CN116234334A - Tin-lead mixed perovskite solar cell based on double-layer metal electrode and preparation method thereof - Google Patents
Tin-lead mixed perovskite solar cell based on double-layer metal electrode and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 claims description 12
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
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- -1 iodide ions Chemical class 0.000 abstract description 2
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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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Abstract
The invention discloses a preparation method of a double-layer metal serving as an electrode for replacing gold/silver and applied to a low-band-gap tin-lead mixed perovskite solar cell. The perovskite solar cell device mainly comprises transparent conductive glass, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a first metal electrode layer and a second metal electrode layer. The perovskite component mainly comprises formamidino organic molecules, inorganic molecules with a half tin and half lead proportion and iodide ions, wherein the first metal electrode layer is reduced metal tin, and the second metal electrode layer is non-noble metal. The preparation method comprises the following steps: spin-coating a hole transport layer on a clean ITO glass substrate; then spin coating tin-lead mixed perovskite film; then spin coating an electron transport layer; and finally evaporating the first metal electrode layer and the second metal electrode layer. The battery device prepared by the invention has higher photoelectric conversion efficiency and more excellent stability, particularly air preservation stability, and lays a good foundation for the practical application of perovskite solar cells.
Description
Technical Field
The invention relates to a preparation method of a low-band-gap tin-lead mixed perovskite solar cell by taking double-layer metal instead of gold/silver as an electrode, belonging to the technical field of solar cells.
Background
With the rapid development of society, the demand for energy is increasing, and new sustainable clean energy is receiving extensive attention from scientists. Organic-inorganic Perovskite Solar Cells (PSCs) have been intensively studied for their excellent photoelectric properties, and their photoelectric conversion efficiency has reached surprisingly 25.7%. The highest efficiency is still maintained for lead-based perovskite, and scientists gradually shift the eyes to metal tin with similar properties to lead in order to reduce the environmental pollution and human health problems caused by lead metal, and tin-based perovskite solar cells are also coming to the moment of rapid development. In recent years, research into Sn or Sn-Pb based PSCs has also progressed significantly, wherein the Power Conversion Efficiency (PCE) of Sn-Pb based hybrid PSCs has exceeded 20%. However, tin-based perovskite still faces Sn 2+ And (3) the problem of easy oxidation is that perovskite is easy to decompose, so that the device is low in efficiency and poor in stability. Various methods have been employed to reduce oxidation, such as the introduction of antioxidants, component engineering, etc., to improve efficiency, but long-term stability, particularly air stability, remains a serious challenge.
On the one hand, the current narrow-band gap Sn-Pb PSCs (> 20%) with higher PCE mainly take FA-MA mixed A-site cations as main components, and when the content of volatile MA cations exceeds 30%, the perovskite structure is unstable, so that the stability of the device is poor. Yan et al have also demonstrated in their previous studies that decreasing the MA ratio to 10% can significantly improve the photostability of Sn-Pb PSCs. However, the photovoltaic performance of FA-based Sn-Pb mixed PSCs has so far fallen behind that of FA-MA mixed corresponding devices.
On the other hand, conventional perovskite solar cells commonly use noble metal gold/silver or carbon paste as a counter electrode. Noble metal gold/silver is expensive, and the battery device has the problem of high cost and difficulty in realizing large-scale application. Meanwhile, halide which is easily decomposed by perovskite is easy to diffuse through the electron transport layer and the electrode to generate oxidation-reduction reaction to corrode the electrode, so that the service life of the device is reduced, and the long-term stability is poor. While carbon electrodes have advanced, their battery efficiency has far behind that of metal electrodes. In order not to sacrifice efficiency, the reduction of the device cost is achieved while the reduction of the decomposition rate of perovskite halides improves the operational stability.
At present, a perovskite solar cell with low cost, high photoelectric conversion rate and good stability is not yet available.
Disclosure of Invention
In order to solve the problems of high cost and instability faced by the application of the existing gold/silver noble metal to the tin-lead perovskite solar cell as an electrode, and the problem of long-term stability caused by easy oxidation of tin-based perovskite, the invention aims to provide a method for replacing gold/silver by using a double-layer metal structure as an electrode, wherein the defect caused by easy oxidation of divalent tin in perovskite is reduced by using a metal Sn with reducibility as a lower layer metal, and the conductivity of the cell is increased and the cost is reduced by using a non-noble metal Cu with better conductivity as an upper layer metal. The device prepared by the invention has the characteristics of high efficiency, good nitrogen storage stability and more excellent air placement stability.
The invention mainly aims at the fact that the proportion of the pure FA-based tin and lead without MA ions is 1:1, the perovskite solar cell uses metallic tin and metallic copper with better conductivity as double-layer metallic electrodes to replace the traditional gold/silver electrodes for the first time, thereby greatly reducing the overall cost of the device and simultaneously obtaining good photoelectric conversion efficiency. Most notably, the metallic tin has a certain reducibility, can not only effectively block the diffusion of halide ions to stabilize the electrode, but also can be used as an antioxidant to reduce Sn in perovskite 2+ The oxidation-stable perovskite of (C) and metallic tin are expected to form SnO 2 As an electron transport layer, the extraction ability of electrons is improved and the transport of holes is prevented. The prepared device has good photoelectric performance and excellent air stability, and lays a foundation for practical application of perovskite solar cells.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a tin-lead mixed perovskite solar cell based on a double-layer metal electrode, which is characterized in that: the light-emitting diode comprises a transparent conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a first metal electrode layer and a second electrode layer which are sequentially stacked on the transparent conductive substrate; the first metal electrode layer includes a metal having a reducing property; the second metal electrode layer includes a non-noble metal having good electrical conductivity.
Further, the transparent conductive substrate is ITO conductive glass; the hole transport layer is inorganic metal oxide NiO x The method comprises the steps of carrying out a first treatment on the surface of the The tin-lead mixed perovskite light absorption layer is HC (NH) 2 ) 2 Pb 0.5 Sn 0.5 I 3 A film; the electron transmission layer is PCBM; the first metal electrode layer is a tin-based metal with reducibility; the second metal electrode layer is a copper metal with low price, stability and good conductivity.
In a second aspect, the invention provides a method for preparing the tin-lead mixed perovskite solar cell according to the first aspect, which comprises the following steps:
(1) Cleaning the transparent conductive substrate;
(2) Spin-coating NiOx aqueous solution on a transparent conductive substrate, and annealing on a heating plate to obtain a NiOx hole transport layer;
(3) Uniformly spin-coating a tin-lead mixed perovskite precursor solution on the hole transport layer in an inert atmosphere, and annealing to obtain a tin-lead mixed perovskite light absorption layer;
(4) Dissolving PCBM in chlorobenzene to prepare a solution, and uniformly spin-coating the solution on a perovskite light absorption layer to form an electron transport layer;
(5) First evaporating a first metal electrode layer on an electron transport layer;
(6) And evaporating a second metal electrode layer on the first metal electrode layer.
Further, in the step (1), the method for cleaning the transparent substrate is as follows: firstly, deionized water, absolute ethyl alcohol, isopropanol, acetone and absolute ethyl alcohol are sequentially used for cleaning, then the cleaning solution is placed in the absolute ethyl alcohol for standing and preservation, when the cleaning solution is used, high-purity nitrogen is used for drying, and finally ultraviolet ozone treatment is carried out to ensure that the surface of the cleaning solution has good wettability.
Further, in the step (2), niO x The preparation method of the aqueous solution comprises the following steps: reacting ammonia water with nickel nitrate hexahydrate aqueous solution, stirring, standing, taking out supernatant, centrifugally washing lower powder with deionized water, vacuum drying the obtained product, and annealing to obtain NiO x A powder; the NiO obtained is then treated x Dissolving the powder in water to obtain NiO x An aqueous solution. Preferably, the annealing temperature is 270 ℃ and the annealing time is 2 hours.
Further, in the step (2), the spinning speed is 4000rpm/s, the spinning time is 30-60 s, and the annealing treatment is performed for 20-40 min at the temperature of 100-200 ℃ on a heating plate.
Further, in the step (3), the preparation method of the tin-lead perovskite solution is as follows: HC (NH) 2 ) 2 SnI 3 And HC (NH) 2 ) 2 PbI 3 Uniformly mixing the precursor solution and filtering; and uniformly dripping the tin-lead mixed perovskite precursor liquid onto the hole transport layer for spin coating, uniformly and rapidly dripping a chlorobenzene anti-solvent when the spin coating is finished, transferring the perovskite intermediate phase film onto a heating table for heating and then annealing treatment, thus obtaining the tin-lead mixed perovskite light absorption layer.
Further, the HC (NH) 2 ) 2 SnI 3 And HC (NH) 2 ) 2 PbI 3 The molar ratio of (2) is 1:1.
Further, in the step (3), the annealing temperature is 120-140 ℃ and the annealing time is 10-30 min.
Further, in the step (4), the dosage ratio of PCBM powder to chlorobenzene is 20-40 mg/1 mL; the spin speed is 2000-3000 rpm/s, and the spin time is 30s.
Further, in the step (5), the first metal electrode layer is uniformly deposited on the electron transport layer by a thermal evaporation method under vacuum condition, and the film thickness is controlled to be 10-30 nm.
Further, in the step (6), a second metal electrode layer is uniformly deposited on the first metal electrode layer by a thermal evaporation method under a vacuum condition, and the film thickness is controlled to be 100-150 nm.
Compared with the prior art, the technical scheme has the following beneficial effects:
(1) The invention adopts the tin metal with reducibility as the lower electrode, can be used as an antioxidant to slow down the oxidation of bivalent tin ions in perovskite, and meanwhile, the tin metal is hopeful to be generated into SnO 2 As an electron transport layer, the extraction capacity of electrons is improved and the entry of holes is prevented, so that the photoelectric conversion efficiency and the air stability of the perovskite solar cell are improved.
(2) The invention adopts the non-noble metal and the metal copper with better conductivity as the upper electrode, can effectively replace the problem of higher cost faced by the traditional gold/silver electrode, and takes an important step for the tin-lead perovskite solar cell to be separated from a glove box to practical application.
(3) The tin-lead mixed perovskite solar cell prepared by the method has the advantages of low preparation cost, high photoelectric conversion efficiency, good nitrogen storage stability, excellent air stability and the like.
Drawings
Fig. 1 is a device structure diagram of a perovskite solar cell.
Wherein in FIG. 1, the transparent conductive substrate is 1-ITO, the hole transport layer is 2-hole, the light absorption layer is 3-perovskite, the electron transport layer is 4-electron, the tin electrode layer is 5-metal, and the copper electrode layer is 6-metal.
Fig. 2 is an SEM plan view of the NiOx thin film prepared in comparative example 1.
Fig. 3 is an SEM plan view of the NiOx film produced in example 2.
Fig. 4 is an SEM plan view of the perovskite thin film produced in example 2.
FIG. 5 is an SEM sectional view of a perovskite thin film as produced in example 2.
Fig. 6 is an XRD pattern of the perovskite thin film produced in example 2.
FIG. 7 is an absorption diagram of the perovskite thin film produced in example 2.
Fig. 8 is a graph of current density versus voltage for the perovskite solar cell produced in comparative example 1.
Fig. 9 is a graph of current density versus voltage for the perovskite solar cell produced in example 1.
Fig. 10 is a graph of current density versus voltage for the perovskite solar cell produced in example 2.
Fig. 11 is a graph of nitrogen protection stability in the dark of the unpackaged perovskite solar cell produced in example 2.
Detailed Description
The present invention will be described in further detail below with reference to the attached drawings and specific embodiments, which are only a part of the present invention, but not all the present invention, and any technical improvements and modifications related to the present invention will fall within the protection scope of the present invention.
Example 1
(1) Cleaning a substrate: cutting the large transparent conductive ITO glass into uniform size of 1.5cm x 1.3cm by using a cutting knife, then flushing the ITO surface with ultrapure water, and performing ultrasonic cleaning treatment in an ultrasonic machine for 10-15 min. Then sequentially placing the materials in absolute ethyl alcohol, isopropanol, acetone and absolute ethyl alcohol solution for ultrasonic cleaning for 10-15 min, placing the materials in the absolute ethyl alcohol solution for standing and preserving after cleaning, drying the surface by high-purity nitrogen when the materials are used, and placing the materials in an ultraviolet ozone instrument for 15-30 min to enhance the wettability of the materials.
(2) Hole transport layer preparation: firstly, weighing nickel nitrate hexahydrate, dispersing and dissolving in ultrapure water, slowly dripping ammonia water, stirring and reacting for 30-60 min, standing for 30min after the reaction is completed, pouring out supernatant, centrifugally washing lower-layer solid for 3 times by using ultrapure water, placing in a culture dish, spreading, vacuum drying overnight at 100 ℃ in a vacuum drying oven, crushing the dried powder, calcining in a muffle furnace for 2 h, and calcining at 250-300 ℃ to obtain NiO x Nanoparticle powder. NiO is then added to x Dispersing and dissolving the powder into ultrapure water to prepare NiO with the concentration of 5-10 mg/ml x An aqueous solution. After filtration, 50ul of the solution is taken out by a pipette and evenly dropped on the prepared conductive glass substrate, spin coating is carried out by a spin coater with the rotating speed of 4000rpm/s,spin coating for 30s, and annealing at 150deg.C for 30min on a heating table to obtain NiO x And a hole transport layer.
(3) Perovskite light absorption layer preparation: the prepared HC (NH) 2 ) 2 SnI 3 And HC (NH) 2 ) 2 PbI 3 Precursor solution is prepared according to a mole ratio of 1:1 for 30-60 min to be uniformly mixed to obtain HC (NH) 2 ) 2 Pb 0.5 Sn 0.5 I 3 Perovskite solution. And (2) sucking 45ul of perovskite precursor solution, uniformly dripping the perovskite precursor solution onto the hole transmission layer prepared in the step (2), spin-coating by using a spin coater at a rotation speed of 5000rpm/s for 30s, rapidly and uniformly dripping 200ul of chlorobenzene anti-solvent solution at the time of 10-20 s of the last, and then moving the solution onto a heating plate to be annealed at 130 ℃ for 20min to obtain the perovskite light absorption layer.
(4) And (3) preparing an electron transport layer: firstly, weighing 30mg of PCBM powder sample, then adding 1ml of chlorobenzene solution, stirring uniformly, and filtering to prepare 30mg/ml of PCBM solution. And (3) sucking 35ul of the perovskite light absorption layer by using a pipetting gun, uniformly dripping the perovskite light absorption layer onto the perovskite light absorption layer prepared in the step (3), and spin-coating by using a spin coater at a rotating speed of 3000rpm/s for 30s to obtain the PCBM electron transport layer.
(5) Electrode evaporation: a layer of tin metal is uniformly deposited above the electron transport layer by a thermal evaporation method under vacuum condition by using a vacuum coating instrument, the thickness of the tin metal layer is displayed as 10nm by a film thickness monitor, and then a layer of copper metal is uniformly deposited on the tin metal layer, so that the thickness of the tin metal layer can be controlled to be 100-150 nm.
J-V test: at AM1.5, the active layer effective area is 0.045cm 2 Under the condition, the battery is tested to obtain the open circuit voltage of 0.774V and the short circuit current density of 28mA cm -2 The fill factor was 0.753 and the photoelectric conversion efficiency was 16.31%.
Example 2
(1) Cleaning a substrate: same as in example 1
(2) Hole transport layer preparation: same as in example 1
(3) Perovskite light absorption layer preparation: same as in example 1
(4) And (3) preparing an electron transport layer: same as in example 1
(5) Electrode evaporation: a layer of tin metal is uniformly deposited above the electron transport layer by a thermal evaporation method under vacuum condition by using a vacuum coating instrument, the thickness of the tin metal layer is 20nm as shown by a film thickness monitor, and then a layer of copper metal is uniformly deposited on the tin metal layer, so that the thickness of the tin metal layer can be controlled to be 100-150 nm.
J-V test: at AM1.5, the active layer effective area was 0.06cm 2 Under the condition, the battery is tested to obtain an open circuit voltage of 0.828V and a short circuit current density of 30.11mA cm -2 The fill factor was 0.74 and the photoelectric conversion efficiency was 18.46%.
Example 3
(1) Cleaning a substrate: same as in example 1
(2) Hole transport layer preparation: same as in example 1
(3) Perovskite light absorption layer preparation: same as in example 1
(4) And (3) preparing an electron transport layer: same as in example 1
(5) Electrode evaporation: a layer of tin metal is uniformly deposited above the electron transport layer by a thermal evaporation method under vacuum condition by using a vacuum coating instrument, the thickness of the tin metal layer is 30nm as shown by a film thickness monitor, and then a layer of copper metal is uniformly deposited on the tin metal layer, so that the thickness of the tin metal layer can be controlled to be 100-150 nm.
J-V test: at AM1.5, the active layer effective area was 0.06cm 2 Under the condition, the battery is tested to obtain an open circuit voltage of 0.828V and a short circuit current density of 30.11mA cm -2 The fill factor was 0.74 and the photoelectric conversion efficiency was 18.46%.
Comparative example 1
(1) Cleaning a substrate: same as in example 1
(2) Hole transport layer preparation: same as in example 1
(3) Perovskite light absorption layer preparation: same as in example 1
(4) And (3) preparing an electron transport layer: same as in example 1
(5) Electrode evaporation: and uniformly depositing a silver metal electrode layer above the electron transport layer by a thermal evaporation method under a vacuum condition by using a vacuum coating instrument, wherein the thickness of the electron layer is 150-200 nm as shown by a film thickness monitor.
J-V test: at AM1.5, the active layer has an effective area of 0.06cm 2 The battery was tested under the conditions of (2). Obtaining an open circuit voltage of 0.702V and a short circuit current density of 29.88mA cm -2 The fill factor was 0.695, and the photoelectric conversion efficiency was 14.578%.
Correlation testing and data analysis:
FIGS. 2 and 3 are respectively vapor deposited silver electrode and NiO in vapor deposited double metal electrode device x The SEM plan view of the film shows that the nickel oxide particles are uniform and dense in size. Fig. 4 shows an SEM plan view of a perovskite thin film, showing that the perovskite particles are large and uniform and dense. Fig. 5 shows a cross-sectional view of the device after vapor deposition of a double-layer metal electrode, and it can be seen that the perovskite thin film has a thickness of about 570 nm.
FIGS. 6 and 7 show XRD patterns and UV absorption spectra, respectively, of the prepared perovskite, and XRD characteristic peaks and absorption peaks thereof show perovskite components and HC (NH) 2 ) 2 Pb 0.5 Sn 0.5 I 3 Perovskite phase anastomosis.
Fig. 8 shows the J-V curves of the evaporated silver electrode device, and fig. 9 and 10 show the J-V curves of the evaporated 10nm and 20nm thick tin metal and the double metal electrode device combined with copper metal, respectively, and it can be seen that the evaporated 20nm thick tin metal and copper metal double metal electrode device has higher open circuit voltage and short circuit current, indicating that it has the best photoelectric conversion efficiency.
Fig. 11 is a long-term stability test curve of a 20nm thick tin and copper metal vapor deposited bi-metallic electrode unpackaged device stored in nitrogen, showing that the device performance remained more than ninety percent of the initial efficiency after one month of storage, indicating that the device had a good long-term stability.
The present invention is not limited to the above-mentioned embodiments, but any modifications, equivalents, improvements and modifications within the scope of the invention will be apparent to those skilled in the art.
Claims (10)
1. A tin-lead mixed perovskite solar cell based on double-layer metal electrodes is characterized in that: the light-emitting diode comprises a transparent conductive substrate, a hole transport layer, a perovskite light absorption layer, an electron transport layer, a first metal electrode layer and a second electrode layer which are sequentially stacked on the transparent conductive substrate; the first metal electrode layer includes a metal having a reducing property; the second metal electrode layer includes a non-noble metal having good electrical conductivity.
2. The tin-lead mixed perovskite solar cell according to claim 1, wherein: the transparent conductive substrate is ITO conductive glass; the hole transport layer is inorganic metal oxide NiO x The method comprises the steps of carrying out a first treatment on the surface of the The tin-lead mixed perovskite light absorption layer is HC (NH) 2 ) 2 Pb 0.5 Sn 0.5 I 3 A film; the electron transmission layer is PCBM; the first metal electrode layer is a tin-based metal with reducibility; the second metal electrode layer is copper metal.
3. The method for manufacturing a tin-lead mixed perovskite solar cell according to claim 1 or 2, comprising the steps of:
(1) Cleaning the transparent conductive substrate;
(2) Spin-coating NiOx aqueous solution on a transparent conductive substrate, and annealing on a heating plate to obtain a NiOx hole transport layer;
(3) Uniformly spin-coating a tin-lead mixed perovskite precursor solution on the hole transport layer in an inert atmosphere, and annealing to obtain a tin-lead mixed perovskite light absorption layer;
(4) Dissolving PCBM in chlorobenzene to prepare a solution, and uniformly spin-coating the solution on a perovskite light absorption layer to form an electron transport layer;
(5) First evaporating a first metal electrode layer on an electron transport layer;
(6) And evaporating a second metal electrode layer on the first metal electrode layer.
4. A method according to claim 3, wherein in step (1), the transparent substrate is cleaned by the following method: firstly, deionized water, absolute ethyl alcohol, isopropanol, acetone and absolute ethyl alcohol are sequentially used for cleaning, then the cleaning solution is placed in the absolute ethyl alcohol for standing and preservation, when the cleaning solution is used, high-purity nitrogen is used for drying, and finally ultraviolet ozone treatment is carried out.
5. A method according to claim 3, wherein in step (2), niO x The preparation method of the aqueous solution comprises the following steps: reacting ammonia water with nickel nitrate hexahydrate aqueous solution, stirring, standing, taking out supernatant, centrifugally washing lower powder with deionized water, vacuum drying the obtained product, and annealing to obtain NiO x A powder; the NiO obtained is then treated x Dissolving the powder in water to obtain NiO x An aqueous solution.
6. The method according to claim 3, wherein in the step (2), the spin-coating speed is 4000rpm/s, the spin-coating time is 30 to 60s, and the annealing treatment is performed on a heating plate at 100 to 200 ℃ for 20 to 40min.
7. A method according to claim 3, wherein in step (3), the tin-lead perovskite solution is prepared by: HC (NH) 2 ) 2 SnI 3 And HC (NH) 2 ) 2 PbI 3 Uniformly mixing the precursor solution and filtering; and uniformly dripping the tin-lead mixed perovskite precursor liquid onto the hole transport layer for spin coating, uniformly and rapidly dripping a chlorobenzene anti-solvent when the spin coating is finished, transferring the perovskite intermediate phase film onto a heating table for heating and then annealing treatment, thus obtaining the tin-lead mixed perovskite light absorption layer.
8. A method according to claim 3, wherein in step (4) the PCBM powder is used in an amount of 20 to 40 mg/1 ml; the spin speed is 2000-3000 rpm/s, and the spin time is 30s.
9. A method according to claim 3, wherein in the step (5), the first metal electrode layer is uniformly deposited on the electron transport layer by thermal evaporation under vacuum, and the film thickness is controlled to be 10 to 30nm.
10. A method according to claim 3, wherein in the step (6), a second metal electrode layer is uniformly deposited on the first metal electrode layer by a thermal evaporation method under vacuum conditions, and the film thickness is controlled to be 100-150 nm.
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