JP6782453B2 - Devices and manufacturing methods using lead zirconate titanate niobate film laminates and lead zirconate titanate niobate film laminates - Google Patents

Description

The present invention relates to an element using a lead zirconate titanate film laminate, a lead zirconate titanate niobate film laminate, and a method for manufacturing the same. In particular, the present invention relates to a lead zirconate titanate film laminate in which crystal orientation is controlled, an element using the lead zirconate titanate niobate film laminate, and a method for producing the same.

In recent years, due to the demand for miniaturization of electronic devices, MEMS (Micro Electro Mechanical Systems) technology that applies semiconductor manufacturing processes has been put into practical use, and its use in various fields such as optical devices as well as electronic devices has been promoted. ing. Lead zirconate titanate (PZT), which is a piezoelectric material, is used in MEMS as a sensor for acceleration sensors, gyros, infrared detection elements, etc., and as an actuator material for movable mirrors, ultrasonic transducers, etc.

Patent Document 1 describes that in PZT having a perovskite structure, the degree of orientation in the (100) direction or the (001) direction is increased by using a dry film forming method such as sputtering, ion plating, or chemical vapor deposition. An ultrasonic surgical apparatus with an ultrasonic generating layer that can be driven at a low voltage is described. Further, it is known that a PZT film obtained by adding niobium (Nb) to PZT improves physical property values such as a piezoelectric constant. Such improvement in physical property values is remarkable, for example, when the composition ratio of Nb / (Zr + Ti) is about 10 mol%.

For example, Patent Document 2 describes that a lead zirconate titanate niobate laminate, which is an epitaxial film formed in a specific orientation on a sapphire substrate, improves the characteristics. Further, Patent Document 3 describes that the power generation amount of the piezoelectric material is increased by adjusting the material physical properties (compliance and piezoelectric constant) by adding niobium to the bulk sintered body of lead zirconate titanate. Has been done. Further, in some documents, improvement of properties by lead zirconate titanate niobate has been reported (for example, Non-Patent Documents 1 to 5).

On the other hand, the sol-gel method is known as an industrially superior film forming method for PZT and lead zirconate titanate niobate. The sol-gel method is a film-forming method in which an alkoxide-based sol is formed into a gel state by heating or the like, so that the area can be easily increased and the reproducibility is excellent. However, when niobium is added to lead zirconate titanate niobate so that the composition ratio of Nb / (Zr + Ti) is higher than 10 mol%, the (100) orientation or (001) orientation is relative to other orientation directions. There is a problem that a highly oriented lead zirconate titanate niobate film having a high orientation of 80% or more cannot be obtained. For example, when a precursor solution in which niobium is added at a high concentration of Nb / (Zr + Ti) of 13 mol% is used and a film is formed by the sol-gel method, the (100) orientation or (001) orientation is The strength ratio to other orientations (PZT [100] / (PZT [100] + PZT [110] + PZT [111])) is about 13%, and the orientation becomes low.

Japanese Patent No. 5385930 Japanese Patent No. 4543985 Japanese Patent No. 5305263

T. Fujii, Y. Hishinuma, T. Mita and Takayuki Naono, "characterization of Nb-doped Pb (Zr, Ti) O3 films sintered on stainless steel and silicon sintered by RF-magnetron sputtering for MEMS applications", Sensors and Actuators A 163 (2010) 220-225 T. Kobayashi, M. Ichiki and R. Maeda, "Influence of Pt / Ti Sputtering Temperature on the Orientation of CSD-Derived Pb (Zr0.52Ti0.48) O3", Ferroelectrics 357 (2007) 233-242 H. Matsuo, Y. Kawai, S. Tanaka and M. Esashi, "Investigation for (100)-/ (001) -Oriented Pb (Zr, Ti) O3 Films Using Platinum Nanofacets and PbTiO3 Seeding Layer", Japanese Journal of Applied Physics 49 (2010) 061503 Hiroshi Ishiwara et al., New Development of Ferroelectric Memory, CMC Publishing (2004/02) Chapter of Mr. Kijima T Uryu, T Kobayashi, N Makimoto, S Yoshimi, K Fujimoto, K Suzuki, T Itoh and R Maeda, Proc. PowerMEMS 2012 (2012) 323

As an attempt to control the growth of the lead zirconate titanate niobate film in the (100) orientation or the (001) orientation, a solid oxide other than lead zirconate titanate is used as a base, or a vapor phase other than the sol-gel method is used as the base. Conventionally, a method of forming by a film forming method has been studied. However, since these methods introduce a step of forming the base layer by a method other than the sol-gel method, the manufacturing process becomes complicated.

The present invention solves the above-mentioned problems, controls the crystal orientation, and has a high degree of orientation of (100) or (001) orientation. Lead zirconate titanate niobate film laminate, lead zirconate titanate niobate. An object of the present invention is to provide an element using a lead acid acid film laminate and a method for producing the same.

According to one embodiment of the present invention, a lead zirconate titanate film having a peak ratio in the (100) direction or (001) direction to 60% or more of all peaks detected by the X-ray diffractometry, and the zirconate titanate. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is determined according to the orientation direction of the lead zirconate titanate film arranged in contact with the lead acid acid film. A lead zirconate titanate titanate film comprising a lead zirconate titanate niobium having a molar concentration of 60% or more and 10 mol% or more of the total number of moles of titanium and zirconium. Laminates are provided.

According to one embodiment of the present invention, there is provided a lead film laminate of lead zirconate titanate niobate having a high degree of orientation (100) or (001).

In the lead zirconate titanate film laminate, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate film is 70% or more. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate niobate film may be 80% or more.

According to one embodiment of the present invention, there is provided a lead film laminate of lead zirconate titanate niobate having a high degree of orientation (100) or (001).

According to one embodiment of the present invention, a lead zirconate titanate niobate film laminate arranged between a first electrode, a second electrode, and the first electrode and the second electrode. The lead zirconate titanate titanate laminated body comprises lead zirconate titanate having a peak ratio of 60% or more in the (100) direction or the (001) direction to all peaks detected by the X-ray diffractometry. The lead film is arranged in contact with the lead zirconate titanate film, and depending on the orientation direction of the lead zirconate titanate film, the direction (100) or the direction (100) with respect to all peaks detected by the X-ray diffractometry. A lead zirconate titanate niobium film having a peak ratio of 60% or more in the (001) direction and a molar concentration of niobium of 10 mol% or more with respect to the total number of moles of titanium and zirconium is provided. The element is provided.

According to one embodiment of the present invention, an element using a lead film laminate of lead zirconate titanate niobate having a high degree of orientation of (100) orientation or (001) orientation is provided.

In the element, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate film is 70% or more, and the lead zirconate titanate niobate The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the film may be 80% or more.

According to one embodiment of the present invention, an element using a lead film laminate of lead zirconate titanate niobate having a high degree of orientation of (100) orientation or (001) orientation is provided.

According to one embodiment of the present invention, the support portion, the flexible portion whose one end is supported by the support portion, the weight portion supported by the other end of the flexible portion, and the flexible portion are located. Provided is a semiconductor device including a stress-electric conversion means for converting and detecting the displacement of the weight portion into an electric signal, wherein the stress-electric conversion means is configured by using the element.

According to one embodiment of the present invention, there is provided a semiconductor device in which an element using a lead zirconate titanate niobate film laminate having a high degree of orientation (100) or (001) orientation is arranged.

According to one embodiment of the present invention, a first precursor solution containing titanium, zirconium and lead in a predetermined composition ratio is applied onto a substrate, fired, and heat-treated at a predetermined temperature for X-ray diffraction. A lead zirconate titanate film having a peak ratio of 60% or more in the (100) direction or (001) direction to all peaks detected by the method is formed, and contains titanium, zirconium, lead and niobium in a predetermined composition ratio. The second precursor solution is applied onto the lead zirconate titanate film, fired, and heat-treated at a predetermined temperature, and the X-ray diffraction is performed according to the orientation direction of the lead zirconate titanate film. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the method is 60% or more, and the molar concentration of niobium is 10 mol% with respect to the total number of moles of titanium and zirconium. Provided is a method for producing a lead film laminate of lead zirconate titanate niobate that forms the lead zirconate titanate niobate film as described above.

According to one embodiment of the present invention, a lead film laminate of lead zirconate titanate niobate having a high degree of orientation (100) or (001) can be produced.

According to one embodiment of the present invention, a first electrode is formed on a substrate, and a first precursor solution containing titanium, zirconium and lead in a predetermined composition ratio is applied onto the first electrode. , And heat-treated at a predetermined temperature to form a lead zirconate titanate film having a peak ratio in the (100) direction or (001) direction of 60% or more with respect to all peaks detected by the X-ray diffractometry. , A second precursor solution containing titanium, zirconium, lead and niobium in a predetermined composition ratio is applied onto the lead zirconate titanate film and then fired in the orientation direction of the lead zirconate titanate film. Correspondingly, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffractometry is 60% or more, and the molar concentration of niobium is the total number of moles of titanium and zirconium. Provided is a method for manufacturing an element for forming a lead zirconate titanate niobate film having a value of 10 mol% or more and forming a second electrode on the lead zirconate titanate niobate film.

According to one embodiment of the present invention, it is possible to manufacture an element using a lead film laminate of lead zirconate titanate niobate having a high degree of orientation (100) or (001).

According to the present invention, a lead zirconate titanate niobate film laminate having a high degree of orientation of (100) or (001) orientation, and a lead zirconate titanate niobate film laminate thereof, in which crystal orientation is controlled, are used. Elements and methods of manufacturing them are provided.

There is a schematic view (side view) of the Nb-PZT film laminate 100 which concerns on one Embodiment. It is a figure which shows the manufacturing process of the Nb-PZT film laminate 100 which concerns on one Embodiment. It is a schematic view (side view) of the element 200 using the Nb-PZT film laminate which concerns on one Embodiment. It is a figure which shows the manufacturing process of the element 200 which concerns on one Embodiment. It is a figure which shows the manufacturing process of the element 200 which concerns on one Embodiment. It is a top view of the semiconductor device 1000 which concerns on one Embodiment. It is sectional drawing of the semiconductor device 1000 in line AA'in FIG. It is a figure explaining the manufacturing process of the semiconductor device 1000 which concerns on one Embodiment by the sectional view along the line AA'in FIG. It is a figure explaining the manufacturing process of the semiconductor device 1000 which concerns on one Embodiment by the sectional view along the line AA'in FIG. It is a figure explaining the manufacturing process of the semiconductor device 1000 which concerns on one Embodiment by the sectional view along the line AA'in FIG. It is a figure explaining the manufacturing process of the semiconductor device 1000 which concerns on one Embodiment by the sectional view along the line AA'in FIG. It is a figure which shows the diffraction peak of the laminated body of the comparative example 1. It is a figure which shows the diffraction peak of the laminated body of the comparative example 2. It is a figure which shows the diffraction peak of the laminated body of the comparative example 3. It is a figure which shows the diffraction peak of the laminated body of an Example. It is a figure which shows the number of layers and the peak abundance ratio of the laminated body of Example and Comparative Example. It is a figure which shows the relationship between the molar concentration of Nb and Raman shift. It is a schematic diagram which shows the acceleration sensor 2000 of an Example.

In the sol-gel method, the orientation of the lead zirconate titanate niobate film whose orientation decreases with the addition of niobium by using the lead zirconate titanate film as the nucleus (or seed layer) for crystallization in the sol-gel method. They found that it was possible to control sex.

Hereinafter, the lead zirconate titanate niobate film laminate according to the present invention, the element using the lead zirconate titanate niobate film laminate, and the manufacturing method thereof will be described with reference to the drawings. However, the lead film laminate of lead zirconate titanate niobate of the present invention, the element using the lead film laminate of lead zirconate titanate niobate, and the manufacturing method thereof can be carried out in many different embodiments. It is not construed as being limited to the description contents of the embodiments and examples shown in. In the drawings referred to in the present embodiment and the examples, the same parts or parts having the same functions are designated by the same reference numerals, and the repeated description thereof will be omitted.

(Lead zirconate titanate niobate film laminate)
FIG. 1 is a schematic view (side view) of a lead zirconate titanate niobate film laminate (hereinafter referred to as Nb-PZT film laminate) 100 according to the present invention. The Nb-PZT film laminate 100 includes a lead zirconate titanate film (hereinafter referred to as PZT film) in which the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffractometry is 60% or more. 110 and 110 are arranged in contact with the PZT film 110, and the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffractometry is 60% depending on the orientation direction of the PZT film 110. As described above, the lead zirconate titanate niobate film (hereinafter, Nb-) in which the molar concentration of niobium (Nb) is 10 mol% or more with respect to the total number of moles of titanium (Ti) and zirconium (Zr). It is provided with (referred to as PZT film) 130. Further, as shown in FIG. 1, the Nb-PZT film laminate 100 may be formed on the base material 150 or may be arranged on the base material 150.

As shown in the examples, an Nb-PZT film having a low Nb content can obtain an orientation similar to that of the PZT film, but the molar concentration of Nb is the total number of moles of Ti and Zr. In the case of 10 mol% or more, the orientation of the conventional Nb-PZT film was significantly reduced. The PZT film 110 having a perovskite structure has high orientation in the (100) direction or the (001) direction. For example, Non-Patent Document 2 describes that the orientation of a PZT film can be controlled depending on the film forming conditions. In the present invention, the PZT film 110 arranged as a seed layer acts as a starting point for the Nb-PZT film 130 to grow crystals, and the molar amount is 10 mol% or more with respect to the total number of moles of Ti and Zr. The Nb-PZT film 130 containing Nb at a concentration is imparted with high orientation in the (100) direction or the (001) direction.

In the present specification, the orientation of the PZT film 110 and the Nb-PZT film 130 is evaluated by using an X-ray diffraction method (hereinafter referred to as XRD). That is, the orientation is evaluated by the peak ratio of all the peaks detected by XRD to the peaks in the (100) direction or the (001) direction. By controlling the orientation of the PZT film 110 as described above, the peak ratio of the PZT film 110 in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method becomes 60% or more. In the present invention, by using the highly oriented PZT film 110 as the seed layer, the (100) direction or the (001) direction with respect to all the peaks detected by the X-ray diffraction method depends on the orientation direction of the PZT film 110. The orientation of the Nb-PZT film 130 can be controlled so that the peak ratio of Nb-PZT film 130 is 60% or more.

Further, more preferably, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the PZT film 110 is 70% or more, and the X-ray diffraction method of the Nb-PZT film 130 The peak ratio in the (100) direction or the (001) direction to all the peaks detected by is 80% or more. According to one embodiment of the present invention, there is provided an Nb-PZT film laminate 100 having a high degree of orientation of (100) orientation or (001) orientation.

A method for producing the Nb-PZT film laminate 100 will be described. FIG. 2 shows a manufacturing process of the Nb-PZT film laminate 100 according to the embodiment of the present invention. A first precursor solution containing Ti, Zr and Pb at a predetermined composition ratio is applied onto the base material 150 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form the first coating layer 111 (FIG. 2A). Here, as the base material 150, a general substrate used in the manufacturing process of MEMS or a semiconductor device can be used, and for example, a silicon substrate, a glass substrate, a sapphire substrate, or the like can be used. It is not limited.

The first precursor solution is a precursor solution for forming the PZT film 110 by the sol-gel method, and is an organic solution containing Ti, Zr and Pb in a predetermined composition ratio. The first precursor solution is composed of lead (II) oxide, zirconium (IV) oxide, titanium (IV) oxide, isoamyl acetate, n-butyl acetate, n-hexyl acetate and a stabilizer. It is preferable that Ti, Zr and Pb are contained in the first precursor solution in a composition ratio of 48:52:120.
The drying temperature for forming the first coating layer 111 can be arbitrarily set by the solvent contained in the first precursor solution. In the present embodiment, it is, for example, about 100 ° C. or higher and 150 ° C. or lower. The firing temperature for forming the first coating layer 111 is, for example, about 230 ° C. or higher and 270 ° C. or lower.

The base material 150 on which the first coating layer 111 is formed is heat-treated at a predetermined temperature and crystallized to form a PZT film 110 (FIG. 2B). By crystallization, the PZT film 110 has a perovskite structure, and the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more. Here, the conditions of the heat treatment for forming the PZT film 110 are, for example, about 580 ° C. or higher and 670 ° C. or lower.

In the present embodiment, since the PZT film 110 is a seed layer for controlling the crystal orientation of the Nb-PZT film 130, its thickness may be thin, for example, the thickness of one layer formed by the sol-gel method. It may be, for example, about 100 nm or more and 150 nm or less.

Next, a second precursor solution containing Ti, Zr, Pb and Nb at a predetermined composition ratio is applied onto the PZT film 110 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form a second coating layer 131 (FIG. 2 (c)). The second precursor solution is a solution obtained by adding a niobium compound to the first precursor solution. Here, the second precursor solution is a precursor solution for forming the Nb-PZT film 130 by the sol-gel method, and is an organic solution containing Ti, Zr, Pb and Nb in a predetermined composition ratio, and Nb. The molar concentration of Ti and Zr is 10 mol% or more with respect to the total number of moles. It is preferable that Ti, Zr, Pb and Nb are contained in the second precursor solution in a composition ratio of 48:52:13.

The drying temperature for forming the second coating layer 131 can be arbitrarily set by the solvent contained in the second precursor solution. In the present embodiment, it is, for example, about 100 ° C. or higher and 150 ° C. or lower. The firing temperature for forming the second coating layer 131 is, for example, about 280 ° C. or higher and 320 ° C. or lower.

The base material 150 on which the second coating layer 131 is formed is heat-treated at a predetermined temperature and crystallized to form an Nb-PZT film 130 on the PZT film 110 (FIG. 2 (d)). In the present invention, the PZT film 110 is crystallized by using it as a crystallization nucleus (or seed layer), so that the Nb-PZT film 130 has a perovskite structure according to the crystal structure of the PZT film 110, and is subjected to an X-ray diffraction method. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by is 60% or more. Here, the conditions of the heat treatment for forming the Nb-PZT film 130 are, for example, about 580 ° C. or higher and 670 ° C. or lower according to the heat treatment temperature at which the PZT film 110 is crystallized.

In the present embodiment, the thickness of the Nb-PZT film laminate 100 may be about 1 μm including the PZT film 110, and the thickness of one layer of the Nb-PZT film formed by the sol-gel method is 100 nm or more and 150 nm or less. Therefore, about 7 layers can be laminated to form the Nb-PZT film 130. In this case, the Nb-PZT film 130 can be formed by repeating the steps of coating, drying, firing and heat treatment described above one layer at a time.

Conventionally, the orientation of the Nb-PZT film has decreased with the addition of Nb, but in the Nb-PZT film laminate 100 according to the present embodiment, the molar concentration of Nb is the total number of moles of Ti and Zr. It is possible to control the orientation even if it is 10 mol% or more with respect to the value.

(Elements using lead zirconate titanate niobate film laminate)
As another embodiment of the present invention, the device using the above-mentioned Nb-PZT film laminate will be described. FIG. 3 is a schematic view (side view) of the element 200 using the Nb-PZT film laminate according to the embodiment of the present invention. The element 200 includes a first electrode 261 and a second electrode 263, and an Nb-PZT film laminate arranged between the first electrode 261 and the second electrode 263. The Nb-PZT film laminate is an element that functions as a sensor or actuator material. In the element 200, the Nb-PZT film laminate is a piezoelectric body, and the force applied to the piezoelectric body is converted into a voltage to function as a sensor. Further, it is a passive element utilizing the piezoelectric effect of converting the voltage applied to the Nb-PZT film laminate into force. Such a piezoelectric body is also called a piezo element.

The Nb-PZT film laminate is arranged in contact with the PZT film 210 having a peak ratio of 60% or more in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method, and the PZT film 210. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more, and the molar concentrations of Nb are Ti and Zr, depending on the orientation direction of the PZT film 210. The Nb-PZT film 230 is provided with 10 mol% or more based on the total number of moles. Further, as shown in FIG. 3, the element 200 may be formed on the base material 150 or may be arranged on the base material 150.

As described above, the orientation of the PZT film 210 and the Nb-PZT film 230 is evaluated by the peak ratio of all the peaks detected by XRD to the peaks in the (100) direction or the (001) direction. The peak ratio of the PZT film 210 in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more. Further, in the present invention, by using the highly oriented PZT film 210 as the seed layer, the direction (100) or (001) with respect to all the peaks detected by the X-ray diffraction method depends on the orientation direction of the PZT film 210. The orientation of the Nb-PZT film 230 can be controlled so that the peak ratio in the direction of) is 60% or more.

Further, more preferably, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the PZT film 210 is 70% or more, and the X-ray diffraction method of the Nb-PZT film 230 The peak ratio in the (100) direction or the (001) direction to all the peaks detected by is 80% or more. According to one embodiment of the present invention, there is provided an element 200 having a high degree of orientation of the (100) orientation or (001) orientation of the Nb-PZT film laminate.

A method of manufacturing the element 200 will be described. 4 and 5 show a manufacturing process of the element 200 according to the embodiment of the present invention. The first electrode 261 is formed on the base material 150 (FIG. 4A). Since the details of the base material 150 have been described above, the description thereof will be omitted. The first electrode 261 is an electrode for extracting electric charges or applying a voltage from the Nb-PZT film laminate which is a piezoelectric material, and is formed of a metal generally used for MEMS, for example, copper (Cu) or aluminum. (Al), gold (Au), silver (Ag) and the like can be used, but the present invention is not limited thereto. The first electrode 261 can be formed by sputtering, vapor deposition, or the like, but is not limited thereto.

A first precursor solution containing Ti, Zr and Pb at a predetermined composition ratio is applied onto the first electrode 261 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form the first coating layer 211 (FIG. 4 (b)). Since the details of the first precursor solution have been described above, the description thereof will be omitted. As described above, the drying temperature for forming the first coating layer 111 can be arbitrarily set by the solvent contained in the first precursor solution.

The base material 150 on which the first coating layer 211 is formed is heat-treated at a predetermined temperature and crystallized to form a PZT film 210 (FIG. 4 (c)). By crystallization, the PZT film 210 has a perovskite structure, and the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more.

Next, a second precursor solution containing Ti, Zr, Pb and Nb at a predetermined composition ratio is applied onto the PZT film 210 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form a second coating layer 231 (FIG. 4 (d)). Since the details of the second precursor solution have been described above, the description thereof will be omitted. As described above, the drying temperature for forming the second coating layer 231 can be arbitrarily set by the solvent contained in the second precursor solution.

The base material 150 on which the second coating layer 231 is formed is heat-treated at a predetermined temperature and crystallized to form an Nb-PZT film 230 on the PZT film 210 (FIG. 5A). In the present invention, by crystallization using the PZT film 210 as a crystallization nucleus (or seed layer), the Nb-PZT film 230 has a perovskite structure according to the crystal structure of the PZT film 210, and is subjected to an X-ray diffraction method. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by is 60% or more. By repeating the steps of coating, drying, firing, and heat treatment described above one layer at a time, an Nb-PZT film laminate having a desired thickness can be formed.

A second electrode 263 is formed on the Nb-PZT film 230 (FIG. 5 (b)). Since the second electrode 263 can be formed of the same material as the first electrode 261 and in the same manufacturing process, detailed description thereof will be omitted. By the above steps, the element 200 according to the present embodiment can be formed.

Conventionally, the orientation of the Nb-PZT film has decreased with the addition of Nb, but in the element 200 according to the present embodiment, the molar concentration of Nb contained in the Nb-PZT film laminate is Ti and Zr. It is possible to control the orientation of the crystal even if it is 10 mol% or more with respect to the total number of moles.

(Semiconductor device)
As another embodiment of the present invention, the semiconductor device including the above-mentioned element 200 will be described. An acceleration sensor will be described as an example of the semiconductor device, but the semiconductor device according to the present invention is not limited to these, and devices in which the element 200 can be used are widely shown. FIG. 6 is a top view of the semiconductor device 1000 according to the embodiment of the present invention. Further, FIG. 7 is a cross-sectional view of the semiconductor device 1000 in line AA'of FIG. The semiconductor device 1000 includes a support portion 1210, a flexible portion whose one end is supported by the support portion 1210 (a first axial flexible portion 1231 and a second axial flexible portion 1235), and a flexible portion. It is provided with a weight portion 1250 supported at the other end of the body, and a stress-electric conversion means located in a flexible portion that converts the displacement of the weight portion 1250 into an electric signal and detects it. In the present embodiment, the stress-electric conversion means (element E1 +, element E1-, element E2 +, element E2-, element E3 +, element E3-, element E4 +, element E4-) is configured by using the above-mentioned element 200.

The semiconductor device 1000 includes a first axially flexible portion 1231, a second axially flexible portion 1235, a first axially flexible portion 1231, and a second axially flexible portion 1235. It has an intersection 1239 (weight support) and a weight 1250. An opening 1270 is arranged adjacent to the weight portion 1250 to separate the weight portion 1250 and the support portion 1210. Here, the first axial direction and the second axial direction are directions orthogonal to each other, and can also be referred to as an X-axis direction and a Y-axis direction.

In order to detect the acceleration in the first axial direction, the element E1 +, the element E1-, the element E2 +, and the element E2- formed by the element 200 are arranged in the flexible portion 1231 in the first axial direction, and wiring is performed. By 1150, it is pulled out to the terminal V1 +, the terminal V1-, the terminal V2 + and the terminal V2-, respectively.

In order to detect the acceleration in the second axial direction, the element E3 +, the element E3-, the element E4 +, and the element E4- formed by the element 200 are arranged in the flexible portion 1235 in the second axial direction, and wiring is performed. By 1150, it is pulled out to the terminal V3 +, the terminal V3-, the terminal V4 + and the terminal V4-, respectively.

In the present embodiment, the element E1 +, the element E1-, the element E2 +, the element E2-, the element E3 +, the element E3-, the element E4 +, and the element E4- are formed by the first electrode layer 1161 and the second electrode layer 1163. It is composed of an Nb-PZT film laminate arranged between the first electrode layer 1161 and the second electrode layer 1163. The Nb-PZT film laminate is arranged in contact with the PZT film 1110 and the PZT film 1110 in which the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more. , The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 60% or more, and the molar concentrations of Nb are Ti and Zr, depending on the orientation direction of the PZT film 1110. The Nb-PZT film 1130, which is 10 mol% or more based on the total number of moles of the above, is provided.

A weight portion 1250 is formed on the lower side of the intersection 1239, and the weight portion 1250 swings in response to acceleration to flex the first axially flexible portion 1231 and the second axially flexible portion 1235. No. The semiconductor device 1000 can detect the acceleration of this deflection by a sensor circuit that detects the acceleration in the first axial direction and a sensor circuit that detects the acceleration in the second axial direction.

The first axially flexible portion 1231 and the second axially flexible portion 1235 are supported by the support portion 1210, and the support portion 1210 is provided with the above-mentioned terminals V1 +, terminal V1-, terminal V2 +, and terminal V2-. , Terminal V3 +, terminal V3-, terminal V4 +, terminal V4-, and ground terminal (GND) are arranged. The first electrode layer 1161 is connected to the ground terminal (GND).

In the present embodiment, an example is shown in which the semiconductor device 1000 has a flexible portion 1231 in the first axial direction and a flexible portion 1235 in the second axial direction, but the semiconductor device 1000 according to the present invention is a beam. A diaphragm-shaped flexible portion may be used instead of the shaped flexible portion. That is, the elements that support the weight portion with the diaphragm and detect the acceleration in the first axial direction and the second axial direction may be arranged in the axial direction orthogonal to the upper surface of the diaphragm.

In the semiconductor device 1000 having such a structure, the weight portion 1250 sways due to vibration, and the elements E1 + and the elements E1-arranged in the first axially flexible portion 1231 and the second axially flexible portion 1235. , Element E2 +, element E2-, element E3 +, element E3-, element E4 +, and element E4-. Since the amount of polarization of each element depends on stress, charge transfer (current) is generated by applying acceleration such as vibration. This current is detected by terminals V1 +, terminal V1-, terminal V2 +, terminal V2-, terminal V3 +, terminal V3-, terminal V4 + and terminal V4-, and a detector (not shown) connected to the ground terminal (GND). be able to.

The manufacturing method of the semiconductor device 1000 according to this embodiment will be described below. 8 to 10 are views for explaining the manufacturing process of the semiconductor device 1000 with a cross-sectional view taken along the line AA'of FIG. A silicon oxide film 1103 and a silicon film 1105 are sequentially formed on a silicon wafer 1101 which is a base material (FIG. 8 (a)). An SOI substrate manufactured by a bonding method or the like may be used. The silicon oxide film 1103 also functions as an etching stopper layer in the process described later. In the present embodiment, the element E1 +, the element E1-, the element E2 + and the element E2- are attached to the flexible portion 1231 in the first axial direction, and the element E3 +, the element E3-, the element E4 + and the element E4- are attached to the second axis. It is formed on each of the flexible portions 1235 in the direction.

The first electrode layer 1161 is formed on the silicon film 1105 (FIG. 8 (b)). Since the forming material and forming method of the first electrode layer 1161 are the same as those of the first electrode 261 described above, detailed description thereof will be omitted. A first precursor solution containing Ti, Zr and Pb at a predetermined composition ratio is applied onto the first electrode layer 1161 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form a first coating layer. Since the details of the first precursor solution have been described above, the description thereof will be omitted. As described above, the drying temperature for forming the first coating layer can be arbitrarily set by the solvent contained in the first precursor solution.

The silicon wafer 1101 on which the first coating layer is formed is heat-treated at a predetermined temperature and crystallized to form a PZT film 1110 (FIG. 8 (c)). By crystallization, the PZT film 1110 has a perovskite structure, and the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method becomes 60% or more.

Next, a second precursor solution containing Ti, Zr, Pb and Nb at a predetermined composition ratio is applied onto the PZT film 1110 and dried at a predetermined temperature. Further, it is fired at a predetermined temperature to form a second coating layer. Since the details of the second precursor solution have been described above, the description thereof will be omitted. As described above, the drying temperature for forming the second coating layer can be arbitrarily set by the solvent contained in the second precursor solution.

The silicon wafer 1101 on which the second coating layer is formed is heat-treated at a predetermined temperature and crystallized to form an Nb-PZT film 1130 on the PZT film 1110 (FIG. 8 (d)). In the present invention, the Nb-PZT film 1130 has a perovskite structure according to the crystal structure of the PZT film 1110 by crystallization using the PZT film 1110 as a crystallization nucleus (or seed layer), and an X-ray diffraction method is performed. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by is 60% or more. As described above, the Nb-PZT film laminate having a desired thickness can be formed by repeating the steps of coating, drying, firing, and heat treatment described above one layer at a time.

A mask 1301 is formed on the Nb-PZT film 1130 (FIG. 9A). A known resist material can be used as the material of the mask 1107. The Nb-PZT film 1130 and the PZT film 1110 on which the mask 1107 is arranged are subjected to RIE (Reactive Ion Etching) or wet etching to form bottomed holes (FIG. 9 (b)).

Next, the mask 1301 is removed to form the mask 1303 on the Nb-PZT film 1130 (FIG. 9 (c)). A second electrode layer 1163 is formed on the Nb-PZT film 1130 on which the mask 1303 is arranged, and the element E1 +, the element E1-, the element E2 +, the element E2-, the element E3 +, the element E3-, the element E4 +, and the element E4- , Terminal V1 +, terminal V1-, terminal V2 +, terminal V2-, terminal V3 +, terminal V3-, terminal V4 +, and terminal V4-. Further, a ground terminal (GND) connected to the first electrode layer 1161 is formed through the bottomed hole (FIG. 10 (a)). Since the second electrode layer 1163 can be formed of the same material as the first electrode 261 described above and in the same manufacturing process, detailed description thereof will be omitted.

Mask 1305 is formed to remove mask 1303 and form wiring 1150 (FIG. 10B). Wiring 1150 is formed on the Nb-PZT film 1130, and each element and each terminal are connected (FIG. 10 (c)). The wiring 1150 is formed of a metal generally used for MEMS, and for example, copper (Cu), aluminum (Al), gold (Au), silver (Ag) and the like can be used, but the wiring 1150 is not limited thereto. Absent. The wiring 1150 can be formed by sputtering, vapor deposition, or the like, but is not limited thereto. Each element and each terminal can also be formed in the same process using the same material as the wiring 1150.

After that, the mask 1305 is removed, the silicon film 1105 is etched by RIE or the like until the upper surface of the silicon oxide film 1103 is exposed, an opening is provided, and the support portion 1210, the first axially flexible portion 1231, and the like. A second axially flexible portion 1235 and an intersection portion 1239 are formed. Further, in order to form a gap at an interval required for the weight portion 1250 to be displaced downward, a mask 1307 is used to form an opening 1270 along the inner frame of the support portion 1210 (FIG. 11 (a)). .. The gap is, for example, about 5 to 10 μm.

Further, in order to form the support portion 1210 and the weight portion 1250, a mask 1309 is formed on the lower surface of the silicon wafer 1101 (FIG. 11B). The silicon wafer 1101 and the silicon oxide film 1103 are etched using the mask 1309 until the lower surface of the silicon film 1105 is exposed (FIG. 11 (c). For etching, for example, DRIE (Deep Reactive Ion Etching) is used.

Finally, the silicon wafer is diced to separate the accelerometer. As a result, the semiconductor device 1000 is configured. The semiconductor device 1000 can be mounted on a mounting substrate or a package substrate. The above is an example of a method for manufacturing an acceleration sensor, and the order can be appropriately changed and is not limited to the above order.

Further, the support substrate may be arranged under the support portion 1210. The support substrate and the support portion 1210 can be joined by direct joining, joining with an adhesive, or the like. The support substrate is, for example, a semiconductor such as glass, metal, insulating resin, or Si. The bonding method can be appropriately selected from anode bonding, direct bonding, eutectic bonding, bonding with an adhesive, and the like.

Conventionally, the orientation of the Nb-PZT film has decreased with the addition of Nb, but in the semiconductor device according to the present embodiment, the molar concentration of Nb contained in the device is the total number of moles of Ti and Zr. It is possible to control the orientation of the crystal even if it is 10 mol% or more.

(Example)
As an example of the present invention, an Nb-PZT film was formed on a substrate on which the first electrode was formed, using the PZT film as a seed layer. 1 μm thick SiO ₂ was formed on both sides of a 4-inch Si wafer by thermal oxidation. This is a barrier layer for preventing a reaction between the electrode material and Si due to thermal diffusion. Next, 150 nm Pt / 15 nm Ti was formed as an electrode layer by sputtering. Using the PZT-20 (120/52/48) precursor, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method having an orientation ratio of 80% or more is 80%. In order to obtain the above PZT film, the substrate temperature at the time of film formation of the electrode layer was set to 200 ° C. with reference to Non-Patent Document 2.

A first precursor solution (High Purity Chemical Laboratory) having a composition ratio of Pb / Zr / Ti / = 120/52/48 is discharged onto the formed electrode layer at an appropriate amount of 100 rpm to the extent that it wets and spreads over the entire wafer. It was spin-coated at 2000 rpm for 60 seconds and dried on a hot plate at 120 ° C. for 2 minutes. Then, a first coating layer was formed by firing at 250 ° C. for 5 minutes. Next, in a rapid thermal annealing furnace, after vacuuming, the temperature rise gradient was set to 100 ° C./sec and crystallization was performed at 650 ° C. for 2 minutes under an atmospheric oxygen atmosphere to obtain a PZT film.

Next, a second precursor solution (High Purity Chemical Laboratory) having a composition ratio of Pb / Zr / Ti / Nb = 120/52/48/13 is spread over the entire wafer at an appropriate amount of 100 rpm on the PZT film. The mixture was discharged, spin-coated at 2000 rpm for 60 seconds, and dried on a hot plate at 120 ° C. for 2 minutes. Then, a first coating layer was formed by firing at 300 ° C. for 5 minutes. Next, in a rapid thermal annealing furnace, after evacuation, the temperature rise gradient was set to 100 ° C./sec and crystallization was performed at 650 ° C. for 2 minutes under an atmospheric oxygen atmosphere to obtain an Nb-PZT film. In this example, six more Nb-PZT films are formed, one PZT film is formed, and the Nb-PZT film (the molar concentration of Nb is 13 mol% with respect to the total number of moles of Ti and Zr). ) Was obtained as a laminate containing 7 layers.

(Comparative Example 1)
As Comparative Example 1, a laminate containing eight layers of PZT film was obtained by the same method as in Example without forming an Nb-PZT film.

(Comparative Example 2)
As Comparative Example 2, it was carried out using a second precursor solution (High Purity Chemistry Laboratory) having a composition ratio of Pb / Zr / Ti / Nb = 120/52/48/3 without forming a PZT film. By the same method as in the example, a laminate containing 8 layers of Nb-PZT film (the molar concentration of Nb is 3 mol% with respect to the total number of moles of Ti and Zr) was obtained.

(Comparative Example 3)
As Comparative Example 3, it was carried out using a second precursor solution (High Purity Chemistry Laboratory) having a composition ratio of Pb / Zr / Ti / Nb = 120/52/48/13 without forming a PZT film. By the same method as in the example, a laminate containing 8 layers of Nb-PZT film (the molar concentration of Nb is 13 mol% with respect to the total number of moles of Ti and Zr) was obtained.

The thickness of the laminates of Examples and Comparative Examples 1 to 3 was 0.9 μm.

(Evaluation of crystal orientation)
The crystal orientation after film formation of the first layer, the fourth layer and the eighth layer of the laminates of Examples and Comparative Examples 1 to 3 was evaluated. Bruker's D8 DISCOVER was used for the measurement of X-ray diffraction. The measured diffraction peaks are shown in FIGS. 12 to 15. FIG. 12 shows the diffraction peak of Comparative Example 1, (a) shows the diffraction peak after the first layer, (b) shows the fourth layer, and (c) shows the diffraction peak after the eighth layer is formed. FIG. 13 shows the diffraction peak of Comparative Example 2, in which (a) shows the first layer, (b) shows the fourth layer, and (c) shows the diffraction peak after the eighth layer is formed. FIG. 14 shows the diffraction peak of Comparative Example 3, in which (a) shows the first layer, (b) shows the fourth layer, and (c) shows the diffraction peak after the eighth layer is formed. FIG. 15 shows the diffraction peaks of the examples, (a) shows the diffraction peaks after the first layer, (b) shows the fourth layer, and (c) shows the diffraction peaks after the formation of the eighth layer. In FIGS. 12 to 15, ●: PZT (100) / (001), ▲: PZT (110), ■: PZT (111), ○: PZT (200) / (002), ★: Pt (111). ) Is shown.

As is clear from FIG. 12, in the laminated body of Comparative Example 1, the peak intensities increase at (100) / (001) and (200) / (002) according to the number of layers of the PZT film. Further, as is clear from FIG. 13, a comparison in which an PZT film is not formed and eight layers of Nb-PZT films (the molar concentration of Nb is 3 mol% with respect to the total number of moles of Ti and Zr) is included. The laminated body of Example 2 also showed almost the same result as that of Comparative Example 1. This indicates that the low Nb content has a small effect on the crystal orientation.

On the other hand, as is clear from FIG. 14, a comparison in which no PZT film is formed and eight layers of Nb-PZT film (the molar concentration of Nb is 13 mol% with respect to the total number of moles of Ti and Zr) is included. In the laminated body of Example 3, the peak intensities of (100) / (001) and (200) / (002) are remarkably smaller than those of Comparative Examples 1 and 2, but the peak intensities of (111) are large. , It became clear that the orientation was low as in the past.

On the other hand, as is clear from FIG. 15, a PZT film is formed as a seed layer, and an Nb-PZT film (the molar concentration of Nb is 13 mol% with respect to the total number of moles of Ti and Zr) is formed. In the laminated body of the example containing 7 layers, the same tendency as in Comparative Examples 1 and 2 was observed, and large peaks at (100) / (001) and (200) / (002) were detected.

The peak intensity data of FIGS. 12 to 15 are summarized in FIG. From the results of FIG. 16, in the laminate according to this example, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the PZT film is 70% or more, and Nb- It has been clarified that the PZT film exhibits high orientation such that the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method is 80% or more. Table 1 shows the peak abundance ratios of Examples and Comparative Examples 1 to 3.

The orientation of this example is comparable to Comparative Example 1 in which only the PZT film is laminated, and the PZT film is not formed, and the eight layers of Nb-PZT film (the molar concentration of Nb is the number of moles of Ti and Zr). It was superior to Comparative Example 2 containing 3 mol% with respect to the total value.

(Raman spectroscopic analysis)
The relationship between the molar concentration of Nb and Raman shift was investigated. HORIBA's LabRAM was used for Raman spectroscopic analysis. The measurement result is shown in FIG. From the result of FIG. 17, it was clarified that the peak shifts to the low wavenumber side according to the amount of Nb added.

(Acceleration sensor)
As an example, the acceleration sensor 2000 shown in FIG. 18 was manufactured. A silicon oxide film 2103 having a thickness of 1 μm and a silicon film 2105 having a thickness of 5 μm were sequentially formed on a silicon substrate 2101 having a thickness of 725 μm. A 15 nm Ti and a 175 nm Pt were laminated on the silicon film 2105 to form the first electrode layer 2161. A 2 μm-thick Nb-PZT film laminate 2100 was formed.

The procedure for forming the 2 μm-thick Nb-PZT film laminate 2100 is as follows. The first layer was formed with the composition Pb / Zr / Ti / Nb = 120/52/48/0 of the precursor solution. The precursor solution is discharged at an appropriate amount of 100 rpm to the extent that it wets and spreads over the entire wafer, then spin-coated at 2000 rpm and 60 sec, dried on a hot plate at 120 ° C. and 2 min, and fired at 250 ° C. and 5 min. did. Next, in a rapid thermal annealing furnace, after evacuation, crystallization was performed at 650 ° C. for 2 min under an atmospheric pressure oxygen atmosphere with a temperature rise gradient of 100 ° C./sec. Further, the second and subsequent layers were formed 17 times using Pb / Zr / Ti / Nb = 120/52/48/13. The heat treatment conditions are as described above except that the firing temperature is 300 ° C. A total of 18 layers were formed to form a 2 μm-thick Nb-PZT film laminate 2100.

A second electrode layer 2163 was formed by laminating Ti at 15 nm and Pt at 175 nm on the Nb-PZT film laminate 2100. Next, Pt / Ti to be the upper electrode was patterned by reactive ion etching (RIE), and the Nb-PZT film laminate 2100 was processed into a device shape by wet etching. Next, Pt / Ti as the lower electrode and the silicon oxide film 2103 as the barrier layer were removed by RIE. Further, contact pads 2170 and 2190 for wiring by wire bonding were formed by wet etching after sputter film formation of Au / Cr. The silicon film 2105 was processed by a Bosch process (Deep RIE) in order to process it into a beam shape. Finally, the silicon substrate 2101 was removed by Deep RIE to prepare a cantilever structure.

100: Nb-PZT film laminate, 110: PZT film, 111: first coating layer, 150: base material, 130: Nb-PZT film, 131: second coating layer, 200: element, 210: PZT film, 211: 1st coating layer, 230: Nb-PZT film, 231: 2nd coating layer, 261: 1st electrode, 263: 2nd electrode, 1000: semiconductor device, 1101: silicon Wafer, 1103: Silicon oxide film, 1105: Silicon film, 1107: Mask, 1109: Insulation layer, 1150: Wiring, 1110: PZT film, 1130: Nb-PZT film, 1161: First electrode layer, 1163: Second Electrode layer, 1210: support part, 1231: first axially flexible part, 1235: second axially flexible part, 1239: intersection, 1250: weight part, 1270: opening, 1301: Mask, 1303: Mask, 2000: Acceleration sensor, 2100: Nb-PZT film laminate, 2101: Silicon substrate, 2103: Silicon oxide film, 2105: Silicon film, 2161: First electrode layer, 2163: Second electrode Layer 2170: Contact pad, 2190: Contact pad, E1 +: Element, E1-: Element, E2 +: Element, E2-: Element, E3 +: Element, E3-: Element, E4 +: Element, E4-: Element, V1 +: Terminal, V1-: terminal, V2 +: terminal, V2-: terminal, V3 +: terminal, V3-: terminal, V4 +: terminal, V4-: terminal, GND: ground terminal

Claims (7)

A lead zirconate titanate film having a peak ratio in the (100) direction or (001) direction of 60% or more with respect to all peaks detected by the X-ray diffraction method.
It is arranged in contact with the lead zirconate titanate film, and depending on the orientation direction of the lead zirconate titanate film, the (100) direction or the (001) direction with respect to all the peaks detected by the X-ray diffractometry. It is characterized by comprising a lead zirconate titanate niobate film having a peak ratio of 60% or more and a molar concentration of niobide of 10 mol% or more with respect to the total number of moles of titanium and zirconium. Lead zirconate titanate titanate laminated body. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate film is 70% or more.
The first aspect of claim 1, wherein the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate niobate film is 80% or more. Lead zirconate titanate niobate film laminate. A lead film laminate of lead zirconate titanate niobate disposed between the first electrode, the second electrode, and the first electrode and the second electrode is provided.
The lead zirconate titanate film laminate has a lead zirconate titanate film having a peak ratio of 60% or more in the (100) direction or (001) direction to all peaks detected by X-ray diffraction.
It is arranged in contact with the lead zirconate titanate film, and depending on the orientation direction of the lead zirconate titanate film, the (100) direction or the (001) direction with respect to all the peaks detected by the X-ray diffractometry. It is characterized by comprising a lead zirconate titanate niobium film having a peak ratio of 60% or more and a molar concentration of niobium of 10 mol% or more with respect to the total number of moles of titanium and zirconium. Element to do. The peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate film is 70% or more.
The third aspect of claim 3, wherein the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffraction method of the lead zirconate titanate niobate film is 80% or more. element. Support part and
A flexible part whose one end is supported by the support part,
A weight portion supported on the other end of the flexible portion and a weight portion
It is provided with a stress-electric conversion means located in the flexible portion and detecting the displacement of the weight portion by converting it into an electric signal.
A semiconductor device, wherein the stress-electric conversion means is configured by using the element according to claim 3 or 4. A first precursor solution containing titanium, zirconium and lead in a predetermined composition ratio is applied onto the substrate, fired and heat treated at a predetermined temperature for all peaks detected by X-ray diffraction. A lead zirconate titanate film having a peak ratio of 60% or more in the 100) direction or the (001) direction is formed.
A second precursor solution containing titanium, zirconium, lead and niobium in a predetermined composition ratio is applied onto the lead zirconate titanate film, fired, and heat-treated at a predetermined temperature to produce the lead zirconate titanate. Depending on the orientation direction of the lead acid acid film, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffractometry is 60% or more, and the molar concentration of niobium is titanium. A method for producing a lead zirconate titanate niobate film laminate, which comprises forming a lead zirconate titaninate film having a total number of moles with zirconium of 10 mol% or more. A first electrode is formed on the base material,
A first precursor solution containing titanium, zirconium and lead in a predetermined composition ratio is applied onto the first electrode, fired and heat-treated at a predetermined temperature, and all detected by the X-ray diffraction method. A lead zirconate titanate film having a peak ratio of 60% or more in the (100) direction or the (001) direction to the peak is formed.
A second precursor solution containing titanium, zirconium, lead and niobium in a predetermined composition ratio is applied onto the lead zirconate titanate film, fired, and heat-treated at a predetermined temperature to produce the lead zirconate titanate. Depending on the orientation direction of the lead film, the peak ratio in the (100) direction or the (001) direction to all the peaks detected by the X-ray diffractometry is 60% or more, and the molar concentrations of niobium are titanium and zirconium. A lead zirconate titanate niobate film of 10 mol% or more is formed with respect to the total number of moles of
A method for manufacturing an element, which comprises forming a second electrode on the lead zirconate titanate niobate film.