CN102443850B - Ferroelectric crystal lead magnesio-niobate-lead stannate-lead titanates and its production and use - Google Patents
Ferroelectric crystal lead magnesio-niobate-lead stannate-lead titanates and its production and use Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 229910019653 Mg1/3Nb2/3 Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- XMFOQHDPRMAJNU-UHFFFAOYSA-N Lead(II,IV) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 239000006184 cosolvent Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 230000003203 everyday Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims 1
- 230000005616 pyroelectricity Effects 0.000 claims 1
- 230000005621 ferroelectricity Effects 0.000 abstract description 17
- 238000000634 powder X-ray diffraction Methods 0.000 abstract description 4
- 210000003622 mature neutrocyte Anatomy 0.000 abstract description 3
- 229940071182 stannate Drugs 0.000 abstract description 3
- 125000005402 stannate group Chemical group 0.000 abstract description 3
- 239000002178 crystalline material Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 238000005259 measurement Methods 0.000 abstract 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 229910003781 PbTiO3 Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910002058 ternary alloy Inorganic materials 0.000 description 4
- 230000001808 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 240000004375 Petrea volubilis Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002999 depolarising Effects 0.000 description 2
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 2
- -1 niobium ytterbium lead Chemical compound 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N Barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N Lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium(0) Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention discloses a kind of ferroelectric crystal lead magnesio-niobate lead stannate lead titanates and its production and use.This crystalline material belongs to perovskite structure, there is MPB district, and its chemical formula is (1 x y) Pb (Mg1/3Nb2/3)O3‑xPbSnO3‑yPbTiO3, it is abbreviated as PMN PSn PT.Wherein, x=0～0.5, y=0.3～0.5.Described crystal uses o or top-seeded solution growth successful growth PMN PSn PT crystal.By X ray powder diffraction, ferroelectricity, dielectric and piezo-electric measurement, analyze its structure, ferroelectricity, dielectric and piezoelectricity.Preferred ingredient 0.52PMN 0.10PSn 0.38PT crystal is a kind of single domain crystal, and piezoelectricity and one-domain structure have preferable heat stability, are with a wide range of applications.
Description
Technical field
The present invention relates to a kind of novel ferroelectric crystal and preparation method thereof.Specifically, the present invention relates to tool
There is the ferroelectric single crystal material of quasi-homotype phase boundary (MPB) structure
(1-x-y)Pb(Mg1/3Nb2/3)O3-xPbSnO3-yPbTiO3, it is abbreviated as PMN-PSn-PT, and the preparation of crystal
Method, structure and electric property, belong to crystal technology and functional material field.
Background technology
Ferroelectricity/piezoelectric, owing to possessing the advantages such as excellent data-collection performance, fast response time, extensively should
For various functional devices, such as sensor, transducer, sonar, driver, wave filter, micro-speaker etc.,
Irreplaceable important function is played in national economy with national defense safety.The forties in last century finds metatitanic acid
Barium (BaTiO3) piezoelectric, it is found that lead zirconate titanate (Pb (Zr the fifties1-xTix)O3), it is called for short PZT.
PZT ceramic material is that one is widely used in transducer (transducer) and the biography of executor (actuator)
System piezoelectric, occupies leading position in piezoelectricity application always.There is quasi-homotype phase boundary in this material
(morphotropic phase boundary), is abbreviated as MPB.PZT shows piezoelectric property at MPB,
The piezoelectric coefficient d of PZT piezoelectric ceramics33～700pC/N, electromechanical coupling factor k33～70%.Along with to MPB's
Research, relaxation ferroelectric (relaxor ferroelectric) is found.In recent years, there is perovskite knot
Structure relaxation ferroelectric near MPB is widely used in executor and ultrasonic sensing owing to having high piezoelectricity
On device.Relaxation ferroelectric has complex perovskite structure, and general structure is: Pb (B1, B2)O3
(B1=Mg2+, Zn2+, Sc3+, In3+..., B2=Nb5+, Ta5+, W6+…).Relaxation ferroelectric and lead titanates (PbTiO3)
The solid solution formed shows the dielectric and piezoelectric properties more excellent than PZT material.Wherein than more typical just
It is PMN-PT: (1-x) Pb (Mg1/3Nb2/3)-xPbTiO3And lead zinc niobate-lead titanates (PMNT):
(1-x)Pb(Zn1/3Nb2/3)-xPbTiO3(PZNT) system.Such monocrystal material component shows near MPB
Go out high electromechanical coupling factor (k33＞ 90%), extra-high voltage coefficient (d33＞ 2000pC/N) and big strain
(＞ 1%) and become the core piezoelectric of ultrasonic transducer, sensor and driver of a new generation.Therefore,
One that prepared by relevant relaxor ferroelectric monocrystal, piezoelectric property and applied research have become as in ferroelectric material important
Problem.Owing to there is some intrinsic defect in PMNT monocrystalline, the most in recent years, to PMNT ferro-electricity single crystal
Study on the modification becomes the focus of ferroelectric crystal area research, including two parts: one is appropriate its of doping
Its ion changes the performance of PMNT monocrystalline, such as manganese, aluminum doping PMNT monocrystalline；Two is in binary PMNT
Add ternary component on the basis of ferro-electricity single crystal, reach to put forward high performance purpose, such as niobium ytterbium lead plumbate-niobium magnesium
Titanate-zirconate: (1-x-y) Pb (Yb1/2Nb1/2)O3-xPb(Mg1/3Nb2/3)O3-yPbTiO3(PYN-PMN-PT)、
Lead niobate lead indate-lead-PMN-PT: (1-x-y) Pb (In1/2Nb1/2)O3-xPb(Mg1/3Nb2/3)O3-yPbTiO3
(PIN-PMN-PT), lead magnesio-niobate-lead zirconate titanate: (1-x-y) Pb (Mg1/3Nb2/3)O3-xPbZrO3-yPbTiO3
(PMN-PZT) etc..On the basis of this kind of ternary system ferro-electricity single crystal relatively binary system PMNT, Curie temperature improves a lot,
And maintain piezoelectricity and the mechanical-electric coupling performance of binary ferro-electricity single crystal system.Therefore, ternary system ferro-electricity single crystal
Exploitation, preparation and performance study be the focus of present ferro-electricity single crystal research field.
Lead stannate (PbSnO3) it is a kind of monoclinic phase perovskite structure, itself and lead titanates (PbTiO3) formed
The character that solid solution performance is similar with PZT, and PMN-PZT shows the piezoelectric property of excellence, and have
High-curie temperature.Thus can expect that lead stannate can form solid solution with PMNT, and there is the piezoelectricity of excellence
Energy.In view of above consideration, in order to develop a kind of novel ferroelectric monocrystal material, we carry out to lead magnesio-niobate-
Lead stannate-lead titanates: (1-x-y) Pb (Mg1/3Nb2/3)O3-xPbSnO3-yPbTiO3(PMN-PSn-PT) solid solution
The research of system.Research ternary system PMN-PSn-PT MPB region and near the preparation side of monocrystalline of component
Method, structure and electric property, provide a kind of novel ferro-electricity single crystal for piezoelectricity field.
Summary of the invention
It is an object of the invention to develop a kind of novel ferro-electricity single crystal and study its preparation technology, for ferroelectricity list
Brilliant material increases a kind of new product.This crystalline material can be widely used in the field such as piezoelectricity, pyroelectric electric device.
A kind of novel ferroelectric single crystal material that the present invention provides, it is characterised in that: crystal is entitled: niobium magnesium
Lead plumbate-lead stannate-lead titanates.The chemical composition of crystal is:
(1-x-y)Pb(Mg1/3Nb2/3)O3-xPbSnO3-yPbTiO3, it is abbreviated as: PMN-PSn-PT, belongs to perovskite knot
Structure.Wherein, x=0～0.5, y=0.3～0.5.There is quasi-homotype phase boundary (MPB) district in this solid solution.
Described chemical composition, the chemical composition of the ferroelectric single crystal material of ternary system is preferably:
0.52PMN-0.10PSn-0.38PT。
The preparation method of ferroelectric crystal materials of the present invention, is that the high temperature being suitable for growing based on this system is molten
Liquid method, it is characterised in that comprise the following specific steps that:
A) by initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5Carry out by the chemical composition of crystal
Proportioning；
B) cosolvent uses PbO or Pb3O4And H3BO3Or B2O3Composite auxiliary solvent；
C) by crystal raw material and cosolvent mixed grinding in a reservoir；
D) powder of mix homogeneously is loaded in platinum crucible, and platinum crucible is placed in crystal growing furnace change
Material；
E) raw material is heated to more than supersolubility temperature (between 950-1200 DEG C) in crystal growing process, permanent
Temperature certain time, then lower the temperature with the speed of every day 1-20 DEG C.Growth terminates, and lowers the temperature annealing with 5-30 DEG C/h,
Rear taking-up crystal.
Raw material PbO or Pb used3O4、MgO、RiO2、SnO2、Nb2O5For oxide powder.
The platinum crucible used is column type crucible.
The crystal growing furnace used is stratie, and heating element heater is resistance wire or siliconit or silicon molybdenum
Rod.
The preparation method of ferroelectric crystal materials of the present invention, is top seed crystal based on energy growing large-size
Method, it is characterised in that comprise the following specific steps that:
A) by initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5Carry out by the chemical composition of crystal
Proportioning；
B) cosolvent uses PbO or Pb3O4And H3BO3Or B2O3Composite auxiliary solvent；
C) by crystal raw material and cosolvent mixed grinding in a reservoir；
D) powder of mix homogeneously is loaded in platinum crucible, and platinum crucible is placed in crystal growing furnace change
Material；
E) raw material is heated to more than supersolubility temperature (between 950-1200 DEG C) in crystal growing process, permanent
Temperature certain time.Then find supersolubility temperature (at 950 DEG C-1100 DEG C with the seed crystal of o growth
Between).Introducing seeded growth at supersolubility temperature, in growth course, brilliant rotational speed rate is 5-30rpm, cooling speed
Rate is every day 0.2-5 DEG C.Growth terminates, and lowers the temperature annealing with 5-30 DEG C/h, takes out crystal afterwards.
Raw material PbO or Pb used3O4、MgO、TiO2、SnO2、Nb2O5For oxide powder.
The platinum crucible used is column type crucible.
Seeded growth direction is (001) or (110) or (111) direction.
The crystal growing furnace used is stratie, and heating element heater is resistance wire or siliconit or silicon molybdenum
Rod.
The preparation method of crystal of the present invention all uses cosolvent, cosolvent PbO or Pb3O4And H3BO3
Or B2O3Composite auxiliary solvent.Growing crystal mass good, do not have cosolvent inclusion enclave, compositional uniformity is good.Should
Crystal can be used for for sonar sensor, underwater acoustic transducer, driver, the device of ultrasonic motor equipressure electrical domain
On part.
Ferroelectric single crystal material PMN-PSn-PT of the present invention has MPB structure.At PbTiO3(PT) content
It is tripartite's perovskite structure time less, at PbTiO3Four directions perovskite structure it is transitioned into when content is more.According to
The difference of the ratio of PMN, PSn and PT, grows MPB district and neighbouring PMN-PSn-PT crystal thereof
Curie temperature Tc can be between 140～300 DEG C, piezoelectric coefficient d33(500-2500pC/N)。PMN-PSn-PT
Architecture is stable, shows good heat stability.
The X-ray powder diffraction of prepared ferroelectric single crystal material 0.52PMN-0.10PSn-0.38PT shows
Crystal at room temperature has pure tripartite's perovskite structure；(001) the dielectric temperature spectrum display of the crystal cut in direction
Curie temperature TCIt is 155 DEG C (1kHz), rhombohedral-tetragonal phase temperature TrtIt is 45 DEG C, tripartite-four directions occurs
Phase transition temperature shows that component is positioned at MPB district；When frequency is 1kHz, the dielectric constant under room temperature reaches 1900,
Dielectric loss is 0.05, and high-k is higher than 8500 (1kHz)；(001) electricity of direction crystal cut
Hysteresis curves research shows, coercive field 2EcFor 9.5kV/cm, residual polarization 2PrIt is 50 μ C/cm2；(001)
The piezoelectric coefficient d of direction crystal cut33Reach 1350pC/N；0.52PMN-0.10PSn-0.38PT crystal shows
Going out poling, the crystal i.e. grown need not polarize and just shows higher piezoelectric modulus (1350pC/N),
And lower the temperature still without depolarization phenomenon after being incubated four hours higher than Curie temperature (200 DEG C), this
Heat treatment number of times, more than not observing that depolarization occurs for ten times, shows that 0.52PMN-0.10PSn-0.38PT is brilliant
Body has stable single domain.
Figure of description
The PMN-PSn-PT crystal of the preparation method growth of Fig. 1: the present invention.
The X-ray powder diffraction spectrum of Fig. 2: 0.52PMN-0.10PSn-0.38PT crystal, shows that the crystal of growth is
Pure tripartite's Perovskite Phase.
The relation that the dielectric constant of Fig. 3: 0.52PMN-0.10PSn-0.38PT crystal, dielectric loss vary with temperature
Curve.
The ferroelectric hysteresis loop of Fig. 4: 0.52PMN-0.10PSn-0.38PT crystal.
The piezoelectric coefficient d of Fig. 5: 0.52PMN-0.10PSn-0.38PT crystal33Change with heat treatment number of times.At Re
Reason process: from room temperature to 200 degree Celsius, is incubated 4 hours, then naturally rings to room temperature.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention done the most detailed, complete explanation, but be not intended to
Present disclosure.
Crystal growing furnace of the present invention is designed, designed processing；Powder diffractometer for structural analysis
Use Rigaku diffractometer (Rigaku, Japan)；Dielectric temperature spectrum Germany Novocontrol
The Alpha-A wideband dielectric/electric impedance analyzer of company；Ferroelectric hysteresis loop is produced by Aixacct company of Germany
Aix-ACCT TF2000 ferroelectricity analyser records (frequency is 2Hz), and alternating temperature equipment uses self-control tube furnace,
The Trek 610D that voltage is produced by Trek company of the U.S. provides.
Embodiment 1:
Use o growth PMN-PSn-PT ferroelectric single crystal material.
By initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5, cosolvent uses PbO or Pb3O4
And H3BO3Or B2O3Composite auxiliary solvent, proportionally weighs, mixed grinding.The powder of mix homogeneously is loaded
In platinum crucible, and platinum crucible is placed in material in crystal growing furnace.The material changed is heated to supersaturation
More than temperature, constant temperature certain time, then slow cooling growth；Between foam material temperature is 950-1200 DEG C,
Lower the temperature with the speed of every day 1-20 DEG C；In growth course, available platinum wire is suspended in liquid level central authorities, to be formed into
Core center, reduces nucleation quantity and promotes nucleating growth；Growth terminates, and lowers the temperature annealing with 10-30 DEG C/h,
Rear taking-up crystal.By the X-ray powder diffraction of crystal of growth, dielectric, ferroelectricity, piezoelectric property are surveyed
Examination is analyzed, and determines its structure and performance.
Embodiment 2:
Use top-seeded solution growth growth PMN-PSn-PT ferro-electricity single crystal.
By initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5, cosolvent uses PbO or Pb3O4
And H3BO3Or B2O3Composite auxiliary solvent, proportionally weighs, mixed grinding.The powder of mix homogeneously is loaded
In platinum crucible, and platinum crucible is placed in material in crystal growing furnace.The material changed is heated to supersaturation
More than temperature, constant temperature certain time, growing point is found to grow with seed crystal；About 950-1100 DEG C life
Long, brilliant rotational speed rate is 5-30rpm, and rate of temperature fall is every day 0.2-5 DEG C；Growth terminates, and crystal proposes liquid level,
Lower the temperature annealing with 10-30 DEG C/h.The monocrystalline grown is the square crystal appearing (001) natural aufwuchsplate,
Crystal mass is good, does not has cosolvent inclusion enclave, and compositional uniformity is good.X-ray by the crystal to growth
Powder diffraction, dielectric, ferroelectricity, piezoelectric property test analysis, determine its structure and performance.
Embodiment 3:
PMN-PSn-PT in embodiment one and two is grown ferroelectric crystal materials (shown in Fig. 1) and carries out structure
And performance test, preferred ingredient 0.52PMN-0.10PSn-0.38PT carries out structure and performance test.
A) crystal is cut one small pieces grind be finely ground to powder body be used for powder diffraction use.According to gained ferroelectric crystal
Powder diffractogram shows that room temperature 0.52PMN-0.10PSn-0.38PT ferroelectric crystal is tripartite's perovskite structure
(shown in Fig. 2).
B) obtained ferroelectric crystal materials is cut small pieces by (001) direction, then will with different sand paper
Section two sides polishes smooth.The two sides polished smooth by silver electrode, it is not necessary to polarization.The sample prepared
For piezoelectric property d33Test with dielectric temperature spectrum.Measured unpolarized 0.52PMN-0.10PSn-0.38PT
The piezoelectric modulus of crystal is 1350pC/N (shown in Fig. 5), is shown to be single domain ferroelectric.After having surveyed piezoelectric modulus
Carry out the spectrum test of dielectric temperature.Measure the dielectric temperature spectrum of 0.52PMN-0.10PSn-0.38PT ferroelectric crystal, temperature
From-50 DEG C to 300 DEG C.Dielectric thermogram shows the Curie temperature T of the ferroelectric crystal materials obtainedCIt it is 155 DEG C；
Rhombohedral-tetragonal phase temperature T is obtained on dielectric thermogramrtIt it is 45 DEG C.There is rhombohedral-tetragonal phase temperature in crystal
Show that crystal composition is positioned at MPB district.Dielectric constant and dielectric loss under room temperature are respectively 1900 and 0.05
(shown in Fig. 3).
C) obtained 0.52PMN-0.10PSn-0.38PT ferroelectric crystal materials is cut one by (001) direction
Small pieces, then polish smooth section two sides with different sand paper.The two sides polished smooth by silver electrode
Test for ferroelectric hysteresis loop.Measure the ferroelectric hysteresis loop under not same electric field.AC field in +/-15kV/cm
It is issued to saturated, now coercive field 2EcFor 9.5kV/cm, residual polarization 2PrIt is 50 μ C/cm2(Fig. 4 institute
Show).
D) the above-mentioned 0.52PMN-0.10PSn-0.38PT crystal for piezoelectricity test is connected in tube furnace,
Carrying out the piezoelectricity of crystal and the stability test of single domain, temperature is from room temperature to 200 DEG C, and 200 DEG C of holdings
4 hours, then drop to room temperature and carry out piezoelectric property test.This heat treatment process is carried out ten times, the piezoelectricity obtained
Coefficient d33For 1200-1440pC/N (shown in Fig. 5), show 0.52PMN-0.10PSn-0.38PT crystal
Piezoelectricity and single domain have good temperature stability.
From above-described embodiment, PMN-PSn-PT ferroelectric crystal materials has preferable ferroelectricity, piezoelectric property
And temperature stability, and be a kind of single domain crystal, the temperature stability that piezoelectricity and single domain have had, because of
This has application prospect.It addition, embodiment in detail above is not intended to present disclosure, as long as in the present invention
Technology and Knowledge Scheme in, make corresponding amendment or replace, all because of in the claim of the present invention.
Claims (7)
1. ferroelectric single crystal material lead magnesio-niobate-lead stannate-lead titanates, it is characterised in that: this materials chemistry formula is
(1-x-y)Pb(Mg1/3Nb2/3)O3-xPbSnO3-yPbTiO3, belong to typical perovskite structure, wherein,
X=0～0.5, does not include x=0, y=0.3～0.5, and this material exists quasi-homotype phase battery limit (BL).
Ferroelectric single crystal material the most according to claim 1, is characterised by: the chemical composition of this material is
0.52PMN-0.10PSn-0.38PT。
Ferroelectric single crystal material the most according to claim 1, is characterised by: this material constituent part is a kind of single
Farmland ferroelectric crystal.
4. a preparation method for the ferroelectric single crystal material described in claim 1, including following growth step:
A) by initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5Enter by the chemical composition of crystal
Row proportioning；
B) cosolvent uses PbO or Pb3O4And H3BO3Or B2O3Composite auxiliary solvent；
C) by crystal raw material and cosolvent mixed grinding in a reservoir；
D) powder of mix homogeneously is loaded in platinum crucible, and platinum crucible is placed in material in crystal growing furnace；
E) in crystal growing process, raw material is heated between 950-1200 DEG C, constant temperature certain time, then with
The speed cooling of every day 1-20 DEG C；Growth terminates, and lowers the temperature annealing with 5-30 DEG C/h, takes out crystal afterwards.
5. a preparation method for the ferroelectric single crystal material described in claim 1, including following growth step:
A) by initial feed PbO or Pb3O4、MgO、TiO2、SnO2、Nb2O5Enter by the chemical composition of crystal
Row proportioning；
B) cosolvent uses PbO or Pb3O4And H3BO3Or B2O3Composite auxiliary solvent；
C) by crystal raw material and cosolvent mixed grinding in a reservoir；
D) powder of mix homogeneously is loaded in platinum crucible, and platinum crucible is placed in material in crystal growing furnace；
E) in crystal growing process, raw material is heated between 950-1200 DEG C, constant temperature certain time；Then use
The seed crystal of o growth finds supersolubility temperature, introduces seeded growth, growth at supersolubility temperature
During brilliant rotational speed rate be 5-30rpm, rate of temperature fall is every day 0.2-5 DEG C；Growth terminates, with 5-30 DEG C/h
Cooling annealing, takes out crystal afterwards.
The preparation method of ferroelectric single crystal material the most according to claim 5, it is characterised in that: described seed crystal
The direction of growth is (001) or (110) or (111) direction.
7. the purposes of the ferroelectric single crystal material described in a claim 1, it is characterised in that: this material is used for preparing
Piezoelectricity, the device in pyroelectricity field.
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