WO2019090824A1 - Perovskite solar cell, dual layer metal electrode and preparation method therefor - Google Patents

Perovskite solar cell, dual layer metal electrode and preparation method therefor Download PDF

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WO2019090824A1
WO2019090824A1 PCT/CN2017/112225 CN2017112225W WO2019090824A1 WO 2019090824 A1 WO2019090824 A1 WO 2019090824A1 CN 2017112225 W CN2017112225 W CN 2017112225W WO 2019090824 A1 WO2019090824 A1 WO 2019090824A1
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layer
thin film
film layer
metal
metal thin
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陈炜
陈锐
吴邵航
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华中科技大学鄂州工业技术研究院
华中科技大学
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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
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • 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
    • 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
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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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  • the present disclosure relates to solar cell preparation technology, and more particularly to a perovskite solar cell, a two-layer metal electrode for a perovskite solar cell, and a method of fabricating the same.
  • perovskite solar cells Since its first report in 2009, perovskite solar cells have been favored by researchers for their ultra-low material cost and solution preparation processes, and the energy conversion efficiency has increased from the initial 3.8% to 22.1%. With the deepening of research, the efficiency of the battery is likely to exceed the maturity of monocrystalline silicon solar cells. Among the new generation of photovoltaic technologies, perovskite solar cells are likely to be the first to achieve industrialization.
  • perovskite solar cells have entered the threshold of industrialization, but the stability of the device constitutes the bottleneck of its industrial application.
  • the stability of the battery device and the chemical decomposition of the halide perovskite material under the action of moisture have a great relationship with the chemical corrosion of the commonly used metal electrode.
  • the metal Au or Ag reacts with the perovskite to form AuI 3 or AgI, etc., while Au and Ag penetrate into the perovskite layer, destroying its electrical properties, causing irreparable damage to device performance.
  • the purpose of the present disclosure is to overcome the above technical deficiencies, and to provide a two-layer metal electrode for a perovskite solar cell and a preparation method thereof, which solves the technical problem that the metal electrode of the perovskite solar cell has low stability in the prior art.
  • the technical solution of the present disclosure provides a double-layer metal electrode for a perovskite solar cell, comprising a first metal thin film layer and a second metal laid on a surface of one side of the first metal thin film layer. a thin film layer; wherein the first metal thin film layer is chemically inert, and the second metal thin film layer has high electrical conductivity.
  • the present disclosure also provides a method for preparing a two-layer metal electrode for a perovskite solar cell, including The following steps:
  • the present disclosure also provides a perovskite solar cell comprising a glass substrate, a transparent conductive electrode, a hole transport layer, a perovskite film, an electron transport layer, and the above double layer metal electrode, which are stacked in this order from bottom to top.
  • the first metal thin film layer of the double metal electrode is disposed adjacent to the electron transport layer.
  • the present disclosure forms a chemically inert first metal thin film layer on a low temperature vacuum deposition layer on the electron transport layer, and a high conductivity second metal thin film layer on the first metal thin film layer. It can effectively isolate the penetration of moisture and reduce the chemical corrosion of the second metal film layer without reducing the photoelectric conversion efficiency, which is beneficial to improve the stability of the perovskite solar cell.
  • FIG. 1 is a schematic structural view of a perovskite solar cell of the present disclosure
  • Example 2 is an SEM photograph and an EDS spectrum analysis diagram of an interface of a perovskite solar cell of Example 1 of the present disclosure
  • FIG. 3 is a schematic diagram showing a comparison of photocurrent density-voltage output characteristics of a perovskite solar cell of Example 2 of the present disclosure
  • FIG. 4 is a schematic diagram showing an XRD pattern comparison of a perovskite film of Example 3 of the present disclosure
  • Example 5 is a schematic diagram of a comparison of thermogravi/differential heat of a perovskite powder of Example 4 of the present disclosure mixed with different metals;
  • FIG. 6 is a schematic diagram showing a comparison of storage efficiency changes of a perovskite solar cell of Embodiment 5 of the present disclosure
  • Example 7 is a schematic diagram of comparison of illumination stability of a perovskite solar cell of Example 6 of the present disclosure.
  • FIG. 8 is a schematic diagram showing a comparison of photocurrent density-voltage output characteristics of a perovskite solar cell of Example 7 of the present disclosure.
  • an embodiment of the present disclosure provides a perovskite solar cell including bottom to top. a glass substrate 3, a transparent conductive electrode 4, a hole transport layer 5, a perovskite film 6, an electron transport layer 7, and a double layer metal electrode, which are disposed on the electron transport layer 7 a first metal thin film layer 1 on the surface and a second metal thin film layer 2 disposed on a surface of one side of the first metal thin film layer 1; wherein the first metal thin film layer 1 is chemically inert, the second metal thin film Layer 2 has a high electrical conductivity.
  • the first metal thin film layer 1 of the present embodiment preferably uses a Bi metal thin film layer or a Bi alloy thin film layer.
  • the second metal thin film layer 2 may be a metal thin film layer of Ag, Au, Al, Cu, Ti, Ni or Mo.
  • a transparent conductive electrode 4 may be disposed on the upper surface of the glass substrate 3, and a hole transport layer 5 may be disposed on the upper surface of the transparent conductive electrode 4, and in the hole transport layer 5
  • the upper surface is provided with a perovskite film 6, and then an electron transport layer 7 is disposed on the surface of the perovskite film 6.
  • the above preparation method can be fabricated by a conventional conventional method, for example, spin coating, blade coating or slit coating can be employed.
  • the coating method is sequentially applied to the film; then, a chemically inert first metal film layer 1 is deposited on the surface of the electron transport layer 7 by vacuum evaporation, and a layer of Bi metal is deposited on the surface of the electron transport layer 7.
  • the film layer or the Bi alloy film layer has an evaporation temperature generally lower than 1000 ° C during vapor deposition, and the vacuum degree of the vacuum evaporation is less than 10 -3 Pa, and the evaporation rate is
  • a second metal thin film layer 2 having high conductivity may be deposited on the first metal thin film layer 1 by vacuum evaporation or magnetron sputtering.
  • a metal thin film layer of Ag, Au, Al, Cu, Ti, Ni or Mo is disposed on the upper surface of the metal thin film layer 1.
  • the thickness of the coating film of Bi or its alloy is 5 to 80 nm, and the film formation is dense, and it is difficult to react with the water, oxygen and halide perovskite film, so that the water can effectively prevent the perovskite film 6 And the perovskite film 6 corrodes the metal electrode, thereby improving the stability of the perovskite solar cell; moreover, the metal Bi and its alloy are easily evaporated at a low temperature, and the evaporation process does not cause thermal decomposition of the perovskite solar cell, ensuring Its coating stability.
  • the vacuum evaporation method is employed, and the vacuum degree of the vacuum evaporation is ⁇ 10 -3 Pa, and the evaporation rate is The thickness of the evaporation is 50-200 nm.
  • metals such as Ag and Au are expensive, which increases the material cost of the device.
  • the second metal thin film layer 2 is a metal thin film layer of Cu, Ti, Ni or Mo
  • the thermal effect of the vapor deposition causes thermal decomposition of the perovskite film, resulting in corresponding solar cell devices. Poor performance. Therefore, these metal thin films are usually coated by a low power magnetron sputtering method.
  • the operating pressure of the magnetron sputtering coating of the present embodiment is 0.1-100 Pa
  • the sputtering power density is 1-100 W/cm 2
  • the sputtering thickness is 100- 2000nm.
  • the Bi metal thin film layer or the Bi alloy thin film layer of the embodiment is used as a key buffer layer to prevent damage of the underlying perovskite film by high energy plasma when sputtering a metal film such as Ti, Ni, Mo, etc., without affecting device efficiency. Under the premise, the material cost of the device is greatly reduced, which is beneficial to the industrialization of the perovskite solar cell.
  • the perovskite solar cell using the double-layer metal electrode of the present embodiment has better performance, and different perovskite films and perovskite solar cells under the same preparation conditions are compared and analyzed.
  • FIG. 2 it is an interface SEM photograph and an EDS spectrum analysis diagram of a perovskite solar cell based on a Bi/Ag and Bi/Mo double-layer metal electrode, wherein (a) in FIG. 2 is Bi/Ag.
  • the double metal electrode that is, the first metal thin film layer is a 20 nm thick Bi metal layer, the second metal thin film layer is a 150 nm thick Ag metal layer;
  • (b) in FIG. 2 is a Bi/Mo double layer metal electrode, that is, the first One metal thin film layer is a 20 nm thick Bi metal layer, and the second metal thin film layer is a 500 nm thick Mo metal layer.
  • the five groups of perovskite solar cells differed in that: the first group of single-layer Ag metal electrodes; the second group was double-layer metal electrodes, and the first layer was Bi
  • the metal layer and the second layer are Ag metal layers, the Bi metal layer has a thickness of 10 nm; the third group is a double metal electrode, and the first layer is a Bi metal layer, the second layer is an Ag metal layer, and the Bi metal layer has a thickness of 80 nm.
  • the fourth group is a double-layer metal electrode, and the first layer is a Bi-Sn alloy metal layer, the second layer is an Ag metal layer, the Bi-Sn alloy metal layer has a thickness of 10 nm; the fifth group is a double-layer metal electrode, and The first layer is a Bi-Cu alloy metal layer, the second layer is an Ag metal layer, and the Bi-Cu alloy metal layer has a thickness of 10 nm.
  • the above five groups of perovskite solar cells with an area of 1 cm 2 were selected, and their photoelectric conversion efficiencies were obtained at an illumination intensity of 100 mW/cm 2 .
  • the photoelectric conversion efficiencies of the first to fifth groups were respectively: Standard Ag electrode, efficiency is 17.53%; 10nm Bi and Ag double-layer metal electrode, efficiency is 16.94%; 80nm Bi and Ag double-layer metal electrode, efficiency is 13.21%; 10nm Bi-Sn alloy and Ag double-layer metal electrode, efficiency It is 18.06%; 10 nm Bi-Cu alloy and Ag double-layer metal electrode, the efficiency is 18.25%. From the above data, it can be seen that when the thickness of the Bi metal layer in the double-layered metal electrode is appropriate, it is possible to obtain photoelectric conversion efficiency similar to that of the standard Ag metal electrode.
  • halide perovskite (CH 3 NH 3 PbI 3 ) films were selected at 35 ° C, 70% humidity, and different decomposition methods were selected to measure the decomposition products (PbI 2 ) formed by chemical decomposition under the action of moisture.
  • the number, as shown in Figure 4, is from the bottom to the top of the XRD pattern of the first to eighth.
  • the first one is: the first group of halide perovskite film is under standard metal Ag electrode (which is equivalent to uncovered Bi) for two days;
  • the second is: the second group of halide perovskite film is in Bi metal The film is covered for two days, which is equivalent to the first metal film layer being a Bi metal film and the second metal film layer being an Ag metal film layer;
  • the third is: the third group of halide perovskite film is covered by the Bi-Sn metal film
  • the fourth is: the fourth group of halide perovskite film is covered by the Bi-Cu metal film In two days, it is equivalent to the first metal film layer being a Bi-Cu alloy film, and the second metal film layer is an Ag metal film layer;
  • the fifth is: the first group of halide perovskite film is under a standard metal Ag electrode ( It is equivalent to not covering Bi)
  • the perovskite (CH 3 NH 3 PbI 3 ) powder is separately mixed with the metal powder of Bi, Ag, Al and Cu at a mass ratio of 1:1, and slowly heated at a rate of 5 ° C/min from room temperature to 400 ° C. The weight loss and exotherm were tested under N 2 atmosphere. The test results are shown in Fig. 5. It shows that there is no chemical reaction between Bi metal and perovskite film, which indicates that Bi metal has strong corrosion resistance. Metals such as Ag, Al, and Cu have a reaction exotherm and mass loss within 100 ° C, which indicates that the halide perovskite chemically corrodes the above metal in a very low temperature range.
  • the eight groups of perovskite solar cells differed in that the first group was a single-layer Al metal electrode; the second group was a single-layer Cu metal electrode; the third group was a single Layer Ag metal electrode; the fourth group is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Al metal layer; the fifth group is a double layer metal electrode, and the first layer is a Bi metal layer, The second layer is a Cu metal layer; the sixth layer is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Ag metal layer; the seventh group is a double layer metal electrode, and the first layer is Bi-Sn The alloy layer and the second layer are Ag metal layers; the eighth group is a double-layer metal electrode, and the first layer is a Bi-Cu alloy layer, and the second layer is an Ag metal layer.
  • the above-mentioned eight sets of perovskite solar cells were tested for long-term storage efficiency under the following conditions: unpackaged device dark State preservation, 50-70% humidity, 25 ° C ambient temperature.
  • the test results are shown in Fig. 6.
  • the stability of the perovskite solar cell corresponding to the double-layer metal electrode based on the metal Bi or Bi alloy is significantly better, and the stability is significantly higher than that of the conventional single-layer metal electrode.
  • the eight groups of perovskite solar cells differed in that the first group was a single-layer Al metal electrode; the second group was a single-layer Cu metal electrode; the third group was a single Layer Ag metal electrode; the fourth group is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Al metal layer; the fifth group is a double layer metal electrode, and the first layer is a Bi metal layer, The second layer is a Cu metal layer; the sixth layer is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Ag metal layer; the seventh group is a double layer metal electrode, and the first layer is Bi-Sn The alloy layer and the second layer are Ag metal layers; the eighth group is a double-layer metal electrode, and the first layer is a Bi-Cu alloy layer, and the second layer is an Ag metal layer.
  • perovskite solar cells were tested for light stability under the following conditions: unpackaged device, anhydrous oxygen-free N 2 gas environment, ambient temperature of 25 ° C, and white LED providing continuous illumination of 100 mW/cm 2 intensity; The continuous detection of the maximum power point of the battery, the experimental results shown in Figure 7, the light stability of the perovskite solar cell based on the two-layer metal electrode has been significantly improved, and the practicality is greatly improved.
  • the eight groups of perovskite solar cells differed in that the first group was formed by magnetron sputtering on the upper surface of the electron transport layer to form Ti metal electrodes; the second group was directly On the upper surface of the electron transport layer, magnetron sputtering is used to form a Ni metal electrode; the third group is a magnetron sputtering on the upper surface of the electron transport layer to form a Mo metal electrode; and the fourth group is a vapor deposition layer on the upper surface of the electron transport layer.
  • the Bi metal layer acts as a buffer layer and then magnetron sputtering to form a Ti metal electrode; the fifth group first deposits a Bi metal layer on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form a Ni metal electrode.
  • the sixth group firstly deposits a layer of Bi metal on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form a Mo metal electrode;
  • the seventh group first deposits a layer of Bi on the upper surface of the electron transport layer.
  • the eighth group first vapor-deposits a layer of Bi-Cu alloy layer on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form Mo Metal electrode.
  • the area of the above eight sets of perovskite solar cells was set to 1 cm 2 , which was generated by an optical mask, and irradiated at a light intensity of 100 mW/cm 2 of a 3A-level solar simulator, and the photoelectric conversion efficiency thereof was measured.
  • Fig. 8 it is the "photocurrent density-voltage" output characteristic curve of eight sets of perovskite solar cells. It can be seen from the above comparison curve that direct magnetron sputtering of metal electrodes can significantly damage the battery, and the efficiency of the battery is very high. Low ( ⁇ 4%); and the use of low-temperature evaporation of Bi or Bi-based alloy as a buffer layer can effectively avoid damage to the perovskite and interface materials during the sputtering process. Based on Bi or Bi-based alloys and magnetron sputtering, the base metals Ti, Ni, Mo, etc. constitute a double-layer metal electrode, instead of expensive Ag or Au, the cost of the electrode material is greatly reduced without losing the efficiency of the battery.
  • the battery efficiency based on the Bi/Ti double-layer metal electrode is 11.48%
  • the battery efficiency based on the Bi/Ni double-layer metal electrode is 14.05%
  • the battery efficiency based on the Bi/Mo double-layer metal electrode is 15.45%
  • the battery efficiency of the Sn/Mo double-layer metal electrode was 16.04%
  • the battery efficiency based on the Bi-Sn/Mo double-layer metal electrode was 16.61%.
  • the cost of the electrode material is reduced, which is advantageous for industrialization.

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Abstract

A perovskite solar cell, a dual layer metal electrode used for a perovskite solar cell and a preparation method therefor. The perovskite solar cell comprises a glass substrate (3), a transparent conductive electrode (4), a hollow transmission layer (5), a perovskite thin film (6), an electron transmission layer (7) and a dual layer metal electrode; the dual layer metal electrode comprises a first metal thin film layer (1) and a second metal thin film layer (2), the preparation method therefor comprising: depositing the first metal thin film layer (1) on a side surface of the electron transmission layer (7), and depositing the second metal thin film layer (2) on the first metal thin film layer. By means of depositing a first metal thin film layer having chemical inertness on the electron transmission layer by low-temperature vacuum evaporation, and providing a second metal thin film layer having high conductivity on the first metal thin film layer, the permeation of moisture may be effectively isolated and the chemical corrosion of the second metal thin film layer may be reduced without reducing the efficiency of photoelectric conversion, being beneficial in improving the stability of a perovskite solar cell.

Description

钙钛矿太阳能电池、双层金属电极及其制备方法Perovskite solar cell, double-layer metal electrode and preparation method thereof 技术领域Technical field
本公开涉及太阳能电池制备技术，尤其是涉及一种钙钛矿太阳能电池、用于钙钛矿太阳能电池的双层金属电极及其制备方法。The present disclosure relates to solar cell preparation technology, and more particularly to a perovskite solar cell, a two-layer metal electrode for a perovskite solar cell, and a method of fabricating the same.
背景技术Background technique
随着能源的日益紧缺，人们对新能源尤其是太阳能电池的研究日益关注。传统的硅电池相对来说成本较高，生产制造过程中能耗大、污染大，而新一代的染料敏化电池、有机太阳能电池等效率太低且稳定性很差，所以它们在工业化上还存在很多问题。With the increasing shortage of energy, people are paying more and more attention to the research of new energy sources, especially solar cells. Traditional silicon batteries are relatively expensive, and the energy consumption and pollution in the manufacturing process are large. The new generation of dye-sensitized batteries and organic solar cells are too low in efficiency and poor in stability, so they are industrialized. There are many problems.
钙钛矿太阳能电池自2009年第一次报道以来，以其超低材料成本、可溶液制备工艺而受到研究人员的青睐，能量转换效率由最初的3.8％提升到了22.1％。随着研究的不断深入，电池的效率极有可能超过目前发展成熟的单晶硅太阳能电池。在新一代光伏技术中，钙钛矿太阳能电池有可能率先实现产业化。Since its first report in 2009, perovskite solar cells have been favored by researchers for their ultra-low material cost and solution preparation processes, and the energy conversion efficiency has increased from the initial 3.8% to 22.1%. With the deepening of research, the efficiency of the battery is likely to exceed the maturity of monocrystalline silicon solar cells. Among the new generation of photovoltaic technologies, perovskite solar cells are likely to be the first to achieve industrialization.
在光电转化效率方面，钙钛矿太阳能电池已经跨入产业化的门槛，但器件的稳定性问题构成了其产业化应用的瓶颈。电池器件的稳定性与卤化物钙钛矿材料在湿气作用下发生化学分解，与常用的金属电极发生化学腐蚀有很大的关系，如金属Au或者Ag与钙钛矿会反应生成AuI3或AgI等，同时Au和Ag会渗透到钙钛矿层，破坏其电学性质，从而会对器件性能造成不可修复的损伤。In terms of photoelectric conversion efficiency, perovskite solar cells have entered the threshold of industrialization, but the stability of the device constitutes the bottleneck of its industrial application. The stability of the battery device and the chemical decomposition of the halide perovskite material under the action of moisture have a great relationship with the chemical corrosion of the commonly used metal electrode. For example, the metal Au or Ag reacts with the perovskite to form AuI 3 or AgI, etc., while Au and Ag penetrate into the perovskite layer, destroying its electrical properties, causing irreparable damage to device performance.
发明内容Summary of the invention
本公开的目的在于克服上述技术不足，提出一种用于钙钛矿太阳能电池的双层金属电极及其制备方法，解决现有技术中钙钛矿太阳能电池的金属电极稳定性低的技术问题。The purpose of the present disclosure is to overcome the above technical deficiencies, and to provide a two-layer metal electrode for a perovskite solar cell and a preparation method thereof, which solves the technical problem that the metal electrode of the perovskite solar cell has low stability in the prior art.
为达到上述技术目的，本公开的技术方案提供一种用于钙钛矿太阳能电池的双层金属电极，包括第一金属薄膜层及铺设于所述第一金属薄膜层一侧表面的第二金属薄膜层；其中，所述第一金属薄膜层具有化学惰性，所述第二金属薄膜层具有高导电率。In order to achieve the above technical purpose, the technical solution of the present disclosure provides a double-layer metal electrode for a perovskite solar cell, comprising a first metal thin film layer and a second metal laid on a surface of one side of the first metal thin film layer. a thin film layer; wherein the first metal thin film layer is chemically inert, and the second metal thin film layer has high electrical conductivity.
同时，本公开还提供一种用于钙钛矿太阳能电池的双层金属电极的制备方法，包括 如下步骤：Meanwhile, the present disclosure also provides a method for preparing a two-layer metal electrode for a perovskite solar cell, including The following steps:
(1)采用真空蒸镀方法在电子传输层一侧表面沉积一层具有化学惰性的第一金属薄膜层；(1) depositing a chemically inert first metal thin film layer on one side of the electron transport layer by vacuum evaporation;
(2)采用真空蒸镀或磁控溅射的方法在第一金属薄膜层上沉积一层具有高导电率的第二金属薄膜层。(2) depositing a second metal thin film layer having high conductivity on the first metal thin film layer by vacuum evaporation or magnetron sputtering.
而且，本公开还提供一种钙钛矿太阳能电池，其包括由下至上依次层叠设置的玻璃基底、透明导电电极、空穴传输层、钙钛矿薄膜、电子传输层及上述双层金属电极，所述双层金属电极的第一金属薄膜层靠近所述电子传输层设置。Moreover, the present disclosure also provides a perovskite solar cell comprising a glass substrate, a transparent conductive electrode, a hole transport layer, a perovskite film, an electron transport layer, and the above double layer metal electrode, which are stacked in this order from bottom to top. The first metal thin film layer of the double metal electrode is disposed adjacent to the electron transport layer.
与现有技术相比，本公开通过在电子传输层上低温真空蒸镀一层具有化学惰性的第一金属薄膜层，并在第一金属薄膜层上设置高导电率的第二金属薄膜层，其可在不降低光电转化效率的基础上，有效的隔离湿气的渗透并降低对第二金属薄膜层的化学腐蚀，其有利于提高钙钛矿太阳能电池的稳定性。Compared with the prior art, the present disclosure forms a chemically inert first metal thin film layer on a low temperature vacuum deposition layer on the electron transport layer, and a high conductivity second metal thin film layer on the first metal thin film layer. It can effectively isolate the penetration of moisture and reduce the chemical corrosion of the second metal film layer without reducing the photoelectric conversion efficiency, which is beneficial to improve the stability of the perovskite solar cell.
附图说明DRAWINGS
图1是本公开的钙钛矿太阳能电池的结构示意图；1 is a schematic structural view of a perovskite solar cell of the present disclosure;
图2是本公开的实施例1的钙钛矿太阳能电池的界面SEM照片与EDS能谱分析图；2 is an SEM photograph and an EDS spectrum analysis diagram of an interface of a perovskite solar cell of Example 1 of the present disclosure;
图3是本公开的实施例2的钙钛矿太阳能电池的光电流密度-电压输出特性曲线对比示意图；3 is a schematic diagram showing a comparison of photocurrent density-voltage output characteristics of a perovskite solar cell of Example 2 of the present disclosure;
图4是本公开的实施例3的钙钛矿薄膜的XRD图谱对比示意图；4 is a schematic diagram showing an XRD pattern comparison of a perovskite film of Example 3 of the present disclosure;
图5是本公开的实施例4的钙钛矿粉末与不同金属混合的热重/差热对比示意图；5 is a schematic diagram of a comparison of thermogravi/differential heat of a perovskite powder of Example 4 of the present disclosure mixed with different metals;
图6是本公开的实施例5的钙钛矿太阳能电池的存储效率变化对比示意图；6 is a schematic diagram showing a comparison of storage efficiency changes of a perovskite solar cell of Embodiment 5 of the present disclosure;
图7是本公开的实施例6的钙钛矿太阳能电池的光照稳定性对比示意图；7 is a schematic diagram of comparison of illumination stability of a perovskite solar cell of Example 6 of the present disclosure;
图8是本公开的实施例7的钙钛矿太阳能电池的光电流密度-电压输出特性曲线对比示意图。8 is a schematic diagram showing a comparison of photocurrent density-voltage output characteristics of a perovskite solar cell of Example 7 of the present disclosure.
具体实施方式Detailed ways
为了使本公开的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本公开进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。The present disclosure will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the disclosure and are not intended to limit the disclosure.
请参阅图1，本公开的实施例提供了一种钙钛矿太阳能电池，其包括由下至上依次 层叠设置的玻璃基底3、透明导电电极4、空穴传输层5、钙钛矿薄膜6、电子传输层7及双层金属电极，所述双层金属电极包括设于所述电子传输层7上表面的第一金属薄膜层1及铺设于所述第一金属薄膜层1一侧表面的第二金属薄膜层2；其中，所述第一金属薄膜层1具有化学惰性，所述第二金属薄膜层2具有高导电率。其中，本实施例所述第一金属薄膜层1优选采用Bi金属薄膜层或Bi合金薄膜层。而所述第二金属薄膜层2则可采用Ag、Au、Al、Cu、Ti、Ni或Mo金属薄膜层。Referring to FIG. 1 , an embodiment of the present disclosure provides a perovskite solar cell including bottom to top. a glass substrate 3, a transparent conductive electrode 4, a hole transport layer 5, a perovskite film 6, an electron transport layer 7, and a double layer metal electrode, which are disposed on the electron transport layer 7 a first metal thin film layer 1 on the surface and a second metal thin film layer 2 disposed on a surface of one side of the first metal thin film layer 1; wherein the first metal thin film layer 1 is chemically inert, the second metal thin film Layer 2 has a high electrical conductivity. The first metal thin film layer 1 of the present embodiment preferably uses a Bi metal thin film layer or a Bi alloy thin film layer. The second metal thin film layer 2 may be a metal thin film layer of Ag, Au, Al, Cu, Ti, Ni or Mo.
如图1所示，在制备钙钛矿太阳能电池时，可在玻璃基底3上表面设置透明导电电极4，在透明导电电极4的上表面设置空穴传输层5，并在空穴传输层5的上表面设置钙钛矿薄膜6，接着在钙钛矿薄膜6表面设置电子传输层7，上述制备方法可采用现有的常规方式制作，例如可采用旋涂，刮刀涂布或狭缝涂布等镀膜方式依次镀膜；然后，可采用真空蒸镀方法在电子传输层7一侧表面沉积一层具有化学惰性的第一金属薄膜层1，具体在电子传输层7上表面蒸镀一层Bi金属薄膜层或Bi合金薄膜层，蒸镀时蒸发温度一般低于1000℃，而且其真空蒸镀的真空度小于10-3Pa、蒸镀速度为
Figure PCTCN2017112225-appb-000001
当第一金属薄膜层1蒸镀后，则可采用真空蒸镀或磁控溅射的方法在第一金属薄膜层1上沉积一层具有高导电率的第二金属薄膜层2，具体在第一金属薄膜层1上表面设置一层Ag、Au、Al、Cu、Ti、Ni或Mo金属薄膜层。As shown in FIG. 1, in the preparation of a perovskite solar cell, a transparent conductive electrode 4 may be disposed on the upper surface of the glass substrate 3, and a hole transport layer 5 may be disposed on the upper surface of the transparent conductive electrode 4, and in the hole transport layer 5 The upper surface is provided with a perovskite film 6, and then an electron transport layer 7 is disposed on the surface of the perovskite film 6. The above preparation method can be fabricated by a conventional conventional method, for example, spin coating, blade coating or slit coating can be employed. The coating method is sequentially applied to the film; then, a chemically inert first metal film layer 1 is deposited on the surface of the electron transport layer 7 by vacuum evaporation, and a layer of Bi metal is deposited on the surface of the electron transport layer 7. The film layer or the Bi alloy film layer has an evaporation temperature generally lower than 1000 ° C during vapor deposition, and the vacuum degree of the vacuum evaporation is less than 10 -3 Pa, and the evaporation rate is
Figure PCTCN2017112225-appb-000001
After the first metal thin film layer 1 is evaporated, a second metal thin film layer 2 having high conductivity may be deposited on the first metal thin film layer 1 by vacuum evaporation or magnetron sputtering. A metal thin film layer of Ag, Au, Al, Cu, Ti, Ni or Mo is disposed on the upper surface of the metal thin film layer 1.
本实施例采用Bi或其合金镀膜的厚度为5～80nm，其成膜致密，难与水、氧和卤化物钙钛矿薄膜发生反应，故其可很好的防止水对钙钛矿薄膜6和钙钛矿薄膜6对金属电极的腐蚀，进而提高钙钛矿太阳能电池的稳定性；而且，金属Bi及其合金低温易蒸发，蒸镀过程不会造成钙钛矿太阳能电池的热分解，保证其镀膜稳定性。In this embodiment, the thickness of the coating film of Bi or its alloy is 5 to 80 nm, and the film formation is dense, and it is difficult to react with the water, oxygen and halide perovskite film, so that the water can effectively prevent the perovskite film 6 And the perovskite film 6 corrodes the metal electrode, thereby improving the stability of the perovskite solar cell; moreover, the metal Bi and its alloy are easily evaporated at a low temperature, and the evaporation process does not cause thermal decomposition of the perovskite solar cell, ensuring Its coating stability.
其中，当第二金属薄膜层2为Ag、Au或Al金属薄膜层时，其采用真空蒸镀方法，且真空蒸镀的真空度＜10-3Pa、蒸镀速度为
Figure PCTCN2017112225-appb-000002
蒸镀厚度为50-200nm。但是在实际应用时，Ag、Au等金属价格昂贵，提高了器件的材料成本。Wherein, when the second metal thin film layer 2 is an Ag, Au or Al metal thin film layer, the vacuum evaporation method is employed, and the vacuum degree of the vacuum evaporation is <10 -3 Pa, and the evaporation rate is
Figure PCTCN2017112225-appb-000002
The thickness of the evaporation is 50-200 nm. However, in practical applications, metals such as Ag and Au are expensive, which increases the material cost of the device.
而当第二金属薄膜层2为Cu、Ti、Ni或Mo金属薄膜层时，由于其蒸发温度一般大于1200℃，蒸镀的热效应会造成钙钛矿薄膜的热分解，造成相应太阳能电池器件的性能很差。故这些金属薄膜通常采用低功率磁控溅射方法进行镀膜。为了避免在溅射时损坏钙钛矿太阳能电池的性能，本实施例磁控溅射镀膜时的操作气压为0.1-100Pa、溅射功率密度为1-100W/cm2、溅射厚度为100-2000nm。本实施例的Bi金属薄膜层或Bi合金薄膜层作为关键的缓冲层，防止溅射Ti、Ni、Mo等金属薄膜时高能量等离子体对底层钙钛矿膜的损伤，在不影响器件效率的前提下大大降低了器件的材料成本，有利于 钙钛矿太阳能电池的产业化。When the second metal thin film layer 2 is a metal thin film layer of Cu, Ti, Ni or Mo, since the evaporation temperature is generally greater than 1200 ° C, the thermal effect of the vapor deposition causes thermal decomposition of the perovskite film, resulting in corresponding solar cell devices. Poor performance. Therefore, these metal thin films are usually coated by a low power magnetron sputtering method. In order to avoid damage to the performance of the perovskite solar cell during sputtering, the operating pressure of the magnetron sputtering coating of the present embodiment is 0.1-100 Pa, the sputtering power density is 1-100 W/cm 2 , and the sputtering thickness is 100- 2000nm. The Bi metal thin film layer or the Bi alloy thin film layer of the embodiment is used as a key buffer layer to prevent damage of the underlying perovskite film by high energy plasma when sputtering a metal film such as Ti, Ni, Mo, etc., without affecting device efficiency. Under the premise, the material cost of the device is greatly reduced, which is beneficial to the industrialization of the perovskite solar cell.
为了便于说明本实施例采用双层金属电极的钙钛矿太阳能电池具有更佳的性能，现将相同制备条件下的不同钙钛矿薄膜和钙钛矿太阳能电池进行对比分析。For convenience of description, the perovskite solar cell using the double-layer metal electrode of the present embodiment has better performance, and different perovskite films and perovskite solar cells under the same preparation conditions are compared and analyzed.
实施例1Example 1
如图2所示，其为基于Bi/Ag和Bi/Mo双层金属电极的钙钛矿太阳能电池的界面SEM照片与EDS能谱分析图，其中，图2中的(a)为Bi/Ag双层金属电极，即第一金属薄膜层为20nm厚的Bi金属层，第二金属薄膜层为150nm厚的Ag金属层；图2中的(b)为Bi/Mo双层金属电极，即第一金属薄膜层为20nm厚的Bi金属层，第二金属薄膜层为500nm厚的Mo金属层。As shown in FIG. 2, it is an interface SEM photograph and an EDS spectrum analysis diagram of a perovskite solar cell based on a Bi/Ag and Bi/Mo double-layer metal electrode, wherein (a) in FIG. 2 is Bi/Ag. The double metal electrode, that is, the first metal thin film layer is a 20 nm thick Bi metal layer, the second metal thin film layer is a 150 nm thick Ag metal layer; (b) in FIG. 2 is a Bi/Mo double layer metal electrode, that is, the first One metal thin film layer is a 20 nm thick Bi metal layer, and the second metal thin film layer is a 500 nm thick Mo metal layer.
实施例2Example 2
在相同条件制备五组钙钛矿太阳能电池，五组钙钛矿太阳能电池的不同之处在于：第一组的单层Ag金属电极；第二组为双层金属电极，且第一层为Bi金属层、第二层为Ag金属层，Bi金属层厚度为10nm；第三组为双层金属电极，且第一层为Bi金属层、第二层为Ag金属层，Bi金属层厚度为80nm；第四组为双层金属电极，且第一层为Bi-Sn合金金属层、第二层为Ag金属层，Bi-Sn合金金属层厚度为10nm；第五组为双层金属电极，且第一层为Bi-Cu合金金属层、第二层为Ag金属层，Bi-Cu合金金属层厚度为10nm。Five sets of perovskite solar cells were prepared under the same conditions. The five groups of perovskite solar cells differed in that: the first group of single-layer Ag metal electrodes; the second group was double-layer metal electrodes, and the first layer was Bi The metal layer and the second layer are Ag metal layers, the Bi metal layer has a thickness of 10 nm; the third group is a double metal electrode, and the first layer is a Bi metal layer, the second layer is an Ag metal layer, and the Bi metal layer has a thickness of 80 nm. The fourth group is a double-layer metal electrode, and the first layer is a Bi-Sn alloy metal layer, the second layer is an Ag metal layer, the Bi-Sn alloy metal layer has a thickness of 10 nm; the fifth group is a double-layer metal electrode, and The first layer is a Bi-Cu alloy metal layer, the second layer is an Ag metal layer, and the Bi-Cu alloy metal layer has a thickness of 10 nm.
选取面积为1cm2的上述五组钙钛矿太阳能电池，并在光照强度为100mW/cm2下获取其光电转换效率，由图3可知，第一组至第五组的光电转化效率分别为：标准Ag电极，效率为17.53％；10nm Bi和Ag双层金属电极，效率为16.94％；80nm Bi和Ag双层金属电极，效率为13.21％；10nm Bi-Sn合金和Ag双层金属电极，效率为18.06％；10nm Bi-Cu合金和Ag双层金属电极，效率为18.25％。由上述数据可知，当双层金属电极中Bi金属层的厚度合适时，其能够获得与标准Ag金属电极类似的光电转化效率。The above five groups of perovskite solar cells with an area of 1 cm 2 were selected, and their photoelectric conversion efficiencies were obtained at an illumination intensity of 100 mW/cm 2 . As can be seen from Fig. 3, the photoelectric conversion efficiencies of the first to fifth groups were respectively: Standard Ag electrode, efficiency is 17.53%; 10nm Bi and Ag double-layer metal electrode, efficiency is 16.94%; 80nm Bi and Ag double-layer metal electrode, efficiency is 13.21%; 10nm Bi-Sn alloy and Ag double-layer metal electrode, efficiency It is 18.06%; 10 nm Bi-Cu alloy and Ag double-layer metal electrode, the efficiency is 18.25%. From the above data, it can be seen that when the thickness of the Bi metal layer in the double-layered metal electrode is appropriate, it is possible to obtain photoelectric conversion efficiency similar to that of the standard Ag metal electrode.
实施例3Example 3
取四组卤化物钙钛矿(CH3NH3PbI3)薄膜在35℃、70％湿度下，选择不同的覆盖方式，测量其在湿气作用下的化学分解形成的分解产物(PbI2)的数量，如图4所示，由下至上为第一条至第八条的XRD图谱。其中，第一条为：第一组卤化物钙钛矿薄膜在标准金属Ag电极下(其相当于未覆盖Bi)两天；第二条为：第二组卤化物钙钛矿薄膜在Bi金属薄膜覆盖两天，其相当于第一金属薄膜层为Bi金属薄膜、第二金属薄膜层为Ag金属薄膜层；第三条为：第三组卤化物钙钛矿薄膜在Bi-Sn金属薄膜覆盖两天， 其相当于第一金属薄膜层为Bi-Sn合金薄膜、第二金属薄膜层为Ag金属薄膜层；第四条为：第四组卤化物钙钛矿薄膜在Bi-Cu金属薄膜覆盖两天，其相当于第一金属薄膜层为Bi-Cu合金薄膜、第二金属薄膜层为Ag金属薄膜层；第五条为：第一组卤化物钙钛矿薄膜在标准金属Ag电极下(其相当于未覆盖Bi)三十天；第六条为：第二组卤化物钙钛矿薄膜在Bi金属薄膜覆盖三十天，其相当于第一金属薄膜层为Bi金属薄膜、第二金属薄膜层为Ag金属薄膜层；第七组为：第三组卤化物钙钛矿薄膜在Bi-Sn金属薄膜覆盖三十天，其相当于第一金属薄膜层为Bi-Sn合金薄膜、第二金属薄膜层为Ag金属薄膜层；第八条为：第四组卤化物钙钛矿薄膜在Bi-Cu金属薄膜覆盖三十天，其相当于第一金属薄膜层为Bi-Cu合金薄膜、第二金属薄膜层为Ag金属薄膜层。Four groups of halide perovskite (CH 3 NH 3 PbI 3 ) films were selected at 35 ° C, 70% humidity, and different decomposition methods were selected to measure the decomposition products (PbI 2 ) formed by chemical decomposition under the action of moisture. The number, as shown in Figure 4, is from the bottom to the top of the XRD pattern of the first to eighth. Among them, the first one is: the first group of halide perovskite film is under standard metal Ag electrode (which is equivalent to uncovered Bi) for two days; the second is: the second group of halide perovskite film is in Bi metal The film is covered for two days, which is equivalent to the first metal film layer being a Bi metal film and the second metal film layer being an Ag metal film layer; the third is: the third group of halide perovskite film is covered by the Bi-Sn metal film For two days, it is equivalent to the first metal film layer being a Bi-Sn alloy film, and the second metal film layer is an Ag metal film layer; the fourth is: the fourth group of halide perovskite film is covered by the Bi-Cu metal film In two days, it is equivalent to the first metal film layer being a Bi-Cu alloy film, and the second metal film layer is an Ag metal film layer; the fifth is: the first group of halide perovskite film is under a standard metal Ag electrode ( It is equivalent to not covering Bi) for thirty days; the sixth is: the second group of halide perovskite film is covered in the Bi metal film for 30 days, which is equivalent to the first metal film layer is Bi metal film, the second metal The film layer is an Ag metal film layer; the seventh group is: a third group of halide perovskite film The Bi-Sn metal film is covered for 30 days, which is equivalent to the first metal film layer being a Bi-Sn alloy film, and the second metal film layer is an Ag metal film layer; the eighth is: the fourth group of halide perovskites The film is covered with a Bi-Cu metal film for 30 days, which corresponds to the first metal film layer being a Bi-Cu alloy film and the second metal film layer being an Ag metal film layer.
由图4可知，第一组的标准Ag电极对钙钛矿的保护作用较弱，经30天老化后样品中的PbI2衍射峰明显增强，说明钙钛矿分解严重。而第二组至第四组的基于Bi或Bi基合金的双层金属电极，能够对湿气有效屏蔽，延缓钙钛矿薄膜的分解，在老化30天之后，PbI2衍射峰仍较弱，说明钙钛矿分解程度很小，即Bi和Bi合金对钙钛矿薄膜的保护作用较为明显。It can be seen from Fig. 4 that the protective effect of the first group of standard Ag electrodes on perovskites is weak, and the PbI 2 diffraction peaks in the samples are significantly enhanced after 30 days of aging, indicating that the perovskite decomposition is severe. The second to fourth sets of Bi or Bi-based alloy-based double-layer metal electrodes can effectively shield the moisture and delay the decomposition of the perovskite film. After 30 days of aging, the PbI 2 diffraction peak is still weak. It indicates that the degree of decomposition of perovskite is very small, that is, the protective effect of Bi and Bi alloy on perovskite film is obvious.
实施例4Example 4
将钙钛矿(CH3NH3PbI3)粉末分别与Bi、Ag、Al、Cu金属粉以质量比1∶1分别混合，并在室温到400℃范围内，按速度5℃/min缓慢升温，N2气氛条件下测试其失重及放热，测试结果如图5所示，其说明Bi金属与钙钛矿薄膜之间没有发生化学反应，其说明Bi金属具有较强的抗腐蚀能力，而Ag、Al、Cu等金属在100℃以内即存在反应放热和质量损失，其说明在很低的温度范围内，卤化物钙钛矿即对上述金属产生了化学腐蚀。The perovskite (CH 3 NH 3 PbI 3 ) powder is separately mixed with the metal powder of Bi, Ag, Al and Cu at a mass ratio of 1:1, and slowly heated at a rate of 5 ° C/min from room temperature to 400 ° C. The weight loss and exotherm were tested under N 2 atmosphere. The test results are shown in Fig. 5. It shows that there is no chemical reaction between Bi metal and perovskite film, which indicates that Bi metal has strong corrosion resistance. Metals such as Ag, Al, and Cu have a reaction exotherm and mass loss within 100 ° C, which indicates that the halide perovskite chemically corrodes the above metal in a very low temperature range.
实施例5Example 5
在相同条件制备八组钙钛矿太阳能电池，八组钙钛矿太阳能电池的不同之处在于：第一组为单层Al金属电极；第二组为单层Cu金属电极；第三组为单层Ag金属电极；第四组为双层金属电极，且第一层为Bi金属层、第二层为Al金属层；第五组为双层金属电极，且第一层为Bi金属层、第二层为Cu金属层；第六组为双层金属电极，且第一层为Bi金属层、第二层为Ag金属层；第七组为双层金属电极，且第一层为Bi-Sn合金层、第二层为Ag金属层；第八组为双层金属电极，且第一层为Bi-Cu合金层、第二层为Ag金属层。Eight sets of perovskite solar cells were prepared under the same conditions. The eight groups of perovskite solar cells differed in that the first group was a single-layer Al metal electrode; the second group was a single-layer Cu metal electrode; the third group was a single Layer Ag metal electrode; the fourth group is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Al metal layer; the fifth group is a double layer metal electrode, and the first layer is a Bi metal layer, The second layer is a Cu metal layer; the sixth layer is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Ag metal layer; the seventh group is a double layer metal electrode, and the first layer is Bi-Sn The alloy layer and the second layer are Ag metal layers; the eighth group is a double-layer metal electrode, and the first layer is a Bi-Cu alloy layer, and the second layer is an Ag metal layer.
将上述八组钙钛矿太阳能电池进行长期储存效率测试，测试条件为：未封装器件暗 态保存，50-70％湿度，25℃环境温度。测试结果如图6所示，基于金属Bi或Bi合金的双层金属电极对应的钙钛矿太阳能电池的稳定性明显更好，其稳定性明显高于常规单层金属电极。The above-mentioned eight sets of perovskite solar cells were tested for long-term storage efficiency under the following conditions: unpackaged device dark State preservation, 50-70% humidity, 25 ° C ambient temperature. The test results are shown in Fig. 6. The stability of the perovskite solar cell corresponding to the double-layer metal electrode based on the metal Bi or Bi alloy is significantly better, and the stability is significantly higher than that of the conventional single-layer metal electrode.
实施例6Example 6
在相同条件制备八组钙钛矿太阳能电池，八组钙钛矿太阳能电池的不同之处在于：第一组为单层Al金属电极；第二组为单层Cu金属电极；第三组为单层Ag金属电极；第四组为双层金属电极，且第一层为Bi金属层、第二层为Al金属层；第五组为双层金属电极，且第一层为Bi金属层、第二层为Cu金属层；第六组为双层金属电极，且第一层为Bi金属层、第二层为Ag金属层；第七组为双层金属电极，且第一层为Bi-Sn合金层、第二层为Ag金属层；第八组为双层金属电极，且第一层为Bi-Cu合金层、第二层为Ag金属层。Eight sets of perovskite solar cells were prepared under the same conditions. The eight groups of perovskite solar cells differed in that the first group was a single-layer Al metal electrode; the second group was a single-layer Cu metal electrode; the third group was a single Layer Ag metal electrode; the fourth group is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Al metal layer; the fifth group is a double layer metal electrode, and the first layer is a Bi metal layer, The second layer is a Cu metal layer; the sixth layer is a double layer metal electrode, and the first layer is a Bi metal layer and the second layer is an Ag metal layer; the seventh group is a double layer metal electrode, and the first layer is Bi-Sn The alloy layer and the second layer are Ag metal layers; the eighth group is a double-layer metal electrode, and the first layer is a Bi-Cu alloy layer, and the second layer is an Ag metal layer.
将上述八组钙钛矿太阳能电池进行光照稳定性测试，测试条件为：未封装器件，无水无氧N2气环境，25℃环境温度，白光LED提供100mW/cm2强度的持续光照；进而在电池的最大功率点连续检测，实验结果如图7所示，基于双层金属电极的钙钛矿太阳能电池的光照稳定性得到了显著提高，实用性大大提高。The above eight groups of perovskite solar cells were tested for light stability under the following conditions: unpackaged device, anhydrous oxygen-free N 2 gas environment, ambient temperature of 25 ° C, and white LED providing continuous illumination of 100 mW/cm 2 intensity; The continuous detection of the maximum power point of the battery, the experimental results shown in Figure 7, the light stability of the perovskite solar cell based on the two-layer metal electrode has been significantly improved, and the practicality is greatly improved.
实施例7Example 7
在相同条件制备八组钙钛矿太阳能电池，八组钙钛矿太阳能电池的不同之处在于：第一组为直接在电子传输层上表面磁控溅射形成Ti金属电极；第二组为直接在电子传输层上表面磁控溅射形成Ni金属电极；第三组为直接在电子传输层上表面磁控溅射形成Mo金属电极；第四组为先在电子传输层上表面蒸镀一层Bi金属层作为缓冲层，然后再磁控溅射形成Ti金属电极；第五组为先在电子传输层上表面蒸镀一层Bi金属层作为缓冲层，然后再磁控溅射形成Ni金属电极；第六组为先在电子传输层上表面蒸镀一层Bi金属层作为缓冲层，然后再磁控溅射形成Mo金属电极；第七组为先在电子传输层上表面蒸镀一层Bi-Sn合金层作为缓冲层，然后再磁控溅射形成Mo金属电极；第八组先在电子传输层上表面蒸镀一层Bi-Cu合金层作为缓冲层，然后再磁控溅射形成Mo金属电极。Eight sets of perovskite solar cells were prepared under the same conditions. The eight groups of perovskite solar cells differed in that the first group was formed by magnetron sputtering on the upper surface of the electron transport layer to form Ti metal electrodes; the second group was directly On the upper surface of the electron transport layer, magnetron sputtering is used to form a Ni metal electrode; the third group is a magnetron sputtering on the upper surface of the electron transport layer to form a Mo metal electrode; and the fourth group is a vapor deposition layer on the upper surface of the electron transport layer. The Bi metal layer acts as a buffer layer and then magnetron sputtering to form a Ti metal electrode; the fifth group first deposits a Bi metal layer on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form a Ni metal electrode. The sixth group firstly deposits a layer of Bi metal on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form a Mo metal electrode; the seventh group first deposits a layer of Bi on the upper surface of the electron transport layer. -Sn alloy layer as a buffer layer, and then magnetron sputtering to form a Mo metal electrode; the eighth group first vapor-deposits a layer of Bi-Cu alloy layer on the upper surface of the electron transport layer as a buffer layer, and then magnetron sputtering to form Mo Metal electrode.
将上述八组钙钛矿太阳能电池的面积设置为1cm2，其由光学掩膜产生，并在3A级太阳光模拟器的100mW/cm2输出光强下照射，测量其光电转换效率。The area of the above eight sets of perovskite solar cells was set to 1 cm 2 , which was generated by an optical mask, and irradiated at a light intensity of 100 mW/cm 2 of a 3A-level solar simulator, and the photoelectric conversion efficiency thereof was measured.
如图8所示，其为八组钙钛矿太阳能电池的“光电流密度-电压”输出特性曲线，由上述对比曲线可知，直接磁控溅射金属电极，会显著损伤电池，电池的效率非常低 (＜4％)；而采用低温蒸镀的Bi或Bi基合金作为缓冲层，可以有效避免溅射过程对钙钛矿和界面材料的损伤。基于Bi或Bi基合金和磁控溅射的贱金属Ti、Ni、Mo等构成双层金属电极，替代昂贵的Ag或Au，在不损失电池效率的同时使得电极材料的成本大幅降低。其中，基于Bi/Ti双层金属电极的电池效率为11.48％，基于Bi/Ni双层金属电极的电池效率为14.05％，基于Bi/Mo双层金属电极的电池效率为15.45％，基于Bi-Sn/Mo双层金属电极的电池效率为16.04％，基于Bi-Sn/Mo双层金属电极的电池效率为16.61％。在实现高光电转换效率的同时降低了电极材料的成本，有利于产业化。As shown in Fig. 8, it is the "photocurrent density-voltage" output characteristic curve of eight sets of perovskite solar cells. It can be seen from the above comparison curve that direct magnetron sputtering of metal electrodes can significantly damage the battery, and the efficiency of the battery is very high. Low (<4%); and the use of low-temperature evaporation of Bi or Bi-based alloy as a buffer layer can effectively avoid damage to the perovskite and interface materials during the sputtering process. Based on Bi or Bi-based alloys and magnetron sputtering, the base metals Ti, Ni, Mo, etc. constitute a double-layer metal electrode, instead of expensive Ag or Au, the cost of the electrode material is greatly reduced without losing the efficiency of the battery. Among them, the battery efficiency based on the Bi/Ti double-layer metal electrode is 11.48%, the battery efficiency based on the Bi/Ni double-layer metal electrode is 14.05%, and the battery efficiency based on the Bi/Mo double-layer metal electrode is 15.45%, based on Bi- The battery efficiency of the Sn/Mo double-layer metal electrode was 16.04%, and the battery efficiency based on the Bi-Sn/Mo double-layer metal electrode was 16.61%. In order to achieve high photoelectric conversion efficiency, the cost of the electrode material is reduced, which is advantageous for industrialization.
以上所述本公开的具体实施方式，并不构成对本公开保护范围的限定。任何根据本公开的技术构思所做出的各种其他相应的改变与变形，均应包含在本公开权利要求的保护范围内。 The specific embodiments of the present disclosure described above are not intended to limit the scope of the disclosure. Any other various changes and modifications made in accordance with the technical idea of the present disclosure are intended to be included within the scope of the appended claims.

Claims (10)

  1. 一种用于钙钛矿太阳能电池的双层金属电极，其特征在于，包括第一金属薄膜层及铺设于所述第一金属薄膜层一侧表面的第二金属薄膜层；其中，所述第一金属薄膜层具有化学惰性，所述第二金属薄膜层具有高导电率。A two-layer metal electrode for a perovskite solar cell, comprising: a first metal thin film layer and a second metal thin film layer disposed on a surface of one side of the first metal thin film layer; wherein A metal thin film layer is chemically inert, and the second metal thin film layer has high electrical conductivity.
  2. 根据权利要求1所述的双层金属电极，其特征在于，所述第一金属薄膜层为Bi金属薄膜层或Bi合金薄膜层。The two-layer metal electrode according to claim 1, wherein the first metal thin film layer is a Bi metal thin film layer or a Bi alloy thin film layer.
  3. 根据权利要求2所述的双层金属电极，其特征在于，所述第二金属薄膜层为Ag、Au、Al、Cu、Ti、Ni或Mo金属薄膜层。The two-layer metal electrode according to claim 2, wherein the second metal thin film layer is a metal thin film layer of Ag, Au, Al, Cu, Ti, Ni or Mo.
  4. 一种用于钙钛矿太阳能电池的双层金属电极的制备方法，其特征在于，包括如下步骤：A method for preparing a two-layer metal electrode for a perovskite solar cell, comprising the steps of:
    (1)采用真空蒸镀方法在电子传输层一侧表面沉积一层具有化学惰性的第一金属薄膜层；(1) depositing a chemically inert first metal thin film layer on one side of the electron transport layer by vacuum evaporation;
    (2)采用真空蒸镀或磁控溅射的方法在第一金属薄膜层上沉积一层具有高导电率的第二金属薄膜层。(2) depositing a second metal thin film layer having high conductivity on the first metal thin film layer by vacuum evaporation or magnetron sputtering.
  5. 根据权利要求4所述的制备方法，其特征在于，所述第一金属薄膜层为Bi金属薄膜层或Bi合金薄膜层；所述第二金属薄膜层为Ag、Au、Al、Cu、Ti、Ni或Mo金属薄膜层。The preparation method according to claim 4, wherein the first metal thin film layer is a Bi metal thin film layer or a Bi alloy thin film layer; and the second metal thin film layer is Ag, Au, Al, Cu, Ti, Ni or Mo metal film layer.
  6. 根据权利要求5所述的制备方法，其特征在于，所述步骤(1)中真空蒸镀的真空度小于10-3Pa、蒸镀速度为
    Figure PCTCN2017112225-appb-100001
    蒸发温度小于1000℃。    The preparation method according to claim 5, wherein the vacuum degree of the vacuum evaporation in the step (1) is less than 10 -3 Pa, and the evaporation rate is
    Figure PCTCN2017112225-appb-100001
    The evaporation temperature is less than 1000 °C.
  7. 根据权利要求6所述的制备方法，其特征在于，第一金属薄膜层蒸镀的厚度为5～80nm。The preparation method according to claim 6, wherein the first metal thin film layer is vapor-deposited to have a thickness of 5 to 80 nm.
  8. 根据权利要求5所述的制备方法，其特征在于，当第二金属薄膜层为Ag、Au或Al金属薄膜层时，其采用真空蒸镀方法，且真空蒸镀的真空度＜10-3Pa、蒸镀速度为
    Figure PCTCN2017112225-appb-100002
    蒸镀厚度为50-200nm。    The preparation method according to claim 5, wherein when the second metal thin film layer is an Ag, Au or Al metal thin film layer, the vacuum evaporation method is employed, and the vacuum degree of vacuum evaporation is <10 -3 Pa. The evaporation rate is
    Figure PCTCN2017112225-appb-100002
    The thickness of the evaporation is 50-200 nm.
  9. 根据权利要求5所述的制备方法，其特征在于，当第二金属薄膜层为Cu、Ti、Ni或Mo金属薄膜层时，其采用磁控溅射方法，且操作气压为0.1-100Pa、溅射功率密度为1-100W/cm2、溅射厚度为100-2000nm。The preparation method according to claim 5, wherein when the second metal thin film layer is a Cu, Ti, Ni or Mo metal thin film layer, the magnetron sputtering method is employed, and the operating gas pressure is 0.1-100 Pa, and the sputtering is performed. The emission power density is 1-100 W/cm 2 and the sputtering thickness is 100-2000 nm.
  10. 一种钙钛矿太阳能电池，其特征在于，包括由下至上依次层叠设置的玻璃基底、透明导电电极、空穴传输层、钙钛矿薄膜、电子传输层及权利要求1～3任一所述的双层 金属电极，所述双层金属电极的第一金属薄膜层靠近所述电子传输层设置。 A perovskite solar cell comprising: a glass substrate, a transparent conductive electrode, a hole transport layer, a perovskite film, an electron transport layer, and any one of claims 1 to 3, which are stacked in this order from bottom to top Double layer A metal electrode, the first metal thin film layer of the double metal electrode being disposed adjacent to the electron transport layer.
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