Patent Description:
As a material having excellent piezoelectricity and excellent ferroelectricity, there is known a perovskite-type oxide material such as lead zirconate titanate (Pb(Zr, Ti)O<NUM>, hereinafter referred to as PZT). The PZT is used in a ferroelectric random access memory (FeRAM) which is a non-volatile memory, by taking advantage of the ferroelectricity thereof. Furthermore, in recent years, a MEMS piezoelectric element including a PZT film has been put into practical use by fusing with micro electro-mechanical systems (MEMS) technology. A PZT film is applied as a piezoelectric film in a piezoelectric element having a lower electrode, a piezoelectric film, and an upper electrode on a substrate. This piezoelectric element has been developed into various devices such as an inkjet head (an actuator), a micromirror device, an angular velocity sensor, a gyro sensor, and an oscillation power generation device.

For applying a piezoelectric element to a device, the piezoelectric element is required to have long-term stability. <CIT> describes that a metal oxide layer is provided between the electrode and a piezoelectric film in order to suppress the deterioration of piezoelectric characteristics caused by an electric field. <CIT> describes that the deterioration of the piezoelectric characteristics is due to the fact that in a case where an electric field is applied to a piezoelectric element in a state where water droplets are attached to the piezoelectric element, the moisture is electrolyzed and penetrates into the piezoelectric film in the form of ions, and a material constituting the piezoelectric layer is reduced to generate oxygen pores. Here, the deterioration of the piezoelectric characteristics is suppressed by compensating for oxygen pores in the piezoelectric film with oxygen in a metal oxide layer provided adjacent to the piezoelectric film.

<CIT> also discloses a configuration in which an oxide conductive layer is provided as an upper electrode layer that is provided adjacent to the piezoelectric film.

In <CIT>, examples of the oxide conductive layer include indium-tin-oxide (ITO), iridium oxide (IrOx), ruthenium oxide (RuOx), and platinum oxide (PtOx). Ir, Ru, Pt, and the like are very expensive. On the other hand, ITO is inexpensive and suitable for suppressing the manufacturing cost of the piezoelectric element.

According to the examination by the inventors of the present invention, in a piezoelectric element including ITO as an oxide conductive layer on a piezoelectric film, there is no difference in electric resistance and adhesiveness as compared with a case where IrO<NUM> is provided as the oxide conductive layer, and the electric resistance and the adhesiveness are favorable. On the other hand, the inventors of the present invention found that a piezoelectric element including ITO on a piezoelectric film has a small electrostatic capacity of the piezoelectric film as compared with a piezoelectric element including IrO<NUM> on the piezoelectric film. The decrease in the electrostatic capacity means a decrease in the piezoelectric characteristics of the piezoelectric element.

The technology according to the present disclosure has been made in consideration of the above circumstances, and an object of the present disclosure is to provide a piezoelectric element and a manufacturing method for a piezoelectric element, in which a manufacturing cost can be suppressed and a decrease in piezoelectric characteristics is suppressed.

Specific means for solving the above problems include the following aspects.

The piezoelectric element according to the present disclosure is a piezoelectric element comprising, on a substrate in the following order, a lower electrode layer, a piezoelectric film containing a perovskite-type oxide as a main component, and an upper electrode layer, in which at least a region of the upper electrode layer closest to a side of the piezoelectric film is composed of an oxide conductive layer containing In, and regarding an interface region between the piezoelectric film and the oxide conductive layer of the upper electrode layer, in an intensity profile of binding energy, which is acquired by an X-ray photoelectron spectroscopy measurement, in a case where a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to oxygen is defined as α, and a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to an OH group is defined as γ, a peak intensity ratio γ/α satisfies Expression (<NUM>).

In the piezoelectric element according to the present disclosure, it is preferable that in the intensity profile of the binding energy, the peak intensity ratio γ/α satisfies Expression (<NUM>).

In the piezoelectric element according to the present disclosure, it is preferable that the perovskite-type oxide contains Pb, Zr, Ti, and O.

In the piezoelectric element according to the present disclosure, it is preferable that the perovskite-type oxide is a compound represented by General Formula (<NUM>), <MAT>.

In the piezoelectric element according to the present disclosure, it is preferable that the oxide conductive layer contains at least one of Zn, Sn, or Ga.

A manufacturing method for a piezoelectric element according to one aspect of the present disclosure includes a sputtering step of forming a film of the oxide conductive layer containing In on the piezoelectric film of a laminate including the lower electrode layer and the piezoelectric film on the substrate, where in the sputtering step, a substrate set temperature is set to <NUM> or higher.

A manufacturing method for a piezoelectric element according to another aspect of the present disclosure carries out 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 heating treatment at <NUM> or higher.

According to the piezoelectric element and the manufacturing method of a piezoelectric element according to the present disclosure, it is possible to realize a piezoelectric element in which the manufacturing cost can be suppressed and the deterioration of the piezoelectric characteristics is suppressed.

Hereinafter, embodiments according to the present invention will be described with reference to the drawings. In the drawings below, the layer thickness of each of the layers and the ratio therebetween are appropriately changed and drawn for easy visibility, and thus they do not necessarily reflect the actual layer thickness and ratio.

<FIG> is a schematic cross-sectional view showing a layer configuration of a piezoelectric element <NUM> according to one embodiment. As shown in <FIG>, a piezoelectric element <NUM> includes, on a substrate <NUM>, a lower electrode layer <NUM>, a piezoelectric film <NUM>, and an upper electrode layer <NUM> in this order.

In the upper electrode layer <NUM>, at least a region closest to a side of the piezoelectric film is composed of an oxide conductive layer 18a containing In. The phrase "containing In" refers to containing <NUM> at% or more of In among the metal elements contained in the oxide conductive layer. The content of In is not limited as long as it is <NUM> at% or more; however, the content of In in the metal elements contained in the oxide conductive layer 18a is preferably <NUM> at% or more and <NUM> at% or less, and more preferably <NUM> at% or more.

The oxide conductive layer 18a containing In may further contain at least one of Zn, Sn, or Ga, in addition to In. In a case of adding a metal other than In, it is possible to adjust the carrier density of the amorphous oxide layer. The oxide conductive layer 18a containing In is preferably ITO, indium-zinc-oxide (IZO), or indium-gallium-zinc-oxide (IGZO), and particularly preferably ITO.

The present embodiment shows an example in which the upper electrode layer <NUM> has a single layer structure and consists of the oxide conductive layer 18a containing In. It is noted that the upper electrode layer <NUM> may have a laminated structure instead of a single layer structure, and in a case where a laminated structure is provided, it is sufficient that the oxide conductive layer 18a is disposed closest to the side of the piezoelectric film. In addition, in a case where the upper electrode layer <NUM> has a laminated structure, a metal layer may be included.

Regarding an interface region <NUM> between the piezoelectric film <NUM> and the upper electrode layer <NUM>, in an intensity profile of binding energy, which is acquired by an X-ray photoelectron spectroscopy measurement, a peak intensity ratio γ/α of an intensity γ of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to an OH group to an intensity α of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to oxygen satisfies Expression (<NUM>).

It is noted that although the details of the measuring method for the intensity profile of the binding energy will be described later in Examples, α and γ shall be determined as follows. The interface region <NUM> is subjected to a photoelectron spectroscopy measurement to acquire an intensity profile in which the vertical axis indicates intensity and the lateral axis indicates binding energy. In this case, an intensity profile in a range of at least <NUM> eV to <NUM> eV is acquired, and a spectrum derived from the 3d<NUM>/<NUM> orbital of In appearing in the vicinity of <NUM> eV is acquired. The spectrum derived from the In 3d<NUM>/<NUM> orbital, which is observed in the vicinity of <NUM> eV includes a peak derived from In bonded to oxygen (that is, derived from an I-O bond) and a peak derived from In bonded to an OH group (that is, that is, derived from an I-OH bond). Here, assuming that the binding energy of the In-O bond is <NUM> ± <NUM> [eV] and the binding energy of the In-OH bond is <NUM> ± <NUM> [eV], the peak derived from the In-O bond and the peak derived from the In-OH bond are separated from each other in the spectrum derived from the 3d<NUM>/<NUM> orbital of In. It is noted that for the binding energy, the database of the National Institute of Standards and Technology (NIST) ([online], [searched on March <NUM>, <NUM>], and the Internet, <URL: https://srdata. gov/xps/main_search_menu. aspx>, were referenced. A peak value of the peak derived from the In-O bond was defined as the intensity α of binding energy of the In-O bond, and a peak value of the peak derived from the In-OH bond was defined as the intensity γ of binding energy of the In-OH bond.

The inventors of the present invention have found that in a case of adopting the above-described piezoelectric element configuration, it is possible to realize the piezoelectric element <NUM> that maintains high piezoelectric characteristics without deteriorating the piezoelectric characteristics of the piezoelectric film <NUM> (see Examples below). As described above, in a case of providing the oxide conductive layer 18a in a region of the upper electrode layer <NUM> closest to the side of the piezoelectric film <NUM>, oxygen elements are less likely to come out from the piezoelectric film <NUM> as compared with a case where the region closest to the side of the piezoelectric film <NUM> is a metal, and an effect of improving long-term stability is obtained. On the other hand, in a case of forming a film of the oxide conductive layer 18a in the upper electrode layer <NUM> on the piezoelectric film <NUM> by a sputtering method, it is easy to form the interface region <NUM> including an OH group between the piezoelectric film <NUM> and the upper electrode layer <NUM>. Although the details of the manufacturing method for a piezoelectric element will be described later, each layer of the present piezoelectric element is formed into a film by a sputtering method. The inventors of the present invention have found that in a case of sufficiently reducing the OH group in the interface region <NUM>, it is possible to realize a piezoelectric element having high piezoelectric characteristics. In addition, the oxide conductive layer containing In is a material that is used as a transparent electrode layer in the field of the liquid crystal display and is inexpensive. As a result, it is possible to produce at a low cost the piezoelectric element <NUM> having favorable piezoelectric characteristics without causing the deterioration of the piezoelectric characteristics.

It is noted that in the above-described intensity profile of the binding energy, the peak intensity ratio γ/α more preferably satisfies Expression (<NUM>).

Further, in a case where Expression (<NUM>) is satisfied, a piezoelectric element having higher piezoelectric characteristics can be obtained.

It is noted that although the lower limit value of γ/α is <NUM>, it is preferable to satisfy <NUM> ≤ γ/α. A piezoelectric element satisfying <NUM> ≤ γ/α can be manufactured at a low cost.

It is noted that the details of the measuring method for the intensity profile of the binding energy will be described later in Examples.

The piezoelectric film <NUM> contains, as a main component, a perovskite-type oxide represented by the general formula ABO<NUM>.

In the general formula, A is an A site element, which is one of Pb, barium (Ba), lanthanum (La), Sr, bismuth (Bi), lithium (Li), sodium (Na), calcium (Ca), cadmium (Cd), magnesium (Mg), or potassium (K), or a combination of two or more thereof.

In the general formula, B is a B site element, which is one of Ti, Zr, vanadium (V), Nb (niobium), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), Ru, cobalt (Co), Ir, nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), In, tin, antimony (Sb), or a lanthanide element, or a combination of two or more thereof.

Regarding A:B:O, a reference ratio is <NUM>:<NUM>:<NUM>; however, the ratio may deviate within a range in which a perovskite structure is obtained.

It is noted that the piezoelectric film <NUM> is preferably occupied by <NUM>% by mole or more of the perovskite-type oxide. Further, it is preferable that the piezoelectric film <NUM> consists of a perovskite-type oxide (however, it contains unavoidable impurities).

The perovskite-type oxide is preferably a lead zirconate titanate (PZT) type that contains lead (Pb), zirconium (Zr), titanium (Ti), and oxygen (O).

In particular, it is preferable that the perovskite-type oxide is a compound represented by General Formula (<NUM>), which contains an additive B in the B site of PZT.

Pb{(ZrxTi<NUM>-x)<NUM>-yB1y}O<NUM>     (<NUM>).

Here, B1 is preferably one or more elements selected from vanadium (V), niobium (Nb), tantalum (Ta), antimony (Sb), molybdenum (Mo), and tungsten (W). Here, <NUM> < x < <NUM> and <NUM> < y < <NUM> are satisfied. It is noted that regarding Pb:{(ZrxTi<NUM>-x)<NUM>-yB1y}:O in General Formula (<NUM>), a reference ratio thereof is <NUM>:<NUM>:<NUM>; however, the ratio may deviate within a range in which a perovskite structure is obtained.

B1 may be a single element such as V only or Nb only, or it may be a combination of two or three or more elements, such as a mixture of V and Nb or a mixture of V, Nb, and Ta. In a case where B1 is these elements, a very high piezoelectric constant can be realized in combination with Pb of the A site element.

The thickness of the piezoelectric film <NUM> is generally <NUM> or more, and it is, for example, <NUM> to <NUM>. However, it is preferably <NUM> or more.

The substrate <NUM> is not particularly limited, and examples thereof include substrates such as silicon, glass, stainless steel, yttrium-stabilized zirconia, alumina, sapphire, and silicon carbide. As the substrate <NUM>, a laminated substrate such as a thermal oxide film-attached silicon substrate having a SiO<NUM> oxide film formed on the surface of the silicon substrate, may be used.

The lower electrode layer <NUM> is paired with the upper electrode layer <NUM> and is an electrode for applying a voltage to the piezoelectric film <NUM>. The main component of the lower electrode layer <NUM> is not particularly limited, and examples thereof include metals such as gold (Au), platinum (Pt), iridium (Ir), ruthenium (Ru), Ti, Mo, Ta, aluminum (Al), copper (Cu), and silver (Ag), and metal oxides thereof, as well as combinations thereof. In addition, indium tin oxide (ITO), LaNiO<NUM>, SrRuO<NUM> (SRO), or the like may be used. Various intimate attachment layers or seed layers may be included between the piezoelectric film <NUM> and the lower electrode layer <NUM> and between the lower electrode layer <NUM> and the substrate <NUM>.

Here, "lower" and "upper" do not respectively mean top and bottom in the vertical direction. As a result, an electrode disposed on the side of the substrate with the piezoelectric film being interposed is merely referred to as the lower electrode, and an electrode disposed on the side of the piezoelectric film opposite to the substrate is merely referred to as the upper electrode.

The layer thicknesses of the lower electrode layer <NUM> and the upper electrode layer <NUM> are not particularly limited, and they are preferably about <NUM> to <NUM> and more preferably <NUM> to <NUM>.

A first embodiment and a second embodiment of a manufacturing method for the piezoelectric element <NUM> will be described.

In the first embodiment of the manufacturing method for the piezoelectric element <NUM>, first, the lower electrode layer <NUM> and the piezoelectric film <NUM> are sequentially subjected to film formation on the substrate <NUM> by a sputtering method. Next, the upper electrode layer <NUM> is subjected to film formation on the piezoelectric film <NUM>. The film forming step of the upper electrode layer <NUM> includes a sputtering step of forming a film of the oxide conductive layer 18a containing In on the piezoelectric film <NUM> of a laminate including the lower electrode layer <NUM> and the piezoelectric film <NUM> on the substrate <NUM>.

In the sputtering step of forming the film of the oxide conductive layer 18a containing In, the substrate set temperature is set to <NUM> or higher. The substrate set temperature is preferably <NUM> or lower, and more preferably <NUM> or higher and <NUM> or lower. With this film formation, the interface region <NUM> in which a peak intensity ratio γ/α is <NUM> or less is formed between the piezoelectric film <NUM> and the oxide conductive layer 18a, where a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to oxygen is denoted as α, and a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to an OH group is denoted as γ in an intensity profile of binding energy, which is acquired by an X-ray photoelectron spectroscopy measurement.

It is noted that in the sputtering step of forming the film of the oxide conductive layer 18a, it is preferable that the film forming chamber is subjected to vacuuming until the back pressure reaches <NUM> × <NUM>-<NUM> or less.

In the second embodiment of the manufacturing method for the piezoelectric element <NUM>, first, the lower electrode layer <NUM> and the piezoelectric film <NUM> are sequentially subjected to film formation on the substrate <NUM> by a sputtering method. Next, the upper electrode layer <NUM> is subjected to film formation on the piezoelectric film <NUM>. The film forming step of the upper electrode layer <NUM> includes a sputtering step of forming a film of the oxide conductive layer 18a containing In on the piezoelectric film <NUM> of a laminate including the lower electrode layer <NUM> and the piezoelectric film <NUM> on the substrate <NUM>. Further, a laminate, in which the lower electrode layer <NUM>, the piezoelectric film <NUM>, and the oxide conductive layer 18a containing In are laminated on the substrate <NUM>, is subjected to a heating treatment at <NUM> or higher. The temperature of the heating treatment is preferably <NUM> or lower, and more preferably <NUM> or higher and <NUM> or lower. The heating treatment is a vacuum annealing treatment. In this case, a substrate may not be heated in the sputtering film formation of the oxide conductive layer 18a containing In, and the substrate set temperature may be room temperature (RT). The heating time is preferably about <NUM> hours (h) to <NUM>.

According to the manufacturing methods according to the first embodiment and the second embodiment, the peak intensity ratio γ/α in the interface region <NUM> between the piezoelectric film <NUM> and the oxide conductive layer 18a containing In can be set to <NUM> or less in the intensity profile of binding energy in the interface region <NUM>, which is acquired by an X-ray photoelectron spectroscopy measurement. As a result, it is possible to obtain the piezoelectric element <NUM>, in which the manufacturing cost is suppressed, without deteriorating the piezoelectric characteristics of the piezoelectric film <NUM>.

As described above, in a case of forming a film of the oxide conductive layer 18a in the upper electrode layer <NUM> on the piezoelectric film <NUM> by a sputtering method, it is easy to form the interface region <NUM> including an OH group at an interface between the piezoelectric film <NUM> and the upper electrode layer <NUM>. In a case of sufficiently reducing the back pressure in the film forming chamber before subjecting the oxide conductive layer 18a to sputtering film formation, the residual gas can be reduced, and as a result, the amount of OH groups can be reduced. However, the effect of suppressing the content of the OH group contained in the interface region <NUM> is not sufficient only by adjusting the back pressure. On the other hand, in the first embodiment, since the oxide conductive layer 18a containing In is formed into a film at a substrate set temperature of <NUM> or higher, the OH group can be sufficiently removed. Similarly, in the second embodiment, since the oxide conductive layer 18a containing In is subjected to a heating treatment at <NUM> or higher after the film formation, the OH group can be sufficiently removed.

There is a case where a treatment, in which amorphous ITO is formed into a film and then an annealing treatment is carried out to improve the crystallinity, is carried out as a method of forming an ITO layer. However, the temperature of this annealing treatment is generally about <NUM> to <NUM>. The OH groups adsorbed to the surface of the film forming surface can be eliminated at approximately <NUM>. On the other hand, it is necessary to carry out heating to <NUM> or higher in order to eliminate the OH group bonded to a metal such as In. In the manufacturing method according to the first embodiment and/or the second embodiment, a large amount of OH groups can be eliminated by carrying out heating at <NUM> or higher during or after film formation. Therefore, according to the manufacturing methods according to the first embodiment and the second embodiment, it is possible to obtain the piezoelectric element <NUM>, in which the OH group in the interface region <NUM> is sufficiently suppressed.

Hereinafter, Examples and Comparative Examples according to the present disclosure will be described.

First, a manufacturing method for a piezoelectric element of each of Examples and Comparative Examples will be described. The description of the manufacturing method will be made with reference to the reference numerals of the respective layers of the piezoelectric element <NUM> shown in <FIG>.

As the substrate <NUM>, a <NUM> square thermal oxide film-attached silicon substrate was used. The lower electrode layer <NUM> was formed into a film on the substrate <NUM> by radio-frequency (RF) sputtering. Specifically, as the lower electrode layer <NUM>, a Ti layer having a thickness of <NUM> and an Ir layer having a thickness of <NUM> were laminated on the substrate <NUM> in this order. The sputtering conditions for each layer were as follows.

The substrate with the lower electrode layer was placed in an RF sputtering apparatus, and an Nb-doped PZT film of <NUM> was formed, where the Nb-doping amount to the B site was set to <NUM> at%. The sputtering conditions in this case were as follows.

The steps up to the film formation of the piezoelectric film are common to all Examples and Comparative Examples. The following method or film forming condition for forming the upper electrode layer is different between Examples and Comparative Examples.

Next, as the upper electrode layer <NUM> having a thickness of <NUM>, an oxide layer containing In was formed on the surface of the piezoelectric film <NUM> by sputtering. For each of Examples and Comparative Examples, the upper electrode layer <NUM> consisting of the upper electrode layer material shown in Table <NUM> was formed. It is noted that an ITO target was used in a case of forming an ITO layer as the oxide layer containing In, an IZO target was used in a case of forming an IZO layer as the oxide layer containing In, and an IGZO target was used in a case of forming an IGZO layer as the oxide layer containing In. As the targets, targets all having a diameter of <NUM> inches and 4N, manufactured by Toshima Manufacturing Co. , were used.

A substrate after forming a piezoelectric film was placed in a film forming chamber of a direct current (DC) sputtering apparatus, each of Examples and Comparative Examples was subjected to vacuuming to the back pressure shown in Table <NUM>, and then an Ar/O<NUM> mixed gas was introduced into the apparatus so that the film formation pressure was <NUM> Pa. The substrate set temperature of the Ar/O<NUM> mixed gas as the film forming gas was set to room temperature (RT), and the target input power was set to <NUM> W. The condition of the O<NUM> flow rate ratio was set in advance so that the oxide conductive layer had the lowest resistance in each target, and then film formation was carried out. For each of Examples and Comparative Examples, the substrate set temperature in the film formation was set as shown in Table <NUM>. In a case where the substrate set temperature was not room temperature (RT), the heating unit was set to the substrate set temperature in advance and heated, and after being stabilized, the substrate was transported and set at the film formation position. The time taken by the substrate being substantially heated from the moment when the substrate was set until the film formation was completed and the substrate was discharged was <NUM> hour.

It is noted that for Comparative Examples <NUM>, <NUM>, <NUM>, and <NUM>, Examples <NUM> to <NUM>, and Examples <NUM> and <NUM>, a heating treatment (vacuum annealing) was carried out after the formation of the film of the upper electrode layer. The temperature and the time of the heating treatment were set to the temperature and the time described in parentheses, which are described in the column of "Heating treatment temperature after film formation" in Table <NUM>. It is noted that the description of "non" in Table <NUM> means that the heating treatment was not carried out.

It is noted that after the electrode layer was formed into a film, the heating treatment was carried out as it was without being taken out from the film forming chamber. It is noted that the heating time is the time taken from the moment when the temperature reached a set temperature until the set temperature was maintained.

The piezoelectric constant d<NUM> was measured. The piezoelectric element produced as described above was cut into a strip shape of <NUM> × <NUM> to produce a cantilever, and according to the method described in <NPL>, the measurement of the piezoelectric constant d<NUM> was carried out with an applied voltage of sine wave of -<NUM> V ± <NUM> V. The results are shown in Table <NUM>.

For each of Examples and Comparative Examples, the measurement of the dielectric constant was carried out using an evaluation sample <NUM> shown in <FIG>. The evaluation sample <NUM> was produced by using a metal mask having an opening having a diameter of <NUM> at the time of forming the upper electrode layer in the above-described manufacturing method. A sputtering film formation was carried out through a metal mask to obtain the evaluation sample <NUM> including the circular upper electrode layer <NUM> having a diameter of <NUM>.

The dielectric constant was measured. For each of Examples and Comparative Examples, the measurement of the dielectric constant was carried out using the evaluation sample <NUM> and using an impedance analyzer manufactured by Agilent Technologies, Inc. The results are shown in Table <NUM>.

The OH content in the interface region was evaluated by the photoelectron spectroscopy measurement of the interface region.

<FIG> are explanatory views of a production method for a sample for the photoelectron spectroscopy measurement. <FIG> is a schematic cross-sectional view of a part of a piezoelectric element, and <FIG> is a schematic view of a cut surface of a measurement sample obtained from the piezoelectric element shown in <FIG>.

A measurement sample for composition analysis was produced for the piezoelectric element of each of Examples and Comparative Examples by using an oblique cutting method. As shown in <FIG>, a diamond knife was inserted into the surface of the piezoelectric element at an angle θ, and the piezoelectric element was cut obliquely. As a result, such a cut surface as shown in <FIG> was obtained. As shown in <FIG>, on the cut surface, the interface region <NUM> having a thickness t shown in <FIG> is exposed with a width of <NUM>/sinθ times. It is noted that the thickness t of the interface region <NUM> was estimated to be about <NUM>, and the angle θ was set such that the width of the interface region <NUM> exposed to the cut surface after oblique excavation was <NUM> or more.

A measurement area (an area surrounded by a circle in <FIG>) was set such that the piezoelectric film <NUM> was slightly included in the cut surface obtained as described above and subjected to the photoelectron spectroscopy measurement.

From the intensity profile acquired by the photoelectron spectroscopy measurement, the peak of binding energy of the bond between In and O (the In-O bond) and the peak of binding energy of the bond between In and OH (the In-OH bond) were separated, the peak intensities α and γ were determined respectively, and the peak intensity ratio γ/α was calculated. Table <NUM> shows the peak intensity ratios γ/α determined for each of Examples and Comparative Examples.

<FIG> show graphs in which, for Comparative Example <NUM>, a peak due to an In-O bond (<FIG>) and a peak due to an In-OH bond (<FIG>) are separated from the intensity profile of binding energy, acquired by the photoelectron spectroscopy measurement. Similarly, <FIG> show graphs in which, for Example <NUM>, a peak due to an In-O bond (<FIG>) and a peak due to an In-OH bond (<FIG>) are separated from the intensity profile of binding energy, acquired by the photoelectron spectroscopy measurement. In each of <FIG> and <FIG>, the intensity of the vertical axis is standardized with the peak value of the In-O bond as <NUM>. It is noted that from the measured intensity profile, the In-O bond was subjected to peak separation as <NUM> ± <NUM> [eV] in terms of the binding energy of In<NUM>O<NUM>, and the In-OH bond was subjected to peak separation as <NUM> ± <NUM> [eV] in terms of the binding energy of In(OH)<NUM>.

As shown in Table <NUM>, it is revealed that in Examples <NUM> to <NUM> in which γ/α ≤ <NUM> is satisfied at the interface between the piezoelectric film and the oxide conductive layer which is the upper electrode layer, the dielectric constant is high and the piezoelectric constant is high as compared with Comparative Examples <NUM> to <NUM> in which γ/α exceeds <NUM>. In addition, in a case where γ/α ≤ <NUM> is satisfied, the dielectric constant is high and the piezoelectric constant is also high as compared with Examples in which <NUM> < γ/α ≤ <NUM> is satisfied. It is still more preferable that γ/α is smaller than <NUM>.

Claim 1:
A piezoelectric element (<NUM>) comprising, on a substrate (<NUM>) in the following order:
a lower electrode layer (<NUM>);
a piezoelectric film (<NUM>) containing a perovskite-type oxide as a main component; and
an upper electrode layer (<NUM>),
wherein at least a region of the upper electrode layer closest to a side of the piezoelectric film is composed of an oxide conductive layer (18a) containing In,
characterized in that in an interface region (<NUM>) between the piezoelectric film and the oxide conductive layer of the upper electrode layer, when an intensity profile of binding energy, which is acquired by an X-ray photoelectron spectroscopy measurement, in a case where a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to oxygen is defined as α, and a peak intensity of binding energy derived from a 3d<NUM>/<NUM> orbital of In bonded to an OH group is defined as γ, a peak intensity ratio γ/α satisfies formula (<NUM>), <MAT>