Piezoelectric element and method for manufacturing the same

Abstract

Provided are: an inexpensive piezoelectric element (1), in which the deterioration of piezoelectric characteristics is suppressed; and a method for manufacturing a piezoelectric element.　The piezoelectric element comprises, in the following order on a substrate (11): a lower electrode layer (12); a piezoelectric film (15) mainly composed of a perovskite oxide; and an upper electrode layer (18), wherein at least a region, closest to the piezoelectric film side, of the upper electrode layer is composed of an oxide conductive layer (18a) containing In, and in the intensity profile of the bonding energy as measured by X-ray photoelectron spectrometry, for an interface region between the piezoelectric film and the oxide conductive layer of the upper electrode layer, when a peak intensity of a bonding energy derived from the 3d5 / 2 orbit of In bonded to oxygen is α, and a peak intensity of a bonding energy derived from the 3d5 / 2 orbit of In bonded to a OH group is γ, the peak intensity ratio satisfies γ / α ≦ 0.25.

Description

[Technical Field]

[0001] The present disclosure relates to a piezoelectric element and a method for manufacturing a piezoelectric element. [Background technology]

[0002] Perovskite oxide materials such as lead zirconate titanate (Pb(Zr,Ti)O3, hereafter referred to as PZT) are known as materials with excellent piezoelectric and ferroelectric properties. Taking advantage of its ferroelectric properties, PZT is used in FeRAM (Ferroelectric Random Access Memory), a non-volatile memory. Furthermore, in recent years, by combining with MEMS (Micro Electro-Mechanical Systems) technology, MEMS piezoelectric elements with PZT films are being put into practical use. PZT films are used as the piezoelectric film in piezoelectric elements that have a lower electrode, a piezoelectric film, and an upper electrode on a substrate. These piezoelectric elements are used in inkjet heads (actuators, actuators), micromirror devices, angular velocity sensors, gyro sensors, and vibration-powered devices It has been deployed to various devices, including smartphones.

[0003] Piezoelectric elements are required to have long-term stability when used in devices. Japanese Patent Application Laid-Open No. 2006-086223 discloses the provision of a metal oxide layer between the electrode and the piezoelectric film to suppress deterioration of piezoelectric properties caused by an electric field. Japanese Patent Application Laid-Open No. 2006-086223 also describes that the deterioration of piezoelectric properties occurs when an electric field is applied to a piezoelectric element with water droplets attached thereto, resulting in electrolysis of the water in the form of ions, which penetrate into the piezoelectric film and reduce the material constituting the piezoelectric layer, generating oxygen vacancies. The oxygen vacancies in the piezoelectric film are then compensated for by oxygen in a metal oxide layer provided adjacent to the piezoelectric film, suppressing the deterioration of piezoelectric properties.

[0004] Japanese Patent Application Laid-Open No. 2013-197496 also discloses a configuration in which an oxide conductive layer is provided as an upper electrode layer adjacent to a piezoelectric film. Summary of the Invention [Problem to be solved by the invention]

[0005] In Japanese Patent Laid-Open No. 2006-086223, the oxide conductive layer is made of ITO (Indium-Tin-Oxide), IrOx (Iridium Oxide), RuOx (Ruthenium Oxide), Examples of ITO include Ir (iron), Ru (ruthenium), and PtOx (platinum oxide). Ir, Ru, and Pt are very expensive. In contrast, ITO is inexpensive and is suitable for reducing the manufacturing costs of piezoelectric elements.

[0006] According to the inventors' investigations, piezoelectric elements having ITO as an oxide conductive layer on a piezoelectric film were found to have good electrical resistance and adhesion, with no difference compared to piezoelectric elements having IrO2 as an oxide conductive layer. However, the inventors discovered that piezoelectric elements having ITO on the piezoelectric film had a lower capacitance of the piezoelectric film than piezoelectric elements having IrO2 on the piezoelectric film. A decrease in capacitance means a decrease in the piezoelectric properties of the piezoelectric element.

[0007] The technology disclosed herein has been made in consideration of the above circumstances, and aims to provide a piezoelectric element and a method for manufacturing a piezoelectric element that can reduce manufacturing costs and suppress deterioration of piezoelectric characteristics. [Means for solving the problem]

[0008] Specific means for solving the above problems include the following aspects.

[0009] A piezoelectric element according to the present disclosure is a piezoelectric element including, on a substrate, a lower electrode layer, a piezoelectric film containing a perovskite oxide as a main component, and an upper electrode layer, in this order, At least a region of the upper electrode layer closest to the piezoelectric film is made of an oxide conductive layer containing In, In the intensity profile of the binding energy obtained by X-ray photoelectron spectroscopy in the interface region between the piezoelectric film and the oxide conductive layer of the upper electrode layer, the 3d 5 / 2 The peak intensity of the binding energy derived from the orbital is defined as α, and the 3d 5 / 2 When the peak intensity of the binding energy derived from the orbital is γ, the peak intensity ratio γ / α satisfies the following formula (1). γ / α≦0.25 (1)

[0010] In the piezoelectric element of the present disclosure, it is preferable that the peak intensity ratio γ / α in the intensity profile of the binding energy satisfies the following formula (2). γ / α≦0.1 (2)

[0011] In the piezoelectric element of the present disclosure, the perovskite oxide preferably contains Pb, Zr, Ti, and O.

[0012] In the piezoelectric element of the present disclosure, the perovskite oxide is a compound represented by the following general formula (3): Pb{(Zr x Ti 1-x ) y-1 B1 y}O3(3) 0 <x<1、0<y<0.3、 B1 is preferably one or more elements selected from V, Nb, Ta, Sb, Mo and W.

[0013] In the piezoelectric element of the present disclosure, the oxide conductive layer preferably contains at least one of Zn, Sn, and Ga.

[0014] A method for manufacturing a piezoelectric element according to one aspect of the present disclosure includes a sputtering step of forming an oxide conductive layer containing In on a piezoelectric film of a laminate including a lower electrode layer and a piezoelectric film on a substrate, In the sputtering process, the substrate temperature is set to 350° C. or higher.

[0015] In another embodiment of the method for manufacturing a piezoelectric element according to the present disclosure, a laminate in which a lower electrode layer, a piezoelectric film, and an oxide conductive layer containing In are laminated on a substrate is subjected to a heat treatment at 350° C. or higher. [Effects of the Invention]

[0016] According to the piezoelectric element and the method for manufacturing the piezoelectric element of the present disclosure, it is possible to reduce manufacturing costs and realize a piezoelectric element in which deterioration of the piezoelectric characteristics is suppressed. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 2 is a cross-sectional view showing a layer structure of a piezoelectric element according to an embodiment. [Figure 2] FIG. 2 is a diagram showing a schematic configuration of an evaluation sample. [Figure 3] FIG. 1 is an explanatory diagram of a method for preparing a sample for photoelectron spectroscopy. [Figure 4] FIG. 4A shows the peak of the In—O bond extracted from the bond energy profile for the interface region of Comparative Example 3, and FIG. 4B shows the peak of the In—OH bond. [Figure 5] FIG. 5A shows the peaks of the In—O bonds extracted from the bond energy profile for the interfacial region of Example 6, and FIG. 5B shows the peaks of the In—OH bonds. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the thicknesses and ratios of each layer are appropriately modified for ease of viewing, and do not necessarily reflect the actual thicknesses and ratios.

[0019] (piezoelectric element) 1 is a cross-sectional view showing the layer structure of a piezoelectric element 1 according to one embodiment. As shown in Fig. 1, the piezoelectric element 1 includes a substrate 11 on which a lower electrode layer 12, a piezoelectric film 15, and an upper electrode layer 18 are arranged in this order.

[0020] The upper electrode layer 18 is composed of an oxide conductive layer 18a containing In, at least in the region closest to the piezoelectric film. "Containing In" means that the oxide conductive layer contains 3 at% or more of In among the metal elements. There are no restrictions on the In content as long as it is 3 at% or more, but the In content of the metal elements contained in the oxide conductive layer 18a is preferably 5 at% or more and 90 at% or less, and more preferably 30 at% or more.

[0021] The oxide conductive layer 18a containing In may further contain at least one of Zn, Sn, and Ga in addition to In. By adding a metal other than In, it is possible to adjust the carrier density of the amorphous oxide layer. As the oxide conductive layer 18a containing In, ITO, IZO (Indium-Zinc-Oxide), or IGZO (Indium-Gallium-Zinc-Oxide) is preferred, and ITO is particularly preferred.

[0022] In this embodiment, the upper electrode layer 18 has a single-layer structure and is made of an oxide conductive layer 18a containing In. The upper electrode layer 18 may have a multi-layer structure instead of a single-layer structure. If the upper electrode layer 18 has a multi-layer structure, it is sufficient that the oxide conductive layer 18a is disposed closest to the piezoelectric film. If the upper electrode layer 18 has a multi-layer structure, it may include a metal layer.

[0023] In the intensity profile of the binding energy obtained by X-ray photoelectron spectroscopy measurement of the interface region 16 between the piezoelectric film 15 and the upper electrode layer 18, the 3d 5 / 2 Bond energy strength α derived from orbitals and 3d of In bonded to OH group 5 / 2 The peak intensity ratio γ / α of the binding energy intensity γ derived from the orbital satisfies the following formula (1). γ / α≦0.25 (1)

[0024] The method for measuring the intensity profile of the binding energy will be described in detail in the Examples below, but α and γ are determined as follows: Photoelectron spectroscopy is performed on the interface region 16 to obtain an intensity profile with the vertical axis representing intensity and the horizontal axis representing binding energy. At this time, an intensity profile is obtained in the range of at least 440 eV to 450 eV, and the 3d intensity of In appearing near 445 eV is obtained. 5 / 2 Obtain a spectrum derived from the orbit. 44 In3d observed around 5 eV 5 / 2 The spectrum derived from the orbital contains a peak derived from In bonded to oxygen (i.e., I-O bond) and a peak derived from In bonded to OH group (i.e., I-OH bond). Here, the bond energy of the In-O bond is 444.6±0.3 [eV], and the bond energy of the In-OH bond is 445.3±0.3 [eV]. 5 / 2 From the spectrum derived from the orbit The peaks due to In-O bonds and the peaks due to In-OH bonds are separated. The bond energies are calculated from the NIST (National Institute of Standards and Technology) database ([online], [searched March 23, 2021], internet,<URL:https: / / srdata.nist.gov / xps / main_search_menu.aspx> The peak value of the peak derived from the In-O bond was taken as the bond energy intensity α of the In-O bond, and the peak value of the peak derived from the In-OH bond was taken as the bond energy intensity γ of the In-OH bond.

[0025] The inventors have found that the above-described piezoelectric element configuration allows for the realization of a piezoelectric element 1 that maintains high piezoelectric properties without degrading the piezoelectric properties of the piezoelectric film 15 (see Examples below). As described above, providing an oxide conductive layer 18a in the region of the upper electrode layer 18 closest to the piezoelectric film 15 makes it less likely for oxygen elements to escape from the piezoelectric film 15, thereby improving long-term stability, compared to when the region closest to the piezoelectric film 15 is made of metal. On the other hand, when the oxide conductive layer 18a is formed on the piezoelectric film 15 by sputtering, an interface region 16 containing OH groups is likely to be formed between the piezoelectric film 15 and the upper electrode layer 18. Details of the method for manufacturing a piezoelectric element will be described later, but each layer of this piezoelectric element is formed by sputtering. The inventors have found that a piezoelectric element with high piezoelectric properties can be realized by sufficiently reducing the OH groups in this interface region 16. Furthermore, an oxide conductive layer containing In is a material used as a transparent electrode layer in the field of liquid crystal displays and is inexpensive. Therefore, the piezoelectric element 1 having good piezoelectric characteristics can be produced at low cost without causing a deterioration in the piezoelectric characteristics.

[0026] In the intensity profile of the binding energy, it is more preferable that the intensity ratio γ / α satisfies the following formula (2). γ / α≦0.1 (2)

[0027] Furthermore, when the above formula (2) is satisfied, a piezoelectric element with even higher piezoelectric properties can be obtained.

[0028] The lower limit of γ / α is 0, but it is preferable that 0.03≦γ / α be satisfied. A piezoelectric element that satisfies 0.03≦γ / α can be manufactured inexpensively.

[0029] The method for measuring the intensity profile of the binding energy will be explained later in the Examples.

[0030] The piezoelectric film 15 is mainly composed of a perovskite oxide represented by the general formula ABO3. In the general formula, A is an A-site element and is one or a combination of two or more of Pb, Ba (barium), La (lanthanum), Sr, Bi (bismuth), Li (lithium), Na (sodium), Ca (calcium), Cd (cadmium), Mg (magnesium), and K (potassium). In the general formula, B is a B-site element, and is one or a combination of two or more of Ti, Zr, V (vanadium), Nb (niobium), Ta (tantalum), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Fe (iron), Ru, Co (cobalt), Ir, Ni (nickel), Cu (copper), Zn (zinc), Ga (gallium), In, tin, antimony (Sb), and lanthanide elements. In the general formula, O is oxygen. The standard ratio of A:B:O is 1:1:3, but it may deviate within the range that allows for a perovskite structure.

[0031] Preferably, perovskite oxide accounts for 80 mol % or more of the piezoelectric film 15. Furthermore, it is more preferable that the piezoelectric film 15 is made of perovskite oxide (however, it contains inevitable impurities).

[0032] Perovskite oxides include lead zirconate titanate (PZT), which contains Pb (lead), Zr (zirconium), Ti (titanium), and O (oxygen). It is preferable that the system is a

[0033] In particular, the perovskite oxide is preferably a compound represented by the following general formula (3) which contains an additive B in the B site of PZT. Pb{(Zr x Ti 1-x ) 1-y B1 y}O3(3) Here, B1 is preferably at least one element selected from V (vanadium), Nb (niobium), Ta (tantalum), Sb (antimony), Mo (molybdenum), and W (tungsten). Here, 0 < x < 1 and 0 < y < 0.3. In the general formula (3), Pb: {(Zr x Ti 1-x ) 1-y B1 y}:O is based on 1:1:3, but may deviate within the range where a perovskite structure can be obtained

[0034] B1 may be a single element such as only V or only Nb, or a combination of two or more elements such as a mixture of V and Nb, or a mixture of V, Nb, and Ta. When B1 is these elements, a very high piezoelectric constant can be realized in combination with the Pb of the A-site element.

[0035] The thickness of the piezoelectric film 15 is usually 200 nm or more, for example, 0.2 μm to 5 μm, but 1 μm or more is preferred.

[0036] The substrate 11 is not particularly limited, and examples include substrates such as silicon, glass, stainless steel, yttrium-stabilized zirconia, alumina, sapphire, and silicon carbide. As the substrate 11, a laminated substrate such as a silicon substrate with a thermal oxide film having a SiO2 oxide film formed on its surface may be used.

[0037] The lower electrode layer 12 forms a pair with the upper electrode layer 18 and is an electrode for applying a voltage to the piezoelectric film 15. The main component of the lower electrode layer 12 is not particularly limited, and examples include metals or metal oxides such as Au (gold), Pt (platinum), Ir (iridium), Ru (ruthenium), Ti, Mo, Ta, Al (aluminum), Cu (copper), Ag (silver), and combinations thereof. Also, ITO (Indium Tin Oxide), LaNiO3, SRO (SrRuO3), etc. may be used. Various adhesion layers and seed layers may be included between the piezoelectric film 15 and the lower electrode layer 12, and between the lower electrode layer 12 and the substrate 11.

[0038] Here, "lower" and "upper" do not mean upper and lower in the vertical direction; rather, the electrode arranged on the substrate side across the piezoelectric film is referred to as the lower electrode, and the electrode arranged on the opposite side of the piezoelectric film from the substrate is referred to as the upper electrode.

[0039] There are no particular limitations on the thickness of the lower electrode layer 12 and the upper electrode layer 18, but it is preferably about 50 nm to 300 nm, and more preferably 100 nm to 300 nm.

[0040] (Manufacturing method of piezoelectric element) A first embodiment and a second embodiment of the method for manufacturing the piezoelectric element 1 will be described.

[0041] -First embodiment- In the first embodiment of the method for manufacturing the piezoelectric element 1, first, the lower electrode layer 12 and the piezoelectric film 15 are formed in this order on the substrate 11 by sputtering. Next, the upper electrode layer 18 is formed on the piezoelectric film 15. The process of forming the upper electrode layer 18 includes a sputtering step of forming an oxide conductive layer 18a containing In on the piezoelectric film 15 of the laminate including the lower electrode layer 12 and the piezoelectric film 15 on the substrate 11.

[0042] During the sputtering process for depositing the oxide conductive layer 18a containing In, the substrate temperature is set to 350° C. or higher. The substrate temperature is preferably set to 400° C. or lower, more preferably 350° C. or higher and 360° C. or lower. This deposition results in a 3d bond of In bonded to oxygen between the piezoelectric film 15 and the oxide conductive layer 18a in the intensity profile of the bond energy obtained by X-ray photoelectron spectroscopy. 5 / 2 The peak intensity of the binding energy derived from the orbital is defined as α, and the 3d 5 / 2 When the peak intensity of the binding energy derived from the orbital is taken as γ, an interface region 16 is formed in which the peak intensity ratio γ / α is 0.25 or less.

[0043] In the sputtering process for forming the oxide conductive layer 18a, the deposition chamber was set to 1×10 -4It is preferable to perform evacuation until the back pressure reaches the following value:

[0044] -Second embodiment- In the second embodiment of the method for manufacturing the piezoelectric element 1, first, the lower electrode layer 12 and the piezoelectric film 15 are formed in this order on the substrate 11 by sputtering. Next, the upper electrode layer 18 is formed on the piezoelectric film 15. The process of forming the upper electrode layer 18 includes a sputtering step of forming an In-containing oxide conductive layer 18a on the piezoelectric film 15 of a laminate including the lower electrode layer 12 and the piezoelectric film 15 on the substrate 11. Furthermore, the laminate including the lower electrode layer 12, the piezoelectric film 15, and the In-containing oxide conductive layer 18a stacked on the substrate 11 is subjected to a heat treatment at 350°C or higher. The heat treatment temperature is preferably 400°C or lower, more preferably 350°C or higher and 360°C or lower. The heat treatment is a vacuum annealing treatment. In this case, the substrate is not heated during the sputtering deposition of the In-containing oxide conductive layer 18a, and the substrate temperature can be set to room temperature (RT). The heating time is preferably about 0.5 to 3 hours.

[0045] According to the manufacturing methods of the first and second embodiments, the interface region 16 between the piezoelectric film 15 and the In-containing oxide conductive layer 18a can have a peak intensity ratio γ / α of 0.25 or less in the intensity profile of the bond energy at the interface region 16 obtained by X-ray photoelectron spectroscopy. Therefore, it is possible to obtain a piezoelectric element 1 with reduced manufacturing costs without deteriorating the piezoelectric properties of the piezoelectric film 15.

[0046] As described above, when the oxide conductive layer 18a is formed on the piezoelectric film 15 by sputtering the upper electrode layer 18, an interface region 16 containing OH groups is likely to be formed at the interface between the piezoelectric film 15 and the upper electrode layer 18. By sufficiently lowering the back pressure of the deposition chamber before sputtering the oxide conductive layer 18a, residual gas can be reduced, resulting in a reduction in the amount of OH groups. However, adjusting the back pressure alone is not sufficient to suppress the amount of OH groups contained in the interface region 16. In contrast, in the first embodiment, the oxide conductive layer 18a containing In is formed at a substrate set temperature of 350°C or higher, which allows the OH groups to be sufficiently removed. Similarly, in the second embodiment, a heat treatment at 350°C or higher is performed after the oxide conductive layer 18a containing In is formed, which allows the OH groups to be sufficiently removed.

[0047] One method for forming an ITO layer involves depositing an amorphous ITO film and then annealing it to improve its crystallinity. However, this annealing is generally performed at a temperature of approximately 200°C to 250°C. OH groups adsorbed on the surface of the film can be desorbed at approximately 120°C. On the other hand, to desorb OH groups bonded to metals such as In, heating to 350°C or higher is required. In the manufacturing methods of the first and second embodiments, heating to 350°C or higher during or after film deposition can desorb many OH groups. Therefore, the manufacturing methods of the first and second embodiments can provide a piezoelectric element 1 in which OH groups in the interface region 16 are sufficiently suppressed. [Example]

[0048] Examples and comparative examples of the present disclosure will be described below.

[0049] First, a method for manufacturing the piezoelectric elements of the examples and comparative examples will be described, with reference to the reference numerals of the layers of the piezoelectric element 1 shown in FIG.

[0050] (Bottom electrode layer deposition) A 25 mm square silicon substrate with a thermal oxide film was used as the substrate 11. A lower electrode layer 12 was formed on the substrate 11 by RF (radio-frequency) sputtering. Specifically, As the lower electrode layer 12, a 20 nm thick Ti layer and a 150 nm thick Ir layer were laminated in this order on the substrate 11. The sputtering conditions for each layer were as follows.

[0051] -Ti layer sputtering conditions- Target-substrate distance: 100 mm Target input power: 600W Ar gas pressure: 0.2 Pa Substrate temperature setting: 350℃

[0052] -Ir layer sputtering conditions- Target-substrate distance: 100 mm Target input power: 600W Ar gas pressure: 0.2 Pa Substrate temperature setting: 350℃

[0053] (Piezoelectric film deposition) The substrate with the lower electrode layer was placed in an RF sputtering device, and a 2 μm thick Nb-doped PZT film with a Nb doping amount of 10 at % in the B site was formed under the following sputtering conditions:

[0054] -Piezoelectric film sputtering conditions- Target-substrate distance: 60 mm Target input power: 500W Degree of vacuum: 0.3 Pa, Ar / O2 mixed atmosphere (O2 volume fraction 2.0%) Substrate temperature setting: 700℃

[0055] The above steps up to the deposition of the piezoelectric film are common to all Examples and Comparative Examples. The following method or deposition conditions for depositing the upper electrode layer differ between Examples and Comparative Examples.

[0056] (Top electrode layer formation) Next, an In-containing oxide layer was formed as the upper electrode layer 18 with a thickness of 150 nm on the surface of the piezoelectric film 15 by sputtering. For each example and comparative example, the upper electrode layer 18 was formed from the upper electrode layer material shown in Table 1. When forming an ITO layer as the In-containing oxide layer, an ITO target was used, when forming an IZO layer, an IZO target was used, and when forming an IGZO layer, an IGZO target was used. All targets used were 4-inch diameter, 4N targets manufactured by Toshima Manufacturing Co., Ltd.

[0057] The substrate after piezoelectric film formation was placed in the deposition chamber of a DC (direct current) sputtering device. For each example and comparative example, the device was evacuated to the back pressure shown in Table 1, and then an Ar / O mixed gas was introduced into the device so that the deposition pressure was 0.18 Pa. The substrate temperature setting for the Ar / O mixed gas deposition gas was RT (room temperature), and the target input power was 200 W. The O flow rate ratio was set in advance to produce the lowest-resistance oxide conductive layer for each target. For each example and comparative example, the substrate temperature setting during deposition was as shown in Table 1. When the substrate temperature setting was not RT (room temperature), the heating unit was set to the substrate temperature setting in advance, and after stabilization, the substrate was transported and set in the deposition position. The time required for the substrate to be substantially heated from the time the substrate was set until deposition was completed and the substrate was removed was approximately one hour.

[0058] (heat treatment) In addition, for Comparative Examples 1, 3, 5, and 6, Examples 1-3, and Examples 5 and 6, a heat treatment (vacuum annealing) was performed after the upper electrode layer was formed. The heat treatment temperature and time were the temperature and time shown in parentheses in the "Post-film formation heat treatment temperature" column in Table 1. In Table 1, "non" means that no heat treatment was performed.

[0059] After the electrode layer was formed, the substrate was heated without being removed from the deposition chamber. The heating time was the time during which the set temperature was maintained from the time the set temperature was reached.

[0060] <piezoelectric constant d 31 Measurement> Piezoelectric constant d 31 The piezoelectric constant d 31 The piezoelectric element prepared as described above was cut into a strip of 2 mm x 25 mm to prepare a cantilever, and measurements were carried out by applying a sinusoidal voltage of -10 V ± 10 V according to the method described in I. Kanno et al. Sensor and Actuator A 107 (2003) 68. The results are shown in Table 1.

[0061] <Dielectric constant measurement> The dielectric constant measurements were carried out for each example and comparative example using evaluation sample 2 shown in Figure 2. Evaluation sample 2 was produced by using a metal mask with a 400 μm diameter opening when forming the upper electrode layer in the above-mentioned manufacturing method. Evaluation sample 2 including a circular upper electrode layer 18 with a diameter of 400 μm was obtained by sputtering deposition through the metal mask.

[0062] The dielectric constant was measured. The dielectric constant was measured using an impedance analyzer manufactured by Agilent Technologies for each of the Examples and Comparative Examples, using Evaluation Sample 2. The results are shown in Table 1.

[0063] <Evaluation of OH content in the interfacial region> The OH content in the interface region was evaluated by photoelectron spectroscopy of the interface region. Fig. 3 is an explanatory diagram of a method for preparing a sample for photoelectron spectroscopy measurement, in which Fig. 3A is a schematic cross-sectional view of a portion of a piezoelectric element, and Fig. 3B is a schematic cut surface view of a measurement sample obtained from the piezoelectric element shown in Fig. 3A.

[0064] For each example and comparative example, a measurement sample for composition analysis was prepared using an oblique cutting method. As shown in FIG. 3A, a diamond knife was inserted at an angle θ relative to the surface of the piezoelectric element, and the piezoelectric element was cut obliquely. This resulted in the cut surface shown in FIG. 3B. As shown in FIG. 3B, the interface region 16 having the thickness t shown in FIG. 3A is exposed on the cut surface with a width equal to 1 / sinθ. The thickness t of the interface region 16 was estimated to be approximately 10 nm, and the angle θ was set so that the width of the interface region 16 exposed on the cut surface after oblique cutting was 5 μm or more.

[0065] A measurement area (area surrounded by a circle in FIG. 3B) was set on the cut surface obtained as described above so as to include a small amount of the piezoelectric film 15, and photoelectron spectroscopy measurement was carried out.

[0066] From the intensity profile obtained by photoelectron spectroscopy, the bond energy peak of the bond between In and O (In-O bond) and the bond energy peak of the bond between In and OH (In-OH bond) were separated, and the respective peak intensities α and γ were obtained, and the peak intensity ratio γ / α was calculated. The peak intensity ratios γ / α obtained for each Example and Comparative Example are shown in Table 1.

[0067] FIG. 4 is a graph showing the peak due to the In-O bond (FIG. 4A) and the peak due to the In-OH bond (FIG. 4B) separated from the intensity profile of bond energy obtained by photoelectron spectroscopy for Comparative Example 3. Similarly, FIG. 5 is a graph showing the peak due to the In-O bond (FIG. 5A) and the peak due to the In-OH bond (FIG. 5B) separated from the intensity profile of bond energy obtained by photoelectron spectroscopy for Example 6. In FIGS. 4 and 5, the intensity on the vertical axis is normalized by setting the peak value of the In-O bond to 1. The In-O bond is the bond energy of In2O3, and is 444.6±0.3[ eV] and the In-OH bond is In(OH)3, which has a bond energy of 445.3±0. The energy was set at 3 eV, and peaks were separated from the measured intensity profile.

[0068] [Table 1]

[0069] As shown in Table 1, Examples 1 to 8, in which γ / α≦0.25 is satisfied at the interface between the piezoelectric film and the oxide conductive layer serving as the upper electrode layer, clearly have higher dielectric constants and piezoelectric constants than Comparative Examples 1 to 6, in which γ / α exceeds 0.25. Furthermore, when γ / α≦0.1 is satisfied, the dielectric constants and piezoelectric constants were higher than those of Examples in which 0.1<γ / α≦0.25 were satisfied. It is more preferable that γ / α is less than 0.1.

[0070] Piezoelectric elements satisfying γ / α≦0.25 were obtained by heating the upper electrode layer to 350°C or higher during film formation, or by performing heat treatment at 350°C or higher after film formation. On the other hand, even when heat treatment was performed, heating below 350°C, specifically at 300°C, was unable to suppress γ / α to 0.25 or less.

[0071] The disclosure of Japanese Patent Application No. 2021-058186, filed on March 30, 2021, is incorporated herein by reference in its entirety. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A piezoelectric element comprising a lower electrode layer, a piezoelectric film mainly composed of a perovskite oxide, and an upper electrode layer in this order on a substrate, At least a region of the upper electrode layer closest to the piezoelectric film is made of an oxide conductive layer containing In, In the intensity profile of binding energy obtained by X-ray photoelectron spectroscopy measurement of the interface region between the piezoelectric film and the oxide conductive layer of the upper electrode layer, 3d ５／２ The peak intensity of the binding energy derived from the orbital is α, and the 3d ５／２ A piezoelectric element in which a peak intensity ratio γ / α, where γ is the peak intensity of binding energy derived from an orbital, satisfies the following formula (1): γ / α≦0.25 (1)

2. 2. The piezoelectric element according to claim 1, wherein in the intensity profile of the binding energy, the peak intensity ratio γ / α satisfies the following formula (2): γ / α≦0.1 (2)

3. 3. The piezoelectric element according to claim 1, wherein the perovskite oxide contains Pb, Zr, Ti, and O.

4. The perovskite oxide is a compound represented by the following general formula (3): P｡{(Cr ｘ Ti １－ｘ ) ｙ－１ B1 ｙ }O ３ (3) 0<x<1, 0<y<0.3, 4. The piezoelectric element according to claim 3, wherein B1 is one or more elements selected from the group consisting of V, Nb, Ta, Sb, Mo, and W.

5. The piezoelectric element according to claim 1 , wherein the oxide conductive layer contains at least one of Zn, Sn, and Ga.

6. A method for manufacturing a piezoelectric element according to any one of claims 1 to 5, comprising: a sputtering step of depositing the In-containing oxide conductive layer on the piezoelectric film of a laminate including the lower electrode layer and the piezoelectric film on the substrate, In the sputtering step, the substrate temperature is set to 350° C. or higher.

7. A method for manufacturing a piezoelectric element according to any one of claims 1 to 5, comprising: A method for manufacturing a piezoelectric element, comprising: subjecting a laminate in which the lower electrode layer, the piezoelectric film, and the oxide conductive layer containing In are laminated on the substrate to a heat treatment at 350° C. or higher.

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