CN104152999A - Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor - Google Patents
Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor Download PDFInfo
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Abstract
The invention discloses a potassium-sodium niobate-based leadless piezoelectric monocrystalline and a growth method therefor. The piezoelectric monocrystalline has a perovskite structure, the chemical formula is (K<x>Na<1-x>)<1-y>Li<y>(Nb<1-z>M<z>)O3, wherein, M represents a transition metal element, x is more than 0 and less than 1, y is more than 0 and less than 1 and z is more than 0 and less than 1. The method comprises steps: raw material power and fluxing agents are weighed and mixed; starting materials are put into a crucible; heat preservation is carried out for 3-20h at the temperature of 500-1100 DEG C, the temperature is raised to 1000-1300 DEG C, heat preservation is carried out for 2-20h, the starting materials are melt, then the crucible is subjected to decline crystallization at a speed of 0.1-1.2mm/h, the crucible is cooled to room temperature and otassium-sodium niobate-based leadless piezoelectric monocrystallines are obtained. In the growth method, a fluxing agent adding Bridgman method is employed for the first time and growth of transition-metal-doped potassium-sodium niobate-based leadless piezoelectric monocrystalline is achieved, the obtained crystal has a pure perovskite structure, has no other impurity phase, and has good piezoelectric and ferroelectric performances. The technology is simple and the sintering temperature is low.
Description
Technical field
The present invention relates to a kind of functional materials single crystal technology field, relate in particular to a kind of potassium-sodium niobate lithium radical leadless piezoelectric monocrystal and growth method.
Background technology
Piezoelectric is the very important functional materials of a class, can realize the conversion between mechanical energy and electric energy by piezoelectric effect.Piezoelectric, due to physicalies such as its special piezoelectricity, ferroelectric, dielectric, pyroelectricity and photoelectricity, is widely used in the fields such as electronics, communication, aerospace, medical treatment, military affairs.And along with world economy and scientific and technological fast development, its range of application will constantly expand.But so far, the piezoelectric of dominance is lead-containing materials, and as Pb-based lanthanumdoped zirconate titanates etc., such material remains the main raw of the electronic components such as the various piezoelectric ultrasonic transducers of preparation, sensor, wave filter, resonator at present, yet in these lead base piezoelectrics, plumbous component (PbO or Pb
3o
4) make a gesture of measuring account for raw material gross weight 60% even more than, in production, use and waste gas treatment process, environmental pollution is serious, in addition, tellurian lead resource is also very limited, the extensive use of lead base piezoelectric and social sustainable development idea are runed counter to.Thereby the leadless piezoelectric material material system of the friendly type of development environment becomes the task of top priority.
Potassium-sodium niobate ((K
xna
1-x) NbO
3be abbreviated as KNN) base leadless piezoelectricity material have simple in structure, piezoelectric property good, Curie temperature is high and the feature of component to environment and human body close friend etc., be a kind of excellent performance, there is the leadless piezoelectric material material of very large application prospect, be considered to be expected to most substitute the leadless piezoelectric material material of the lead base piezoelectrics such as PZT.In recent years, lot of domestic and international scholar has done a large amount of research to potassium-sodiumniobate lead-free piezoelectric material, but research mainly concentrates on pottery.And pottery is at high temperature to carry out in making processes, the element evaporations such as K, Na are serious, make potassium sodium niobate ceramic be difficult to densification and sintering character a little less than, affected the raising of potassium sodium niobate ceramic performance.And monocrystalline has optimum crystallographic orientation and anisotropy, the monocrystalline of same composition and ceramic phase ratio, monocrystalline will have more excellent performance, and unleaded being most likely on monocrystalline of piezoelectric is achieved.But also there is a quadrature-cubic ferroelectric transition temperature in pure potassium-sodium niobate monocrystalline below Curie temperature, affected its application in practice, thereby mostly by doping, this temperature has been moved to low temperature direction, improve its Curie temperature simultaneously.
In the potassium-sodium niobate-based monocrystalline of doping, studying more is the monocrystalline of lithium doping.Make a general survey of present stage, mainly contain the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal of growths such as adopting high temperature flux method, solid reaction process and crystal pulling method both at home and abroad.Equally because single crystal preparation technique is at high temperature carried out, potassium, sodium volatilization are seriously, the growth of potassium-sodium niobate lithium radical leadless piezoelectric monocrystal is still more difficult, composition departs from, and the monocrystalline size that growth obtains is less, and a little less than thereby leakage current makes ferroelectric properties greatly, can not record the saturated problems such as ferroelectric hysteresis loop.Prepared monocrystal material performance is still undesirable.How the monocrystalline of large, the piezoelectric property of preparation size and ferroelectric properties excellence, is still the problem that KNN system leadless piezoelectric monocrystalline is urgently studied and solved.
Falling crucible method (being called again Bridgman Method) is because following several advantages become the conventional growing method of investigator: one, raw material is sealed in crucible, reduce the impact of volatility of raw material on uneven components and perfection of crystal, prevented the pollution that poisonous gas leakage causes simultaneously; Two, falling crucible method can be controlled to check figure order by thermograde or seed crystal induction nucleation, utilizes crucible shape to realize how much simultaneously and eliminates, and promotes the growth of large size single crystal; Three, can grow by many crucibles, a stove fecund, has improved working efficiency, is easy to accomplish scale production simultaneously.How to utilize the falling crucible method potassium-sodium niobate lithium base piezoelectric monocrystal of growing at low temperatures, and the leadless piezoelectric monocrystalline of growing large-size, belong to a large invention in fact.
Summary of the invention
The technical problem that leakage current is large, ferroelectric properties is weak that the present invention is directed to potassium-sodium niobate lithium radical leadless piezoelectric monocrystal in prior art, object is to provide a kind of novel leadless piezoelectric monocrystalline.Described leadless piezoelectric monocrystalline is also potassium-sodium niobate lithium radical leadless piezoelectric monocrystal, it mixes transition metal atoms M for example Fe, Cu or Mn in potassium-sodium niobate lithium radical leadless piezoelectric monocrystal, thereby transition metal atoms replaces the Nb on B position in ABO3 structure, the replacement of M can change the shape of oxygen octahedra, thereby the internal stress that changes crystals makes ferroelectric domain size decreases, and the valent variation of M can make the density in oxygen room in crystal decline, thereby leakage current density is declined, ferroelectric properties improves, when added external electric field is 4kV/cm, (K
0.5na
0.5)
0.95li
0.05(Nb
0.995mn
0.005) O
3leakage current be about 9 * 10
-8a/cm
2, and unadulterated (K
0.5na
0.5)
0.95li
0.05nbO
3leakage current be about 2.1 * 10
-6a/cm
2, mix the leakage current density of monocrystalline after Mn and reduce two orders of magnitude.
The novel potassium-sodium niobate lithium radical leadless piezoelectric monocrystal of the present invention is perovskite structure, and doped with transition metal, its chemical formula is (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3wherein M represents transition metal, 0<x<1,0<y<1,0<z<1, preferably, 0.4≤x≤0.6,0<y≤0.4,0<z≤0.2, x=0.5 more preferably, 0.05≤y≤0.1,0.005≤z≤0.015.M for example can be Fe, Cu or Mn.
The present invention utilizes transition metal atoms M to replace uhligite ABO
3nb in structure on B position, changes the shape of oxygen octahedra and the internal stress of crystals, thereby makes ferroelectric domain size decreases; And the valent variation of M declines the density in oxygen room in crystal, thereby leakage current density is declined, and doping improves ferroelectric properties.
The present invention is also higher for the growth technique temperature of potassium-sodium niobate lithium radical leadless piezoelectric monocrystal in prior art, Na, K element evaporation are serious, monocrystalline composition departs from, affect the technical problem of perfection of crystal, object is to provide a kind of method of the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal of the present invention of growing.The chemical formula of described potassium-sodium niobate lithium radical leadless piezoelectric monocrystal is (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3, wherein M represents transition metal, for example, can be Fe, Cu or Mn, 0<x<1,0<y<1,0<z<1, preferably, 0.4≤x≤0.6,0<y≤0.4,0<z≤0.2, more preferably x=0.5,0.05≤y≤0.1,0.005≤z≤0.015.
The method of growth potassium-sodium niobate lithium radical leadless piezoelectric monocrystal of the present invention is falling crucible method, specifically comprises the steps:
Step 1, according to (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3stoichiometric ratio takes K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5with transition metal oxide raw material powder;
Step 2, takes and accounts for raw material powder and amount to 0～90%, preferably 0～60%, more preferably 5%～20%, 10%～20% fusing assistant most preferably, and mix with raw material powder crystal growth with expecting;
Step 3, will rise expects puts into crucible, then crucible is packed into and drawn in lower pipe, is then placed in crystal growing furnace;
Step 4, crucible is at 500～1100 ℃ of insulation 3～20h, then temperature to 1000～1300 ℃ raise, insulation 2～20h has made to expect and has all melted, then crucible declines with the speed of 0.1～1.2mm/h, during through temperature gradient field between high-temperature zone in crystal growing furnace and cold zone, melt gradually crystalline growth becomes crystal;
Step 5, grows complete, and in stove, temperature obtains potassium-sodium niobate lithium radical leadless piezoelectric monocrystal with the speed cool to room temperature of 10～200 ℃/h.
The present invention utilizes Bridgman-Stockbarge method for growing potassium-sodium niobate lithium radical leadless piezoelectric monocrystal, in growth technique, raw material is sealed in crucible, has reduced K in raw material, Na volatilization degree, makes composition farthest reduce and depart from, and improves perfection of crystal.
Although falling crucible method for additive method by sealed crucible to reduce to greatest extent the volatilization of K, Na, this volatilization still more or less inevitably occurs.Therefore in raw material of the present invention, add fusing assistant, made up on the one hand the inevitably volatilization of K, Na in falling crucible method, accomplished that monocrystalline composition does not really depart from, improved the integrity of monocrystalline; On the other hand, interpolation due to fusing assistant, greatly reduced the temperature of falling crucible method technique, the reduction significantly of this temperature has not only reduced the requirement to equipment, saving time, economize can, but also due to the reduction of technological temperature, further alleviate the volatilization of crystal composition and depart from, further promoted the formation of advantageous results.
Be preferably, in step 4, crucible is at 800～1000 ℃ of insulation 8～12h, then temperature to 1150～1250 ℃ preferably 1200 ℃ raise, the preferred 10h of insulation 5～15h has made to expect and has all melted, then crucible declines with the speed of the preferred 0.4mm/h of 0.3～0.6mm/h, and during through temperature gradient field between high-temperature zone in crystal growing furnace and cold zone, melt gradually crystalline growth becomes crystal.
Step 3, described crucible is platinum crucible, described in to draw lower pipe be alumina ceramic tube.
Wherein, described fusing assistant comprises 20%～100% sodium carbonate or salt of wormwood, and 0%～80% sodium halide or potassium halide, and described per-cent is mol ratio.Described fusing assistant is K
2cO
3; Or mol ratio is 50%～70%:30%～50%, be preferably KCl and the K of 63.4%:36.6%
2cO
3mixture; Or mol ratio is 25%～40%:35%～45%:20%～30%, be preferably KCl, the K of 35.47%:39.02%:25.51%
2cO
3mixture with KF.
Bridgman-Stockbarge method for growing potassium-sodium niobate lithium radical leadless piezoelectric monocrystal of the present invention also further comprises step 5, with solvent cleaning potassium niobate sodium base leadless piezoelectric monocrystal.Described solvent can be deionized water, alcohol or inorganic weak acid.
Step 1 of the present invention takes the K after 300～350 ℃ of dry 3h
2cO
3, Na
2cO
3, Li
2cO
3; And K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5be greater than 99.99% with the purity of transition metal oxide raw material powder.
Positive progressive effect of the present invention is: the present invention adopts the falling crucible method of interpolation fusing assistant to realize the growth of transient metal doped potassium-sodium niobate lithium radical leadless piezoquartz first.The piezoquartz of gained is pure perovskite structure, and without other dephasigns, leakage current is less, and has good piezoelectric property and ferroelectric properties.Another technique of the present invention is simple, has advantages of that sintering temperature is lower, and can obtain large-sized piezoelectric monocrystal.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal powder of embodiment 1;
Fig. 2 is the X-ray diffractogram of the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal powder of embodiment 2;
Fig. 3 is the X-ray diffractogram of the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal powder of embodiment 3.
Embodiment
Embodiment 1～12 (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3piezoelectric monocrystal (M=Mn)
One. by K
2cO
3, Na
2cO
3, Li
2cO
3at about 300 ℃, dry 3h, after according to chemical formula (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3take K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5and MnO
2raw material powder.
Two. take fusing assistant, and fully mix to such an extent that crystal growth is expected with rising.
Three. will rise expects packs in platinum crucible, crucible is contained in to alumina-ceramic and draws in lower pipe, is then placed in crucible lowering method crystal growth stove.
Four. crucible is at T1 temperature insulation t1 hour, and rising temperature, to T2 temperature, is incubated t2 hour, made to expect and be all fused into melt, then crucible declines with v1 speed, and during through temperature gradient field between high-temperature zone in growth furnace and cold zone, melt gradually crystalline growth becomes crystal.
Five. crystal growth is complete, and in stove, temperature naturally cools to room temperature with v2 speed, and crystal is come out of the stove.
Six. carefully peel off crucible, take out crystal, with by obtaining potassium-sodium niobate lithium radical leadless piezoelectric monocrystal after deionized water wash.
Design parameter is as shown in table 1.
Table 1 (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3growthing process parameter
By the potassium-sodium niobate lithium radical leadless piezoelectric monocrystal grind into powder of embodiment 1,2,3 gained, utilize its structure of X-ray diffraction analysis, respectively as shown in Figure 1, 2, 3, the structure that can find out potassium-sodium niobate lithium radical leadless piezoelectric monocrystal from Fig. 1～3 is pure perovskite structure, without other dephasigns, generates.
Embodiment 13 (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3piezoelectric monocrystal (M=Fe)
One. by K
2cO
3, Na
2cO
3, Li
2cO
3at about 300 ℃, dry 3h, after according to chemical formula (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3take K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5and Fe
2o
3raw material powder, x=0.15 wherein, y=0.20, z=0.005.
Two. take fusing assistant, and fully mix to such an extent that crystal growth is expected with rising.Fusing assistant is 10% K
2cO
3and KCl, KCl:K
2cO
3mol ratio be 63.4%:36.6%.After fully mixing, formed and expected.
Three. will rise expects packs in platinum crucible, crucible is contained in to alumina-ceramic and draws in lower pipe, is then placed in crucible lowering method crystal growth stove.
Four. crucible was 1000 ℃ of insulations 10 hours, and rising temperature to 1300 ℃, is incubated 10 hours, made to expect and be all fused into melt, then crucible declines with the speed of 0.4mm/h, and during through temperature gradient field between high-temperature zone in growth furnace and cold zone, melt gradually crystalline growth becomes crystal.
Five. crystal growth is complete, and in stove, temperature naturally cools to room temperature with the speed of 100 ℃/h, and crystal is come out of the stove.
Six. carefully peel off crucible, take out crystal, with by obtaining potassium-sodium niobate lithium radical leadless piezoelectric monocrystal after deionized water wash.
Embodiment 14 (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3piezoelectric monocrystal (M=Cu)
One. by K
2cO
3, Na
2cO
3, Li
2cO
3at about 300 ℃, dry 3h, after according to chemical formula (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3take K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5with CuO raw material powder, x=0.85 wherein, y=0.10, z=0.005.
Two. take fusing assistant, and fully mix to such an extent that crystal growth is expected with rising.Fusing assistant is 10% K
2cO
3and KCl, KCl:K
2cO
3mol ratio be 63.4%:36.6%.After fully mixing, formed and expected.
Three. will rise expects packs in platinum crucible, crucible is contained in to alumina-ceramic and draws in lower pipe, is then placed in crucible lowering method crystal growth stove.
Four. crucible was 800 ℃ of insulations 10 hours, and rising temperature to 1300 ℃, is incubated 10 hours, made to expect and be all fused into melt, then crucible declines with the speed of 0.4mm/h, and during through temperature gradient field between high-temperature zone in growth furnace and cold zone, melt gradually crystalline growth becomes crystal.
Five. crystal growth is complete, and in stove, temperature naturally cools to room temperature with the speed of 100 ℃/h, and crystal is come out of the stove.
Six. carefully peel off crucible, take out crystal, with by obtaining potassium-sodium niobate lithium radical leadless piezoelectric monocrystal after deionized water wash.
Effect embodiment
By (the K of embodiment 1 gained
0.5na
0.5)
0.95li
0.05(Nb
0.995mn
0.005) O
3monocrystalline and the not (K of containing transition metal atom
0.5na
0.5)
0.95li
0.05nbO
3it is under 4kV/cm, to carry out leakage current test adding external electric field that monocrystalline adopts respectively ordinary method.
Experimental result shows, when added external electric field is 4kV/cm, and (K of the present invention
0.5na
0.5)
0.95li
0.05(Nb
0.995mn
0.005) O
3the leakage current of monocrystalline is about 9 * 10
-8a/cm
2, and (the K of unadulterated transition metal atoms
0.5na
0.5)
0.95li
0.05nbO
3the leakage current of monocrystalline is about 2.1 * 10
-6a/cm
2, mix the leakage current density of monocrystalline of the present invention after Mn atom and reduced two orders of magnitude, thereby greatly improve its piezoelectric property and ferroelectric properties.
Claims (9)
1. a potassium-sodium niobate lithium radical leadless piezoelectric monocrystal, is characterized in that described potassium-sodium niobate lithium radical leadless piezoelectric monocrystal is perovskite structure, and doped with transition metal, its chemical formula is (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3wherein M represents transition metal, 0<x<1,0<y<1,0<z<1, preferably, 0.4≤x≤0.6,0<y≤0.4,0<z≤0.2, x=0.5 more preferably, 0.05≤y≤0.1,0.005≤z≤0.015.
2. potassium-sodium niobate lithium radical leadless piezoelectric monocrystal as claimed in claim 1, is characterized in that, M is Fe, Cu or Mn.
3. a method for growth potassium-sodium niobate lithium radical leadless piezoelectric monocrystal claimed in claim 1, is characterized in that, the chemical formula of described potassium-sodium niobate lithium radical leadless piezoelectric monocrystal is (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3wherein M represents transition metal, 0<x<1,0<y<1,0<z<1, preferably, 0.4≤x≤0.6,0<y≤0.4,0<z≤0.2, x=0.5 more preferably, 0.05≤y≤0.1,0.005≤z≤0.015; Described method specifically comprises the steps:
Step 1, according to (K
xna
1-x)
1-yli
y(Nb
1-zm
z) O
3stoichiometric ratio takes K
2cO
3, Na
2cO
3, Li
2cO
3, Nb
2o
5with transition metal oxide raw material powder;
Step 2, takes and accounts for raw material powder and amount to 0～90%, preferably 0～60%, more preferably 5%～20%, 10%～20% fusing assistant most preferably, and mix with raw material powder crystal growth with expecting;
Step 3, will rise expects puts into crucible, then crucible is packed into and drawn in lower pipe, is then placed in crystal growing furnace;
Step 4, crucible is at 500～1100 ℃ of insulation 3～20h, then temperature to 1000～1300 ℃ raise, insulation 2～20h has made to expect and has all melted, then crucible declines with the speed of 0.1～1.2mm/h, during through temperature gradient field between high-temperature zone in crystal growing furnace and cold zone, melt gradually crystalline growth becomes crystal;
Step 5, grows complete, and in stove, temperature obtains potassium-sodium niobate lithium radical leadless piezoelectric monocrystal with the speed cool to room temperature of 10～200 ℃/h.
4. method as claimed in claim 3, it is characterized in that, in step 4, crucible is at 800～1000 ℃ of insulation 8～12h, then raise temperature to 1150～1250 ℃ preferably 1200 ℃, the preferred 10h of insulation 5～15h all fusings that made to expect, then crucible is with the speed decline of the preferred 0.4mm/h of 0.3～0.6mm/h, during through temperature gradient field between high-temperature zone in crystal growing furnace and cold zone, melt gradually crystalline growth becomes crystal.
5. method as claimed in claim 3, is characterized in that, step 3, described crucible is platinum crucible, described in to draw lower pipe be alumina ceramic tube.
6. method as claimed in claim 3, is characterized in that in step 2, and described fusing assistant comprises 20%～100% sodium carbonate or salt of wormwood, and 0%～80% sodium halide or potassium halide, and described per-cent is mol ratio.
7. method as claimed in claim 3, is characterized in that in step 2, and described fusing assistant is K
2cO
3; Or mol ratio is 50%～70%:30%～50%, be preferably KCl and the K of 63.4%:36.6%
2cO
3mixture; Or mol ratio is 25%～40%:35%～45%:20%～30%, be preferably KCl, the K of 35.47%:39.02%:25.51%
2cO
3mixture with KF.
8. method as claimed in claim 3, is characterized in that also further comprising step 5, with solvent cleaning potassium niobate sodium base leadless piezoelectric monocrystal.
9. method as claimed in claim 3, is characterized in that, described solvent is deionized water, alcohol or inorganic weak acid.
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| CN107675257A (en) * | 2017-11-13 | 2018-02-09 | 桂林电子科技大学 | A kind of low loss ferro-electricity monocrystalline piezoelectric material and preparation method thereof |
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| CN105002560A (en) * | 2015-08-27 | 2015-10-28 | 中国电子科技集团公司第二十六研究所 | Preparation method with component controllability and directional crystallization for near-stoichiometric lithium niobate (N-SLN) crystal |
| CN105002560B (en) * | 2015-08-27 | 2017-08-25 | 中国电子科技集团公司第二十六研究所 | The controllable crystallographic orientation preparation method of component of lithium niobate crysal near stoichiometric ratio |
| CN107268084A (en) * | 2016-04-08 | 2017-10-20 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
| CN107268084B (en) * | 2016-04-08 | 2019-10-15 | 中国科学院上海硅酸盐研究所 | Potassium-sodium niobate-zirconic acid bismuth sodium leadless piezoelectric monocrystalline and its growing method |
| CN106087058A (en) * | 2016-06-22 | 2016-11-09 | 桂林电子科技大学 | A kind of K0.5na0.5nbO3base ferroelectric piezoelectric single crystal and preparation method thereof |
| CN107675257A (en) * | 2017-11-13 | 2018-02-09 | 桂林电子科技大学 | A kind of low loss ferro-electricity monocrystalline piezoelectric material and preparation method thereof |
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