Perovskite photovoltaic-radiation photovoltaic integrated cell with high radiation resistance

Abstract

A perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance, belonging to the field of photovoltaic devices, includes an antireflective film, a transparent scintillator substrate, a transparent conductive layer, a first charge transport layer, a perovskite absorption layer, a second charge transport layer, and electrodes, sequentially stacked along the incident light direction. The transparent scintillator substrate transmits visible-near-infrared light from the solar spectrum and absorbs ultraviolet light or high-energy radiation incident on the cell, converting ultraviolet light and high-energy radiation into radiative emission that can be absorbed by the perovskite absorption layer. The perovskite absorption layer absorbs the visible-near-infrared light transmitted through the transparent scintillator substrate and the radiative emission generated by the transparent scintillator substrate, and generates photogenerated charge carriers. This invention can improve the irradiation stability of perovskite cells while reusing the energy of spatially broad-spectrum photons and ionizing radiation.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic device technology, and in particular to a perovskite photovoltaic-radiation integrated cell with high radiation resistance. Background Technology

[0002] Currently, spacecraft, deep space probes, and long-term unmanned platforms primarily utilize multi-junction gallium arsenide (GaAs) or high-efficiency crystalline silicon (crystalline silicon) solar cells as power sources. Among these, multi-junction structures such as InGaP / GaAs / Ge exhibit high conversion efficiency and good radiation resistance, and have been widely used in satellite energy systems. However, these cells typically suffer from high epitaxial fabrication costs, complex processes, high rigidity, high costs associated with area expansion, and limited power density improvement. For large-area, lightweight, and low-cost space energy devices, the development of new photovoltaic materials and device structures remains crucial.

[0003] Perovskite semiconductors, with their high light absorption coefficients, tunable band gaps, low-temperature solution processing, and lightweight fabrication potential, have been considered important candidate materials for space photovoltaics in recent years. However, conventional perovskite photovoltaic devices still face stability challenges in the space environment due to factors such as ultraviolet light, ionizing radiation, high-energy particles, and temperature cycling. In particular, under the influence of high-energy ultraviolet light and ionizing radiation, defects in the perovskite lattice, ion composition, and charge transport interfaces are prone to accumulation and interface degradation, leading to a decrease in the device's open-circuit voltage, short-circuit current, and fill factor.

[0004] Therefore, this invention proposes a perovskite photovoltaic-radiophotovoltaic integrated cell structure with high radiation resistance and broad spectral response, balancing space photovoltaic output, irradiation stability, and radiation energy recovery. By introducing a scintillator substrate with radiophotovoltaic conversion function, this substrate can absorb ultraviolet light, X-rays, gamma rays, electron beams, or other high-energy particles and generate radiative emission. The generated visible light is further absorbed by the perovskite absorption layer and converted into electrical energy. Thus, this invention can improve the irradiation stability of perovskite cells while realizing the reuse of broad-spectrum photon and ionizing radiation energy in space. Summary of the Invention

[0005] The purpose of this invention is to solve the key technical problems of existing space solar cells in terms of cost, structure, spectral response and reliability, and to provide a perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance, which combines the photovoltaic effect and the radiative photovoltaic effect, and can significantly improve the energy conversion efficiency and device stability under space radiation environment.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A perovskite photovoltaic-radio-photovoltaic integrated cell with high radiation resistance includes an antireflection film, a transparent scintillator substrate, a transparent conductive layer, a first charge transport layer, a perovskite absorption layer, a second charge transport layer, and electrodes, which are sequentially stacked along the incident light direction.

[0008] The antireflection film is disposed on the light-incident side of the transparent scintillator substrate to reduce the reflection loss at the light-incident interface of the transparent scintillator substrate and improve the transmission efficiency of sunlight and ultraviolet light.

[0009] The transparent scintillator substrate is used to transmit visible-near infrared light in the solar spectrum and to absorb ultraviolet light or high-energy radiation directed at the battery, converting the ultraviolet light and high-energy radiation into radiation that can be absorbed by the perovskite absorption layer.

[0010] The perovskite absorption layer is used to absorb visible-near-infrared light transmitted through the transparent scintillator substrate and radiative emission generated by the transparent scintillator substrate, and to generate photogenerated carriers.

[0011] The first charge transport layer and the second charge transport layer are used to transport photogenerated carriers of different polarities, respectively.

[0012] The transparent conductive layer and electrodes are used to form an external electrical output channel.

[0013] The antireflective coating is a single-layer film, a double-layer film, or a multilayer composite film. The antireflective coating is a multilayer dielectric film composed of alternating high-refractive-index and low-refractive-index dielectric layers; the low-refractive-index dielectric layer is selected from one or more of SiO2, MgF2, Al2O3, and porous silica, and the high-refractive-index dielectric layer is selected from one or more of Ta2O5, TiO2, Nb2O5, HfO2, ZrO2, Si3N4, and AlN.

[0014] The antireflective coating can be prepared by electron beam evaporation, thermal evaporation, magnetron sputtering, atomic layer deposition, chemical vapor deposition, or sol-gel method. The antireflective coating has 1 to 30 layers, preferably 2 to 12 layers; the thickness of a single layer is 1 to 300 nm, preferably 5 to 150 nm; and the total thickness is 10 to 2000 nm, preferably 50 to 500 nm.

[0015] The transparent scintillator substrate includes, but is not limited to, one or more of oxide scintillators, halide scintillators, silicate scintillators, tungstate scintillators, garnet-structured scintillators, perovskite-structured scintillators, or composite scintillators thereof. Preferably, the transparent scintillator substrate is selected from cerium-doped gadolinium aluminum gallium garnet (GAGG:Ce), terbium / cerium co-doped gadolinium yttrium aluminum gallium garnet ((Gd,Y,Tb,Ce)3Al2Ga3O 12The scintillator substrate is one or more of the following: cerium-doped yttrium aluminum garnet (YAG:Ce), cerium-doped lutetium silicate (LSO:Ce), cerium-doped lutetium yttrium silicate (LYSO:Ce), thallium-doped cesium iodide (CsI:Tl), sodium-doped cesium iodide (CsI:Na), thallium-doped sodium iodide (NaI:Tl), bismuth germanate (BGO), barium fluoride (BaF2), lead tungstate (PbWO4), cesium lead bromide perovskite (CsPbBr3), methylammonium lead bromide perovskite (MAPbBr3), and two-dimensional layered lead halide perovskite scintillators. More preferably, the transparent scintillator substrate is an aluminum gallium garnet structure scintillator containing at least two elements selected from Gd, Y, Tb, and Ce, and its composition includes, but is not limited to, Gd3Al2Ga3O. 12 Ce、(Gd,Y)3Al2Ga3O 12 Ce、(Gd,Tb)3Al2Ga3O 12 Ce、(Gd,Y,Tb,Ce)3Al2Ga3O 12 Or derived compositions thereof after adjusting the elemental ratios. Such materials can produce visible light radiation under excitation by ultraviolet light, X-rays, gamma rays, electron beams or other high-energy particles, and at least partially overlap with the absorption spectrum or external quantum efficiency response range of the perovskite absorption layer.

[0016] The perovskite absorber layer has an ABX3 structure or a derivative thereof, wherein the A-site cation is selected from methylammonium ion (MA). + ), formamidinium ion (FA) + ), cesium ions (Cs) + ), rubidium ions (Rb + ) and potassium ions (K + One or more of the following; the B-site metal cation is selected from lead ions (Pb). 2+ ), tin ions (Sn) 2+ ) and germanium ions (Ge 2+ One or more of the following; the X-position anion is selected from iodide ions (I0). - ), bromide ions (Br) - ) and chloride ions (Cl - One or more of the following are perovskites: organic-inorganic hybrid perovskites, all-inorganic perovskites, tin-based perovskites, tin-lead mixed perovskites, wide-bandgap perovskites, narrow-bandgap perovskites, low-dimensional perovskites, quasi-two-dimensional perovskites, or two-dimensional / three-dimensional mixed perovskites. The bandgap of the perovskite absorption layer can be 1.0~2.5 eV, preferably 1.2~2.3 eV.

[0017] In some preferred embodiments, the perovskite absorber layer may be selected from MAPbI3, FAPbI3, CsPbI3, CsPbBr3, CsPbI2Br, CsPbIBr2, FA1-x Cs x PbI3, FA 1-x MA x PbI3, Cs a (MA b FA 1-b ) 1-a Pb(I c Br 1-c 3. Tin-lead mixed narrow bandgap perovskites, two-dimensional / three-dimensional mixed perovskites, or low-dimensional perovskite materials containing large-sized organic spacer cations.

[0018] The electrode is made of either gold or silver vapor-deposited, with a thickness of 50~200 nm.

[0019] The transparent conductive layer comprises one or more of indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), indium zinc oxide (IZO), silver nanowires, graphene, or a transparent conductive polymer. The thickness of the transparent conductive layer can be 20~500 nm.

[0020] When the first charge transport layer is a hole transport layer and the second charge transport layer is an electron transport layer, the device has an inverted structure. In another embodiment, the first charge transport layer is an electron transport layer and the second charge transport layer is a hole transport layer, and the device has a conventional structure. Thus, the device structure of the present invention is not limited to a perovskite solar cell structure of a specific polarity.

[0021] The hole transport layer includes nickel oxide (NiO). x The hole transport layer may be one or more of the following: molybdenum oxide, tungsten oxide, vanadium oxide, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD), poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), carbazole-based hole transport materials, or self-assembled monolayer materials. The hole transport layer thickness may be 1~300 nm.

[0022] The electron transport layer includes fullerene (C 60 [6,6]-phenyl-C 61 methyl butyrate (PC) 61 BM), [6,6]-phenyl-C 71 methyl butyrate (PC) 71 The electron transport layer may be one or more of the following: BM, tin dioxide (SnO2), titanium dioxide (TiO2), zinc oxide (ZnO), indium oxide, niobium oxide, or organic small molecule electron transport materials. The thickness of the electron transport layer may be 1~300 nm.

[0023] The perovskite photovoltaic-radiophotovoltaic integrated cell is used as a space photovoltaic power source, a radiation environment energy harvesting device, a micro-radiophotovoltaic power source, a radiation detection auxiliary power supply device, or a long-term unattended energy device.

[0024] The transparent scintillator substrate generates radiative emission under excitation by ultraviolet light, X-rays, gamma rays, electron beams, beta rays, proton beams, neutron radiation, or heavy ion radiation. The radiative emission is at least partially located within the absorption spectrum of the perovskite absorption layer, or at least partially within the external quantum efficiency response range of the perovskite photovoltaic device. Thus, incident radiation energy can be converted into visible or near-visible photons by the transparent scintillator substrate, then converted into photogenerated charge carriers by the perovskite absorption layer, and finally output as electrical energy via the charge transport layer and electrodes. The energy conversion path in this invention includes at least one of the following:

[0025] (1) Visible-near-infrared light in sunlight or AMO spectrum is directly absorbed by the perovskite absorption layer and generates photovoltaic output;

[0026] (2) Ultraviolet light in sunlight or spatial spectrum is absorbed by transparent scintillator substrate and converted into perovskite absorbable photons through photoluminescence or downconversion luminescence;

[0027] (3) X-rays, gamma rays, electron beams or other ionizing radiation deposit energy in a transparent scintillator substrate and induce scintillating light emission, which is further absorbed by the perovskite absorption layer and generates radiative photovoltaic output;

[0028] (4) The transparent scintillator substrate absorbs radiation energy while reducing the direct damage of high-energy radiation to the perovskite absorption layer and interface layer, thereby improving the device's irradiation stability.

[0029] Compared with the prior art, the beneficial effects achieved by the technical solution of this invention are:

[0030] 1. This invention directly integrates a transparent scintillator substrate onto the light-incident side of a perovskite photovoltaic device, making it simultaneously a device support layer, a radiation protection layer, and a radiation energy conversion layer. Compared with traditional cover glass or simple encapsulation barrier layers, this structure not only reduces the direct damage of ultraviolet light and ionizing radiation to the perovskite absorption layer, but also converts some of the radiation energy into photons that can be absorbed by the perovskite.

[0031] 2. This invention enables dual-mode output of photovoltaic and radiative photovoltaic. Under sunlight or AMO irradiation, the perovskite absorber layer directly generates photovoltaic output; under excitation by X-rays, gamma rays, electron beams, or other ionizing radiation, the transparent scintillator substrate generates radiative emission, which the perovskite absorber layer further converts into electrical energy.

[0032] 3. This invention can improve the spatial broadband energy utilization capability. The transparent scintillator substrate can absorb high-energy ultraviolet light and generate visible light emission, which can make up for the problems of insufficient response and poor stability of perovskite devices in the deep ultraviolet band, and is beneficial to improving the output performance of the device in the spatial AMO spectrum.

[0033] 4. This invention reduces optical reflection loss at the air / transparent scintillator substrate interface by setting an anti-reflection film on the light-incident side of the transparent scintillator substrate, thereby improving the transmission and coupling efficiency of photons in the sunlight, ultraviolet light and scintillating light bands.

[0034] 5. This invention is applicable to a wide range of perovskite systems. The perovskite absorber layer can be an organic-inorganic hybrid perovskite, an all-inorganic perovskite, a tin-lead mixed perovskite, a low-dimensional perovskite, or a two-dimensional / three-dimensional mixed perovskite, and is not limited to a single tricationic mixed perovskite system.

[0035] 6. The present invention has a simple structure, with a transparent scintillator substrate and perovskite photovoltaic unit stacked and integrated, without the need for an additional complex optical coupling system. It is compatible with existing thin-film perovskite cell fabrication processes and is suitable for applications such as space photovoltaics, radiation environment energy harvesting, micro-radiation photovoltaic power sources and radiation detection auxiliary power supply. Attached Figure Description

[0036] Figure 1 This is a schematic diagram of a perovskite photovoltaic-radiophotovoltaic integrated cell structure based on an antireflective film / transparent scintillator substrate, according to an embodiment of the present invention.

[0037] Figure 2 The image shows the optical performance curves after the antireflection film was prepared in an embodiment of the present invention.

[0038] Figure 3 These are the JV curves of space perovskite solar cells under the spatial AM0 spectrum of Embodiment 1 and Comparative Example 1 of the present invention.

[0039] Figure 4 These are the JV and PV curves of a space perovskite solar cell under UVA irradiation (center wavelength 345 nm) in Example 1 and Comparative Example 1 of the present invention.

[0040] Figure 5 These are the JV and PV curves of a space perovskite solar cell under UVC band (center wavelength 265 nm) irradiation in Embodiment 1 and Comparative Example 1 of the present invention.

[0041] Figure 6 The output performance curve of Example 1 under X-ray excitation is shown.

[0042] Figure 7 The output performance curve of Example 1 under γ-ray excitation is shown.

[0043] Figure 8 The output performance curve of Example 1 under electron beam excitation is shown.

[0044] Figure 9 The curves show the normalized efficiency retention rates of Example 1 and Comparative Example 1 after composite ultraviolet irradiation.

[0045] Figure 10 The curves show the dynamic changes in current density and output power retention rate under continuous X-ray irradiation in Example 1. Detailed Implementation

[0046] To better understand the technical solution and beneficial effects of the present invention, embodiments and comparative examples are provided below in conjunction with the accompanying drawings and specific processes. These are preferred embodiments of an integrated photovoltaic-radiophotovoltaic space cell structure using an anti-reflective film / GAGG:Ce substrate, and comparative examples using a conventional glass substrate. Unless otherwise specified, the device structure, material ratios, and fabrication processes of both are consistent.

[0047] Example 1

[0048] This embodiment provides a perovskite photovoltaic-radiophotovoltaic integrated cell based on an antireflective coating / GAGG:Ce transparent scintillator substrate. The device, from the light-incident side to the back electrode, sequentially includes an antireflective coating, a transparent scintillator substrate, a transparent conductive layer, a hole transport layer, a perovskite absorption layer, an electron transport layer, and a metal electrode.

[0049] The antireflective coating is disposed on the incident light side of the GAGG:Ce transparent scintillator substrate and consists of three pairs of alternating high / low refractive index structures, totaling six layers. Matrix optimization is performed with the GAGG:Ce main emission band as the center, significantly reducing the average reflectivity in the visible light range. The film thicknesses from bottom to top are: SiO2 (97.39 nm), Ta2O5 (28.59 nm), SiO2 (17.07 nm), Ta2O5 (79.54 nm), SiO2 (7.88 nm), and Ta2O5 (28.92 nm).

[0050] The transparent scintillator substrate is made of cerium-doped gadolinium aluminum gallium garnet (GAGG:Ce) crystal with a thickness of 1.0 mm. This substrate can produce visible light emission under ultraviolet light, X-rays, gamma rays and electron beam excitation, and has high radiation stability.

[0051] The transparent conductive layer is made of indium tin oxide (ITO) and is deposited on the surface of the GAGG:Ce substrate by magnetron sputtering. The thickness is 150~180 nm and the sheet resistance is not higher than 20 Ω / □.

[0052] The hole transport layer is made of nickel oxide (NiO). xThe solution was prepared by spin coating and had a thickness of 30 nm.

[0053] The perovskite absorber layer uses Cs 0.05 (MA 0.15 FA 0.85 ) 0.95 PbI 0.85 Br 0.15 The thickness is 500 nm. This perovskite layer can absorb visible-near infrared light from sunlight, and at the same time absorb visible light generated by the GAGG:Ce substrate under radiative excitation, thereby realizing dual-mode energy conversion of photovoltaic and radiative photovoltaic.

[0054] The electron transport layer uses PC. 61 The metal electrode is a BM with a thickness of 50 nm. The metal electrode is a silver electrode with a thickness of 200 nm.

[0055] The metal electrode is a silver electrode deposited by thermal evaporation, with a thickness of 200 nm.

[0056] The preparation steps in this embodiment are as follows:

[0057] Step 1: Antireflective film preparation. First, the GAGG:Ce substrate was sequentially ultrasonically cleaned, dried, and surface-treated. Then, an antireflective film was deposited on the incident light side of the GAGG:Ce substrate. The antireflective film adopted a SiO2 / Ta2O5 alternating multilayer structure, with a total of 6 layers. Along... Figure 1 As shown from bottom to top, the antireflective coating consists of a SiO2 layer, a Ta2O5 layer, another SiO2 layer, another Ta2O5 layer, another SiO2 layer, and another Ta2O5 layer, with corresponding thicknesses of 97.39 nm, 28.59 nm, 17.07 nm, 79.54 nm, 7.88 nm, and 28.92 nm, respectively. This film system can reduce interface reflection on the incident light side of the GAGG:Ce substrate in the visible light band and improve the effective coupling between incident light and photons in the scintillation emission band.

[0058] Step 2: Preparation of the transparent conductive layer. After ultrasonic cleaning and drying, the GAGG:Ce substrate was treated with ultraviolet ozone and then an indium tin oxide layer was deposited on the GAGG:Ce substrate using magnetron sputtering. The magnetron sputtering power was 35 W, the target material was indium tin oxide (In2O3:SnO2 = 90:10 wt%), and the sputtering thickness was 150~180 nm, thus obtaining a GAGG:Ce substrate with conductive properties.

[0059] Step 3: Hole transport layer preparation. NiO... x Nanocrystals were mixed with deionized water to prepare a dispersion with a concentration of 10 mg / mL, and sonicated for 30 minutes. Then, NiO was added... xThe solution was spin-coated onto the substrate from step two at 4000 rpm for 30 s, and then annealed at 150 °C for 30 min to obtain NiO. x Hole transport layer.

[0060] Step 4: Preparation of the perovskite absorber layer. Lead iodide (PbI2), lead bromide (PbBr2), formamidinium iodide (FAI), methyl ammonium bromide (MABr), and cesium iodide (CsI) are mixed in stoichiometric ratios. 0.05 (MA 0.15 FA 0.85 ) 0.95 PbI 0.85 Br 0.15 A 1.4 M precursor solution was prepared by dissolving N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) in a mixed solvent at a volume ratio of 4:1 and stirring for 12 hours. The perovskite precursor solution was then spin-coated at 1000 rpm for 5 s, followed by spin-coating at 5000 rpm for 20 s. Three s before the end of the spin-coating, 150 μL of chlorobenzene was added dropwise as an antisolvent for extraction. Finally, the spin-coated device was annealed on a heating stage at 100 °C for 30 min.

[0061] Step 5: Preparation of the electron transport layer. Methyl phenyl-C61-butyrate (PC) is used. 61 BM) was dissolved in chlorobenzene to prepare a solution with a concentration of 30 mg / mL, and then PC was added. 61 The BM solution was spin-coated onto the device obtained in step four at 3000 rpm for 30 seconds and then annealed at 100°C for 10 minutes.

[0062] Step Six: Electrode Preparation. Under a vacuum degree ≤ 5 × 10⁻⁶. -4 Under Pa conditions, based on the device from step five, a 200 nm silver electrode is deposited using a thermal evaporation device to obtain a complete perovskite photovoltaic-radiophotovoltaic integrated cell.

[0063] Comparative Example 1

[0064] Comparative Example 1 provides a perovskite solar cell on a conventional glass substrate. The difference between this device and Example 1 is that the transparent scintillator substrate is replaced with a conventional optical glass substrate, and there is no anti-reflection coating. The materials, thicknesses, and fabrication processes of the remaining transparent conductive layer, hole transport layer, perovskite absorber layer, electron transport layer, and metal electrode are the same as those in Example 1.

[0065] Since ordinary optical glass does not possess significant radiative emission capabilities, it is difficult to convert incident radiation energy into visible light that can be absorbed by perovskites under X-ray, gamma-ray, or electron beam excitation. Therefore, this comparative example is used to illustrate the role of transparent scintillator substrates in radiation energy conversion and radiation protection.

[0066] To verify the performance of the device of the present invention in terms of photovoltaic output, ultraviolet photon conversion, high-energy radiation energy utilization, and radiation stability under spatial AMO spectroscopy, comparative tests were conducted on Example 1 and Comparative Example 1. The tests included JV testing under spatial AMO spectroscopy, JV and PV testing under 345 nm and 265 nm ultraviolet light excitation, radiative photovoltaic output testing under X-ray, gamma-ray, and electron beam excitation, and UVA / UVB / UVC composite ultraviolet irradiation stability testing, as well as the dynamic changes in current density and output power retention rate under continuous X-ray irradiation in Example 1. All the above tests were conducted based on the devices prepared in Example 1 and Comparative Example 1, and the test results are used to illustrate the role of the transparent scintillator substrate in the integrated photovoltaic-radiative photovoltaic energy conversion.

[0067] Figure 3 The JV curves for Example 1 and Comparative Example 1 are shown in the AM0 spectrum. The test results show that the photoelectric conversion efficiency of the device in Example 1 is 21.49%, the open-circuit voltage is 1.168 V, and the short-circuit current density is 31.37 mA / cm². 2 The fill factor is 0.801; the photoelectric conversion efficiency of the device in Comparative Example 1 is 21.02%, the open-circuit voltage is 1.161 V, and the short-circuit current density is 30.72 mA / cm². 2 The fill factor is 0.805. In Example 1, after using a GAGG:Ce transparent scintillator substrate, AMO photovoltaic output performance exceeding that of ordinary glass substrate devices was achieved, and slightly higher photoelectric conversion efficiency and short-circuit current density were observed.

[0068] Figure 4 and Figure 5 The JV and PV curves of the cells in Example 1 and Comparative Example 1 under UVA (center wavelength 345 nm) and UVC (center wavelength 265 nm) irradiation, respectively, are shown. The results indicate that, compared to Comparative Example 1, the space cell in Example 1 exhibits higher open-circuit voltage, shorter-circuit current density, and maximum output power under 345 nm UV light irradiation, which are 1.12 V and 4.95 mA / cm², respectively. 2 and 4.34 mW / cm 2 The maximum output power is 1.4 times that of the conventional structure. Under 265 nm UVC irradiation, the perovskite space cell of Comparative Example 1 almost failed, with negligible output power, while the space cell of Example 1 still exhibited 0.9 V and 85 μA / cm² under 265 nm UVC irradiation. 2 61.06 μW / cm 2The open-circuit voltage, short-circuit current density, and maximum output power are all measured. Therefore, in space scenarios with a high proportion of ultraviolet photons, battery structures based on GAGG:Ce substrates exhibit stronger performance and development potential.

[0069] Under high-energy radiation irradiation, high-energy rays first deposit energy on the GAGG:Ce transparent scintillator substrate, inducing GAGG:Ce to emit visible light. This emitted light enters the perovskite absorption layer and is further absorbed, generating photogenerated electrons and holes, which are then separated and collected by the charge transport layer to form an external electrical output.

[0070] Figure 6 The image shows the electrical output performance curves of Example 1 under X-ray excitation generated by a 50 kV X-ray tube. The test results show that, under X-ray excitation, Example 1 can produce stable and measurable radiative photovoltaic output, with an open-circuit voltage of 0.83 V and a short-circuit current density of 16.64 μA / cm². 2 The maximum output power density is 10.84 μW / cm³. 2 This indicates that the integrated structure can convert X-ray deposition energy into electrical energy through a scintillation-perovskite photoelectric conversion process.

[0071] Figure 7 The output performance curves of Example 1 under gamma-ray excitation are shown. The test results show that the open-circuit voltage of Example 1 under gamma-ray excitation is 0.68 V, and the short-circuit current density is 0.72 μA / cm². 2 The maximum output power density is 0.354 μW / cm³. 2 This result demonstrates that the device of the present invention can indirectly convert γ-ray deposition energy into photons usable by the perovskite photovoltaic unit and further output electrical energy, thereby expanding the application scope of perovskite devices in ionizing radiation energy harvesting scenarios.

[0072] Figure 8 The image shows the electrical output performance curves of Example 1 under electron beam excitation. Test results show that when the electron beam energy is 18 keV and the beam current is 1 mA, the open-circuit voltage of the device is 0.815 V, and the short-circuit current density is 12.58 μA / cm². 2 The maximum output power density is 8.25 μW / cm³. 2 This result demonstrates that the present invention can convert electron beam deposition energy into visible light through a transparent scintillator substrate, and then the perovskite photovoltaic unit completes the electrical output.

[0073] Figure 9 The figures show a stability comparison curve for the normalized energy conversion efficiency between Example 1 and Comparative Example 1. The results indicate that when the combined ultraviolet irradiation energy density reaches 5 kWh / m², the efficiency is significantly improved. 2At that time, Example 1 still maintained approximately 92% of its initial efficiency, while Comparative Example 1 only maintained approximately 71%. When the irradiation energy density reached 15 kWh / m², 2 At that time, Example 1 still maintained approximately 87% of the initial efficiency, meeting the stability requirements corresponding to the IEC 61215 UV pretreatment standard, while Comparative Example 1 only maintained approximately 54%. Further improvements to 20 kWh / m 2 Subsequently, Example 1 maintained an initial efficiency of approximately 82%, while Comparative Example 1 decreased to approximately 49%. These results demonstrate that the GAGG:Ce transparent scintillator substrate can effectively reduce the damage to the perovskite absorption layer and interface layer caused by composite ultraviolet irradiation, and improve the stability of the device in the space ultraviolet environment through ultraviolet absorption and spectral conversion.

[0074] Figure 10 The figure shows the current density and output power retention rate variation curves of Example 1 under continuous X-ray irradiation. To investigate the operational stability of the device under continuous ionizing radiation excitation conditions, Example 1 was subjected to continuous X-ray irradiation testing, and its current density and output power changes were recorded in real time. The test results show that during continuous X-ray irradiation, the overall changes in current density and output power retention rate of Example 1 were small. After 18,000 min of X-ray irradiation with a total dose of 53.5 kGy, the device output power still maintained 84.1% of the initial value. This result indicates that the GAGG:Ce transparent scintillator substrate can not only convert X-ray energy into usable photons, but also maintain relatively stable photovoltaic output under continuous irradiation conditions.

[0075] Comparative Example 2

[0076] The difference between Comparative Example 2 and Example 1 is that no anti-reflective coating was provided.

[0077] Figure 2 This is the optical response curve of the antireflection film in an embodiment of the present invention. The antireflection film adopts a SiO2 / Ta2O5 alternating high and low refractive index film system. The test results show that... Figure 2 In the left side of the middle figure, the transmittance of the uncoated Comparative Example 2 in the visible light region is about 80%. After coating with the antireflection film, the transmittance of the Sample 1 in the 500~800nm ​​range is increased to about 90% overall, and it shows a higher peak transmittance near 385nm. This indicates that the antireflection film can reduce Fresnel reflection loss at the incident light interface and improve the effective photon transmittance of the GAGG:Ce substrate. Figure 2The right-hand side of the figure further shows that after coating with the antireflective film, the reflectivity of the sample in Example 1 was reduced to 0-2% in the wavelength range above 400 nm, and maintained a low reflectivity level in the visible to near-infrared bands. These results demonstrate that the SiO2 / Ta2O5 multilayer antireflective film can effectively reduce the reflection loss at the GAGG:Ce incident light interface, providing an optical basis for obtaining higher effective incident photon flux in the subsequent perovskite absorption layer.

[0078] The aforementioned AMO sunlight, ultraviolet light, X-ray, gamma-ray, electron beam, and continuous irradiation tests collectively demonstrate that the perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance proposed in this invention can simultaneously achieve solar photovoltaic output, ultraviolet spectral conversion output, and radiation-excited radiative photovoltaic output. Compared with traditional substrate structures, this device exhibits stronger energy utilization and irradiation stability under high-energy ultraviolet and ionizing radiation environments, meeting the requirements of space photovoltaic and radiation environment energy harvesting devices for broad-spectrum response and stable output.

Claims

1. A perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance, characterized in that: It includes an antireflection film, a transparent scintillator substrate, a transparent conductive layer, a first charge transport layer, a perovskite absorption layer, a second charge transport layer, and electrodes, which are stacked sequentially along the incident light direction; The antireflection film is disposed on the light-incident side of the transparent scintillator substrate to reduce the reflection loss at the light-incident interface of the transparent scintillator substrate and improve the transmission efficiency of sunlight and ultraviolet light. The transparent scintillator substrate is used to transmit visible-near infrared light in the solar spectrum and to absorb ultraviolet light or high-energy radiation directed at the battery, converting the ultraviolet light and high-energy radiation into radiation that can be absorbed by the perovskite absorption layer. The perovskite absorption layer is used to absorb visible-near-infrared light transmitted through the transparent scintillator substrate and radiative emission generated by the transparent scintillator substrate, and to generate photogenerated carriers. The first charge transport layer and the second charge transport layer are used to transport photogenerated carriers of different polarities, respectively. The transparent conductive layer and electrodes are used to form an external electrical output channel.

2. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The antireflective film is a single-layer film, a double-layer film, or a multi-layer composite film.

3. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The antireflective coating is a multilayer dielectric film composed of alternating high-refractive-index dielectric layers and low-refractive-index dielectric layers; the low-refractive-index dielectric layer is selected from one or more of SiO2, MgF2, Al2O3 and porous silicon oxide, and the high-refractive-index dielectric layer is selected from one or more of Ta2O5, TiO2, Nb2O5, HfO2, ZrO2, Si3N4 and AlN.

4. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The antireflective coating has 1 to 30 layers, with a single layer thickness of 1 to 300 nm and a total thickness of 10 to 2000 nm.

5. A perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The transparent scintillator substrate is selected from one or more of the following: cerium-doped gadolinium aluminum gallium garnet, terbium / cerium co-doped gadolinium yttrium aluminum gallium garnet, cerium-doped yttrium aluminum garnet, cerium-doped lutetium silicate, cerium-doped lutetium silicate yttrium, thallium-doped cesium iodide, sodium-doped cesium iodide, thallium-doped sodium iodide, bismuth germanate, barium fluoride, lead tungstate, cesium lead bromide perovskite, methylammonium lead bromide perovskite, and two-dimensional layered lead halide perovskite scintillators.

6. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The first charge transport layer is a hole transport layer, and the second charge transport layer is an electron transport layer; or, the first charge transport layer is an electron transport layer, and the second charge transport layer is a hole transport layer.

7. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The perovskite absorber layer has an ABX3 structure or a derivative thereof, wherein the A-site cation is selected from one or more of methylammonium ion, formamidine ion, cesium ion, rubidium ion and potassium ion; the B-site metal cation is selected from one or more of lead ion, tin ion and germanium ion; and the X-site anion is selected from one or more of iodide ion, bromide ion and chloride ion.

8. The perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: The thickness of the transparent scintillator substrate is 0.05–10 mm; the thickness of the perovskite absorber layer is 50–2000 nm.

9. A perovskite photovoltaic-radiophotovoltaic integrated cell with high radiation resistance as described in claim 1, characterized in that: At least a portion of the wavelengths of the radiation emitted by the stimulated transparent scintillator substrate are within the absorption spectrum range of the perovskite absorption layer.

10. The application of the perovskite photovoltaic-radiophotovoltaic integrated cell according to any one of claims 1 to 9 as a space photovoltaic power source, a radiation environment energy harvesting device, a micro-radiophotovoltaic power source, a radiation detection auxiliary power supply device, or a long-term unattended energy device.

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