WO2024255400A1 - 一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 - Google Patents

一种钙钛矿/硅异质结叠层太阳能电池及其制备方法 Download PDF

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WO2024255400A1
WO2024255400A1 PCT/CN2024/085621 CN2024085621W WO2024255400A1 WO 2024255400 A1 WO2024255400 A1 WO 2024255400A1 CN 2024085621 W CN2024085621 W CN 2024085621W WO 2024255400 A1 WO2024255400 A1 WO 2024255400A1
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transparent conductive
conductive layer
layer
front transparent
solar cell
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French (fr)
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王永磊
何博
刘杨
顾小兵
刘童
徐希翔
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Longi Green Energy Technology Co Ltd
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Longi Green Energy Technology Co Ltd
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Priority claimed from CN202310713067.9A external-priority patent/CN116705909A/zh
Priority claimed from CN202310729455.6A external-priority patent/CN116669501A/zh
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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
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • 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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
    • H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
    • 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
    • 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
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

Definitions

  • the present application relates to the field of solar energy technology, and in particular to a perovskite/silicon heterojunction stacked solar cell and a preparation method thereof.
  • Organic-inorganic hybrid perovskite solar cells have attracted widespread attention worldwide as a new type of high-efficiency, low-cost solar cell.
  • the photoelectric conversion efficiency of single-junction small-area perovskite cells has rapidly climbed from 3.8% in 2009 to more than 25%, and the photoelectric conversion efficiency of perovskite/silicon heterojunction stacked cells has also reached more than 33%.
  • the rapid efficiency development has made it the focus of current photovoltaic research institutions and companies.
  • perovskite solar cells Compared with traditional thin-film solar cells (copper indium gallium selenide, cadmium telluride, etc.), perovskite solar cells have the advantages of high conversion efficiency, simple preparation process and low-cost potential, and have become the thin-film solar cell technology with the most industrial prospects.
  • the cutoff wavelength of the spectral response of the solar cell can be controlled, making it the most ideal top cell absorption layer material.
  • Silicon heterojunction solar cell technology has the advantages of simple process (texture cleaning ⁇ amorphous silicon deposition ⁇ TCO deposition ⁇ silver electrode printing), low preparation temperature ( ⁇ 220°C), high conversion efficiency (>25%), symmetrical structure (double-sided), etc., and is considered to be the third generation of battery technology after PERC cells.
  • Silicon heterojunction cells have high infrared band absorption, strong weak light effect and structural advantages that can match p-i-n, making them one of the best bottom cell choices.
  • the "perovskite/silicon-based heterojunction" stacked cell structure is formed by perovskite cells (top cells) and silicon-based heterojunction cells (bottom cells) to achieve distributed absorption of the solar spectrum, and has achieved a conversion efficiency of more than 33%.
  • the preparation temperature of silicon heterojunction solar cells is less than 220°C, and the preparation temperature of perovskite solar cells is less than 150°C
  • TCO front transparent conductive layer
  • the present application provides a perovskite/silicon heterojunction stacked solar cell and a preparation method thereof, so as to solve or at least partially solve the problems existing in the prior art.
  • the present application provides a method for preparing a perovskite/silicon heterojunction tandem solar cell, comprising: preparing a silicon heterojunction bottom cell; sequentially preparing a composite layer, a hole transport layer, a perovskite absorption layer, an electron transport layer and a front transparent conductive layer on one side of the silicon heterojunction bottom cell; protecting the silicon heterojunction bottom cell and the perovskite absorption layer, and heating the front transparent conductive layer to at least partially crystallize the front transparent conductive layer in the prepared tandem solar cell.
  • the protecting the silicon heterojunction bottom cell and the perovskite absorption layer and heat-treating the front transparent conductive layer so that the front transparent conductive layer in the prepared stacked solar cell is at least partially crystallized comprises: using laser to treat the front transparent conductive layer so that the front transparent conductive layer is at least partially crystallized, and the laser does not damage the silicon heterojunction bottom cell and the perovskite absorption layer.
  • the laser makes the temperature of the front transparent conductive layer reach 400-800°C; the laser is a violet laser with a wavelength of 355nm; the pulse width of the laser is 0.75-20ns; the X-ray diffraction pattern of the front transparent conductive layer has a characteristic peak at a diffraction angle 2 ⁇ of 30.73° ⁇ 0.02.
  • the laser is applied by using a galvanometer system.
  • the protecting the silicon heterojunction bottom cell and the perovskite absorption layer and heating the front transparent conductive layer so that the front transparent conductive layer in the prepared stacked solar cell is at least partially crystallized comprises: controlling the temperature of the prepared stacked solar cell so as to protect the silicon heterojunction bottom cell and the perovskite absorption layer; and providing a heat source to at least partially crystallize the front transparent conductive layer.
  • the temperature control is achieved by placing the prepared stacked solar cell on a temperature control table, wherein the side of the stacked solar cell away from the front transparent conductive layer is in contact with the temperature control table; the temperature of the temperature control table is set at -20 to -10°C.
  • the heat source makes the temperature of the front transparent conductive layer reach 350-400°C; the heat source is provided for 1-10 min; the heat source provides heat in a manner selected from one or more of thermal radiation, thermal conduction, and thermal convection; the heat source is selected from one or more of an infrared heating lamp, a hot table, and hot air; the X-ray diffraction pattern of the front transparent conductive layer has a characteristic peak at a diffraction angle 2 ⁇ of 30.52° ⁇ 0.02.
  • the material of the front transparent conductive layer is selected from one of ITO, IWO, IZO and ITiO.
  • the material of the front transparent conductive layer is ITO.
  • the thickness of the front transparent conductive layer is 30-150 nm.
  • the silicon heterojunction bottom cell comprises a back transparent conductive layer, a P-type amorphous silicon layer, a first intrinsic amorphous silicon layer, an N-type crystalline silicon substrate, a second intrinsic amorphous silicon layer, and an N-type amorphous silicon layer which are stacked in sequence.
  • the method further comprises: preparing a metal electrode on a side of the silicon heterojunction bottom cell away from the composite layer, and on a side of the front transparent conductive layer or the treated front transparent conductive layer away from the composite layer.
  • the present application also provides a perovskite/silicon heterojunction tandem solar cell, comprising: a silicon heterojunction bottom cell, a composite layer, a hole transport layer, a perovskite absorption layer, an electron transport layer and a front transparent conductive layer stacked in sequence, wherein the front transparent conductive layer is at least partially crystallized.
  • the tandem solar cell is prepared by the above-mentioned preparation method.
  • the present application provides a perovskite/silicon heterojunction tandem solar cell and a preparation method thereof, wherein a front transparent conductive layer is heated on the basis of protecting a silicon heterojunction bottom cell and a perovskite absorption layer, so that the material of the front transparent conductive layer can be crystallized without affecting the silicon tandem cell substrate, thereby improving the optical and electrical properties of the material of the front transparent conductive layer and improving the overall efficiency of the tandem cell.
  • FIG1 is a schematic diagram of a stacked solar cell according to an embodiment of the present invention.
  • FIG2 is a schematic diagram showing the effect of laser treatment on the transmittance of an ITO layer in an embodiment of the present invention
  • FIG3 shows an XRD diffraction diagram of an ITO layer before and after laser treatment in an embodiment of the present invention
  • FIG4 is a schematic diagram showing the effect of heat treatment on the transmittance of an ITO layer in an embodiment of the present invention.
  • FIG. 5 shows an XRD diffraction diagram of an ITO layer before and after heat treatment in an embodiment of the present invention.
  • the TCO film layer prepared at this time can be directly crystallized and has good electrical and optical properties.
  • the crystallization temperature of ITO material is 200°C.
  • the substrate temperature needs to be heated to 300-350°C, and a crystallized ITO film layer can be directly obtained.
  • the other method is to prepare the TCO film layer at low temperature and then perform heat treatment. Magnetron sputtering is directly performed on the substrate material at room temperature. The TCO film layer prepared at this time is amorphous. Then heat treatment is performed to crystallize the amorphous TCO film layer.
  • the crystallized TCO film layer also has good electrical and optical properties. For example, the crystallization temperature of ITO material is 200°C. After preparing the ITO film layer at room temperature, the substrate temperature is heated to 250°C to obtain a crystallized ITO film layer.
  • the present application provides a method for preparing a perovskite/silicon heterojunction stacked solar cell, comprising the following steps:
  • S2 On one side of the silicon heterojunction bottom cell, a composite layer, a hole transport layer, and a perovskite layer are sequentially prepared. Mineral absorption layer, electron transport layer and front transparent conductive layer.
  • the silicon heterojunction bottom cell can be various types of silicon heterojunction bottom cells known in the art, and can be prepared by methods known in the art.
  • the structure of the silicon heterojunction bottom cell is shown in Figure 1, including a back transparent conductive layer 1-1, a P-type amorphous silicon layer 1-2, a first intrinsic amorphous silicon layer 1-3, an N-type crystalline silicon substrate 1-4, a second intrinsic amorphous silicon layer 1-5, and an N-type amorphous silicon layer 1-6 stacked in sequence.
  • the back transparent conductive layer 1-1 is used to collect carriers and transmit them to the metal electrode.
  • the material of the back transparent conductive layer 1-1 can be ITO, IWO, IZO, ITiO, etc.
  • the P-type amorphous silicon layer 1-2 forms the back electric field of the silicon heterojunction solar cell and can be prepared by PECVD.
  • the first intrinsic amorphous silicon layer 1-3 and the second intrinsic amorphous silicon layer 1-5 mainly play the role of passivating the dangling bonds on the surface of the crystalline silicon substrate and can be prepared by PECVD.
  • the N-type crystalline silicon substrate 1-4 serves as the bottom cell light absorption layer to convert photons into photogenerated carriers (electron-hole pairs).
  • the N-type amorphous silicon layers 1-6 constitute the emitter of the heterojunction cell and can be prepared by PECVD method.
  • step S2 sequentially preparing a composite layer, a hole transport layer, a perovskite absorption layer, an electron transport layer and a front transparent conductive layer means preparing a composite layer on a silicon heterojunction bottom cell, then preparing a hole transport layer on the composite layer, then preparing a perovskite absorption layer on the hole transport layer, then preparing an electron transport layer on the perovskite absorption layer, and finally preparing a front transparent conductive layer on the electron transport layer.
  • the final stacked cell structure can be shown in Figure 1.
  • the composite layer can realize the passage of photogenerated carriers from the perovskite layer to the silicon heterojunction, and TCO materials such as ITO, IWO, IZO, ITiO, etc.
  • the hole transport layer can select one or more materials from Spiro-TTB, Spiro-OMeTAD, Spiro-TAD CuSCN, NiO x , NiMgO x , V 2 O 5 and MoO 3 .
  • the perovskite absorption layer usually has a band gap of more than 1.6 eV, and its components are generally a single component system such as (Cs0.15FA0.85)Pb(I0.7Br0.3)3.
  • the material of the electron transport layer is generally C60 , PCBM, SnO2 , etc.
  • the material of the front transparent conductive layer can be selected from ITO, IWO, IZO, ITiO, etc., preferably ITO.
  • the thickness of the front transparent conductive layer is generally 30-150nm.
  • the composite layer, hole transport layer, perovskite absorption layer, electron transport layer and front transparent conductive layer can all be prepared by methods known in the art. Those skilled in the art can adjust the materials, thickness and preparation process used in each layer according to actual needs.
  • step S3 the front transparent conductive layer can be heated while protecting the silicon heterojunction bottom cell and the perovskite absorption layer, so that the prepared laminated solar cell
  • the front transparent conductive layer is at least partially crystallized.
  • step S3 can be achieved by treating the front transparent conductive layer with a laser to at least partially crystallize the front transparent conductive layer, and the laser does not damage the silicon heterojunction bottom cell and the perovskite absorption layer.
  • the temperature at which the laser is applied to the front transparent conductive layer should be such that the TCO material can crystallize.
  • the laser causes the temperature of the front transparent conductive layer to reach 400-800°C, for example, it can be 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C, 500°
  • the laser is a violet laser with a wavelength of 355nm.
  • the violet laser with a wavelength of 355nm is used so that most of the laser is absorbed by the TCO material of the front transparent conductive layer, so the area where its thermal effect is generated is mainly the front transparent conductive layer, and the silicon heterojunction bottom cell and the perovskite absorption layer will not be damaged.
  • the pulse width of the laser is 0.75-20ns, for example, it can be 0.75ns, 1ns, 2ns, 3ns, 4ns, 5ns, 6ns, 7ns, 8ns, 9ns, 10ns, 11ns, 12ns, 13ns, 14ns, 15ns, 16ns, 17ns, 18ns, 19ns, 20ns, or any range between these values.
  • the laser is applied by using a galvanometer system.
  • the galvanometer is simply a scanning galvanometer used in the laser industry, and its professional term is a high-speed scanning galvanometer Galvo scanning system.
  • the so-called galvanometer can also be called an ammeter. Its design concept completely follows the design method of the ammeter.
  • the lens replaces the needle, and the signal of the probe is replaced by a computer-controlled -5V-5V or -10V-+10V DC signal to complete the predetermined action.
  • this typical control system uses a pair of folding mirrors. The difference is that the stepper motor driving this set of lenses is replaced by a servo motor.
  • the use of position sensors and the design of negative feedback loops further ensure the accuracy of the system, and the scanning speed and repeated positioning accuracy of the entire system reach a new level. This can achieve the purpose of fast and accurate processing, thereby reducing processing time and increasing processing speed while ensuring the crystallization of the TCO material of the front transparent conductive layer.
  • the temperature of the front transparent conductive layer reaches 400-800° C. due to the laser.
  • the laser when the front transparent conductive layer is treated with laser, the laser is a violet laser with a wavelength of 355nm, the pulse width of the laser is 0.75-20ns, and the laser is applied by a galvanometer system.
  • the laser when the front transparent conductive layer is treated with laser, the laser causes the temperature of the front transparent conductive layer to reach 400-800°C, the laser is a violet laser with a wavelength of 355nm, the pulse width of the laser is 0.75-20ns, and the laser is applied by a galvanometer system.
  • step S3 can be achieved by controlling the temperature of the prepared laminated solar cell, thereby protecting the silicon heterojunction bottom cell and the perovskite absorption layer; and providing a heat source to at least partially crystallize the front transparent conductive layer.
  • the temperature control of the laminated cell prepared in step S2 is to keep the substrate of the laminated cell at a low temperature when the front transparent conductive layer is heat treated, so as to ensure that the substrate is not affected when the TCO material of the front transparent conductive layer is crystallized.
  • Various methods or devices known in the art can be selected for temperature control, for example, the laminated cell can be placed on a temperature control table, wherein the side of the laminated solar cell away from the front transparent conductive layer is in contact with the temperature control table, that is, the front transparent conductive layer is away from the temperature control table.
  • the temperature of the temperature control platform is set at -20 to -10°C, for example, -20°C, -19.5°C, -19°C, -18.5°C, -18°C, -17.5°C, -17°C, -16.5°C, -16°C, -15.5°C, -15°C, -14.5°C, -14°C, -13.5°C, -13°C, -12.5°C, -12°C, -11.5°C, -11°C, -10.5°C, -10°C, or any range between these values.
  • various types of temperature control platforms can be selected as long as the laminated solar cell can be fully temperature controlled.
  • the laminated solar cell is brought into close contact with the temperature control platform by vacuum adsorption to achieve a better temperature control effect.
  • the heat source can at least partially crystallize the front transparent conductive layer.
  • the temperature of the laminated cell substrate is controlled by a temperature control platform and the front transparent conductive layer is heated, a temperature difference exists in the front transparent conductive layer from the side close to the silicon heterojunction bottom cell to the side far from the silicon heterojunction bottom cell. The existence of the temperature difference helps the orientation of the crystal growth of the TCO material during crystallization, thereby obtaining a better quality film layer.
  • the existence of temperature difference in the front transparent conductive layer helps the orientation of crystal growth of TCO material during crystallization, thereby obtaining a better quality film layer.
  • the temperature difference during the crystallization process will not cause detachment and mismatch between the various film layers of the stacked battery.
  • the TCO material of the front transparent conductive layer after crystallization has better optical and electrical properties, thereby improving the overall efficiency of the stacked battery.
  • silicon wafers, perovskite materials and TCO materials all have very small thermal expansion coefficients and have certain flexibility, so the temperature difference during the crystallization process will not cause detachment and mismatch between the various film layers of the stacked battery.
  • the TCO material of the front transparent conductive layer after crystallization has better optical and electrical properties, thereby improving the overall efficiency of the stacked battery.
  • the heat source causes the temperature of the front transparent conductive layer to reach 350-400°C, for example, 350°C, 351°C, 352°C, 353°C, 354°C, 355°C, 356°C, 357°C, 358°C, 359°C, 360°C, 361°C, 362°C, 363°C, 364°C, 365°C, 366°C, 367°C, 368°C, 369°C, 370°C, 371°C, 372°C , 373°C, 374°C, 375°C, 376°C, 377°C, 378°C, 379°C, 380°C, 381°C, 382°C, 383°C, 384°C, 385°C, 386°C, 387°C, 388°C, 389°C, 390°C, 391°C, 392°C, 393°C, 394°C, 3
  • the heat source is provided for 1-10 min, for example, it can be 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 5.5 min, 6 min, 6.5 min, 7 min, 7.5 min, 8 min, 8.5 min, 9 min, 9.5 min, 10 min, or any range between these values.
  • IR heating lamps those skilled in the art can adjust the power of the heating lamp, the distance from the control console, etc. as needed.
  • hot table those skilled in the art can adjust the temperature of the hot table, the distance from the control console, etc. as needed.
  • hot air those skilled in the art can adjust the temperature, flow rate, and distance from the control console of the heated air as needed.
  • the temperature of the temperature control table is set at -20 to -10°C, and the heat source is infrared.
  • the external heating lamp provides heat for 1-10 minutes, and the heat source makes the temperature of the front transparent conductive layer reach 350-400°C.
  • the temperature of the temperature control table is set at -20 to -10°C, the heat source is a hot table, and the heat source provides heat for 1-10 minutes, and the heat source makes the temperature of the front transparent conductive layer reach 350-400°C.
  • the temperature of the temperature control table is set at -20 to -10°C, the heat source is hot air, and the heat source provides heat for 1-10 minutes, and the heat source makes the temperature of the front transparent conductive layer reach 350-400°C.
  • the above-mentioned limitations on various parameters of the heat source are merely exemplary.
  • the heat source used does not cause damage to the laminated battery substrate, such as the silicon heterojunction bottom battery and the perovskite absorption layer
  • those skilled in the art can select an appropriate heating device as the heat source, and adjust various parameters such as the temperature of the heat source, the distance from the control console, the power, and the time.
  • the preparation method of the present application may also include the step of preparing a metal electrode.
  • the step of preparing the electrode may be between steps S2 and S3, that is, after the metal electrode is prepared, the front transparent conductive layer is heat-treated.
  • a metal electrode 3-1 is prepared on the side of the silicon heterojunction bottom battery away from the composite layer 1-7, and on the side of the front transparent conductive layer 2-4 away from the composite layer 1-7.
  • the step of preparing the electrode may also be after S4, that is, the metal electrode 3-1 is prepared on the side of the silicon heterojunction bottom battery away from the composite layer 1-7, and on the side of the heated front transparent conductive layer 2-4 away from the composite layer 1-7.
  • the metal electrode 3-1 may be a conventional metal electrode in the art, such as silver, copper, etc.
  • the preparation method of the present application overcomes the problem that the front transparent conductive layer cannot be crystallized in the existing preparation of laminated batteries. By heating the front transparent conductive layer and keeping the laminated battery substrate at a low temperature, the material of the front transparent conductive layer can be crystallized without affecting the laminated battery substrate, thereby improving the optical and electrical properties of the material of the front transparent conductive layer, so as to improve the overall efficiency of the laminated battery.
  • the present application also provides a perovskite/silicon heterojunction stacked solar cell.
  • the stacked solar cell includes a silicon heterojunction bottom cell, a composite layer 1-7, a hole transport layer 2-1, a perovskite absorption layer 2-2, an electron transport layer 2-3 and a front transparent conductive layer 2-4 stacked in sequence, wherein the front transparent conductive layer 2-4 is at least partially crystallized.
  • the silicon heterojunction bottom cell includes a back transparent conductive layer 1-1, a P-type amorphous silicon layer 1-2, a first intrinsic amorphous silicon layer 1-3, an N-type crystalline silicon substrate 1-4, a second intrinsic amorphous silicon layer 1-5, and an N-type amorphous silicon layer 1-6 stacked in sequence.
  • the degree of crystallization of the front transparent conductive layer 2-4 can be characterized by a detection method known in the art. For example, X-ray diffraction can be used for detection.
  • the X-ray diffraction pattern of the front transparent conductive layer 2-4 has a characteristic peak at a diffraction angle 2 ⁇ of 30.52° ⁇ 0.02(222).
  • the characteristic peak of the front transparent conductive layer 2-4 may be located at 2 ⁇ of 30.50°, 30.51°, 30.52°, 30.53°, 30.54°, or any value between these values.
  • the perovskite/silicon heterojunction stacked solar cell is prepared by any one of the above-mentioned preparation methods.
  • the structure of the prepared tandem solar cell is shown in Figure 1.
  • the perovskite/silicon heterojunction tandem solar cell includes a back transparent conductive layer 1-1, a P-type amorphous silicon layer 1-2, a first intrinsic amorphous silicon layer 1-3, an N-type crystalline silicon substrate 1-4, a second intrinsic amorphous silicon layer 1-5, an N-type amorphous silicon layer 1-6, a composite layer 1-7, a hole transport layer 2-1, a perovskite absorption layer 2-2, an electron transport layer 2-3 and a front transparent conductive layer 2-4, wherein a metal electrode 3-1 is provided on the side of the back transparent conductive layer 1-1 and the front transparent conductive layer 2-4 away from the composite layer 1-7.
  • the preparation method of the perovskite/silicon heterojunction tandem solar cell includes the following steps:
  • N-type crystalline silicon substrates 1-4 are commercial grade M6 N-type silicon wafers with a resistivity of 1-10 ⁇ .cm and a thickness of 150-200 ⁇ m. The silicon wafers are successively polished, textured and cleaned.
  • the first intrinsic amorphous silicon layer 1-3 and the second intrinsic amorphous silicon layer 1-5 are deposited on both sides of the silicon wafer by PECVD to form the front and back passivation layer films.
  • the N-type amorphous silicon layer (thickness 5-15nm) doped with phosphorus (doping concentration 10 19-20 cm -3 ) is deposited on the front side of the silicon wafer, i.e., the second intrinsic amorphous silicon layer 1-5, by PECVD to form the front field structure, i.e., the N-type amorphous silicon layer 1-6, whose conduction band is about -3.7eV.
  • the P-type amorphous silicon layer (thickness 5-15nm) doped with boron (doping concentration 10 19-20 cm -3 ) is deposited on the back side of the silicon wafer, i.e., the first intrinsic amorphous silicon layer 1-3, by PECVD to form the back emitter structure, i.e., the P-type amorphous silicon layer 1-2.
  • the back transparent conductive material layer 1-1 (thickness 70-120nm) is prepared by magnetron sputtering method, and its material is ITO. 1-1 to 1-6 constitute the bottom cell structure of the perovskite/silicon heterojunction tandem solar cell.
  • a layer of gradient ITO material is prepared as the composite layer 1-7 by magnetron sputtering, with a thickness of 20 nm.
  • NiO x layer was prepared by magnetron sputtering as the hole transport layer 2-1.
  • a layer of C60 is prepared by evaporation, and then ALD is used at 80-120° C. for 130-190 cycles to prepare 10-20 nm SnO 2 as the electron transport layer 2-3.
  • a 70-120 nm ITO film is prepared by magnetron sputtering to form the front transparent conductive layer 2-4.
  • Fine grid lines and main grid lines, i.e., metal electrodes 31, are prepared on the upper and lower surfaces by screen printing to form a complete perovskite/silicon heterojunction stacked solar cell.
  • step (8) can be performed by selecting a picosecond laser with a wavelength of 355nm, using a galvanometer system, setting its power to 4W, pulse frequency to 1500KHz, pulse width to 750 picoseconds, processing speed to 6000mm/s, and focus position to 45mm from the processing surface (i.e., the surface of the front transparent conductive layer).
  • the laser system is used to process the perovskite/silicon heterojunction stacked solar cell, so that the front transparent conductive layer can be crystallized, wherein the spot overlap rate is about 65% and the process time is 65s.
  • step (8) can be performed by placing the prepared perovskite/heterojunction stacked cell on a temperature control table, with the back electrode located at the bottom and in close contact with the temperature control table through vacuum adsorption, and the front transparent conductive layer 2-4 located at the top.
  • the temperature of the temperature control table is set to -20°C.
  • hot air is provided by a gas tank with heating and insulation functions. The hot air temperature is 350°C, the flow rate is 5L/min, and it is blown onto the temperature control table through the air hole size of the cloth. The blowing time is 10 minutes.
  • Step (8) of Example 2 is: place the prepared perovskite/heterojunction stacked cell on a temperature control table, with the back electrode located at the bottom and in close contact with the temperature control table through vacuum adsorption, and the front transparent conductive layer back located at the top.
  • the temperature of the temperature control table is set to -20°C.
  • An IR heating lamp is provided above the temperature control table, the IR heating lamp has a power of 2KW, and is 30cm away from the temperature control table. The heating time is 5min.
  • Step (8) of Example 3 is: placing the prepared perovskite/heterojunction stacked battery on a temperature-controlled platform, with the back electrode at the bottom and It is in close contact with the temperature control platform through vacuum adsorption, with the transparent conductive layer on the top.
  • the temperature of the temperature control platform is set to -20°C.
  • a hot plate is provided above the temperature control platform, with a temperature of 350°C and a distance of 1mm from the temperature control platform.
  • the heating time is 2min.
  • Comparative Example 1 only includes steps (1) to (7), i.e., does not include step (8).
  • the performance of the perovskite/silicon heterojunction stacked solar cell prepared by the laser treatment scheme of Example 1 and Comparative Example 1 is tested, and the results are shown in Table 1.
  • Example 1 greatly improves the efficiency of the laminated battery after adding the laser treatment step.
  • the present application also characterizes the effect of laser treatment on ITO from the optical, electrical and structural aspects.
  • ITO as the front transparent conductive layer, a 100nm thick ITO single film is prepared on a glass substrate. Specifically, a 100nm thick ITO single film is prepared on a glass substrate. The ITO single film is laser treated using the laser conditions in Example 1, and the changes in film performance before and after laser treatment are compared.
  • the optical aspect is based on transmittance.
  • the transmittance of the ITO single film before and after laser treatment is shown in Figure 2.
  • laser treatment can improve the transmittance of the ITO single film, thereby increasing the incident light and improving the short-circuit current density of the battery.
  • the Hall test results of the ITO single film before and after laser treatment are shown in Table 2.
  • laser treatment can improve the electrical properties of ITO, thereby reducing the internal series resistance of the battery, improving the transfer of charge, and improving the efficiency of the battery.
  • the X-ray diffraction (XRD) test results of the ITO single film before and after laser treatment are shown in Figure 3.
  • the ITO film layer after laser treatment has a characteristic peak at a diffraction angle 2 ⁇ of 30.73° in the X-ray diffraction spectrum. This shows that the laser treatment method can make the ITO film layer partially crystallize, thereby improving the electrical and optical properties of the ITO film layer.
  • the performance of the perovskite/silicon heterojunction stacked solar cell prepared by the temperature control and heat source treatment scheme of Example 1 and Examples 2, 3 and Comparative Example 1 is tested, and the results are shown in Table 3.
  • the present application also characterizes the effects of heating treatment on ITO from the aspects of optics, electricity and structure.
  • ITO as the front transparent conductive layer
  • a 100nm thick ITO single film is prepared on a glass substrate.
  • the ITO single film is heat-treated under conventional conditions of the prior art, that is, the ITO single film is heated at 250°C for 30min.
  • the optical aspect is based on transmittance as the basis for judgment.
  • the transmittance of the ITO single film before and after the heating treatment is shown in Figure 4. It can be seen from Figure 4 that heating treatment can improve the transmittance of the ITO single film, thereby increasing the incident light and improving the short-circuit current density of the battery.
  • the Hall test results of the ITO single film before and after the heating treatment are shown in Table 4. It can be seen from Table 4 that heating treatment can improve the electrical properties of ITO, thereby reducing the internal series resistance of the battery, improving the transfer of charge, and improving the efficiency of the battery.
  • the X-ray diffraction (XRD) test results of the ITO single film before and after the heating treatment are shown in Figure 5.
  • the heating treatment method can make the ITO film layer partially crystallized, thereby improving the electrical and optical properties of the ITO film layer.

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Abstract

本申请提供了一种钙钛矿/硅异质结叠层太阳能电池及其制备方法，包括制备硅异质结底电池；在所述硅异质结底电池的一侧依次制备复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层；对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化。通过在对硅异质结底电池和钙钛矿吸收层进行保护的基础上，加热前透明导电层，使得可以在不影响硅叠层电池基底的基础上，使前透明导电层的材料达到晶化，从而提升前透明导电层的材料的光学性能与电学性能，并提升叠层电池的整体效率。

Description

一种钙钛矿/硅异质结叠层太阳能电池及其制备方法
相关申请的交叉引用
本申请要求在2023年6月15日提交中国专利局、申请号为202310713067.9，名称为“钙钛矿/硅异质结叠层太阳能电池及其制备方法”的中国专利申请的优先权，以及在2023年6月19日提交中国专利局、申请号为202310729455.6，名称为“钙钛矿/硅异质结叠层太阳能电池及其制备方法”的中国专利申请的优先权，前述两件专利申请的全部内容通过引用结合在本申请中。
技术领域
本申请涉及太阳能技术领域，具体涉及一种钙钛矿/硅异质结叠层太阳能电池及其制备方法。
背景技术
有机-无机杂化钙钛矿太阳能电池作为新型高效率、低成本太阳能电池在全世界范围内被广泛关注。短短几年时间里，单结小面积钙钛矿电池的光电转换效率从2009年的3.8％迅速攀升到25％以上，钙钛矿/硅异质结叠层电池的光电转换效率也达到了33％以上。迅猛的效率发展使其成为当下光伏研究机构及企业的重点关注对象。与传统薄膜太阳能电池(铜铟镓硒、碲化镉等)相比，钙钛矿太阳能电池具有高转换效率、简单制备工艺以及低成本潜力等优势，并成为最具产业化前景的薄膜太阳能电池技术。通过调节前驱体溶液的成分配比，可实现太阳能电池光谱响应截止波长的调控，使之成为最理想的顶电池吸收层材料。
硅异质结太阳能电池技术具有工艺简单(制绒清洗→非晶硅沉积→TCO沉积→银电极印刷)、制备温度低(＜220℃)、转换效率高(＞25％)、对称结构(可双面)等优势，被认为是PERC电池之后的第三代电池技术。硅异质结电池高的红外波段吸收、强的弱光效应以及可匹配p-i-n的结构优势，使其成为最佳的底电池选择之一。以钙钛矿电池(顶电池)与硅基异质结电池(底电池)形成“钙钛矿/硅基异质结”叠层电池结构，实现太阳光谱的分配吸收，已经获得33％以上的转换效率。
由于硅异质结太阳能电池与钙钛矿太阳能电池都无法耐受高温(硅异质结太阳能电池制备温度＜220℃，钙钛矿太阳能电池制备温度＜150℃)，在 制备前透明导电层(TCO)时，只能进行低温制备，并且无法对制备的TCO材料进行常规加热处理。这也导致TCO材料无法晶化，其电学性能与光学性能无法达到最佳状态，从而限制了叠层电池的效率提升。
发明内容
本申请提供了一种钙钛矿/硅异质结叠层太阳能电池及其制备方法，以解决或者至少部分解决现有技术中存在的问题。
本申请的技术方案如下：
本申请提供一种钙钛矿/硅异质结叠层太阳能电池的制备方法，包括：制备硅异质结底电池；在所述硅异质结底电池的一侧依次制备复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层；对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化。
优选地，所述对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化，包括：采用激光处理所述前透明导电层使所述前透明导电层至少部分晶化，并且所述激光不损伤所述硅异质结底电池和所述钙钛矿吸收层。
优选地，所述激光使所述前透明导电层的温度达到400-800℃；所述激光为波长355nm的紫光激光；所述激光的脉冲宽度为0.75-20ns；所述前透明导电层的X射线衍射图谱在衍射角2θ为30.73°±0.02处具有特征峰。
优选地，采用激光处理所述前透明导电层时通过采用振镜系统来施加所述激光。
优选地，所述对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化，包括：将制备得到的叠层太阳能电池进行控温，从而对所述硅异质结底电池和所述钙钛矿吸收层进行保护；提供热源使所述前透明导电层至少部分晶化。
优选地，所述控温通过将制备得到的叠层太阳能电池放置在控温台上实现，所述叠层太阳能电池远离所述前透明导电层的一侧与控温台接触；所述控温台的温度设置在-20至-10℃。
优选地，所述热源使所述前透明导电层的温度达到350-400℃；所述热源提供的时间为1-10min；所述热源提供热的方式选自热辐射、热传导、热对流中的一种或两种以上；所述热源选自红外加热灯、热台、热空气中的一种或两种以上；所述前透明导电层的X射线衍射图谱在衍射角2θ为30.52°±0.02处具有特征峰。
优选地，所述前透明导电层的材料选自ITO、IWO、IZO、ITiO中的一种。优选地，所述前透明导电层的材料为ITO。优选地，所述前透明导电层的厚度为30-150nm。
优选地，所述硅异质结底电池包括依次层叠设置的背透明导电层、P型非晶硅层、第一本征非晶硅层、N型晶硅衬底、第二本征非晶硅层、N型非晶硅层。
优选地，所述方法还包括：在所述硅异质结底电池远离所述复合层的一侧，以及所述前透明导电层或经处理的前透明导电层远离所述复合层的一侧制备金属电极。
本申请还提供一种钙钛矿/硅异质结叠层太阳能电池，包括：依次层叠设置的硅异质结底电池、复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层，所述前透明导电层至少部分晶化。优选地，所述叠层太阳能电池由上述的制备方法制备得到。
本申请提供一种钙钛矿/硅异质结叠层太阳能电池及其制备方法，通过在对硅异质结底电池和钙钛矿吸收层进行保护的基础上，加热前透明导电层，使得可以在不影响硅叠层电池基底的基础上，使前透明导电层的材料达到晶化，从而提升前透明导电层的材料的光学性能与电学性能，并提升叠层电池的整体效率。
附图说明
附图用于更好地理解本申请，不构成对本申请的不当限定。其中：
图1表示本发明实施例中叠层太阳能电池的一种示意图；
图2表示本发明实施例中显示激光处理对ITO层透过率的影响示意图；
图3表示本发明实施例中显示激光处理前后ITO层的XRD衍射图；
图4表示本发明实施例中显示热处理对ITO层透过率的影响示意图；
图5表示本发明实施例中显示热处理前后ITO层的XRD衍射图。
附图标记：
1-1背透明导电层，1-2P型非晶硅层，1-3第一本征非晶硅层，1-4N型
晶硅衬底；1-5第一本征非晶硅层，1-6N型非晶硅层，1-7复合层，2-1空穴传输层，2-2钙钛矿吸收层，2-3电子传输层，2-4前透明导电层，3-1金属电极。
具体实施例
以下对本申请的示范性实施例做出说明，其中包括在一些实施例中的各种细节以助于理解，应当将它们认为仅仅是示范性的。因此，本领域普通技术人员应当认识到，可以对这里描述的实施例做出各种改变和修改，而不会背离本申请的范围和精神。同样，为了清楚和简明，以下的描述中省略了对公知功能和结构的描述。
现有的非叠层的常规太阳能电池的TCO膜层制备工艺主要有两种：
一种为高温制备TCO膜层。即将基底温度加热至TCO材料的晶化温度以上，直接磁控溅射成膜。此时制备的TCO膜层可以直接晶化，具有良好的电学与光学性能。例如，ITO材料的晶化温度为200℃，高温制备ITO膜层时需要将基底温度加热至300-350℃，可以直接得到晶化的ITO膜层。
另一种为低温制备TCO膜层后，再进行热处理。在室温下直接在基底材料商磁控溅射成膜，此时制备的TCO膜层为非晶态。然后再进行热处理，使非晶态的TCO膜层晶化，晶化后的TCO膜层也具有良好的电学与光学性能。例如，ITO材料的晶化温度为200℃，室温制备ITO膜层后，再将基底温度加热至250℃，可以得到晶化的ITO膜层。
如上文所述，由于硅异质结太阳能电池与钙钛矿太阳能电池都无法耐受高温，因此在制备前透明导电层的TCO材料时，只能进行低温制备，并且无法对制备的TCO材料进行常规热处理。前透明导电层TCO材料的低温制备工艺虽然匹配了硅异质结太阳电池与钙钛矿太阳电池的制备工艺，但是也导致TCO材料无法晶化，其电学性能与光学性能无法达到最佳状态，从而限制了叠层电池的效率提升。针对前透明导电层的TCO材料无法晶化的问题，本申请提供一种钙钛矿/硅异质结叠层太阳能电池的制备方法，包括以下步骤：
S1：制备硅异质结底电池。
S2：在所述硅异质结底电池的一侧依次制备复合层、空穴传输层、钙钛 矿吸收层、电子传输层和前透明导电层。
S3、对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化其中，步骤S1中，硅异质结底电池可以是本领域已知的各种类型的硅异质结底电池，可以采用本领域已知的方法制备。
在一个具体的实施方式中，硅异质结底电池的结构如图1所示，包括依次层叠设置的背透明导电层1-1、P型非晶硅层1-2、第一本征非晶硅层1-3、N型晶硅衬底1-4、第二本征非晶硅层1-5、N型非晶硅层1-6。其中，背透明导电层1-1用于收集载流子并传输至金属电极。背透明导电层1-1的材料可以为ITO、IWO、IZO、ITiO等。P型非晶硅层1-2形成硅异质结太阳能电池的背面电场，可以采用PECVD法制备。第一本征非晶硅层1-3和第二本征非晶硅层1-5，主要起到钝化晶硅衬底表面的悬挂键作，可以采用PECVD法制备。N型晶硅衬底1-4作为底电池光吸收层，将光子转换为光生载流子(电子-空穴对)。N型非晶硅层1-6构成异质结电池发射级，可以采用PECVD法制备。
步骤S2中，依次制备复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层是指在硅异质结底电池上制备复合层，然后在复合层上制备空穴传输层，然后在空穴传输层上制备钙钛矿吸收层，再在钙钛矿吸收层上制备电子传输层，最后在电子传输层上制备前透明导电层。最终形成的叠层电池结构可以如图1所示。其中，复合层可以实现光生载流子从钙钛矿层到硅异质结中的穿越，通常选用TCO材料，例如ITO、IWO、IZO、ITiO等。空穴传输层可以选择Spiro-TTB、Spiro-OMeTAD、Spiro-TAD CuSCN、NiOx、NiMgOx、V2O5和MoO3中的一种或几种材料。钙钛矿吸收层，通常带隙一般在1.6eV以上，组分一般为(Cs0.15FA0.85)Pb(I0.7Br0.3)3等单一的成分体系。电子传输层的材料一般为C60、PCBM、SnO2等。前透明导电层的材料可以选自ITO、IWO、IZO、ITiO等，优选为ITO。前透明导电层的厚度通常为30-150nm。复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层均可以采用本领域已知的方法制备。本领域技术人员可以根据实际需要调整各层使用的材料、厚度以及制备工艺。
在步骤S3中，可以在对硅异质结底电池和钙钛矿吸收层进行保护的基础上，同时对前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的 前透明导电层至少部分晶化。在一个具体的实施方式中，步骤S3可以由采用激光处理所述前透明导电层使所述前透明导电层至少部分晶化，并且所述激光不损伤所述硅异质结底电池和所述钙钛矿吸收层的方式实现。
激光施加到前透明导电层的温度应该使的TCO材料能够晶化。在一个具体的实施方式中，激光使前透明导电层的温度达到400-800℃，例如可以为400℃、410℃、420℃、430℃、440℃、450℃、460℃、470℃、480℃、490℃、500℃、510℃、520℃、530℃、540℃、550℃、560℃、570℃、580℃、590℃、600℃、610℃、620℃、630℃、640℃、650℃、660℃、670℃、680℃、690℃、700℃、710℃、720℃、730℃、740℃、750℃、760℃、770℃、780℃、790℃、800℃，或这些数值之间的任意范围。在400-800℃可以实现TCO材料的晶化。
在一个具体的实施方式中，激光为波长为355nm的紫光激光。采用波长为355nm的紫光激光，使得大部分激光被前透明导电层的TCO材料吸收，所以其热效应的产生区域主要为前透明导电层，不会损伤硅异质结底电池和钙钛矿吸收层。在一个具体的实施方式中，激光的脉冲宽度为0.75-20ns，例如可以为0.75ns、1ns、2ns、3ns、4ns、5ns、6ns、7ns、8ns、9ns、10ns、11ns、12ns、13ns、14ns、15ns、16ns、17ns、18ns、19ns、20ns，或这些数值之间的任意范围。
本领域技术人员可以根据激光的波长、脉冲宽度等要求，选择各种市售的激光设备进行上述激光处理。在一个具体的实施方式中，在采用激光处理前透明导电层时，通过采用振镜系统施加激光。振镜简单来讲是用在激光行业的一种扫描振镜，其专业名词叫做高速扫描振镜Galvo scanning system。所谓振镜，又可以称之为电流表计，它的设计思路完全沿袭电流表的设计方法，镜片取代了表针，而探头的信号由计算机控制的-5V—5V或-10V－+10V的直流信号取代，以完成预定的动作。
同转镜式扫描系统相同，这种典型的控制系统采用了一对折返镜，不同的是，驱动这套镜片的步进电机被伺服电机所取代，在这套控制系统中，位置传感器的使用和负反馈回路的设计思路进一步保证了系统的精度，整个系统的扫描速度和重复定位精度达到一个新的水平。这样可以达到快速精确加工的目的，从而在保证前透明导电层的TCO材料晶化的同时降低加工时间，提高加工速度。
在一个具体的实施方式中，采用激光处理前透明导电层时，激光使前透明导电层的温度达到400-800℃。
在一个具体的实施方式中，采用激光处理前透明导电层时，激光为波长为355nm的紫光激光，激光的脉冲宽度为0.75-20ns，采用振镜系统施加激光。在一个具体的实施方式中，采用激光处理前透明导电层时，激光使前透明导电层的温度达到400-800℃，激光为波长为355nm的紫光激光，激光的脉冲宽度为0.75-20ns，采用振镜系统施加激光。
可以理解，上述对激光各种参数的限定仅仅是示例性的，为了实现使前透明导电层至少部分晶化，同时所采用的激光不会对硅异质结底电池和钙钛矿吸收层造成损伤，本领域技术人员可以选择适当的激光设备，调整激光的功率、脉冲频率、脉冲宽度、激光脉冲宽度、加工速度、焦点位置、激光采用的模式等各种参数。在另一个具体的实施方式中，步骤S3可以由将制备得到的叠层太阳能电池进行控温，从而对所述硅异质结底电池和所述钙钛矿吸收层进行保护；以及提供热源使所述前透明导电层至少部分晶化的方式实现。
具体的，对步骤S2制备得到的叠层电池进行温控，是为了在对前透明导电层进行热处理时，使叠层电池的基底保持在低温状态，从而在完成前透明导电层的TCO材料的晶化时保证基底不受影响。可以选择本领域已知的各种方式或设备进行温控，例如可以将叠层电池放置在控温台上，其中叠层太阳能电池远离前透明导电层的一侧与控温台接触，即前透明导电层远离控温台。
在一个具体的实施方式中，控温台的温度设置在-20至-10℃，例如可以为-20℃、-19.5℃、-19℃、-18.5℃、-18℃、-17.5℃、-17℃、-16.5℃、-16℃、-15.5℃、-15℃、-14.5℃、-14℃、-13.5℃、-13℃、-12.5℃、-12℃、-11.5℃、-11℃、-10.5℃、-10℃，或这些数值之间的任意范围。其中，可以选用各种类型的控温台，只要能对叠层太阳能电池进行充分控温即可。在一个具体的实施方式中，通过真空吸附使叠层太阳能电池与控温台紧密接触，以达到更好的控温效果。
进一步的，热源可以使前透明导电层至少部分晶化。此外，由于采用控温台对叠层电池基底进行控温，并加热前透明导电层，使得前透明导电层从靠近硅异质结底电池的一侧到远离硅异质结底电池的一侧存在温差。温差的存在有助于TCO材料在晶化时晶体生长的取向性，从而得到更优质的膜层。
此外，前透明导电层中温差的存在有助于TCO材料在晶化时晶体生长的取向性，从而得到更优质的膜层。晶化过程中的温差不会导致叠层电池各个膜层之间的脱离与失配。晶化后的前透明导电层的TCO材料具有更好的光学性能与电学性能，进而提升叠层电池的整体效率。另外，硅片、钙钛矿材料及TCO材料都具有非常小的热膨胀系数，并且具有一定的柔性，所以晶化过程中的温差不会导致叠层电池各个膜层之间的脱离与失配。晶化后的前透明导电层的TCO材料具有更好的光学性能与电学性能，进而提升叠层电池的整体效率。
在一个具体的实施方式中，热源使前透明导电层的温度达到350-400℃，例如可以为350℃、351℃、352℃、353℃、354℃、355℃、356℃、357℃、358℃、359℃、360℃、361℃、362℃、363℃、364℃、365℃、366℃、367℃、368℃、369℃、370℃、371℃、372℃、373℃、374℃、375℃、376℃、377℃、378℃、379℃、380℃、381℃、382℃、383℃、384℃、385℃、386℃、387℃、388℃、389℃、390℃、391℃、392℃、393℃、394℃、395℃、396℃、397℃、398℃、399℃、400℃，或这些数值之间的任意范围。
在一个具体的实施方式中，热源提供的时间为1-10min，例如可以为1min、1.5min、2min、2.5min、3min、3.5min、4min、4.5min、5min、5.5min、6min、6.5min、7min、7.5min、8min、8.5min、9min、9.5min、10min，或这些数值之间的任意范围。
本申请的热源提供热的方式可以选自热辐射、热传导、热对流中的一种或两种以上，例如可以是单一的热辐射、热传导或热对流，也可以是热辐射组合物热传导，热辐射组合热对流，热传导组合热对流，或者热辐射、热传导、热对流三者的组合。对于提供上述各种供热方式的热源，本领域技术人员可以选择相应的热源。在一个具体的实施方式中，热源选自红外(IR)加热灯、热台、热空气中的一种或两种以上。对于红外(IR)加热灯，本领域技术人员可以根据需要调整加热灯的功率、距离控制台的距离等。对于热台，本领域技术人员可以根据需要调整热台的温度、距离控制台的距离等。对于热空气，本领域技术人员可以根据需要调整加热空气的温度、流速、距离控制台的距离等。
在一个具体的实施方式中，控温台的温度设置在-20至-10℃，热源为红 外加热灯，热源提供时间为1-10min，所述热源使所述前透明导电层的温度达到350-400℃。在一个具体的实施方式中，控温台的温度设置在-20至-10℃，热源为热台，热源提供时间为1-10min，所述热源使所述前透明导电层的温度达到350-400℃。在一个具体的实施方式中，控温台的温度设置在-20至-10℃，热源为热空气，热源提供时间为1-10min，所述热源使所述前透明导电层的温度达到350-400℃。
可以理解，上述对热源各种参数的限定仅仅是示例性的，为了实现使前透明导电层至少部分晶化，同时所采用的热源不会对叠层电池基底，如硅异质结底电池和钙钛矿吸收层造成损伤，本领域技术人员可以选择适当的加热装置作为热源，调整热源的温度、距离控制台的距离、功率、时间等各种参数。
进一步地，本申请的制备方法还可以包括制备金属电极的步骤。其中制备电极的步骤可以在步骤S2和S3之间，即制备完金属电极之后，再对前透明导电层进行加热处理。此时，如图1所示，在硅异质结底电池远离复合层1-7的一侧，以及所述前透明导电层2-4远离复合层1-7的一侧制备金属电极3-1。制备电极的步骤也可以在S4之后，即对在硅异质结底电池远离复合层1-7的一侧，以及经加热处理的前透明导电层2-4远离复合层1-7的一侧制备金属电极3-1。金属电极3-1可以为本领域常规的金属电极，如银、铜等。本申请的制备方法克服了现有的叠层电池制备中不能使前透明导电层晶化的问题，通过加热处理前透明导电层，同时保持叠层电池基底低温，可以在不影响叠层电池基底的基础上，使前透明导电层的材料达到晶化，从而提升前透明导电层的材料的光学性能与电学性能，以提升叠层电池的整体效率。
本申请还提供一种钙钛矿/硅异质结叠层太阳能电池。如图1所示，该叠层太阳能电池包括依次层叠设置的硅异质结底电池、复合层1-7、空穴传输层2-1、钙钛矿吸收层2-2、电子传输层2-3和前透明导电层2-4，其中前透明导电层2-4至少部分晶化。在一个具体的实施方式中，硅异质结底电池包括依次层叠设置的背透明导电层1-1、P型非晶硅层1-2、第一本征非晶硅层1-3、N型晶硅衬底1-4、第二本征非晶硅层1-5、N型非晶硅层1-6。前透明导电层2-4的晶化程度可以采用本领域已知的检测方法进行表征。例如，可以采用X射线衍射进行检测。
在一个具体的实施方式中，前透明导电层2-4的X射线衍射图谱在衍射角2θ为30.52°±0.02(222)处具有特征峰。前透明导电层2-4的特征峰可以位于2θ为30.50°、30.51°、30.52°、30.53°、30.54°处，或者这些数值之间的任意数值处。
进一步地，所述钙钛矿/硅异质结叠层太阳能电池通过上述的任意一种制备方法制备得到。
实施例
实施例1
制备的叠层太阳能电池的结构如图1所示。钙钛矿/硅异质结叠层太阳能电池包括依次层叠设置的背透明导电层1-1、P型非晶硅层1-2、第一本征非晶硅层1-3、N型晶硅衬底1-4、第二本征非晶硅层1-5、N型非晶硅层1-6、复合层1-7、空穴传输层2-1、钙钛矿吸收层2-2、电子传输层2-3和前透明导电层2-4，其中在背透明导电层1-1和前透明导电层2-4远离复合层1-7的一侧设置有金属电极3-1。钙钛矿/硅异质结叠层太阳能电池的制备方法包括以下步骤：
(1)N型晶硅衬底1-4，为商业级M6的N型硅片，电阻率在1-10Ω.cm，厚度为150-200μm。硅片依次经历抛光、制绒及清洗程序。
采用PECVD在硅片双侧分别沉积第一本征非晶硅层1-3和第二本征非晶硅层1-5(厚度为5-10nm)构成正面和背面钝化层薄膜。利用PECVD在硅片正面即第二本征非晶硅层1-5上沉积磷掺杂(掺杂浓度1019-20cm-3)的N型非晶硅层(厚度为5-15nm)构成前场结构，即N型非晶硅层1-6，其导带约-3.7eV。采用PECVD在硅片背面即第一本征非晶硅层1-3上沉积硼掺杂(掺杂浓度1019-20cm-3)的P型非晶硅层(厚度为5-15nm)构成背发射极结构，即P型非晶硅层1-2。使用磁控溅射法制备(厚度为70-120nm)背透明导电材料层1-1，其材料为ITO。1-1至1-6构成了钙钛矿/硅异质结叠层太阳能电池的底电池结构。
(2)使用磁控溅射法制备一层渐变的ITO材料作为复合层1-7，厚度为20nm。
(3)使用磁控溅射制备50nm的NiOx层，作为空穴传输层2-1。
(4)通过热蒸发工艺制备钙钛矿前驱层：采用共蒸方法蒸镀厚度为 350-450nm的碘化铅及溴化铯混合层，其中溴化铯(CsBr)速率为碘化铅(PbI2)速率为形成钙钛矿吸收层薄膜的主体结构；配置FAI及FABr混合溶液，摩尔浓度比为1.5:2.5mol/ml至3.5:0.5mol/ml,溶剂采用乙醇或异丙醇；取70-100μL的FAI及FABr混合溶液同碘化铅及溴化铯层反应，并在140-190℃条件下退火20-50min，形成钙钛矿吸收层2-2。
(5)先采用蒸镀法制备一层C60，进一步利用ALD在80-120℃条件下，进行130-190次循环，制备出10-20nm SnO2，作为电子传输层2-3。
(6)通过磁控溅射法制备出70-120nm的ITO薄膜，构成前透明导电层2-4。
(7)通过丝网印刷，制备上下表面的细栅线与主栅线即金属电极31，形成完整的钙钛矿/硅异质结叠层太阳能电池。
(8)一种实现方式中，步骤(8)可以执行：选择波长为355nm皮秒级激光，采用振镜系统，分别设定其功率为4W，脉冲频率为1500KHz，脉冲宽度750皮秒，加工速度6000mm/s，焦点位置距离加工表面(即前透明导电层表面)45mm。使用该激光系统对钙钛矿/硅异质结叠层太阳能电池进行加工处理，可以使前透明导电层达到晶化，其中光斑重叠率约65％，工艺时间65s。另一种实现方式中，步骤(8)可以执行：将制备完毕的钙钛矿/异质结叠层电池置于控温台上，背电极位于下方并通过真空吸附与控温台紧密接触，前透明导电层2-4位于上方。控温台设置温度为-20℃。在控温台上方通过带有加热与保温功能的储气罐提供热空气，热空气温度为350℃，流量5L/min，通过布气孔尺寸吹淋在控温台上，吹淋时间为10min。
实施例2
实施例2与实施例1的区别仅在于步骤(8)不同。实施例2的步骤(8)为：将制备完毕的钙钛矿/异质结叠层电池置于控温台上，背电极位于下方并通过真空吸附与控温台紧密接触，前透明导电层背位于上方。控温台设置温度为-20℃。在控温台上方提供IR加热灯管，IR加热灯管功率为2KW，距离控温台30cm。加热时间为5min。
实施例3
实施例3与实施例1的区别仅在于步骤(8)不同。实施例3的步骤(8)为：将制备完毕的钙钛矿/异质结叠层电池置于控温台上，背电极位于下方并 通过真空吸附与控温台紧密接触，前透明导电层背位于上方。控温台设置温度为-20℃。在控温台上方提供热台，热台设定温度350℃，距离控温台1mm。加热时间为2min。
对比例1
对比例1与实施例1、2、3的区别仅在于，对比例1只包括步骤(1)-(7)，即不包括步骤(8)。对实施例1采用激光的处理方案和对比例1制备得到的钙钛矿/硅异质结叠层太阳能电池进行性能检测，结果如表1所示。
表1
由表1的结果可以看出，实施例1的方法在增加了激光处理步骤之后，使得叠层电池的效率得到大幅提升。为了进一步验证上述表1的结果，本申请还针对激光处理对ITO的影响从光学、电学和结构等各方面进行了表征。使用ITO作为前透明导电层，在玻璃基底上制备100nm厚度的ITO单膜。具体地，在玻璃基底上制备100nm厚度的ITO单膜。采用实施例1中的激光条件对ITO单膜进行激光处理，对比激光处理前后的膜层性能变化。
其中，光学方面以透过率为判定依据，激光处理前后，ITO单膜的透过率如图2所示。从图2可以看出，激光处理可以提升ITO单膜的透过率，进而增加入射光，提升电池的短路电流密度。激光处理前后，ITO单膜的霍尔测试结果如表2所示。从表2可以看出，激光处理可以提升ITO的电学性能，进而降低电池的内部串联电阻，改善电荷的传输，提升电池的效率。
表2
激光处理前后，ITO单膜的X射线衍射(XRD)测试结果如图3所示。从图3可以看出，激光处理后的ITO膜层在X射线衍射图谱在衍射角2θ为30.73°处具有特征峰。说明激光处理方式可以使ITO膜层达到部分结晶，从而提升ITO膜层的电学与光学性能。对实施例1采用控温及热源的处理方案以及实施例2、3和对比例1制备得到的钙钛矿/硅异质结叠层太阳能电池进行性能检测，结果如表3所示。
表3
由表3的结果可以看出，实施例1-3的方法在增加了加热处理步骤之后，使得叠层电池的效率得到大幅提升。为了进一步验证上述表3的结果，本申请还针对加热处理对ITO的影响从光学、电学和结构等各方面进行了表征。使用ITO作为前透明导电层，在玻璃基底上制备100nm厚度的ITO单膜。具体地，在玻璃基底上制备100nm厚度的ITO单膜。采用现有技术在的常规条件对ITO单膜进行加热处理，即将ITO单膜在250℃下加热30min。其中，光学方面以透过率为判定依据，加热处理前后，ITO单膜的透过率如图4所示。从图4可以看出，加热处理可以提升ITO单膜的透过率，进而增加入射光，提升电池的短路电流密度。加热处理前后，ITO单膜的霍尔测试结果如表4所示。从表4可以看出，加热处理可以提升ITO的电学性能，进而降低电池的内部串联电阻，改善电荷的传输，提升电池的效率。
表4
加热处理前后，ITO单膜的X射线衍射(XRD)测试结果如图5所示。从图5可以看出，加热处理方式可以使ITO膜层达到部分结晶，从而提升ITO膜层的电学与光学性能。
尽管以上结合对本申请的实施方案进行了描述，但本申请并不局限于上述的具体实施方案和应用领域，上述的具体实施方案仅仅是示意性的、指导性的，而不是限制性的。本领域的普通技术人员在本说明书的启示下和在不脱离本申请权利要求所保护的范围的情况下，还可以做出很多种的形式，这些均属于本申请保护之列。

Claims (14)

  1. 一种钙钛矿/硅异质结叠层太阳能电池的制备方法，其特征在于，包括：
    制备硅异质结底电池；
    在所述硅异质结底电池的一侧依次制备复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层；
    对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化。
  2. 根据权利要求1所述的方法，其特征在于，所述对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化，包括：
    采用激光处理所述前透明导电层使所述前透明导电层至少部分晶化，并且所述激光不损伤所述硅异质结底电池和所述钙钛矿吸收层。
  3. 根据权利要求2所述的方法，其特征在于，所述激光使所述前透明导电层的温度达到400-800℃；
    所述激光为波长355nm的紫光激光；
    所述激光的脉冲宽度为0.75-20ns；
    所述前透明导电层的X射线衍射图谱在衍射角2θ为30.73°±0.02处具有特征峰。
  4. 根据权利要求2或3所述的方法，其特征在于，采用激光处理所述前透明导电层时通过采用振镜系统来施加所述激光。
  5. 根据权利要求1所述的方法，其特征在于，所述对所述硅异质结底电池和所述钙钛矿吸收层进行保护，并对所述前透明导电层进行加热处理，使制备获得的叠层太阳能电池中的前透明导电层至少部分晶化，包括：
    将制备得到的叠层太阳能电池进行控温，从而对所述硅异质结底电池和所述钙钛矿吸收层进行保护；
    提供热源使所述前透明导电层至少部分晶化。
  6. 根据权利要求5所述的方法，其特征在于，所述控温通过将制备得到的叠层太阳能电池放置在控温台上实现，所述叠层太阳能电池远离所述前透明导电层的一侧与控温台接触；所述控温台的温度设置在-20至-10℃。
  7. 根据权利要求5或6所述的方法，其特征在于，所述热源使所述前透明导电层的温度达到350-400℃；
    所述热源提供的时间为1-10min；
    所述热源提供热的方式选自热辐射、热传导、热对流中的一种或两种以上；
    所述热源选自红外加热灯、热台、热空气中的一种或两种以上；
    所述前透明导电层的X射线衍射图谱在衍射角2θ为30.52°±0.02处具有特征峰。
  8. 根据权利要求1-7任一项所述的方法，其特征在于，所述前透明导电层的材料选自ITO、IWO、IZO、ITiO中的一种。
  9. 根据权利要求8所述的方法，其特征在于，所述前透明导电层的材料为ITO。
  10. 根据权利要求1-9任一项所述的方法，其特征在于，所述前透明导电层的厚度为30-150nm。
  11. 根据权利要求1-10任一项所述的方法，其特征在于，所述硅异质结底电池包括依次层叠设置的背透明导电层、P型非晶硅层、第一本征非晶硅层、N型晶硅衬底、第二本征非晶硅层、N型非晶硅层。
  12. 根据权利要求1-11任一项所述的方法，其特征在于，所述方法还包括：
    在所述硅异质结底电池远离所述复合层的一侧，以及所述前透明导电层或经加热处理的前透明导电层远离所述复合层的一侧制备金属电极。
  13. 一种钙钛矿/硅异质结叠层太阳能电池，其特征在于，包括：依次层叠设置的硅异质结底电池、复合层、空穴传输层、钙钛矿吸收层、电子传输层和前透明导电层，所述前透明导电层至少部分晶化。
  14. 根据权利要求13所述的叠层太阳能电池，其特征在于，所述叠层太阳能电池由权利要求1-12中任一项所述的制备方法制备得到。
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