CN104600207B - Transparent electrode and preparation method and application thereof - Google Patents

Abstract

The invention discloses a transparent electrode, its preparation method and application, and belongs to the technical field of transparent electrodes. The technical problem that the metal oxide flexible electrode is not resistant to bending and has poor electrical conductivity in the prior art is solved. The transparent electrode includes a flexible substrate and a conductive layer arranged in sequence from bottom to top, the conductive layer is etched with grooves of a metal grid structure, the etching depth reaches the upper surface of the flexible substrate, and deposited in the grooves of the metal grid structure There is metal, and the deposited metal forms the metal gate. The electrode basically maintains the transmittance of the transparent electrode in the visible light region, reduces the surface resistance of the transparent electrode, the transmittance in the visible light region is 70%-85%, and the surface resistance is 3Ω/□-12Ω/□; The bending performance of the transparent electrode is improved, and the transparent electrode can also maintain good conductivity after bending. The surface resistance of the transparent electrode of the present invention increases below 10% after 400 times of bending, and the conductivity basically does not decrease.

Description

Transparent electrode and its preparation method and application

technical field

The invention belongs to the technical field of transparent electrodes, and in particular relates to a transparent electrode and its preparation method and application.

Background technique

Flexible transparent electrodes based on metal oxides (such as: ITO, FTO, AZO, etc.) are mainly composed of flexible substrates and conductive layers, have high visible light transmittance, and are widely used in flexible electronic devices such as organic solar cells and light-emitting diodes. However, there are still some problems in this flexible transparent electrode: on the one hand, because the material of the flexible substrate generally adopts high molecular polymer, such as polyethylene terephthalate (PET), polyimide (PI), etc. High temperature resistance limits the high temperature post-treatment process of the conductive layer, so the flexible transparent electrode has a lower conductivity than the transparent electrode on the glass substrate; on the other hand, the conductive layer is made of inorganic materials such as metal oxides, such as tin-doped oxide Indium (ITO), which is brittle and hard, does not match the mechanical properties of the flexible substrate. It is easy to break when bent, and the conductivity drops sharply after bending.

In order to solve the above problems, in the prior art, a conductive polymer PEDOT (a polymer of 3,4-ethylenedioxythiophene monomer) is deposited on a flexible substrate, and then an ITO layer is magnetron sputtered on the conductive polymer PEDOT. The flexibility of the PEDOT layer can improve the bendability of the electrode to a certain extent, but the conductivity of the PEDOT layer is still poor, and at the same time it will reduce the light transmittance, and the overall performance of the electrode is not good (Flexible PEDOT:PSS/ITO hybrid transparent conducting electrode for organic photovoltaics, Solar Energy Materials & Solar Cells 115 (2013) 71–78). Therefore, it is of great significance to solve the problem that metal oxide flexible electrodes are not resistant to bending, while maintaining or improving the excellent light transmittance and electrical conductivity of metal oxide electrodes, to expand their applications.

Contents of the invention

The purpose of the present invention is to solve the technical problems of metal oxide flexible electrodes in the prior art, such as not being resistant to bending and having poor electrical conductivity, and to provide a transparent electrode and its preparation method and application.

The transparent electrode of the present invention includes a flexible substrate and a conductive layer arranged in sequence from bottom to top, the conductive layer is etched with grooves of a metal mesh structure, the etching depth reaches the upper surface of the flexible substrate, and the metal mesh structure Metal is deposited in the groove, and the deposited metal forms a metal gate.

Preferably, the material of the flexible substrate is polyethylene terephthalate (PET) or polyimide (PI), and the material of the conductive layer is tin-doped indium oxide (ITO), fluorine-doped tin dioxide (FTO) or aluminum-doped zinc oxide (AZO), the thickness of the conductive layer is 50nm-200nm.

Preferably, the structure of the metal grid is a fence structure or a grid structure, and the grid pattern of the grid structure is a square, a rectangle or a regular hexagonal honeycomb shape.

Preferably, the grid line width of the metal gate is 50 μm-200 μm, the distance from the nearest two parallel grid lines is 0.4 mm-5 mm, and the etched volume of the conductive layer accounts for 3% of the total volume of the conductive layer -15%.

Preferably, the metal is aluminum, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, titanium or alloys.

The preparation method of the transparent electrode of the present invention comprises the following steps:

Step 1, depositing a water-soluble conductive polymer on the conductive layer of the metal oxide transparent electrode to obtain a polymer film;

The metal oxide transparent electrode includes a flexible substrate and a conductive layer arranged in sequence from bottom to top;

Step 2, using a laser etching process to etch the grooves of the metal grid structure on the polymer film, and the etching depth reaches the upper surface of the flexible substrate;

The linear speed of the laser etching is 400mm/s-1500mm/s, and the working power is 0.8W-4.7W;

Step 3, depositing a metal layer with a thickness of 100nm-200nm on the upper surface of the unetched polymer film and the upper surface of the exposed flexible substrate to form a metal gate;

Step 4, put the metal oxide transparent electrode with the metal grid into deionized water and ultrasonically remove the unetched polymer film and the metal layer on the unetched polymer film to obtain a transparent electrode.

Preferably, in the first step, the water-soluble conductive polymer is PEDOT:PSS.

Preferably, in the first step, the thickness of the deposited polymer film is 50nm-500nm.

Preferably, in step 4, the ultrasonic time is 10s-15s.

The present invention also provides the application of the above-mentioned transparent electrode in preparing solar cells.

Compared with prior art, the beneficial effect of the present invention:

1. The transparent electrode of the present invention embeds the metal grid into the conductive layer, which maintains the transmittance of the transparent electrode in the visible light region, reduces the surface resistance of the transparent electrode, and has a transmittance of 70%-85% in the visible light region. The surface square resistance is 3Ω/□-12Ω/□; the bending performance of the transparent electrode is increased, and the transparent electrode can also maintain good conductivity after bending. The surface square resistance of the transparent electrode of the present invention is bent 400 times The increase is below 10%, and the conductivity basically does not decrease; in addition, the embedded structure does not have the problem of protruding metal gates, which can meet the preparation requirements of flexible electronic devices such as organic solar cells and light-emitting diodes;

2. The preparation method adopted by the transparent electrode of the present invention is simple and quick, with high preparation efficiency and low equipment cost, and there is no limit to the area of the prepared transparent electrode, which can realize large-scale batch processing and is easy for large-scale industrialization.

3. The solar cell prepared by using the transparent electrode of the present invention has good performance.

Description of drawings

Fig. 1 is the structural representation of transparent electrode of the present invention;

2 is a top view of the transparent electrodes of Embodiment 1 and Embodiment 4 of the present invention;

3 is a top view of a transparent electrode according to Embodiment 2 of the present invention;

Fig. 4 is a top view of the transparent electrodes of Embodiment 3 and Embodiment 5 of the present invention;

FIG. 5 is a top view of a transparent electrode according to Embodiment 6 of the present invention;

Fig. 6 is a flow chart of the process for preparing a transparent electrode in the present invention;

7 is a schematic structural view of a solar cell prepared with a transparent electrode of the present invention;

Fig. 8 is the current-voltage characteristic curve of the solar cell of the embodiment 7 of the present invention;

Fig. 9 is the current-voltage characteristic curve of the solar cell of the embodiment 8 of the present invention;

In the figure, 1. Substrate, 2. Conductive layer, 3. Metal gate, 4. Polymer film, 5. Metal layer, 6. Hole transport layer, 7. Photosensitive layer, 8. Electron transport layer, 9. Metal Electrode, 10, connecting piece.

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with specific embodiments, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the claims of the present invention.

As shown in Figure 1, the transparent electrode of the present invention includes a flexible substrate 1 and a conductive layer 2 arranged in sequence from bottom to top, wherein the conductive layer 2 is etched with grooves of a metal grid structure, and the etching depth reaches the flexible substrate 1 On the upper surface of the conductive layer 2, the etched volume accounts for 3%-15% of the total volume of the conductive layer 2; metal is deposited in the groove of the metal grid structure, and the deposited metal forms a metal grid 3. The transmittance of the transparent electrode in the visible light region is 70%-85%, the surface square resistance is 3Ω/□-12Ω/□, and the upper surface is flat without obvious protrusion. After 400 times of bending, the surface resistance increases below 10%.

In the present invention, the material of the flexible substrate 1 can be PET, PI and the like. The material of the conductive layer 2 can be ITO, FTO or AZO, and the thickness is 50nm-200nm. The metal can be one of aluminum, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum and titanium, or an alloy, and the thickness of the metal grid 3 is also 50nm-200nm. And it is the same as the thickness of the conductive layer 2 .

The metal grid structure (that is, the structure of the metal grid 3 ) is not particularly limited, and any metal grid structure in the prior art can be realized, which can be a fence structure or a grid structure. If it is a fence structure, as shown in Figure 2, the metal grid structure is composed of multiple parallel grid lines and two connecting pieces 10, the tops of the multiple parallel grid lines are connected to one connecting piece 10, and the multiple parallel grid lines The bottom end of the straight line is connected to another connecting piece 10, and the distance between the grid lines is the distance between two adjacent parallel grid lines. If it is a grid structure, as shown in Figure 3-5, the grid can be square, rectangular, regular hexagonal honeycomb, etc.; if it is a square, as shown in Figure 5, the metal grid structure consists of two sets of parallel grids perpendicular to each other. Lines, the distance between two adjacent parallel straight lines is equal, the edge profile is a square, and the grid line spacing is the distance between two adjacent and parallel grid lines; if it is a regular hexagonal honeycomb shape, as shown in Figure 3 and Figure As shown in 4, the metal grid structure is a honeycomb structure, and the distance between the grid lines is the distance between the parallel sides of the regular hexagonal honeycomb; the grid line width of the metal grid structure is 50 μm-200 μm, and the two closest parallel grids The line distance is 0.4mm-5mm, and the minimum precision depends on the laser etching process.

As shown in Figure 6, the preparation method of the transparent electrode of the present invention comprises the following steps:

Step 1, after cleaning, deposit a water-soluble conductive polymer on the upper surface of the conductive layer 2 of the metal oxide transparent electrode to obtain a polymer film with a thickness of 50nm-500nm, preferably 200nm;

Among them, the transparent electrode is mainly composed of a flexible substrate 1 and a conductive layer 2. The material of the flexible substrate 1 can be PET, PI, etc.; the material of the conductive layer 2 can be ITO, FTO or AZO, with a thickness of 50nm-200nm, preferably metal oxide The transparent electrode is ITO/PET transparent electrode; the water-soluble conductive polymer can be PEDOT:PSS;

The deposition method can be spin coating, spray coating, scrape coating, screen printing, etc., preferably spin coating and spray coating;

Step 2, using a laser etching process to etch the groove of the metal grid structure on the polymer film 4, and etch through the conductive layer 2, and the etching depth reaches the upper surface of the flexible substrate 1;

Among them, the linear speed of the laser etching process is 400mm/s-1500mm/s, and the working power is 0.8W-4.7W; if the linear speed is less than 400mm/s, the laser etching points are too dense, which will damage the flexible substrate 1. If the linear speed If it is greater than 1500mm/s, the laser etching points are too sparse to form a continuous line; if the working power is less than 0.8W, the laser energy is lower than the etching threshold of the conductive layer 2 and cannot be etched; if the working power is greater than 4.7W, the laser energy is relatively large. Damage the flexible base 1, causing deformation of the flexible base 1;

The volume of the conductive layer 2 to be etched accounts for 3%-15% of the total volume of the conductive layer 2. There is no special limitation on the metal grid structure, and any metal grid structure in the prior art can be realized, which can be a fence structure or a grid structure ; If it is a fence structure, as shown in Figure 2, the metal mesh grid structure is made up of multiple parallel grid lines and two connecting pieces 10, the tops of many parallel grid lines are connected on a connecting piece 10, and many parallel grid lines The bottom end of the straight line is connected to another connecting piece 10, and the distance between the grid lines is the distance between two adjacent parallel grid lines; if it is a grid structure, as shown in Figure 3-5, the grid can be square, Rectangular, regular hexagonal honeycomb, etc.; if it is square, as shown in Figure 5, the metal grid structure is composed of two sets of parallel grid lines perpendicular to each other. The distance between two adjacent parallel straight lines is equal, and the edge contour is square. The grid line spacing is the distance between two adjacent and parallel grid lines; if it is a regular hexagonal honeycomb shape, as shown in Figure 3 and Figure 4, the metal grid structure is a honeycomb structure, and the grid line spacing is a regular hexagonal honeycomb The distance between the parallel opposite sides of the shape; the grid line width of the metal grid structure is 50μm-200μm, and the distance between the nearest two parallel grid lines is 0.4mm-5mm, and the minimum accuracy depends on the laser etching process;

Step 3, depositing a metal layer 5 on the upper surface of the unetched polymer film 4 and the upper surface of the exposed flexible substrate 1 after etching, the thickness of the metal layer 5 is the same as that of the conductive layer 2, and deposited on the exposed flexible substrate 1. The metal layer 5 on the surface of the substrate 1 forms a metal gate 3;

Wherein, the material of metal layer 5 can be aluminum, silver, copper, gold, nickel, platinum, zinc, tin, iron, cobalt, manganese, molybdenum, titanium or alloy, preferably aluminum or silver, also can be alloy;

The deposition method can be vacuum evaporation, scraping, screen printing, spraying, etc., preferably vacuum evaporation;

Step 4: Put the transparent electrode with the metal grid 3 into deionized water and ultrasonically remove the unetched polymer film 4 and the metal layer 5 on it. The ultrasonic time is generally 10s-15s, and then clean to obtain a transparent electrode The transmittance of the transparent electrode in the visible light region is 70%-85%, the surface resistance is 3Ω/□-12Ω/□, and the upper surface is flat without obvious protrusion. After 400 times of bending, the surface resistance increases below 10%.

The transparent electrode prepared by the invention can be used to prepare solar cells, and its specific method is the same as the method for preparing solar cells with transparent electrodes in the prior art. That is, a hole transport layer 6, a photosensitive layer 7, an electron transport layer 8, and a metal electrode 9 are sequentially prepared on the upper surface of the transparent electrode from bottom to top, as shown in Figure 7; the preparation method can be vacuum evaporation, scraping, spraying, etc. , the material of the hole transport layer 6 can be PEDOT:PSS, and the thickness can be 20nm-60nm; the material of the photosensitive layer 7 can be polythiophene or a narrow bandgap polymer, such as PBDT-TFQ (see the literature for the synthesis method: Prominent Short-Circuit Currents ofFluorinated Quinoxaline-Based Copolymer Solar Cells with a Power ConversionEfficiency of8.0%. CHEMISTRYOF MATERIALS volume: 24 period: 24 pages), thickness can be 100nm-150nm; The material of electron transport layer 8 can be Ca, and thickness can be 15nm- 20nm; the material of the metal electrode 9 can be Al, and the thickness can be 100nm-200nm.

Among the present invention, PEDOT:PSS is the aqueous solution of a kind of polymer, mainly is made of two kinds of substances of PEDOT and PSS, and PEDOT is the polymer of EDOT (3,4-ethylenedioxythiophene monomer), and PSS is poly Styrene Sulfonate. It is commercially available. The model of PEDOT:PSS used in this embodiment is Al4083, spin coating can directly use Al4083, the spray ink formula is: PEDOT:PSS volume fraction 18%, deionized water volume fraction 9%, isopropanol volume fraction is 73% %.

Below in conjunction with embodiment further illustrate the present invention.

Example 1

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the ITO/PET transparent electrode with deionized water, isopropanol and acetone in sequence, dry it with high-purity nitrogen gas, treat it in a UV ozone processor for 20 minutes, and then place it on a spin coater stand, at 2000rpm Spin-coat a 50nm thick PEDOT:PSS film at a rotating speed; wherein, the flexible substrate 1 of the ITO/PET transparent electrode is PET, the conductive layer 2 is ITO with a thickness of 180nm, and the upper surface area of the ITO/PET transparent electrode is 30mm×30mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 The upper surface; the metal grid structure is a fence structure, the line width is 0.1mm, and the distance between two adjacent grid lines is 1mm; the volume of the etched conductive layer 2 accounts for 10% of the total volume of the conductive layer 2, and the laser etching is used The linear speed is 600mm/s, the working current used for etching is 1.84W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Place the grooved transparent electrode in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 Pa, place it on the upper surface of the unetched PEDOT:PSS film and the exposed flexible substrate 1 after etching. A metal aluminum layer with a thickness of 180 nm is thermally evaporated on the surface to form a metal gate 3;

Step 4. Peel off the metal aluminum layer:

Place the transparent electrode evaporated with a metal aluminum layer in deionized water for 10s, remove the unetched PEDOT:PSS film and the metal aluminum layer on it, take it out, use isopropanol and acetone to clean the surface, and after drying, get Metal gate ITO transparent electrode, as shown in Figure 2.

On the conductive layer 2 of the metal grid ITO transparent electrode of embodiment 1, print a length of 1 cm and two silver pastes with a spacing of 1 cm. After drying, use an ohmmeter to conduct a resistance test on the metal grid ITO transparent electrode of embodiment 1. Measurement. After testing, the light transmittance of the metal grid ITO transparent electrode of Example 1 is 74%, and the surface resistance is 3.6Ω/□.

Example 2

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the patterned ITO/PET transparent electrode used to prepare the battery module with deionized water, isopropanol and acetone in sequence, dry it with high-purity nitrogen, treat it in a UV ozone processor for 20 minutes, and then use ultrasonic The spraying instrument sprays and deposits a PEDOT:PSS film with a thickness of 200nm on the upper surface of the conductive layer 2; wherein, the spraying process parameters are 0.3mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.1MPA Air flow, spraying three times; the flexible substrate 1 used to prepare the patterned ITO/PET transparent electrode of the battery module is PET, the conductive layer 2 is ITO with a thickness of 180nm, and the pattern of the conductive layer 2 is that five long sides are parallel to each other Rectangular, the upper surface area of the ITO/PET transparent electrode is 90mm×90mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 The upper surface; the grid of the metal grid structure is a regular hexagonal honeycomb shape, the line width is 0.1mm, the distance between the opposite sides of the regular hexagonal honeycomb shape is 1.5mm, and the volume of the etched conductive layer 2 accounts for the total volume of the conductive layer 2 13%, the linear speed used for laser etching is 600mm/s, the working current used for etching is 1.84W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Place the grooved transparent electrode in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 Pa, place it on the upper surface of the unetched PEDOT:PSS film and the exposed flexible substrate 1 after etching. A metal aluminum layer with a thickness of 180 nm is thermally evaporated on the surface to form a metal gate 3;

Step 4. Peel off the metal aluminum layer:

Place the transparent electrode evaporated with a metal aluminum layer in deionized water for 15s, remove the unetched PEDOT:PSS film and the metal aluminum layer on it, take it out, use isopropanol and acetone to clean the surface, and after drying, get Metal gate ITO transparent electrode, as shown in Figure 3.

On the conductive layer 2 of the metal grid ITO transparent electrode of embodiment 2, print a length of 1 cm and two silver pastes with a spacing of 1 cm. After drying, use an ohmmeter to conduct a resistance test on the metal grid ITO transparent electrode of embodiment 2. Measurement. After testing, the light transmittance of the metal grid ITO transparent electrode of Example 2 is 72%, and the surface resistance is 5.2Ω/□.

Example 3

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the ITO/PI transparent electrode with deionized water, isopropanol and acetone in sequence, blow it dry with high-purity nitrogen, treat it in a UV ozone processor for 20 minutes, and then spray on the upper surface of the conductive layer 2 with an ultrasonic sprayer Deposit a PEDOT:PSS film with a thickness of 100nm; among them, the spraying process parameters are 0.15mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.1MPA air flow, spray three times; ITO/PI The flexible substrate 1 of the transparent electrode is PI, the conductive layer 2 is ITO with a thickness of 100nm, and the upper surface area of the ITO/PI transparent electrode is 70mm×70mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 The upper surface; the grid of the metal grid structure is a regular hexagonal honeycomb shape, the line width is 0.05mm, the distance between the opposite sides of the regular hexagonal honeycomb shape is 2mm, and the volume of the etched conductive layer 2 accounts for 2% of the total volume of the conductive layer 2 5%, the linear speed used for laser etching is 400mm/s, the working current used for etching is 0.8W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Place the grooved transparent electrode in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 , on the upper surface of the unetched PEDOT:PSS film and the upper surface of the exposed flexible substrate 1 after etching Thermally evaporating a metal aluminum layer with a thickness of 100 nm to form a metal gate 3;

Step 4. Peel off the metal aluminum layer:

Place the transparent electrode evaporated with a metal aluminum layer in deionized water for 12s, remove the unetched PEDOT:PSS film and the metal aluminum layer on it, take it out, clean the surface with isopropanol and acetone, and dry it to get Metal gate ITO transparent electrode, the structure is shown in Figure 4.

On the conductive layer 2 of the metal grid ITO transparent electrode of embodiment 3, printing length is 1cm, two silver pastes with a spacing of 1cm, after drying, use an ohmmeter to carry out the resistance of the metal grid ITO transparent electrode of embodiment 3 Measurement. After testing, the light transmittance of the metal grid ITO transparent electrode of Example 3 is 83%, and the surface resistance is 11Ω/□.

Example 4

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the ITO/PET transparent electrode with deionized water, isopropanol and acetone in sequence, dry it with high-purity nitrogen gas, treat it in a UV ozone processor for 20 minutes, and then place it on a spin coater stand, at 2000rpm Spin-coat a 50nm thick PEDOT:PSS film at a rotating speed; wherein, the substrate 1 of the ITO/PET transparent electrode is PET, the conductive layer 2 is ITO with a thickness of 200nm, and the upper surface area of the ITO/PET transparent electrode is 50mm×50mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 The upper surface; the metal grid structure is a fence structure, the line width is 0.2mm, the distance between adjacent grid lines is 5mm, the volume of the etched conductive layer 2 accounts for 4% of the total volume of the conductive layer 2, and the laser etching is used The line speed is 1500mm/s, the working current used for etching is 4.7W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Put the transparent electrode engraved with a metal grid structure in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 Pa, the upper surface of the unetched PEDOT:PSS film and the exposed flexible substrate 1 A metal silver layer with a thickness of 200 nm is thermally evaporated on the upper surface to form a metal grid 3;

Step 4. Peel off the metallic silver layer:

Place the transparent electrode evaporated with a metal silver layer into deionized water for 15s, remove the unetched PEDOT:PSS film and the metal silver layer on it, take it out, use isopropanol and acetone to clean the surface, after drying, place in The upper and lower ends of the metal grid 3 are printed with two silver pastes with a length of 1 cm and a width of 1 cm. After drying, a metal grid ITO transparent electrode is obtained, as shown in FIG. 2 , a metal grid ITO transparent electrode is obtained.

On the conductive layer 2 of the metal grid ITO transparent electrode of embodiment 4, print a length of 1 cm and two silver pastes with a spacing of 1 cm. After drying, use an ohmmeter to conduct a resistance test on the metal grid ITO transparent electrode of embodiment 4. Measurement. After testing, the light transmittance of the metal grid ITO transparent electrode of Example 4 is 81%, and the surface resistance is 8Ω/□.

Example 5

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the ITO/PI transparent electrode with deionized water, isopropanol and acetone in sequence, blow it dry with high-purity nitrogen, treat it in a UV ozone processor for 20 minutes, and then spray on the upper surface of the conductive layer 2 with an ultrasonic sprayer Deposit a PEDOT:PSS film with a thickness of 100nm; among them, the spraying process parameters are 0.15mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.1MPA air flow, spray three times; ITO/PI The flexible substrate 1 of the transparent electrode is PI, the conductive layer 2 is ITO with a thickness of 100nm, and the upper surface area of the ITO/PI transparent electrode is 70mm×70mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 The upper surface; the grid of the metal grid structure is a regular hexagonal honeycomb shape, the line width is 0.75mm, the distance between the opposite sides of the regular hexagonal honeycomb shape is 1mm, and the volume of the etched conductive layer 2 accounts for 2% of the total volume of the conductive layer 2. 15%, the linear speed used for laser etching is 400mm/s, the working current used for etching is 1.1W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Place the grooved transparent electrode in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 , on the upper surface of the unetched PEDOT:PSS film and the upper surface of the exposed flexible substrate 1 after etching Thermally evaporating a metal aluminum layer with a thickness of 100 nm to form a metal gate 3;

Step 4. Peel off the metal aluminum layer:

Place the transparent electrode evaporated with a metal aluminum layer in deionized water for 12s, remove the unetched PEDOT:PSS film and the metal aluminum layer on it, take it out, clean the surface with isopropanol and acetone, and dry it to get Metal gate ITO transparent electrode, the structure is shown in Figure 4.

The conductive performance of the metal grid ITO transparent electrode of Example 5 after bending was tested, and the bending curvature was 7 mm. The results are shown in Table 1. It can be seen that the surface resistance of the transparent electrode prepared by the present invention does not increase significantly after repeated bending.

Example 6

Preparation method of metal gate ITO transparent electrode:

Step 1. Preparation of PEDOT:PSS film:

After cleaning the conductive layer 2 of the ITO/PI transparent electrode with deionized water, isopropanol and acetone in sequence, blow it dry with high-purity nitrogen, treat it in a UV ozone processor for 20 minutes, and then spray on the upper surface of the conductive layer 2 with an ultrasonic sprayer Deposit a PEDOT:PSS film with a thickness of 100nm; among them, the spraying process parameters are 0.15mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.1MPA air flow, spray three times; ITO/PI The flexible substrate 1 of the transparent electrode is PI, the conductive layer 2 is ITO with a thickness of 100nm, and the upper surface area of the ITO/PI transparent electrode is 70mm×70mm;

Step 2. Laser etching the grooves of the metal grid structure:

Place the transparent electrode spin-coated with the PEDOT:PSS film on the workbench of the laser marking machine, use the laser marking machine to etch the groove of the metal grid structure on the PEDOT:PSS film, and the etching depth reaches the bottom of the flexible substrate 1 Upper surface; the grid of the metal grid structure is square, the line width is 0.75 mm, and the distance between opposite sides is 1 mm. The volume of the etched conductive layer 2 accounts for 15% of the total volume of the conductive layer 2, which is used for laser etching. The line speed is 400mm/s, the working current used for etching is 1.1W, and other parameters are default;

Step 3, preparation of the metal grid 3:

Place the grooved transparent electrode in a vacuum evaporation apparatus, and after vacuuming to 3×10 ^-4 , on the upper surface of the unetched PEDOT:PSS film and the upper surface of the exposed flexible substrate 1 after etching Thermally evaporating a metal aluminum layer with a thickness of 100 nm to form a metal gate 3;

Step 4. Peel off the metal aluminum layer:

Place the transparent electrode evaporated with a metal aluminum layer in deionized water for 12s, remove the unetched PEDOT:PSS film and the metal aluminum layer on it, take it out, clean the surface with isopropanol and acetone, and dry it to get Metal gate ITO transparent electrode, the structure is shown in Figure 5.

The conductive performance of the metal grid ITO transparent electrode of Example 6 after being bent was tested, and the bending curvature was 7 mm. The results are shown in Table 1. It can be seen that the surface resistance of the transparent electrode prepared by the present invention does not increase significantly after repeated bending.

Example 7

Preparation method of polymer solar cell based on metal gate ITO transparent electrode:

Step 1. After treating the metal grid ITO transparent electrode prepared in Example 1 with ozone in an ultraviolet ozone cleaning machine for 20 minutes, place it on the template frame used for spraying, and place a corresponding mask (15 mm × 15 mm in size) on the transparent electrode. ), using an ultrasonic sprayer to spray PEDOT:PSS with a thickness of 50nm on the upper surface of the transparent electrode, and annealing on a hot stage at 150°C for 20min to obtain a hole transport layer 6; wherein, the process parameter used for spraying is 0.2mL/min Flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.4MPA air flow, spraying twice;

Step 2: Use an ultrasonic sprayer to spray PBDT-TFQ ink on the upper surface of the hole transport layer 6 with a spray thickness of 150 nm, then transfer it to a glove box, and anneal at 140° C. for 10 minutes under a nitrogen atmosphere to obtain a photosensitive layer 7; , the process parameters used for spraying are 0.3mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.4MPa air flow, and spray twice;

Step 3. Transfer the transparent electrode sprayed with the hole transport layer 6 and the photosensitive layer 7 to a vacuum evaporation apparatus, vacuumize to 2×10 ^-4 Pa, use a mask plate with an area of 10mm×10mm, and place on the photosensitive layer 30nm of Ca and 150nm of Al are sequentially thermally evaporated on 7 to obtain an electron transport layer 8 and a metal electrode 9 to complete the preparation of a polymer solar cell. The material and structure of the battery are PET/Al metal gate+ITO(180nm)/PEDOT:PSS(50nm)/PBDT-TFQ:PCBM[70](150nm)/Ca(30nm)/Al(150nm) from bottom to top . The effective area of the battery is controlled by the mask plate area of the vapor-deposited metal Al electrode, which is 1 cm ² .

The polymer solar cell prepared in Example 7 is tested under AM 1.5G simulated sunlight (irradiation intensity is 100 mW/cm2), the performance parameters of the cell are shown in Table 1, and the current-voltage characteristic curve obtained by the test ( I-V curve) as shown in Figure 8.

Example 8

Preparation method of polymer solar cell module based on metal gate ITO transparent electrode:

Step 1. After treating the metal grid ITO transparent electrode prepared in Example 2 with ozone in an ultraviolet ozone cleaning machine for 20 minutes, place it on the template frame used for spraying, and place a corresponding mask (15 mm × 15 mm in size) on the transparent electrode. ), using an ultrasonic sprayer to spray PEDOT:PSS with a thickness of 50nm on the upper surface of the transparent electrode, and annealing on a hot stage at 150°C for 20min to obtain a hole transport layer 6; wherein, the process parameter used for spraying is 0.2mL/min Flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.4MPA air flow, spraying twice;

Step 2: Use an ultrasonic sprayer to spray PBDT-TFQ as ink on the upper surface of the hole transport layer 6, with a spray thickness of 150 nm, and anneal at 140°C for 10 minutes in a nitrogen atmosphere to obtain a photosensitive layer 7; wherein, the process parameters used for spraying 0.3mL/min flow rate, 20mm/s nozzle moving speed, 60mm nozzle height, 3.5W ultrasonic power, 0.4MPa air flow, spray twice;

Step 3. Transfer the transparent electrode sprayed with the hole transport layer 6 and the photosensitive layer 7 to a vacuum evaporation apparatus, vacuumize to 2×10 ^-4 Pa, use a mask plate with an area of 10mm×10mm, and place on the photosensitive layer 30nm of Ca and 150nm of Al are sequentially thermally evaporated on 7 to obtain an electron transport layer 8 and a metal electrode 9 to complete the preparation of a polymer solar cell. The material and structure of the battery are PET/Al metal gate+ITO(180nm)/PEDOT:PSS(50nm)/PBDT-TFQ:PCBM[70](150nm)/Ca(30nm)/Al(150nm) from bottom to top . The module is composed of 5 modules connected in series, the size of each module is 70mm×11mm, the entire battery area is 90mm×90mm, and the dead zone ratio of the module is 20%.

The polymer solar cell module prepared in Example 8 is tested under AM 1.5G simulated sunlight (irradiation intensity is 100 mW/cm2), the performance parameters of the battery are shown in Table 2, and the current-voltage characteristics of the test result The curve (I-V curve) is shown in FIG. 9 .

Table 1 Performance changes of the transparent electrodes of Example 5 and Example 6 after bending

The battery performance parameter of table 2 embodiment 7 and embodiment 8

Example Battery area (cm ² ) Jsc(mA/cm ² ) Voc(V) FF PCE(%) Example 7 1 9.20 0.66 0.51 3.12 Example 8 38.5 1.31 2.85 0.433 1.62

Apparently, the descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those of ordinary skill in the technical field, without departing from the principle of the present invention, some improvements and modifications can also be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention .

Claims (10)

1. transparency electrode, including the flexible substrates (1) and conductive layer (2) being arranged in order from bottom to up it is characterised in that described lead The groove of metallic mesh structure, the upper surface of etching depth to flexible substrates (1), and metallic mesh knot are etched with electric layer (2) In the groove of structure, deposition has metal, and the metal of deposition forms metal gates (3)；

The preparation method of described transparency electrode comprises the following steps:

Step one, metal-oxide transparent electrode the upper connate water soluble conductive polymer of conductive layer (2), obtain polymer thin Film (4)；

Described metal-oxide transparent electrode includes the flexible substrates (1) being arranged in order from bottom to up and conductive layer (2)；

Step 2, using laser etching process in the upper groove etching metallic mesh structure of thin polymer film (4), etching depth reaches Upper surface to flexible substrates (1)；

The linear velocity of described laser ablation is 400mm/s-1500mm/s, and operating power is 0.8w-4.7w；

On the exposed upper surface of flexible substrates (1) after step 3, the upper surface in the thin polymer film (4) not etched and etching Deposit thickness is the metal level (5) of 100nm-200nm, forms metal gates (3)；

Step 4, the metal-oxide transparent electrode with metal gates (3) is put into ultrasonic in deionized water, remove do not etch Thin polymer film (4) and the thin polymer film (4) that do not etch on metal level (5), obtain transparency electrode.

2. transparency electrode according to claim 1 is it is characterised in that the material of described flexible substrates (1) is poly- to benzene two Formic acid glycol ester or polyimides, the material of conductive layer (2) is tin-doped indium oxide, fluorine-doped tin dioxide or mixes aluminum oxidation Zinc, the thickness of conductive layer (2) is 50nm-200nm.

3. transparency electrode according to claim 1 is it is characterised in that described metallic mesh structure is fence structure or grid Lattice structure, the comb mesh pattern of described lattice structure is square, rectangle or positive hexagon cellular shape.

4. transparency electrode according to claim 1 is it is characterised in that the grid line live width of described metallic mesh structure is 50 μ M-200 μm, the distance of two closest parallel grid lines is 0.4mm-5mm, and the volume that conductive layer (2) is etched accounts for conductive layer (2) 3%-15% of cumulative volume.

5. transparency electrode according to claim 1 it is characterised in that described metal be aluminum, silver, copper, gold, nickel, platinum, zinc, Stannum, ferrum, cobalt, manganese, molybdenum, titanium or alloy.

6. the preparation method of the transparency electrode described in claim 1-5 any one is it is characterised in that comprise the following steps:

Step one, metal-oxide transparent electrode the upper connate water soluble conductive polymer of conductive layer (2), obtain polymer thin Film (4)；

Described metal-oxide transparent electrode includes the flexible substrates (1) being arranged in order from bottom to up and conductive layer (2)；

Step 2, using laser etching process in the upper groove etching metallic mesh structure of thin polymer film (4), etching depth reaches Upper surface to flexible substrates (1)；

The linear velocity of described laser ablation is 400mm/s-1500mm/s, and operating power is 0.8w-4.7w；

On the exposed upper surface of flexible substrates (1) after step 3, the upper surface in the thin polymer film (4) not etched and etching Deposit thickness is the metal level (5) of 100nm-200nm, forms metal gates (3)；

Step 4, the metal-oxide transparent electrode with metal gates (3) is put into ultrasonic in deionized water, remove do not etch Thin polymer film (4) and the thin polymer film (4) that do not etch on metal level (5), obtain transparency electrode.

7. the preparation method of transparency electrode according to claim 6 is it is characterised in that in described step one, water solublity is led Electric polymer is pedot:pss.

8. the preparation method of transparency electrode according to claim 6 is it is characterised in that in described step one, deposition poly- The thickness of compound thin film (4) is 50nm-500nm.

9. the preparation method of transparency electrode according to claim 6 is it is characterised in that in described step 4, ultrasonic time For 10s-15s.

10. application in preparing solaode for the transparency electrode described in claim 1-5 any one.