CN115247261A - Terbium-doped tin oxide film photoluminescent material and preparation method thereof - Google Patents
Terbium-doped tin oxide film photoluminescent material and preparation method thereof Download PDFInfo
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- CN115247261A CN115247261A CN202110063874.1A CN202110063874A CN115247261A CN 115247261 A CN115247261 A CN 115247261A CN 202110063874 A CN202110063874 A CN 202110063874A CN 115247261 A CN115247261 A CN 115247261A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 197
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 166
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000005424 photoluminescence Methods 0.000 claims abstract description 63
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims abstract description 52
- 238000004528 spin coating Methods 0.000 claims abstract description 40
- 238000000137 annealing Methods 0.000 claims abstract description 33
- ULJUVCOAZNLCJZ-UHFFFAOYSA-K trichloroterbium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Tb+3] ULJUVCOAZNLCJZ-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004151 rapid thermal annealing Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000010408 film Substances 0.000 claims description 225
- 239000004065 semiconductor Substances 0.000 claims description 25
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910002601 GaN Inorganic materials 0.000 claims description 19
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 19
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 229910052732 germanium Inorganic materials 0.000 claims description 19
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 18
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 149
- 239000011259 mixed solution Substances 0.000 description 35
- 230000008569 process Effects 0.000 description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 20
- 230000007062 hydrolysis Effects 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 20
- 229910052710 silicon Inorganic materials 0.000 description 20
- 239000010703 silicon Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 17
- 230000007704 transition Effects 0.000 description 13
- 229910052771 Terbium Inorganic materials 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 229940071182 stannate Drugs 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000005090 crystal field Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- -1 terbium ions Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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Abstract
The invention relates to a terbium-doped tin oxide film photoluminescence material and a preparation method thereof, wherein the method comprises the following steps: dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol, and stirring at a first temperature to obtain a solution A; adding deionized water into the solution A to obtain a solution B; stirring the solution B at a first temperature in an open manner until the solvent is completely volatilized to form xerogel, and then adding ethanol to obtain a solution C; reducing the temperature to a second temperature, stirring at the second temperature, and adding acetic acid into the solution C to adjust the pH value to obtain a solution D; stirring the solution D at a third temperature for a period of time, and standing at room temperature for 24 hours to obtain a solution E; spin-coating the solution E on a substrate to prepare a film, and heating the film on a heating table to obtain a film based on the substrate; and annealing by adopting rapid thermal annealing equipment to obtain the terbium-doped tin oxide film photoluminescent material. The product prepared by the invention has excellent photoluminescence performance.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a terbium-doped tin oxide film photoluminescent material and a preparation method thereof.
Background
SnO 2 The semiconductor is a wide-bandgap semiconductor, the forbidden band width is 3.6eV, the carrier mobility is high, the phonon energy is low, and the transmittance in visible and near-infrared wave bands is very high. Doping Sb or F can greatly improve SnO 2 Has a high electron concentration, and is an excellent conductive material. Currently prepared SnO 2 The process of (2) generally obtains a high quality thin film by vacuum vapor deposition. If modified SnO 2 So that the material has excellent performance, which is a topic worthy of research.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the terbium-doped tin oxide film photoluminescence material and the preparation method thereof, the preparation method has the advantages of simple process, low cost and short reaction period, and the obtained terbium-doped tin oxide film has photoluminescence performance and strong luminescence performance.
In order to solve the above technical problems, the present invention provides a technical solution: a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol, and stirring at a first temperature to obtain a solution A;
step two, adding deionized water into the mixed solution A to obtain a solution B;
step three, stirring the solution B in an open manner at the first temperature until the solvent is completely volatilized to form xerogel, and then adding ethanol to obtain a solution C;
step four, reducing the temperature to a second temperature, stirring at the second temperature, and adding acetic acid into the solution C to adjust the pH value to obtain a solution D;
step five, stirring the solution D for a period of time at a third temperature in an open way, and standing for 24 hours at room temperature to obtain a solution E;
step six, spin-coating the solution E on a substrate to prepare a film, and heating the film on a heating table to obtain a film based on the substrate;
and step seven, annealing the film on the substrate obtained in the step six by adopting rapid thermal annealing equipment to obtain the terbium-doped tin oxide film photoluminescence material.
Wherein the mass volume ratio of the stannous chloride dihydrate, the terbium chloride hexahydrate and the absolute ethyl alcohol in the step one is (0.1-1) g, (0.0001-0.05) g, (0.5-10) ml.
Wherein the volume ratio of the deionized water added in the second step to the ethanol added in the first step is (10-1000) mul, (0.5-10) ml.
Wherein the first temperature of the third step is 50-100 ℃; the volume ratio of the ethanol added in the third step to the ethanol added in the first step is (0.5-1): 1.
Wherein the second temperature of the fourth step is 10-90 ℃; the volume ratio of the acetic acid added in the fourth step to the ethanol in the first step is (10-1000) microliter (0.5-10) ml.
Wherein the third temperature in the fifth step is 10-100 ℃; stirring for 1-10h in the third step.
The substrate comprises a semiconductor substrate, wherein the semiconductor substrate comprises a crystalline silicon substrate, a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate; and the number of spin-coating layers in the sixth step is 1-10.
Wherein, the heating temperature on the heating table in the sixth step is 30-250 ℃; in the seventh step, the time of the annealing treatment is 1-100s, and the temperature of the annealing treatment is 300-5000 ℃.
And the annealing treatment time in the seventh step is 10-100s, and the terbium-doped tin oxide film photoluminescent material contains crystalline terbium-doped tin oxide.
The embodiment of the invention also comprises a second technical scheme that: the 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 photoluminescence material emits green light in a 555nm wave band.
The terbium-doped tin oxide film photoluminescent material comprises crystalline terbium-doped tin oxide.
The invention has the beneficial effects that:
(1) According to the embodiment of the invention, the terbium-doped tin oxide film with the photoluminescence performance is prepared by combining a sol-gel method and a rapid heat treatment method. The invention has the advantages of cheap and easily obtained raw materials, no need of expensive instruments and equipment, simple synthesis process, low cost, short reaction period, no environmental pollution and low thermal budget. According to the embodiment of the invention, the crystallinity of the prepared terbium-doped tin oxide film is improved by controlling the forming process of sol-gel. And the prepared terbium-doped tin oxide film has stronger visible light photoluminescence characteristics.
(2) In the embodiment of the invention, the terbium-doped tin oxide film is prepared by adopting rapid thermal 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, and the defects in the embodiment of the invention are mainly oxygen vacancy defects; the terbium-doped tin oxide film is obtained by rapid cooling, and in the rapid cooling process, the defects can not be repaired, so that the symmetry of a crystal field is deteriorated, the transition probability of terbium ions is improved, and the obtained terbium-doped tin oxide film has high luminous intensity. Tb 3+ Absorbing visible light, wherein the green emission comes from 5 D 4 → 7 F J Transition, the higher energy level of blue light originating from 5 D 3 → 7 F J Transition, but the transition is easily passed through Tb (b) 5 D 3 )+Tb( 7 F 6 )→Tb( 5 D 4 )+Tb( 7 F 6 ) The embodiment of the invention can improve Tb by quenching in the cross relaxation process 3+ Is/are as follows 5 D 4 → 7 F J Transition and 5 D 3 → 7 F J and (3) obtaining the terbium-doped tin oxide film with stronger luminous intensity under the condition of quenching caused by transition. The terbium-doped tin oxide film prepared by the embodiment of the invention can be widely applied to the fields of silicon-based light sources, LED light sources, display devices and the like.
Drawings
FIG. 1 is a process flow diagram of a terbium-doped tin oxide film prepared in example 1 of the present invention.
FIG. 2 is a photoluminescence chart of terbium-doped tin oxide thin films prepared in example 1 of the present invention and comparative example 1.
Fig. 3 is an XRD pattern of terbium-doped tin oxide thin films prepared in example 1 of the present invention and comparative example 1.
FIG. 4 is a scanning electron micrograph of terbium-doped tin oxide prepared according to example 1 of the present invention.
Detailed Description
The embodiment of the invention provides a preparation method of a terbium-doped tin oxide film photoluminescent material, which comprises the following steps:
dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol, and stirring at a first temperature to obtain a solution A.
And step two, adding deionized water into the mixed solution A to obtain a solution B. According to the embodiment of the invention, the hydrolysis of stannous chloride dihydrate and terbium chloride hexahydrate can be accelerated by adding deionized water into the mixed solution A.
And step three, stirring the solution B in an open way at the first temperature until the solvent is completely volatilized to form xerogel, and then adding ethanol to obtain a solution C.
And step four, reducing the temperature to the second temperature, stirring at the second temperature, and adding acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D at a third temperature for a period of time in an open way, and standing at room temperature for 24 hours to obtain a solution E.
And step six, spin-coating the solution E on a substrate to prepare a film, and heating the film on a heating table to obtain a film based on the substrate.
And seventhly, annealing the film on the substrate obtained in the sixth step by adopting rapid thermal annealing equipment to obtain the terbium-doped tin oxide film photoluminescence material.
According to the embodiment of the invention, the terbium-doped tin oxide film with photoluminescence performance is prepared by combining a sol-gel method and a rapid heat treatment method. The invention has the advantages of cheap and easily obtained raw materials, simple synthesis process, low cost, short reaction period, no environmental pollution and low thermal budget. According to the embodiment of the invention, the crystallinity of the prepared terbium-doped tin oxide film is improved by controlling the forming process of sol-gel.
In the embodiment of the invention, the terbium-doped tin oxide film is prepared by adopting rapid thermal 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, and the defects in the embodiment of the invention are mainly oxygen vacancy defects; the terbium-doped tin oxide film is obtained by rapid cooling, and in the rapid cooling process, the defects can not be repaired, so that the symmetry of a crystal field is deteriorated, the transition probability of terbium ions is improved, and the obtained terbium-doped tin oxide film has high luminous intensity. Tb 3+ Absorbing visible light, wherein the green emission comes from 5 D 4 → 7 F J Transition, the higher energy level of blue light originating from 5 D 3 → 7 F J Transition, but the transition is easily passed through Tb (b) 5 D 3 )+Tb( 7 F 6 )→Tb( 5 D 4 )+Tb( 7 F 6 ) The embodiment of the invention can improve Tb 3+ Is 5 D 4 → 7 F J Transition and 5 D 3 → 7 F J and quenching caused by transition to obtain the terbium-doped tin oxide film with stronger luminous intensity. The terbium-doped tin oxide film prepared by the embodiment of the invention can be widely applied to the fields of silicon-based light sources, LED light sources, display devices and the like.
In the embodiment of the invention, rapid thermal annealing equipment is adopted for annealing treatment, wherein the temperature rise speed of the rapid thermal annealing is 200 ℃/s; the temperature reduction speed is 100-200 ℃/s. In the embodiment of the invention, the atmosphere of the annealing treatment is air atmosphere.
In the embodiment of the invention, the mass volume ratio of the stannous chloride dihydrate, the terbium chloride hexahydrate and the absolute ethyl alcohol in the step one is (0.1-1) g, (0.0001-0.05) g, (0.5-10) ml. According to the embodiment of the invention, the ratio of stannous chloride dihydrate, terbium chloride hexahydrate and absolute ethyl alcohol is controlled, so that the effect of the formed sol-gel is optimal, and the doping amount of terbium is controlled, so that the prepared terbium-doped tin oxide film photoluminescence material has better luminous performance.
In the embodiment of the invention, the volume ratio of the deionized water added in the second step to the ethanol added in the first step is (10-1000) microliter (0.5-10) ml. The adding amount of the deionized water is controlled so as to control the hydrolysis degree and the hydrolysis speed of the stannous chloride dihydrate and the terbium chloride hexahydrate, so that the hydrolysis efficiency is better.
In the embodiment of the invention, the first temperature of the third step is 50-100 ℃; the volume ratio of the ethanol added in the third step to the ethanol added in the first step is (0.5-1): 1. The temperature for forming the dried gel is controlled to be 50-100 ℃, so that the forming speed and the forming effect of the dried gel can be controlled to achieve better conditions. According to the embodiment of the invention, the concentration of the formed solution C is optimized by controlling the amount of the added ethanol.
In the embodiment of the invention, the second temperature of the fourth step is 10-90 ℃; the volume ratio of the acetic acid added in the fourth step to the ethanol added in the first step is (10-1000) microliter (0.5-10) ml. According to the embodiment of the invention, the acetic acid achieves the effect of adjusting the pH value by controlling the amount of the added acetic acid, so that the surface of the film prepared in the step six and based on the substrate is smooth. In the embodiment of the invention, acetic acid as a stabilizer can play a stabilizing effect.
In the embodiment of the invention, the third temperature in the fifth step is 10-100 ℃; the stirring in the third step is carried out for 1 to 10 hours. In the embodiment of the present application, the third temperature may be the same as or different from the second temperature.
In an embodiment of the present invention, the substrate includes a semiconductor substrate including a crystalline silicon substrate, a germanium substrate, a gallium arsenide substrate, or a gallium nitride substrate. The substrate provided by the embodiment of the invention adopts the semiconductor substrate, so that the semiconductor substrate-based terbium stannate film can be applied to the fields of silicon-based light sources, LED light sources, integrated circuits and the like.
In the embodiment of the invention, the number of spin-coating layers in the sixth step is 1-10. In the embodiment of the invention, the number of spin-coating layers is 1, 2, 3, 5, 6, 8 or 10, and the like, and the thickness of the prepared film can be set as required by spin-coating the solution A with different numbers of layers, and the photoluminescence performance is optimal under the thickness. In the embodiment of the invention, the thickness of the terbium stannate film is 1-100nm.
In the embodiment of the invention, the heating temperature on the heating table in the sixth step is 30-250 ℃; in the seventh step, the time of the annealing treatment is 1-100s, and the temperature of the annealing treatment is 300-5000 ℃. According to the embodiment of the invention, the temperature for heating on the heating table is controlled to be 30-250 ℃, so that the terbium stannate film is prepared. According to the embodiment of the invention, the prepared terbium-doped tin oxide film is further subjected to high-temperature annealing treatment, so that the photoluminescence intensity of the terbium-doped tin oxide film is enhanced.
In the embodiment of the invention, the annealing treatment time in the seventh step is 10-100s, and the terbium-doped tin oxide film photoluminescent material contains crystalline terbium-doped tin oxide. According to the invention, by controlling the annealing time, the obtained terbium-doped tin oxide film photoluminescence material has stronger crystallinity and stronger photoluminescence performance.
The embodiment of the invention also comprises a second technical scheme that: the 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 photoluminescence material emits green light at a visible light waveband and a 550nm waveband. The terbium stannate film provided by the embodiment of the invention can be applied to the fields of silicon-based light sources, LED light sources, display devices, integrated circuits and the like. According to the embodiment of the invention, the terbium-doped tin oxide film prepared by combining the sol-gel method and the rapid heat treatment method is uniformly distributed, and the photoluminescence intensity of the film in a visible waveband is stronger.
In an embodiment of the invention, the terbium-doped tin oxide thin film photoluminescent material comprises crystalline terbium-doped tin oxide. The terbium-doped tin oxide film photoluminescent material provided by the embodiment of the invention contains crystalline terbium-doped tin oxide, and has better crystallinity and photoluminescence performance.
The following examples are presented to further illustrate the methods of the present invention and are not intended to limit the invention to these examples.
Example 1:
fig. 1 shows a process flow chart of the method for preparing a terbium-doped tin oxide thin film photoluminescent material according to the embodiment, in particular, a method for preparing a terbium-doped tin oxide thin film photoluminescent material, which includes the steps of:
step one, respectively dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
Step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 10s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
As shown in FIG. 2, the terbium-doped tin oxide film prepared in the embodiment of the invention has strong luminous intensity and wide luminous wavelength range, can form photoluminescence in the wavelength range of 485nm to 635nm, and has the maximum photoluminescence intensity up to 9.2 multiplied by 10 at 555nm 4 Green light is emitted, and the light intensity is strongest. Emitting indigo light at 500nm wavelength and yellow light at 590nm wavelength; the photoluminescence intensity of red light under the wavelength of 630nm and the wave band of 500nm is 2.3 multiplied by 10 4 The photoluminescence intensity is 3.3X 10 at 590nm band 4 The photoluminescence intensity at the wavelength of 630nm is 1.7 multiplied by 10 4 。
Referring to fig. 3, wherein the RPT-treated line is the XRD pattern of the terbium-doped tin oxide film prepared in the example of the present invention, it can be seen from fig. 3 that the diffraction peaks in the (110), (101) and (211) planes correspond to the characteristic peaks of the tin oxide phase, and the terbium-doped tin oxide film in the example of the present invention, which is less in terbium content and is not shown in the XRD pattern, is formed to contain the crystalline terbium-doped tin oxide film. As shown in FIG. 4, the terbium-doped tin oxide film prepared by the embodiment of the invention has a flat surface and good uniformity.
According to the embodiment of the invention, the terbium-doped tin oxide film is prepared by combining a sol-gel method and a rapid heat treatment method, and the prepared terbium-doped tin oxide film has better photoluminescence performance. According to the invention, the terbium-doped tin oxide film is prepared by adopting rapid thermal 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 the rapid heating, the terbium-doped tin oxide film is obtained by rapid cooling, and the defects can not be repaired in the rapid cooling process, so that the symmetry of a crystal field is deteriorated, the transition probability of terbium ions is improved, and the terbium-doped tin oxide film has strong luminous intensity.
The terbium-doped tin oxide film prepared by the embodiment of the invention contains crystalline terbium-doped tin oxide.
By combining the example 1 and the comparative example 1 of the present invention, as shown in fig. 2 and fig. 3, it can be seen that the terbium-doped tin oxide films prepared by the tubular furnace in the example 1 and the comparative example 1 of the present invention each contain crystalline terbium-doped tin oxide, the temperature rise speed of the terbium-doped tin oxide films prepared by the tubular furnace is low, the thermal budget is large, and the prepared terbium-doped tin oxide films have no photoluminescence characteristics. The terbium-doped tin oxide film prepared by the preparation method of the embodiment of the invention has stronger photoluminescence property, so that the photoluminescence property of the crystalline terbium-doped tin oxide film is obviously enhanced.
Example 2:
this example differs from example 1 in that the amount of terbium chloride hexahydrate in step one was changed to 0.0036g, and the same as in example 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.0036g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 10s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The terbium-doped tin oxide film prepared by the embodiment of the invention has photoluminescence characteristics, and has strong green light emission and green light emission at a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 3:
the difference between this example and example 1 is that the amount of deionized water in step two was changed to 500. Mu.l, and the other steps are the same as in example 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 500 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E. And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 10s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The terbium-doped tin oxide film prepared by the embodiment of the invention has photoluminescence characteristics, and has strong green light emission and green light emission at a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 4:
the difference between this embodiment and embodiment 1 is that the temperature of the RTP treatment in step seven is changed to 900 ℃, and the other steps are the same as those in embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film at 900 ℃ for 10s by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared by the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 5:
the difference between this example and example 1 is that the temperature of the RTP treatment in step seven is changed to 800 ℃, and the other steps are the same as those in example 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film at 800 ℃ for 10s by adopting rapid thermal annealing equipment (RTP), so as to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 6:
the difference between this example and example 1 is that the temperature of the RTP treatment in step seven is 700 ℃, and the other steps are the same as those in example 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film at 700 ℃ for 10s by adopting rapid thermal annealing equipment (RTP), so as to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 7:
the difference between this example and example 1 is that the temperature of the RTP treatment in step seven is changed to 600 ℃, and the other steps are the same as those in example 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E. And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film at 600 ℃ for 10s by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 8:
the difference between this embodiment and embodiment 1 is that the RTP processing time in step seven is 20s, and the other steps are the same as those in embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 20s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared by the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 9:
the difference between this embodiment and embodiment 1 is that the RTP processing time in step seven is 30s, and the other steps are the same as those in embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 30s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, and the terbium-doped tin oxide film has photoluminescence characteristics, and emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 10:
the difference between this embodiment and embodiment 1 is that the RTP processing time in step seven is 40s, and the others are the same as embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 40s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP) to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared by the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 11:
the difference between this embodiment and embodiment 1 is that the RTP processing time in step seven is 50s, and the other steps are the same as those in embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
Step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 50s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP) to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared by the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 12:
the difference between this embodiment and embodiment 1 is that the RTP processing time in step seven is 60s, and the other steps are the same as those in embodiment 1, specifically as follows:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 60s at 1000 ℃ by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 13:
the embodiment of the invention provides a preparation method of a terbium-doped tin oxide film photoluminescent material, which comprises the following steps:
step one, dissolving 0.1g of stannous chloride dihydrate and 0.00001g of terbium chloride hexahydrate in 0.5ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 10 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
Step three, stirring the solution B at 50 ℃ in an open way until the solvent is completely volatilized to form xerogel, and adding 0.25ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 10 ℃, and adding 10 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 10 hours at 10 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, preparing the solution E into a film on the substrate by adopting a spin coating method, spin-coating 1 layer, and heating the film on a heating table at the temperature of 30 ℃ for 30 minutes. The substrate of the embodiment of the invention 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.
And seventhly, annealing the prepared film for 100s at 300 ℃ by adopting rapid thermal annealing equipment (RTP) to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, the terbium-doped tin oxide film has photoluminescence characteristics, and the terbium-doped tin oxide film emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 14:
the embodiment of the invention provides a preparation method of a terbium-doped tin oxide film photoluminescent material, which comprises the following steps:
step one, dissolving 1g of stannous chloride dihydrate and 0.05g of terbium chloride hexahydrate in 10ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 1000 mul of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 100 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 10ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 90 ℃, and adding 1000 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 1h at 100 ℃ in an open way, and standing for 24 h at room temperature to obtain a solution E.
And step six, preparing the solution E into a film on the substrate by adopting a spin coating method, spin-coating 1 layer, and heating the film on a heating table at the temperature of 250 ℃ for 10 minutes. The substrate of the embodiment of the invention 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.
And seventhly, annealing the prepared film at 1300 ℃ for 80s by adopting rapid thermal annealing equipment (RTP), so as to obtain the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, and the terbium-doped tin oxide film has photoluminescence characteristics, and emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide film prepared in the embodiment of the invention contains crystalline terbium-doped tin oxide.
Example 15:
the embodiment of the invention provides a preparation method of a terbium-doped tin oxide film photoluminescence material, which comprises the following steps:
step one, dissolving 0.1g of stannous chloride dihydrate and 0.05g of terbium chloride hexahydrate in 8ml of absolute ethyl alcohol in sequence to form a mixed solution A.
And step two, adding 600 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 80 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 10ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 60 ℃, and adding 800 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 8 hours at 60 ℃ in an open manner, and standing for 24 hours at room temperature to obtain a solution E.
And step six, preparing the solution E into a film on a substrate by adopting a spin coating method, spin-coating 10 layers, and heating the film on a heating table at the temperature of 200 ℃ for 20 minutes. The substrate of the embodiment of the invention is a gallium arsenide substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a silicon substrate, a germanium substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film at 1200 ℃ for 1s by adopting rapid thermal annealing equipment (RTP), and obtaining the terbium-doped tin oxide film.
The performance of the terbium-doped tin oxide film prepared in the embodiment of the invention is similar to that of the terbium-doped tin oxide film prepared in the embodiment 1, and the terbium-doped tin oxide film has photoluminescence characteristics, and emits green light with strong intensity in a 555nm wave band. The terbium-doped tin oxide thin film prepared by the embodiment of the invention contains amorphous terbium-doped tin oxide.
Comparative example 1:
a preparation method of a terbium-doped tin oxide film photoluminescence material comprises the following steps:
step one, respectively dissolving 0.226g of stannous chloride dihydrate and 0.011g of terbium chloride hexahydrate in 3.5ml of absolute ethyl alcohol to form a mixed solution A.
And step two, adding 250 mu l of deionized water into the mixed solution A to accelerate the hydrolysis process to obtain a solution B.
And step three, stirring the solution B at 70 ℃ in an open manner until the solvent is completely volatilized to form xerogel, and adding 3.5ml of absolute ethyl alcohol to obtain a solution C.
And step four, changing the stirring temperature to 50 ℃, and adding 250 mu l of acetic acid into the solution C to adjust the pH value to obtain a solution D.
And step five, stirring the solution D for 3 hours at 50 ℃ in an open way, and standing for 24 hours at room temperature to obtain a solution E.
And step six, taking 40 mu l of solution E, preparing a film on the substrate by adopting a spin coating method, spin-coating 3 layers, and heating the film on a heating table at 150 ℃. The substrate of the embodiment of the invention is a silicon substrate, and in other embodiments, the substrate can also be a semiconductor substrate such as a germanium substrate, a gallium arsenide substrate or a gallium nitride substrate.
And seventhly, annealing the prepared film for 10s at 1000 ℃ by adopting a tubular furnace to obtain the terbium-doped tin oxide film. Wherein the temperature rising speed of the tubular furnace is 5 ℃/min, and the temperature reducing speed is 5 ℃/min.
As shown in fig. 2, the terbium-doped tin oxide film prepared in the present comparative example has zero luminescence intensity and no photoluminescence characteristics, as shown in fig. 3, wherein the line of the tube furnace process is the XRD pattern of the terbium-doped tin oxide film prepared in the example of the present invention, and as can be seen from fig. 3, the diffraction peaks in the (110), (101) and (211) planes correspond to the characteristic peaks of the tin oxide phase, and the terbium content in the example of the present invention is small and is not shown in the XRD pattern, indicating that the terbium-doped tin oxide film containing a crystalline state is formed.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Any modification, equivalent replacement or improvement made by those skilled in the art based on the above description and within the principle of the method and the present invention shall be included in the protection scope of the present invention. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of a terbium-doped tin oxide film photoluminescence material is characterized by comprising the following steps:
dissolving stannous chloride dihydrate and terbium chloride hexahydrate in ethanol, and stirring at a first temperature to obtain a solution A;
step two, adding deionized water into the solution A to obtain a solution B;
step three, stirring the solution B in an open way at the first temperature until the solvent is completely volatilized to form xerogel, and then adding ethanol to obtain a solution C;
step four, reducing the temperature to a second temperature, stirring at the second temperature, and adding acetic acid into the solution C to adjust the pH value to obtain a solution D;
step five, stirring the solution D for a period of time at a third temperature in an open way, and standing for 24 hours at room temperature to obtain a solution E;
step six, spin-coating the solution E on a substrate to prepare a film, and heating the film on a heating table to obtain a film based on the substrate;
and seventhly, annealing the film on the substrate obtained in the sixth step by adopting rapid thermal annealing equipment to obtain the terbium-doped tin oxide film photoluminescence material.
2. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, characterized by: the mass volume ratio of the stannous chloride dihydrate, the terbium chloride hexahydrate and the absolute ethyl alcohol in the step one is (0.1-1) g, (0.0001-0.05) g, (0.5-10) ml.
3. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, characterized by: the volume ratio of the deionized water added in the second step to the ethanol in the first step is (10-1000) microliter (0.5-10) ml.
4. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, characterized by: the first temperature of the third step is 50-100 ℃; the volume ratio of the ethanol added in the third step to the ethanol added in the first step is (0.5-1): 1.
5. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, characterized by: the second temperature of the fourth step is 10-90 ℃; the volume ratio of the acetic acid added in the fourth step to the ethanol added in the first step is (10-1000) microliter (0.5-10) ml.
6. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, characterized by: the third temperature in the fifth step is 10-100 ℃; and in the third step, stirring for 1-10h.
7. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, wherein: 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-coated layers in the sixth step is 1-10.
8. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, wherein: heating the heating table in the sixth step at the temperature of 30-250 ℃; the time of the annealing treatment in the seventh step is 1-100s, and the temperature of the annealing treatment is 300-1300 ℃.
9. The method for preparing a terbium-doped tin oxide thin film photoluminescent material as claimed in claim 1, wherein: and the annealing time in the seventh step is 10-100s, and the terbium-doped tin oxide film photoluminescent material contains crystalline terbium-doped tin oxide.
10. A terbium-doped tin oxide thin film photoluminescent material, characterized by being prepared by the method for preparing a terbium-doped tin oxide thin film photoluminescent material according to any one of claims 1 to 9, wherein the terbium-doped tin oxide thin film material is photoluminescent in a visible light band and emits green light in a 555nm band.
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