CN113149647A - Ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film - Google Patents
Ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film Download PDFInfo
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 22
- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 21
- 150000002500 ions Chemical class 0.000 title claims abstract description 21
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000010345 tape casting Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 34
- 239000010955 niobium Substances 0.000 claims description 30
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 18
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 14
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 9
- -1 rare earth nitrate Chemical class 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 8
- 229910019660 Nb(OH)5 Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
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- 238000005520 cutting process Methods 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002738 chelating agent Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 abstract description 12
- 229910052691 Erbium Inorganic materials 0.000 abstract description 8
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 3
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- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
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- 230000035945 sensitivity Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
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- 206010063385 Intellectualisation Diseases 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 238000001272 pressureless sintering Methods 0.000 description 1
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- 239000006188 syrup Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film and a preparation method thereof3+/Yb3+Double doping of K0.5Na0.5NbO3Drying the sol (RE = Er, Ho and Tm) to obtain dry gel, then sintering to obtain nano powder, and carrying out non-pressure sintering at 950-1050 ℃ by adopting a tape casting process to obtain RE with a pure perovskite structure, compact structure, fine and uniform crystal grains and strong up-conversion luminescence under 980 nm excitation light3+/Yb3+Double doping of K0.5Na0.5NbO3And (3) thick film. The invention has simple process steps, lower cost and good repeatability,easy operation and controllable thick film thickness, and is expected to be applied to the fields of microelectronic devices, information communication, clinical medicine and the like.
Description
Technical Field
The invention belongs to the field of rare earth doped lead-free piezoelectric materials, and relates to a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film and a preparation method thereof.
Background
With the development of science and technology, electronic devices and optoelectronic devices are moving towards miniaturization, integration and intellectualization, and especially, the fast development of the field of Micro Electro Mechanical Systems (MEMS) is achieved, and the traditional ferroelectric block cannot meet the requirements of the microelectronic devices due to size limitation, so that the research of ferroelectric materials is developed from block materials to film materials. The ferroelectric thick film is less influenced by interfaces, surfaces and the like than the thin film due to the piezoelectric property of the ferroelectric thick film, and the thickness of the ferroelectric thick film reaches the micron level, so that the ferroelectric thick film can generate larger driving force and higher sensitivity; compared with a block material, the thick film has lower working voltage (less than 5V) and higher use frequency, and can be well applied to a semiconductor integration process. The thick film has a thickness far smaller than that of the bulk material, but has electrical properties similar to that of the bulk material, and can bear a larger electric field compared with the thin film, so that higher polarization strength is obtained, and the performance of the ferroelectric material is improved. The device made of the thick film material can reduce the size of an electronic component and can be produced in a large scale, and the thickness of the lead-free piezoelectric film is an urgent demand for pursuing miniaturization, high power, high sensitivity and integrated devices. However, the research on thick films at home and abroad mainly focuses on lead-based materials, and reports on KNN-based lead-free thick films are less.
In recent years, researchers introduce a proper amount of rare earth elements into ferroelectric materials, so that the ferroelectric materials are endowed with photoluminescence characteristics while electrical properties are enhanced, and meanwhile, the effects of reducing sintering temperature, improving density and the like can be achieved. The selection of proper matrix material is favorable for improving the pumping of the rare earth and the spectral efficiency of laser emission, and the potassium-sodium niobate K0.5Na0.5NbO3 (KNN) -based materials are considered to be the most promising replacements for the traditional Pb (Zr, Ti) O materials due to their high Curie temperature and large electromechanical coupling coefficient3One of the candidates for the base material. When the rare earth ions are introduced into the ferroelectric material, the f-f electric dipole transition forbidden resistance of the rare earth ions per se is broken, so that the ferroelectric material is made to haveThe obtained material has excellent optical performance; in addition, the radius of the rare earth ion is equal to that of the alkali metal ion Na+ (0.97 Å)、K+The (1.33A) radii are close to each other, so that the A position ions of the KNN group thick film can be easily replaced by doping the rare earth ions as donor ions.
Disclosure of Invention
The invention aims to provide a method for preparing KNN-based thick film material with excellent optical performance under the condition of pressureless sintering by preparing KNN-based powder through a sol-gel method and then adopting a tape casting process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, stirring at 80 ℃ until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: according to the chemical composition general formula xRE3+/0.06Yb3+-(K0.5Na0.5)NbO3 (x = 0.005, 0.01, 0.015, RE = Er, Ho, Tm) raw material (RE (NO) was weighed out in a mass ratio3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 And = y: 0.2426: 0.3360: 0.2584: 1.0676, wherein y = 0.0199-0.0601), and preparing a RE/Yb double-doped potassium-sodium niobate precursor solution.
(3) Milling: drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and grinding and sieving the powder to obtain the superfine powder.
(4) Pulping: the xRE prepared by the sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 10-14 hours, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 10-14 hours at room temperature to obtain uniformly mixed slurry, and then continuously stirring in a fume hood to evaporate the solvent until the slurry is reduced to 20-30 mL. xRE required in preparation of slurries3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.03-0.05, v1 = 0.03-0.05, v2 = 0.03-0.05, and w = 0.08-0.10.
(5) Casting: and (3) casting the slurry on a casting machine, wherein the height between a cutter and a glass substrate is 500-700 mu m, and taking down the dried slurry by using a blade.
(6) Tabletting: and cutting the prepared casting sheet into wafers (the diameter R = 8 mm), overlapping the wafers into 3-6 wafers, placing the wafers in a mold, and pressing the wafers into a green body with the thickness of 0.2-0.4 mm under the pressure of 100-200 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 2-4 hours at the temperature of 750-850 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering at 950-1040 ℃ for 3-6 h, and naturally cooling to room temperature to obtain the xRE prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
In the step (2), the concentration of the prepared RE/Yb double-doped potassium-sodium niobate precursor solution is 0.3M.
In the step (2), K in the heat treatment process is compensated+、Na+The volatilization of (2) is carried out, and 5 percent of CH is added in the material preparation3COOK and 5% CH3COONa。
In the step (2), self-prepared fresh Nb (OH) is adopted5As a niobium source.
The specific steps of the step (2) are as follows: (1) according to xRE3+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing rare earth nitrate, potassium acetate and sodium acetate according to the stoichiometric proportion, dissolving the rare earth nitrate, the potassium acetate and the sodium acetate in glacial acetic acid, and stirring the mixture for 3 hours at the temperature of 75 ℃; weighing appropriate amount of oxalic acid, dissolving in deionized water, and adding Nb (OH)5Adding the precipitate into an oxalic acid solution, dissolving at 80 ℃, adding citric acid after complete dissolution, and dissolving for 2 hours at room temperature; fully mixing the two solutions to obtain a precursor solution; (2) stirring the precursor solution at room temperature for 2 h, and dropwise adding ammonia water until the solution becomes clear; adding a proper amount of acetylacetone as a chelating agent, adding a proper amount of formamide, and continuously stirring for 2 hours to obtain a RE/Yb double-doped potassium-sodium niobate precursor solution.
In the step (3), the aperture of the screen is 200 meshes.
In the step (4), the volume ratio of the absolute ethyl alcohol to the butanone in the mixed solvent is 2: 1.
In the step (6), the diameter of the die used for slicing is 8 mm.
And (6) filling carbon paper at two ends of the mould during tabletting so as to prevent the cast sheet from adhering to the surface of the mould.
In the step (8), the temperature rise rate is 0.5-1 ℃/min in the sintering temperature rise process.
Said raw material RE (NO)3)3·5H2O, Yb(NO3)3·5H2O, Nb2O5, CH3COOK, CH3COONa, C6H8O7·H2O, C2H2O4·2H2O, (NH4)2C2O4·H2And all O are analytically pure.
The invention has the beneficial effects that: incorporation of rare earth ions by sol-gel methodPreparation of RE/Yb double doping (K) in KNN lattice0.5Na0.5)NbO3The precursor solution is dried into dry gel, the required nano powder is obtained by sintering, and the upconversion luminous efficiency is improved by the tape casting process, so that the lead-free piezoelectric thick film with the thickness less than 1 mu m, high density and excellent optical performance is obtained. The preparation method has the advantages of simple process steps, low cost, good repeatability, easiness in operation and controllable thick film thickness, is expected to be applied to the fields of microelectronic devices, information communication, clinical medicine and the like, and further expands the application range of the KNN-based material.
Drawings
FIG. 1 shows the 0.01Er obtained in example 33+/0.06Yb3+-(K0.5Na0.5)NbO3XRD pattern of thick film sample;
FIG. 2 shows the 0.01Er obtained in example 33+/0.06Yb3+-(K0.5Na0.5)NbO3SEM images of thick film samples;
FIG. 3 shows the 0.01Er obtained in example 33+/0.06Yb3+-(K0.5Na0.5)NbO3The thick film sample is subjected to up-conversion luminescence spectrum under the excitation of 980 nm laser;
FIG. 4 shows the 0.01Er obtained in example 33+/0.06Yb3+-(K0.5Na0.5)NbO3Solid photographs of thick film samples.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
A preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, and stirring at 80 deg.CStirring until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: according to the chemical composition general formula xRE3+/0.06Yb3+-(K0.5Na0.5)NbO3 (x = 0.005, 0.01, 0.015, RE = Er, Ho, Tm) raw material (RE (NO) was weighed out in a mass ratio3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 And = y: 0.2426: 0.3360: 0.2584: 1.0676, wherein y = 0.0199-0.0601), and preparing a RE/Yb double-doped potassium-sodium niobate precursor solution.
(3) Milling: drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and grinding and sieving the powder to obtain the superfine powder.
(4) Pulping: the xRE prepared by the sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 10-14 hours, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 10-14 hours at room temperature to obtain uniformly mixed slurry, and then continuously stirring in a fume hood to evaporate the solvent until the slurry is reduced to 20-30 mL. xRE required in preparation of slurries3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.03-0.05, v1 = 0.03-0.05, v2 = 0.03-0.05, and w = 0.08-0.10.
(5) Casting: and (3) casting the slurry on a casting machine, wherein the height between a cutter and a glass substrate is 500-700 mu m, and taking down the dried slurry by using a blade.
(6) Tabletting: and cutting the prepared casting sheet into wafers (the diameter R = 8 mm), overlapping the wafers into 3-6 wafers, placing the wafers in a mold, and pressing the wafers into a green body with the thickness of 0.2-0.4 mm under the pressure of 100-200 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 2-4 hours at the temperature of 750-850 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering at 950-1050 ℃ for 3-6 h, and naturally cooling to room temperature to obtain the xRE prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
(9) And (3) performance testing: the prepared samples were subjected to X-ray diffraction analysis (XRD), scanning electron microscopy analysis (SEM) and up-conversion luminescence test.
Example 1
A preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, stirring at 80 ℃ until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: tm according to the general formula of chemical composition3+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing the raw materials (Tm (NO) in a mass ratio of3)3·6H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 = 00401: 0.2426: 0.3360: 0.2584: 1.0676) to prepare a thulium/ytterbium double-doped potassium-sodium niobate precursor solution.
(3) Milling: drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and sieving the powder by a 200-mesh sieve to obtain the superfine thulium/ytterbium double-doped potassium-sodium niobate nano powder.
(4) Pulping: the above 0.01Tm prepared by a sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 10 hours, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 10 hours at room temperature to obtain uniformly mixed slurry, and then continuously stirring in a fume hood to evaporate the solvent until the slurry is reduced to 20 mL. 0.01Tm required for preparation of syrup3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.03, v1 = 0.03, v2 = 0.03, and w = 0.08.
(5) Casting: the above slurry was cast on a casting machine with a height of 500 μm between the cutter and the glass substrate, and was removed with a blade after drying.
(6) Tabletting: the cast sheet obtained above was cut into a wafer (diameter R = 8 mm), and the wafer was stacked into 3 sheets, placed in a mold, and pressed into a green compact having a thickness of 0.2 mm under a pressure of 100 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 2 h at the temperature of 750 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering at 950 ℃ for 3 h, and naturally cooling to room temperature to obtain the 0.01Tm prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
(9) Performance ofAnd (3) testing: the prepared samples were subjected to XRD, SEM and up-conversion luminescence tests. The test result shows that the sample has no second phase except the perovskite diffraction peak, compact structure, average grain size of 0.37 mu m and up-conversion blue light: (1G4 → 3H6) And red light emission (1G4 → 3F4)。
Example 2
A preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, stirring at 80 ℃ until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: er according to the chemical composition general formula of 0.013+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing raw material (Er (NO) according to the mass ratio3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 = 0.0399: 0.2426: 0.3360: 0.2584: 1.0676), preparing erbium/ytterbium double-doped potassium-sodium niobate precursor solution.
(3) Milling: drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and sieving the powder by a 200-mesh sieve to obtain the superfine erbium/ytterbium double-doped potassium-sodium niobate nano powder.
(4) Pulping: the above 0.01Er prepared by the sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 12 hours, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 12 hours at room temperature to obtain uniformly mixed slurry, and then continuously stirring in a fume hood to evaporate the solvent until the slurry is reduced to 20 mL. 0.01Er required for preparing slurry3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.03, v1 = 0.04, v2 = 0.04, and w = 0.08.
(5) Casting: the above slurry was cast on a casting machine with a height of 600 μm between the cutter and the glass substrate, and was removed with a blade after drying.
(6) Tabletting: the cast sheet obtained above was cut into a circular sheet (diameter R = 8 mm), and the circular sheet was stacked to 5 sheets, placed in a mold, and pressed into a green compact having a thickness of 0.2 mm under a pressure of 100 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 3 hours at the temperature of 750 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering at 1050 ℃ for 4 h, and naturally cooling to room temperature to obtain the 0.01Er prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
(9) And (3) performance testing: the prepared samples were subjected to XRD, SEM and up-conversion luminescence tests. The test result shows that the sample has no second phase except the perovskite diffraction peak, compact structure, average grain size of 0.28 mu m and up-conversion green light: (2H11/2 → 4I15/2And4S3/2 → 4I15/2) And red light emission (4F9/2 → 4I15/2)。
Example 3
A preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, stirring at 80 ℃ until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: er according to the chemical composition general formula of 0.013+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing raw material (Er (NO) according to the mass ratio3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 = 0.0399: 0.2426: 0.3360: 0.2584: 1.0676), preparing erbium/ytterbium double-doped potassium-sodium niobate precursor solution.
(3) Milling: drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and sieving the powder by a 200-mesh sieve to obtain the superfine erbium/ytterbium double-doped potassium-sodium niobate nano powder.
(4) Pulping: the above 0.01Er prepared by the sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 14 hours, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 12 hours at room temperature to obtain uniformly mixed slurry, and then continuously stirring in a fume hood to evaporate the solvent until the slurry is reduced to 20 mL. 0.01Er required for preparing slurry3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.04, v1 = 0.04, v2 = 0.04, and w = 0.09.
(5) Casting: the above slurry was cast on a casting machine with a height of 600 μm between the cutter and the glass substrate, and was removed with a blade after drying.
(6) Tabletting: the cast sheet obtained above was cut into a circular sheet (diameter R = 8 mm), and the circular sheet was laminated to 4 sheets, placed in a mold, and pressed into a green compact having a thickness of 0.3 mm under a pressure of 100 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 4 hours at the temperature of 800 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering for 4 h at 1030 ℃, and naturally cooling to room temperature to obtain the 0.01Er prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
(9) And (3) performance testing: the prepared sample is 0.01Er3+/0.06Yb3+-K0.5Na0.5NbO3XRD, SEM and up-conversion luminescence tests were carried out, and the test results and physical photographs are shown in FIGS. 1 to 4. FIG. 1 shows that no second phase is present in the sample except for the perovskite diffraction peak, indicating that Er and Yb have completely diffused into the KNN lattice; FIG. 2 shows that the sample has good crystallinity, compact structure and uniform grain distribution, and the average grain size obtained by calculation is 0.24 μm, which shows that the doping of a proper amount of rare earth ions can play a role in refining grains, and the inset shows that the thickness of the sample is about 0.1 μm; FIG. 3 shows that the sample exhibits a photochromic effect under excitation at 980 nm, a weak green emission at 530 nm and a strong green emission at 550 nm, corresponding to each other2H11/2 → 4I15/2And4S3/2 → 4I15/2and red emission around 660 nm corresponds to4F9/2 → 4I15/2A transition of (c); FIG. 4 is a physical photograph of cast sheet and thick film samples.
Example 4
A preparation method of a ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide (Nb) were weighed out in stoichiometric ratio2O5) Dissolving in 15 mL hydrofluoric acid (HF), and reacting at 80 ℃ for 12 h to obtain a light yellow clear solution as solution A; 25.0325 g of ammonium oxalate ((NH) were weighed out4)2C2O4·H2O), dissolving in deionized water, stirring at 80 ℃ until the solution is completely dissolved, and slowly dropwise adding the solution A into the ammonium oxalate solution to obtain an ammonium niobium oxalate solution; adding a proper amount of ammonia water into the ammonium niobium oxalate solution to obtain white Nb (OH)5Precipitating, centrifuging several times to remove impurity ions, and adding fresh Nb (OH)5Putting the precipitate into a drying oven, and drying for 5h at 80 ℃;
(2) preparing materials: according to the chemical composition general formula of 0.015Ho3+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing raw materials (Ho (NO))3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 = 0.0595: 0.2426: 0.3360: 0.2584: 1.0676), preparing a holmium/ytterbium double-doped potassium-sodium niobate precursor solution.
(3) Milling: and drying the precursor solution at 80 ℃ to obtain dry gel, putting the dry gel into a crucible, firing the dry gel into powder at 700 ℃, and sieving the powder by a 200-mesh sieve to obtain the superfine holmium/ytterbium double-doped potassium-sodium niobate nano powder.
(4) Pulping: 0.015Ho prepared by the sol-gel method3+/0.06Yb3+-(K0.5Na0.5)NbO3Stirring the nano powder and a dispersant (triethanolamine) in a mixed solvent of absolute ethyl alcohol and butanone for 14 h, then adding a plasticizer (polyethylene glycol, dibutyl phthalate) and a binder (polyvinyl butyral), stirring for 14 h at room temperature to obtain uniformly mixed slurry, and then stirring in a fume hoodThe solvent was evaporated by continued stirring until the slurry was reduced to 30 mL. 0.015Ho required for preparing the slurries3+/0.06Yb3+-(K0.5Na0.5)NbO3The mass ratio of the powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.05, v1 = 0.05, v2 = 0.05, and z = 0.10.
(5) Casting: the above slurry was cast on a casting machine with a height of 700 μm between the cutter and the glass substrate, and was removed with a blade after drying.
(6) Tabletting: the cast sheet obtained above was cut into a circular piece (diameter R = 8 mm), and the circular piece was stacked to 6 pieces, placed in a mold, and pressed into a green compact having a thickness of 0.4 mm under a pressure of 100 MPa.
(7) Rubber discharging: and (3) placing the green body in a muffle furnace, preserving heat for 3 hours at the temperature of 850 ℃ for removing glue, and then naturally cooling the green body to room temperature along with the furnace.
(8) And (3) sintering: placing the green body treated in the step (7) in a muffle furnace, sintering at 1040 ℃ for 6 h, and naturally cooling to room temperature to obtain 0.015Ho prepared based on a tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
(9) And (3) performance testing: the prepared samples were subjected to XRD, SEM and up-conversion luminescence tests. The test result shows that the sample has no second phase except for the perovskite diffraction peak, but the surface crystal grains have melting phenomenon, the average crystal grain size is about 0.37 mu m, and the sample has up-conversion green light (5S2 → 5I8) And red light emission (5F5 → 5I8And5S2 → 5I7)。
the above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. The ytterbium and up-conversion rare earth luminescent ion double-doped potassium-sodium niobate thick film is characterized in thatIn the following steps: chemical composition general formula xRE3 +/0.06Yb3+-(K0.5Na0.5)NbO3，x = 0.005、0.01、0.015，RE = Er、Ho、Tm。
2. A method of preparing the ytterbium and up-conversion rare earth luminescent ion double-doped potassium sodium niobate thick film of claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) self-made niobium source: 7.9825 g of niobium pentoxide is dissolved in 15 mL of hydrofluoric acid and reacts for 12 h at 80 ℃ to obtain a light yellow clear solution serving as solution A; 25.0325 g of ammonium oxalate is dissolved in deionized water, stirred at 80 ℃ until the ammonium oxalate is completely dissolved, and the solution A is slowly dripped to obtain ammonium niobium oxalate solution; adding a proper amount of ammonia water to obtain white Nb (OH)5Precipitating, centrifuging for many times to remove impurity ions, drying at 80 ℃ for 5h, and grinding for later use;
(2) preparing materials: weighing raw material RE (NO) according to mass ratio3)3·5H2O : Yb(NO3)3·5H2O : CH3COOK: CH3COONa: Nb(OH)5 Preparing a RE/Yb double-doped potassium-sodium niobate precursor solution by adopting a sol-gel method, wherein the y is 0.2426: 0.3360: 0.2584: 1.0676, and the y is 0.0199-0.0601;
(3) milling: drying the precursor solution in the step (2) at 80 ℃, burning the precursor solution into powder at 700 ℃, grinding and sieving the powder to obtain superfine powder;
(4) pulping: stirring the superfine powder obtained in the step (3) and a dispersant triethanolamine in a mixed solvent of absolute ethyl alcohol and butanone for 10-14 hours, then adding plasticizer polyethylene glycol, dibutyl phthalate and binder polyvinyl butyral, stirring for 10-14 hours at room temperature to obtain uniformly mixed slurry, and continuously stirring to evaporate the solvent until the slurry is reduced to 20-30 mL; the mass ratio of the superfine powder to the triethanolamine to the polyethylene glycol to the dibutyl phthalate to the polyvinyl butyral is 1: u: v 1: v 2: w, wherein u = 0.03-0.05, v1 = 0.03-0.05, v2 = 0.03-0.05, and w = 0.08-0.10;
(5) casting: carrying out tape casting on the slurry obtained in the step (4) on a tape casting machine, wherein the height between a cutter and a glass substrate is 500-700 mu m, and taking down the cutter after the cutter and the glass substrate are dried;
(6) tabletting: cutting the casting sheet in the step (5) into round sheets with the diameter R = 8 mm, stacking the round sheets into 3-6 round sheets, placing the round sheets in a mold, and pressing the round sheets into green bodies with the thickness of 0.2-0.4 mm under the pressure of 100-200 MPa;
(7) rubber discharging: placing the green body obtained in the step (6) in a muffle furnace, preserving heat for 2-4 hours at the temperature of 750-850 ℃ for removing glue, and then naturally cooling to room temperature;
(8) and (3) sintering: placing the green body after the rubber discharge in a muffle furnace, sintering at 950-1050 ℃ for 3-6 h, and naturally cooling to room temperature to obtain the xRE prepared based on the tape casting method3+/0.06Yb3+-(K0.5Na0.5)NbO3And (3) thick film.
3. The method of claim 2, wherein: the concentration of the RE/Yb double-doped potassium-sodium niobate precursor solution prepared in the step (2) is 0.3M.
4. The method of claim 2, wherein: in step (2), K in the heat treatment process is compensated+，Na+The volatilization of (2) is carried out, and 5 percent of CH is added in the material preparation3COOK and 5% CH3COONa。
5. The method of claim 2, wherein: the specific steps of the step (2) are as follows:
(1) according to xRE3+/0.06Yb3+-(K0.5Na0.5)NbO3Weighing rare earth nitrate, potassium acetate and sodium acetate according to the stoichiometric proportion, dissolving the rare earth nitrate, the potassium acetate and the sodium acetate in glacial acetic acid, and stirring the mixture for 3 hours at the temperature of 75 ℃; weighing appropriate amount of oxalic acid, dissolving in deionized water, and adding Nb (OH)5Adding the precipitate into an oxalic acid solution, dissolving at 80 ℃, adding citric acid after complete dissolution, and dissolving for 2 hours at room temperature; fully mixing the two solutions to obtain a precursor solution;
(2) stirring the precursor solution at room temperature for 2 h, and dropwise adding ammonia water until the solution becomes clear; adding a proper amount of acetylacetone as a chelating agent, adding a proper amount of formamide, and continuously stirring for 2 hours to obtain a RE/Yb double-doped potassium-sodium niobate precursor solution.
6. The method of claim 2, wherein: the aperture of the screen in the step (3) is 200 meshes.
7. The method of claim 2, wherein: in the mixed solvent in the step (4), the volume ratio of the absolute ethyl alcohol to the butanone is 2: 1.
8. The method of claim 2, wherein: and (6) the diameter of the die is 8 mm.
9. The method of claim 2, wherein: in the step (6), during tabletting, carbon paper is padded at two ends of the mould to prevent the cast sheet from adhering to the surface of the mould.
10. The method of claim 2, wherein: in the step (8), the temperature rise rate in the sintering temperature rise process is 0.5-1 ℃/min.
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