JPH09321361A - Piezoelectric vibrator component and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To expand the available range up to the high frequency band by using a Pb-contained Perovskite type ferroelectric single crystal film the c-axis of which is oriented in a direction perpendicular to the film surface for a piezoelectric material for making a piezoelectric vibrator component having a pair of electrodes opposed with this material inbetween. SOLUTION: A ferroelectric single crystal film 1 of a Pb-containing Perovskite type compd. is grown on a single crystal seed substrate 2 by dipping the substrate in a supersaturated melt of Pb-containing material. The substrate well matches the lattice const. of the film at an epitaxial growth temp., has a thermal expansion curve similar to that of the film and is little damaged by a soln. of this material. The compd. is shown by the formula (0<=a<x, x/y=0.8-1.1), and the spontaneous polarization (c-direction) is oriented perpendicular to the substrate surface. The film l is spontaneously polarized in c-axis, superior in dielectric property and formed from a melt below Curie point. Its baked product is usable in up to the high frequency band.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-frequency piezoelectric vibrating component using a piezoelectric material, and more particularly to a piezoelectric vibrating component using a lead-containing perovskite type ferroelectric single crystal film as a piezoelectric material and a method for manufacturing the same. .

[0002]

2. Description of the Related Art Conventionally, a piezoelectric vibrating component using a sintered body as a piezoelectric material has been widely known.

An example of this piezoelectric vibration component is a resonator in which electrodes facing each other are formed on both sides of a piezoelectric ceramic substrate and the thickness longitudinal vibration of the piezoelectric ceramic substrate is utilized. With such a resonator, the resonance frequency is 80 MH
The thickness of the substrate had to be about 30 μm to achieve about z.

However, the sintered body used as the above-mentioned piezoelectric material has a problem that cracks or cracks are generated at the time of processing due to the presence of crystal grain boundaries and the existence of voids. Therefore, the high frequency range (60M
In the region above about Hz), it was impossible to manufacture a vibrating component using a fired body.

A resonator having a resonance frequency of about 80 MHz using piezoelectric ceramics can be manufactured by utilizing the third harmonic, but in this case, the thickness of the substrate is 10
Since it is about 0 μm, the resonator becomes large.

Therefore, in any case, problems of poor workability and miniaturization remain.

Therefore, the present invention uses a lead-containing perovskite type ferroelectric single crystal film as a piezoelectric material and uses it even in a high frequency region (a high frequency region in which cracks or cracks occur during processing of the fired body) which is not possible with the fired body. An object of the present invention is to provide a piezoelectric vibrating component that is possible and easy to downsize.

The ferroelectric single crystal film is a single crystal film containing lead and having a perovskite type crystal structure represented by the chemical formula ABO ₃ (A part (hereinafter referred to as A site) contains lead). Yes, it is known to show remarkable dielectric properties, piezoelectric properties, optical properties, etc. (Introduction to electrical properties for ceramicists, Uchida Otsukaku, P.84 (1990) ・ Ferroelectricity and high temperature superconductivity, P.52 ~ 6
7, Yukabo (1993)). As the dielectric material, PbTiO ₃ , (PbL
a) There are ferroelectric materials represented by TiO ₃ , Pb (TiZr) O ₃ , and (PbLa) (TiZr) O ₃ . Most of these ferroelectrics have a tetragonal crystal structure and spontaneously polarize in the c-axis direction, and exhibit excellent dielectric properties, piezoelectric properties, optical properties, and the like.

Devices utilizing these excellent characteristics include, in addition to the above-mentioned piezoelectric vibrating component, a capacitor utilizing dielectric properties, a piezoelectric element or oscillator utilizing piezoelectric properties, an optical modulator utilizing optical properties, and the like. An optical switch etc. are mentioned. Further, in recent years, application to a dielectric memory device has been studied. In addition, this single crystal film has many advantages in material science (thin film material engineering, P.4-5, Kaibundou (1989)).

However, in order to obtain good characteristics in these devices, it is necessary to form a ferroelectric single crystal film of good film quality, which has the following problems.

As a method of producing a film made of the above ferroelectric substance, a vapor phase method such as a sputtering method or a liquid phase method such as a sol-gel method is generally used. The film produced by this method is generally polycrystalline. Since it is in the state, the direction of spontaneous polarization observed in the ferroelectric substance is different for each crystal grain, and the polarization direction is random as a whole, and almost no ferroelectric property is exhibited. Therefore, when a ferroelectric single crystal film was formed by a vapor phase method such as a sputtering method or a liquid phase method such as a sol-gel method, sufficient characteristics could not be exhibited even when applied to the above device. .

As a countermeasure for this, there is a method of applying an electric field in a direction perpendicular to the film to forcibly align the c-axis directions of the crystal grains (hereinafter referred to as polarization operation). However, when the c-axis directions of the crystal grains are forcibly aligned by this polarization operation, stress is generated due to the deformation of the crystal lattice, cracks may occur inside the film, or the substrate and the film may separate.
It could not be used as a thin film material in the above device.

Also, JJAP, vol.30, No.9B, P.2145 ~ 2148
In (1991), when a PbTiO ₃ film is formed by a sputtering method or the like using an MgO substrate or the like, the temperature difference between the substrate temperature during film formation and the Curie point of the formed film, the substrate The compressive stress acting in parallel to the film surface is generated due to the difference in lattice constant between the film and the film, and this compressive stress can provide a polycrystalline film in which most of the c-axis component is oriented in the direction perpendicular to the film surface. It is shown.

And J. Mat. Sci. Lett., No. 14, P. 629-6.
32 (1995), the compressive stress increases as the temperature difference ΔT between the substrate temperature during film formation and the Curie point of the film formed increases, and the degree of c-axis orientation increases. It is shown.

However, in order to obtain good characteristics when applied to the above-mentioned device, the degree of c-axis orientation is almost 100% (hereinafter, a film in which approximately 100% of the c-axis component is oriented in the direction perpendicular to the film surface is used. (referred to as a c-axis alignment film) is required, but in order to obtain a c-axis alignment film according to the description in the above document, it is necessary to set ΔT to about 500 ° C., and under this condition, a good quality film cannot be obtained. Have difficulty.

For example, when forming a c-axis oriented film made of PbTiO ₃ , the substrate temperature at the time of film formation must be as high as 990 ° C. When the film formation is performed at this substrate temperature, The re-evaporation of PbO from the deposited film becomes significant,
A film with high crystal perfection cannot be obtained. On the other hand, the substrate temperature at which a film with high crystal perfection and high quality is obtained is 60
Although it is set to about 0 ° C., a c-axis oriented film having a degree of c-axis orientation of almost 100% cannot be obtained at this substrate temperature.

As described above, it has been difficult to obtain a perfect c-axis oriented film with a perovskite type ferroelectric containing lead.

Further, even if a c-axis oriented film having a c-axis oriented degree of almost 100% is obtained, if the c-axis oriented film is a polycrystalline film, high characteristics as in the case of a single crystal cannot be obtained. (Single crystal (manufacturing and prospect), Uchida Old Crane, P.37-40 (1990)). For example, when a polycrystalline film is used for an optical device, when light passes through the polycrystalline film, the loss at the crystal grain boundary becomes large, and good characteristics cannot be obtained.

Further, generally used for forming a dielectric thin film on a substrate, a vapor phase method such as CVD and vapor deposition, a sol-gel method, a hydrothermal synthesis method, a liquid phase epitaxial method, a liquid phase method such as electrodeposition. The coating method (solid-phase method) such as spin coating, doctor blade, and screen printing also has the following problems.

Gas phase method (Surface science, vol.16, No.7, P.410-414
(1995)), most of them have a grain boundary, are not single crystals, and when the film thickness is about 1 μm or more, a c-axis oriented film having sufficient c-axis orientation is obtained. I can't.

In the sol-gel method, the obtained film becomes polycrystalline, and the hydrothermal synthesis method (JJAP, vol. 30, No. 9B, P. 2174-21) is used.
77, (1991)), only aggregates of fine crystals were obtained.

Coating Method (Journal of the Ceramic Society of Japan, Volume 103 N
O.7, P.660 to 663 (1995)), the obtained film becomes polycrystalline.

By the way, in the film formation by the liquid phase epitaxial method, since the growth is performed in a state close to the liquid phase-solid phase equilibrium, it is generally said that a high quality single crystal film can be obtained (ELEMENTARY CRYSTAL GROWTH, Saan). Publishers,
P.489-520, (1994)).

As an example of producing an oxide single crystal film by this method, garnet ferrite on a GGG (gadolinium gallium garnet) substrate, LiNbO ₃ or LiTaO ₃ on a LiNbO ₃ or LiTaO ₃ substrate (LiTaO ₃ 31 (P.105 (1989)) and high temperature superconducting materials (App
L. Phys. Lett., vol. 66 (11), No. 13, P. 1421, 1995) and the like are known.

However, in order to form a lead-containing perovskite ferroelectric single crystal film which is a c-axis oriented film by this method, the following conditions must be met, but it is not easy to satisfy all of these conditions. It was

First, it is necessary to prepare (find the melt composition) a melt (solution or melt) capable of forming a film at a temperature below the Curie point of the obtained lead perovskite ferroelectric. That is, the supercooling temperature of the melt, that is, the temperature at which film formation (epitaxial growth) is performed by the liquid phase epitaxial method must be lower than the Curie point of the film.

However, in the liquid phase epitaxial method, it is generally difficult to prepare a melt (solution or melt) capable of forming a film at 500 ° C. or lower (to find out the melt composition). This is because it is difficult to study the melt composition satisfying this condition because there is almost no phase diagram showing the melt composition that the target composition produces and the range in which epitaxial growth can be performed at low temperatures (Journal of the Crystallographic Society of Japan, No. 20).
Vol. 4, No. 4, P. 389 (1993)).

When a film is formed at a temperature equal to or higher than the Curie point of the lead perovskite ferroelectric, the crystal structure of the film changes in the cooling process after the film formation, and as a result, cracks due to large internal stress occur. In addition, a 90 ° domain structure in which a c-axis component and an a-axis component are mixed in a direction perpendicular to the substrate, does not result in perfect c-axis orientation.

Next, in the film formation (epitaxial growth) by the liquid phase epitaxial method, the melt and the substrate come into contact with each other at a high temperature, but the melt must not react with the substrate at this time (The Crystallographic Society of Japan). Magazine Volume 31, P.1
05 (1989)).

However, in a melt using a general flux, the flux component causes the substrate to dissolve in the melt (Journal of Crystal Growth, vol.
3 No. 4, P.443-444 (1968)), it is also necessary to carefully consider the flux components.

Further, as the ferroelectric substance according to the present invention, a compound containing a lead-containing compound as an essential main component is PbO,
PbF _2, it is preferable to use a self-flux such as PbCl _2, since these high vapor pressure at high temperature, melt composition will vary, it is difficult to maintain the supercooled state of the liquid phase. Further, since the flux containing lead has a particularly high corrosiveness with respect to the substrate, the phenomenon of dissolution of the substrate in the melt appears remarkably.

As described above, in order to use the lead-containing perovskite ferroelectric single crystal film exhibiting excellent dielectric properties, piezoelectric properties, optical properties and the like in the above device, it is necessary to solve the above problems. . As a solution to this problem, in the present invention, a melt (solution or melt) composition capable of forming a film at a temperature equal to or lower than the Curie point of a lead perovskite ferroelectric is found, and the melt is formed by a liquid phase epitaxial method. The film is made.

The film formation by the liquid phase epitaxial method has a film formation rate higher than that of the MO-CVD method or the sputtering method.
Since the film forming speed is fast (about 10 to 100 times), it is suitable for industrialization.

The piezoelectric constant (d ₃₃ ) of the lead perovskite ferroelectric substance is about 2 to 3 times that of the ceramic material. Further, it has excellent workability because it does not have grain boundaries or pores unlike ceramic materials.

The electro-optic constant of the lead perovskite ferroelectric is about 4 to 3 times that of lithium niobate (LiNbO ₃ ).

[0036]

A piezoelectric vibrating component according to claim 1 is a piezoelectric vibrating component comprising a piezoelectric material and at least one pair of electrodes facing each other with the piezoelectric material sandwiched therebetween. It is a lead-containing perovskite-type ferroelectric single crystal film in which the c-axis is oriented in a direction perpendicular to the film surface.

A piezoelectric vibrating component according to a second aspect is the first aspect.
In the piezoelectric vibrating component described above, the composition formula of the ferroelectric single crystal film is (Pb _xa M1 _a ) M2 _y O _z , and M1 of the composition formula is an alkali metal, an alkaline earth metal or bismuth. Alternatively, M2 represents at least one kind of lanthanum, and M2 represents titanium, zircon, or an element containing both titanium and zircon as a main component.

According to a third aspect of the present invention, there is provided a method of manufacturing a piezoelectric vibrating component, wherein a perovskite-type lead-containing type is provided on a single crystal seed substrate in a melt having a supercooling temperature lower than the Curie point of a ferroelectric single crystal film to be formed. A step of epitaxially growing a ferroelectric single crystal film; a step of subjecting the single crystal seed substrate to an etching treatment to expose a surface of the ferroelectric single crystal film on the single crystal seed substrate side; And a step of forming at least one pair of electrodes facing each other on both sides of the crystal film.

A method of manufacturing a piezoelectric vibrating component according to claim 4 is the same as the method of manufacturing a piezoelectric vibrating component according to claim 3,
The melt comprises a lead supply component and a titanium supply component in which lead oxide and lead fluoride are mixed in a range of 8: 2 to 4: 6, and the titanium supply component is the total number of moles of the lead component of the lead supply component. It is characterized in that it is contained in a molar ratio of 0.02 to 0.15.

A method of manufacturing a piezoelectric vibrating component according to claim 5 is the same as the method of manufacturing a piezoelectric vibrating component according to claim 4.
The melt contains at least one kind selected from an alkali metal compound, an alkaline earth metal compound, a zirconium compound, a lanthanum compound, and a rare earth element compound in an amount of 0.01 to 0.6 with respect to the total number of moles of the lead component of the lead supply component. It is characterized in that it is contained in a molar ratio of.

A method for manufacturing a piezoelectric vibrating component according to claim 6 is the same as the method for manufacturing a piezoelectric vibrating component according to claim 4.
The melt comprises at least one of a boron compound, a bismuth compound, an alkali metal compound and an alkaline earth metal compound in a molar ratio of 0.0125 to 1.00 with respect to the total number of moles of the lead component of the lead supplying component. It is characterized by containing.

According to a seventh aspect of the present invention, there is provided a method of manufacturing a piezoelectric vibrating component according to any one of the third to sixth aspects, wherein the single crystal seed substrate is at least one side of a unit crystal lattice. Is used in the range of 3.50 to 4.30 A or 5.00 to 6.00 A.

A method of manufacturing a piezoelectric vibrating component according to claim 8 is the method of manufacturing a piezoelectric vibrating component according to any one of claims 3 to 6, wherein the single crystal seed substrate is strontium titanate (SrTiO ₃ ). , Magnesium oxide (MgO), lanthanum aluminate (LaAlO ₃ ), yttrium aluminate (YAl
O ₃ ), neodymium aluminate (NdAlO ₃ ), lanthanum gallate (LaGaO ₃ ), neodymium gallate (NdGaO ₃ ), praseodymium gallate (PrGaO ₃ ), strontium lanthanum gallate (LaSrGaO ₄ ), sapphire (Al ₂ O) ₃ ) or the like, or a substrate obtained by substituting a part of its constituent elements with another element.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION A piezoelectric vibrating component according to the present invention comprises:
For example, as shown in FIG. 1, a structure in which an electrode 3a is formed on the front surface of the ferroelectric single crystal film 1 formed on the single crystal seed substrate 2 and an electrode 3b is formed on the back surface (surface on the single crystal seed substrate side). It has become.

Next, a process for producing a piezoelectric vibrating component using a lead-containing perovskite type ferroelectric single crystal film formed on a single crystal seed substrate by a liquid phase epitaxial method described later will be described.

First, the single crystal seed substrate 2 is subjected to etching to expose the back surface (the surface on the single crystal seed substrate side) of the ferroelectric single crystal film 1. Next, the front surface electrode 3a and the back surface electrode 3b are formed on the front surface and the back surface of the ferroelectric single crystal film 1 by the vapor deposition method or the sputtering method, and at the same time, the extraction electrodes 3c and 3d connected to these are provided outside the vibration region. .

The piezoelectric vibrating component can be easily manufactured by the above steps. Next, the lead-containing perovskite type ferroelectric single crystal film and the manufacturing method thereof will be described.

[Lead-Containing Perovskite-Type Ferroelectric Single Crystal Film] The lead-containing perovskite-type ferroelectric single crystal film is a lead-containing perovskite-type structure single crystal film having a high degree of c-axis orientation. Here, the perovskite structure is one type of the crystal structure of a compound represented by the general formula ABO _z , and a typical compound is perovskite (CaT).
iO ₃ ) is known. In the above general formula, A and B represent cations, and when the crystal constitutes a stoichiometric ratio,
The A / B molar ratio is 1 and z is 3.

However, normally, it is rare that the composition ratio is exactly as described above, but when the A / B molar ratio deviates from the range of 0.8 to 1.1, the crystal quality is deteriorated and the insulating property is deteriorated. It becomes difficult to secure the sex. It should be noted that z is determined so that the total charge amount in the crystal represented by the above general formula becomes 0 when the A / B molar ratio is determined.

Since the ferroelectric single crystal film is a lead-containing perovskite type compound, its composition formula can be expressed as follows.

(Pb _xa M1 _a ) M2 _y O _z (1) In this composition formula (1), a and x have a relationship of 0 ≦ a <x, and x and y have x / y = The relationship of 0.8 to 1.1 is satisfied.
z is included in the range of 2.8 to 3.2, and a part of oxygen atoms may be replaced with a halogen atom such as a chlorine atom or a fluorine atom.

M1 usually represents a monovalent, divalent, or trivalent element, and examples thereof include alkali metals, alkaline earth metals, bismuth, lanthanum, and the like, or a combination thereof. Among these, lithium, Sodium, barium, strontium, calcium, magnesium, bismuth,
Lanthanum is preferred.

M2 is usually titanium, but part of it may be replaced with zirconium, tin, niobium or the like.

The ferroelectric single crystal film is a film grown in a direction in which the spontaneous polarization azimuth (c-axis) is perpendicular to the substrate, and the film thickness is at least 2 μm or more. It has a smooth surface without post-processing (surface processing).

The film thickness is preferably in the range of 2 to 100 μm, and particularly preferably in the range of 5 to 70 μm from the viewpoints of practicality, economy and easiness of film formation. Here, the film thickness is the average value of the numerical values obtained by observing the cross section of the film with a microscope after forming the film and measuring 10 points at 0.1 mm intervals.

[Manufacturing Method of Lead-Containing Perovskite Type Ferroelectric Single Crystal Film] Next, a manufacturing method of the lead-containing perovskite type ferroelectric single crystal film by the liquid phase epitaxial method will be described. Here, the liquid phase epitaxial method is a method in which a single crystal seed substrate is immersed in a melt (solution or melt) in a supercooled state or a supersaturated state to grow an epitaxial crystal on this substrate.

The above-mentioned single crystal seed substrate has good conformity with the lattice constant of the film at the epitaxial growth temperature, has a thermal expansion curve close to that of the film, and is not easily damaged by the lead-containing raw material melt. Is used.
If a substrate that does not match the lattice constant of the film is used, the film may become polycrystalline or may not grow at all, and if the difference in the thermal expansion curves is large, the stress due to the difference in thermal expansion may May cause film cracking or peeling.

In order to match the lattice constants of the single crystal substrate and the film, a single crystal seed substrate in which at least two sides of the unit crystal lattices a, b and c have a length of 3.50 to 4.30 A, Alternatively, it is necessary to use a single crystal substrate in the range of 5.00 to 6.00 A, which is obtained by multiplying the value by about 2 ^0.5 (a value close to the square root of 2). Here, when a single crystal substrate in the range of 5.00 to 6.00 A is used, it can be matched with the diagonal line of the unit cell of the film, and epitaxial growth can be performed.

By the way, when the directions of the crystal axes are aligned, the a-axis may be aligned in the direction parallel to the substrate, or the c-axis may be aligned, but the one in which the c-axis is aligned in the direction perpendicular to the substrate surface. However, since high characteristics are obtained when used in a device such as a piezoelectric element, a substrate having a lattice constant close to that of the a-axis and the b-axis of the ferroelectric single crystal film is used as the single crystal seed substrate. By using the substrate having such a lattice constant, the c-axis of the ferroelectric single crystal film can be aligned in the direction perpendicular to the substrate surface.

Specifically, strontium titanate (SrT
iO ₃ ), magnesium oxide (MgO), lanthanum aluminate (La
AlO ₃ ), yttrium aluminate (YAlO ₃ ), neodymium aluminate (NdAlO ₃ ), lanthanum gallate (LaGaO ₃ ), neodymium gallate (NdGaO ₃ ), praseodymium gallate
(PrGaO ₃ ), strontium lanthanum gallate (LaSrGaO _3
4 ), a single crystal seed substrate such as sapphire (Al ₂ O ₃ ) or a substrate in which some of its constituent elements are replaced with other elements can be used, but strontium titanate (SrTiO ₃ ) and magnesium oxide can be used. (MgO) and lanthanum aluminate (LaAlO ₃ ) single crystal seed substrates are less likely to be damaged by the lead raw material melt, and thus are suitable as single crystal seed substrates for forming a ferroelectric single crystal film containing lead. is there.

Next, a method for producing the above solution or melt will be described.

First, a method of preparing the raw material mixture so that the ferroelectric single crystal film formed by the liquid phase epitaxial method has the composition represented by the above composition formula (1) will be described. This raw material mixture usually has a lead supply component and a titanium supply component as basic components.

As the lead supply component, for example, lead oxide (P
bO, PbO ₂ , Pb ₃ O ₄ etc.) and lead fluoride (PbF ₂ ) ratio converted to Pb molar ratio (lead oxide: lead fluoride =) in the range of 8: 2 to 4: 6. What is contained can be used.

As the titanium supply component, for example, titanium oxide (TiO ₂ ) can be used, and the ratio of Ti atoms is 0.02 to 0.15 with respect to the total number of moles of Pb contained in the lead supply component. It is prepared so as to be contained in the range of molar ratio. If this ratio is less than 0.02, the film quality is deteriorated and it is difficult to put it into practical use. If it is more than 0.15, the temperature during film formation (film growth temperature) is a general lead-based ferroelectric. Above the upper limit of the Curie point of 500 ° C., a c-axis oriented film cannot be obtained.

Further, with respect to the basic composition consisting of the lead supply component and the titanium supply component, a component for improving crystal growth and a component for controlling the crystal growth temperature (controlling the supercooled state) as desired ( Hereinafter, a component for improving crystal growth or controlling a crystal growth temperature may be added as a component relating to crystal growth).

As the component for growing the crystal, a boron supplying component using boron oxide (B ₂ O ₃ ) or the like, or a bismuth supplying component using bismuth oxide (Bi ₂ O ₃ ) or the like is preferable. Alkali metal supply components using alkali metal compounds such as potassium oxide (K ₂ O) and potassium fluoride (KF) (potassium supply component), alkaline earth metal compounds such as calcium oxide (CaO) (calcium supply component) The alkaline earth metal supply component used may be used. Further, two or more kinds of these components for crystal growth may be used.

The components relating to the crystal growth described above have the following effects.

With respect to the above-mentioned boron supply component, it has the action of increasing the viscosity of the melt, the action of suppressing the evaporation of the lead supply component, the action of lowering the crystal growth temperature, and the action of stabilizing the supercooled state. However, depending on the amount of the boron supply component added, the viscosity of the melt excessively increases and the supply of solute to the substrate is hindered, which is not preferable.

In such a case, since the bismuth supply component, the alkali metal supply component, and the alkaline earth supply component have an action of lowering the viscosity, the excessively increased viscosity due to the addition of these components can be reduced to a preferable viscosity. Can be controlled.

Of the above-mentioned components for crystal growth, the components to be taken into the film must be selected according to the use of the ferroelectric single crystal film. Further, when it is not desired to include a component for crystal growth in the film, a component made of boron or potassium which is a component that is not incorporated in the film may be used. Here, it is considered that boron and potassium are not contained in the formed single crystal film because boron has an extremely small ionic radius, and potassium has an extremely large ionic radius as compared with Pb. To be

Further, in order that these components relating to crystal growth effectively exert their effects, the molar ratio of Pb contained in the lead supply component to the total number of moles is ((Pb contained in the lead supply component is Total number of moles: Crystal growth component =) 8
It is preferably in the range of 0: 1 to 1: 1 and more preferably in the range of 15: 1 to 2: 1.

In the above, in order to improve the crystal growth and to control the crystal growth temperature (control the supercooled state), the boron supply component, the bismuth supply component, the alkali metal supply component, the alkaline earth In order to replace a part of the elements of A site (Pb) and B site (Ti) of the ferroelectric single crystal film having the perovskite type crystal structure with other metal elements, a component supplying component was added to the melt. A compound of such a metal element may be added to the melt.

[0073] Examples of the metal element, an alkali metal, alkaline earth metal, zirconium, lanthanum, rare earth elements, and examples of the _{compound, LiCO 3, SrCO 3, MgCO} 3
And carbonic acid compounds such as Bi ₂ O ₃ , ZrO ₂ , La ₂ O ₃ and Y ₂ O ₃ , and halides such as LiF, NaF and NaCl. These may be used alone or in combination of two or more. You may use it. Further, these compounds are preferably added in the range of 0.01 to 0.6 mol, and more preferably in the range of 0.01 to 0.4 mol, relative to 1 mol of the Pb supply component in the raw material mixture.

A typical example of the metal element in which a part of the A site (Pb) or B site (Ti) element of the ferroelectric single crystal film is replaced is PZT, that is, Pb (ZrTi).
O ₃ and PLT, that is, (PbLa) TiO ₃ and PLZT, that is, (PbLa) (ZrTi) O ₃ .

[0075]

EXAMPLE Next, a Pb _0.96 Ca film having a thickness of 15 μm was formed on a MgO single crystal substrate by a liquid phase epitaxial method.
Resonance frequency of 1 using _0.04 TiO ₃ ferroelectric single crystal film
A case where a 60 MHz resonator is manufactured will be described.
The method for forming the ferroelectric single crystal film will be described later.

First, the MgO single crystal substrate on which the ferroelectric single crystal film of Pb _0.96 Ca _0.04 TiO ₃ was formed was subjected to etching using a phosphoric acid solution to expose the back surface of the ferroelectric single crystal film. Let

Next, opposing gold electrodes having an electrode diameter of 200 μmφ were formed on the front surface and the back surface of this ferroelectric single crystal film by the sputtering method.

When the operation of the resonator was confirmed, it worked normally.

A method for forming the lead-containing perovskite type ferroelectric single crystal film will be described in the following examples.

[Example 1] An example in which a boron supply component is used as a component for crystal growth will be described.

First, PbO and Pb which are lead supply components
F _2, a raw material composed of B ₂ O ₃ is a TiO ₂ and boron providing component is titanium feed _{component, PbO: PbF 2 = 5.5:} 4.5 TiO 2: (PbO + PbF 2 + TiO 2 + B 2 O 3) =
_{5: 100 (PbO + PbF 2} ): B 2 O3 = 7: was thoroughly mixed with 1 molar ratio.

Next, this mixture was placed in a platinum crucible,
Using an electric furnace, the temperature is raised to 700 ° C. at 200 to 400 ° C./hour, the temperature is maintained at 700 ° C. for 1 hour, and the molten solution is stirred for 1 hour while using the blade made of platinum. And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 450 ° C.

Next, in this solution, SrTi of (100) plane was added.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

The film thus formed was transparent, had a pale yellow color, and had a glossy and smooth surface. The film thickness was uniform throughout and was 4 μm. or,
When the film composition was examined by fluorescent X-ray analysis, it was found that PbO and T
It was confirmed that the ratio of iO ₂ was PbTiO ₃ of 1: 1. Here, FIG. 1 shows a differential interference microscope photograph of the film surface.

Further, when the crystallinity of the film was examined by the back surface Laue method, spots having a clean 4-fold symmetry as shown in FIG. 2 were observed, and it was confirmed that the film was a single crystal.

When the crystal structure of the film was measured by X-ray diffraction, a peak only on the (00n) plane of the film was observed as shown in FIG. 3, and it was confirmed that the film was c-axis oriented.

When observed with a polarization microscope,
Existence of a region having an a axis in the direction perpendicular to the substrate surface, that is, 9
The presence of 0 ° domain was not observed. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The c-axis length determined by X-ray diffraction was 4.113 A, and the Curie temperature determined by thermal analysis was 481 ° C. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

Next, in order to evaluate the crystallinity of the film, the film surface was chemically etched with HF + dilute nitric acid, and etch pits due to crystal defects such as dislocations were observed. But,
The defect density was as low as 10 to 10 ² / cm ^2, and this defect density was a value comparable to that of a commercially available single crystal substrate, which confirmed that the film quality was very good.

[Example 2] An example in which a boron supply component and a calcium supply component (alkaline earth metal supply component) are used as components for crystal growth will be described.

First, PbO and Pb which are lead supply components
A raw material composed of F ₂ , TiO ₂ which is a titanium supply component, B ₂ O ₃ which is a boron supply component and CaCO ₃ which is a calcium supply component is PbO: PbF ₂ = 5.5: 4.5 (PbO + PbF ₂ ): TiO ₂ : CaCO ₃ = 500:
They were mixed well in a molar ratio of 20: 1 (PbO + PbF ₂ ): B ₂ O ₃ = 6: 1.

Next, this mixture was placed in a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 400 ° C.

Next, a (100) plane MgO single crystal substrate was immersed in this solution, and the substrate was rotated at 100 rpm to give 1
After crystal growth for 0 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured by a microscope, it was confirmed that the film was formed with a thickness of about 5 μm on the substrate. The film had a smooth mirror surface.

When the composition of this film was analyzed by fluorescent X-ray, the approximate composition was Pb _0.96 Ca _0.04 TiO ₃ (however, it was calculated that Ca was all contained in the A site due to its ionic radius). ).

When the crystal structure of the film was measured by X-ray diffraction, the film was composed of only the (00n) plane and no 90 ° domain was found. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The c-axis length obtained by X-ray diffraction was 4.
130A, the Curie temperature obtained by thermal analysis is
It was 447 degreeC. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

[Example 3] An example in which a part of the A site is replaced with lanthanum will be described.

First, PbO and Pb which are lead supply components
A raw material composed of F ₂ , TiO ₂ which is a titanium supply component, B ₂ O ₃ which is a boron supply component and La ₂ O ₃ which is a substitution component is PbO: PbF ₂ = 5.5: 4.5 (PbO + PbF ₂ ). _{: TiO 2: La 2 O 3} = 1000:
They were mixed well at a molar ratio of 50: 1 (PbO + PbF ₂ ): B ₂ O ₃ = 6: 1.

Next, this mixture was placed in a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and maintained at 380 ° C.

Next, in this solution, SrTi of (100) plane was added.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured with a microscope, it was confirmed that the film was formed on the substrate to a thickness of about 5 μm. The film had a smooth mirror surface.

When the composition of this film was analyzed by fluorescent X-ray, the approximate composition was Pb _0.96 La _0.04 TiO ₃ (however, La was calculated based on its ionic radius to be contained in all A sites). ).

When the crystal structure of the film was measured by X-ray diffraction, it was composed of only the (00n) plane and no 90 ° domain was found. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The c-axis length obtained by X-ray diffraction was 4.
The Curie temperature obtained by thermal analysis is
It was 417 degreeC. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

[Example 4] An example in which a part of the B site (B portion of the film having the perovskite type crystal structure represented by the chemical formula ABO ₃ ) is replaced with zirconium will be described.

First, PbO and Pb which are lead supply components
A raw material composed of F ₂ , TiO ₂ which is a titanium supply component, B ₂ O ₃ which is a boron supply component and ZrO ₂ which is a substitution component is PbO: PbF ₂ = 5.5: 4.5 (PbO + PbF ₂ ): TiO ₂ : ZrO ₂ = 100:
The mixture was well mixed at a molar ratio of 3: 2 (PbO + PbF ₂ ): B ₂ O ₃ = 7: 1.

Next, this mixture was placed in a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 420 ° C.

Next, in this solution, SrTi of (100) plane was added.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured with a microscope, it was confirmed that the film was formed on the substrate in a thickness of about 5 μm. The film had a smooth mirror surface.

Further, when the composition of this film was analyzed by fluorescent X-ray, the approximate composition was Pb (Ti _0.88 Zr _0.12 ) O ₃ (however, Zr is all contained in the B site due to its ionic radius). Calculated as).

When the crystal structure of the film was measured by X-ray diffraction, the film was composed of only the (00n) plane and no 90 ° domain was found. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The c-axis length obtained by X-ray diffraction was 4.
The Curie temperature obtained by thermal analysis is 095 A.
It was 455 ° C. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

This crystal is generally called PZT and is an important piezoelectric material widely used in industry.

[Example 5] An example in which a part of the A site is replaced with lanthanum and a part of the B site is replaced with zirconium will be described.

First, PbO and Pb which are lead supply components
F _2, a raw material composed of ZrO ₂ is B ₂ O ₃ and substituted components TiO _2, a boron supply component is titanium feed _{component, PbO: PbF 2 = 5.5:} 4.5 (PbO + PbF 2): TiO _{2: La 2 O 3: ZrO} 2 = 1000: 25: 0.5: 25 (PbO + PbF 2): B 2 O 3 = 5: was thoroughly mixed with 1 molar ratio.

Next, this mixture was put in a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 420 ° C.

Next, in this solution, SrTi of (100) plane was added.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured by a microscope, it was confirmed that the film was formed on the substrate to a thickness of about 5 μm. The film had a smooth mirror surface.

When the composition of this film was analyzed by fluorescent X-ray, the approximate composition was (Pb _0.98 La _0.02 ) (Ti _0.88 Z
r _0.15 ) O ₃ (however, it was calculated that all of La was included in the A site and all of Zr was included in the B site).

When the crystal structure of the film was measured by X-ray diffraction, the film was composed of only the (00n) plane and no 90 ° domain was found. Therefore, in the direction perpendicular to the substrate
It was confirmed that the C-axis was a perfectly oriented film.

The c-axis length obtained by X-ray diffraction was 4.
108A, and the Curie temperature determined by thermal analysis is
It was 436 ° C. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

[Example 6] An example in which a part of the A site is replaced with sodium will be described.

First, PbO and Pb which are lead supply components
A raw material composed of F ₂ , TiO ₂ which is a titanium supply component, B ₂ O ₃ which is a boron supply component and Na ₂ O which is a substitution component is PbO: PbF ₂ = 5.5: 4.5 (PbO + PbF ₂ ): TiO ₂ : Na ₂ O = 1000: 25: 2 (PbO + PbF ₂ ): B ₂ O ₃ = 5: 1 and mixed well.

Next, this mixture was put into a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 400 ° C.

Next, this solution was mixed with LaAl of (100) plane.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured with a microscope, it was confirmed that the film was formed on the substrate with a thickness of about 5 μm. The film had a smooth mirror surface.

When the composition of this film was analyzed by fluorescent X-ray, the approximate composition was (Pb _0.99 Na _0.01 ) TiO ₃ (however, it was calculated that all Na was contained in the A site).

When the crystal structure of the film was measured by X-ray diffraction, the film was composed of only the (00n) plane and no 90 ° domain was found. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The C-axis length obtained by X-ray diffraction was 4.
114A, the Curie temperature determined by thermal analysis is
It was 451 ° C. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

[Embodiment 7] An embodiment in which a part of the A site is replaced with bismuth will be described.

First, PbO and Pb which are lead supply components
A raw material composed of F ₂ , TiO ₂ which is a titanium supply component, B ₂ O ₃ which is a boron supply component and Bi ₂ O ₃ which is a substitution component is PbO: PbF ₂ = 5.5: 4.5 (PbO + PbF ₂ ). _{: TiO 2: Bi 2 O 3} = 1000:
The mixture was well mixed at a molar ratio of 25: 3 (PbO + PbF ₂ ): B ₂ O ₃ = 5: 1.

Next, this mixture was placed in a platinum crucible,
Using an electric furnace, the temperature was raised to 800 ° C. at 200 to 400 ° C./hour, held at 800 ° C. for 1 hour, and then the molten solution was stirred for 1 hour (using a blade made of platinum). And stirred at 200 r.p.m.). 100 ℃ every hour thereafter
The temperature was lowered at and kept at 400 ° C.

Then, SrTi of (100) plane was added to this solution.
The O ₃ single crystal substrate was dipped, the substrate was rotated at 100 rpm to grow the substrate for 10 minutes, the substrate was pulled above the liquid surface, the substrate was rotated at 500 rpm for 1 minute, and the solution was shaken off. . Next, after cooling this substrate to room temperature at 10 ° C. to 200 ° C. per minute, it was immersed in dilute nitric acid to remove the solidified material of the raw material solution adhering to its surface, washed with water, and then dried.

When the film thus formed was measured by a microscope, it was confirmed that the film was formed on the substrate in a thickness of about 5 μm. The film had a smooth mirror surface.

When the composition of this film was analyzed by fluorescent X-ray, the approximate composition was (Pb _0.97 Bi _0.03 ) TiO ₃ (however, it was calculated that all Na was contained in the A site).

When the crystal structure of the film was measured by X-ray diffraction, the film was composed of only the (00n) plane and no 90 ° domain was found. Therefore, it was confirmed that the film was a film in which the c-axis was perfectly oriented in the direction perpendicular to the substrate.

The c-axis length obtained by X-ray diffraction was 4.
The Curie temperature obtained by thermal analysis is 117 A.
It was 462 ° C. Therefore, it can be seen that the film growth was carried out below the Curie temperature.

[0139]

According to the present invention, since the lead-containing perovskite type ferroelectric single crystal film is used as the piezoelectric material, it is possible to easily realize a high frequency and a small size of the piezoelectric vibration component.

[Brief description of drawings]

FIG. 1A is a plan view and FIG. 1B is a cross-sectional view showing an example of a piezoelectric vibrating component according to the present invention.
It is.

FIG. 2 shows a photomicrograph (differential interference photomicrograph) of the film surface.

FIG. 3 is an X-ray photograph measured by a back surface Laue method.

FIG. 4 shows an X-ray diffraction pattern obtained by measuring the crystal structure of the film by X-ray diffraction.

[Explanation of symbols]

 1 Ferroelectric Single Crystal Film 2 Single Crystal Seed Substrate 3a, 3b Electrodes 3c, 3d Extraction Electrode

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 21, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction contents]

As described above, it has been difficult to obtain a perfect c-axis oriented film from a perovskite type ferroelectric crystal containing lead.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

First, it is necessary to prepare (find the melt composition) a melt (solution or melt) capable of forming a film at a temperature below the Curie point of the obtained lead- containing perovskite type ferroelectric. That is, the supercooling temperature of the melt, that is, the temperature at which film formation (epitaxial growth) is performed by the liquid phase epitaxial method must be lower than the Curie point of the film.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

When a film is formed at a temperature equal to or higher than the Curie point of the lead- containing perovskite type ferroelectric, the crystal structure of the film changes in the cooling process after the film formation, and as a result, cracks due to large internal stress occur. . In addition, a 90 ° domain structure in which a c-axis component and an a-axis component are mixed in a direction perpendicular to the substrate, does not result in perfect c-axis orientation.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction contents]

As described above, in order to use the lead-containing perovskite type ferroelectric single crystal film exhibiting excellent dielectric properties, piezoelectric properties, optical properties and the like in the above device, it is necessary to solve the above problems. is there. As a solution to this problem, in the present invention, a melt (solution or melt) composition capable of forming a film at a temperature below the Curie point of a lead- containing perovskite type ferroelectric is found, and a liquid phase epitaxial method using the melt is found. The film is formed by.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

Further, a lead- containing perovskite type ferroelectric single crystal is used.
The piezoelectric constant (d33) of the crystal is about 2 to 3 times that of the ceramic material. Further, it has excellent workability because it does not have grain boundaries or pores unlike ceramic materials.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

Further, a lead- containing perovskite type ferroelectric single crystal
Electrooptical constant of crystal is lithium niobate single crystal (LiNbO
It is about 4 to 3 times that of 3).

[Procedure amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0070

[Correction method] Change

[Correction contents]

Of the above-mentioned components for crystal growth, the components to be taken into the film must be selected according to the use of the ferroelectric single crystal film. Also, if you do not want to include a component according to the crystal growth in the film, may be used components consisting of boron and potassium is a component that is not incorporated into the film. Here, it is considered that boron and potassium are not contained in the formed single crystal film because boron has an extremely small ionic radius, and potassium has an extremely large ionic radius as compared with Pb. To be

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0139]

According to the present invention, since the Ru with lead-containing perovskite-type ferroelectric single crystal film as a piezoelectric material, adapted to the frequency and size of the piezoelectric vibration component can be easily realized.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication H03H 3/02 H01L 41/18 101D 9/17 41/22 Z

Claims (8)

[Claims] 1. A piezoelectric vibrating component comprising a piezoelectric material and at least one pair of electrodes facing each other with the piezoelectric material sandwiched therebetween, wherein the piezoelectric material has a c-axis oriented in a direction perpendicular to a film surface. A piezoelectric vibrating component, which is a perovskite type ferroelectric single crystal film containing lead. 2. The piezoelectric vibrating component according to claim 1, wherein
The compositional formula of the ferroelectric single crystal film is (Pb _xa M1 _a ) M2 _y O _z , and M1 in the compositional formula represents at least one of alkali metal, alkaline earth metal, bismuth, and lanthanum. , M2 represents titanium, zircon, or an element containing both titanium and zircon as a main component. 3. A step of epitaxially growing a lead-containing perovskite type ferroelectric single crystal film on a single crystal seed substrate in a melt having a supercooling temperature equal to or lower than the Curie point of the ferroelectric single crystal film to be formed. Etching the single crystal seed substrate to expose a surface of the ferroelectric single crystal film on the single crystal seed substrate side, and at least one pair facing each other on both surfaces of the ferroelectric single crystal film. And a step of forming electrodes of the same. 4. The method of manufacturing a piezoelectric vibration component according to claim 3, wherein the melt contains lead oxide and lead fluoride in an amount of 8: 2.
It is composed of a lead supply component and a titanium supply component mixed in a range of 4: 6, and contains the titanium supply component in a molar ratio of 0.02 to 0.15 with respect to the total number of moles of the lead component of the lead supply component. A method for manufacturing a piezoelectric vibrating component, comprising: 5. The method of manufacturing a piezoelectric vibrating component according to claim 4, wherein the melt contains at least one of an alkali metal compound, an alkaline earth metal compound, a zirconium compound, a lanthanum compound, and a rare earth element compound. A method for manufacturing a piezoelectric vibrating component, characterized in that the lead supplying component is contained in a molar ratio of 0.01 to 0.6 with respect to the total number of moles of the lead supplying component. 6. The method for manufacturing a piezoelectric vibrating component according to claim 4, wherein the melt contains at least one of a boron compound, a bismuth compound, an alkali metal compound and an alkaline earth metal compound as a lead supply component. The method for producing a piezoelectric vibrating component, wherein the lead component is contained in a molar ratio of 0.0125 to 1.00 with respect to the total number of moles of the lead component. 7. The method of manufacturing a piezoelectric vibrating component according to claim 3, wherein the single crystal seed substrate comprises:
The length of at least one side of the unit crystal lattice is 3.50 to
4. A method of manufacturing a piezoelectric vibrating component, which uses a material in the range of 4.30 A or 5.00 to 6.00 A. 8. The method for manufacturing a piezoelectric vibrating component according to claim 3, wherein the single crystal seed substrate comprises:
Strontium titanate (SrTiO ₃ ), magnesium oxide (M
gO), lanthanum aluminate (LaAlO ₃ ), yttrium aluminate (YAlO ₃ ), neodymium aluminate (NdAlO ₃ ), lanthanum gallate (LaGaO ₃ ), neodymium gallate (NdGaO)
₃ ), praseodymium gallate (PrGaO ₃ ), strontium lanthanum gallate (LaSrGaO ₄ ), sapphire (Al ₂ O ₃ ).
A method for manufacturing a piezoelectric vibrating component, characterized in that a single crystal substrate such as or the like, or one in which a part of its constituent elements is replaced with another element is used.