WO2024255400A1 - Cellule solaire stratifiée à hétérojonction de pérovskite/silicium et son procédé de préparation - Google Patents

Cellule solaire stratifiée à hétérojonction de pérovskite/silicium et son procédé de préparation 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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Chinese (zh)
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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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Publication of WO2024255400A1 publication Critical patent/WO2024255400A1/fr
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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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  • Manufacturing & Machinery (AREA)
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Abstract

La présente demande concerne une cellule solaire stratifiée à hétérojonction de pérovskite/silicium et son procédé de préparation. Le procédé de préparation consiste à préparer une cellule inférieure à hétérojonction de silicium ; sur un côté de la cellule inférieure à hétérojonction de silicium, à séquentiellement préparer une couche composite, une couche de transport de trous, une couche d'absorption de pérovskite, une couche de transport d'électrons et une couche conductrice transparente avant ; à protéger la cellule inférieure à hétérojonction de silicium et la couche d'absorption de pérovskite, et à chauffer la couche conductrice transparente avant, de telle sorte que la couche conductrice transparente avant dans la cellule solaire stratifiée préparée est au moins partiellement cristallisée. Par chauffage de la couche conductrice transparente avant sur la base de la protection de la cellule inférieure à hétérojonction de silicium et de la couche d'absorption de pérovskite, le matériau de la couche conductrice transparente avant peut être cristallisé sans affecter un substrat de cellule stratifiée de silicium, les performances optiques et les performances électriques du matériau de la couche conductrice transparente avant étant ainsi améliorées, et l'efficacité globale d'une cellule stratifiée étant ainsi accrue.
PCT/CN2024/085621 2023-06-15 2024-04-02 Cellule solaire stratifiée à hétérojonction de pérovskite/silicium et son procédé de préparation Ceased WO2024255400A1 (fr)

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CN202310713067.9 2023-06-15
CN202310713067.9A CN116705909A (zh) 2023-06-15 2023-06-15 钙钛矿/硅异质结叠层太阳能电池及其制备方法
CN202310729455.6A CN116669501A (zh) 2023-06-19 2023-06-19 钙钛矿/硅异质结叠层太阳能电池及其制备方法
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