TW202118108A - Transparent organic solar cell module with patterned electrodes and manufacturing method thereof - Google Patents

Abstract

A transparent organic solar cell module with patterned electrodes includes a patterned indium tin oxide layer disposed on a substrate, the patterned indium tin oxide layer being used as a cathode; an electron transport layer disposed on the indium tin oxide layer; an active layer disposed on the electron transport layer; a hole transport layer disposed on the active layer; and an upper electrode disposed on the hole transport layer. Wherein the upper electrode is a metal electrode deposited by screen printing or a high vacuum thermal evaporation machine to form the transparent organic solar cell module with patterned electrodes. The invention utilizes a patterned metal electrode to manufacture a transparent organic solar cell, and can be applied to an agricultural greenhouse of agricultural and electric symbiosis, and a building integrated solar energy.

Description

Light-permeable organic solar cell module with patterned electrodes and manufacturing method thereof

The present invention relates to a light-permeable organic solar cell module, in particular to a light-permeable organic solar cell module with patterned electrodes.

As Taiwan’s land is narrow and densely populated, the continued promotion of solar energy policies in the future will inevitably affect the use of agricultural land. According to Article 30 of the "Applying for Agricultural Land for Permitted Use of Agricultural Facilities" of the Council of Agriculture, green energy facilities shall not affect agriculture For production and operation, the output standard of its agricultural production must reach more than 70% of the average output of the last three years of the agricultural statistics annual report. This makes it impossible to install opaque silicon solar cells that dominate the market on agricultural land. In order to resolve the conflict between a balanced energy policy and the competition between agricultural development, light-permeable organic solar cells are installed in agricultural greenhouses, which can not only grow crops, but also provide Self-sufficient power demand will be the best way to achieve the coexistence and common prosperity of the photovoltaic industry and agriculture.

Translucent modules will be manufactured on general commercial transparent conductive substrates (ITO). The ITO film layer is usually selected as the lower transparent conductive electrode of the module, and the upper electrode part is currently known to be transparent. There are two electrode preparation methods. The first method is to deposit a layer of about 100 nm thick metal electrode using thermal evaporation in the past, but this thickness can no longer make the module transparent, so reduce the metal The thickness of the electrode is intuitively the easiest way to achieve light transmittance. However, the thickness of the metal electrode is highly trade-off related to its conductivity. Decreasing the thickness to increase the light transmittance will cause the conductivity to decrease. , Which in turn causes a decline in the photoelectric conversion performance of the module.

Another way to prepare a transparent electrode is to use a transparent conductive material, such as silver nanowires or high-conductivity polymers, which can be used to prepare transparent electrodes. These materials usually use solutions. The process is coating, so the contact situation between it and the active layer that is covered on the lower layer needs to be fully evaluated, especially the problem of film uniformity that will appear during large-area coating, and to achieve better electrodes Conductivity, these alternative light-permeable electrode materials also need to moderately increase the thickness of their film layer, but the accompanying decline in light transmittance.

The purpose of the present invention is to provide a light-permeable organic solar cell module with patterned electrodes and a method for manufacturing the same, which uses patterned silver electrodes in combination with light-permeable conductive polymers (which can also be used as a hole transport layer ) To achieve the preparation of transparent electrodes.

In order to achieve the above-mentioned object, the present invention provides a light-transmissive organic solar cell module with patterned electrodes, which includes a patterned indium tin oxide layer disposed on a substrate, and the patterned indium tin oxide layer serves as a cathode; A transmission layer disposed on the indium tin oxide layer; an active layer disposed on the electron transmission layer; a hole transmission layer disposed on the active layer; and an upper electrode disposed on the hole transmission layer Wherein, the upper electrode is vapor-deposited with a metal electrode using a screen printing or high-vacuum thermal evaporator to form the patterned electrode transparent organic solar cell module.

In order to achieve the above-mentioned object, the present invention further provides a method for manufacturing a light-permeable organic solar cell module with patterned electrodes, which includes the following steps: forming an indium tin oxide layer on a substrate; patterning the indium tin oxide layer; cleaning Surface treatment of the indium tin oxide layer and the substrate with ozone O3 plasma; forming an electron transport layer on the indium tin oxide layer; forming an active layer on the electron transport layer; forming a hole transport on the active layer Layer; forming an upper electrode on the hole transport layer, wherein the upper electrode is a metal electrode vaporized using a screen printing or high vacuum thermal evaporation machine to form the patterned light-transmitting organic solar cell module.

Compared with the conventional transparent organic solar cell module, the present invention has the following advantages: 1. The present invention uses patterned metal electrodes to manufacture light-permeable organic solar cells, which can be applied to agricultural greenhouses and building-integrated photovoltaics (BIPV) for the symbiosis of agriculture and electricity. The invention can be applied to solar windows with dual functions of heat insulation and power generation. 2. Through the patterned design of the silver electrode and the design of the silver electrode busbar on the active layer, the shielding rate of the silver electrode can be greatly reduced by 57.4% to achieve good light transmittance characteristics, and its performance is as good as that of all electrodes. Compared with the design, its relative performance is only slightly reduced.

The present invention uses patterned silver electrode manufacturing method to achieve the preparation of transparent electrodes. When making silver electrodes, screen printing process or thermal evaporation is used to make finger electrodes and make busbar electrodes on the active layer.

Example 1: The light-permeable organic solar cell module is composed of organic solar cell elements connected in series. The element structure is a trans structure, and each element is composed of a lower electrode (indium tin oxide ITO and glass plate or soft base). Material PET), electron transport layer (aluminum zinc oxide AZO, Al: ZnO), active layer (P3HT: PC ₆₁ BM), hole transport layer (PEDOT: PSS), silver electrode (Ag) are stacked . Figure 1 is a schematic diagram of the transparent organic solar cell module with patterned electrodes of the present invention. As shown in Figure 1, the light-permeable organic solar cell module 10 with patterned electrodes includes a substrate 12, a patterned indium tin oxide layer 14, an electron transport layer 16, an active layer 18, and a hole transport Layer 20 and an upper electrode 22. The patterned indium tin oxide layer 14 serves as a cathode and is disposed on the substrate 12, which may be a glass plate or a flexible substrate.

In the present invention, the indium tin oxide layer 14 and the substrate 12 are cut into a size of 13×10 cm2 with a glass cutter, and then moved to a laser machine to turn on the set module pattern, such as cutting one piece per 1.6cm width. For the laser beam, the laser parameter setting current is 28A, the cutting speed of the indium tin oxide layer 14 and the flexible substrate is 280 mm/s; the cutting speed of the indium tin oxide layer 14 and the glass plate is 20 mm/s, QSW (Q-switched, Q switch) is 10 KHZ. After the laser cutting is completed and patterning, the electric meter is used to measure the resistance of each section as a basis for judging whether there is a cut. The laser-cut patterned module is wiped with acetone on the surface of the indium tin oxide layer 14 and the substrate 12 to remove the dirt and grease on the surface of the indium tin oxide layer 14, and then dried with a nitrogen spray gun to complete the cleaning step. Put the cleaned indium tin oxide layer 14 and the substrate 12 face up into the O3 plasma cleaning machine, perform plasma treatment for 18 minutes, and then perform the coating procedure of each film layer.

The electron transport layer 16 is disposed on the indium tin oxide layer 14, and aluminum zinc oxide AZO is used as the electron transport layer 16. The solution is configured to take 1 g of zinc acetate, 15 ml of aluminum acetate, and 60 mg of Zonyl® FS-300 surfactant , Add 10 ml of deionized water (18.2 MΩ•cm) and stir at room temperature for 6-10 hours, and then filter with a 45μm filter membrane. Before coating the film, dilute the solution with AZO: deionized water at a volume ratio of 1:1, and fill the solution into the injection syringe of the batch coater. The coating parameter is the distance between the slit coating knife tip and the sample. 0.2-0.25 mm, coating flow and speed are 0.2 ml/min and 0.5 m/min.

The active layer 18 is arranged on the electron transport layer 16, using P3HT poly(3-hexylthiophene) poly(3-hexylthiophene) and PC ₆₁ BM 6,6]-phenyl-C61-butyric acid methyl ester carbon sixty As the material of the active layer 18, the derivative is dissolved in o-xylene/3 vol% DIO solvent at a weight ratio of 1:1 at a concentration of 15 mg/ml, and heated and stirred at 60 ℃ for 12 hours to complete the solution configuration. Inject the configured active layer 18 solution into the slit coating equipment, set the substrate temperature to 60℃, the gap between the slit cutter head and the sample is 0.4-0.45 mm, and the coating flow and speed are 2.0 ml/min and 2.0 m/ min, the active layer 18 is coated on the electron transport layer 16. Before coating the film, the substrate is cleaned with a spray gun, and then the substrate is placed on the pre-heated substrate, fixed on the substrate by vacuum suction, and left for 3 minutes to make the substrate and the heated substrate After reaching thermal equilibrium, the film is coated by slit coating. After the film is coated, it is allowed to stand for 3 minutes to dry on the heated substrate to form a thin film.

The hole transport layer 20 is disposed on the active layer 18. The hole transport layer 20 uses a light-transmissive conductive polymer material, such as PEDOT:PSS, poly (3,4-ethylenedioxythiophene) poly (3,4-ethylenedioxy) Thiophene): poly(styrenesulfonate) poly(styrenesulfonate) and IPA isopropyl alcohol isopropyl alcohol are prepared in equal volume (1:1), and then mixed evenly by ultrasonic vibration, and the PEDOT:PSS mixture is injected into the slit coating equipment Set the substrate temperature to 80 ℃, the gap between the slit cutter head and the sample is 0.4-0.45 mm, the coating flow and speed are 0.5 ml/min and 0.1 m/min, and 20 layers of hole transmission are applied to the active layer 18. on. Before coating the film, the substrate is cleaned with a spray gun, and then the substrate is placed on the pre-heated substrate, fixed on the substrate by vacuum suction, and left for 3 minutes to make the substrate and the heated substrate After reaching thermal equilibrium, the film is coated by slit coating. After the film is coated, it is allowed to stand for 3 minutes to dry on the heated substrate to form a film. After the hole transport layer is coated, it is then placed in an oven set at 130° C. to bake for 10 min to dry the surface and thermally anneal the active layer 18 at the same time.

The upper electrode 22 is disposed on the hole transport layer 20, and the upper electrode 20 is a metal electrode deposited using a screen printing or high-vacuum thermal evaporation machine to form the patterned electrode transparent organic solar cell module 10. Lay the stacked film layer of the coated electron transport layer 16, active layer 18, and hole transport layer 20 on the pattern sheet of the vapor-deposited electrode, and place the stacked film in the high-vacuum thermal vapor deposition machine system and vacuumize When the cavity is below 6×10 ^-6 torr, the vapor deposition thickness of the silver electrode is 0.3 Å/s at the first 10 nm, and then the metal electrode silver is vapor-deposited to 100 nm at a plating rate of 1.5 Å/s to complete. The upper electrode 22 is made.

Figure 2 is a schematic diagram of the transparent organic solar cell with patterned electrodes of the present invention. The light-permeable organic solar cell 50 with patterned electrodes is a single cell element of the light-permeable organic solar cell module 10 with patterned electrodes. As shown in Figure 2, the light-permeable organic solar cell 50 with patterned electrodes includes a substrate 52 and a cathode bottom electrode of a patterned indium tin oxide region 54, an electron transport region 56, an active region 58, and a hole The transmission area 60 and the metal electrode 62.

Figure 3 is a schematic diagram of the patterned electrode of the present invention. As shown in FIG. 3, the shape of the patterned electrode 70 is a grid with finger electrodes 72. The patterned electrode 70 is an enlarged schematic diagram of the metal electrode 62.

Figure 4 is a flow chart of the manufacturing method of the transparent organic solar cell module with patterned electrodes of the present invention. First, an indium tin oxide layer is formed on the substrate and an indium tin oxide layer is formed on the substrate, as shown in step S10. Secondly, the indium tin oxide layer is patterned, as shown in step S20.

Next, clean and ozone O3 plasma surface treatment of the indium tin oxide layer and the substrate, as shown in step S30.

Next, an electron transport layer is formed on the indium tin oxide layer, as shown in step S40.

Next, an active layer is formed on the electron transport layer, as shown in step S50.

Secondly, a hole transport layer is formed on the active layer, as shown in step S60.

Finally, an upper electrode is formed on the hole transport layer, as shown in step S70. The upper electrode uses a screen printing or high-vacuum thermal evaporation machine to evaporate a metal electrode to form the patterned light-permeable organic solar cell module.

Table 1. The photoelectric conversion efficiency change of the ^{light-transmitting module (1x9x6 cm 2} ) made by designing the silver electrode bus in different areas Jsc (mA/cm ² ) V _oc (V) FF (%) PCE (%) Opaque organic solar cell module with all silver electrodes (1x9x6 cm ² ) 1.396 3.556 58.0 2.9 Light transmissive organic solar cell module with grid silver electrode (1x9x6 cm ² ) Grid silver electrode (a) (Design the bus bar in the series area between the components) 1.244 3.262 38.6 1.6 Grid silver electrode (b) (design the bus bar on the active layer) 1.428 3.563 52.8 2.7

Figure 5 is the performance diagram of the transparent organic solar cell with the patterned electrode of the present invention. The patterning design of the present invention is divided into two types: grid silver electrode (a) and grid silver electrode (b). Compared with the all-silver electrode design, the shielding rate of the silver electrode can be greatly reduced by 57.4%. And achieve good light transmission characteristics. However, in terms of photoelectric conversion efficiency, the photoelectric conversion efficiency of the grid silver electrode (b) design is much better than that of the grid silver electrode (a) design. Compared with the all-silver electrode design, the photoelectric conversion efficiency of the grid silver electrode (a) design is greatly reduced by 44.8%. However, the photoelectric conversion efficiency of the grid silver electrode (b) design is compared with that of the all-silver electrode design. The relative efficiency drops only slightly by about 6.9%.

10: Light-permeable organic solar cell module with patterned electrodes 12: substrate 14: Patterned indium tin oxide layer 16: electron transport layer 18: active layer 20: hole transport layer 22: Upper electrode 50: Transparent organic solar cell with patterned electrodes 52: Base 54: Patterned indium tin oxide area 56: Electronic Transmission Area 58: active area 60: Electric hole transmission area 62: Metal electrode 70: Patterned electrode 72: Finger electrode S10-S70: steps

Figure 1 is a schematic diagram of the transparent organic solar cell module with patterned electrodes of the present invention. Figure 2 is a schematic diagram of the transparent organic solar cell with patterned electrodes of the present invention. Figure 3 is a schematic diagram of the patterned electrode of the present invention. Figure 4 is a flow chart of the manufacturing method of the transparent organic solar cell module with patterned electrodes of the present invention. Figure 5 is the performance diagram of the transparent organic solar cell with the patterned electrode of the present invention.

10: Light-permeable organic solar cell module with patterned electrodes

12: substrate

14: Patterned indium tin oxide layer

16: electron transport layer

18: active layer

20: hole transport layer

22: Upper electrode

Claims (8)

A light-permeable organic solar cell module with patterned electrodes, including: A patterned indium tin oxide layer is disposed on a substrate, and the patterned indium tin oxide layer serves as a cathode; An electron transport layer disposed on the indium tin oxide layer; An active layer is arranged on the electron transport layer; A hole transport layer is formed on the active layer; and An upper electrode is arranged on the hole transport layer, wherein the upper electrode is vapor-deposited with a metal electrode using a screen printing or a high-vacuum thermal evaporation machine to form the patterned electrode transparent organic solar cell module. The light-permeable organic solar cell module with patterned electrodes according to claim 1, wherein the upper electrode is a metal electrode. The light-permeable organic solar cell module with patterned electrodes according to claim 1, wherein the shape of the patterned electrodes is a grid. The light-permeable organic solar cell module with patterned electrodes according to claim 1, wherein the substrate is a glass plate or a flexible substrate. A method for manufacturing a light-permeable organic solar cell module with patterned electrodes includes the following steps: Forming an indium tin oxide layer on a substrate; Patterning the indium tin oxide layer; Clean and ozone O3 plasma surface treatment of the indium tin oxide layer and the substrate; Forming an electron transport layer on the indium tin oxide layer; Forming an active layer on the electron transport layer; Forming a hole transport layer on the active layer; An upper electrode is formed on the hole transport layer, wherein the upper electrode is vapor-deposited with a metal electrode using a screen printing or a high-vacuum thermal vapor deposition machine to form the patterned light-transmitting organic solar cell module. The method for manufacturing a light-permeable organic solar cell module with patterned electrodes according to claim 5, wherein the upper electrode is a metal electrode. The method for manufacturing a light-permeable organic solar cell module with patterned electrodes according to claim 5, wherein the shape of the patterned electrodes is a grid. The method for manufacturing a light-permeable organic solar cell module with patterned electrodes according to claim 5, wherein the substrate is a glass plate or a flexible substrate.

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