KR20000047419A - Method for fabricating piezoelectric/electrostrictive thick film using seeding layer - Google Patents

Abstract

PURPOSE: A piezo-electric/electrostriction film forming method is provided for an excellent thick film typed piezo-electric/electrostriction film on a plate by applying a ceramic paste mixed ceramic with ceramic sol of the same or a similar ingredient, or ceramic sol with ceramic oxide-powder as a sheeting layer. CONSTITUTION: A piezo-electric/electrostriction thick film is formed a sheeting layer on a plate and directly formed a piezo-electric/electrostriction film on the plate. Then a specifically formed piezo-electric/electrostriction thick film is attached to the sheeting plate. The present invention comprises a plate providing step; a sheeting layer forming step by applying a mixed ceramic paste; a post-treatment step of the formed sheeting layer for promoting a reaction and restraining an unnecessary reaction; a thick film typed piezo-electric/electrostriction film forming step on the post-treated sheeting layer; and a piezo-electric/electrostriction film attaching step with the plate.

Description

Method for fabricating piezoelectric / electrostrictive thick film using seeding layer}

The present invention relates to a method for forming a piezoelectric / electric strainer film, and more particularly, a method of forming a piezoelectric / electric strainer film by applying a seeding layer of the same or similar component as the piezoelectric / electric strainer film between the substrate and the piezoelectric / electric strainer film. It is about.

In order to manufacture various film-type devices using ceramics, a method of forming a piezoelectric / electric strained film is mainly used by attaching a ceramic sol having a viscosity controlled or a ceramic powder modified to an appropriate form to a substrate. When the piezoelectric / distortion layer is formed by attaching a ceramic sol or ceramic powder to the substrate, particularly when forming a piezoelectric / distortion layer in the form of a thick film, the adhesion of the substrate and the piezoelectric / distortion layer is the most important factor that determines the quality of the device. .

When the material of the substrate is a ceramic having the same or similar properties as the ceramic attached to the substrate, there is no problem in adhesion between the substrate and the piezoelectric / electric strain film.

However, even if the material of the substrate is non-ceramic such as metal or resin, or the substrate is ceramic, when the crystal structure, surface properties, reactivity, etc. are different between the ceramic used as the substrate and the ceramic used for the production of the piezoelectric / electric strain film, the substrate and the piezoelectric Low adhesiveness with electro-distortion film.

Low adhesion between the substrate and the piezoelectric / distortion film may cause separation of the substrate and the piezoelectric / distortion film, cracking in the direction perpendicular to the piezoelectric / electric distortion film, or deterioration of ceramic material due to repeated use of the device. Problems occur.

In particular, as the thickness of the piezoelectric / distortion film to be formed becomes thicker, mechanical stress generated during drying of the piezoelectric / electric distortion film has a great influence on the adhesion between the substrate and the piezoelectric / electric distortion film.

Therefore, the problem of improving the adhesion between the substrate and the piezoelectric / electrodistortion film should be considered more seriously when manufacturing the piezoelectric / electrodistortion film of the thick film type.

In order to secure the adhesion between the piezoelectric / electric warp film and the substrate and to suppress unnecessary reaction on the contact surface, a method of using a buffer layer, a method of reducing the mechanical stress by thinning a film to be formed at one time, and a method of bonding using an adhesive Method and the like.

The buffer layer is inserted between the substrate and the piezoelectric / distortion layer, which is the most representative method for securing the adhesion between the substrate and the piezoelectric / distortion layer. This method is a method of depositing a metal thin film on a substrate by a sol-gel coating method, sputtering method, an electrochemical method, and the like, followed by heat treatment to form a buffer layer, and to form a piezoelectric / electric distortion film on the buffer layer. In this case, a metal thin film such as titanium thin film or platinum thin film is mainly used as the buffer layer.

FIG. 1 illustrates a method of inserting a conventional buffer layer used in the related art, and illustrates a case of forming a piezoelectric / electrodistor film on the formed buffer layer after forming a buffer layer by depositing titanium or platinum on a substrate and then performing heat treatment. .

FIG. 2 illustrates a method of inserting a buffer layer after surface treating a substrate. The surface of a silicon substrate is thermally oxidized to form a silicon dioxide (SiO ₂ ) layer, and titanium is formed on the top of the silicon dioxide layer formed by thermal oxidation. Alternatively, after forming a buffer layer by depositing and heat treating a platinum thin film, a piezoelectric / electric distortion film is formed on the buffer layer.

However, the above methods require a heat treatment at a high temperature in the process of surface-treating the substrate or in the formation of the buffer layer, so that the process is complicated and the stability is lowered by repeated heat treatment at a high temperature.

Next, there is a method of reducing the mechanical strain by making the film thickness as thin as possible at one time.

In this method as shown in Fig. 3, a thin piezoelectric / distortion film having a thickness of several hundred nm is formed on a substrate by deposition or coating, and then heat-processed at a high temperature. Get the act.

In the case of forming a thick film piezoelectric / distortion film by this method, components of the initially formed piezoelectric / electric distortion film may be diffused onto the substrate by repeated thermal history. Such piezoelectric / distortion film diffusion has an advantage of making the adhesion between the piezoelectric / distortion film and the substrate strong, but there is a problem in that an interfacial reaction occurs between the substrate and the piezoelectric / distortion film, thereby deteriorating material or deteriorating physical properties.

In addition, there is a problem in that the thickness of the piezoelectric / distortion film in the form of a thick film which can be obtained by repeating the process of manufacturing the piezoelectric / electric distortion film in the form of a thin film several times is problematic.

Next, there is a method of bonding the substrate and the piezoelectric / electric strain film using an adhesive. This method is mainly used in the case of adhering a piezoelectric / electric distortion film composed of separately formed ceramic bulk to a substrate.

In this method, as shown in FIG. 4, a thermosetting resin-based adhesive is usually applied between the substrate and the piezoelectric / electrodistor film, and a piezoelectric / electric strain film of a thin plate shape and molded separately is attached, and then the substrate and the piezoelectric / Adhesion of the front distortion film.

However, when the adhesive is used, the thickness of the adhesive layer is about 7-15 μm thick, and the interface of the adhesive layer is uneven or the pores are formed in the adhesive layer, thereby deteriorating quality and yield.

In addition, there has been a method of using a seeding layer in the past, but a conventional method of using a seeding layer is a dry process such as sol-gel multiple coating, sputtering, or electro-crystallization. It is limited to manufacturing a piezoelectric / electric distortion film of a thin film form having a thickness of 1 μm or less by using a) or the like, and is not used when a printing method, a molding method, or the like is applied, or when a piezoelectric / electric distortion film of a thick film type is manufactured. .

In order to solve the above problems, the present invention provides a thick film-type piezoelectric / It is an object of the present invention to provide a method for forming an electrostrictive film.

1 is a process chart showing a bonding method of a piezoelectric / electric strained film and a substrate using a conventional buffer layer;

FIG. 2 is a process diagram showing a method of bonding a piezoelectric / electrodistor film and a substrate using thermal oxidation and a buffer layer of a conventional substrate.

FIG. 3 is a process chart showing a method of manufacturing a piezoelectric / electric distortion film of a thick film type by repeated molding of a conventional piezoelectric / electric distortion film;

4 is a process chart showing a method of bonding a piezoelectric / electric warp film and a substrate in a thick film form using a conventional adhesive;

FIG. 5 is a process diagram showing an embodiment of a method of forming a piezoelectric / electric warp thick film using the seeding layer of the present invention which directly forms a piezoelectric / electric warp film on a substrate formed after molding the seeding layer on the substrate;

FIG. 6 is a process diagram showing an embodiment of a method of forming a piezoelectric / electric warp thick film using the seeding layer of the present invention to attach a separately formed piezoelectric / electric warp thick film after molding the seeding layer on the substrate;

FIG. 7 is a process diagram showing an embodiment of a method of forming a piezoelectric / electric warp thick film using the seeding layer of the present invention in which a seeding layer is formed on a substrate and then separately formed and fired.

The present invention for achieving the above object comprises the steps of providing a substrate; Ceramic sol solution of the same or similar component as piezoelectric / electric distortion film on the substrate, or non-explosive redox combustion reaction at low temperature of 100-500 ℃, particle size less than 5㎛, lead (Pb), titanium (Ti) Ceramic paste of the same or similar component as the piezoelectric / distortion film prepared by mixing a ceramic oxide powder having a) as a basic component and a ceramic sol solution having the same or similar components as the ceramic oxide powder prepared based on water or an organic solvent. Forming a seeding layer by applying; Post-processing the seeding layer formed to enhance the reactivity of the seeding layer and to suppress unnecessary reaction with the substrate or piezoelectric / distortion film; Forming a thick film piezoelectric / distortion film on the post-treated seeding layer; Forming the piezoelectric / electric distortion film by heat-treating the formed piezoelectric / electric distortion film at 100-600 ° C. and firing the seeding layer and the piezoelectric / electric distortion film. A method of forming a piezoelectric / electric strained thick film using a seeding layer capable of forming the piezoelectric / electric strained film of the film is characterized.

The present invention also provides a method comprising the steps of providing a substrate; Ceramic sol solution of the same or similar component as piezoelectric / electric distortion film on the substrate, or non-explosive redox combustion reaction at low temperature of 100-500 ℃, particle size less than 5㎛, lead (Pb), titanium ( Ceramics of the same or similar component as the piezoelectric / electric distortion film prepared by mixing a ceramic oxide powder having Ti as a basic component and a ceramic sol solution having the same or similar components as the ceramic oxide powder prepared based on water or an organic solvent. Forming a seeding layer by applying a paste; Partially drying the shaped seeding layer at room temperature-150 ° C. to impart a suitable viscosity for adhesion; Manufactured by non-explosive redox combustion reaction at low temperature of 100-500 ℃ on partially dry seeding layer, using ceramic oxide powder with particle size of 5㎛ or less and lead (Pb) and titanium (Ti) as basic elements Attaching separately formed or separately formed and fired piezoelectric / distortion films; Heat-treating the attached piezoelectric / distortion film at 100-600 ° C. to produce a piezoelectric / distortion film-bonded substrate, and forming a thick film-type piezoelectric / distortion film having excellent adhesion to the substrate only by heat treatment at low temperature. There is a feature in the method of forming a piezoelectric / electric warp thick film using a seeding layer which can be used.

Hereinafter, the present invention will be described in detail.

The method of forming a piezoelectric / electric strainer thick film using the seeding layer of the present invention is a method of forming a piezoelectric / electric strainer film directly on a substrate on which the seeding layer is formed after forming a seeding layer on a substrate and forming a seeding layer on the substrate. There is a method of attaching a separately formed piezoelectric / electrical distortion thick film on a substrate on which the seeding layer is formed.

In this case, a metal or ceramics in which electrodes are treated on the top is used as the substrate. Metals include stainless steel (SUS) and nickel (Ni), and ceramics include metal oxides such as aluminum oxide (Al ₂ O ₃ ), nonmetal oxides such as silicon dioxide (SiO ₂ ), and silicon carbide (SiC). It is preferable to use nonmetal carbides such as nonmetal carbides such as silicon nitride and silicon nitride (Si ₃ N ₄ ).

In addition, as a material of the seeding layer for improving the adhesion between the substrate and the piezoelectric / electric distortion film, a ceramic sol solution of the same or similar component as that of the piezoelectric / electric distortion film is used, or the ceramic sol solution and the ceramic oxide powder are mixed. Prepared ceramic paste is used.

The ceramic sol solution used as the seeding layer is prepared by dissolving a ceramic component based on water or an organic solvent. At this time, the concentration of the ceramic sol solution is preferably set to 0.1-5M.

Various organic solvents can be used as the base, but it is preferable to use one selected from acetic acid, dimethylformamide, methoxyethanol, glycols and alcohols.

The ceramic sol solution may be used as it is or diluted with water or an organic solvent which can be used as a base, acetic acid, dimethylformamide, methoxyethanol, glycols, and alcohols.

The ceramic paste used as the seeding layer is prepared by mixing ceramic oxide powder with a ceramic sol having the same or similar components as the ceramic powder. use.

The ceramic oxide powder used in the present invention is prepared by dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium to prepare a solution or dispersion mixture containing the ceramic component, the solution in which the ceramic component is dissolved or dispersed. Or adding a citric acid in an amount or more necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component to the dispersion mixture, and preparing a mixed solution and heat-treating the mixed solution at 100-500 ° C., Further heat treatment at 700-900 ° C. may further comprise increasing crystallinity.

The raw material containing the ceramic component is selected from a ceramic component such as an oxide, carbonate or nitrate of the ceramic component, a salt of an organic or inorganic substance, or a complex of ceramic components.

As the ceramic component, it is preferable to use a piezoelectric / electrically distorted ceramic element having lead (Pb) and titanium (Ti) as a basic component. In particular, it is preferable to use a ceramic element as a component containing lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), magnesium (Mg), niobium (Nb).

As a solvent or dispersion medium for dissolving or dispersing the ceramic component raw material, one or more selected from among those capable of dissolving or dispersing the raw material containing the ceramic component in water or an organic solvent is used. Among the organic solvents, dimethyl formamide, methoxyethanol, acetic acid, glycols and alcohols are mainly used.

As a combustion aid, citric acid, an organic compound that can cause a combustion reaction, is used. In the conventional method, citric acid has been used to impart homogeneity of the reaction as a complexing agent, not as a combustion aid, and has been applied in processes such as the Pechini process. By using can cause a controlled combustion reaction rate.

The mixed solution is prepared by adding citric acid to a solvent or dispersed solution or dispersion mixture of ceramic components. The amount of citric acid to be added is added to the amount or more necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic element. The rate of progress of the reaction can be controlled depending on the amount of citric acid added.

The mixed solution mixed with citric acid is heat-treated at 100-500 ° C. As the temperature of the heat treatment increases, the crystallinity of the ceramic phase increases, but when the heat treatment temperature is 100 ° C. or higher, the combustion reaction of citric acid can be sufficiently initiated. The reaction may occur even when the heat treatment is performed above 500 ° C., but the heat treatment is performed at a higher temperature. Is meaningless compared to conventional methods.

More preferably, the heat treatment is carried out at 150-300 ° C., and the temperature range can adequately secure the crystallinity of the ceramic phase even at a very low temperature.

Citric acid is removed in the combustion reaction, and the ceramic oxide is formed without scattering by non-explosive reaction.

In this reaction, components other than the ceramic component are removed by the combustion reaction, thereby forming a pure ceramic oxide powder in which impurities do not remain.

The ceramic oxide powder prepared by the above method is a fine and uniform particle size distribution having a particle size of 5 μm or less, especially 1 μm or less, and the primary particles are in the form of an individual or a soft aggregate. Present, it is a fully burned ceramic phase and does not lose weight by further heat treatment.

In addition, since the surface is excellent in reactivity, the molding may be performed only by heat treatment at low temperature when molding using it, and thus, the degree of freedom of the substrate may be high and various methods of printing or coating the diaphragm may be applied.

In order to increase the crystallinity of the ceramic oxide powder prepared, the ceramic oxide powder prepared may be further heat treated at 700-900 ° C.

The ceramic paste is prepared by mixing the ceramic oxide powder prepared by this method and the ceramic sol solution prepared by the method described above.

At this time, it is preferable to use PZT, PMN or their solid solution (PZT-PMN) composite oxide as the ceramic oxide powder.

In addition, the ceramic oxide powder is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce), chromium (Cr) , Antimony (Sb), iron (Fe), yttrium (Y), tantalum (Ta), tungsten (W), strontium (Sr), calcium (Ca), bismuth (Bi), tin (Sn), manganese (Mn) It may further comprise one or more elements of.

When the ceramic oxide powder and the ceramic sol solution are mixed, the content of the ceramic sol solution is preferably 1-200 parts by weight based on the ceramic oxide powder. This is because when the content of the ceramic sol solution is 200 parts by weight or more, the ceramic oxide powder is diluted too much, so that the viscosity of the mixture is low, and when the content of the ceramic sol solution is less than 1 part by weight, the amount of the ceramic oxide powder is too large and the viscosity becomes too high.

It is particularly preferable that the content of the ceramic sol solution be 10-100 parts by weight based on the ceramic oxide powder.

When the ceramic oxide powder and the ceramic sol solution are mixed, the liquid ceramic sol solution uniformly coats the surface of the solid ceramic oxide powder and connects the ceramic oxide powder particles to effectively fill the pores between the powders.

In the powder-sol mixture thus formed, the ceramic oxide powder having the characteristics of ceramics is surrounded by the ceramic sol solution of the same or similar component and has a proper fluidity. The ceramic sol acts as a reaction medium on the surface of the ceramic oxide powder and thus the powder surface. The reactivity of is improved.

In addition, the organic component contained in the sol enables to secure the stability of the contact interface when the mixture comes into contact with a separate organic substance in the future, thereby providing dispersibility and homogeneity.

In such a system, since the sol is thermally decomposed at a low temperature and converted into the same or similar composition as the ceramic oxide powder, a ceramic system with improved inter-particle connectivity can be obtained even at low temperatures.

In order to ensure the stability of the mixture of the ceramic oxide powder and the ceramic sol solution and the fluidity required for molding, an organic solvent for controlling properties may be added. Various physical solvents may be used as the organic solvent for controlling physical properties, but it is preferable to use glycols or alcohols having a certain viscosity and low vapor pressure at room temperature.

When adding an organic solvent for controlling physical properties to the mixture of ceramic oxide powder and ceramic sol solution, the amount of the organic solvent for controlling physical properties is preferably 1-100 parts by weight based on the ceramic oxide powder. This is because if the amount of the organic solvent for controlling physical properties is less than 1 part by weight, the effect of adding the organic solvent for controlling physical properties is not effective, and if the amount is more than 100 parts by weight, the mixture does not maintain viscosity and is too diluted to deteriorate moldability during molding.

The addition amount of the organic solvent for controlling the physical properties is particularly preferably 10 to 40 parts by weight based on the ceramic oxide powder. In this range, the organic solvent for controlling the physical properties can be added while maintaining the viscosity of the mixture as appropriate.

In addition, a small amount of organic matter may be added to the mixture of the ceramic oxide powder and the ceramic sol solution in order to improve the dispersibility and homogeneity of the mixture in which the solvent for controlling physical properties is added. At this time, it is preferable to use long-chain alcohols or polar organic solvents to add.

Among the long chain alcohols, it is preferable to use pentanol or hexanol, and it is preferable to use acetylacetone or methoxyethanol as the polar organic solvent.

It is preferable that the addition amount of an organic substance shall be 1-100 weight part with respect to a ceramic oxide powder. This is because if the added amount of the organic substance is less than 1 part by weight, there is no effect of adding the organic substance. If the added amount is more than 100 parts by weight, the mixture does not maintain the viscosity and is too diluted, resulting in poor moldability.

The addition amount of the organic material is particularly preferably 10 to 40 parts by weight based on the ceramic oxide powder. In this range, the addition of the organic material can be effected while maintaining the viscosity of the mixture as appropriate.

First, a case in which a seeding layer is formed on a substrate using the ceramic sol solution or ceramic paste, and then a piezoelectric / electric distortion film is directly formed on the formed seeding layer will be described.

The seeding layer is formed by applying the ceramic sol solution or ceramic paste prepared as described above to the substrate. Various methods can be used to apply the ceramic sol solution or the ceramic paste to the substrate, but the ceramic sol solution is applied to the substrate using the coating method, and the ceramic paste is generally applied to the substrate using the printing method. to be.

At this time, the thickness of the seeding layer to be formed is preferably 1 µm or less, more preferably 200-300 nm.

Patterning may be imparted to the seeding layer using a suitable masking tool when forming the seeding layer.

The molded seeding layer is post-processed in various ways to improve the reactivity of the seeding layer while suppressing unnecessary reactions with the piezoelectric / electric strain film or the substrate. As a post-treatment method, drying, oxidation / reduction, surface treatment, heat treatment at low temperature, and the like may be used. These methods may be used alone or in combination of two or more methods.

In the method of stabilizing the seeding layer by drying, the molded seeding layer is dried at room temperature -150 ℃, more preferably at 50-70 ℃.

The drying step is the most cautionary step when forming the seeding layer, and should not cause cracks or pores on the surface or structure of the ceramic sol when the seeding layer is dried.

In order to prevent cracks or pores from occurring on the surface or structure of the dried seeding layer, use a drying chamber in which the vapor of the organic solvent used as a base when the ceramic sol, which is a raw material of the seeding layer, is saturated. It is preferable to use the method of making it dry, and making a solvent volatilize at appropriate temperature.

At this time, even if the seeding layer is pyrolysis under the dry conditions and the ceramic phase is formed or modified into a gel, it does not adversely affect the adhesion with the piezoelectric / electric distortion film formed in the post process.

Various methods may be used for oxidation / reduction of the seeding layer, and representative methods include drying in air and partially air oxidation.

As a method of surface-treating a seeding layer, the method in which the board | substrate with which the seeding layer was shape | molded is put in a chamber, and the vapors, such as alcohol, are used.

In the method of heat-treating the seeding layer at low temperature, the seeding layer is ceramicized by heat-treating and baking at 100-600 degreeC, More preferably, 150-300 degreeC.

The piezoelectric / electric warp thick film is directly formed on the seeding layer post-treated by the above-described method. As a method of forming the piezoelectric / electric warp thick film on the seeding layer, a printing method, a molding method, or a coating method is used.

In the case of forming the piezoelectric / electric distortion thick film by the printing method, the molding method, or the coating method, ceramic paste is used as the material of the piezoelectric / electric distortion thick film. By using a ceramic paste.

The printing method is a method of forming a piezoelectric / electric distortion film having a predetermined thickness by printing a ceramic paste on a substrate using a screen or the like, and the molding method of forming a piezoelectric / electric distortion film by applying a ceramic paste to an uneven mold formed on a substrate. That's how.

The coating method is a method of forming a piezoelectric / electric distortion film by coating a ceramic paste on a substrate by spin coating or the like. When the coating method is used, the process of forming a piezoelectric / electric distortion film of less than 1 μm is repeated and thickened. In the case of using the coating method, the film may be formed on the substrate as a whole and then processed. Alternatively, the piezoelectric / electric distortion film of a desired pattern may be formed by masking.

In this case, the film may be formed on the substrate as a whole for post-processing, or a piezoelectric / electric distortion film type device having a desired pattern may be formed by installing a screen, a mold or a mask on the substrate.

The piezoelectric / electrodistor film formed on the substrate on which the seeding layer is formed by the above methods is heat-treated at 100-600 ° C, more preferably 150-300 ° C. The heat treatment removes the solvent and the added organic matter, and the piezoelectric / distortion film is fired, and the seeding layer is converted into a thin film made of ceramic fine powder to complete the piezoelectric / electric distortion film formed on the substrate.

Heat treatment at a low temperature of 100-600 ° C is sufficient for the reaction that water on the surface of the ceramic oxide powder hydrolyzes the ceramic sol solution and that the ceramic constituents of the ceramic sol solution liberated by hydrolysis are combined with the ceramic oxide powder. This is because the same reaction as firing can be achieved by the reaction of the liver. In addition, organic matter added during the heat treatment is removed.

Next, the case where the preformed piezoelectric / distortion film is attached to the formed seeding layer after the seeding layer is formed on the substrate will be described.

The seeding layer is formed by applying the ceramic sol solution or ceramic paste prepared as described above to the substrate. In this case, the ceramic sol solution is applied to the substrate using the coating method, and the ceramic paste is generally applied to the substrate using the printing method.

At this time, the thickness of the seeding layer to be formed is preferably 1 µm or less, more preferably 200-300 nm, and patterning may be applied to the seeding layer by using a suitable masking tool.

The molded seeding layer is partially dried at room temperature-150 ° C., more preferably 50-70 ° C. to impart a suitable viscosity for adhesion. In this case, in order to prevent cracks or pores from occurring on the surface or structure of the seeding layer, the solvent is dried by using a drying chamber in which the vapor of the organic solvent used as a base is saturated when preparing a ceramic sol which is a raw material of the seeding layer. Preference is given to using a method of volatilizing at an appropriate temperature.

By means of partial drying, a piezoelectric / electric strainer in the form of a thick film separately or a piezoelectric / electric strainer in the form of a separately formed and calcined thick film is attached to a seeding layer having an appropriate viscosity.

After the piezoelectric / distortion film is attached, heat treatment is performed at 100-600 ° C., more preferably 150-300 ° C. to prepare a joined body of the piezoelectric / electric distortion film and the substrate.

The separately formed piezoelectric / distortion thick film effectively bonds the piezoelectric / electric distortion film and the seeding layer as the sol is thermally decomposed, and the seeding layer and the piezoelectric / electric distortion film are fired by heat treatment. However, when the piezoelectric / electrodistortion thick film formed and fired separately is used, the firing of the piezoelectric / predistortion thick film does not occur, only the seeding layer is fired, and only the bonding of the seeding layer and the piezoelectric / electrodistortion thick film occurs.

After attaching the piezoelectric / distortion film in the form of a thick film on the seeding layer, a pre-baking at 100-150 ° C. may be added before the heat treatment to induce an effective adhesion reaction under mild conditions. In addition, the heat treatment may be performed while applying a predetermined pressure to uniformly bond the piezoelectric / distortion film and the substrate during the heat treatment.

In the above methods, the piezoelectric / electric warp thick film is preferably molded to have a thickness of 1-100 μm, and particularly preferably to have a thickness of 5-30 μm.

Since the seeding layer has excellent adhesion to the substrate and at the same time has a chemical affinity with the piezoelectric / electric distortion film existing on the upper side, the adhesion of the piezoelectric / electric distortion film and the substrate is greatly improved by applying the seeding layer.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are illustrative of the invention and do not limit the scope of the invention.

(Example 1)

Diacetic acid-based 2M PZT sol was diluted with ethanol to prepare a ceramic sol diluent, and a photosensitive film was used as a mold to carry a dip coating by supporting an SUS substrate with a fine pattern.

A ceramic sol-coated SUS substrate was placed in a drying chamber and dried at 100 ° C., and then filled with a PZT / PMN paste in a micro pattern formed on the substrate to form a thick film piezoelectric / electric distortion film.

The formed piezoelectric / distortion film was dried at 130 ° C. for 1 hour and heat treated at 300 ° C. for 2 hours to complete the piezoelectric / electric distortion film formed on the substrate.

(Example 2)

A methoxyethanol base 0.5M PZT sol was spin coated onto a nickel substrate. The ceramic sol-coated substrate was dried at room temperature using a drying plate saturated with methoxyethanol vapor, and then heat-treated at 300 ° C. for 1 hour to form a PZT thin film.

The PZT / PMN paste was printed on the formed PZT thin film layer by screen printing to form a thick film, dried at 70 ° C. for 1 hour, and heat treated at 250 ° C. for 1 hour to complete the piezoelectric / electric warp thick film bonded to the substrate.

(Example 3)

The surface was activated by spin coating a dimethylformamide base 2M PZT sol on a nickel substrate and then drying the ceramic sol-coated substrate in air at room temperature.

PZT / PMN paste was plated on the surface-activated PZT sol layer using a mask provided with a micropattern to form a piezoelectric / electric distortion film. The formed film was dried at 130 ° C. for 1 hour and heat-treated at 300 ° C. for 2 hours to complete the piezoelectric / electric warp thick film bonded to the substrate.

(Example 4)

Acetic acid-based 2M PZT sol was spin-coated on a SUS substrate, and then dried at 50 ° C. for 5 minutes to give an appropriate viscosity for adhesion. A PZT / PMN sintered film with a thickness of 40 μm was separately attached on the ceramic sol layer given appropriate viscosity.

After the pre-baking at 130 ° C. for 1 hour while applying pressure to the upper part of the attached sintered film, the resultant was heat-treated again at 200 ° C. for 2 hours to complete the piezoelectric / electric warp thick film bonded to the substrate.

(Example 5)

Ceramic paste was prepared by mixing acetic acid-based 2M PZT sol and PZT / PMN fine powder, and the ceramic layer was formed by screen printing the prepared ceramic paste on a thermosetting resin substrate using a screen having a thickness of 1 μm.

The molded ceramic layer was dried at room temperature for 1 hour to give an appropriate viscosity for adhesion, and then a PZT / PMN sintered film having a thickness of 40 μm was separately attached on the ceramic layer.

After preheating at 130 ° C. for 1 hour while applying pressure on the attached sintered film, heat treatment was performed at 200 ° C. for 2 hours to complete the piezoelectric / electric warp thick film bonded to the substrate.

As described above, the method of forming the piezoelectric / electric warp thick film bonded to the substrate using the seeding layer can form a thick film piezoelectric / electric warp film having excellent adhesion to the substrate by heat treatment at low temperature, thereby simplifying the process and securing stability. It is effective.

In addition, by repeatedly stacking piezoelectric / distortion films in the form of thin films using screen printing, the piezoelectric / distortion films in the form of thick films are obtained, as well as the piezoelectric / distortion films in the form of thick films having firm adhesion to the substrate once or 2-3 times. It is also very effective when forming by the process.

In addition, there is no problem that the quality and the yield of the bonded body are not reduced due to the unevenness of the adhesive layer, the generation of internal pores, and the condition of the post-treatment conditions, even when the preformed piezoelectric / distortion film is bonded to the substrate. Can be secured.

Claims (59)

Providing a substrate; Ceramic sol solution of the same or similar component as piezoelectric / electric distortion film on the substrate, or non-explosive redox combustion reaction at low temperature of 100-500 ℃, particle size less than 5㎛, lead (Pb), titanium (Ti) Ceramic paste of the same or similar component as the piezoelectric / distortion film prepared by mixing a ceramic oxide powder having a) as a basic component and a ceramic sol solution having the same or similar components as the ceramic oxide powder prepared based on water or an organic solvent. Forming a seeding layer by applying; Post-processing the shaped seeding layer to enhance the reactivity of the seeding layer and to suppress unwanted reactions with the substrate or piezoelectric / distortion film; Forming a thick film piezoelectric / distortion film on the post-treated seeding layer; Heat-treating the formed piezoelectric / distortion film at 100-600 ° C. to bond the substrate and the piezoelectric / distortion film while firing the seeding layer and the piezoelectric / distortion film, A method of forming a piezoelectric / electric distortion film using a seeding layer capable of forming a thick film piezoelectric / electric distortion film having excellent adhesion to a substrate even by heat treatment at low temperature. The method of claim 1, wherein the substrate is a metal or ceramic on which an electrode is treated. 3. The method of claim 2, wherein the metal is stainless steel (SUS) or nickel (Ni). 3. The method of claim 2, wherein the ceramic is ceramic oxide, carbide, or nitride. The piezoelectric / electric warp thick film forming method using a seeding layer according to claim 1, wherein the ceramic oxide powder has a particle size of 1 or less. The method of claim 1, wherein the ceramic oxide comprises PZT, PMN, or a solid solution thereof (PZT-PMN) composite oxide. The method of claim 6, wherein the ceramic oxide is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce), Chromium (Cr), Antimony (Sb), Iron (Fe), Yttrium (Y), Tantalum (Ta), Tungsten (W), Strontium (Sr), Calcium (Ca), Bismuth (Bi), Tin (Sn), A method of forming a piezoelectric / electric warp thick film using a seeding layer, further comprising one or more elements of manganese (Mn). 2. The method of forming a piezoelectric / electric distortion thick film using a seeding layer according to claim 1, wherein the thickness of the piezoelectric / electric distortion film is molded to 1-100 탆. 9. The method of forming a piezoelectric / electric warp thick film according to claim 8, wherein the thickness of the piezoelectric / electric warp film is molded to 5-30 mu m. The piezoelectric / electric distortion film of claim 1, which is prepared by non-explosive redox combustion at a low temperature of 100-500 ° C., has a particle size of 5 μm or less, and is based on lead (Pb) and titanium (Ti). Piezoelectric using a seeding layer characterized by using a ceramic paste prepared by mixing a ceramic oxide powder comprising a component element and a ceramic sol solution of the same or similar component as the ceramic oxide powder prepared based on water or an organic solvent. How to form a thick film before and after. The method of claim 10, wherein the ceramic oxide is formed of PZT, PMN or their solid solution (PZT-PMN) composite oxide. The method of claim 11, wherein the ceramic oxide is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce), Chromium (Cr), Antimony (Sb), Iron (Fe), Yttrium (Y), Tantalum (Ta), Tungsten (W), Strontium (Sr), Calcium (Ca), Bismuth (Bi), Tin (Sn), A method of forming a piezoelectric / electric warp thick film using a seeding layer, further comprising one or more elements of manganese (Mn). The method of claim 10, wherein the piezoelectric / distortion thick film is formed by a printing method, a molding method, or a coating method. The piezoelectric / electric strain using the seeding layer according to claim 1, wherein the piezoelectric / distortion film is formed by mixing a ceramic oxide powder dispersed in an organic dispersion medium and a ceramic sol solution prepared based on an organic solvent. Formation of thick film. 15. The method of claim 14, wherein the ceramic oxide powder is formed of PZT, PMN or their solid solution (PZT-PMN) composite oxide. The method of claim 15, wherein the ceramic oxide powder is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce) , Chromium (Cr), antimony (Sb), iron (Fe), yttrium (Y), tantalum (Ta), tungsten (W), strontium (Sr), calcium (Ca), bismuth (Bi), tin (Sn) And a piezoelectric / electric warp thick film using the seeding layer, further comprising one or more elements of manganese (Mn). The method of forming a piezoelectric / electric warp thick film according to claim 1, wherein the seeding layer has a thickness of 1 µm or less. 18. The method of claim 17, wherein the seeding layer has a thickness of 200-300 nm. The method of claim 1, wherein the seeding layer is post-processed. The piezoelectric / using seeding layer is characterized in that one or two or more methods of drying, oxidation / reduction, surface treatment, and heat treatment at low temperature are selected and used. How to form a thick film before and after. 20. The method of claim 19, wherein the seeding layer is dried at room temperature -150 [deg.] C. 20. The method of claim 19, wherein the seeding layer is dried by using a drying chamber in which a vapor of an organic solvent used as a base in the preparation of a ceramic sol solution, which is a material of the seeding layer, is saturated and then volatilized at a suitable temperature. A piezoelectric / electric warp thick film forming method using a seeding layer, characterized in that. 20. The method of claim 19, wherein the seeding layer is oxidized / reduced using a method of drying the seeding layer in air and partially air oxidation the seeding layer. Formation method. 20. The method of claim 19, wherein the seeding layer is surface treated by inserting a substrate formed with the seeding layer into a chamber and flowing organic gas therein. . 20. The method of claim 19, wherein the low temperature heat treatment of the seeding layer is performed at 100-600 占 폚. The piezoelectric / distortion thick film forming method using a seeding layer according to claim 1, wherein the piezoelectric / distortion film is heat-treated at 150 to 300 ° C. Providing a substrate; Ceramic sol solution of the same or similar component as piezoelectric / electric distortion film on the substrate, or non-explosive redox combustion reaction at low temperature of 100-500 ℃, particle size less than 5㎛, lead (Pb), titanium ( Ceramics of the same or similar component as the piezoelectric / electric distortion film prepared by mixing a ceramic oxide powder having Ti as a basic component and a ceramic sol solution having the same or similar components as the ceramic oxide powder prepared based on water or an organic solvent. Forming a seeding layer by applying a paste; Partially drying the shaped seeding layer at room temperature-150 ° C. to impart a suitable viscosity for adhesion; Manufactured by non-explosive redox combustion reaction at low temperature of 100-500 ℃ on partially dry seeding layer, using ceramic oxide powder with particle size of 5㎛ or less and lead (Pb) and titanium (Ti) as basic elements Attaching separately formed piezoelectric / distortion films; Heat-treating the attached piezoelectric / distortion film at 100-600 ° C., and firing the seeding layer and the piezoelectric / distortion film, thereby manufacturing a bonded body of the piezoelectric / electric distortion film and the substrate, A method of forming a piezoelectric / electric distortion film using a seeding layer capable of forming a thick film piezoelectric / electric distortion film having excellent adhesion to a substrate even by heat treatment at low temperature. 27. The method of claim 26, wherein the substrate is a metal or ceramic on which an electrode is treated. 28. The method of claim 27, wherein the metal is stainless steel (SUS) or nickel (Ni). 28. The method of claim 27, wherein the ceramic is ceramic oxide, carbide, or nitride. 27. The method of claim 26, wherein the ceramic oxide powder has a particle size of 1 µm or less. 27. The method of claim 26, wherein the ceramic oxide powder is formed of PZT, PMN or their solid solution (PZT-PMN) composite oxide. The method of claim 31, wherein the ceramic oxide powder is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce) , Chromium (Cr), antimony (Sb), iron (Fe), yttrium (Y), tantalum (Ta), tungsten (W), strontium (Sr), calcium (Ca), bismuth (Bi), tin (Sn) And a piezoelectric / electric warp thick film using the seeding layer, further comprising one or more elements of manganese (Mn). 27. The method of claim 26, further comprising pre-baking at 100-150 [deg.] C. prior to heat treatment after attaching the piezoelectric / distortion film. 27. The method of claim 26, wherein the piezoelectric / distortion thick film is formed by applying a predetermined pressure during the heat treatment to uniformly bond the piezoelectric / distortion film to the substrate during the heat treatment. 27. The method of forming a piezoelectric / electric warp thick film according to claim 26, wherein the thickness of the piezoelectric / electric warp film is molded to 1-100 mu m. 36. The method of forming a piezoelectric / electric warp thick film according to claim 35, wherein the thickness of the piezoelectric / electric warp film is molded to 5 to 30 mu m. 27. The method of forming a piezoelectric / electric warp thick film according to claim 26, wherein the seeding layer has a thickness of 1 µm or less. 38. The method of claim 37, wherein the seeding layer has a thickness of 200-300 nm. 27. The method of forming a piezoelectric / electric warp thick film according to claim 26, wherein the partial drying of the seeding layer is performed at room temperature-150 deg. 40. The method of forming a piezoelectric / electric warp thick film according to claim 39, wherein the partial drying of the seeding layer is performed at 50-70 ° C. The method of claim 26, wherein the partial drying of the seeding layer is dried by using a drying chamber in which the vapor of the organic solvent used as a base is saturated when preparing the ceramic sol solution which is the material of the seeding layer, and then volatilizing the solvent at an appropriate temperature. A piezoelectric / electric warp thick film forming method using a seeding layer, characterized in that the method. 27. The method of claim 26, wherein the piezoelectric / distortion film is heat treated at 150-300 占 폚. Providing a substrate; Ceramic sol solution of the same or similar component as piezoelectric / electric distortion film on the substrate, or non-explosive redox combustion reaction at low temperature of 100-500 ℃, particle size less than 5㎛, lead (Pb), titanium ( Ceramics of the same or similar component as the piezoelectric / electric distortion film prepared by mixing a ceramic oxide powder having Ti as a basic component and a ceramic sol solution having the same or similar components as the ceramic oxide powder prepared based on water or an organic solvent. Forming a seeding layer by applying a paste; Partially drying the shaped seeding layer at room temperature-150 ° C. to impart a suitable viscosity for adhesion; Attaching a separately formed and calcined piezoelectric / electric distortion film on the partially dry seeding layer; Heat-treating the attached piezoelectric / distortion film at 100-600 ° C. and baking the seeding layer, thereby manufacturing a bonded body of the piezoelectric / electric distortion film and the substrate, A method of forming a piezoelectric / electric distortion film using a seeding layer capable of forming a thick film piezoelectric / electric distortion film having excellent adhesion to a substrate even by heat treatment at low temperature. 45. The method of claim 43, wherein the substrate is a metal or ceramic on which electrodes are treated. 45. The method of claim 44, wherein the metal is stainless steel (SUS) or nickel (Ni). 45. The method of claim 44, wherein the ceramic is ceramic oxide, carbide, or nitride. 44. The method of claim 43, wherein the ceramic oxide powder has a particle size of 1 µm or less. 44. The method of claim 43, wherein the ceramic oxide powder uses PZT, PMN or their solid solution (PZT-PMN) composite oxide. 49. The method of claim 48, wherein the ceramic oxide powder is nickel (Ni), lanthanum (La), barium (Ba), zinc (Zn), lithium (Li), cobalt (Co), cadmium (Cd), cerium (Ce). , Chromium (Cr), antimony (Sb), iron (Fe), yttrium (Y), tantalum (Ta), tungsten (W), strontium (Sr), calcium (Ca), bismuth (Bi), tin (Sn) And a piezoelectric / electric warp thick film using the seeding layer, further comprising one or more elements of manganese (Mn). 44. The method of claim 43, further comprising pre-baking at 100-150 ° C. prior to heat treatment after attaching the piezoelectric / distortion film. . 44. The method of claim 43, wherein the piezoelectric / distortion thick film is formed by applying a predetermined pressure during the heat treatment to uniformly bond the piezoelectric / distortion film to the substrate during the heat treatment. 44. The method for forming a piezoelectric / electric warp thick film according to claim 43, wherein the thickness of the piezoelectric / electric warp film is molded to 1-100 µm. 53. The method for forming a piezoelectric / electric warp thick film according to claim 52, wherein the thickness of the piezoelectric / electric warp film is molded to 5 to 30 mu m. 44. The method of forming a piezoelectric / electric warp thick film according to claim 43, wherein the seeding layer has a thickness of 1 µm or less. 55. The method for forming a piezoelectric / electric warp thick film according to claim 54, wherein the seeding layer has a thickness of 200-300 nm. 44. The method for forming a piezoelectric / electric warp thick film according to claim 43, wherein the partial drying of the seeding layer is performed at room temperature-150 deg. The method of forming a piezoelectric / electric warp thick film according to claim 56, wherein the partial drying of the seeding layer is performed at 50-70 ° C. 45. The method of claim 43, wherein the partial drying of the seeding layer is carried out by drying using a drying chamber in which the vapor of the organic solvent used as a base is saturated when preparing the ceramic sol solution, which is a material of the seeding layer, and then volatilizing the solvent at an appropriate temperature. A piezoelectric / electric warp thick film forming method using a seeding layer, characterized in that the method. 44. The method of claim 43, wherein the piezoelectric / distortion film is heat treated at 150-300 ° C.