CN110556480A - All-solid-state solar cell based on synchronous deposition quantum dots and preparation method thereof - Google Patents
All-solid-state solar cell based on synchronous deposition quantum dots and preparation method thereof Download PDFInfo
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
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- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/152—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising zinc oxide, e.g. ZnO
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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Abstract
2The invention discloses an all-solid-state solar cell based on synchronous deposition of quantum dots and a preparation method thereof, wherein the device structure comprises a conductive substrate/an electron transmission compact layer/an electron transmission mesoporous layer/the quantum dots/a hole transmission layer/a metal electrode.
Description
Technical Field
The invention relates to an all-solid-state solar cell based on synchronous deposition quantum dots and a preparation method thereof, belonging to the technical field of photovoltaics.
Background
Photovoltaic power generation is receiving increasing attention from governments and scientists of various countries as an important form of current new energy utilization. It is the goal and pursuit of researchers in the academic world to explore new solar cells that combine high efficiency, low cost, and good stability. At present, photovoltaic cells with high market share mainly comprise silicon-based solar cells (monocrystalline silicon, polycrystalline silicon and amorphous silicon) and semiconductor compound thin-film solar cells (cadmium telluride, copper indium gallium selenide and the like). However, the energy consumption in the production process of the silicon-based battery is high; thin film solar cells involve the use of many rare elements. In recent years, perovskite solar cells have gained particular attention, and the photoelectric conversion efficiency has rapidly risen to 25.2%, but the highly undesirable stability of devices becomes a fatal disadvantage, and the industrialization process still needs a long way. Among the next generation of new solar cells, quantum dot solar cells have attracted attention due to their advantages of high theoretical conversion efficiency, adjustable spectral absorption range, multi-exciton generation effect, and various kinds of quantum dots. The liquid quantum dot solar cell which is researched more has the problems of difficult packaging, easy leakage, poor stability and the like, and the problems can be overcome by developing an all-solid-state solar cell device. The development of all-solid-state devices is of great significance in improving the stability of the quantum dot solar cell and promoting the quantum dot solar cell to advance to practicality.
Narrow-bandgap quantum dots, such as lead sulfide (PbS) and silver sulfide (Ag 2 S), can easily expand the spectral absorption range to the near-infrared region by means of quantum size effect, and are a class of broad-spectrum light absorption materials (Yan Dou et al, chem.comm.2018,54, 12598-12601; Jin bouk Heo et al, RSC adv.2017,7,3072-3077) with great potential.
Disclosure of Invention
aiming at the defects in the prior art, the invention provides an all-solid-state solar cell based on synchronous deposition quantum dots and a preparation method thereof. The method synchronously deposits narrow-band gap and wide-band gap quantum dots on a mesoporous film substrate by a continuous ionic layer adsorption and reaction method (SILAR), thereby constructing the high-efficiency all-solid-state photovoltaic device. The invention has the advantages of good device stability, low cost, simple process, easy operation and the like.
The invention relates to an all-solid-state solar cell based on synchronous deposition of quantum dots, wherein the device structure of the all-solid-state solar cell is a conductive substrate/an electron transmission compact layer/an electron transmission mesoporous layer/the quantum dots/a hole transmission layer/a metal electrode. Wherein the thickness of the electron transmission dense layer is 30-70 nm; the thickness of the electron transmission mesoporous layer is 0.5-5 μm.
The invention relates to a preparation method of an all-solid-state solar cell based on synchronous deposition quantum dots, which comprises the following steps:
Step 1: cleaning of conductive substrates
Cutting the conductive substrate according to the required size, sequentially performing ultrasonic treatment for 10-30min by using liquid detergent, deionized water, acetone, ethanol and isopropanol, drying the glass by using an air gun after cleaning, further treating for 10-30min by using an ultraviolet ozone cleaning machine, and storing for later use;
Step 2: preparation of the dense layer
Placing the conductive substrate cleaned in the step 1 in a spin coater, sucking a certain amount of compact layer precursor solution by a liquid transfer gun to drop on the substrate, spin-coating for 5-10s at the rotation speed of 300-;
And step 3: preparation of mesoporous layer
spin-coating the mesoporous layer slurry on the film sample prepared in the step 2 by adopting a spin-coating process, spin-coating for 10-50s at the rotation speed of 1000-;
And 4, step 4: deposition of quantum dots
Synchronously depositing narrow-band gap quantum dots and wide-band gap quantum dots on the film sample prepared in the step 3 by using an SILAR method, namely immersing the film into a prepared cation precursor solution and anion precursor solution in sequence, wherein the immersion time is 0.5-5min each time, and taking out the film after each immersion, fully washing the film by using methanol, and drying the film by using a nitrogen gun; repeating the SILAR cycle process for 1-15 times to obtain quantum dot deposition on the film, wherein the deposition amount can be regulated and controlled by the SILAR cycle times;
And 5: preparation of hole transport layer
Preparing a hole transport layer on the film sample prepared in the step 4 by adopting a spin coating process, spin-coating for 10-50s at the rotation speed of 1000-4000rpm, and then placing on a heating table at the temperature of 80-140 ℃ for heat treatment for 5-30 min;
Step 6: evaporation of electrodes
and (3) placing the sample prepared in the step (5) in a thermal evaporation device, and evaporating a metal electrode to finally finish the preparation of the all-solid-state solar cell, wherein the device structure is a conductive substrate/an electron transmission compact layer/an electron transmission mesoporous layer/quantum dots/a hole transmission layer/a metal electrode.
In the step 1, the conductive substrate is FTO, ITO or AZO conductive glass.
In step 2, the compact layer is TiO 2, ZnO or SnO 2, and the compact layer precursor solution is a corresponding titanium source, zinc source and tin source solution respectively, wherein the titanium source is a 0.1-0.5M bis (acetylacetonate) diisopropyl titanate solution, the solvent is n-butyl alcohol, the zinc source is a 0.5-1.0M zinc nitrate solution, the solvent is a mixed solution of ethanolamine and 2-methoxyethanol (volume ratio of 1:20), the tin source is a 0.05-0.5M tin chloride solution, and the solvent is ethanol.
In the step 3, the mesoporous layer is TiO 2, ZnO or SnO 2, the mesoporous layer slurry is prepared by mixing oxide nanoparticles with the particle size of 10-80nm with ethyl cellulose and terpineol according to the mass ratio of 1 (0.4-0.6) to (3.0-4.0), and obtaining the uniformly dispersed mesoporous layer slurry by combining magnetic stirring and ultrasonic means.
And 4, preparing a mixed cation precursor solution corresponding to the narrow bandgap quantum dots and the wide bandgap quantum dots, wherein the cation precursor solution corresponding to the narrow bandgap PbS and the Ag 2 S quantum dots is a Pb 2+ solution or an Ag + solution, the solvent is ethanol, the cation precursor solution corresponding to the wide bandgap CdS and ZnS quantum dots is a Cd 2+ solution or a Zn 2+ solution or a mixed solution of Cd 2 + and Zn 2+, the solvent is ethanol, the anion precursor solution is an S 2- solution, and the solvent is an aqueous solution or a mixed solution of water and ethanol.
in step 4, the sum of the mixed cation concentrations in the cation precursor solution is the same as the concentration of S 2- in the anion precursor solution, and the cation concentration and the anion concentration are preferably 0.02-0.4M and 0.15M.
In step 5, the hole transport layer is Spiro-OMeTAD or P3 HT.
in step 6, the metal electrode is a gold or silver electrode.
Compared with the prior art, the invention has the beneficial effects that:
the method can obtain the high-performance all-solid-state quantum dot solar cell. The battery prepared by the method has the 'all-solid-state' characteristic, and can overcome the problems of difficult packaging, easy leakage and poor stability of the liquid battery, thereby ensuring excellent device stability. Secondly, the battery prepared by the method has the characteristic of wide spectrum absorption, can improve the photon capturing efficiency and increase the generation quantity of photon-generated carriers. The battery prepared by the method has the characteristic of high charge collection efficiency, and the charge recombination is reduced and the charge collection efficiency is improved by effectively passivating the surface defect state of the narrow-bandgap quantum dots by the wide-bandgap quantum dots. The method has the characteristics of simplicity and easiness in operation, the preparation of the quantum dots is operated at room temperature, the process is simple, the cost is low, and the defects that the conventionally used colloidal quantum dots need to be synthesized under the high-temperature condition (150 plus 300 ℃), the steps are complicated, and a large amount of organic solvent needs to be used are avoided. The method has good application prospect in the aspect of constructing the high-efficiency all-solid-state quantum dot solar cell.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a cross section of a cell (FTO/TiO 2/quantum dot/Spiro-OMeTAD/Ag). As can be seen from FIG. 1, the mesoporous TiO 2 film is porous and has a thickness of about 1.7 μm.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the FTO/TiO 2/quantum dot film from FIG. 2, it can be seen that the mesoporous TiO 2 film has a loose porous structure, which facilitates the in-situ growth of quantum dots therein.
FIG. 3 is an X-ray diffraction pattern of FTO/TiO 2/quantum dot film from FIG. 2, it can be seen that the diffraction peaks of PbS and CdS quantum dots confirm the successful deposition of quantum dots on TiO 2 film, and the peak intensity of quantum dots is much weaker than that of TiO 2 diffraction peak due to the relatively lower loading of quantum dots.
FIG. 4 is the UV-VIS-NIR absorption spectrum of FTO/TiO 2/Quantum dot film from FIG. 4 it can be seen that the photoanode film absorption spectrum of the present invention extends into the NIR region.
FIG. 5 is a photocurrent density-voltage (J-V) curve of a broad-spectrum all-solid-state quantum dot solar cell prepared by the method of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following specific embodiments and accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
1. And cleaning the conductive substrate. Cutting FTO conductive glass according to a certain size, and sequentially performing ultrasonic treatment for 15min by using liquid detergent, deionized water, acetone, ethanol and isopropanol. And after cleaning, drying the glass by using an air gun, further treating for 15min by using an ultraviolet ozone cleaning machine, and storing for later use.
2. preparing a TiO 2 compact layer, dissolving 0.2M bis (acetylacetone) diisopropyl titanate in n-butyl alcohol, mixing and stirring for 30min, further filtering the solution by using a nylon filter tip for later use, placing the FTO substrate cleaned and prepared in the step 1 in a glue homogenizer, sucking a certain amount of the compact layer precursor solution to be dropped on the substrate by using a liquid-transferring gun, spin-coating for 5s at a rotating speed of 500rpm and spin-coating for 30s at a rotating speed of 2000rpm in sequence, then placing the substrate on a heating table, carrying out heat treatment at 135 ℃ for 10min, and further placing the substrate in a muffle furnace to sinter for 40min at 450 ℃.
3. TiO 2 mesoporous layer slurry is prepared by dispersing TiO 2 nanoparticles with the particle size of 20nm, ethyl cellulose and terpineol in an ethanol solution according to a certain proportion, wherein the mass ratio of oxide particles to ethyl cellulose to terpineol is 1 (0.4-0.6) to (3.0-4.0), and magnetic stirring and ultrasonic means are combined to obtain evenly dispersed TiO 2 mesoporous layer slurry, TiO 2 mesoporous layer slurry is spin-coated on a film sample prepared in the step 2 by adopting a spin-coating process, the film is spin-coated for 30s at the rotating speed of 3000rpm, the steps are repeated for 3 times, after the spin-coating is finished, the film is dried for 30min at 70 ℃, and is placed in a muffle furnace for sintering for 40min at 450 ℃.
4. And (3) depositing quantum dots with narrow band gaps and wide band gaps on the film sample prepared in the step (3) synchronously by using an SILAR method, namely, sequentially immersing the TiO 2 film into prepared cation and anion precursor solutions for 2min each time, fully washing the immersed film with ethanol each time, blowing the immersed film with a nitrogen gun each time, preparing the quantum dots on the basis of different types of cation precursor solutions (the solvent is ethanol solution) and anion precursor solutions (the solvent is water), and repeating the SILAR cycle process for 8 times.
5. and preparing a hole transport layer. And (3) preparing a hole transport layer Spiro-OMeTAD on the film sample prepared in the step (4) by adopting a spin coating process, and spin-coating at the rotating speed of 2500rpm for 30 s. Subsequently, the plate was placed on a heating stage at 95 ℃ for heat treatment for 10 min.
6. And (3) carrying out evaporation on the electrode, namely putting the sample prepared in the step (5) into a thermal evaporation device, and evaporating a silver electrode, and finally, finishing the preparation of the all-solid-state quantum dot solar cell, wherein the device structure is FTO glass/TiO 2 compact layer/TiO 2 mesoporous layer/quantum dot/hole transport layer/Ag electrode.
Table 1 solar cell performance based on different types of cationic precursor solutions
As can be seen from table 1, different concentrations of the cationic precursor had a greater effect on device performance.
Example 2:
1. And cleaning the conductive substrate. Cutting FTO conductive glass according to a certain size, and sequentially performing ultrasonic treatment for 15min by using liquid detergent, deionized water, acetone, ethanol and isopropanol. And after cleaning, drying the glass by using an air gun, further treating for 15min by using an ultraviolet ozone cleaning machine, and storing for later use.
2. Preparing a TiO 2 compact layer, dissolving 0.2M bis (acetylacetone) diisopropyl titanate in n-butyl alcohol, mixing and stirring for 30min, further filtering the solution by using a nylon filter tip for later use, placing the FTO substrate cleaned and prepared in the step 1 in a spin coater, sucking a certain amount of the compact layer precursor solution by using a liquid transfer gun to drop on the substrate, spin-coating for 5s at a rotating speed of 500rpm and spin-coating for 30s at a rotating speed of 2000rpm in sequence, then placing the substrate on a heating table, carrying out heat treatment at 135 ℃ for 10min, and further placing the substrate in a muffle furnace to sinter for 40min at 450 ℃.
3. TiO 2 mesoporous layer slurry is prepared by dispersing TiO 2 nanoparticles with the particle size of 20nm, ethyl cellulose and terpineol in an ethanol solution according to a certain proportion, wherein the mass ratio of oxide particles to ethyl cellulose to terpineol is 1 (0.4-0.6) to (3.0-4.0), and magnetic stirring and ultrasonic means are combined to obtain evenly dispersed TiO 2 mesoporous layer slurry, TiO 2 mesoporous layer slurry is spin-coated on a film sample prepared in the step 2 by adopting a spin-coating process, the film is spin-coated for 30s at the rotating speed of 3000rpm, the steps are repeated for 3 times, after the spin-coating is finished, the film is dried for 30min at 70 ℃, and is placed in a muffle furnace for sintering for 40min at 450 ℃.
4. And (3) synchronously depositing narrow-band gap and wide-band gap quantum dots on the film sample prepared in the step (3) by adopting an SILAR method, namely immersing the TiO 2 film into the prepared cation and anion precursor solution for 2min each time, fully washing the immersed film by using methanol each time, and drying the immersed film by using a nitrogen gun, wherein the cation precursor solution is a mixed ethanol solution of 0.01M Pb (CH 3 COO) 2, 0.07M Cd (CH 3 COO) 2 and 0.07M Zn (CH 3 COO) 2, the anion precursor solution is a 0.15M Na 2 S aqueous solution, and the SILAR cycle process is repeated for a certain number of times to obtain a proper amount of quantum dot deposition on the film.
5. And preparing a hole transport layer. And (3) preparing a hole transport layer Spiro-OMeTAD on the film sample prepared in the step (4) by adopting a spin coating process, and spin-coating at the rotating speed of 2500rpm for 30 s. Subsequently, the plate was placed on a heating stage at 95 ℃ for heat treatment for 10 min.
6. and (3) carrying out evaporation on the electrode, namely putting the sample prepared in the step (5) into a thermal evaporation device, and evaporating a silver electrode, and finally, finishing the preparation of the all-solid-state quantum dot solar cell, wherein the device structure is FTO glass/TiO 2 compact layer/TiO 2 mesoporous layer/quantum dot/hole transport layer/Ag electrode.
TABLE 2 solar cell Performance based on different SILAR cycle times
As can be seen from table 2, different numbers of SILAR cycles have a greater effect on device performance.
example 3:
1. and cleaning the conductive substrate. Cutting FTO conductive glass according to a certain size, and sequentially performing ultrasonic treatment for 15min by using liquid detergent, deionized water, acetone, ethanol and isopropanol. And after cleaning, drying the glass by using an air gun, further treating for 15min by using an ultraviolet ozone cleaning machine, and storing for later use.
2. Preparing a compact layer by respectively adopting TiO 2, ZnO and SnO 2 as compact layers, wherein precursor solutions of the compact layers are respectively 0.2M bis (acetylacetone) diisopropyl titanate solution, a solvent is n-butyl alcohol, a zinc source is 0.8M zinc nitrate solution, the solvent is a mixed solution of ethanolamine and 2-methoxy ethanol (volume ratio is 1:20), a tin source is 0.1M tin chloride solution, and the solvent is ethanol, placing the FTO substrate cleaned and prepared in the step 1 in a spin coater, sucking a certain amount of the precursor solution of the compact layers on the substrate by a liquid transfer gun, spin-coating for 5s at a rotating speed of 500rpm and spin-coating for 30s at a rotating speed of 2000rpm in sequence, then placing the substrate on a heating table, carrying out heat treatment at 135 ℃ for 10min, and further placing the substrate in a muffle furnace and sintering for 40min at 450 ℃.
3. preparing a mesoporous layer, namely respectively adopting TiO 2, ZnO and SnO 2 as the mesoporous layer, dispersing TiO 2 and ZnO or SnO 2 nano particles with the particle size of 20nm, ethyl cellulose and terpineol in an ethanol solution according to a certain proportion, wherein the mass ratio of the oxide particles to the ethyl cellulose to the terpineol is 1, (0.4-0.6) to (3.0-4.0), combining magnetic stirring and ultrasonic means to obtain uniformly dispersed mesoporous layer slurry, adopting a spin coating process to spin-coat the mesoporous layer slurry on the film sample prepared in the step 2, spin-coating for 30s at the rotating speed of 3000rpm, repeating for 3 times, after the spin coating is finished, drying the film at 70 ℃ for 30min, and sintering the film in a muffle furnace at 450 ℃ for 40 min.
4. And (3) synchronously depositing narrow-band gap and wide-band gap quantum dots on the film sample prepared in the step (3) by adopting an SILAR method, namely immersing the film into the prepared cation and anion precursor solutions in sequence, wherein the immersion time is 2min each time, fully washing the film by using methanol after taking out the film for each immersion, and drying the film by using a nitrogen gun, wherein the cation precursor solution is a mixed ethanol solution of 0.01M Pb (CH 3 COO) 2, 0.07M Cd (CH 3 COO) 2 and 0.07M Zn (CH 3 COO) 2, the anion precursor solution is a 0.15M Na 2 S aqueous solution, and repeating the SILAR cycle process for 8 times.
5. And preparing a hole transport layer. And (3) preparing a hole transport layer Spiro-OMeTAD on the film sample prepared in the step (4) by adopting a spin coating process, and spin-coating at the rotating speed of 2500rpm for 30 s. Subsequently, the plate was placed on a heating stage at 95 ℃ for heat treatment for 10 min.
6. And (5) evaporation of the electrode. And (5) placing the sample prepared in the step (5) in a thermal evaporation device, and evaporating a silver electrode. And finally, completing the preparation of the all-solid-state quantum dot solar cell, wherein the device structure is FTO glass/a compact layer/a mesoporous layer/quantum dots/a hole transport layer/an Ag electrode.
Table 3 solar cell performance based on different electron transport materials
as can be seen from table 3, different numbers of SILAR cycles have a greater effect on device performance.
Claims (10)
1. An all-solid-state solar cell based on synchronous deposition quantum dots is characterized in that: the device structure is conductive substrate/electron transmission compact layer/electron transmission mesoporous layer/quantum dot/hole transmission layer/metal electrode.
2. the all-solid-state solar cell according to claim 1, characterized in that:
The thickness of the electron transmission dense layer is 30-70 nm; the thickness of the electron transmission mesoporous layer is 0.5-5 μm.
3. The preparation method of the all-solid-state solar cell based on the synchronously deposited quantum dots, which is characterized by comprising the following steps:
Step 1: cleaning of conductive substrates
cutting the conductive substrate according to the required size, sequentially performing ultrasonic treatment for 10-30min by using liquid detergent, deionized water, acetone, ethanol and isopropanol, drying the glass by using an air gun after cleaning, further treating for 10-30min by using an ultraviolet ozone cleaning machine, and storing for later use;
Step 2: preparation of the dense layer
Placing the conductive substrate cleaned in the step 1 in a spin coater, sucking a certain amount of compact layer precursor solution by a liquid transfer gun to drop on the substrate, spin-coating for 5-10s at the rotation speed of 300-;
And step 3: preparation of mesoporous layer
Spin-coating the mesoporous layer slurry on the film sample prepared in the step 2 by adopting a spin-coating process, spin-coating for 10-50s at the rotation speed of 1000-;
And 4, step 4: deposition of quantum dots
Synchronously depositing narrow-band gap quantum dots and wide-band gap quantum dots on the film sample prepared in the step 3 by using an SILAR method, namely immersing the film into a prepared cation precursor solution and anion precursor solution in sequence, wherein the immersion time is 0.5-5min each time, and taking out the film after each immersion, fully washing the film by using methanol, and drying the film by using a nitrogen gun; repeating the SILAR cycle process for 1-15 times to obtain quantum dot deposition on the film, wherein the deposition amount can be regulated and controlled by the SILAR cycle times;
and 5: preparation of hole transport layer
Preparing a hole transport layer on the film sample prepared in the step 4 by adopting a spin coating process, spin-coating for 10-50s at the rotation speed of 1000-4000rpm, and then placing on a heating table at the temperature of 80-140 ℃ for heat treatment for 5-30 min;
Step 6: evaporation of electrodes
and (5) placing the sample prepared in the step (5) in a thermal evaporation device, and evaporating the metal electrode to finally finish the preparation of the all-solid-state solar cell.
4. The production method according to claim 3, characterized in that:
In the step 1, the conductive substrate is FTO, ITO or AZO conductive glass.
5. the production method according to claim 3, characterized in that:
In step 2, the precursor solutions of the compact layer are respectively corresponding titanium source, zinc source and tin source solutions; wherein the titanium source is 0.1-0.5M bis (acetylacetonate) diisopropyl titanate solution, the zinc source is 0.5-1.0M zinc nitrate solution, and the tin source is 0.05-0.5M tin chloride solution.
6. The production method according to claim 3, characterized in that:
In the step 3, oxide nanoparticles with the particle size of 10-80nm are mixed with ethyl cellulose and terpineol according to the mass ratio of 1 (0.4-0.6) to (3.0-4.0), and magnetic stirring and ultrasonic means are combined to obtain uniformly dispersed mesoporous layer slurry, wherein the oxide nanoparticles are TiO 2, ZnO or SnO 2.
7. The production method according to claim 3, characterized in that:
in step 4, the cation precursor solution is a mixed cation precursor solution corresponding to the preparation of narrow bandgap quantum dots and wide bandgap quantum dots, wherein the cation precursor solution corresponding to the narrow bandgap PbS and Ag 2 S quantum dots is a Pb 2+ solution or an Ag + solution, the cation precursor solution corresponding to the wide bandgap CdS and ZnS quantum dots is a Cd 2+ solution or a Zn 2+ solution or a mixed solution of Cd 2+ and Zn 2+, and the anion precursor solution is an S 2- solution.
8. The method of claim 7, wherein:
In step 4, the sum of the mixed cation concentrations in the cation precursor solution is the same as the concentration of S 2- in the anion precursor solution, and is 0.02-0.4M.
9. The production method according to claim 3, characterized in that:
In step 5, the hole transport layer is Spiro-OMeTAD or P3 HT.
10. The production method according to claim 3, characterized in that:
in step 6, the metal electrode is a gold or silver electrode.
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