Three-dimensional confined large-area perovskite single-crystal thin film x-ray detector array and method

Abstract

The application relates to a preparation method of a three-dimensional limited large-area perovskite single-crystal thin film X-ray detector array, which comprises the following steps: preparing a metal array electrode on a substrate layer; preparing a first pattern layer on the metal array electrode; etching a PMMA layer and a first photoresist on the metal array electrode to form an isolation groove; dropping a MAPbI3 supersaturated solution on the isolation groove; covering a soft plate on the first photoresist and the MAPbI3 supersaturated solution; removing the soft plate under the condition of heating to form a MAPbI3 single-crystal thin film array on the metal array electrode; and removing the remaining PMMA layer and the first photoresist to complete the preparation of the perovskite single-crystal thin film X-ray detector array. The crystal array prepared by the method has high crystal quality which is equivalent to that of a bulk perovskite single crystal, and the thickness and area of the crystal array are controllable.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of perovskite X-ray detectors, and relates to a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array and a method. BACKGROUND

[0002] X-rays have very strong penetration ability, and therefore have been widely applied to non-destructive detection of internal information of objects in various fields such as industrial inspection, security inspection, medical examination, scientific research, etc. In the application of X-ray detectors, perovskite X-ray detectors have experienced very vigorous development in just a few years since their emergence, and have rapidly become a hot topic in the field of high-energy particle detection. Research shows that perovskite-based materials are expected to prepare a new generation of low-cost and high-performance X-ray detectors.

[0003] High-quality perovskite single crystals have low defects, and have more excellent photoelectric properties and stability than corresponding polycrystalline thin films. So far, various solution-grown single crystal technologies have been developed, including solution cooling method, anti-solvent vapor phase assisted crystallization method, inverse temperature crystallization method, etc. Although these methods successfully grow large-size single crystals, the crystal preferentially grows along its thickness direction (i.e. out-of-plane direction), so these methods are time-consuming, and it usually takes several days to obtain a larger lateral size. The space-restricted growth technology can effectively inhibit the growth of the crystal along the out-of-plane direction. This technology restricts the perovskite solution between two substrates with a micron-level gap. Under the geometric constraint in the vertical direction, the lateral growth of the crystal along the in-plane direction can be significantly promoted, and a few microns or even a few hundred nanometers of crystal with a larger lateral size and a smaller longitudinal thickness is obtained. However, the lateral size of the obtained crystal is still less than 1mm, which is insufficient to meet the application of large-scale X-ray detectors. The main reason is that under the geometric constraint in the vertical direction, the transport of the precursor solution will be very slow and chaotic, so the solute cannot be continuously supplemented to the nucleation site for continuous growth of the crystal, thereby limiting the size of the lateral crystal. In addition, the crystal growth rate in the space-restricted growth method is quite limited, and it is difficult to be compatible with the current high-throughput solution deposition technology. These problems make it still a great challenge to efficiently prepare large-area single crystals with controllable thickness. SUMMARY

[0004] In order to solve the above problems existing in the prior art, the application provides a preparation method of a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array. The technical problem to be solved by the application is solved through the following technical scheme.

[0005] The application provides a preparation method of a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array, which comprises the following steps:

[0006] Step 1, preparing a substrate layer;

[0007] Step 2, preparing a metal array electrode on the substrate layer, the metal array electrode comprising a plurality of metal electrodes arranged in an array on the substrate layer;

[0008] Step 3, preparing a first pattern layer on the metal array electrode, the first pattern layer comprising a PMMA layer covering the metal array electrode and the first photoresist on the PMMA layer;

[0009] Step 4, etching the PMMA layer and the first photoresist on the metal array electrode to form an isolation groove on each of the metal electrodes, wherein the remaining PMMA layer and the first photoresist are in a grid shape;

[0010] Step 5, dropping a MAPbI3 supersaturated solution on the isolation groove;

[0011] Step 6, covering the first photoresist and the MAPbI3 supersaturated solution with a soft plate;

[0012] Step 7, removing the soft plate at a preset speed under heating to form a MAPbI3 single crystal thin film array on the metal array electrode, the MAPbI3 single crystal thin film array comprising a plurality of MAPbI3 single crystals arranged in an array;

[0013] Step 8, removing the remaining PMMA layer and the first photoresist to complete the preparation of the perovskite single crystal thin film X-ray detector array.

[0014] In an embodiment of the application, the step 1 comprises:

[0015] The substrate layer is sequentially placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning, to obtain the cleaned substrate layer.

[0016] In an embodiment of the application, the step 2 comprises:

[0017] Step 2.1, spin-coating a second photoresist on the cleaned substrate layer by a spin-coating process, and removing the second photoresist at the metal electrode array pattern by a photoetching process, to obtain a grid-shaped metal electrode array pattern;

[0018] Step 2.2, depositing a metal electrode material on the remaining second photoresist and the metal electrode array pattern, and stripping the metal electrode material and the remaining second photoresist except the metal electrode array pattern, to prepare the metal array electrode.

[0019] In an embodiment of the application, the second photoresist comprises a 6112 photoresist.

[0020] In an embodiment of the application, the step 3 comprises:

[0021] Step 3.1, spin-coating the PMMA layer covering the metal array electrode on the substrate layer and the metal array electrode, and performing annealing treatment;

[0022] Step 3.2, spin-coating the first photoresist on the PMMA layer after annealing treatment, and forming the first pattern layer after annealing treatment.

[0023] In an embodiment of the application, the step 8 comprises:

[0024] Using chlorobenzene to dissolve the PMMA layer, removing the remaining PMMA layer and the first photoresist, to complete the preparation of the perovskite single-crystal thin film X-ray detector array.

[0025] In an embodiment of the application, after the step 8, further comprising:

[0026] Repeating the steps 3-8 to prepare a multi-layer MAPbI3 single-crystal thin film array.

[0027] In an embodiment of the application, the first photoresist comprises SU-8 photoresist.

[0028] In an embodiment of the application, the soft plate comprises a PDMS soft plate.

[0029] An embodiment of the application further provides a three-dimensional limited large-area perovskite single-crystal thin film X-ray detector array, which is prepared by using the preparation method of any one of the above embodiments, and comprises:

[0030] a substrate layer;

[0031] a metal array electrode, which is located on the substrate layer, and comprises a plurality of metal electrodes arranged in an array on the substrate layer;

[0032] a MAPbI3 single-crystal thin film array, which is located on the metal array electrode, and comprises a plurality of MAPbI3 single crystals arranged in an array.

[0033] Compared with the prior art, the application has the following beneficial effects:

[0034] The preparation method of the X-ray detector array of the present application utilizes three-dimensional geometric channel orientation to induce precursor solution flow, increases solute migration speed, and limits in-plane and out-of-plane crystallization of crystals during crystallization, so that single crystals can grow in a large area, crystallinity is improved, and thickness is accurately controlled. The crystal array prepared by this method has high crystal quality comparable to that of bulk perovskite single crystals, and the thickness and area are controllable. This method is widely applicable to growing different perovskite single crystal arrays in a large area on different substrates, making it possible to manufacture various optoelectronic devices. The perovskite X-ray detector prepared by this method has excellent performance.

[0035] Other aspects and features of the present application will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, illustrating by way of example the principles of the application. It should be understood, however, that the drawings solely are for purposes of illustration and are not intended to limit the scope of the application as described by the appended claims. It should be further understood that the drawings are not necessarily drawn to scale and that, unless otherwise indicated, they are merely intended to conceptually illustrate the structures and procedures described herein. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a flowchart of a preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array provided by an embodiment of the present application;

[0037] Figures 2a-2l is a process diagram of a preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array provided by an embodiment of the present application;

[0038] Figures 3a-3l is a process diagram of a preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array provided by an embodiment of the present application;

[0039] Figure 4 is a structural diagram of a perovskite single crystal thin film X-ray detector array provided by an embodiment of the present application. DETAILED DESCRIPTION

[0040] The present application will be further described below in conjunction with specific embodiments, but the embodiments of the present application are not limited thereto.

[0041] Embodiment One

[0042] See Figure 1 , Figures 2a-2l , Figure 1 is a flowchart of a preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array provided by an embodiment of the present application, Figures 2a-2lis a process schematic diagram of a preparation method of a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array provided by the embodiment of the present application, the embodiment of the present application provides a preparation method of a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array, the preparation method comprises:

[0043] Step 1, please refer to Figure 2a , a substrate layer 1 is prepared.

[0044] Specifically, the substrate layer is sequentially placed into acetone, anhydrous ethanol and deionized water for ultrasonic cleaning, to obtain the cleaned substrate layer, wherein the cleaning time is 3-10 min.

[0045] Optionally, the substrate layer 1 comprises silicon, sapphire or ITO, etc.

[0046] Optionally, the cleaning time of the silicon substrate layer 1 is preferably 3-5 min.

[0047] Step 2, a metal array electrode is prepared on the substrate layer, the metal array electrode comprises a plurality of metal electrodes, and the plurality of metal electrodes are arranged in an array on the substrate layer.

[0048] Step 2.1, please refer to Figure 2b and 2c , a second photoresist 2 is spin-coated on the cleaned substrate layer 1 by a spin-coating process, and the second photoresist 2 at the metal electrode array pattern is removed by a photoetching process, to obtain a grid-shaped metal electrode array pattern.

[0049] Optionally, the second photoresist 2 comprises 6112 photoresist. The 6112 photoresist is used

[0050] Optionally, the spin-coating speed of the 6112 photoresist is 4000 rpm, the time is 30 s, and the annealing temperature is 100 DEG C.

[0051] Optionally, the photoetching exposure time is 1.2 s.

[0052] Optionally, the developing solution in the photoetching process is NMP-3, and the developing time is 45 s.

[0053] Step 2.2, please refer to Figure 2d and 2e , a metal electrode material 3 is deposited on the remaining second photoresist 2 and the metal electrode array pattern, and the metal electrode material and the remaining second photoresist 2 except the metal electrode array pattern are stripped, to prepare a metal array electrode 4.

[0054] Further, the metal electrode material 3 is deposited by an E-beam (electron beam) process, etc.

[0055] Optionally, the metal electrode material comprises Au, Ag, Pt or alloy, etc.

[0056] Optionally, the thickness of the Au electrode is 180 nm.

[0057] Step 3, preparing a first pattern layer on the metal array electrode, the first pattern layer comprising a PMMA (polymethyl methacrylate) layer covering the metal array electrode and a first photoresist on the PMMA layer.

[0058] Step 3.1, referring to Figure 2f , a PMMA layer 5 covering the metal array electrode 4 is spin-coated on the substrate layer 1 and the metal array electrode 4 by a spin-coating process, and annealing treatment is performed.

[0059] Optionally, the spin-coating speed of the PMMA layer 5 is 4000 rpm, the time is 60 s, and the annealing temperature is 90°C.

[0060] Step 3.2, spin-coating a first photoresist 6 on the PMMA layer 5 after annealing treatment, and forming a first pattern layer after annealing treatment.

[0061] Optionally, the first photoresist 6 comprises SU-8 photoresist. The reason for using SU-8 photoresist is that, compared with other photoresists, SU-8 photoresist is not compatible with perovskite and will not react, and because SU-8 photoresist is difficult to remove, PMMA is arranged below the SU-8 photoresist, PMMA can be dissolved in chlorobenzene, and the upper SU-8 photoresist can be removed at the same time when PMMA is removed by chlorobenzene, and chlorobenzene will not react with perovskite, while photoresists such as 6112 photoresist need to be removed by acetone, and acetone will damage perovskite. Optionally, the spin-coating speed of the SU-8 photoresist is 8000 rpm, the time is 60 s, and the annealing temperature is 90°C.

[0062] Optionally, the thickness of the SU-8 photoresist is 1-20 μm.

[0063] Step 4, referring to Figure 2g , etching the PMMA layer 5 and the first photoresist 6 on the metal array electrode to form an isolation groove 7 on each metal electrode, wherein the remaining PMMA layer 5 and the first photoresist 6 are grid-shaped.

[0064] Further, the etching process comprises photoetching, oxygen ion etching, ion beam etching, etc.

[0065] Optionally, the photoetching exposure time is 2 min.

[0066] Optionally, an ethyl lactate 98% developing solution is used, and the developing time is 60 s.

[0067] Optionally, the length of the isolation groove is 100-1000 μm, and the width is 100-1000 μm.

[0068] Step 5, please refer to Figure 2h The MAPbI3 supersaturated solution 8 is dropped on the isolation groove 7.

[0069] The MAPbI3 supersaturated solution is prepared as follows: 254.4 mg of MAI is taken, 461.5 mg of PbI2 is added, 1 mL of GBL solution is added, and stirring is performed at 80°C, and then slow cooling is performed to obtain the MAPbI3 supersaturated solution.

[0070] Step 6, please refer to Figure 2i The soft plate 9 is covered on the first photoresist 6 and the MAPbI3 supersaturated solution 8.

[0071] Optionally, the soft plate includes a PDMS (Polydimethylsiloxane) soft plate. Because the PDMS does not react with the perovskite and is soft in material, the purpose of gradually uncovering and volatilizing the solvent can be achieved.

[0072] Step 7, please refer to Figure 2j and Figure 2k Under the condition of heating, the soft plate 9 is removed at a preset speed to form a MAPbI3 single crystal thin film array 10 on the metal array electrode 4, and the MAPbI3 single crystal thin film array 10 includes a plurality of MAPbI3 single crystals arranged in an array.

[0073] Specifically, the device to which the MAPbI3 supersaturated solution is dropped is placed on a hot stage, and a PDMS soft plate is covered, the PDMS soft plate is slowly moved, and the growth of the MAPbI3 single crystal thin film array 10 is completed as the solvent volatilizes.

[0074] Optionally, the constant temperature heating temperature on the hot stage is 80-300°C, and the PDMS soft plate is moved in the horizontal direction, and the moving speed is 0.01-0.2 mm / s -1 The temperature and speed in this range can ensure that the single crystal structure is orderly formed while the MAPbI3 supersaturated solution volatilizes.

[0075] Step 8, please refer to Figure 2l The remaining PMMA layer 5 and the first photoresist 6 are removed.

[0076] Specifically, chlorobenzene is used to dissolve the PMMA layer 5, and the remaining PMMA layer 5 and the first photoresist 6 are removed.

[0077] That is, the device prepared by the above method is soaked with chlorobenzene to remove the remaining PMMA layer 5 and the first photoresist 6 by dissolving the PMMA layer 5, so as to obtain a MAPbI3 single crystal thin film array.

[0078] Step 9, repeat steps 3-8 to prepare a multi-layer MAPbI3 single crystal thin film array, thereby the thickness of the MAPbI3 single crystal thin film array can be increased.

[0079] Wherein, in each preparation of the MAPbI3 single crystal thin film array, the multiple growth of the MAPbI3 single crystal thin film array can be realized by preparing the first pattern layer with different sizes (i.e. different width and / or length), and the area of the MAPbI3 single crystal thin film array can be expanded. Based on the above steps, a size-controllable, large-area and high-thickness MAPbI3 single crystal thin film array can be obtained.

[0080] The present application forms an array-arranged isolation groove on the basis of the metal array electrode, and the array-arranged isolation groove is distributed in the grid-shaped structure formed by the remaining PMMA layer and the first photoresist. Based on this, the MAPbI3 supersaturated solution is added dropwise in the isolation groove, and a layer of PDMS soft plate is covered thereon, thereby forming a three-dimensional geometric channel. Therefore, when the above structure is heated, the MAPbI3 supersaturated solution volatilizes by heating, and at the same time, by controlling the tearing speed of the PDMS soft plate, the recovery speed of the MAPbI3 supersaturated solution is controlled. Under the condition of a certain tearing speed, the volatilization speed of the MAPbI3 supersaturated solution is slow, so the three-dimensional geometric channel formed by the present application can be used to directionally induce the flow of the MAPbI3 supersaturated solution, and the solute migration speed is improved. Therefore, some crystals will be formed at the beginning, and with the volatilization during heating and the tearing of the PDMS soft plate, the crystals grown later will grow according to the crystal direction of the crystals grown before, thereby growing into a whole single crystal. Therefore, the in-plane and out-of-plane crystallization of the crystal is limited during the crystallization process, so that the single crystal can grow in a large area, the crystallinity is improved, and the thickness is controlled accurately.

[0081] Example two

[0082] The present application further provides a specific preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array based on example one, which comprises:

[0083] Step 1), as shown in Figure 3a , a Si substrate is selected and sequentially placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning for 3-10 min.

[0084] Step 2), as shown in Figures 3b-3cAs shown in the figure, 6112 photoresist is prepared on the cleaned Si substrate by a spin coating process, and a metal electrode array pattern is obtained by a photolithography and development process.

[0085] Step 3), as shown in the figure, Figures 3d-3e As shown in the figure, Au electrodes are prepared on the metal electrode array pattern by an E-beam process, etc., and an Au / Si array metal electrode is obtained after peeling.

[0086] Step 4), as shown in the figure, Figure 3f As shown in the figure, an SU-8 / PMMA pattern layer is prepared, a PMMA layer is deposited on the Au / Si array metal electrode by a spin coating process, then an SU-8 photoresist is deposited on the PMMA layer by a spin coating process, and the SU-8 / PMMA pattern layer is completed after annealing, to obtain an SU-8 / PMMA / Si substrate, wherein the thickness of the SU-8 / PMMA is 5 μm.

[0087] Step 5), as shown in the figure, Figure 3g As shown in the figure, an arrayed pattern is prepared, and an isolation groove is etched on the SU-8 / PMMA / Si substrate obtained in the previous step by a photolithography, oxygen ion etching, ion beam etching process, etc., and the groove depth is 5 μm.

[0088] Step 6), as shown in the figure, Figures 3h-3k As shown in the figure, an arrayed MAPbI3 single crystal thin film is prepared, first, a MAPbI3 supersaturated solution is added on the prepared arrayed pattern, then the SU-8 / PMMA / Au / Si substrate with the added MAPbI3 supersaturated solution is placed on a hot stage and covered with a PDMS soft plate, and the PDMS soft plate is slowly moved, and the MAPbI3 single crystal thin film growth is completed as the solvent volatilizes.

[0089] Step 7), as shown in the figure, Figure 3l As shown in the figure, the SU-8 / PMMA pattern is removed, the MAPbI3 / SU-8 / PMMA / Au / Si is soaked in chlorobenzene, the SU-8 / PMMA pattern is removed by dissolving the PMMA layer, and thus a perovskite single crystal thin film array is obtained.

[0090] Example Three

[0091] The embodiment of the present application further provides another specific preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array on the basis of the embodiment one, and the preparation method comprises the following steps:

[0092] Step 1), a Si substrate is selected and sequentially placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning for 3-10 minutes.

[0093] Step 2), 6112 photoresist is prepared on the cleaned Si substrate by a spin coating process, and a metal electrode array pattern is obtained by a photolithography and development process.

[0094] Step 3), Au electrodes are prepared on the metal electrode array pattern by an E-beam process, and after peeling, Au / Si array metal electrodes are obtained.

[0095] Step 4), an SU-8 / PMMA pattern layer is prepared, a PMMA layer is deposited on the Au / Si array metal electrode by a spin coating process, then SU-8 photoresist is deposited on the PMMA layer by a spin coating process, and after annealing, the SU-8 / PMMA pattern layer is completed, and an SU-8 / PMMA / Si substrate is obtained, wherein the thickness of the SU-8 / PMMA is 10 μm.

[0096] Step 5), an arrayed pattern is prepared, and an isolation groove is etched on the SU-8 / PMMA / Si substrate obtained in the previous step by a photolithography, oxygen ion etching, ion beam etching process, and the groove depth is 5 μm.

[0097] Step 6), an arrayed MAPbI3 single crystal thin film is prepared, first, a MAPbI3 supersaturated solution is added on the prepared arrayed pattern, then the SU-8 / PMMA / Au / Si substrate with the added MAPbBr3 supersaturated solution is placed on a hot stage, and a PDMS soft plate is covered, and the PDMS soft plate is slowly moved, and the MAPbI3 single crystal thin film growth is completed as the solvent volatilizes.

[0098] 7) Remove the SU-8 / PMMA pattern, immerse the MAPbI3 / SU-8 / PMMA / Au / Si in chlorobenzene, remove the SU-8 / PMMA pattern by dissolving the PMMA layer, and thus obtain a perovskite single crystal thin film array.

[0099] Example Four

[0100] The embodiment of the present application further provides another specific preparation method of a three-dimensional limited large-area perovskite single crystal thin film X-ray detector array based on the embodiment one, and the preparation method comprises the following steps:

[0101] Step 1), a Si substrate is selected and sequentially placed in acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning for 3-10 min.

[0102] Step 2), 6112 photoresist is prepared on the cleaned Si substrate by a spin coating process, and a metal electrode array pattern is obtained by a photolithography and development process.

[0103] Step 3), Au electrodes are prepared on the metal electrode array pattern by an E-beam process, and after peeling, Au / Si array metal electrodes are obtained.

[0104] Step 4), preparing SU-8 / PMMA pattern layer, using spin coating process to deposit PMMA layer on Au / Si array metal electrode, then using spin coating process to deposit SU-8 photoresist on PMMA layer, completing SU-8 / PMMA pattern layer after annealing, obtaining SU-8 / PMMA / Si substrate, wherein the thickness of SU-8 / PMMA is 5 μm.

[0105] Step 5), preparing arrayed pattern, using photoetching, oxygen ion etching, ion beam etching and the like to etch isolation groove on the SU-8 / PMMA / Si substrate obtained in the previous step, and the groove depth is 5 μm.

[0106] Step 6), preparing arrayed MAPbI3 single crystal thin film, first dropping MAPbI3 supersaturated solution on the prepared arrayed pattern, then placing the SU-8 / PMMA / Au / Si substrate with MAPbBr3 supersaturated solution on a hot stage, covering PDMS soft plate, slowly moving the PDMS soft plate, and completing MAPbI3 single crystal thin film growth along with solvent evaporation.

[0107] Step 7), removing SU-8 / PMMA pattern, using chlorobenzene to soak MAPbI3 / SU-8 / PMMA / Au / Si, removing SU-8 / PMMA pattern by dissolving PMMA layer, thereby obtaining perovskite single crystal thin film array, and obtaining MAPbI3 / Au / Si.

[0108] Step 8), preparing SU-8 / PMMA pattern layer, using spin coating process to deposit PMMA layer on the MAPbI3 / Au / Si substrate, then using spin coating process to deposit SU-8 photoresist on PMMA layer after annealing, completing SU-8 / PMMA pattern layer after annealing, obtaining SU-8 / PMMA / MAPbI3 / Au / Si substrate, wherein the thickness of SU-8 / PMMA is 10 μm.

[0109] Step 9), preparing arrayed pattern, using photoetching, oxygen ion etching, ion beam etching and the like to etch isolation groove on the SU-8 / PMMA / MAPbI3 / Au / Si substrate obtained in the previous step, and the groove depth is 5 μm.

[0110] Step 10), second growth of MAPbI3 single crystal thin film, dropping MAPbI3 supersaturated solution on the prepared SU-8 / PMMA / MAPbI3 / Au / Si with isolation groove, then placing the SU-8 / PMMA / MAPbI3 / Au / Si substrate with MAPbI3 supersaturated solution on a hot stage, covering PDMS soft plate, slowly moving the PDMS soft plate, and completing second growth of MAPbI3 single crystal thin film along with solvent evaporation.

[0111] Step 11), removing the SU-8 / PMMA pattern, the second-growth MAPbI3 single crystal thin film is soaked with chlorobenzene, the SU-8 / PMMA pattern is removed by dissolving the PMMA layer, so as to obtain a perovskite single crystal thin film array.

[0112] Example Five

[0113] See Figure 4 , the embodiment of the present application further provides a three-dimensional restriction large-area perovskite single crystal thin film X-ray detector array prepared by any one of the above embodiments, the perovskite single crystal thin film X-ray detector array comprises:

[0114] a substrate layer 1;

[0115] a metal array electrode 4, the metal array electrode 4 is located on the substrate layer 1, and the metal array electrode 4 comprises a plurality of metal electrodes arranged in an array on the substrate layer 1;

[0116] a MAPbI3 single crystal thin film array 10, the MAPbI3 single crystal thin film array is located on the metal array electrode 4, and the MAPbI3 single crystal thin film array 10 comprises a plurality of MAPbI3 single crystals arranged in an array.

[0117] In the description of the application, the terms "first", "second" are only used for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Therefore, the features defined as "first", "second" can explicitly or implicitly include one or more of the features. In the description of the application, the meaning of "a plurality of" is two or more, unless otherwise specifically limited.

[0118] In the description of the present application, the description of the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristic data points described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In the present application, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristic data points described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in the present application.

[0119] The above is further detailed description of the present application in combination with specific preferred embodiments, and cannot be deemed as limitation of the specific implementation of the present application to these descriptions. For those skilled in the art to which the present application belongs, without departing from the concept of the present application, a number of simple deductions or substitutions can be made, and all of them shall be deemed as falling within the protection scope of the present application.

Claims

1. A method for preparing a three-dimensional confined large-area perovskite single-crystal thin-film X-ray detector array, characterized in that, The preparation method comprises: Step 1, preparing a substrate layer; Step 2, preparing a metal array electrode on the substrate layer, the metal array electrode comprising a plurality of metal electrodes arranged in an array on the substrate layer; Step 3, preparing a first pattern layer on the metal array electrode, the first pattern layer comprising a PMMA layer covering the metal array electrode and a first photoresist on the PMMA layer; Step 4, etching the PMMA layer and the first photoresist on the metal array electrode to form an isolation groove on each of the metal electrodes, wherein the remaining PMMA layer and the first photoresist are in a grid shape; Step 5, dropping a MAPbI3 supersaturated solution on the isolation groove; Step 6, covering a soft plate on the first photoresist and the MAPbI3 supersaturated solution; Step 7, under the condition of heating, simultaneously removing the soft plate at a preset speed to form a MAPbI3 single crystal thin film array on the metal array electrode, the MAPbI3 single crystal thin film array comprising a plurality of MAPbI3 single crystals arranged in an array; Step 8, removing the remaining PMMA layer and the first photoresist to complete the preparation of the perovskite single crystal thin film X-ray detector array; The step 2 comprises: Step 2.1, spin-coating a second photoresist on the cleaned substrate layer by a spin-coating process, and removing the second photoresist at the metal electrode array pattern by a photoetching process to obtain a grid-shaped metal electrode array pattern; Step 2.2, depositing a metal electrode material on the remaining second photoresist and the metal electrode array pattern, and stripping the metal electrode material and the remaining second photoresist except the metal electrode array pattern to prepare the metal array electrode; The step 7 comprises: The device with the MAPbI3 supersaturated solution dropped thereon is placed on a hot stage and covered with a soft plate, and the soft plate is slowly moved to complete the growth of the MAPbI3 single crystal thin film array as the solvent volatilizes; the hot stage is heated at a constant temperature of 80-300 DEG C, and the soft plate is moved along the horizontal direction at a speed of 0.01-0.2 mm / s.

2. The method of claim 1, wherein the method comprises: The step 1 comprises: The substrate layer is sequentially placed in acetone, anhydrous ethanol and deionized water for ultrasonic cleaning to obtain a cleaned substrate layer.

3. The method of claim 2, wherein the method comprises: The second photoresist comprises a 6112 photoresist.

4. The method of claim 1, wherein the method is performed by a method comprising: The step 3 comprises: Step 3.1, spin-coating the PMMA layer covering the metal array electrode on the substrate layer and the metal array electrode, and performing annealing treatment; Step 3.2, spin-coating the first photoresist on the PMMA layer after the annealing treatment to form the first pattern layer after annealing treatment.

5. The method of claim 1, wherein the method is performed by a method comprising: The step 8 comprises: The PMMA layer is dissolved by using chlorobenzene to remove the remaining PMMA layer and the first photoresist to complete the preparation of the perovskite single crystal thin film X-ray detector array.

6. The method of claim 1, wherein the method is performed by a method comprising: After the step 8, further comprising: The steps 3-8 are repeated to prepare a multilayer MAPbI3 single crystal thin film array.

7. The method of claim 1, wherein the method comprises: The first photoresist comprises a SU-8 photoresist.

8. The method of claim 1, wherein the method is performed by a method comprising: providing a substrate; depositing a perovskite single-crystal thin film on the substrate; and depositing a metal oxide layer on the perovskite single-crystal thin film. The soft plate comprises a PDMS soft plate.

9. A three-dimensional confined large-area perovskite single-crystal thin-film X-ray detector array, characterized in that, A perovskite single-crystal thin film X-ray detector array prepared by the preparation method of any one of claims 1 to 8, comprising: a substrate layer; a metal array electrode on the substrate layer, the metal array electrode comprising a plurality of metal electrodes arranged in an array on the substrate layer; a MAPbI3 single-crystal thin film array on the metal array electrode, the MAPbI3 single-crystal thin film array comprising a plurality of MAPbI3 single crystals arranged in an array.

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