CN103952761A - Iron, chromium, manganese or cobalt doped lanthanum-gallium tantalate and lanthanum-gallium niobate crystals and melt method growth method thereof - Google Patents
Iron, chromium, manganese or cobalt doped lanthanum-gallium tantalate and lanthanum-gallium niobate crystals and melt method growth method thereof Download PDFInfo
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- CN103952761A CN103952761A CN201410084097.9A CN201410084097A CN103952761A CN 103952761 A CN103952761 A CN 103952761A CN 201410084097 A CN201410084097 A CN 201410084097A CN 103952761 A CN103952761 A CN 103952761A
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Abstract
The invention discloses an iron, chromium, manganese or cobalt co doped lanthanum-gallium tantalate and lanthanum-gallium niobate crystals and a melt method growth method thereof, and the molecular formula is La3M0.5Ga5.5(1-x)M'5.5xO14(M=Ta and Nb, M'=Fe, Cr, Mn and Co, and 0<x<=1); the melt method growth method is as follows: proportionally preparing La2O3, M2O5, Ga2O3 and M'2O3, fully mixing, compacting for forming, sintering at high temperature to obtain a material used as a crystal growth initial raw material; putting the crystal growth initial raw material into a crucible, heating for fully melting into an initial melt for melt method growth, then growing with a pulling method, a crucible declining method, a temperature gradient method and other melt methods to obtain a piezoelectric single crystal which is high in performance price ratio and more advantageous to the popularization and application, and can be widely used in the communication, high temperature pressure detection and other fields.
Description
Technical field
The present invention relates to piezoquartz and field of crystal growth, be specifically related to tantalic acid gallium lanthanum, niobic acid gallium lanthanum crystal and the melt-method growth process thereof of a kind of iron, chromium, manganese or cobalt doping.
Technical background
Piezoquartz is the important materials of surface acoustic wave device, and the piezoquartz of development is the important factor of impelling surface acoustic wave device fast development.Taking spread spectrum, in the new generation of wireless system of mark, surface acoustic wave device becomes the irreplaceable device of front end after the letter in all kinds of system of broadband wireless communication of new generation, intermediate-freuqncy signal processing owing to having the feature of distortion in large broadband, excellent passband selectivity, minimum band, processing capability in real time.Quartz, Lithium niobium trioxide, lithium tantalate are to be early used to make surface acoustic wave device, wherein dielectric, piezo-electric modulus and the electromechanical coupling factor of quartz are relatively little, but there is good temperature stability, thereby applicable preparation requires high surface acoustic wave device to temperature stability; The electromechanical coupling factor of lithium niobate crystals is large, propagation loss is little, is the important materials of preparing broadband low loss surface acoustic wave device; Lithium tantalate also has large electromechanical coupling factor, sound attenuation minimum, and temperature stability is better than Lithium niobium trioxide, but in early days because its fusing point is higher than Lithium niobium trioxide, growing technology complexity, therefore be not applied on surface acoustic wave device.But 1977 Japan
after large size Lithium niobium trioxide is grown successfully, lithium tantalate starts with being used on surface acoustic wave device.
In recent years, people have developed novel piezoelectric monocrystalline LGS (La
3ga
5siO
14, lower brief note is LGS), it has moderate electromechanical coupling factor, good temperature stability, can meet the basic demand of surface acoustic wave device to substrate material; Its acoustic surface wave propagation speed is low, and this is highly beneficial to realizing device miniaturization; Its good high-temperature stability is expected to for hot environment well, is that much high-end fortune is applied as the important piezoquartz of space industry.These advantages make people pay much attention to LGS, and its performance, crystal growth have been done to a large amount of research work.Because the Ga component raw material in LGS is very expensive, limit its popularization and application; And there is volatilization in Ga in growth, control and the crystal mass of crystal growth are had a significant impact, thereby people substitute and do a lot of work the Ga in LGS, substituting Ga with Al is La
3ga
5-xal
xsiO
14but the maximum x value of the alternative LGS of Al is 1.5, and in the time of x=0.9, growing crystal there will be serious cracking, thereby it is limited that Al replaces the obtained cost of Ga.In order to obtain the piezoquartz than LGS more excellent performance, people have been developed the tantalic acid gallium lanthanum La of analog structure
3ga
5.5ta
0.5o
14(LGT), niobic acid gallium lanthanum La
3ga
5.5nb
0.5o
14(LGN), they are piezoquartzs that over-all properties is more good.But can see, the Ga component ratio in LGT, LGN is higher, thereby cost can be higher, and its popularization and application has been brought to certain difficulty.
Summary of the invention
The object of the present invention is to provide a kind of iron, chromium, manganese or cobalt codoped tantalic acid gallium lanthanum, niobic acid gallium lanthanum crystal and melt-method growth process thereof, thereby the piezoelectric monocrystal of excellent there is important application prospect in fields such as communication, high temperature pressure detections.
For achieving the above object, the technical solution used in the present invention is as follows:
Tantalic acid gallium lanthanum, the niobic acid gallium lanthanum crystal of iron, chromium, manganese or cobalt doping, its molecular formula can be expressed as La
3m
0.5ga
5.5 (1-x)m '
5.5xo
14, wherein, M=Ta, Nb, M '=Fe, Cr, Mn, Co, the span of x is: 0<x≤1.
Iron of the present invention, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, comprise the following steps:
(1) adopt La
2o
3, M
2o
5, Ga
2o
3, M '
2o
3as raw material, by following chemical equation:
prepare burden, it is fully mixed, through being pressed into after cake or cylindrical block material, at 900-1300 DEG C, calcining and within 80-200 hour, occur, after solid state reaction, to obtain the required polycrystal raw material of growing crystal; Or compound is pressed into after cake or cylindrical block material, can be without extra sintering directly as crystal growth initial feed;
(2) the crystal growth initial feed of above-mentioned preparation is put into growth platinum crucible, iridium crucible, molybdenum crucible or tungsten crucible, by induction heating or resistive heating fully fusing, obtain crystal growth melt; Then adopt crystal growth method by melt technique-crystal pulling method, falling crucible method, warm terraced method, heat-exchanging method, kyropoulos, top-seeded solution growth or fusing assistant growing method to grow.
Described growth atmosphere can be air atmosphere, oxidizing atmosphere, argon gas atmosphere, nitrogen atmosphere, CO
2atmosphere or CO atmosphere.
Described crystal growth method by melt comprises and does not adopt seeded growth and use seed crystal oriented growth; For adopting seed crystal oriented growth, seed crystal is Fe, Cr, Mn or Co doping tantalic acid gallium lanthanum, niobic acid gallium langasite single crystal or pure tantalic acid gallium lanthanum, niobic acid gallium langasite single crystal, seed crystal direction <100>, <010> or <001> direction.
Owing to having Ga volatilization in described crystal growth, there is the Segregation of Fe, Cr, Mn, Co simultaneously, the crystal composition and the furnish component that grow have difference, but all within the specified scope of right 1; If the effective segregation coefficient of Fe, Cr, Mn, Co is k, to consider after solidifying effect, the raw material of the monocrystalline that preparation growth concentration is x should be by following chemical equation:
prepare.
In described batching, raw materials used La
2o
3, Ta
2o
5, Nb
2o
5, Ga
2o
3, Cr
2o
3, Mn
2o
3, Co
2o
3, Fe
2o
3, can adopt other compound of corresponding La, Ta, Nb, Ga, Cr, Mn, Co, Fe to replace, raw material synthetic method comprises that high temperature solid state reaction, liquid phase are synthesized, gas-phase synthesizing method, can finally form compound L a by chemical reaction but need to meet
3m
0.5ga
5.5 (1-x)m '
5.5xo
14this condition.
Beneficial effect of the present invention:
The present invention invents Fe, the Cr, Mn, the Co unit that adopt price relatively cheap and usually partly replaces Ga, obtains La
3m
0.5ga
5.5 (1-x)m '
5.5xo
14(M=Ta, Nb, M '=Fe, Cr, Mn, Co, 0<x≤1), keeping under the situation of its piezoelectric property, structure, improve or overcome Ga volatilization to the impact on quality in crystal growth, acquisition has the piezoquartz that cost performance is high, be more conducive to popularization and application, can be widely used in the field such as communication, high temperature pressure detection.
Embodiment
Need to establish the tantalic acid gallium lanthanum crystal La that required preparation Cr doping content is 10at%
3ta
0.5ga
4.95cr
0.55o
14, the required raw material of crystals growth is the effect of segregation (being k=1) that 100g ignores Cr, crystal growth method by melt method is as follows:
(1) adopt La
2o
3, Ga
2o
3, Cr
2o
3, Ta
2o
5as raw material, by following chemical equation:
prepare burden;
Get 44.23g La in this ratio nominal
2o
3, 10.00g Ta
2o
5, 41.98g Ga
2o
3, 13.78g Cr
2o
3fully mix, obtain ingredients mixture;
(2) just mixture is pressed into round pie, calcines 100 hours at 1000 DEG C, obtains crystal growth initial feed;
(3) crystal growth initial feed is put into growth iridium crucible, utilize JGD60 type single crystal growing furnace system, by Frequency Induction Heating fully fusing, obtain crystal growth initial melt; Then adopt method of crystal growth by crystal pulling technique, taking the tantalic acid gallium langasite single crystal of <001> direction as seed crystal oriented growth, obtain the Cr doping tantalic acid gallium langasite single crystal of <001> direction growth.
Claims (6)
1. tantalic acid gallium lanthanum, the niobic acid gallium lanthanum crystal of iron, chromium, manganese or cobalt doping, is characterized in that, its molecular formula can be expressed as La
3m
0.5ga
5.5 (1-x)m '
5.5xo
14, wherein, M=Ta, Nb, M '=Fe, Cr, Mn, Co, the span of x is: 0<x≤1.
2. iron as claimed in claim 1, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, is characterized in that comprising the following steps:
(1) adopt La
2o
3, M
2o
5, Ga
2o
3, M '
2o
3as raw material, by following chemical equation:
prepare burden, it is fully mixed, through being pressed into after cake or cylindrical block material, at 900-1300 DEG C, calcining and within 80-200 hour, occur, after solid state reaction, to obtain the required polycrystal raw material of growing crystal; Or compound is pressed into after cake or cylindrical block material, can be without extra sintering directly as crystal growth initial feed;
(2) the crystal growth initial feed of above-mentioned preparation is put into growth platinum crucible, iridium crucible, molybdenum crucible or tungsten crucible, by induction heating or resistive heating fully fusing, obtain crystal growth melt; Then adopt crystal growth method by melt technique-crystal pulling method, falling crucible method, warm terraced method, heat-exchanging method, kyropoulos, top-seeded solution growth or fusing assistant growing method to grow.
3. iron according to claim 2, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, is characterized in that, described growth atmosphere can be air atmosphere, oxidizing atmosphere, argon gas atmosphere, nitrogen atmosphere, CO
2atmosphere or CO atmosphere.
4. iron according to claim 2, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, is characterized in that, described crystal growth method by melt comprises and do not adopt seeded growth and use seed crystal oriented growth; For adopting seed crystal oriented growth, seed crystal is Fe, Cr, Mn or Co doping tantalic acid gallium lanthanum, niobic acid gallium langasite single crystal or pure tantalic acid gallium lanthanum, niobic acid gallium langasite single crystal, seed crystal direction <100>, <010> or <001> direction.
5. iron according to claim 2, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, it is characterized in that: owing to having Ga volatilization in described crystal growth, there is the Segregation of Fe, Cr, Mn, Co simultaneously, the crystal composition and the furnish component that grow have difference, but all within the specified scope of right 1; If the effective segregation coefficient of Fe, Cr, Mn, Co is k, to consider after solidifying effect, the raw material of the monocrystalline that preparation growth concentration is x should be by following chemical equation:
prepare.
6. iron according to claim 2, chromium, manganese or the tantalic acid gallium lanthanum of cobalt doping, the melt-method growth process of niobic acid gallium lanthanum crystal, is characterized in that, in described batching, and raw materials used La
2o
3, Ta
2o
5, Nb
2o
5, Ga
2o
3, Cr
2o
3, Mn
2o
3, Co
2o
3, Fe
2o
3, can adopt other compound of corresponding La, Ta, Nb, Ga, Cr, Mn, Co, Fe to replace, raw material synthetic method comprises that high temperature solid state reaction, liquid phase are synthesized, gas-phase synthesizing method, can finally form compound L a by chemical reaction but need to meet
3m
0.5ga
5.5 (1-x)m '
5.5xo
14this condition.
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| CN201410084097.9A CN103952761A (en) | 2014-03-07 | 2014-03-07 | Iron, chromium, manganese or cobalt doped lanthanum-gallium tantalate and lanthanum-gallium niobate crystals and melt method growth method thereof |
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Cited By (2)
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|---|---|---|---|---|
| CN108301046A (en) * | 2018-03-14 | 2018-07-20 | 江苏海林电子新材料科技有限公司 | A kind of optical crystal and its growing method of the preparation of large scale doped gallium lanthanum crystal |
| CN112607775A (en) * | 2020-12-28 | 2021-04-06 | 中山大学 | Ho3+Activated green down-conversion phosphor and method of making |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108301046A (en) * | 2018-03-14 | 2018-07-20 | 江苏海林电子新材料科技有限公司 | A kind of optical crystal and its growing method of the preparation of large scale doped gallium lanthanum crystal |
| CN112607775A (en) * | 2020-12-28 | 2021-04-06 | 中山大学 | Ho3+Activated green down-conversion phosphor and method of making |
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Inventor after: Zhang Qi Inventor after: Zhang Yonghua Inventor before: Zhang Qingli Inventor before: Zhang Qi Inventor before: Sun Guihua Inventor before: Lv Zhiping Inventor before: Dou Renqin |
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Application publication date: 20140730 |