CN103972396A - Polymer solar cell device and preparing method thereof - Google Patents

Abstract

The invention belongs to the technical field of polymer solar cell material and device preparation, and particularly relates to a polymer solar cell device and a preparing method of the polymer solar cell device. The polymer solar cell device sequentially comprises a substrate, a transparent conductive metallic oxide layer, an anode modification layer, a photoelectric active layer, a cathode modification layer and a counter electrode layer. According to the isopropyl alcohol cathode modification layer prepared through an alcoholic solution processing method, the good environmental compatibility can be achieved. Compared with a traditional active metal low-work-content cathode modification layer, the isopropyl alcohol cathode modification layer is better in stability and longer in service life. Due to the fact that the polymer solar cell device has the advantages in the aspects of adjustment of photoelectric field distribution inside the cell device, ohmic contact achieved between the polymer solar cell device and a photoelectric active layer and the like, the polymer solar cell device is excellent in performance. Meanwhile, the polymer solar cell device has the advantages in operation technology, experiment repeatability, production cost and the like, so that the cell device meets the requirement for large-scale industrial production.

Description

A kind of polymer solar cell device and preparation method thereof

technical field

The invention belongs to the technical field of polymer solar cell materials and device preparation, and in particular relates to a polymer solar cell device and a preparation method thereof.

Background technique

Organic and polymer thin-film solar cells, which have emerged in recent years, have attracted much attention due to their outstanding advantages such as low cost, light weight, simple manufacturing process, and large-area flexible devices. By optimizing the design and synthesis of new polymer donor materials and fullerene derivative acceptor materials and optimizing the microphase separation structure of the donor and acceptor in the active layer, the photoelectric conversion efficiency of bulk heterojunction polymer solar cells can be significantly improved. Has reached the level of amorphous silicon cells. However, traditional bulk heterojunction polymer solar cells are easily oxidized due to the use of low work function active metals such as calcium and magnesium as the cathode layer, resulting in poor stability of the battery, which is not conducive to the stability and life of the device. Alkali metal and alkaline earth metal halides such as LiF need to be vacuum thermally evaporated, and the required thickness is extremely thin, usually less than 1 nanometer, which is difficult to accurately control and has poor device repeatability. Therefore, the development of stable, solution-processable cathodic modification layers has attracted much attention.

Contents of the invention

The object of the present invention is to provide a fully solution processed polymer solar cell and a preparation method thereof. In the present invention, zirconium isopropoxide is used as an electron collection material in polymer solar cell devices.

Aiming at the deficiencies of the prior art, the invention provides a polymer solar cell device and a preparation method thereof.

A polymer solar cell device, wherein a substrate, a transparent conductive metal oxide layer, an anode modification layer, a photoelectric active layer, a cathode modification layer and a counter electrode layer are connected in sequence in the polymer solar cell device; the transparent conductive metal The oxide electrode layer and the counter electrode layer are respectively connected with the load or the test device; the material of the cathode modification layer is zirconium isopropoxide membrane material.

The characteristic design of the polymer solar cell device of the present invention is:

A laminated substrate, a carrier for supporting the entire device;

A transparent conductive metal oxide electrode layer for serving as an electrode of the device;

Anode modification layer (hole collection layer), used to realize the effective collection of holes;

A photoelectrically active layer for realizing photoelectric conversion;

Cathode modification layer (electron collection layer) for effective collection of electrons;

The top electrode layer serves as the counter electrode for the device.

The material of the substrate is glass or polyester film material.

The transparent conductive metal oxide electrode layer is made of one or more oxide materials selected from In, Sn, Zn and Cd.

The material of the anode modification layer is PEDOT:PSS or one or more oxide materials in Mo, V, W and Ni.

The thickness of the zirconium isopropoxide film is

The material of the counter electrode layer is Al, Ag, Au or composite electrode materials thereof.

A preparation method of a polymer solar cell device, the method adopts full solution processing, and its specific steps are as follows:

(a) preparing a transparent conductive metal oxide electrode layer on the substrate;

(b) Spin-coat PEDOT:PSS solution on the transparent conductive metal oxide electrode layer, and bake to obtain the anode modification layer;

(c) sequentially preparing a photoelectric active layer, spin-coating a zirconium alcohol solution of isopropoxide and preparing a counter electrode layer on the anode modification layer to obtain the polymer solar cell device.

The solvent in the isopropanol zirconium alcohol solution in the step is one or more of methanol, ethanol, isopropanol and isooctanol.

The concentration of zirconium isopropoxide in the zirconium isopropoxide alcohol solution in the step is 0.2 mg/mL˜10 mg/mL.

The spin-coating speed of the spin-coating zirconium isopropoxide alcohol solution in the step is 800rpm-5000rpm.

The beneficial effects of the present invention are:

The zirconium isopropoxide cathode modification layer prepared by the alcohol solution processing method of the present invention can achieve good environmental compatibility, and has better stability and longer life than the traditional active metal low work function cathode modification layer. service life. Due to its active role in regulating the photoelectric field division inside the battery device and forming ohmic contacts with the photoelectric active layer, polymer solar cells show excellent performance. At the same time, the present invention has advantages in aspects such as operation technology, experiment repeatability, production cost, etc., and is suitable for the requirements of large-scale industrial production.

Description of drawings

Fig. 1 is the structural schematic diagram of polymer solar cell of the present invention;

Fig. 2 is the current-voltage characteristic curve of the obtained ITO/PEDOT:PSS/P3HT:PC ₆₀ BM/Al polymer solar cell device of embodiment 1 of the present invention;

Fig. 3 is the current-voltage characteristic curve of ITO/PEDOT:PSS/P3HT:PC ₆₀ BM/zirconium isopropoxide/Al polymer solar cell device obtained in Example 2 of the present invention;

Fig. 4 is the current-voltage characteristic curve of the obtained ITO/PEDOT:PSS/P141:PC ₆₀ BM/Al polymer solar cell device of embodiment 3 of the present invention;

Fig. 5 is the current-voltage characteristic curve of ITO/PEDOT:PSS/P141:PC ₆₀ BM/zirconium isopropoxide/Al polymer solar cell device obtained in Example 4 of the present invention;

Labels in the figure:

1-substrate; 2-transparent conductive metal oxide layer; 3-anode modification layer; 4-photoelectric active layer; 5-cathode modification layer; 6-counter electrode layer; 7-load or test device.

Detailed ways

The present invention provides a polymer solar cell device and a preparation method thereof. The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.

A polymer solar cell device, in which a substrate 1, a transparent conductive metal oxide layer 2, an anode modification layer 3, a photoelectric active layer 4, a cathode modification layer 5 and a counter electrode layer 6 are connected in sequence ; The cathode modification layer 5 is made of zirconium isopropoxide film material.

The material of the substrate 1 is glass or polyester film material.

The transparent conductive metal oxide electrode layer 2 is made of one or more oxide materials selected from In, Sn, Zn and Cd.

The material of the anode modification layer 3 is one or more oxide materials selected from PEDOT:PSS or Mo, V, W and Ni.

The thickness of the zirconium isopropoxide film is

The material of the counter electrode layer 6 is Al, Ag, Au or composite electrode materials thereof.

Example 1

The transparent conductive glass sputtered with indium tin oxide (ITO) was ultrasonically cleaned twice with detergent, tap water, deionized water, acetone, and isopropanol in sequence, dried with nitrogen, and spin-coated with PEDOT at a speed of 2000rpm: The PSS solution was baked and annealed at 150° C. for 15 minutes, and cooled naturally to obtain an anode modification layer. The treated experimental sample was then transferred into the glove box, and then the mixed solution of P3HT and PC ₆₀ BM with a total concentration of 40 mg/mL (wherein the mass ratio of P3HT and PC ₆₀ BM was 1:1, and the concentration of a single material was 20 mg /mL, the solvent is dichlorobenzene) directly spin-coated on the above-mentioned anode modification layer under the rotating speed of 800rpm, as the photoelectric active layer, and carried out solvent annealing 2 hours. Finally, 100nm-thick aluminum was vacuum-deposited at 5×10 ^-5 Pa as the cathode. In the obtained polymer solar cell, the thickness of PEDOT:PSS is The prepared device has an open circuit voltage of 0.53 volts, a short circuit current of 8.59 milliamperes per square centimeter, a fill factor of 56.4% and a conversion efficiency of 2.58% under simulated sunlight irradiation of 100 milliwatts per square centimeter. Figure 2 shows the current-voltage curves of the device without light irradiation and under simulated sunlight irradiation of 100 mW/cm2.

Example 2

The transparent conductive glass sputtered with indium tin oxide (ITO) was ultrasonically cleaned twice with detergent, tap water, deionized water, acetone, and isopropanol in sequence, dried with nitrogen, and spin-coated with PEDOT at a speed of 2000rpm: The PSS solution was baked and annealed at 150° C. for 15 minutes, and cooled naturally to obtain an anode modification layer. The treated experimental sample was then transferred into the glove box, and then the mixed solution of P3HT and PC ₆₀ BM with a total concentration of 40 mg/mL (wherein the mass ratio of P3HT and PC ₆₀ BM was 1:1, and the concentration of a single material was 20 mg /mL, the solvent is dichlorobenzene) directly spin-coated on the above-mentioned anode modification layer under the rotating speed of 800rpm, as the photoelectric active layer. After solvent annealing for 2 hours, then spin-coat an ethanol solution of zirconium isopropoxide with a concentration of 1.5 mg/ml at a speed of 3000 rpm, without annealing, to obtain a cathode modification layer, and finally, vacuum vapor-deposit it at 5×10 ^-5 Pa 100nm aluminum as cathode. The prepared device has an open circuit voltage of 0.60 volts, a short circuit current of 10.94 mA per square centimeter, a fill factor of 68.1% and a conversion efficiency of 4.47% under simulated sunlight irradiation of 100 milliwatts per square centimeter. Figure 3 shows the current-voltage curves of the device without light irradiation and under simulated sunlight irradiation of 100 mW/cm2.

Example 3

The transparent conductive glass sputtered with indium tin oxide (ITO) was ultrasonically cleaned twice with detergent, tap water, deionized water, acetone, and isopropanol in sequence, dried with nitrogen, and spin-coated with PEDOT at a speed of 2000rpm: The PSS solution was baked and annealed at 150° C. for 15 minutes, and cooled naturally to obtain an anode modification layer. The treated experimental sample was then transferred into the glove box, and then the mixed solution of P3HT and PC ₆₀ BM with a total concentration of 40 mg/mL (wherein the mass ratio of P3HT and PC ₆₀ BM was 1:1, and the concentration of a single material was 20 mg /mL, the solvent is dichlorobenzene) directly spin-coated on the above-mentioned anode modification layer under the rotating speed of 900rpm, as the photoelectric active layer. Finally, 100nm-thick aluminum was vacuum-deposited at 5×10 ^-5 Pa as the cathode. The obtained polymer solar cell device has an open circuit voltage of 0.79 volts, a short circuit current of 9.21 milliamperes per square centimeter, a fill factor of 64.64% and a conversion efficiency of 4.74% under 100 milliwatts per square centimeter of simulated sunlight irradiation. Figure 4 shows the current-voltage curves of the device without light irradiation and under simulated sunlight irradiation of 100 mW/cm2.

Example 4

The transparent conductive glass sputtered with indium tin oxide (ITO) was ultrasonically cleaned twice with detergent, tap water, deionized water, acetone, and isopropanol in sequence, dried with nitrogen, and spin-coated with PEDOT at a speed of 2000rpm: The PSS solution was baked and annealed at 150° C. for 15 minutes, and cooled naturally to obtain an anode modification layer. The treated experimental sample was then transferred into the glove box, and then the mixed solution of P3HT and PC ₆₀ BM with a total concentration of 40 mg/mL (wherein the mass ratio of P3HT and PC ₆₀ BM was 1:1, and the concentration of a single material was 20 mg /mL, the solvent is dichlorobenzene) directly spin-coated on the above-mentioned anode modification layer under the rotating speed of 900rpm, as the photoelectric active layer. Then spin-coat an ethanol solution of zirconium isopropoxide with a concentration of 0.6 mg/ml at a speed of 3000 rpm, without annealing, to obtain a cathode modification layer, and finally vacuum-deposit 100 nm-thick aluminum at 5×10 ^-5 Pa as the cathode . The prepared device has an open circuit voltage of 0.89 volts, a short circuit current of 12.32 milliamps per square centimeter, a fill factor of 71.5% and a conversion efficiency of 7.84% under simulated sunlight irradiation of 100 milliwatts per square centimeter. Figure 5 shows the current-voltage curves of the device without light irradiation and under simulated sunlight irradiation of 100 mW/cm2.

Claims (10)

1. A polymer solar cell device, characterized in that: substrate (1), transparent conductive metal oxide layer (2), anode modification layer (3), photoelectric active layer (4) in the polymer solar cell device ), the cathode modification layer (5) and the counter electrode layer (6) are connected in sequence; the material of the cathode modification layer (5) is a zirconium isopropoxide film material. 2. A polymer solar cell device according to claim 1, characterized in that: the substrate (1) is made of glass or polyester film. 3. A polymer solar cell device according to claim 1, characterized in that: the transparent conductive metal oxide electrode layer (2) is made of one or more of In, Sn, Zn and Cd oxide material. 4. A polymer solar cell device according to claim 1, characterized in that: the material of the anode modification layer (3) is one or more of PEDOT:PSS or Mo, V, W and Ni oxide material. 5. a kind of polymer solar cell device according to claim 1 is characterized in that: the thickness of described zirconium isopropoxide film is 6. A polymer solar cell device according to claim 1, characterized in that: the material of the counter electrode layer (6) is Al, Ag, Au or a composite electrode material thereof. 7. A method for preparing a polymer solar cell device according to any one of claims 1 to 6, wherein the method adopts full solution processing, and the specific steps are as follows: (a) preparing a transparent conductive metal oxide electrode layer (2) on the substrate (1); (b) Spin-coat PEDOT:PSS solution on the transparent conductive metal oxide electrode layer (2), and bake to obtain the anode modification layer (3); (c) sequentially preparing a photoelectric active layer (4), spin-coating a zirconium isopropoxide alcohol solution and preparing a counter electrode layer (6) on the anode modification layer (3), to obtain the polymer solar cell device. 8. the preparation method of a kind of polymer solar cell device according to claim 7 is characterized in that: in the zirconium alcohol solution of isopropoxide described in the step (b), solvent is methyl alcohol, ethanol, isopropanol and isooctyl alcohol one or more of. 9. The preparation method of a kind of polymer solar cell device according to claim 7, characterized in that: the concentration of zirconium isopropoxide in the zirconium isopropoxide alcoholic solution described in step (b) is 0.2mg/mL～ 10mg/mL. 10 . The method for preparing a polymer solar cell device according to claim 7 , characterized in that: in the step (b), the spin coating speed of the zirconium isopropoxide alcohol solution is 800 rpm to 5000 rpm. 11 .