CN103880421A - High-efficiency potassium-sodium niobate based lead-free piezoelectric fluorescent material and preparation method thereof - Google Patents

High-efficiency potassium-sodium niobate based lead-free piezoelectric fluorescent material and preparation method thereof Download PDF

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CN103880421A
CN103880421A CN201410043984.1A CN201410043984A CN103880421A CN 103880421 A CN103880421 A CN 103880421A CN 201410043984 A CN201410043984 A CN 201410043984A CN 103880421 A CN103880421 A CN 103880421A
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preparation
leadless piezoelectric
fluorescent material
luminescent material
free piezoelectric
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张奇伟
孙海勤
张涛
张胤
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Inner Mongolia University of Science and Technology
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Inner Mongolia University of Science and Technology
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Abstract

The invention relates to a high-efficiency potassium-sodium niobate based lead-free piezoelectric fluorescent material, belonging to the technical field of lead-free piezoelectric multifunctional luminous materials. The lead-free piezoelectric fluorescent material comprises the following components by mass percent: (K[0.5+y]Na0.5)[1-x]Sm[x](Nb[1-z]Mz)O3, wherein M is selected from one or more of metal elements Zr<4+>, Sn<4+>, Ti<4+> and Si<4+>; x is not less than 0 and not more than 0.03; y is not less than -0.05 and not more than +0.05; and z is not less than 0 and not more than 0.02. The lead-free piezoelectric fluorescent material is obtained by introducing a rare earth element into a perovskite structure matrix, wherein the introduced rare earth element is Sm<3+>; and high-efficiency luminous characteristics are obtained by adjusting and controlling the stoichiometric ratio of A and the ion substitution of B in the perovskite structure ABO3.

Description

A kind of efficient potassium niobate sodium base leadless piezoelectricity fluorescent material and preparation method
Technical field
The present invention is specifically related to a kind of novel efficient and has perovskite structure leadless piezoelectric luminescent material and preparation method, belongs to light-electric multifunctional material field.
Background technology
In recent years, along with the development of novel material Science and Technology, and various electron device functionalization, miniaturization and intelligentized requirement.Using ferroelectric, piezoelectrics as starting point, the light-electric multi-functional characteristic of the way exploitation advanced material by doping has started to cause various countries investigator's concern.Rare earth element has the incomparable spectral quality of general element, can be used as luminescence center and is doped in various substrate materials, thereby can be widely used in solid luminescent material field.
In recent years, some experts and scholars both domestic and external separately ward off strange footpath, some exploratory studys have been carried out in luminous aspect to leadless piezoelectric material material, by introducing after rare earth ion, some leadless piezoelectric material material is not in worsening its piezoelectric property, the fluorescent characteristic having had, this makes to have stepped an important step in the development of leadless piezoelectric material material, widen to a certain extent the Application Areas of leadless piezoelectric material material, make it be expected to be applied to more field, as all many-sides such as flat pannel display, normal lighting, sensor, information storage, biological detection, biologic medicals.2005, the people such as Wang XS reported Pr 3+the leadless piezoelectric ceramics system BaTiO of doping 3-CaTiO 3there is light-machine-electric multi-functional (Adv. Mater., 2005,17:1254 – 1258); 2007, the people such as people and Chen S (J. Am. Ceram. Soc., 2007,90 (2): 664-666) such as Wu MJ (J. Am. Ceram. Soc., 2007,90 (11): 3642-3645.) found Er 3+(the Bi of doping 0.5na 0.5) TiO 3(BNT) there is up-conversion luminescence character and good piezoelectric property.In addition, recent research person is by rare earth Pr 3+the leadless piezoelectric ceramics Bi of doping 0.5na 0.5tiO 3(BNT) conduct a preliminary study (J. Appl. Phys., 2011,110:016102-3), find a small amount of rare earth Pr 3+the BNT pottery of doping all has piezoelectric property and luminescent properties simultaneously.
But, the report of above various documents, its weak luminous efficiency has limited the application of such material in light-electric multifunction device.Therefore, develop and probe into new light-electric multifunctional material, the luminous efficiency that improves perovskite structure piezoelectric becomes current matter of utmost importance to be solved.According to current investigated data, up to the present not about the relevant report that how to obtain high efficiency leadless piezoelectric luminescent material class.
Summary of the invention
The object of this invention is to provide a kind of preparation and preparation method with high efficiency potassium niobate sodium base leadless piezo-luminescence material, to overcome the deficiencies in the prior art.
Having the leadless piezoelectric luminescent material of perovskite structure, is in perovskite structure matrix, to introduce rare earth element to obtain, and the rare earth element wherein introduced is Sm 3+, by regulation and control perovskite structure ABO 3the stoichiometric ratio of middle A position and the ion substitution of B position obtain the high efficiency characteristics of luminescence, and its chemical composition general formula can be expressed as: (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, wherein M is metallic element Zr 4+, Ti 4+, Sn 4+, Si 4+in one or more ions; The span of x: 0≤x≤0.03; The span of y :-0.05≤y≤+ 0.05; The span of z: 0≤z≤0.02.Wherein selected raw material is: NaCO 3, KCO 3, Nb 2o 5, Sm 2o 3, ZrO 2, TiO 2, SnO 2, SiO 2.
The preparation method of efficient leadless piezoelectric luminescent material provided by the present invention specifically comprises the steps:
Adopt traditional electronic ceramic powder preparation technology, pass through solid reaction process, according to the molar ratio ingredient of certain above-mentioned chemical general formula, the raw material preparing is placed in to nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water ball milling 20～24 hours, discharging is crossed 200 mesh sieves after drying, and the powder after sieving is 800 oc～1000 oc pre-burning 4 hours, calcined temperature curve is: 30 oC-500 oc(2h)-800 oc(or 1000 oc) (insulation 4h)-cool to room temperature with the furnace, obtains the single-phase perovskite structure powder that has after grinding.After grinding, obtain initial powder.Then, the polyvinyl alcohol (PVA) of employing 8～10% carries out granulation as binding agent to above-mentioned composite powder, under 10～100 MPa pressure, is pressed into the ceramic green sheet of desired size size by forming mould.
Ceramic green sheet is through 550 oafter sticky processing of row of C, 1100 oc～1250 ounder C, be incubated 2～4 hours, can obtain described leadless piezoelectric luminescent material.
Wherein the mass ratio of zirconia ball and ball milling material is 1.2～1.5; The mass ratio of dehydrated alcohol or deionized water and ball milling material is 1.5～3.0.
The present invention adopts traditional electronic ceramic technology, development obtains a kind of blue-light excited red green emission luminescent material of high-level efficiency that has, by preparation technology's control, make the potassium-sodium niobate that itself does not have the characteristics of luminescence have high efficiency photoluminescence property, the principal feature of this material is as follows:
(1) fluorescent material (K in the present invention 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3excite the blue wave band of predominant wavelength at 400nm-500nm, excite main peak at 407nm, fully mate with current mature InGaN blue led chip light emitting spectrum;
(2) this fluorescent material transmitting peak wavelength is positioned at 597nm, presents strong red emission characteristic;
(3) high luminous efficiency (η >0.24) is the maximum of the current rear-earth-doped perovskite ferroelectric materials luminous intensity of reporting;
(4) in addition, have the potassium-sodium niobate sill of perovskite structure, itself can also be applied in ultrasonic transducer, ultrasonic delayer, sensor, nondestructive testing, piezoelectric transformer, mechanics of communication as a kind of high-temperature piezoelectric material.Therefore,, owing to having Multifunctional photoelectric processor characteristic, this material, except being used for white light LEDs technology, is also expected to be applied in the fields such as, photoelectric sensing integrated, micro electronmechanical at photoelectricity.
(5) adopt traditional electronic ceramic technology, technique is simple, and cost is low, the side effect of material system environment-protecting asepsis, and excellent performance, applicable to exploitation and the design of Multifunctional photoelectric processor integrated device.
 
Brief description of the drawings
Fig. 1, (K 0.5na 0.5) 0.99sm 0.01(Nb 1-zzr z) O 3the excitation and emission spectra figure of system pottery;
Fig. 2, (K 0.5+yna 0.5) 0.99sm 0.01nbO 3(y<0) the utilizing emitted light spectrogram of system pottery;
Fig. 3, (K 0.5+yna 0.5) 0.99sm 0.01nbO 3(y>0) the utilizing emitted light spectrogram of system pottery.
 
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, these embodiment are only not used in and limit the scope of the invention for the present invention is described.
Preparation (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, wherein M is Zr 4+ion, the span of x: 0≤x≤0.03; The span of y :-0.05≤y≤+ 0.05; The span of z: 0≤z≤0.02.
Embodiment 1
Preparation (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, wherein x=0.01, y=0, z=0, i.e. (K 0.5na 0.5) 0.99sm 0.01nbO 3.According to stoichiometric ratio, take 10.364g K 2cO 3, 7.950 g Na 2cO 3, 39.913g Nb 2o 5with 0.524g Sm 2o 3powder is placed in nylon ball grinder, adds zirconia ball and dehydrated alcohol or deionized water, ball milling 24 hours, and after discharging oven dry, powder is crossed 200 mesh sieves, and the powder after sieving is put into corundum crucible 880 oc pre-burning 4 hours, obtains pre-burning powder after grinding.The polyvinyl alcohol (PVA) of employing 8% carries out granulation as binding agent, and under 15 MPa pressure, dry method is pressed into diameter phi=10 mm green sheet, through 550 oafter sticky processing of row of C, sample is under air atmosphere, and sintering temperature is 1130 oc, was incubated after 4 hours, obtained block ceramic sample.This block is the red emission fluorescent material (K of the present embodiment 1 0.5na 0.5) 0.99sm 0.01nbO 3.
By (the K of embodiment 1 gained 0.5na 0.5) 0.99sm 0.01nbO 3block ceramic sample carries out luminescent properties test, obtains as (the K in Fig. 1 0.5na 0.5) 0.99sm 0.01nbO 3excitation and emission spectra figure.The excitation wavelength of the potassium-sodium niobate sill of the present embodiment is positioned at the scope of 400nm-500nm, matches with the luminescent spectrum of commercial LED blue chip.The main peak of its emission spectrum is positioned at the red emission of 597nm, and the quantum yield of transmitting reaches η=0.24.
Embodiment 2
Preparation (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, M is metallic element Sn 4+, wherein x=0.01, y=0, z=0.002,0.005,0.008,0.010 and 0.015, i.e. (K 0.5na 0.5) 0.99sm 0.01(Nb 0.998sn 0.002) O 3, (K 0.5na 0.5) 0.99sm 0.01(Nb 0.995sn 0.005) O 3, (K 0.5na 0.5) 0.99sm 0.01(Nb 0.992sn 0.008) O 3, (K 0.5na 0.5) 0.99sm 0.01(Nb 0.99sn 0.01) O 3, (K 0.5na 0.5) 0.99sm 0.01(Nb 0.985sn 0.015) O 3, (K 0.5na 0.5) 0.99sm 0.01(Nb 0.998sn 0.002) O 3.Choose K 2cO 3, Na 2cO 3, Nb 2o 5, Sm 2o 3and SnO 2as starting raw material, according to stoichiometric ratio, take appropriate starting raw material, its experiment condition is consistent with embodiment 1.Its luminescent properties test result as shown in Figure 1, with (K 0.5na 0.5) 0.99sm 0.01nbO 3compare Sn 4+replacement in B position has significantly strengthened (K 0.5na 0.5) 0.99sm 0.01nbO 3luminous intensity, luminous efficiency is improved significantly, its quantum yield η >0.24.Wherein excite with the position of emission peak and do not change, there is good frequency stability.Can obviously find out best optimization component z=0.01 from Fig. 1.
Embodiment 3
Preparation (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, wherein x=0.01, y>0 or y<0, z=0, i.e. (K 0.5+yna 0.5) 0.99sm 0.01nbO 3, wherein y=-0.005 ,-0.015 ,-0.030 ,-0.050 ,+0.005 ,+0.015 ,+0.030 ,-0.050.Choose K 2cO 3, Na 2cO 3, Nb 2o 5, Sm 2o 3as starting raw material, according to stoichiometric ratio, take appropriate starting raw material, its experiment condition is consistent with embodiment 1.Its luminescent properties test result as shown in Figure 2,3, with inexcessive (K 0.5na 0.5) 0.99sm 0.01nbO 3compare the excessive or not enough remarkable (K that strengthened of K 0.5na 0.5) 0.99sm 0.01nbO 3luminous intensity, luminous efficiency is improved significantly.Can obviously find out from Fig. 2 and Fig. 3, the best composition that K is excessive or not enough is respectively y=-0.050, y=+0.005.
It will be appreciated by those skilled in the art that other embodiment and variation, the specific embodiment that the invention is not restricted to point out above.

Claims (3)

1. there is a high efficiency leadless piezoelectric luminescent material, it is characterized in that, comprise the component of following mass percent: (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3, wherein M is metallic element Zr 4+, Sn 4+, Ti 4+, Si 4+in one or more ions; The span of x: 0≤x≤0.03; The span of y :-0.05≤y≤+ 0.05; The span of z: 0≤z≤0.02.
2. a preparation method with high efficiency leadless piezoelectric luminescent material, is characterized in that, preparation method's step is as follows:
1) adopt solid phase reaction method preparation (K 0.5+yna 0.5) 1-xsm x(Nb 1-zm z) O 3fluorescent material, chooses burning
Thing or carbonate NaCO 3, KCO 3, Nb 2o 5, Sm 2o 3, ZrO 2, TiO 2, SnO 2, SiO 2as starting raw material;
2) take the required raw material of powder according to stoichiometric ratio;
3) by step 2) in the raw material that takes be placed in nylon ball grinder, add zirconia ball and dehydrated alcohol or deionized water ball milling 20～24 hours, wherein the mass ratio of zirconia ball and ball milling material is 1.2～1.5; The mass ratio of dehydrated alcohol or deionized water and ball milling material is 1.5～3.0, and discharging is crossed 200-300 mesh sieve after drying, and obtains mixed powder;
4) by step 3) in mixed powder put into corundum crucible, 800 DEG C～1000 DEG C pre-burnings 4 hours, calcined temperature curve is: 30 DEG C-500 DEG C insulation 2h-800 DEG C or 1000 DEG C of insulation 4h-cool to room temperature with the furnace, and after grinding, obtain the single-phase powder with perovskite structure;
5) with 8～10% polyvinyl alcohol as binding agent to step 4) in powder carry out granulation, under 10～100 MPa pressure, be pressed into the ceramic green sheet of desired size size by forming mould;
6) by step 5) in ceramic green sheet through the row of 550 DEG C is sticky process after, at 1100 DEG C～1250 DEG C, be incubated 2～4 hours, temperature rise rate is 3 DEG C/min, can obtain described leadless piezoelectric luminescent material.
3. the preparation method with high efficiency leadless piezoelectric luminescent material according to claim 2, is characterized in that, described leadless piezoelectric luminescent material has high luminous efficiency: η >0.24.
CN201410043984.1A 2014-01-29 2014-01-29 High-efficiency potassium-sodium niobate based lead-free piezoelectric fluorescent material and preparation method thereof Pending CN103880421A (en)

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CN107353002A (en) * 2017-08-10 2017-11-17 内蒙古科技大学 Reversible and controllable fluorescence photochromic piezoelectric and preparation method thereof
CN109384465A (en) * 2018-11-19 2019-02-26 福州大学 A kind of preparation method of samarium doping potassium-sodium niobate crystalline ceramics
KR20220023392A (en) * 2020-08-21 2022-03-02 홍익대학교 산학협력단 Piezo-luminescent multi-characteristic nanoparticles and method for manufacturing the same
CN115159983A (en) * 2022-07-01 2022-10-11 中国科学院上海硅酸盐研究所 Sodium niobate-based relaxor antiferroelectric ceramic material and preparation method thereof
CN116178009A (en) * 2023-03-17 2023-05-30 江苏师范大学 High-orientation potassium-sodium niobate-based transparent piezoelectric ceramic and preparation method thereof
CN116813344A (en) * 2023-07-10 2023-09-29 石河子大学 Sodium niobate-based composite energy storage ceramic material

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107353002A (en) * 2017-08-10 2017-11-17 内蒙古科技大学 Reversible and controllable fluorescence photochromic piezoelectric and preparation method thereof
CN109384465A (en) * 2018-11-19 2019-02-26 福州大学 A kind of preparation method of samarium doping potassium-sodium niobate crystalline ceramics
KR20220023392A (en) * 2020-08-21 2022-03-02 홍익대학교 산학협력단 Piezo-luminescent multi-characteristic nanoparticles and method for manufacturing the same
KR102468845B1 (en) * 2020-08-21 2022-11-17 홍익대학교 산학협력단 Piezo-luminescent multi-characteristic nanoparticles and method for manufacturing the same
CN115159983A (en) * 2022-07-01 2022-10-11 中国科学院上海硅酸盐研究所 Sodium niobate-based relaxor antiferroelectric ceramic material and preparation method thereof
CN115159983B (en) * 2022-07-01 2023-03-10 中国科学院上海硅酸盐研究所 Sodium niobate-based relaxor antiferroelectric ceramic material and preparation method thereof
CN116178009A (en) * 2023-03-17 2023-05-30 江苏师范大学 High-orientation potassium-sodium niobate-based transparent piezoelectric ceramic and preparation method thereof
CN116178009B (en) * 2023-03-17 2023-12-15 江苏师范大学 High-orientation potassium-sodium niobate-based transparent piezoelectric ceramic and preparation method thereof
CN116813344A (en) * 2023-07-10 2023-09-29 石河子大学 Sodium niobate-based composite energy storage ceramic material

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