Light-emitting photovoltaic device and manufacturing method and application thereof

Abstract

The invention discloses a light-emitting photovoltaic device and a manufacturing method and application thereof.The device comprises a first electrode layer, a hole transport layer, a photoelectric conversion function layer, an electron transport layer and a second electrode layer which are sequentially connected, and the photoelectric conversion function layer comprises a perovskite layer with a wide optical band gap; and the energy levels of the electron transport layer, the hole transport layer and the photoelectric conversion function layer are matched, so that the light-emitting photovoltaic device can realize a light-emitting function and a photovoltaic function at the same time. The light-emitting photovoltaic device integrates a photovoltaic function and a light-emitting function, has the advantages of being low in cost, easy to scale, high in energy conversion efficiency, capable of achieving high open-circuit voltage, capable of being applied to a flexible substrate and the like, and is suitable for various application scenes such as intelligent building equipment and electronic products. And a brand new technical scheme is provided for the fields of self-powered intelligent equipment, transparent display equipment and the like.

Description

Technical Field

[0001] This invention belongs to the field of optoelectronic energy technology, specifically relating to a light-emitting photovoltaic device, its manufacturing method, and its application. Background Technology

[0002] With the increasing global demand for renewable energy, solar energy, as a green and clean energy source, has gradually become an important direction for energy transformation in various countries. Solar photovoltaic technology has been widely used in various fields due to its sustainability, low carbon emissions and abundant resources.

[0003] Solar photovoltaic (PV) devices, utilizing photovoltaic technology, can effectively convert solar energy into electrical energy. Furthermore, transparent PV devices maintain good light transmittance, effectively combining architectural aesthetics with energy utilization needs. This allows buildings to not only capture solar energy but also maintain transparency in lighting and visibility, making their application on transparent surfaces such as buildings, windows, and vehicle windows a highly promising market opportunity. Therefore, luminescent photovoltaic devices are widely regarded as an ideal solution for next-generation green buildings.

[0004] However, existing solar photovoltaic devices still face challenges in balancing high transmittance and high open-circuit voltage. Furthermore, solar photovoltaic devices must be connected to other light-emitting devices to achieve their light-emitting function, rather than directly integrating photovoltaic and light-emitting functions on the same device. As a result, light-emitting systems using solar photovoltaic devices often suffer from high costs and bulky structures. Summary of the Invention

[0005] To overcome the shortcomings of the prior art, one objective of this invention is to propose a light-emitting photovoltaic device. This device aims to overcome the bottleneck of existing technologies where it is difficult to integrate light-emitting and photovoltaic functions in light-emitting photovoltaic devices, and where high transmittance, high open-circuit voltage, and high brightness are mutually constrained. Through optimized material selection and device structure, this device not only achieves integrated light-emitting photovoltaic functionality but also successfully achieves high visible light transmittance (73%), high open-circuit voltage (2V and above), and high luminous brightness (16000 cd / m²). 2 Excellent performance (and above).

[0006] The second objective of this invention is to provide an application of a transparent device in smart buildings, offering a novel technical solution for fields such as self-powered smart windows and indoor lighting, thereby enhancing the practical application value of photovoltaic devices.

[0007] The third objective of this invention is to provide an application of transparent devices in electronic products, offering a novel technical solution for self-powered intelligent devices and transparent displays, thereby enhancing the practical application value of light-emitting photovoltaic devices.

[0008] The first aspect of the present invention is to provide a photovoltaic device that achieves high on-voltage photovoltaic performance and high brightness luminous performance on the same device while ensuring high transmittance. The luminous photovoltaic device includes a first electrode layer, a hole transport layer, a photoelectric conversion functional layer, an electron transport layer and a second electrode layer connected in sequence.

[0009] The photoelectric conversion functional layer includes a perovskite layer with a band gap greater than 2.0V;

[0010] Both the electron transport layer and the hole transport layer contain materials whose energy levels match those of the photoelectric conversion functional layer;

[0011] The difference between the LUMO energy level of the electron transport layer and the bottom conduction band energy level of the perovskite layer is no greater than 0.3 eV, and the difference between the HOMO energy level of the hole transport layer and the top valence band energy level of the perovskite layer is no greater than 0.3 eV.

[0012] Specifically, the perovskite layer includes a perovskite thin film with a pre-adjusted optical bandgap to enhance the absorption of blue light and ultraviolet light and enhance the transmittance of visible light and near-infrared light, wherein the optical bandgap width of the perovskite thin film is not less than a preset width value.

[0013] The electron transport layer includes a transport layer that matches the energy level of the perovskite layer, and the thickness of the electron transport layer ranges from 20 to 75 nm.

[0014] Optionally, the second electrode layer includes a transparent electrode layer, which may include a conductive polymer layer, a metal layer, an oxide layer, a carbon-based material layer, or a composite transparent electrode layer.

[0015] Alternatively, the second electrode layer may include an opaque electrode layer, which may include a conductive polymer layer, a metal layer, an oxide layer, a carbon-based material layer, or a composite structure.

[0016] Furthermore, the light-emitting photovoltaic device also includes a buffer wetting layer disposed between the hole transport layer and the photoelectric conversion functional layer, and a work function modification layer disposed between the electron transport layer and the second electrode layer;

[0017] The buffer wetting layer includes a PVP layer, a PEIE layer, or a PEG layer, and the thickness of the buffer wetting layer ranges from 0.1 to 15 nm.

[0018] The work function modification layer includes a lithium fluoride layer, and the thickness of the work function modification layer ranges from 0.1 to 15 nm.

[0019] Furthermore, the hole transport layer includes a first hole transport layer connected to the first electrode layer and a second hole transport layer connected to the photoelectric conversion functional layer;

[0020] The first hole transport layer includes a PTAA layer, a Poly-TPD layer, or a NiOx layer, etc., and the thickness of the first hole transport layer ranges from 1 to 40 nm.

[0021] The second hole transport layer includes a 2PACz layer, a 4PACz layer, a Poly-2PACz layer, or a Poly-4PACz layer, etc., and the thickness of the second hole transport layer ranges from 1 to 40 nm.

[0022] This invention also proposes a preparation method for preparing the light-emitting photovoltaic device as described above, the method comprising:

[0023] The first electrode layer is prepared by cleaning the transparent conductive substrate with glass cleaner, ultrasonically treating it in deionized water and ethanol respectively, drying it with nitrogen gas and then irradiating it with ultraviolet light.

[0024] After the hole transport layer is prepared, a buffer wetting layer is prepared by solution spin coating, and the hole transport layer and the photoelectric conversion functional layer are prepared sequentially on the prepared buffer wetting layer by solution spin coating.

[0025] Under conditions where the vacuum level is less than a preset vacuum value, the electron transport layer is prepared by thermal evaporation. A work function adjustment layer is deposited on the prepared electron transport layer by thermal evaporation, and the second electrode layer is prepared on the deposited work function adjustment layer.

[0026] A second aspect of the present invention is to provide an intelligent building device, the intelligent building device including a light-emitting photovoltaic device as described above, the intelligent building device further including an electrochromic device powered by the light-emitting photovoltaic device, the light-emitting photovoltaic device and the electrochromic device forming a circuit loop;

[0027] The circuit loop is used to deepen the color of the electrochromic device and reduce its transmittance when a positive bias voltage is applied.

[0028] The circuit loop is also used to make the color of the electrochromic device lighter and increase its transmittance when a negative bias voltage is applied.

[0029] A third aspect of the present invention provides the application of transparent light-emitting devices in electronic products. Specifically, an electronic device is proposed, including an electrical device and a light-emitting photovoltaic device as described above, wherein the light-emitting photovoltaic device covers the surface of the electrical device to convert light energy into electrical energy and supply power to the electrical device.

[0030] The present invention has at least the following beneficial effects:

[0031] The light-emitting photovoltaic device proposed in this invention reduces the low-energy disorder of the photoelectric functional conversion layer and the POT2T layer; ensures energy level matching between the photoelectric functional layer and the POT2T layer; and utilizes the passivation effect of the POT2T layer on the photoelectric conversion functional layer to reduce energy loss, thus ensuring that the light-emitting photovoltaic device has bidirectional conversion capability of photoelectric generation and electroelectric generation. The high open-circuit voltage photovoltaic performance and high brightness luminous performance of this light-emitting photovoltaic device ensure good practical application prospects and environmental adaptability.

[0032] The combined design of the second electrode layer of this photovoltaic device optimizes the energy level barrier between the electrode and the electron transport layer and ensures high transmittance. The anti-reflection layer can significantly reduce light reflection and improve light transmittance. By selectively absorbing the high-energy blue and ultraviolet portions of the solar spectrum and transmitting visible and near-infrared light, the device maintains high visible light transmittance without affecting its dual functions of light emission and photovoltaics, greatly expanding its application range.

[0033] Furthermore, the various layers of the light-emitting photovoltaic device are prepared by spin coating solution and thermal evaporation without the need for complex circuit connections, which has the advantages of low cost and easy scalability. While reducing production costs, it simplifies the preparation process. Moreover, the light-emitting photovoltaic device can be applied on flexible substrates, thus having the advantages of portability and flexibility. The extremely thin thickness also lays the foundation for the high integration of the light-emitting photovoltaic device.

[0034] Based on this, the intelligent building equipment proposed in this invention can combine luminescent photovoltaic devices and electrochromic devices. This allows the electrochromic devices to switch from a transparent state to a colored state, or vice versa, through power supply from the luminescent photovoltaic devices rather than an external power source. The luminescent photovoltaic devices can also effectively separate the solar radiation bands used by the electrochromic devices, making fuller use of solar spectral energy, significantly improving overall energy efficiency, reducing dependence on traditional energy sources, and enhancing building sustainability. The high open-circuit voltage ensures a large transmittance adjustment window for the electrochromic devices, and the high luminous brightness establishes the luminous and display functions of this intelligent building equipment, improving its performance and user experience. Furthermore, it can be further integrated with display functions to form a multifunctional system integrating dynamic dimming, lighting, and display.

[0035] In addition, the light-emitting photovoltaic device proposed in this invention has wide applications in electronic devices. It can supply power to electronic devices while ensuring high transmittance, saving energy and increasing the standby time of electronic products.

[0036] Therefore, this invention proposes a light-emitting photovoltaic device, its manufacturing method and application. The light-emitting photovoltaic device proposed in this invention integrates photovoltaic and light-emitting functions, and has the advantages of low cost, easy scalability, high energy conversion efficiency, high open-circuit voltage, and applicability to flexible substrates. It is suitable for various application scenarios such as smart building materials and electronic products, and provides a brand-new technical solution for fields such as self-powered smart devices and transparent display devices. Attached Figure Description

[0037] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 This is an example diagram of the overall structure of a light-emitting photovoltaic device;

[0039] Figure 2 An example diagram of the overall structure of another embodiment of a light-emitting photovoltaic device;

[0040] Figure 3 This is a schematic diagram of the preparation method provided in Example 2;

[0041] Figures 4(a), 4(b), and 4(c) are schematic diagrams of the relevant performance of light-emitting photovoltaic devices containing opaque metal electrode layers. Figure 4(a) is a schematic diagram of the photovoltaic performance of a non-transparent light-emitting photovoltaic device, and Figures 4(b) and 4(c) are schematic diagrams of the light-emitting performance of a non-transparent light-emitting photovoltaic device.

[0042] Figures 5(a) and 5(b) are schematic diagrams showing the charging and discharging process of a light-emitting photovoltaic device with an opaque metal electrode layer and a supercapacitor, and demonstrating its photovoltaic and light-emitting performance applications. Figure 5(a) shows the light-emitting photovoltaic device charging the supercapacitor and demonstrating its photovoltaic performance application, while Figure 5(b) shows the supercapacitor discharging and causing the light-emitting photovoltaic device to emit light, thus demonstrating its light-emitting performance.

[0043] Figures 6(a), 6(b), and 6(c) are schematic diagrams of the relevant performance of a light-emitting photovoltaic device containing a transparent metal electrode layer, wherein Figure 6(a) is a schematic diagram of the photovoltaic performance of the light-emitting photovoltaic device, and Figures 6(b) and 6(c) are schematic diagrams of the light-emitting performance of the light-emitting photovoltaic device.

[0044] Figures 7(a) and 7(b) are schematic diagrams showing the charging and discharging process of a photovoltaic device with a transparent metal electrode layer and a supercapacitor, and demonstrating its photovoltaic and luminescent performance applications. Figure 7(a) is a schematic diagram showing the photovoltaic device charging a supercapacitor and demonstrating its photovoltaic performance applications, and Figure 7(b) is a schematic diagram showing the photovoltaic device emitting light by discharging a supercapacitor, thereby demonstrating its luminescent performance.

[0045] Figure 8(a) and Figure 8(b) are schematic diagrams of the overall structure and working principle of the intelligent building equipment and schematic diagrams of the transmittance of the intelligent building equipment under positive and negative bias.

[0046] Figure 9(a) and Figure 9(b) are spectral analysis diagrams of the electrochromic device under different voltages; Figure 9(a) is the transmittance spectrum of the electrochromic device under different voltages, and Figure 9(b) is the Commission Internationale de l'Eclairage (CIE 1931) coordinate diagram of the electrochromic device under different voltages.

[0047] Figure 10 This is an example diagram showing how a light-emitting photovoltaic device can be placed over the display screen of an alarm clock to drive it. Detailed Implementation

[0048] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0049] Various embodiments of the invention will be described more fully below. The invention may have various embodiments, and adjustments and changes may be made therein. However, it should be understood that there is no intention to limit the various embodiments of the invention to the specific embodiments disclosed herein, but rather the invention should be understood to cover all modifications, equivalents, and / or alternatives falling within the spirit and scope of the various embodiments of the invention.

[0050] In the following, the terms “comprising” or “may include” as used in various embodiments of the invention indicate the presence of the disclosed functions, operations, or elements, and do not limit the addition of one or more functions, operations, or elements. Furthermore, as used in various embodiments of the invention, the terms “comprising,” “having,” and their cognates are intended only to indicate a specific feature, number, step, operation, element, component, or combination of the foregoing, and should not be construed as primarily excluding the presence of one or more other features, numbers, steps, operations, elements, components, or combinations of the foregoing, or the possibility of adding one or more combinations of the foregoing.

[0051] In various embodiments of the invention, the expression "or" or "at least one of A and / or B" includes any combination or all combinations of the words listed simultaneously. For example, the expression "A or B" or "at least one of A and / or B" may include A, may include B, or may include both A and B.

[0052] The expressions used in the various embodiments of the present invention (such as "first," "second," etc.) may modify various constituent elements in the various embodiments, but do not limit the corresponding constituent elements. For example, the above expressions do not limit the order and / or importance of the elements. The above expressions are only used for the purpose of distinguishing one element from other elements. For example, a first user device and a second user device refer to different user devices, although both are user devices. For example, a first element may be referred to as a second element without departing from the scope of the various embodiments of the present invention, and similarly, a second element may also be referred to as a first element.

[0053] It should be noted that, in this invention, unless otherwise explicitly specified and defined, terms such as "installation," "connection," and "fixation" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0054] In this invention, those skilled in the art should understand that the terms indicating orientation or positional relationship in the text are based on the orientation or positional relationship shown in the accompanying drawings, and are only for the purpose of facilitating the description of this invention 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 of this invention.

[0055] The terminology used in the various embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to limit the various embodiments of the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the various embodiments of the invention pertain. The terms (such as those defined in a generally used dictionary) are to be interpreted as having the same meaning as in the context of the relevant technical field and are not to be interpreted as having an idealized or overly formal meaning, unless clearly defined in the various embodiments of the invention.

[0056] Example 1

[0057] Please see Figures 1-2 This embodiment proposes a light-emitting photovoltaic device, comprising a first electrode layer, a hole transport layer, a buffer wetting layer, a photoelectric conversion functional layer, an electron transport layer, a work function modification layer, and a second electrode layer connected in sequence.

[0058] Specifically, the photoelectric conversion functional layer can generate photogenerated carriers when receiving light, and transfer the carriers to the hole transport layer and the electron transport layer respectively to form a current; under the condition of an applied voltage, the hole transport layer collects holes in the first electrode layer and injects them into the photoelectric conversion functional layer, and the electron transport layer collects electrons from the second electrode layer and injects them into the photoelectric conversion functional layer. Electrons and holes achieve radiative recombination in the functional layer, thereby emitting light.

[0059] The energy disorder of the photoelectric conversion functional layer is not higher than the first preset energy value, and the energy disorder of the electron transport layer is not higher than the second preset energy value, so that the open-circuit voltage of the light-emitting photovoltaic device is not less than the preset voltage value; in this embodiment, the first preset energy value is 0.02eV, the second preset energy value is 0.03eV, and the preset voltage value is 2.0V, which can effectively ensure the effective output of the open-circuit voltage;

[0060] Preferably, the photoelectric conversion functional layer includes a perovskite layer with a band gap greater than 2.0V, the difference between the valence band top energy level of the photoelectric conversion functional layer and the HOMO energy level of the second hole transport layer does not exceed a third preset energy value, the close HOMO energy level between the valence band top energy level of the photoelectric conversion functional layer and the second hole transport layer ensures the effective extraction and injection of charge carriers, and the buffer wetting layer increases the wettability of the precursor solution of the photoelectric functional conversion layer, thereby improving the coverage and crystal quality of the film;

[0061] Meanwhile, the energy difference between the conduction band bottom level of the photoelectric conversion functional layer and the LUMO energy level of the electron transport layer does not exceed the fourth preset energy value. The close energy levels ensure the effective extraction and injection of charge carriers. In a specific embodiment, the third preset energy value and the fourth preset energy value are both 0.3eV.

[0062] In this embodiment, the hole transport layer may include a first hole transport layer connected to the first electrode layer and a second hole transport layer connected to the photoelectric conversion functional layer through a buffer wetting layer.

[0063] The first hole transport layer may include, but is not limited to, PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) layer, Poly-TPD (poly[bis(4-phenyl)(4-butylphenyl)amine]) layer, and NiOx (nickel oxide) layer. The first hole transport layer can be prepared by solution spin coating method, and the thickness range is 1-40 nm.

[0064] The second hole transport layer may include, but is not limited to, self-assembled layers such as 2PACz (2-(9H-carbazole-9-yl)ethylphosphonic acid), 4PACz (4-(9H-carbazole-9-yl)butylphosphonic acid), Poly-2PACz (poly2PACz), and Poly-4PACz (poly4PACz). The second hole transport layer can be prepared by solution spin coating and has a thickness ranging from 1 to 40 nm.

[0065] The photoelectric conversion functional layer may include a perovskite layer with an optical bandgap width not less than a preset width value. In this embodiment, the perovskite layer includes a perovskite thin film with a pre-adjusted bandgap to enhance the absorption capacity of blue light and ultraviolet light and enhance the transmittance capacity of visible light and near-infrared light. Its structure is ABX3, where A is one or more of methylamine (MA), formamidinium (FA), and Cs, B is one or two of Pb and Sn, and X is one or two of Cl and Br. The photoelectric conversion functional layer can be prepared by solution spin coating or vapor deposition, and the thickness range is 20-700 nm.

[0066] Therefore, the light-emitting photovoltaic device proposed in this embodiment can realize the dual functions of electroluminescence and photovoltaics. That is, the light-emitting photovoltaic device can convert the solar energy absorbed by the photoelectric conversion functional layer into electrical energy, and / or convert the electrical energy into light energy on the photoelectric conversion functional layer. By integrating the light-emitting function into the light-emitting photovoltaic device itself, it is expected to realize lighting and display functions simultaneously in fields such as smart building curtain walls.

[0067] Preferably, perovskite materials have advantages such as high absorption coefficient and high defect tolerance. Therefore, in this embodiment, the perovskite layer is used as the photoelectric functional conversion layer. The advantage of the bipolar carrier transport of perovskite makes it possible for the optoelectronic device prepared based on it to obtain high light rotation performance.

[0068] Preferably, in this embodiment, the small molecule organic compound POT2T (2,4,6-tris[3-(diphenylphosphino)phenyl]-1,3,5-triazole) can be used as the electron transport layer of the wide bandgap semiconductor. The excellent energy level matching between POT2T and perovskite is beneficial to the extraction and injection of charge carriers. At the same time, the P=O bond (phosphooxy double bond) in POT2T can effectively passivate interface defects and reduce nonradiative recombination losses, thereby improving the open-circuit voltage, and no additional surface modification layer is required. The electron transport layer can be prepared by vacuum evaporation, with a thickness ranging from 20-75 nm. The phosphooxy groups on the electron transport layer can bond with the photoelectric functional conversion layer, passivate interface defects, and suppress nonradiative recombination.

[0069] The relatively low energy disorder of perovskite materials and POT2T further increases the quasi-Fermi level splitting of perovskite materials, thereby improving the open-circuit voltage of optoelectronic devices. This solves the problems of high deep-level defect density, energy level mismatch between material layers and transport layers, and high energy disorder in wide-bandgap near-ultraviolet response solar cells in the prior art, thus removing the limitations on improving open-circuit voltage and luminescence performance.

[0070] Optionally, the buffer wetting layer may include, but is not limited to, PVP (polyvinylpyrrolidone), PEIE (polyethyleneimine ethoxylate), and PEG (polyethylene glycol). The buffer wetting layer can be prepared by solution spin coating and has a thickness ranging from 0.1 to 15 nm. The work function modification layer may include a LiF (lithium fluoride) layer. The work function modification layer can be prepared by vacuum evaporation and has a thickness ranging from 0.1 to 15 nm.

[0071] Therefore, the light-emitting photovoltaic device proposed in this embodiment breaks through the bottleneck of mutual constraints between high open-circuit voltage, high transmittance and light-emitting performance in existing light-emitting photovoltaic devices. It successfully integrates high open-circuit voltage, high visible light transmittance and good light-emitting performance. The response band should be concentrated in the deep blue light and near-ultraviolet band, and it has high visible light and near-infrared light transmittance, which improves the overall energy utilization efficiency. It can realize the acquisition of electrical energy from solar spectrum energy and use electrical energy to provide lighting and display functions or drive external circuit components.

[0072] In this embodiment, the first electrode layer includes a transparent conductive glass electrode layer, and the second electrode layer includes a transparent metal electrode layer or an opaque metal electrode layer.

[0073] The transparent conductive glass electrode layer may include ITO transparent conductive glass or FTO transparent conductive glass, and the sheet resistance of the transparent conductive glass is in the range of 8-15Ω, the light transmittance is 80%-90%, and the thickness is 140nm.

[0074] The transparent metal electrode layer can include an Al electrode layer and an Ag electrode layer. The transparent metal electrode layer can be prepared by vacuum evaporation. The thickness of the Al electrode layer in the transparent metal electrode layer ranges from 0.1 to 30 nm, and the thickness of the Ag electrode layer ranges from 1 to 30 nm. The thinner Al electrode reduces the energy level barrier of the electron transport layer and the Ag electrode, thereby improving the transmittance of the device while ensuring the conductivity of the electrode.

[0075] The opaque metal electrode layer may include an Al electrode layer. The opaque metal electrode layer can also be prepared by vacuum evaporation. The thickness of the Al electrode layer in the opaque metal electrode layer ranges from 30 to 400 nm, and is preferably 100 nm.

[0076] Furthermore, the light-emitting photovoltaic device proposed in this embodiment also includes an anti-reflection layer connected to the transparent metal electrode layer to improve light transmittance. The anti-reflection layer can reduce surface reflection of light, thereby improving the light absorption efficiency of the light-emitting photovoltaic device, and thus working in conjunction with the transparent metal electrode layer. Preferably, the anti-reflection layer may include a molybdenum trioxide (MoO3) layer or a lithium fluoride (LiF) layer prepared by vacuum evaporation, and the thickness of the anti-reflection layer ranges from 1 to 70 nm.

[0077] Preferably, the refractive index of the antireflection layer is in the visible light range of 2.0-2.4. The visible light range of 2.0-2.4 can better match the refractive index of air and perovskite, thereby reducing reflection loss at the interface and improving light transmittance.

[0078] Please see again Figure 1 In one specific embodiment, when the second electrode layer includes a transparent metal electrode layer, the first electrode layer includes ITO glass, the hole transport layer may include a PTAA hole transport layer with a thickness of 10 nm and a 2PACz hole transport layer with a thickness of 10 nm, the photoelectric conversion functional layer may include a perovskite layer with a thickness of 50 nm, the electron transport layer includes a POT2T electron transport layer with a thickness of 45 nm, and the second electrode layer includes an Al electrode layer with a thickness of 1 nm and an Ag electrode layer with a thickness of 12 nm.

[0079] The buffer wetting layer includes a 1 nm thick PVP wetting modification layer, with a 2PAC hole transport layer and a perovskite layer connected to both sides of the PVP wetting modification layer, respectively; the work function modification layer includes a 1 nm thick LiF modification layer, with a POT2T electron transport layer and an Al electrode layer connected to both sides of the LiF modification layer, respectively; the antireflection film includes a 30 nm thick MoO3 thin film connected to the Ag electrode layer;

[0080] In this embodiment, the extremely thin Al electrode solves the problem of the large energy level barrier between the electron transport layer and the Ag electrode, while the thinner Ag electrode can also have high light transmittance while ensuring the continuity and good conductivity of the electrode film.

[0081] Please see again Figure 2 In another optional embodiment, when the second electrode layer includes an opaque metal electrode layer, the first transparent electrode layer includes ITO glass, the hole transport layer may include a PTAA hole transport layer with a thickness of 10 nm and a 2PACz hole transport layer with a thickness of 10 nm, the photoelectric conversion functional layer may include a Perovskite layer with a thickness of 50 nm, the electron transport layer includes a POT2T electron transport layer with a thickness of 45 nm, and the second transparent electrode layer includes an Al electrode layer with a thickness of 100 nm.

[0082] The buffer wetting layer includes a 1 nm thick PVP wetting modification layer, with a 2PACz hole transport layer and a perovskite layer connected to both sides of the PVP wetting modification layer, respectively; the work function modification layer includes a 1 nm thick LiF modification layer, with a perovskite layer and an Al electrode layer connected to both sides of the LiF modification layer, respectively.

[0083] Example 2

[0084] This embodiment presents a preparation method for fabricating the light-emitting photovoltaic device proposed in Example 1. Please refer to [link / reference needed]. Figure 3 The specific steps of the preparation method are as follows:

[0085] S100: The transparent conductive substrate is cleaned with glass cleaner, ultrasonically treated in deionized water and ethanol respectively, and dried with nitrogen gas and then irradiated with ultraviolet light to prepare the first electrode layer.

[0086] In one specific embodiment, step S100 involves ultrasonically treating the transparent conductive substrate in deionized water and ethanol for 10 minutes each, drying it with nitrogen, and then irradiating it with an ultraviolet lamp for 20 minutes.

[0087] S200: On the first electrode layer that has been prepared, a hole transport layer and a photoelectric conversion functional layer are sequentially prepared by solution spin coating.

[0088] For example, in step S200, a toluene solution coated with PTAA can be dissolved on the prepared transparent conductive substrate by rotating it at a speed of 3000-3500 rpm for 30-50 seconds, and after coating, it can be heated and annealed on a hot stage at 100 degrees Celsius for 10 minutes to complete the preparation of the first hole transport layer; then, an isopropanol solution of 2 PACz is coated on the first hole transport layer by rotating it at a speed of 3000-3500 rpm for 30-50 seconds, and after coating, it can be heated and annealed on a hot stage at 100 degrees Celsius for 10 minutes.

[0089] Furthermore, the preparation method proposed in this embodiment can also coat the second hole transport layer with isopropanol solution of PVP by rotating it at a speed of 3000-3500 rpm for 30-40 seconds after the second hole transport layer is coated in step S200, and then heat and anneal it on a hot table at 100 degrees Celsius for 5 minutes after coating to complete the preparation of the buffer wetting layer.

[0090] Correspondingly, in step S200, an organic-inorganic hybrid perovskite precursor solution can be prepared at room temperature. A quantitative amount of FABr (methylammonium bromide), PbBr2 (lead bromide), PbCl2 (lead chloride), and CsBr (cesium bromide) are dissolved in DMSO (dimethyl sulfoxide) and stirred at 60 degrees Celsius for 4 hours to dissolve it. The precursor solution is then coated onto the buffer wetting layer by rotating at 3000 rpm for 45 seconds. Immediately after the perovskite active layer is completely coated by rotation, it is fumigated in a DMF (dimethylformamide) solvent atmosphere for 20 minutes and then transferred to an 80-degree Celsius hot plate for annealing for 8-15 minutes.

[0091] It should be noted that by fumigating the photoelectric conversion functional layer in a DMF atmosphere for 20 minutes, its morphology can be changed from a continuous structure to an island structure, which increases the external coupling output efficiency of the light-emitting photovoltaic device and suppresses phase separation of the light-emitting photovoltaic device. In addition, the photoelectric conversion functional layer has a relatively thin thickness, which ensures the integration of the light-emitting photovoltaic device. The thin thickness and wide light absorption band gap ensure that the transmittance of the layer is close to 100%.

[0092] S300: Under conditions where the vacuum level is less than the preset vacuum value, the electron transport layer and the second electrode layer are prepared sequentially by thermal evaporation.

[0093] For example, step S300 is performed in a vacuum coating machine at a vacuum level of less than 5 × 10⁻⁶. -4 Under Pa conditions, small molecule POT2T was deposited by thermal evaporation to prepare the electron transport layer;

[0094] For example, for a light-emitting photovoltaic device including a transparent metal electrode layer, after the electron transport layer is fabricated, it can be manufactured in a vacuum degree of less than 5 × 10⁻⁶.-4 Under the condition of Pa, the work function adjustment layer is deposited by thermal evaporation, and Al and Ag electrodes of a certain thickness are deposited on the work function modification layer by thermal evaporation to complete the preparation of the second electrode layer. Then, an anti-reflection layer of a certain thickness is deposited on the second electrode layer by thermal evaporation to finally obtain the light-emitting photovoltaic device.

[0095] In the light-emitting photovoltaic device prepared by the above steps, the first hole transport layer and the second hole transport layer can be arranged in an energy cascade, which ensures the injection or extraction of charge carriers.

[0096] In one specific embodiment, the light-emitting photovoltaic device prepared by the fabrication method proposed in this embodiment is tested. Please refer to [link to relevant documentation]. Figures 4(a)-4(c) , Figures 6(a)-6(c) Through testing, the open-circuit voltage of the non-transparent perovskite electroluminescent and photovoltaic dual-function device reached 98.3% of the SQ limit, i.e., 2.14V, and the maximum brightness reached 16000 cd / m². 2 The emission peak is located at approximately 490 nm, with a full width at half maximum (FWHM) of approximately 17 nm. It should be noted that the SQ limit (Shockley-Queisser limit) is the theoretical efficiency limit of a solar cell, used to describe the maximum theoretical energy conversion efficiency that a solar cell can achieve under ideal conditions.

[0097] Furthermore, the preparation method proposed in this embodiment can also be used to perform charge-discharge simulation tests on the light-emitting photovoltaic device. Please refer to [link to relevant documentation]. Figures 5(a)-5(b) , Figures 7(a)-7(b) To demonstrate that a light-emitting photovoltaic device can have the functions of electroluminescence and photovoltaic power generation, the method proposed in this embodiment can also connect the light-emitting photovoltaic device in series with a capacitor to evaluate the light energy conversion efficiency and self-powering capability of the light-emitting photovoltaic device under near-ultraviolet light.

[0098] The experimental results clearly show that after charging for 2500 seconds under simulated sunlight, the voltage of the supercapacitor steadily increases, fully demonstrating that the photovoltaic device can efficiently convert light energy into electrical energy and store it in the capacitor. Subsequently, by using the stored electrical energy to drive the device to operate in LED mode, the photovoltaic device successfully emits light, further confirming its self-powered characteristics in the near-ultraviolet band. This strongly proves that the photovoltaic device possesses both high-efficiency photovoltaic performance and light-emitting performance.

[0099] Example 3

[0100] Please see Figures 8(a)-8(b)This embodiment proposes an intelligent building device, which includes a light-emitting photovoltaic device as proposed in Embodiment 1. The second electrode layer in the light-emitting photovoltaic device applied to the intelligent building device can preferably be a transparent metal electrode layer.

[0101] Optionally, the smart building equipment proposed in this embodiment may include, but is not limited to, indoor lighting fixtures, smart windows, displays, and curtains.

[0102] Furthermore, the intelligent building equipment proposed in this embodiment also includes an electrochromic device powered by a light-emitting photovoltaic device. The light-emitting photovoltaic device and the electrochromic device can form a circuit loop as shown in Figure 8(a). As shown in Figure 8(b), when a positive bias is applied in the circuit loop, ions in the electrochromic device migrate to the electrochromic layer under the action of the electric field. The embedding of ions causes the oxidation state of the electrochromic device to change, thereby deepening its color and reducing its transmittance. When a negative bias is applied in the circuit loop, the ions in the electrochromic device are extracted and return to the ion storage layer. The oxidation state of the material is restored, the color becomes lighter, and the transmittance increases.

[0103] Please see Figures 9(a)-9(b) It should be noted that the high open-circuit voltage of the light-emitting photovoltaic device can increase the adjustment window of the transmittance of the electrochromic device, maximize the energy utilization efficiency, and simplify the system design, thereby ensuring that the smart building equipment proposed in this embodiment can achieve efficient light modulation, and greatly improve the performance of the smart building equipment and the user experience.

[0104] Meanwhile, light-emitting photovoltaic devices primarily respond to deep blue light and near-ultraviolet wavelengths, while electrochromic devices primarily respond to near-infrared wavelengths. This ensures the customized spectral response characteristics of smart building equipment, cleverly achieving effective separation of photovoltaic utilization between the two, and enabling more full utilization of solar spectral energy, significantly improving overall energy efficiency.

[0105] Therefore, this embodiment combines light-emitting photovoltaic devices and electrochromic devices to form a multifunctional building system that integrates dynamic dimming, lighting and display. By using light-emitting photovoltaic devices, it provides a clean, efficient and convenient self-powered solution for smart buildings, which can effectively reduce energy consumption and provide new possibilities for smart buildings and sustainable development.

[0106] Example 4

[0107] The light-emitting photovoltaic device proposed in Example 1 has the potential to be directly integrated into electronic devices with electrical components such as transparent displays, providing energy for identification systems, reducing dependence on external power sources, and extending device lifespan. Based on this, this embodiment proposes an electronic device including electrical components and the light-emitting photovoltaic device proposed in Example 1. The light-emitting photovoltaic device covers the surface of the electrical components to convert light energy into electrical energy and power the electrical components. The second electrode layer in the light-emitting photovoltaic device applied to the electronic device can preferably be a transparent metal electrode layer to ensure good light transmittance and power transmission efficiency.

[0108] For example, please see Figure 10 When electronic devices include alarm clocks, by covering the display screen of the alarm clock with light-emitting photovoltaic devices, the light-emitting photovoltaic devices can efficiently convert light energy into electrical energy under illumination to power the alarm clock. Moreover, thanks to the high light transmittance of the perovskite material in the light-emitting photovoltaic devices, the alarm clock can clearly display information such as time and weather.

[0109] In summary, this invention proposes a light-emitting photovoltaic device, its manufacturing method, and its application. The light-emitting photovoltaic device proposed in this invention integrates photovoltaic and light-emitting functions, and has advantages such as low cost, easy scalability, high energy conversion efficiency, high open-circuit voltage, and applicability to flexible substrates. It is suitable for various application scenarios such as smart building materials and electronic products, and provides a brand-new technical solution for fields such as self-powered smart devices and transparent display devices.

[0110] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A light-emitting photovoltaic device, characterized in that, It includes a first electrode layer, a hole transport layer, a photoelectric conversion functional layer, an electron transport layer, and a second electrode layer connected in sequence. The photoelectric conversion functional layer includes a perovskite layer with a band gap greater than 2.0V; Both the electron transport layer and the hole transport layer contain materials whose energy levels match those of the photoelectric conversion functional layer; The difference between the LUMO energy level of the electron transport layer and the bottom conduction band energy level of the perovskite layer is no greater than 0.3 eV, and the difference between the HOMO energy level of the hole transport layer and the top valence band energy level of the perovskite layer is no greater than 0.3 eV.

2. The light-emitting photovoltaic device according to claim 1, characterized in that, The perovskite layer includes a perovskite thin film with a pre-adjusted optical bandgap to enhance the absorption of blue and ultraviolet light and the transmittance of visible and near-infrared light, wherein the optical bandgap width of the perovskite thin film is not less than a preset width value.

3. The light-emitting photovoltaic device according to claim 1 or 2, characterized in that, The electron transport layer includes a transport layer that matches the energy level of the perovskite layer, and the thickness of the electron transport layer ranges from 20 to 75 nm.

4. The light-emitting photovoltaic device according to claim 1, characterized in that, The second electrode layer includes a transparent electrode layer, which includes a conductive polymer layer, a metal layer, an oxide layer, a carbon-based material layer, or a composite transparent electrode layer; Alternatively, the second electrode layer may include an opaque electrode layer, which may include a conductive polymer layer, a metal layer, an oxide layer, a carbon-based material layer, or a composite structure.

5. The light-emitting photovoltaic device according to claim 1, characterized in that, It also includes a buffer wetting layer disposed between the hole transport layer and the photoelectric conversion functional layer, and a work function modification layer disposed between the electron transport layer and the second electrode layer; The buffer wetting layer includes a PVP layer, a PEIE layer, or a PEG layer, and the thickness of the buffer wetting layer ranges from 0.1 to 15 nm. The work function modification layer includes a lithium fluoride layer, and the thickness of the work function modification layer ranges from 0.1 to 15 nm.

6. The light-emitting photovoltaic device according to claim 1 or 5, characterized in that, The hole transport layer includes a first hole transport layer connected to the first electrode layer and a second hole transport layer connected to the photoelectric conversion functional layer; The first hole transport layer includes a PTAA layer, a Poly-TPD layer, and a NiOx layer, and the thickness of the first hole transport layer ranges from 1 to 40 nm. The second hole transport layer includes a 2PACz layer, a 4PACz layer, a Poly-2PACz layer, or a Poly-4PACz layer, and the thickness of the second hole transport layer ranges from 1 to 40 nm.

7. A method for preparing a light-emitting photovoltaic device as described in any one of claims 1-6, the method comprising: The first electrode layer is prepared by cleaning the transparent conductive substrate with glass cleaner, ultrasonically treating it in deionized water and ethanol respectively, drying it with nitrogen gas and then irradiating it with ultraviolet light. After the hole transport layer is prepared, a buffer wetting layer is prepared by solution spin coating, and the hole transport layer and the photoelectric conversion functional layer are prepared sequentially on the prepared buffer wetting layer by solution spin coating. Under conditions where the vacuum level is less than a preset vacuum value, the electron transport layer is prepared by thermal evaporation. A work function adjustment layer is deposited on the prepared electron transport layer by thermal evaporation, and the second electrode layer is prepared on the deposited work function adjustment layer.

8. A smart building equipment, characterized in that, Including the light-emitting photovoltaic device as described in any one of claims 1-6.

9. The intelligent building equipment according to claim 8, characterized in that, The intelligent building equipment also includes an electrochromic device powered by the light-emitting photovoltaic device, wherein the light-emitting photovoltaic device and the electrochromic device form a circuit loop; The circuit loop is used to deepen the color of the electrochromic device and reduce its transmittance when a positive bias voltage is applied. The circuit loop is also used to make the color of the electrochromic device lighter and increase its transmittance when a negative bias voltage is applied.

10. An electronic device, characterized in that, It includes an electrical device and a light-emitting photovoltaic device as described in any one of claims 1-6, wherein the light-emitting photovoltaic device is integrated with the electrical device to convert light energy into electrical energy and supply power to the electrical device.

Images