CN113690373A - Based on HfS2Organic solar cell as hole transport layer and method for manufacturing the same - Google Patents
Based on HfS2Organic solar cell as hole transport layer and method for manufacturing the same Download PDFInfo
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- CN113690373A CN113690373A CN202110770901.9A CN202110770901A CN113690373A CN 113690373 A CN113690373 A CN 113690373A CN 202110770901 A CN202110770901 A CN 202110770901A CN 113690373 A CN113690373 A CN 113690373A
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a method based on HfS2An organic solar cell which is a hole transport layer and a method for manufacturing the same. The organic solar cell structure comprises an anode layer, a hole transport layer, an active layer, an electron transport layer and a cathode layer from bottom to top; the hole transport layer is HfS2. The organic solar cell of the invention uses HfS2The hole transport layer replaces the traditional PEDOT PSS, the defects of corrosion of ITO and an active layer caused by weak acidity of the PEDOT PSS and low conductivity of the PEDOT PSS are overcome, and meanwhile, the stability and the conversion efficiency of the solar cell are improved. The invention adopts a liquid phase stripping method to prepare the bis-HfS2Hole transport layer with simple processEasy to control, prepared HfS2The film is smooth and compact; simultaneously, HfS was prepared2The process is carried out at room temperature without high temperature heat treatment.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a HfS-based solar cell2An organic solar cell which is a hole transport layer and a method for manufacturing the same.
Background
Organic solar cells, as a new generation of clean and renewable energy technology, have been receiving much attention from researchers at home and abroad in recent decades due to their advantages of low cost, light weight, flexibility, solution preparation, printable production, and wide raw material sources. The photoelectric conversion efficiency of organic solar cells based on such materials has rapidly developed over the last few years, and nowadays single junction devices are approaching 20%.
Currently, the efficient organic solar energy hole transport layer usually adopts PEDOT: PSS. However, PEDOT and PSS have weak acidity, have certain corrosivity on ITO and an active layer, and seriously affect the stability of a device. Meanwhile, the conductivity of the material is low, and the performance of the device is further improved. To solve these problems, V is proposed2O5,WO3,MoO3Etc. as a material substituting for the hole transport layer. However, most of these high temperature oxides rely on vacuum treatment or require complicated processes such as high temperature annealing, which is not favorable for the production of solar cells. And two-dimensional semiconductor HfS2HfS with extremely high carrier mobility and high work function and two-dimensional structure2Has high light transmittance. These advantages indicate HfS2Has great application prospect as the hole transport layer material of the organic solar cell (adv. Mater.2019, 1902965; DOI: 1)0.1002/adma.201902965)。
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a HfS-based method2Provides an organic solar cell of a hole transport layer and a preparation method thereof, and provides a low-temperature liquid phase stripping method which has simple process and is easy to regulate and control and is used for preparing a film based on HfS2An organic solar cell which is a hole transport layer and a method for manufacturing the same.
The purpose of the invention is realized by the following technical scheme:
based on HfS2The organic solar cell is a hole transport layer, and the organic solar cell structure comprises an anode layer, a hole transport layer, an active layer, an electron transport layer and a cathode layer from bottom to top; the hole transport layer is HfS2。
Preferably, the anode layer is Indium Tin Oxide (ITO), the active layer is PBDB-T: ITIC, the electron transport layer is PFN-Br, and the cathode layer is aluminum (Al).
Preferably, the hole transport layer HfS2The thickness is 3-5 nm, the thickness of the active layer is 100-110 nm, the thickness of the electron transport layer is 4-5 nm, and the thickness of the cathode layer is 90-100 nm.
HfS-based as described above2A method for preparing an organic solar cell which is a hole transport layer, comprising the steps of:
(1) carrying out plasma treatment on the surface of the anode layer for 10-15 minutes;
(2) HfS is added2Spin-coating the precursor solution on the surface of the anode layer treated in the step (1) at the rotating speed of 1000-3000 rpm, and annealing at 80-100 ℃ for 5-10 minutes in a protective atmosphere to form the HfS-based anode2A hole transport layer of (a);
(3) in the step (2), the HfS2Spin-coating an active layer precursor solution on the hole transport layer, drying, and annealing at 100-120 ℃ for 7-10 minutes to obtain an active layer;
(4) spin-coating an electron transport layer precursor solution on the active layer in the step (3) to form an electron transport layer;
(5) and (4) evaporating a cathode layer on the electron transport layer in the step (4).
Preferably, the HfS of step (2)2The preparation method of the precursor solution comprises the following steps: HfS is added2Adding the powder into an isopropanol solvent, and performing ultrasonic dispersion in an ice bath; then centrifugating to obtain supernatant fluid which is HfS2A precursor liquid.
Further preferably, the HfS2The mass-to-volume ratio of the powder to the isopropanol solvent is 50 mg: 2-5 mL.
Further preferably, the time of ultrasonic dispersion is 10-20 h.
More preferably, the rotating speed of the centrifugation is 3000-5000 rpm, and the time of the centrifugation is 15-30 min.
Preferably, the hole transport layer after the annealing treatment in the step (2) is subjected to plasma treatment for 0 to 30 minutes.
Preferably, the active layer precursor solution in step (3) contains an additive DIO.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional method using PEDOT PSS as the hole transport layer, the HfS used in the invention2The hole transport layer adopts a solution spin coating method, the process is simple, and the annealing temperature is low. Since HfS2 not only has a work function similar to that of a conventional hole transport material, it also has extremely high conductivity and chemical stability. This makes the device with HfS2 as the hole transport layer have higher photoelectric conversion efficiency and device stability than the device with PEDOT: PSS as the hole transport layer.
Drawings
Fig. 1 is a schematic structural diagram of an organic solar cell of the present invention, wherein 1 is an anode layer, 2 is a hole transport layer, 3 is an active layer, 4 is an electron transport layer, and 5 is a cathode layer.
FIG. 2 shows ITO and HfS of example 12The transmittance of the film.
Fig. 3 is a graph of current density versus voltage for the solar devices of comparative example and example 1.
Fig. 4 is a graph of stability of solar devices of comparative example and example 1.
Detailed Description
The invention is further described with reference to the following examples, which are intended to be illustrative of the invention and are not intended to be limiting. The present invention is not limited to the following examples and embodiments.
Comparative examples
In the comparative example, based on an organic solar cell structure with PEDOT: PSS as a hole transport layer, the device structure includes, from bottom to top, an anode layer, a hole transport layer, an active layer, an electron transport layer, and a cathode layer, and the specific preparation method is as follows:
1. cleaning of the anode substrate: and (3) sequentially carrying out ultrasonic treatment on the substrate (ITO) in an ultrasonic cleaning instrument for 15 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol, and then drying in a vacuum drying oven at 70-80 ℃ to obtain the substrate with a clean surface required by the experiment.
2. Preparation of a hole transport layer by using PEDOT and PSS: the cleaned and dried ITO was subjected to plasma treatment for 10 minutes. The PEDOT PSS solution was spin coated on the ITO surface at 3500rpm for 40 seconds. Finally, PEDOT PSS is annealed at 150 ℃ by 10 to be divided into PEDOT PSS-based hole transport layers with the thickness of 30 nm.
3. Preparation of the active layer: PBDB-T and ITIC are mixed according to the mass ratio of 1: 1 is dissolved in chlorobenzene solution to prepare solution with the concentration of 20mg/mL, and then the volume ratio is 99.5: 0.5 adding DIO additive to the solution to obtain the precursor solution of the active layer. The active layer solution was spin-coated at 2500rpm on a PEDOT: PSS hole transport layer for 60 seconds to form a film. And annealing at 100 ℃ for 10 minutes after the film is completely dried to obtain an active layer with the thickness of 100 nm.
4. Preparation of an electron transport layer: an electron transport layer (spin speed: 3000 rpm; spin time: 30 seconds) was formed by spin-coating a 0.5mg/mL solution of PFN-Br in methanol onto the active layer to a thickness of 5 nm.
5. Preparing a cathode layer: metal Al was evaporated onto the electron transport layer using a vacuum evaporator to form a cathode layer of 100nm thickness.
Example 1
Based on HfS in the present embodiment2An organic solar cell structure being a hole transport layer, the device structure being as shown in fig. 1:the cathode layer comprises an anode layer, a hole transport layer, an active layer, an electron transport layer and a cathode layer from bottom to top, and the preparation method comprises the following steps:
1. cleaning of the anode substrate: and (3) sequentially carrying out ultrasonic treatment on the substrate (ITO) in an ultrasonic cleaning instrument for 15 minutes by using liquid detergent, deionized water, acetone, absolute ethyl alcohol and isopropanol, and then drying in a vacuum drying oven at 70-80 ℃ to obtain the substrate with a clean surface required by the experiment.
2、HfS2For the preparation of the hole transport layer: 50mg of HfS2The powder was added to 2mL of isopropanol solvent and ultrasonically dispersed for 20h in an ice bath. Centrifuging the dispersed suspension at 5000rpm for 15min, and collecting the supernatant as HfS2A precursor liquid. The cleaned and dried ITO was subjected to plasma treatment for 10 minutes. HfS is added2The precursor solution was spin coated on the ITO surface at 2000rpm and annealed at 80 ℃ for 10 minutes in a nitrogen filled glove. For HfS finally2The film is formed on the basis of HfS by plasma treatment for 15 minutes2The hole transport layer of (3) has a thickness of 3 nm.
3. Preparation of the active layer: PBDB-T and ITIC are mixed according to the mass ratio of 1: 1 is dissolved in chlorobenzene solution to prepare solution with the concentration of 20mg/mL, and then the volume ratio is 99.5: 0.5 adding DIO additive to the solution to obtain the precursor solution of the active layer. The active layer solution was applied to HfS at 2500rpm2The hole transport layer was spin-coated for 60 seconds to form a film. And annealing at 100 ℃ for 10 minutes after the film is completely dried to obtain an active layer with the thickness of 100 nm.
4. Preparation of an electron transport layer: an electron transport layer (spin speed: 3000 rpm; spin time: 30 seconds) was formed by spin-coating a 0.5mg/mL solution of PFN-Br in methanol onto the active layer to a thickness of 5 nm.
5. Preparing a cathode layer: metal Al was evaporated onto the electron transport layer using a vacuum evaporator to form a cathode layer of 100nm thickness.
Example 2
Device preparation on the basis of example 1, on HfS2Preparation of hole transport layer without HfS2The film is subjected to plasma treatment.
Example 3
Device preparation on the basis of example 1, on HfS2For HfS in preparation of hole transport layer2The film was plasma treated for 5 minutes.
Example 4
Device preparation on the basis of example 1, on HfS2For HfS in preparation of hole transport layer2The film was subjected to plasma treatment for 10 minutes.
Example 5
Device preparation on the basis of example 1, on HfS2For HfS in preparation of hole transport layer2The film was subjected to plasma treatment for 30 minutes.
Description of Performance parameters
FIG. 2 shows ITO and HfS of example 12Transmittance of thin film, HfS, as can be seen from the film transmittance of FIG. 22The film has high light transmittance which is close to the transmittance of ITO, so that the light absorption of the active layer is facilitated, and the short-circuit current is improved. FIG. 3 is a J-V graph of the organic solar cells of corresponding example 1 and comparative example, and from FIG. 3, it can be seen that HfS2The hole transport layer has a higher current density;
FIG. 4 is a graph of device stability for comparative example and example 1, from which it can be seen that based on HfS2The device which is the hole transport layer (example 1) has more excellent stability over time than the device based on PEDOT: PSS being the hole transport layer (comparative example). After one month of storage, based on HfS2The device performance for the hole transport layer (example 1) still maintained 70% of the initial efficiency, whereas the device based on PEDOT: PSS for the hole transport layer (comparative example) maintained only 40% of the initial efficiency. The above results show that HfS is used2The hole transport layer applied to the organic solar cell has a great development prospect.
TABLE 1
Table 1 shows the performance parameters of the examples. From whichAs can be seen, HfS2After plasma treatment, the short-circuit current, the open-circuit voltage and the fill factor of the device are effectively improved. The optimum is reached in 15 minutes with a conversion efficiency of up to 11.2%, which exceeds that of devices based on PEDOT: PSS as hole transport layer (comparative example). This indicates HfS after plasma treatment2The charge extraction and the charge transportation of the device are improved, and the charge recombination is reduced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. Based on HfS2The organic solar cell is a hole transport layer, and is characterized in that the organic solar cell structure comprises an anode layer, a hole transport layer, an active layer, an electron transport layer and a cathode layer from bottom to top; the hole transport layer is HfS2。
2. The organic solar cell of claim 1, wherein the anode layer is indium tin oxide, the active layer is PBDB-T ITIC, the electron transport layer is PFN-Br, and the cathode layer is aluminum.
3. The organic solar cell of claim 1, wherein the hole transport layer HfS is2The thickness is 3-5 nm, the thickness of the active layer is 100-110 nm, the thickness of the electron transport layer is 4-5 nm, and the thickness of the cathode layer is 90-100 nm.
4. HfS based according to any of the claims 1-32The preparation method of the organic solar cell of the hole transport layer is characterized by comprising the following steps:
(1) carrying out plasma treatment on the surface of the anode layer for 10-15 minutes;
(2) HfS is added2Spin-coating the precursor solution on the surface of the anode layer treated in the step (1) at the rotating speed of 1000-3000 rpm, and annealing at 80-100 ℃ for 5-10 minutes in a protective atmosphere to form the HfS-based anode2A hole transport layer of (a);
(3) in the step (2), the HfS2Spin-coating an active layer precursor solution on the hole transport layer, drying, and annealing at 100-120 ℃ for 7-10 minutes to obtain an active layer;
(4) spin-coating an electron transport layer precursor solution on the active layer in the step (3) to form an electron transport layer;
(5) and (4) evaporating a cathode layer on the electron transport layer in the step (4).
5. The production method according to claim 4, wherein the HfS of step (2)2The preparation method of the precursor solution comprises the following steps: HfS is added2Adding the powder into an isopropanol solvent, and performing ultrasonic dispersion in an ice bath; then centrifugating to obtain supernatant fluid which is HfS2A precursor liquid.
6. The method for preparing as claimed in claim 5, wherein the HfS is2The mass-to-volume ratio of the powder to the isopropanol solvent is 50 mg: 2-5 mL.
7. The preparation method according to claim 5, wherein the ultrasonic dispersion time is 10-20 h.
8. The method according to claim 5, wherein the rotation speed of the centrifugation is 3000-5000 rpm, and the time of the centrifugation is 15-30 min.
9. The production method according to claim 4, wherein the hole transport layer after the annealing treatment in the step (2) is subjected to plasma treatment for 0 to 30 minutes.
10. The method according to claim 4, wherein an additive DIO is contained in the active layer precursor liquid in the step (3).
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