CN116072752A - Thin film solar cell, preparation method thereof, photovoltaic module and power generation equipment - Google Patents
Thin film solar cell, preparation method thereof, photovoltaic module and power generation equipment Download PDFInfo
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- CN116072752A CN116072752A CN202211656121.2A CN202211656121A CN116072752A CN 116072752 A CN116072752 A CN 116072752A CN 202211656121 A CN202211656121 A CN 202211656121A CN 116072752 A CN116072752 A CN 116072752A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/30—Electrical components
- H02S40/32—Electrical components comprising DC/AC inverter means associated with the PV module itself, e.g. AC modules
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- Electromagnetism (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The embodiment of the application discloses a thin film solar cell, a preparation method thereof, a photovoltaic module and power generation equipment. The thin film solar cell is composed of N subcells connected in series with each other, each subcell including: a substrate, a transparent electrode, a first transmission layer, a first light conversion layer, a second transmission layer and a metal electrode which are sequentially laminated; each sub-cell is provided with a first groove, the first groove penetrates through the first transmission layer, the first light conversion layer and the second transmission layer, the first groove is filled with a metal electrode, and the metal electrode is in contact with the transparent electrode; a blocking layer is arranged in the first light conversion layer, and the blocking layer is positioned between the first light conversion layer and the metal electrode; the barrier layer has a graded concentration of inorganic salts. The inorganic salt has the characteristic of compactness, and can effectively block the first light conversion layer and the metal electrode, so that the mutual diffusion of anions in the first light conversion layer and the metal electrode is prevented, the corrosion of the metal electrode is avoided, and the stability of the thin film solar cell is improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a thin film solar cell, a preparation method thereof, a photovoltaic module and power generation equipment.
Background
The energy crisis is becoming more serious, new energy replaces fossil energy to become an epoch-making theme, and solar cells are rapidly developed day by day. Perovskite solar cells become the third generation solar cells most promising for commercialization because of the advantages of high theoretical conversion efficiency, low preparation cost, adjustable forbidden bandwidth and the like, and are applied to the integration of ground power stations and photovoltaic buildings in small scale at present.
In order to manufacture perovskite solar cells with large area and high conversion efficiency, it is often necessary to prepare perovskite cell assemblies by connecting subcells in series, so as to reduce energy loss. However, this causes interdiffusion of the anions of the perovskite and the metal electrode in the subcell, resulting in a decrease in stability. Therefore, how to improve the stability of perovskite battery assemblies is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The application provides a thin film solar cell, a preparation method thereof, a photovoltaic module and power generation equipment, which are used for preventing direct contact between perovskite and a metal electrode, so that the mutual diffusion of anions in the perovskite and the metal electrode is prevented, and the stability of the solar cell is improved.
In a first aspect, embodiments of the present application provide a thin film solar cell, where the thin film solar cell is formed by N subcells, and the N subcells are connected in series with each other, and each subcell includes:
a substrate, a transparent electrode, a first transmission layer, a first light conversion layer, a second transmission layer and a metal electrode which are sequentially laminated; each sub-cell is further provided with a first groove, the first groove penetrates through the first transmission layer, the first light conversion layer and the second transmission layer, the first groove is filled with a metal electrode, and the metal electrode is in contact with the transparent electrode; a blocking layer is arranged in the first light conversion layer, the blocking layer is positioned between the first light conversion layer and the metal electrode, namely the first light conversion layer is in indirect contact with the metal electrode through the blocking layer, and the surface of the blocking layer, which is close to the first groove, and the side wall of the first groove are positioned on the same surface; the barrier layer also has a graded concentration of inorganic salts.
According to the thin film solar cell, the blocking layer is added in the first light conversion layer, the blocking layer contains the inorganic salt with gradually changed concentration, the inorganic salt has the characteristic of compactness, and the first light conversion layer and the metal electrode can be effectively blocked, so that the mutual diffusion of anions in the first light conversion layer and the metal electrode is prevented, the corrosion of the metal electrode is avoided, and the stability of the thin film solar cell is improved.
In one possible implementation, the concentration of the inorganic salt in the blocking layer is gradually increased in a direction from the first light-converting layer to the metal electrode, which is perpendicular to the thickness direction of the subcell. That is, in the blocking layer of the first light conversion layer, the closer to the position of the metal electrode, the higher the concentration of the inorganic salt. It can be appreciated that the higher the concentration of inorganic salts in the barrier layer, the better the barrier layer isolation; the concentration of the inorganic salt reaches the maximum at the contact position of the barrier layer and the metal electrode, thereby preventing the mutual diffusion between anions in the first conversion layer and the metal electrode to the maximum at the contact position of the barrier layer and the metal electrode.
In one possible implementation, the barrier layer comprises graded concentrations of inorganic salts, wherein the inorganic salts comprise oxygen-free inorganic salts and oxygen-containing inorganic salts; the concentration of the oxygen-free inorganic salt gradually increases and then gradually decreases along the direction from the first light conversion layer to the metal electrode, and the concentration of the oxygen-containing inorganic salt gradually increases. In general, there is no obvious interface between the oxygen-free inorganic salt and the oxygen-containing inorganic salt. It will be appreciated that the aerobic inorganic salt is more compact than the anaerobic inorganic salt, so that the barrier effect of the aerobic inorganic salt is better than that of the anaerobic inorganic salt, and therefore, the concentration of the aerobic inorganic salt is increased at the position close to the metal electrode in the barrier layer, the barrier effect can be further improved, and the interdiffusion between the anions in the first conversion layer and the metal electrode is prevented.
In one possible implementation, the inclusion of a light converting material in the first light converting layer, it is the inter-diffusion of anions in the light converting material with the metal electrode that results in instability of the thin film solar cell, the light converting material in this application being perovskite; the concentration of the light conversion material gradually decreases along the direction from the first light conversion layer to the metal electrode, and the concentration of the light conversion material approaches zero at the contact position of the blocking layer and the metal electrode. Also, the concentration of the light conversion material is gradually increased and the concentration of the inorganic salt is gradually decreased in the direction from the metal electrode to the first light conversion layer, and there is no significant interface between the light conversion material and the inorganic salt in the first light conversion layer, that is, there is no significant interface between the blocking layer and the first light conversion layer in the direction from the metal electrode to the first light conversion layer. It can be appreciated that the closer the blocking layer is to the metal electrode, the lower the concentration of the light conversion material gradually approaches zero, that is, no light conversion material is in direct contact with the metal electrode, so that anions in the light conversion material are difficult to diffuse with the metal electrode, thereby improving the stability of the solar cell.
The perovskite in the first light conversion layer generates photoelectric effect under the irradiation of sunlight to generate electron hole pairs, and the electron hole pairs are transmitted through the first transmission layer and the second transmission layer to finally form current so as to convert solar energy into electric energy.
Elemental composition of perovskite, exemplified by ABX 3 Perovskite thin film, A + Is Rb + 、Cs + 、CH 3 NH 3 + (MA + )、H 2 C(＝NH)NH 2 + (FA + ) Wherein B is one or more of Pb, sn and other metal elements, and X is one or more of I, br, cl, F halogen elements. Anions and metals in light-converting materialsElectrode interdiffusion, referred to as ABX 3 Inter-diffusion between the X ions and the metal electrode leads to corrosion of the metal electrode, thereby destabilizing the thin film solar cell.
In one possible implementation, each subcell in the thin film solar cell further includes a second recess extending through the transparent electrode, the second recess being filled with a first transmission layer, the first transmission layer being in contact with the substrate. In general, the projection of the second groove and the first groove in the thickness direction of the subcell is not overlapped, and the projection distance between the second groove and the first groove in the perpendicular direction of the thickness direction of the subcell is smaller. It can be understood that the transparent electrode is divided into a plurality of strip-shaped electrode blocks by the second grooves, different sub-cells respectively correspond to one strip-shaped electrode block, and the sub-cells are mutually connected in series through the respectively corresponding electrode blocks to form a thin film solar cell module, so that the large-area manufacturing of the thin film solar cell is facilitated.
Wherein the transparent electrode is an oxide transparent conductive layer (TCO), and the material of the TCO includes, but is not limited to, one or more of Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), and Indium Zinc Oxide (IZO), and the preparation method of the TCO is not limited in this application; the material of the substrate includes, but is not limited to, a hard substrate such as a glass substrate, a quartz glass substrate, etc., and may also be a plastic polyethylene terephthalate (PET), polyethylene naphthalate (PEN) flexible substrate.
In one possible implementation, a third groove is included between each subcell in the thin film solar cell, the third groove extending at least through the metal electrode and not through the transparent electrode. It will be appreciated that the third grooves are filled with insulating material or no other substance, the metal electrodes of the different sub-cells are not in contact with each other, and the different sub-cells are isolated from each other by the third grooves.
Wherein the material of the metal electrode includes, but is not limited to Al, ag, au, mo, cr, ti, ni, cu, pt or combinations thereof.
In one possible implementation, the subcells in the thin film solar cell are stacked cells, so each subcell further includes a composite layer, a third transmission layer, a second light conversion layer, and a fourth transmission layer disposed in sequence between the second transmission layer and the metal electrode. The laminated battery is two laminated batteries, and physical layers required by stacking three laminated batteries and the like can be stacked in the similar way. It can be appreciated that the stacked cell can further increase the cell density of the thin film solar cell and increase the solar conversion efficiency.
The first transmission layer, the second transmission layer and the third transmission layer and the fourth transmission layer in the laminated battery are respectively used for separating and transmitting the different electric carriers. The first transport layer is an electron transport layer and the second transport layer is a hole transport layer, for example.
Wherein the electron transport layer material is n-type semiconductor with electron transport capability, and specific materials include but are not limited to titanium oxide (TiO) 2 ) Tin oxide (SnO) 2 ) Zinc oxide (ZnO), vanadium oxide (V) 2 O 5 ) And zinc tin oxide (Zn) 2 SnO 4 ) One or more n-type semiconductor materials, fullerene (C60), graphene and fullerene-like derivatives (PCBM). Methods of preparing the electron transport layer include, but are not limited to, solution spin coating, sol-gel, doctor-blading, thermal evaporation, magnetron sputtering, atomic layer deposition, and the like.
While the hole transport layer has hole transport capability, specific materials include, but are not limited to, nickel oxide (NiO), cuprous oxide (Cu 2 O), molybdenum oxide (MoO) 3 ) Copper iodide (CuI), copper thiocyanate (CuSCN), reduced graphene oxide, poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine](PTAA, poly (triaryl amine)), 2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]-9,9' -spirobifluorene (Spiro-OMeTAD), poly 3, 4-ethylenedioxythiophene, polystyrene sulfonate (PEDOT: PSS) and poly [ bis (4-phenyl) (4-butylphenyl) amine ](Ploy-TPD) a combination of one or more materials. The hole transport layer can be prepared by spin coating, doctor blading, thermal evaporation, atomic layer deposition, magnetron sputtering, etc.
In one possible implementation, the subcells in the thin film solar cell further include an interface treatment layer. The interface treatment layer is located between the first transmission layer and the first light conversion layer, or between the second transmission layer and the first light conversion layer, and may also be located between the first transmission layer and the transparent electrode, or between the second transmission layer and the metal electrode. That is, the interface treatment layer is located between the transmission layer and the light conversion layer, or between the electrode and the light conversion layer. Similarly, for a laminated cell, there is also an interface treatment layer, which may be located between the transmission layer and the light conversion layer, or between the electrode and the light conversion layer, such as between the third transmission layer and the second light conversion layer, or between the fourth transmission layer and the metal electrode. Generally, in the same sub-battery, an interface processing layer may be provided, or multiple interface processing layers may be provided according to scene requirements. Generally, the interface treatment layers are located in the same location within different subcells in the same thin film solar cell. It is understood that the interface treatment layer may improve the conversion efficiency of the thin film solar cell.
The material of the interface treatment layer includes, but is not limited to, ionic liquid materials, organic small molecules containing hydroxyl groups, carboxyl groups, carbonyl groups, amino groups, amine groups and other functional groups, organic polymers and the like, fullerene and derivatives thereof, graphene, other inorganic materials and the like, and inorganic salt materials containing Pb and Sn.
In a second aspect, embodiments of the present application provide a photovoltaic module, which may include: a housing, and the thin film solar cell provided by the embodiment of the application; wherein the thin film solar cell may be located in a housing; like this, can protect film solar cell through the casing, avoid film solar cell to receive external interference, improve photovoltaic module's reliability and security.
And moreover, the thin film solar cells arranged in the shell are not limited to one, a plurality of thin film solar cells can be arranged, and the specific number of the thin film solar cells can be set according to actual needs so as to improve the power generation of the photovoltaic module.
Further, the electrical connection relationship of the thin film solar cells may be set as: parallel connection, series connection, or a combination of series and parallel connection; the setting can be specifically performed according to actual needs, and is not limited herein.
In a third aspect, embodiments of the present application provide a power generation apparatus, comprising: according to the photovoltaic module and the inverter electrically connected with the photovoltaic module, which are provided by the embodiment of the application, direct current output by the photovoltaic module can be electrically converted into alternating current, and then the converted alternating current can be integrated into a power grid for use.
The number of the photovoltaic modules included in the power generation device is not limited to two, and may be one or more, and may be specifically set according to actual needs, which is not limited herein.
In this application embodiment, when photovoltaic module is provided with a plurality ofly, the dc-to-ac converter can be provided with a plurality ofly, and a plurality of photovoltaic module can correspond an dc-to-ac converter, also can photovoltaic module and dc-to-ac converter one-to-one. When each photovoltaic module corresponds to one inverter, the inverter is used for converting direct current output by the corresponding photovoltaic module, so that the conversion accuracy is improved; when the photovoltaic modules are provided with a plurality of inverters, not shown, the inverters are electrically connected with the photovoltaic modules, and the inverters can convert direct current output by the photovoltaic modules, so that the number of the inverters is reduced, and the manufacturing cost of the power generation equipment is reduced.
In the embodiment of the present application, the power generation device may include, in addition to the photovoltaic module and the inverter, other structures that may be used to implement the functions of the power generation device, which is not limited herein.
In a fourth aspect, an embodiment of the present application provides a method for manufacturing a thin film solar cell, which may include:
and 4, stacking a metal electrode on one surface of the second transmission layer, which is away from the substrate, wherein the metal electrode fills the first groove, and the blocking layer is positioned between the metal electrode and the first light conversion layer.
According to the preparation method of the thin film solar cell, the first groove is formed by etching, so that the side face of the first light conversion layer is exposed in the first groove, then the exposed first light conversion layer is subjected to in-situ generation to generate inorganic salt with gradually changed concentration, finally the inorganic salt with gradually changed concentration forms a blocking layer, and the inorganic salt has the characteristic of compactness, so that the first light conversion layer and the metal electrode can be effectively blocked, and the mutual diffusion of anions in the first light conversion layer and the metal electrode is prevented, so that the corrosion of the metal electrode is avoided, and the stability of the thin film solar cell is improved.
In one possible implementation, the method for manufacturing a thin film solar cell further includes, after stacking the transparent electrode on the substrate: etching the transparent electrode to form a second groove, penetrating the transparent electrode through the second groove, and then stacking a first transmission layer on the transparent electrode with the second groove, wherein the first transmission layer fills the second groove, and the first transmission layer is in contact with the substrate. The projection of the second groove and the projection of the first groove in the thickness direction of the sub-battery are not overlapped, and the projection distance between the second groove and the first groove in the perpendicular direction of the thickness direction of the sub-battery is smaller. The transparent electrode is divided into a plurality of strip-shaped electrode blocks through the second grooves generated by etching, different sub-batteries respectively correspond to one strip-shaped electrode block, the sub-batteries are connected in series through the respectively corresponding electrode blocks, and a thin film solar cell module is formed, so that the large-area manufacturing of the thin film solar cell is facilitated.
In one possible implementation, in a method for manufacturing a thin film solar cell, the in-situ reacting the light conversion material in the first light conversion layer includes: and placing the thin film solar cell with the first groove in the solution, so that part of the first light conversion layer exposed in the first groove is contacted with the solution, and the light conversion material in the first light conversion layer reacts with solute in the solution in situ to generate compact inorganic salt with gradually changed concentration. The blocking layer is formed by dense inorganic salt with gradually changed concentration, the blocking layer wraps the first light conversion layer exposed in the first groove, the thickness of the blocking layer can be controlled by controlling the soaking time, after the thickness reaches the expected thickness, the thin film solar cell is subjected to vacuum heating or drying by flowing nitrogen, then a metal electrode is deposited, and the blocking layer grown in situ by a solution method can block the light conversion material in the first transmission layer from directly contacting with the metal electrode to inhibit degradation of the metal electrode.
The portion of the first light conversion layer near the first recess reacts first with anions in the solution, and in the direction from the first light conversion layer to the metal electrode, the in-situ reaction of the light conversion material with the solution becomes easier and denser, so that the closer to the metal electrode the position in the first light conversion layer is, the higher the inorganic salt concentration is, and the lower the concentration of the light conversion material in the first light conversion layer is in the direction from the first light conversion layer to the metal electrode because the in-situ reaction consumes the light conversion material.
The solvent adopted by the solution does not damage the first transmission layer, the first light conversion layer and the second transmission layer, the solvent comprises but is not limited to toluene, chlorobenzene, isopropanol or the mixture of the solvents, and the solute in the solution can react with perovskite to generate compact Pb and Sn-containing inorganic salt, wherein Pb and Sn ions come from the perovskite; solutes include, but are not limited to, C 2 S、C 2 Se、C 3 N、C 3 P、C 3 As、C 2 Te、C 2 SO 4 And C 3 PO 4 Wherein C + Including but not limited to, an alkylamine ion or NH 4 + Or other alkali metals such as Na, K, etc., so that the combined solute material includes, but is not limited to Na 2 S、K 2 S、(C 7 H 15 NH 3 ) 2 S、(C 8 H 17 NH 3 ) 2 S、(C 9 H 19 NH 3 ) 2 S、(C 7 H 15 NH 3 ) 2 SO 4 、(C 8 H 17 NH 3 ) 2 SO 4 、(C 9 H 19 NH 3 ) 2 SO 4 、(C 7 H 15 NH 3 ) 3 PO 4 、(C 8 H 17 NH 3 ) 3 PO 4 、(C 9 H 19 NH 3 ) 3 PO 4 Or a mixture of these materials.
The solution process in situ reaction can be represented by the following chemical reaction equation:
ABX 3 +S 2- →A + +BS+3X - (1)
ABX 3 +SO 4 2- →A + +BSO 4 +3X - (2)
3ABX 3 +2PO 4 2- →3A + +B 3 (PO 4 ) 2 +9X - (3) Wherein, BS, BSO 4 And B 3 (PO 4 ) 2 The solvent insoluble in the solution, the chemical formulas (1) - (3) are concurrent and have no sequence, and the in-situ reaction can be realized in the first light conversion layer through the three chemical reactions to generate compact inorganic salt.
In one possible implementation, in a method for manufacturing a thin film solar cell, reacting a light conversion material in a first light conversion layer in situ includes: placing the thin film solar cell in a solution, enabling a first light conversion layer exposed in a first groove to be in contact with the solution, and enabling a light conversion material in the first light conversion layer to react with solute in the solution in situ to generate anaerobic inorganic salt; and then placing the thin film solar cell in oxidizing gas to enable the oxygen-free inorganic salt to react in situ to generate the oxygen-containing inorganic salt.
When the solute contains certain oxygen-containing salts such asSO 4 2- In the case of the class, it is necessary to use a toluene-based solvent for dissolution, but the toluene-based solvent is liable to cause damage to some charge transport layers, especially to charge transport layers containing fullerenes, derivatives thereof, and organic matters. In order to be compatible with the above-mentioned scenario, the present application proposes a method for producing an oxygen-containing inorganic salt by a two-step method, wherein firstly, an oxygen-free salt soluble in a solvent (such as isopropyl alcohol) is reacted with perovskite to produce an oxygen-free inorganic salt containing Pb or Sn, such as PbS or SnS. The solvent can not damage the charge transport layer of fullerene, derivative and organic matters, so that the structure of the thin film solar cell can be effectively protected. However, because the density of the generated oxygen-free inorganic salt is low, a second step is needed to put the barrier layer containing the oxygen-free inorganic salt into gas containing strong oxidizing property such as ozone, plasma oxygen and the like, and the oxygen-free inorganic salt and the oxidizing gas react in situ to form the compact oxygen-containing inorganic salt.
Similarly to the solution method, the portion of the first light conversion layer near the first groove first reacts with the solution in situ to generate an oxygen-free inorganic salt, and in the first light conversion layer, the closer to the metal electrode, the higher the concentration of the oxygen-free inorganic salt, and the closer to the metal electrode, the lower the concentration of the light conversion material in the first light conversion layer, since the light conversion material is consumed by the in situ reaction. When the oxygen-free inorganic salt reacts with the oxidizing gas in situ to generate the oxygen-containing inorganic salt, the oxygen-free inorganic salt in the first light conversion layer is consumed, so that the concentration of the oxygen-free inorganic salt tends to be increased and then decreased along the direction from the first light conversion layer to the metal electrode, and the concentration of the oxygen-containing inorganic salt gradually increases.
Wherein the first step is a solution process to form Pb or Sn-containing oxygen-free inorganic salts, the anions of which include but are not limited to S 2- 、Se 2- 、N 3- 、P 3- 、As 3- 、Te 2- Etc.; the second step is a gas phase process that oxidizes the inorganic salts to dense, aerobic inorganic salts, the anions of which include, but are not limited to: SO (SO) 4 2- 、SeO 4 2- 、NO 4 3- 、PO 4 3- 、AsO 4 3- 、TeO 6 6- Etc., the oxidizing gas includes, but is not limited to, ozone, plasma oxygen, hydrogen peroxide vapor, etc. When the anion in the anaerobic inorganic salt is S 2- When the oxidizing gas is ozone, the oxidation reaction in the second step is:
S 2- +O 3 →SO 4 2- (4)
in one possible implementation, in a method for manufacturing a thin film solar cell, the in-situ reacting the light conversion material in the first light conversion layer includes: and placing the thin film solar cell in the mixed gas, enabling the first light conversion layer exposed in the first groove to be in contact with the mixed gas, and enabling the light conversion material in the first light conversion layer to react with the mixed gas in situ to generate the aerobic inorganic salt with gradually changed concentration.
Wherein the mixed gas includes an oxidizing gas and a non-oxidizing gas containing inorganic salt anions. Oxidizing gases include, but are not limited to, ozone, plasma oxygen, hydrogen peroxide vapor, and the like, and gases providing inorganic salt anionic non-oxygen elements include, but are not limited to, N 2 O 3 、NO、NO 2 、SO 2 、SO 3 、CO 2 And (3) waiting for gas. When the light conversion material is ABX 3 The perovskite type, wherein a is an inorganic ion, is exemplified by the in situ reaction:
2ABX 3 +4CO 2 +O 3 →3X 2 +2BCO 3 +2ACO 3 (5)
a is an organic ion, e.g., a is CH3NH3, the in situ reaction is exemplified by:
2(CH 3 NH 3 )BX 3 +2CO 2 +O 3 →2X 2 +2BCO 3 +2CH 3 NH 2 +2HX (6)
in one possible implementation, in the method for manufacturing a thin-film solar cell, after stacking the metal electrode on the side of the second transmission layer facing away from the substrate, a third groove is etched, where the third groove penetrates at least through the metal electrode, so that each sub-cell is separated from each other. In general, the third groove may also penetrate the second transmission layer and the first light conversion layer, but not penetrate the transparent electrode.
In one possible implementation, in the method for manufacturing a thin film solar cell, when the thin film solar cell is a stacked cell, a composite layer, a third transmission layer, a second light conversion layer, and a fourth transmission layer are sequentially stacked between the second transmission layer and the metal electrode. The laminated battery is two laminated batteries, and physical layers required by stacking three laminated batteries and the like can be stacked in the similar way. It is understood that the stacked cell can further improve the cell density of the thin film solar cell.
In one possible implementation, in the method for manufacturing the thin film solar cell, an interface treatment layer is added in the thin film solar cell, so that the conversion efficiency of the thin film solar cell is improved. The position of the interface treatment layer can be added as follows: the first transmission layer and the first light conversion layer, or the second transmission layer and the first light conversion layer, or the first transmission layer and the transparent electrode, or the second transmission layer and the metal electrode. Therefore, in general, an interface treatment layer is provided between the transmission layer and the light conversion layer, or between the electrode and the light conversion layer. Similarly, for a laminated cell, there is also an interface treatment layer, which is also located between the transmission layer and the light conversion layer, or between the electrode and the light conversion layer. An interface treatment layer is provided between the third transmission layer and the second light conversion layer of the laminated battery, or between the fourth transmission layer and the metal electrode, for example. Generally, in the same sub-battery, an interface processing layer may be provided, or multiple interface processing layers may be provided according to scene requirements. In general, the interface treatment layers are positioned identically in different subcells of the same thin film solar cell. It is understood that the interface treatment layer may improve the conversion efficiency of the thin film solar cell.
Drawings
In order to more clearly describe the technical solutions in the embodiments or the background of the present application, the following description will describe the drawings that are required to be used in the embodiments or the background of the present application.
Fig. 1 is a schematic structural diagram of a perovskite thin film solar cell in the prior art;
FIG. 2 is a schematic diagram of a perovskite thin film solar cell of the prior art;
fig. 3 is a schematic structural diagram of a thin film solar cell according to an embodiment of the present disclosure;
fig. 4 is a schematic structural diagram of another thin film solar cell according to an embodiment of the present disclosure;
fig. 5 is a schematic structural diagram of another thin film solar cell according to an embodiment of the present disclosure;
fig. 6 is a schematic structural diagram of another thin film solar cell according to an embodiment of the present disclosure;
fig. 7 is a schematic structural diagram of another thin film solar cell according to an embodiment of the present disclosure;
FIGS. 8A-8G are schematic process diagrams of a method for fabricating a thin film solar cell according to embodiments of the present application;
fig. 9 is a flowchart of a method for manufacturing a thin film solar cell according to an embodiment of the present application;
fig. 10 is a schematic structural diagram of a photovoltaic module according to an embodiment of the present disclosure;
Fig. 11 is a schematic structural diagram of a power generation device according to an embodiment of the present application.
Reference numerals:
1-substrate, 2-transparent electrode, 3-first transmission layer, 4-first light conversion layer, 5-second transmission layer, 6-metal electrode, 7-oxidation dielectric layer, 8-first groove, 9-second groove, 10-third groove, 11-barrier layer, 11-1-oxygen inorganic salt barrier layer, 11-2-oxygen inorganic salt barrier layer, 12-composite layer, 13-third transmission layer, 14-second light conversion layer, 15-fourth transmission layer, 16-barrier layer ’ 17 interface treatment layer, 101 thin film solar cell, 102 housing, 100 photovoltaic module, 200 inverter, 300 grid
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail with reference to the accompanying drawings.
It should be noted that the same reference numerals in the drawings of the present application denote the same or similar structures, and thus a repetitive description thereof will be omitted. The words expressing the positions and directions described in the present application are described by taking the drawings as an example, but can be changed according to the needs, and all the changes are included in the protection scope of the present application. The drawings of the present application are merely schematic representations, not to scale.
The energy crisis is increasingly serious, new energy layout is accelerated in various countries, and solar cells are regarded as current mature green energy and are paid attention to. The solar cell is continuously developed, the conversion efficiency is continuously increased, the research and experimental stages of the third-generation solar cell are currently carried out, and among a plurality of third-generation solar cells, the perovskite solar cell has the advantages of high theoretical conversion efficiency, low preparation cost, adjustable forbidden band width and the like, and becomes the third-generation solar cell most hopefully realizing commercialization.
The basic structure of the perovskite battery is as shown in fig. 1, and is a sandwich structure, and the battery structure comprises a substrate 1, a transparent electrode 2, a first transmission layer 3, a first light conversion layer 4, a second transmission layer 5 and a metal electrode 6. The first light conversion layer 4 is a perovskite thin film layer and is responsible for generating electron hole pairs by utilizing a photoelectric effect, and then the electron hole pairs are transmitted through the first transmission layer 3 and the second transmission layer 5 to reach an electrode, so that solar energy is finally converted into electric energy. Here, the first transport layer 3 is an electron transport layer, and the second transport layer 5 is a hole transport layer. The chemical formula of the perovskite film layer material is ABX 3 Wherein A is + Including CH 3 NH 3 + (MA + )、NH 2 CH＝NH 2 + (FA + )、Cs + 、Rb + Etc., B 2+ Comprises Pb 2+ 、Sn 2+ Etc., X - Comprising Cl - 、Br - 、I - Plasma, adjust ABX 3 The material composition of the perovskite type solar cell can realize the regulation and control of the forbidden band width of the perovskite type solar cell from 1.2eV to 2.5eV, which is used for laminationThe battery has important significance.
The perovskite solar cell needs to solve the problems of high-efficiency large-area preparation, high conversion efficiency, high stability and the like in order to realize commercial application. Because the transparent electrode 2 in the perovskite battery has weak transverse conductive capability, to realize a battery with large area and high conversion efficiency, a large-area battery is often required to be prepared into a plurality of strip-shaped sub-batteries with short transverse transmission distance, and the perovskite battery assembly is prepared by connecting the sub-batteries in series, so that energy loss is reduced. As shown in fig. 1, the second grooves 9 are formed by etching to divide the transparent electrode 2 into a plurality of elongated transparent electrode blocks, each corresponding to a sub-cell. Since the second grooves 9 need to be filled with the metal electrode 6, this may bring the metal electrode 6 into direct contact with the perovskite in the first light-converting layer 5, and since the anions and metals in the perovskite may diffuse into each other, the stability of the thin film solar cell may be lowered.
In the prior art, as shown in fig. 2, after etching to form the first recess 8, an oxide dielectric layer 7 is deposited on the entire thin film solar cell surface, and then deposition of the metal electrode 6 is performed. The oxidation dielectric layer blocks the first light conversion layer 5 and the metal electrode 6, so that mutual diffusion between the first light conversion layer and the metal electrode is avoided. However, in order to ensure that electron-hole pairs can be transported through the tunneling effect, the thickness of the oxidation dielectric layer 7 is required to be extremely thin, typically less than 1nm, which is very demanding for the process, and the transport efficiency of the electron-hole pairs is reduced due to the presence of the tunneling effect, so that the performance of the solar cell is reduced.
In order to solve the problem of mutual diffusion of anions and metal electrodes in perovskite, and ensure that the conversion efficiency of a solar cell is not reduced, and the preparation cost of the thin film solar cell is not remarkably increased, the embodiment of the application provides the thin film solar cell, a preparation method of the thin film solar cell, a photovoltaic module and power generation equipment. The thin film solar cell, the photovoltaic module and the power generation equipment can be applied to various scenes such as ground power stations, photovoltaic building integration and the like.
As shown in fig. 3, a schematic structural diagram of a thin film solar cell according to an embodiment of the present application is provided, where the thin film solar cell in the present application is composed of N subcells, N is a positive integer greater than 1, the N subcells are connected in series with each other, and each subcell includes:
a substrate 1, a transparent electrode 2, a first transmission layer 3, a first light conversion layer 4, a second transmission layer 5, and a metal electrode 6, which are stacked in this order; each sub-cell is also provided with a first groove 8, the first groove 8 penetrates through the first transmission layer 3, the first light conversion layer 4 and the second transmission layer 5, the first groove 8 is completely filled with the metal electrode 6, and the metal electrode 6 is in contact with the transparent electrode 2; a blocking layer 11 is arranged in the first light conversion layer 4, and the blocking layer 11 is positioned between the first light conversion layer 4 and the metal electrode 6, namely, the first light conversion layer 4 is indirectly contacted with the metal electrode 6 through the blocking layer 11, and the surface of the blocking layer 11 close to the first groove 8 and the side wall of the first groove 8 are positioned on the same surface; the barrier layer 11 also has a graded concentration of inorganic salts. Because the inorganic salt has the characteristic of compactness, anions, generally halogen ions, in perovskite can be effectively prevented from being mutually diffused with the metal electrode 6, so that the corrosion of the metal electrode 6 is avoided, and the stability of the thin film solar cell is improved.
Since the blocking layer 11 is formed by in-situ reaction in the first light conversion layer 4, the part of the first light conversion layer 11 close to the first groove 8 is first subjected to in-situ reaction, and perovskite is easier and denser in-situ reaction from the first light conversion layer 4 to the metal electrode 6, so that the concentration of inorganic salt is higher at the position closer to the metal electrode 6 in the first light conversion layer 4, and the perovskite concentration is lower at the position closer to the metal electrode 6 because the in-situ reaction consumes light conversion material. The cost of the in-situ reaction is relatively reduced, which is conducive to commercialization of perovskite batteries.
In the thin film solar cell, the first transport layer 3 and the second transport layer 5 are respectively an electron transport layer and a hole transport layer, when sunlight irradiates the first light conversion layer 4, namely the perovskite thin film layer, electrons in the perovskite absorb photons to generate energy level transition, the electrons are separated from the constraint of atomic nuclei and become free electrons, electron hole pairs are generated in the perovskite, the electrons reach the transparent electrode through the electron transport layer, holes reach the metal electrode through the hole transport layer, and current is generated by movement of the electrons and the holes, so that solar energy is finally converted into electric energy. In some embodiments, the first transport layer 3 may also be a hole transport layer, and in this case, the second transport layer 5 is an electron transport layer, which is also applicable to the present application.
In the thin film solar cell described above, each subcell further includes a second groove 9 and a third groove 10, and the second groove 9 and the third groove 10 are used for dividing between subcells. Wherein the second groove 9 penetrates the transparent electrode 2, the second groove 9 is filled by the first transmission layer 3, and the first transmission layer 3 is contacted with the substrate 1. In general, the projection of the second groove 9 and the first groove 8 in the thickness direction of the subcell is not overlapped, and the projection distance between the second groove 9 and the first groove 8 in the perpendicular direction of the thickness direction of the subcell is smaller. The third groove 10 penetrates the metal electrode 6, the second transmission layer 5, the first light conversion layer 4 and the first transmission layer 3, and the third groove 10 is filled with an insulating material or is not filled with any other substance. The second groove 9 divides the transparent electrode 2 into a plurality of strip-shaped electrode blocks, different sub-cells respectively correspond to one strip-shaped electrode block, and the third groove 10 isolates the different sub-cells from each other. It should be noted that, as shown in fig. 5, the third recess 10 may extend only through the metal electrode 6, so long as different sub-cells are isolated. The sub-cells are connected in series through the electrode blocks corresponding to each other to form a thin film solar cell module, which is beneficial to large-area manufacture of the thin film solar cell.
The perovskite solar cell shown in fig. 3-5 is a single layer, and the barrier layer in the present application is also applicable to a stacked cell, such as two stacked cells shown in fig. 6, in which, for each sub-cell, a composite layer 12, a third transmission layer 13, a second light conversion layer 14, and a fourth transmission layer 15 are sequentially stacked between the second transmission layer 5 and the metal electrode 6. The third transport layer 13 is of a type consistent with the first transport layer 3, illustratively an electron transport layer, and the fourth transport layer 15 is of a type consistent with the second transport layer 5, illustratively a hole transport layer. A blocking layer 11 and a blocking layer 16 are provided in the first light conversion layer 4 and the second light conversion layer 14 of the laminated cell, respectively, the blocking layer 11 being for blocking perovskite in the first light conversion layer 4 from contacting the metal electrode 6, and the blocking layer 16 being for blocking perovskite in the second light conversion layer 14 from contacting the metal electrode 6. The stacked cell may further increase the conversion efficiency of the perovskite solar cell. In general, the barrier layer of the present application is also applicable to three-layered battery and four-layered battery, and is not specifically exemplified in the present application.
In practical applications of thin film solar cells, an interface treatment layer 17 is generally added between the light conversion layer and the charge transport layer, or between the charge transport layer and the electrode layer, in order to further improve the light conversion efficiency. As shown in fig. 7A to 7B, in fig. 7A, an interface treatment layer 17 is provided between the first light conversion layer 4 and the first transmission layer 3; in fig. 7B, an interface treatment layer 17 is provided between the first transmission layer 3 and the transparent electrode 2. Of course, the interface treatment layer 17 may be disposed at other locations, which are not listed in the present application.
The following describes a method for manufacturing a thin film solar cell in the present application, and fig. 8A to 8G are schematic process diagrams of the method for manufacturing a thin film solar cell, and fig. 9 is a flowchart of the method for manufacturing a thin film solar cell according to an embodiment of the present application. The in-situ reaction mode is adopted in the application, the barrier layer 11 is generated in the first light conversion layer 4, and the in-situ growth by a solution method, the in-situ growth by a solution and gas phase oxidation method and the in-situ gas phase generation method are respectively adopted in the embodiment in the application, so that the barrier layer 11 is generated in three modes. These three methods are described below by way of three specific examples, respectively, and of course, the preparation method includes, but is not limited to, some or all of the following steps.
Firstly, the solution method in-situ growth is carried out, and the specific steps are as follows:
s01: sequentially stacking transparent electrodes 2 on a substrate 1, and etching the transparent electrodes 2 to form second grooves 9;
specifically, as shown in fig. 8A, an Indium Tin Oxide (ITO) transparent electrode 2 is stacked on a glass substrate 1, and then after ITO of a size of 1m×1m is subjected to standard cleaning, as shown in fig. 8B, P1 scribing is performed using a laser, and a second groove 9 is etched to obtain stripe-shaped ITO of a width of about 1cm, the width of the second groove 9 being about 100um.
S02: a first transmission layer 3, a first light conversion layer 4, an interface treatment layer 17 and a first transmission layer 5 are sequentially stacked on the ITO transparent electrode 2;
specifically, a first transmission layer 3 is formed by depositing a nickel oxide film on an ITO transparent electrode 2 by a magnetron sputtering method, and the first transmission layer 3 is a hole transmission layer at the moment, and the thickness is about 60nm; depositing a layer of perovskite by adopting a slit coating method to form a first light conversion layer 4, wherein the thickness of the first light conversion layer is about 500nm; adopting thermal evaporation to deposit a thin film layer MgF 2 Forming an interface treatment layer 17 having a thickness of about 1 nm; and depositing a tin oxide film with a layer thickness of about 40nm by adopting an atomic layer deposition technology to form a second transmission layer 5, wherein the second transmission layer 5 is an electron transmission layer. Fig. 8C shows a thin film solar cell semi-finished product obtained after the step S02. Wherein the interface treatment layer 17 is optional in the present application.
S03: etching to form a first groove 8;
specifically, the laser is used to scribe P2, and the first groove 8 is etched, as shown in fig. 8D, so that the etched line width is about 100um.
S04: in-situ growth is adopted to enable the light conversion material in the first light conversion layer 4 to perform in-situ reaction, so as to generate a blocking layer 11 composed of inorganic salt with gradually changed concentration;
Specifically, a semi-finished thin film solar cell having a first groove 8 is put into a container (C 7 H 15 NH 3 ) 2 SO 4 In toluene/isopropanol (ratio of 5:1) mixed solution, concentration of the solution was 4mM, soaking time was 1min, and perovskite was allowed to react with (C) 7 H 15 NH 3 ) 2 SO 4 In-situ reaction occurs to generate dense inorganic salt, a barrier layer 11 is formed in the first transfer layer 3 as shown in fig. 8E, and then the semi-finished thin film solar cell is vacuum-heated and dried.
S05: a metal electrode 6 is stacked on the second transmission layer 5 and etched to form a third recess 10.
Specifically, a silver film with a layer thickness of about 120nm is deposited on the surface of the semi-finished thin film solar cell by adopting a thermal evaporation method to form a metal electrode 6, the metal electrode 6 fills the first groove 8, and as shown in fig. 8F, the metal electrode 6 is respectively contacted with the barrier layer 11 and the transparent electrode 2; the third groove 10 is etched by performing a P3 scribing process using laser scribing, and as shown in fig. 8G, each of the independent sub-cells connected in series with each other is obtained.
With the barrier layer 11 grown by the solution method, the portion of the first light conversion layer 11 near the first recess 8 first reacts with the solution in situ, and perovskite reacts in situ more easily and more densely along the direction from the first light conversion layer 4 to the metal electrode 6, so that the concentration of inorganic salt is higher at a position near the metal electrode 6 in the first light conversion layer 4, and the concentration of perovskite is lower at a position near the metal electrode 6 because the light conversion material is consumed by the in situ reaction. The cost of the in-situ reaction of the solution method is relatively reduced, which is beneficial to commercialization of perovskite batteries.
The second mode of preparation is in-situ growth by solution and vapor phase oxidation, when the solute contains certain oxygen-containing salts such as SO 4 2- In the case of the class, toluene-based solutes are required to be dissolved, but toluene-based solutes tend to cause damage to some charge transport layers, especially to charge transport layers containing fullerenes, derivatives thereof, and organic substances. In order to be compatible with the above scene, the method adopts a solution and gas phase oxidation two-step method to generate the oxygen-containing salt, and the specific steps are as follows:
s01: sequentially stacking transparent electrodes 2 on a substrate 1, and etching the transparent electrodes 2 to form second grooves 9;
specifically, an Indium Tin Oxide (ITO) transparent electrode 2 is stacked on a glass substrate 1, after ITO having a size of 1m×1m is subjected to standard cleaning, P1 scribing is performed by using laser, and a second groove 9 is etched to obtain stripe-shaped ITO having a width of about 1cm, and the width of the second groove 9 is about 100um.
S02: a first transmission layer 3, a first light conversion layer 4, an interface treatment layer 17 and a first transmission layer 5 are sequentially stacked on the ITO transparent electrode 2;
specifically, a nickel oxide film is deposited on an ITO transparent electrode 2 by a magnetron sputtering method to form a first transmission layer 3, and the first transmission layer 3 is a hole transmission layer with the thickness of about 60nm; depositing a layer of perovskite by adopting a slit coating method to form a first light conversion layer 4, wherein the thickness of the first light conversion layer is about 500nm; depositing a C60 film layer by thermal evaporation to form an interface treatment layer 17, wherein the thickness of the interface treatment layer is about 1 nm; and depositing a tin oxide film with a layer thickness of about 40nm by adopting an atomic layer deposition technology to form a second transmission layer 5, wherein the second transmission layer 5 is an electron transmission layer. Wherein the interface treatment layer 17 is optional in the present application.
S03: etching to form a first groove 8;
specifically, the laser is used for carrying out P2 scribing, and the first groove 8 is formed by etching, wherein the width of the first groove 8 is about 100um.
S04: in-situ growth is adopted to enable the light conversion material in the first light conversion layer 4 to perform in-situ reaction, so as to generate a blocking layer 11 composed of inorganic salt with gradually changed concentration;
specifically, placing the perovskite thin film solar cell semi-finished product after P2 scribing into a solar cell containing Na 2 S in isopropanol mixed solution, the concentration of the solution is 4mM, the soaking time is 1min, and the perovskite and Na are obtained 2 S is subjected to in-situ reaction to generate a barrier layer 11-2 composed of anaerobic inorganic salt, and then the perovskite thin film solar cell semi-finished product is subjected to vacuum heating and drying. The dried perovskite thin film solar cell semi-finished product is put into an ozone environment to oxidize the barrier layer 11-2 to generate the barrier layer 11-1 composed of the aerobic inorganic salt, and the aerobic inorganic salt is more compact than the anaerobic inorganic salt.
S05: a metal electrode 6 is stacked on the second transmission layer 5 and etched to form a third recess 10.
Specifically, a silver film with the thickness of about 120nm is deposited on the surface of a sample by adopting a thermal evaporation method to form a metal electrode 6, the metal electrode 6 fills the first groove 8, and the metal electrode 6 is respectively contacted with the barrier layer 11 and the transparent electrode 2; and (3) carrying out a P3 scribing process by adopting laser, and etching to form a third groove 10 to obtain each independent and mutually-connected sub-cell.
As in the case of the solution method, the oxygen-free inorganic salt generated by the reaction between the anions in the solution and the portions of the first light conversion layer 4 adjacent to the first grooves 8 first has a higher concentration in the portions of the first light conversion layer 4 adjacent to the metal electrodes 6, and the light conversion material is consumed by the in-situ reaction, so that the concentration of the light conversion material is lower in the portions of the first light conversion layer 4 adjacent to the metal electrodes. When the oxygen-free inorganic salt reacts with the oxidizing gas in situ to form the oxygen-containing inorganic salt, the oxygen-free inorganic salt in the first light conversion layer 4 is consumed, so that the concentration of the oxygen-free inorganic salt tends to increase and decrease in the direction from the first light conversion layer to the metal electrode, and the concentration of the oxygen-containing inorganic salt gradually increases.
The third preparation method is that the perovskite directly contacts with the gas to generate in-situ reaction to generate the compact barrier layer 11 composed of the aerobic inorganic salt. The method comprises the following specific steps:
s01: sequentially stacking transparent electrodes 2 on a substrate 1, and etching the transparent electrodes 2 to form second grooves 9;
specifically, an Indium Tin Oxide (ITO) transparent electrode 2 is stacked on a glass substrate 1, after ITO having a size of 1m×1m is subjected to standard cleaning, P1 scribing is performed by using laser, and a second groove 9 is etched to obtain stripe-shaped ITO having a width of about 1cm, and the width of the second groove 9 is about 100um.
S02: a first transmission layer 3, a first light conversion layer 4, an interface treatment layer 17 and a first transmission layer 5 are sequentially stacked on the ITO transparent electrode 2;
specifically, a nickel oxide film is deposited on an ITO transparent electrode 2 by a magnetron sputtering method to form a first transmission layer 3, and the first transmission layer 3 is a hole transmission layer with the thickness of about 60nm; depositing a layer of perovskite by adopting a slit coating method to form a first light conversion layer 4, wherein the thickness of the first light conversion layer is about 500nm; adopting thermal evaporation to deposit a thin film layer MgF 2 Forming an interface treatment layer 17 having a thickness of about 1 nm; depositing a tin oxide film with a thickness of about 40nm by adopting an atomic layer deposition technology to form a second transmission layer 5, wherein the second transmission layer 5 is an electron transferAnd (5) conveying a layer. Wherein the interface treatment layer 17 is optional in the present application.
S03: etching to form a first groove 8;
specifically, the P2 scribing is performed by laser, the first groove 8 is etched, and the width of the etched line is about 100um.
S04: in-situ growth is adopted to enable the light conversion material in the first light conversion layer 4 to perform in-situ reaction, so as to generate a blocking layer 11 composed of inorganic salt with gradually changed concentration;
specifically, the perovskite thin film solar cell semi-finished product after the P2 scribing is placed in an environment containing ozone and carbon dioxide, so that perovskite and gas react in situ to generate a barrier layer 11 composed of compact aerobic inorganic salt.
S05: a metal electrode 6 is stacked on the second transmission layer 5 and etched to form a third recess 10.
Specifically, a silver film with a thickness of about 120nm is deposited on the surface of a semi-finished perovskite thin film solar cell by adopting a thermal evaporation method, a metal electrode 6 is formed, the metal electrode 6 fills the first groove 8, and the metal electrode 6 is respectively contacted with the barrier layer 11 and the transparent electrode 2; and (3) carrying out a P3 scribing process by adopting laser scribing, and etching to form a third groove 10, so as to obtain each independent and mutually-connected sub-cell.
Based on the same technical concept, the embodiment of the present application further provides a photovoltaic module, and fig. 10 is a schematic structural diagram of the photovoltaic module provided by the embodiment of the present application, as shown in fig. 10, the photovoltaic module provided by the embodiment of the present application may include: a housing 102, and the thin film solar cell 101 provided in the embodiments of the present application; wherein the thin film solar cell 101 may be located in the housing 102; in this way, the thin film solar cell 101 can be protected through the shell 102, the thin film solar cell 101 is prevented from being interfered by the outside, and the reliability and the safety of the photovoltaic module are improved.
The number of the thin film solar cells provided in the case is not limited to one, and may be plural, for example, three thin film solar cells may be provided in the power generation device shown in fig. 10, and the number of the thin film solar cells may be set according to actual needs to increase the power generation of the power generation device.
Further, the electrical connection relationship of the thin film solar cells 101 may be set as: parallel connection (as shown in fig. 10), series connection (not shown), or a combination of series and parallel connection (not shown); the setting can be specifically performed according to actual needs, and is not limited herein.
Based on the same technical concept, the embodiment of the present application further provides a power generation device, and fig. 11 is a schematic structural diagram of the power generation device provided in the embodiment of the present application, as shown in fig. 11, including: according to the photovoltaic module 100 and the inverter 200 electrically connected with the photovoltaic module 100 provided in the embodiments of the present application, the dc power output by the photovoltaic module 100 can be converted into ac power by the inverter 200, and then the converted ac power can be integrated into the power grid 300 for use.
The number of the photovoltaic modules 100 included in the power generation apparatus is not limited to two as shown in fig. 11, but may be one or more, and may be specifically set according to actual needs, which is not limited herein.
In this embodiment, as shown in fig. 11, when a plurality of photovoltaic modules 100 are provided, a plurality of inverters 200 may be provided, and the photovoltaic modules 100 and the inverters 200 are disposed in a one-to-one correspondence, so as to implement conversion processing of the inverter 200 on direct current output by the photovoltaic modules 100 that are disposed correspondingly, so as to improve conversion accuracy.
Of course, when the photovoltaic modules are provided in plurality, one inverter may be provided, not shown, and at this time the inverter is electrically connected with each photovoltaic module, and at this time the inverter may perform conversion processing on the direct current output by each photovoltaic module, so as to reduce the number of inverters, and reduce the manufacturing cost of the power generation device.
In the embodiment of the present application, the power generation device may include, in addition to the photovoltaic module and the inverter, other structures that may be used to implement the functions of the power generation device, which is not limited herein.
In embodiments of the present application, the power generation device may be, but is not limited to, a ground power station or a photovoltaic building integrated device.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments of the present application without departing from the spirit and scope of the embodiments of the present application. Thus, if such modifications and variations of the embodiments of the present application fall within the scope of the claims and the equivalents thereof, the present application is intended to encompass such modifications and variations.
Claims (15)
1. A thin film solar cell, comprising N series-connected subcells, N being an integer greater than 1, each subcell comprising: a substrate, a transparent electrode, a first transmission layer, a first light conversion layer, a second transmission layer and a metal electrode which are sequentially laminated;
each of the sub-cells further includes:
a first groove penetrating the first transmission layer, the first light conversion layer and the second transmission layer, the first groove being filled with the metal electrode, the metal electrode being in contact with the transparent electrode;
and the blocking layer is positioned in the first light conversion layer and between the first light conversion layer and the metal electrode, and comprises inorganic salt with gradually changed concentration.
2. The thin film solar cell of claim 1, wherein the barrier layer comprises a graded concentration of inorganic salt comprising: the concentration of the inorganic salt gradually increases along the direction from the first light conversion layer to the metal electrode;
the direction along the first light conversion layer to the metal electrode is perpendicular to the thickness direction of the sub-cell.
3. The thin film solar cell of claim 1, wherein the barrier layer comprises graded concentrations of inorganic salts including oxygen-free inorganic salts and oxygen-containing inorganic salts;
along the direction from the first light conversion layer to the metal electrode, the concentration of the oxygen-free inorganic salt gradually increases and then gradually decreases, and the concentration of the oxygen-containing inorganic salt gradually increases.
4. The thin film solar cell of any one of claims 1-3, wherein the first light conversion layer comprises a light conversion material;
the concentration of the light conversion material gradually decreases in the direction from the first light conversion layer to the metal electrode.
5. The thin film solar cell of any one of claims 1-4, wherein the subcell further comprises: and the second groove penetrates through the transparent electrode, and the second groove is filled by the first transmission layer.
6. The thin film solar cell of any one of claims 1-5, wherein the thin film solar cell comprises N subcells connected in series, including a third recess between the subcells, the third recess extending at least through the metal electrode and not through the transparent electrode.
7. The thin film solar cell of any one of claims 1-6, wherein the subcell is a stacked cell, the subcell further comprising: and a composite layer, a third transmission layer, a second light conversion layer and a fourth transmission layer which are sequentially laminated between the second transmission layer and the metal electrode.
8. The thin film solar cell of any one of claims 1-7, wherein the subcell further comprises an interface treatment layer;
the interface treatment layer is positioned between the first transmission layer or the second transmission layer and the first light conversion layer, or between the first transmission layer and the transparent electrode, or between the second transmission layer and the metal electrode.
9. The thin film solar cell of any one of claims 1-8, wherein the first light conversion layer comprises a light conversion material that is a perovskite.
10. A photovoltaic module, comprising: a housing, a thin film solar cell as claimed in any one of claims 1 to 9;
the thin film solar cell is arranged in the shell.
11. A power generation apparatus, characterized by comprising: the photovoltaic module of claim 10, an inverter electrically connected to the photovoltaic module;
The inverter is used for converting direct current output by the photovoltaic module into alternating current.
12. A method of manufacturing a thin film solar cell according to any one of claims 1 to 9, comprising:
sequentially stacking a transparent electrode, a first transmission layer, a first light conversion layer and a second transmission layer on a substrate;
etching to form a first groove, wherein the first groove penetrates through the first transmission layer, the first light conversion layer and the second transmission layer;
in-situ growth is adopted, so that the light conversion material in the first light conversion layer is subjected to in-situ reaction to generate inorganic salt with gradually changed concentration, the inorganic salt with gradually changed concentration forms a blocking layer, and the blocking layer is positioned in the first light conversion layer;
a metal electrode is stacked on the second transmission layer, and fills the first trench, with the blocking layer between the metal electrode and the first light conversion layer.
13. The method of claim 12, wherein in-situ growing the light conversion material in the first light conversion layer to generate an inorganic salt with graded concentration comprises:
and placing the thin film solar cell in a solution, and enabling the light conversion material in the first light conversion layer to react with solute in the solution in situ to generate inorganic salt with gradually changed concentration.
14. The method of claim 12, wherein in-situ growing the light conversion material in the first light conversion layer to generate an inorganic salt with graded concentration comprises:
placing the thin film solar cell in a solution, and enabling a light conversion material in the first light conversion layer to react with a solute in the solution in situ to generate oxygen-free inorganic salt with gradually changed concentration;
and then placing the thin film solar cell in oxidizing gas to enable the anaerobic inorganic salt to react in situ to generate the aerobic inorganic salt with gradually changed concentration.
15. The method of claim 12, wherein in-situ growing the light conversion material in the first light conversion layer to generate an inorganic salt with graded concentration comprises:
placing the thin film solar cell in mixed gas, and enabling a light conversion material in the first light conversion layer to react with the mixed gas in situ to generate aerobic inorganic salt with gradually changed concentration;
the mixed gas includes an oxidizing gas and a non-oxidizing gas containing inorganic salt anions.
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| PCT/CN2023/139035 WO2024131659A1 (en) | 2022-12-22 | 2023-12-15 | Thin-film solar cell and preparation method therefor, photovoltaic module, and power generation device |
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| CN116613230A (en) * | 2023-06-26 | 2023-08-18 | 云谷（固安）科技有限公司 | Solar cell and preparation method thereof |
| CN117135936A (en) * | 2023-10-27 | 2023-11-28 | 宁德时代新能源科技股份有限公司 | Solar cell module, preparation method and system thereof, battery and power utilization device |
| WO2024131659A1 (en) * | 2022-12-22 | 2024-06-27 | 华为数字能源技术有限公司 | Thin-film solar cell and preparation method therefor, photovoltaic module, and power generation device |
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| CN113383436A (en) * | 2019-01-30 | 2021-09-10 | 纽泰克温图斯公司 | Conversion of halide perovskite surface to insoluble wide band gap lead oxide salt to enhance solar cell stability |
| CN109950341B (en) * | 2019-03-28 | 2020-08-25 | 昆山协鑫光电材料有限公司 | Thin-film solar cell module and method for detecting breaking condition of thin-film solar cell module P2 |
| KR20210144104A (en) * | 2020-05-21 | 2021-11-30 | 한국전자통신연구원 | Perovskite solar cell module |
| CN113745365A (en) * | 2021-10-11 | 2021-12-03 | 华能新能源股份有限公司 | Thin-film solar cell structure and preparation method thereof |
| CN114695674A (en) * | 2022-03-29 | 2022-07-01 | 无锡极电光能科技有限公司 | Perovskite solar device and preparation method thereof |
| CN115411125A (en) * | 2022-08-01 | 2022-11-29 | 华为数字能源技术有限公司 | Thin-film solar cell and preparation method thereof, photovoltaic module and power generation equipment |
| CN116072752A (en) * | 2022-12-22 | 2023-05-05 | 华为数字能源技术有限公司 | Thin film solar cell, preparation method thereof, photovoltaic module and power generation equipment |
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| WO2024131659A1 (en) * | 2022-12-22 | 2024-06-27 | 华为数字能源技术有限公司 | Thin-film solar cell and preparation method therefor, photovoltaic module, and power generation device |
| CN116613230A (en) * | 2023-06-26 | 2023-08-18 | 云谷（固安）科技有限公司 | Solar cell and preparation method thereof |
| CN116613230B (en) * | 2023-06-26 | 2024-05-28 | 云谷（固安）科技有限公司 | Solar cell and preparation method thereof |
| CN117135936A (en) * | 2023-10-27 | 2023-11-28 | 宁德时代新能源科技股份有限公司 | Solar cell module, preparation method and system thereof, battery and power utilization device |
| CN117135936B (en) * | 2023-10-27 | 2024-03-29 | 宁德时代新能源科技股份有限公司 | Solar cell module, preparation method and system thereof, battery and power utilization device |
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