CN1812149A - Porous composite thick film pyroelectric material and preparative method - Google Patents
Porous composite thick film pyroelectric material and preparative method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims description 51
- 238000002360 preparation method Methods 0.000 title claims description 29
- 238000005245 sintering Methods 0.000 claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000919 ceramic Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011521 glass Substances 0.000 claims abstract description 32
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 230000005684 electric field Effects 0.000 claims abstract description 16
- 238000007650 screen-printing Methods 0.000 claims abstract description 13
- 238000003980 solgel method Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000007639 printing Methods 0.000 claims abstract description 3
- 230000005616 pyroelectricity Effects 0.000 claims description 52
- 239000011268 mixed slurry Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 230000010287 polarization Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 4
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
This invention discloses a kind of porous combined thick membrane pyroelectric material and its producing method. It uses sol-gel process to produce Ba<SUB>1-x</SUB>Sr<SUB>x</SUB>TiO<SUB>3</SUB> and Pb<SUB>1-y</SUB>La<SUB>y</SUB>TiO<SUB>3</SUB> ceramics micro-powder; after mixing PbO with HBO<SUB>3</SUB> and sintering, quench in deionized water to produce glass which component is zPbO-(1-z)B<SUB>2</SUB>O<SUB>3</SUB>. Then, ball-mill the produces glass to glass powder; mix the ceramics micro-powder and glass powder, after which adds organic carrier to produce mixture size; use screen printing skill to produce thick membrane green-pressing sample on aluminium oxide electronic ceramic wafer which is coated with silver electrode. Then sinter it to form membrane; use sputtering or printing method to produce silver electrode; polarize silver thick membrane under electric field. This combined thick membrane has high pyroelectric detectivity figure of merit. The pyroelectric coefficient is 335muC/m<SUP>2</SUP>K under room temperature. The detectivity figure of merit is F<SUB>D</SUB> and can reach 8.5muPa<SUP>-1/2</SUP>. It can keep high detectivity figure of merit under 0-200DEG C.
Description
Technical field
The present invention relates to the pyroelectricity material field, especially relate to a kind of porous composite thick film pyroelectricity material and preparation method.
Background technology
Pyroelectricity material is that a class has non-zero macroscopic polarization intensity in certain temperature range, also promptly has the functional material of pyroelectric effect, comprises monocrystalline, pottery and minority polymer.Handle through artificial polarization, pyroelectricity material has tangible macroscopic polarization, and polarization intensity is changed by ambient temperature and changes.
Pyroelectric effect can directly apply to infrared acquisition and heat-electricity conversion.And pyroelectricity thick film and thin-film material have good performance and can with present ic process compatibility, therefore in fire prevention, antitheft, lamp switch has great application prospect and market value in the information products.
The problem that present pyroelectricity detection application is run into mainly concentrates on following four aspects:
(1) pyroelectric ceramics has higher pyroelectricity detection coefficient, but owing to need to be assembled into array behind the mechanical reduction, makes its preparation cost high.The array structure that TIX (Texas Instruments corp.) adopts the assembling of ferroelectric ceramic thin slice to obtain is the core detecting element, has produced the pyroelectric infrared detector that works under the room temperature, and has realized commercialization.Wherein the ferroelectric ceramic thin slice is obtained through machine cut and attenuate by ceramic block, is subjected to the influence of ceramic machinery performance and processing technology, approximately has only 5～10% rate of finished products, and this is the high main cause of this type pyroelectricity detection instrument price.
(2) thus electric heating film can use the modern optical carving technology and prepare array structure easily and be subjected to broad research, but because interfacial effect and skin effect have obviously reduced the spontaneous polarization strength of spontaneous polarization unit in the crystal under the film attitude, make the pyroelectricity of thin-film material survey coefficient approximately have only the respective masses pottery pyroelectric coefficient about 1/100; In addition, it is too high that modern ferroelectric thin film technology of preparing prepares the ferroelectric thin film cost of large tracts of land even compact, so the research of ferroelectric thin film sensitive detection parts is also continuing.
(3) how to improve the detectivity figure of merit of pyroelectricity, i.e. the material that how just can obtain having the better detectivity figure of merit.
According to the pyroelectricity theory as can be known, the linear pyroelectric coefficient of at present main pyroelectricity material is greatly about 1-5 * 10
-8C/cm
2About K, and the detectivity figure of merit of pyroelectricity material is determined by following formula (1):
F
D＝p/{c(ε
rε
0tanδ)
1/2} (1)
Wherein p is a pyroelectric coefficient, and c is the thermal capacitance of the unit volume of material, ε
rBe relative dielectric constant, ε
0=8.853 * 10
-12F/m, tan are dielectric loss.
As can be seen, improve pyroelectric coefficient and all can reach the purpose that improves the pyroelectricity detectivity figure of merit with the dielectric constant, dielectric loss and the thermal capacitance that reduce material.
Aspect electric heating film, people such as Nava Setter are by adding high molecular polymer in precursor solution, use PCT and PZT electric heating film that preparing of sol-gel process success has the nano aperture structure then, reduced thermal capacitance, obtained the higher pyroelectricity detectivity figure of merit.People such as Yao Xi are by preparation porous heat insulation layer, thereby have realized that to reduce heat conduction between thin-film material and the substrate pyroelectricity surveys the raising [ZL96118657.7] of the figure of merit.As thick-film material, have the advantage of thin-film material and block materials concurrently, it has the pyroelectric coefficient close with corresponding ceramic material, and with the MEMS Development of Preparation Technology, has successfully realized the combination of thick film and silicon planner technology.Thick film pyroelectricity detection array through the chemical etching preparation has good performance and lower preparation cost.Aspect the pyroelectricity thick film, people such as M.Prudenzitai use the silk screen method and have prepared the PZT thick film, find that the material with micropore has low thermal capacitance and thermal conductance, can show pyroelectricity detectivity figure of merit F preferably
D, i.e. the better detection rate figure of merit.As seen the thermal capacitance and the heat conduction that reduce material or structure are to improve one of pyroelectricity detectivity figure of merit key factor.
(4) how to improve the operating temperature range of pyroelectricity material.Because the spontaneous polarization of pyroelectricity material exists only in below the Curie temperature, therefore, the pyroelectricity material that utilizes pyroelectric effect to realize that the pyroelectricity detection is selected for use usually has the Curie temperature that is higher than room temperature, to guarantee that material can at room temperature use.Wherein, for the material of Curie temperature far above room temperature, as PLT, PZT etc., near its pyroelectric coefficient room temperature is lower, with this pyroelectric detector spare for preparing, though have the operating temperature range of broad, but under room temperature environment, its detectivity figure of merit is often lower, is generally 2 μ Pa
-1/2And to Curie temperature at material near room temperature, pyroelectric coefficient is higher near room temperature, as BST, but operating temperature range is too narrow.Therefore, these two kinds of materials all can't realize having high pyroelectric property and wide operating temperature range simultaneously.
In order to widen the serviceability temperature scope, people such as Sun Dazhi [ZL98110900.4] make up a plurality of pyroelectricities with different phase transition temperature zones mutually and obtain a pyroelectric ceramics, wherein separate by heat insulation layer between the different units, thereby constituent elements different in certain temperature range undergo phase transition successively, prepare the pyroelectric ceramic material that has high pyroelectric coefficient in 10 ℃ temperature province, its pyroelectric coefficient reaches 920 μ C/m
2About K, pyroelectric coefficient apparently higher than general pyroelectric ceramics, but its method that adopts has increased difficulty, and has been unfavorable for device for a plurality of component pottery fritters with different phase transition temperatures are arranged in a block ceramic on macroscopic view on preparation technology.
Summary of the invention
The object of the present invention is to provide a kind of porous composite thick film pyroelectricity material and preparation method, not only can be convenient to large-area preparation but be easy to integrated, and the NEW TYPE OF COMPOSITE porous thick film material that in super wide 0～200 ℃ of operating temperature range, all has the high pyroelectricity detectivity figure of merit.
The technical solution adopted for the present invention to solve the technical problems is as follows:
1, a kind of porous composite thick film pyroelectricity material, be to be coated with the ground floor silver electrode at aluminium oxide electronic ceramic upper surface of base plate, be coated with one deck porous composite thick film material at ground floor silver electrode upper surface, and deposit one deck silver electrode at the upper surface of porous composite thick film material.
Described thick-film material is with Ba
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3Two kinds of crystalline phases are principal phase, zPbO-(1-z) B
2O
3Glassy phase is the composite material of auxiliary phase; Its composition formula is (1-m) Ba
1-xSr
xTiO
3-mPb
1-yLa
yTiO
3-n[zPbO-(1-z) B
2O
3], 0≤x≤0.30,0.10≤y≤0.20,0.2≤z≤0.80,0≤m≤1,0.08≤n≤0.20 wherein;
In the formula: m is Pb
1-yLa
yTiO
3Molar content in porous composite thick film;
N is zPbO-(1-z) B
2O
3At Pb
1-yLa
yTiO
3Molar content in porous composite thick film;
X is that Sr is at Ba
1-xSr
xTiO
3In molar content;
Y is that La is at Pb
1-yLa
yTiO
3In molar content;
Z is that PbO is at zPbO-(1-z) B
2O
3In molar content.
2, a kind of preparation method of porous composite thick film pyroelectricity material, the step of this method is as follows:
(1) uses the Ba that Prepared by Sol Gel Method has 200nm～400nm particle diameter
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3Ceramic, its molar content are 0≤x≤0.30,0.10≤y≤0.20; Prepared thus powder has high crystalline phase integrity degree and low frit activity.
(2) with PbO and HBO
3Raw material mixes, and wherein mixing mol ratio is PbO=z, HBO
3=2 (1-z); Behind 750-850 ℃ of following sintering 0.5～2h in deionized water quenching to prepare component be zPbO-(1-z) B
2O
3Glass, its molar content is 0.2≤z≤0.80, again its ball milling 6～24h is obtained glass powder;
(3) ceramic for preparing more than the general is a principal crystalline phase, and glass powder is an auxiliary phase, by formula (1-m) Ba
1-xSr
xTiO
3-mPb
1-yLa
yTiO
3-n[zPbO-(1-z) B
2O
3] carry out the proportioning mixing, wherein 0≤m≤1,0.08≤n≤0.20 adds the organic substance carrier simultaneously, then the mixed mixed slurry that gets of ball milling 12～36h; In mixed slurry, the organic substance carrier accounts for 20～25wt%.
(4) use screen printing technique, with above-mentioned mixed slurry is the silk screen printing slurry of preparation thick-film material, be coated with preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode, then in far infrared drying oven under 140～200 ℃ of temperature dry 1～6h, and in 700～850 ℃ of following sintering film forming, sintering time is 20min～300min., and sintering atmosphere is an air atmosphere, and the thickness of porous composite thick film is 10～80 microns;
(5) utilize sputter or printing process to prepare one deck silver electrode at the porous composite thick film upper surface that sinters;
(6) porous composite thick film that will have silver electrode polarizes under electric field, and polarization condition is: in temperature is 150～200 ℃ silicone oil, polarize under the 2kV/mm electric field strength earlier; In temperature is 40～60 ℃ silicone oil, polarize under the 2kV/mm electric field strength then.
Ba in the porous composite thick film material
1-xSr
xTiO
3The Curie temperature of crystalline phase in x=0.30～0 corresponding to 50～120 ℃, Pb
1-yLa
yTiO
3The Curie temperature of crystalline phase in y=0.20～0.10 corresponding to 130～310 ℃; Two kinds of principal crystalline phases show dielectric constant and the pyroelectric coefficient with same order in system.
Described organic substance carrier is the liquid that contains ethyl cellulose, terpinol and coating material.
Glass powder is converted into auxiliary phase and is wrapped in principal crystalline phase particle top layer after sintering process; The principal crystalline phase particle is 200～500nm by the formed particle size in auxiliary phase parcel back; And in porous composite thick film, evenly have the micropore hole between the formed particle in parcel back, wherein the micropore hole is of a size of 20nm～200nm.
The preparation precursor powder requires prepared powder to have crystalline phase integrity degree height, and particle size is at 200nm-400nm, and the characteristics that sintering activity is low are with the counterdiffusion speed of crystalline phase and glassy phase in the reduction sintering process.
By control Ba
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3The chemical constituent of two constituent elements and particle size make each component have with other dielectric constant of the order of magnitude and pyroelectric coefficient.
The component of control calcining system and glassy phase to be realizing the parcel of glassy phase to the crystalline phase particle, thereby is implemented in the homogenization that does not contact and suppress two-phase in the sintering process between the crystalline phase particle as yet.Control the mass transfer densification process by the control calcining system, make the round densification effect in the sintering process keep appropriate level, thereby form loose structure with certain bore hole size.
The present invention compares the useful effect that has with background technology:
1, relative thin membrane material, it is simple that the prepared thick-film material of the present invention has technology, and preparation cost is lower, and the composite material for preparing has high pyroelectricity and surveys coefficient; Relative pyroelectric ceramics and monocrystalline, the prepared thick-film material of the present invention can be compatible mutually with modern integrated circuits technology easily;
2, traditional single-phase pyroelectricity detecting material mainly is divided into two classes, one class is representative with BST, its Curie temperature is lower, be generally 50～90 ℃, but near room temperature, has advantages of high pyroelectric coefficient, and have low dielectric constant and the some loss that is situated between, therefore can obtain the good pyroelectricity detectivity figure of merit, its shortcoming is that operating temperature range is narrow; Another kind of is representative with PLT, has high Curie temperature, be generally 180～350 ℃, the operating temperature range broad, but because near the pyroelectric coefficient room temperature is lower, and the dielectric constant and the dielectric loss of prepared PLT material are greater than the BST material, and therefore, near the pyroelectricity room temperature is surveyed the figure of merit will be starkly lower than BST class material; The resulting composite diphase material of the present invention has overcome the shortcoming of two class materials preferably, has realized the high detectivity figure of merit 0～200 ℃ temperature range;
3, the reduction of the method success of the prepared composite material of the present invention by in material, introducing nano aperture the dielectric constant of material, thermal capacitance and thermal conductance, though pyroelectric coefficient has less reduction, the pyroelectricity of material is surveyed the figure of merit and is obviously improved; Composite thick film of the present invention has the high pyroelectricity detectivity figure of merit, and pyroelectric coefficient is 335 μ C/m near room temperature
2K, detectivity figure of merit FD can reach 8.5 μ Pa
-1/2, and in 0～200 ℃ of temperature range, keep the higher detectivity figure of merit.Available fire alarm, advanced infrared acquisition fields such as complex array infra-red imaging.
Description of drawings
Fig. 1 is that the rete of the high detectivity figure of merit pyroelectricity porous composite thick film material for preparing on the aluminium oxide electronic ceramic substrate of the present invention concerns schematic diagram;
Fig. 2 is the SEM microstructure photo of composite thick film; Fig. 3 (a) is the relation curve of relative dielectric constant and dielectric loss and temperature;
Fig. 3 (b) is the relation curve of pyroelectric coefficient and temperature;
Fig. 3 (c) is the relation curve that pyroelectricity is surveyed the figure of merit and temperature.
Among the figure: 1, aluminium oxide electronic ceramic substrate, 2, silver electrode, 3, the porous composite thick film material.
Embodiment
As shown in Figure 1, material of the present invention is to be coated with ground floor silver electrode 2 at aluminium oxide electronic ceramic substrate 1 upper surface, be coated with one deck porous composite thick film material 3 at ground floor silver electrode 2 upper surfaces, and deposit one deck silver electrode 2 at the upper surface of porous composite thick film material 3.
Embodiments of the invention are as follows:
Embodiment 1:
Use the Ba of Prepared by Sol Gel Method
0.80Sr
0.20TiO
3And Pb
0.82La
0.18TiO
3Ceramic, its component are x=0.20, y=0.18.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 1h in deionized water quenching to prepare component be 0.50PbO-0.50B
2O
3, wherein the glass of z=0.50 obtains glass powder with its ball milling 12h again.By m=0.5, n=0.10 adds the organic substance carrier of 20wt% simultaneously with the above ceramic for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, use silk screen print method with above-mentioned mixed slurry, preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode is being arranged, following dry 1 hour in 150 ℃ then, and in 800 ℃ of following sintering film forming, sintering time is 40min, and sintering atmosphere is an air atmosphere, and the thickness for preparing is 40 microns.The loose structure of wherein prepared thick film can be found out from the SEM photo of Fig. 2 and formed uniform loose structure in the thick film.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is: in temperature is 160 ℃ silicone oil, polarize under the 2kV/mm electric field strength earlier; In temperature is 60 ℃ silicone oil, polarize under the 2kV/mm electric field strength then.In 0～200 ℃ of temperature range, its relative dielectric constant excursion is 700-800, and dielectric loss is 0.02～0.08, shown in Fig. 3 (a).Its pyroelectric coefficient is all at 180 μ C/m
2More than the K, shown in Fig. 3 (b).Thermal capacitance is 1.6 * 10
6J/m
3Calculating its pyroelectricity detectivity figure of merit all reaches in whole temperature range＞3 μ Pa
-1/2, shown in Fig. 3 (c).
Embodiment 2:
Use the BaTiO of Prepared by Sol Gel Method
3And Pb
0.80La
0.20TiO
3Ceramic, its component are x=0, y=0.20.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 2h in deionized water quenching to prepare component be 0.80PbO-0.20B
2O
3, wherein the glass of z=0.80 obtains glass powder with its ball milling 12h again.By m=1, n=0.20 adds the organic substance carrier of 25wt% simultaneously with the above ceramic for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, use silk screen print method with above-mentioned mixed slurry, preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode is being arranged, following dry 1 hour in 150 ℃ then, and in 850 ℃ of following sintering film forming, sintering time is 300min, and sintering atmosphere is an air atmosphere, and the thickness for preparing is 60 microns.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is: in temperature is 160 ℃ silicone oil, polarize under the 2kV/mm electric field strength.In 0～200 ℃ of temperature range, its relative dielectric constant excursion is 400～800, and dielectric loss is 0.02～0.05, and its pyroelectric coefficient is all at 120 μ C/m
2More than the K, thermal capacitance is 1.6 * 10
6J/m
3, calculate its pyroelectricity detectivity figure of merit and all reach in whole temperature range＞1.9 μ Pa
-1/2
Embodiment 3:
Use the Ba of Prepared by Sol Gel Method
0.80Sr
0.20TiO
3And Pb
0.82La
0.18TiO
3Ceramic, its component are x=0.2, y=0.18.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 0.5h in deionized water quenching to prepare component be 0.50PbO-0.50B
2O
3, wherein the glass of z=0.50 obtains glass powder with its ball milling 24h again.By m=0.5, n=0.15 adds the organic substance carrier of 20wt% simultaneously with the above ceramic for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, use silk screen print method with above-mentioned mixed slurry, preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode is being arranged, following dry 1 hour in 150 ℃ then, and in 800 ℃ of following sintering film forming, sintering time is 60min, and sintering atmosphere is an air atmosphere, and the thickness for preparing is 60 microns.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is as implementing example 1.In 0～200 ℃ of temperature range, its pyroelectric coefficient is all at 330 μ C/m
2More than the K; Its change in dielectric constant scope is 550～650, and dielectric loss is 0.01～0.05, and thermal capacitance is 1.7 * 10
6J/m
3, calculate its pyroelectricity detectivity figure of merit and all reach in whole temperature range＞8.5 μ Pa
-1/2
Embodiment 4:
Use the Ba of Prepared by Sol Gel Method
0.90Sr
0.10TiO
3And Pb
0.90La
0.10TiO
3Ceramic, its component are x=0.10, y=0.10.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 2h in deionized water quenching to prepare component be 0.20PbO-0.80B
2O
3, wherein the glass of z=0.20 obtains glass powder with its ball milling 12h again.By m=0, n=0.08 adds the organic substance carrier of 20wt% simultaneously with the above ceramic for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, use silk screen print method with above-mentioned mixed slurry, preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode is being arranged, following dry 1 hour in 150 ℃ then, and in 750 ℃ of following sintering film forming, sintering time is 20min, and sintering atmosphere is an air atmosphere, and the thickness for preparing is 55 microns.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is as implementing example 1.In 0～200 ℃ of temperature range, its pyroelectric coefficient is all at 200 μ C/m
2More than the K; Its change in dielectric constant scope is 350～450, and dielectric loss is 0.01～0.03, and thermal capacitance is 1.8 * 10
6J/m
3, calculate its pyroelectricity detectivity figure of merit and all reach in whole temperature range＞3 μ Pa
-1/2
Embodiment 5:
Use the Ba of Prepared by Sol Gel Method
0.70Sr
0.30TiO
3And Pb
0.82La
0.18TiO
3Ceramic, its component are x=0.30, y=0.18.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 1h in deionized water quenching to prepare component be 0.50PbO-0.50B
2O
3, wherein the glass of z=0.50 obtains glass powder with its ball milling 12h again.By m=0.5, n=0.15 adds the organic substance carrier of 20wt% simultaneously with the above ceramic for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, with above-mentioned mixed slurry is the silk screen printing slurry of thick-film material, be coated with preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver-colored hearth electrode, dry then, and in 700 ℃ of following sintering film forming, sintering time is 120min, and sintering atmosphere is an air atmosphere, and thickness is 30 microns.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is as implementing example 1.In 0～200 ℃ of temperature range, its pyroelectric coefficient is all at 300 μ C/m
2More than the K; Its change in dielectric constant scope is 450～550, and dielectric loss is 0.06～0.1, and thermal capacitance is 1.8 * 10
6J/m
3, calculate its pyroelectricity detectivity figure of merit and all reach in whole temperature range＞7 μ Pa
-1-2
Embodiment 6:
Use the Ba of Prepared by Sol Gel Method
0.80Sr
0.20TiO
3And Pb
0.82La
0.18TiO
3Ceramic, its component are x=0.15, y=0.20.Simultaneously with PbO and HBO
3Raw material mixes, behind 850 ℃ of following sintering 2h in deionized water quenching to prepare component be 0.35PbO-0.35B
2O
3, wherein the glass of z=0.35 obtains glass powder with its ball milling 12h again.By m=0.5, n=0.15 adds the organic substance carrier of 20wt% simultaneously with the above pottery for preparing and glass powder, then ball milling 24h mixed mixed slurry.Use screen printing technique, with above-mentioned mixed slurry is the silk screen printing slurry of thick-film material, be coated with preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver-colored hearth electrode, dry then, and in 800 ℃ of following sintering film forming, sintering time is 200min, and sintering atmosphere is an air atmosphere, and thickness is 20 microns.In thick film upper surface deposition one deck silver electrode, porous composite thick film is polarized under electric field then, polarization condition is as implementing example 1.In 0～200 ℃ of temperature range, its pyroelectric coefficient is all at 330 μ C/m
2More than the K; Its change in dielectric constant scope is 750～850, and dielectric loss is 0.01～0.08, and thermal capacitance is 1.8 * 10
6J/m
3, calculate its pyroelectricity detectivity figure of merit and all reach in whole temperature range＞5 μ Pa
-1/2
Porous composite thick film prepared in the above embodiment all has following characteristics:
1, the prepared powder of sol-gel process has crystalline phase integrity degree height, and particle size is at 200nm-400nm, and the characteristics that sintering activity is low are with the counterdiffusion speed of crystalline phase and glassy phase in the reduction sintering process.
2, by control Ba
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3The chemical constituent of two constituent elements and particle size make each component have with other dielectric constant of the order of magnitude and pyroelectric coefficient.
3, the component of control calcining system and glass powder to be realizing the parcel of auxiliary phase to the principal crystalline phase particle, thereby is implemented in the sintering process homogenization that does not contact and suppress two principal crystalline phases between two kinds of principal crystalline phase particles as yet.Control the mass transfer densification process by the control calcining system, make the round densification effect in the sintering process keep appropriate level, thereby form loose structure with certain bore hole size.
The present invention be especial manufacture go out a kind of not only can be convenient to large-area preparation but also be easy to integrated, and the NEW TYPE OF COMPOSITE porous thick film material that in super wide 0～200 ℃ of operating temperature range, all has the high pyroelectricity detectivity figure of merit.On the one hand, by introducing a kind of low-melting glass phase, realize the stable coexistence of each principal crystalline phase in sintering process in the composite material, because the Curie point of two kinds of materials can appear under the different temperatures, thereby the appearance temperature of passing through Curie point in the system suitably designs, can obtain in wider temperature range, to show high pyroelectric effect, effectively avoid the shortcoming of single-phase pyroelectricity material.On the other hand, such two-phase is compounded in the same system, and dielectric constant has good temperature stability and still has than low-dielectric loss in very wide scope, and can be implemented in all has stable and advantages of high pyroelectric coefficient in the very wide temperature range.Moreover, by in thick film, forming an amount of micropore hole, can reduce the thermal capacitance and the conductive coefficient of material, reach dielectric constant, dielectric loss and the not obvious reduction of maintenance pyroelectric coefficient of obvious reduction material simultaneously, thereby realize the purpose of the raising thick film detectivity figure of merit by a relatively large margin, be expected to be applied to better in various highly sensitive, the high-performance Infrared Detectorss.
Claims (6)
1, a kind of porous composite thick film pyroelectricity material, it is characterized in that: aluminium oxide electronic ceramic substrate (1) upper surface is coated with ground floor silver electrode (2), be coated with one deck porous composite thick film material (3) at ground floor silver electrode (2) upper surface, and deposit one deck silver electrode (2) at the upper surface of porous composite thick film material (3).
2, a kind of porous composite thick film pyroelectricity material according to claim 1, it is characterized in that: described thick-film material is with Ba
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3Two kinds of crystalline phases are principal phase, zPbO-(1-z) B
2O
3Glassy phase is the composite material of auxiliary phase; Its composition formula is (1-m) Ba
1-xSr
xTiO
3-mPb
1-yLa
yTiO
3-n[zPbO-(1-z) B
2O
3], 0≤x≤0.30,0.10≤y≤0.20,0.2≤z≤0.80,0≤m≤1,0.08≤n≤0.20 wherein;
In the formula: m is Pb
1-yLa
yTiO
3Molar content in porous composite thick film;
N is zPbO-(1-z) B
2O
3At Pb
1-yLa
yTiO
3Molar content in porous composite thick film;
X is that Sr is at Ba
1-xSr
xTiO
3In molar content;
Y is that La is at Pb
1-yLa
yTiO
3In molar content;
Z is that PbO is at zPbO-(1-z) B
2O
3In molar content.
3, a kind of preparation method of porous composite thick film pyroelectricity material is characterized in that the step of this method is as follows:
(1) uses the Ba that Prepared by Sol Gel Method has 200nm～400nm particle diameter
1-xSr
xTiO
3And Pb
1-yLa
yTiO
3Ceramic, its molar content are 0≤x≤0.30,0.10≤y≤0.20;
(2) with PbO and HBO
3Raw material mixes, and wherein mixing mol ratio is PbO=z, HBO
3=2 (1-z); Behind 750-850 ℃ of following sintering 0.5-2h in deionized water quenching to prepare component be zPbO-(1-z) B
2O
3Glass, its molar content is 0.2≤z≤0.80, again its ball milling 6～24h is obtained glass powder;
(3) ceramic for preparing more than the general is a principal crystalline phase, and glass powder is an auxiliary phase, by formula (1-m) Ba
1-xSr
xTiO
3-mPb
1-yLa
yTiO
3-n[zPbO-(1-z) B
2O
3] carry out the proportioning mixing, wherein 0≤m≤1,0.08≤n≤0.20 adds the organic substance carrier simultaneously, then the mixed mixed slurry that gets of ball milling 12-36h; In mixed slurry, the organic substance carrier accounts for 20～25wt%.
(4) use screen printing technique, with above-mentioned mixed slurry is the silk screen printing slurry of preparation thick-film material, be coated with preparation thick film green compact sample on the aluminium oxide electronic ceramic substrate of silver electrode, dry under 140～200 ℃ of temperature in far infrared drying oven then, and in 700～850 ℃ of following sintering film forming, sintering time is 20min-300min., and sintering atmosphere is an air atmosphere, and the thickness of porous composite thick film is 10～80 microns;
(5) utilize sputter or printing process to prepare one deck silver electrode at the porous composite thick film upper surface that sinters;
(6) porous composite thick film that will have silver electrode polarizes under electric field, and polarization condition is: in temperature is 150-200 ℃ silicone oil, polarize under the 2kV/mm electric field strength earlier; In temperature is 40-60 ℃ silicone oil, polarize under the 2kV/mm electric field strength then.
4, the preparation method of a kind of porous composite thick film pyroelectricity material according to claim 3 is characterized in that: Ba in the porous composite thick film material
1-xSr
xTiO
3The Curie temperature of crystalline phase in x=0.30～0 corresponding to 50～120 ℃, Pb
1-yLa
yTiO
3The Curie temperature of crystalline phase in y=0.20～0.10 corresponding to 130～310 ℃; Two kinds of principal crystalline phases show dielectric constant and the pyroelectric coefficient with same order in system.
5, the preparation method of a kind of porous composite thick film pyroelectricity material according to claim 3 is characterized in that: described organic substance carrier is the liquid that contains ethyl cellulose, terpinol and coating material.
6, the preparation method of a kind of porous composite thick film pyroelectricity material according to claim 3 is characterized in that: glass powder is converted into auxiliary phase and is wrapped in principal crystalline phase particle top layer after sintering process; The principal crystalline phase particle is 200～500nm by the formed particle size in auxiliary phase parcel back; And in porous composite thick film, evenly have the micropore hole between the formed particle in parcel back, wherein the micropore hole is of a size of 20nm～200nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372803C (en) * | 2006-10-08 | 2008-03-05 | 浙江大学 | Seepage flow type silver/strontium barium titanate/nonex composite material and manufacture method |
| CN101838112A (en) * | 2010-04-30 | 2010-09-22 | 重庆大学 | Three-order nonlinear optical telluro-composite film and preparation method thereof |
| CN102842530A (en) * | 2012-08-15 | 2012-12-26 | 电子科技大学 | Thick film material electronic component and preparation method thereof |
| CN110419127A (en) * | 2017-03-16 | 2019-11-05 | 株式会社村田制作所 | Lithium ion secondary battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300807A (en) * | 1992-01-22 | 1994-04-05 | The United States Of America As Represented By The Secretary Of The Army | Thin film detector and method of manufacture |
| WO1997021848A1 (en) * | 1995-12-14 | 1997-06-19 | Imperial College Of Science, Technology & Medicine | Film or coating deposition and powder formation |
-
2005
- 2005-12-05 CN CNB200510061826XA patent/CN100382350C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100372803C (en) * | 2006-10-08 | 2008-03-05 | 浙江大学 | Seepage flow type silver/strontium barium titanate/nonex composite material and manufacture method |
| CN101838112A (en) * | 2010-04-30 | 2010-09-22 | 重庆大学 | Three-order nonlinear optical telluro-composite film and preparation method thereof |
| CN101838112B (en) * | 2010-04-30 | 2012-07-25 | 重庆大学 | Three-order nonlinear optical telluro-composite film and preparation method thereof |
| CN102842530A (en) * | 2012-08-15 | 2012-12-26 | 电子科技大学 | Thick film material electronic component and preparation method thereof |
| CN102842530B (en) * | 2012-08-15 | 2014-11-19 | 电子科技大学 | Thick film material electronic component and preparation method thereof |
| CN110419127A (en) * | 2017-03-16 | 2019-11-05 | 株式会社村田制作所 | Lithium ion secondary battery |
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