CN104311007A - Preparation method of piezoelectric ceramic transducer (PZT) thick film with micro structure - Google Patents

Abstract

The invention provides a method for preparing a PZT thick film with a microstructure of lead zirconate titanate, which is characterized in that the method includes: preparing a patterned zinc oxide sacrificial layer on the surface of the substrate; coating the PZT slurry on the On the zinc oxide sacrificial layer, carry out pre-crystallization treatment for 1-60 minutes at 200°C-500°C; then carry out crystallization treatment for 1-180 minutes at 600°C-1000°C; The substrate of the PZT slurry is placed in an etching solution, and a PZT thick film with a microstructure is obtained after peeling off. The preparation method can obviously improve the surface smoothness and density of the PZT thick film by adopting the process of improving the slurry and heat treatment. At the same time, the problem that the PZT thick film is difficult to cleanly etch can be overcome by using zinc oxide as the stripping technology of the sacrificial layer.

Description

Preparation method of lead zirconate titanate PZT thick film with microstructure

technical field

The invention relates to the technical field of material preparation, in particular to a preparation method of a lead zirconate titanate PZT thick film with a microstructure.

Background technique

Lead zirconate titanate (Piezoelectric Ceramic Transducer, PZT) film has excellent ferroelectric, piezoelectric, and pyroelectric properties, and is widely used in uncooled infrared detectors, non-volatile ferroelectric memories, microsensors and micro-executions. device etc. Compared with PZT thin films, it is more difficult to prepare and pattern PZT thick films with a thickness of more than 1 micron.

At present, the preparation method of PZT thick film is mainly the 0-3 method. Compared with screen printing and other methods, it has the advantages of low crystallization temperature and better film quality. However, the preparation of PZT thick film by the 0-3 method still has at least the following problems: Disadvantages: The prepared PZT thick film has disadvantages such as low film density and rough surface. The patterning techniques of PZT thick film mainly include: wet etching and dry etching. Since the wet etching of PZT contains highly corrosive acids, it has poor compatibility with the manufacturing process of semiconductors and micro-electromechanical systems, and the wet etching of PZT thick films is difficult, and the pattern lateral corrosion is more serious. Dry etching has the disadvantages of high equipment cost, difficult control of the end point, and easy damage to other thin film layers. In addition, since there is a large amount of PZT powder in the PZT thick film prepared by the 0-3 method, it is easy to leave a large amount of PZT powder regardless of wet or dry etching.

Contents of the invention

The invention provides a preparation method of a lead zirconate titanate PZT thick film with a microstructure, which is used to improve the density and flatness of the PZT thick film and improve its patterning quality; in the preparation process, wet corrosion is avoided The strong acid contained in it causes poor compatibility with the manufacturing process of semiconductors and microelectronic mechanical systems, difficult wet etching, serious pattern lateral corrosion, high cost of dry etching, difficulty in controlling the degree of corrosion, and wet etching and dry etching Problems such as a large amount of PZT powder remaining.

In order to achieve the above object, the invention provides a kind of preparation method with microstructure PZT thick film, described method comprises:

preparing a patterned zinc oxide sacrificial layer on the surface of the substrate;

Coating PZT slurry on the zinc oxide sacrificial layer, and performing a pre-crystallization treatment for 1 to 60 minutes at a temperature of 200°C to 500°C;

Then, under the condition of 600°C-1000°C, carry out crystallization treatment for 1-180 minutes;

The substrate covered with the PZT slurry is placed in the etching solution, and a PZT thick film with a microstructure is obtained after peeling off.

Preferably, the preparation of a patterned zinc oxide sacrificial layer on the surface of the substrate specifically includes:

depositing or depositing a zinc oxide sacrificial layer on the surface of the substrate;

Coating photoresist on the zinc oxide sacrificial layer;

performing photoetching on the photoresist;

performing patterned etching on the zinc oxide sacrificial layer after photolithography;

removing the photoresist on the surface of the substrate.

Preferably, the preparation of a patterned zinc oxide sacrificial layer on the surface of the substrate specifically includes:

Coating photoresist on the substrate surface;

performing photoetching on the surface of the substrate;

After developing, keep the photoresist at the position where the PZT thick film needs to be prepared, and remove the photoresist at other positions except the position where the PZT thick film needs to be prepared;

depositing or depositing a zinc oxide sacrificial layer;

removing the photoresist on the surface of the substrate.

Preferably, the substrates include silicon substrates, gallium nitride substrates, sapphire substrates, ruby substrates, quartz substrates, gallium arsenide substrates, silicon carbide substrates, germanium substrates, and diamond substrates. Any substrate; or any substrate covered with a non-metal film or a metal film; wherein the non-metal film includes: one or more of a silicon dioxide film, a silicon nitride film, and a polysilicon film ; The metal film includes: Pt/Ti metal film or Au/Cr metal film.

Preferably, the depositing or depositing the zinc oxide sacrificial layer specifically includes using any method in sol-gel method, metal-organic decomposition method, sputtering method, metal-organic chemical vapor deposition method, pulsed laser deposition method or hydrothermal method ZnO sacrificial layer prepared.

Preferably, the zinc oxide sacrificial layer has a thickness of 0.01 μm˜1000 μm.

Preferably, the thickness of the PZT thick film is 2 μm˜200 μm.

Preferably, the preparation process of the PZT slurry is:

Add PZT powder to PZT colloid;

Use ultrasonic dispersion to mix into a slurry, and remove particles larger than 250nm after standing and settling;

The particle-removed slurry is concentrated and aged to form a PZT slurry.

Preferably, the etching solution includes any one of phosphoric acid solution, HBr solution, nitric acid and phosphoric acid etching solution, phosphoric acid and acetic acid etching solution, acetic acid solution, sodium hydroxide solution, ammonium chloride solution or ammonia water etching solution.

Therefore, the present invention provides a method for preparing a PZT thick film with a microstructure. The preparation method can significantly improve the surface smoothness and density of the PZT thick film by adopting improved slurry and heat treatment processes. At the same time, the problem that the PZT thick film is difficult to cleanly etch can be overcome by using zinc oxide as the stripping technology of the sacrificial layer. The PZT thick film with microstructure prepared by the preparation method has the advantages of good process compatibility, low damage to other film layers, high patterning quality and the like.

Description of drawings

Fig. 1 is a kind of preparation method flowchart that has microstructure PZT thick film that the embodiment of the present invention 1 provides;

2 is a cross-sectional view after preparing a zinc oxide sacrificial layer on a substrate provided in Example 1 of the present invention;

3 is a cross-sectional view of the patterned zinc oxide sacrificial layer provided in Example 1 of the present invention;

Fig. 4 is the sectional view after preparing the PZT thick film that the embodiment of the present invention 1 provides;

5 is a sectional view of a PZT thick film with a microstructure provided by Embodiment 1 of the present invention;

FIG. 6 is a top view of a PZT thick film with a microstructure provided by Embodiment 1 of the present invention.

Detailed ways

The technical solutions of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. But it is not intended to limit the protection scope of the present invention.

The embodiment of the present invention provides a method for preparing a PZT thick film with a microstructure, which is used to improve the density and flatness of the PZT thick film, and improve its patterning quality.

Example 1

FIG. 1 is a flow chart of the method for preparing a PZT thick film provided by Example 1 of the present invention. 2-6 provide schematic diagrams of the preparation process for each step in the preparation process. Next, according to FIG. 1 and in combination with FIGS. 2-6 , the method for preparing a PZT thick film with a microstructure will be described in detail.

As shown in Figure 1, the preparation method specifically includes the following steps:

Step 101, cleaning the substrate.

Specifically, the substrate is put into an acid cleaning solution or an alkaline cleaning solution for cleaning, and then deionized water is used to rinse the substrate.

The substrate can be any one of silicon substrate, gallium nitride substrate, sapphire substrate, ruby substrate, quartz substrate, gallium arsenide substrate, silicon carbide substrate, germanium substrate, diamond substrate Substrate; or any one of the above-mentioned substrates covered with non-metallic film or metal film. Wherein, the non-metal film includes: one or more of a silicon dioxide film, a silicon nitride film, and a polysilicon film; the metal film includes: a Pt/Ti double-layer metal film or an Au/Cr double-layer metal film .

Optionally, it may also be a substrate including both the above-mentioned non-metal film and metal film.

Step 102, preparing a patterned zinc oxide sacrificial layer on the surface of the substrate.

Specifically, any one of the sol-gel method, metal-organic decomposition method, sputtering method, metal-organic chemical vapor deposition method, pulsed laser deposition method or hydrothermal method is used to prepare a film with a thickness of 0.01μm～1000μm zinc oxide sacrificial layer. As shown in FIG. 2 , a cross-sectional view after preparing a zinc oxide sacrificial layer on the substrate.

The following two methods can be used to prepare a patterned zinc oxide sacrificial layer on the surface of the substrate:

Method 1: first coat a positive photoresist on the surface of the substrate, and expose the positive photoresist using a negative plate that needs to prepare a PZT thick film pattern; or coat a negative photoresist on the surface of the substrate, Use the positive plate that needs to prepare PZT thick film graphics to expose the negative photoresist; thus form a patterned photoresist layer covering the substrate; after development, obtain the remaining at the position where PZT thick film needs to be prepared photoresist, and remove the photoresist at other positions than the position where the PZT thick film needs to be prepared. Then selectively deposit or deposit a zinc oxide sacrificial layer on the substrate with a patterned photoresist layer, and use a stripping solution to remove the photoresist on the substrate after the patterned zinc oxide sacrificial layer is formed. In order to prepare PZT thick film on the substrate later. A schematic diagram of the patterned oxidation sacrificial layer is shown in FIG. 3 .

The second method is to deposit or deposit a zinc oxide sacrificial layer on the substrate, then coat a positive photoresist on the surface of the zinc oxide sacrificial layer, and use a negative plate that needs to prepare a PZT thick film pattern to photolithographically expose the positive photoresist, development; or apply a negative photoresist on the surface of the zinc oxide sacrificial layer, and use the positive version that needs to prepare a PZT thick film pattern to expose and develop the negative photoresist photolithography; then remove the photoresist by acidic or alkaline etching solution The zinc oxide sacrificial layer in the glue area is subjected to wet etching, and finally the photoresist is removed to form a patterned zinc oxide sacrificial layer covering the substrate.

Among them, the etching solution for wet etching includes any one of phosphoric acid solution, HBr solution, nitric acid and phosphoric acid etching solution, phosphoric acid and acetic acid etching solution, acetic acid solution, sodium hydroxide solution, ammonium chloride solution or ammonia water etching solution solution.

Step 103 , coating the PZT slurry on the zinc oxide sacrificial layer, and performing a pre-crystallization treatment at 200° C. to 500° C. for 1 to 60 minutes.

Specifically, add PZT powder to PZT colloid; use ultrasonic dispersion to mix into slurry; place the mixed slurry for 1-15 days to settle, and remove coarse powder particles larger than 250nm in the slurry; then remove particles larger than 250nm The thickened slurry is concentrated and aged, that is, the concentrated slurry is left still for 5-20 days to form a stable PZT slurry containing fine powder particles.

Using the prepared PZT slurry, a PZT wet film was prepared on a substrate with a patterned zinc oxide sacrificial layer by a coating process. Under the condition that the temperature is 200° C. to 500° C., the prepared PZT wet film is subjected to heat preservation pre-crystallization treatment for 1 to 60 minutes.

Step 104, performing crystallization treatment at 600° C. to 1000° C. for 1 to 180 minutes.

Specifically, after the pre-crystallization treatment of the PZT wet film, the crystallization treatment is carried out at a temperature of 600 ° C to 1000 ° C for 1 to 180 minutes, and finally a thick PZT film with a thickness of 2 μm to 200 μm is obtained, as shown in Figure 4 Show.

Step 105, putting the substrate covered with the PZT slurry into an etching solution, and peeling off to obtain a thick PZT film with a microstructure.

After steps 101 to 104 are completed, the substrate is placed in a zinc oxide sacrificial layer etching solution at a temperature ranging from normal temperature to 500° C., the zinc oxide sacrificial layer is released by corrosion, and the thick PZT film on the zinc oxide sacrificial layer is peeled off at the same time. After peeling off, the PZT thick film remaining on the substrate is the PZT thick film obtained by the method provided in the embodiment of the present invention. As shown in Figure 5 and 6. Among them, FIG. 5 is a cross-sectional view of the PZT thick film with microstructure provided in Example 1 of the present invention; FIG. 6 is a top view of the PZT thick film with microstructure provided in Example 1 of the present invention.

The embodiment provided by the present invention adopts the process of improving the slurry and heat treatment, which can obviously improve the surface flatness and density of the PZT thick film. At the same time, the peeling technology of zinc oxide as a sacrificial layer can overcome the problem that the PZT thick film is difficult to etch cleanly, and avoid various problems in the prior art that directly perform wet etching and dry etching on the PZT thick film. The PZT thick film with microstructure prepared by the preparation method has the advantages of good process compatibility, low damage to other film layers, high patterning quality and the like.

The specific process of preparing a PZT thick film with a microstructure using the preparation method described in Example 1 is described below with a number of specific examples.

Example 2

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically as follows:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry for 1 day, and then remove the coarse particles larger than 250nm after slurry precipitation; then remove the slurry after removing the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 5 days to form a PZT slurry containing fine powder.

Prepare a 0.01μm zinc oxide sacrificial layer on the cleaned silicon substrate by radio frequency sputtering; apply a positive photoresist on the surface of the zinc oxide sacrificial layer, and use the negative plate of the PZT thick film pattern to be prepared for positive alignment Photoresist photolithographic exposure and development; put the silicon substrate after photolithographic exposure and development into phosphoric acid, and perform wet patterning of the zinc oxide sacrificial layer to obtain the patterned zinc oxide sacrificial layer as shown in Figure 4 .

Then, use the prepared PZT slurry to prepare a PZT wet film on the patterned zinc oxide sacrificial layer substrate through a coating process, and perform a pre-crystallization treatment on the PZT wet film for 10 minutes at a temperature of 200 ° C. , and then under the condition that the temperature is 650° C., the crystallization treatment is carried out for 20 minutes to obtain a PZT thick film with a thickness of 2 μm.

Put the substrate after the above process into phosphoric acid, etch the zinc oxide sacrificial layer and peel off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film left on the substrate.

Example 3

The embodiment of the present invention uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 15 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the slurry after removing the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 20 days to form a PZT slurry containing fine powder.

Clean the potassium nitride substrate; prepare a zinc oxide sacrificial layer with a thickness of 0.01 μm on the potassium nitride substrate; repeat.

Using the prepared PZT slurry, a PZT wet film was prepared on a substrate with a patterned zinc oxide sacrificial layer through a coating process; at a temperature of 500 ° C, the PZT wet film was subjected to a pre-crystallization treatment of 10 minutes of heat preservation, Then, under the condition of temperature of 700° C., the crystallization treatment was carried out at a temperature of 60 minutes, so as to complete the preparation of a PZT thick film with a thickness of 10 μm.

Etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film left on the substrate, the processing process is the same as that in Embodiment 2.

Example 4

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically as follows:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 10 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 10 days to form a PZT slurry containing fine powder.

Prepare a zinc oxide sacrificial layer of 5 μm on the cleaned potassium arsenide substrate by metal-organic decomposition method; coat negative photoresist on the surface of the zinc oxide sacrificial layer, and use the positive version of the PZT thick film pattern to be prepared. The photoresist is exposed and developed to form a substrate with patterned photoresist; then the substrate is put into phosphoric acid for etching to form a patterned zinc oxide sacrificial layer.

Then, use the prepared PZT slurry to prepare a PZT wet film on the patterned zinc oxide sacrificial layer substrate through a coating process, and perform a pre-crystallization of the PZT wet film at a temperature of 300 ° C for 1 minute. treatment, and then at a temperature of 850° C., a crystallization treatment of 60 minutes was carried out to obtain a PZT thick film with a thickness of 4 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film left on the substrate is the same as that in Example 2 to obtain the PZT thick film.

Example 5

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically as follows:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 6 days, and then remove the coarse particles larger than 250nm after the slurry precipitates; then remove the coarse particles larger than 250nm. Concentrating is carried out, and the concentrated slurry is left still for 15 days to form a PZT slurry containing fine powder.

A zinc oxide sacrificial layer of 0.5 μm was prepared on the cleaned sapphire substrate by metal-organic decomposition method;

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was subjected to a pre-crystallization treatment of 60 minutes of heat preservation at a temperature of 200 ° C, and then Then, under the condition of temperature of 600° C., the crystallization treatment was carried out at a temperature of 180 minutes, so as to complete the preparation of a PZT thick film with a thickness of 20 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 6

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically as follows:

Add PZT powder to PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 8 days, and then remove the coarse particles larger than 250nm after slurry precipitation; then remove the slurry after removing coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 12 days to form a PZT slurry containing fine powder.

Coating photoresist on the cleaned ruby substrate surface; Carry out photoetching to described substrate surface; After developing, keep photoresist at the position that needs to prepare PZT thick film, and remove described need to prepare PZT thick film photoresist at positions other than the position of the substrate; a sol-gel method is used to deposit a zinc oxide sacrificial layer of 15 μm; the photoresist on the surface of the substrate is removed to complete the patterning of the zinc oxide sacrificial layer. Wherein, the process of patterning the zinc oxide sacrificial layer is the same as that of embodiment 2.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was subjected to a pre-crystallization treatment of 30 minutes of heat preservation at a temperature of 200 ° C, and then Then, under the condition of temperature of 1000° C., the crystallization treatment is carried out by keeping the temperature for 1 minute, so as to complete the preparation of the PZT thick film with a thickness of 30 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 7

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically as follows:

Add PZT powder to PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 10 days, and then remove the coarse particles larger than 250nm after slurry precipitation; then remove the slurry after removing coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 18 days to form a PZT slurry containing fine powder.

Apply photoresist on the cleaned quartz substrate surface; carry out photoetching to the substrate surface; after development, keep the photoresist at the position where the PZT thick film needs to be prepared, and remove the need to prepare the PZT thick film The photoresist at other positions than the position of the substrate; the pulsed laser deposition method is used to deposit a zinc oxide sacrificial layer of 1000 μm; the photoresist on the surface of the substrate is removed to complete the patterning of the zinc oxide sacrificial layer. Wherein, the process of patterning the zinc oxide sacrificial layer is the same as that of Embodiment 4.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was subjected to a pre-crystallization treatment of 10 minutes of heat preservation at a temperature of 200 ° C, and then Then, under the condition of temperature of 600° C., the crystallization treatment was carried out at a temperature of 30 minutes, so as to complete the preparation of a PZT thick film with a thickness of 200 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 8

In this embodiment, the method provided in Example 1 is used to prepare a PZT thick film with a microstructure, and the process of preparing the PZT thick film is specifically as follows:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry for 7 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the slurry after removing the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 15 days to form a PZT slurry containing fine powder.

A zinc oxide sacrificial layer of 500 μm was prepared on the cleaned silicon carbide substrate by a hydrothermal method;

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was subjected to a pre-crystallization treatment of 10 minutes of heat preservation at a temperature of 200 ° C, and then Then, under the condition of temperature of 900° C., the crystallization treatment was carried out with heat preservation for 30 minutes, so as to complete the preparation of a PZT thick film with a thickness of 100 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 9

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 5 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 10 days to form a PZT slurry containing fine powder.

Coating photoresist on the cleaned germanium substrate surface; performing photoetching on the substrate surface; after developing, retain photoresist at the position where PZT thick film needs to be prepared, and remove the need to prepare PZT thick film photoresist at positions other than the position of the substrate; a 1 μm zinc oxide sacrificial layer is deposited by radio frequency sputtering; the photoresist on the surface of the substrate is removed to complete the patterning of the zinc oxide sacrificial layer. Wherein, the process of patterning the zinc oxide sacrificial layer can adopt the processing process in embodiment 3 or the processing process in embodiment 4.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was subjected to a pre-crystallization treatment of 10 minutes of heat preservation at a temperature of 200 ° C, and then Then, under the condition of temperature of 600° C., the crystallization treatment was carried out at a temperature of 30 minutes, so as to complete the preparation of a PZT thick film with a thickness of 8 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 10

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 15 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the slurry after removing the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 10 days to form a PZT slurry containing fine powder.

Clean the diamond substrate, and prepare a 3 μm zinc oxide sacrificial layer on the treated diamond substrate by hydrothermal method; the zinc oxide sacrificial layer is patterned, and the process of patterning the zinc oxide sacrificial layer can adopt the process of embodiment 3 or The process in Example 4 was adopted.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was pre-crystallized for 10 minutes at a temperature of 250 ° C, and then Then, under the condition of temperature of 650° C., the crystallization treatment was carried out with heat preservation for 40 minutes, so as to complete the preparation of a PZT thick film with a thickness of 12 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 11

The embodiment of the present invention uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 5 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 10 days to form a PZT slurry containing fine powder.

The silicon substrate was cleaned, and a zinc oxide sacrificial layer of 0.01 μm was prepared on the cleaned silicon substrate by radio frequency sputtering; the zinc oxide sacrificial layer was patterned, and the process of patterning the zinc oxide sacrificial layer was the same as in Example 2.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was pre-crystallized for 10 minutes at a temperature of 350 ° C, and then Then, under the condition of temperature of 850° C., the crystallization treatment was carried out with heat preservation for 40 minutes, so as to complete the preparation of a PZT thick film with a thickness of 15 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 12

The embodiment of the present invention uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 3 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentration is carried out, and the concentrated slurry is left still for 6 days to form a PZT slurry containing fine powder.

Using radio frequency sputtering, prepare a zinc oxide sacrificial layer with a thickness of 1 μm on a silicon substrate covered with a non-metallic silicon nitride film and a patterned Pt/Ti metal film; pattern the zinc oxide sacrificial layer, pattern oxidation The process of the zinc sacrificial layer is the same as that in Example 2.

Using the prepared PZT slurry, a PZT wet film was prepared on a patterned zinc oxide sacrificial layer substrate through a coating process, and the PZT wet film was pre-crystallized for 10 minutes at a temperature of 350 ° C, and then Then, under the condition of a temperature of 750° C., a crystallization treatment was carried out at a temperature of 50 minutes to complete the preparation of a PZT thick film with a thickness of 38 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

In this embodiment, the Pt/Ti double-layer metal thin film is used as the bottom electrode of the PZT ferroelectric thick film for measuring the performance of the PZT thick film or related devices.

In this embodiment, preferably, the entire Pt/Ti double-layer metal thin film can be used as the bottom electrode without patterning.

Example 13

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry for 2 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the slurry after removing the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 18 days to form a PZT slurry containing fine powder.

The preparation process of the PZT thick film in this example is the same as that in Example 12, except that in the example of the present invention, a silicon dioxide film with a thickness of 0.01 μm to 10 μm is first prepared on the silicon substrate by using a cleaned silicon substrate, and then using Sputtering or ion coating equipment, preparing Pt/Ti double-layer metal film on the surface of the prepared silicon dioxide film, and patterning the Pt/Ti double-layer metal film.

Further, a zinc oxide sacrificial layer with a thickness of 2 μm was prepared by radio frequency sputtering; the zinc oxide sacrificial layer was patterned, wherein the process of patterning the zinc oxide sacrificial layer was the same as that in Example 2.

Further, using the prepared PZT slurry, a PZT wet film is prepared on a substrate with a patterned sacrificial layer through a coating process; at a temperature of 450 ° C, the PZT wet film is pre-crystallized for 10 minutes of heat preservation treatment, and then at a temperature of 950° C. for 10 minutes of crystallization treatment to complete the preparation of a PZT thick film with a thickness of 26 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 14

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 3 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 16 days to form a PZT slurry containing fine powder.

The specific process of the preparation method of the PZT thick film in the embodiment of the present invention is the same as that in Embodiment 12, except that in this embodiment, a silicon substrate with a thickness of 0.01 μm to 10 μm is first prepared on the silicon substrate with silicon dioxide and The composite film of silicon nitride, then utilizes sputtering or ion coating equipment, prepares Au/Cr double-layer metal film on the surface of the prepared silicon dioxide film, and patterning Au/Cr double-layer metal film, the etching stripping In order to pass through the process of coating photoresist, exposing and developing, the specific patterning method is the same as the patterning process in embodiment 2.

Further, a zinc oxide sacrificial layer with a thickness of 2 μm was prepared by radio frequency sputtering; a patterned zinc oxide sacrificial layer, wherein the process of patterning the zinc oxide sacrificial layer was the same as the process of patterning the zinc oxide sacrificial layer in Example 2.

Further, use the prepared PZT slurry to prepare a PZT wet film on the substrate with a patterned sacrificial layer through a coating process; at a temperature of 250 ° C, pre-crystallize the PZT wet film for 10 minutes treatment, and then at a temperature of 600° C., a crystallization treatment of 180 minutes is carried out to complete the preparation of a PZT thick film with a thickness of 50 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 15

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 5 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 5 days to form a PZT slurry containing fine powder.

In this embodiment, using a cleaned silicon substrate, firstly, a Pt/Ti double-layer metal film is prepared on the silicon substrate by sputtering or ion plating equipment, and the Pt/Ti double-layer metal film is patterned.

Coating photoresist on substrate surface; And carry out photoetching; After developing, keep photoresist at the position that needs to prepare PZT thick film, and remove the photoresist at other positions except the position that needs to prepare PZT thick film glue; deposit a zinc oxide sacrificial layer of 1 μm by radio frequency sputtering; remove the photoresist on the surface of the substrate to complete the patterning of the zinc oxide sacrificial layer.

Wherein, the process of patterning the zinc oxide sacrificial layer is the same as the process of patterning the zinc oxide sacrificial layer in Example 2. Further, using the prepared PZT slurry, a PZT wet film is prepared on a substrate with a patterned sacrificial layer through a coating process; at a temperature of 350 ° C, the PZT wet film is pre-crystallized for 30 minutes of heat preservation treatment, and then at a temperature of 950° C. for 5 minutes of crystallization treatment to complete the preparation of a PZT thick film with a thickness of 30 μm.

The process of etching the zinc oxide sacrificial layer and peeling off the PZT thick film on the zinc oxide sacrificial layer to obtain the PZT thick film remaining on the substrate is the same as that in embodiment 2.

Example 16

This embodiment uses the method provided in Example 1 to prepare a PZT thick film with a microstructure, and the preparation process of the PZT thick film is specifically:

Add the PZT powder to the PZT colloid, and mix it into a slurry by ultrasonic dispersion; place the mixed slurry statically for 10 days, and then remove the coarse particles larger than 250nm after the slurry is precipitated; then remove the coarse particles larger than 250nm Concentrating is carried out, and the concentrated slurry is left still for 10 days to form a PZT slurry containing fine powder.

The preparation process of the PZT thick film in this example is the same as that in Example 14, except that in the example of the present invention, silicon dioxide and silicon nitride with a thickness of 0.01 μm to 10 μm are first prepared on the silicon substrate using a cleaned silicon substrate. The composite thin film, and then use sputtering or ion plating equipment to prepare a Pt/Ti double-layer metal film on the surface of the prepared silicon dioxide film, and pattern the Pt/Ti double-layer metal film.

Further, a zinc oxide sacrificial layer with a thickness of 3 μm was prepared by radio frequency sputtering; the process of patterning the zinc oxide sacrificial layer was the same as that in Example 2.

Further, use the prepared PZT slurry to prepare a PZT wet film on the substrate with a patterned sacrificial layer through a coating process; at a temperature of 200 ° C, pre-crystallize the PZT wet film for 10 minutes of heat preservation treatment, and then at a temperature of 650° C., a crystallization treatment of 40 minutes of heat preservation is carried out to complete the preparation of a PZT thick film with a thickness of 36 μm.

The process of peeling off the patterned PZT thick film is the same as that of Example 2.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention and are not intended to limit the scope of the present invention. Protection scope, within the spirit and principles of the present invention, any modification, equivalent replacement, improvement, etc., shall be included in the protection scope of the present invention.

Claims (9)

1. a preparation method with microstructure lead zirconate titanate PZT thick film, is characterized in that, described method comprises: preparing a patterned zinc oxide sacrificial layer on the surface of the substrate; Coating PZT slurry on the zinc oxide sacrificial layer, and performing a pre-crystallization treatment for 1 to 60 minutes at a temperature of 200°C to 500°C; Then, under the condition of 600°C-1000°C, carry out crystallization treatment for 1-180 minutes; The substrate covered with the PZT slurry is placed in the etching solution, and a PZT thick film with a microstructure is obtained after peeling off. 2. method according to claim 1, is characterized in that, described zinc oxide sacrificial layer of patterning on the surface of substrate preparation specifically comprises: depositing or depositing a zinc oxide sacrificial layer on the surface of the substrate; Coating photoresist on the zinc oxide sacrificial layer; performing photoetching on the photoresist; performing patterned etching on the zinc oxide sacrificial layer after photolithography; removing the photoresist on the surface of the substrate. 3. method according to claim 1, is characterized in that, described zinc oxide sacrificial layer of patterning on the surface of substrate preparation specifically comprises: Coating photoresist on the substrate surface; performing photoetching on the surface of the substrate; After developing, keep the photoresist at the position where the PZT thick film needs to be prepared, and remove the photoresist at other positions except the position where the PZT thick film needs to be prepared; depositing or depositing a zinc oxide sacrificial layer; removing the photoresist on the surface of the substrate. 4. The method according to claim 1, wherein the substrate comprises a silicon substrate, a gallium nitride substrate, a sapphire substrate, a ruby substrate, a quartz substrate, a gallium arsenide substrate, a silicon carbide substrate Any substrate in substrate, germanium substrate or diamond substrate; Or any described substrate that the surface is coated with non-metallic film or metal film; Wherein said non-metallic film comprises: silicon dioxide film, nitride One or more of silicon film and polysilicon film; the metal film includes: Pt/Ti metal film or Au/Cr metal film. 5. The method according to claim, wherein the depositing or depositing the zinc oxide sacrificial layer specifically comprises the use of sol-gel method, metal-organic decomposition method, sputtering method, metal-organic chemical vapor deposition method, pulse Zinc oxide sacrificial layer prepared by either laser deposition method or hydrothermal method. 6 . The method according to claim 1 , wherein the zinc oxide sacrificial layer has a thickness of 0.01 μm˜1000 μm. 7. The method according to claim 1, characterized in that, the thickness of the 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: Add PZT powder to PZT colloid; Use ultrasonic dispersion to mix into a slurry, and remove particles larger than 250nm after standing and settling; The particle-removed slurry is concentrated and aged to form a PZT slurry. 9. The method according to claim 1, wherein the etching solution comprises phosphoric acid solution, HBr solution, nitric acid and phosphoric acid etching solution, phosphoric acid and acetic acid etching solution, acetic acid solution, sodium hydroxide solution, chlorinated Any solution in ammonium solution or ammonia corrosion solution.