A terbium-doped tin oxide thin film photoluminescence material and a preparation method thereof

Abstract

The application relates to a terbium-doped tin oxide film photoluminescence material and a preparation method thereof. The method comprises the following steps: dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol and stirring at a first temperature to obtain solution A; adding deionized water to the solution A to obtain solution B; stirring the solution B at the first temperature until the solvent is volatilized completely to form a dry gel, and then adding ethanol to obtain solution C; reducing the temperature to a second temperature, stirring at the second temperature, adding acetic acid to the solution C to adjust the pH value, and obtaining solution D; stirring the solution D at a third temperature for a period of time, and then standing at room temperature for 24 hours to obtain solution E; spin coating the solution E on a substrate to prepare a film, and placing the film on a heating table to heat, so that a thin film based on the substrate is obtained; and adopting a rapid thermal annealing device to perform annealing treatment, so that the terbium-doped tin oxide film photoluminescence material is obtained. The product prepared by the application has excellent photoluminescence performance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of light-emitting materials, in particular to a terbium-doped tin oxide thin film photoluminescence material and a preparation method thereof. BACKGROUND

[0002] SnO2 is a wide-bandgap semiconductor with a bandgap of 3.6 eV, high carrier mobility and low phonon energy, and has a high transmittance in the visible and near-infrared wavebands. Doping Sb or F can greatly increase the electron concentration in SnO2, making it an excellent conductive material. At present, the process for preparing SnO2 generally obtains high-quality thin films through vacuum vapor deposition. It is worth studying to improve SnO2 so that it has excellent performance. SUMMARY

[0003] The technical problem to be solved by the application is to provide a terbium-doped tin oxide thin film photoluminescence material and a preparation method thereof. The preparation method is simple in process, low in cost and short in reaction period, the obtained terbium-doped tin oxide thin film has photoluminescence performance, and the luminescence performance is strong.

[0004] To solve the above technical problems, the application provides a technical scheme of a preparation method of a terbium-doped tin oxide thin film photoluminescence material, which comprises the following steps:

[0005] Step one, dissolve stannous chloride dihydrate and terbium chloride hexahydrate in ethanol and stir at a first temperature to obtain solution A;

[0006] Step two, add deionized water to the mixed solution A to obtain solution B;

[0007] Step three, stir solution B at the first temperature until the solvent is almost completely volatilized to form a dry gel, then add ethanol to obtain solution C;

[0008] Step four, reduce the temperature to a second temperature, stir at the second temperature, add acetic acid to solution C to adjust the pH value, and obtain solution D;

[0009] Step five, stir solution D at a third temperature for a period of time, then stand at room temperature for 24 hours to obtain solution E;

[0010] Step six, spin-coat solution E on a substrate to prepare a film, and place the film on a heating table to heat, so as to obtain a thin film based on the substrate;

[0011] Step seven, use a rapid thermal annealing device to anneal the thin film based on the substrate obtained in step six to obtain a terbium-doped tin oxide thin film photoluminescence material.

[0012] The mass-volume ratio of the stannous chloride dihydrate, terbium chloride hexahydrate and anhydrous ethanol in step one is (0.1-1) g:(0.0001-0.05) g:(0.5-10) ml.

[0013] The volume ratio of the deionized water added in step two to the ethanol in step one is (10-1000) mu l:(0.5-10) ml.

[0014] The first temperature in step three is 50-100 DEG C, and the volume ratio of the ethanol added in step three to the ethanol added in step one is (0.5-1):1.

[0015] The second temperature in step four is 10-90 DEG C, and the volume ratio of the acetic acid added in step four to the ethanol in step one is (10-1000) mu l:(0.5-10) ml.

[0016] The third temperature in step five is 10-100 DEG C, and the stirring time in step three is 1-10 h.

[0017] The substrate comprises a semiconductor substrate, and the semiconductor substrate comprises a crystalline silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate; the number of layers of the spin coating in step six is 1-10.

[0018] The heating temperature on the heating table in step six is 30-250 DEG C, and the annealing time in step seven is 1-100 s, and the annealing temperature is 300-5000 DEG C.

[0019] The annealing time in step seven is 10-100 s, and the terbium-doped tin oxide film photoluminescence material comprises crystalline terbium-doped tin oxide.

[0020] The embodiment of the present application also comprises a second technical solution: a terbium-doped tin oxide film photoluminescence material prepared by the preparation method of the terbium-doped tin oxide film photoluminescence material, and the terbium-doped tin oxide film material emits green light at 555 nm wavelength under visible light band photoluminescence.

[0021] The terbium-doped tin oxide film photoluminescence material comprises crystalline terbium-doped tin oxide.

[0022] The present application has the following beneficial effects:

[0023] (1) The embodiment of the present application prepares the terbium-doped tin oxide film with photoluminescence by adopting the sol-gel method and the rapid heat treatment method. The raw materials are cheap and easy to obtain, and the synthesis process is simple, low in cost, short in reaction period, free of environmental pollution and low in thermal budget. The embodiment of the present application controls the formation process of the sol-gel, so that the crystallinity of the prepared terbium-doped tin oxide film is improved. The prepared terbium-doped tin oxide film has strong visible light photoluminescence characteristics.

[0024] (2) The embodiment of the present application prepares the terbium-doped tin oxide film by using the rapid thermal annealing equipment. The rapid heating further anneals the film based on the substrate, and the short-time heating forms a large number of defects in the film. The defects in the embodiment of the present application are mainly oxygen vacancy defects. The rapid cooling obtains the terbium-doped tin oxide film. In the rapid cooling process, the defects cannot be repaired, which causes the poor symmetry of the crystal field, increases the transition probability of the terbium ions, and makes the obtained terbium-doped tin oxide film have strong luminescence intensity. 3+ absorbs visible light, and the emission of green light is from 5 D4→ 7 F J transition, and the blue light from the higher energy level is from 5 D3→ 7 F J transition, but the transition is easily quenched by the cross relaxation process of Tb( 5 D3)+Tb( 7 F6)→Tb( 5 D4)+Tb( 7 F6). 3+ The embodiment of the present application can improve the quenching caused by the 5 D4→ 7 F J transition and 5 D3→ 7 F J transition, and obtain the terbium-doped tin oxide film with strong luminescence intensity. The prepared terbium-doped tin oxide film in the embodiment of the present application can be widely applied in the fields of silicon-based light sources, LED light sources, display devices and the like. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 is the process flow chart of the terbium-doped tin oxide film prepared in Example 1 of the present application.

[0026] Figure 2 is the photoluminescence diagram of the terbium-doped tin oxide film prepared in Example 1 and Comparative Example 1 of the present application.

[0027] Figure 3is an XRD pattern of a terbium-doped tin oxide thin film prepared in Example 1 of the present application and Comparative Example 1.

[0028] Figure 4 is a scanning electron microscope pattern of a terbium-doped tin oxide prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0029] The present application provides a preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0030] Step one, dissolve stannous chloride dihydrate and terbium chloride hexahydrate in ethanol and stir at a first temperature to obtain solution A.

[0031] Step two, add deionized water to the mixed solution A to obtain solution B. The present application can accelerate the hydrolysis of stannous chloride dihydrate and terbium chloride hexahydrate by adding deionized water to the mixed solution A.

[0032] Step three, stir solution B at the first temperature until the solvent is almost completely volatilized to form a dry gel, then add ethanol to obtain solution C.

[0033] Step four, reduce the temperature to a second temperature and stir at the second temperature, then add acetic acid to solution C to adjust the pH value to obtain solution D.

[0034] Step five, stir solution D at a third temperature for a period of time, then place it at room temperature for 24 hours to obtain solution E.

[0035] Step six, spin-coat solution E on a substrate to prepare a film, and place it on a heating stage to obtain a thin film based on the substrate.

[0036] Step seven, use a rapid thermal annealing device to anneal the thin film based on the substrate obtained in step six to obtain a terbium-doped tin oxide thin film photoluminescence material.

[0037] The present application combines sol-gel method and rapid thermal treatment method to prepare a terbium-doped tin oxide thin film with photoluminescence performance. The raw materials of the present application are cheap and easy to obtain, the synthesis process is simple and low-cost, the reaction period is relatively short, and the environment is not polluted, and the thermal budget is low. The present application controls the formation process of sol-gel to improve the crystallinity of the prepared terbium-doped tin oxide thin film.

[0038] This invention employs a rapid thermal annealing apparatus to prepare a terbium-doped tin oxide thin film. Rapid heating further anneals the substrate-based film, and this short-duration heating results in the formation of numerous defects in the film, primarily oxygen vacancy defects. Rapid cooling is then used to obtain the terbium-doped tin oxide thin film. During this rapid cooling process, these defects cannot be repaired, leading to a deterioration in crystal field symmetry and an increased probability of terbium ion transitions. This results in a terbium-doped tin oxide thin film with strong luminescence intensity. 3+ It absorbs visible light, and the emission of green light comes from... 5 D4→ 7 F J Leapfrog development, higher-level blue light sources originate from 5 D3→ 7 F J A transition, but this transition is easily achieved through Tb( 5 D3)+Tb( 7 F6)→Tb( 5 D4)+Tb( 7 The quenching occurs due to the cross-relaxation process of F6), and the embodiments of the present invention can improve Tb 3+ of 5 D4→ 7 F J Leap and 5 D3→ 7 F J The quenching caused by the transition results in a terbium-doped tin oxide film with strong luminescence intensity. The terbium-doped tin oxide film prepared in this embodiment of the invention can be widely used in silicon-based light sources, LED light sources, display devices, and other fields.

[0039] In this embodiment of the invention, a rapid thermal annealing device is used for annealing, wherein the heating rate of the rapid thermal annealing is 200℃ / s, and the cooling rate is 100-200℃ / s. In this embodiment of the invention, the annealing atmosphere is an air atmosphere.

[0040] In this embodiment of the invention, the mass-to-volume ratio of stannous chloride dihydrate, terbium chloride hexahydrate, and anhydrous ethanol in step one is (0.1-1) g:(0.0001-0.05) g:(0.5-10) ml. This embodiment of the invention optimizes the sol-gel effect by controlling the ratio of stannous chloride dihydrate, terbium chloride hexahydrate, and anhydrous ethanol, and controls the terbium doping amount to achieve superior luminescent performance in the prepared terbium-doped tin oxide thin film photoluminescent material.

[0041] In the embodiment of the present application, the volume ratio of the deionized water added in step two to the volume of the ethanol in step one is (10-1000) μl:(0.5-10) ml. By controlling the amount of the deionized water added, the hydrolysis degree and speed of the tin chloride dihydrate and terbium chloride hexahydrate are controlled, so that the hydrolysis efficiency is better.

[0042] In the embodiment of the present application, the first temperature in step three is 50-100℃; the volume ratio of the amount of the ethanol added in step three to the amount of the ethanol added in step one is (0.5-1):1. By controlling the temperature for forming the xerogel to be 50-100℃, the forming speed and effect of the xerogel are controlled to be better. In the embodiment of the present application, the amount of the ethanol added is controlled, so that the concentration of the solution C is optimal.

[0043] In the embodiment of the present application, the second temperature in step four is 10-90℃; the volume ratio of the amount of the acetic acid added in step four to the volume of the ethanol in step one is (10-1000) μl:(0.5-10) ml. In the embodiment of the present application, the amount of the acetic acid added is controlled, so that the acetic acid has the effect of adjusting the pH, and the thin film based on the substrate is prepared to be flat in step six. In the embodiment of the present application, the acetic acid as the stabilizer has the effect of stabilization.

[0044] In the embodiment of the present application, the third temperature in step five is 10-100℃; the stirring time in step three is 1-10h. In the embodiment of the present application, the third temperature can be the same as the second temperature or different.

[0045] In the embodiment of the present application, the substrate includes a semiconductor substrate, and the semiconductor substrate includes a crystalline silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate. The substrate in the embodiment of the present application adopts the semiconductor substrate, so that the terbium chlorostannate thin film based on the semiconductor substrate can be applied to the fields of silicon-based light sources, LED light sources and integrated circuits.

[0046] In the embodiment of the present application, the number of the spin-coated layers in step six is 1-10. In the embodiment of the present application, the number of the spin-coated layers is 1, 2, 3, 5, 6, 8 or 10, etc. By spin-coating different numbers of the solution A, the thickness of the prepared thin film can be set as required, and the photoluminescence performance is optimal at the thickness. In the embodiment of the present application, the thickness of the terbium chlorostannate thin film is 1-100nm.

[0047] In the embodiment of the present application, the temperature of the heating table in step six is 30-250 DEG C; the annealing time in step seven is 1-100 s, and the annealing temperature is 300-5000 DEG C. The temperature of the heating table is controlled to be 30-250 DEG C in the embodiment of the present application, so that the tin terbium chlorate film is prepared. The terbium-doped tin oxide film is prepared through high-temperature annealing in the embodiment of the present application, so that the photoluminescence intensity of the terbium-doped tin oxide film is enhanced.

[0048] In the embodiment of the present application, the annealing time in step seven is 10-100 s, and the terbium-doped tin oxide film photoluminescence material contains crystalline terbium-doped tin oxide. The annealing time is controlled in the present application, so that the crystallinity of the obtained terbium-doped tin oxide film photoluminescence material is strong, and the terbium-doped tin oxide film photoluminescence material has strong photoluminescence performance.

[0049] The embodiment of the present application also includes a second technical solution: a terbium-doped tin oxide film photoluminescence material is prepared by the preparation method of the terbium-doped tin oxide film photoluminescence material, and the terbium-doped tin oxide film material emits green light at a wavelength of 550 nm under visible light. The tin terbium chlorate film in the embodiment of the present application can be applied to the fields of silicon-based light sources, LED light sources, display devices, integrated circuits, etc. The terbium-doped tin oxide film is prepared by combining the sol-gel method and the rapid heat treatment method in the embodiment of the present application, the film is uniformly distributed, and the photoluminescence intensity in the visible band is strong.

[0050] In the embodiment of the present application, the terbium-doped tin oxide film photoluminescence material contains crystalline terbium-doped tin oxide. The terbium-doped tin oxide film photoluminescence material in the embodiment of the present application contains crystalline terbium-doped tin oxide, has good crystallinity, and has good photoluminescence performance.

[0051] The method described in the present application is further illustrated by specific embodiments below, but it does not mean that the present application is limited to these embodiments.

[0052] Embodiment 1:

[0053] As Figure 1 shown in the process flow chart of the preparation method of the terbium-doped tin oxide film photoluminescence material in the present embodiment, specifically, a preparation method of a terbium-doped tin oxide film photoluminescence material, the steps of which include:

[0054] Step one: 0.226 g of stannous chloride dihydrate and 0.011 g of terbium chloride hexahydrate are respectively dissolved in 3.5 ml of anhydrous ethanol to form a mixed solution A.

[0055] Step two: 250 μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and solution B is obtained.

[0056] Step three, solution B is stirred at 70℃ until the solvent is evaporated, forming a dry gel, then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0057] Step four, the stirring temperature is changed to 50℃, 250μl of acetic acid is added to solution C to adjust the pH value, obtaining solution D.

[0058] Step five, solution D is stirred at 50℃ for 3h, and is left at room temperature for 24h to obtain solution E.

[0059] Step six, 40μl of solution E is used to prepare a film on a substrate by spin coating, 3 layers are coated, and the film is heated on a 150℃ heating table. The substrate in the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate, etc.

[0060] Step seven, the prepared film is annealed at 1000℃ for 10s using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0061] As shown in Figure 2 , the terbium-doped tin oxide film prepared in the embodiment of the present application has strong luminescence intensity and a wide luminescence wavelength range, and can form photoluminescence in the wavelength range of 485nm-635nm, and the photoluminescence intensity is the strongest at 555nm, reaching 9.2×10 4 , emitting green light. At 500nm wavelength, blue indigo light is emitted, at 590nm wavelength, yellow light is emitted, at 630nm wavelength, red light is emitted, and the photoluminescence intensity at 500nm wavelength is 2.3×10 4 , the photoluminescence intensity at 590nm wavelength is 3.3×10 4 , and the photoluminescence intensity at 630nm wavelength is 1.7×10 4 .

[0062] As shown in Figure 3 , the spectrum line of RPT treatment is the XRD pattern of the terbium-doped tin oxide film prepared in the embodiment of the present application, and from Figure 3 it can be seen that the diffraction peaks of (110), (101) and (211) crystal faces correspond to the characteristic peaks of tin oxide phase, and the content of terbium in the embodiment of the present application is small, and is not shown in the XRD pattern, indicating that the terbium-doped tin oxide film containing crystalline state is formed. As shown in Figure 4 , the terbium-doped tin oxide film prepared in the embodiment of the present application has a smooth surface and good uniformity.

[0063] The embodiment of the present application prepares the terbium-doped tin oxide film by adopting the sol-gel method and the rapid heat treatment method, and the prepared terbium-doped tin oxide film has good photoluminescence performance. The embodiment of the present application prepares the terbium-doped tin oxide film by using the rapid heat annealing equipment, the film based on the substrate is further annealed by rapid heating, a large number of defects are formed in the film by short-time heating, the terbium-doped tin oxide film is obtained by rapid cooling, and the defects cannot be repaired in the process of rapid cooling, which causes the crystal field symmetry to be poor, the terbium ion transition probability is improved, and the obtained terbium-doped tin oxide film has strong luminous intensity.

[0064] The terbium-doped tin oxide film prepared by the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0065] As shown in the embodiment 1 and the comparative example 1 of the present application, Figure 2 and Figure 3 It can be seen that the embodiment 1 and the comparative example 1 of the present application both obtain the crystalline terbium-doped tin oxide, the terbium-doped tin oxide film prepared by the tubular furnace under the same condition has slow heating speed, high heat budget, and the prepared terbium-doped tin oxide film has no photoluminescence characteristic. The terbium-doped tin oxide film prepared by the preparation method of the embodiment of the present application has strong photoluminescence characteristic, and the photoluminescence performance of the crystalline terbium-doped tin oxide film is significantly enhanced.

[0066] Embodiment 2:

[0067] The difference between this embodiment and the embodiment 1 is that the amount of terbium chloride hexahydrate in step one is changed to 0.0036 g, and the other steps are the same as those in the embodiment 1, and the specific steps are as follows:

[0068] A preparation method of a terbium-doped tin oxide film photoluminescence material, comprising the following steps:

[0069] In step one, 0.226 g of stannous chloride dihydrate and 0.0036 g of terbium chloride hexahydrate are sequentially dissolved in 3.5 ml of anhydrous ethanol to form a mixed solution A.

[0070] In step two, 250 μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and a solution B is obtained.

[0071] In step three, the solution B is stirred at 70℃ in an open state until the solvent is almost volatilized, a dry gel is formed, 3.5 ml of anhydrous ethanol is added, and a solution C is obtained.

[0072] In step four, the stirring temperature is changed to 50℃, 250 μl of acetic acid is added to the solution C to adjust the pH value, and a solution D is obtained.

[0073] Step five, solution D is stirred at 50℃ for 3h, and is left at room temperature for 24h to obtain solution E.

[0074] Step six, 40μl of solution E is taken and is prepared into a film on a substrate by spin coating method, and is spin coated for 3 layers and is heated on a heating table at 150℃. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0075] Step seven, the prepared film is annealed at 1000℃ for 10s by using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0076] The terbium-doped tin oxide film prepared in the embodiment of the present application has photoluminescence properties, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0077] Embodiment 3:

[0078] The difference between this embodiment and embodiment 1 is that the amount of deionized water in step two is changed to 500μl, and the other steps are the same as those in embodiment 1, and are as follows:

[0079] A preparation method of a terbium-doped tin oxide film photoluminescence material, comprising the following steps:

[0080] Step one, 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate are sequentially dissolved in 3.5ml of anhydrous ethanol to form a mixed solution A.

[0081] Step two, 500μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process to obtain solution B.

[0082] Step three, solution B is stirred at 70℃ until the solvent is almost completely volatilized to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0083] Step four, the stirring temperature is changed to 50℃, 250μl of acetic acid is added to solution C to adjust the pH value to obtain solution D.

[0084] Step five, solution D is stirred at 50℃ for 3h, and is left at room temperature for 24h to obtain solution E. Step six, 40μl of solution E is taken and is prepared into a film on a substrate by spin coating method, and is spin coated for 3 layers and is heated on a heating table at 150℃. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0085] Step seven, the prepared thin film is annealed at 1000℃ for 10s by using rapid thermal annealing equipment (RTP), and a terbium-doped tin oxide thin film is obtained.

[0086] The terbium-doped tin oxide thin film prepared in the embodiment has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0087] Embodiment 4:

[0088] The embodiment is different from embodiment 1 in that the temperature of RTP treatment in step seven is changed to 900℃, and the other steps are the same as those in embodiment 1, and the specific steps are as follows:

[0089] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0090] Step one, 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate are sequentially dissolved in 3.5ml of anhydrous ethanol to form a mixed solution A.

[0091] Step two, 250μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and a solution B is obtained.

[0092] Step three, the solution B is stirred at 70℃ until the solvent is almost completely volatilized to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain a solution C.

[0093] Step four, the stirring temperature is changed to 50℃, 250μl of acetic acid is added to the solution C to adjust the pH value, and a solution D is obtained.

[0094] Step five, the solution D is stirred at 50℃ for 3h, and is placed at room temperature for 24h to obtain a solution E.

[0095] Step six, 40μl of the solution E is taken and is prepared into a film on a substrate by using a spin coating method, and is heated on a heating table at 150℃. The substrate in the embodiment is a silicon substrate, and in other embodiments, the substrate can also be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0096] Step seven, the prepared thin film is annealed at 900℃ for 10s by using rapid thermal annealing equipment (RTP), and a terbium-doped tin oxide thin film is obtained.

[0097] The terbium-doped tin oxide thin film prepared in the embodiment has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0098] Example 5:

[0099] The difference between this example and Example 1 is that the temperature of RTP treatment in step seven is changed to 800℃, and the others are the same as Example 1, which are as follows:

[0100] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0101] Step one, 0.226g stannous chloride dihydrate and 0.011g terbium chloride hexahydrate are sequentially dissolved in 3.5ml anhydrous ethanol to form a mixed solution A.

[0102] Step two, 250μl deionized water is added to the mixed solution A to accelerate the hydrolysis process, and solution B is obtained.

[0103] Step three, solution B is stirred at 70℃ until the solvent is almost completely volatilized to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0104] Step four, the stirring temperature is changed to 50℃, 250μl acetic acid is added to solution C to adjust the pH value, and solution D is obtained.

[0105] Step five, solution D is stirred at 50℃ for 3h, and then is placed at room temperature for 24h to obtain solution E.

[0106] Step six, 40μl of solution E is prepared into a film on a substrate by using a spin coating method, and is heated on a 150℃ heating table. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can also be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0107] Step seven, the prepared thin film is annealed at 800℃ for 10s by using a rapid thermal annealing device (RTP), and a terbium-doped tin oxide thin film is obtained.

[0108] The performance of the terbium-doped tin oxide thin film prepared in the embodiment of the present application is similar to that of Example 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0109] Example 6:

[0110] The difference between this example and Example 1 is that the temperature of RTP treatment in step seven is changed to 700℃, and the others are the same as Example 1, which are as follows:

[0111] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0112] Step one, dissolve 0.226g stannous chloride dihydrate and 0.011g terbium chloride hexahydrate in 3.5ml anhydrous ethanol in sequence to form a mixed solution A.

[0113] Step two, add 250μl deionized water to the mixed solution A to accelerate the hydrolysis process and obtain solution B.

[0114] Step three, stir solution B at 70℃ until the solvent is almost evaporated to form a dry gel, then add 3.5ml anhydrous ethanol to obtain solution C.

[0115] Step four, change the stirring temperature to 50℃, add 250μl acetic acid to solution C to adjust the pH value and obtain solution D.

[0116] Step five, stir solution D at 50℃ for 3h, and then place it at room temperature for 24h to obtain solution E.

[0117] Step six, take 40μl solution E and prepare a film on a substrate by spin coating 3 layers, and then place it on a heating table at 150℃. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can also be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0118] Step seven, anneal the prepared film at 700℃ for 10s by using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0119] The terbium-doped tin oxide film prepared in the embodiment of the present application has similar performance to that of example 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0120] Example 7:

[0121] The difference between this embodiment and example 1 is that the temperature of RTP treatment in step seven is changed to 600℃, and other steps are the same as those in example 1, which are as follows:

[0122] A preparation method of a terbium-doped tin oxide film photoluminescence material, comprising the following steps:

[0123] Step one, dissolve 0.226g stannous chloride dihydrate and 0.011g terbium chloride hexahydrate in 3.5ml anhydrous ethanol in sequence to form a mixed solution A.

[0124] Step two, add 250μl deionized water to the mixed solution A to accelerate the hydrolysis process and obtain solution B.

[0125] Step three, solution B is stirred at 70℃ until the solvent is evaporated, forming a dry gel, then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0126] Step four, the stirring temperature is changed to 50℃, 250μl of acetic acid is added to solution C to adjust the pH value to obtain solution D.

[0127] Step five, solution D is stirred at 50℃ for 3h, and is left at room temperature for 24h to obtain solution E.

[0128] Step seven, the prepared film is annealed at 600℃ for 10s by using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0129] The terbium-doped tin oxide film prepared in the embodiment has similar performance to that of embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0130] Embodiment 8:

[0131] The embodiment is different from embodiment 1 in that the RTP treatment time in step seven is changed to 20s, and other aspects are the same as those of embodiment 1, and details are as follows:

[0132] A preparation method of a terbium-doped tin oxide film photoluminescence material, comprising the following steps:

[0133] Step one, 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate are sequentially dissolved in 3.5ml of anhydrous ethanol to form a mixed solution A.

[0134] Step two, 250μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process to obtain solution B.

[0135] Step three, solution B is stirred at 70℃ until the solvent is evaporated, forming a dry gel, then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0136] Step four, the stirring temperature is changed to 50℃, 250μl of acetic acid is added to solution C to adjust the pH value to obtain solution D.

[0137] Step five, solution D is stirred at 50℃ for 3h, and is left at room temperature for 24h to obtain solution E.

[0138] Step six, 40 μl of solution E is taken and spin-coated on a substrate to form a film, spin-coated for 3 layers, and placed on a heating table at 150°C. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate, etc.

[0139] Step seven, the prepared film is annealed at 1000°C for 20 s using a rapid thermal annealing device (RTP), to obtain a terbium-doped tin oxide film.

[0140] The terbium-doped tin oxide film prepared in the embodiment of the present application has similar performance to that of embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555 nm. The terbium-doped tin oxide film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0141] Embodiment 9:

[0142] The difference between this embodiment and embodiment 1 is that the RTP treatment time in step seven is changed to 30 s, and the rest is the same as embodiment 1, as follows:

[0143] A preparation method of a terbium-doped tin oxide film photoluminescence material, comprising the following steps:

[0144] Step one, 0.226 g of stannous chloride dihydrate and 0.011 g of terbium chloride hexahydrate are sequentially dissolved in 3.5 ml of anhydrous ethanol to form a mixed solution A.

[0145] Step two, 250 μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, to obtain solution B.

[0146] Step three, solution B is stirred at 70°C in an open container until the solvent is almost completely volatilized, to form a dry gel, and then 3.5 ml of anhydrous ethanol is added to obtain solution C.

[0147] Step four, the stirring temperature is changed to 50°C, 250 μl of acetic acid is added to solution C to adjust the pH value, to obtain solution D.

[0148] Step five, solution D is stirred at 50°C in an open container for 3 h, and then left to stand at room temperature for 24 h, to obtain solution E.

[0149] Step six, 40 μl of solution E is taken and spin-coated on a substrate to form a film, spin-coated for 3 layers, and placed on a heating table at 150°C. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate, etc.

[0150] Step seven, the prepared film is annealed at 1000°C for 30 s using a rapid thermal annealing device (RTP), to obtain a terbium-doped tin oxide film.

[0151] The terbium-doped tin oxide thin film prepared in the embodiment has the similar performance to that of the embodiment 1, has the photoluminescence characteristic, and emits green light at 555 nm wavelength. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0152] Embodiment 10

[0153] The embodiment is different from the embodiment 1 in that the time of the RTP treatment in the step seven is changed to 40 s, and the other steps are the same as those of the embodiment 1, and the embodiment is specifically as follows:

[0154] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0155] In step one, 0.226 g of stannous chloride dihydrate and 0.011 g of terbium chloride hexahydrate are sequentially dissolved in 3.5 ml of anhydrous ethanol to form a mixed solution A.

[0156] In step two, 250 μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and a solution B is obtained.

[0157] In step three, the solution B is stirred at 70 °C until the solvent is almost volatilized, a dry gel is formed, 3.5 ml of anhydrous ethanol is added, and a solution C is obtained.

[0158] In step four, the stirring temperature is changed to 50 °C, 250 μl of acetic acid is added to the solution C to adjust the pH value, and a solution D is obtained.

[0159] In step five, the solution D is stirred at 50 °C for 3 h, and is placed at room temperature for 24 hours to obtain a solution E.

[0160] In step six, 40 μl of the solution E is taken, a film is prepared on a substrate by using a spin coating method, the film is coated for 3 layers, and is placed on a heating table at 150 °C. The substrate in the embodiment is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate, etc.

[0161] In step seven, the prepared film is annealed at 1000 °C for 40 s by using a rapid thermal annealing device (RTP), and a terbium-doped tin oxide thin film is obtained.

[0162] The terbium-doped tin oxide thin film prepared in the embodiment has the similar performance to that of the embodiment 1, has the photoluminescence characteristic, and emits green light at 555 nm wavelength. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0163] Embodiment 11

[0164] The embodiment is different from embodiment 1 in that the time of RTP treatment in step seven is changed to 50s, and the others are the same as embodiment 1, and the specific implementation is as follows:

[0165] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0166] Step one, 0.226g stannous chloride dihydrate and 0.011g terbium chloride hexahydrate are sequentially dissolved in 3.5ml anhydrous ethanol to form a mixed solution A.

[0167] Step two, 250ul deionized water is added to the mixed solution A to accelerate the hydrolysis process, and solution B is obtained.

[0168] Step three, solution B is stirred at 70℃ until the solvent is almost volatilized to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0169] Step four, the stirring temperature is changed to 50℃, 250ul acetic acid is added to solution C to adjust the pH value, and solution D is obtained.

[0170] Step five, solution D is stirred at 50℃ for 3h, and then is placed at room temperature for 24h to obtain solution E.

[0171] Step six, 40ul of solution E is taken and is prepared into a film on a substrate by using a spin coating method, and is heated on a 150℃ heating table. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can also be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate and the like semiconductor substrate.

[0172] Step seven, the prepared thin film is annealed at 1000℃ for 50s by using a rapid thermal annealing device (RTP), and a terbium-doped tin oxide thin film is obtained.

[0173] The performance of the terbium-doped tin oxide thin film prepared in the embodiment of the present application is similar to that of embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0174] Embodiment 12:

[0175] The embodiment is different from embodiment 1 in that the time of RTP treatment in step seven is changed to 60s, and the others are the same as embodiment 1, and the specific implementation is as follows:

[0176] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0177] Step one, 0.226g stannous chloride dihydrate, 0.011g terbium chloride hexahydrate are dissolved in 3.5ml anhydrous ethanol in turn to form a mixed solution A.

[0178] Step two, 250μl deionized water is added to the mixed solution A to accelerate the hydrolysis process to obtain solution B.

[0179] Step three, solution B is stirred at 70℃ until the solvent is evaporated to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain solution C.

[0180] Step four, the stirring temperature is changed to 50℃, 250μl acetic acid is added to solution C to adjust the pH value to obtain solution D.

[0181] Step five, solution D is stirred at 50℃ for 3h, and then is placed at room temperature for 24h to obtain solution E.

[0182] Step six, 40μl of solution E is prepared into a film on a substrate by spin coating 3 layers, and is placed on a heating table at 150℃. The substrate of the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can be a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate, etc.

[0183] Step seven, the prepared film is annealed at 1000℃ for 60s by using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0184] The terbium-doped tin oxide film prepared in the embodiment of the present application has similar performance to that of example 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0185] Example 13:

[0186] The embodiment of the present application provides a preparation method of a terbium-doped tin oxide film photoluminescence material, which comprises the following steps:

[0187] Step one, 0.1g stannous chloride dihydrate, 0.00001g terbium chloride hexahydrate are dissolved in 0.5ml anhydrous ethanol in turn to form a mixed solution A.

[0188] Step two, 10μl deionized water is added to the mixed solution A to accelerate the hydrolysis process to obtain solution B.

[0189] Step three, solution B is stirred at 50℃ until the solvent is evaporated to form a dry gel, and then 0.25ml of anhydrous ethanol is added to obtain solution C.

[0190] Step four, change the stirring temperature to 10℃, add 10μl acetic acid to solution C to adjust the pH value, and obtain solution D.

[0191] Step five, stir solution D at 10℃ for 10h, and stand at room temperature for 24h to obtain solution E.

[0192] Step six, prepare a film on a substrate by using the spin coating method for solution E, spin coat 1 layer, and place on a heating table at 30℃ for heating for 30min. The substrate of the embodiment of the present application is a germanium substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a silicon substrate, a gallium arsenide substrate, or a gallium nitride substrate.

[0193] Step seven, anneal the prepared film at 300℃ for 100s by using a rapid thermal annealing device (RTP) to obtain a terbium-doped tin oxide film.

[0194] The terbium-doped tin oxide film prepared in the embodiment of the present application has similar performance to that of embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide film prepared in the embodiment of the present application contains crystalline terbium-doped tin oxide.

[0195] Embodiment 14:

[0196] The embodiment of the present application provides a preparation method of a terbium-doped tin oxide film photoluminescence material, which comprises the following steps:

[0197] Step one, sequentially dissolve 1g stannous chloride dihydrate and 0.05g terbium chloride hexahydrate in 10ml anhydrous ethanol to form a mixed solution A.

[0198] Step two, add 1000μl deionized water to the mixed solution A to accelerate the hydrolysis process, and obtain solution B.

[0199] Step three, stir solution B at 100℃ until the solvent is evaporated, form a dry gel, and then add 10ml anhydrous ethanol to obtain solution C.

[0200] Step four, change the stirring temperature to 90℃, add 1000μl acetic acid to solution C to adjust the pH value, and obtain solution D.

[0201] Step five, stir solution D at 100℃ for 1h, and stand at room temperature for 24h to obtain solution E.

[0202] Step six, prepare a film on a substrate by using the spin coating method for solution E, spin coat 1 layer, and place on a heating table at 250℃ for heating for 10min. The substrate of the embodiment of the present application is a gallium nitride substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a silicon substrate, a gallium arsenide substrate, or a germanium substrate.

[0203] Step seven, the prepared thin film is annealed at 1300℃ for 80s by using rapid thermal annealing equipment (RTP), and a terbium-doped tin oxide thin film is obtained.

[0204] The terbium-doped tin oxide thin film prepared in the embodiment has similar performance to that of the embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0205] Embodiment 15

[0206] The embodiment of the present application provides a preparation method of a terbium-doped tin oxide thin film photoluminescence material, which comprises the following steps:

[0207] Step one, 0.1g of stannous chloride dihydrate and 0.05g of terbium chloride hexahydrate are sequentially dissolved in 8ml of anhydrous ethanol to form a mixed solution A.

[0208] Step two, 600μl of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and a solution B is obtained.

[0209] Step three, the solution B is stirred at 80℃ in an open state until the solvent is almost volatilized, a dry gel is formed, 10ml of anhydrous ethanol is added, and a solution C is obtained.

[0210] Step four, the stirring temperature is changed to 60℃, 800μl of acetic acid is added to the solution C to adjust the pH value, and a solution D is obtained.

[0211] Step five, the solution D is stirred at 60℃ in an open state for 8h, and is placed at room temperature for 24h to obtain a solution E.

[0212] Step six, the solution E is prepared into a film on a substrate by using a spin coating method, 10 layers are coated, and the film is placed on a heating table at 200℃ for 20min. The substrate in the embodiment of the present application is a gallium arsenide substrate, and in other embodiments, the substrate can be a semiconductor substrate such as a silicon substrate, a germanium substrate or a gallium nitride substrate.

[0213] Step seven, the prepared thin film is annealed at 1200℃ for 1s by using rapid thermal annealing equipment (RTP), and a terbium-doped tin oxide thin film is obtained.

[0214] The terbium-doped tin oxide thin film prepared in the embodiment has similar performance to that of the embodiment 1, has photoluminescence characteristics, and emits green light at a wavelength of 555nm. The terbium-doped tin oxide thin film prepared in the embodiment contains crystalline terbium-doped tin oxide.

[0215] Comparative example 1

[0216] A preparation method of a terbium-doped tin oxide thin film photoluminescence material, comprising the following steps:

[0217] In step one, 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate are respectively dissolved in 3.5ml of anhydrous ethanol to form a mixed solution A.

[0218] In step two, 250ul of deionized water is added to the mixed solution A to accelerate the hydrolysis process, and a solution B is obtained.

[0219] In step three, the solution B is stirred at 70℃ until the solvent is almost completely volatilized to form a dry gel, and then 3.5ml of anhydrous ethanol is added to obtain a solution C.

[0220] In step four, the stirring temperature is changed to 50℃, and 250ul of acetic acid is added to the solution C to adjust the pH value, and a solution D is obtained.

[0221] In step five, the solution D is stirred at 50℃ for 3h, and then is placed at room temperature for 24h to obtain a solution E.

[0222] In step six, 40ul of the solution E is used to prepare a film on a substrate by spin coating for 3 layers, and the film is heated on a heating table at 150℃. The substrate in the embodiment of the present application is a silicon substrate, and in other embodiments, the substrate can also be a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate, etc.

[0223] In step seven, the prepared film is annealed in a tube furnace at 1000℃ for 10s to obtain a terbium-doped tin oxide thin film. The heating rate of the tube furnace is 5℃ / min, and the cooling rate is 5℃ / min.

[0224] As shown in Figure 2 , the luminescence intensity of the terbium-doped tin oxide thin film prepared in the comparative example is zero, and the film does not have photoluminescence characteristics, as shown in Figure 3 , the spectrum line of the tube furnace treatment is the XRD pattern of the terbium-doped tin oxide thin film prepared in the embodiment of the present application, and from Figure 3 , it can be seen that the diffraction peaks of (110), (101) and (211) crystal faces correspond to the characteristic peaks of the tin oxide phase, and the content of terbium in the embodiment of the present application is small, and is not shown in the XRD pattern, which indicates that the terbium-doped tin oxide thin film containing crystalline state is formed.

[0225] Obviously, the above embodiments are only examples for the purpose of clear illustration, and are not intended to limit the embodiments. Any modification, equivalent replacement, improvement made on the basis of the above description within the method and principle of the present application should be included in the protection scope of the present application. It is not necessary and impossible to enumerate all the embodiments here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method for preparing a terbium-doped tin oxide thin film photoluminescence material, characterized in that, The method comprises the following steps: Step one, dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol, stirring at a first temperature to obtain solution A; step two, adding deionized water to solution A to obtain solution B; step three, stirring solution B at the first temperature until the solvent is almost completely volatilized to form a dry gel, then adding ethanol to obtain solution C; step four, reducing the temperature to a second temperature, stirring at the second temperature, adding acetic acid to solution C to adjust the pH value to obtain solution D; step five, stirring solution D at a third temperature for a period of time, then standing at room temperature for 24 hours to obtain solution E; step six, spin coating solution E on a substrate to prepare a film, and heating the film on a heating table to obtain a thin film on the substrate; step seven, annealing the thin film on the substrate obtained in step six by using a rapid thermal annealing device to obtain a terbium-doped tin oxide thin film photoluminescence material; The mass-volume ratio of stannous chloride dihydrate, terbium chloride hexahydrate and anhydrous ethanol in step one is (0.1-1) g:(0.0001-0.05) g:(0.5-10) ml. The temperature rising speed of the annealing treatment by using the rapid thermal annealing device is 200 ℃ / s, and the temperature falling speed is 100-200 ℃ / s; the annealing treatment time in step seven is 1-100 s, and the annealing treatment temperature is 300-1300 ℃.

2. The method of claim 1, wherein the method is characterized by: The volume ratio of deionized water added in step two to the volume of ethanol in step one is (10-1000) μl:(0.5-10) ml.

3. The method for preparing the terbium-doped tin oxide thin film photoluminescent material as described in claim 1, characterized in that: The first temperature in step three is 50-100 ℃; the volume ratio of the amount of ethanol added in step three to the amount of ethanol added in step one is (0.5-1):

1.

4. The method of claim 1, wherein the method further comprises: depositing a layer of a terbium-doped tin oxide film on the substrate; and annealing the layer of the terbium-doped tin oxide film. The second temperature in step four is 10-90 ℃; the volume ratio of acetic acid added in step four to the volume of ethanol in step one is (10-1000) μl:(0.5-10) ml.

5. The method of claim 1, wherein the method further comprises: depositing a layer of a terbium-doped tin oxide film on the substrate; and annealing the layer of the terbium-doped tin oxide film. The third temperature in step five is 10-100 ℃; the stirring time in step three is 1-10 h.

6. The method for preparing the terbium-doped tin oxide thin film photoluminescent material as described in claim 1, characterized in that: The substrate comprises a semiconductor substrate, and the semiconductor substrate comprises a crystalline silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate; the number of spin coating layers in step six is 1-10.

7. The method of claim 1, wherein the method further comprises: depositing a layer of a terbium-doped tin oxide film on the substrate; and annealing the layer of the terbium-doped tin oxide film. The heating temperature on the heating table in step six is 30-250 ℃.

8. The method for preparing the terbium-doped tin oxide thin film photoluminescent material as described in claim 1, characterized in that: The annealing treatment time in step seven is 10-100 s, and the terbium-doped tin oxide thin film photoluminescence material comprises crystalline terbium-doped tin oxide.

9. A terbium-doped tin oxide thin film photoluminescent material, characterized in that, The terbium-doped tin oxide thin film photoluminescence material prepared by the method of any one of claims 1-8 can emit green light at a wavelength of 555 nm under visible light. The terbium-doped tin oxide thin film photoluminescence material prepared by the method of any one of claims 1-8 can emit green light at a wavelength of 555 nm under visible light.

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