Optoelectronic device and method of manufacture, electrical consumer and electrical generator

Abstract

This application relates to optoelectronic devices and their fabrication methods, as well as electrical devices and power generation devices. The optoelectronic device includes a perovskite layer comprising perovskite grains. The crystalline phases of the perovskite grains include cubic and non-cubic phases; the cubic phase accounts for more than or equal to 97% of the mass of the perovskite layer; the non-cubic phase includes at least one of tetragonal, orthorhombic, and other phases; the other phases account for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase; and the dielectric constant of the perovskite layer is greater than or equal to 5. This optoelectronic device exhibits high energy conversion efficiency.

Description

Technical Field

[0001] This application relates to the field of optoelectronic device technology, and further to optoelectronic devices and their preparation methods, electrical devices and power generation devices. Background Technology

[0002] Optoelectronic devices are a class of devices that utilize photoelectric conversion mechanisms to perform photoelectric conversion. They can convert light energy into electrical energy for use in photovoltaics, or electrical energy into light energy for use in displays, lighting, and other fields. Accordingly, optoelectronic devices can be either photovoltaic devices or light-emitting devices. Taking photovoltaic devices as an example, as a highly efficient device that directly converts solar energy into electrical energy, they have been widely used in many fields. For instance, they are widely used on the rooftops of residential, commercial, and industrial buildings to form distributed photovoltaic power generation systems, or combined with energy storage devices for off-grid power systems, or integrated into portable electronic devices to provide power support for outdoor scenarios.

[0003] The core functional layer for photoelectric conversion in photovoltaic devices is the light-absorbing layer. Representative photovoltaic devices include crystalline silicon solar cells and perovskite solar cells. In perovskite solar cells, the light-absorbing layer is a perovskite layer containing perovskite material. Due to their high conversion efficiency and the ability to be fabricated using low-cost solution methods, perovskite solar cells have attracted widespread attention from the industry. Photoelectric conversion efficiency is crucial for the practical application of perovskite solar cells. Therefore, researching ways to improve the energy conversion efficiency of photovoltaic devices is of great significance. Summary of the Invention

[0004] According to various embodiments and examples of this application, this application provides optoelectronic devices and their fabrication methods, electrical devices, and power generation devices. The optoelectronic device exhibits high energy conversion efficiency.

[0005] In some embodiments of the first aspect of this application, an optoelectronic device is provided, which includes a perovskite layer comprising perovskite grains, wherein the crystalline phase of the perovskite grains includes a cubic phase and a non-cubic phase.

[0006] The cubic phase accounts for more than or equal to 97% of the mass of the perovskite layer; the non-cubic phase includes at least one of tetragonal phase, orthorhombic phase and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase.

[0007] The dielectric constant of the perovskite layer is greater than or equal to 5.

[0008] By controlling the specific composition ratio of different crystal phases in the perovskite layer, making the cubic phase predominant and minimizing the proportion of non-cubic phases other than the tetragonal and orthorhombic phases, while also controlling the proportion of the tetragonal phase to be higher than that of the orthorhombic phase, the above crystal phase composition can improve the absorbance of the perovskite layer, increase the utilization rate of incident light, and the cubic phase has a stronger charge transport capability, which is beneficial to the transport of charge carriers. A small amount of tetragonal phase is beneficial to controllably preventing the transformation of cubic perovskite to non-cubic phase. At the same time, controlling the dielectric constant of the perovskite layer within a relatively high range can significantly reduce charged defects and significantly suppress the scattering effect of possible charged defects, thereby significantly increasing the effective transport distance of photogenerated charge carriers in the perovskite layer. Thus, through the synergy of the aforementioned multiple effects, the energy conversion efficiency of optoelectronic devices can be significantly improved.

[0009] In some embodiments of this application, the one-dimensional integral curve of the GIWAXS two-dimensional diffraction pattern of the perovskite layer satisfies one or more of the following characteristics:

[0010] (t1) The dominant crystal plane of the cubic phase is one of (100) and (111);

[0011] (t2) The dominant crystal plane of the tetragonal phase is one of (100) and (111);

[0012] (t3) The dominant crystal plane of the orthorhombic phase is one of (100) and (111).

[0013] By controlling the dominant crystal faces of one or more of the cubic, tetragonal, and orthorhombic phases of perovskite grains to have the aforementioned types, it is beneficial to obtain perovskite layers with excellent light absorption and effective charge transport distance. At the same time, it is also beneficial to better control the increase in internal resistance that may be caused by a relatively large dielectric constant.

[0014] In some embodiments of this application, the dielectric constant of the perovskite layer is 5 to 16, and optionally 6.5 to 15.

[0015] By controlling the dielectric constant of the perovskite layer within the aforementioned range, it is beneficial to promote carrier transport within the perovskite layer and reduce the impact of defects on lattice stability. This results in not only excellent light absorption and charge transport capabilities but also a good balance between the stability of the perovskite crystal structure. Consequently, both high energy conversion efficiency and high device stability can be achieved.

[0016] In some embodiments of this application, the thickness of the perovskite layer is 200nm~1500nm, and can be selected as 400nm~1000nm.

[0017] By combining the aforementioned technical solutions, good light absorption and effective carrier transport can be maintained even within a large perovskite layer thickness range, thereby effectively improving the energy conversion efficiency of optoelectronic devices with thicker perovskite layers.

[0018] In some embodiments of this application, the perovskite layer satisfies one or more of the following characteristics:

[0019] (a1) The tetragonal phase accounts for more than or equal to 65% of the mass of the non-cubic phase;

[0020] (a2) The orthorhombic phase accounts for less than or equal to 30% of the mass of the non-cubic phase;

[0021] (a3) The other phases include at least the triclinic phase.

[0022] By controlling the mass ratio of cubic and / or tetragonal phases in the non-cubic phase within the aforementioned range, it is beneficial to better improve the absorbance of the perovskite layer, thereby better improving the energy conversion efficiency.

[0023] In some embodiments of this application, based on the XRD diffraction pattern of the perovskite layer, the dominant crystal plane of the cubic phase is (100) or (111); when the dominant crystal plane of the cubic phase is (100), the half-width at half-maximum (WHM) of the diffraction peak of the (100) plane is 0.05°~0.20°; or, when the dominant crystal plane of the cubic phase is (111), the half-width at half-maximum (WHM) of the diffraction peak of the (111) plane is 0.05°~0.30°.

[0024] By controlling the full width at half maximum (FWHM) of the diffraction peaks of the dominant cubic crystal plane in the XRD diffraction pattern of the perovskite layer within the aforementioned range, the crystallinity of the perovskite grains is higher, the surface perovskite grains have a more regular crystal structure, and the atomic arrangement is more ordered. This helps to reduce grain boundaries and defects in the perovskite layer, reduce the probability of nonradiative recombination of charge carriers, and improve the carrier mobility. On the other hand, controlling the FWHM within the aforementioned range also indicates that the crystal orientation is more uniform, which is beneficial to reducing the scattering and trapping effects of charge carriers during transport, and improving the overall carrier transport rate.

[0025] In some embodiments of this application, the perovskite layer includes a first additive, which is an organic material; at least a portion of the first additive is located at the grain boundaries of the perovskite grains.

[0026] Optionally, the first additive includes at least one of hydrocarbon-based haloamines and hydrocarbon-based pseudohalogenated amines;

[0027] Optionally, the first additive includes C 3-20 Hydrocarbon-based haloamines, and optionally, the first additive includes C 6-20Hydrocarbon-based halogenated amines.

[0028] By controlling the distribution of the first additive at the grain boundaries of perovskite grains, it is beneficial to passivate grain boundary defects while reducing the probability of defects that may enter the lattice. This can improve the dielectric constant of perovskite to a certain extent while achieving higher absorbance, thereby improving energy conversion efficiency.

[0029] In some embodiments of this application, the halogen in the hydrocarbon-based haloamine includes at least one of chlorine, bromine, and iodine.

[0030] By controlling the first additive to include at least one of chlorine, bromine, and iodine, it is beneficial to better passivate grain boundary defects and achieve better energy conversion efficiency.

[0031] In some embodiments of this application, the perovskite layer comprises a first perovskite material, wherein the molar percentage of the first additive to the first perovskite material in the perovskite layer is 1% to 10%, and the molar amount of the first perovskite material is calculated based on the molar amount of divalent cations in the first perovskite material. This approach is advantageous in improving the dielectric constant of the perovskite to a certain extent while better leveraging the advantages of grain boundary defects and achieving higher absorbance, thereby improving energy conversion efficiency.

[0032] In some embodiments of this application, the content of the first additive at the grain boundaries of the perovskite grains in the perovskite layer is higher than its content within the crystalline phase of the perovskite grains. This is more advantageous in passivating grain boundary defects while simultaneously reducing the probability of defects that may enter the crystal lattice and cause defects. It also helps to minimize the adverse effects of defects caused by the additive entering the perovskite lattice on the dielectric constant of the perovskite layer, and is more conducive to improving energy conversion efficiency.

[0033] In some embodiments of this application, the average size of the perovskite grains in the perovskite layer is 0.6 μm to 3 μm. By controlling the average size of the perovskite grains in the perovskite layer to be within the aforementioned relatively large range, it is beneficial to reduce the number of grain boundaries and achieve better energy conversion efficiency and device stability.

[0034] In some embodiments of this application, the perovskite layer comprises a first perovskite material; the first perovskite material comprises at least one halogen selected from iodine, chlorine, and bromine.

[0035] Optionally, the first perovskite material includes iodine and bromine.

[0036] Optionally, the molar ratio of iodine to bromine in the perovskite layer is (0~1):(0~1), and more preferably (0.8~1):(0~0.2).

[0037] The first perovskite materials of the aforementioned halogen types are conducive to the better formation of the aforementioned crystal phase composition.

[0038] In addition, the aforementioned first additives effectively passivate possible charged defects in the first perovskite material, which is beneficial to improving the dielectric constant of the perovskite layer and thus improving the energy conversion efficiency.

[0039] In some embodiments of this application, the perovskite layer comprises a first perovskite material; the first perovskite material comprises at least one of formamidinium ionic groups and methylamine ionic groups; optionally, in the perovskite layer, the molar ratio of formamidinium ionic groups to methylamine ionic groups is q. FA :q MA , where q FA The value is 0.8~1, q MA The range is 0 to 0.2.

[0040] Optionally, q FA The value is 0.9~1, q MA The value is 0.05~0.1;

[0041] Optionally, q FA q MA The sum is 0.95~1, and optionally, q FA q MA The sum is 1.

[0042] The first perovskite material of the aforementioned atomic group type is conducive to the better formation of the aforementioned crystal phase structure.

[0043] In some embodiments of this application, the thickness direction of the perovskite layer is denoted as the Z-direction, and the area of ​​the perovskite layer on a projection plane perpendicular to the Z-direction is greater than or equal to 0.09 cm². 2 Optionally, greater than or equal to 1m 2 .

[0044] By combining the aforementioned technical solutions, good light absorption and effective carrier transport can be maintained even with a large perovskite layer area, thereby effectively improving the energy conversion efficiency of optoelectronic devices with large-area perovskite layers.

[0045] In some embodiments of this application, the optoelectronic device includes a photovoltaic device or a light-emitting device. The aforementioned perovskite layer can be used in photovoltaic devices or light-emitting devices to help improve the energy conversion efficiency of photovoltaic devices or light-emitting devices, and in some embodiments, it can also improve device stability.

[0046] In some embodiments of this application, the optoelectronic device is a photovoltaic device; the photovoltaic device includes a solar cell, and the solar cell includes the perovskite layer.

[0047] The aforementioned perovskite layer can be incorporated into solar cells to improve their photoelectric conversion efficiency. Furthermore, it can also enhance device stability.

[0048] In some embodiments of this application, the optoelectronic device includes a solar cell, which is a multi-junction solar cell, and the multi-junction solar cell includes a first cell unit, which includes the perovskite layer.

[0049] The aforementioned perovskite layer can be incorporated into multi-junction solar cells to improve their photoelectric conversion efficiency. Furthermore, it can also enhance device stability.

[0050] In some embodiments of this application, the multi-junction solar cell further includes a second cell stacked with the first cell; the second cell and the first cell are connected by an interconnect layer, or the second cell and the first cell are isolated by an insulating layer; the second cell includes a second light-absorbing layer, and the band gap of the second light-absorbing layer is different from that of the perovskite layer.

[0051] By setting up multiple light-absorbing layers with different band gaps (including a perovskite layer and a second light-absorbing layer), multi-junction solar cells can effectively absorb light of different wavelengths, broadening the spectral range of light absorbed by multi-junction solar cells and improving their photoelectric conversion efficiency.

[0052] In some embodiments of this application, the second light-absorbing layer in the second battery cell includes a semiconductor active material, which includes one or more of the following: a second perovskite material, a silicon-containing semiconductor material, copper zinc tin sulfide, copper zinc tin selenide, copper zinc tin selenide sulfide, copper indium gallium selenide, copper indium gallium diselenide, copper indium selenide, cadmium telluride, gallium arsenide, and organic active materials.

[0053] The aforementioned embodiments can be universally applied to the aforementioned different types of multi-junction solar cells.

[0054] In some embodiments of this application, the multi-junction solar cell includes a first electrode, a perovskite layer, an interconnect layer, a second light-absorbing layer, and a second electrode stacked together; wherein the interconnect layer is located between the perovskite layer and the second light-absorbing layer; the first electrode is located on the side of the perovskite layer opposite to the interconnect layer, and the second electrode is located on the side of the second light-absorbing layer opposite to the interconnect layer. Thus, the two cell units in the multi-junction solar cell are connected through the interconnect layer to achieve current matching between the two cell units. This results in a relatively smaller size, the ability to absorb light of different wavelengths, a wider absorption spectrum range for the multi-junction solar cell, and an improved photoelectric conversion efficiency.

[0055] In some embodiments of this application, the multi-junction solar cell includes a first electrode, a perovskite layer, a third electrode, an insulating layer, a fourth electrode, a second light-absorbing layer, and a second electrode stacked together. The third electrode, the insulating layer, and the fourth electrode are stacked between the perovskite layer and the second light-absorbing layer. The third electrode is disposed on the side of the insulating layer facing the perovskite layer, and the fourth electrode is disposed on the side of the insulating layer facing the second light-absorbing layer. The first electrode is located on the side of the perovskite layer away from the third electrode, and the second electrode is located on the side of the second light-absorbing layer away from the fourth electrode. Thus, the multi-junction solar cell forms a mechanically stacked cell. The insulating layer isolates the two cell units, preventing direct conduction of charge carriers and eliminating the need for current matching. Furthermore, each cell has its own separate positive and negative electrodes for current extraction, allowing for flexible circuit adjustments.

[0056] In some embodiments of this application, the optoelectronic device is a photovoltaic device; the optoelectronic device satisfies one or more of the following characteristics:

[0057] (b1) The perovskite layer is contained in the inverse or formal structure of the optoelectronic device;

[0058] (b2) The optoelectronic device includes a first charge transport layer and a second charge transport layer, wherein the perovskite layer is located between the first charge transport layer and the second charge transport layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer;

[0059] (b3) The optoelectronic device includes a first electrode and a second electrode, and the perovskite layer is disposed between the first electrode and the second electrode;

[0060] Optionally, the optoelectronic device includes at least one charge transport layer and the perovskite layer disposed between the first electrode and the second electrode; the at least one charge transport layer includes at least one of a first charge transport layer located between the first electrode and the perovskite layer and a second charge transport layer located between the second electrode and the perovskite layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer.

[0061] The aforementioned implementation methods can be universally applied to photovoltaic devices with either conventional or inverted structures, thereby improving photoelectric conversion efficiency. Furthermore, they can also enhance device stability.

[0062] In some embodiments of the second aspect of this application, a method for fabricating an optoelectronic device is provided, which can be used to fabricate the optoelectronic device of the first aspect of this application.

[0063] In some embodiments of this application, a method for fabricating an optoelectronic device is provided, which includes the following steps:

[0064] A perovskite precursor solution is provided; wherein the perovskite precursor solution comprises a perovskite precursor material and a first solvent;

[0065] The perovskite precursor solution is coated and vacuum dried to remove part of the first solvent, thus preparing a perovskite intermediate phase film layer.

[0066] An additive dispersion containing a first additive and a second solvent is coated onto the surface of the perovskite mesophase film layer, and after standing, laser gradient annealing is performed to form a perovskite layer; wherein, the first additive is an organic material, and the second solvent includes isopropanol and N,N-dimethylformamide; the laser gradient annealing includes a first-stage annealing at a first temperature, and then a second-stage annealing at a second temperature; the first temperature is 85℃~95℃, and the second temperature is higher than the first temperature;

[0067] The formed perovskite layer comprises perovskite grains, the crystalline phases of which include cubic and non-cubic phases; the cubic phase accounts for more than or equal to 97% of the mass of the perovskite layer; the non-cubic phase includes at least one of tetragonal, orthorhombic, and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase; and the dielectric constant of the perovskite layer is greater than or equal to 5.

[0068] The aforementioned preparation method employs a unique strategy of separately adding the perovskite precursor solution and the first additive, followed by subsequent diffusion. This strategy ensures that the first additive is primarily distributed along the grain boundaries, inducing high-quality crystallization of the perovskite and forming specific proportions of different crystal phases. This results in higher absorbance and improved utilization of incident light. Furthermore, the cubic phase exhibits stronger charge transport capabilities, which is beneficial for carrier transport. Simultaneously, the first additive largely avoids entering the perovskite crystal, reducing the probability of charged defects arising from its entry into the lattice. This significantly suppresses the scattering effect of potential charged defects, thereby significantly increasing the effective transport distance of photogenerated carriers within the perovskite layer and achieving a relatively high dielectric constant. In the prepared perovskite layer, the first additive remaining at the grain boundaries can continue to passivate interface defects. Thus, both high crystal quality and fewer charged defects are achieved simultaneously. This not only improves the utilization of incident light but also promotes the effective transport of carriers within the perovskite layer. The synergistic effect of these multiple actions significantly enhances the energy conversion efficiency of optoelectronic devices.

[0069] In the aforementioned process, the perovskite precursor solution without additives is coated and vacuum dried to remove some solvent, while retaining some solvent molecules in the perovskite mesophase film. Then, an additive dispersion containing the first additive is coated onto the perovskite mesophase film and allowed to stand to allow the first additive to diffuse along the mesophase boundary, inducing perovskite crystallization. In the subsequent laser annealing process, laser gradient annealing is used. During the first stage of annealing, the system is controlled to prevent large-scale, rapid perovskite crystallization, allowing the residual solvent to carry the first additive out of the crystal. Then, a second stage of higher-temperature annealing achieves high-quality crystallization, allowing the first additive to... The agent is confined to the grain boundaries and does not enter the perovskite crystal much, which can significantly reduce the charged defects in the crystal, significantly suppress the scattering effect of possible charged defects, improve the crystal quality, and significantly increase the effective transport distance of photogenerated carriers in the perovskite layer. This results in the aforementioned special phase ratio, with the cubic phase accounting for the majority (e.g., ≥97%, based on the quality of the perovskite layer), the tetragonal phase accounting for a higher proportion than the orthorhombic phase, and the proportion of other phases being as small as possible (e.g., ≤5%, based on the quality of the non-cubic phase). At the same time, it also has a high dielectric constant (e.g., ≥5), effectively avoiding the adverse effects of defects caused by additives in other processes entering the perovskite lattice on the dielectric constant of the perovskite layer.

[0070] The above preparation method can still achieve high energy conversion efficiency even with a high perovskite layer thickness.

[0071] The above preparation method is simple and easy to operate, and can significantly improve energy conversion efficiency without the need for additional equipment, which is beneficial to reducing costs.

[0072] In some embodiments of this application, the method for fabricating the optoelectronic device satisfies one or more of the following features:

[0073] (c1) In the step of vacuum drying to remove part of the first solvent, the temperature of the vacuum drying is 0℃~70℃, the pressure of the vacuum drying is 5Pa~500Pa, and the duration of the vacuum drying is 2s~40s. By controlling the above process parameters, it is beneficial to better control the residual amount of the first solvent, so that in the subsequent laser annealing process, the first additive can be better controlled to mainly diffuse along the grain boundary, and basically not enter or enter the perovskite crystal.

[0074] (c2) In the second solvent, the volume ratio of isopropanol and N,N-dimethylformamide is (25~99):1; the isopropanol (IPA) in the second solvent has very weak solubility for perovskite, but can effectively dissolve the passivating agent. N,N-dimethylformamide (DMF) has a dissolving effect on perovskite. By using isopropanol and a small amount of N,N-dimethylformamide as a co-solvent, the passivating agent can be effectively penetrated into the perovskite layer while ensuring effective secondary dissolution of perovskite, thereby fully passivating defects.

[0075] (c3) The mass-volume concentration of the first additive in the additive dispersion is 0.5 mg / mL to 10 mg / mL;

[0076] (c4) The temperature for the settling is 0℃~70℃, the settling time is 2min~5min, and the ambient humidity for the settling is less than or equal to 3%RH; this is conducive to better control of the diffusion of the first additive along the intermediate phase boundary.

[0077] (c5) The duration of the first stage annealing at the first temperature is 1s to 5s; the temperature of the second stage annealing at the second temperature is 95℃ to 105℃, and the duration is 5s to 15s. At this time, it is beneficial to form high-quality perovskite crystals and form the perovskite crystal phase in the aforementioned proportion.

[0078] In some embodiments of the third aspect of this application, an electrical device is provided, which includes at least one of the optoelectronic devices described in the first aspect of this application and optoelectronic devices prepared by the preparation method of the optoelectronic devices described in the second aspect of this application.

[0079] In some embodiments of the fourth aspect of this application, a power generation device is provided, which includes at least one of the optoelectronic devices described in the first aspect of this application and optoelectronic devices prepared by the preparation method of the optoelectronic devices described in the second aspect of this application.

[0080] Both the power-consuming devices and power-generating devices containing the aforementioned optoelectronic devices can leverage the advantages of optoelectronic devices.

[0081] Details of one or more embodiments or examples of this application are set forth in the following drawings and description. Other features, objects, and advantages of this application will become apparent from the specification, drawings, and claims. Attached Figure Description

[0082] To better describe and illustrate the embodiments, examples, or models provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments, examples, or models, or the best mode of these applications as currently understood. Furthermore, the same reference numerals denote the same parts throughout the drawings. It should also be noted that the drawings are drawn in a simplified form and are only used to facilitate and clarify the illustration of this application. The various dimensions of each part shown in the drawings are arbitrarily shown and may be precise or not drawn to scale. For example, the dimensions of parts are appropriately exaggerated in some places in the drawings to make the illustration clearer. Unless otherwise specified, the parts in the drawings are not drawn to scale. This application does not limit every dimension of every part. In the drawings:

[0083] Figure 1 This is a schematic diagram of the structure of a perovskite layer in an optoelectronic device according to an embodiment of this application. The perovskite layer includes perovskite grains, which include cubic phase grains and non-cubic phase grains. The non-cubic phase grains include tetragonal phase grains and orthorhombic phase grains.

[0084] Figure 2 This is a schematic diagram of the structure of a perovskite layer in an optoelectronic device according to an embodiment of this application. The perovskite layer includes perovskite grains and grain boundaries between adjacent perovskite grains.

[0085] Figure 3 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of the present application. The optoelectronic device includes a perovskite layer and at least one charge transport layer stacked together.

[0086] Figure 4 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of the present application. The optoelectronic device includes a first charge transport layer, a perovskite layer and a second charge transport layer stacked together, wherein the first charge transport layer and the second charge transport layer are respectively disposed on both sides of the perovskite layer in the thickness direction of the perovskite layer.

[0087] Figure 5This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of the present application. The optoelectronic device includes a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode stacked together. In the thickness direction of the perovskite layer, the first charge transport layer and the second charge transport layer are respectively disposed on both sides of the perovskite layer. The first electrode is disposed on the side of the first charge transport layer away from the perovskite layer, and the second electrode is disposed on the side of the second charge transport layer away from the perovskite layer.

[0088] Figure 6 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of the present application. The optoelectronic device includes a substrate layer, a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode stacked together. In the thickness direction of the perovskite layer, the first charge transport layer and the second charge transport layer are respectively disposed on both sides of the perovskite layer. The first electrode is disposed on the side of the first charge transport layer away from the perovskite layer, the second electrode is disposed on the side of the second charge transport layer away from the perovskite layer, and the substrate layer is disposed on the side of the first electrode away from the perovskite layer.

[0089] Figure 7 This is a schematic diagram of the structure of an inverted optoelectronic device according to an embodiment of this application. The optoelectronic device includes a substrate layer, an incident electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a back electrode stacked together. In the thickness direction of the perovskite layer, the hole transport layer and the electron transport layer are respectively disposed on both sides of the perovskite layer. The incident electrode is disposed on the side of the hole transport layer away from the perovskite layer, the back electrode is disposed on the side of the electron transport layer away from the perovskite layer, and the substrate layer is disposed on the side of the incident electrode away from the perovskite layer.

[0090] Figure 8 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of this application. The optoelectronic device includes a substrate layer, an incident electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a back electrode stacked together. In the thickness direction of the perovskite layer, the hole transport layer and the electron transport layer are respectively disposed on both sides of the perovskite layer. The incident electrode is disposed on the side of the electron transport layer away from the perovskite layer, the back electrode is disposed on the side of the hole transport layer away from the perovskite layer, and the substrate layer is disposed on the side of the incident electrode away from the perovskite layer.

[0091] Figure 9 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of the present application. The optoelectronic device is provided with a first channel region, a second channel region and a third channel region.

[0092] Figure 10 This is a schematic diagram of an electrical device according to an embodiment of this application, in which an optoelectronic device is used as a power generation device.

[0093] Explanation of reference numerals in the attached figures:

[0094] 10, Optoelectronic device; 100, Perovskite layer; Z, Thickness direction of perovskite layer; 111, Cubic phase grain; 112, Non-cubic phase grain; 1121, Tetragonal phase grain; 1122, Orthorhombic phase grain; 110, Perovskite grain; 120, Grain boundary of perovskite grain; 300, Charge transport layer; 310, First charge transport layer; 320, Second charge transport layer; 410, First electrode; 420, Second electrode; 500, Substrate layer; 610, Hole transport layer; 620, Electron transport layer; 700, Light-receiving side electrode; 800, Back electrode; P1, First channel region; P2, Second channel region; P3, Third channel region; 6, Electrical device. Detailed Implementation

[0095] The following describes in detail, with appropriate reference to the accompanying drawings, some embodiments and examples of the optoelectronic device and its fabrication method, as well as the power supply and power generation device of this application. However, some unnecessary details may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided for the purpose of enabling those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0096] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be included or excluded independently and can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when describing a parameter as an integer ≥ 2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 for that parameter. For instance, when describing a parameter as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0097] In this application, the term "numerical value" includes the number itself and its reasonable approximations. The definition of "numerical value" can apply to discrete numerical points or to the endpoints of a numerical range. Unless otherwise specified, the term "approximation" covers a numerical interval based on a reasonable range of fluctuations of the number itself. This reasonable range of fluctuations can vary depending on the type and magnitude of the number. This reasonable range of fluctuations can be reasonably determined based on the accuracy of the testing or measurement method. Therefore, when referring to a numerical value or a numerical range, unless otherwise specified, it should be understood that the numerical value includes its reasonable approximation, and the numerical range includes reasonable approximations at both endpoints. Those skilled in the art will understand that acceptable fluctuation ranges of the relevant approximations can be included within the definition of the numerical value or the numerical range. In this application, unless otherwise specified, "N1" can be reasonably understood as "about N1," and "N1~N2" can be reasonably understood as "about N1 to about N2," where N1 and N2 are two unequal numerical values.

[0098] In this application, unless otherwise specified, "about" means within a reasonable range above and below the number, and the range of fluctuation may vary depending on the type and value of the number. For example, a range of ±10%, ±5%, ±2%, ±1% may be allowed.

[0099] In this application, the terms "multiple," "various," or "multiple items" are used unless otherwise specified, referring to a quantity greater than or equal to 2. For example, "one or more" means one item or two or more (greater than or equal to) items. It can be understood that when "any number of" items are involved, it refers to any suitable combination of multiple items, that is, a combination of "any number of" items in a manner that does not conflict and enables the implementation of this application.

[0100] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0101] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding.

[0102] Those skilled in the art will understand that, unless otherwise specified, the order in which the steps are written in the various embodiments or methods of this application does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of this application may be performed sequentially or randomly, but are preferably performed sequentially. For example, if method M includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, method M may also include step (c), meaning that step (c) can be added to method M in any order. For example, method M may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0103] In this application, open-ended technical features or solutions described using terms such as "containing," "comprising," or "including" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, if 'a' includes a1, a2, and a3, it may also include other members or exclude additional members unless otherwise specified. This can be considered as providing both features or solutions where "a consists of a1, a2, and a3" or "a is selected from a1, a2, and a3," and features or solutions where "a includes not only a1, a2, and a3, but also other members."

[0104] In this application, unless otherwise specified, M (e.g., m1) means that m1 is a non-limiting example of M, and it is understood that M is not limited to m1.

[0105] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. Unless otherwise specified, the descriptions such as "optionally include" and "optionally contain" in this application, taking "optionally include" as an example, mean "may include or not include."

[0106] In this application, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. Any and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "M and / or N" represents the group consisting of M, N, and "a combination of M and N". "Containing M and / or N" can mean "containing M, containing N, and containing both M and N", or "containing M, containing N, or containing both M and N", and can be appropriately understood according to the context.

[0107] In this document, the word "suitable" in "suitable combination" or "suitable method" refers to the technical solution that can implement this application.

[0108] In this document, terms such as "preferred," "better," and "good" are merely descriptions of implementation methods or embodiments that achieve better results and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0109] In this application, terms such as "further," "even more," "especially," "for example," "as," "example," and "exemplary" are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0110] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0111] In this application, the term "room temperature" generally refers to 4℃~35℃, and may refer to 20℃±5℃. In some embodiments or examples of this application, room temperature refers to 20℃~30℃.

[0112] In this application, when a unit is specified for a data range, if the unit is only followed by the right endpoint, it indicates that the units for the left and right endpoints are the same. For example, 3~5μm or 3-5μm both mean that the unit for the left endpoint "3" and the right endpoint "5" is μm (micrometer), and both have the same meaning as 3μm~5μm. Furthermore, similar descriptions of other parameters such as temperature and concentration are interpreted in the same way.

[0113] In this application, unless otherwise specified, wt% means weight percentage, which is numerically equal to the corresponding mass percentage.

[0114] In this application, unless otherwise specified, the number of carbon atoms in a compound or group may be described using the subscript "C". For example, "C 6-10 "" indicates that it has 6 to 10 carbon atoms, "C 6-10 "Each time it appears, it can be independently classified as C6, C7, C8, C9, or C..." 10 For example, “C” 1-6 "" indicates that it has 1 to 6 carbon atoms, "C 1-6 "Each time it appears, it can be independently classified as C1, C2, C3, C4, C5, or C6. For example, 'C'..." 1-3 "" indicates that it has 1 to 3 carbon atoms, "C 1-3 Each occurrence can be independently designated as C1, C2, or C3. For example, "C..." 1-6 "alkyl" indicates an alkyl group having 1 to 6 carbon atoms, "C 1-6 Each time the word "alkyl" appears, it can be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, or C6 alkyl.

[0115] In the description of the embodiments or examples of this application, the terms "center", "longitudinal", "lateral", "length", "height", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", etc., indicating the orientation or positional relationship are only for the convenience of describing the embodiments of this application and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation on the embodiments of this application.

[0116] In this application, unless otherwise expressly specified and limited, in the device structure, the first feature "above" or "below" the second feature can be in direct contact with the first feature, or indirect contact between the first and second features through an intermediate medium. In this application, unless otherwise expressly specified and limited, the first feature "above" or "below" the second feature can indicate a horizontal relative position, or it can simply indicate the existence of an attachment relationship without specifying a horizontal relative position.

[0117] In this application, the exemplary descriptions such as "in some implementations (or embodiments)" and "in one implementation (or embodiment)" may cover, but are not limited to, the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0118] In this application, the terms "first," "second," and "third" in the following contexts are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features.

[0119] In this application, unless otherwise specified, "layered arrangement" refers to the description of the stacking direction between layered structures and does not constitute a limitation on the structural composition of the stacked body. For example, "including stacked structural layer A and structural layer B" means that the stacking direction of structural layer A and structural layer B is along their respective thickness directions; that is, the thickness direction of structural layer A is consistent with or substantially consistent with the thickness direction of structural layer B. It is understood that structural layer A and structural layer B can be arranged adjacent to each other, and it is also permissible to arrange other intermediate structural layers between structural layer A and structural layer B.

[0120] Unless otherwise stated, the improvements described in this application are not intended to be limited to any theoretical constraints.

[0121] In this application, unless otherwise specified, an "optoelectronic device" is a device capable of photoelectric conversion using a photoelectric conversion mechanism, which includes the process of converting light energy into electrical energy and vice versa. An optoelectronic device can be a photovoltaic device or a light-emitting device. In this application, unless otherwise specified, the core functional layer that exchanges energy with photons can be called the "active layer," which includes a semiconductor active material. In a photovoltaic device, the semiconductor active material absorbs photons to generate carrier pairs (which are electron-hole pairs), and this active layer can be called the "light-absorbing layer" or "light-absorbing layer." In a light-emitting device, the semiconductor active material recombines injected electrons and holes and releases photons, and this active layer can be called the "light-emitting layer." Optoelectronic devices can achieve photoelectric conversion through any suitable mechanism. Photovoltaic devices can convert light energy into electrical energy based on a light-absorbing layer, and light-emitting devices can convert electrical energy into light energy based on a light-emitting layer.

[0122] In this application, unless otherwise specified, "active layer" refers to a structural layer comprising a semiconductor active material. The semiconductor active material can be any suitable type of semiconductor active material capable of photoelectric conversion. Non-limiting examples of semiconductor active materials may include one or more of perovskite materials, silicon-containing semiconductor materials, copper zinc tin sulfide, copper zinc tin selenide, copper zinc tin selenide sulfide, copper indium gallium selenide, copper indium gallium diselenide, copper indium selenide, cadmium telluride, and organic active materials. Exemplarily, the semiconductor active material may include one or more of perovskite materials, gallium arsenide (GaAs), cadmium telluride (CdTe), copper indium selenide (CIGS), and organic active materials.

[0123] In this application, unless otherwise stated, a "photovoltaic device" is a photoelectric device capable of converting solar energy into electrical energy using a photoelectric conversion mechanism. The active layer in a photovoltaic device can generate carrier pairs (which can be electron-hole pairs) upon excitation by incident photons. The flow of electrons and holes generates current, thereby realizing the conversion from light energy to electrical energy. The active layer in a photovoltaic device can be referred to as a "light-absorbing layer." Application examples of photovoltaic devices may include, but are not limited to, solar cells.

[0124] In this application, unless otherwise specified, "solar cell" refers to a battery capable of converting solar energy into electrical energy using a photoelectric conversion mechanism. It is understood that a solar cell includes a light-absorbing layer. When the light-absorbing layer comprises perovskite material, the solar cell is a "perovskite solar cell".

[0125] In this application, unless otherwise specified, a "light-emitting device" is a photoelectric device capable of converting electrical energy into solar energy using a photoelectric conversion mechanism. The active layer in a photoelectric device can recombine injected charge carriers (electrons and holes), releasing energy in the form of photons. Non-limiting examples of light-emitting devices may include light-emitting diodes (LEDs), laser diodes (LDs), etc. Applications of light-emitting devices may include, but are not limited to, lighting and display applications.

[0126] In this application, unless otherwise specified, "energy conversion efficiency" refers to the efficiency of converting light energy (or electrical energy) into electrical energy (or light energy) in an optoelectronic device. In photovoltaic devices, energy conversion efficiency refers to the efficiency of converting light energy into electrical energy, generally referred to as photoelectric conversion efficiency (PCE). In light-emitting devices, energy conversion efficiency refers to the efficiency of converting electrical energy into light energy, which can be expressed as external quantum efficiency (EQE).

[0127] In this application, unless otherwise specified, "charge carrier" can be an electron or a hole. "Carrier pair" refers to an electron-hole pair.

[0128] In some embodiments of this application, when the photovoltaic device is operating, after the light-absorbing layer is illuminated, the internal electrons gain energy and break free from the binding force of the light-absorbing layer to form negatively charged electron carriers, and simultaneously form positively charged hole carriers, thus generating electron-hole pairs. The free electrons and free holes propagate in opposite directions, causing electrons and holes to flow and forming an external current, thereby realizing the conversion of light energy into electrical energy. Furthermore, after the light-absorbing layer absorbs photons, it is stimulated to generate electron-hole pairs. These pairs further dissociate to form free carriers with opposite charges. The free electrons propagate towards the negative electrode, and the free holes propagate towards the positive electrode. Both types of free carriers are collected by their respective electrodes, further forming a photocurrent in the circuit of the photovoltaic device.

[0129] In some embodiments of this application, in a photovoltaic device, free electrons are transported to the negative electrode through an electron transport layer, and free holes are transported to the positive electrode through a hole transport layer. The two types of free carriers are collected by their respective electrodes, and further form a photocurrent in the circuit of the photovoltaic device.

[0130] In photovoltaic devices, the electron transport layer can extract and transport electron carriers and block free holes from passing through.

[0131] In photovoltaic devices, the hole transport layer can extract and transport hole carriers and block free electrons from passing through.

[0132] In some embodiments of this application, when the light-emitting device is operating, an external forward bias voltage is applied to inject electrons from the cathode and holes from the anode. The injected charge carriers (electrons and holes) are transported to the light-emitting layer, where they recombine, releasing energy and emitting light in the form of photons. The cathode is typically connected to the negative terminal of the power supply, and the anode is typically connected to the positive terminal of the voltage.

[0133] In light-emitting devices, the electron transport layer is responsible for injecting and transporting electron carriers and can block free holes from passing through.

[0134] In light-emitting devices, the hole transport layer is responsible for injecting and transporting hole carriers and can block free electrons from passing through.

[0135] In this application, unless otherwise specified, from the perspective of the type of semiconductor active material, optoelectronic devices whose active layer includes perovskite material can be referred to as "perovskite devices". The active layer in a perovskite device can be referred to as a "perovskite layer". From an application perspective, perovskite devices can be used in both photovoltaic and light-emitting fields; that is, perovskite devices can function as both photovoltaic devices and light-emitting devices.

[0136] In this application, unless otherwise specified, "perovskite layer" refers to the active layer comprising perovskite material. The perovskite layer has a certain thickness, for example, but not limited to 100nm~2000nm, and optionally 200nm~1500nm.

[0137] In this application, the "thickness direction of the perovskite layer" can be denoted as the Z direction, and the direction perpendicular to the Z direction can be denoted as the transverse direction.

[0138] In this application, unless otherwise specified, the perovskite layer includes two surfaces that are opposite to each other in its thickness direction (Z direction), which may be referred to as the first surface and the second surface, respectively. The distance between the first surface and the second surface may approximately correspond to the thickness of the perovskite layer. In some embodiments of this application, the first surface and the second surface of the perovskite layer respectively contact different structural layers disposed adjacent to the perovskite layer. In some embodiments, the first surface and the second surface of the perovskite layer respectively contact different charge transport layers.

[0139] Optoelectronic devices can be either photovoltaic (PV) devices or light-emitting devices. A representative PV device is the perovskite solar cell, in which the light-absorbing layer is a perovskite layer containing perovskite material. Due to its high conversion efficiency and the ability to be fabricated using low-cost solution methods, perovskite solar cells have attracted widespread attention from industry. Photovoltaic conversion efficiency is crucial for the practical application of perovskite solar cells. Therefore, researching ways to improve the energy conversion efficiency of optoelectronic devices is of great significance.

[0140] To achieve high energy conversion efficiency, much attention is paid to improving the crystal quality of perovskite to form a direct bandgap semiconductor, reducing energy loss caused by the effect of phonons during light absorption, thereby achieving higher light absorption characteristics. Passivating defects by introducing additives is one approach to improve device efficiency. Common methods of introducing additives are: (1) adding the additive directly to the perovskite precursor solution; (2) introducing the additive by coating it on the surface of the perovskite layer after obtaining the crystallized perovskite layer. However, both methods have shortcomings. Method (1) involves adding the additive directly to the perovskite precursor solution to induce the perovskite to oriented and crystallize with high quality; however, the additive added to the perovskite precursor solution has a high probability of entering the perovskite lattice, causing the additive to remain in the perovskite crystal after completing the crystallization induction effect, resulting in the generation of defect states such as gaps. These defect states often carry specific charges, causing scattering of charge carriers passing through these defects, affecting the transport and final extraction and collection of photogenerated charge carriers in the perovskite layer. Method (2), which involves introducing passivating material after perovskite crystallization, can only act on defects at the perovskite layer interface. Moreover, while passivating interface defects, it may also affect interface charge transport, thus limiting the improvement of device efficiency. Therefore, it is necessary to develop new solutions to improve the energy conversion efficiency of optoelectronic devices.

[0141] According to various embodiments and examples of this application, this application provides optoelectronic devices and their fabrication methods, electrical devices, and power generation devices. The optoelectronic device exhibits high energy conversion efficiency.

[0142] In some embodiments of this application, an optoelectronic device is provided, comprising a perovskite layer 100, wherein the perovskite layer 100 comprises perovskite grains 110, the perovskite grains 110 comprising cubic phase grains 111 and non-cubic phase grains 112, and the non-cubic phase grains 112 comprising tetragonal phase grains 1121 and orthorhombic phase grains 1122. See also... Figure 1 .

[0143] In this application, unless otherwise specified, terms such as “cubic phase grains,” “non-cubic phase grains,” “tetragonal phase grains,” “orthorhombic phase grains,” “other phase grains,” and “triclinic phase grains” refer to perovskite grains, which are perovskite grains with the corresponding crystal phase structures.

[0144] In this application, unless otherwise specified, terms such as “cubic phase,” “non-cubic phase,” “tetragonal phase,” “orthorhombic phase,” “other phases,” and “triclinic phase” in the perovskite layer refer to the crystalline phases of the perovskite grains.

[0145] It is understood that the perovskite layer includes a perovskite material (denoted as the first perovskite material). In some embodiments of this application, the first perovskite material accounts for more than or equal to 95% of the mass of the perovskite layer, and may be selected as 95% to 100%.

[0146] In some embodiments of this application, the perovskite layer includes a cubic phase; further, the cubic phase is used as the main phase of the perovskite grains, and the cubic phase has a high mass ratio in the perovskite layer.

[0147] In some embodiments of this application, an optoelectronic device is provided, which includes a perovskite layer, the perovskite layer including perovskite grains, the crystalline phase of the perovskite grains including a cubic phase; the cubic phase has a high mass percentage in the perovskite layer (e.g., ≥97%); the perovskite layer has a high dielectric constant (e.g., ≥5).

[0148] In some embodiments, the crystalline phase of the perovskite grains also includes a non-cubic phase, which includes at least one of a tetragonal phase, an orthorhombic phase, and other phases; the other phases account for a low mass percentage (e.g., ≤5%) of the non-cubic phase.

[0149] In some further embodiments, the mass percentage of the tetragonal phase in the non-cubic phase is higher than that of the orthorhombic phase in the non-cubic phase.

[0150] In some embodiments of this application, an optoelectronic device is provided, comprising a perovskite layer, the perovskite layer comprising perovskite grains, the crystalline phase of the perovskite grains comprising a cubic phase and a non-cubic phase; the cubic phase having a higher mass percentage in the perovskite layer (e.g., greater than or equal to 97%); the non-cubic phase comprising at least one of a tetragonal phase, an orthorhombic phase, and other phases; the other phase having a lower mass percentage in the non-cubic phase (e.g., less than or equal to 5%); the tetragonal phase having a higher mass percentage in the non-cubic phase than the orthorhombic phase; and the perovskite layer having a higher dielectric constant (e.g., greater than or equal to 5).

[0151] In some embodiments of this application, an optoelectronic device is provided, comprising a perovskite layer, the perovskite layer comprising perovskite grains, the crystalline phase of the perovskite grains comprising a cubic phase and a non-cubic phase; the cubic phase having a mass percentage greater than or equal to 97% in the perovskite layer; the non-cubic phase comprising at least one of a tetragonal phase, an orthorhombic phase, and other phases; the other phase having a mass percentage less than or equal to 5% in the non-cubic phase; the tetragonal phase having a higher mass percentage in the non-cubic phase than the orthorhombic phase; and the dielectric constant of the perovskite layer being greater than or equal to 5.

[0152] In this application, unless otherwise specified, "cubic phase," "tetragonal phase," and "orthorhombic phase" have their common meanings in the art. The cubic phase is the crystal system with the highest symmetry, and its unit cell is a cube (i.e., the lattice parameters satisfy a=b=c, α=β=γ=90°, where a, b, and c represent the lengths of the three axes, and α, β, and γ represent the included angles of the three axes). The tetragonal phase has lower symmetry than the cubic phase, and its unit cell is a square prism with a square base (i.e., the lattice parameters satisfy a=b≠c, α=β=γ=90°). The orthorhombic phase has lower symmetry than the tetragonal phase, and its unit cell is a cuboid with three unequal sides (i.e., the lattice parameters satisfy a≠b≠c, α=β=γ=90°). The cubic phase has the narrowest band gap and the highest absorbance, but it is metastable at room temperature and may transform into non-cubic phases such as the tetragonal phase, which have lower symmetry but are more stable. The tetragonal phase has a slightly larger band gap than the cubic phase, which better balances light absorption, stability, and carrier transport. The orthorhombic phase exhibits further decreased symmetry and a further increased band gap. In this application, all crystal phases other than the cubic phase are collectively referred to as "non-cubic phases," and the non-cubic phases other than the tetragonal and orthorhombic phases are simply referred to as "other phases." Non-limiting examples of other phases include the triclinic phase.

[0153] In some embodiments of this application, the perovskite layer includes a cubic phase, the cubic phase comprising 97% or more of the perovskite layer by mass. Further, the cubic phase comprises 97% or more of the perovskite layer by mass and less than 100%. Exemplarily, the cubic phase may also comprise any of the following percentages: 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, etc.

[0154] In some embodiments of this application, the perovskite layer comprises a tetragonal phase, that is, the perovskite layer comprises a non-cubic phase.

[0155] In some embodiments of this application, the perovskite layer includes a non-cubic phase, wherein the mass percentage of the tetragonal phase in the non-cubic phase is higher than that of the orthorhombic phase. It is understood that the mass percentage of the orthorhombic phase in the non-cubic phase can be 0, meaning the perovskite layer may not contain perovskite grains of the orthorhombic phase.

[0156] In some embodiments of this application, the perovskite layer includes a non-cubic phase, and the mass percentage of other phases in the non-cubic phase is less than or equal to 5%. Exemplarily, the mass percentage of other phases in the non-cubic phase may also be less than or equal to any of the following percentages, or be any of the following percentages, or be selected from a range consisting of any two of the following percentages: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc. It is understood that the mass percentage of other phases in the non-cubic phase may be 0, that is, the perovskite layer may not contain perovskite grains of other phases.

[0157] In this application, the perovskite layer can be tested using grazing incidence wide-angle X-ray scattering (GIWAXS) to obtain the types and relative contents of crystalline phases in the perovskite layer. Unless otherwise specified, α-Al₂O₃ is used as a standard sample for GIWAXS testing. The high collimation of the GIWAXS light source allows for accurate measurement of the proportions of cubic, tetragonal, orthorhombic, and other phases (such as triclinic phases) in the perovskite layer. For example, the proportions of the peak areas of the diffraction peaks corresponding to the dominant crystal planes of different crystals are calculated as the proportions of cubic, tetragonal, orthorhombic, and other phases in the perovskite layer. This can be performed using the Shanghai Synchrotron Radiation Facility GIWAXS beamline, but is not limited to this method.

[0158] GIWAXS technology is based on grazing incidence geometry, where X-rays pass parallel to the sample surface at extremely small angles (e.g., 0.1°~0.5°, close to the critical angle for total internal reflection). GIWAXS can detect depths from nanometers to hundreds of nanometers, enhancing and collecting signals from ultrathin surfaces. Based on GIWAXS, two-dimensional diffraction images can be obtained, i.e., the diffraction pattern received by the detector. This two-dimensional (2D) diffraction pattern includes diffraction information in all directions. Signals distributed along the horizontal direction reflect in-plane structure information, while signals distributed along the vertical direction reflect out-of-plane structure information. From the 2D diffraction pattern of GIWAXS, crystal structure type or phase information can be obtained. The converted one-dimensional (1D) pattern can be compared with standard data of known crystal structures (such as the ICSD database) to determine the crystal phase, dominant crystal planes, and peak areas of their diffraction peaks.

[0159] Based on the GIWAXS 2D diffraction pattern, the following information about the thin film can be obtained:

[0160] (1) Crystal structure type or phase; the 1D spectrum obtained by conversion can be compared with the standard data of known crystal structures (such as ICSD database).

[0161] (2) Grain orientation and texture; the direction of the crystal arrangement relative to the substrate can be distinguished, and information such as whether there is a preferred orientation, preferred orientation, in-plane orientation, and out-of-plane orientation can be determined. Among them, the appearance of arc-shaped or discrete spots in the diffraction pattern indicates a preferred orientation, and the length of the arc can reflect the degree of dispersion of the orientation. The shorter the arc, the more concentrated the orientation.

[0162] (3) Interplanar spacing and lattice constant.

[0163] In this application, "crystal plane indices" can be used to distinguish different crystal planes. A crystal plane index (hkl) represents a set of parallel crystal planes with equal interplanar spacing, on which the node distribution pattern is the same. Those skilled in the art of crystallography are generally familiar with how to identify the crystal plane index of a given crystal plane. In this application, the crystal plane indices involved include, but are not limited to, (100) and (111), and the corresponding crystal planes of perovskite grains can be referred to as the (100) crystal plane and the (111) crystal plane, respectively.

[0164] In this application, unless otherwise stated, in the 2D diffraction pattern of GIWAXS, the horizontal direction corresponds to the in-plane component (q). xy This can reflect the periodic structural information parallel to the thin film surface; the vertical direction corresponds to the out-of-plane component (q). z This reflects the periodic structural information along the normal direction (perpendicular to the surface). The distance from the center position of the diffraction signal (e.g., the center position of the diffraction arc) to q... xy -q z The distance to the center of a determined image directly reflects the interplanar spacing of the corresponding crystal plane. Crystal planes with different crystal plane indices have different interplanar spacings (e.g., calculated using Bragg's formula). The q corresponding to the center position of the diffraction signal (e.g., diffraction arc, diffraction spot) is determined by... xy and q z It can calculate lattice parameters, including interplanar spacing, and thus distinguish different types of crystal phases and crystal faces.

[0165] According to the 2D diffraction pattern, along q xy -q z The selected angle direction in the figure can be used to obtain a one-dimensional (1D) integral curve through integration.

[0166] In this application, unless otherwise stated, the "dielectric constant" of a perovskite layer is a dimensionless physical parameter that describes the ease with which the internal charge of a first perovskite material is polarized under the influence of an external electric field, and thus its ability to weaken the external electric field. The dielectric constant reflects the strength of the lattice electrostatic force on free charge carriers in the perovskite; a higher dielectric constant indicates a weaker lattice electrostatic force on free charge carriers; a lower dielectric constant indicates a stronger lattice electrostatic force on free charge carriers, potentially even preventing photogenerated dipoles from separating into free charge carriers. The dielectric constant of a perovskite layer is affected by factors such as charged defects. Although theoretically, the dielectric constant of a perovskite layer can be increased by minimizing charged defects and their scattering effects, commonly used methods for increasing the dielectric constant usually require sacrificing other properties; the dielectric constant of common perovskites is typically less than 5.

[0167] In this application, the microwave resonance method can be used to test and analyze the perovskite layer to obtain its dielectric constant. The basic principle of the microwave resonance method is that when the solid material under test is placed in a microwave resonant environment, the dielectric properties of the material will change the electromagnetic field distribution within the cavity, causing a shift in the resonant frequency. By measuring this frequency change and combining it with the geometric parameters of the resonant cavity, the relative dielectric constant of the material can be calculated.

[0168] In this application, the dielectric constant of the perovskite layer can be tested using a Japanese AET microwave dielectric constant tester.

[0169] In detail, the dielectric constant of the perovskite layer can be tested using the following method: Place the perovskite thin film sample in a resonant cavity, ensuring sufficient interaction; then use a microwave source and a spectrum analyzer to test the resonant frequencies at different frequencies. Subsequently, based on the frequency variations and the resonant cavity assembly parameters, the dielectric constant of the perovskite can be calculated.

[0170] In some embodiments of the first aspect of this application, an optoelectronic device is provided, which includes a perovskite layer, the perovskite layer including perovskite grains, and the crystalline phase of the perovskite grains including a cubic phase and a non-cubic phase.

[0171] The cubic phase accounts for 97% or more of the mass of the perovskite layer; the non-cubic phase includes at least one of the tetragonal phase, orthorhombic phase and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase.

[0172] The dielectric constant of the perovskite layer is greater than or equal to 5.

[0173] By controlling the specific composition ratio of different crystal phases in the perovskite layer, making the cubic phase predominant and minimizing the proportion of non-cubic phases other than the tetragonal and orthorhombic phases, while also controlling the proportion of the tetragonal phase to be higher than that of the orthorhombic phase, the above crystal phase composition can improve the absorbance of the perovskite layer, increase the utilization rate of incident light, and the cubic phase has a stronger charge transport capability, which is beneficial to the transport of charge carriers. A small amount of tetragonal phase is beneficial to controllably preventing the transformation of cubic perovskite to non-cubic phase. At the same time, controlling the dielectric constant of the perovskite layer within a relatively high range can significantly reduce charged defects and significantly suppress the scattering effect of possible charged defects, thereby significantly increasing the effective transport distance of photogenerated charge carriers in the perovskite layer. Thus, through the synergy of the aforementioned multiple effects, the energy conversion efficiency of optoelectronic devices can be significantly improved.

[0174] In some embodiments of this application, the one-dimensional integral curve of the GIWAXS two-dimensional diffraction pattern of the perovskite layer satisfies one or more of the following characteristics:

[0175] (t1) The dominant crystal plane of the cubic phase is one of (100) and (111);

[0176] (t2) The dominant crystal plane of the tetragonal phase is one of (100) and (111);

[0177] (t3) The dominant crystal plane of the orthorhombic phase is one of (100) and (111).

[0178] The physical meaning of "preferred crystal facet" as used in this application is: the preferred crystal facet corresponds to the preferred orientation of the grain, also known as the "preferred orientation crystal facet", indicating that the perovskite grain preferentially grows along the crystal facet during the growth process, and the final main exposed crystal facet is also the preferred crystal facet.

[0179] In this application, unless otherwise specified, the dominant crystal planes of different phases of perovskite grains can be determined as follows: the crystal plane corresponding to the strongest diffraction signal of the corresponding phase in the XRD one-dimensional diffraction pattern or GIWAXS two-dimensional diffraction pattern is determined as the dominant crystal plane.

[0180] By controlling the dominant crystal faces of one or more of the cubic, tetragonal, and orthorhombic phases of perovskite grains to have the aforementioned types, it is beneficial to obtain perovskite layers with excellent light absorption and effective charge transport distance. At the same time, it is also beneficial to better control the increase in internal resistance that may be caused by a relatively large dielectric constant.

[0181] In some embodiments of this application, the dielectric constant of the perovskite layer is greater than or equal to 5, and can be selected as 5 to 16, or more preferably 6.5 to 15.

[0182] By controlling the dielectric constant of the perovskite layer within the aforementioned range, it is beneficial to promote carrier transport within the perovskite layer and reduce the impact of defects on lattice stability. This results in not only excellent light absorption and charge transport capabilities but also a good balance between the stability of the perovskite crystal structure. Consequently, both high energy conversion efficiency and high device stability can be achieved.

[0183] In some embodiments of this application, the dielectric constant of the perovskite layer may also be any of the following values ​​or a range selected from any two of the following values: 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14, 14.5, 15, 15.5, 16, etc. The dielectric constant of the perovskite layer may also be selected from any suitable range of the following: 6.5 to 13, etc.

[0184] In some embodiments of this application, the thickness of the perovskite layer is 200 nm to 1500 nm, optionally 400 nm to 1000 nm, and may also be any of the following values ​​or a range selected from any two of the following values: 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, etc. Exemplarily, the thickness of the perovskite layer may also be any of the following ranges: 400 nm to 800 nm, 400 nm to 600 nm, 200 nm to 600 nm, 200 nm to 800 nm, etc.

[0185] By combining the aforementioned technical solutions, good light absorption and effective carrier transport can be maintained even within a large perovskite layer thickness range, thereby effectively improving the energy conversion efficiency of optoelectronic devices with thicker perovskite layers.

[0186] In this application, scanning electron microscopy (SEM) can be used to test the longitudinal section of the perovskite layer to obtain thickness information. "Longitudinal section of the perovskite layer" refers to a section obtained by cutting along the thickness direction of the perovskite layer, which is parallel to the thickness direction (Z-direction) of the perovskite layer. Non-limiting examples of SEM instruments include the Sigma 300 scanning electron microscope from ZEISS GmbH, Germany; the EVO 15 backscatter scanning electron microscope from ZEISS GmbH, Germany; the Zeiss SUPRA 55; and the Apreo 2 SEM field emission scanning electron microscope.

[0187] In this application, the longitudinal section of the perovskite layer can be obtained by using a glass cutter to create scratches on the substrate side (such as the FTO glass side) of the perovskite sample, and by using special pliers to utilize the stress concentration at the scratches to cleave the sample and prepare the perovskite cross-section sample for SEM.

[0188] In this application, unless otherwise specified, "longitudinal section of the perovskite layer" refers to a section obtained by cutting along the thickness direction of the perovskite layer, which is substantially parallel to the thickness direction (Z direction) of the perovskite layer.

[0189] In some embodiments of this application, the perovskite layer satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0190] (a1) The mass percentage of the tetragonal phase in the non-cubic phase is greater than or equal to 65%, and optionally greater than or equal to 80%. For example, the mass percentage of the tetragonal phase in the non-cubic phase may also be any of the following percentages, or greater than or equal to any of the following percentages, or selected from any two of the following percentages: 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 75%, 80%, 85%, 90%, 95%, etc. The mass percentage of the tetragonal phase in the non-cubic phase may also be a range consisting of any of the aforementioned percentages and 100%, such as 65%~100%, 80%~100%, etc.

[0191] (a2) The mass percentage of the orthorhombic phase in the non-cubic phase is less than or equal to 30%; for example, the mass percentage of the orthorhombic phase in the non-cubic phase may also be any of the following percentages, or less than or equal to any of the following percentages, or selected from any two of the following percentages: 1%, 2%, 4%, 5%, 6%, 8%, 10%, 15%, 20%, 25%, 30%, etc.; the mass percentage of the orthorhombic phase in the non-cubic phase may also be 0 and any of the aforementioned percentages, for example, a range such as 0~25%, 0~20%, etc.

[0192] (a3) Other phases include at least the triclinic phase.

[0193] By controlling the mass ratio of cubic and / or tetragonal phases in the non-cubic phase within the aforementioned range, it is beneficial to better improve the absorbance of the perovskite layer, thereby better improving the energy conversion efficiency.

[0194] In some embodiments of this application, the mass percentage of the triclinic phase in the non-cubic phase is less than or equal to 5%, and may also be less than or equal to any of the following percentages, or be any of the following percentages, or be selected from a range consisting of any two of the following percentages: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc. The mass percentage of the triclinic phase in the non-cubic phase may also be 0 and a range consisting of any of the aforementioned percentages, such as 0~5%, 0~1%, etc.

[0195] In some embodiments of this application, the mass percentage of the non-cubic phase in the perovskite layer is less than or equal to 3%, and may also be less than or equal to any of the following percentages, or be any of the following percentages, or be selected from a range consisting of any two of the following percentages: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, etc. The mass percentage of the triclinic phase in the non-cubic phase may also be 0 and a range consisting of any of the aforementioned percentages, such as 0% and less than or equal to 3%, 0% and less than or equal to 2%, 0% and less than or equal to 1%, 1% to 3%, etc.

[0196] In some embodiments of this application, based on the XRD diffraction pattern of the perovskite layer, the dominant crystal plane of the cubic phase is (100) or (111); in some embodiments, when the dominant crystal plane of the cubic phase is (100), the half-width at half-maximum (WHM) of the diffraction peak of the (100) plane is 0.05° to 0.20°; or, when the dominant crystal plane of the cubic phase is (111), the half-width at half-maximum (WHM) of the diffraction peak of the (111) plane is 0.05° to 0.30°.

[0197] In this application, "full width at half maximum" refers to the peak width (unit: degrees (°) corresponding to half the maximum intensity of the diffraction peak of the dominant crystal plane. It can generally be expressed as FWHM (Full Width at Half Maximum). The data of the full width at half maximum in the corresponding spectrum can be obtained by measuring the data of the full width at half maximum in the corresponding spectrum through analysis software (such as Jade, Origin, PeakFit) or other means.

[0198] By controlling the full width at half maximum (FWHM) of the diffraction peaks of the dominant cubic crystal plane in the XRD diffraction pattern of the perovskite layer within the aforementioned range, the crystallinity of the perovskite grains is higher, the surface perovskite grains have a more regular crystal structure, and the atomic arrangement is more ordered. This helps to reduce grain boundaries and defects in the perovskite layer, reduce the probability of nonradiative recombination of charge carriers, and improve the carrier mobility. On the other hand, controlling the FWHM within the aforementioned range also indicates that the crystal orientation is more uniform, which is beneficial to reducing the scattering and trapping effects of charge carriers during transport, and improving the overall carrier transport rate.

[0199] In some embodiments of this application, the perovskite layer includes a first additive, which is an organic material; at least a portion of the first additive is located at the grain boundaries of the perovskite grains.

[0200] In some of these embodiments, the first additive includes at least one of a hydrocarbon haloamine and a hydrocarbon pseudohalogenated amine;

[0201] In some of these embodiments, the first additive includes C 3-20 Hydrocarbon-based haloamines, optionally, the first additive includes C 6-20 Hydrocarbon-based halogenated amines.

[0202] In this application, "hydroalkyl pseudohalogenated amine" refers to a substance formed by replacing the halogen in a hydrocarbon-based haloamine with a pseudohalogen.

[0203] In this application, unless otherwise specified, "pseudohalogens" has the common meaning in the art. Pseudohalogens, also known as halogen-like elements, refer to atomic groups composed of two or more elements that, as a whole, possess chemical properties similar to halogens. Non-limiting examples of pseudohalogens include thiocyanate-type atomic groups. In this application, unless otherwise specified, "thiocyanate-type atomic group" refers to an elemental composition of SCN that can form a thiocyanate group (SCN). - A halogenated group, existing in the form of a halogen, can exhibit a form similar to that of a halogen as a whole. Anionic pseudohalogens can be called pseudohalogen anions. Non-limiting examples of pseudohalogens may include one or more of thiocyano (SCN), oxocyano (OCN), etc. Non-limiting examples of pseudohalogen anions may include SCN. - OCN - CNO - OSCN - SH - CN - SeCN - One or more of the following.

[0204] For example, the carbon atoms in the alkyl halogenated amine can be 3 to 20, optionally 6 to 20, or any of the following values ​​or a range selected from any two of the following values: 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0205] By controlling the distribution of the first additive at the grain boundaries of perovskite grains, it is beneficial to passivate grain boundary defects while reducing the probability of defects that may enter the lattice. This can improve the dielectric constant of perovskite to a certain extent while achieving higher absorbance, thereby improving energy conversion efficiency.

[0206] In some embodiments of this application, the halogen in the hydrocarbon-based haloamine includes at least one of chlorine, bromine, and iodine.

[0207] By controlling the first additive to include at least one of chlorine, bromine, and iodine, it is beneficial to better passivate grain boundary defects and achieve better energy conversion efficiency.

[0208] In some embodiments of this application, the first additive includes C 6-20 Hydrocarbon-based halogenated amines. C 6-20 The number of carbon atoms in a hydrocarbon haloamine can be 6 to 20, or any of the following values ​​or a range selected from any two of the following values: 6, 8, 10, 12, 14, 16, 18, 20, etc.

[0209] In some embodiments of this application, the alkyl halide amine satisfies one or more of the following characteristics:

[0210] (1) The number of carbon atoms in the hydrocarbon haloamine is 6~20, and can be 6~10;

[0211] (2) The hydrocarbon group in the hydrocarbon halide is an aliphatic hydrocarbon group, which may be an alkyl group; optionally, the halogen includes at least one of chlorine, bromine and iodine; further optionally, the halogen in the hydrocarbon halide includes at least one of chlorine and bromine.

[0212] (3) The hydrocarbon group in the hydrocarbon halogenated amine is a chain hydrocarbon group, which can be a straight-chain alkyl group;

[0213] (4) The hydrocarbon group in the hydrocarbon halide is a substituted or unsubstituted aryl group, for example, the hydrocarbon group in the hydrocarbon halide can be phenethyl; further optionally, the halogen in the hydrocarbon halide includes iodine.

[0214] In this application, unless otherwise specified, "hydrocarbon group" refers to an organic group consisting of carbon and hydrogen atoms. Hydrocarbon groups can be alkyl, aryl, or aralkyl. The definitions of alkyl and aryl are provided in the relevant descriptions within the context of this application.

[0215] In this application, "aliphatic hydrocarbon group" refers to the residue formed after an aliphatic hydrocarbon loses at least one hydrogen atom. Unless otherwise specified, "aliphatic hydrocarbon group" in this application specifically refers to a monovalent aliphatic hydrocarbon group. Aliphatic hydrocarbon groups include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups.

[0216] In this application, the term "alkyl" refers to a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3) and octyl (-(CH2)7CH3), etc.

[0217] In this application, the term "alkane group" refers to a group formed when an alkane loses one hydrogen atom, in which all carbon atoms are connected by carbon-carbon single bonds and do not form a ring, and the remaining valence bonds are combined with hydrogen atoms. This includes straight-chain alkane groups and branched-chain alkane groups.

[0218] In some embodiments of this application, the alkyl halogenated amines include one or more of octylamine chloride, octylamine bromide, phenylethylamine iodide, propylamine chloride, propylamine iodide, and the context example types.

[0219] In some embodiments of this application, the first additive includes C 6-20 Alkyl halide amines (optionally, the first additive includes C) 6-10 Alkyl halide amine); in some embodiments of this application, the halogen includes at least one of chlorine, bromine and iodine, and optionally, the halogen includes at least one of chlorine and bromine.

[0220] In some embodiments of this application, the first additive includes phenylethyl halogenated amine, and optionally, the halogen includes iodine.

[0221] In some embodiments of this application, the perovskite layer includes a first perovskite material. Further, the molar percentage of the first additive to the first perovskite material in the perovskite layer is 1% to 10%, or it can be any of the following percentages or a range selected from any two of the following percentages: 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., wherein the molar amount of the first perovskite material is calculated as the molar amount of divalent cations in the first perovskite material. In this case, it is advantageous to improve the dielectric constant of the perovskite to a certain extent while better utilizing the advantages of grain boundary defects and achieving higher absorbance, which is beneficial for improving energy conversion efficiency.

[0222] In some embodiments of this application, the content of the first additive at the grain boundaries of the perovskite grains is higher than its content within the crystalline phase of the perovskite grains. This is more advantageous in passivating grain boundary defects while reducing the probability of defects that may enter the lattice and cause defects. It also helps to minimize the adverse effects of defects caused by the additive entering the perovskite lattice on the dielectric constant of the perovskite layer, thus improving energy conversion efficiency. Those skilled in the art can use appropriate methods to confirm this, such as performing elemental distribution analysis based on the longitudinal section of the perovskite layer to confirm the distribution positions of relevant elements in the first perovskite material and the first additive. Based on the distribution areas of relevant elements in the first perovskite material, the region where the perovskite crystalline phase is located can be determined. Furthermore, based on the distribution areas of relevant elements in the first additive and the content of the first additive in different regions, the content of the first additive in different regions can be compared.

[0223] In some embodiments of this application, the mass of the first additive distributed at the grain boundaries of the perovskite grains is greater than or equal to 90% of the total mass of the first additive in the perovskite layer. It may also be greater than or equal to any of the following percentages, or greater than or equal to any of the following percentages and less than or equal to 100%, or be any of the following percentages, or be selected from any two of the following percentages: 90%, 91%, 92%, 93%, 94%, 95%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, etc.

[0224] In some embodiments of this application, the average size of the perovskite grains in the perovskite layer is 0.6 μm to 3 μm, and may also be any of the following values ​​or a range selected from any two of the following values: 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.8 μm, 2 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.8 μm, 3 μm, etc. By controlling the average size of the perovskite grains in the perovskite layer to be within the aforementioned relatively large range, it is beneficial to reduce the number of grain boundaries and achieve better energy conversion efficiency and device stability.

[0225] The average size of perovskite grains can be measured using a scanning electron microscope (SEM). Specifically, SEM images of the perovskite layer surface or cross-section are randomly taken at different locations on the effective subcell (non-dead zone). The longest diameter of multiple grains is manually or automatically counted using software (such as ImageJ or Nano Measure), and the average value is calculated; this average size is the perovskite grain size.

[0226] Figure 2This is a schematic diagram of the structure of a perovskite layer 100 in an optoelectronic device according to an embodiment of this application. The perovskite layer 100 includes perovskite grains 110 and grain boundaries 120 between adjacent perovskite grains.

[0227] In this application, "grain boundary between adjacent perovskite grains" may also be referred to as the interface of perovskite grains.

[0228] In some embodiments of this application, the content of the first additive at the grain boundaries of the perovskite grains is higher than its content within the crystalline phase of the perovskite grains. It is understood that the "content of the first additive at the grain boundaries of the perovskite grains" and the "content of the first additive within the crystalline phase of the perovskite grains" are measured using the same unit of measurement, such as mass or molar quantity. This is more advantageous in passivating grain boundary defects while simultaneously reducing the probability of defects that may enter the crystal lattice, thus minimizing the adverse effects of defects caused by the additive entering the perovskite lattice on the dielectric constant of the perovskite layer, and further improving energy conversion efficiency.

[0229] In this application, suitable elemental analysis methods can be used to confirm the elemental composition at different thicknesses of the perovskite layer. These methods may include, but are not limited to, time-of-flight secondary ion mass spectrometry (TOF-SIMS), and instruments such as PHI nanoTOF Ⅲ Time-of-Flight SIMS can be used. A suitable ion source (such as Cs) can be selected. + Bi 3+ (etc.), primary ion energy (e.g., 0.5keV~30keV), imaging region size (e.g., 500×500μm) 2 100×100μm 2 Test parameters such as mass range and mass resolution, sputtering parameters (such as sputtering time, sputtering area, sputtering rate, analysis mode (such as depth profile mode, neutralization mode, etc.)) are used to obtain the three-dimensional distribution information of the corresponding elements or components in the sample to be tested.

[0230] Based on the three-dimensional distribution information of an element or component, a person skilled in the art can determine whether the element or component is distributed in the perovskite crystal phase. If the element or component is distributed in the perovskite crystal phase, the first perovskite material can be considered to contain the element or composition.

[0231] In some embodiments of this application, the first perovskite material in the perovskite layer includes a perovskite-type metal halide.

[0232] In some embodiments of this application, the perovskite layer includes a first perovskite material; the first perovskite material includes at least one halogen selected from iodine, chlorine, and bromine.

[0233] In some embodiments of this application, the first perovskite material includes at least one of iodine and bromine.

[0234] In some embodiments of this application, the first perovskite material includes iodine and bromine.

[0235] In some embodiments of this application, the molar ratio of iodine to bromine in the perovskite layer is (0~1):(0~1), and may further be (0.8~1):(0~0.2).

[0236] The first perovskite materials of the aforementioned halogen types are conducive to the better formation of the aforementioned crystal phase composition.

[0237] In addition, the aforementioned first additives effectively passivate possible charged defects in the first perovskite material, which is beneficial to improving the dielectric constant of the perovskite layer and thus improving the energy conversion efficiency.

[0238] Not limited to the aforementioned theory, when the perovskite material in the perovskite layer includes both iodine and bromine elements, it is also beneficial to achieve higher crystallinity and a more suitable band gap for the perovskite.

[0239] In some embodiments of this application, the molar ratio of iodine to bromine in the perovskite layer is (1-q1):q1, where q1 is a value selected from 0 to 1, and can be selected from 0 to 0.2; q1 can also be any of the following values ​​or a range selected from any two of the following values: 0, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.15, 0.16, 0.18, 0.2, 0.22, 0.24, 0.25, 0.26, 0.28, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.65, 0.7, 0.75, 0.8, 0.9, 1, etc.

[0240] In some embodiments of this application, the perovskite layer includes a first perovskite material; the first perovskite material includes at least one of formamidinium ionic groups and methylamine ionic groups; optionally, in the perovskite layer, the molar ratio of formamidinium ionic groups to methylamine ionic groups is q. FA :q MA , where q FA The value is 0.8~1, q MA The range is 0 to 0.2.

[0241] Optionally, q FA The value is 0.9~1, q MA The value is 0.05~0.1;

[0242] Optionally, q FA q MAThe sum is 0.95~1, and optionally, q FA q MA The sum is 1.

[0243] In this application, unless otherwise specified, "formamidinium ionic group" refers to an atomic group with the elemental composition CH5N2, which can exist in the perovskite layer in the form of formamidinium cation and has the ability to serve as an A-site cation in perovskite materials.

[0244] In this application, unless otherwise specified, "methylamine ionic group" refers to a group with the elemental composition CH6N, which can exist in the perovskite layer in the form of methylamine cation and has the ability to serve as an A-site cation in perovskite materials.

[0245] Understandable, q MA When the value is 0, it indicates that the first perovskite material does not contain methylamine ionic groups.

[0246] The first perovskite material of the aforementioned atomic group type is conducive to the better formation of the aforementioned crystal phase structure.

[0247] For example, q FA It can be 0.8 to 1, or 0.8 to 0.95, or any of the following values ​​or a range of any two of the following values: 0.8, 0.82, 0.84, 0.85, 0.86, 0.88, 0.9, 0.92, 0.94, 0.95, 0.96, 0.98, 0.99, 1, etc.

[0248] For example, q MA It can be 0~0.2, can be selected from 0.05~0.2, or can be any of the following values ​​or a range composed of any two of the following values: 0, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.12, 0.14, 0.15, 0.16, 0.18, 0.2, etc.

[0249] In some embodiments of this application, the thickness direction of the perovskite layer is denoted as the Z-direction, and the area of ​​the perovskite layer on a projection plane perpendicular to the Z-direction is greater than or equal to 0.09 cm². 2 Optionally, greater than or equal to 1m 2 .

[0250] By combining the aforementioned technical solutions, good light absorption and effective carrier transport can be maintained even with a large perovskite layer area, thereby effectively improving the energy conversion efficiency of optoelectronic devices with large-area perovskite layers.

[0251] In some embodiments of this application, the area of ​​the perovskite layer on the projection plane perpendicular to the Z direction can be any of the following values, or greater than or equal to any of the following values, or selected from a range consisting of any two of the following values: 0.09 cm 2 0.1 cm 2 0.12 cm 2 0.125 cm 2 0.15 cm 2 0.16 cm 2 0.175 cm 2 0.18 cm 2 0.2cm 2 0.22 cm 2 0.225 cm 2 0.25 cm 2 1 cm 2 4 cm 2 9 cm 2 10 cm 2 16 cm 2 20 cm 2 25 cm 2 36cm 2 49 cm 2 50 cm 2 60 cm 2 64 cm 2 65 cm 2 70 cm 2 80 cm 2 81 cm 2 90 cm 2 100 cm 2 120cm 2 121 cm 2 125 cm 2 130 cm 2 140 cm 2 144 cm 2 150 cm 2 160 cm 2 169 cm 2 170 cm 2 180cm 2 190 cm 2 196 cm 2 200 cm 2 225 cm 2 250 cm 2 256 cm2 、260 cm 2 、280 cm 2 、289 cm 2 、290cm 2 、300 cm 2 、320 cm 2 、324 cm 2 、325 cm 2 、330 cm 2 、350 cm 2 、360 cm 2 、361 cm 2 、370 cm 2 、380cm 2 、400 cm 2 、440 cm 2 、441 cm 2 、450 cm 2 、480 cm 2 、484 cm 2 、500 cm 2 、600 cm 2 、625 cm 2 、660cm 2 、676 cm 2 、680 cm 2 、700 cm 2 、720 cm 2 、729 cm 2 、730 cm 2 、780 cm 2 、784 cm 2 、800 cm 2 、820cm 2 、840 cm 2 、841 cm 2 、850 cm 2 、860 cm 2 、900 cm 2 、950 cm 2 、961 cm 2 、980 cm 2 、0.1 m 2 、0.12m 2 、0.14 m 2 、0.15 m 2 、0.16 m 2 、0.18 m 2 、0.2 m 2 、0.3 m 20.4 m 2 0.5 m 2 0.6 m 2 0.7 m 2 0.8m 2 0.9 m 2 10000 cm 2 (1 m 2 ), 1.1 m 2 1.2 m 2 1.3 m 2 1.4 m 2 1.5 m 2 1.6 m 2 1.7 m 2 1.8m 2 1.9 m 2 2 m 2 2.1 m 2 2.2 m 2 2.3 m 2 2.4 m 2 2.5 m 2 2.6 m 2 2.7 m 2 2.8 m 2 2.9 m 2 3m 2 3.2 m 2 3.4 m 2 3.5 m 2 3.6 m 2 3.7 m 2 3.8 m 2 4 m 2 4.2 m 2 4.4 m 2 4.5 m 2 wait.

[0252] In some embodiments of this application, the optoelectronic device includes a photovoltaic device or a light-emitting device. The aforementioned perovskite layer can be used in photovoltaic devices or light-emitting devices to help improve the energy conversion efficiency of photovoltaic devices or light-emitting devices, and in some embodiments, it can also improve device stability.

[0253] In optoelectronic devices, one of the first electrode and the second electrode is a positive electrode, and the other is a negative electrode.

[0254] In optoelectronic devices, at least one of the first electrode and the second electrode is a transparent electrode. Either transparent electrode can be used for light incident.

[0255] In some embodiments of this application, in the optoelectronic device, both the first electrode and the second electrode can be transparent electrodes.

[0256] Unless otherwise specified, when the first and second electrodes each consist of only one transparent electrode, that transparent electrode is defined as the "incident-side electrode". When the optoelectronic device includes two transparent electrodes, the transparent electrode that provides higher device efficiency when light is incident on the corresponding transparent electrode is defined as the "incident-side electrode". In this case, the other electrode can be defined as the "back electrode".

[0257] It is understood that the incident light-side electrode is a transparent electrode. The back electrode may or may not be a transparent electrode; for example, the back electrode may be a metal electrode. The meanings of transparent electrode and metal electrode are well known to those skilled in the art, and their implications are understandable.

[0258] In some embodiments of this application, one of the "first electrode" and the "second electrode" is a transparent electrode for light incident. In some embodiments, the first electrode is a transparent electrode.

[0259] In some embodiments of this application, the second electrode is a metal electrode.

[0260] In some embodiments of this application, the first electrode is a transparent electrode and the second electrode is a metal electrode.

[0261] In some embodiments of this application, the optoelectronic device includes a photovoltaic device, which includes a multi-junction solar cell.

[0262] In this application, unless otherwise specified, a "multi-junction solar cell" refers to a solar cell in which two or more cell cells made of semiconductor active materials with different band gaps are stacked together in series optically and / or electrically. Multi-junction solar cells can broaden the absorption spectrum of solar cells, maximizing the conversion of light energy into electrical energy, and also help reduce thermal relaxation losses. Multi-junction solar cell design is an important way to overcome the Shockley-Queisser limit efficiency of single-junction solar cells. A multi-junction solar cell includes at least two cell cells, each cell cell including at least one light-absorbing layer, and each light-absorbing layer has a different band gap.

[0263] It is understandable that a "cell" in a multi-junction solar cell includes at least a light-absorbing layer. The light-absorbing layers in different cells can provide different band gaps.

[0264] In this application, unless otherwise specified, "battery cell" and "battery section" have the same meaning and can be used interchangeably.

[0265] In this application, unless otherwise specified, "light-absorbing layer" and "light-absorbing layer" have the same meaning and can be used interchangeably.

[0266] In this application, unless otherwise specified, "band gap" has a commonly known meaning in the art and can be analyzed, compared, and confirmed using conventional methods within the art. Without limitation, the band gap of a material can be determined by its absorption or emission spectra; commonly used optical methods include ultraviolet-visible absorption spectroscopy, photoluminescence spectroscopy, and Raman spectroscopy.

[0267] When solar cells are multi-junction solar cells, they are advantageous in improving the utilization rate of incident light, while also retaining the aforementioned advantages of high photoelectric conversion efficiency. Multi-junction solar cells can be monolithic integrated tandem solar cells or mechanically tandem solar cells, offering flexibility in form and a wide range of applications.

[0268] In some embodiments of this application, the optoelectronic device is a photovoltaic device; the photovoltaic device includes a solar cell, which includes the aforementioned perovskite layer.

[0269] The aforementioned perovskite layer can be incorporated into solar cells to improve their photoelectric conversion efficiency. Furthermore, it can also enhance device stability.

[0270] In some embodiments of this application, the optoelectronic device includes a solar cell, which is a multi-junction solar cell. The multi-junction solar cell includes a first cell unit, which includes a light-absorbing layer (which may be referred to as a first light-absorbing layer or first light-absorbing layer). The first light-absorbing layer may include the aforementioned perovskite layer.

[0271] The first light-absorbing layer includes a first semiconductor active material.

[0272] In some embodiments of this application, the first light-absorbing layer is the aforementioned perovskite layer. In this case, the first semiconductor active material includes the first perovskite material.

[0273] In some embodiments of this application, the optoelectronic device includes a solar cell, which is a multi-junction solar cell. The multi-junction solar cell includes a first cell unit, which includes a perovskite layer.

[0274] The aforementioned perovskite layer can be incorporated into multi-junction solar cells to improve their photoelectric conversion efficiency. Furthermore, it can also enhance device stability.

[0275] In some embodiments of this application, the multijunction solar cell further includes a second cell stacked with the first cell cell; the second cell cell and the first cell cell are connected by an interconnect layer, or the second cell cell and the first cell cell are isolated by an insulating layer; the second cell cell includes a light absorption layer (which may be referred to as the second light absorption layer or the second light-absorbing layer), and the second light absorption layer and the first light absorption layer have different band gaps.

[0276] In some embodiments of this application, the interconnect layer includes a carrier recombination layer or a tunneling layer. In some embodiments, the interconnect layer can be a carrier recombination layer or a tunneling layer.

[0277] In some embodiments of this application, the interconnect layer includes a carrier recombination layer.

[0278] In some embodiments of this application, the interconnect layer includes a tunneling layer.

[0279] In some embodiments of this application, the second light-absorbing layer and the perovskite layer have different band gaps. Thus, by providing multiple light-absorbing layers with different band gaps, the multi-junction solar cell can effectively absorb light of different wavelengths, broadening the spectral range of absorbed light and improving the photoelectric conversion efficiency of the multi-junction solar cell.

[0280] In some embodiments, the multijunction solar cell is a tandem solar cell.

[0281] In some embodiments of this application, the multijunction solar cell further includes a second cell stacked with the first cell cell; the second cell cell and the first cell cell are connected by an interconnect layer, or the second cell cell and the first cell cell are isolated by an insulating layer; the second cell cell includes a light-absorbing layer (i.e., a second light-absorbing layer), and the second light-absorbing layer and the perovskite layer have different band gaps.

[0282] By setting up multiple light-absorbing layers with different band gaps (including a perovskite layer and a second light-absorbing layer), multi-junction solar cells can effectively absorb light of different wavelengths, broadening the spectral range of light absorbed by multi-junction solar cells and improving their photoelectric conversion efficiency.

[0283] In some embodiments of this application, the light-absorbing layer (i.e., the second light-absorbing layer) in the second battery cell includes a semiconductor active material (which may be referred to as the second semiconductor active material). The second semiconductor active material includes one or more of the following: a second perovskite material, a silicon-containing semiconductor material, a copper zinc tin sulfide, a copper zinc tin selenide, a copper zinc tin selenide sulfide, a copper indium gallium selenide, a copper indium gallium diselenide, a copper indium selenide, cadmium telluride, gallium arsenide, and organic active materials.

[0284] The aforementioned embodiments can be universally applied to the aforementioned different types of multi-junction solar cells.

[0285] In some embodiments of this application, a carrier recombination layer or a tunneling layer is provided between the monolithically integrated battery cells.

[0286] In this application, unless otherwise specified, the "carrier recombination layer" is a structural layer in which electrons and holes transported from two different battery cells recombine, enabling the two battery cells to achieve ohmic connection and share the positive and negative electrodes.

[0287] In some embodiments of this application, a carrier recombination layer is provided between the first battery cell and the second battery cell.

[0288] In some embodiments of this application, interconnection structures are provided between the battery cells connected in series, which can provide tunneling junctions (also known as tunneling layers) to realize tunneling conduction and electrical series connection between different battery cells, while maintaining optical transparency so that photons can pass smoothly through the previous battery cell to the next battery cell.

[0289] In some embodiments of this application, an interconnection structure is provided between the first battery cell and the second battery cell.

[0290] In some embodiments of this application, a tunnel junction may be formed between the first battery cell and the second battery cell.

[0291] In some embodiments of this application, the charge carrier recombination layer is a structural layer in which electrons transported from the first battery cell and holes transported from the second battery cell recombine, or in which holes transported from the first battery cell and electrons transported from the second battery cell recombine, thereby connecting the first battery cell and the second battery cell in series.

[0292] In some embodiments of this application, a multi-junction solar cell includes a first electrode, a perovskite layer, an interconnect layer, a second light-absorbing layer (i.e., a second light-absorbing layer), and a second electrode stacked together. The interconnect layer is located between the perovskite layer and the second light-absorbing layer. The first electrode is located on the side of the perovskite layer facing away from the interconnect layer, and the second electrode is located on the side of the second light-absorbing layer facing away from the interconnect layer. Thus, two cell units in a multi-junction solar cell are connected through the interconnect layer to achieve current matching between the two cell units. This results in a relatively smaller size, the ability to absorb light of different wavelengths, a wider absorption spectrum range for the multi-junction solar cell, and an improved photoelectric conversion efficiency. The interconnect layer may include a carrier recombination layer or a tunneling layer.

[0293] In some embodiments of this application, a multi-junction solar cell includes a first electrode, a perovskite layer, a third electrode, an insulating layer, a fourth electrode, a light-absorbing layer (i.e., a second light-absorbing layer), and a second electrode stacked together. The third electrode, insulating layer, and fourth electrode are stacked between the perovskite layer and the second light-absorbing layer. The third electrode is located on the side of the insulating layer facing the perovskite layer, and the fourth electrode is located on the side of the insulating layer facing the second light-absorbing layer. The first electrode is located on the side of the perovskite layer away from the third electrode, and the second electrode is located on the side of the second light-absorbing layer away from the fourth electrode. Thus, the multi-junction solar cell forms a mechanically stacked cell. The insulating layer isolates the two cell units, preventing direct conduction of charge carriers and eliminating the need for current matching. Furthermore, each cell has its own independent positive and negative electrodes for current extraction, allowing for flexible circuit adjustments.

[0294] In this application, unless otherwise specified, a multi-junction solar cell with two battery cells may also be referred to as a "tandem solar cell". A tandem solar cell may be a two-terminal structure or a four-terminal structure.

[0295] In some embodiments of this application, the tandem solar cell has a two-end structure. In this case, two cell units are directly connected in series through a tunneling layer or a carrier recombination layer. The tandem solar cell only has two output electrodes, one positive and the other negative, and the current between the two cell units remains consistent. This type of tandem solar cell can also be called a monolithic integrated tandem cell, which refers to cell units stacked along the thickness direction that are electrically connected in series between a pair of electrode layers. Different cell units are connected through a carrier recombination layer or a tunneling layer to achieve current matching between adjacent cell units, so that adjacent cell units form an integrated structure of electrical and optical series connection.

[0296] In some embodiments of this application, the tandem solar cell includes a first electrode, a first light-absorbing layer, a carrier recombination layer, a second light-absorbing layer, and a second electrode. The first light-absorbing layer and the second light-absorbing layer are respectively disposed on both sides of the carrier recombination layer. The first electrode is located on the side of the first light-absorbing layer away from the carrier recombination layer, and the second electrode is located on the side of the second light-absorbing layer away from the carrier recombination layer.

[0297] In some embodiments of this application, the tandem solar cell includes a first electrode, a first light-absorbing layer, a tunneling layer, a second light-absorbing layer, and a second electrode. The first light-absorbing layer and the second light-absorbing layer are respectively disposed on both sides of the tunneling layer. The first electrode is located on the side of the first light-absorbing layer away from the tunneling layer, and the second electrode is located on the side of the second light-absorbing layer away from the tunneling layer.

[0298] In some embodiments of this application, the tandem solar cell has a four-terminal structure. In this case, the cell cells are electrically independent and operate independently, with coupling between the cell cells only through optical means; no carrier recombination layer or tunneling layer is provided between the cell cells. Each cell cell has its own pair of electrodes (positive and negative), and the entire tandem solar cell has four electrical output terminals, corresponding to the four electrodes. Two cell cells are isolated in the stacking direction by an insulating layer to prevent short circuits between the two cell cells.

[0299] In some implementations, the bandgap of the perovskite layer (i.e., the first light-absorbing layer) is Eg2, where 1.65 eV ≤ Eg2 ≤ 2.2 eV; the bandgap of the second light-absorbing layer is Eg1, where 1.1 eV ≤ Eg1 ≤ 1.6 eV. This bandgap configuration of the perovskite layer and the second light-absorbing layer effectively absorbs both short-wavelength and long-wavelength light, improving the photoelectric conversion efficiency of the multi-junction solar cell. In this implementation, the cell unit corresponding to the second light-absorbing layer is a narrow-bandgap solar cell, and the cell unit corresponding to the perovskite layer is a wide-bandgap solar cell.

[0300] In some embodiments, the second light-absorbing layer comprises one or more of the following compounds: a second perovskite material, a silicon-containing semiconductor material, copper zinc tin sulfide, copper zinc tin selenide, copper zinc tin selenide sulfide, copper indium gallium selenide, copper indium gallium diselenide, copper indium selenide, cadmium telluride, gallium arsenide, organic active materials, etc. These materials can absorb light of different wavelengths with the perovskite layer, thereby broadening the spectral range of light absorption in the multi-junction solar cell and improving its photoelectric conversion efficiency. In some embodiments of this application, the definition of the second perovskite material is the same as that of the first perovskite material, but the composition differs to obtain a second light-absorbing layer with a different bandgap, used to absorb light of different wavelengths with the perovskite layer, broadening the absorption spectral range of the multi-junction solar cell and improving its photoelectric conversion efficiency. Exemplarily, the second light-absorbing layer comprises a second perovskite material, thereby obtaining a perovskite-perovskite multi-junction solar cell. In another example, the second light-absorbing layer comprises a crystalline silicon material, thereby obtaining a perovskite-crystalline silicon multi-junction solar cell.

[0301] Organic active materials are typically composed of blends of electron donor and electron acceptor materials. Common electron donor materials include poly(3-hexylthiophene) (P3HT), wide-bandgap polymer donor PM6, and high-efficiency polymer donor D18, while common electron acceptor materials include fullerene acceptors (such as PC). 61 BM, PC 71 BM, etc.), and non-fullerene acceptors (such as Y6 series materials, indendrothiophene derivatives, BTP series, etc.). Exemplary organic active materials include PM6:Y6 and P3HT:PC.61 One of BM, D18:BTP-eC9, etc. can be used to obtain multiple types.

[0302] Silicon-containing semiconductor materials include, but are not limited to, crystalline silicon materials or amorphous silicon materials. Crystalline silicon materials can include monocrystalline silicon or polycrystalline silicon.

[0303] In some embodiments, a multi-junction solar cell includes a first electrode and a second electrode, with a first light-absorbing layer and a second light-absorbing layer both located between the first electrode and the second electrode, the first light-absorbing layer being closer to the first electrode and the second light-absorbing layer being closer to the second electrode.

[0304] In some implementations, the first electrode in a multi-junction solar cell is a transparent electrode. This allows light to enter the multi-junction solar cell from the first electrode. Furthermore, the band gap of the second light-absorbing layer is Eg1, 1.1 eV ≤ Eg1 ≤ 1.6 eV; the band gap of the perovskite layer is Eg2, 1.65 eV ≤ Eg2 ≤ 2.2 eV. Thus, light entering from the first electrode first passes through the perovskite layer, where it absorbs short-wavelength light (such as ultraviolet to visible light), and then enters the second light-absorbing layer, where it absorbs longer-wavelength light (such as near-infrared light). This allows for greater utilization of different wavelengths of light, improving the photoelectric conversion efficiency of the multi-junction solar cell. Furthermore, the perovskite layer, acting as the top light-absorbing layer, absorbs ultraviolet-visible light, protecting the second light-absorbing layer, which acts as the bottom light-absorbing layer.

[0305] In other embodiments, the bandgap of the second light-absorbing layer is Eg3, where 1.65 eV ≤ Eg3 ≤ 2.2 eV; and the bandgap of the perovskite layer is Eg4, where 1.1 eV ≤ Eg4 ≤ 1.6 eV. Thus, the bandgap settings of the second light-absorbing layer and the perovskite layer can absorb short-wavelength and long-wavelength light respectively, improving the photoelectric conversion efficiency of the multi-junction solar cell. In this embodiment, the cell unit corresponding to the second light-absorbing layer is a wide-bandgap solar cell, and the cell unit corresponding to the perovskite layer is a narrow-bandgap solar cell.

[0306] In other embodiments, the second light-absorbing layer comprises a third perovskite material. Thus, the resulting multi-junction solar cell is a perovskite-perovskite multi-junction solar cell. In some embodiments of this application, the third perovskite material is defined as the same type as the first perovskite material described above, but with a different composition to obtain a second light-absorbing layer with a different bandgap. This layer is used to absorb light of different wavelengths with the perovskite layer, broadening the absorption spectrum range of the multi-junction solar cell and improving its photoelectric conversion efficiency. Exemplarily, the third perovskite material includes APbI. z Br 3-z The material shown is defined as follows: 0 < z < 3.

[0307] In other embodiments, the second electrode in a multi-junction solar cell is a transparent electrode. This allows light to enter the multi-junction solar cell through the second electrode. Furthermore, the band gap of the second light-absorbing layer is Eg3, 1.65 eV ≤ Eg3 ≤ 2.2 eV; the band gap of the perovskite layer is Eg4, 1.1 eV ≤ Eg4 ≤ 1.6 eV. Thus, light entering from the second electrode first passes through the second light-absorbing layer, which absorbs short-wavelength light (such as ultraviolet to visible light), and then enters the perovskite layer, where it absorbs longer-wavelength light (such as near-infrared light). This allows for greater utilization of different wavelengths of light, improving the photoelectric conversion efficiency of the multi-junction solar cell. Furthermore, the second light-absorbing layer, acting as the top cell's light-absorbing layer, absorbs ultraviolet-visible light, protecting the perovskite layer as the bottom cell's light-absorbing layer.

[0308] In some embodiments, a multi-junction solar cell includes a first electrode, a perovskite layer, an interconnect layer, a second light-absorbing layer, and a second electrode stacked together, with the interconnect layer located between the perovskite layer and the second light-absorbing layer. The interconnect layer may include a carrier recombination layer or a tunneling layer. Thus, the multi-junction solar cell forms a monolithic integrated tandem cell, with two cell units connected by an interconnect layer (e.g., through a carrier recombination layer or a tunneling layer) to achieve current matching between the two cell units. It has a relatively smaller size, can absorb light of different wavelengths, broadens the absorption spectrum range of the multi-junction solar cell, and improves the photoelectric conversion efficiency of the multi-junction solar cell.

[0309] In some embodiments, a multijunction solar cell includes a first electrode, a perovskite layer, a tunneling layer, a second light-absorbing layer, and a second electrode stacked together, with the tunneling layer located between the perovskite layer and the second light-absorbing layer.

[0310] In some implementations, a multijunction solar cell includes a first charge transport layer, a second charge transport layer, a third charge transport layer, and a fourth charge transport layer.

[0311] In this application, the first charge transport layer, the second charge transport layer, the third charge transport layer, and the fourth charge transport layer are used to transport the first charge carrier, the second charge carrier, the third charge carrier, and the fourth charge carrier, respectively. One of the first charge carrier and the second charge carrier is an electron and the other is a hole. One of the third charge carrier and the fourth charge carrier is an electron and the other is a hole.

[0312] In some embodiments, a multi-junction solar cell includes a first electrode, an optional first charge transport layer, a perovskite layer, an optional second charge transport layer, a carrier recombination layer or a tunneling layer, an optional third charge transport layer, a second light absorption layer, an optional fourth charge transport layer, and a second electrode, all stacked together. Where the first to fourth charge carriers are present, the first and third charge transport layers are identical and selected from either an electron transport layer or a hole transport layer, and the second and fourth charge transport layers are identical and selected from either an electron transport layer or a hole transport layer. Thus, a first electrode, an optional first charge transport layer, a perovskite layer, and an optional second charge transport layer form a first battery cell; an optional third charge transport layer, a second light absorption layer, an optional fourth charge transport layer, and a second electrode form a second battery cell. A carrier recombination layer is used to recombine and annihilate electrons generated from the perovskite layer and holes generated from the second light absorption layer (or holes generated from the perovskite layer and electrons generated from the second light absorption layer) that are transported towards the carrier recombination layer, thereby achieving low-ohmic tunnel recombination between the first battery cell containing the perovskite layer and the second battery cell containing the second light absorption layer, ensuring the connectivity between the two battery cells. A tunneling layer is located between the two battery cells, and its main function is to achieve efficient transport of electrons and holes. Through the tunneling effect, the tunneling layer allows electrons and holes to be transported from the bottom battery to the top battery, thereby reducing energy loss due to electron thermal relaxation and improving the photoelectric conversion efficiency of the battery. Exemplarily, the second light absorption layer includes a second perovskite material, thus resulting in a perovskite-perovskite multi-junction solar cell. In another example, the second light-absorbing layer comprises crystalline silicon, thereby resulting in a perovskite-crystalline silicon multijunction solar cell.

[0313] In some embodiments of this application, multi-junction solar cells may include all four charge transport layers simultaneously, or only one or more of them; this is not limited here. The presence of charge transport layers helps to extract and transport electrons or holes generated by the perovskite layer or the second light-absorbing layer, enhancing the extraction and transport effects and improving the performance of the multi-junction solar cell. The materials for the corresponding electron transport layer and hole transport layer are selected as defined in the context; the materials for the electron transport layer or hole transport layer corresponding to the first and second cell units may be the same or different.

[0314] In some embodiments, a multi-junction solar cell includes a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, a carrier recombination layer or a tunneling layer, an optional hole transport layer, a second light absorption layer, an optional electron transport layer, and a second electrode, all stacked together.

[0315] In this application, the carrier recombination layer comprises one or more of the following: metallic materials, transparent conductive oxides, and carbon materials. Further, the transparent conductive oxide layer comprises, but is not limited to, one or more of the following: fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), indium gallium zinc oxide (IGZO), and antimony-doped tin oxide (ATO). Further, the metallic materials include, but are not limited to, one or more of the following: gold, copper, silver, platinum, aluminum, and iron. Further, the carbon materials include, but are not limited to, one or more of the following: graphite, graphene, and carbon nanotubes.

[0316] In some implementations, the thickness of the carrier recombination layer is 0.1 nm to 200 nm. For example, it can be 0.1 nm, 0.8 nm, 1 nm, 2 nm, 10 nm, 30 nm, 50 nm, 90 nm, 100 nm, 130 nm, 150 nm, 160 nm, 200 nm, or any two of the above values ​​as endpoints.

[0317] In some implementations, the components of the tunneling layer include, but are not limited to, PEDOT (poly(3,4-ethylenedioxythiophene)) and transparent metal oxides.

[0318] In other embodiments, a multi-junction solar cell includes a first electrode, a perovskite layer, a third electrode, an insulating layer, a fourth electrode, a second light-absorbing layer, and a second electrode stacked together. The third electrode, insulating layer, and fourth electrode are stacked between the perovskite layer and the second light-absorbing layer. The third electrode is positioned on the side of the insulating layer facing the perovskite layer, and the fourth electrode is positioned on the side of the insulating layer facing the second light-absorbing layer. In this way, the multi-junction solar cell forms a mechanically stacked cell. The insulating layer isolates the two cell units, preventing direct parallel connection of charge carriers and eliminating the need for current matching. Furthermore, each cell unit has its own independent positive and negative electrodes for current extraction, allowing for flexible circuit adjustments.

[0319] In some embodiments, a multi-junction solar cell includes a first electrode, an optional fifth charge transport layer, a perovskite layer, an optional sixth charge transport layer, a third electrode, an insulating layer, a fourth electrode, an optional seventh charge transport layer, a second light-absorbing layer, an optional eighth charge transport layer, and a second electrode stacked together. The fifth charge transport layer is selected from either a hole transport layer or an electron transport layer; the sixth charge transport layer is selected from either a hole transport layer or an electron transport layer different from the fifth charge transport layer; the seventh charge transport layer is selected from either a hole transport layer or an electron transport layer; and the eighth charge transport layer is selected from either a hole transport layer or an electron transport layer different from the seventh charge transport layer. The definitions and material selections of the corresponding hole transport layers or electron transport layers are as described above and will not be repeated here. Thus, a first electrode, optionally a fifth charge transport layer, a perovskite layer, optionally a sixth charge transport layer, and a third electrode form a first battery cell; a fourth electrode, optionally a seventh charge transport layer, a second light-absorbing layer, optionally an eighth charge transport layer, and a second electrode form a second battery cell. The first and second battery cells are electrically isolated by an insulating layer. Each battery cell has two electrodes, for a total of four electrodes. The circuits of the two battery cells are independent of each other, forming a four-terminal multi-junction solar cell. This allows for adjustment of the current in the multi-junction solar cell. Exemplarily, the second light-absorbing layer comprises a second perovskite material, resulting in a perovskite-perovskite multi-junction solar cell. In another example, the second light-absorbing layer comprises crystalline silicon, resulting in a perovskite-crystalline silicon multi-junction solar cell.

[0320] Furthermore, since the third and fourth electrodes are located in the middle of the multi-junction solar cell, in order to further increase the light energy utilization of the multi-junction solar cell and enable the remaining light after absorption by one cell to enter the next cell, the third and fourth electrodes can be set as light-transmitting electrodes, and the materials can be selected from one or more of the above-mentioned transparent conductive oxides.

[0321] In some embodiments, the material of the insulating layer includes, but is not limited to, glass or an insulating adhesive. Further, the glass is transparent glass; further, the insulating adhesive is a transparent adhesive.

[0322] In some embodiments, the multi-junction solar cell may also include multi-junction solar cells composed of 3, 4, or 5 cells, such as 3-junction solar cells, 4-junction solar cells, 5-junction solar cells, etc., and may be mechanically stacked cells, monolithically integrated stacked cells, or hybrid stacked cells composed of both, without limitation here.

[0323] In some embodiments of this application, the optoelectronic device is a photovoltaic device; the optoelectronic device satisfies one or more of the following characteristics:

[0324] (b1) The perovskite layer is contained in the inverse or formal structure of the optoelectronic device;

[0325] (b2) The optoelectronic device includes a first charge transport layer and a second charge transport layer, with a perovskite layer between the first charge transport layer and the second charge transport layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer; at this time, the first charge transport layer is used to transport a first charge carrier, and the second charge transport layer is used to transport a second charge carrier, wherein one of the first charge carrier and the second charge carrier is a hole and the other is an electron;

[0326] (b3) The optoelectronic device includes a first electrode and a second electrode, and a perovskite layer is disposed between the first electrode and the second electrode;

[0327] Optionally, the optoelectronic device includes at least one charge transport layer and a perovskite layer disposed between a first electrode and a second electrode; the charge transport layer includes at least one of a first charge transport layer located between the first electrode and the perovskite layer and a second charge transport layer located between the second electrode and the perovskite layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer.

[0328] The aforementioned implementation methods can be universally applied to photovoltaic devices with either conventional or inverted structures, thereby improving photoelectric conversion efficiency. Furthermore, they can also enhance device stability.

[0329] In some embodiments of this application, the optoelectronic device includes at least one charge transport layer and a perovskite layer disposed between a first electrode and a second electrode.

[0330] In some embodiments of this application, the optoelectronic device includes a stacked perovskite layer 110 and at least one charge transport layer 300, as can be seen in [reference]. Figure 3 Furthermore, the charge transport layer can be either an electron transport layer or a hole transport layer. Figure 3 The perovskite layer and charge transport layer are arranged adjacently. It is understood that other functional layers, such as passivation layers, barrier layers, buffer layers, and interface layers, can be disposed between the perovskite layer 100 and the charge transport layer 300. The charge transport layer can be a suitable first charge transport layer as described in the context. It is understood that the optoelectronic device may also include other charge transport layers.

[0331] In some embodiments of this application, the optoelectronic device includes a first charge transport layer 310, a perovskite layer 100, and a second charge transport layer 320 stacked together. The first charge transport layer 310 and the second charge transport layer 320 are respectively disposed on opposite sides of the perovskite layer 100 in the thickness direction (Z direction) of the perovskite layer. (See reference...) Figure 4 It can be seen that... Figure 4 The perovskite layer and the first and second charge transport layers located on either side are respectively disposed adjacent to each other. It can be understood that the first and second charge transport layers can be disposed independently without being adjacent to the perovskite layer. For example, other functional layers, such as passivation layers, barrier layers, buffer layers, interface layers, etc., can be disposed between at least one of the first and second charge transport layers and the perovskite layer. In some embodiments, one of the first and second charge transport layers is a hole transport layer, and the other is an electron transport layer.

[0332] In some embodiments of this application, the optoelectronic device includes a first electrode and a second electrode, with a perovskite layer and at least one charge transport layer located between the first electrode and the second electrode.

[0333] In some embodiments of this application, the optoelectronic device includes a first electrode and a second electrode. The first electrode is located on the side of the first charge transport layer away from the perovskite layer, and the second electrode is located on the side of the light-absorbing layer away from the first charge transport layer. The first charge transport layer can be an electron transport layer or a hole transport layer. In some embodiments, the optoelectronic device further includes a second charge transport layer located between the perovskite layer and the second electrode.

[0334] In some embodiments of this application, the optoelectronic device includes a first charge transport layer and a second charge transport layer, wherein the first charge transport layer and the second charge transport layer are located on opposite sides of the perovskite layer in the thickness direction of the perovskite layer. Further, one of the first charge transport layer and the second charge transport layer is an electron transport layer, and the other is a hole transport layer. In some embodiments, the first charge transport layer is a hole transport layer. In other embodiments, the first charge transport layer is an electron transport layer.

[0335] Figure 5 This is a schematic diagram of the structure of an optoelectronic device according to one embodiment of this application. The optoelectronic device includes a first electrode 410, a first charge transport layer 310, a perovskite layer 100, a second charge transport layer 320, and a second electrode 420 stacked together. In the thickness direction (Z direction) of the perovskite layer, the first charge transport layer 310 and the second charge transport layer 320 are respectively disposed on opposite sides of the perovskite layer 100. The first electrode 410 is disposed on the side of the first charge transport layer 310 away from the perovskite layer 100, and the second electrode 420 is disposed on the side of the second charge transport layer 320 away from the perovskite layer 100. In some embodiments, the first electrode is a transparent electrode, and the second electrode is a metal electrode.

[0336] Figure 6This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of this application. The optoelectronic device includes a substrate layer 500, a first electrode 410, a first charge transport layer 310, a perovskite layer 100, a second charge transport layer 320, and a second electrode 420 stacked together. In the thickness direction (Z direction) of the perovskite layer, the first charge transport layer 310 and the second charge transport layer 320 are respectively disposed on both sides of the perovskite layer 100. The first electrode 410 is disposed on the side of the first charge transport layer 310 away from the perovskite layer 100, and the second electrode 420 is disposed on the side of the second charge transport layer 320 away from the perovskite layer 100. The substrate layer 500 is disposed on the side of the first electrode 410 away from the perovskite layer 100.

[0337] In some embodiments of this application, the optoelectronic device can be a formal structure or an inverse structure.

[0338] In some embodiments of this application, the optoelectronic device is an inverted pin structure or a formal nip structure.

[0339] Figure 7 This is a schematic diagram of the structure of an inverted optoelectronic device according to an embodiment of this application. The optoelectronic device includes a substrate layer 500, an incident light-side electrode 700, a hole transport layer 610, a perovskite layer 100, an electron transport layer 620, and a back electrode 800 stacked together. In the thickness direction (Z direction) of the perovskite layer, the hole transport layer 610 and the electron transport layer 620 are respectively disposed on both sides of the perovskite layer 100. The incident light-side electrode 700 is disposed on the side of the hole transport layer 610 away from the perovskite layer 100, the back electrode 800 is disposed on the side of the electron transport layer 620 away from the perovskite layer 100, and the substrate layer 500 is disposed on the side of the incident light-side electrode 700 away from the perovskite layer 100.

[0340] Figure 8 This is a schematic diagram of the structure of an optoelectronic device according to an embodiment of this application. The optoelectronic device includes a substrate layer 500, an incident light-side electrode 700, an electron transport layer 620, a perovskite layer 100, a hole transport layer 610, and a back electrode 800 stacked together. In the thickness direction (Z direction) of the perovskite layer, the hole transport layer 610 and the electron transport layer 620 are respectively disposed on both sides of the perovskite layer 100. The incident light-side electrode 700 is disposed on the side of the electron transport layer 620 away from the perovskite layer 100. The back electrode 800 is disposed on the side of the hole transport layer 610 away from the perovskite layer 100. The substrate layer 500 is disposed on the side of the incident light-side electrode 700 away from the perovskite layer 100.

[0341] It is understood that the hole transport layer includes a hole transport material. When the hole transport layer is located on the light-incident side of the light-absorbing layer (such as a perovskite layer), those skilled in the art can select a suitable type of hole transport material to achieve the desired transmittance.

[0342] It is understood that the hole transport layer includes hole transport materials. Without limitation, the hole transport materials in the hole transport layer may include, but are not limited to, one or more of the following materials and their derivatives: hole transport organic materials and hole transport inorganic materials.

[0343] In some embodiments of this application, the hole transport material includes hole transport organics. Without limitation, the hole transport organics may include, but are not limited to, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid, 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, poly-3-hexylthiophene, methoxytriphenylamine-fluoroformamidinium, triphenylamine with a triphenylene core, 3,4-ethylenedioxythiophene-methoxytriphenylamine, N-(4-aniline)carbazole-spirobifluorene, polythiophene, carbazole-based monomers or polymers (such as [4-(3,6-dimethoxy-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (MeO-4PACz), [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid... The hole transport material comprises one or more of the following: [4-(9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), [4-(3,6-dibromo-9H-carbazole-9-yl)butyl]phosphonic acid (Br-4PACz), [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz), [2-(9H-carbazole-9-yl)ethyl]phosphonic acid (2PACz), [2-(3,6-dibromo-9H-carbazole-9-yl)ethyl]phosphonic acid (Br-2PACz), triphenylamine monomers or polymers, aromatic monomers or polymers, etc. In some embodiments of this application, the hole transport material includes hole transport inorganic substances. Non-limitingly, the hole transport inorganic material may include, but is not limited to, one or more of metal oxides (which may be referred to as the first metal oxide), cuprous iodide and cuprous thiocyanate, molybdenum sulfide, etc.; wherein, the metal oxide in the hole transport material may include, but is not limited to, one or more of nickel oxide, molybdenum oxide, cuprous oxide, vanadium oxide, and tungsten oxide. As a non-limiting example, in the hole transport material, the metal element in the first metal oxide may include one or more of nickel (Ni), molybdenum (Mo), copper (Cu), vanadium (V), and tungsten (W).

[0344] It is understood that the electron transport layer includes electron transport materials. When the electron transport layer is located on the light-incident side of the light-absorbing layer (such as a perovskite layer), those skilled in the art can select appropriate types of electron transport materials to achieve the desired transmittance.

[0345] It is understood that the electron transport layer includes electron transport materials. Without limitation, the electron transport materials in the electron transport layer may include, but are not limited to, one or more of the following materials and their derivatives, impurities, and passivated materials: fullerenes and their derivatives, imide compounds, metal oxides, metal sulfides, metal fluorides, cyano-containing polyphenylacetylene, boron-containing polymers, copper bath, red phenanthroline, hydroxyquinoline aluminum, oxadiazole compounds, quinone compounds, etc.; exemplarily, fullerenes and their derivatives include, but are not limited to, [6,6]-phenyl-C 61 methyl butyrate (PC) 61 BM), [6,6]-phenyl-C 71 methyl butyrate (PC) 71 BM), Fullerene C 60 Fullerene C 61 Fullerene C 70 The imide compounds include, but are not limited to, one or more of perylene imide materials, naphthalene imide materials, phthalimide, succinimide, N-bromosuccinimide, glutarimide, or maleimide; metal oxides (which may be referred to as second metal oxides), perylene imide materials, naphthalene imide materials, etc. Among these, the metal oxides in the electron transport materials may include one or more of tin oxide, zinc oxide, etc. As a non-limiting example, in the electron transport materials, the metal element in the second metal oxide may include one or more of tin (Sn), magnesium (Mg), indium (In), molybdenum (Mo), titanium (Ti), and zinc (Zn). Metal sulfides include indium sulfide or zinc sulfide; metal fluorides include one or more of lithium fluoride (LiF), sodium fluoride, magnesium fluoride (MgF2), and calcium fluoride (CaF2).

[0346] Without limitation, the metal oxide in the first charge transport layer may refer to a first metal oxide (in which case the first charge transport layer is a hole transport layer) or a second metal oxide (in which case the first charge transport layer is an electron transport layer).

[0347] In some embodiments of this application, the first charge transport layer is a hole transport layer. In this case, in addition to the first metal oxide, the first charge transport layer may also include one or more other types of hole transport materials, as can be seen from the context.

[0348] In some embodiments of this application, the first charge transport layer is an electron transport layer. In this case, in addition to the second metal oxide, the first charge transport layer may also include one or more other types of electron transport materials, as can be seen from the context.

[0349] In this application, the terms "first metal oxide" and "second metal oxide" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features.

[0350] In this application, unless otherwise specified, "perovskite material" refers to a class of semiconductor materials having a crystal structure similar to that of the natural mineral calcium titanate (CaTiO3). Typically, perovskite materials comprise a first cation, a second cation, and an anion. The anion and the second cation together form an octahedral structure, with the anion located at the body center of the octahedron and the second cation located at the six vertices. The first cation fills the voids between the octahedra to achieve charge balance and maintain crystal structure stability. Adjacent octahedral structures are connected by sharing vertices, thus forming a continuous crystal lattice structure. Unless otherwise specified, the first cation may be denoted as A and referred to as an A-site ion or A-site cation; the second cation may be denoted as B and referred to as a B-site ion or B-site cation; and the anion may be denoted as X and referred to as an X-site ion or X-site anion.

[0351] The definition of the first perovskite material can be found in the context of this application, or a suitable material from the perovskite materials described below may be selected. The definitions of the second and third perovskite materials can also be found in the context of this application, or a suitable material from the perovskite materials described below may be selected.

[0352] In some embodiments of this application, the first cation is relatively large and the second cation is relatively small.

[0353] In some embodiments of this application, the perovskite tolerance factor is in the range of 0.85 to 1.0. This is advantageous for obtaining a more stable perovskite crystal structure.

[0354] In this application, "perovskite tolerance factor (t)" has a meaning known in the art, and its calculation formula is as follows: , where R A R is the ionic radius of the A-site ion. B R is the ionic radius of the B-site ion. X Let X be the ionic radius of the ion at the X site.

[0355] The first cation in a perovskite material can be an organic cation, an inorganic cation, or a mixture of organic and inorganic cations; it is understood that the first cation in a perovskite material can be one or more types. In some embodiments of this application, the first cation includes a monovalent cation, and more specifically, it can be a monovalent cation.

[0356] The second cation in a perovskite material can be an organic cation, an inorganic cation, or a mixture of organic and inorganic cations; it is understood that the type of the second cation in the perovskite material can be one or more. In some embodiments of this application, the second cation includes a divalent cation, and more specifically, a divalent cation. In some embodiments of this application, the second cation includes a combination of a monovalent cation (denoted as C) and a trivalent cation (denoted as D).

[0357] In some embodiments of this application, the anions in the perovskite material include one or more of halogens and pseudohalogens. The definition of "pseudohalogens" can be found above; anionic pseudohalogens can be referred to as pseudohalogen anions. Non-limiting examples of pseudohalogens may include one or more of thiocyano (SCN), oxocyano (OCN), etc. Non-limiting examples of pseudohalogen anions may include SCN. - OCN - CNO - OSCN - SH - CN - SeCN - One or more of the following. It is understood that pseudohalogens present in perovskite materials can act as X-site ions. In some embodiments of this application, the X-site anion is a monovalent anion.

[0358] In some embodiments of this application, the perovskite material includes perovskite-type metal halides.

[0359] Unless otherwise stated in this application, the anions in perovskite materials or perovskite-type metal halides may include one or more of halogen anions and pseudohalogen anions.

[0360] In some embodiments of this application, the anion in the perovskite material or perovskite-type metal halide is selected from one or more of halogen anions and pseudohalogen anions.

[0361] In some embodiments of this application, the perovskite material or perovskite-type metal halide may include at least one of ABX3 and A2CDX6; wherein A is a monovalent cation, B is a divalent cation, X is a monovalent anion, C is a monovalent cation, and D is a trivalent cation.

[0362] Without limitation, in perovskite-type metal halides, A can be a monovalent inorganic cation, a monovalent organic cation, or a mixed cation of monovalent organic and monovalent inorganic cations.

[0363] In some embodiments of this application, in the perovskite material or perovskite-type metal halide, A is a monovalent inorganic cation; optionally, A includes Li. + Na + K + 、Rb + and Cs + One or more of them.

[0364] In some embodiments of this application, in the perovskite material or perovskite-type metal halide, A is a monovalent organic cation. Optionally, A includes at least one of methylamino, ethylamino, propylamino, butylamino, pentamino, hexamino, formamidinyl, and imidazolyl.

[0365] Without limitation, the A in perovskite materials or perovskite-type metal halides may include Cs. + K + 、Rb + Li + One or more of monovalent organic cations, etc.

[0366] Non-limiting examples of monovalent organic cations include (NR) 31 R 32 R 33 R 34 ) + 、(R 31 R 32 N=CR 33 R 34 ) + 、(R 31 R 32 NC(R 35 )=NR 33 R 34 ) + or (R) 31 R 32 NC(NR 35 R 36 )=R 33 R 34 ) + , where R 31 R 32 R 33 R 34 R 35 and R 36 Each is independently selected from H and C. 1-20 Alkyl, aryl, substituted C 1-20 Alkyl or substituted aryl; wherein, C 1-20 Alkyl and substituted C 1-20 The "C" in alkyl 1-20 Each alkyl group can be independently selected as C. 1-15Alkyl, further optionally C 1-10 Alkyl, and further optionally C 1-8 Alkyl, and further optionally C 1-6 Alkyl, and further optionally C 1-4 Alkyl, and further optionally C 1-3 Alkyl, and further optionally methyl. The "aryl" in aryl and substituted aryl groups can each independently be C10. 6-20 Aryl, further optionally C 6-12 Aryl, and further alternatively C 6-10 Aryl, further optionally phenyl or naphthyl, and further optionally phenyl. Substituted C 1-20 In alkyl and substituted aryl groups, each substituent is independently C1. 1-10 Hydrocarbon group, further optionally C 1-6 Alkyl or C 6-10 Aryl, and may further be methyl or phenyl.

[0367] Non-limiting examples of monovalent organic cations include CH3NH3 + (Methylamine, MA) + ), NH2CH=NH2 + (Formamidin, can be written as FA) + ), dimethylamine cation, ethylamine cation, propylamine cation, butylamine cation, pentamine cation, hexamine cation, imidazole cation.

[0368] In some embodiments of this application, in the perovskite-type metal halide, A includes a monovalent organic cation and Cs. + One or more of them.

[0369] In some embodiments of this application, in the perovskite material or perovskite-type metal halide, B includes divalent cations of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, and europium.

[0370] In some embodiments of this application, in the perovskite material or perovskite-type metal halide, C represents a monovalent inorganic cation; optionally, C includes Cs. + Ag + K + and Ru + One or more of the following.

[0371] In some embodiments of this application, D represents a trivalent metal cation; optionally, D includes Bi. 3+ Ni 3+ Fe 3+ Sb 3+ In 3+and Cu 3+ One or more of them, and further optionally, D includes In 3+ Bi 3+ Sb 3+ One or more of them.

[0372] In some embodiments of this application, X represents a halide anion; optionally, X includes F. - Cl - ,Br - and I - One or more of them, and optionally, X includes Cl - ,Br - and I - One or more of them.

[0373] In some embodiments of this application, the perovskite material includes perovskite-type metal halides, and the monovalent cation of the perovskite material includes FA. + and Cs + .

[0374] In some embodiments of this application, the perovskite material includes perovskite-type metal halides, and the monovalent cation of the perovskite material includes FA. + MA + and Cs + .

[0375] In this application, unless otherwise specified, the term "aryl" refers to an aromatic hydrocarbon group derived from an aromatic cyclic hydrocarbon compound by losing one hydrogen atom, that is, forming a monovalent linking site directly on the ring. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl; for polycyclic rings, at least one is an aromatic ring system. For example, "C6- 10 "Aryl" refers to an aryl group containing 6 to 10 carbon atoms. Each time it appears, it can be independently C6 aryl, C8 aryl, C9 aryl, or C6 aryl. 10 Aryl. For example, "C6- 20 "Aryl" refers to an aryl group containing 6 to 20 carbon atoms. Each time it appears, it can be independently, but is not limited to, C6 aryl (such as phenyl), C8 aryl (such as benzocyclobutenyl), C9 aryl (such as indenyl), C6 aryl, C8 aryl, C9 ... 10 Aryl (such as naphthyl), C 12 Aryl (such as acenaphthene, biphenyl), C 13 Aryl (such as fluorene), C 14 Aryl (such as anthracene, phenanthrene), C 18 Aryl (such as phenylene) or C 20Aryl groups (such as dinaphthalene-based phenyl groups). Examples of suitable aromatic cyclic hydrocarbons that can be derived to form aryl groups include, but are not limited to: benzene, benzocyclobutene, biphenyl, indene, naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, triphenylene, dinaphthalene-based phenyl groups and their derivatives.

[0376] Without limitation, in perovskite-type metal halides, B can be an inorganic cation.

[0377] In some embodiments of this application, in the perovskite-type metal halide, B includes a divalent cation. Optionally, B includes a divalent cation of one or more of the following elements: lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, europium, etc.

[0378] Without limitation, B in perovskite-type metal halides may include Pb. 2+ Sn 2+ Fe 2+ Mn 2+ Ni 2+ 、Ge 2+ Co 2+ and Sb 2+ One or more of them.

[0379] In perovskite-type metal halides, X can be an inorganic anion, an organic anion, or a mixture of organic and inorganic anions.

[0380] In some embodiments of this application, in the perovskite-type metal halide, X is a halide anion; optionally, X includes F. - Cl - ,Br - and I - One or more of them, and optionally, X includes Cl - ,Br - and I - One or more of the following. In some embodiments, X in the perovskite metal halide can be I. - ,Br - and Cl - One or more of them.

[0381] Without limitation, X in perovskite-type metal halides may include I. - ,Br - One or two of them. X can be I. - ,Br - Or a combination thereof. In some embodiments, X is I. - .

[0382] Non-limitingly, in perovskite-type metal halides, C can be an inorganic cation, an organic cation, or a mixed organic-inorganic cation. In some embodiments of this application, C is a monovalent inorganic cation; optionally, C includes Cs. + Ag + K + and Ru + One or more of the following. In some embodiments of this application, C can be silver ions (Ag). + ).

[0383] In a non-limiting sense, in perovskite metal halides, D can be an inorganic cation, an organic cation, or a mixed organic-inorganic cation.

[0384] In some embodiments of this application, D is a trivalent metal cation; optionally, D includes Bi. 3+ Ni 3+ Fe 3+ Sb 3+ In 3+ , and Cu 3+ One or more of them, and further optionally, D includes In 3+ Bi 3+ Sb 3+ One or more of these. In some embodiments, D is a bismuth cation (Bi). 3+ ), antimony cation (Sb) 3+ ) and indium cation (In 3+ At least one of the following.

[0385] It is understood that electrodes include conductive materials. For electrodes that can be used as incident light electrodes, those skilled in the art can select appropriate types of conductive materials to achieve the desired transmittance.

[0386] Non-limiting, the first electrode and the second electrode may each independently comprise a conductive material. The conductive material in the first electrode and the conductive material in the second electrode may each independently comprise an organic conductive material, an inorganic conductive material, or an organic-inorganic mixed conductive material.

[0387] As an example, organic-inorganic hybrid conductive materials include both organic and inorganic conductive components.

[0388] As a non-limiting example, organic conductive materials may include conductive polymers, wherein non-limiting examples of conductive polymers may include one or more of PEDOT (poly-3,4-ethylenedioxythiophene), polythiophene, polyacetylene, etc.

[0389] As a non-limiting example, inorganic conductive materials may include one or more of transparent conductive oxides, metallic conductive materials, and carbon conductive materials. Non-limiting examples of transparent conductive oxides may include one or more of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), boron-doped zinc oxide (BZO), indium zinc oxide (IZO), tungsten-doped indium oxide (IWO), indium gallium zinc oxide (IGZO), and antimony-doped tin oxide (ATO). Metallic conductive materials may include one or more of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), molybdenum (Mo), and tungsten (W).

[0390] In some embodiments of this application, non-limiting examples of inorganic conductive materials include metallic conductive materials. Further, metallic conductive materials may include any one of gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), or any suitable mixture of the aforementioned elements.

[0391] In some embodiments of this application, one of the first electrode and the second electrode is a metal electrode. The metal electrode may include one or more metallic elements selected from gold (Au), silver (Ag), copper (Cu), aluminum (Al), nickel (Ni), chromium (Cr), bismuth (Bi), platinum (Pt), magnesium (Mg), molybdenum (Mo), tungsten (W), etc.

[0392] In some embodiments of this application, the electrode material of the first electrode includes at least one of indium tin oxide (ITO), lanthanide-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), boron-doped zinc oxide (BZO), aluminum-doped zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), tungsten-doped indium oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, Mg, Mo, W and their alloys, graphite, graphene, and carbon nanotubes; optionally, it includes at least one of Ag, Cu, C, Au, Al, ITO, AZO, BZO or IZO, and further optionally, it includes at least one of Cu, Ag, and Au.

[0393] In some embodiments of this application, the second electrode is a back electrode. The back electrode may include one or more of the following: indium tin oxide (ITO), lanthanide-doped indium oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), boron-doped zinc oxide (BZO), aluminum-doped zinc oxide (AZO), indium zinc oxide (IZO), gallium zinc oxide (GZO), tungsten-doped indium oxide (IWO), Au, Ag, Cu, Al, Ni, Cr, Bi, Pt, and Mg.

[0394] The substrate layer involved in the embodiments or examples of this application can be, but is not limited to, a rigid substrate layer or a flexible substrate layer. A non-limiting example of a rigid substrate layer is a glass substrate layer. In some embodiments, the rigid substrate layer is transparent glass. In some embodiments, the substrate layer is provided by a transparent conductive oxide film glass (TCO glass), wherein the glass serves as the substrate layer, and the TCO is a transparent conductive oxide film material; non-limiting examples of TCO materials include ITO, FTO, etc.

[0395] In some embodiments of this application, the material of the flexible substrate layer may be, for example, but not limited to, organic polymer materials. Furthermore, it may be composed of one or more of the following materials mixed in different proportions: including but not limited to polyvinyl alcohol (PVA), polyester (PET), polyimide (PI), polyethylene naphthalate (PEN), polydimethylsiloxane (PDMS), etc.

[0396] It is understood that the structure of the optoelectronic device involved in this application is not limited to the structural layers listed above. Other functional layers or interface layers, such as buffer layers and insertion layers, can also be introduced as needed. In some embodiments, the optoelectronic device can be provided with a buffer layer of appropriate energy level, which can play one or more roles such as reducing the energy level barrier, promoting energy level matching, improving carrier extraction efficiency, passivating interface defect states, protecting the light-absorbing layer, inhibiting the oxidation and decomposition of water molecules and oxygen on the battery, improving energy conversion efficiency, and improving device stability. Depending on the location of the buffer layer, the type of buffer layer can include four types: a buffer layer between the hole transport layer and the anode, a buffer layer between the electron transport layer and the cathode, a buffer layer between the hole transport layer and the light-absorbing layer, and a buffer layer between the electron transport layer and the light-absorbing layer. Materials that can be used for buffer layers in optoelectronic devices can include, but are not limited to, Cu2O, NiO, AZO, TiO2, etc. In some embodiments, an insertion layer can be provided between the electron transport layer and the second electrode. This insertion layer is used to block the transport of holes and can also be called a hole blocking layer. Examples of materials for the insertion layer include bath copper phosphate (BCP) and tin oxide.

[0397] In some embodiments of this application, the optoelectronic device includes the following stacked structure: a transparent conductive glass substrate layer, a hole transport layer, a perovskite layer, an electron transport layer, a hole blocking layer (optional), and a back electrode (the back electrode can be a metal electrode or a transparent conductive electrode).

[0398] In this application, unless otherwise specified, "sequentially stacked" refers to the direction of stacking between layered structures and does not constitute a limitation on the structural composition of the stacked body. For example, "including stacked structural layer A and structural layer B" means that the stacking direction of structural layer A and structural layer B is along their respective thickness directions; that is, the thickness direction of structural layer A is consistent with or substantially consistent with the thickness direction of structural layer B. It is understood that other intermediate structural layers are allowed to be set between structural layer A and structural layer B.

[0399] The following are some other descriptions of the structure of optoelectronic devices.

[0400] In some embodiments of this application, the optoelectronic device 10 includes Figure 9 The structure shown ( Figure 9 The structure shown is a schematic cross-sectional view of the device along the thickness direction. The optoelectronic device 10 includes a substrate layer 500, a first electrode 410, a first charge transport layer 310, a perovskite layer 100, a second charge transport layer 320, and a second electrode 420 stacked together. The positional relationship of each structural layer is as follows: Figure 8Similarly, the optoelectronic device 10 is further provided with three types of cross-layer channel regions: a first channel region P1, a second channel region P2, and a third channel region P3. Utilizing the channel group formed by the first channel region P1, the second channel region P2, and the third channel region P3, the solar cell is divided into several series-connected sub-cells. Each sub-cell includes a first channel region P1, a second channel region P2, and a third channel region P3 arranged sequentially, with the second channel region P2 located between the first channel region P1 and the third channel region P3. The first channel region P1, the second channel region P2, and the third channel region P3 can be connected to the structural layers that are spaced apart, thereby connecting the circuit between the first electrode of one sub-cell and the second electrode of the adjacent sub-cell, forming a series structure. The first channel region P1, the second channel region P2, and the third channel region P3 can each be an independent linear channel region, formed by laser etching or a mask. The number of first channel regions P1, second channel regions P2, and third channel regions P3 can each be one or more independently. The number of first channel regions P1, second channel regions P2, and third channel regions P3 corresponds to the number of sub-cells. Without limitation, the first channel regions P1, second channel regions P2, and third channel regions P3 can be configured as follows: the first channel region P1 is used to divide the first electrode 410 to prevent short circuits between adjacent sub-cells; the second channel region P2 is used to penetrate and divide the second charge transport layer 320, the perovskite layer 100, and the first charge transport layer 310, with the interior of the second channel region filled with a conductive material such that both ends of the conductive material are connected to the second electrode 420 and the first electrode 410 respectively. The material of this conductive material can be the same as the material of the second electrode 420 to achieve integral fabrication during the fabrication process of the second electrode 420, or it can be a different material from the second electrode 420; the third channel region P3 is used to penetrate and at least divide the second electrode 420. Figure 9 In the example, the third channel region P3 is used to penetrate and divide the second electrode 420, the second charge transport layer 320, the perovskite layer 100, and the first charge transport layer 310. One end of the third channel region P3 is connected to the surface of the first electrode 410, and the other end extends out of the outer surface of the second electrode 420. The purpose is to isolate the second electrode between two adjacent sub-cells to prevent short circuits. In this way, a series connection between adjacent sub-cells is achieved.

[0401] In some embodiments of this application, Figure 9 The substrate 500 in the structure shown is a light-incident glass substrate.

[0402] In some embodiments of this application, the filling material in the first channel region P1 of the optoelectronic device can be the same as the first charge transport layer, or it can be filled with an insulating material, as long as it can prevent short circuits between adjacent series-connected sub-cells.

[0403] In some embodiments of this application, the filling material in the second channel region P2 of the optoelectronic device may be consistent with the second electrode.

[0404] In some embodiments of this application, the width of the first channel region P1 is 10~50μm, such as 15μm, 30μm, etc.

[0405] In some embodiments of this application, the width of the second channel region P2 is 10~200μm, for example 50μm or 150μm. Further, the interval between the second channel region P2 and the first channel region P1 can be 20~80μm, for example 20μm, 30μm, or 50μm.

[0406] In some embodiments of this application, the width of the third channel region P3 is 10~50μm, such as 15μm, 25μm, etc. Further, the interval between the third channel region P3 and the second channel region P2 can be 20~100μm, such as 30μm, 50μm.

[0407] In some embodiments of this application, the optoelectronic device includes an encapsulating adhesive layer.

[0408] Encapsulating adhesive layers can be used to protect the stability of optoelectronic devices, for example, by isolating them from water, oxygen, and other corrosive substances.

[0409] In some embodiments of this application, the encapsulating adhesive layer includes one or more of the following: epoxy encapsulating adhesive, silicone encapsulating adhesive, polyurethane encapsulating adhesive, UV-curable encapsulating adhesive, ethylene-vinyl acetate copolymer, polyvinyl butyral, ethylene octene copolymer, polyisobutylene, and polyolefin encapsulating adhesive.

[0410] The encapsulating adhesive layer can be stacked using existing techniques in the field. After the optoelectronic device is fabricated, the encapsulating adhesive layer can be stacked at the final structural layer of the solar cell device. In some embodiments of this application, the final structural layer can be a second electrode. For example, lamination technology can be used to laminate the arranged optoelectronic devices or components including the optoelectronic devices with the encapsulating adhesive film, thereby creating an encapsulating adhesive layer on the side of the second electrode facing away from the light-absorbing layer.

[0411] Unless otherwise stated, the encapsulating film and encapsulating layer in this application are transparent materials.

[0412] In some embodiments of the second aspect of this application, a method for fabricating an optoelectronic device is provided, which can be used to fabricate the optoelectronic device of the first aspect of this application.

[0413] In some embodiments of the second aspect of this application, a method for fabricating an optoelectronic device is provided, which can be used to fabricate the photovoltaic device of the first aspect of this application.

[0414] In some embodiments of this application, a method for fabricating an optoelectronic device is provided, which includes the following steps:

[0415] S100: Provides a perovskite precursor solution; wherein the perovskite precursor solution contains a perovskite precursor material and a first solvent;

[0416] S200: The perovskite precursor solution is coated and vacuum dried to remove part of the first solvent to prepare a perovskite intermediate phase film layer.

[0417] S300: An additive dispersion containing a first additive and a second solvent is coated on the surface of a perovskite mesophase film layer, and after standing, laser gradient annealing is performed to form a perovskite layer; wherein, the first additive is an organic material, and the second solvent includes isopropanol and N,N-dimethylformamide; the laser gradient annealing includes a first stage annealing at a first temperature, and then a second stage annealing at a second temperature; the first temperature is 85℃~95℃, and the second temperature is higher than the first temperature;

[0418] The formed perovskite layer can be found in the description of the first aspect of this application.

[0419] In this application, unless otherwise specified, "perovskite precursor solution" refers to a solution and may also be referred to as perovskite precursor solution.

[0420] In this application, unless otherwise specified, "perovskite precursor material" refers to a material used to form a perovskite crystal structure, also known as a "precursor material for perovskite materials," which provides the basic elements in the perovskite crystal structure. Typically, the elemental composition of the perovskite precursor material matches the chemical elemental composition of the target perovskite material. For example, the target perovskite material can adopt the general structural formula ABX3, in which case the corresponding raw materials may include AX, BX2, etc., and divalent metal cations (such as Pb). 2+ The sum of the atomic ratios of the components is 1; for example, the target perovskite material can be FA. 0.95 MA 0.05 Pb(I 0.95 Br 0.05 3. At this time, the divalent metal cation is Pb. 2+ .

[0421] Unless otherwise specified, the perovskite precursor material used in step S100 is the target perovskite material for synthesis, which is the first perovskite material.

[0422] Typically, the temperature for vacuum drying is significantly lower than the perovskite crystallization temperature, while the temperature for laser gradient annealing is higher than the perovskite crystallization temperature.

[0423] Unless otherwise stated in this application, "perovskite crystallization temperature" refers to the initial crystallization temperature of perovskite, which is the lowest temperature at which the perovskite precursor begins to undergo a phase transition and transform into perovskite crystals.

[0424] In some embodiments, the formed perovskite layer includes a perovskite layer comprising perovskite grains, the crystalline phase of the perovskite grains comprising a cubic phase and a non-cubic phase; the cubic phase accounts for more than or equal to 97% of the mass of the perovskite layer; the non-cubic phase includes at least one of a tetragonal phase, an orthorhombic phase, and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase; and the dielectric constant of the perovskite layer is greater than or equal to 5.

[0425] Unless otherwise stated, one or more methods, such as X-ray diffraction (XRD) and GIWAXS, can be used in this application to analyze the crystallization of perovskite phases. The testing methods are described in the context of this application.

[0426] Unless otherwise stated, X-ray diffraction (XRD) is used in this application to analyze the crystallization of the perovskite phase. The XRD pattern of the perovskite intermediate phase film in this application does not show obvious characteristic peaks of the perovskite phase. After annealing, sharp diffraction peaks of the perovskite phase can be observed in the XRD pattern of the obtained perovskite layer.

[0427] Unless otherwise specified in this application, XRD testing can be performed using the following instruments and methods: an X-ray source of Cu Kα1 (wavelength 1.54056 Å), a scanning range (2θ) of 0–80°, and a scanning rate of 10° / min. Furthermore, a TWIST-TUBE light source and an EIGER2 detector can be selected. Even further, a Bruker D8 DISCOVER instrument can be used. The incident angle can be selected from 2° to 90°. See also the test methods in the Examples section below.

[0428] The aforementioned preparation method employs a unique strategy of separately adding the perovskite precursor solution and the first additive, followed by subsequent diffusion. This strategy ensures that the first additive is primarily distributed along the grain boundaries, inducing high-quality crystallization of the perovskite and forming specific proportions of different crystal phases. This results in higher absorbance and improved utilization of incident light. Furthermore, the cubic phase exhibits stronger charge transport capabilities, which is beneficial for carrier transport. Simultaneously, the first additive largely avoids entering the perovskite crystal, reducing the probability of charged defects arising from its entry into the lattice. This significantly suppresses the scattering effect of potential charged defects, thereby significantly increasing the effective transport distance of photogenerated carriers within the perovskite layer and achieving a relatively high dielectric constant. In the prepared perovskite layer, the first additive remaining at the grain boundaries can continue to passivate interface defects. Thus, both high crystal quality and fewer charged defects are achieved simultaneously. This not only improves the utilization of incident light but also promotes the effective transport of carriers within the perovskite layer. The synergistic effect of these multiple actions significantly enhances the energy conversion efficiency of optoelectronic devices.

[0429] In the aforementioned process, the perovskite precursor solution without additives is coated and vacuum dried to remove some solvent, while retaining some solvent molecules in the perovskite mesophase film. Then, an additive dispersion containing the first additive is coated onto the perovskite mesophase film and allowed to stand to allow the first additive to diffuse along the mesophase boundary, inducing perovskite crystallization. In the subsequent laser annealing process, laser gradient annealing is used. During the first stage of annealing, the system is controlled to prevent large-scale, rapid perovskite crystallization, allowing the residual solvent to carry the first additive out of the crystal. Then, a second stage of higher-temperature annealing achieves high-quality crystallization, allowing the first additive to... The agent is confined to the grain boundaries and does not enter the perovskite crystal much, which can significantly reduce the charged defects in the crystal, significantly suppress the scattering effect of possible charged defects, improve the crystal quality, and significantly increase the effective transport distance of photogenerated carriers in the perovskite layer. This results in the aforementioned special phase ratio, with the cubic phase accounting for the majority (e.g., ≥97%, based on the quality of the perovskite layer), the tetragonal phase accounting for a higher proportion than the orthorhombic phase, and the proportion of other phases being as small as possible (e.g., ≤5%, based on the quality of the non-cubic phase). At the same time, it also has a high dielectric constant (e.g., ≥5), effectively avoiding the adverse effects of defects caused by additives in other processes entering the perovskite lattice on the dielectric constant of the perovskite layer.

[0430] The above preparation method can still achieve high energy conversion efficiency even with a high perovskite layer thickness.

[0431] The above preparation method is simple and easy to operate, and can significantly improve energy conversion efficiency without the need for additional equipment, which is beneficial to reducing costs.

[0432] In some embodiments of this application, the target perovskite material includes divalent metal cations. Further, the concentration of the divalent metal cations in the perovskite precursor solution can be 0.5 mol / L to 3 mol / L, optionally 1 mol / L to 2 mol / L, or any of the following concentrations or a range selected from any two of the following concentrations: 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.8 mol / L, 2 mol / L, 2.2 mol / L, 2.4 mol / L, 2.5 mol / L, 3 mol / L, etc.

[0433] In some embodiments of this application, the solvent for the perovskite precursor solution may include one or more of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).

[0434] In some embodiments of this application, the second solvent includes isopropanol (IPA) and N,N-dimethylformamide (DMF). In some embodiments, the volume ratio of isopropanol to DMF is (25~99):1. Exemplarily, the volume ratio may also be any of the following ratios or a range selected from any two of the following ratios: 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 86:1, 88:1, 90:1, 92:1, 94:1, 95:1, 96:1, 97:1, 98:1, 99:1, etc., but is not limited thereto.

[0435] In some embodiments of this application, the volume percentage of isopropanol in the total volume of isopropanol and DMF is 25% to 99%. Exemplarily, the volume percentage of isopropanol in the total volume of isopropanol and DMF can also be any of the following values ​​or a range selected from any two of the following values: 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 97%, 98%, 99%, etc., but is not limited thereto.

[0436] In some embodiments of this application, the method for fabricating the optoelectronic device satisfies one or more of the following features (any numerical parameter of the following features may also be selected from any suitable value or range in the context):

[0437] (c1) In the step of vacuum drying to remove part of the first solvent, the temperature of vacuum drying is 0℃~70℃, the pressure of vacuum drying is 5Pa~500Pa, and the duration of vacuum drying is 2s~40s. By controlling the above process parameters, it is beneficial to better control the residual amount of the first solvent, so that in the subsequent laser annealing process, the first additive can be better controlled to diffuse mainly along the grain boundary, and basically not enter or enter the perovskite crystal.

[0438] (c2) In the second solvent, the volume ratio of isopropanol to N,N-dimethylformamide is (25~99):1, and can also be any of the following ratios or a range selected from any two of the following ratios: 25:1, 30:1, 5:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 96:1, 98:1, 99:1, etc.; Isopropanol (IPA) in the second solvent has very weak solubility for perovskite, but can effectively dissolve the passivating agent. N,N-dimethylformamide (DMF) has a dissolving effect on perovskite. By using isopropanol and a small amount of N,N-dimethylformamide as a co-solvent, the passivating agent can be effectively penetrated into the perovskite layer while ensuring effective secondary dissolution of the perovskite, thereby fully passivating the defects;

[0439] (c3) The mass-volume concentration of the first additive in the additive dispersion is 0.5 mg / mL to 10 mg / mL;

[0440] (c4) The temperature for standing is 0℃~70℃, the standing time is 2min~5min, and the ambient humidity for standing is less than or equal to 3%RH; this is conducive to better control of the diffusion of the first additive along the intermediate phase boundary.

[0441] (c5) The duration of the first-stage annealing at the first temperature is 1s to 5s; the temperature of the second-stage annealing at the second temperature is 95℃ to 105℃, and the duration is 5s to 15s. At this time, it is beneficial to form high-quality perovskite crystals and form the perovskite crystal phase in the aforementioned proportion.

[0442] In some embodiments of this application, in step S200, during the preparation of the perovskite mesophase film, the percentage of the residual mass of the first solvent in the film after vacuum drying to the initial mass of the first solvent in the film before vacuum drying (F... S It can be 10% to 25%, or any of the following percentages, or a range selected from any two of the following percentages: 10%, 12%, 14%, 15%, 16%, 18%, 20%, 22%, 24%, 25%, etc. SFor the test results, please refer to the section below on "Confirming the distribution of residual solvent in the perovskite intermediate phase film layer using TOF-SIMS test".

[0443] In this application, unless otherwise specified, the description of "ambient humidity" shall be understood as follows: taking 3%RH (relative humidity 3%) as an example, "3%RH" means that the water vapor content in the air accounts for 3% of the saturated water vapor content at the same temperature.

[0444] In some embodiments of this application, laser annealing employs nanosecond-level pulsed lasers.

[0445] In some embodiments of this application, the power for the first stage annealing at the first temperature is 100W~200W, and the power for the second stage annealing at the second temperature is 550W~650W.

[0446] In some embodiments of this application, laser annealing uses blue laser light with a wavelength of 400nm to 500nm. The perovskite component and its intermediate phases have relatively high absorption rates for blue light, which is more conducive to controlling large-area uniform annealing.

[0447] The definition of the first additive can also be found in the first aspect of this application.

[0448] In optoelectronic devices, structural layers other than the perovskite layer can be prepared using one or more of the following methods, including but not limited to: chemical bath deposition, electrochemical deposition, chemical vapor deposition, thermal evaporation, atomic layer deposition, magnetron sputtering, precursor liquid spin coating, precursor liquid slot coating, precursor liquid blade coating, and mechanical pressing. Appropriate methods can be selected to stack the structural layers with adjacent structural layers based on the material properties of each layer. In some embodiments of this application, structural layers in optoelectronic devices can be prepared using one or more of the following methods, including but not limited to: thermal evaporation, precursor liquid coating, etc., wherein the precursor liquid coating method can be precursor liquid spin coating, precursor liquid blade coating, precursor liquid spraying, etc.

[0449] In some embodiments of this application, the method for fabricating a photovoltaic device includes the following steps:

[0450] S10: Perform P1 etching on the first electrode: Perform P1 etching on the first electrode stacked on the substrate layer to form a P1 etching line, exposing the substrate layer to obtain the first substrate, which is then cleaned for later use. The first electrode can be a transparent electrode. The location of the formed P1 etching line can be found in [reference needed]. Figure 9 .

[0451] S20: A first charge transport layer is formed on the first electrode.

[0452] In some implementations, the first charge transport layer may be a hole transport layer.

[0453] S30: A perovskite layer is formed on the first charge transport layer. See the context for photovoltaic device fabrication methods.

[0454] S40: Form a second charge transport layer on the perovskite layer. Perform P2 etching to the depth of the first electrode near the hole transport layer surface. (See reference...) Figure 9 .

[0455] When the first charge transport layer is a hole transport layer, the second charge transport layer is an electron transport layer; when the first charge transport layer is an electron transport layer, the second charge transport layer is a hole transport layer.

[0456] S50: Form a second electrode on the second charge transport layer, perform P3 etching, and etch to the surface of the first electrode near the hole transport layer, then clean the edges. The location of the formed P3 etching line can be found in [reference needed]. Figure 9 .

[0457] In some embodiments of the third aspect of this application, an electrical device is provided, which includes at least one of the optoelectronic devices described in the first aspect of this application and optoelectronic devices prepared by the preparation method of the optoelectronic devices described in the second aspect of this application.

[0458] In some embodiments of the sixth aspect of this application, a power generation device is provided, which includes at least one of the optoelectronic devices described in the first aspect of this application and optoelectronic devices prepared by the preparation method of the optoelectronic devices described in the second aspect of this application.

[0459] Both the power-consuming devices and power-generating devices containing the aforementioned optoelectronic devices can leverage the advantages of optoelectronic devices.

[0460] In some embodiments, the aforementioned optoelectronic device can be a power generation device or power generation apparatus that functions as an electrical device. The type of power generation device or power generation apparatus may include, but is not limited to, integrated power generation. The location of the power generation device or power generation apparatus may include, but is not limited to, the roof or back panel of a vehicle.

[0461] Furthermore, the aforementioned electrical devices may include mobile devices, such as mobile phones and laptops, electric vehicles, electric trains, ships and satellites, power generation systems, etc., but are not limited to these.

[0462] Figure 10 This is an example of an electrical device. The electrical device 6 is a car, and can further be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc.

[0463] Another example of an electrical device could be a mobile phone, tablet, laptop, calculator, etc.

[0464] Another example of an electrical device could be a wearable device, such as a watch.

[0465] Non-limiting examples of light-emitting devices may include light-emitting diodes (LEDs), laser diodes (LDs), etc. Applications of light-emitting devices may include, but are not limited to, lighting and display applications.

[0466] In some embodiments, the aforementioned optoelectronic devices or optoelectronic components can be used as light-emitting devices in a display device. Non-limiting examples of display devices include displays, photodetectors, etc.

[0467] The following describes some embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where the technology or conditions are not specified in the embodiments, they are performed according to the description above, or according to the technology or conditions described in the literature in this field, or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially, or can be synthesized from commercially available products using conventional methods.

[0468] In the following examples, unless otherwise specified, room temperature refers to 20°C to 30°C.

[0469] In the following examples, the inversion structure is used as a non-limiting example of an optoelectronic device. It is understood that it can also be set as a formal structure. In the test method section, a photovoltaic device is used as an example of performance testing for optoelectronic devices; it is understood that optoelectronic devices can be tested in accordance with the relevant tests for light-emitting devices.

[0470] For test results where specific testing methods are not specified below, please refer to the descriptions above, such as the confirmation of dominant crystal planes and perovskite layer thickness testing.

[0471] The hole transport materials are PTAA (poly(4-phenyl)(2,4,6-trimethylphenyl)amine), FAI (formamidine iodocarboxylate), MABr (methylbromomethylamine), MACl (chloromethylamine), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), IPA (isopropanol), DMSO (dimethyl sulfoxide), and DMF (N,N-dimethylformamide).

[0472] VCD stands for vacuum drying.

[0473] The photoelectric conversion efficiency of photovoltaic devices is used as an example of the energy conversion efficiency of optoelectronic devices.

[0474] I. Fabrication of optoelectronic devices (which can be used as photovoltaic devices and in solar cells)

[0475] Example 1.

[0476] Step S1: Take a 1m × 2m fluorine-doped tin oxide (FTO) substrate (FTO conductive glass electrode, first electrode / glass substrate), and use an infrared laser to etch P1. The width of P1 is about 30μm. Divide the entire glass into 161 sub-cells (with the long side as the extension direction of the sub-cell). The series resistance of different sub-cells is greater than 10MΩ (i.e., 1 × 10⁻⁶). 7 The FTO conductive glass, with an area of ​​10 mm above and below the etched surface (Ω), was then cleaned using deionized water, acetone, ethanol, and isopropanol, respectively, for 15 minutes each. It was then placed in a 70°C drying oven for 120 minutes to remove residual organic impurities, resulting in a clean and dry substrate material. This substrate was then treated with UV-ozone for 15 minutes and transferred to a nitrogen-filled glove box. The thickness of the first electrode is approximately 500 nm.

[0477] Step S2, preparation of the hole transport layer: PTAA is used as the hole transport material. PTAA is dissolved in toluene to form a 2 mg / mL solution. This solution is coated onto an FTO substrate and then annealed at 100°C for 10 min to obtain a thin and flat hole transport layer (approximately 20 nm thick). The hole transport layer is used to extract photogenerated holes and block electrons.

[0478] Step S3, Preparation of the perovskite layer:

[0479] Step S3-1, Preparation of perovskite precursor solution: PbI2, FAI, PbBr2, MABr, and MACl (MACl with a molar percentage of 20 mol% relative to Pb, used as an additive) are dissolved in a mixed solvent of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at a volume ratio of 5.5:1 (first solvent), according to FAI... 0.95 MA 0.05 Pb(I 0.95 Br 0.05 The elements in the chemical formula were mixed to prepare a basic solution of perovskite precursor with a molar ratio of 1.4 mol / L. The solution was stirred overnight in a glove box filled with nitrogen to obtain the perovskite precursor solution.

[0480] Step S3-2, Preparation of perovskite mesophase film (using medium-level VCD) + Introduction of the first additive: The perovskite precursor solution obtained in step S3-1 is filtered using a polytetrafluoroethylene filter. The filtered precursor solution is coated onto the hole transport layer and subjected to medium-level vacuum drying for 20 seconds (temperature 25℃, pressure 100Pa) to remove some of the first solvent, obtaining the perovskite mesophase film (or referred to as the perovskite precursor film). The first additive, phenylethyl ammonium chloride (PEACl, the first additive), is dissolved at a concentration of 2 mg / mL in a mixed solvent (IPA:DMF=99:1, volume ratio) to obtain an additive dispersion. The additive dispersion is then coated onto the perovskite mesophase film with a coating thickness of approximately 7 μm (wet film), and allowed to stand at 25℃ (≤3%RH) for 3 min to allow the first additive to diffuse along the mesophase boundary.

[0481] Step S3-3: The perovskite mesophase film layer coated with the additive dispersion is subjected to laser annealing. Based on nanosecond pulsed laser, a 450nm wavelength blue laser is used at 90℃ and a power of 150W (first temperature, corresponding to the first annealing stage). The laser spot covers the entire surface (i.e., the laser spot covers an area of ​​at least 2m²). 2 The perovskite wet film is irradiated for 4 seconds, and then the power is increased to 600W and held at 100℃ (the second temperature, corresponding to the second annealing stage) for 10 seconds to form a perovskite thin film (corresponding to the perovskite layer) with a thickness of about 500nm.

[0482] Step S4, Preparation of the electron transport layer: Fullerene C 60 An electron transport layer solution was prepared by dissolving 20 mg / mL in o-dichlorobenzene. The electron transport layer solution was then coated using a slit coating method with a moving speed of 50 mm / s and a liquid injection speed of 130 μL / s to prepare a wet electron transport layer film on the perovskite layer. After drying, an electron transport layer with a thickness of approximately 40 nm was obtained.

[0483] Step S5, preparation of the interface layer: Dissolve BCP in methanol to form a 0.5 mg / mL solution, coat it on the electron transport layer, and then anneal it on a heating stage at 70°C for 10 minutes to form an interface layer (as a hole blocking layer) with a thickness of about 5 nm.

[0484] The aforementioned half-component is laser-etched with P2, which has a width of 60 μm and a depth down to the FTO layer. The spacing between P2 and P1 is 100 μm.

[0485] Step S6, fabrication of the back electrode (second electrode): Using a vacuum thermal evaporation deposition apparatus, a 100 nm thick copper electrode is deposited on the interface layer prepared in step S5 at a rate of 0.5~2 Å / s (1 Å / s in this example); P3 laser scribing is performed, with a width of 50 μm and a depth reaching the FTO layer. The interval between P3 and P2 is 80 μm, and the positions of the etched lines are P1 / P2 / P3 in sequence. (See reference...) Figure 9 Optoelectronic devices were fabricated.

[0486] The prepared optoelectronic devices can be used as photovoltaic devices for device performance testing.

[0487] Examples 2-3 used essentially the same method as Example 1 to prepare optoelectronic devices including a perovskite layer, the difference being the different resting time in step S3-2, as shown in Table 1. The remaining steps were the same as in Example 1.

[0488] Example 4 uses essentially the same method as Example 1 to prepare an optoelectronic device including a perovskite layer. The difference is that the concentration of the perovskite precursor material in the perovskite precursor solution in step S3-1 is different, as shown in Table 1. The remaining operation steps are the same as in Example 1.

[0489] Step S3-1, Preparation of perovskite precursor solution: PbI2, FAI, PbBr2, MABr, and MACl (MACl molar percentage relative to Pb is 20 mol%) are dissolved in a mixed solvent of dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at a volume ratio of 5.5:1, according to FAI... 0.95 MA 0.05 Pb(I 0.95 Br 0.05 The elements in the chemical formula were mixed in a molar ratio of 3 to prepare a basic solution of perovskite precursor of 2.0 mol / L. The solution was stirred overnight in a glove box filled with nitrogen to obtain perovskite precursor solution.

[0490] Step S3-2: Except that the perovskite precursor solution is replaced with the perovskite precursor solution provided in step S3-1 of this example, the same operating steps as in Example 1 are used to prepare the perovskite intermediate phase film layer.

[0491] Step S3-3, except that the perovskite mesophase film layer is replaced with the perovskite mesophase film layer prepared in step S3-2 in this example, the other operation steps are the same as in Example 1, and the thickness of the final perovskite layer is about 930 nm.

[0492] Examples 5-8 employ essentially the same method as Example 1 to prepare optoelectronic devices including a perovskite layer. The difference lies in that one or two parameters, such as the type and concentration of the first additive in the additive dispersion in step S3-2, are different (see Table 1). The remaining operational steps are the same as in Example 1.

[0493] In Example 9, the composition of the target perovskite material was changed by replacing FA. 0.95 Cs 0.05 For PbI3, please refer to Table 1. The remaining operating steps are the same as in Example 1.

[0494] Comparative Example 1 prepared an optoelectronic device including a perovskite layer using essentially the same method as Example 1, except that step S3 was different, omitting the coating of the additive dispersion and the standing step, and using different drying and annealing methods, changing the vacuum drying time, and replacing laser annealing with hot-stage annealing. The remaining operation steps were the same as in Example 1, and can also be found in Table 1.

[0495] Step S3-1 is the same as in Example 1.

[0496] Step S3-2: Filter the solution obtained in step S3-1 using a polytetrafluoroethylene filter head, coat the filtered precursor liquid onto the hole transport layer, and vacuum dry for 60 seconds (temperature 25℃, pressure 100Pa) to remove the first solvent in the perovskite precursor liquid as much as possible, and obtain a perovskite precursor film.

[0497] Step S3-3: Transfer the perovskite precursor film to a heating stage and anneal at 110°C for 8 minutes to obtain a fully crystallized perovskite layer.

[0498] Comparative Example 2. An optoelectronic device comprising a perovskite layer was prepared using essentially the same method as in Example 1, except that step S3 was different, omitting the coating of the additive dispersion and the standing step, and also changing the laser annealing method (to a single-power annealing method). The remaining operation steps were the same as in Example 1, and can also be found in Table 1.

[0499] Step S3-1: The perovskite precursor solution is prepared using the same method as in Example 1.

[0500] Step S3-2, omitting the first additive and settling: Filter the perovskite precursor liquid obtained in step S3-1 using a polytetrafluoroethylene filter head, coat the filtered perovskite precursor liquid onto the hole transport layer, and perform medium vacuum drying for 20 seconds (temperature 25℃, pressure 100Pa) to remove some of the solvent, thereby obtaining a perovskite precursor film.

[0501] Step S3-3: The perovskite precursor film is laser annealed using a nanosecond pulsed laser with a wavelength of 450nm and a power of 600W. The film is held at 100℃ for 15s to form a perovskite film.

[0502] Comparative Example 3. An optoelectronic device comprising a perovskite layer was prepared using essentially the same method as in Example 1, except that the laser gradient annealing in step S3-3 was replaced with hot-stage annealing. The remaining steps were the same as in Example 1, and can also be found in Table 1.

[0503] Step S3-3: Transfer the perovskite mesophase film coated with additive dispersion to a heating stage and anneal at 110°C for 8 minutes to obtain a fully crystallized perovskite layer.

[0504] Comparative Example 4. An optoelectronic device comprising a perovskite layer was prepared using essentially the same method as in Example 1, except that the step of coating the additive dispersion was performed after the perovskite crystallization was completed. The remaining operational steps were the same as in Example 1, and can also be found in Table 1.

[0505] S3 uses the following method to prepare the perovskite layer and coating additive dispersion:

[0506] Step S3-1: Prepare perovskite precursor solution using the same method as in Example 1;

[0507] Step S3-2, Preparation of perovskite intermediate phase film layer: The perovskite precursor liquid obtained in step S3-1 is filtered using a polytetrafluoroethylene filter head. The filtered precursor liquid is coated on the hole transport layer and subjected to medium vacuum drying for 20 seconds (temperature 25℃, pressure 100Pa) to remove part of the first solvent, thereby obtaining the perovskite precursor film.

[0508] Step S3-3: The perovskite precursor film is annealed on a hot stage. The perovskite precursor film is transferred to the hot stage and annealed at 110°C for 8 minutes to form a perovskite film with a thickness of about 500 nm.

[0509] Steps S3-4: The first additive, phenylethyl ammonium chloride (PEACl, the first additive), is dissolved in isopropanol at a concentration of 2 mg / mL to obtain an additive dispersion. This dispersion is then coated onto the perovskite layer and allowed to stand at 25°C for 30 seconds, followed by 100... o C annealing for 10 seconds, thickness approximately 3nm.

[0510] II. Testing and Analysis Methods

[0511] (a) Testing of materials, membrane samples, and samples obtained from disassembly, etc.

[0512] 1. Grazing incidence wide-angle X-ray scattering (GIWAXS) method:

[0513] (1) Preparation of perovskite thin film samples: In a low humidity (relative humidity less than 2%) or inert gas environment, the perovskite optoelectronic device is etched open with a diamond glass cutter. At this time, the backplate glass, along with the adhesive film and the second electrode, is separated from the perovskite layer. The side with the perovskite layer is picked up with tweezers. Using a pipette or dropper, a small amount of chlorobenzene and o-xylene solvent is brought into partial and brief contact with the exposed perovskite layer. The surface of the perovskite layer is repeatedly rinsed to remove the electron transport layer material on the surface of the perovskite layer, resulting in the bare perovskite layer. The sample is fixed on the sample stage with conductive adhesive and placed in a vacuum chamber.

[0514] (2) Based on the GIWAXS beamline of the Shanghai Synchrotron Radiation Facility. It features a 5.5-micron monochromatic light detector to resolve minute lattice variations in perovskite thin films, and a white light detector to support rapid scanning. For perovskite thin film samples, the grazing incidence angle was set to 0.2°~0.5° (close to the critical angle for total internal reflection) to enhance surface sensitivity; the X-ray wavelength was selected as 0.1-0.2 nm (tunable at the synchrotron radiation source). A two-dimensional detector was used to record diffraction spots and analyze the (hkl) crystal plane distribution; the orientation factor (e.g., ...) was calculated using the Debye-Scherrer ring integral intensity. <100> (Face preference orientation degree).

[0515] Based on the GIWASX test results, the types and proportions of cubic, tetragonal, orthorhombic, and other phases in the perovskite layer can be confirmed, as well as the different types of crystal faces, which can be referred to in the previous description.

[0516] 2. Dielectric constant of the perovskite layer

[0517] Microwave resonance method: When the solid material under test is placed in a microwave resonant environment, the dielectric properties of the material change the electromagnetic field distribution within the cavity, causing a shift in the resonant frequency. By measuring this frequency change and combining it with the geometric parameters of the resonant cavity, the relative permittivity of the material can be calculated.

[0518] The dielectric constant of the perovskite layer was measured using a Japanese AET microwave dielectric constant tester.

[0519] 3. XRD analysis was performed to detect the crystallization of the perovskite mesophase film.

[0520] Test instrument: Bruker D8 Advance.

[0521] XRD test parameters: The X-ray source was Cu Kα1 (wavelength 1.54056 Å), the scanning range (2θ) was 0~80°, the scanning rate was 10° / min, and the incident angle range was 2°~90°. The X-ray tube was set to TWIST-TUBE, and the detector was EIGER2.

[0522] The X-ray diffractometer is started to begin measurements. X-rays pass through the sample, interact with the crystal, and produce diffracted light, which is then received and recorded by the detector to obtain the XRD data of the perovskite layer. First, background is subtracted by linear or polynomial fitting, and then the target peaks are marked with their ranges.

[0523] 4. Confirm the distribution of residual solvent in the perovskite mesophase film layer.

[0524] Test method: Time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0525] Instrument: PHI nanoTOF Ⅲ Time-of-Flight SIMS.

[0526] The higher solvent residue at the lower interface compared to the upper interface was confirmed by the following method: TOF-SIMS was used to perform in-depth profiling analysis of the perovskite mesophase film after vacuum drying (VCD) treatment, and the solvent molecule signal intensity (I1) at different depths was monitored. This signal intensity (I0) was then compared with that in the coated perovskite mesophase film before VCD treatment to obtain the solvent mass M1 in the VCD-treated sample and the solvent mass M0 in the coated sample before VCD treatment. This yielded the percentage of solvent residue F in the perovskite mesophase film. S =M1 / M0×100%.

[0527] (ii) Device performance testing

[0528] 1. Initial performance of the device (optoelectronic devices used in solar cells)

[0529] Under normal temperature and pressure (25℃, 1 atmosphere), a standard light source with AM1.5G was used to simulate sunlight, conforming to the national standard IEC61215. The light intensity was corrected using crystalline silicon solar cells to achieve the intensity of one solar cell. The current-voltage characteristic curve (i.e., current-voltage curve) of the solar cell under the illumination of the light source was measured using a four-channel digital source meter (Keithley 2440). The open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF), and photoelectric conversion efficiency (PCE) of the solar cell were obtained.

[0530] The photoelectric conversion efficiency (PCE) is calculated as follows:

[0531] PCE = Pout / Pin

[0532] = Voc×Jsc×[(Vmpp×Jmpp) / (Voc×Jsc)] / Pin

[0533] = Voc×Jsc×FF / Pin

[0534] Wherein, Pout, Pin, Voc, Jsc, Vmpp, Jmpp, and FF represent the battery's operating output power, incident light power, open-circuit voltage, short-circuit current, maximum power point voltage, maximum power point current, and fill factor, respectively. The incident light power is 100 mW / cm². 2 .

[0535] 2. Device stability determination (aging test)

[0536] After the initial performance test of the device is completed, the cell under test is placed in an atmospheric environment (relative humidity of 65%-85%, ambient temperature of about 15℃-40℃) and left in the dark for 1000 hours. The energy conversion efficiency is then tested again (each test continues until there is no hysteresis in the forward and reverse scans, and the photoelectric conversion efficiency is recorded). The ratio of the photoelectric conversion efficiency after 1000 hours of atmospheric placement to the initial efficiency is calculated and used as the normalized efficiency of the solar cell after 1000 hours of placement, which can be denoted as "1000h retention rate".

[0537] 1000h retention rate = retest efficiency / initial efficiency × 100%. The higher the initial normalized efficiency, the better the device stability.

[0538] III. Test Result Analysis

[0539] In the optoelectronic devices prepared in Examples 1-9, the crystalline phase of the perovskite layer all includes a cubic phase with a high mass percentage, and the content of other phases all satisfies the condition that the mass percentage of other phases in the non-cubic phase is less than or equal to 5%. For example, no other phases can be detected in the perovskite layer in Examples 1-4. In addition, the mass percentage of the tetragonal phase in the perovskite layer is higher than that of the orthorhombic phase. See Table 2.

[0540] In the optoelectronic devices prepared in Examples 1-9, the dielectric constant of the perovskite layer is in the range of 5 to 16. For example, the dielectric constant of the perovskite layer in Examples 1-4 is ≥5, further in the range of 5 to 16, and even further in the range of 6.5 to 15. See Table 2 for details.

[0541] The optoelectronic devices prepared in Examples 1-9 all exhibit high photoelectric conversion efficiencies, as shown in Table 2. Exemplarily, the photoelectric conversion efficiency of Example 1 is higher than that of Comparative Examples 1-4.

[0542] Furthermore, the optoelectronic devices prepared in Examples 1-9 also exhibit high device stability. See Table 2 for details. Exemplarily, the device stability of Example 1 is higher than that of Comparative Examples 1-4.

[0543] The dominant crystal planes of each crystalline phase in the perovskite layer, taking Example 1 as an example, can be found in Table 3.

[0544] Taking Example 1 as an example, according to the TOF-SIMS test results, the first additive remaining in the perovskite layer is mainly distributed at the grain boundaries of the perovskite grains and basically does not enter the perovskite crystalline phase.

[0545] Taking Example 1 as an example, based on the XRD test results of the perovskite mesophase film, no obvious characteristic diffraction peaks of the perovskite crystal phase were observed, indicating that the perovskite mesophase film obtained before coating with the additive dispersion had no significant crystallinity. However, after annealing, stronger diffraction peaks of the perovskite crystal phase were observed in the XRD pattern of the formed perovskite layer.

[0546] In Comparative Example 1, the vacuum drying time was extended to 60 seconds, and laser annealing was replaced with hot-stage annealing. This resulted in the first additive being unable to be effectively removed to the grain boundaries by the residual solvent, leading to an increase in defects within the perovskite crystal, a decrease in the dielectric constant, a decrease in the effective diffusion distance of charge carriers, a decrease in the photoelectric conversion efficiency of the optoelectronic device, and a decrease in device stability. Simultaneously, hot-stage annealing could not directionally remove the solvent, resulting in uneven additive distribution. In Comparative Example 1, the higher content of the triclinic phase led to a decrease in the absorbance of the perovskite; the lower content of the tetragonal phase in the non-cubic phase made the cubic phase more prone to transformation into the non-cubic phase, resulting in a decrease in the stability of the cubic phase.

[0547] In Comparative Example 2, the steps of coating the additive dispersion and allowing it to stand were omitted, which resulted in the perovskite grains not being effectively passivated. A large number of defects existed within the crystal and at the grain boundaries, leading to a decrease in the photoelectric conversion efficiency of the optoelectronic device and a reduction in device stability.

[0548] In Comparative Example 3, laser annealing was replaced with hot stage annealing, which made it impossible to directionally remove the solvent, resulting in uneven distribution of the first additive, reduced photoelectric conversion efficiency of the optoelectronic device, and decreased device stability.

[0549] In Comparative Example 4, the step of coating the additive dispersion was set after the perovskite crystallization was completed. This resulted in the first additive being unable to effectively passivate defects in the crystal, leading to a large number of defects in the crystal. Consequently, the dielectric constant and the effective charge migration distance decreased, resulting in a decrease in the photoelectric conversion efficiency of the optoelectronic device and a reduction in device stability.

[0550] Table 1.

[0551]

[0552] In Table 1, "concentration of the first additive" refers to the concentration of the first additive in the additive dispersion.

[0553] In Table 1, "residual solvent content" refers to the percentage of the residual mass of the first solvent in the film after vacuum drying during step S3-2 of preparing the perovskite mesophase film, compared to the initial mass of the first solvent in the film before vacuum drying.

[0554] In Table 1, PEACl is phenylethyl ammonium chloride (CAS: 156-28-5), PEABr is phenylethyl ammonium bromide (CAS: 53916-94-2), OACl is octyl ammonium chloride (CAS: 1838-08-0), and PACl is propyl ammonium chloride (CAS: 556-53-6, where the octyl group in OACl is replaced with the propyl group).

[0555] Table 2.

[0556]

[0557] Table 3. Preferred crystal facets of the perovskite crystalline phase in Example 1.

[0558]

[0559] In Table 3, the dominant crystal plane in the cubic phase is (100), and the full width at half maximum (FWHM) of the diffraction peaks of the (100) plane is in the range of 0.05° to 0.20°, approximately 0.09°.

[0560] It is understood that the above embodiments and examples are merely illustrative. Those skilled in the art may also use other preparation methods to obtain the optoelectronic device of the first aspect of this application. For example, the optoelectronic device described in the first aspect of this application may be obtained by adjusting other process parameters without using the aforementioned first additive. This application does not limit the preparation method of the optoelectronic device described in the first aspect.

[0561] The descriptions of the various implementation methods and embodiments above tend to emphasize the differences between them. Similarities or resemblances can be referenced interchangeably, and for the sake of brevity, they will not be repeated here. The technical features of the implementation methods and embodiments described above can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments have been described. However, as long as the combinations of these technical features do not contradict each other, they should be considered within the scope of this specification.

[0562] It should be noted that this application is not limited to the above-described embodiments and examples. The above-described embodiments and examples are merely examples, and any embodiments and examples that have the same structure and achieve the same effect as the technical concept within the scope of this application are included in the technical scope of this application. The embodiments and examples described above only illustrate several embodiments and examples of this application, and although the descriptions are relatively detailed, they should not be construed as limiting the scope of the patent. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments or examples, and other ways of constructing embodiments or examples by combining some of the constituent elements of the embodiments or examples, are also included in the scope of this application without departing from the spirit of this application.

Claims

1. An optoelectronic device, characterized in that, It includes a perovskite layer, wherein the perovskite layer comprises perovskite grains, and the crystalline phase of the perovskite grains includes a cubic phase and a non-cubic phase; The cubic phase accounts for 97% or more of the mass of the perovskite layer; The non-cubic phase includes at least one of tetragonal phase, orthorhombic phase, and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase. The dielectric constant of the perovskite layer is greater than or equal to 5.

2. The optoelectronic device according to claim 1, characterized in that, The one-dimensional integral curve of the GIWAXS two-dimensional diffraction pattern of the perovskite layer satisfies one or more of the following characteristics: (t1) The dominant crystal plane of the cubic phase is one of (100) and (111); (t2) The dominant crystal plane of the tetragonal phase is one of (100) and (111); (t3) The dominant crystal plane of the orthorhombic phase is one of (100) and (111).

3. The optoelectronic device according to claim 1 or 2, characterized in that, The dielectric constant of the perovskite layer is 5~16, and can be selected as 6.5~15.

4. The optoelectronic device according to any one of claims 1 to 3, characterized in that, The thickness of the perovskite layer is 200nm~1500nm, and can be selected as 400nm~1000nm.

5. The optoelectronic device according to any one of claims 1 to 4, characterized in that, The perovskite layer satisfies one or more of the following characteristics: (a1) The tetragonal phase accounts for more than or equal to 65% of the mass of the non-cubic phase; (a2) The orthorhombic phase accounts for less than or equal to 30% of the mass of the non-cubic phase; (a3) The other phases include at least the triclinic phase.

6. The optoelectronic device according to claim 2, characterized in that, Based on the XRD diffraction pattern of the perovskite layer, the dominant crystal plane of the cubic phase is (100) or (111); when the dominant crystal plane of the cubic phase is (100), the half-width at half-maximum (WHM) of the diffraction peak of the (100) plane is 0.05°~0.20°; or, when the dominant crystal plane of the cubic phase is (111), the half-width at half-maximum (WHM) of the diffraction peak of the (111) plane is 0.05°~0.30°.

7. The optoelectronic device according to any one of claims 1 to 6, characterized in that, The perovskite layer includes a first additive, which is an organic material; at least a portion of the first additive is located at the grain boundaries of the perovskite grains. Optionally, the first additive includes at least one of hydrocarbon-based haloamines and hydrocarbon-based pseudohalogenated amines; Optionally, the first additive includes C 3-20 Hydrocarbon-based haloamines, and optionally, the first additive includes C 6-20 Hydrocarbon-based halogenated amines.

8. The optoelectronic device according to claim 7, characterized in that, The halogen in the alkyl halogenated amine includes at least one of chlorine, bromine, and iodine.

9. The optoelectronic device according to claim 8, characterized in that, The perovskite layer includes a first perovskite material, wherein the molar percentage of the first additive to the first perovskite material in the perovskite layer is 1% to 10%, and the molar amount of the first perovskite material is calculated based on the molar amount of divalent cations in the first perovskite material.

10. The optoelectronic device according to claim 8 or 9, characterized in that, In the perovskite layer, the content of the first additive at the grain boundaries of the perovskite grains is higher than its content within the crystal phase of the perovskite grains.

11. The optoelectronic device according to any one of claims 1 to 10, characterized in that, The average size of the perovskite grains in the perovskite layer is 0.6 μm to 3 μm.

12. The optoelectronic device according to any one of claims 1 to 11, characterized in that, The perovskite layer includes a first perovskite material; the first perovskite material includes at least one halogen selected from iodine, chlorine, and bromine. Optionally, the first perovskite material includes iodine and bromine. Optionally, the molar ratio of iodine to bromine in the perovskite layer is (0~1):(0~1), and more preferably (0.8~1):(0~0.2).

13. The optoelectronic device according to any one of claims 1 to 12, characterized in that, The perovskite layer comprises a first perovskite material; the first perovskite material comprises at least one of formamidinium ionic groups and methylamine ionic groups; optionally, in the perovskite layer, the molar ratio of formamidinium ionic groups to methylamine ionic groups is q. FA :q MA , where q FA The value is 0.8~1, q MA The range is 0 to 0.

2. Optionally, q FA The value is 0.9~1, q MA The value is 0.05~0.1; Optionally, q FA q MA The sum is 0.95~1, and optionally, q FA q MA The sum is 1.

14. The optoelectronic device according to any one of claims 1 to 13, characterized in that, The thickness direction of the perovskite layer is denoted as the Z-direction. On a projection plane perpendicular to the Z-direction, the area of ​​the perovskite layer is greater than or equal to 0.09 cm². 2 Optionally, greater than or equal to 1m 2 .

15. The optoelectronic device according to any one of claims 1 to 14, characterized in that, The optoelectronic devices include photovoltaic devices or light-emitting devices.

16. The optoelectronic device according to any one of claims 1 to 15, characterized in that, The optoelectronic device is a photovoltaic device; the photovoltaic device includes a solar cell, and the solar cell includes the perovskite layer.

17. The optoelectronic device according to any one of claims 1 to 16, characterized in that, The optoelectronic device includes a solar cell, which is a multi-junction solar cell. The multi-junction solar cell includes a first cell unit, which includes the perovskite layer.

18. The optoelectronic device according to claim 17, characterized in that, The multijunction solar cell further includes a second cell stacked with the first cell; the second cell and the first cell are connected by an interconnect layer, or the second cell and the first cell are isolated by an insulating layer; the second cell includes a second light-absorbing layer, and the band gap of the second light-absorbing layer is different from that of the perovskite layer.

19. The optoelectronic device according to claim 18, characterized in that, The second light-absorbing layer in the second battery cell includes a semiconductor active material, which includes one or more of the following: a second perovskite material, a silicon-containing semiconductor material, copper zinc tin sulfide, copper zinc tin selenide, copper zinc tin selenide sulfide, copper indium gallium selenide, copper indium gallium diselenide, copper indium selenide, cadmium telluride, gallium arsenide, and organic active materials.

20. The optoelectronic device according to claim 18 or 19, characterized in that, The multi-junction solar cell includes a first electrode, a perovskite layer, an interconnect layer, a second light-absorbing layer, and a second electrode stacked together; wherein the interconnect layer is located between the perovskite layer and the second light-absorbing layer; the first electrode is located on the side of the perovskite layer opposite to the interconnect layer, and the second electrode is located on the side of the second light-absorbing layer opposite to the interconnect layer; or, The multi-junction solar cell includes a first electrode, a perovskite layer, a third electrode, an insulating layer, a fourth electrode, a second light-absorbing layer, and a second electrode stacked together; wherein the third electrode, the insulating layer, and the fourth electrode are stacked between the perovskite layer and the second light-absorbing layer, the third electrode is disposed on the side of the insulating layer facing the perovskite layer, the fourth electrode is disposed on the side of the insulating layer facing the second light-absorbing layer, the first electrode is located on the side of the perovskite layer away from the third electrode, and the second electrode is located on the side of the second light-absorbing layer away from the fourth electrode.

21. The optoelectronic device according to any one of claims 1 to 20, characterized in that, The optoelectronic device is a photovoltaic device; the optoelectronic device satisfies one or more of the following characteristics: (b1) The perovskite layer is contained in the inverse or formal structure of the optoelectronic device; (b2) The optoelectronic device includes a first charge transport layer and a second charge transport layer, wherein the perovskite layer is located between the first charge transport layer and the second charge transport layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer; (b3) The optoelectronic device includes a first electrode and a second electrode, and the perovskite layer is disposed between the first electrode and the second electrode; Optionally, the optoelectronic device includes at least one charge transport layer and the perovskite layer disposed between the first electrode and the second electrode; the at least one charge transport layer includes at least one of a first charge transport layer located between the first electrode and the perovskite layer and a second charge transport layer located between the second electrode and the perovskite layer; wherein, one of the first charge transport layer and the second charge transport layer is a hole transport layer and the other is an electron transport layer.

22. A method for fabricating an optoelectronic device, characterized in that, Includes the following steps: A perovskite precursor solution is provided; wherein the perovskite precursor solution comprises a perovskite precursor material and a first solvent; The perovskite precursor solution is coated and vacuum dried to remove part of the first solvent, thus preparing a perovskite intermediate phase film layer. An additive dispersion containing a first additive and a second solvent is coated onto the surface of the perovskite mesophase film layer, and after standing, laser gradient annealing is performed to form a perovskite layer; wherein, the first additive is an organic material, and the second solvent includes isopropanol and N,N-dimethylformamide; the laser gradient annealing includes a first-stage annealing at a first temperature, and then a second-stage annealing at a second temperature; the first temperature is 85℃~95℃, and the second temperature is higher than the first temperature; The formed perovskite layer comprises perovskite grains, the crystalline phases of which include cubic and non-cubic phases; the cubic phase accounts for more than or equal to 97% of the mass of the perovskite layer; the non-cubic phase includes at least one of tetragonal, orthorhombic, and other phases; the other phase accounts for less than or equal to 5% of the mass of the non-cubic phase; the tetragonal phase accounts for a higher mass of the non-cubic phase than the orthorhombic phase; and the dielectric constant of the perovskite layer is greater than or equal to 5.

23. The method for fabricating an optoelectronic device according to claim 22, characterized in that, The method for fabricating the optoelectronic device satisfies one or more of the following characteristics: (c1) In the step of performing vacuum drying to remove part of the first solvent, the temperature of the vacuum drying is 0°C to 70°C, the pressure of the vacuum drying is 5Pa to 500Pa, and the duration of the vacuum drying is 2s to 40s. (c2) In the second solvent, the volume ratio of isopropanol to N,N-dimethylformamide is (25~99):1; (c3) The mass-volume concentration of the first additive in the additive dispersion is 0.5 mg / mL to 10 mg / mL; (c4) The temperature for the standing test is 0℃~70℃, the standing time is 2min~5min, and the ambient humidity for the standing test is less than or equal to 3%RH; (c5) The duration of the first stage annealing at the first temperature is 1s to 5s; (c6) The second stage of annealing is carried out at a temperature of 95℃~105℃ for a duration of 5s~15s.

24. An electrical appliance, characterized in that, It includes at least one of the optoelectronic devices according to any one of claims 1 to 21 and the optoelectronic devices prepared by the preparation method of any one of claims 22 to 23.

25. A power generation device, characterized in that, It includes at least one of the optoelectronic devices according to any one of claims 1 to 21 and the optoelectronic devices prepared by the preparation method of any one of claims 22 to 23.

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