Transparent conductive substrate and optoelectronic device

Abstract

This application provides a transparent conductive substrate and an optoelectronic device, belonging to the field of semiconductor device technology. The transparent conductive substrate includes: a boron-doped substrate, which comprises at least one of high borosilicate glass, polyethylene terephthalate containing boron dopants, epoxy resin containing boron dopants, or soda-lime glass containing boron dopants; and a conductive layer located on the boron-doped substrate; wherein the mass fraction of boron in the boron-doped substrate is 3.7% to 4.7%, and the target thickness of the boron-doped substrate is from... 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of B and the thickness of the boron-doped substrate was determined to be consistent with the expected... 10 The thickness corresponding to the shielding efficiency of element B. 10 The atomic number density of boron is based on the density of the boron-doped substrate, the mass fraction of boron, and... 10 The elemental abundance of B is determined. Using the transparent conductive substrate of this application to fabricate optoelectronic devices is beneficial for improving the radiation stability of the devices.

Description

Technical Field

[0001] This application relates to the field of semiconductor device technology, and in particular to a transparent conductive substrate and an optoelectronic device. Background Technology

[0002] Deep space exploration equipment needs to have operational reliability and long-term stability in extreme environments, including robustness against high doses of cosmic ray irradiation. Therefore, improving the operational reliability and long-term stability of optoelectronic devices in extreme environments is particularly important. Summary of the Invention

[0003] In view of this, in order to at least partially solve the aforementioned technical problems, embodiments of this application provide a transparent conductive substrate and an optoelectronic device to improve the irradiation stability of the optoelectronic device.

[0004] According to one aspect of the embodiments of this application, a transparent conductive substrate is provided, comprising: a boron-doped substrate, wherein the boron-doped substrate comprises at least one selected from borosilicate glass, polyethylene terephthalate comprising boron dopants, epoxy resin comprising boron dopants, or soda-lime glass comprising boron dopants; and a conductive layer located on the boron-doped substrate; wherein the mass fraction of boron in the boron-doped substrate is 3.7% to 4.7%, and the target thickness of the boron-doped substrate is from... 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of B and the thickness of the boron-doped substrate was determined to be consistent with the expected... 10 The thickness corresponding to the shielding efficiency of element B. 10 The atomic number density of boron is based on the density of the boron-doped substrate, the mass fraction of boron, and... 10 The elemental abundance of B is determined. 10 The neutron reaction cross section of B represents the reaction between the neutrons incident on the boron-doped substrate and the boron-doped substrate. 10 The probability that B will react.

[0005] According to another aspect of the embodiments of this application, an optoelectronic device is provided, including the above-described transparent conductive substrate.

[0006] According to the above embodiments of this application, a transparent conductive substrate is formed by using a boron-doped substrate and a conductive layer. While ensuring light transmittance, the transparent conductive substrate can shield against cosmic ray irradiation, reduce the risk of material quality deterioration due to increased material defect density after neutron irradiation, and improve the irradiation stability of optoelectronic devices including the transparent conductive substrate. Attached Figure Description

[0007] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings of the embodiments will be briefly described below. Obviously, the drawings described below only relate to some embodiments of this application, and are not intended to limit this application.

[0008] Figure 1 A cross-sectional schematic diagram of the transparent conductive substrate provided in an embodiment of this application;

[0009] Figure 2 A cross-sectional schematic diagram of a perovskite solar cell provided in an embodiment of this application;

[0010] Figure 3 The images are scanning electron microscope (SEM) images of different perovskite thin film samples; (a) and (b) are SEM images of the perovskite thin film sample of Example 1 that was not irradiated by neutrons (i.e., unirradiated); (c) and (d) are SEM images of the perovskite thin film sample of Comparative Example 1 that was irradiated by neutrons; (e) and (f) are SEM images of the perovskite thin film sample of Example 1 that was irradiated by neutrons.

[0011] Figure 4 X-ray diffraction patterns of the perovskite thin film sample of Comparative Example 1 that was not irradiated (i.e., unirradiated), the perovskite thin film sample of Comparative Example 1 that was irradiated by neutrons, and the perovskite thin film sample of Example 1 that was irradiated by neutrons.

[0012] Figure 5 The space charge confinement current images are for the device sample of Comparative Example 2 that was not irradiated (i.e., unirradiated), the device sample of Comparative Example 2 that was irradiated by neutrons, and the device sample of Example 2 that was irradiated by neutrons.

[0013] Figure 6A The results of electrical performance testing (i.e., JV testing) of the perovskite solar cell of Example 3 before irradiation are shown.

[0014] Figure 6B The electrical performance test results of the perovskite solar cell of Comparative Example 3 before irradiation were obtained under an AM1.5 solar simulator.

[0015] Figure 7A A comparison of the electrical performance test results of w / B and w / B irradiated with 0 dose of neutrons under an AM1.5 solar simulator;

[0016] Figure 7B A comparison of the electrical performance test results of w / o B and neutron-irradiated w / o B under an AM1.5 solar simulator;

[0017] Figure 7CA comparison of the electrical performance test results of w / B and w / B irradiated by neutrons under an AM1.5 solar simulator;

[0018] Figure 8 The average rate of change in electrical performance of different perovskite solar cells and perovskite solar cells after 14 days of rest.

[0019] Explanation of reference numerals in the attached figures:

[0020] 1-Boron-doped substrate; 2-Conductive layer; 3-Hole transport layer; 4-Perovskite light-absorbing layer; 5-Electron transport layer; 6-Top electrode. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this application clearer, the following detailed description is provided in conjunction with specific embodiments and the accompanying drawings. However, this application can be implemented in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to make the invention thorough and complete, and to fully convey the scope of this application to those skilled in the art. In the drawings, for clarity, the dimensions and relative dimensions of layers and regions may be exaggerated, and the same reference numerals denote the same elements throughout.

[0022] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of this application. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0023] In related technologies, optoelectronic devices used in high-radiation environments such as space and nuclear industry suffer from performance degradation or even functional failure after being exposed to neutron radiation in such environments. To improve the reliability and long-term stability of optoelectronic devices in extreme environments, the material of the functional layer of the optoelectronic device can be adjusted or the functional layer can be modified.

[0024] For example, radiation resistance techniques for perovskite solar cells mainly focus on two aspects: additive engineering and novel transport layers. For instance, replacing 2,2',7,7'-tetrakis(N,N-p-methoxyaniline)-9,9'-spirodifluorene (spiro-OMeTAD) with poly(3-hexylthiophene) (P3HT) as the hole transport layer in perovskite solar cells has been found to alleviate the decay of open-circuit voltage and short-circuit current after neutron irradiation, but the fill factor has decreased more significantly. For example, a new type of cerium oxide (CeO) has been proposed. xThe "dual passivation" post-treatment strategy, synergistic with n-octylammonium iodide (OAI), improves the durability of solar cells under high-dose proton irradiation conditions while minimizing efficiency degradation. However, the above techniques suffer from at least the following drawbacks: inadequate shielding and potential performance degradation of the device itself.

[0025] In view of this, in order to realize the application of optoelectronic devices in fields such as deep space exploration and radiation shielding, the embodiments of this application use a transparent conductive substrate doped with boron to fabricate optoelectronic devices to achieve effective neutron shielding. Therefore, the embodiments of this application provide a transparent conductive substrate and an optoelectronic device including the transparent conductive substrate, enabling the optoelectronic device including the transparent conductive substrate to achieve excellent radiation stability.

[0026] According to an exemplary embodiment of this application, this application provides a transparent conductive substrate, with reference to... Figure 1 As shown, the transparent conductive substrate may include a boron-doped substrate 1 and a conductive layer 2 located on the boron-doped substrate 1.

[0027] The boron-doped substrate 1 may include at least one of borosilicate glass, polyethylene terephthalate containing boron dopants, epoxy resin containing boron dopants, or soda-lime glass containing boron dopants. In some embodiments, the boron dopants may include at least one of elemental boron, boron oxide, boron carbide, or boron trifluoride, thereby the boron-doped substrate 1 may be soda-lime glass doped with boron oxide, polyethylene terephthalate doped with boron carbide, or epoxy resin doped with boron trifluoride.

[0028] Studies have shown that an excessively high boron mass fraction (e.g., greater than 4.7%) in the boron-doped substrate 1 leads to increased brittleness and a higher susceptibility to cracking, consequently reducing the yield and stability of optoelectronic devices fabricated on transparent conductive substrates. Conversely, an excessively low boron mass fraction (e.g., less than 3.7%) results in insufficient neutron shielding efficiency. Furthermore, at low mass fractions, increasing the thickness of the boron-doped substrate 1 is necessary to improve shielding efficiency, which in turn reduces the transmittance of the transparent conductive substrate. Therefore, by controlling the boron mass fraction in the boron-doped substrate 1 within the range of 3.7% to 4.7%, good neutron shielding efficiency and transmittance can be achieved. For example, the fraction could be 3.7%, 3.8%, 3.9%, 4.0%, 4.2%, 4.5%, or 4.7%, but is not limited to these values.

[0029] In some embodiments, 10 The atomic number density of B can be determined based on the density of the boron-doped substrate, the mass fraction of boron, and... 10 The elemental abundance of boron (B) is determined based on the density of the boron-doped substrate, the mass fraction of boron, and... 10The elemental abundance of B determines the... 10 The atomic number density of B. As one implementation method, 10 The atomic number density of boron can be determined based on the density of the boron-doped substrate, the mass fraction of boron, the relative atomic mass of boron, and... 10 The elemental abundance of boron (B) is determined based on the density of the boron-doped substrate, the mass fraction of boron, the relative atomic mass of boron, and... 10 The elemental abundance of B is determined. 10 The atomic number density of B.

[0030] For example, based on Avogadro's constant, the density of the boron-doped substrate, the mass fraction of boron, and 10 The product of the abundances of element B and the ratio of the relative atomic mass of boron are obtained. 10 The atomic number density of B. As one implementation method, 10 The atomic number density of B can satisfy the following equation (1.1).

[0031] (1.1);

[0032] in, express 10 The atomic number density of B. This indicates the density of the boron-doped substrate. This represents Avogadro's constant, with a value of 6.022. 10 23 mol -1 . The value represents the relative atomic mass of boron in the boron-doped substrate, and is 10.811 g / mol. This indicates the mass fraction of boron in the boron-doped substrate. express 10 The elemental abundance of B. It can be considered as the inherent abundance of boron in nature, which is 19.81%.

[0033] In some embodiments, the mass fraction of boron can be determined based on the relative atomic mass of boron in the boron-doped substrate, the relative atomic mass of the boron-containing dopant, and the mass fraction of the boron-containing dopant; that is, the mass fraction of boron is determined based on the relative atomic mass of boron in the boron-doped substrate, the relative atomic mass of the boron-containing dopant, and the mass fraction of the boron-containing dopant. As another implementation, the mass fraction of boron is determined by multiplying the ratio of the relative atomic mass of boron in the boron-doped substrate to the relative atomic mass of the boron-containing dopant by the mass fraction of the boron-containing dopant.

[0034] For example, the boron-containing dopant can be boron oxide, and the mass fraction of boron can satisfy the following equation (1.2).

[0035] (1.2);

[0036] in, This represents the relative atomic mass of boron oxide, with a value of 69.62 g / mol. This indicates the mass fraction of boron oxide.

[0037] In some embodiments, 10 The neutron reaction cross section of B can represent the reaction between neutrons incident on the boron-doped substrate and the boron-doped substrate. 10 The probability of B reacting. The target thickness of the boron-doped substrate can be from... 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of B and the thickness of the boron-doped substrate was determined to be consistent with the expected... 10 The thickness corresponding to the shielding efficiency of element B, i.e., from 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of B and the thickness of the boron-doped substrate was determined to be consistent with the expected result. 10 The target thickness of the boron-doped substrate corresponding to the shielding efficiency of element B.

[0038] Specifically, assuming the thickness of the boron-doped substrate is τ cm, it can be equivalent to an equivalent thickness of τ / Each independent substrate layer The value tends to 0, so that two adjacent independent substrate layers 10 B nuclei do not shield each other. The incident neutron beam passes through the substrate and 10 The probability of nuclear reactions occurring in B is equal and independent. This applies to a single incident neutron and the substrate layer. 10 The nuclear reaction equation for B and the total probability P of being shielded satisfy the following equations (1.3) and (1.4).

[0039] (1.3);

[0040] (1.4);

[0041] in, This indicates the equivalent thickness of the substrate layer. express 10 Neutron reaction cross section of B. This indicates the incident neutrons in the substrate and the neutrons in the substrate. 10 The probability of nuclear reaction B occurring. 1- This indicates that the incident neutrons in the substrate did not interact with the substrate.10 The probability of B undergoing a nuclear reaction. Indicates τ / In each substrate layer, the incident neutron did not interact with τ / In each substrate layer 10 The probability of B undergoing a nuclear reaction. Indicates τ / Incident neutrons and τ / in each substrate layer In each substrate layer 10 The probability of B undergoing a nuclear reaction. It can take the value 3842 barns. According to the following formula (1.5), It can take the value 3842×

[0042] (1.5);

[0043] According to equation (1.6), equation (1.4) can be converted into equation (1.7).

[0044] (1.6);

[0045] in, This represents the natural logarithm, and its value can be 2.71828.

[0046] (1.7).

[0047] In some embodiments, the boron-containing dopant of the boron-doped substrate can be boron oxide, and the mass fraction of boron oxide can be 12.8%. According to equations (1.1) and (1.2), N is obtained. Boron-10 =1.023 21 cm -3 N Boron-10 Substituting into equation (1.7), we get P = Assumptions and expectations 10 With the shielding efficiency of element B set to 90.5%, the target thickness of the boron-doped substrate needs to be set to 0.6 cm. Assuming expected... 10 With the boron element shielding efficiency set to greater than 99.9%, the target thickness of the boron-doped substrate needs to be greater than or equal to 2 cm. Given a target thickness greater than 2 cm, further increasing the target thickness may affect the expected... 10 The improvement in shielding efficiency of element B is limited, so the target thickness can be set to less than or equal to 2 cm.

[0048] In the embodiments of this application, since fast neutrons are the main component of secondary particles produced by collisions between cosmic rays and spacecraft outer shells, for incident fast neutrons, the boron-doped substrate... 10B can undergo nuclear reactions with incident fast neutrons and scatter alpha particles with lower penetrating power, thus effectively shielding against incident neutron radiation. Therefore, according to... 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of boron and the thickness of the boron-doped substrate can be determined based on expectations. 10 The shielding efficiency of boron element is used to determine the target thickness of the boron-doped substrate, achieving... 10 Controllable adjustment of boron shielding efficiency. By controlling the mass fraction of boron in the boron-doped substrate between 3.7% and 4.7%, the shielding efficiency can be adjusted without damaging the boron-doped substrate, according to the expected results. 10 By adjusting the target thickness of the boron-doped substrate to improve the shielding efficiency of element B, a transparent conductive substrate that balances excellent neutron shielding efficiency and light transmittance can be obtained.

[0049] In some embodiments, the target thickness of the boron-doped substrate can be 0.6 cm to 2 cm. By controlling the target thickness of the boron-doped substrate within the above range, a neutron shielding efficiency of over 90.5% can be achieved.

[0050] In some embodiments, the transmittance of the transparent conductive substrate in the visible light band can be between 85% and 90%, for example, 85%, 86%, 88% or 90%, but is not limited to the values ​​mentioned.

[0051] In some embodiments, the mass fraction of rare earth elements in the boron-doped substrate can be 0.3% to 0.5%.

[0052] In some embodiments, rare earth elements may include at least one of cerium, erbium, or barium. Studies have found that by controlling the mass fraction of rare earth elements in the boron-doped substrate within the aforementioned range, it is possible to achieve 10 12 ~10 15 p·cm -2 Shielding of incident protons.

[0053] In some embodiments, when preparing soda-lime glass using a high-temperature melting method, barium oxide or cerium oxide is added during the melting process.

[0054] In some embodiments, the conductive layer may include at least one of fluorine-doped tin oxide or indium-doped tin oxide.

[0055] According to an exemplary embodiment of this application, this application provides an optoelectronic device including the above-described transparent conductive substrate.

[0056] In some embodiments, the optoelectronic device may include a solar cell. For example, the solar cell may be at least one of a perovskite solar cell, a silicon-based solar cell, an organic solar cell, a gallium arsenide solar cell, or a copper indium gallium selenide solar cell.

[0057] The following is combined Figure 2 Taking perovskite solar cells as an example, this paper will explain perovskite solar cells.

[0058] Figure 2 This is a cross-sectional schematic diagram of a perovskite solar cell provided in an embodiment of this application.

[0059] refer to Figure 2 As shown, a perovskite solar cell may include a transparent conductive substrate (which may include a boron-doped substrate 1 and a conductive layer 2 located on the boron-doped substrate 1), a hole transport layer 3 located on the conductive layer 2, a perovskite light-absorbing layer 4 located on the hole transport layer 3, an electron transport layer 5 located on the perovskite light-absorbing layer 4, and a top electrode 6 located on the electron transport layer 5.

[0060] In some embodiments, a fluorine-doped tin oxide (FTO) layer can be deposited on a boron-doped substrate using magnetron sputtering. A hole transport layer 3, a perovskite light-absorbing layer 4, an electron transport layer 5, and a top electrode 6 are then sequentially formed on the FTO layer.

[0061] In some embodiments, the top electrode 6 may include a metallic electrode or a non-metallic electrode. For example, a metallic electrode may include gold (Au), chromium (Cr), or titanium (Ti). A non-metallic electrode may include carbon (C).

[0062] The following schematic illustration illustrates the design of a transparent conductive substrate and an optoelectronic device including the transparent conductive substrate. It should be noted that this illustration is merely a specific embodiment of this application and does not limit the scope of protection of this application.

[0063] Example 1

[0064] A hole transport layer and a perovskite absorber layer were prepared on a transparent conductive substrate to obtain a perovskite thin film sample.

[0065] 1. Prepare a transparent conductive substrate.

[0066] 1.1. Provide a boron-doped substrate. The boron-doped substrate is high borosilicate glass. The mass fraction of B2O3 in the high borosilicate glass is 12.8%. 10 The abundance of boron (B) is 19.81%. The density of high borosilicate glass is 2.3 g / cm³. 3 .

[0067] According to equations (1.1) and (1.2), the boron-doped substrate is obtained. It is 1.023 21 cm -3 Given that the expected shielding efficiency is greater than or equal to 90.5%, according to Equation (1.7), the thickness of the borosilicate glass should be greater than or equal to 0.6 cm (i.e. 6 mm). Therefore, a transparent conductive substrate is prepared using borosilicate glass with dimensions of 150 mm × 150 mm × 6 mm.

[0068] 1.2. Preparation of FTO thin films on boron-doped substrates.

[0069] FTO thin films were prepared on boron-doped substrates using magnetron sputtering with a Sn+15%wt SnF2 target. The preparation process involved weighing 100 g of tin (Sn) powder and 15%wt (15 g) of tin difluoride (SnF2) and grinding them uniformly in a mortar. The resulting powder was poured into a beaker, acetone solution was added, and the mixture was mechanically stirred for 2 hours followed by manual stirring with a glass rod for 0.5 hours, alternating between the two processes five times. The slurry was heated to 70°C for 48 hours in a vacuum drying oven to obtain a dried powder. This powder was then placed in a mold and pressed at 100 MPa to obtain a cylinder with a thickness of 5 mm. The cylinder was then placed in an oven and heated to 110°C for heat treatment.

[0070] A Sn+15wt% SnF2 target was placed in the vacuum chamber of a magnetron sputtering apparatus, and an FTO thin film was deposited on a boron-doped substrate at 150 °C under an Ar / O2 atmosphere. The target-substrate distance was 60 mm. The sputtering pressure was 0.3 Pa. The base vacuum was 1.0 × 10⁻⁶. 3 Pa. Ar flow rate: 60 sccm. Deposition rate: 20 nm / min. FTO film thickness: 300 nm.

[0071] 2. Clean the transparent conductive substrate.

[0072] The transparent conductive substrate was sequentially placed in deionized water, acetone, isopropanol, and ethanol solvents, and ultrasonically cleaned for 10 minutes in each solvent. The surface solvent was then dried with nitrogen gas, and the substrate was placed in a UV ozone cleaner at 30 °C for 20 minutes.

[0073] 3. Prepare a hole transport layer on a transparent conductive substrate.

[0074] Hole transport layer (2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl)phosphonic acid (i.e., MeO-2PACz) was prepared on a transparent conductive substrate in a nitrogen atmosphere in a glove box.

[0075] Specifically, a 0.5 mg / mL ethanol solution of MeO-2PACz was prepared, and 100 μL of the MeO-2PACz solution was added dropwise onto a transparent conductive substrate. The spin-coating parameters were set as follows: spin speed 4000 rpm, spin time 30 s. After spin-coating, the transparent conductive substrate was placed on a hot plate and annealed at 100°C for 10 minutes to form an FTO / MeO-2PACz substrate.

[0076] The FTO / MeO-2PACz substrate was then placed on a spin coater and the spin speed was set to 4000 rpm. After the spin speed stabilized, 100 μL of isopropanol solution was added dropwise for washing twice to remove MeO-2PACz molecules that had not formed chemical bonds with FTO.

[0077] 4. Prepare a perovskite absorber layer on the hole transport layer.

[0078] In a nitrogen atmosphere within a glove box, a perovskite light-absorbing layer Rb was fabricated on the hole transport layer. 0.05 Cs 0.05 MA 0.05 FA 0.85 Pb(I 0.95 Br 0.05 )3, and chemical passivation of the surface of the perovskite light absorption layer.

[0079] To prepare the perovskite precursor solution, specifically, weigh CsI, RbI, MABr, FAI, PbI2, and PbBr2 powders according to the molar ratio of the perovskite components as described above, and dissolve them in a 1.5 M solution of a mixed solution of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) (DMF to DMSO volume ratio of 4:1). Then, heat and stir at 50°C for 2 hours using a magnetic stirrer before use.

[0080] A perovskite light-absorbing layer was prepared on the hole transport layer. Specifically, 50 μL of perovskite precursor solution was dropped onto an FTO / MeO-2PACz substrate. The spin coater was set to a multi-step spin-coating mode: the first spin-coating speed was 1000 rpm, the spin-coating time was 10 s, and the acceleration was 1000 rpm / s. The second spin-coating speed was 3000 rpm, the spin-coating time was 30 s, and the acceleration was 2000 rpm / s. Ten seconds before the end of the second spin-coating step, 150 μL of the antisolvent chlorobenzene was continuously and rapidly added dropwise. The sample was then annealed on a 100°C hot plate for 20 minutes.

[0081] Chemical passivation was performed on the upper surface of the perovskite light-absorbing layer. Specifically, isopropanol solutions of 0.5 mg / mL ethylenediamine dihydroiodide (EDAI2) and 0.5 mg / mL methylammonium iodide (MAI) were prepared, heated and stirred at 70 °C for 2 hours, and then filtered to obtain a mixed solution of EDAI2 and MAI. After the perovskite film was annealed and cooled, 100 μL of the EDAI2 and MAI mixture was added dropwise, and spin-coating was performed at a spin-coating speed of 5000 rpm and a spin-coating time of 60 s.

[0082] Comparative Example 1

[0083] Perovskite thin film samples were prepared using the same method as in Example 1, except that the transparent conductive substrate was replaced with an FTO substrate. The FTO substrate had dimensions of 150 mm × 150 mm × 6 mm. The FTO substrate had a transmittance of 85% in the 400–700 nm wavelength range.

[0084] Example 2

[0085] A hole transport layer and a perovskite absorber layer were fabricated on a transparent conductive substrate using the same method as in Example 1. The difference from Example 1 is that a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) layer and a top electrode were also fabricated on the perovskite absorber layer to obtain a device sample.

[0086] A PTAA layer was prepared on the perovskite absorber layer.

[0087] Specifically, 30 mg of PTAA was weighed using an electronic analytical balance. 1 mL of chlorobenzene solvent was added to a 4 mL glass bottle containing PTAA using a pipette with a 1000 μL capacity to dissolve the PTAA. The bottle was shaken and stirred for at least 8 hours until the solute was observed to be almost completely dissolved. The PTAA solution was filtered through a 0.22 μm PTFE filter before use. A perovskite absorber layer was prepared using the same method as in Example 1. The PTAA solution was spin-coated onto the perovskite absorber layer at a speed of 4000 rpm for 30 seconds with an acceleration of 2000 rpm / s to prepare a hole transport layer. After spin-coating, the sample was transferred to a 100°C hot plate and annealed for 10 minutes.

[0088] A top electrode is fabricated on a PTAA layer. Specifically, at a depth below 4 × 10⁻⁶... -4 Ag was deposited at a vacuum level of Pa, with a thickness of 100 nm.

[0089] Comparative Example 2

[0090] The difference from Example 2 is that the transparent conductive substrate is replaced with an FTO substrate. The FTO substrate has dimensions of 150mm × 150mm × 6mm. The FTO substrate has a transmittance of 85% in the 400~700nm wavelength range.

[0091] Example 3

[0092] A hole transport layer and a perovskite absorber layer were fabricated on a transparent conductive substrate using the same method as in Example 1. The difference from Example 1 is that an electron transport layer and a top electrode were also fabricated on the perovskite absorber layer to obtain a perovskite solar cell.

[0093] An electron transport layer is fabricated on a perovskite light-absorbing layer.

[0094] Specifically, a 20 mg / mL solution of methyl [6,6]-phenyl-C61-butyrate (PCBM) was prepared, heated at 70 °C for 2 hours, and then 30 μL was added dropwise to the surface of the perovskite absorber layer. The spin-coating parameters were set as follows: spin-coating rate of 1000 rpm, spin-coating time of 30 s, and acceleration of 200 rpm / s. After spin-coating, the layer was annealed at 70 °C for 10 min.

[0095] A top electrode is fabricated on the electron transport layer.

[0096] Specifically, below 4×10 -4 Under a vacuum of Pa, 5 nm thick 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 100 nm thick Ag were deposited by vapor deposition.

[0097] Comparative Example 3

[0098] Perovskite solar cells were fabricated using the same method as in Example 3, except that the transparent conductive substrate was replaced with an FTO substrate. The FTO substrate had dimensions of 150 mm × 150 mm × 6 mm. The FTO substrate had a transmittance of 85% in the 400–700 nm wavelength range.

[0099] The 8.7 × 10⁸ helium-neon laser fusion device produced the energy. 7 n / cm -3 Fast neutrons with a dose and energy of 10.1 MeV were used to irradiate the perovskite thin film sample of Example 1, the perovskite thin film sample of Comparative Example 1, the device sample of Example 2, and the device sample of Comparative Example 2, respectively, to obtain irradiated perovskite thin film samples and irradiated device samples.

[0100] Figure 3The images show scanning electron microscope (SEM) images of different perovskite thin film samples; (a) and (b) are SEM images of the perovskite thin film sample of Example 1 that was not irradiated (i.e., unirradiated). (c) and (d) are SEM images of the perovskite thin film sample of Comparative Example 1 that was irradiated with neutrons. (e) and (f) are SEM images of the perovskite thin film sample of Example 1 that was irradiated with neutrons.

[0101] See Figure 3 Figures (a) to (b) show that before fast neutron irradiation, the perovskite film of Example 1 exhibited a low defect density, with no obvious lead iodide precipitation or film degradation observed, maintaining good film quality. (Comparison) Figure 3 Figures (c) to (d) show that, under fast neutron irradiation, the perovskite thin film sample of Comparative Example 1 exhibited a significant degree of lead iodide precipitation caused by neutron irradiation. This indicates that the perovskite thin film sample of Comparative Example 1 showed a greater degree of degradation, an unsatisfactory defect density, and low neutron irradiation stability. These phenomena were effectively suppressed in the irradiated Example 1, as shown in Figures (e) to (f), demonstrating the suppressive effect of the high borosilicate substrate of Example 1 on neutron irradiation.

[0102] Figure 4 The X-ray diffraction patterns are those of the perovskite thin film sample of Comparative Example 1 that was not irradiated (i.e., unirradiated), the perovskite thin film sample of Comparative Example 1 that was irradiated by neutrons, and the perovskite thin film sample of Example 1 that was irradiated by neutrons.

[0103] refer to Figure 4 As shown, compared to the unirradiated perovskite film sample of Comparative Example 1, the characteristic peak of the neutron-irradiated perovskite film sample of Comparative Example 1 shows a slight left shift, indicating that the lattice of the neutron-irradiated perovskite film of Comparative Example 1 is distorted, leading to an increase in the defect density in the perovskite film. Compared to the neutron-irradiated perovskite film sample of Comparative Example 1, the left shift of the characteristic peak of the neutron-irradiated perovskite film sample of Example 1 is smaller. This indicates that, compared to Example 1, the neutron-irradiated perovskite film sample of Comparative Example 1 exhibits more neutron-induced lattice distortion and defect sites. Example 1, by using a transparent conductive substrate containing boron, can effectively shield neutrons and reduce neutron-induced lattice distortion and defect sites.

[0104] Figure 5 The images show the space charge confinement current of the device sample of Comparative Example 2 that was not irradiated (i.e., unirradiated), the device sample of Comparative Example 2 that was irradiated with neutrons, and the device sample of Example 2 that was irradiated with neutrons.

[0105] refer to Figure 5As shown, the defect-filling limiting voltage V of the device sample in Comparative Example 2 without irradiation. TFL1 (i.e., the voltage corresponding to the inflection point of the curve), is less than the defect-filling limit voltage V of the device sample in Comparative Example 2 that has been irradiated with neutrons. TFL2 The defect-filling limiting voltage V of the device sample from Example 2 irradiated with neutrons TFL3 .

[0106] In addition, the defect-filling limiting voltage V of the device sample in Example 2 irradiated with neutrons TFL3 The defect-filling limiting voltage V is less than that of the device sample in Comparative Example 2, which was irradiated with neutrons. TFL2 Due to the defect filling limiting voltage V TFL The defect filling limit voltage V is positively correlated with defect density. TFL The higher the value, the greater the defect density. According to... Figure 5 It can be seen that by replacing the FTO substrate with the transparent conductive substrate of Example 2, the increase in defect density of the perovskite film after neutron irradiation can be effectively suppressed.

[0107] Figure 6A The results are the electrical performance test (i.e., JV test) results of the perovskite solar cell of Example 3 before irradiation under an AM1.5 solar simulator.

[0108] Figure 6B The electrical performance test results of the perovskite solar cell of Comparative Example 3 before irradiation were obtained using an AM1.5 solar simulator.

[0109] refer to Figure 6A , Figure 6B As shown, the current density (i.e., Jsc) of the perovskite solar cell in Example 3 before irradiation was 25.85 mA / cm². 2 Open-circuit voltage (i.e., V) OC The voltage is 1.177V. The fill factor (FF) is 81.99%, and the power conversion efficiency (PCE) is 24.94%. The Jsc of the perovskite solar cell in Comparative Example 3 before irradiation is 25.65 mA / cm². 2 V OC The voltage was 1.175V. The FF was 81.75%. The PCE was 24.64%. This indicates that, compared to the perovskite solar cell of Comparative Example 3 before irradiation, the electrical performance of the perovskite solar cell of Example 3 before irradiation did not change significantly. This demonstrates that replacing the FTO substrate with a transparent conductive substrate has a limited impact on the external light flux received by the perovskite thin film, and using a transparent conductive substrate for neutron shielding has a limited impact on the intrinsic efficiency of the perovskite solar cell device.

[0110] Two sets of perovskite solar cells (labeled w / B) were fabricated using the same method as in Example 3, and 8.7 × 10⁸ solar cells were generated using a large-scale helium-neon laser fusion device. 7 n / cm -3 One group of perovskite solar cells was irradiated with fast neutrons at a dose of 10.1 MeV to obtain neutron-irradiated perovskite solar cells (labeled as neutron-irradiated w / B). Another group of perovskite solar cells was irradiated with 0-dose fast neutrons (i.e., the perovskite solar cells were taken to the neutron irradiation experimental site and shielded behind multiple layers of boron-containing polyethylene; this can be considered as 0-dose neutron irradiation), resulting in 0-dose neutron-irradiated perovskite solar cells (labeled as 0-dose neutron-irradiated w / B). The electrical performance of the perovskite solar cells before and after irradiation was tested, and the results are shown in Table 1.

[0111] Perovskite solar cells (labeled w / o B) were fabricated using the same method as in Comparative Example 3. An 8.7 × 10⁸ solar cell was generated using a large-scale helium-neon laser fusion device. 7 n / cm -3 The perovskite solar cells were irradiated with fast neutrons at a dose of 10.1 MeV (labeled as w / o B after neutron irradiation). The electrical performance of the perovskite solar cells before and after irradiation was tested, and the test results are shown in Table 1.

[0112] Figure 7A A comparison chart showing the electrical performance test results (i.e., JV test) of w / B and w / B irradiated with 0 dose of neutrons under an AM1.5 solar simulator.

[0113] refer to Figure 7A As shown, compared to w / B, the photoelectric conversion efficiency of w / B irradiated with 0 dose neutrons is increased. This is due to the decrease in strain and the reduction in defect density caused by the rearrangement of ions inside the perovskite. The increase is within 5% of the intrinsic efficiency.

[0114] Figure 7B A comparison chart showing the electrical performance test results of w / o B and neutron-irradiated w / o B under an AM1.5 solar simulator.

[0115] refer to Figure 7B As shown, compared to w / o B, the photoelectric conversion efficiency and open-circuit voltage of w / o B after neutron irradiation are reduced. This is due to the precipitation of lead iodide caused by neutron irradiation, which leads to an increase in defects in the perovskite thin film.

[0116] Figure 7CA comparison of the electrical performance test results of w / B and w / B irradiated by neutrons under an AM1.5 solar simulator.

[0117] refer to Figure 7C As shown, compared to w / B, the photoelectric conversion efficiency of w / B after neutron irradiation does not decrease significantly, and the open-circuit voltage hardly decreases. This is because the transparent conductive substrate can effectively shield neutrons, thereby suppressing the increase of defects in the perovskite thin film caused by neutron irradiation.

[0118] Table 1. Electrical performance test results of different perovskite solar cells

[0119]

[0120] Unirradiated w / B, irradiated w / B, and irradiated w / o B were left to stand for 14 days to obtain unirradiated w / B aged for 14 days (labeled as (unirradiated w / B aged for 14 days), irradiated w / B aged for 14 days (labeled as irradiated w / B aged for 14 days), and irradiated w / o B aged for 14 days (labeled as irradiated w / B aged for 14 days).

[0121] Figure 8 The average rate of change in electrical performance is given for different perovskite solar cells and perovskite solar cells after 14 days of rest. The rate of change in electrical performance is defined as the statistical result of the ratio of the change in electrical performance obtained from JV testing after irradiation to the intrinsic electrical performance of the device.

[0122] refer to Figure 8 As shown, compared to w / B, the PCE and V of w / B irradiated with neutrons are higher. OC Electrical parameters such as Jsc all decreased. Compared to w / B, the electrical parameters of perovskite solar cells with w / o B irradiated by neutrons showed a more significant decrease.

[0123] Compared to neutron-irradiated w / B, the performance of w / B cells that have been left to stand for 14 days after neutron irradiation deteriorates further. For example, the photoelectric conversion efficiency of w / B cells irradiated by neutrons decreases by approximately 12% compared to w / B cells. The photoelectric conversion efficiency of w / B cells left to stand for 14 days after neutron irradiation decreases by approximately 16%.

[0124] Compared to neutron-irradiated w / o B, the photoelectric conversion efficiencies (PCE), Jsc, and FF of neutron-irradiated w / o B all show a smaller decrease compared to the intrinsic efficiency. This indicates that using a boron-doped substrate can effectively shield neutron radiation, suppress the degradation of electrical performance after radiation, and improve the irradiation stability of the device.

[0125] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of this application. It should be understood that the above descriptions are merely specific embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A transparent conductive substrate, characterized in that, include: A boron-doped substrate, wherein the boron-doped substrate comprises at least one of borosilicate glass, polyethylene terephthalate comprising boron dopants, epoxy resin comprising boron dopants, or soda-lime glass comprising boron dopants; A conductive layer is located on the boron-doped substrate; The boron-doped substrate has a boron content of 3.7% to 4.7% by mass, and the target thickness of the boron-doped substrate is from... 10 B element shielding efficiency and 10 Atomic number density of B 10 The mapping relationship between the neutron reaction cross section of B and the thickness of the boron-doped substrate was determined to be consistent with the expected... 10 The thickness corresponding to the shielding efficiency of element B, the 10 The atomic number density of boron is based on the density of the boron-doped substrate, the mass fraction of boron, and... 10 The elemental abundance of B is determined, the aforementioned 10 The neutron reaction cross section of B represents the reaction between the neutron incident on the boron-doped substrate and the boron-doped substrate. 10 The probability that B will react.

2. The transparent conductive substrate according to claim 1, characterized in that, The target thickness of the boron-doped substrate is 0.6 cm to 2 cm.

3. The transparent conductive substrate according to claim 1 or 2, characterized in that, The boron-containing dopant includes at least one of elemental boron, boron oxide, boron carbide, or boron trifluoride.

4. The transparent conductive substrate according to claim 1 or 2, characterized in that, The transmittance of the transparent conductive substrate in the visible light band is between 85% and 90%.

5. The transparent conductive substrate according to claim 1 or 2, characterized in that, The boron-doped substrate has a rare earth element mass fraction of 0.3% to 0.5%, and the rare earth element includes at least one of cerium, erbium, or barium.

6. The transparent conductive substrate according to claim 1 or 2, characterized in that, The conductive layer includes at least one of fluorine-doped tin oxide or indium-doped tin oxide.

7. The transparent conductive substrate according to claim 1 or 2, characterized in that, The 10 The atomic number density of B is based on the density of the boron-doped substrate, the mass fraction of boron, the relative atomic mass of boron, and... 10 The elemental abundance of B is determined, and the mass fraction of boron is determined based on the relative atomic mass of boron in the boron-doped substrate, the relative atomic mass of the boron-containing dopant, and the mass fraction of the boron-containing dopant.

8. An optoelectronic device, characterized in that, Includes a transparent conductive substrate according to any one of claims 1 to 7.

9. The optoelectronic device according to claim 8, characterized in that, The optoelectronic device includes a solar cell.

10. The optoelectronic device according to claim 9, characterized in that, The solar cell includes at least one of perovskite solar cells, silicon-based solar cells, organic solar cells, gallium arsenide solar cells, or copper indium gallium selenide solar cells.

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