阅读说明：本技术 膜结构体、压电体膜及超导体膜 (Film structure, piezoelectric film, and superconductor film ) 是由 木岛健 小西晃雄 于 2019-12-27 设计创作，主要内容包括：根据本发明,对于各种压电材料,能够将具有单晶的晶体结构的压电体膜形成在本发明的膜结构体之上。本发明的膜结构体具备：基板；形成于所述基板上的、含氧化锆的具有四方晶的晶体结构的缓冲膜；形成于所述缓冲膜上的、外延生长的含铂族元素的金属膜；以及形成于所述金属膜上的、外延生长的含Sr(Ti-(1-x),Ru-(x))O-(3)(0≤x≤1)的膜。(According to the present invention, a piezoelectric film having a single-crystal structure can be formed on the film structure of the present invention for various piezoelectric materials. The membrane structure of the present invention comprises: a substrate; a buffer film having a tetragonal crystal structure and containing zirconium oxide formed on the substrate; an epitaxially grown metal film containing a platinum group element formed on the buffer film; and epitaxially grown Sr (Ti) -containing film formed on the metal film 1‑x ，Ru x )O 3 (x is more than or equal to 0 and less than or equal to 1).)

1. A film structure comprising:

a substrate;

a buffer film having a tetragonal crystal structure and containing zirconium oxide formed on the substrate;

an epitaxially grown metal film containing a platinum group element formed on the buffer film; and

epitaxially grown Sr (Ti) -containing film formed on the metal film_1-x，Ru_x)O₃Wherein x is 0. ltoreq. x.ltoreq.1.

2. The film structure according to claim 1, wherein the thickness of the metal film is 20nm to 150 nm.

3. The film structure according to claim 1 or 2, wherein the buffer film further contains a rare earth element or an alkaline earth element.

4. The membrane structure according to any one of claims 1 to 3, wherein the surface area of the buffer membrane is 1.30 to 1.60 in comparison with a plane.

5. The film structure according to any one of claims 1 to 4, wherein the substrate is oriented in a (100) plane, (110) plane, or (111) plane.

6. The film structure according to any one of claims 1 to 5, wherein the buffer film is epitaxially grown in accordance with an orientation of the substrate.

7. A single-crystal piezoelectric film formed on the film described in any one of claims 1 to 6.

8. The piezoelectric film according to claim 7, which has a trigonal crystal structure.

9. The piezoelectric film of claim 8, wherein the material is BiFeO₃、LiNbO₃Or LiTaO₃。

10. The piezoelectric film according to claim 7, which has a crystal structure of a hexagonal system.

11. The piezoelectric film of claim 10, wherein the material is AlN.

12. The piezoelectric film according to claim 7, which has a tungsten bronze type crystal structure.

13. The piezoelectric film according to claim 7, which has a crystal structure of a bismuth layer type.

14. The piezoelectric film of claim 13, wherein the material is Bi₄Ti₃O₁₂Or (Bi)_4-xLa_x)Ti₃O₁₂Wherein x is more than or equal to 0 and less than 1.

15. The piezoelectric film of claim 7 being formed from ABO₃The perovskite oxide is shown.

16. The piezoelectric film of claim 7 wherein the material is lead zirconate titanate.

17. The piezoelectric film of claim 16, wherein the lead zirconate titanate is Pb (Zr)_0.3，Ti_0.7)O₃。

18. A single-crystal superconductor film formed on the film of any one of claims 1 to 6.

19. The superconductor film of claim 18 which is a bismuth-based superconductor.

20. The superconductor film of claim 19, wherein the material is Bi₂SrCa₂Cu₃O₁₀。

21. The superconductor film of claim 18 being an yttrium-based superconductor.

22. The superconductor film of claim 21, wherein the material of the yttrium based superconductor is YBa₂Cu₃O₇。

Technical Field

The present invention relates to a film structure including a buffer film capable of forming a single-crystal piezoelectric film or a superconductor film on a substrate by epitaxial growth, the piezoelectric film, and the superconductor film.

Background

Sensors play an important role today in the internet of things (IoT) age, with a market size of $ 200 billion worldwide and expanding at 7-8% market growth rate, producing as many as 900 billion sensors annually worldwide. Among them, MEMS sensor technology using piezoelectric materials such as PZT is particularly active, and is widely used for various applications such as a gyro sensor for automatic driving, a piezoelectric microphone, a high-frequency filter for 5G communication, and a vibration power generation element.

With the development of the internet of things technology, the MEMS sensor technology using such piezoelectric materials is required to be miniaturized/thinned and highly sensitive year by year. On the other hand, in order to increase sensitivity, it is necessary to make polarization uniform to ensure sufficient piezoelectric properties, but in a piezoelectric material which is usually a polycrystalline ceramic sintered body, polarization is not uniform. Further, there is a limit to making the ceramic sintered body thinner. Therefore, in recent years, attempts have been made to obtain a piezoelectric material as a single crystal of a thin film by epitaxial growth (for example, refer to patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 5-072428

Disclosure of Invention

Problems to be solved by the invention

In an effort to make such a thin film single-crystallized, since the piezoelectric material is mostly an oxide, it is difficult to make the piezoelectric material single-crystallized by epitaxial growth, for example, in the case of using a single-crystal Si substrate. Therefore, for example, an oxide crystal such as YSZ (Yttria-stabilized zirconia) may be used as the buffer layer, but since this oxide crystal is different from the crystal system of the piezoelectric material, the piezoelectric material is affected by the crystal system of the buffer layer at the time of crystal formation of the piezoelectric material, and there is a problem that it is difficult to obtain in-plane single crystallinity as a thin film. Further, since the lattice constants of the respective piezoelectric materials are different, it is necessary to study the structure of the buffer layer for each piezoelectric material, and it is also difficult to select the buffer layer.

Means for solving the problems

In order to solve the above problem, a film structure of the present invention includes: a substrate; a buffer film formed on the substrate and containing zirconium oxide and having a tetragonal crystal structure; an epitaxially grown metal film containing a platinum group element formed on the buffer film; and epitaxially grown Sr (Ti) -containing film formed on the metal film_1-x，Ru_x)O₃(x is more than or equal to 0 and less than or equal to 1).

Effects of the invention

According to the present invention, a film having a single crystal structure can be formed on the film structure of the present invention for various piezoelectric materials and superconducting materials.

Drawings

FIG. 1 is a cross-sectional view of a substrate having a buffer film formed thereon according to the present invention.

Fig. 2 is a cross-sectional view of a substrate having a lower electrode formed on a buffer film according to the present invention.

Fig. 3 is a sectional view of a membrane structure including a buffer film according to the present invention.

FIG. 4(a) shows ZrO formed on the substrate 11₂A STEM image obtained by observing a cross section of the buffer film 12 as a film; (b) the lower diagram of (1) is an electron diffraction diagram of the substrate 11, and the upper diagram is an electron diffraction diagram of the buffer film 12.

Fig. 5 is a STEM image obtained by observing a cross section when the buffer film 12 having the following thickness is formed: (a)1 nm; (b)12 nm; (c)15 nm; (d)25 nm.

Fig. 6 shows the result of measuring the θ -2 θ spectrum by XRD with respect to the film structure 101.

Fig. 7 is a STEM image obtained by observing a cross section when the conductive film 13 having the following thickness is formed: (a)10 nm; (b)20 nm; (c)150 nm.

Fig. 8 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 1.

Fig. 9 shows a lattice diagram based on STEM observed in a cross section of PZT (30/70) as the piezoelectric film 14 of example 1.

FIG. 10(a) is a polar view of the Si (220) plane of the film structure 101 of example 1, and (b) is ZrO₂(220) The pole figure of the surface, (c) is the pole figure of Pt (220), and (d) is the pole figure of PZT (202).

Fig. 11 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14 of example 1.

Fig. 12 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 2.

Fig. 13(a) is a graph showing the X-ray diffraction pattern by phi scanning of the substrate 11 of the film structure 101 of example 2, and (b) is a graph showing the X-ray diffraction pattern by phi scanning of the piezoelectric film 14 of the film structure 101 of example 2.

Fig. 14 shows a lattice diagram based on STEM observed as a cross section of the BTO of the piezoelectric film 14 of example 2.

Fig. 15 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14 of example 2.

Fig. 16 is a graph showing piezoelectricity of the BTO as the piezoelectric film 14 of example 2.

Fig. 17 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 3.

Fig. 18(a) is a graph showing the X-ray diffraction pattern by phi scanning of the substrate 11 of the film structure 101 of example 3, and (b) is a graph showing the X-ray diffraction pattern by phi scanning of the piezoelectric film 14 of the film structure 101 of example 3.

Fig. 19 shows a STEM-based lattice diagram observed as a cross section of the BFO of the piezoelectric film 14 of example 3.

Fig. 20 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14 of example 3.

Fig. 21 is a graph showing the piezoelectricity of the BFO as the piezoelectric film 14 of example 3.

Fig. 22 shows the result of measuring the out-of-plane θ -2 θ spectrum by XRD for the film structure 101 of example 4.

Fig. 23(a) is a graph showing the X-ray diffraction pattern by phi scanning of the substrate 11 of the film structure 101 of example 4, and (b) is a graph showing the X-ray diffraction pattern by phi scanning of the piezoelectric film 14 of the film structure 101 of example 4.

Fig. 24 shows a STEM-based lattice diagram observed as a cross section of the BLT of the piezoelectric film 14 of example 4.

Fig. 25 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14 of example 4.

Fig. 26 is a graph showing the piezoelectricity of the BLT as the piezoelectric film 14 of example 4.

Fig. 27 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 5.

Fig. 28 is a graph showing an X-ray diffraction pattern based on phi-scanning for the film structural body 101 of example 5.

Fig. 29 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 6.

Fig. 30 is a graph showing an X-ray diffraction pattern based on phi-scanning for the film structural body 101 of example 6.

Fig. 31 shows the results of STEM observation of the cross sections of the buffer film 12 and the conductive film 13 on the sample on which the PZT (30/70) film of example 1 was formed.

Fig. 32 shows the results of observing the cross sections of the buffer film 12 and the conductive film 13 in the STEM sample in which the BFO film of example 3 was formed.

Fig. 33 shows the results of observing the cross sections of the buffer film 12 and the conductive film 13 in the STEM sample in which the BLT film of example 4 was formed.

Fig. 34(a) is a lattice diagram showing a cross section of the interface between the conductive film 13 and the film 16 when the BFO film of example 3 is formed, and (b) is a lattice diagram showing a cross section of the interface between the conductive film 13 and the film 16 when the BLT film of example 4 is formed.

Fig. 35 shows the results of measuring the X-ray diffraction pattern of phi-scanning by XRD method for AlN in the film structure 101 of example 7.

FIG. 36 shows the membrane structure 101 for example 8 for LiNbO₃The X-ray diffraction pattern obtained by scanning phi by XRD method was measured.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

It should be noted that the disclosure is merely exemplary, and appropriate modifications that can be easily made by those skilled in the art while maintaining the spirit of the present invention are certainly within the scope of the present invention. In the drawings, the width, thickness, shape, and the like of each portion are schematically shown in comparison with the embodiments in order to make the description clearer, but the present invention is only illustrative and is not limited to the explanation of the present invention.

In the present specification and the drawings, the same elements as those described above in the existing drawings are sometimes denoted by the same reference numerals, and detailed description thereof is appropriately omitted.

In the drawings used in the embodiments, hatching (hashing) added for distinguishing the components may be omitted from the drawings.

(embodiment mode)

FIG. 1 is a cross-sectional view of a substrate having a buffer film formed thereon according to the present invention. As shown in fig. 1, a buffer film 12 is formed on a substrate 11.

The substrate 11 is, for example, a silicon (Si) substrate. In addition to Si, for example, an soi (silicon on insulator) substrate, a substrate formed of various semiconductor crystals other than Si, a substrate formed of various oxide single crystals such as sapphire, or garnet Al may be used₃Fe₂Si₃O₁₂) A substrate, a glass substrate having a polysilicon film formed on the surface thereof, or the like. These substrates may be not only 4 inches but also 6 inches or 8 inches.

The orientation of the substrate 11 may be arbitrary, and if it is a Si substrate, for example, Si (100), Si (110), Si (111), or the like may be used.

The buffer film 12 contains zirconium oxide (ZrO) epitaxially grown on the substrate 11₂) And is composed of a film portion 12a and a protruding portion 12 b. Known as ZrO₂The crystal system undergoes a monoclinic → tetragonal → cubic phase transition in response to the added energy, and in the present invention, the buffer film 12 has a tetragonal crystal structure. The buffer film 12 is preferably epitaxially grown in accordance with the orientation of the substrate 11.

It has been reported that, regarding the piezoelectric material, if the crystal system is tetragonal, or if tetragonal is contained even though it is not tetragonal, the performance is improved, and it is considered that the provision of tetragonal zirconia as a buffer film exerts an advantageous effect on the single crystal formation of the piezoelectric material.

Monocrystalline ZrO₂Contains a maximum of 8% crystal defects, and it is considered that, if crystal defects are present, the vacancies of the defects have elastic force with adjacent atoms toward a direction of decreasing lattice strain. It is believed that the degree of this elastic force is proportional to the vacancy concentration. The buffer film 12 of the present invention can utilize this elastic force to function to change the crystal structure.

As shown in fig. 1, the buffer film 12 has a protruding portion 12 b. It is considered that the formation of the protruding portion 12b in this manner is caused by the formation of a pyramid (pyramid) structure and the crystal growth by anisotropic growth along a certain axis or a certain edge of the crystal when the concentration of the raw material is supersaturated during the deposition of the buffer film 12.

The buffer film 12 may contain not only ZrO₂And may further contain a rare earth element or an alkaline earth element. Of these, ZrO₂Oxygen defects may be included. In addition, transition metal elements such as Al, Sc, Mn, Fe, Co, Ni, and the like may be included to improve the characteristics.

Preferably, the film portion 12a is 10nm or more, and the protrusion 12b is 3 to 8 nm.

Fig. 2 is a cross-sectional view of the substrate shown in fig. 1, on which the lower electrode is formed on the buffer film 12. The lower electrode includes a conductive film 13 and a film 16 epitaxially grown on the buffer film 12. The conductive film 13 can be formed using various metals, and for example, Ru, Rh, Pd, Os, Ir, and Pt as platinum group elements can be used. These materials are known to be physically/chemically similar to each other.

The film 16 contains a composite oxide represented by the following general formula (chemical formula 1), such as Strontium Titanate (STO), Strontium Titanate Ruthenate (STRO), or Strontium Ruthenate (SRO). It is noted that 0. ltoreq. x. ltoreq.1 is satisfied.

Sr(Ti_1-x，Ru_x)O₃… (chemical formula 1)

The lower electrode preferably has a planar surface, and the conductive film 13 may have a thickness of at least 20nm, and the film 16 may have a thickness thinner than that of the conductive film 13.

Fig. 3 is a sectional view showing a film structure 101 of the present invention in which a piezoelectric film 14 and a conductive film 15 as an upper electrode are further formed on the substrate shown in fig. 2.

The material of the piezoelectric film 14 is, for example, lead zirconate titanate (PZT) or barium titanate (BaTiO)₃) And the like perovskite type oxides. Alternatively, for example, trigonal bismuth ferrite (BiFeO) may be used₃). Likewise, a trigonal lithium niobate (LiNbO) may be used₃) Lithium tantalate (LiTaO)₃). For example, hexagonal aluminum nitride (AlN) can be used.

For example, a tungsten bronze type ferroelectric film or a bismuth layer junction can be used as the piezoelectric film 14A ferroelectric film is formed. As a material having a crystal structure of a tungsten bronze type ferroelectric film, for example, Ba is mentioned₂NaNb₅O₁₅。

The crystal structure of the bismuth layer structure ferroelectric film is represented by the general formula (Bi)₂O₂)²⁺(A_m-1B_m O_3m+1)^2-(m is 1 to 5) or Bi₂A_m-1B_mO_3m+3(m is 1 to 5) and is represented by (Bi)₂O₂)²⁺A plurality of perovskite-like structures are provided between the layers. The ferroelectric material having a bismuth layered structure is, for example, bismuth titanate (Bi)₄Ti₃O₁₂). Alternatively, for example, bismuth lanthanum titanate (Bi) can be used_4-xLa_x)Ti₃O₁₂(0＜x＜1)。

Not limited to the piezoelectric film 14, a perovskite-structured YBa film may be used₂Cu₃O₇Yttrium-based superconductor such as (YBCO) and Bi₂SrCa₂Cu₃O₁₀A bismuth-based superconductor such as (BSCCO) is used as a material to form the superconductor film 14.

If a material for forming such a piezoelectric film or superconductor film as described above is used, a single-crystal piezoelectric film 14 or superconductor film 14 can be formed on the buffer film 12.

A conductive film 15 is formed on the piezoelectric film 14. The conductive film 15 can be formed using the same material as the conductive film 13. The film 16 can be expected to have an effect of improving the adhesion between the conductive film 13 and the piezoelectric film 14.

Examples

The present embodiment will be described in more detail below with reference to examples. The present invention is not limited to the following examples.

In examples 1 to 4, the film structure 101 shown in fig. 3 was produced using a (100) -oriented Si substrate as the substrate 11. As for the piezoelectric film 14, PZT (30/70) (Pb (Zr) was used in example 1_0.3，Ti_0.7)O₃) Example 2 BTO (BaTiO)₃) Example 3 BFO (BiFeO) was used₃) Example 4 uses BLT ((Bi)_3.25，La_0.75)Ti₃O₁₂) Film formation is performed as a sputtering material.

First, ZrO is formed on substrate 11 by electron beam deposition₂The film serves as a buffer film 12. The conditions at this time are as follows.

The device comprises the following steps: electron beam evaporation device

Pressure: 7.0X 10^-3Pa

Evaporation source: zr + O₂

O₂Flow rate: 10sccm

Acceleration voltage/emission current: 7.5kV/1.8mA

Thickness: 25nm

Substrate temperature: 600 deg.C

FIG. 4(a) shows ZrO formed on the substrate 11₂The film was used as the buffer film 12, and the cross section thereof was observed to obtain a STEM image. The lower diagram of fig. 4(b) is an electron diffraction diagram of the substrate 11, and the upper diagram of fig. 4(b) is an electron diffraction diagram of the buffer film 12.

As shown in fig. 4(a), it can be seen that: the cushion film 12 includes a protrusion 12b having a pyramid-shaped surface, and is composed of a film portion 12a and the protrusion 12 b. As is clear from the upper diagram of FIG. 4(b), the buffer film 12 is fine ZrO₂The assembly of single crystals is epitaxially grown on the upper surface of the substrate 11.

Fig. 5 shows a cross-sectional view of the buffer film 12 at each film formation time by STEM. FIG. 5(a) shows the state when the buffer film 12 of 1nm is formed, FIG. 5(b) shows the state when the buffer film 12 of 12nm is formed, FIG. 5(c) shows the state when the buffer film 12 of 15nm is formed, and FIG. 5(d) shows the state when the buffer film 12 of 25nm is formed. In fig. 5(b) to (d), white broken lines are emphasized to clarify the shape of the protrusion 12 b.

As shown in fig. 5(a), it can be seen that: immediately after the buffer film 12 is formed, the protruding portion 12b is not formed. The film formation time at this time was 3 seconds. Next, a sample in which the buffer film 12 was formed for 1 minute was prepared, and its cross section was observed (fig. 5 (b)). As shown in fig. 5(b), it can be seen that: the height of the projection 12b is not uniform. Next, a sample in which the buffer film 12 was formed for 5 minutes was prepared, and its cross section was observed (fig. 5 (c)). As shown in fig. 5(c), the height of the projection 12b is more uniform than that of the projection 12b shown in fig. 5 (b). Next, a sample in which the buffer film 12 was formed for 8 minutes was prepared, and its cross section was observed (fig. 5 (d)). As shown in fig. 5(d), the height of the projection 12b is more uniform than that of the projection 12b shown in fig. 5(b) or (c).

The heights of the projections 12b shown in fig. 5(b) to (d) were averaged based on the respective images, and were 2.2nm in fig. 5(b), 3.33nm in fig. 5(c), and 4.67nm in fig. 5 (d). The projections 12b were rectangular pyramids, and the diagonal length of the bottom surface was 3.3nm in fig. 5(b), 5.0nm in fig. 5(c), and 7.0nm in fig. 5 (d).

From the above results, as the buffer film 12 is formed, the size of the rectangular pyramid becomes larger, and the height of the protruding portion 12b becomes larger as the film formation time elapses. When the surface area of the buffer film 12 is 1.0 when the buffer film 12 is viewed as a plane when the buffer film 12 is formed for 0.05 minute (3 seconds) (fig. 5(a)), the surface area of the buffer film 12 in fig. 5(b) - (d) is 1.30 to 1.60 times.

The film formation rate was calculated to be 3.33[ nm/sec ] in FIG. 5(a), 2.0[ nm/sec ] in FIG. 5(b), 0.50[ nm/sec ] in FIG. 5(c), and 0.52[ nm/sec ] in FIG. 5 (d). Thus, the film formation rates of the buffer film 12 with different film thicknesses are known as follows: when a film thicker than 15nm is formed, the film formation rate becomes constant.

Fig. 6 shows the results of measuring the θ -2 θ spectrum by XRD after the conductive films 13 and 16 are formed by the method described later. As shown in FIG. 6, ZrO of the buffer film 12 was found from the peak position₂Has a crystal structure of tetragonal crystal oriented in the (200) plane.

Next, a platinum (Pt) film is formed as the conductive film 13 on the buffer film 12 by a sputtering method. The conditions at this time are as follows.

The device comprises the following steps: DC sputtering device

Pressure: 1.2X 10^-1Pa

Evaporation source: pt

Electric power: 100W

Thickness: 150nm

Substrate temperature: 450 to 600 DEG C

Fig. 7 is a STEM image obtained by forming a Pt film as the conductive film 13 on the buffer film 12 and observing the cross section thereof. Fig. 7(a) shows a state where the conductive film 13 of 10nm is formed, fig. 7(b) shows a state where the conductive film 13 of 20nm is formed, and fig. 7(c) shows a state where the conductive film 13 of 150nm is formed.

As shown in fig. 7(a), it can be seen that: the surface of the conductive film 13 is substantially planarized even with a film thickness of 10 nm. Further, as shown in fig. 7(b), the surface of the conductive film 13 is further planarized by setting the film thickness to 20nm, and even when 150nm is formed in this state, the surface is maintained flat as shown in fig. 7 (c).

Next, SrRuO is formed on the conductive film 13 by sputtering₃(SRO) film as film 16. The conditions at this time are as follows.

The device comprises the following steps: RF magnetron sputtering device

Power: 300W

Gas: ar (Ar)

Pressure: 1.8Pa

Thickness: 20nm

Substrate temperature: 600 deg.C

Next, the piezoelectric film 14 is formed on the film 16. In examples 1 to 4, the formation conditions were the same, and only the sputtering material was different.

The device comprises the following steps: RF magnetron sputtering device

Materials: example 1: PZT (30/70)]Pb(Zr_0.3，Ti_0.7)O₃、

Example 2: BTO]BaTiO₃、

Example 3: BFO]BiFeO₃、

Example 4: BLT](Bi_3.25，La_0.75)Ti₃O₁₂

Power: 1500W

Gas: Ar/O₂

Pressure: 1.0Pa

Substrate temperature: 450 deg.C

(example 1)

In example 1, Si/ZrO was used as the film structure 101₂Film formation was performed by the method of/Pt/SRO/PZ/Pt. Si (100) is used for the substrate 11. After PZT (30/70) as the piezoelectric film 14 was formed, the film thickness was measured by XRF using a fluorescent X-ray analyzer (AZX400) manufactured by Rigaku corporation, and was 1.0 μm.

Fig. 8 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 1. As shown in fig. 8, it can be seen that: the PZT (30/70) is preferentially oriented in the c-axis. Lattice constant a and lattice constant c were obtained based on the X-ray diffraction pattern, and the c/a axis ratio was calculated to be 1.046.

Fig. 9 shows a lattice diagram based on STEM obtained by observing PZT (30/70) as the piezoelectric film 14 in the cross section of the film structure 101. As shown in fig. 9, it was confirmed that the piezoelectric film 14 was a single crystal without lattice disorder such as dislocation.

Fig. 10 shows the results of measuring the pole figure by the XRD method for each layer in the film structure 101 of example 1 and examining the in-plane orientation relationship of the film of each layer. FIG. 10(a) is a polar view of the Si (220) plane, and FIG. 10(b) is ZrO₂(220) FIG. 10(c) is a polar view of Pt (220), and FIG. 10(d) is a polar view of PZT (202).

As shown in fig. 10(a) to (d), peaks of 4-fold symmetry were observed, and it was found that epitaxial growth was performed so that the in-plane orientation was aligned with the substrate.

Fig. 11 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14 of example 1. As shown in FIG. 11, the piezoelectric film 14 of example 1 exhibited good characteristics, and the residual polarization Pr was 50 μ C/cm²The coercive electric field Ec is 180 kV/cm.

(example 2)

In example 2, as Si/ZrO₂Film formation was performed in a manner of/Pt/SRO/BTO. Si (100) is used for the substrate 11. After formation of BTO as the piezoelectric film 14, the film thickness was measured by XRF, and found to be 1.0 μm.

Fig. 12 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 2. In fig. 12, the upper side curve shows the results of out-of-plane measurement, and the lower side curve shows the results of in-plane measurement.

As shown in fig. 12, the piezoelectric film 14 is preferentially oriented in the (001) plane. In addition, an a axis and a c axis of the piezoelectric film 14 are calculated from the measurement result, and the result is that the a axis is 0.4012nm and the c axis is 0.4262 nm. Therefore, the c/a ratio was 1.044, and it was found that the c-axis length was longer than 1.01 which is the total (bulk) value.

Fig. 13 shows a graph of X-ray diffraction patterns based on phi-scanning for the film structure 101 of example 2. (a) Is a pattern of the substrate 11, and (b) is a pattern of the piezoelectric film 14. As can be seen from fig. 13, the piezoelectric film 14 has a 4-fold axis of symmetry at the same angle as the substrate 11, and is formed by the Cube-On-Cube method up to the piezoelectric film 14.

Fig. 14 shows a lattice diagram based on STEM obtained by observing the BTO as the piezoelectric film 14 in the cross section of the film structure 101 of example 2. As shown in fig. 14, it was confirmed that the piezoelectric film 14 was a single crystal without lattice disorder such as dislocation.

Fig. 15 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14. As shown in FIG. 15, the piezoelectric film 14 of example 2 exhibited a ferroelectric property.

Fig. 16 is a diagram showing the piezoelectricity of the piezoelectric film 14 by a d33 meter. d33 is a d33 constant measuring instrument (model: LTFA-01) manufactured by Lead Tehno, Inc., and d33 can be measured even without the conductive film 15 as an upper electrode. Specifically, when the device detects a change in the amount of charge by applying a force to the film structure 101 and using an integration circuit, and when the device has piezoelectricity, a pulse-shaped waveform can be observed by applying or not applying a force at a constant time interval as shown in fig. 16. In this case, the value of d33 was 24.88 (pC/N).

(example 3)

In example 3, as Si/ZrO₂Film formation was performed in a manner of/Pt/SRO/BFO. Si (100) is used for the substrate 11. After BFO was formed as the piezoelectric film 14, the film thickness was measured by XRF, and was 2.1 μm.

Fig. 17 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 3. In fig. 17, the upper side curve shows the results of out-of-plane measurement, and the lower side curve shows the results of in-plane measurement. As shown in fig. 17, the piezoelectric film 14 is preferentially oriented in the (001) plane.

FIG. 18 is a schematic diagram showing a display deviceA plot of the scanned X-ray diffraction pattern. (a) Is a pattern of the substrate 11, and (b) is a pattern of the piezoelectric film 14. As can be seen from fig. 18, after the piezoelectric film 14 is formed, the piezoelectric film 14 has a 4-fold axis of symmetry at the same angle as the substrate 11, and is formed by the Cube-On-Cube method up to the piezoelectric film 14.

Fig. 19 shows a STEM-based lattice diagram obtained by observing BFO as the piezoelectric film 14 in the cross section of the film structure 101. As shown in fig. 19, it was confirmed that the piezoelectric film 14 was a single crystal without lattice disorder such as dislocation.

Fig. 20 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14. As shown in FIG. 20, the piezoelectric film 14 of example 3 exhibited good characteristics, and the residual polarization Pr was 60 μ C/cm²The coercive electric field Ec is 100 kV/cm.

Fig. 21 is a graph showing the measurement result according to d33 for the piezoelectric film 14. As shown in fig. 21, the piezoelectric film 14 has piezoelectricity. The d33 value at this time was 16.69 (pC/N).

(example 4)

In example 4, as Si/ZrO₂Film formation was performed in accordance with the method of/Pt/SRO/BLT. Si (100) is used for the substrate 11. After BLT was formed as the piezoelectric film 14, the film thickness was measured by XRF, and found to be 1.0 μm.

Fig. 22 shows the results of measuring the θ -2 θ spectrum by the XRD method for the film structure 101 of example 4. Fig. 22 shows the results of the out-of-plane measurements. As shown in fig. 22, the piezoelectric film 14 is preferentially oriented in the (001) plane.

FIG. 23 is a schematic diagram showing a display deviceA plot of the scanned X-ray diffraction pattern. (a) The pattern of the substrate 11 is (b) the pattern up to the piezoelectric film body 14 is formed. As can also be seen from FIG. 24, a pressure is formedThe piezoelectric film 14 has a 4-fold axis of symmetry at the same angle as the substrate 11, and the piezoelectric film 14 is formed in a Cube-On-Cube manner.

Fig. 24 shows a STEM-based lattice diagram obtained by observing BLT as the piezoelectric film 14 in a cross section of the film structure 101. As shown in fig. 24, it was confirmed that the piezoelectric film 14 was a single crystal without lattice disorder such as dislocation. In fig. 25, W1 is a perovskite layer, and W2 is a bismuth oxide layer.

Fig. 25 is a graph showing the voltage dependence of the polarization of the piezoelectric film 14. As shown in FIG. 25, the piezoelectric film 14 of example 4 exhibited a ferroelectric property, and the residual polarization Pr was 4. mu.C/cm²The coercive electric field Ec was 4.5 kV/cm.

Fig. 26 is a graph showing the measurement result according to d33 for the piezoelectric film 14. As shown in fig. 26, the piezoelectric film 14 has piezoelectricity. The d33 value at this time was 164.7 (pC/N).

(example 5)

In example 5, as Si/ZrO₂Film formation was performed by the method of/Pt/SRO/PZT. Si (111) is used for the substrate 11. After PZT was formed as the piezoelectric film 14, the film thickness was measured by XRF, and found to be 1.0 μm. As a material of PZT, a target of Pb/Zr/Ti (130/52/48) was used.

Fig. 27 shows the results of measuring the θ -2 θ spectrum by XRD for the sample prepared in example 5. As shown in fig. 27, all of the substrate 11, the buffer film 12, the conductive film 13, and the piezoelectric film 14 are oriented in the (111) plane.

FIG. 28 shows XRD-based measurement of the sample prepared in example 5 with the (111) plane as the diffraction planeThe result of the scan. As shown in fig. 28, the substrate 11, the conductive film 13, and the piezoelectric film 14 exhibit 3-fold symmetry. The conductive film 13 is an epitaxially grown single crystal film even if the peak is shifted by 60 °, and the piezoelectric film 14 is also an epitaxially grown single crystal film.

(example 6)

In example 6, as Si/ZrO₂Film formation was performed by the method of/Pt/SRO/PZT. The substrate 11 uses Si (110). After PZT was formed as the piezoelectric film 14, the film thickness was measured by XRF, and found to be 1.0 μm. As a material of PZT, a target of Pb/Zr/Ti (130/52/48) was used.

Fig. 29 shows the results of measuring the θ -2 θ spectrum by XRD for the sample prepared in example 2. As shown in fig. 29, the substrate 11 and the conductive film 13 are preferentially oriented in the (110) plane.

FIG. 30 shows XRD-based measurement of the sample prepared in example 6 with the (111) plane as the diffraction planeThe result of the scan. As shown in fig. 30, the substrate 11, the conductive film 13, and the piezoelectric film 14 exhibit 2-fold symmetry. Thus, the piezoelectric film 14 can be said to be an epitaxially grown single crystal film.

From the results of examples 1 to 6, it is also understood that the buffer film 12 is epitaxially grown in accordance with the orientation of the substrate 11, and that the various piezoelectric films 14 formed thereon are also epitaxially grown. This is considered to be because, as explained below, after the buffer film 12 is formed, the crystal structure of the buffer film 12 changes in accordance with the piezoelectric material on which the film is formed.

Fig. 31 shows the results of STEM observation of the cross sections of the buffer film 12 and the conductive film 13 for the sample on which the PZT (30/70) film of example 1 was formed. As shown in FIG. 31(a), the length between the projections 12b was 4.2 nm. Fig. 31(b) is an enlarged view of the protruding portion 12 b.

Fig. 32 shows the results of STEM observation of the cross sections of the buffer film 12 and the conductive film 13 for the sample on which the BFO film of example 3 was formed. As shown in FIG. 32(a), the length between the projections 12b was 3.9 nm. Fig. 32(b) is an enlarged view of the protruding portion 12 b.

Fig. 33 shows the results of STEM observation of the cross sections of the buffer film 12 and the conductive film 13 for the sample on which the BLT film of example 4 was formed. As shown in FIG. 33(a), the length between the projections 12b was 5.5 nm. Fig. 33(b) is an enlarged view of the protruding portion 12 b.

As shown in fig. 31 to 33, the height of the protruding portion 12b varies in accordance with the lattice constant of the piezoelectric film 14. For example, the lattice constant of the BFO a axis shown in fig. 32 is 0.3971nm, which is the shortest compared to PZT in fig. 31 and BLT in fig. 33. At this time, as shown in fig. 32(b), the height of the protruding portion 12b is 6.3nm, and it is considered that the protruding portion 12b extends upward in accordance with BFO having a short lattice constant in the process of forming BFO as the piezoelectric film 14.

On the other hand, the lattice constant of the a-axis of BLT shown in fig. 33 is 0.5411nm, which is the longest as compared with PZT in fig. 31 and BFO in fig. 32. At this time, as shown in fig. 33(b), the height of the protruding portion 12b is 2.8nm, and it is considered that the protruding portion 12b is compressed downward in accordance with the BLT having a long lattice spacing in the process of forming the BLT as the piezoelectric film 14.

As described above, the buffer film 12, particularly the protruding portion 12b, deforms according to the type of the piezoelectric film 14, and further, the lattice spacing between the conductive film 13 and the film 16 on the buffer film 12 also fluctuates. Fig. 34(a) is a lattice diagram showing a cross section of the interface between the conductive film 13 and the film 16 when the BFO film is formed, and fig. 34(b) is a lattice diagram showing a cross section of the interface between the conductive film 13 and the film 16 when the BLT film is formed.

The molecular distance between the conductive film 13 and the film 16 when the BLT film is formed as shown in fig. 34(b) is longer than the molecular distance between the conductive film 13 and the film 16 when the BFO film is formed as shown in fig. 34 (a).

(example 7)

In example 7, as Si/ZrO₂Film formation was performed by a Pt/SRO/AlN method. Si (100) is used for the substrate 11. The production conditions up to the SRO film were the same as in examples 1 to 6. AlN was formed under the following conditions.

The device comprises the following steps: RF magnetron sputtering device

Power: 200W

Gas: ar (Ar)

Pressure: 0.5Pa

Film forming time: 60 minutes

Substrate temperature: 200 deg.C

Fig. 35 shows the results of measuring the X-ray diffraction pattern of phi-scanning by XRD method for AlN in the film structure 101 of example 7. As shown in fig. 35, it can be seen that: for AlN films, 6-fold symmetry is exhibited, with single crystallization in (0001) single orientation. Note that 1 and 2 of the circled numbers shown in fig. 35 are shown rotated by 90 ° in plane.

(example 8)

In example 8, as Si/ZrO₂/Pt/SRO/LiNbO₃Film formation was performed in the (LN) system. Si (100) is used for the substrate 11. The production conditions up to the SRO film were the same as in examples 1 to 6. LN film formation was performed under the following conditions.

The device comprises the following steps: RF magnetron sputtering device

Power: 160W

Gas: Ar/O₂In a ratio of 2%

Pressure: 0.8Pa

Film forming time: 9 hours

Substrate temperature: 400 deg.C

Fig. 36 shows the results of measuring the X-ray diffraction pattern of phi-scanning by XRD method for LN with respect to the film structure 101 of example 8. As shown in fig. 35, it can be seen that: the LN film exhibited 4-fold symmetry and was single-crystallized in the (001) single orientation.

From the results of examples 1 to 8 above, it is also understood that when the epitaxially grown Pt film and SRO film are formed on the buffer film containing zirconium, and the piezoelectric film is formed thereon, a single-crystal piezoelectric film can be formed.

Description of the reference numerals

11: a substrate;

12: a buffer film;

12 a: a membrane section;

12 b: a protrusion;

13. 15: a conductive film;

14: a piezoelectric film/superconductor film;

16: a film;

101: a membrane structure.