Method for preparing transparent antimony-based chalcogenide film and photoelectric detector through selective deposition

Abstract

The invention provides a method for preparing a transparent antimony-based chalcogenide film and a photoelectric detector through selective deposition. The transparent photoelectric detector structure provided by the invention comprises a transparent glass substrate, a patterned substrate, a light absorption layer, a wide-band-gap oxide covering layer and a transparent conductive electrode. The transparent light absorption layer is an antimony-based chalcogenide film and is selectively deposited on the patterned substrate. The antimony-based chalcogenide film has different growth orientations and adhesion coefficients on different substrates, and regional selective deposition of the antimony-based chalcogenide film on the patterned substrate can be realized by regulating and controlling the temperature of the substrate. The method provided by the invention breaks through the limitation of the existing transparent photoelectric detector material, and avoids the pattern edge interface damage caused by the traditional patterning methods, such as a stripping method, an etching method and a laser ablation process. The prepared transparent photoelectric detector has the advantages of being simple in preparation, accurate in transparency regulation and control, wide in spectral response in the range of 405-980 nm and the like.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of photoelectric detectors, and particularly relates to a method for preparing a transparent antimony-based chalcogenide film and a photoelectric detector by selective deposition. BACKGROUND

[0002] As an important class of optoelectronic devices, transparent photoelectric detectors have enabled many important technologies in the information age, such as eye tracking, light field imaging, non-contact user interface, etc. Among the existing materials of transparent photoelectric detectors, organic materials have low carrier mobility, poor long-term stability and high exciton binding energy; perovskite materials have poor stability and toxicity; wide-bandgap inorganic materials have narrow detection wavelength and slow response speed. In addition, there are inevitable limitations in large-area manufacturing, low cost and mechanical flexibility. Antimony-based chalcogenides, including antimony selenide, antimony sulfide and antimony sulfoselenide, are attractive candidates for the fabrication of photoelectric detectors, thermoelectric devices and solar cells due to their low toxicity, excellent chemical stability, good carrier mobility along the chain direction and high light absorption coefficient (>10 5 cm -1 ) in the visible region. However, transparent detectors based on antimony-based chalcogenides have not been reported yet.

[0003] Among the current several transparent device technologies, region-selective transmission can be easily adjusted without causing changes in color rendering index due to its inherent neutral color and the fact that the average visible light transmittance is proportional to the light transmission area, making it almost suitable for any non-transparent material. Common means of achieving patterning include chemical stripping, reactive ion etching, laser ablation, printing technology, etc. For inorganic materials, the preparation process usually causes damage to the absorption layer. Therefore, it is of great significance to develop new materials and new technologies that meet the requirements of low cost, large area and non-damaging preparation for the development of transparent photoelectric detectors. SUMMARY

[0004] The purpose of the present application is to propose a selective deposition method to solve the problem of interface damage introduced by patterning methods such as stripping, etching and laser ablation, and to apply this method to the preparation of antimony-based chalcogenide film transparent photoelectric detectors, in order to break through the limitations of existing transparent detector materials and achieve large-area, low-cost manufacturing.

[0005] A transparent antimony-based chalcogenide film prepared by selective deposition provided by the present application has a structure as shown in the structural schematic diagram Figure 2As shown, the structure includes a transparent region and an opaque region. The transparent region is a transparent glass substrate, and the opaque region, from bottom to top, consists of a transparent glass substrate, a patterned substrate, and a light-absorbing layer. The transparent glass substrate is made of soda-lime glass, quartz, FTO, or ITO conductive glass. The patterned substrate provides growth sites for the selective deposition of antimony-based chalcogenide thin films and is made of materials that facilitate the chemisorption of antimony-based chalcogenide thin films, such as metal oxides (ZnO, ZnSnO, SnO2, etc.), transition metal chalcogenides (MoSe2, PdSe, MoS2, etc.), Mo, etc. The pattern design size is smaller than the resolution of the human eye. The light-absorbing layer is made of antimony-based chalcogenide, including antimony selenide, antimony sulfide, and antimony sulfoselenide. The antimony-based chalcogenide is prepared by thermal evaporation and selectively deposited on the patterned substrate.

[0006] A method for selective deposition to prepare transparent antimony-based chalcogenide thin films, the preparation process is as follows: Figure 1 As shown, it includes the following steps:

[0007] S1. Immerse the soda-lime glass substrate in diluted FTO glass cleaning solution for 20 minutes, wipe it repeatedly with a lint-free cloth, rinse with deionized water, and dry with a nitrogen gun. For quartz, FTO, or ITO conductive glass, use acetone, isopropanol, anhydrous ethanol, and deionized water for ultrasonic cleaning in sequence, 15 minutes each time, and dry with dry air after cleaning.

[0008] S2. Photolithography pattern. This includes the following steps:

[0009] a. Spin coating: Place the cleaned transparent glass substrate on a hot plate at 200 ℃ for 5 min to remove residual moisture from the surface; AZ1500 photoresist was spin-coated using a two-step spin-coating method. The first step was spin-coating at 500 rpm for 10 s, and the second step was spin-coating at 3000 rpm for 30 s. Then, it was baked on a hot plate at 100 ℃ for 60 s to remove residual solvent. The photoresist thickness was 2 μm.

[0010] b. Exposure: Photolithography is performed using an ultraviolet lithography machine, with an exposure dose of 80 mJ / cm². 2 ;

[0011] c. Development: Immerse the exposed sample in a 2.38% tetramethylammonium hydroxide solution for 60 seconds, then rinse with deionized water for 30 seconds and dry with a nitrogen gun.

[0012] S3. Prepare a patterned substrate. This can be done using methods such as magnetron sputtering, atomic layer deposition, and thermal evaporation. The substrate must be kept at a low temperature to avoid damaging the photoresist pattern and causing high-temperature carbonization.

[0013] Further, in S3, the deposited sample is immersed in an N-methylpyrrolidone solution to remove the photoresist, rinsed with deionized water, and dried with dry air.

[0014] S4. Antimony-based chalcogenide thin films are prepared by thermal evaporation. The temperature of the soda-lime glass substrate is set to be greater than 300°C; the temperature of the FTO substrate is set to be greater than 390°C; for antimony selenide, near-space sublimation is used, with a preferred source evaporation temperature of 505°C, a soda-lime glass substrate temperature of 310°C, and an FTO substrate temperature of 395°C.

[0015] The method for preparing antimony-based chalcogenide transparent thin films disclosed in this invention is a selective deposition method. Generally, as the substrate temperature increases, the critical radius of the crystal nucleus, the barrier to stable nucleus formation, the diffusion length, and the desorption rate of adsorbed atoms all increase. Antimony-based chalcogenide thin films have different growth orientations and adhesion coefficients on different substrates. By selecting a suitable substrate and patterned substrate, and controlling the substrate temperature, selective deposition of antimony-based chalcogenide thin films on the patterned substrate can be achieved.

[0016] A transparent antimony-based chalcogenide thin-film photodetector prepared by selective area deposition is shown in the schematic diagram below. Figure 3 As shown, the structure includes a transparent region and an opaque region. The transparent region, from bottom to top, consists of a transparent glass substrate, an oxide capping layer, and a transparent conductive electrode. The opaque region, from bottom to top, consists of a transparent glass substrate, a patterned substrate, a light-absorbing layer, an oxide capping layer, and a transparent conductive electrode. The fabrication process is as follows: Figure 1 As shown, the transparent glass substrate is soda-lime glass or quartz; the patterned substrate is a wide-bandgap oxide such as ZnO, ZnSnO, SnO2, MgO, Ga2O3, and Al2O3, prepared by atomic layer deposition or magnetron sputtering; the light-absorbing layer is grown on the patterned substrate and is made of antimony-based chalcogenides, including antimony selenide, antimony sulfide, and antimony sulfoselenide, prepared by thermal evaporation; the oxide capping layer is a wide-bandgap oxide such as ZnO, ZnSnO, and SnO2, prepared by atomic layer deposition or magnetron sputtering; the transparent conductive electrode material is AZO or ITO, prepared by magnetron sputtering.

[0017] The present invention has the following beneficial effects:

[0018] (1) Selective deposition method has a simple preparation process and a large saturated vapor pressure, which makes it easy to thermally evaporate and prepare antimony-based chalcogenides over a large area. It has potential application value in transparent detectors, transparent photovoltaics and flexible devices.

[0019] (2) Precise control of transparency. A lattice of antimony selenide nanorods with a filling ratio of 10% was prepared by selective area deposition, and an average visible light transmittance (AVT) of up to 89.1% was obtained.

[0020] (3) Selective deposition method can directly realize the patterning of antimony-based chalcogenide films, solving the problem of interface damage introduced by patterning methods such as stripping, etching, and laser ablation;

[0021] (4) The transparent photodetector based on the antimony selenide array exhibits a wide spectral detection capability under high transparency. Among them, the transparent device with a 10% fill ratio has a responsivity of 0.017 A / W and a specific detectivity of 7.6 × 10⁻⁶ under 638 nm light illumination. 4 Jones. Attached Figure Description

[0022] Figure 1 A flowchart illustrating the selective deposition process for preparing transparent antimony-based chalcogenide thin films and their photodetectors.

[0023] Figure 2 A schematic diagram of the structure of a transparent antimony-based chalcogenide thin film prepared by selective deposition.

[0024] Figure 3 A schematic diagram of a transparent antimony-based chalcogenide thin film photodetector prepared by selective deposition.

[0025] Figure 4 SEM images of antimony selenide selectively deposited on different substrates: (a) glass / ZnO substrate; (b) glass / Mo / MoSe2 substrate; (c) FTO / Mo / MoSe2 substrate.

[0026] Figure 5 Transmission spectrum of antimony selenide thin film with a 10% filling ratio.

[0027] Figure 6 The photoelectric performance tests of the photodetector conducted in Example 2: (a) A 10% filled antimony selenide transparent detector at different wavelengths, with a power intensity of approximately 445.9 mW / cm². 2 (a) Photoresponse under illumination; (b) Power density-dependent IT curve of the device at 638 nm; (c) Relationship between specific detectivity and incident power density. Detailed Implementation

[0028] Example 1

[0029] A method for selective deposition to prepare transparent antimony selenide thin films, comprising the following specific steps:

[0030] S1. Immerse the soda-lime glass substrate in diluted FTO conductive glass cleaning solution for 20 minutes, then wipe it repeatedly with a lint-free cloth, rinse with deionized water, and dry with air. For FTO conductive glass, use acetone, isopropanol, anhydrous ethanol, and deionized water to ultrasonically clean the FTO glass sequentially, 15 minutes each time, and dry with air after cleaning.

[0031] S2. Photolithography. First, the cleaned soda-lime glass or FTO conductive glass is placed on a hot plate and baked at 200℃ for 5 minutes to remove residual moisture. After cooling, AZ1500 photoresist is spin-coated using a two-step method: first, spin-coating at 500 rpm for 10 seconds, and second, spin-coating at 3000 rpm for 30 seconds. Then, it is baked on a hot plate at 100℃ for 60 seconds to remove residual solvent, resulting in a photoresist thickness of 2 μm. Photolithography is performed using an MLA150 laser direct-write lithography machine with an exposure dose of 80 mJ / cm². 2 The exposed sample was immersed in a 2.38% tetramethylammonium hydroxide solution for 60 seconds for development, then rinsed with deionized water for 30 seconds and dried with a nitrogen gun.

[0032] S3. Substrate Pattern Preparation. For ZnO substrates, atomic layer deposition was used, with the central region of the heating chamber set at 100 ℃ and the surrounding area at 150 ℃. After temperature stabilization, the carrier gas flow rate was set to 20 sccm, the zinc source pulse time to 20 s, the cleaning time to 10 s, the water pulse time to 10 s, the cleaning time to 15 s, and the deposition thickness to 50 nm. For Mo substrates, magnetron sputtering was used, with a thickness of 800 nm.

[0033] Further, in S3, the deposited ZnO or Mo sample is immersed in an N-methylpyrrolidone solution to remove the photoresist, rinsed with deionized water, and dried with dry air to obtain ZnO and Mo substrate patterns. The ZnO pattern consists of a hexagonal lattice with a diameter of 30 μm and a percentage of 10%, while the Mo pattern consists of a hexagonal lattice with a diameter of 50 μm and a grid with a linewidth of 20 μm and a percentage of 50%. Further, the Mo pattern is selenized at 600°C.

[0034] S4. This invention employs a near-space sublimation method to prepare antimony selenide nanorod arrays. Preferably, for a soda-lime glass substrate, a substrate temperature of 310 °C, a source evaporation temperature of 505 °C, and a deposition time of 2.5 min were used to prepare an antimony selenide array with a thickness of approximately 1 μm and a 10% filling ratio, and an antimony selenide mesh with a 50% filling ratio. For an FTO conductive glass substrate, a substrate temperature of 395 °C, a source evaporation temperature of 505 °C, and a deposition time of 2.5 min were used to prepare an antimony selenide array with a thickness of approximately 1 μm and a 50% filling ratio.

[0035] like Figure 4 As shown in (ac), transparent antimony selenide films with filling ratios of 10% and 50% were successfully deposited selectively on three substrates: glass / ZnO, glass / Mo / MoSe2, and FTO / Mo / MoSe2. The antimony selenide pattern was consistent with the substrate pattern. The selective deposition method showed good conformality and versatility, and could achieve selective deposition of different shaped patterns on different substrate combinations.

[0036] like Figure 5 As shown, the transmittance of the transparent film was further measured, exhibiting flat transmission over a broadband range of 350–1100 nm, indicating the neutral color characteristics of the transparent antimony selenide film. The calculated AVT of the 10% transparent film was 89.1%, close to the theoretical value of the experimental design.

[0037] Example 2

[0038] A transparent antimony selenide thin-film photodetector prepared by selective area deposition.

[0039] Based on the sodium-calcium glass / ZnO / antimony selenide array structure prepared in Example 1, an atomic layer deposition of a 50 nm ZnO capping layer was performed, followed by magnetron sputtering of 300 nm AZO interdigitated electrodes with a finger width of 30 μm, a spacing of 30 μm, and an interdigitation length of 1 mm, to obtain a transparent photodetector with a 10% filling ratio of antimony selenide.

[0040] The prepared antimony selenide transparent photodetector was tested under a -20 V bias. The antimony selenide transparent photodetector was illuminated with light at 405 nm, 532 nm, 638 nm, 780 nm, 830 nm, and 9800 nm, respectively, with a cycle of 10 seconds on and 10 seconds off. The test was performed using a Keithley 2450 digital source meter.

[0041] Figure 6 (a) shows a transparent detector with a 10% fill ratio at a power intensity of approximately 445.9 mW / cm². 2 The light response under different wavelengths of light clearly shows that the detector exhibits a broad spectral response characteristic from the visible light to the near-infrared range. Figure 6 (b) The time-current characteristics of the transparent device tested under 638 nm illumination of different intensities are described. The transparent device exhibits a relatively stable photoresponse over the five test cycles. Figure 6 (c) shows the relationship between the detector's responsivity and specific detectivity under 638 nm illumination and the incident light power density. The device operates at 1.3 mW / cm². 2 Under illumination, the highest values ​​of R and D* for the transparent device are 0.017 A / W and 7.6 × 10⁻⁶, respectively.4 Jones.

[0042] The above description of the present invention is only the preferred embodiment of the present invention and is not intended to limit the implementation of the present invention. Those skilled in the art can easily make corresponding modifications or alterations based on the main concept and spirit of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of protection claimed in the claims.

Claims

1. A transparent antimony-based chalcogenide thin film prepared by selective area deposition, characterized in that, It includes a light-transmitting area and an opaque area. The light-transmitting area is a transparent glass substrate, and the opaque area consists of a transparent glass substrate, a patterned substrate, and a light-absorbing layer from bottom to top. The light-absorbing layer is an antimony-based chalcogenide compound, including antimony selenide, antimony sulfide, and antimony sulfoselenide, which is selectively deposited on the patterned substrate to achieve full-spectrum transmission.

2. A method for selective deposition to prepare transparent antimony-based chalcogenide thin films, characterized in that, Includes the following steps: S1. Clean the transparent glass substrate; S2. Spin-coat photoresist onto a transparent glass substrate and photolithographically pattern it to form a periodic hollow microstructure; S3. Prepare a patterned substrate and remove the photoresist; S4. Prepare the light-absorbing layer.

3. The method for preparing transparent antimony-based chalcogenide thin films by selective deposition according to claim 2, characterized in that, The transparent glass substrate is made of soda-lime glass, quartz, FTO, or ITO conductive glass. For soda-lime glass, it is immersed in diluted FTO glass cleaning solution for 20 minutes, wiped with a lint-free cloth, rinsed with deionized water, and then dried with a nitrogen gun. For quartz, FTO, or ITO conductive glass, it is ultrasonically cleaned sequentially with acetone, isopropanol, anhydrous ethanol, and deionized water, each cleaning session lasting 15 minutes. After cleaning, it is dried with dry air.

4. The method for selective deposition to prepare transparent antimony-based chalcogenide thin films according to claim 2, characterized in that, The photolithography process includes photoresist coating, exposure, and development. The spin coating process is a two-step spin coating method: the first step is spin coating at 500 rpm for 10 s, and the second step is spin coating at 3000 rpm for 30 s. Then, it is baked on a hot plate at 100 ℃ for 60 s to remove residual solvent. The photoresist thickness is greater than 2 μm. The size of the pattern design is smaller than the resolution of the human eye. The development process involves immersing the exposed sample in a 2.38% tetramethylammonium hydroxide solution for 60 seconds, followed by rinsing with deionized water for 30 seconds and drying with a nitrogen gun.

5. The method for preparing transparent antimony-based chalcogenide thin films by selective deposition according to claim 2, characterized in that, The patterned substrate is a material that facilitates the chemisorption of antimony-based chalcogenide thin films, such as metal oxides (ZnO, ZnSnO, SnO2, etc.), transition metal chalcogenides (MoSe2, PdSe, MoS2, etc.), Mo, etc. The material selection needs to meet the requirement that the adsorption of antimony-based chalcogenide thin films on transparent glass substrates and patterned substrates has a large difference, so as to achieve selective deposition.

6. The method for preparing transparent antimony-based chalcogenide thin films by selective deposition according to claim 2, characterized in that, The antimony-based chalcogenide thin film is prepared by thermal evaporation, and selective deposition on a patterned substrate is achieved by controlling the substrate temperature. For antimony selenide, when prepared by near-space sublimation, the substrate temperature needs to be set to be greater than 300°C for glass substrates and greater than 390°C for FTO substrates.

7. A transparent antimony-based chalcogenide thin-film photodetector prepared by selective area deposition, characterized in that, It includes a light-transmitting area and an opaque area. The light-transmitting area consists of a transparent glass substrate, an oxide capping layer, and a transparent conductive electrode from bottom to top. The opaque region structure, from bottom to top, consists of a transparent glass substrate, a patterned substrate, a light-absorbing layer, an oxide capping layer, and a transparent conductive electrode. The transparent glass substrate is soda-lime glass or quartz. The patterned substrate is a wide-bandgap oxide such as ZnO, ZnSnO, or SnO2. The light-absorbing layer is selectively deposited on the patterned substrate and is made of antimony-based chalcogenides, including antimony selenide, antimony sulfide, and antimony sulfoselenide. The oxide capping layer is a wide-bandgap oxide such as ZnO, ZnSnO, SnO2, MgO, Ga2O3, or Al2O3. The transparent conductive electrode material is AZO or ITO.

8. A method for selectively depositing transparent antimony-based chalcogenide thin-film photodetectors, characterized in that, Includes the following steps: S1. Clean the transparent glass substrate; S2. Spin-coat photoresist onto a transparent glass substrate and photolithographically pattern it to form a periodic hollow microstructure; S3. Prepare a wide-bandgap oxide patterned substrate and remove the photoresist; S4. Prepare an antimony-based chalcogenide thin film light-absorbing layer; S5, Deposit a wide-bandgap oxide capping layer; S6. Prepare AZO or ITO interdigitated electrodes.

9. The method for selectively depositing a transparent antimony-based chalcogenide thin film photodetector according to claim 8, characterized in that, The wide-bandgap oxide patterned layer is prepared by atomic layer deposition or magnetron sputtering.

10. A method for selectively depositing a transparent antimony-based chalcogenide thin film photodetector according to claim 8, characterized in that, The oxide capping layer is prepared by atomic layer deposition or magnetron sputtering.

11. The method for selectively depositing a transparent antimony-based chalcogenide thin film photodetector according to claim 8, characterized in that, The AZO or ITO transparent electrode is prepared by magnetron sputtering.

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