CN109234809A - Gallium adulterates cacoclasite crystal and preparation method and application - Google Patents
Gallium adulterates cacoclasite crystal and preparation method and application Download PDFInfo
- Publication number
- CN109234809A CN109234809A CN201811324131.XA CN201811324131A CN109234809A CN 109234809 A CN109234809 A CN 109234809A CN 201811324131 A CN201811324131 A CN 201811324131A CN 109234809 A CN109234809 A CN 109234809A
- Authority
- CN
- China
- Prior art keywords
- crystal
- piezo
- cacoclasite
- gallium
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/34—Silicates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to gallium doping cacoclasite crystal and preparation method and application, which is Ca2Al(2‑x)GaxSiO7, 0 < x < 2.The present invention provides a kind of method that fraction replaces, and reduces aluminate melt viscosity, aluminate crystal quality and rate of crystalline growth is improved, by fraction Al in aluminate crystal raw material2O3Use Ga2O3Replace, grows Ca2Al2‑xGaxSiO7Crystal, the gallium doping cacoclasite piezo-electric crystal of offer has both excellent piezoelectric property, resistivity height, lower cost, is easy to crystallize and be easy to the advantages that growing large-size monocrystalline, it can be used for making surface acoustic wave, acoustic bulk wave piezoelectric device and high-temperature piezoelectric element etc., there is application prospect.
Description
Technical field
The present invention relates to a kind of new type high temperature piezo-electric crystal and preparation method and applications, in particular to mix gallium cacoclasite
Crystal and the preparation method and application thereof belongs to crystal and device arts.
Background technique
By the high temperature pressure of piezoelectric material development, gas, flow and vibrating sensor etc. in national economy, military and national defense
It is widely used in.Pyrostat is the key components in high temp sensitive system.Applied in hot environment
The stability of sensor be it is vital, stability is mainly determined by piezoelectric material stability.It grinds both at home and abroad at present
The piezoelectric crystal material studied carefully and applied mainly has α-SiO2、GaPO4、LiTaO3、La3Ga5SiO14(LGS) and ReCa4O(BO3)4
Deng.
Quartz is that a kind of research is earliest and most important piezoelectric crystal material, and there are zero-temperature coefficient cut types for quartz crystal, utilize
The frequency stability of the device of quartz production is good, is widely used for the core original part of production clock and watch, but the crystal is generated at 350 DEG C
Twin crystal, 573 DEG C nearby occur α-βphasetransition, seriously affect the overall performance of crystal, drop the use temperature range of crystal significantly
It is low；The piezo-electric crystal that lithium columbate crystal is functional and usage amount is big, the crystal piezoelectric modulus is big, acoustic propagation velocity is high, machine
Electric coupling coefficient is big, machining property is good, is to prepare excellent PZT (piezoelectric transducer), SAW device and micro- sonic delay line
Material, but the resistivity of the crystal is at 600 DEG C only 106Ω cm causes use temperature upper limit to be no more than 600 DEG C.Piezoelectricity
Ceramics are also a kind of widely used piezoelectric material, and the discovery of lead zirconate titanate PZT is mileage new in piezoelectric ceramics development history
Upright stone tablet, based on PZT, by addition Cr, Mn it is element modified or part replace PZT in Pb, the PZT type pressure of different purposes is made
Electroceramics, ternary, four-component-system piezoelectric ceramics come into being, but leaded piezoelectric material has the risk of pollution environment, constrains this
The application of class material；GaPO4Crystal has many advantages, such as high resistivity, low-loss, at 930 DEG C nearby there are phase transformation, makes it super
It is restricted in high temperature application, and uses the more difficult acquisition large-size high-quality monocrystalline of hydro-thermal method；Nineteen eighty-two, former Soviet Union scientist
The dielectric and piezoelectric properties of the barium silicate that begins one's study (LGS) piezo-electric crystal, and LGS monocrystalline is reported with zero frequency temperature system
Number cut type, compared with quartz crystal, LGS crystal can use Czochralski grown, and transformation temperature height, electromechanical coupling factor and piezoelectricity system
Number is big, but contains gallium element in LGS crystal, makes the increased costs of LGS crystal, limits its scope of application, applies more at present
In fields such as the aerospaces for disregarding cost, the resistivity of LGS crystal at high temperature, which is not still able to satisfy, in practical applications is needed
It wants, researcher is also dedicated to improve its high-temperature resistivity, such as the influence etc. of research growth atmosphere, Doped ions to resistivity.
The above piezoelectric material there are phase transformation resistivity is low or piezoelectric modulus is low or dielectric loss is big or
Crystal symmetry is low etc., it is difficult to meet high-temperature piezoelectric application increasing need.Therefore, it seeks with larger piezoelectric sensitivity
The piezo-electric crystal of property, high thermal stability, lesser noise signal and symmetry with higher, becomes current piezo technology
Research hotspot has a very important significance.
Ca2Al2SiO7(CAS) crystal is a kind of good selection, but the piezo-electric crystal, piezoelectric property still need into
One step improves.Chinese patent document CN106480502A discloses a kind of melilite structure high-temperature piezoelectric crystal and its preparation side
Method, the structural formula of the crystal are as follows: Ca2Al2SiO7(CAS), CaCO is mainly used3、Al2O3、SiO2It is counted for raw material according to chemistry
Amount ratio weighs raw material and is uniformly mixed briquetting, sintering obtains polycrystal material, under the nitrogen atmosphere of 0.5~2vol% oxygen, uses
Czochralski grown high-temperature piezoelectric crystal.Manabu Hagiwara seminar of Japan in 2013 obtains CAS crystal with Czochralski grown
And report the part electricity of CAS crystal, elastic constant, ε11=10.6, s11=9.06pm2/ N is surveyed using two kinds of cut type samples
Obtain the piezoelectric constant d of CAS crystal14=6.04pC/N, d36=4.04pC/N, k31=16.5%.CAS crystal is reported simultaneously to exist
Excellent properties in terms of high-temperature piezoelectric, piezoelectric modulus change rate is 100ppm/ DEG C in 20~700 DEG C, and temperature with higher is steady
It is qualitative.The crystal a- and c- axis resistivity at 800 DEG C are up to 108Ω·cm.Sample is given to apply pressure at 700 DEG C, it can be with
It sensitively detects electric signal and no current leakage, show the excellent high-temperature piezoelectric performance of CAS crystal and is passed in high temperature
Feel the potential using value of technical field.Although Hagiwara seminar has reported the growth of larger size CAS crystal, the crystalline substance
Body crystallinity is poor, there is obvious bubble and wrappage in crystal, limits it and further applies.
Therefore, research with room temperature to fusing point without phase-change, have that piezoelectric property is good, resistivity is high, lower cost, easy
In the piezo-electric crystal of crystallization and growing large-size, become urgent problem to be solved.For this purpose, proposing the present invention.
Summary of the invention
The present invention is directed to the deficiency of existing high-temperature piezoelectric crystalline material, provide a kind of room temperature to fusing point without phase-change, there is pressure
Electrical property is good, resistivity is high, lower cost, is easy to crystallization and new type high temperature piezo-electric crystal and its preparation of growing large-size
Method.The present invention also provides the measuring method of the crystal and applications.
Technical scheme is as follows:
A kind of gallium doping cacoclasite piezo-electric crystal, chemical general formula Ca2Al(2-x)GaxSiO7, wherein 0 < x < 2；Institute
Stating crystal has and cacoclasite Ca2Al2SiO7The identical crystal structure of crystal belongs to space group- 42m point group.
According to the present invention, the gallium adulterates cacoclasite piezo-electric crystal, wherein Ca2+A are occupied, half Al3+It occupies
B, half Al3+And Si4+C are occupied at random jointly, Ga3+It is occupied at B, C.By adjusting x value 0.05~1.90
In range, the CAGS crystal of different Al/Ga component ratios can be obtained；Can requirement for related application to crystal property come
Determine specific x value.
, according to the invention it is preferred to, the gallium doping cacoclasite piezo-electric crystal is congruent melting compound, fusing point
It is preceding without phase-change.
, according to the invention it is preferred to, the gallium adulterates cacoclasite piezo-electric crystal, chemical general formula Ca2Al(2-x)
GaxSiO7, 0.17≤x≤0.65；It is further preferred that the gallium adulterates cacoclasite piezo-electric crystal, chemical general formula is
Ca2Al1.83Ga0.17SiO7、Ca2Al1.7Ga0.3SiO7、Ca2Al1.4Ga0.6SiO7。
According to the present invention, when x value is 0.17, the cell parameter of the gallium doping cacoclasite piezo-electric crystal is The piezoelectric constant d of the gallium doping cacoclasite piezo-electric crystal14For 10.52pC/N, d36For
3.24pC/N；At 600 DEG C, 700 DEG C, 800 DEG C, c- axis high-temperature resistivity ρ is respectively 2.3 × 109Ω·cm、3.7×108Ω·
cm、8.1×107Ω·cm。
Compare CGS piezo-electric crystal, and not only piezoelectric property increases CAGS piezo-electric crystal of the invention, but also is produced into
This significant decrease；The CAS piezo-electric crystal poor for crystallinity, CAGS piezo-electric crystal, which embodies, is easy to crystallization and growing large-size
Advantage, piezoelectric constant d14It is also obviously improved.Moreover, CAGS piezo-electric crystal resistivity of the invention be higher than it is identical at this temperature
LGS, CGS crystal, and lg ρ and 1/T is in a linear relationship, meets Arrhenius empirical equation.
According to the present invention, the preparation method of gallium doping cacoclasite piezo-electric crystal, using pulling growth legal system
It is standby, include the following steps:
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs CaCO respectively3、Al2O3、
Ga2O3And SiO2Each powder, briquetting after CAS and CGS raw material are mixed respectively, is then sintered at 1400 DEG C and 1200 DEG C respectively,
Obtain CAS and CGS polycrystal material；
(b) polycrystal material obtained in step (a) is fitted into crucible in proportion, was warming up to 1500~1700 DEG C through 10 hours
It is completely melt polycrystal material, then by 10~30 DEG C of melt overheat, constant temperature stablizes melt state, is then cooled to temperature of sowing
Degree；Use CAS crystal as seed crystal, seed crystal is dropped into bath surface and receives diameter, is carried out when seed crystal diameter is received carefully to 2-3mm
Shouldering, then begins to isodiametric growth, and control revolving speed is 8-20rpm, pull rate 0.5-5mmh-1；
(c) crystal is detached from melt after growing, crystal is cooled to room temperature.
According to the present invention, as a preferred embodiment, the heating method in step (b) is added using medium frequency induction power supply
Heat；
The crucible is Iridium Crucible；
The diameter of the isodiametric growth is 15-40mm；
The pull rate is 1-1.5mmh-1；
The shouldering, isodiametric growth are controlled by the upper automatic automatic diamenter control system of weighing, crystal growth to required ruler
After very little, automatic automatic diamenter control system is exited.The automatic automatic diamenter control system is this field conventional system.
According to the present invention, as a preferred embodiment, the rate of temperature fall in step (c) is 20-30 DEG C/h.
According to the present invention, gallium doping cacoclasite crystal is as production surface acoustic wave, acoustic bulk wave piezoelectric device
And the application of high-temperature piezoelectric element.
What the present invention did not elaborated, press state of the art.
It the principle of the present invention and has the beneficial effect that:
Compared with prior art, the present invention provides a kind of fraction method of substitution, reduces aluminate melt viscosity, improves aluminic acid
Salt crystal quality and rate of crystalline growth；The present invention is by fraction Al in aluminate crystal raw material2O3Use Ga2O3Replace, growth
Ca2Al2-xGaxSiO7Crystal, the gallium doping cacoclasite piezo-electric crystal provided have both excellent piezoelectric property, resistivity it is high,
Lower cost is easy to crystallize and be easy to the advantages that growing large-size monocrystalline, can be used for making surface acoustic wave, acoustic bulk wave piezoelectricity device
Part and high-temperature piezoelectric element etc. have application prospect.
Detailed description of the invention
Fig. 1 is the photo of 1 gained CAGS crystal of embodiment；
Fig. 2 is that 1 gained CAGS of embodiment and CAS crystal compare photo, irradiates crystal using the green laser pen of 5mW, swashs
Light successively passes through CAGS and CAS crystal；
Fig. 3 is the rocking curve of 1 gained CAGS of embodiment Yu CAS crystal prototype (001) face；
Fig. 4 is the resistivity of 1 gained CAGS crystal of embodiment and the relation curve comparison diagram of temperature.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Embodiment 1
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 9:1, is containing 0.36%
Under the nitrogen atmosphere of oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material,
Stablize melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed crystal, by seed
Crystalline substance drops to bath surface, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering to required diameter
In the process, revolving speed uniformly drops to 15rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.83Ga0.17SiO7Crystal.
Cell parameter, piezoelectric constant and the high-temperature resistivity data ginseng of gained crystal are shown in Table 1.
The cell parameter and piezoelectric constant of each crystal of table 1
Seen from table 1: present invention gained crystal has crystal structure identical with cacoclasite crystal.
Fig. 1 is the photo of gained CAGS crystal, as seen from Figure 1: habit is regular, transparent, bubble-free, without polycrystalline.
Fig. 2 is that CAGS and CAS crystal compare photo, irradiates crystal using the green laser pen of 5mW, laser successively passes through
CAGS and CAS crystal, as seen from Figure 2: there is obvious optical path in CAS crystal, shows there is serious scattering phenomenon, has compared with multiple scattering
Grain, illustrates that crystal quality is poor；CAGS crystals do not find any scattering particles, illustrate that crystal quality of the invention has obviously
It improves.
Fig. 3 is the rocking curve of gained CAGS and CAS crystal prototype (001) face, as seen from Figure 3: gained CAGS crystal
Crystalline quality is good, and is better than CAS crystal.
Fig. 4 is the resistivity of CAGS, CAS, CGS crystal and the relation curve of temperature, and as seen from Figure 4: CAGS and CAS is brilliant
Body all has higher high-temperature resistivity.
Embodiment 2
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 9:1, is containing 0.36%
Under the nitrogen atmosphere of oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material,
Stablize melt state, is then cooled to temperature of sowing, uses<001>direction CAS crystal as seed crystal, by seed
Crystalline substance drops to bath surface, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering to required diameter
In the process, revolving speed uniformly drops to 15rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.83Ga0.17SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Embodiment 3
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 9:1, is containing 1% oxygen
Nitrogen atmosphere under, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material, constant temperature
Stablize melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed crystal, it will be under seed crystal
Bath surface is dropped to, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering to required diameter process
In, revolving speed uniformly drops to 15rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.83Ga0.17SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Embodiment 4
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 9:1, is containing 0.36%
Under the nitrogen atmosphere of oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material,
Stablize melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed crystal, by seed
Crystalline substance drops to bath surface, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering to required diameter
In the process, revolving speed uniformly drops to 15rpm, with 3mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.83Ga0.17SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Embodiment 5
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 9:1, is containing 0.36%
Under the nitrogen atmosphere of oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material,
Stablize melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed crystal, by seed
Crystalline substance drops to bath surface, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 30rpm, shouldering to required diameter
In the process, revolving speed uniformly drops to 25rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.83Ga0.17SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Embodiment 6
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 1:1, is containing 0.36%
Under the nitrogen atmosphere of oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so melts polycrystal material,
Stablize melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed crystal, by seed
Crystalline substance drops to bath surface, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering to required diameter
In the process, revolving speed uniformly drops to 15rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm, stop lifting；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.02Ga0.98SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Embodiment 7
Gallium adulterates the preparation method of cacoclasite piezo-electric crystal, is prepared, is included the following steps: using pulling growth method
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs purity respectively
99.99% CaCO3、Al2O3、Ga2O3And SiO2Each powder, wherein Ga2O3Excessive 2wt.% mixes CAS and CGS raw material respectively
Then briquetting after even is sintered 50 hours at 1400 DEG C and 1200 DEG C respectively, obtains CAS and CGS polycrystal material；
(b) CAS the and CGS polycrystal material obtained in (a) is fitted into crucible according to the molar ratio of 0.95:0.05, is being contained
Under the nitrogen atmosphere of 0.36% oxygen, by the way of mid-frequency induction heating, being warming up within 10 hours 1600 DEG C or so makes polycrystalline
Material fusing, stablizes melt state, is then cooled to temperature of sowing, uses<100>direction CAS crystal as seed
Seed crystal is dropped to bath surface by crystalline substance, starts to carry out crystal growth, in growth course, with the revolving speed seeding of 20rpm, shouldering is arrived
During required diameter, revolving speed uniformly drops to 15rpm, with 1.5mmh-1Pull rate, isodiametric growth to 50mm stops mentioning
It draws；
(c) by crystal pull to being detached from melt, then by the rate of temperature fall of 30 DEG C/h it is down to room temperature, finally obtained
Ca2Al1.92Ga0.08SiO7Crystal.
Gained crystal has crystal structure described in embodiment 1 and crystal property and piezoelectric property.
Be it is necessary to described herein finally: above embodiments are served only for making technical solution of the present invention further detailed
Explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention
The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of gallium adulterates cacoclasite piezo-electric crystal, which is characterized in that the piezo-electric crystal chemical general formula is Ca2Al(2-x)
GaxSiO7, wherein 0 < x < 2；Belong to space group- 42m point group.
2. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that Ca in the piezo-electric crystal2+
A are occupied, half Al3+B are occupied, half Al3+And Si4+C are occupied at random jointly, Ga3+It is occupied at B, C.
3. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that the piezo-electric crystal is consistent
Melting compound, before fusing point without phase-change.
4. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that 0.17≤x≤0.65.
5. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that the gallium adulterates calcium aluminium
Melilite piezo-electric crystal, chemical general formula Ca2Al1.83Ga0.17SiO7、Ca2Al1.7Ga0.3SiO7Or Ca2Al1.4Ga0.6SiO7。
6. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that when x value is 0.17,
The cell parameter of gallium doping cacoclasite piezo-electric crystal is
7. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that when x value is 0.17,
The piezoelectric constant d of the gallium doping cacoclasite piezo-electric crystal14For 10.52pC/N, d36For 3.24pC/N.
8. gallium according to claim 1 adulterates cacoclasite piezo-electric crystal, which is characterized in that when x value is 0.17,
At 600 DEG C, 700 DEG C, 800 DEG C, c- axis high-temperature resistivity ρ is respectively 2.3 × 109Ω·cm、3.7×108Ω·cm、8.1×
107Ω·cm。
9. the preparation method of the described in any item gallium doping cacoclasite piezo-electric crystals of claim 1-8, using pulling growth
Method preparation, includes the following steps:
(a) according to Ca2Al2SiO7(CAS) and Ca2Ga2SiO7(CGS) stoichiometric ratio weighs CaCO respectively3、Al2O3、Ga2O3
And SiO2Each powder, briquetting after CAS and CGS raw material are mixed respectively, is then sintered at 1400 DEG C and 1200 DEG C respectively, obtains
CAS and CGS polycrystal material；
(b) polycrystal material obtained in step (a) is fitted into crucible in proportion, be warming up within 10 hours 1500~1700 DEG C make it is more
Crystalline substance material is completely melt that, then by 10~30 DEG C of melt overheat, constant temperature stablizes melt state, is then cooled to temperature of sowing；Make
It uses CAS crystal as seed crystal, seed crystal is dropped into bath surface and receives diameter, carry out shouldering when seed crystal diameter is received carefully to 2-3mm,
Isodiametric growth is then begun to, control revolving speed is 8-20rpm, pull rate 0.5-5mmh-1；
(c) crystal is detached from melt after growing, crystal is cooled to room temperature.
10. the described in any item gallium doping cacoclasite crystal of claim 1-8 are as production surface acoustic wave, acoustic bulk wave piezoelectricity
The application of device and high-temperature piezoelectric element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811324131.XA CN109234809A (en) | 2018-11-08 | 2018-11-08 | Gallium adulterates cacoclasite crystal and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811324131.XA CN109234809A (en) | 2018-11-08 | 2018-11-08 | Gallium adulterates cacoclasite crystal and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109234809A true CN109234809A (en) | 2019-01-18 |
Family
ID=65077539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811324131.XA Pending CN109234809A (en) | 2018-11-08 | 2018-11-08 | Gallium adulterates cacoclasite crystal and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109234809A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135754A (en) * | 2021-04-29 | 2021-07-20 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029417A (en) * | 2007-01-25 | 2007-09-05 | 中国科学院上海硅酸盐研究所 | Class-1 piezoelectric monocrystal |
| CN101792928A (en) * | 2010-03-30 | 2010-08-04 | 山东大学 | High temperature piezocrystal of melilite structure and preparation method and application thereof |
| CN103014865A (en) * | 2012-12-31 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Aluminum gallium strontium tantalum silicate piezoelectric crystal and preparation method thereof |
| CN104695017A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院上海硅酸盐研究所 | Aluminum-gallium-niobium-calcium silicate piezo-electric crystal and preparation method thereof |
| WO2015081706A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院上海硅酸盐研究所 | Calcium tantalum gallium aluminum silicate piezoelectric crystal and method of preparing same |
| CN106480502A (en) * | 2015-08-27 | 2017-03-08 | 中国科学院上海硅酸盐研究所 | A kind of melilite structure high-temperature piezoelectric crystal and preparation method thereof |
-
2018
- 2018-11-08 CN CN201811324131.XA patent/CN109234809A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029417A (en) * | 2007-01-25 | 2007-09-05 | 中国科学院上海硅酸盐研究所 | Class-1 piezoelectric monocrystal |
| CN101792928A (en) * | 2010-03-30 | 2010-08-04 | 山东大学 | High temperature piezocrystal of melilite structure and preparation method and application thereof |
| CN103014865A (en) * | 2012-12-31 | 2013-04-03 | 中国科学院上海硅酸盐研究所 | Aluminum gallium strontium tantalum silicate piezoelectric crystal and preparation method thereof |
| CN104695017A (en) * | 2013-12-05 | 2015-06-10 | 中国科学院上海硅酸盐研究所 | Aluminum-gallium-niobium-calcium silicate piezo-electric crystal and preparation method thereof |
| WO2015081706A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院上海硅酸盐研究所 | Calcium tantalum gallium aluminum silicate piezoelectric crystal and method of preparing same |
| CN106480502A (en) * | 2015-08-27 | 2017-03-08 | 中国科学院上海硅酸盐研究所 | A kind of melilite structure high-temperature piezoelectric crystal and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 尹延如: "影响提拉法⽣长氧化物晶体质量的若⼲关键因素研究", 《中国优秀博士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135754A (en) * | 2021-04-29 | 2021-07-20 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
| CN113135754B (en) * | 2021-04-29 | 2022-06-03 | 安徽工业大学 | Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106747412B (en) | A kind of Ti base LTCC microwave dielectric ceramic material and preparation method thereof | |
| CN103173861B (en) | For the doping type tantalic acid gallium lanthanum crystal and preparation method thereof of high temperature piezoelectric device | |
| Ge et al. | Growth, optical and electrical properties of pure and Mn-doped Na0. 5Bi0. 5TiO3 lead-free piezoelectric crystals | |
| CN103173850A (en) | Monocrystalline silicon producing process | |
| WO2015081706A1 (en) | Calcium tantalum gallium aluminum silicate piezoelectric crystal and method of preparing same | |
| CN101275279B (en) | Piezo crystal having four-lattice structure | |
| CN115747950A (en) | Preparation method of KTN single crystal | |
| CN109234809A (en) | Gallium adulterates cacoclasite crystal and preparation method and application | |
| CN110079861A (en) | Yttrium phosphate strontium crystal and the preparation method and application thereof | |
| CN104419984A (en) | Preparation method of perovskite-structure relaxor ferroelectric single crystal lead indium niobate-lead magnesium niobate-lead titanate | |
| CN103014865A (en) | Aluminum gallium strontium tantalum silicate piezoelectric crystal and preparation method thereof | |
| Xiong et al. | Growth and high temperature properties of Ca3Ta (Al0. 9Ga0. 1) 3Si2O14 crystals with ordered langasite structure | |
| CN106637405A (en) | An infinitely mixable and meltable ferroelectric solid solution monocrystalline lead scandium niobate-lead magnesium niobate-lead titanate and a preparing method thereof | |
| CN103993348B (en) | The growing method of rare earth orthoferrite monocrystalline and application | |
| CN110067024A (en) | Photoelectric functional crystal M3RE(PO4)3And preparation method thereof | |
| CN104005088B (en) | The Czochralski grown method of the magnesium aluminate spinel crystal of transition-metal ion doping | |
| CN104152999A (en) | Potassium-sodium niobate-based leadless piezoelectric monocrystalline and growth method therefor | |
| Wang et al. | An effective growth method to improve the homogeneity of relaxor ferroelectric single crystal Pb (In1/2Nb1/2) O3‐Pb (Mg1/3Nb2/3) O3‐PbTiO3 | |
| CN104962986A (en) | Preparation process of Bi4+nTi3FenO12+3n crystal of bismuth-layer structure | |
| CN115341284B (en) | High-concentration gradient neodymium doped gadolinium yttrium aluminum garnet laser crystal and preparation method thereof | |
| CN103603047B (en) | Chromium, manganese or cobalt doped callium-lanthanum silicate crystal and melt-method growth process thereof | |
| CN106480502A (en) | A kind of melilite structure high-temperature piezoelectric crystal and preparation method thereof | |
| CN104695017A (en) | Aluminum-gallium-niobium-calcium silicate piezo-electric crystal and preparation method thereof | |
| CN106192006A (en) | Compound lithium vanadate sodium optical crystal and its production and use | |
| CN101792928B (en) | High temperature piezocrystal of melilite structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190118 |