CN1304637C - Process for preparing functional gradient film of lead zirconate titanate ceramics - Google Patents
Process for preparing functional gradient film of lead zirconate titanate ceramics Download PDFInfo
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- CN1304637C CN1304637C CNB011267593A CN01126759A CN1304637C CN 1304637 C CN1304637 C CN 1304637C CN B011267593 A CNB011267593 A CN B011267593A CN 01126759 A CN01126759 A CN 01126759A CN 1304637 C CN1304637 C CN 1304637C
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- 229910052451 lead zirconate titanate Inorganic materials 0.000 title abstract description 7
- 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 title abstract description 3
- 239000000919 ceramic Substances 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- AMVVEDHCBDQBJL-UHFFFAOYSA-N [Ca][Zr] Chemical compound [Ca][Zr] AMVVEDHCBDQBJL-UHFFFAOYSA-N 0.000 claims 1
- 230000005616 pyroelectricity Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 230000005621 ferroelectricity Effects 0.000 abstract description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 4
- 229910020698 PbZrO3 Inorganic materials 0.000 abstract 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 abstract 1
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 229940046892 lead acetate Drugs 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 33
- 239000010409 thin film Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- -1 zirconium iso-propoxide alkoxide Chemical group 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a method for preparing functional gradient films of lead zirconate titanate, which belongs to the field of functional films. The present invention is characterized in that precursor solutions use trihydrated lead acetate, zirconium isopropoxide (zirconium nitrate or zirconium acetate) and butyl titanate as raw materials; ethylene glycol monomethyl ether is used as solvents; the PZT(x) precursor solutions are prepared according to the proportion of Pb(Zr(1-x)Tix)O3 (x is larger than or equal to zero and less than or equal to one), and x intervals are from 0.05 to 0.10. PZT functional gradient films with the gradient distribution of Zr/Ti ingredients are prepared. Gradient layers can be three layers or multiple layers. The present invention can be based on PbZrO3 by changing the gradient of the Zr/Ti ingredients and changing the gradient of the Zr/Ti ingredients, or the present invention is based on PZT which deviates PbZrO3 and PbTiO3 by changing the gradient of the Zr/Ti ingredients. The functional gradient ferroelectric films are more compact than pure PZT films and have the characteristics of ferroelectricity, dielectric and pyroelectricity. The present invention is one of ideal functional gradient materials for preparing non-refrigerating infrared sensors.
Description
Technical field
The present invention relates to the preparation method of the function gradient film of a kind of Pb-based lanthanumdoped zirconate titanates (PZT) pyroelectric ceramics, more precisely, relate to the preparation method of a kind of non-refrigerating infrared sensor with the PZT pyroelectric function gradient film.Belong to function ceramics film field.
Background technology
Pb-based lanthanumdoped zirconate titanates (PZT) film, have effects such as good dielectric, piezoelectricity, ferroelectric, pyroelectricity, in microelectronic, has great application prospect, be one of ideal material of microelectromechanical systems (MEMS), can be used for making large value capacitor, non-volatility ferroelectric storer, piezoelectric actuator, surface acoustic wave device, infrared eye etc.The method for preparing the PZT ferroelectric membranc has a lot, as sputtering method, and the metallorganics precipitator method (MOD), sol-gel method etc., wherein sol-gel method has that cost is low, treatment temp is low, be easy to the film forming advantage of big area, thereby becomes topmost method.Use the alkoxide solution of metallic lead, zirconium and titanium in the world; utilize the MOD technology; prepare the PZT gradient film of Zr/Ti ratio from 55/45 to 75/25, be characterized in all using metal alkoxide, thereby the cost height; the alkoxide of domestic at present still unleaded and zirconium; once with the plumbous alkoxide that replaces lead of acetate trihydrate, utilize easy sol-gel method craft, do not need to distill the water configuration precursor liquid that decrystallizes; preparation PZT ferroelectric membranc, and obtained patent protection.We have developed a kind of method for preparing pyroelectricity PZT gradient function film on this basis of previous patent, and difference mainly is the gradient-structure of film, secondly are to replace the zirconium iso-propoxide alkoxide with acetic acid zirconium or zirconium nitrate, further reduce cost.The PZT gradient film is finer and close than the film of pure single component, and specific inductivity height, ferroelectric properties are good, the pyroelectric property excellence.
Summary of the invention
The object of the present invention is to provide the preparation method, particularly gradient-structure of a kind of preparation Pb-based lanthanumdoped zirconate titanates (PZT) function gradient film to comprise the selection of preparation, particularly gradient-structure of precursor liquid of the molconcentration of different titaniums.Do not need rectifying equally, need not add water, need not add stablizer, utilize three crystal water in the plumbic acetate, come the control hydrolysis degree, key is earlier the plumbic acetate that contains 3 crystal water to be dissolved in fully dissolving in the ethylene glycol monomethyl ether, add corresponding zirconium, titanium solution again, whole precursor liquid process for preparation only needs 1-2 hour, the precursor liquid good stability, resting period is long, as deposits that to make the film effect again after 365 days constant.PZT function gradient film with this precursor liquid preparation is functional.The objective of the invention is to implement by following gradient-structure and solution process for preparation:
1. the plumbic acetate that at first will contain three crystal water is dissolved in the ethylene glycol monomethyl ether, and control is heated to 70 ℃, stirs 30 minutes, obtains clarifying plumbic acetate solution.Add zirconium iso-propoxide (or zirconium nitrate, acetic acid zirconium be dissolved in Glacial acetic acid) and butyl (tetra) titanate then successively, lead, zirconium, titanium three molconcentration are than being Pb: Zr: Ti=1.05-1.10: 1-X: X, (0≤X≤1).The X spacing is 0.05-0.10.Solution is heated to 70 ℃, stirs 60 minutes, and the spent glycol methyl ether is regulated concentration to the 0.2-0.3 mol, and the preparation that obtains clear is the required precursor liquid of pzt thin film of Gradient distribution with the Zr/Ti composition.
Preparation PZT gradient film.With above-mentioned concentration is that the precursor liquid of 0.2 mol is removed impurity after filtration, and whirl coating film forming legal system film is selected Pt/Ti/SiO
2/ Si is a substrate.The pzt thin film gradient-structure serves as a mark with the mol content percentage ratio of Ti, can be divided into upwards gradient composition and gradient composition downwards, with X spacing 0.1 is example, and upwards gradient composition is PZT0, PZT10, PZT20, PZT30, PZT40, PZT50, gradient composition is respectively PZT50, PZT40 downwards, PZT30, PZT20, PZT10, PZT0.The whirl coating speed control is at 3000-4000 rev/min, 30 seconds time, every kind of precursor liquid whirl coating 1 time or 2 times, the number of plies can be 3 layers or multilayer, be placed on 300 ℃-450 ℃ the hot plate pre-treatment then 10 minutes, through the film forming of repeatedly film forming-pre-treatment-again, obtain certain thickness gradient PZT film, again through 550 ℃-650 ℃, anneal is 10 minutes under oxygen atmosphere, 100 ℃/second of temperature rise rates, it is perfect to obtain crystallization, the PZT gradient film of preferred orientation.Film thickness 150-350nm, every layer thickness depends on precursor liquid concentration, whirl coating speed and time.
A kind of technology for preparing the PZT gradient film provided by the invention.Compare with pure pzt thin film, the gradient ferroelectric membranc is finer and close, has excellent pyroelectricity characteristic.The method that adopts is compared and had tangible advantage at present: do not need rectifying, whole process only needs 1-2 hour, and the precursor liquid resting period is long, and good stability is at room temperature deposited after 365 days and made film, and performance is constant.This kind functionally gradient iron spot film, than the pzt thin film densification, have good ferroelectric, dielectric and pyroelectricity characteristic, be one of ideal functionality gradient material of preparation non-refrigerating infrared sensor.
Description of drawings
Fig. 1 is two kinds of structure iron of the PZT of the gradient up and down ferroelectric membranc of method preparation provided by the invention, pre-sintering temperature is at 350 ℃, obviously obvious in (111) face preferred orientation feature, and Auger spectroscopy analysis (AES) spectrum that Fig. 2 distributes for this component, X-coordinate is represented the time, unit second, ordinate zou is represented the shared percentage ratio of atom.Fig. 3 is the ferroelectric hysteresis loop of this component, and X-coordinate is represented voltage, unit volt (V), and ordinate zou is represented polarizability, the μ C/cm of unit
2It is the Au electrode with vacuum evaporation method sedimentation diameter 0.2mm on the gradient pzt thin film, measures under the sinusoidal signal of 1kHz with improved Sawyer-Tower circuit tester, shows among the figure that its Offset that polarizes is up to 42 μ C/cm
2Fig. 4 is the pyroelectric property of gradient film upwards, and X-coordinate is represented temperature, unit centigradetemperature ℃, and ordinate zou is represented pyroelectric coefficient, the μ C/m of unit
2K.It is the Cr/Au electrode with vacuum evaporation method sedimentation diameter 0.8mm on the gradient pzt thin film, measures with dynamic method, shows among the figure that 20-80 ℃ of temperature range, its pyroelectric coefficient is up to 400 μ C/m
2K.
Embodiment
Further illustrate substantive distinguishing features of the present invention and obvious improvement below by six embodiment, but the present invention only is confined to the described embodiment of described embodiment by no means.
Concentration is that metal ion molconcentration is than being Pb: Zr: Ti=1.10: 1-X: X (x=0,0.10,0.20,0.30,0.40,0.50) in the precursor liquid of 0.2 mol, and wherein Pb is excessive 0.1 mole, mainly is because plumbous volatilization in annealing process.3600 rev/mins of whirl coating speed, 30 seconds time, 320 ℃ of pretreatment temperatures, 10 minutes time, repeat six times, the first layer is PZT50, and the second layer is PZT40, the 3rd layer is PZT30, the 4th layer is PZT20, and layer 5 is PZT10, and layer 6 is PZT0, this is the gradient film of " downwards ", obtaining thickness is the film of 230nm, every kind of precursor liquid whirl coating once, every layer thickness is basic identical, again through 600 ℃, anneal is 10 minutes under oxygen atmosphere, and 100 ℃ of temperature rise rates obtain crystallization and improve " downwards " the gradient pzt thin film with (111) orientation, the Au electrode of evaporation Φ 0.2mm on film is measured its ferroelectric properties again.Fig. 1-the 4th, the structure iron of pyroelectricity gradient pzt thin film, AES spectrum, ferroelectricity and pyroelectricity characteristic.
Embodiment 2
Metal ion molconcentration is than being Pb: Zr: Ti=1.10: 1-X: X (x=0,0.10,0.20 in the precursor liquid, 0.30,0.40,0.50), 3000 rev/mins of three first layers whirl coating speed, the three layers of whirl coating speed in back are 3800 rev/mins, and three first layers thickness is different with back threeply degree, 30 seconds time, 350 ℃ of pretreatment temperatures, 10 minutes time repeated six times, and the first layer is PZT0, the second layer is PZT10, the 3rd layer is PZT20, and the 4th layer is PZT30, and layer 5 is PZT40, layer 6 is PZT50, this is the gradient film of " making progress ", and through 600 ℃, rapid anneal is 10 minutes under oxygen atmosphere, 100 ℃ of temperature rise rates, obtaining thickness is 200nm, and the upwards gradient pzt thin film of random orientation is improved in crystallization, and all the other are with embodiment 1.
Embodiment 3
Metal ion molconcentration is than being Pb: Zr: Ti=1.10: 1-X: X (x=0.60,0.70,0.80 in the precursor liquid, 0.90,100), precursor liquid concentration is 0.3 mol, whirl coating speed 3600 is changeed minute, 30 seconds time, 350 ℃ of pretreatment temperatures, 10 minutes time repeated five times, and the first layer is PZT100, the second layer is PZT90, and the 3rd layer is PZT80, and the 4th layer is PZT70, layer 5 is PZT60,, this is the gradient film of " making progress ".Through 550 ℃, anneal is 10 minutes under oxygen atmosphere, 100 ℃ of temperature rise rates, and obtaining thickness is " making progress " gradient pzt thin film that 350nm, crystallization are perfect, have (100) orientation, all the other are with embodiment 2.
Embodiment 4
Metal ion molconcentration is than being Pb: Zr: Ti=1.10: 1-X: X (x=0.60,0.70,0.80 in the precursor liquid, 0.90,100), precursor liquid concentration is 0.3 mol, whirl coating speed 3600 is changeed minute, 30 seconds time, 350 ℃ of pretreatment temperatures, 10 minutes time repeated five times, and the first layer is PZT60, the second layer is PZT70, the 3rd layer is PZT80, and the 4th layer is PZT90, and layer 5 is PZT100, this is the gradient film of " downwards ", obtaining thickness is the film of 300nm, and through 600 ℃, rapid anneal is 10 minutes under oxygen atmosphere, 100 ℃ of temperature rise rates, it is perfect to obtain crystallization, is " downwards " gradient pzt thin film of random orientation, and all the other are with embodiment 1.
Embodiment 5
Downward gradient pzt thin film, Pb: Zr: Ti=1.05: 1-X: X, x=0.10,0.15 and 0.20, that is the first layer is PZT10, and the second layer is PZT15, and the 3rd layer is PZT20, and all the other are with embodiment 2.
Embodiment 6
Gradient pzt thin film upwards, Pb: Zr: Ti=1.10: 1-X: X, x=0.25,0.30,0.35 0.40,0.45 five layer of gradient the first layer is PZT25, the second layer is PZT30, the 3rd layer is PZT35, and the 4th layer is PZT40, and layer 5 is PZT45, and all the other are with embodiment 1.
Claims (1)
1. a method for preparing the Pb-based lanthanumdoped zirconate titanates function gradient film comprises the preparation of precursor liquid, the selection of film-forming process, it is characterized in that:
(1) plumbic acetate that will contain three crystal water is dissolved in the ethylene glycol monomethyl ether, add zirconium nitrate, acetic acid zirconium then and be dissolved in the solution and the butyl (tetra) titanate of Glacial acetic acid, lead, zirconium, titanium three molconcentration are than being Pb: Zr: Ti=1.05-1.10: 1-X: X, 0≤X≤1, the X spacing is 0.05-0.10, regulate concentration to the 0.2-0.3 mol, being mixed with the Zr/Ti composition is the required precursor liquid of zirconium calcium titanate film of Gradient distribution;
(2) precursor liquid is removed impurity after filtration, and whirl coating film forming legal system film is selected Pt/Ti/SiO
2/ Si is a substrate, the whirl coating speed control is at 3000-4000 rev/min, 30 seconds time, is placed on 300 ℃-450 ℃ the hot plate pre-treatment then 10 minutes, every kind of precursor liquid whirl coating 1 time or 2 times, through the film forming of repeatedly film forming-pre-treatment-again, obtain certain thickness function gradient film up or down, again through 550 ℃-650 ℃, rapid anneal is 10 minutes under the oxygen atmosphere, temperature rise rate is 100 ℃/s, and it is perfect to obtain crystallization, the PZT function gradient film of random orientation or preferred orientation; The gradient number of plies can be 3 layers or multilayer.
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| CN1263070A (en) * | 2000-02-16 | 2000-08-16 | 中国科学院上海硅酸盐研究所 | Simple and effective preparation method of lead zirconate titanate film |
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| CN1263070A (en) * | 2000-02-16 | 2000-08-16 | 中国科学院上海硅酸盐研究所 | Simple and effective preparation method of lead zirconate titanate film |
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