CN100429334C - Pyroelectric single crystal material of PMN-PT and application thereof - Google Patents
Pyroelectric single crystal material of PMN-PT and application thereof Download PDFInfo
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- CN100429334C CN100429334C CNB2004100890724A CN200410089072A CN100429334C CN 100429334 C CN100429334 C CN 100429334C CN B2004100890724 A CNB2004100890724 A CN B2004100890724A CN 200410089072 A CN200410089072 A CN 200410089072A CN 100429334 C CN100429334 C CN 100429334C
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Abstract
The present invention relates to a lead magnesio-niobate and lead titanate (PMNT) pyroelectric single crystal material and the application thereof, which belongs to the field of pyroelectric single crystals. The composition of the single crystal material is (1-x)PMN-xPT, wherein x is between 0.24 and 0.38; when the crystallographic directions are <111>, <011> and <001>, the pyroelectric coefficient achieves 950 muC/m<2>K, the current response optimum value achieves 380 pm/V, the detection optimum value achieves 98.9 muPa<-1/2> and the thermal diffusivity achieves 4.43*10<-7>m<2>/s; in addition, the use temperature of the PMNT single crystal achieves 80 DEG C, and the PMNT single crystal has the advantages of stable room temperature performance and easy manufacture. The PMNT single crystal used as thermoelectric converted response element can be manufactured into a pyroelectric detector with good performance to be applied to infrared detection and imaging devices.
Description
Technical field
The present invention relates to a kind of pyroelectric single crystal material of PMN-PT and application thereof, belong to the pyroelectric single crystal field.
Background technology
PMN-PT (PMNT) monocrystalline (composition x is 0.30-0.35) near the mutually accurate homotype phase boundary in tripartite phase-four directions and＜have superior piezoelectricity, electromechanical coupling performance and higher field on 001〉direction to cause strain, make it have huge and application prospects at aspects such as ultrasonic transducer, driving mechanism and senser elements, and people such as Luo Hao Sue adopted the Bridgman method successfully to realize the batch process (ZL 99 1 13472.9) of high quality P MNT monocrystalline, and this has all promoted the research to the PMNT monocrystalline greatly.Is that the research of about 0.38 and＜001〉direction high electro-optical properties is also carried out at the PMNT monocrystalline forming x.Yet, the PMNT monocrystalline be yet there are no report up to now in the application aspect the pyroelectric electric device.
Since the Gulf War, night vision (imaging) function of the infrared focal plane array device that US military uses, the infrared scientific circles in the world have been startled, the development of infrared detector has developed in the whole world rapidly, and the pyroelectric electric device that uses under the room temperature is as the very important non-refrigerated infrared detector of a class, because its broad spectrum response, cost be low, need not freeze, be easy to carry, compact construction and easy to use, in military, commercialization and civilian infrared detector and demonstrate more and more important position.The mechanism that pyroelectricity is surveyed device can be divided into conversion and hot two processes to electricity of infrared wavelength light to heat, and wherein heat realizes to the pyroelectric effect of electric conversion by pyroelectricity material, it also is the part that pyroelectric detector carries out most critical in the infrared acquisition process, corresponding pyroelectricity material also is the core parts of pyroelectric detector, and the quality of its performance has directly influenced the effect of infrared acquisition.Pyroelectric detector and array type device based on the pyroelectric property of ferroelectric material (comprising monocrystalline and pottery), obtained widespread use, in recent years Yan Jiukaifa emphasis and focus are the preparations of novel ferroelectric body and ferroelectric membranc, and utilize novel ferroelectric body and ferroelectric membranc to combine with unicircuit, make array formula (comprising linear array and focal plane array) pyroelectric electric device, because the breakthrough on their performances, corresponding pyroelectric detector has been played the part of the key player in infrared technique, have broad application prospects and huge market potential.The pyroelectricity material of practice mainly comprises lithium tantalate (LT) and TGS (TGS) series monocrystal and mixes up the zirconium niobium iron acid lead (PZ-FN) of modification and lead titanate (PT) pottery of modification etc. at present.
In monocrystal material, the thermal diffusivity of LT is too big, be difficult to improve the horizontal thermal time constant of pyroelectric detector, and its pyroelectric coefficient is lower, specific inductivity is low, is not suitable for the small area detector in the detector array; TGS series pyroelectric coefficient is than higher, and thermal diffusivity is smaller, but hydrolysis easily needs sealing to use, and because the Curie temperature of material has only about 49 ℃, and pyroelectric property is bigger with variation of temperature, processing is used very inconvenient.These functional limitations of pyroelectricity material have limited the use range of pyroelectric detector greatly.People wish to seek out the novel pyroelectric single crystal material of excellent combination property always, and it is big to have a pyroelectric coefficient, the current-responsive figure of merit, the voltage responsive figure of merit and survey figure of merit height, and thermal diffusivity is little, stable performance, and characteristics such as processing use easily.
Summary of the invention
The present invention is (1-x) Pb (Mg with the chemical constitution of the pyroelectric single crystal material of PMN-PT of the PMNT monocrystalline acquisition of Bridgman method growth
1/3Nb
2/3) O
3-xPbTiO
3, wherein x is 0.24-0.38.
The objective of the invention is to by sign the pyroelectric coefficient and the correlated performance of above-mentioned PMNT monocrystalline, pyroelectric property that this monocrystalline of assay is comprehensive and the application prospect on infrared acquisition thereof, and use this PMNT monocrystalline to realize preparing pyroelectric detector spare.
Having adopted the growth of Bridgman method to form x in the present invention is the PMNT monocrystalline of 0.24-0.30, with the XRD diffraction method monocrystalline that grows out has been carried out orientation, chosen＜111,＜011〉and＜001〉three low index crystallographic direction, adopt dynamic method to measure the pyroelectric coefficient of this PMNT monocrystalline, the powder specific heat under corresponding dielectric properties and the room temperature and the thermal diffusivity of monocrystalline have been measured, calculated the pyroelectric property index under this monocrystalline room temperature, the result shows that forming x is＜111 for the 0.24-0.38 direction 〉,＜011〉and＜001 the PMNT monocrystalline be that well behaved pyroelectricity material is (when x is 0.24-0.30, crystallographic direction is＜111〉time, the performance performance is excellent), can in infrared acquisition and imaging, be widely used and used this single crystal preparation pyroelectricity single-element detector and linear array detector, and measure the performance of this detector.
Main contents of the present invention comprise:
(1) growth of PMNT monocrystalline and aftertreatment
It is that the growing method that adopted of ZL 99 1 13472.9 is realized that the patent No. has been adopted in the growth of PMNT monocrystalline, and the raw material of growth is a purity greater than 99.99% PbO, Pb
3O
4, MgO, Nb
2O
5, TiO
2Powder be made into mixing raw material by (1-x) PMN-xPT chemical formula, x is 0.24,0.30,0.31,0.33 and 0.38, grow PMNT monocrystalline with respective nominal composition with the Bridgman method, use XRD diffraction direction finder then respectively along＜111 〉,＜011〉and＜001〉direction carry out orientation, cut again, promptly make and have different the composition and the PMNT monocrystal material of direction.
(2) measurement of PMNT monocrystal pyroelectric coefficient and dielectric properties
The growth of PMNT monocrystalline involved in the present invention is that the employing patent No. is that the Bridgman method crystal growing apparatus that ZL 99 113472.9 is adopted is realized, pyroelectric coefficient is to measure with the dynamic method measuring apparatus of The Hong Kong Polytechnic University, the dielectric properties of 10kHz are to measure with HP4194A type electric impedance analyzer, the specific heat of monocrystal is with Tianjin, island DSC-50 differential scanning calorimeter and adopts sapphire (SAPP) to measure 0.7PMN-0.3PT monocrystalline＜111 as the standard model of reference〉thermal diffusivity of direction is to measure by the anti-LFA427 of the company laser heat conductivility tester of speeding of Germany.
Pyroelectric coefficient after the polarization of PMNT monocrystalline is to measure by dynamic method.To forming x is 0.24,0.30,0.31,0.33 and 0.38 PMNT monocrystalline is along＜111 〉,＜011〉and＜electrostrictive coefficient p=p-ip is released in the re-heat of 001〉direction room temperature polarization back in 25 ℃ of-56 ℃ of scopes, and " measure; selected AC driving temperature amplitude is 1 ℃ in the measurement, frequency is 5mHz.
Fig. 1 (a) example provided＜and the re-heat of 111〉direction 0.70PMN-0.30PT monocrystalline releases the relation of electrostrictive coefficient and temperature, and when 25 ℃ were increased to 56 ℃, pyroelectric coefficient was from 850 μ C/m
2K is increased to 1200 μ C/m
2K, numerical value is bigger, varies with temperature more steadily, and the imaginary part that electrostrictive coefficient is released in re-heat is about 50 μ C/m
2K, less relatively.
PMNT monocrystalline corresponding specific inductivity and dielectric loss factor in 25 ℃ of-56 ℃ of scopes are measured with HP4194A, Fig. 1 (b) example has provided＜dielectric properties of 111〉direction 0.70PMN-0.30PT monocrystalline and the relation of temperature, when 25 ℃ are increased to 56 ℃, specific inductivity 640 is increased to 1100, dissipation factor varies with temperature not quite, remain on about 2 ‰, less relatively.
(3) measurement of thermal property
The quality specific heat of PMNT monocrystal changes not quite with forming under the room temperature, be about 3.1J/gK, and the density of PMNT monocrystalline is about 8.01g/cm under the room temperature
3, the volume specific heat under the room temperature is about 2.5 * 10 like this
6J/m
3K.
0.70PMN-0.30PT monocrystalline＜111 under the room temperature〉the thermal diffusivity measuring result of direction is 4.43 * 10
-7m
2/ s, other pyroelectricity material relatively, thermal diffusivity is less.
(4) the pyroelectric property index under the room temperature
From the angle of pyroelectricity material own, estimating the pyroelectric property quality has 3 important index, comprises current-responsive figure of merit F
i=p/c
p, voltage responsive figure of merit F
v=p/ (c
pε
0ε
r) and survey figure of merit F
d=p/ (c
p(ε
0ε
rTan δ)
1/2), wherein p is a pyroelectric coefficient, c
pBe volume specific heat (J/m
3), ε
0=8.85 * 10
-12F/m is a permittivity of vacuum, ε
rIt is specific inductivity.
Pyroelectric property index to the PMNT monocrystalline is calculated, and is displayed in Table 1 out.As can be seen from Table 1, for the PMNT monocrystalline, be 0.24 and 0.30 o'clock forming x,＜111〉direction pyroelectric coefficient and pyroelectricity figure of merit index are all than higher, and the pyroelectric coefficient of 0.76PMN-0.24PT monocrystalline has reached 950 μ C/m
2K, the current-responsive rate has reached 380pm/V, and the detection figure of merit of 0.70PMN-0.30PT monocrystalline has reached 98.9 μ Pa
-1/2The comprehensive pyroelectric property of 0.70PMN-0.30PT monocrystalline is compared with pyroelectricity material commonly used, be shown in table 2,, be about 0.06m though the voltage responsive figure of merit as can be seen and other material compared are little
2/ C, yet pyroelectric coefficient is big, the current-responsive figure of merit and detection figure of merit height, thermal diffusivity is little, and form x be 0.24 and 0.30＜111〉directed PMNT monocrystalline temperature-rise period in first phase point temperature greater than 80 ℃, promptly use temperature can reach 80 ℃, use stable under the room temperature than stability, and the PMNT monocrystalline is processed easily, these characteristics have all shown chooses suitable operating mode (as current working mode), the PMNT monocrystalline is a kind of pyroelectricity material of excellent combination property, aspect infrared acquisition and the image device great application prospect is being arranged.
(5) Zhi Bei pyroelectric detector and performance thereof
With＜111〉the 0.69PMN-0.31PT single crystal preparation of direction the infrared eye of unit infrared eye and linear array.
Prepared single-element detector uses the blackbody temperature of 500K, and when the operating frequency of 300H frequency was tested, measured signal to noise ratio was 2.1/0.08, and the voltage responsive rate of detector is 431V/W, and noise equivalent power is 1.4 * 10
-9WHz
-1/2, detectivity is 6.3 * 10
7CmHz
1/2W
-1
Prepared linear array detector uses the blackbody temperature of 500K, and when the operating frequency of 12.5Hz was tested, measured signal to noise ratio was 19.5/0.12, and the voltage responsive rate is 57 * 10
3V/W, detectivity is 8.55 * 10
7CmHz
1/2W
-1
Measured detector performance is close with the performance of pyroelectric detector commonly used at present, has proved that this PMNT monocrystalline can obtain actual application in infrared acquisition.
Description of drawings
Fig. 1 shows＜pyroelectric coefficient of 111〉direction 0.70PMN-0.30PT monocrystalline and the relation of dielectric properties and temperature.
Table 2 show x be 0.24,0.30,0.31,0.33 and 0.38 and crystallographic direction be＜111,＜011〉and＜pyroelectric property index under 001〉direction the PMNT monocrystalline room temperature.
Table 3 shows pyroelectricity material PMNT monocrystalline and consists of the comparison that 0.30 pyroelectricity on＜111〉direction is used relevant performance and pyroelectricity material performance commonly used now.
Embodiment
Further specify the present invention below in conjunction with preferred embodiment.
Embodiment 1
With purity greater than 99.99% PbO, Pb
3O
4, MgO, Nb
2O
5, TiO
2The raw material powder be made into mixing raw material by the 0.70PMN-0.30PT chemical formula, grow the PMNT monocrystalline with the Bridgman method, with XRD diffraction direction finder edge＜111〉orientation, cutting, the pyroelectricity material of pyroelectric property excellence be can prepare behind the edge＜111〉direction polarization, infrared acquisition and imager are used for preparing.
Embodiment 2
With purity greater than 99.99% PbO, Pb
3O
4, MgO, Nb
2O
5, TiO
2The raw material powder be made into mixing raw material by the 0.76PMN-0.24PT chemical formula, grow the PMNT monocrystalline with the Bridgman method, with XRD diffraction direction finder edge＜111〉orientation, cutting, the pyroelectricity material of pyroelectric property excellence be can prepare behind the edge＜111〉direction polarization, infrared acquisition and imager are used for preparing.
Table 1
Table 2
| Material (temperature ℃) | p 10 -4Cm -2K -1 | ε r | tanδ | c 10 6Jm -3K -1 | K 10 -7m 2s -1 | F i nAcm/w | F v m 2C -1 | F d 10 -5Pa -1/2 |
| TGS series | ||||||||
| TGS(35) | 5.5 | 55 | 0.025 | 2.6 | 3.3 | 2.1 | 0.43 | 6.1 |
| DTGS(40) | 5.5 | 43 | 0.020 | 2.4 | 3.3 | 2.3 | 0.60 | 8.3 |
| ATGSAs(25) | 7.0 | 32 | 0.01 | 0.99 | 16.6 | |||
| ATGSP(25) | 6.2 | 31 | 0.01 | 0.98 | 16.8 | |||
| Polymkeric substance | ||||||||
| PVDF | 0.27 | 12 | 0.015 | 2.43 | 0.62 | 0.11 | 0.10 | 0.88 |
| Monocrystalline | 2.5 | |||||||
| PMNT | 8.55 | 640 | 0.002 | 4.43 | 342 | 0.06 | 9.89 | |
| SBN-50 * | 5.5 | 400 | 0.003 | 2.34 | 2.35 | 0.07 | 7.2 | |
| LiTaO 3 | 2.3 | 47 | 0.005 | 3.2 | 13.0 | 0.72 | 0.17 | 4.9 |
| Pottery | ||||||||
| The PZ-FN pottery | 3.8 | 290 | 0.003 | 2.5 | 1.52 | 0.06 | 5.8 | |
| The PT pottery | 3.8 | 220 | 0.011 | 2.5 | 1.52 | 0.08 | 3.3 |
Claims (4)
1, a kind of lead magnoniobate one lead titanate pyroelectric single crystal material is characterized in that its chemical constitution is (1-x) Pb (Mg
1/3Nb
2/3) O
3-xPbTiO
3, wherein x is 0.24-0.38, crystallographic direction is＜and 111 〉,＜011〉and＜001〉direction.
2, by the described a kind of pyroelectric single crystal material of PMN-PT of claim 1, it is characterized in that x is 0.24-0.30.
3, by claim 1 or 2 described a kind of pyroelectric single crystal material of PMN-PT, it is characterized in that crystallographic direction is＜111〉direction.
4, by the response element of the described a kind of pyroelectric single crystal material of PMN-PT of claim 1, be applied to infrared acquisition and infrared imagery technique as the conversion of heat-electricity.
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| CN101628810B (en) * | 2009-08-12 | 2012-05-30 | 中国科学院上海硅酸盐研究所 | High transparent and high electro-optical property doped PMN-PT electro-optic ceramic material and preparation method thereof |
| CN103199736A (en) * | 2012-01-09 | 2013-07-10 | 中国科学院上海硅酸盐研究所 | Composite structure piezoelectric energy collector driven by cantilever |
| CN103943771A (en) * | 2014-05-12 | 2014-07-23 | 中国科学院上海硅酸盐研究所 | Relaxation ferroelectric monocrystal pyroelectric infrared detector and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080777C (en) * | 1999-02-11 | 2002-03-13 | 中国科学院上海硅酸盐研究所 | Method for preparing relaxing ferroelectric single crystal lead magnoniobate |
| CN1382841A (en) * | 2002-03-12 | 2002-12-04 | 中国科学院上海硅酸盐研究所 | Melt method for growing sosoloid monocrystal of lead lead-titanate niobium-zincate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1080777C (en) * | 1999-02-11 | 2002-03-13 | 中国科学院上海硅酸盐研究所 | Method for preparing relaxing ferroelectric single crystal lead magnoniobate |
| CN1382841A (en) * | 2002-03-12 | 2002-12-04 | 中国科学院上海硅酸盐研究所 | Melt method for growing sosoloid monocrystal of lead lead-titanate niobium-zincate |
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