CN103880420A - Preparation method for lead zirconate-titanate piezoelectric film - Google Patents

Preparation method for lead zirconate-titanate piezoelectric film Download PDF

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CN103880420A
CN103880420A CN201210566762.9A CN201210566762A CN103880420A CN 103880420 A CN103880420 A CN 103880420A CN 201210566762 A CN201210566762 A CN 201210566762A CN 103880420 A CN103880420 A CN 103880420A
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stable state
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CN103880420B (en
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李明利
纪松
钱坤明
张延松
丁昂
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No 52 Institute of China North Industries Group Corp
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Abstract

A preparation method for a lead zirconate-titanate piezoelectric film is characterized by employing a sol-gel process for preparation, firstly respectively preparing a PbTiO3 seed crystal layer stable-state sol and a PbZr1-xTixO3 stable-state sol; coating a substrate with the PbTiO3 seed crystal layer stable-state sol in a rotation manner as a transition layer and a seed crystal layer; and finally coating the prepared substrate with the PbZr1-xTixO3 stable-state sol in a rotation manner, so as to obtain the PbTiO3 seed crystal layer induced preferred-orientation grown PbZr1-xTixO3 piezoelectric film. According to the preparation method, by deposing PbTiO3 on the substrate in advance as the transition layer and the seed crystal layer, the nucleation free energy of the PZT film is reduced, thereby reducing crystallization temperature and improving the microstructure of PZT film; and through the induction effect of the seed crystal layer, lead zirconate-titanate (PbZr1-xTixO3) piezoelectric film grows along a preferred crystalline phase, thereby obtaining a high-piezoelectric-coefficient piezoelectric film.

Description

A kind of preparation method of lead zirconate titanate piezoelectric film
Technical field
The present invention relates to a kind of preparation method of lead zirconate titanate piezoelectric film, specifically a kind of lead zirconate titanate piezoelectric film that adopts sol-gel technology to prepare high (111) orientation degree and high tension electricity coefficient.
Background technology
Piezoelectric membrane is the core of various microsensors and performer, and people have prepared respectively as PbTiO by several different methods such as magnetron sputtering method, sol-gel method (Sol-Ge1), electrophoretic deposition and pulsed laser depositions (PLD) 3(lead titanate), PbZr 1-xti xo 3(PZT) (Pb-based lanthanumdoped zirconate titanates), Pb 1-xca xtiO 3(PCT) (calcium lead titanate), (Pb xla 1-x) (Zr yti 1-y) O 3(PLZT) lead base class piezoelectric membrane such as (lead lanthanum zirconate titanate).
Sol-gel method (Sol-Gel method) is as one piezoelectric membrane preparation method cheaply, have that film composition stoichiometric ratio is easily controlled, membrane structure densification, easily form large-area uniform thin film easily and the advantage such as IC technique is integrated, therefore, be the pzt thin film preparation method who is most widely used in current MEMS device.
Piezoelectric membrane must be deposited on electro-conductive material, and the electro-conductive material conventionally adopting is Pt, but because Pt interface binding power is not high and easily form Platinum Silicide when thermal treatment, thus Pt can not Direct precipitation on base material.Meanwhile, silicon diffuses to from base material the formation that PZT layer can cause Jiao Lvshi phase.Therefore in order to prevent reaction and diffusion, must introduce transition layer, present method adopts sol-gel technology deposition PbTiO 3as transition layer, utilize the inducing action of inculating crystal layer to prepare the lead zirconate titanate piezoelectric film of high tension electricity coefficient simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of lead zirconate titanate piezoelectric film, adopts sol-gel technology to be prepared, and utilizes PbTiO 3the inducing action of inculating crystal layer, makes PZT piezoelectric membrane crystal grain along the growth of (111) crystalline phase preferred orientation, and the PZT piezoelectric membrane of preparation has higher piezo-electric modulus.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of preparation method of lead zirconate titanate piezoelectric film, comprises the following steps:
1) prepare first respectively PbTiO 3inculating crystal layer stable state colloidal sol and PbZr 1-xti xo 3stable state colloidal sol, wherein 0.47≤x≤0.48;
2) by PbTiO 3inculating crystal layer stable state colloidal sol rotates-is coated on substrate, in air atmosphere, even glue 30 ~ 60s under rotating speed with 2500 ~ 3500r/min, the wet film forming is 180 ~ 200 ℃ of oven dry, be controlled in 0.9～1.1L/min oxygen gas flow rate, temperature rise rate with 45 ~ 55 ℃/min carries out anneal under 500 ~ 700 ℃ of differing tempss, and repeats this technique 1 ~ 3 time according to the number of plies of inculating crystal layer, obtains and deposits PbTO 3the substrate of transition layer;
3) by PbZr 1-xti xo 3stable state colloidal sol rotates-is coated in step 2) on prepared substrate, in air atmosphere, even glue 30-60s under rotating speed with 2500 ~ 3500r/min, the wet film forming is 180 ~ 200 ℃ of oven dry, be controlled in 0.9～1.1L/min oxygen gas flow rate, temperature rise rate with 45 ~ 55 ℃/min carries out anneal under 500 ~ 700 ℃ of differing tempss, obtains PbTiO 3the PbZr of inculating crystal layer induction preferred orientation growth 1-xti xo 3piezoelectric membrane.
As improvement, described PbTiO 3the preparation process of inculating crystal layer stable state colloidal sol is: being that 0.09 ~ 0.11mol/L acetate trihydrate is plumbous by 50mL concentration mixes in flask with 100mL2-methyl cellosolve, and the titanium isopropylate that is then 0.09 ~ 0.11mol/L by 50mL concentration in another flask mixes with 100mL2-methyl cellosolve; When the distillation of plumbic acetate solution for vacuum, stir titanium isopropoxide solution; After plumbic acetate solution for vacuum has been distilled, in glove-box, titanium isopropoxide solution is added in plumbic acetate solution, then, by flask sealing, from glove-box, takes out and carry out again vacuum distilling; After 2-5h, solution is transferred in the device that contains magnetic stirring bar, slowly added 2-10mL methane amide as drying control agent, then by container sealing, and on mixing platform, stir 12 ~ 16h.
Finally, described PbZr 1-xti xo 3the preparation process of stable state colloidal sol is: being that 0.09 ~ 0.11mol/L acetate trihydrate is plumbous by 50mL concentration mixes in flask with 100mL2-methyl cellosolve, and the zirconium-n-propylate that the titanium isopropylate that is then 0.046 ~ 0.048mol/L by 50mL concentration in another flask and concentration are 0.052 ~ 0.054mol/L mixes with 100mL2-methyl cellosolve; In carrying out the distillation of plumbic acetate solution for vacuum, stir the 2-methyl cellosolve solution of zirconium-n-propylate, titanium isopropylate, and keep flask sealing, Zr/Ti solution is joined to then vacuum distilling in plumbic acetate solution; After 2-5h, solution is transferred in the device that contains magnetic stirring bar, slowly added 2-10mL methane amide as drying control agent; Then by container sealing, and on mixing platform, stir 12 ~ 16h.
Compared with prior art, the invention has the advantages that: on substrate, deposit in advance PbTiO 3as transition layer, can reduce the nucleation free energy of pzt thin film, thereby reduce crystallization temperature, improve the microstructure of PZT film, be conducive to the generation of pure perovskite phase PZT, and by the inducing action of inculating crystal layer, make Pb-based lanthanumdoped zirconate titanates (PbZr 1-xti xo 3) (111) the crystalline phase preferred orientation growth of piezoelectric membrane edge, can obtain the piezoelectric membrane with high tension electricity coefficient.The present invention adopts sol-gel technology to be prepared, and technique is simple, preparation cost is low, and the piezoelectric membrane of preparation has higher preferred orientation and high tension electricity coefficient.
Accompanying drawing explanation
Fig. 1 (a), 1 (b), 1 (c) are PbZr of the present invention 1-xti xo 3preparation technology's schema of piezoelectric membrane;
Fig. 2 is PbTiO of the present invention 3, PbZr 1-xti xo 3xRD spectrum with PZT/PT sample.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1
Being that 0.1mol/L acetate trihydrate is plumbous by 50mL concentration mixes in 500mL flask with 100mL2-methyl cellosolve, and the titanium isopropylate that is then 0.1mol/L by 50mL concentration in another 500mL flask mixes with 100mL2-methyl cellosolve.When the distillation of plumbic acetate solution for vacuum, stir titanium isopropoxide solution.After plumbic acetate solution for vacuum has been distilled, in glove-box, the titanium isopropoxide solution mixing is added in plumbic acetate solution.Then by flask sealing, from glove-box, take out and carry out again vacuum distilling.After 3h, solution is transferred in the device that contains magnetic stirring bar, slowly added 3mL methane amide as drying control agent.Then by container sealing, and on mixing platform, stir 12h.Being that 0.1mol/L acetate trihydrate is plumbous by 50mL concentration mixes in 500mL flask with 100mL2-methyl cellosolve, and the zirconium-n-propylate that the titanium isopropylate that is then 0.047mol/L by 50mL concentration in another 500mL flask and concentration are 0.053mol/L mixes with 100mL2-methyl cellosolve.In carrying out the distillation of plumbic acetate solution for vacuum, stir the methyl cellosolve solution of Zr and Ti, and keep flask sealing.Zr/Ti solution joins then vacuum distilling in plumbic acetate solution.After 3h, solution is transferred in the device that contains magnetic stirring bar, slowly added 5mL methane amide as drying control agent.Then by container sealing, and on mixing platform, stir 12h.PbTiO 3inculating crystal layer solution rotating-be coated in substrates of different, in air atmosphere, even glue 30s under the rotating speed with 3000r/min, the wet film of formation is 180 ℃ of oven dry.Be controlled in 1L/min oxygen gas flow rate, at 700 ℃, carry out anneal with the temperature rise rate of 50 ℃/min.The substrate obtaining is retained for subsequent use.PbZr 1-xti xo 3stable state colloidal sol rotates-is coated on the substrate of previous step gained, in air atmosphere, and even glue 60s under the rotating speed with 3000r/min, the wet film of formation is 200 ℃ of oven dry.Be controlled in 1L/min oxygen gas flow rate, under 700 ℃ of differing tempss, carry out anneal with the temperature rise rate of 50 ℃/min.Obtain PbTiO 3the PbZr of inculating crystal layer induction preferred orientation growth 1-xti xo 3piezoelectric membrane.(111) orientation degree of pzt thin film sample is 88.7% after tested.
From the PbTiO of Fig. 2 3, PbZr 1-xti xo 3visible in composing with the XRD of PZT/PT sample, the film of preparation is all well-crystallized's crystalline structure under various conditions; (111) peak diffracted intensity that adds the pzt thin film of buffer layer obviously strengthens, and the diffracted intensities such as (100), (110), (220) and (211) peak are suppressed.Pzt thin film (111) orientation degree α represents with the ratio of the diffracted intensity sum at (100), (111), (110) peak with the diffracted intensity at (111) peak.
∝ = 1 ( 111 ) 1 ( 100 ) + 1 ( 110 ) + 1 ( 111 ) Formula (1)
(1) formula of utilization is calculated, and (111) orientation degree of pzt thin film sample of adding buffer layer has nearly reached 90%, and is only 45% without (111) orientation degree of the pzt thin film sample of buffer layer.This shows: buffer layer makes the grain orientation of the pzt thin film of growing be enhanced in (111) direction thereon, and has obtained effective inhibition in the orientation of other directions.
Embodiment 2
Being that 0.1mol/L acetate trihydrate is plumbous by 50mL concentration mixes in 500mL flask with 100mL2-methyl cellosolve, and the titanium isopropylate that is then 0.1mol/L by 50mL concentration in another 500mL flask mixes with 100mL2-methyl cellosolve.When the distillation of plumbic acetate solution for vacuum, stir titanium isopropoxide solution.After plumbic acetate solution for vacuum has been distilled, in glove-box, the titanium isopropoxide solution mixing is added in plumbic acetate solution.Then by flask sealing, from glove-box, take out and carry out again vacuum distilling.After 3h, solution is transferred in the device that contains magnetic stirring bar, slowly added 3mL methane amide as drying control agent.Then by container sealing, and on mixing platform, stir 12h.Being that 0.1mol/L acetate trihydrate is plumbous by 50mL concentration mixes in 500mL flask with 100mL2-methyl cellosolve, and the zirconium-n-propylate that the titanium isopropylate that is then 0.047mol/L by 50mL concentration in another 500mL flask and concentration are 0.053mol/L mixes with 100mL2-methyl cellosolve.In carrying out the distillation of plumbic acetate solution for vacuum, stir the methyl cellosolve solution of Zr and Ti, and keep flask sealing.Zr/Ti solution joins then vacuum distilling in plumbic acetate solution.After 3h, solution is transferred in the device that contains magnetic stirring bar, slowly added 5mL methane amide as drying control agent.Then by container sealing, and on mixing platform, stir 12h.PbTiO 3inculating crystal layer solution rotating-be coated in substrates of different, in air atmosphere, even glue 30s under the rotating speed with 3000r/min, the wet film of formation is 180 ℃ of oven dry.Be controlled in 1L/min oxygen gas flow rate, at 700 ℃, carry out anneal with the temperature rise rate of 50 ℃/min.Repeat above-mentioned spin coating and annealing process 3 times, the substrate of acquisition is retained for subsequent use.PbZr 1-xti xo 3stable state colloidal sol rotates-is coated on the substrate of previous step gained, in air atmosphere, and even glue 60s under the rotating speed with 3000r/min, the wet film of formation is 200 ℃ of oven dry.Be controlled in 1L/min oxygen gas flow rate, under 700 ℃ of differing tempss, carry out anneal with the temperature rise rate of 50 ℃/min.Obtain PbTiO 3the PbZr of inculating crystal layer induction preferred orientation growth 1-xti xo 3piezoelectric membrane.(111) orientation degree of pzt thin film sample is 92.3% after tested.

Claims (3)

1. a preparation method for lead zirconate titanate piezoelectric film, is characterized in that: comprise the following steps:
1) prepare first respectively PbTiO 3inculating crystal layer stable state colloidal sol and PbZr l-xti xo 3stable state colloidal sol, wherein 0.47≤x≤0.48;
2) by PbTiO 3inculating crystal layer stable state colloidal sol rotates-is coated on substrate, in air atmosphere, even glue 30 ~ 60s under rotating speed with 2500 ~ 3500r/min, the wet film forming is 180 ~ 200 ℃ of oven dry, be controlled in 0.9～1.1L/min oxygen gas flow rate, temperature rise rate with 45 ~ 55 ℃/min carries out anneal under 500 ~ 700 ℃ of differing tempss, and repeats this technique 1 ~ 3 time according to the number of plies of inculating crystal layer, obtains and deposits PbTO 3the substrate of transition layer;
3) by PbZr l-xti xo 3stable state colloidal sol rotates-is coated in step 2) on prepared substrate, in air atmosphere, even glue 30-60s under rotating speed with 2500 ~ 3500r/min, the wet film forming is 180 ~ 200 ℃ of oven dry, be controlled in 0.9～1.1L/min oxygen gas flow rate, temperature rise rate with 45 ~ 55 ℃/min carries out anneal under 500 ~ 700 ℃ of differing tempss, obtains PbTiO 3the PbZr of inculating crystal layer induction preferred orientation growth l-xti xo 3piezoelectric membrane.
2. preparation method according to claim 1, is characterized in that: described PbTiO 3the preparation process of inculating crystal layer stable state colloidal sol is: being that 0.09 ~ 0.11mol/L acetate trihydrate is plumbous by 50mL concentration mixes in flask with 100mL2-methyl cellosolve, and the titanium isopropylate that is then 0.09 ~ 0.11mol/L by 50mL concentration in another flask mixes with 100mL2-methyl cellosolve; When the distillation of plumbic acetate solution for vacuum, stir titanium isopropoxide solution; After plumbic acetate solution for vacuum has been distilled, in glove-box, titanium isopropoxide solution is added in plumbic acetate solution, then, by flask sealing, from glove-box, takes out and carry out again vacuum distilling; After 2-5h, solution is transferred in the device that contains magnetic stirring bar, slowly added 2-10mL methane amide as drying control agent, then by container sealing, and on mixing platform, stir 12 ~ 16h.
3. preparation method according to claim 1, is characterized in that: described PbZr l-xti xo 3the preparation process of stable state colloidal sol is: being that 0.09 ~ 0.11mo1/L acetate trihydrate is plumbous by 50mL concentration mixes in flask with 100mL2-methyl cellosolve, and the zirconium-n-propylate that the titanium isopropylate that is then 0.046 ~ 0.048mol/L by 50mL concentration in another flask and concentration are 0.052 ~ 0.054mol/L mixes with 100mL2-methyl cellosolve; In carrying out the distillation of plumbic acetate solution for vacuum, stir the 2-methyl cellosolve solution of Zr/Ti, and keep flask sealing, Zr/Ti solution is joined to then vacuum distilling in plumbic acetate solution; After 2-5h, solution is transferred in the device that contains magnetic stirring bar, slowly added 2-10mL methane amide as drying control agent; Then by container sealing, and on mixing platform, stir 12 ~ 16h.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107256866A (en) * 2017-06-12 2017-10-17 湘潭大学 A kind of preparation method of flexible epitaxial ferroelectric film
CN109608194A (en) * 2018-12-13 2019-04-12 广东工业大学 A kind of lead zirconate titanate thick film ceramics and its preparation method and application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101864568A (en) * 2009-04-14 2010-10-20 冯士维 Method for preparing high-orientation PZT piezoelectric thin film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN101864568A (en) * 2009-04-14 2010-10-20 冯士维 Method for preparing high-orientation PZT piezoelectric thin film

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107256866A (en) * 2017-06-12 2017-10-17 湘潭大学 A kind of preparation method of flexible epitaxial ferroelectric film
CN107256866B (en) * 2017-06-12 2019-11-15 湘潭大学 A kind of preparation method of flexibility epitaxial ferroelectric film
CN109608194A (en) * 2018-12-13 2019-04-12 广东工业大学 A kind of lead zirconate titanate thick film ceramics and its preparation method and application
CN109608194B (en) * 2018-12-13 2022-06-03 广东工业大学 Lead zirconate titanate thick film ceramic and preparation method and application thereof

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