CN113097391B - Method for optimizing morphology and performance of active layer of organic solar cell - Google Patents
Method for optimizing morphology and performance of active layer of organic solar cell Download PDFInfo
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Abstract
The invention discloses a method for optimizing the appearance and performance of an active layer of an organic solar cell, which regulates and controls the cold crystallization temperature by changing the proportion of an additive or the thermal annealing temperature so as to realize the regulation and control of the appearance and performance of the active layer; the microstructure of the active layer film is characterized through a transmission electron microscope, and the relation between the cold crystallization temperature and the phase separation is researched; characterizing the crystallinity of a donor-acceptor in the active layer film by adopting a grazing incidence wide-angle X-ray diffraction technology, and researching the relation between the cold crystallization temperature and the crystallinity of the donor-acceptor; and then, obtaining the optimized cold crystallization temperature by changing the processing technology, guiding the performance optimization of the device by using the optimized cold crystallization temperature, and then preparing the organic solar cell under different processing technologies. The introduced cold crystallization temperature can be applied to the prediction of physical and chemical properties of the organic photoelectric film such as phase separation, crystallinity and the like and the optimization of device performance.
Description
Technical Field
The invention belongs to the field of organic solar cells, and particularly relates to a method for optimizing the appearance and performance of an active layer of an organic solar cell.
Background
Organic solar cells have attracted much attention because of their advantages of being flexible, lightweight, solution processable, and capable of large-area roll-to-roll printing. At present, the photoelectric conversion efficiency of a single organic solar cell exceeds 18 percent, and reaches the standard of commercial application. The device structure of the organic solar cell consists of Indium Tin Oxide (ITO) conductive glass, an electron hole transport layer, an active layer and a metal electrode. Generally, the method for improving the photoelectric conversion efficiency of the organic solar cell comprises designing and synthesizing a novel donor-acceptor material, optimizing a device preparation process, regulating the appearance of an active layer and regulating an interface transmission layer. The active layer is the most important component of an organic solar cell device, and is a place where a photoelectric conversion process occurs, and the working efficiency of the device is mainly affected by one of the appearance influence factors of the active layer. And factors affecting the morphology of the active layer include molecular orientation, domain size, domain purity, and crystallinity. If the donor-acceptor phase separation in the active layer is too large, excitons cannot be effectively diffused to the donor-acceptor interface to be dissociated, so that the short-circuit current of the device is reduced; if the phase separation of the active layer in the donor-acceptor is too small, the charges generated by exciton dissociation cannot be extracted into a pure phase region in time, so that exciton recombination or recombination in the transmission process is caused, and the filling factor of the device is reduced. Molecular orientation between the donor and acceptor affects exciton dissociation and charge transport, and crystallinity can be divided into donor and acceptor crystallinity, which is closely related to carrier mobility. At present, the new material system can only be optimized in technological parameters by adopting a repeated trial and error method to ensure that the appearance of an active layer reaches the best, but the method lacks theoretical guidance and wastes time and labor. Meanwhile, the morphology parameters are often changed simultaneously in the optimization process, and influence is caused mutually, and the morphology is complex and difficult to characterize. Therefore, an instructive method for optimizing morphology and performance is needed.
The solution method is a main method for preparing the active layer film of the organic solar cell, and achieves the purpose of regulating and controlling the appearance by changing the processing technology to control the volatilization rate of the solution. This process is essentially determined by a variety of thermodynamic and kinetic factors. Thermodynamic factors include the choice of donor and acceptor materials and component ratios. The kinetic factors include the state of the solution, the film forming method, and the subsequent processes. The state of the solution can be adjusted by changing the solvent and using additives; the film forming method comprises spin coating, blade coating, slit extrusion film forming and the like; the subsequent treatment includes thermal annealing, solvent annealing, and the like. Therefore, the dynamics factors for regulating and controlling the morphology are very many, so that the morphology optimization process is complex, and the morphology characterization method is complex. Therefore, it is necessary to provide a quantitative parameter to establish the relation between the processing technology, the morphology and the performance, and provide guidance for morphology optimization.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for optimizing the appearance and performance of an active layer of an organic solar cell.
The invention is realized by adopting the following technical scheme:
a method for optimizing the appearance and performance of an active layer of an organic solar cell comprises the following steps:
step 1: preparing an organic mixture solution, and regulating and controlling the appearance of an active layer through two processing technologies, namely changing the proportion of additives in the organic mixture solution or carrying out thermal annealing treatment at different temperatures on a film sample, wherein the film sample is obtained after multiple blade coating;
and 2, step: performing differential scanning calorimetry test on the film samples treated in the step 1 to obtain corresponding cold crystallization temperatures; then, carrying out transmission electron microscope and grazing incidence wide-angle X-ray diffraction test on the active layer film prepared by blade coating, representing the appearance of the active layer film, and constructing the relation between the cold crystallization temperature and the appearance of the active layer film;
and step 3: the optimized cold crystallization temperature is obtained by changing the processing technology, and is used for guiding the performance optimization of the device to prepare the organic solar cell under different processing technologies.
The further improvement of the invention is that in the step 1, the solvent of the organic mixture solution is chloroform, the donor and acceptor materials in the solute are PBDB-T and IT-M respectively, the mass ratio of the donor and acceptor materials is 1.9-1.1, and the mass ratio of the solute to the solvent is 9-11 mg/mL.
The invention has the further improvement that in the step 1, the additive is diiodooctane, namely DIO, the volume ratio of the additive to the solvent is 0-1%, the used thermal annealing temperature is 25-160 ℃, and the annealing time is 9-11 min.
A further development of the invention is that, in step 1, the film sample is drawn under the following conditions: 300-400 mu m, blade coating speed: 40-50 mm/s.
The further improvement of the invention is that in the step 2, the temperature range of the differential scanning calorimetry test is 30-300 ℃, the heating rate is 10 ℃/min, and the cold crystallization temperature comes from the exothermic peak generated in the first heating scanning process.
The further improvement of the invention is that in step 3, the preparation process of the organic solar cell comprises the following steps: spin-coating a zinc oxide layer on the surface of cleaned indium tin oxide glass at the rotating speed of 4000-5000 r/min for 30-40 s, annealing the indium tin oxide glass sheet on a hot table at the temperature of 190-200 ℃ after spin-coating, wherein the annealing time is 30-40 min, and then coating an organic mixture solution on the glass sheet by a blade under the height: 300-400 mu m, blade coating speed: 40-50 mm/s, then putting the glass sheet into a mask plate, performing evaporation in a vacuum coating machine, firstly performing evaporation on molybdenum trioxide with the thickness of 8-10 nm, and then performing evaporation on aluminum with the thickness of 80-90 nm to obtain the organic solar cell.
The invention has at least the following beneficial technical effects:
(1) The method introduces the cold crystallization temperature, and can be applied to the prediction of the physical and chemical properties of the organic photoelectric film, such as phase separation, crystallinity and the like.
(2) The method can be applied to optimizing the preparation process of the organic solar cell and improving the photoelectric conversion efficiency of the cell.
(3) The method can shorten the time of the morphology optimization process of the organic solar cell and reduce the cost of optimizing the photoelectric conversion efficiency of the organic solar cell.
(4) The invention provides a quick quality inspection method which can be applied to judging the influence of process fluctuation on the performance of a battery product.
Drawings
FIG. 1 is a graph of cold crystallization temperature as a function of different DIO ratios. Wherein the proportion of DIO is 0%, 0.01%, 0.025%, 0.05%, 0.1%, 0.25%, 0.5% and 1%, respectively.
FIG. 2 is a graph of cold crystallization temperature as a function of different thermal annealing temperatures. Wherein the thermal annealing temperature is 25 deg.C, 80 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C and 160 deg.C, respectively, and the annealing time is 10min.
FIG. 3 is a graph showing the variation of the cold crystallization temperature with the thermal annealing temperature, in the DIO proportion of 0.5%. Wherein the thermal annealing temperature is 25 deg.C, 80 deg.C, 120 deg.C and 160 deg.C respectively, and the annealing time is 10min.
Fig. 4 is a TEM image of the organic solar cell active layer thin film under the untreated condition.
FIG. 5 is a TEM image of the organic solar cell active layer thin film at a DIO ratio of 0.5%.
FIG. 6 is a TEM image of the organic solar cell active layer thin film at a DIO ratio of 1% by weight.
FIG. 7 is a TEM image of the organic solar cell active layer thin film tested after annealing at 160 ℃ for 10min.
FIG. 8 is a TEM image of the organic solar cell active layer thin film tested after annealing at 160 ℃ for 10min at 0.5% DIO ratio.
Fig. 9 is a two-dimensional GIWAXS diagram of an organic solar cell active layer film under no-treatment conditions.
FIG. 10 is a two-dimensional GIWAXS graph of the active layer thin film of the organic solar cell at 0.5% DIO ratio.
FIG. 11 is a two-dimensional GIWAXS graph of the organic solar cell active layer thin film at 1% DIO ratio.
Fig. 12 is a two-dimensional GIWAXS plot of the organic solar cell active layer film tested after annealing at 160 ℃ for 10min.
FIG. 13 is a two-dimensional GIWAXS graph of the organic solar cell active layer film tested after annealing at 160 ℃ for 10min at a DIO ratio of 0.5%.
Fig. 14 is a schematic view of an inverted device structure of an organic solar cell.
Fig. 15 is a J-V curve of an inverted organic solar cell under different processing techniques.
Detailed Description
The invention is further described below with reference to the following figures and examples.
Example 1
The following examples will illustrate the optimization of the morphology and properties of the active layer by varying the ratio of additives to control the cold crystallization temperature.
a) Preparing an organic mixture solution. Weigh 9 vials of donor and acceptor materials in a 1. Chloroform was then added to dissolve the donor and acceptor materials, with a solute to solvent mass ratio of 9mg/mL. After mixing, the mixture was heated to 50 ℃ with stirring and kept heated for 8h. After 8h, DIO was added to the organic mixture solution at additive ratios of 0%, 0.01%, 0.025%, 0.05%, 0.1%, 0.25%, 0.5% and 1%, respectively, and heated at 50 ℃ for 1h to obtain solutions of different additive ratios. The structural formula of the donor material PBDB-T is as follows:
the structural formula of the receptor material IT-M is as follows:
b) The microscopic glass slides, large glass slides and scrapers were cleaned, blown dry with a nitrogen gun, and surface treated in an ultraviolet ozone cleaner (UVO) for 20min.
c) The knife coating equipment was adjusted. Adjusting the substrate to be horizontal; fixing a large glass sheet, a microscopic glass slide and a silicon wafer; and adjusting the silicon wafer to enable the lower edge of the silicon wafer to be parallel to the large glass sheet. The vertical height (i.e., gap) between the front edge of the silicon wafer and the large glass sheet was set to 300 μm, and the doctor blade coating speed was set to 40mm/s. Then, a film is formed on the microscopic glass slide by adopting a blade coating film forming mode, and the blade coating is repeatedly carried out in such a way.
d) The microscope slides were transferred to the glove box large chamber and the negative pressure was pumped for 48h to ensure complete removal of solvent and additives. After 48h, the dried film was scraped off for DSC testing. Accurately weighing the mass of the sample, setting the initial temperature to be 30 ℃, the termination temperature to be 300 ℃, and the temperature rising and reducing speed to be 10 ℃/min. In the test process, an exothermic peak appearing in a DSC first heating scanning curve is the cold crystallization temperature Tcc. The relationship between the cold crystallization temperature and the additive ratio as measured by DSC is shown in FIG. 1. When 0% (As cast), 0.01%, 0.025%, 0.05%, 0.1%, 0.25%, 0.5% and 1% of the additive were added, the Tcc was measured at 161.8 deg.C, 144.2 deg.C, 139.3 deg.C, 134.9 deg.C, 119.2 deg.C, 113.6 deg.C, 106.1 deg.C and 103.2 deg.C, respectively. It can be seen that the larger the proportion of additive added, the lower the Tcc and the slower and slower the decrease.
e) The next is characterization of the film morphology, including TEM and GIWAXS tests.
The specific sample preparation method of the TEM comprises the following steps: the blank glass sheet was cleaned and subjected to UVO for 20min. And spin-coating a PEDOT PSS layer at the rotation speed of 2000r/min for 30s, annealing in air at 140 ℃ for 2min, and spin-coating an organic mixture solution on the PEDOT PSS layer. And (3) inoculating 2/3 deionized water into a culture dish, drawing a small circle at the edge of the film by using tweezers, floating the small circle in water, then immersing the common carbon support film into the water, just fishing the small film to the carbon film, and airing. TEM was then tested, as cast, DIO addition 0.5% and 1% TEM As shown in FIGS. 4, 5 and 6. According to the experimental results, the present inventors found that the larger the additive ratio, the larger the degree of phase separation of the film.
The sample preparation conditions for GIWAXS are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. Drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min, improving the surface activity, and preparing a sample by using a blade coating film forming mode, wherein the sample preparation conditions are that gap is 300 mu m, and the blade coating speed is as follows: 40mm/s. As cast, plus 0.5% and 1% DIO, the two-dimensional GIWAXS profiles are shown in FIG. 9, FIG. 10 and FIG. 11. According to the experimental results, the invention finds that the larger the proportion of the additive, the stronger the crystallinity of the film. In summary, the larger the additive ratio, the lower the Tcc and the slower the decrease, and the larger the degree of phase separation of the film, the stronger the crystallinity.
f) And finally, preparing the organic solar cell. The structure schematic diagram of the organic solar cell inverter is shown in fig. 14. And spin-coating a ZnO layer on the surface of the cleaned ITO glass at the rotating speed of 4000r/min for 30s. And annealing on a hot bench at 190 ℃ for 30min after the spin coating. Then, the solution was drawn down on a glass plate under the conditions of gap 300. Mu.m, drawing speed: 40mm/s. Then putting the glass sheet into a mask plate, carrying out evaporation in a vacuum coating machine, and firstly evaporating 8nm MoO 3 Then, 80nm of Al was evaporated. After the evaporation is finished, J-V test is carried out, and the test is finishedAs shown in fig. 15. The Tcc of the DSC test were 161 ℃, 106 ℃ and 103 ℃ respectively, under the As cast, 0.5% DIO and 1% DIO conditions. It can be seen that when the proportion of DIO is less than 0.5%, tcc decreases faster as the DIO proportion increases; when the proportion of DIO is greater than 0.5%, tcc hardly changes as the DIO proportion continues to increase. Note that excessive DIO did not affect Tcc, and 0.5% DIO was the optimum additive ratio. J-V test results show that under the As cast condition, the open-circuit voltage of the device is 0.93V, and the short-circuit current is 13.50mA/cm 2 The fill factor was 44% and the power conversion efficiency was 5.52%. When 0.5% DIO was added, the open-circuit voltage of the device was 0.92V and the short-circuit current was 16.41mA/cm 2 The fill factor was 61% and the power conversion efficiency was 9.21%. When 1% of DIO was added, the open-circuit voltage of the device was 0.79V and the short-circuit current was 13.83mA/cm 2 The fill factor was 48% and the power conversion efficiency was 5.24%. It can be seen that when 0.5% DIO was added, the optimum Tcc was obtained. Under the proportion, the active layer film has proper phase separation and crystallinity, so that the short-circuit current and the filling factor of the device are improved, and the optimal power conversion efficiency is achieved. The excessive DIO (1%) has little influence on Tcc, but the thin film phase separation of the active layer is too large, the crystallization is too strong, the short-circuit current and the filling factor of the device are both low, and the power conversion efficiency is also poor.
Example 2
The following examples will illustrate the optimization of the morphology and performance of the active layer by varying the temperature of the thermal anneal to control the cold crystallization temperature.
a) Preparing an organic mixture solution. 9 bottles of donor and acceptor materials were weighed into a glass vial at a mass ratio of 1.1. Chloroform was then added to dissolve the donor and acceptor materials, with a solute to solvent mass ratio of 11mg/mL. After mixing, the mixture was heated to 50 ℃ with stirring and kept heated for 8h.
b) The microscopic glass slide, the large glass slide and the scraper are cleaned, dried by a nitrogen gun and put into an ultraviolet ozone cleaner (UVO) for surface treatment for 20min.
c) The equipment for the blade coating was adjusted. Adjusting the substrate to be horizontal; fixing a large glass sheet, a microscopic glass slide and a silicon wafer; and adjusting the silicon wafer to enable the lower edge of the silicon wafer to be parallel to the large glass sheet. The gap was set at 400 μm and the knife coating speed was 50mm/s. Then, a film is formed on the microscopic glass slide by adopting a blade coating film forming mode, and the blade coating is repeatedly carried out in such a way.
d) The microscope slides were transferred to the glove box large chamber and negative pressure was pumped for 48h to ensure complete removal of solvent and additives. After 48h, the films were thermally annealed for 10min at 25 deg.C (As cast), 80 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C and 160 deg.C, respectively. The dried film was then scraped off for DSC testing. Accurately weighing the mass of the sample, setting the initial temperature to be 30 ℃, the termination temperature to be 300 ℃, and the temperature rising and reducing speed to be 10 ℃/min. In the testing process, an exothermic peak appearing in a DSC first heating scanning curve is the cold crystallization temperature Tcc. The relationship between the cold crystallization temperature and the thermal annealing temperature measured by DSC is shown in FIG. 2. When the films were subjected to thermal annealing at 25 deg.C (As cast), 80 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C and 160 deg.C for 10min, the Tcc measured were 161.8 deg.C, 194.9 deg.C, 199.5 deg.C, 203.5 deg.C, 207.5 deg.C, 209.4 deg.C, 210.5 deg.C and 211.7 deg.C, respectively. It can be seen that the higher the thermal annealing temperature, the higher the Tcc, and the slower the increase.
e) The next is characterization of the film morphology, including TEM and GIWAXS tests.
The specific sample preparation method of the TEM comprises the following steps: the blank glass sheet was cleaned and subjected to UVO for 20min. And spin-coating a PEDOT PSS layer at the rotation speed of 2000r/min for 30s, annealing in air at 140 ℃ for 2min, and spin-coating an organic mixture solution on the PEDOT PSS layer. And (3) inoculating 2/3 deionized water into a culture dish, drawing a small circle at the edge of the film by using tweezers, floating the small circle in water, then immersing the common carbon support film into the water, just fishing the small film to the carbon film, and airing. Then, TEM was performed, and As cast and TEM was thermally annealed at 160 ℃ for 10min are shown in FIGS. 4 and 7. According to the experimental result, the invention finds that the thermal annealing temperature has little influence on the phase separation degree of the film.
The sample preparation conditions for GIWAXS are as follows: cutting the silicon wafer into a proper size, and sequentially cleaning the silicon wafer with deionized water and ethanol twice. Drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min, improving the surface activity, and preparing a sample by using a blade coating film forming mode, wherein the sample preparation conditions are that gap is 400 mu m, and the blade coating speed is as follows: 50mm/s. Two-dimensional GIWAXS plots of As cast and 160 ℃ thermal annealing for 10min are shown in fig. 9 and 12. The results show that the higher the temperature of the thermal annealing, the stronger the crystallinity of the film compared to As cast. The optimal morphology can only be formed when the active layer film has suitable phase separation and crystallinity. Under the As cast condition, the phase separation degree of the active layer film is small, and the crystallinity of the film must be improved to realize the optimal morphology. When the temperature of thermal annealing is increased from 25 ℃ to 160 ℃, tcc rises more and more slowly, the degree of phase separation of the active layer thin film is almost constant, and crystallinity is gradually enhanced, that is, crystallinity at 160 ℃ is the strongest.
f) And finally, preparing the organic solar cell. The structure schematic diagram of the organic solar cell inverter is shown in fig. 14. And spin-coating a ZnO layer on the cleaned ITO glass surface at the rotating speed of 5000r/min for 40s. And annealing on a hot bench at 200 ℃ for 40min after the spin coating. The solution was then drawn down on a glass slide under the conditions of gap 400 μm, draw down speed: 50mm/s. Then putting the glass sheet into a mask plate, carrying out evaporation in a vacuum coating machine, and firstly carrying out evaporation on MoO with the thickness of 10nm 3 Then, 90nm of Al is evaporated. After the completion of the evaporation, the J-V test was performed, and the test results are shown in fig. 15. J-V test results show that under the As cast condition, the open-circuit voltage of the device is 0.93V, and the short-circuit current is 13.50mA/cm 2 The fill factor was 44% and the power conversion efficiency was 5.52%. Under the condition of thermal annealing at 160 ℃ for 10min, the open-circuit voltage of the device is 0.89V, and the short-circuit current is 16.04/cm 2 The fill factor was 50% and the power conversion efficiency was 7.17%. Therefore, the crystallinity of the active layer film is obviously enhanced by thermal annealing at 160 ℃, and the short-circuit current of the device is mainly promoted, so that the power conversion efficiency of the device is promoted.
Example 3
The following examples will illustrate the optimization of the morphology and performance of the active layer by combining additives and thermal annealing temperature to control the cold crystallization temperature.
a) Preparing an organic mixture solution. Weigh 4 bottles of donor and acceptor materials in a mass ratio of 1 into a glass vial. Chloroform was then added to dissolve the donor and acceptor materials, with a solute to solvent mass ratio of 10mg/mL. After mixing, the mixture was heated to 50 ℃ with stirring and kept heated for 8h. After 8h, DIO was added to 4 bottles of organic mixture solution in an additive ratio of 0.5% and heated for 1h while maintaining 50 ℃.
b) The microscopic glass slide, the large glass slide and the scraper are cleaned, dried by a nitrogen gun and put into an ultraviolet ozone cleaner (UVO) for surface treatment for 20min.
c) The equipment for the blade coating was adjusted. Adjusting the substrate to be horizontal; fixing a large glass sheet, a microscopic glass slide and a silicon wafer; and adjusting the silicon wafer to enable the lower edge of the silicon wafer to be parallel to the large glass sheet. Gap was set at 350 μm and the knife coating speed was set at 45mm/s. Then, a film is formed on the microscopic glass slide by adopting a blade coating film forming mode, and the blade coating is repeatedly carried out in such a way.
d) The microscope slides were transferred to the glove box large chamber and negative pressure was pumped for 48h to ensure complete removal of solvent and additives. After 48h, the films were thermally annealed for 10min at 25 deg.C (As cast), 80 deg.C, 120 deg.C and 160 deg.C, respectively. The dried film was then scraped off for DSC testing. Accurately weighing the mass of the sample, setting the initial temperature to be 30 ℃, the termination temperature to be 300 ℃, and the temperature rising and reducing speed to be 10 ℃/min. In the testing process, an exothermic peak appearing in a DSC first heating scanning curve is the cold crystallization temperature Tcc. The relationship between the cold crystallization temperature and the thermal annealing temperature measured by DSC is shown in FIG. 3. When the films were subjected to thermal annealing at 25 deg.C (As cast), 80 deg.C, 120 deg.C and 160 deg.C, respectively, for 10min, the Tcc values were measured at 106.1 deg.C, 132.4 deg.C, 183.0 deg.C and 202.1 deg.C, respectively. It can be seen that the higher the thermal annealing temperature, the higher the Tcc, and the slower the increase.
e) The next is characterization of the film morphology, including TEM and GIWAXS tests.
The specific sample preparation method of the TEM comprises the following steps: the blank glass sheet was cleaned and subjected to UVO for 20min. And spin-coating a PEDOT PSS layer at the rotation speed of 2000r/min for 30s, annealing in air at 140 ℃ for 2min, and spin-coating an organic mixture solution on the PEDOT PSS layer. And (3) connecting 2/3 deionized water with a culture dish, drawing a small circle at the edge of the film by using tweezers, floating the small circle in water, then soaking the common carbon support film in water, fishing the small film to the carbon film, and airing. Then, TEM was subjected to a TEM test, and 0.5% by weight of TEM was thermally annealed at 25 ℃ and 160 ℃ for 10min at a DIO ratio as shown in FIGS. 4 and 8. According to the experimental result, the invention finds that the thermal annealing temperature has little influence on the phase separation degree of the film.
The sample preparation conditions for GIWAXS are as follows: cutting the silicon wafer into proper sizes, and cleaning the silicon wafer twice by using deionized water and ethanol in sequence. Drying the cleaned silicon wafer by using a nitrogen gun, carrying out UVO treatment for 20min, improving the surface activity, and preparing a sample by using a blade coating film forming mode, wherein the sample preparation conditions are that gap is 350 mu m, and the blade coating speed is as follows: 45mm/s.0.5% DIO ratio, 25 ℃ and 160 ℃ thermal annealing for 10min, two-dimensional GIWAXS profiles are shown in FIGS. 9 and 13. As a result, it was found that when the DIO ratio was 0.5%, the increase in Tcc was gradually decreased with the increase in the thermal annealing temperature, the degree of phase separation of the active layer thin film was almost constant, and the crystallinity was gradually increased, that is, the crystallinity was the strongest at 160 ℃. It can be seen that the thermal annealing temperature has little effect on Tcc for the same additive ratio. It is known that DIO 0.5% is the optimum additive ratio and 160 ℃ is the optimum thermal annealing temperature, and therefore, it can be predicted that: the highest power conversion efficiency was achieved by performing 160 ℃ thermal annealing at a DIO ratio of 05% for 10min.
f) And finally, preparing the organic solar cell. The structure schematic diagram of the organic solar cell inverter is shown in fig. 14. And spin-coating a ZnO layer on the surface of the cleaned ITO glass at the rotating speed of 4500r/min for 35s. After the spin coating, annealing is carried out on a hot bench at 195 ℃, and the annealing time is 35min. Then, the solution was drawn on a glass plate under the conditions of gap:350 μm, drawing speed: 45mm/s. Then putting the glass sheet into a mask plate, carrying out evaporation in a vacuum coating machine, and firstly evaporating 9nm MoO 3 Then, 85nm of Al is evaporated. After the completion of the evaporation, the J-V test was performed, and the test results are shown in fig. 15. When 0.5% DIO was added, the open-circuit voltage of the device was 0.92V and the short-circuit current was 16.41mA/cm 2 The fill factor is 61%, and the power conversion efficiency is 9.21%; when comprehensively considered to addWhen adding agent and thermal annealing, 0.5% of additive is added firstly, then the film is annealed at 160 ℃, the open-circuit voltage of the device is 0.93V, and the short-circuit current is 16.80mA/cm 2 The fill factor was 66% and the power conversion efficiency was 10.31%. Therefore, the subsequent thermal annealing treatment is carried out on the film, so that the crystallinity of the film is further enhanced, the short-circuit current and the filling factor of the device are improved, and the power conversion efficiency of the device is improved. Consistent with the foregoing conclusions, the processing technology predicted by Tcc can indeed guide the optimization of the morphology and performance of the active layer of the organic solar cell.
Claims (6)
1. A method for optimizing the appearance and performance of an active layer of an organic solar cell is characterized by comprising the following steps:
step 1: preparing an organic mixture solution, and regulating and controlling the morphology of an active layer by changing the proportion of an additive in the organic mixture solution, wherein an active layer film is obtained by blade coating for many times, the solvent of the organic mixture solution is chloroform, donor and acceptor materials in a solute are PBDB-T and IT-M respectively, the mass ratio of the donor to the acceptor materials is 1;
and 2, step: performing differential scanning calorimetry test on the active layer film treated in the step 1 to obtain corresponding cold crystallization temperature; then, carrying out transmission electron microscope and grazing incidence wide-angle X-ray diffraction test on the active layer film prepared by blade coating, representing the appearance of the active layer film, and constructing the relation between the cold crystallization temperature and the appearance of the active layer film;
and 3, step 3: the optimized cold crystallization temperature is obtained by changing the processing technology, and is used for guiding the performance optimization of the device to prepare the organic solar cell under different processing technologies.
2. The method for optimizing the shape and the performance of the active layer of the organic solar cell according to claim 1, wherein in the step 1, the volume ratio of the additive to the solvent is 0 to 1%.
3. The method for optimizing the appearance and the performance of the active layer of the organic solar cell according to claim 1, wherein in the step 1, the doctor-blade coating conditions of the active layer film are height: 300 to 400 mu m, blade coating speed: 40 to 50mm/s.
4. The method for optimizing the morphology and the performance of the active layer of the organic solar cell according to claim 1, wherein in the step 2, the temperature range of a differential scanning calorimetry test is 30 to 300 ℃, and the heating rate is 10 ℃/min.
5. The method of claim 1, wherein in step 2, the cold crystallization temperature is derived from an exothermic peak generated during the first temperature-rising scan.
6. The method for optimizing the morphology and the performance of the active layer of the organic solar cell according to claim 1, wherein in the step 3, the preparation process of the organic solar cell comprises: spin-coating a zinc oxide layer on the surface of cleaned indium tin oxide glass at the rotating speed of 4000 to 5000r/min for 30 to 40s, annealing the indium tin oxide glass sheet on a hot table at the temperature of 190 to 200 ℃ after spin-coating for 30 to 40min, and then blade-coating the organic mixture solution on the glass sheet under the blade-coating conditions of height: 300-400 mu m, blade coating speed: and 40-50mm/s, then putting the glass sheet into a mask, evaporating in a vacuum film coating machine, evaporating molybdenum trioxide at 8-10nm, and evaporating aluminum at 80-90nm to obtain the organic solar cell.
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