WO1990013149A1 - SOL GEL PROCESS FOR PREPARING Pb(Zr,Ti)O3 THIN FILMS - Google Patents
SOL GEL PROCESS FOR PREPARING Pb(Zr,Ti)O3 THIN FILMS Download PDFInfo
- Publication number
- WO1990013149A1 WO1990013149A1 PCT/CA1990/000123 CA9000123W WO9013149A1 WO 1990013149 A1 WO1990013149 A1 WO 1990013149A1 CA 9000123 W CA9000123 W CA 9000123W WO 9013149 A1 WO9013149 A1 WO 9013149A1
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- WIPO (PCT)
- Prior art keywords
- film
- substrate
- oxide
- solution
- firing
- Prior art date
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- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 238000003980 solgel method Methods 0.000 title abstract description 15
- 229910020294 Pb(Zr,Ti)O3 Inorganic materials 0.000 title abstract 2
- 239000010408 film Substances 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 238000010304 firing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 31
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 15
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229940046892 lead acetate Drugs 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 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 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- 239000005350 fused silica glass Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910000809 Alumel Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- -1 Magnesium tantalate Yttrium Barium Copper Oxides Chemical class 0.000 claims description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 3
- 238000001771 vacuum deposition Methods 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 241000282337 Nasua nasua Species 0.000 claims 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 6
- 239000011550 stock solution Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 4
- 239000002738 chelating agent Substances 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229960000583 acetic acid Drugs 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 101100270435 Mus musculus Arhgef12 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003781 PbTiO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical class [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- CJXLIMFTIKVMQN-UHFFFAOYSA-N dimagnesium;oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mg+2].[Mg+2].[Ta+5].[Ta+5] CJXLIMFTIKVMQN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
- H10N30/706—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings characterised by the underlying bases, e.g. substrates
- H10N30/708—Intermediate layers, e.g. barrier, adhesion or growth control buffer layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
- H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
- H10N30/077—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition
- H10N30/078—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by liquid phase deposition by sol-gel deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
Definitions
- This invention relates to the production of thin-film piezoelectric materials. More particularly this invention relates to a sol-gel process for producing thin films of ferroelectric or piezoelectric materials such as Pb(Zr,Ti)0 3 , known as PZT, or lanthanum doped PZT, known as PLZT, or PZT doped with elements such as niobium and the product thereof. It also relates to a sol gel process for producing crack free thin films of other complex oxides such as zirconia, calcium apatite, and barium titanate, among others.
- the ferroelectric effect is the property of certain crystalline dielectric materials to retain polarization following their polarization.
- the piezoelectric effect is the property of certain crystalline dielectric materials, when polarized, to generate an electric field or potential of one polarity when a compressive force is applied and the reverse polarity when a tensile force is applied. Conversely, a piezoelectric material will tend to compress if an electric field of one polarity is applied and to expand if an electric field of the opposite polarity is applied.
- Undoped PZT is an opaque ferroelectric cerami and therefore its nonlinear optical effects, if any, canno be measured.
- the addition of lanthanum to form La doped PZT, or PLZT causes the material to becom transparent and to show large electro-optic effects.
- PZT has a large pyro electric response, large electro-mechanical coupling coeffi cient high dielectric constant and a large spontaneou polarization, all of which are useful properties for incor poration-into infra red detectors, surface acoustic wav devices, ferroelectric nonvolatile semiconductor memories, and devices requiring transtarent high permittivity layer such as electroluminescent displays.
- PZT, or PLZT (lanthanu doped) thin films have been developed over the past decade, primarily using techniques such as flash and electron bea evaporation, rf sputtering, ion beam deposition an epitaxial growth by rf sputtering.
- Such technique are generally difficult to control, are relatively tim consuming and require expensive apparatus.
- Chemical sol ge processing of PZT of PLZT thin films has also bee suggested.
- Sol gel processing offers significant advantage over vacuum deposition techniques such as easier compositio control and film homogeneity, easier fabrication of larg area thin films, low cost and short processing cycles.
- sol gel processing is not without its difficulties, particularly with respect to fabricating relatively thic crack free PZT thin films.
- the thickness of PZT or PLZ thin f ilm strongly influences f ilm properties such as dielectric constant, remanent polarization and coercive field.
- “complex oxide” includes:
- an object of the present invention to overcome the deficiencies of the prior art and provide an improved sol gel processing method for making thin film piezoelectric materials which are substantially crack free, and which have improved physical properties.
- Another object of the invention is to provide PZT thin films having a piezoelectric coupling coefficient of at least 1%. It is yet another object of the invention to provide crack free complex oxide thin films by an improved sol gel process. 4 Statement of Invention
- a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof to said solution;
- a composite comprising a substrate having deposite thereon a substantially crack-free ferroelectric poly crystalline lead zirconate titanate thin film having piezoelectric coupling coefficient of at least 1%.
- a metho for preparing a composite comprising a substrate havin deposited thereon a crack free complex oxide thin film, comprising:
- Fig. 1 is a block flow diagram illustrating sol gel processing of PZT films. Detailed Description of Preferred Embodiments
- Sol gel processing has been described previously (see, for example, Sol-Gel Processing of PbTi0 3 , PbZr0 3 , PZT and PLZT Thin Films, Budd et al Brit. Cer. Proc. 3_6 (1985) pp 107-121) and depends upon the fact that the components of a complex solution can remain mixed during firing if a gel, a form of polymerised liquid, can be formed.
- the standard procedure normally includes the steps of (a) forming a stock solution (b) coating the solution onto a substrate either by spin or dip coating (c) firing the wet film or coating to an inorganic form, (d) annealing at high temperature to obtain the required structure and (e) polarizing the film to induce piezoelectric activity.
- a new stable precursor solution using a chelating agent has been developed and an additive which controls and improves the firing cycle for film fabrication and which improves the surface smoothness of the final film and substantially eliminates macro cracking of the final surface has also been developed.
- Figure 1 illustrates a preferred process for making the improved PZT and PZLT films of the present invention.
- the choice of the precursor compounds and the solvents therefor is important to success.
- the compounds should have high metal content and high solubility in the selected solvent. They should thermally decompose without evaporating and be chemically compatible with each other.
- Preferred compounds having the aforesaid properties include: Lead acetate, Zirconium propoxide and Titanium propoxide.
- the solven must have an appropriate boiling point and suitabl viscosity and surface tension properties.
- Preferre solvents include water and propanol.
- the chelating agent which is required to prevent hydrolysis of the properties i preferably glacial acetic acid although other acids can b used.
- a firing additive selected from glycerol, ethylene glycol,
- 2 0 is '-stdded first because it reacts with the acetic acid t fort ⁇ a non-hydrolysable solution which in turn protects th titanium isopropoxide from hydrolysis and condensation whe it is added. (inversely, if titanium isopropoxide is adde fiist it reacts with the acetic acid to form mono o
- the zirconium-titanium bearin mixture is agitated, preferably in an ultra sonic cleanin
- the firing additive which controls the viscosity and the decomposition temperature is selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol or mixtures thereof, and can then be added to the stock solution.
- Ethylene glycol or glycerol is preferably added in the proportion of 1 ml to 10 g of lead acetate in the solution depending on the thickness of film required.
- the viscosity and surface tension of the solution can then be adjusted by adding water, propanol or mixtures thereof. Thinner films result from lower viscosity solutions and propanol reduces surface tension thereby improving wettability of the substrate.
- PZT may be deposited on numerous substrates such as silica wafers, mica, fused quartz, borosilicate glass, Corning 7509 glass coated with stannic oxide based trans ⁇ parent conducting coating, and stainless steel, gold or platinum plates. Crack free surface coatings are most easily applied to conducting glass substrates but in the case of fused quartz it is preferable to first apply a special surface treatment as described in more detail below. Substrates must be thoroughly cleaned before depositing the coating, preferably by boiling in water with a detergent, rinsing in distilled water followed by ultra sound to remove organic contaminants and vapour degreasing in methanol. After cleaning, the precursor films, such as those described in Table 1, can be deposited on the substrate by spin coating, dip coating or by painting.
- the spin coating technique is preferred for flat substrate surfaces as the thickness of the film may be controlled by the speed of rotation of the spinner and the concentration and viscosity of the solution.
- a spinner such as a "Headway Research Incorporated photoresist spinner" operated at 8500 rpm for 20 seconds is particularly suitable. More complex shapes cannot readily be prepared by spin coating and recourse may be had to dip coating or painting. In this case it is usually necessary to dilute the above stock solution with propanol or a mixture of propanol and water.
- the film thickness can be controlled by the amount of propanol and water or the ratio of propanol to water and by controlling the speed of pulling the dip coated article.
- an organo-metallic film After an organo-metallic film has been deposited and dried it must be pyrolysed to remove the organics and induce the solid state reaction which produces the PZT. An increase in the density of the film and sufficient time for a solid state diffusion reaction to take place are both required.
- the normal approach to avoid cracking is to pyrolyse the film rapidly by transferring the substrate to a surface which is well above the pyrolysing temperature. According to the present invention, the pyrolysis may be better controlled if the time or temperature range over which the film is in a viscous liquid state is extended.
- a firing additive selected from ethylene glycol, glycerol and tetra ethylene glycol
- a firing additive selected from ethylene glycol, glycerol and tetra ethylene glycol
- the resulting films are crack-free, very transparent and have improved surface smoothness.
- Glycerol and tetra ethylene glycol are preferred additives.
- the wet film may be fired by raising the temperature gradually which is particularly advantageous especially when coating metallic substrates such as stainless steel or alumel.
- a thin intermediate or buffer layer may be deposited onto the substrate and fired on prior to the deposition of PZT.
- the thickness of the buffer layer depends on the substrate and film composition but 100 A is usually sufficient.
- Alumina A1 2 0 3
- Alumina A1 2 0 3
- a typical mixture for this purpose is shown in Table 1 (b) , above.
- conducting coatings indium tin oxide or stannic oxide conducting coatings may be used.
- Other conducting coatings include Al, Au, Cr, Ni and Co which may be produced by known vacuum deposition or chemical techniques.
- the firing schedule which pyrolyses the organo-metallic compounds to an inorganic film is key to the preparation of crack free films having the desired crystal structure, grain size, transparency and surface roughness.
- the solvents evaporate with a consequent large change in volume and the generation of internal stress at temperatures between room temperature and about 250°C.
- the lead acetate dehydrates, melts and decomposes.
- the dried film becomes "wet” again and the organic compounds begin to decompose.
- the internal stress is relaxed and the volume change of the film continues.
- the organic film changes to a fine mixture of oxides of lead, titanium, zirconium and free carbon.
- the free carbon oxidizes and the mixture of oxides transforms to a transparent amorphous PZT film.
- As fired films are basically amorphous and need annealing at temperatures up to about 600°C for up to six hours in order to cause the amorphous structure to change to a perovskite structure.
- the crystal structure of the film is generally that of randomly oriented crystallites, although some evidence of at least some orientation exists.
- it is necessar to electrically pole the films by application of an electric field of between 2 and 3 KV/mm when the films are held at temperature of about 175°C.
- Films produced by the aforesai processing steps have been shown to have properties superior to those obtainable by other processing methods.
- the best piezoelectric coupling coefficient heretofore achieved, in zinc oxide is of the order of 0.7%.
- films according to the present invention have a piezoelectric coupling coefficient of at least 1.0%.
- PZT thin films have numerous applications including use in electro-optic displays and electroluminescent devices. They are used in electronic applications such as ferro ⁇ electric gate insulators or capacitors in non-volatile memories.
- a third field of use includes high frequency ultrasonic transducers for non-destructive evaluation and medical and biological purposes, while a fourth field includes fibre optic sensors and devices.
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Abstract
A method for preparing crack free transparent ferroelectric polycrystalline Pb(Zr,Ti)O3 thin films (PZT or PLZT) and other complex oxide thin films by a sol-gel process and the product thereof is described. A stock solution containing the organic precursors to the metal oxides together with a chelating agent may be spin coated onto a flat substrate or dip coated or painted onto a curved substrate or even metallic wire, and subsequently dried and fired. The addition of firing additives to the solution prevents cracking of the film. Alternatively an intermediate layer of Al2O3 or other oxide may be deposited on the substrate before deposition of the PZT or other oxide materials.
Description
SOL GEL PROCESS FOR PREPARING Pb(Zr,Ti)03 THIN FILMS
Field of Invention
This invention relates to the production of thin-film piezoelectric materials. More particularly this invention relates to a sol-gel process for producing thin films of ferroelectric or piezoelectric materials such as Pb(Zr,Ti)03, known as PZT, or lanthanum doped PZT, known as PLZT, or PZT doped with elements such as niobium and the product thereof. It also relates to a sol gel process for producing crack free thin films of other complex oxides such as zirconia, calcium apatite, and barium titanate, among others.
Background of Invention The ferroelectric effect is the property of certain crystalline dielectric materials to retain polarization following their polarization. The piezoelectric effect is the property of certain crystalline dielectric materials, when polarized, to generate an electric field or potential of one polarity when a compressive force is applied and the reverse polarity when a tensile force is applied. Conversely, a piezoelectric material will tend to compress if an electric field of one polarity is applied and to expand if an electric field of the opposite polarity is applied.
Thin film materials which are transparent and show good optically non linear properties are in great demand for integrated optics among other uses for such thin f ilm
materials. Undoped PZT is an opaque ferroelectric cerami and therefore its nonlinear optical effects, if any, canno be measured. However, the addition of lanthanum to form La doped PZT, or PLZT, causes the material to becom transparent and to show large electro-optic effects. I addition to electro-optic properties, PZT has a large pyro electric response, large electro-mechanical coupling coeffi cient high dielectric constant and a large spontaneou polarization, all of which are useful properties for incor poration-into infra red detectors, surface acoustic wav devices, ferroelectric nonvolatile semiconductor memories, and devices requiring transtarent high permittivity layer such as electroluminescent displays.
Several methods for producing PZT, or PLZT (lanthanu doped) thin films have been developed over the past decade, primarily using techniques such as flash and electron bea evaporation, rf sputtering, ion beam deposition an epitaxial growth by rf sputtering. However such technique are generally difficult to control, are relatively tim consuming and require expensive apparatus. Chemical sol ge processing of PZT of PLZT thin films has also bee suggested. Sol gel processing offers significant advantage over vacuum deposition techniques such as easier compositio control and film homogeneity, easier fabrication of larg area thin films, low cost and short processing cycles. However, sol gel processing is not without its difficulties, particularly with respect to fabricating relatively thic crack free PZT thin films. The thickness of PZT or PLZ
thin f ilm strongly influences f ilm properties such as dielectric constant, remanent polarization and coercive field.
While the present invention will be described with particular reference to the production of PZT and PLZT thin films, the sol-gel processing method is equally applicable to other complex oxide thin films. As used herein the term
"complex oxide" includes:
Alumina • Zirconia
Calcium titanate
Calcium apatite
Lithium niobate
Barium titanate
Tantalum zirconate
Magnesium tantalate
Yttrium Barium Copper Oxides
Yttrium Oxide
Barium Calcium Thalium Copper Oxide
Object of Invention
It is, therefore, an object of the present invention to overcome the deficiencies of the prior art and provide an improved sol gel processing method for making thin film piezoelectric materials which are substantially crack free, and which have improved physical properties.
Another object of the invention is to provide PZT thin films having a piezoelectric coupling coefficient of at least 1%. It is yet another object of the invention to provide crack free complex oxide thin films by an improved sol gel process.
4 Statement of Invention
By one aspect of this invention there is provided a method for preparing a composite of a substrate havin deposited thereon a crack-free ferroelectri polycrystalline lead zirconate titanate thin film, comprising
(a) dissolving lead acetate in acetic acid, adding thereto zirconium propoxide followed by titanium isopropoxide in relative proportions to produce a selected ratio of metals, and agitating
10 until all solids are in solution;
(b) adding a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof, to said solution;
15
(c) adjusting viscosity of said solution;
(d) coating said substrate with said solution so as to form a wet film thereon;
(e) firing said coated substrate at a
20 temperature in the range 300°C-550°C so as to pyrolyse said film;
(f) annealing said pyrolysed film at a temperature up to about 600 °C for sufficient time to produce a perovskite structure in said film;
25 and
(g) electrically poling said film so as to produce piezoelectric properties therein.
By another aspect of this invention there is provided a method for preparing a composite of a substrate having deposited thereon a crack free ferroelectric polycrystalline lead zirconate titanate thin film, comprising:
(a) depositing an oxide film on said substrate;
(b) dissolving lead acetate in acetic acid, adding thereto zirconium propoxide followed by titanium isopropoxide in relative proportions to produce a selected ratio of metals, and agitating until all solids are in solution;
(c) adding a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof to said solution;
(d) adjusting viscosity of said solution;
(e) coating said oxide coated substrate with said solution so as to form a wet film thereon;
(fj firing said coated substrate at a temperature in the range 300°C-550°C so as to pyrolize said film.
(g) annealing said pyrolysed film at a temperature up to about 600°C for sufficient time to produce a perovskite structure in said film; and
(h) electrically poling said film so as to produce piezoelectric properties therein.
6 By yet another aspect of this invention there i provided a composite comprising a substrate having deposite thereon a substantially crack-free ferroelectric poly crystalline lead zirconate titanate thin film having piezoelectric coupling coefficient of at least 1%. By further aspect of this invention there is provided a metho for preparing a composite comprising a substrate havin deposited thereon a crack free complex oxide thin film, comprising:
(a) preparing a solution containing precursors for said complex oxides;
(b) adding to said solution a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof in relative proportions and amounts so as to provide a solution having a selected viscosity; _ c) coating said substrate with said solution so as to form a wet film thereon; and
(d) firing said coated substrate at a temperature in the range 300°C-550°C so as to pyrolyse said film.
Brief Description of Drawings
Fig. 1 is a block flow diagram illustrating sol gel processing of PZT films.
Detailed Description of Preferred Embodiments
Sol gel processing has been described previously (see, for example, Sol-Gel Processing of PbTi03, PbZr03, PZT and PLZT Thin Films, Budd et al Brit. Cer. Proc. 3_6 (1985) pp 107-121) and depends upon the fact that the components of a complex solution can remain mixed during firing if a gel, a form of polymerised liquid, can be formed. The standard procedure normally includes the steps of (a) forming a stock solution (b) coating the solution onto a substrate either by spin or dip coating (c) firing the wet film or coating to an inorganic form, (d) annealing at high temperature to obtain the required structure and (e) polarizing the film to induce piezoelectric activity. It has now been discovered that the basic process can be improved in ways which are vital to industrial application and which permit the use of a wide range of compositions. Specifically a new stable precursor solution using a chelating agent has been developed and an additive which controls and improves the firing cycle for film fabrication and which improves the surface smoothness of the final film and substantially eliminates macro cracking of the final surface has also been developed. Figure 1 illustrates a preferred process for making the improved PZT and PZLT films of the present invention. The choice of the precursor compounds and the solvents therefor is important to success. The compounds should have high metal content and high solubility in the selected solvent. They should thermally decompose without evaporating and be chemically compatible with each other. Preferred compounds
having the aforesaid properties include: Lead acetate, Zirconium propoxide and Titanium propoxide. The solven must have an appropriate boiling point and suitabl viscosity and surface tension properties. Preferre solvents include water and propanol. The chelating agent, which is required to prevent hydrolysis of the properties i preferably glacial acetic acid although other acids can b used. In order to substantially eliminate macroscopi cracking and to improve the surface smoothness of the film, a firing additive selected from glycerol, ethylene glycol,
10 tetra ethylene glycol, polyethylene glycol and mixture thereof is preferably incorporated.
*_
Preparation of Solutions for PZT films
Lead acetate is dissolved in heated acetic acid in the
15 proportion of 2 g lead acetate to 1 ml acetic acid an heated to 105°C to remove water. The dehydrated solutio should be cooled below 80°C before sequentially adding th required quantities of zirconium propoxide and titaniu isopiropoxide. It is essential that the zirconium propoxid
20 is '-stdded first because it reacts with the acetic acid t fortα a non-hydrolysable solution which in turn protects th titanium isopropoxide from hydrolysis and condensation whe it is added. (inversely, if titanium isopropoxide is adde fiist it reacts with the acetic acid to form mono o
25 diacetylates and condensation occurs with the formation o polytitanyl aσetylates. The zirconium-titanium bearin mixture is agitated, preferably in an ultra sonic cleanin
tank, until all of the solids present have dissolved. The firing additive which controls the viscosity and the decomposition temperature, is selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol or mixtures thereof, and can then be added to the stock solution. Ethylene glycol or glycerol is preferably added in the proportion of 1 ml to 10 g of lead acetate in the solution depending on the thickness of film required. The viscosity and surface tension of the solution can then be adjusted by adding water, propanol or mixtures thereof. Thinner films result from lower viscosity solutions and propanol reduces surface tension thereby improving wettability of the substrate.
Particularly suitable solutions for preparing single layer films 1 m thick of (a) PZT having a composition near the morphotropic phase boundary (Zr/Ti = 53.5/46.5) and (b) alumina are shown below in Table 1.
Table 1
Film Chemical Quantity
(a) PZT Lead Acetate Pb(CH-,C0->)-,3H O 12 . . 00 g Acetic Acid CH3COOH 6 ml Zirconium propoxide Zr(C3H2θ)4 5. . 54 g Titanium isopropoxide Tif(CH-,j cHO]/ 2 , . 18 g Ethylene Glycol 0HCH.,CH50H 1 , .2 ml Distilled Water H20 6 ml
(b) Al70τ Aluminum isopropoxide Al[ (CH-,) ^CHO], 4 = g Nitric Acid HNO, ~ 5 ml
Ethylene Glycol OHCHpCH OH 4 ml Propanol CH3CH2CH2OH 4 ml
The final solution, which is stable in air, may be filtered through a membrane filter (pore size 0.22 μm) and stored in a sealed container.
Substrate Surface Preparations
PZT may be deposited on numerous substrates such as silica wafers, mica, fused quartz, borosilicate glass, Corning 7509 glass coated with stannic oxide based trans¬ parent conducting coating, and stainless steel, gold or platinum plates. Crack free surface coatings are most easily applied to conducting glass substrates but in the case of fused quartz it is preferable to first apply a special surface treatment as described in more detail below. Substrates must be thoroughly cleaned before depositing the coating, preferably by boiling in water with a detergent, rinsing in distilled water followed by ultra sound to remove organic contaminants and vapour degreasing in methanol. After cleaning, the precursor films, such as those described in Table 1, can be deposited on the substrate by spin coating, dip coating or by painting. The spin coating technique is preferred for flat substrate surfaces as the thickness of the film may be controlled by the speed of rotation of the spinner and the concentration and viscosity of the solution. A spinner such as a "Headway Research Incorporated photoresist spinner" operated at 8500 rpm for 20 seconds is particularly suitable. More complex shapes cannot readily be prepared by spin coating and recourse may be had to dip coating or painting. In this case it is
usually necessary to dilute the above stock solution with propanol or a mixture of propanol and water. The film thickness can be controlled by the amount of propanol and water or the ratio of propanol to water and by controlling the speed of pulling the dip coated article.
Firing
Heretofore films made by sol gel processing have usually suffered macro cracking during firing. Such cracking can be substantially reduced or eliminated by the use of firing additives to the stock solution or, in certain cases, by deposition of an intermediate buffer layer.
After an organo-metallic film has been deposited and dried it must be pyrolysed to remove the organics and induce the solid state reaction which produces the PZT. An increase in the density of the film and sufficient time for a solid state diffusion reaction to take place are both required. The normal approach to avoid cracking is to pyrolyse the film rapidly by transferring the substrate to a surface which is well above the pyrolysing temperature. According to the present invention, the pyrolysis may be better controlled if the time or temperature range over which the film is in a viscous liquid state is extended. This may be accomplished by adding a relatively small amount of a firing additive selected from ethylene glycol, glycerol and tetra ethylene glycol to the stock solution in order to raise the viscous state temperature. The resulting films are crack-free, very transparent and have improved surface
smoothness. Glycerol and tetra ethylene glycol are preferred additives. When using glycerol the wet film may be fired by raising the temperature gradually which is particularly advantageous especially when coating metallic substrates such as stainless steel or alumel.
It is known that in normal ceramics, firing cracks can be controlled if the material is maintained under a compressive load. In a preferred, and alternate, embodiment of the present invention, this technique may be applied and is particularly useful on substrates such as silicon and borosilicate glass. A thin intermediate or buffer layer may be deposited onto the substrate and fired on prior to the deposition of PZT. The thickness of the buffer layer depends on the substrate and film composition but 100 A is usually sufficient. For applications requiring a transparent insulating layer Alumina (A1203) has good properties and is easy to fabricate by sol gel processing. A typical mixture for this purpose is shown in Table 1 (b) , above. For transparent, conducting coatings indium tin oxide or stannic oxide conducting coatings may be used. Other conducting coatings include Al, Au, Cr, Ni and Co which may be produced by known vacuum deposition or chemical techniques.
The firing schedule which pyrolyses the organo-metallic compounds to an inorganic film is key to the preparation of crack free films having the desired crystal structure, grain size, transparency and surface roughness. The solvents
evaporate with a consequent large change in volume and the generation of internal stress at temperatures between room temperature and about 250°C. As the temperature increases the lead acetate dehydrates, melts and decomposes. At this stage, the dried film becomes "wet" again and the organic compounds begin to decompose. The internal stress is relaxed and the volume change of the film continues. At the end of this stage, the organic film changes to a fine mixture of oxides of lead, titanium, zirconium and free carbon. At still higher temperature, the free carbon oxidizes and the mixture of oxides transforms to a transparent amorphous PZT film.
It is believed that the high boiling point and latent heat of vaporization of the ethylene glycol raises the solution evaporation temperature in the first phase towards the "melt" temperature in the second phase. This retains atom mobility and significantly reduces the tendency to crack. Raising the firing temperature also reduces this tendency. Films can be fired either in an oven or by placing the substrate on a hot plate. In the latter case, the rapid rise in temperature and the fact that the substrate temperature is higher than the film temperature lead to fewer cracks in the fired film. As the wet film pyrolyses and solidifies on the hot expanded substrate, the tendency on cooling is to create compressive or lower tensile stress. There are, however, some limitations on the speed and temperature of firing. In the case of thick films, the firing temperature should be limited to 350-C-
550°C as the films become milky and less transparent at higher firing temperatures.
Annealing
As fired films are basically amorphous and need annealing at temperatures up to about 600°C for up to six hours in order to cause the amorphous structure to change to a perovskite structure.
Electrical Post Treatment After annealing the crystal structure of the film is generally that of randomly oriented crystallites, although some evidence of at least some orientation exists. In order to induce piezoelectric properties, however, it is necessar to electrically pole the films by application of an electric field of between 2 and 3 KV/mm when the films are held at temperature of about 175°C. Films produced by the aforesai processing steps have been shown to have properties superior to those obtainable by other processing methods. For example, the best piezoelectric coupling coefficient heretofore achieved, in zinc oxide, is of the order of 0.7%. In contrast films according to the present invention have a piezoelectric coupling coefficient of at least 1.0%.
PZT thin films have numerous applications including use in electro-optic displays and electroluminescent devices. They are used in electronic applications such as ferro¬ electric gate insulators or capacitors in non-volatile memories. A third field of use includes high frequency
ultrasonic transducers for non-destructive evaluation and medical and biological purposes, while a fourth field includes fibre optic sensors and devices.
While this invention has been described with particular reference to PZT and PLZT, it will be appreciated that the processing techniques described are equally applicable to the deposition of other complex oxide crack-free thin films such as those listed hereinabove. It has been found that the thickness of the crack-free film and the smoothness of the film can -be controlled specifically by the composition and viscosity of the firing additive. Modification of the polyethylene glycol mixture is therefore important. It has also been found advantageous to process and fire under vacuum in order to extract the water uniformly and •cause uniform decarbonization.
Claims
1. A method for preparing a composite of a substrat having deposited thereon a crack-free ferroelectric . polycrystalline lead zirconate titanate thin film, i which a substrate is coated with a solution containin precursors of said thin film, fired and electricall poled, and characterized by:
(a) dissolving lead acetate in acetic acid, adding thereto zirconium propoxide followed by
10 titanium isopropoxide in relative proportions to produce a selected ratio of metals, and agitating until all solids are in solution;
(b) adding a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol,
1-. polyethylene glycol and mixtures thereof to said solution;
(c) adjusting viscosity of said solution;
(d) firing said coated substrate at a temper gU _%,„, ature in the range 300 -C-550 - C so as to pyrolyse
■ 20 said film; and
'■ ( e) annealing said pyrolysed f ilm at a temperature up to about 600 °C for sufficient time to produce a perovskite structure in said film;
25 2. A method as claimed in claim 1 characterized in that said substrate is selected from silicon, silicon coated with metals such as aluminum, platinum, titanium nitride, mica, fused quartz, glass , alumina, stainless steel , alumel , gold and platinum.
3. A method as claimed in claim 2 characterized in that said coating step is selected from spin coati . ng, di.p coati. ng and painting.
4. A method as claimed in claim 1 characterized in that the viscosity of said solution is adjusted by addition of a di luent selected from water , propanol and mixtures thereof .
5. A method for preparing a composite of a substrate having deposited thereon a crack free ferro¬ electric polycrystalline lead zirconate titanate thin film, characterized by:
( a ) depos iting an oxide f i lm on sa id substrate ;
(b) dissolving lead acetate in acetic acid, adding thereto zirconium propoxide followed by titanium isopropoxide in relative proportions to produce a selected ratio of metals , and agitating until all solids are in solution;
( c) adding a f iring agent selected from glycerol , ethylene glycol , tetra ethyl glycol , polyethylene glycol and mixtures thereof to said solution;
(d) adjusting viscosity of said solution; (e) coating said oxide coated substrate with said solution so as to form a wet film thereon;
( f ) f iring said coated substrate at a temperature in the range 300 °C-550 °C so as to pyrolize said film;
( g) annealing said pyrolysed f ilm at a temperature up to about 600°C for sufficient time to produce a perovskite structure in said film; and
(h) electrically poling said film so as to produce piezoelectric properties therein.
6. A method as claimed in Claim 5 characterized in that said substrate is coated with an organic oxide or nitrate precursor solution , which is dried and fired at a temperature in the range 400- 600 °C so as to deposit said oxide film on said substrate .
7. A method as claimed in Claim 5 characterized in that said oxide f ilm is depos ited by vacuum deposition.
8. A method as claimed in Claim 5 characterized in that said oxide film is selected from alumina, indium tin oxide and stannic oxide.
9. A method as claimed in Claim 6 wherein said oxide film is selected from alumina, indium tin oxide and stannic oxide .
10. A method as claimed in Claim 8 characterized in that said oxide film is selected from alumina , indium tin oxide and stannic oxide.
11 . A compos ite compr i s ing a substrate having deposited thereon a ferroelectric polycrystalline lead zirconate titanate thin film characterized in that said thin film is substantially crack-free and has a piezoelectric coupling coefficient of at least 1% .
12 . A composite as claimed in Claim 11 characterized in that said substrate is selected from, silicon , mica , fused quartz , alumina , glass , stainless steel, alumel, gold and platinum.
13. A method for preparing a composite comprising a substrate having deposited thereon a crack free complex oxide thin film, characterized by:
(a) preparing a solution containing precursors for said complex oxides;
(b) adding to said solution a firing agent selected from glycerol, ethylene glycol, tetra ethylene glycol, polyethylene glycol and mixtures thereof in relative proportions and amounts so as to provide a solution having a selected viscosity;
(c) coating said substrate with said solution so as to form a wet film thereon; and (d) firing said coated substrate at a temperature in the range 300°C-550°C so as to pyrolyse said film.
14. A method as claimed in claim 13 characterized in that said complex oxides are selected from:
Alumina Zirconia
Calcium titanate Calcium apatite Lithium niobate Barium titanate Tantalum zirconate Magnesium tantalate Yttrium Barium Copper Oxides
Yttrium Oxide . Barium Calcium Thalium Copper Oxide.
15. A method as claimed in claim 14 characterized in that said firing is effected in vaccuo.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US471,509 | 1983-03-02 | ||
US34377489A | 1989-04-27 | 1989-04-27 | |
US343,774 | 1989-04-27 | ||
US47150990A | 1990-01-29 | 1990-01-29 |
Publications (1)
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WO1990013149A1 true WO1990013149A1 (en) | 1990-11-01 |
Family
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PCT/CA1990/000123 WO1990013149A1 (en) | 1989-04-27 | 1990-04-18 | SOL GEL PROCESS FOR PREPARING Pb(Zr,Ti)O3 THIN FILMS |
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