopts a preparation method that 1 donor (PBDB-T-2F) is deposited first and then 2 blended receptors (PY-IT: PDI-2T) are deposited to form films in sequence. The method not only realizes the regulation effect of the sequential deposition strategy on the ideal vertical phase distribution form, but also successfully reserves the regulation effect of the ternary strategy on the exciton diffusion behavior. To illustrate the strategyThe invention uses the in-situ low-pressure oxygen plasma film etching technology to analyze and explain the vertical phase distribution form in detail. In addition, transient optical response research on the device shows that the exciton diffusion length is increased by introducing the third component, so that more excitons are ensured to be diffused to a donor-acceptor interface under the ideal phase separation condition, and more carriers are promoted to be generated. The organic photovoltaic device prepared by adopting the ternary-assisted stepwise solution deposition strategy balances the vertical charge transfer performance and the three-dimensional exciton diffusion behavior, not only solves the problem of non-ideal vertical phase distribution form caused by the thermodynamic behavior of solution film formation in the preparation process of the all-polymer photovoltaic device, but also successfully overcomes the problem of insufficient exciton diffusion distance under the ideal distribution form. On the basis, the three-element auxiliary step-by-step solution deposition method effectively realizes the short-circuit current density J of the organic solar cellSCAnd the power conversion efficiency PCE is effectively improved, and the simple operation process is suitable for the commercial production of the organic photovoltaic device and has good application prospect.
Interpretation of terms:
1. PBDB-T-2F is a polymer material, the molecular formula of which is poly [ (2,6- (4,8-bis (5- (2-ethylhexyl) -4-fluorothiophen-2-yl) benzol [1,2-b:4,5-b '] dithiophene)) -co- (1,3-di (5-thiophen-2-yl) -5,7-bis (2-ethy-exyl) -benzol [1,2-c:4,5-c' ] dithiophene-4,8-dione, and the PBDB-T-2F is mainly used as a donor material of an organic solar cell.
2. PY-IT, a polymer photovoltaic material, the molecular formula of which is Poly [ (2,2'- ((2Z,2' Z) - ((12,13-bis (2-octyldocecyl) -3, 9-dimethylcell-12, 13-dihydo [1,2,5] thiadiazolo [3,4e ] thono [ 2', 3': 4 ', 5' ] thono [ 2', 3': 4,5] pyrono [3,2-g ] thono [ 2', 3': 4,5] thono [3,2-b ] -indole-2,10-diyl) bis (methylenediol) bis (5-methyl-3-oxo-2, 3-dihydroxy-1H-indole-2, 1-diene)) diol-2, 1-diol) 2, 5-diol) as a main solar energy receptor.
3. PDI-2T is a polymer photovoltaic material, the molecular formula of which is Poly [ [1,2,3,8,9,10-hexahydro-2,9-bis (1-nonyldecl) -1,3,8, 10-tetraoxaanthra [2,1,9-def:6,5,10-d ' e ' f ' ] diisoquinoline-5,12-diyl ] [2, 2' -bithiophene-ne ] -5,5 ' -diyl ], mainly used as a receptor material of an organic solar cell.
4. PDINN is a polymer photovoltaic material, namely, Aliphatic amine-functionalized graphene-diimide, which is mainly used as an electron transport layer material of an organic solar cell.
5. The PEDOT is PSS which is a polymer photovoltaic material, the molecular formula of which is Poly (3, 4-ethylenedioxythiopene) and Poly (styrene sulfonate) and is mainly used as a hole transport layer material of an organic solar cell.
The technical scheme of the invention is as follows:
a full-polymer organic photovoltaic device based on ternary-assisted stepwise solution deposition sequentially comprises a glass substrate, a transparent conductive film (anode), a hole transport layer, an organic active layer, an electron transport layer and a top electrode (cathode) from bottom to top, wherein the active layer comprises a polymer donor material and two polymer acceptor materials. The ternary assisted sequential solution deposition method is a preparation process of an active layer in the device structure. The anode and cathode are two metal electrodes of the cell structure, also called positive and negative electrodes. The other layers except the active layer are consistent with the preparation process in the current conventional organic solar cell.
According to the invention, the polymer donor material is PBDB-T-2F, the polymer acceptor material is PY-IT, and the other polymer acceptor material is PDI-2T as a third component.
The invention is based on the active layer preparation technology of the ternary auxiliary step-by-step solution deposition, and the organic photovoltaic device is prepared by utilizing the polymer material: and (3) adopting a step-by-step solution deposition method, firstly spin-coating a PBDB-T-2F solution to deposit a film, and then spin-coating a PY-IT and PDI-2T blended solution on the PBDB-T-2F film to deposit a film, so as to obtain the organic photovoltaic device.
In a traditional binary full polymer system (PBDB-T-2F: PY-IT) with non-ideal molecular configuration, donor and acceptor components are relatively uniformly distributed in an active layer, and an obvious donor enrichment area and an acceptor enrichment area are not available. The device prepared by adopting the ternary-assisted stepwise solution deposition method comprisesA more desirable vertical component distribution profile is one in which the acceptor material is more distributed at the cathode to form an acceptor-rich region near the cathode and the donor material is more distributed at the anode to form a donor-rich region near the anode. The ideal vertical phase distribution form forms a relatively ideal charge transfer channel, and realizes a more ideal carrier transport behavior in the active layer. According to the optimized device prepared by the ternary-assisted stepwise solution deposition method, the device not only has an ideal vertical component distribution form, but also has the exciton diffusion length (16nm) prolonged by 3-4nm compared with a PY-IT pure phase in a PY-IT (poly-p-phenylene diamine-imide) 2T mixed acceptor phase, so that more photogenerated excitons can be fully ensured to be diffused to a dissociation interface under the vertical component distribution form, and the number density of photogenerated carriers in an active layer is effectively improved. The preparation process not only increases the yield of photon-generated carriers, but also inhibits the distribution of defect states in the active layer and weakens the current loss of the device caused by trap-assisted recombination. In addition, a donor enrichment region near the anode forms a good hole transmission channel, an acceptor enrichment region near the cathode forms a good electron transmission channel, and the formation of the carrier transmission channel is beneficial to the extraction of photo-generated carriers by the electrode, so that the photo-generated current of the all-polymer system is improved. The device test result shows that the ternary auxiliary step solution deposition method improves the short-circuit current density of the all-polymer solar cell to 23.97mA cm-2And the open-circuit voltage is improved to 0.949V, the photoelectric conversion efficiency is effectively broken through and is improved to 16.03 percent.
According to the invention, the thickness of the organic active layer is preferably 100nm, and under the standard sunlight environment, the thickness of the organic active layer with the thickness of 100nm is an optimal value, so that the organic active layer is not too thin to sufficiently absorb photons, and is not too thick to cause the performance reduction of the device due to the limitation of point and transmission capability. The mass ratio of PBDB-T-2F to PY-IT to PDI-2T in the all-polymer device prepared by the ternary solution step-by-step spin coating is 1.00:1.00:0.03, and the parameters of the device are not ideal under other ratios. At the most preferable thickness and ratio of each component of the active layer, the photoelectric conversion efficiency of the organic solar cell device is optimized.
According to the invention, the glass substrate attached with the ITO transparent conductive film is a transparent conductive substrate, the thickness of the ITO transparent conductive film is 130nm, the material of the hole transport layer is PEDOT: PSS, the thickness of the hole transport layer is 30nm, the material of the electron transport layer is PDINN, the thickness of the electron transport layer is 5nm, the material of the top electrode is aluminum (Al), and the thickness of the top electrode is 100 nm.
The preparation method of the organic solar cell structure comprises the following steps:
(1) cleaning a transparent conductive substrate, wherein the transparent conductive substrate is a glass substrate attached with an ITO transparent conductive film;
(2) preparing a hole transport layer PEDOT (PSS) film on the transparent conductive substrate obtained in the step (1) by adopting a conventional preparation method;
(3) preparing an organic active layer film, comprising:
a. respectively weighing 10mg of PBDB-T-2F, 15mg of PY-IT and 0.15-75mg of PDI-2T by using a high-precision electronic analytical balance, then adding 0.5-2mL of high-purity chloroform solvent (AR > 99%) into the weighed PBDB-T-2F, blending PY-IT and PDI-2T, adding 0.5-3mL of high-purity chloroform solvent (AR > 99%), placing the mixture on a heatable magnetic stirrer, and stirring for 2-5h at the temperature of 30-50 ℃ to obtain pure PBDB-T-2F solution and PDI-2T with the concentrations of 5-20 mg/mL: PY-IT blending solution;
b. and (3) performing high-precision pipettor on the obtained PY-IT: adding 1% vol chloronaphthalene additive into the PDI-2T blend solution, and continuously stirring for 30min to obtain PY-IT: a mixed receptor solution with the mass ratio of PDI-2T of 1:0.01 to 1: 0.05;
c. in an inert gas (N)2) Spin-coating the PBDB-T-2F solution prepared in the step a on the substrate with the hole transport layer obtained in the step (2) in a glove box, waiting for 30s, and then adding PY-IT prepared in the step b: spin-coating the PDI-2T blended solution on a PBDB-T-2F film, and annealing the obtained film attached with the active layer material in inert gas for 5-10 min;
(4) depositing an electron transport layer (PDNN) film on the organic active layer;
(5) and evaporating the metal electrode material on the electron transport layer.
Most preferably, in the step (3) a, 1mL of high-purity chloroform solvent (AR > 99%) is added to the weighed PBDB-T-2F, and the mixture is placed on a heatable magnetic stirrer and stirred for 2.5h at 40 ℃ to obtain a pure PBDB-T-2F solution with the concentration of 10 mg/mL; 0.45mg of PDI-2T and 1.5mL of a high-purity chloroform solvent (AR > 99%) were added to the weighed PY-IT, and the mixture was stirred at 40 ℃ for 2.5 hours with a heatable magnetic stirrer to obtain a receptor solution having a concentration of 10.3mg/mL, and the mass ratio of PY-IT to PDI-2T in the obtained blend solution was 1: 0.03. At the solution concentration and the corresponding stirring temperature, all the components can be fully dissolved in the chloroform solvent.
According to the invention, in the step (3) c, the spin-coating speed of the solution of the active layer is as follows: the spin-coating speed of PBDB-T-2F is 2500-. The thickness of the obtained PBDB-T-2F layer is 40-60nm, and the thickness of the obtained PY-IT, PDI-2T layer is 40-60 nm.
Further preferably, in the step (3) c, the spin-coating speed of PBDB-T-2F is 3000rpm, and the spin-coating speed of PY-IT: PDI-2T blending solution is 3000 rpm. The thickness of the obtained PBDB-T-2F layer is 45nm, and the thickness of the obtained PY-IT-PDI-2T layer is 55 nm. In the donor and acceptor layer device with the size, ideal vertical phase distribution of donor and acceptor components can be fully realized, the active layer can fully absorb sunlight, and composite current and voltage loss caused by overlarge thickness is avoided. The annealing temperature of the active layer is 100 ℃, and the annealing time is 10 min. The annealing temperature can volatilize residual solvent in the active layer film, improve the crystallinity of each phase of the donor and the acceptor and improve the transport capacity of carriers. Meanwhile, the annealing process can also enable the donor film and the receptor film which are spun in steps in the step (3) c to form good mutual permeation, and is beneficial to forming good vertical phase distribution and a carrier transport channel.
The preparation technology of the ternary auxiliary step-by-step solution deposition active layer has the advantage of breaking through the problem that part of photogenerated excitons cannot reach the interface of the donor and the acceptor for separation when the two phases of the donor and the acceptor are excessively separated in the traditional binary solution step-by-step deposition technology. In addition, the introduction of a trace amount of third component prolongs the diffusion distance of the photoproduction exciton, effectively ensures the photoproduction charge density and simultaneously does not generate negative influence on the distribution form of the vertical components of the donor and the acceptor in the step deposition.
Most of the existing ternary component schemes are that three materials are blended to form a blending solution of 1 donor +2 receptors or 2 donors +1 receptors to prepare a bulk heterojunction active layer structure through one-step spin coating, and the preparation method is not beneficial to forming an ideal vertical component distribution structure in an all-polymer system. Compared with the scheme, the ternary auxiliary step-by-step spin coating scheme has the difference that the donor solution and the receptor solution are subjected to layer-by-layer spin coating to prepare the film, and the scheme has the advantage that the ideal vertical component distribution of the donor and the receptor can be formed in the active layer film, namely a good donor enrichment region and a good receptor enrichment region are formed.
In addition, the small molecule or fullerene material has smaller size, and the vertical distribution mode of the small molecule or fullerene material is easy to regulate and control when the small molecule or fullerene material is blended with a polymer, compared with a system consisting of a polymer donor and a small molecule or fullerene receptor, the scheme aims at a full polymer system which is difficult to regulate and control, namely all donor and acceptor materials in an active layer are high molecular polymers. The high molecular polymer has a longer chain structure and a non-planar molecular shape, so that a more complex blending behavior can occur when a polymer donor and a polymer receptor are blended, and the vertical component distribution is solidified during the solvent volatilization in the annealing process, which causes that the vertical phase distribution in the film prepared by one-step spin coating is difficult to regulate and control.
The invention has the beneficial effects that:
compared with the traditional pure feed and receptor solution step-by-step deposition strategy, the invention introduces the third component into the receptor component, and realizes the ternary auxiliary distributed deposition technology. The technology has the following advantages: (1) the relatively ideal vertical phase distribution form in the traditional binary solution step-by-step deposition technology is reserved, the ideal component distribution comprises a donor enrichment area near the anode of the battery and an acceptor enrichment area near the cathode of the battery, corresponding hole and electron transmission channels are formed, and the efficient transportation and collection of photogenerated carriers in the active layer are realized; (2) compared with the traditional binary solution fractional deposition strategy, the introduction of the third component effectively improves the diffusion behavior of the photo-generated excitons, ensures that more photo-generated excitons in the active layer are diffused to a donor interface and a receptor interface for dissociation under the ideal component distribution form, and breaks through the limitation of the traditional binary solution fractional deposition strategy that the balance relation between the exciton diffusion length and the phase separation scale is restricted; (3) the device prepared by the ternary auxiliary solution fractional deposition method has higher photoelectric conversion efficiency, the photoelectric conversion efficiency can be broken through to more than 16% by using the method, the technology is based on the solution fractional deposition strategy and the ternary strategy, the universality is higher, and a new idea is developed for the future organic photovoltaic industrialization process. (4) The preparation process provided by the scheme is simpler, and the time and resource consumption of the preparation process are greatly reduced.
Drawings
FIG. 1 is a schematic diagram of the ternary assisted step-by-step solution deposition process for preparing an active layer of an organic solar cell in accordance with the present invention;
FIG. 2a is an in situ fault absorption spectrum of an active layer of an organic solar cell prepared by ternary assisted step-by-step solution deposition of comparative example 1;
FIG. 2b is the distribution of donor and acceptor components along the vertical direction of the film calculated from the in-situ tomographic absorption spectroscopy of example 2;
FIG. 2c is an in-situ fault absorption spectrum of an active layer of an organic solar cell prepared by the ternary blended solution one-step solution deposition method of comparative example 1;
FIG. 2d is the distribution of donor and acceptor components along the vertical direction of the film calculated from the in situ fault absorption spectrum of example 2;
FIG. 3a is a schematic view of a vertical composition distribution of an active layer of an organic photovoltaic device prepared by a conventional one-step solution deposition method;
FIG. 3b is a schematic illustration of the vertical composition distribution of an active layer of an organic photovoltaic device made using the ternary assisted step solution deposition process of the present invention;
FIG. 4 is a height image of an AFM surface prepared by a ternary assisted sequential solution deposition process according to the present invention;
FIG. 5a is a transient absorption response curve of a pure acceptor phase (PY-IT) at high and low excitation light power densities;
FIG. 5b is a transient absorption response curve of the mixed acceptor phase (PY-IT: PDI-2T) at high and low excitation light power densities.
Detailed Description
The present invention will be further described by way of examples, but not limited thereto, with reference to the accompanying drawings.
Example 1:
a full polymer organic photovoltaic device based on ternary auxiliary step-by-step solution deposition is composed of a glass substrate, a transparent conductive film (anode), a hole transport layer, an organic photosensitive active layer, an electron transport layer and a top metal electrode (cathode) from bottom to top, wherein the preparation method of the organic photosensitive active layer is the ternary auxiliary step-by-step solution deposition method disclosed by the invention, as shown in figure 1. The organic photosensitive active layer comprises a high-molecular polymer donor and a high-molecular polymer acceptor.
The transparent conductive substrate is a glass substrate attached with an ITO transparent conductive film, wherein the thickness of the ITO is 130nm, and the square resistance is less than 15 omega cm-2. PSS (polymer PEDOT), the thickness of which is 30nm, a PDINN, the thickness of which is 5nm, and an aluminum (Al) electrode, the thickness of which is 100nm, are used as the hole transport layer.
The high molecular polymer donor is PBDB-T-2F, and the high molecular polymer receptor is PY-IT and PDI-2T. The ternary-assisted distributed solution deposition strategy is an organic photosensitive active layer preparation strategy, and the preparation process comprises the following steps: a. forming a donor material film on the hole transport layer by spin coating PBDB-T-2F solution deposition, wherein the thickness is 45 nm; b. and spin-coating PY-IT PDI-2T mixed solution on the donor film to deposit to form an acceptor material film with the thickness of 55 nm. The total thickness of the organic photosensitive active layer is 100 nm.
The mass ratio of two polymer materials in the PY-IT-PDI-2T mixed solution is 1:0.03, and the mass ratio of PBDB-T-2F to PY-IT-PDI-2T in the full polymer device prepared by the three-component solution step-by-step spin coating is 1:1: 0.03.
A ternary-assisted stepwise solution deposition strategy is adopted in the preparation of the organic photosensitive active layer, so that relatively ideal vertical component distribution of a donor and a receptor is formed, the problem of limited photoelectric conversion efficiency of a device caused by insufficient exciton diffusion length when the phase separation scale is too large is solved, and a new thought is provided for the industrialization process of the organic photovoltaic field in the future.
Example 2
A method of making the ternary assisted step-by-step solution deposition based all-polymer organic photovoltaic device of example 1 comprising the steps of:
(1) cleaning the transparent conductive substrate: sequentially carrying out water bath ultrasonic cleaning on a transparent conductive substrate (namely a glass substrate attached with an ITO transparent conductive film) by using a detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol in an ultrasonic machine for 20min, and drying by using high-purity nitrogen (more than 99%) after cleaning; putting the blow-dried transparent conductive substrate into an ultraviolet irradiation machine, and irradiating for 15min by using ultraviolet light;
(2) preparing a hole transport layer: in the air, a layer of hole transport layer material PEDOT, PSS with the thickness of 30nm is coated on the transparent conductive substrate treated by ultraviolet light by a spin coater, and then the substrate coated with the hole transport layer material is placed on an annealing table at 150 ℃ for annealing for 15 min; wherein PEDOT, PSS is purchased from Xian Baolaite Limited company, and PEDOT, PSS and ultrapure water are diluted according to the proportion of 1:1 and are stirred for 30min on a magnetic stirrer at the temperature of 30 ℃ before use;
(3) preparing an organic photosensitive active layer: blend of pure PBDB-T-2F, PY-IT PDI-2T was dissolved in highly pure chloroform solvent (AR > 99%, concentration 5-10mg mL)-1) In the method, a blend of PY-IT: PDI-2T is dissolved in a highly pure chloroform solvent (AR > 99%, wherein the concentration of PY-IT is 5-10mg mL-1PDI-2T and PY-IT with the mass ratio of 3 wt percent), placing the preliminarily prepared solution on a magnetic stirring heating table, and stirring for 2.5 hours at the temperature of 40 ℃ to obtain a fully dissolved solution; spin-coating the PBDB-T-2F solution on the substrate annealed in the step (2) in an inert gas nitrogen glove box, waiting for 30s of solvent evaporation process to form a PBDB-T-2F film in an unstable crystalline state on the substrate, and continuing to mix the PY-IT with the PDI-2T solutionSpin-coating on PBDB-T-2F film, placing the substrate with the active layer on an annealing table at 100 deg.C, annealing for 10min, and taking down;
(4) preparing an electron transport layer: PDINN was dissolved in a high purity methanol solvent (AR > 99%, concentration 1.5 mgmL)-1) Placing the preliminarily prepared PDINN solution on a magnetic stirring table, and stirring for 5 hours at room temperature to obtain a fully dissolved PDINN solution; spin-coating the fully dissolved PDINN solution on the organic photosensitive active layer annealed in the step (3) by using a spin coater;
(5) preparing a metal electrode: transferring the substrate with the hole transport layer/organic photosensitive active layer/electron transport layer obtained in the step (4) into a physical vapor deposition chamber, and after a vacuum-pumping system is started, reducing the pressure of the chamber to 2.5 multiplied by 10-4And Pa, heating the aluminum target material, and preparing an Al electrode on the substrate, wherein the thickness of the electrode is 100 nm.
The detailed steps for preparing the organic photosensitive active layer in the step (3) are as follows:
A. weighing high molecular polymer by using a high-precision electronic balance (weighing range is 0.02-30mg), wherein 10.0mg of high molecular polymer donor (Solamer, > 99%) PBDB-T-2F is weighed and placed into a No. 1 glass sample bottle, and 0.45mg of high molecular polymer receptor (Solamer, > 99%) is weighed and placed into a No. 2 glass sample bottle according to the proportion, so that the mass ratio of PY-IT to PDI-2T in the No. 2 sample bottle is 1: 0.03;
B. placing the glass sample bottle in the step A into a glove box protected by nitrogen, adding 1mL of high-purity chloroform solvent (Sigma Aldrich, AR > 99%) into the sample bottle No. 1 under the nitrogen atmosphere, placing the sample bottle on a magnetic heating stirrer, heating and stirring the sample bottle at the temperature of 40 ℃ for 2.5 hours to obtain a fully-dissolved polymer donor solution with the concentration of 10mgmL-1；
C. Adding 1.5mL of high-purity chloroform solvent (Sigma Aldrich, AR > 99%) into sample bottle No. 2 under nitrogen atmosphere, placing on a magnetic heating stirrer, heating and stirring at 40 deg.C for 2.5h to obtain well-dissolved polymer acceptor solution with total concentration of 10.3mg mL-1Wherein the concentration of PY-IT is 10mg mL-1Concentration of PDI-2TDegree of 0.3mg mL-1；
D. C, under the nitrogen atmosphere, adding a chloronaphthalene additive (Sigma Aldrich, > 99%) into the receptor solution No. 2 sample bottle obtained in the step C according to the proportion of 1% vol, and continuously stirring for 30min to prepare an active layer by spin coating;
E. spin-coating the donor solution in the sample bottle No. 1 prepared in the step B on a PEDOT/PSS hole transport layer by using a spin coater in a nitrogen atmosphere, wherein the rotating speed is 3000rpm as shown in figure 1, and an organic donor layer with the thickness of 45nm is obtained;
F. under the nitrogen atmosphere, spin-coating the receptor solution in the sample bottle No. 2 prepared in the step D on the organic donor layer prepared in the step E by using a spin coater, wherein the rotating speed is 3000rpm as shown in figure 1, a PY-IT (PDI-2T) organic receptor layer is obtained on the organic donor layer, and the total thickness of the organic photosensitive active layer is 100 nm;
G. placing the substrate attached with the organic photosensitive active layer obtained in the step F on an electric heating annealing table in a nitrogen atmosphere, and annealing at 100 ℃ for 10 min;
conventional strategies for the preparation of organic photosensitive active layers by stepwise solution deposition typically employ orthogonal solvents, i.e., solvents used for the second layer of solution have no or only very poor solubility for the first layer of organic film. The same solvent is selected in the preparation process of the ternary-assisted stepwise solution deposition method, and the strategy is matched with the thermal annealing process to realize the formation of a bicontinuous interpenetrating network between the donor and the receptor in the organic photosensitive active layer, thereby being beneficial to forming a proper donor enrichment area and a proper receptor enrichment area.
Example 3
A method of making an all-polymer organic photovoltaic device based on three-way assist step-wise solution deposition as described in example 1, the steps being as described in example 2, except that in step (3) B, C, stirring was carried out on a heatable magnetic stirrer at 30 ℃ for 5 h.
Example 4
A method of making the three-way assist based step-wise solution deposition all polymer organic photovoltaic device of example 1, the steps are as described in example 2, except that in step (3) B, C, stirring is carried out on a heatable magnetic stirrer at 50 ℃ for 2 h.
Example 5
A method of making a ternary assisted step-wise solution deposition based all-polymer organic photovoltaic device as described in example 1, the steps were as described in example 2, except that in step (3) E, F, the PBDB-T-2F spin speed was 2500rpm and the PY-IT: PDI-2T blend solution spin speed was 2500 rpm. The thickness of the obtained PBDB-T-2F layer is 40nm, and the thickness of the obtained PY-IT-PDI-2T layer is 60 nm.
Example 6
A method of making a ternary assisted step-wise solution deposition based all-polymer organic photovoltaic device as described in example 1 was performed as described in example 2, except that in step (3) E, F, the PBDB-T-2F spin speed was 3500rpm and the PY-IT: PDI-2T blend solution spin speed was 3500 rpm. The thickness of the obtained PBDB-T-2F layer is 60nm, and the thickness of the obtained PY-IT, PDI-2T layer is 40 nm.
Examples of the experiments
According to the device structure described in example 1 and the operation steps of the ternary assisted step-by-step solution deposition strategy described in example 2, organic photovoltaic devices were prepared and tested under illumination by AAA solar simulator. Wherein the spectral distribution of the solar simulator is AM1.5G, and the illumination intensity is calibrated to be 100mW cm by using a standard silicon cell-2。
Comparative example 1
An organic solar cell prepared according to the ternary assisted step-by-step solution deposition strategy described in example 2, with the following differences:
and (5) not executing the step (5), wherein the obtained device structure is as follows from top to bottom: electron transport layer (PDINN, 5nm), all-polymer photosensitive active layer (100nm), hole transport layer (PEDOT: PSS, 30nm), ITO (130nm), glass substrate.
An organic solar cell prepared according to the ternary assisted step-by-step solution deposition strategy described in example 2, with the following differences:
preparing a ternary active layer by adopting a one-step solution spin-coating method in the step (3): weighing high molecular polymer by a high-precision electronic balance, and respectively weighing PBDB-T-2F14 mg, PY-IT14 mg and PDI-2T0.42 mg (Solarmer, > 99%) according to the proportion; the weighed high molecular polymers form a PBDB-T-2F, PY-IT, PDI-2T ternary system; pouring the weighed high molecular polymer into a sample bottle, adding 2mL of high-purity chloroform solvent into the sample bottle under the atmosphere of a nitrogen-protected glove box, placing the sample bottle on a magnetic heating stirrer, and heating and stirring the sample bottle for 2.5 hours at the temperature of 40 ℃ to obtain a fully dissolved solution; under the nitrogen atmosphere, adding a chloronaphthalene additive into the solution of the active layer according to the volume ratio of 1%, and continuously stirring for 30 minutes to prepare the active layer by spin coating; and under the nitrogen atmosphere, the prepared active layer solution is spin-coated on the hole transport layer by using a spin coater at the rotating speed of 3000rpm to obtain the bulk heterojunction organic active layer with the thickness of 100 nm. And (5) the step (5) is not executed, and the obtained device structure is as follows from top to bottom: electron transport layer (PDINN, 5nm), all-polymer photosensitive active layer (prepared by one-step solution deposition method, 100nm), hole transport layer (PEDOT: PSS, 30nm), ITO (130nm), glass substrate.
The organic material of the device is etched layer by layer under the action of low-pressure oxygen plasma etching, thereby obtaining an absorption spectrum of each layer of material, as shown in fig. 2a and 2 c. In fig. 2a and 2c, the absorption peak of the electron transport layer PDINN is clearly seen in the uppermost layer from the top to the bottom of the etching direction. And then obtaining the depth position of the film absorption curve corresponding to the active layer according to the etching time, and obtaining the relative content distribution of the donor and the acceptor at the position according to the relative intensity of the absorption peak of the donor and acceptor materials in the absorption spectral line. Comparing fig. 2b and fig. 2d, the organic solar cell prepared by the ternary assisted stepwise solution deposition strategy has an acceptor material enrichment region with a thickness of 50nm at a position of 0nm (cathode), a donor material enrichment region with a thickness of 50nm near 100nm (anode), and the donor and acceptor enrichment regions are both more enriched than corresponding regions in the ternary active layer prepared by the one-step solution spin coating method. As shown in fig. 3a and 3b, comparing the schematic diagrams of fig. 3a and 3b, it can be seen that the vertical phase distribution of the donor and acceptor materials in the organic photosensitive active layer obtained by the step-by-step solution deposition method is more ideal. The acceptor material is more distributed near the cathode to form a good energy band structure and an electron transmission area, which is beneficial to the movement of photo-generated electrons to the cathode under the action of an electric field and the timely extraction of the photo-generated electrons by the cathode. In a similar way, more donor materials are distributed near the anode to form a good energy band structure and a good hole transmission region, so that photogenerated holes move towards the metal anode under the action of an electric field and are extracted in time. In addition, the surface roughness of the organic photosensitive active layer is also controlled within a desired level as shown in fig. 4.
Comparative example 2
An organic solar cell prepared according to the ternary assisted step-by-step solution deposition strategy described in example 2, with the following differences:
in the step (3), a binary one-step solution spin coating method is adopted to prepare a binary active layer: the high molecular polymer was weighed with a high precision electronic balance, and PBDB-T-2F14 mg, PY-IT14 mg (Solarmer,>99%); the weighed high molecular polymers form a PBDB-T-2F PY-IT binary system; pouring the weighed high molecular polymer into a sample bottle, adding 2mL of high-purity chloroform solvent into the sample bottle under the atmosphere of a nitrogen-protected glove box, placing the sample bottle on a magnetic heating stirrer, and heating and stirring the sample bottle for 2.5 hours at the temperature of 40 ℃ to obtain a fully dissolved solution, wherein the concentration of PBDB-T-2F and the concentration of PY-IT are respectively 7mgmL-1，7mgmL-1(ii) a Under the nitrogen atmosphere, adding a chloronaphthalene additive into the solution of the active layer according to the volume ratio of 1%, and continuously stirring for 30 minutes to prepare the active layer by spin coating; and under the nitrogen atmosphere, the prepared active layer solution is spin-coated on the hole transport layer by using a spin coater at the rotating speed of 3000rpm to obtain the bulk heterojunction organic active layer with the thickness of 100 nm.
Comparative example 3
An organic solar cell prepared according to the ternary assisted step-by-step solution deposition strategy described in example 2, with the following differences:
in the step (3), a binary stepwise solution spin-coating method is adopted to prepare a binary active layer: the high molecular polymer is weighed by a high-precision electronic balance, PBDB-T-2F20mg is respectively weighed according to the proportion and put into a No. 1 sample bottle, PY-IT20 mg is put into a No. 2 sample bottle (Solarmer,>99％)；adding 2mL of high-purity chloroform solvent into No. 1 and No. 2 sample bottles under the atmosphere of a glove box protected by nitrogen, placing the sample bottles on a magnetic heating stirrer, and heating and stirring at the temperature of 40 ℃ for 2.5h to obtain fully dissolved solutions, wherein the concentrations of PBDB-T-2F and PY-IT are respectively 10mgmL-1，10mgmL-1(ii) a Under the nitrogen atmosphere, adding a chloronaphthalene additive into a No. 2 sample bottle according to the volume ratio of 1%, and continuously stirring for 30 minutes to prepare an active layer by spin coating; under the nitrogen atmosphere, the prepared No. 1 solution is spin-coated on the hole transport layer by using a spin coater, the rotating speed is 3000rpm, and a donor active layer with the thickness of 45nm is obtained; the prepared solution No. 2 was spin-coated on the donor active layer using a spin coater at 3000rpm to obtain an organic photosensitive active layer having a total thickness of 100 nm.
The efficiency of the device prepared in this comparative example was tested under an AAA solar simulator, and the test results are shown in table 1:
TABLE 1
Figure BDA0003458622270000121
As can be seen by comparing the data in the table 1, in the organic photovoltaic devices prepared based on different preparation methods, the filling factor and the photoelectric conversion efficiency of the devices prepared by the three-element auxiliary step-by-step solution spin coating are remarkably improved compared with those of the other three methods, and the three-element auxiliary step-by-step deposition efficient organic solar cell is realized.
Comparative example 4
The film structure of the comparative example is glass and an organic active layer from bottom to top. The corresponding exciton kinetics extracted from the transient absorption spectra are shown in fig. 5a, 5 b. The results of the transient absorption kinetics process for extracting the blend of the pure PY-IT layer and the PY-IT: PDI-2T from the transient absorption spectrum are shown in Table 2:
TABLE 2
Figure BDA0003458622270000122
PDI-2T blending system has longer exciton diffusion length, and pure PY-IT exciton diffusion coefficient is smaller, which shows that PDI-2T as second material provides effective gain effect for exciton diffusion in PY-IT, and is helpful for JSCIs raised. In fig. 5, the abscissa represents time, the ordinate represents the light absorption intensity after normalization, and the whole represents the change of the light absorption intensity of the sample with the lapse of time.

Claims (10)

1. The full-polymer organic photovoltaic device based on ternary-assisted stepwise solution deposition is characterized by sequentially comprising a glass substrate, a transparent conductive film, a hole transport layer, an organic active layer, an electron transport layer and a top electrode from bottom to top, wherein the active layer comprises a polymer donor material and two polymer acceptor materials.
2. The ternary assisted step-solution deposition based all-polymer organic photovoltaic device according to claim 1, wherein the polymer donor material is PBDB-T-2F, the polymer acceptor material is PY-IT, and another polymer acceptor material is PDI-2T as a third component.
3. The ternary assisted step solution deposited all polymer organic photovoltaic device according to claim 1, wherein the thickness of the organic active layer is 100 nm.
4. The ternary assisted step-wise solution deposition based all-polymer organic photovoltaic device according to claim 2, wherein the mass ratio of PBDB-T-2F: PY-IT: PDI-2T in the ternary assisted step-wise solution deposition based all-polymer organic photovoltaic device is 1.00:1.00: 0.03.
5. The ternary assisted stepwise solution deposition based all-polymer organic photovoltaic device according to claim 1, wherein the glass substrate with attached transparent conductive film of ITO is a transparent conductive substrate with a thickness of 130nm, the hole transport layer material is PEDOT: PSS with a thickness of 30nm, the electron transport layer material is PDINN with a thickness of 5nm, the top electrode material is aluminum (Al) with a thickness of 100 nm.
6. A method for preparing a full polymer organic photovoltaic device based on ternary assisted stepwise solution deposition as claimed in claim 4, comprising the steps of:
(1) cleaning a transparent conductive substrate, wherein the transparent conductive substrate is a glass substrate attached with an ITO transparent conductive film;
(2) preparing a hole transport layer PEDOT (PSS) film on the transparent conductive substrate obtained in the step (1);
(3) preparing an organic active layer film, comprising:
a. respectively weighing 10mg of PBDB-T-2F, 15mg of PY-IT and 0.15-75mg of PDI-2T by using a high-precision electronic analytical balance, then adding 0.5-2mL of high-purity chloroform solvent into the weighed PBDB-T-2F, blending PY-IT and PDI-2T, adding 0.5-3mL of high-purity chloroform solvent, placing the mixture on a heatable magnetic stirrer, and stirring for 2-5h at the temperature of 30-50 ℃ to obtain a pure PBDB-T-2F solution with the concentration of 5-20mg/mL, PDI-2T: PY-IT blending solution;
b. and (3) performing high-precision pipettor on the obtained PY-IT: adding 1% vol chloronaphthalene additive into the PDI-2T blend solution, and continuously stirring for 30min to obtain PY-IT: a mixed receptor solution with the mass ratio of PDI-2T of 1:0.01 to 1: 0.05;
c. spin-coating the PBDB-T-2F solution prepared in the step a on the substrate with the hole transport layer obtained in the step (2) in an inert gas glove box, waiting for 30s, and then adding PY-IT prepared in the step b: spin-coating the PDI-2T blended solution on a PBDB-T-2F film, and annealing the obtained film attached with the active layer material in inert gas for 5-10 min;
(4) depositing an electron transport layer (PDNN) film on the organic active layer;
(5) and evaporating the metal electrode material on the electron transport layer.
7. The method for preparing an all-polymer organic photovoltaic device based on ternary assisted stepwise solution deposition according to claim 6, wherein in the step (3) a, 1mL of high-purity chloroform solvent is added into the weighed PBDB-T-2F, the mixture is placed on a heatable magnetic stirrer, and the stirring is carried out for 2.5h under the condition of 40 ℃ to obtain a pure PBDB-T-2F solution with the concentration of 10 mg/mL; 0.45mg of PDI-2T and 1.5mL of high-purity chloroform solvent are added into the weighed PY-IT, the mixture is placed on a heatable magnetic stirrer and stirred for 2.5h at the temperature of 40 ℃ to obtain a receptor solution with the concentration of 10.3mg/mL, and the mass ratio of PY-IT to PDI-2T in the obtained blending solution is 1: 0.03.
8. The method for preparing an all-polymer organic photovoltaic device based on ternary assisted stepwise solution deposition according to claim 6, wherein in the step (3) c, the spin coating speed of the active layer solution is as follows: the spin-coating speed of the PBDB-T-2F is 2500-.
9. The method of claim 8, wherein in step (3) c, the spin-coating speed of PBDB-T-2F is 3000rpm, the spin-coating speed of PY-IT: PDI-2T blend solution is 3000rpm, the thickness of the obtained PBDB-T-2F layer is 45nm, and the thickness of the obtained PY-IT: PDI-2T layer is 55 nm.
10. The method for preparing an all-polymer organic photovoltaic device based on three-way assist step-by-step solution deposition according to claim 6, wherein in the step (3) c, the annealing temperature of the active layer is 100 ℃ and the annealing time is 10 min.
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