CN104311007A - Preparation method of piezoelectric ceramic transducer (PZT) thick film with micro structure - Google Patents
Preparation method of piezoelectric ceramic transducer (PZT) thick film with micro structure Download PDFInfo
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- CN104311007A CN104311007A CN201410515474.XA CN201410515474A CN104311007A CN 104311007 A CN104311007 A CN 104311007A CN 201410515474 A CN201410515474 A CN 201410515474A CN 104311007 A CN104311007 A CN 104311007A
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Abstract
The invention provides a preparation method of a piezoelectric ceramic transducer (PZT) thick film with a micro structure. The preparation method is characterized by comprising the following steps: preparing a graphical zinc oxide sacrificial layer on the surface of a substrate; coating the zinc oxide sacrificial layer with PZT slurry, performing pre-crystallization treatment for 1-60 minutes at 200-500 DEG C; at 600-1000 DEG C, performing crystallization treatment for 1-180 minutes; and putting the substrate, surface of which is coated with the PZT slurry, into a corrosive liquid, and then stripping to obtain the PZT thick film with the micro structure. By adopting a process of improving the slurry and the thermal treatment, the preparation method disclosed by the invention can be used for obviously improving the surface evenness and the density of the PZT thick film. And meanwhile, by virtue of a stripping technology that adopts the zinc oxide as the sacrificial layer, the problem that the PZT thick film is difficult to etch completely can be overcome.
Description
Technical field
The present invention relates to technical field of material, particularly relate to a kind of preparation method with microstructure lead zirconate titanate PZT thick film.
Background technology
Pb-based lanthanumdoped zirconate titanates (Piezoelectric Ceramic Transducer, PZT) film has excellent ferroelectric, piezoelectricity, pyroelectric property, is widely used in uncooled infrared detecting instrument, non-volatility ferroelectric storer, microsensors and microactuators etc.Relative to pzt thin film, the preparation of the PZT thick film of thickness more than 1 micron is with graphical more difficult.
At present, preparation method's mainly 0-3 method of PZT thick film, relative to methods such as silk screen printings, it is low that it has Tc, the advantages such as film quality is better, but adopt 0-3 legal system still to there is at least following shortcoming for PZT thick film: the shortcomings such as the film density of the PZT thick film of preparation is low, surface irregularity.The imaging technique of PZT thick film mainly contains: wet etching, dry etching two kinds.Due in the wet etching of PZT containing the stronger acid that is corrosive, so with the manufacturing process poor compatibility of semi-conductor and microelectromechanical systems, and the wet etching of PZT thick film is comparatively difficult, and figure sideetching is comparatively serious.It is high to there is equipment cost in dry etching, and terminal is difficult to control, the shortcomings such as other thin film layer of easy damaged.In addition owing to having a large amount of PZT powders, so wet method or dry etching are all easy to residual a large amount of PZT powder in the standby PZT thick film of 0-3 legal system.
Summary of the invention
The invention provides a kind of preparation method with microstructure lead zirconate titanate PZT thick film, in order to improve density, the planeness of PZT thick film, and improve its patterned quality; In preparation process, avoid in wet etching and cause the manufacturing process poor compatibility with semi-conductor and microelectromechanical systems containing stronger acid, wet etching difficulty, figure sideetching is comparatively serious, dry etching cost is high, and extent of corrosion is difficult to control and wet etching and dry etching and remains the problems such as a large amount of PZT powders.
For achieving the above object, the invention provides a kind of preparation method with microstructure PZT thick film, described method comprises:
Patterned zinc oxide sacrifice layer is prepared on the surface of substrate;
PZT slurry is coated on described zinc oxide sacrifice layer, under 200 DEG C ~ 500 DEG C conditions, carries out the pre-crystallized process of 1 ~ 60 minute;
Again under 600 DEG C ~ 1000 DEG C conditions, carry out the crystallization treatment of 1 ~ 180 minute;
Described substrate surface being covered with described PZT slurry is inserted in corrosive fluid, obtains the PZT thick film with microstructure after stripping.
Preferably, the described surface at substrate is prepared patterned zinc oxide sacrifice layer and is specifically comprised:
Deposit or depositing zinc oxide sacrifice layer on the surface of the substrate;
Described zinc oxide sacrifice layer applies photoresist material;
Photoetching is carried out to described photoresist material;
Described zinc oxide sacrifice layer after photoetching is graphically etched;
Remove the photoresist material of described substrate surface.
Preferably, the described surface at substrate is prepared patterned zinc oxide sacrifice layer and is specifically comprised:
At substrate surface coating photoresist material;
Photoetching is carried out to described substrate surface;
After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film;
Deposit or depositing zinc oxide sacrifice layer;
Remove the photoresist material of described substrate surface.
Preferably, described substrate comprises any one substrate in silicon substrate, gan substrate, sapphire substrate, ruby substrate, quartz substrate, gallium arsenide substrate, silicon carbide substrate, germanium substrate, diamond substrate; Or surface is covered with the arbitrary described substrate of non-metallic film or metallic membrane; Wherein said non-metallic film comprises: in silicon dioxide film, silicon nitride film, polysilicon film one or more; Described metallic membrane comprises: Pt/Ti metallic film or Au/Cr metallic film.
Preferably, described deposit or depositing zinc oxide sacrifice layer specifically comprise the zinc oxide sacrifice layer that in employing sol-gel method, metal-organic decomposition method, sputtering method, Metalorganic Chemical Vapor Deposition, pulsed laser deposition or hydrothermal method prepared by either method.
Preferably, the thickness of described zinc oxide sacrifice layer is 0.01 μm ~ 1000 μm.
Preferably, the thickness of described PZT thick film is 2 μm ~ 200 μm.
Preferably, the preparation process of described PZT slurry is:
PZT powder is added in PZT colloid;
Adopt ultrasonic disperse to be mixed into slurry, staticly settle the particle that rear removal is greater than 250nm;
To removing, the slurry of particle concentrates, ageing, forms PZT slurry.
Preferably, described corrosive fluid comprises the arbitrary solution in the etchant solution of the etchant solution of phosphoric acid solution, HBr solution, nitric acid and phosphoric acid, phosphoric acid and acetic acid, acetum, sodium hydroxide solution, ammonium chloride solution or ammoniacal liquor corrosive fluid.
Therefore, a kind of preparation method with microstructure PZT thick film provided by the invention, this preparation method, by adopting improvement slurry and process of thermal treatment, can significantly improve surface finish and the density of PZT thick film.Meanwhile, by the lift-off technology of zinc oxide as sacrifice layer, the problem that PZT thick film is difficult to clean etching can be overcome.The PZT thick film with microstructure adopting this preparation method to prepare have processing compatibility good, to other rete damage low, graphical quality advantages of higher.
Accompanying drawing explanation
A kind of preparation method's schema with microstructure PZT thick film that Fig. 1 provides for the embodiment of the present invention 1;
The sectional view prepared on substrate after zinc oxide sacrifice layer that Fig. 2 provides for the embodiment of the present invention 1;
Sectional view after the patterned oxide zinc sacrifice layer that Fig. 3 provides for the embodiment of the present invention 1;
Sectional view after the preparation PZT thick film that Fig. 4 provides for the embodiment of the present invention 1;
The sectional view with microstructure PZT thick film that Fig. 5 provides for the embodiment of the present invention 1;
The vertical view with microstructure PZT thick film that Fig. 6 provides for the embodiment of the present invention 1.
Embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.But be not intended to limit the scope of the invention.
Embodiments provide a kind of preparation method with microstructure PZT thick film, in order to improve density, the planeness of PZT thick film, and improve its patterned quality.
Embodiment 1
The method flow diagram of the preparation PZT thick film that Fig. 1 provides for the embodiment of the present invention 1.Fig. 2-6 provides the preparation process schematic diagram of each step in preparation process.Below, according to Fig. 1 and composition graphs 2-Fig. 6, the preparation method with microstructure PZT thick film is described in detail.
As shown in Figure 1, described preparation method specifically comprises the steps:
Step 101, cleaning substrate.
Concrete, substrate is put into acidic cleaning solution or alkaline cleaning fluid cleans, re-use deionized water afterwards and substrate is rinsed well.
Described substrate can be the arbitrary substrate in silicon substrate, gan substrate, sapphire substrate, ruby substrate, quartz substrate, gallium arsenide substrate, silicon carbide substrate, germanium substrate, diamond substrate; Or surface is covered with any one substrate above-mentioned of non-metallic film or metallic membrane.Wherein, described non-metallic film comprises: one or more in silicon dioxide film, silicon nitride film, polysilicon film; Described metallic membrane comprises: Pt/Ti double-layer metal film or Au/Cr double-layer metal film.
Alternatively, also can be the substrate simultaneously comprising above-mentioned non-metallic film and metallic membrane.
Step 102, prepares patterned zinc oxide sacrifice layer on the surface of substrate.
Particularly, adopt any one method in sol-gel method, metal-organic decomposition method, sputtering method, Metalorganic Chemical Vapor Deposition, pulsed laser deposition or hydrothermal method, thickness preparing by substrate is after cleaning 0.01 μm ~ 1000 μm zinc oxide sacrifice layers.As shown in Figure 2, the sectional view after zinc oxide sacrifice layer is prepared by substrate.
Prepare patterned zinc oxide sacrifice layer on the surface of substrate and can adopt the following two kinds method:
Method one, is first coated with positive photoresist over the substrate surface, utilizes the egative forme needing to prepare PZT thick film figure to expose positive photoresist; Or on described substrate surface, be coated with negative photoresist, utilize the legal copy needing to prepare PZT thick film figure to expose negative photoresist; Formed thus and be overlying on on-chip patterned photoresist layer; After development, obtain at the photoresist material needing the position of preparing PZT thick film to remain, and eliminate the photoresist material of other positions outside the described position needing to prepare PZT thick film.Then selectivity deposition or deposit zinc oxide sacrifice layer on the substrate with graphical photoresist layer, after formation patterned oxide zinc sacrifice layer, adopt the solution that removes photoresist to carry out process of removing photoresist, on-chip photoresist material is removed, so that prepare PZT thick film afterwards on substrate.The schematic diagram of the oxidation sacrifice layer after graphical as shown in Figure 3.
Method two, at deposition on substrate or deposit zinc oxide sacrifice layer, then at zinc oxide sacrificial layer surface coating positive photoresist, utilizes and needs the egative forme preparing PZT thick film figure to positive photoresist photolithographic exposure, development; Or negative photoresist is coated with in zinc oxide sacrificial layer surface, utilize and need the legal copy preparing PZT thick film figure to negative photoresist photolithographic exposure, development; Then by acid or alkaline corrosion liquid, wet etching is carried out to the zinc oxide sacrifice layer removing photoresist material region, finally photoresist material is removed, formed and be overlying on on-chip patterned zinc oxide sacrifice layer.
Wherein, the corrosive fluid of wet etching comprises any one solution in the etchant solution of the etchant solution of phosphoric acid solution, HBr solution, nitric acid and phosphoric acid, phosphoric acid and acetic acid, acetum, sodium hydroxide solution, ammonium chloride solution or ammoniacal liquor corrosive fluid.
Step 103, is coated in PZT slurry on described zinc oxide sacrifice layer, under 200 DEG C ~ 500 DEG C conditions, carries out the pre-crystallized process of 1 ~ 60 minute.
Particularly, PZT powder is added in PZT colloid; Ultrasonic disperse is adopted to be mixed into slurry; After the slurry static placement be mixed into being precipitated for 1-15 days, remove the coarse powder particles being greater than 250nm in slurry; To removing, the slurry after being greater than 250nm coarse particles concentrates, ageing again, that is, by slurry static the placements 5-20 days again after concentrated, form that contain fine particle, stable PZT slurry.
Use the PZT slurry prepared, on the substrate with patterned oxide zinc sacrifice layer, prepare PZT wet film by coating processes.Be under the condition of 200 DEG C ~ 500 DEG C in temperature, the PZT wet film of preparation carried out the pre-crystallized process of insulation of 1 ~ 60 minute.
Step 104, under 600 DEG C ~ 1000 DEG C conditions, carries out the crystallization treatment of 1 ~ 180 minute.
Particularly, after PZT wet film carries out pre-crystallized process, then be that under the condition of 600 DEG C ~ 1000 DEG C, carry out the insulation crystallization treatment of 1 ~ 180 minute, finally obtaining thickness is 2 μm ~ 200 μm PZT thick films, as shown in Figure 4 in temperature.
Step 105, described substrate surface being covered with described PZT slurry is inserted in corrosive fluid, obtains the PZT thick film with microstructure after stripping.
After completing steps 101 to 104, substrate is put into the zinc oxide sacrifice layer corrosion liquid that temperature is normal temperature to 500 DEG C, corrosion release zinc oxide sacrifice layer, peels off the PZT thick film on described zinc oxide sacrifice layer simultaneously.After stripping, be retained in the PZT thick film that method that described on-chip PZT thick film is the embodiment of the present invention and provides obtains.As shown in Figure 5,6.Wherein, the sectional view with microstructure PZT thick film that provides for the embodiment of the present invention 1 of Fig. 5; The vertical view with microstructure PZT thick film that Fig. 6 provides for the embodiment of the present invention 1.
Embodiment provided by the invention adopts improvement slurry and process of thermal treatment, can significantly improve surface finish and the density of PZT thick film.Meanwhile, by the lift-off technology of zinc oxide as sacrifice layer, the problem that PZT thick film is difficult to clean etching can be overcome, and avoid in prior art, directly PZT thick film be carried out to the various problems of wet etching and dry etching.The PZT thick film with microstructure adopting this preparation method to prepare have processing compatibility good, to other rete damage low, graphical quality advantages of higher.
Following with the preparation method described in multiple specific examples explanation employing embodiment 1, preparation has the detailed process of the PZT thick film of microstructure.
Embodiment 2
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 1 day, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 5 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Adopt the method for radio-frequency sputtering, the silicon substrate cleaned up is prepared the zinc oxide sacrifice layer of 0.01 μm; Zinc oxide sacrificial layer surface is coated with positive photoresist, utilizes the egative forme of the PZT thick film figure needing preparation to positive photoresist photolithographic exposure, development; Silicon substrate after photolithographic exposure, development is put into phosphoric acid, carries out wet method pattern zinc oxide sacrifice layer, obtain graphical rear oxidation zinc sacrifice layer as shown in Figure 4.
Then, use the PZT slurry prepared, on patterned zinc oxide sacrifice layer substrate, PZT wet film is prepared by coating processes, be under the condition of 200 DEG C in temperature, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 650 DEG C, carry out the insulation crystallization treatment of 20 minutes, obtain the PZT thick film that thickness is 2 μm in temperature.
Substrate after above-mentioned technique is put into phosphoric acid, and etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, obtain staying on-chip PZT thick film.
Embodiment 3
The method that the embodiment of the present invention adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 15 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 20 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Cleaning potassium nitride substrate; Potassium nitride substrate is prepared the zinc oxide sacrifice layer that thickness is 0.01 μm; The process of patterned oxide zinc sacrifice layer is identical with the process of embodiment 2 patterned oxide zinc sacrifice layer, here repeats no more.
Use the PZT slurry prepared, on the substrate with patterned oxide zinc sacrifice layer, prepare PZT wet film by coating processes; Be under the condition of 500 DEG C in temperature, PZT wet film carried out to the pre-crystallized process of insulation in 10 minutes, then be, under the condition of 700 DEG C, carry out the insulation crystallization treatment of 60 minutes, carried out the preparation that thickness is the PZT thick film of 10 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, obtain staying on-chip PZT thick film, and its treating processes is identical with the treating processes implementing 2.
Embodiment 4
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 10 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 10 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Adopt metal-organic decomposition method, the arsenic potassium substrate cleaned up is prepared the zinc oxide sacrifice layer of 5 μm; At zinc oxide sacrificial layer surface coating negative photoresist, utilize and need the legal copy of the PZT thick film figure of preparation to expose negative photoresist, develop, form the substrate with graphical photoresist material; Then substrate is put into phosphoric acid to etch, form patterned oxide zinc sacrifice layer.
Then, use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, be under the condition of 300 DEG C in temperature, PZT wet film carried out to the pre-crystallized process of insulation in 1 minute, and then be under the condition of 850 DEG C in temperature, carry out the insulation crystallization treatment of 60 minutes, obtain the PZT thick film that thickness is 4 μm.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film obtains the treating processes of PZT thick film with embodiment 2.
Embodiment 5
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 6 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 15 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Adopt metal-organic decomposition method, the sapphire substrate cleaned up is prepared the zinc oxide sacrifice layer of 0.5 μm; The process of patterned oxide zinc sacrifice layer can adopt the treating processes of embodiment 3 or adopt the treating processes in embodiment 4.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 60 minutes, and then be, under the condition of 600 DEG C, carry out the insulation crystallization treatment of 180 minutes, carried out the preparation that thickness is the PZT thick film of 20 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 6
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 8 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 12 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
The ruby substrate surface cleaned up is coated with photoresist material; Photoetching is carried out to described substrate surface; After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film; Adopt sol-gel method, the zinc oxide sacrifice layer of deposit 15 μm; Remove the photoresist material of described substrate surface, complete the graphical of zinc oxide sacrifice layer.Wherein, the process of patterned oxide zinc sacrifice layer is identical with embodiment 2.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 30 minutes, and then be, under the condition of 1000 DEG C, carry out the insulation crystallization treatment of 1 minute, carried out the preparation that thickness is the PZT thick film of 30 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 7
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 10 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 18 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Photoresist material is coated with on the surface at the quartz substrate cleaned up; Photoetching is carried out to described substrate surface; After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film; Adopt pulsed laser deposition, the zinc oxide sacrifice layer of deposit 1000 μm; Remove the photoresist material of described substrate surface, complete the graphical of zinc oxide sacrifice layer.Wherein, the process of patterned oxide zinc sacrifice layer is identical with embodiment 4.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 600 DEG C, carry out the insulation crystallization treatment of 30 minutes, carried out the preparation that thickness is the PZT thick film of 200 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 8
The method that the present embodiment adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and process prepared by PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 7 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 15 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Adopt hydrothermal method, the silicon carbide substrate cleaned up is prepared the zinc oxide sacrifice layer of 500 μm; The process of patterned oxide zinc sacrifice layer can adopt the treating processes of embodiment 3 or adopt the treating processes in embodiment 4.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 900 DEG C, carry out the insulation crystallization treatment of 30 minutes, carried out the preparation that thickness is the PZT thick film of 100 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 9
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 5 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 10 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
The germanium substrate surface cleaned up is coated with photoresist material; Photoetching is carried out to described substrate surface; After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film; Adopt radio frequency sputtering method, the zinc oxide sacrifice layer of deposit 1 μm; Remove the photoresist material of described substrate surface, complete the graphical of zinc oxide sacrifice layer.Wherein, the process of patterned oxide zinc sacrifice layer can adopt the treating processes of embodiment 3 or adopt the treating processes in embodiment 4.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 600 DEG C, carry out the insulation crystallization treatment of 30 minutes, carried out the preparation that thickness is the PZT thick film of 8 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 10
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 15 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 10 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Cleaning diamond substrate, adopts hydrothermal method, and the diamond substrate processed is prepared the zinc oxide sacrifice layer of 3 μm; Zinc oxide sacrifice layer is graphical, and the process of patterned oxide zinc sacrifice layer can adopt the treating processes of embodiment 3 or adopt the treating processes in embodiment 4.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 250 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 650 DEG C, carry out the insulation crystallization treatment of 40 minutes, carried out the preparation that thickness is the PZT thick film of 12 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying on-chip PZT thick film is identical with embodiment 2.
Embodiment 11
The method that the embodiment of the present invention adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 5 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 10 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Cleaning silicon substrate, adopts radio frequency sputtering method, and the silicon substrate cleaned up is prepared the zinc oxide sacrifice layer of 0.01 μm; Carry out graphically to zinc oxide sacrifice layer, the process of patterned oxide zinc sacrifice layer is identical with embodiment 2.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 350 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 850 DEG C, carry out the insulation crystallization treatment of 40 minutes, carried out the preparation that thickness is the PZT thick film of 15 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying PZT thick film on substrate is identical with embodiment 2.
Embodiment 12
The method that the embodiment of the present invention adopts embodiment 1 to provide prepares a kind of PZT thick film with microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 3 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 6 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
Adopt radio frequency sputtering method, the silicon substrate being covered with nonmetal silicon nitride film and graphical Pt/Ti metallic film on surface prepares thickness for being 1 μm of zinc oxide sacrifice layer; Carry out graphically to zinc oxide sacrifice layer, the process of patterned oxide zinc sacrifice layer is identical with the treating processes in embodiment 2.
Use the PZT slurry prepared, pass through coating processes, PZT wet film prepared by patterned zinc oxide sacrifice layer substrate, under the condition of temperature 350 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 750 DEG C, carry out the insulation crystallization treatment of 50 minutes, carried out the preparation that thickness is the PZT thick film of 38 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying PZT thick film on substrate is identical with embodiment 2.
In the present embodiment, Pt/Ti double-layer metal film as the bottom electrode of PZT ferroelectric thick film, for the measurement to PZT thick film or related device performance.
In the present embodiment, preferably, Pt/Ti double-layer metal film also can whole film as bottom electrode, do not need graphical.
Embodiment 13
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 2 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 18 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
In the present embodiment, the preparation process of PZT thick film is identical with embodiment 12, the just embodiment of the present invention, adopt the silicon substrate cleaned up, first the silica membrane that thickness is 0.01 μm ~ 10 μm is prepared on a silicon substrate, then sputtering or ion beam coating equipment is utilized, Pt/Ti double-layer metal film is prepared on the surface at the silica membrane of preparation, and graphical Pt/Ti double-layer metal film.
Further, adopt radio frequency sputtering method, prepare the zinc oxide sacrifice layer that thickness is 2 μm; Carry out graphically to zinc oxide sacrifice layer, wherein, the process of patterned oxide zinc sacrifice layer is identical with the process in embodiment 2.
Further again, use the PZT slurry prepared, on the substrate with the sacrifice layer graphically, prepare PZT wet film by coating processes; Under the condition of temperature 450 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 950 DEG C, carry out the insulation crystallization treatment of 10 minutes, carried out the preparation that thickness is the PZT thick film of 26 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying PZT thick film on substrate is identical with embodiment 2.
Embodiment 14
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 3 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 16 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
The detailed process of the preparation method of the PZT thick film of the embodiment of the present invention is identical with embodiment 12, just the present embodiment, use the silicon substrate cleaned up, first preparing on a silicon substrate thickness is the 0.01 μm ~ silicon-dioxide of 10 μm and the laminated film of silicon nitride, then sputtering or ion beam coating equipment is utilized, Au/Cr double-layer metal film is prepared on the surface at the silica membrane of preparation, and graphical Au/Cr double-layer metal film, it is by coating photoresist material that described etching is peeled off, exposure, the process of development, concrete graphic method is identical with patterning process in embodiment 2.
Further, adopt radio frequency sputtering method, prepare the zinc oxide sacrifice layer that thickness is 2 μm; Patterned oxide zinc sacrifice layer, wherein the process of the process of patterned oxide zinc sacrifice layer middle patterned oxide zinc sacrifice layer identical with embodiment 2 is identical.
Further again, use the PZT slurry prepared, on the substrate with the sacrifice layer graphically, prepare PZT wet film by coating processes; Under the condition of temperature 250 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 600 DEG C, carry out the insulation crystallization treatment of 180 minutes, carried out the preparation that thickness is the PZT thick film of 50 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying PZT thick film on substrate is identical with embodiment 2.
Embodiment 15
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 5 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 5 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
In the present embodiment, use the silicon substrate cleaned up, first utilize sputtering or ion beam coating equipment, preparing Pt/Ti double-layer metal film on a silicon substrate, and graphical Pt/Ti double-layer metal film.
Be coated with photoresist material over the substrate surface; And carry out photoetching; After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film; Adopt radio frequency sputtering method, the zinc oxide sacrifice layer of deposit 1 μm; Remove the photoresist material of described substrate surface, complete the graphical of zinc oxide sacrifice layer.
Wherein, the process of patterned oxide zinc sacrifice layer is identical with the process of patterned oxide zinc sacrifice layer in embodiment 2.Further again, use the PZT slurry prepared, on the substrate with the sacrifice layer graphically, prepare PZT wet film by coating processes; Under the condition of temperature 350 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 30 minutes, and then be, under the condition of 950 DEG C, carry out the insulation crystallization treatment of 5 minutes, carried out the preparation that thickness is the PZT thick film of 30 μm in temperature.
Etching oxidation zinc sacrifice layer and the PZT thick film peeled off on zinc oxide sacrifice layer, the process obtaining staying PZT thick film on substrate is identical with embodiment 2.
Embodiment 16
The method preparation that the present embodiment adopts embodiment 1 to provide has the PZT thick film of microstructure, and the preparation process of PZT thick film is specially:
PZT powder is added in PZT colloid, is mixed into slurry by ultrasonic disperse; By static for mixed slurry placement 10 days, after then removing slurry sediment, be greater than the coarse particles of 250nm; Concentrate removing the slurry after being greater than 250nm coarse particles again, and by the static placement 10 days again of the slurry after concentrated, form the PZT slurry containing fine powder.
The preparation process of the PZT thick film of the present embodiment is identical with embodiment 14, the just embodiment of the present invention, use the silicon substrate cleaned up, first preparing on a silicon substrate thickness is the 0.01 μm ~ silicon-dioxide of 10 μm and the laminated film of silicon nitride, then sputtering or ion beam coating equipment is utilized, Pt/Ti double-layer metal film is prepared on the surface at the silica membrane of preparation, and graphical Pt/Ti double-layer metal film.
Further, adopt radio frequency sputtering method, prepare the zinc oxide sacrifice layer that thickness is 3 μm; Patterned oxide zinc sacrifice layer, process is identical with embodiment 2.
Further again, use the PZT slurry prepared, on the substrate with the sacrifice layer graphically, prepare PZT wet film by coating processes; Under the condition of temperature 200 DEG C, PZT wet film is carried out to the pre-crystallized process of insulation in 10 minutes, and then be, under the condition of 650 DEG C, carry out the insulation crystallization treatment of 40 minutes, carried out the preparation that thickness is the PZT thick film of 36 μm in temperature.
The process peeling off graphical PZT thick film is identical with embodiment 2.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection domain be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. have a preparation method for microstructure lead zirconate titanate PZT thick film, it is characterized in that, described method comprises:
Patterned zinc oxide sacrifice layer is prepared on the surface of substrate;
PZT slurry is coated on described zinc oxide sacrifice layer, under 200 DEG C ~ 500 DEG C conditions, carries out the pre-crystallized process of 1 ~ 60 minute;
Again under 600 DEG C ~ 1000 DEG C conditions, carry out the crystallization treatment of 1 ~ 180 minute;
Described substrate surface being covered with described PZT slurry is inserted in corrosive fluid, obtains the PZT thick film with microstructure after stripping.
2. method according to claim 1, is characterized in that, the described surface at substrate is prepared patterned zinc oxide sacrifice layer and specifically comprised:
Deposit or depositing zinc oxide sacrifice layer on the surface of the substrate;
Described zinc oxide sacrifice layer applies photoresist material;
Photoetching is carried out to described photoresist material;
Described zinc oxide sacrifice layer after photoetching is graphically etched;
Remove the photoresist material of described substrate surface.
3. method according to claim 1, is characterized in that, the described surface at substrate is prepared patterned zinc oxide sacrifice layer and specifically comprised:
At substrate surface coating photoresist material;
Photoetching is carried out to described substrate surface;
After development, needing the position of preparing PZT thick film to retain photoresist material, and removing the photoresist material of other positions outside the described position needing to prepare PZT thick film;
Deposit or depositing zinc oxide sacrifice layer;
Remove the photoresist material of described substrate surface.
4. method according to claim 1, is characterized in that, described substrate comprises the arbitrary substrate in silicon substrate, gan substrate, sapphire substrate, ruby substrate, quartz substrate, gallium arsenide substrate, silicon carbide substrate, germanium substrate or diamond substrate; Or surface is covered with the arbitrary described substrate of non-metallic film or metallic membrane; Wherein said non-metallic film comprises: in silicon dioxide film, silicon nitride film, polysilicon film one or more; Described metallic membrane comprises: Pt/Ti metallic film or Au/Cr metallic film.
5. the method according to claim, it is characterized in that, described deposit or depositing zinc oxide sacrifice layer specifically comprise the zinc oxide sacrifice layer that in employing sol-gel method, metal-organic decomposition method, sputtering method, Metalorganic Chemical Vapor Deposition, pulsed laser deposition or hydrothermal method prepared by either method.
6. method according to claim 1, is characterized in that, the thickness of described zinc oxide sacrifice layer is 0.01 μm ~ 1000 μm.
7. method according to claim 1, is characterized in that, the thickness of described PZT thick film is 2 μm ~ 200 μm.
8. method according to claim 1, is characterized in that, the preparation process of described PZT slurry is:
PZT powder is added in PZT colloid;
Adopt ultrasonic disperse to be mixed into slurry, staticly settle the particle that rear removal is greater than 250nm;
To removing, the slurry of particle concentrates, ageing, forms PZT slurry.
9. method according to claim 1, it is characterized in that, described corrosive fluid comprises the arbitrary solution in the etchant solution of the etchant solution of phosphoric acid solution, HBr solution, nitric acid and phosphoric acid, phosphoric acid and acetic acid, acetum, sodium hydroxide solution, ammonium chloride solution or ammoniacal liquor corrosive fluid.
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| CN116053368A (en) * | 2023-04-03 | 2023-05-02 | 南昌凯捷半导体科技有限公司 | Red light LED chip with ZnO sacrificial layer and manufacturing method thereof |
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