KR-20260067055-A - SINGLE CRYSTALLINE PEROVSKITE THIN FILM TRANSFER METHOD, PHOTO DETECTOR MANUFACTURED BY THE SAME AND THE MANUFACTURING METHOD THEREOF

KR20260067055AKR 20260067055 AKR20260067055 AKR 20260067055AKR-20260067055-A

Abstract

One embodiment of the present invention provides a single-crystal perovskite thin film transfer method in which a buffer layer is formed on a large-area single-crystal perovskite thin film grown on a substrate by one-step vapor phase epitaxy, and then a thermal release tape is applied to transfer the film to a photoelectric material layer deposited on a target substrate; a photodetector having a heterojunction structure manufactured by the single-crystal perovskite thin film transfer method; and a method for manufacturing the same.

Inventors

박진섭
탄자오종

Assignees

한양대학교 산학협력단

Dates

Publication Date: 20260512
Application Date: 20241105

Claims (12)

A step of forming a single-crystal perovskite thin film by growing on a first substrate; A step of forming a buffer layer containing a polymer on top of the single-crystal perovskite thin film; A step of attaching one side of a thermal release tape to the upper surface of the buffer layer, and then peeling and removing the first substrate from the single-crystal perovskite thin film; A step of attaching the exposed surface of the single-crystal perovskite thin film on the other side of the thermal release tape to a second substrate, and then removing the thermal release tape to transfer the single-crystal perovskite thin film; Step of removing the above buffer layer; and A step comprising heat-treating the laminate of the second substrate and the single-crystal perovskite thin film. Single-crystal perovskite thin film transfer method.
In paragraph 1, The above single-crystal perovskite thin film has an ABX3 crystal structure, wherein A is a monovalent metal ion, B is a divalent metal cation, and X is a monovalent anion. Single-crystal perovskite thin film transfer method.
In paragraph 2, The metal forming the above A is any one of Cs, Rb, K, Ba, MA( CH₃NH₃ , Methylammonium)( NH₂ ) ₂CH (Formamidinium) or a mixture thereof . Single-crystal perovskite thin film transfer method.
In paragraph 2, The metal forming the above B is, any one of Pb, Ag, Au, Bi, Cu, In, K, Na, Sb, or Sn Single-crystal perovskite thin film transfer method.
In paragraph 2, The element forming the above X is, Br, Cl, I, F, or any combination thereof Single-crystal perovskite thin film transfer method.
In paragraph 1, The above polymer is, One type selected from the group consisting of PMMA (polymethyl methacrylate), PUA (polyurethane acrylate), PS (polystyrene), PC (polycarbonate), PVA (polyvinyl alcohol), COP (cyclic olefin copolymer), PET (polyethylene terephthalate), PVB (polyvinyl butadiene), PDMS (polydimethylsiloxane)-based polymers and copolymers thereof Single-crystal perovskite thin film transfer method.
A transparent substrate formed from a transparent material; A photoelectric material layer formed on the upper surface of the above transparent substrate; A single-crystal perovskite thin film transferred to the above photovoltaic material layer using a buffer layer; and A self-biased structure comprising an electrode layer formed on top of the single-crystal perovskite thin film, wherein the single-crystal perovskite thin film and the photoelectric material layer have a vertical heterostructure. Photodetector.
In Paragraph 7, Under a 405 nm light source and -0.6 V reverse bias, the photocurrent is -1.02 x 10⁻⁶ to -1.07 x 10⁻⁶ A and the dark current is -4.5 x 10⁻¹⁰ to -5.5 x 10⁻¹⁰ A Photodetector.
In Paragraph 7, Detection performance at 0.5 V bias is 4 x 10¹² to 5 x 10¹² Jones, with a photosensitivity of 1.5 to 2.5 A/W, and an on/off ratio of 4 x 10³ to 5 x 10³ under 1 mW/ cm² - 450 nm light irradiation. Photodetector.
A step of forming a single-crystal perovskite thin film by growing on a first substrate; A step of forming a buffer layer containing a polymer on top of the single-crystal perovskite thin film; A step of attaching one side of a thermal release tape to the upper surface of the buffer layer, and then peeling and removing the first substrate from the single-crystal perovskite thin film; A step of attaching the exposed surface of the single-crystal perovskite thin film on the other side of the thermal release tape to the process material layer of a second substrate having a photoelectric material layer formed on the upper side of a transparent substrate, and then removing the thermal release tape to transfer the single-crystal perovskite thin film to the second substrate; Step of removing the above buffer layer; A step of heat-treating the laminate of the second substrate and the single-crystal perovskite thin film; and The step of forming an electrode layer on the upper surface of the single-crystal perovskite thin film, Having a vertical heterostructure between the single-crystal perovskite thin film and the photovoltaic material layer, thereby having self-bias Method for manufacturing a photodetector.
In Paragraph 10, The above transparent substrate is Formed from one or more selected from indium-tin-oxide (ITO), indium-zinc-oxide (IZO), indium-tin-zinc oxide (ITZO), indium-copper-oxide (ICO), indium-tungsten-oxide (IWO), fluorine-tin-oxide (FTO), tin oxide (SnO2), indium oxide ( In2O3 ), cadmium:zinc oxide ( Cd : ZnO ), fluorine:tin oxide (F: SnO2 ), indium:tin oxide (In: SnO2 ), gallium:tin oxide (Ga: SnO2 ), and aluminum:zinc oxide (Al:ZnO; AZO). Method for manufacturing a photodetector.
In Paragraph 10, The above photoelectric material layer Formed of one or more selected from zinc oxide (ZnO), indium oxide ( In₂O₃ ), tin oxide ( SnO₂ ), tungsten oxide ( WO₃ ), and titanium oxide ( TiO₂ ) . Method for manufacturing a photodetector.

Description

Single crystal line perovskite thin film transfer method, photodetector having a heterojunction structure manufactured thereby, and method for manufacturing the same The present invention relates to a photodetector, and more specifically, to a method for transferring a single-crystal perovskite thin film by forming a buffer layer on a large-area single-crystal perovskite thin film grown on a substrate by one-step vapor epitaxy and then applying a thermal release tape to transfer it to a photoelectric material layer deposited on a target substrate, a photodetector having a heterojunction structure manufactured by the same, and a method for manufacturing the same. Polycrystalline halide perovskites, such as polycrystalline CsPbBr₃, possess excellent optoelectronic properties, including a high defect tolerance, long carrier lifetime, and excellent absorption coefficients. Furthermore, polycrystalline halide perovskites are compatible with low-temperature solution processes, providing an easy and cost-effective fabrication method for manufacturing various optoelectronic devices. Consequently, photodetectors with polycrystalline CPB active layers have been widely investigated over the past decade. However, polycrystalline films always contain abundant grain boundaries (GBs) where defects (vacancies and dangling bonds) are concentrated, leading to high trap density. Particularly for photodetectors, GBs provide pathways for unwanted ion migration and trap-supported recombination, resulting in high leakage current and slow response speeds. On the other hand, single-crystal halide perovskites have a long-range aligned crystal structure and exhibit few defects due to the absence of grain boundaries. Therefore, single-crystal CsPbBr₃ (CPB) offers advantages over polycrystalline materials in terms of carrier mobility, lifetime, and light absorption coefficient. Consequently, the development of CPB single-crystal films (SCF) is essential for advancing perovskite-based photodetectors. Various manufacturing methods have been designed to produce high-quality CPB SCF. These include inverse temperature crystallization (ITC), chemical vapor deposition (CVD), and cutting large melt-growth bulk into films. Among these, vapor phase epitaxy (VPE) is particularly advantageous in that it allows for easy shape control and the growth of large films. However, directly forming CPB heterostructures using VPE has inherent limitations in selecting a suitable substrate. In addition, there have been attempts to fabricate various typical optoelectronic devices using SCF transferred by peeling CPB SCF grown on conventional muscovite and attaching it to an Au electrode. However, CPB SCF transferred by this method has the problem of being discontinuous and containing numerous cracks, making it unsuitable for constructing vertical structure devices. Large-area single-crystal perovskite thin films, such as CsPbBr3, deposited via chemical vapor deposition (CVD) for the development of photosensors have advantages such as controllable thickness and low trap density. However, because CVD is significantly affected by the growth substrate, there is a limitation in that only a limited number of growth substrates can be used. Furthermore, conventional dry transfer technology separates the single-crystal CPB from the initial substrate using polyvinyl alcohol (PVA) or thermal release tape (TRT) when transferring large-area single-crystal perovskite thin films. Consequently, defects such as cracks may occur during transfer, contamination may remain, and there are problems that degrade the transport characteristics of the device. For this reason, large-area single-crystal perovskite thin films deposited via CVD are difficult to apply, so the development of transfer technology for single-crystal perovskite thin films is required. FIG. 1 is a flowchart of a method for manufacturing a photodetector including a single-crystal perovskite thin film transfer method of an embodiment of the present invention. FIG. 2 is a process diagram of a method for manufacturing a photodetector including a single-crystal perovskite thin film transfer method of an embodiment of the present invention. Figure 3 is a diagram showing the manufacturing process of a photodetector using the single-crystal perovskite thin film transfer method of the experimental example. Figure 4 is an SEM image of the early growth stage of CsPbBr3 . Figure 5 shows (a) a CsPbBr3 thin film grown on muscovite, (b) an optical microscope (OM) image of the SCF (scale bar: 300 μm), (c) a scanning electron microscope image of the edge of the SCF (scale bar: 5 μm), (d) an atomic force microscope image of a 15 μm x 15 μm area (scale bar: 5 μm), and (e) an EDS mapping image of the film (scale bar: 5 μm). Figure 6 is a graph showing the compositional ratios of Cs, Pb, and Br in SCF. FIG. 7 shows (a) a graph showing the XRD pattern of CsPbBr3 grown on muscovite (inset: rocking curve (RC) of the (100) peak), (b) a gra