CN109560202B - Perovskite battery with nano structure at anode grating protrusion and preparation method thereof - Google Patents
Perovskite battery with nano structure at anode grating protrusion and preparation method thereof Download PDFInfo
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- CN109560202B CN109560202B CN201811399195.6A CN201811399195A CN109560202B CN 109560202 B CN109560202 B CN 109560202B CN 201811399195 A CN201811399195 A CN 201811399195A CN 109560202 B CN109560202 B CN 109560202B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/87—Light-trapping means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a perovskite battery with a nano structure at the convex part of an anode grating, which comprises glass, wherein an anode layer, a hole transmission layer, an active layer, an electron transmission layer and a cathode layer are sequentially arranged on the glass, the anode layer is provided with gratings which periodically protrude out of the anode layer, and the surface of the convex part of the gratings is provided with an insulating nano structure. The invention also discloses a preparation method of the perovskite battery with the nano structure at the convex part of the anode grating. The invention has the advantages that: the perovskite battery with the nano structure at the convex part of the anode grating is provided, and the light absorption of the solar battery on incident light with the wavelength within the range of 500-800 nm is improved by utilizing the composite structure of the nano grating and the insulating nano particles, so that the photoelectric conversion efficiency of a battery device is improved. The current carrier recombination efficiency at the anode interface is reduced, the current carrier collection efficiency is improved, and the series resistance of the battery is reduced. The nano grating and the insulating nano structure can be obtained by only one photoetching process, so that the cost is saved.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite cell with a nanostructure at the convex part of an anode grating and a preparation method thereof.
Background
Active layer material (CH) for perovskite solar cell 3 NH 3 PbX 3 X = Cl, Br, I) has high light absorption efficiency and long carrier diffusion length, and is considered as the thin film solar cell technology with the most potential for development in the future. At present, the maximum photoelectric conversion efficiency of the perovskite solar cell can reach 22%. The intrinsic absorption spectrum of the perovskite material is below 800nm, wherein the wavelength of less than 500nm is the strong absorption range of the perovskite material, and the absorption efficiency of the perovskite material to red and yellow light with the wavelength of 600-800 nm is low.
In the prior art, nanoparticles are typically introduced to enhance absorption of perovskite materials at the red-yellow range. The conventional method for introducing nanoparticles is a coating method, in which a solution containing nanoparticles is coated on a thin film, and the solution is heated to volatilize a solvent, so that the nanoparticles are deposited on the thin film. The positions of the nano particles deposited by the method are randomly distributed, and for the perovskite battery device, the randomly distributed nano particles have limited light absorption enhancement effect due to the high refractive index of the perovskite material. Furthermore, the process of coating the nanoparticles often introduces solvents or other impurities into the perovskite material, resulting in a dramatic reduction in the performance of the perovskite. Light enters an active layer of the device from the anode and can generate high-density photon-generated carriers near an anode interface, so that the carrier recombination efficiency is directly influenced by the impurity density of the anode interface, the series resistance of the device can be effectively reduced by reducing the interface state density and the impurity density of the anode interface, and the load performance of the device is improved.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a perovskite solar cell with a nanostructure at the projection of an anode grating and a method for manufacturing the same, which are mainly used to enhance the absorption of red light and yellow light by the perovskite solar cell.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the perovskite battery with the nanostructure at the convex part of the anode grating comprises glass, wherein an anode layer, a hole transmission layer, an active layer, an electron transmission layer and a cathode layer are sequentially arranged on the glass, the anode layer is provided with the grating which periodically protrudes out of the anode layer, and the surface of the convex part of the grating is provided with the insulating nanostructure. Sunlight is incident from the glass to the inside of the device.
Further, the anode layer is made of Indium Tin Oxide (ITO) or transparent Aluminum Zinc Oxide (AZO).
Further, the cathode layer is made of silver (Ag) or gold (Au) or aluminum (Al).
Furthermore, the period of the grating is 200-400 nm, the height of the grating is 10-70 nm, and the grating is rectangular or trapezoidal.
The invention also discloses a preparation method of the perovskite battery with the nano structure at the convex part of the anode grating, which comprises the following steps:
step 1: depositing an anode layer and an insulating layer film on the glass;
step 2: coating photoresist on the insulating layer film, and exposing the photoresist;
and step 3: developing the photoresist, etching the insulating layer film to form an insulating nano structure which periodically protrudes out of the anode layer, etching the anode layer with a certain thickness by using the insulating nano structure formed after etching as a mask to form a grating, and removing the photoresist;
and 4, step 4: sequentially manufacturing a hole transport layer, an active layer and an electron transport layer above the grating and the insulating nano structure;
and 5: and depositing a cathode layer on the top of the electron transmission layer, thereby preparing the perovskite battery with the nano structure at the convex part of the anode grating.
Further, step 31 is further included between step 3 and step 4: heating to the melting point of the insulating layer material to melt the insulating nanostructure, and cooling to obtain hemispherical or semi-ellipsoidal nanoparticles. When the melting point of glass and all other materials on the chip is higher than that of the materials to be melted and reflowed, a method of directly heating the glass substrate can be utilized; when the melting point of any other material on the glass and the chip is lower than that of the material to be thermally melted and reflowed, the material with the low melting point is directly melted by a direct heating mode, so that the laser is selected to be thermally annealed, irradiates an insulating layer on the grating to be melted, is removed, and then reflows into a spherical shape.
Further, the heating method of the insulating nanostructure is to directly heat the glass substrate or to irradiate the surface of the insulating layer with laser to melt the insulating layer.
Furthermore, the diameter of the nano particles is 70-180 nm.
Further, the method for depositing the anode layer in step 1 is sputtering or evaporation.
Further, the method for depositing the insulating layer film in step 1 is chemical vapor deposition.
Further, the exposure of the photoresist in step 2 is mask exposure or holographic exposure, and the photoresist is positive or negative.
Further, the method for etching the insulating layer thin film in step 3 is dry etching or wet etching, and the method for etching the cathode layer is dry etching.
Further, the method for manufacturing the hole transport layer, the active layer and the electron transport layer in step 4 is blade coating.
Further, the anode layer is a transparent Indium Tin Oxide (ITO) film or a transparent Aluminum Zinc Oxide (AZO) film, and the cathode layer is one of a silver (Ag) film, a gold (Au) film and an aluminum (Al) film.
Further, the insulating layer film is one of a silicon dioxide (SiO 2) film, a silicon (Si) film and a PMMA film.
The invention has the following beneficial effects: the composite structure of the nanometer grating and the insulating nanometer particles is utilized to scatter incident light into the device, so that the effective optical path of the incident light with the wavelength within the range of 500-800 nm is increased, and the absorption of red light and yellow light by the perovskite solar cell is further improved. The nano grating and the insulating nano structure can be obtained by only one photoetching process, the process is mature, and the cost is saved. Compared with the traditional randomly distributed nano particle structure obtained by adopting a coating method, the self-alignment process is adopted in the invention, so that the insulating nano particles and the grating have one-to-one corresponding position relationship, and the nano particles are completely positioned at the convex position of the grating. In the perovskite solar cell device structure, the nano particle and periodic grating composite structure with the corresponding relation has a better absorption enhancing effect than the nano particle and periodic grating composite structure which are randomly distributed.
Drawings
Fig. 1 is a schematic structural view of a solar cell according to the present invention.
Fig. 2 is a flow chart of a process for manufacturing a solar cell according to the present invention.
Fig. 3 is a schematic structural diagram of a strip-shaped comb electrode.
Fig. 4 is a schematic view of the shape of the insulating nanostructure when the heating step is omitted.
Description of the main component symbols: 10. glass; 100. a silicon dioxide (SiO 2) film; 1. an anode layer; 2. a hole transport layer; 3. an active layer; 4. an electron transport layer; 5. a cathode layer; 6. a grating; 7. an insulating nanostructure; 8. photoresist; 9. and (5) masking the film plate.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
As shown in fig. 1, the perovskite battery with the nanostructure at the convex part of the anode grating comprises glass 10, wherein an anode layer 1, a hole transport layer 2, an active layer 3, an electron transport layer 4 and a cathode layer 5 are sequentially arranged on the glass 10, the anode layer 1 is a transparent ITO thin film or an AZO thin film, and the cathode layer 5 is a metal thin film made of materials such as gold (Au), silver (Ag), aluminum (Al) and the like. The anode layer 1 is provided with gratings 6 protruding from the anode layer 1 periodically, the surface of the protruding part of the grating 6 is provided with an insulating nano structure 7, the insulating nano structure 7 is made of silicon dioxide (SiO 2), silicon (Si) or PMMA, the insulating nano structure is hemispherical or semi-ellipsoidal, and the diameter of the insulating nano structure is 70-180 nm. The period of the grating 6 is 200-400 nm, the height is 10-70 nm, and the shape is rectangular or trapezoidal.
The preparation method of the perovskite solar cell with the nano structure at the convex part of the anode grating as shown in fig. 2 comprises the following steps:
step 1: a transparent conductive film, which is an Indium Tin Oxide (ITO) film or an Aluminum Zinc Oxide (AZO) film, is deposited on the glass 10 by sputtering or evaporation, and a silicon dioxide (SiO 2) film 100 is deposited on the transparent conductive film by chemical vapor deposition.
Step 2: coating a photoresist 8 on a silicon dioxide (SiO 2) film 100, placing a mask plate 9 above the photoresist 8, and performing mask exposure on the photoresist 8; the photoresist 8 may be subjected to full-area exposure by a holographic exposure method.
And step 3: and etching the silicon dioxide (SiO 2) film 100 to form the insulating nano structure 7 by dry etching to etch the transparent conductive film with a certain thickness by dry etching or wet etching to remove the photoresist 8. The strip comb-shaped electrode can also be formed by controlling the etching depth of the transparent conductive film, as shown in fig. 3.
Step 31: heating to the melting point of the silicon dioxide (SiO 2) film 100 to melt the insulating nano structure 7, cooling to form hemispherical or semi-ellipsoidal nano particles, wherein the diameter of the prepared nano particles is 70-180 nm, and the heating method is to melt the insulating nano structure 7 by adopting laser irradiation; this step can also be omitted, in which case the insulating nanostructures 7 do not form a hemispherical or semi-ellipsoidal shape, as shown in fig. 4.
And 4, step 4: and sequentially coating a hole transport layer 2, an active layer 3 and an electron transport layer 4 on the manufactured composite nano grating in a blade coating mode.
And 5: and a metal film is deposited on the top of the electron transmission layer 4, and the metal film is made of gold (Au), silver (Ag) or aluminum (Al) and the like, so that the perovskite battery with the nano structure at the convex part of the anode grating is prepared.
The following table compares the performance of the perovskite cell with the nanostructure at the anode grating protrusions to the conventional cell:
while the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (14)
1. The preparation method of the perovskite battery with the nanostructure at the convex part of the anode grating is characterized in that the perovskite battery with the nanostructure at the convex part of the anode grating comprises glass, an anode layer, a hole transport layer, an active layer, an electron transport layer and a cathode layer are sequentially arranged on the glass, the anode layer is provided with the grating which periodically protrudes out of the anode layer, and the surface of the convex part of the grating is provided with the insulating nanostructure;
also comprises the following steps:
step 1: depositing an anode layer and an insulating layer film on the glass;
step 2: coating photoresist on the insulating layer film, and exposing the photoresist;
and step 3: developing the photoresist, etching the insulating layer film to form an insulating nano structure which periodically protrudes out of the anode layer, etching the anode layer with a certain thickness by using the insulating nano structure formed after etching as a mask to form a grating, and removing the photoresist;
and 4, step 4: sequentially manufacturing a hole transport layer, an active layer and an electron transport layer above the grating and the insulating nano structure;
and 5: and depositing a cathode layer on the top of the electron transmission layer, thereby preparing the perovskite battery with the nano structure at the convex part of the anode grating.
2. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: the anode layer is made of transparent indium tin oxide or transparent aluminum zinc oxide.
3. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: the cathode layer is made of silver or gold or aluminum.
4. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: the period of the grating is 200-400 nm, the height of the grating is 10-70 nm, and the grating is rectangular or trapezoidal.
5. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 4, wherein: step 31 is also included between step 3 and step 4: heating to the melting point of the insulating nano material to melt the insulating nano structure, and cooling to form hemispherical or semi-ellipsoidal nano particles.
6. The method of claim 5 for preparing a perovskite battery with a nanostructure on the projection of an anode grating, wherein the method comprises the following steps: the heating method of the insulating nano structure is to directly heat the glass or to melt the glass by laser irradiation.
7. The method of claim 5 for preparing a perovskite battery with a nanostructure on the projection of an anode grating, wherein the method comprises the following steps: the diameter of the nano particles is 70-180 nm.
8. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: the method for depositing the anode layer in the step 1 is sputtering or evaporation.
9. The method for preparing a perovskite battery with a nanostructure on the convex part of an anode grating as claimed in claim 1, wherein the method comprises the following steps: the method for depositing the insulating layer film in the step 1 is chemical vapor deposition or blade coating.
10. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: and in the step 2, the exposure of the photoresist adopts mask exposure or holographic exposure, and the photoresist is positive photoresist or negative photoresist.
11. The method for preparing a perovskite battery with a nanostructure on the convex part of an anode grating as claimed in claim 1, wherein the method comprises the following steps: and 3, etching the insulating layer film by using a dry etching method or a wet etching method, and etching the anode layer by using a dry etching method.
12. The method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in claim 1, wherein: and 4, blade coating is adopted as a method for manufacturing the hole transport layer, the active layer and the electron transport layer in the step 4.
13. A method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in any one of claims 1 to 12, wherein: the anode layer is a transparent indium tin oxide film or a transparent aluminum zinc oxide film, and the cathode layer is one of a silver film, a gold film and an aluminum film.
14. A method of making a perovskite battery with nanostructures on the projections of an anode grating as claimed in any one of claims 1 to 12, wherein: the insulating layer film is one of a silicon dioxide film, a silicon film and a PMMA film.
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