Piezoelectric material composition, method of manufacturing same, piezoelectric device, and apparatus including piezoelectric device

Abstract

The invention relates to a piezoelectric material composition, a method of manufacturing the same, a piezoelectric device, and an apparatus including the piezoelectric device. A piezoelectric material composition according to one aspect of the present disclosure may be represented by Formula 1. [Formula 1] aPbZrO3-bPbTiO3-(1-a-b) Pb (NicNb1-c) O3 + x mol% A + y vol% BaTiO3 wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15 < = a < = 0.24, 0.29 < = b < = 0.38, 0.30 < = c < = 0.35, 0.00 < = x < = 3.00, and 0.00 < = y < = 7.00.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of Korean Patent Application No. 10-2013-0115727, filed on August 31, 2023, which is hereby incorporated by reference as if fully set forth herein. Technical Field

[0003] The present disclosure relates to piezoelectric material compositions, methods of making the same, piezoelectric devices, and apparatus including the same. Background Art

[0004] Piezoelectric devices including piezoelectric materials are widely used for ultrasonic vibrators, transducers, and actuators in the fields of ultrasonic equipment, imaging equipment, audio equipment, communication equipment, and sensors. Summary of the Invention

[0005] The inventors of the present invention have recognized that the following problems may arise when the developed piezoelectric material is put into practical use.

[0006] Compared to dynamic speakers using coils, piezoelectric devices including piezoelectric materials can be miniaturized and have higher vibration efficiency, and thus can be applied to display devices including light-emitting display devices, such as televisions (TVs).

[0007] Therefore, a material having high piezoelectric characteristics is required to apply an acoustic device including a piezoelectric device to a display device or apparatus.

[0008] One aspect of the present disclosure is to provide a piezoelectric material composition that can have high piezoelectric characteristics.

[0009] One aspect of the present disclosure is to provide a method of manufacturing a piezoelectric material composition, which can provide a piezoelectric material composition having high piezoelectric characteristics by orienting grains of a piezoelectric material using a template, thereby enhancing the piezoelectric characteristics.

[0010] One aspect of the present disclosure is to provide a piezoelectric device having high piezoelectric characteristics and an apparatus including the piezoelectric device.

[0011] One aspect of the present disclosure is directed to providing a piezoelectric device having a composition for developing various combinations of materials providing two or more crystal structures at room temperature, and a piezoelectric device including a material having enhanced piezoelectric characteristics.

[0012] Additional features, advantages, and aspects of the present disclosure will be set forth in the following description, and in part will be apparent from the description, or may be learned by practicing the inventive concepts provided herein. Other features, advantages, and aspects of the present disclosure may be realized and obtained through the structures specifically pointed out in the written description or structures derivable therefrom, the claims thereof, and the accompanying drawings.

[0013] A piezoelectric material composition according to one aspect of the present disclosure may be represented by Formula 1.

[0014] [Formula 1]

[0015] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0016] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0017] The method of manufacturing a piezoelectric material composition according to one aspect of the present disclosure may include mixing a matrix material and a seed material to prepare a slurry, shaping the slurry to prepare a green tape, and sintering the green tape to prepare a sinter. The sinter may be represented by Formula 1.

[0018] [Formula 1]

[0019] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0020] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0021] A piezoelectric device according to one aspect of the present disclosure may include a piezoelectric device layer including a piezoelectric material composition including a first material and a second material surrounded by the first material; a first electrode portion disposed on a first surface of the piezoelectric device layer; and a second electrode portion disposed on a second surface different from the first surface of the piezoelectric device layer. The piezoelectric device layer may be represented by Formula 1.

[0022] [Formula 1]

[0023] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0024] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0025] An apparatus according to one aspect of the present disclosure may include a vibration member and a piezoelectric device disposed on a rear surface of the vibration member. The piezoelectric device may include a piezoelectric device layer comprising a first material and a second material surrounded by the first material; a first electrode portion disposed on a first surface of the piezoelectric device layer; and a second electrode portion disposed on a second surface different from the first surface of the piezoelectric device layer. The piezoelectric device layer may be represented by Formula 1.

[0026] [Formula 1]

[0027] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0028] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0029] According to one aspect of the present disclosure, a piezoelectric material composition having high piezoelectric characteristics, a piezoelectric device including the piezoelectric material composition, and an apparatus including the piezoelectric device may be provided.

[0030] According to one aspect of the present disclosure, since the piezoelectric material composition has high piezoelectric characteristics, piezoelectric devices and apparatuses each including the piezoelectric material composition can be driven with a low driving voltage.

[0031] According to one aspect of the present disclosure, a method of manufacturing a piezoelectric material composition may enable low-temperature sintering, and thus may significantly reduce the time and cost of manufacturing a piezoelectric device, thereby significantly improving the productivity of the piezoelectric device.

[0032] According to one aspect of the present disclosure, productivity can be improved, and thus optimization of the manufacturing process can be achieved.

[0033] Other systems, methods, features, and advantages will be or become apparent to one skilled in the art upon examination of the following figures and detailed description. All such additional systems, methods, features, and advantages are intended to be included within this description, be within the scope of the present disclosure, and be protected by the following claims. Nothing in this section should be construed as limiting the claims. Other aspects and advantages are discussed below in conjunction with aspects of the present disclosure.

[0034] It is to be understood that both the foregoing description and the following detailed description of the present disclosure are exemplary and explanatory and are intended to provide further explanation of the disclosure as claimed. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this disclosure, illustrate aspects of the disclosure and together with the description serve to explain the principles of the disclosure.

[0036] Figure 1 is a cross-sectional view illustrating a piezoelectric device according to one aspect of the present disclosure.

[0037] Figure 2 A method of manufacturing a piezoelectric device according to one aspect of the present disclosure is shown.

[0038] Figure 3 A method of manufacturing a matrix material of a piezoelectric material composition according to one aspect of the present disclosure is shown.

[0039] Figure 4 A method of manufacturing a seed material for a piezoelectric material composition according to one aspect of the present disclosure is shown.

[0040] Figure 5 Shown in preparation Figure 4 The grain changes that occur during the three seeding steps.

[0041] Figures 6A to 6C Scanning electron microscopy (SEM) images show that the Figure 5 The grain changes that occur during the three seeding steps.

[0042] Figure 7 is a graph showing an X-ray diffraction pattern relative to the CuO content of a piezoelectric material composition according to one aspect of the present disclosure.

[0043] Figure 8 is a graph showing relative density (%), dielectric constant ε, and CuO content of the piezoelectric material composition according to one aspect of the present disclosure.T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ Picture.

[0044] Figures 9A to 9D Shown are X-ray diffractometer (XRD) measurement values ​​of the seed content of a piezoelectric material composition according to one aspect of the present disclosure.

[0045] Figures 10A to 10D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0046] Figures 11A to 11D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0047] Figures 12A to 12D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0048] Figure 13 The Lotgering factor with respect to the BaTiO 3 content and the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure is shown.

[0049] Figure 14 is a graph showing relative density (%), dielectric constant ε, and relative sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure. T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ Picture.

[0050] Figure 15 A car sound device according to one aspect of the present disclosure is shown.

[0051] Figure 16 is a perspective view of a display device according to one aspect of the present disclosure.

[0052] Figure 17 According to one aspect of the present disclosure Figure 16 A cross-sectional view taken along line II' in FIG.

[0053] Figure 18 According to one aspect of the present disclosure Figure 16 piezoelectric device.

[0054] Throughout the drawings and detailed description, unless otherwise described, the same drawing reference numerals should be understood to refer to the same elements, features, and structures. The size, length, thickness, and depiction of layers, regions, and elements may be exaggerated for clarity, illustration, and / or convenience. DETAILED DESCRIPTION

[0055] Reference will now be made in detail to aspects of the present disclosure, examples of which may be illustrated in the accompanying drawings. In the following description, where a detailed description of well-known methods, functions, structures, or configurations may unnecessarily obscure aspects of the present disclosure, such detailed descriptions of such well-known functions or configurations may be omitted for the sake of brevity. The described progression of processing steps and / or operations are non-limiting examples.

[0056] The order of steps and / or operations is not limited to the order set forth herein and may be changed to occur in an order different from that described herein, except for steps and / or operations that must occur in a specific order. In one or more examples, two consecutive operations may be performed substantially simultaneously, or the two operations may be performed in a reverse order or a different order depending on the functions or operations involved.

[0057] The advantages and features of the present disclosure and their implementation methods are illustrated by referring to the exemplary aspects described in the accompanying drawings. However, the present disclosure can be implemented in different forms and should not be construed as being limited to the exemplary aspects set forth herein. On the contrary, these exemplary aspects are examples and are provided to make the present disclosure thorough and complete, to help those skilled in the art understand the inventive concept without limiting the scope of protection of the present disclosure.

[0058] The shapes, dimensions (e.g., size, length, width, height, thickness, position, radius, diameter, and area), proportions, ratios, angles, quantities, and number of elements disclosed herein (including those shown in the accompanying drawings) are merely examples, and thus, the present disclosure is not limited to the details shown. Any implementation described herein as "example" is not necessarily to be construed as preferred or advantageous over other implementations. However, it should be noted that the relative sizes of components shown in the accompanying drawings are part of this disclosure.

[0059] When the terms "including," "having," "comprising," "containing," "consisting of," "made of," or "formed of" are used with respect to one or more elements, one or more other elements may be added unless a term such as "only" is used. The terms used in the present disclosure are only for describing example aspects and are not intended to limit the scope of the present disclosure. Terms in the singular may include plural forms unless the context clearly indicates otherwise.

[0060] The word "exemplary" is used to mean serving as an example or illustration, unless otherwise stated. An embodiment is an example embodiment. An aspect is an example aspect. "Aspect," "example," and the like should not be construed as preferred or advantageous over other implementations. An aspect, an example, or an example aspect, etc., may refer to one or more aspects, one or more examples, or one or more example aspects, etc., unless otherwise stated. Furthermore, the term "may" encompasses all meanings of the term "can."

[0061] In one or more aspects, unless otherwise expressly stated, elements, features, or corresponding information (e.g., levels, ranges, dimensions, or sizes, etc.) are interpreted as including errors or tolerances, even when no explicit description of such errors or tolerances is provided. Errors or tolerances may be caused by various factors (e.g., process factors, internal or external influences, or noise, etc.). When interpreting a numerical value, the value is interpreted as including the error range unless otherwise expressly stated.

[0062] When describing a positional relationship, when, for example, "on," "above," "upper," "above," "below," "below," "near," "near," "adjacent," "next to," or "on or to the side of" are used to describe the positional relationship between two parts (e.g., layers, films, regions, components, or parts, etc.), one or more other parts may be located between the two parts, unless more restrictive terms such as "immediately," "directly," or "near" are used. For example, when a structure is described as being located "on," "above," "upper," "above," "below," "above," "below," "near," "near," "adjacent," "next to," or "on or to the side of" another structure, the description should be interpreted as including situations where the structures are in contact with each other and situations where one or more additional structures are disposed or interposed therebetween. In addition, the terms "front," "back," "back," "left," "right," "top," "bottom," "downward," "upward," "upper," "lower," "up," "down," "column," "row," "vertical," and "horizontal" refer to any reference system.

[0063] Spatially relative terms, such as "under," "below," "lower," "on," "above," and "upper," etc., may be used to describe the relationship between various elements (e.g., layers, films, regions, components or portions, etc.) as shown in the accompanying drawings. Spatially relative terms should be understood as terms that include different orientations of elements in use or operation in addition to the orientation depicted in the drawings. For example, if the elements shown in the drawings are turned over, elements described as "under" or "below" other elements will be oriented "above" the other elements. Thus, the term "under" as an example term can include all orientations of "above" and "under." Similarly, the exemplary terms "above" or "upper" can include both an orientation of "above" and "under."

[0064] When describing temporal relationships, when the temporal sequence is described as, for example, "after", "subsequently", "next", "before", "in front of" or "precedes", discontinuities or discontinuities may be included, so that one or more other events may occur in between, unless more restrictive terms such as "just", "immediately" or "directly" are used.

[0065] It should be understood that although the terms "first" or "second" etc. can be used in this article to describe various elements (for example, layers, films, regions, components or parts, etc.), these elements should not be limited by these terms to any specific order, priority or quantity of, for example, elements. These terms are only used to distinguish one element from another element. For example, without departing from the scope of this disclosure, the first element can be referred to as the second element, and similarly, the second element can be referred to as the first element. In addition, without departing from the scope of this disclosure, according to the convenience of those skilled in the art, the first element and the second element, etc. can be arbitrarily named. For the sake of brevity, the function or structure of these elements (for example, the first element and the second element, etc.) is not limited by the sequence number or name in front of the element. In addition, the first element can include one or more first elements. Similarly, the second element, etc. can include one or more second elements, etc.

[0066] When describing elements of the present disclosure, the terms "first," "second," "A," "B," "(a)," or "(b)," etc. may be used. These terms are intended to identify corresponding elements from other elements, and these terms are not used to define the nature, sequence, basis, order, or quantity of the elements.

[0067] When an element (for example, a layer, film, region, component or part, etc.) is described as being “connected,” “coupled,” “attached” or “adhered” to another element, the element may be not only directly connected, coupled, attached or adhered to the other element, but also indirectly connected, coupled, attached or adhered to the other element with one or more intermediate elements or layers disposed or interposed between the elements, unless otherwise specified.

[0068] When an element (e.g., a layer, film, region, component, or portion) is “in contact with” or “overlaps with” another element, the element may not only be directly in contact with or overlap with the other element, but may also be indirectly in contact with or overlap with the other element with one or more intermediate elements disposed or interposed between the elements, unless otherwise specified.

[0069] The term "at least one" should be understood to include any and all combinations of one or more of the associated listed items. For example, the phrases "at least one of the first, second, or third item" and "at least one of the first, second, and third items" can each mean (i) a combination of items provided by one or more of the first, second, and third items, or (ii) only one of the first, second, and third items.

[0070] The expression "a first element, a second element, and / or" a third element should be understood to cover one of the first, second, and third elements, and any and all combinations of the first, second, and third elements. For example, A, B, and / or C covers only A; only B; only C; any of A, B, and C (e.g., A, B, or C); some combination of A, B, and C (e.g., A and B; A and C; or B and C); and all of A, B, and C. In addition, the expression "A / B" can be understood to mean A and / or B. For example, the expression "A / B" can mean only A; only B; A or B; or A and B.

[0071] In one or more aspects, unless otherwise indicated, for convenience, the terms "between" and "among" can be simply used interchangeably. For example, the expression "between a plurality of elements" can be understood as among a plurality of elements. In another example, the expression "among a plurality of elements" can be understood as between a plurality of elements. In one or more examples, the number of elements can be two. In one or more examples, the number of elements can be more than two. In addition, when an element (e.g., a layer, film, region, component or part, etc.) is referred to as being "between" at least two elements, the element can be the only element between the at least two elements, or one or more intermediate elements can also be present.

[0072] In one or more aspects, unless otherwise specified, for convenience, the phrases "one another" and "mutually" may be used interchangeably. For example, the expression "different from each other" may be understood to mean different from each other. In another example, the expression "different from each other" may be understood to mean different from each other. In one or more examples, the number of elements involved in the aforementioned expression may be two. In one or more examples, the number of elements involved in the aforementioned expression may be more than two.

[0073] In one or more aspects, the phrases "one or more of" and "more than one" are simply used interchangeably for convenience unless otherwise indicated.

[0074] The features of the various embodiments of the present disclosure may be partially or completely coupled or combined with each other, may be technically associated with each other, and may be operated, linked, or driven together in various ways. Aspects of the present disclosure may be implemented or executed independently of each other, or may be implemented or executed together in a mutually dependent or related relationship. In one or more aspects, the components of each device according to various aspects of the present disclosure may be operably coupled and configured.

[0075] Unless otherwise defined, the terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the exemplary aspects belong. It should also be understood that terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and should not be interpreted in an idealized or overly formal sense, unless otherwise expressly defined herein.

[0076] In the following description, various exemplary aspects of the present disclosure will be described in detail with reference to the accompanying drawings. With respect to the reference numerals of the elements of each drawing, the same elements may be shown in other drawings, and the same reference numerals may refer to the same elements, unless otherwise specified. The same or similar elements may be denoted by the same reference numerals even if they are depicted in different drawings.

[0077] In addition, for the sake of convenience of description, the proportions, dimensions, sizes and thicknesses of each element shown in the drawings may be different from the actual proportions, dimensions, sizes and thicknesses. Therefore, aspects of the present disclosure are not limited to the proportions, dimensions, sizes and thicknesses shown in the drawings.

[0078] The inventors of the present invention developed a sintering method for a piezoelectric material composition and the composition of a templated grain growth (TGG) piezoelectric material composition through numerous experiments, thereby developing a piezoelectric material with high piezoelectric properties. For example, TGG can be a process in which TGG is performed using a seed crystal. For example, non-TGG can be a process in which a random grain growth process is performed without using a seed crystal.

[0079] Figure 1: is a cross-sectional view showing a piezoelectric device according to one aspect of the present disclosure. : is a cross-sectional view showing a piezoelectric device including a piezoelectric material composition manufactured by a TGG process.

[0080] refer to Figure 1 The piezoelectric device 10 according to one aspect of the present disclosure may include a piezoelectric material composition 11 , a first electrode layer 12 , and a second electrode layer 13 .

[0081] The piezoelectric material composition 11 may be provided between the first electrode layer 12 and the second electrode layer 13. The piezoelectric material composition 11 may be represented by Formula 1 below.

[0082] [Formula 1]

[0083] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0084] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0085] The piezoelectric material composition 11 may include a plurality of crystal grains configured with a first material 11a and a second material 11b. Each of the plurality of crystal grains configured with the first material 11a and the second material 11b may be divided by a grain boundary GB. The first material 11a may be represented by the following formula 2.

[0086] [Formula 2]

[0087] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A

[0088] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.00.

[0089] The first material 11a may be a material other than the second material 11b in Formula 1. For example, the first material 11a may be a material other than BaTiO3 as the second material 11b in Formula 1. For example, Formula 2 can be obtained by removing BaTiO3 as a seed material in Formula 1. For example, the first material 11a may include one of Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO, and NiO. For example, when the first material 11a includes CuO, CuO may be added to the piezoelectric material composition of Formula 1 at 0 mol% to 3 mol%. For example, CuO may be added to the piezoelectric material composition of Formula 1 at 3 mol% or less. For example, CuO may be added to the piezoelectric material composition of Formula 1 at 1.0 mol%.

[0090] Therefore, one aspect of the present disclosure may include CuO, and thus the sinterability of the piezoelectric material may be further enhanced.

[0091] Furthermore, one aspect of the present disclosure may include CuO, thereby providing a piezoelectric material composition capable of sintering at a low temperature.

[0092] The grains of the first material 11a may grow based on the crystal orientation of the second material 11b. For example, the aspect ratio of the second material 11b may be 5 to 20. For example, the piezoelectric material composition 11 according to another aspect of the present disclosure may include a plurality of first materials 11a. For example, the plurality of first materials 11a may have the same or substantially the same crystal orientation. For example, the plurality of first materials 11a may have a (001) crystal orientation. For example, the plurality of first materials 11a may have a crystal structure grown in a (001) orientation. For example, the first material 11a according to one aspect of the present disclosure may be configured to surround the second material 11b. The first material 11a according to one aspect of the present disclosure may be obtained by referring to the following Figure 2 and 3 The method for preparing the matrix material is described.

[0093] The second material 11b may be formed within the first material 11a. The second material 11b may be surrounded by the first material 11a. The second material 11b may be positioned at the center of the first material 11a. For example, the center may not correspond precisely to the center (or center) of a certain volume of the first material 11a, but may be a certain region including the center (or center) of the certain volume of the first material 11a. For example, the center may be a region extending from the center of the first material 11a within the certain volume of the first material 11a. Therefore, in one aspect of the present disclosure, even when the second material 11b is positioned offset from the center (or center) of the first material 11a, this is still within the scope of the present disclosure. For example, the second material 11b may be positioned within each of the plurality of first materials 11a, and in grain orientation growth, the second material 11b may be positioned near a grain boundary (GB) that serves as a boundary between the plurality of first materials 11a. The second material 11b according to one aspect of the present disclosure may be a seed material. For example, the second material 11b may include BaTiO3. For example, BaTiO3 can be added to the piezoelectric material composition of Formula 1 at 0% to 7% by volume. For example, BaTiO3 can be added to the piezoelectric material composition of Formula 1 at 7% by volume or less. For example, the second material 11b can be used as a template so that the first material 11a grows in the crystal orientation of the second material 11b during the sintering process. For example, the first material 11a can be sintered based on the crystal orientation of the second material 11b. Therefore, the crystal orientations of the plurality of first materials 11a can be oriented in the same or substantially the same orientation. The second material 11b according to one aspect of the present disclosure can be oriented by referring to the following: Figure 2 and 4 The method for preparing seed crystal material is described.

[0094] The first electrode layer 12 and the second electrode layer 13 may be configured to face each other with the piezoelectric material composition 11 therebetween. For example, the first electrode layer 12 may be configured at the first surface (or lower surface) of the piezoelectric material composition 11, and the second electrode layer 13 may be configured at the second surface (or upper surface) of the piezoelectric material composition 11. The piezoelectric material composition 11 according to one aspect of the present disclosure may be used as a piezoelectric device 10 based on the first electrode layer 12 and the second electrode layer 13 configured at the first surface (or lower surface) and the second surface (or upper surface), respectively.

[0095] Figure 2 A method of manufacturing a piezoelectric device according to one aspect of the present disclosure is shown. Figure 1 A method of making a piezoelectric device including a piezoelectric material composition according to one aspect of the present disclosure.

[0096] refer to Figure 2According to one aspect of the present disclosure, a method (S100) for manufacturing a piezoelectric device including a piezoelectric material composition may include preparing a seed material and a matrix material of the piezoelectric material composition (S110), mixing the matrix material and the seed material to prepare a slurry (S120), molding the slurry to prepare a molded element (S130), sintering the molded element to prepare a sintered material (S140), and forming an electrode in the sintered piezoelectric material composition (S150). The piezoelectric material composition may be represented by the following Formula 1.

[0097] [Formula 1]

[0098] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0099] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0100] First, in the step S110 of preparing the matrix material and seed material of the piezoelectric material composition, the matrix material can be obtained by removing BaTiO3 as a seed in Formula 1, and can be prepared by the method S10 for preparing the matrix material described below. For example, the seed material may have a composition of BaTiO3 and may have a size of 5 μm or more, but aspects of the present disclosure are not limited thereto. For example, based on the filtering method, the seed may have a value of 5 μm or less. The aspect ratio of the seed may be 5 to 40 or 10 to 15. The seed may be prepared by the method S20 for manufacturing the seed described below. For example, the seed material may be added to the piezoelectric material composition of Formula 1 at 7% by volume or less, but aspects of the present disclosure are not limited thereto. Therefore, the step S110 of preparing the matrix material and seed material of the piezoelectric material composition may be performed.

[0101] Subsequently, method 100 may include mixing the matrix material with the seed material to prepare a slurry S120. Mixing the matrix material with the seed material to prepare the slurry S120 may include preparing a slurry including the matrix material and mixing the seed material with the matrix material.

[0102] The step of preparing a slurry including a matrix material can add an appropriate amount of a dispersant and a solvent to the matrix material having the composition of Formula 1. For example, the solvent can include one or more of ethanol, methanol, isopropanol, methyl ethyl ketone (MEK), toluene and distilled water, but aspects of the present disclosure are not limited thereto. By adding an appropriate amount of a dispersant and a solvent to the matrix material, a slurry in which the matrix material is well dispersed in the solvent can be prepared. According to one aspect of the present disclosure, the dispersant can reduce the viscosity of the slurry including the matrix material and can be used to disperse the first material 11a and the second material 11b in the solvent. For example, the step of preparing the slurry can be prepared by performing four grinding steps, but aspects of the present disclosure are not limited to the number of grinding steps.

[0103] For example, a slurry grinding can be performed by adding an appropriate amount of solvent and dispersant to the prepared matrix material slurry. The primary slurry grinding can be ball milling. For example, the primary slurry grinding can be performed in the range of 100rpm to 150rpm for 24 hours to 72 hours, but aspects of the present disclosure are not limited thereto. For example, the primary slurry grinding can be performed in the range of 100rpm to 150rpm for 12 hours to 16 hours, but aspects of the present disclosure are not limited thereto. For example, the primary slurry grinding can be wet grinding. For example, the primary slurry grinding can be performed after the matrix powder, solvent and dispersant are placed in a Nalgene bottle such as nylon or high-density polyethylene (HDPE) together with a ZrO2 ball (e.g., YSZ ball), and then in the range of 100rpm to 150rpm for 24 hours to 72 hours, but aspects of the present disclosure are not limited thereto.

[0104] For example, after the primary slurry grinding, a secondary slurry grinding can be performed by further adding an appropriate amount of a binder and a plasticizer. The secondary slurry grinding can be ball milling. For example, the secondary slurry grinding can be performed in the range of 100 rpm to 150 rpm for 6 hours to 24 hours. For example, the secondary slurry grinding can be wet grinding. For example, after the binder and the plasticizer are added to the primary slurry grinding, the secondary slurry grinding can be performed in the range of 100 rpm to 150 rpm for 6 hours to 25 hours together with ZrO2 balls (e.g., YSZ balls), but aspects of the present disclosure are not limited thereto.

[0105] The binder (or adhesive or adhesive) can provide stiffness, flexibility, ductility, durability, toughness, and smoothness to the molded element (or green tape). The binder may include at least one of polyvinyl butyral (PVB) resin, polyvinyl alcohol (PVA), and polyethylene glycol (PEG), but aspects of the present disclosure are not limited thereto, and binders in the field of piezoelectric material compositions may be used.

[0106] A plasticizer may be added to provide elasticity and plasticity to the molded element. The plasticizer may include at least one of phthalate plasticizers, adipate plasticizers, phosphate plasticizers, polyether plasticizers, and polyester plasticizers, and may be a plasticizer material in the field of piezoelectric material compositions.

[0107] The step of mixing the seed material with the matrix material may be mixing the seed material with the slurry including the matrix material prepared in the previous step and may be performed by three slurry millings and four slurry millings. For example, three slurry millings may be performed at a low speed of 20 rpm to 30 rpm for 3 to 6 hours without balls, but aspects of the present disclosure are not limited thereto. For example, the milling process may be performed for a short time at a speed lower than that of the first slurry milling and the second slurry milling. For example, three slurry millings may be performed at a speed of 20 rpm to 30 rpm for 3 to 6 hours by adding the seed after removing the ZrO2 balls, but aspects of the present disclosure are not limited thereto.

[0108] For example, four slurry millings can be performed after three slurry millings. Four slurry millings can be performed by performing three planetary millings for 10 minutes in the range of 500 rpm to 2,000 rpm, but aspects of the present disclosure are not limited thereto. For example, four slurry millings can evenly distribute BT seed materials (e.g., BT seed (BaTiO3)). Therefore, the method for manufacturing a piezoelectric material composition according to one aspect of the present disclosure can mix the seed material with the matrix material to evenly distribute it.

[0109] One aspect of the present disclosure may further include an aging step and a degassing step to remove bubbles and gas after the four slurry millings.

[0110] The degassing step may be to adjust the slurry to have an appropriate viscosity for the molding process and remove bubbles remaining in the slurry in the following step of molding the piezoelectric material. For example, the degassing step may be adjusted to have a viscosity of 1,000 cPs to 3,000 cPs (centipoise) by a vacuum agitator at room temperature, but aspects of the present disclosure are not limited thereto. For example, the degassing step may be adjusted to have a viscosity of 1,700 cPs to 2,400 cPs, or 2,000 cPs (centipoise) by a vacuum agitator at room temperature, but aspects of the present disclosure are not limited thereto. Therefore, bubbles in the slurry can be removed, and the viscosity can be adjusted by evaporating the solvent.

[0111] The aging step can be used to adjust the temperature to room temperature again because the slurry is cooled when the solvent evaporates in the degassing step. For example, in the aging step, stirring can be performed for a short time at a low speed of about 10 rpm by a stirrer, but aspects of the present disclosure are not limited thereto. Thus, the piezoelectric material can be provided in the form of a slurry.

[0112] Subsequently, step S130 of molding (or press-molding) the slurry to prepare a molded element may include manufacturing a molded element having a certain volume and shape by mixing the slurry (or piezoelectric material) in which the matrix material and the seed material prepared in step S120 are mixed with each other.

[0113] For example, the step of molding the slurry (or piezoelectric material) to prepare a molded element may include casting the piezoelectric material, primary molding the cast piezoelectric material, and secondary molding the primary molded piezoelectric material.

[0114] The casting step can be performed by casting a slurry of the matrix material and seed material prepared in the previous step using a casting device (or doctor blade). For example, when casting at temperatures above 90°C, the rapid evaporation rate of the solvent may cause the produced sheet to crack or develop defects such as voids. Therefore, the temperature conditions in each zone of the casting device can be between 30°C and less than 90°C.

[0115] The cast piezoelectric materials (or sheets) can be stacked (or laminated) and then can be heated at 55°C to 75°C with 2,500 psi / cm 2 Up to 4,000 psi / cm 2 The pressure of 3,000 psi / cm2 can be applied to the laminate for 10 to 30 minutes, but aspects of the present disclosure are not limited thereto. For example, the cast piezoelectric material (or sheet) can be stacked and then pressed at 60°C with 3,000 psi / cm2. 2 The mixture was pressed at a pressure of 1000 rpm for 10 minutes, but aspects of the present disclosure are not limited thereto.

[0116] The step of forming the cast piezoelectric material once can be performed by warm isostatic pressing (WIP), and the step of forming the cast piezoelectric material twice can be performed by cold isostatic pressing (CIP), and can be used to increase the density of the sintered material in the following sintering step. In addition, in the piezoelectric material composition according to one aspect of the present disclosure, WIP can be performed in the case of preparing a formed element based on stacking and lamination (such as casting). For example, by WIP, the stacked piezoelectric material can be formed at 60°C with 3,000 psi / cm 2 The above pressure was maintained and pressed for 10 minutes, but aspects of the present disclosure are not limited thereto.

[0117] The step ( S130 ) of molding the piezoelectric material may further include a degreasing step after the primary molding. The degreasing step may be to remove solvents or organic materials. The degreasing step may include holding the molded component in a furnace at a temperature range of 250° C. to 600° C. for 24 to 72 hours, and then cooling the molded component to room temperature, but aspects of the present disclosure are not limited thereto. For example, in the degreasing step, the furnace temperature and holding time may be adjusted based on the types of dispersants, binders, and plasticizers used therein.

[0118] The step S130 of molding the piezoelectric material may include performing secondary molding after the degreasing step. For example, the secondary molding step may be performed by CIP. For example, the secondary molding step may be performed at room temperature, and the piezoelectric material may be maintained at 28,000 psi to 30,000 psi for 8 minutes to 12 minutes, but aspects of the present disclosure are not limited thereto. For example, the secondary molding step may be performed at room temperature, and the piezoelectric material may be maintained at 29,000 psi for 10 minutes, but aspects of the present disclosure are not limited thereto.

[0119] Subsequently, step ( S140 ) of sintering the molded element to prepare a sintered material may be performed within a temperature range, followed by cooling. For example, the sintering temperature may be in the range of 950°C to 1,250°C, but aspects of the present disclosure are not limited thereto. For example, when the molded body is subjected to low-temperature sintering, the low-temperature sintering may be performed at 900°C to 930°C or 700°C to 800°C. For example, the sintering hold time may be 2 hours to 8 hours, but aspects of the present disclosure are not limited thereto.

[0120] Subsequently, step S150 of forming an electrode in the sintered material can form an electrode on the first surface of the piezoelectric material sintered material prepared in the previous step and on the second surface of the piezoelectric material sintered material opposite to the first surface. For example, the second surface may be different from the first surface, or may be opposite to the first surface. For example, the electrode may include a metal, for example, it may be formed by coating a metal (e.g., Ag), but aspects of the present disclosure are not limited thereto, and the electrode may be used without being limited to a general electrode. For example, an electrode may be formed in the sintered material, the temperature may be increased at a heating rate of 5°C / min, the electrode may be maintained at 600°C for 10 minutes, then may be naturally cooled at room temperature, and an electric field of 3kV / mm may be applied at a temperature of 20°C to 40°C for about 20 minutes, thereby performing a polarization (or poling) process on the electrode, but aspects of the present disclosure are not limited thereto.

[0121] According to one aspect of the present disclosure, a method of manufacturing a piezoelectric material composition can significantly reduce the time and cost of manufacturing a piezoelectric device, thereby significantly improving the productivity of the piezoelectric device.

[0122] According to one aspect of the present disclosure, productivity can be improved, and thus optimization of the manufacturing process can be achieved.

[0123] Figure 3 A method for manufacturing a matrix material of a piezoelectric material composition according to one aspect of the present disclosure is shown. Figure 2 A method for fabricating the matrix material is described.

[0124] refer to Figure 3 , the method for manufacturing a matrix material of a piezoelectric material composition according to one aspect of the present disclosure may include a step S11 of weighing the raw materials, a step S12 of mixing the weighed raw materials, a step S13 of calcining and synthesizing the mixed raw materials, and a step S14 of grinding the synthesized matrix material. Step S11 of weighing the raw materials may be performed independently of the manufacturing method, or may be omitted. For example, the method for manufacturing a matrix material according to one or more aspects of the present disclosure may start from mixing raw materials having Formula 2. In the following description, the conditions (e.g., temperature, pressure, and time) based on the method for manufacturing the piezoelectric material composition may not limit the details of the present disclosure.

[0125] First, the step S11 of weighing the raw materials may be to weigh the raw materials based on the molar ratio and add an appropriate amount of solvent.

[0126] The host material according to one aspect of the present disclosure can be represented by Formula 2 below.

[0127] [Formula 2]

[0128] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A

[0129] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.00.

[0130] According to one aspect of the present disclosure, the matrix material satisfying Formula 2 may be a compound including a (Pb, Zr, Ti)-(Pb, Ni, Nb) phase and referred to as PZT-PNN.

[0131] The raw materials of the matrix material satisfying Formula 2 may include lead oxide (PbO), nickel oxide (NiO), zirconium oxide (ZrO2), titanium oxide (TiO2), niobium oxide (Nb2O5) and copper oxide (CuO). However, aspects of the present disclosure are not limited thereto. For example, the raw materials may include materials containing corresponding positive ions (e.g., Pb 2+ 、Ni2+ 、Zr 4+ 、Ti 4+ and Cu 2+ ) oxide. For example, step S11 of weighing the raw materials may be a process of weighing the raw materials based on the molar ratio of the composition to be synthesized, placing the weighed raw materials into a nylon tank, and adding an appropriate amount of solvent (e.g., ethanol), but aspects of the present disclosure are not limited thereto. For example, a matrix material including a PZT-PNN composition according to one aspect of the present disclosure may be prepared by synthesizing a PZT composition powder and a PNN composition powder, mixing the PZT composition powder and the PNN composition powder, and calcining the mixed composition powder, but aspects of the present disclosure are not limited thereto.

[0132] The matrix material according to one aspect of the present disclosure may include CuO. For example, CuO may be added at 3 mol% or less. For example, CuO may be added at 1.0 mol%. Therefore, the piezoelectric material according to one aspect of the present disclosure may include CuO, thereby enabling low-temperature sintering and increasing the sinterability of the piezoelectric material. For example, the low-temperature sintering temperature may be 950°C, but aspects of the present disclosure are not limited thereto.

[0133] Subsequently, step S12 of mixing the raw materials can be mixing and grinding the weighed raw materials and solvent (ethanol) by ball milling. For example, the ball milling process can be performed at a speed of 100 rpm to 150 rpm for 12 to 36 hours, but aspects of the present disclosure are not limited thereto.

[0134] One aspect of the present disclosure may further include a drying step for separating the powder mixed with the solvent after the raw material mixing step ( S12 ). In this drying step, the ground matrix material may be placed in a tray and dried at 100° C., but the present disclosure is not limited thereto. For example, the drying may be performed for 3 hours, but the present disclosure is not limited thereto. Thus, ethanol mixed with the raw material can be removed.

[0135] Subsequently, one aspect of the present disclosure may include a step S13 of calcining the raw material. The step S13 of calcining the raw material may be a phase synthesis of the raw materials mixed once. The calcining step S13 may be to finely grind the dried compound with a mortar after the mixing is completed, put the ground compound into an alumina crucible, increase the temperature of the ground compound at a heating rate of 5°C / min in an electric furnace, calcine the compound at 750°C to 850°C for 3 to 6 hours, and cool or naturally cool the calcined compound at room temperature (or normal temperature). For example, the calcination temperature may be 700°C to 900°C, and the holding time may be 1 to 6 hours, but aspects of the present disclosure are not limited thereto. Therefore, in one aspect of the present disclosure, the carbonate of the raw material may be removed, and the raw material may react uniformly to form a uniform perovskite phase.

[0136] Subsequently, the step S14 of grinding the calcined matrix material may be to put the matrix material, YSZ balls, and a solvent (ethanol) into a Nalgene bottle and grind the matrix material by a ball milling process to form small particles, but aspects of the present disclosure are not limited thereto.

[0137] In addition, the grinding step may further include a drying step for separating the powder mixed with the solvent after the grinding step S14. Here, the drying step may place the ground matrix material in a tray and fully dry the ground matrix material at a temperature of 100° C. For example, the drying may be performed for 3 hours, but aspects of the present disclosure are not limited thereto.

[0138] In addition, according to one aspect of the present disclosure, the step S14 of grinding the synthesized matrix material may further include screening the material.

[0139] The sieving step may be filtering the dry powder finely ground by the mortar through a 40-mesh sieve to produce a powder including particles having a certain size or less. The size of the powder passing through the 40-mesh sieve may be 400 μm or less, but aspects of the present disclosure are not limited thereto.

[0140] Figure 4 A method for producing a seed material of a piezoelectric material composition according to one aspect of the present disclosure is shown. Figure 2 A method for manufacturing a seed material in a method for manufacturing a piezoelectric material composition is described.

[0141] refer to Figure 4, the method for manufacturing a seed material of a piezoelectric material composition according to one aspect of the present disclosure may include a step S21 of weighing the seed material once, a step S22 of preparing a primary seed, a step S23 of weighing twice, a step S24 of preparing a secondary seed, a step S25 of weighing three times, and a step S26 of preparing a tertiary seed. For example, the steps of preparing the primary seed and the secondary seed can be prepared by a molten salt method, and the step S26 of preparing the tertiary seed can be prepared by a topochemical method. For example, the molten salt method can be a process for manufacturing a powder of a specific nanostructure type, and can be a method of mixing a matrix composition with a raw material and a salt-based powder with a low melting point to perform a heat treatment at a high temperature. The salt-based powder can be melted at a high temperature to serve as a solvent, and the raw material can react in the molten solvent to form a powder having a nanostructure. For example, the molten raw material and solvent can be cooled in a molten state, and the salt can be removed by water after cooling. Therefore, a powder having a nanostructure with an intact morphology can be obtained.

[0142] First, the step S21 of weighing the seed material once can be a step of weighing the seed material once based on the molar ratio. Here, the composition to be synthesized can be Bi4Ti3O 12 .

[0143] For example, the step S21 of weighing the seed material once may be a step of weighing Bi2O3, TiO2, NaCl, and KCl based on the molar ratio of the composition to be synthesized and placing the weighed materials into a nylon jar. For example, in the weighing step S21, the ratio of NaCl to KCl may be 1:1, but aspects of the present disclosure are not limited thereto.

[0144] Subsequently, the step S22 of preparing a primary seed crystal may include the steps of mixing weighed materials and performing phase synthesis on the mixed materials.

[0145] For example, the mixing step may be a step of mixing and grinding the primary seed material for 12 hours by a ball milling process. In addition, the step of preparing the primary seed crystals S22 may further include a step of drying to remove water after the mixing and grinding is completed. Here, the drying step may place the primary mixed seed material in a tray and dry the mixed seed material at a temperature of 100° C. to 120° C., but aspects of the present disclosure are not limited thereto.

[0146] For example, the phase synthesis step may be a step of mixing and drying the primary seed materials, calcining the dried primary seed materials at 1,100°C for 6 hours, and cooling or naturally cooling the calcined primary seed materials at room temperature (or normal temperature), but aspects of the present disclosure are not limited thereto. For example, the cooled primary seed materials may be washed with deionized water (DI-water). At this time, the salt contained in the raw materials may be washed. Therefore, Bi4Ti3O having a plate shape may be manufactured according to the following chemical formula 1: 12 .

[0147] [Chemical Formula 1]

[0148] Bi2O3+3TiO2→Bi4Ti3O 12

[0149] Subsequently, the step S23 of weighing the seed material for the second time may be a step of weighing the secondary seed material based on the molar ratio. Here, the molar ratio of the composition to be synthesized in the secondary seed may be BaBi4Ti4O 15 .

[0150] For example, the step S23 of weighing the seed material twice can be based on the molar ratio of the composition to be synthesized (for example, Bi4Ti3O 12 、BaCO3、TiO2、BaC l2 or KCl) and placing the weighed primary material into a nylon jar.

[0151] Subsequently, the step of preparing the secondary seed crystals may include the steps of mixing the materials weighed in the previous step and performing phase synthesis on the mixed materials.

[0152] For example, the weighed material can be mixed with the solvent and mixed by stirring using a magnetic bar. In addition, the step S24 of preparing the secondary seed crystals may further include a step of drying after the mixing is completed. Here, the drying step may place the once mixed secondary seed crystal material in a tray and dry it at a temperature of 100° C. to 120° C., but aspects of the present disclosure are not limited thereto. For example, the drying may be performed for 3 hours while stirring, but aspects of the present disclosure are not limited thereto.

[0153] For example, the step of performing phase synthesis on the mixed material may be a step of mixing and drying the primary seed material, calcining the dried secondary seed material at 1,080°C for 1 hour, and cooling or naturally cooling the calcined primary seed material at room temperature (or normal temperature), but aspects of the present disclosure are not limited thereto. For example, the secondary seed material can be washed with deionized water. At this time, the salt contained in the raw material can be washed. Therefore, BaBi4Ti4O having a plate shape can be manufactured according to the following chemical formula 2: 15 .

[0154] [Chemical Formula 2]

[0155] Bi4Ti3O 12 +BaCO3+4TiO2→BaBi4Ti4O 15 +CO2

[0156] Subsequently, the tertiary weighing step S25 may be a step of placing the secondary seed powder and a material containing sodium (Na) to replace the bismuth (Bi) of the secondary seed powder and weighing the material based on the molar ratio of the composition. Here, the composition of the tertiary seed may be BaTiO3. Therefore, hereinafter, the tertiary seed may be referred to as a "BT seed."

[0157] For example, the three weighing steps S25 can be based on the molar ratio of the composition to be synthesized to weigh the secondary material (e.g., BaBi4Ti4O 15 , BaCO3, NaCl and KCl) are weighed and the weighed secondary materials are placed in a nylon jar.

[0158] Subsequently, the step S26 of preparing tertiary seed crystals may include the steps of mixing the materials weighed three times and performing a topological chemical reaction.

[0159] For example, the mixing step may be a process of putting ethanol into the material weighed three times, putting a magnetic bar into a beaker, and stirring at 80 rpm for 6 hours, but aspects of the present disclosure are not limited thereto.

[0160] In addition, the step of preparing the tertiary seed crystals may further include a step of drying the mixed secondary weighed materials. Here, the drying step may include placing the compound (or mixture) in a dish and drying the compound at a temperature of 80° C. to 100° C. for 3 to 6 hours, but aspects of the present disclosure are not limited thereto.

[0161] In addition, the temperature may be increased from room temperature to 950° C. at a heating rate of 10° C. / min and then maintained for 3 hours, and then the dried mixed powder may be naturally cooled, but aspects of the present disclosure are not limited thereto.

[0162] For example, the step of performing a topochemical reaction may be to place the dried tertiary seed material into a crucible and to perform the reaction at 950° C. for 3 hours, but aspects of the present disclosure are not limited thereto. By performing a topochemical reaction, the Bi contained in the secondary seed may be replaced by Na. Here, the step of performing a topochemical reaction may be referred to as a tertiary calcination. Step S26 of preparing the tertiary seed may further include a step of cleaning the tertiary seed after the topochemical reaction is completed.

[0163] For example, the step of washing the seed crystal three times may be to wash and filter the seed crystal three times with distilled water above 80° C. for two to ten times to remove sodium chloride (NaCl) impregnated on the BT seed crystal, but aspects of the present disclosure are not limited thereto. The residual ions NaCl may be removed by filtration. + and Cl - , and after filtering, it can be dried in an oven at 90° C. to 100° C. for 3 to 6 hours. Therefore, BaTiO 3 can be manufactured according to the following Chemical Formula 3. BaTiO 3 can have a plate shape.

[0164] [Chemical Formula 3]

[0165] BaBi4Ti4O 15 +BaCO3→2BaTiO3+2Bi2O3+CO2

[0166] In addition, in the method for preparing a seed material according to one aspect of the present disclosure, even after washing and filtering, multiple acid treatments with nitric acid may be performed to remove Bi remaining in the BT seed crystals. 3+ ions and Bi2O3, which can then be neutralized and washed with water after acid treatment. For example, nitric acid can be placed in a beaker, a BT seed crystal can be placed, and it can be shaken every 10 minutes. This can be repeated for 10 minutes to 2 hours, but aspects of the present disclosure are not limited thereto. For example, nitric acid can be used to treat the bismuth residual material two to three times for 20 minutes to ionize it, and then it can be filtered. For example, the ratio of sodium chloride (NaCl) to potassium chloride (KCl) can be 1:4 (molar), but aspects of the present disclosure are not limited thereto.

[0167] In addition, in order to remove some residual nitric acid and Bi 3+ Ions can be washed once or twice with distilled water, and then the residual ions Bi can be removed by filtration. 3+ After filtering, the mixture can be dried in an oven at 90°C to 100°C for 3 to 6 hours.

[0168] Therefore, BaTiO 3 having a plate shape according to one aspect of the present disclosure can be prepared.

[0169] Figure 5 Shown in preparation Figure 4 The grain changes that occur during the three seeding steps. Figure 5 in Figure 5 The left side shows a Bi2O2 (Bi2Ti3O 10 ) shows the crystal structure of the primary seed (Bi4Ti3O 12 ), and Figure 5 The central area shows the Bi2O2 (BaBi2Ti4O 13) shows that the secondary seed (BaBi4Ti4O 15 ).exist Figure 5 in Figure 5 The crystal structure having a composition of BaTiO 3 shown on the right side shows a tertiary seed and can be referred to as a BT seed.

[0170] refer to Figure 5 , with Bi2O2(Bi2Ti3O 10 The crystal structure of the primary seed crystal composed of Bi2O2 may be a structure in which a layer of Bi is arranged between Bi2O2 and a layer of Bi is arranged between TiO6 octahedrons. 13 The crystal structure of the secondary seed composed of Bi2O2 can be a structure in which layers of barium (Ba) and bismuth (Bi) are arranged between Bi2O2 and TiO6 octahedra. In addition, the crystal structure of the tertiary seed composed of BaTiO3 can be a structure in which TiO3 octahedra are centered and surrounded by barium (Ba).

[0171] For example, in the step of preparing tertiary seeds, the secondary seeds can be converted into tertiary seeds through a topological chemical reaction. Here, a topological chemical reaction can refer to a chemical reaction in which the orientation direction of the parent crystal grains and the orientation direction of the product crystal grains have different orientation directions but the shape of the crystal particles is maintained.

[0172] Therefore, if Figure 5 As shown, in the process of replacing the titanium (Ti) element of the secondary seed with the barium (Ba) element, the structure in which layers of Ba and Bi are arranged between Bi2O2 and TiO6 octahedra can be changed to a single structure having a BaTiO3 composition.

[0173] Figures 6A to 6C Scanning electron microscope (SEM) images are shown. Figure 5 Grain changes occur during the steps of preparing the tertiary seeds. Figure 6A Displays a seed crystal. Figure 6B Display secondary seeds, Figure 6C Three seedings are shown.

[0174] refer to Figures 6A to 6C , it can be seen that BaTiO 3 seeds with a plate structure are easily manufactured through the steps of preparing primary seeds, secondary seeds, and tertiary seeds.

[0175] Figure 7 is a graph showing an X-ray diffraction pattern relative to the CuO content of a piezoelectric material composition according to one aspect of the present disclosure. Figure 7 In the figure, the X-axis represents the 2θ (degree) value of X-ray diffraction, and the vertical axis represents the relative intensity.

[0176] The inventors of the present invention have measured the Figure 1 The X-ray diffraction pattern of the matrix material of the piezoelectric material composition described above is obtained by analyzing the X-ray diffraction pattern based on the content of copper oxide (CuO). Figure 1 The matrix material of the piezoelectric material composition described may be a matrix material excluding a seed crystal, and may be expressed as a non-TGG piezoelectric material composition. Non-TGG may be a process of random grain growth without a seed crystal. The composition of the non-TGG piezoelectric material composition may be aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%CuO. For example, the piezoelectric material composition according to one aspect of the present disclosure is configured to be 0.15≤a≤0.24, 0.29≤b≤0.38, and 0.30≤c≤0.35. For example, in the piezoelectric material composition according to one aspect of the present disclosure, the value of x (or the CuO content) is prepared to be 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0. For example, in the piezoelectric material composition according to one aspect of the present disclosure, the sintering temperature of each sample is prepared to be 950°C, and the sintering time is prepared to be 10 hours.

[0177] refer to Figure 7 In the non-TGG piezoelectric material composition according to one aspect of the present disclosure, when the CuO content (or the value of x in Formula 1) is 0.0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0, it can be confirmed that grain growth occurs in the (100) orientation and the (110) orientation.

[0178] In addition, when the CuO content (or the value of x in Formula 2) is 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0, respectively, it can be confirmed that the piezoelectric material composition has a pure perovskite structure, there is no change in the crystal structure due to the addition of CuO, and a very small amount of secondary phase is observed. Therefore, in one aspect of the present disclosure, it can be confirmed that the piezoelectric material composition is smoothly sintered at a low temperature of 950°C.

[0179] Figure 8 is a graph showing relative density (%), dielectric constant ε, and relative copper oxide (CuO) content of the piezoelectric material composition according to one aspect of the present disclosure. T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ In the picture. Figure 8 The composition of each sample based on the CuO content of the composition was determined by Figure 5The samples of non-TGG compositions were prepared in the same manner, and the values ​​of x were set to 0.0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0, respectively.

[0180] refer to Figure 8 , in samples having a CuO content of 0.0 and 0.5, respectively, the relative density (%) according to one aspect of the present disclosure was measured to be 77.6% and 92.2%. In all samples having a CuO content of 1.0, 1.5, 2.0, 2.5, and 3.0, respectively, the relative density (%) according to one aspect of the present disclosure represented a value of 99.4% to 99.7%. Therefore, it was confirmed that sintering proceeded smoothly at low temperatures with the addition of CuO, and when 1.0 mol % to 3.0 mol % of CuO was added, it was confirmed that sintering proceeded to a relative density close to 100%.

[0181] Dielectric constant ε T 33 / ε0 was measured to be 2069 in a sample having a CuO content of 0.0, and showed values ​​of 2867 to 3169 in samples having CuO contents of 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0, respectively. When the CuO contents were 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0, respectively, the dielectric constants were measured to be 2867, 2792, 2887, 3088, 3169, and 3140. Therefore, in one aspect of the present disclosure, it was confirmed that when CuO was added, the dielectric constant increased more than when CuO was not added.

[0182] The loss factor tan δ ranged from 0.02 to 0.05 for samples containing CuO contents of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0. While the dielectric constant slightly increased with the addition of CuO compared to the sample without CuO, the difference in dielectric constant was not significant. Furthermore, the loss factor tan δ showed similar values ​​for samples containing CuO contents of 1.0 to 2.5. Therefore, it was confirmed that the CuO content had little effect on the loss factor tan δ.

[0183] Piezoelectric charge constant d 33 The samples with CuO contents of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 exhibited values ​​ranging from 400 pC / N to 550 pC / N. 33The samples with CuO contents of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0 showed values ​​of 400 pC / N, 505 pC / N, 515 pC / N, 535 pC / N, 550 pC / N, 540 pC / N and 520 pC / N, respectively. Compared with the case of CuO content of 0.0, the piezoelectric charge constant d 33 Increase more. In the piezoelectric charge constant d 33 In terms of CuO content, the piezoelectric charge constant d 33 Therefore, in one aspect of the present disclosure, when the CuO content is 2.0, the piezoelectric charge constant d 33 The highest value was obtained, and therefore, it was confirmed that the piezoelectric characteristics were good.

[0184] The electromechanical coupling factor kρ showed values ​​ranging from 0.30 to 0.53 for samples with CuO contents of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0, respectively. The electromechanical coupling factor kρ showed values ​​of 0.30, 0.48, 0.55, 0.57, 0.57, 0.55, and 0.53 for samples with CuO contents of 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0, respectively. Compared to the case with a CuO content of 0.0, the electromechanical coupling factor kρ increased by approximately 0.18 for a CuO content of 0.5. It was confirmed that the electromechanical coupling factor kρ ranged from 0.53 to 0.57 for CuO contents of 1.0 to 3.0. The highest value of 0.57 for CuO contents of 1.5 and 2.0 was confirmed.

[0185] The inventors of the present invention have analyzed the relative density (%), loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ For example, according to one aspect of the present disclosure, it was confirmed that when the optimal condition of the CuO content was 1.0 to 2.0, the piezoelectric material had the best piezoelectric characteristics.

[0186] Figures 9A to 9D Shown are X-ray diffractometer (XRD) measurement values ​​of the seed content of a piezoelectric material composition according to one aspect of the present disclosure.

[0187] The inventors of the present invention have measured the Figure 1 The X-ray diffraction pattern of the change of y in Formula 1 of the piezoelectric material composition described above is analyzed based on the X-ray diffraction pattern of the seed content. Figure 1The piezoelectric material composition described may include a seed crystal and may be expressed as a TGG piezoelectric material composition. The composition of the TGG piezoelectric material composition may be aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%CuO+y volume%BaTiO3. For example, the piezoelectric material composition according to one aspect of the present disclosure is configured to be 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, and 0.00≤x≤3.00. For example, in Figures 9A to 9D In the equation, the value of y (or the content of BaTiO3) is set to 1. For example, in Figures 9A to 9D In the present invention, samples with sintering temperatures of 950° C., 1,050° C., 1,150° C., and 1,250° C. and a sintering time of 10 hours were prepared. Such experimental conditions do not limit the details of the present disclosure.

[0188] refer to Figures 9A to 9D , it was confirmed that the piezoelectric material composition was synthesized in a perovskite structure, and no secondary phase and unreacted phase were observed in all samples.

[0189] Table 1 below can be used as a reference Figures 9A to 9D Described is a table of Lotgering factors for samples sintered at temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C, respectively.

[0190] [Table 1]

[0191] <![CDATA[(Volume %) of BaTiO3]]> Sintering temperature Lotgering factor (%) 1 950℃ 12.7 1 1,050℃ 14.2 1 1,150℃ 27.5 1 1,250℃ 70.0

[0192] Referring to Table 1, the Lotgering factor based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure increases as the sintering temperature increases. For example, the Lotgering factor represents the degree of orientation of the sample, and when the Lotgering factor is 100%, it can be considered that the orientation is completely carried out. For example, the Lotgering factor L f(％) It can be expressed as the following mathematical formula 1.

[0193] [Mathematical formula 1]

[0194]

[0195] In Mathematical Formula 1, p may represent the degree of orientation calculated by Mathematical Formula 1, and p0 may represent the number of randomly oriented piezoelectric material compositions of the same or substantially the same composition. 00l The degree of orientation p can be calculated as the following mathematical formula 2.

[0196] [Mathematical formula 2]

[0197]

[0198] In mathematical formula 2, I (00l) It can represent the diffraction peaks (001) and (002) represented by (001), and I non-(00l) It can represent diffraction peaks such as (110), (111), (210) and (211) that are not represented by (001).

[0199] According to one aspect of the present disclosure, the Lotgering factors of samples having a BaTiO 3 content of 1 volume % of the entire piezoelectric material composition and sintering temperatures of 950° C., 1,050° C., 1,150° C., and 1,250° C. were measured to be 12.7%, 14.2%, 27.5%, and 70.0%, respectively.

[0200] According to one aspect of the present disclosure, it was confirmed that the Lotgering factor increased as the sintering temperature increased to 950°C, 1,050°C, 1,150°C, and 1,250°C under the condition that the BaTiO3 content was 1% by volume of the entire piezoelectric material composition. Therefore, the inventors confirmed that the degree of orientation of the sample was optimal when the sintering temperature was 1,250°C under the condition that the BaTiO3 content was 1% by volume of the entire piezoelectric material composition.

[0201] Figures 10A to 10D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0202] Figures 10A to 10D For analyzing X-ray diffraction patterns relative to seed content, and with Figures 9A to 9D The samples were prepared in the same way. Figures 10A to 10D , the value of y (or the content of BaTiO 3 ) is set to 3. Therefore, hereinafter, only the different elements will be described.

[0203] refer to Figures 10A to 10D , it was confirmed that the piezoelectric material composition was synthesized in a perovskite structure, and no secondary phase and unreacted phase were observed in all samples.

[0204] Table 2 below can be used as a reference Figures 10A to 10D Described is a table of Lotgering factors for samples sintered at temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C, respectively.

[0205] [Table 2]

[0206] <![CDATA[(Volume %) of BaTiO3]]> Sintering temperature Lotgering factor (%) 3 950℃ 36.6 3 1,050℃ 39.4 3 1,150℃ 63.5 3 1,250℃ 88.7

[0207] Referring to Table 2, the Lotgering factor based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure increases as the sintering temperature increases.

[0208] According to one aspect of the present disclosure, the Lotgering factors of samples having a BaTiO3 content of 3 volume % of the entire piezoelectric material composition and sintering temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C were measured to be 36.6%, 39.4%, 63.5%, and 88.7%, respectively.

[0209] According to one aspect of the present disclosure, it was confirmed that the Lotgering factor increased as the sintering temperature increased to 950°C, 1,050°C, 1,150°C, and 1,250°C under the condition that the BaTiO3 content was 3% by volume of the entire piezoelectric material composition. Therefore, the inventors confirmed that the degree of orientation of the sample was optimal when the sintering temperature was 1,250°C under the condition that the BaTiO3 content was 3% by volume of the entire piezoelectric material composition.

[0210] Figures 11A to 11D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0211] Figures 11A to 11D For analyzing X-ray diffraction patterns relative to seed content, and with Figures 9A to 9D The samples were prepared in the same way. Figures 11A to 11D , the value of y (or the content of BaTiO 3 ) is set to 5. Therefore, hereinafter, only the different elements will be described.

[0212] refer to Figures 11A to 11D , it was confirmed that the piezoelectric material composition was synthesized in a perovskite structure, and no secondary phase and unreacted phase were observed in all samples.

[0213] Table 3 below can be used as a reference Figures 11A to 11D Described is a table of Lotgering factors for samples sintered at temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C, respectively.

[0214] [Table 3]

[0215] <![CDATA[(Volume %) of BaTiO3]]> Sintering temperature Lotgering factor (%) 5 950℃ 44.0 5 1,050℃ 38.0 5 1,150℃ 66.5 5 1,250℃ 91.0

[0216] Referring to Table 3, the Lotgering factor based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure slightly decreases as the sintering temperature increases from 950°C to 1,050°C, but increases again as the sintering temperature increases to 1,150°C and 1,250°C.

[0217] According to one aspect of the present disclosure, the Lotgering factors of samples having a BaTiO 3 content of 5 volume % of the entire piezoelectric material composition and sintering temperatures of 950° C., 1,050° C., 1,150° C., and 1,250° C. were measured to be 44.0%, 38.0%, 66.5%, and 91.0%, respectively.

[0218] According to one aspect of the present disclosure, it was confirmed that the Lotgering factor slightly decreased as the sintering temperature increased to 950°C, 1,050°C, 1,150°C, and 1,250°C under the condition that the BaTiO3 content was 5% by volume of the entire piezoelectric material composition. Therefore, the inventors confirmed that the degree of orientation of the sample was optimal when the sintering temperature was 1,250°C under the condition that the BaTiO3 content was 5% by volume of the entire piezoelectric material composition.

[0219] Figures 12A to 12D Shown are XRD measurements of seed content of a piezoelectric material composition according to another aspect of the present disclosure.

[0220] Figures 12A to 12D For analyzing X-ray diffraction patterns relative to seed content, and with Figures 9A to 9D The samples were prepared in the same way. Figures 12A to 12D , the value of y (or the content of BaTiO 3 ) is set to 7. Therefore, hereinafter, only the different elements will be described.

[0221] refer to Figures 12A to 12D , it was confirmed that the piezoelectric material composition was synthesized in a perovskite structure, and no secondary phase and unreacted phase were observed in all samples.

[0222] Table 4 below can be used as a reference Figures 12A to 12D Described is a table of Lotgering factors for samples sintered at temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C, respectively.

[0223] [Table 4]

[0224] <![CDATA[(Volume %) of BaTiO3]]> Sintering temperature Lotgering factor (%) 7 950℃ 53.2 7 1,050℃ 49.2 7 1,150℃ 79.3 7 1,250℃ 91.5

[0225] Referring to Table 4, the Lotgering factor based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure slightly decreases as the sintering temperature increases from 950°C to 1,050°C, but increases again as the sintering temperature increases to 1,150°C and 1,250°C.

[0226] According to one aspect of the present disclosure, the Lotgering factors of samples having a BaTiO3 content of 7 volume % of the entire piezoelectric material composition and sintering temperatures of 950°C, 1,050°C, 1,150°C, and 1,250°C were measured to be 53.2%, 49.2%, 79.3%, and 91.5%, respectively.

[0227] According to one aspect of the present disclosure, it was confirmed that the Lotgering factor slightly decreased as the sintering temperature increased to 950°C, 1,050°C, 1,150°C, and 1,250°C under the condition that the BaTiO3 content was 7% by volume of the entire piezoelectric material composition. Therefore, the inventors confirmed that the degree of orientation of the sample was optimal when the sintering temperature was 1,250°C under the condition that the BaTiO3 content was 7% by volume of the entire piezoelectric material composition.

[0228] Figure 13 The Lotgering factor with respect to the BaTiO 3 content and the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure is shown.

[0229] Figure 13 The Lotgering factor used to analyze the BaTiO3 content and sintering temperature of the piezoelectric material composition is used to analyze the BaTiO3 content and sintering temperature of the piezoelectric material composition. Figures 9A to 9D The samples were prepared in the same manner, and the value of y (or the content of BaTiO3) was set to 1 volume %, 3 volume %, 5 volume % and 7 volume % of the entire piezoelectric material composition. Figure 13 In the figure, the dotted line indicates that the value of y (or the content of BaTiO3) is 1 volume%, the single-dotted line indicates that the value of y (or the content of BaTiO3) is 3 volume%, the double-dotted line indicates that the value of y (or the content of BaTiO3) is 5 volume%, and the thin solid line indicates that the value of y (or the content of BaTiO3) is 7 volume%.

[0230] refer to Figure 13 The Lotgering factor of the piezoelectric material composition according to one aspect of the present disclosure, which is based on the sintering temperature, increased with increasing sintering temperature. When the sintering temperature was 1,250°C, it was confirmed that all samples exhibited a Lotgering factor of 70% or more. Furthermore, according to one aspect of the present disclosure, it was confirmed that the Lotgering factor increased with increasing y (or BaTiO3 content).

[0231] Figure 14 is a graph showing relative density (%), dielectric constant ε, and relative sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure. T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor kρ Picture.

[0232] Figure 14 For analyzing the relative density (%), dielectric constant ε relative to the BaTiO3 content and sintering temperature of the piezoelectric material composition T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ , and prepared Figures 9A to 9D The sintering temperatures were set to 950°C, 1,000°C, 1,050°C, 1,100°C, 1,150°C, 1,200°C, and 1,250°C, and the values ​​of y (or the content of BaTiO3) were set to 1%, 3%, 5%, and 7% by volume of the entire piezoelectric material composition. Figure 14 In the figure, the horizontal axis represents the sintering temperature, the dotted line represents the value of y (or the content of BaTiO3) is 1 volume%, the single-dotted line represents the value of y (or the content of BaTiO3) is 3 volume%, the double-dotted line represents the value of y (or the content of BaTiO3) is 5 volume%, and the thin solid line represents the value of y (or the content of BaTiO3) is 7 volume%.

[0233] refer to Figure 14 , the relative density (%) based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure indicated a value of 90% or more in all samples. The relative density in all samples indicated a value of 95% or more at 950°C to 1,150°C, and indicated a value of 90% to less than 95% at 1,150°C to 1,250°C. Therefore, in one aspect of the present disclosure, it was confirmed that with the addition of BaTiO3, sintering with a relative density of 95% or more was performed at a low temperature of 950°C to 1,150°C. Therefore, in the piezoelectric material composition according to one aspect of the present disclosure, it was confirmed that with the addition of BaTiO3, sintering was smoothly performed at a low temperature of 950°C to 1,150°C.

[0234] Dielectric constant ε based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure T 33 / ε0 had values ​​ranging from 2,700 to 4,000 for all samples. The dielectric constants of all samples had similar values ​​ranging from 2,800 to 3,000 at sintering temperatures between 950°C and 1,200°C. The sample containing 1% by volume of BaTiO3 in the piezoelectric material composition had a value of approximately 3,500 at a sintering temperature of 1,250°C, but decreased again at temperatures above 1,250°C.

[0235] In all samples, it was confirmed that the loss factor tan δ based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure increased as the sintering temperature increased, and then the loss factor decreased. The loss factor value was 0.01 to 0.04.

[0236] In the piezoelectric material composition according to one aspect of the present disclosure, the piezoelectric charge constant d based on the sintering temperature of the piezoelectric material composition is 33 The piezoelectric constant increases with increasing sintering temperature and then decreases at a temperature of 1,250°C. In samples containing 1% and 3% BaTiO3 by volume of the entire piezoelectric material composition, the piezoelectric constant increases from 405 pC / N to 790 pC / N as the sintering temperature increases to 950°C to 1,250°C, and the piezoelectric constant decreases at temperatures exceeding 1,250°C. In samples containing 5% and 7% BaTiO3 by volume of the entire piezoelectric material composition, the piezoelectric constant increases as the sintering temperature increases to 950°C to 1,200°C, and the piezoelectric constant value decreases at temperatures above 1,250°C. The piezoelectric constants of each sample were measured to have values ​​ranging from 400 pC / N to 790 pC / N at sintering temperatures of 950°C to 1,250°C. Therefore, in the piezoelectric material composition according to one aspect of the present disclosure, it was confirmed that the piezoelectric characteristics are enhanced with the addition of BaTiO3 seed crystals.

[0237] The electromechanical coupling factor kρ based on the sintering temperature of the piezoelectric material composition according to one aspect of the present disclosure has a value of 0.41 to 0.62.

[0238] In the piezoelectric material composition according to one aspect of the present disclosure, the relative density (%), the dielectric constant ε T 33 / ε0, loss factor tanδ, piezoelectric charge constant d 33 and electromechanical coupling factor k ρ All samples having values ​​of y (or the content of BaTiO 3 ) of 1 vol %, 3 vol %, 5 vol %, and 7 vol % of the entire piezoelectric material composition had similar characteristics.

[0239] Figure 15 A car sound device according to one aspect of the present disclosure is shown.

[0240] refer to Figure 15 The vehicle sound device according to one aspect of the present disclosure may include a sound device 500. The sound device 500 may be provided or equipped in a vehicle to output a sound S to an interior space IS of the vehicle 800.

[0241] The vehicle 800 may include an interior material (or interior decoration material) 850. In the following description, for convenience of description, the "interior material 850" may be referred to as the "vehicle interior material 850."

[0242] The vehicle interior material 850 may include all components configuring the interior of the vehicle 800, or may include all components provided at the interior space IS of the vehicle 800. For example, the vehicle interior material 850 may be an interior member or interior decoration member of the vehicle 800, but aspects of the present disclosure are not limited thereto.

[0243] The vehicle interior material 850 according to one aspect of the present disclosure may be configured to be exposed at or in the interior or indoor space IS of the vehicle 800. For example, the vehicle interior material 850 may be provided to cover one surface (or inner surface) of at least one of a main frame (or vehicle body), a side frame (or side body), a door frame (or door body), a handle frame (or steering wheel hub), and a seat frame exposed at the interior space IS of the vehicle 800.

[0244] The vehicle interior materials 850 according to one aspect of the present disclosure may include an instrument panel, pillar interior materials (or pillar trims), floor interior materials (or floor carpets), roof interior materials (or roof linings), door interior materials (or door trims), handle interior materials (or steering covers), seat interior materials, rear wrap interior materials (or rear seat shelves), overhead consoles (or interior lighting interior materials), rearview mirrors, glove boxes, and sun visors, but aspects of the present disclosure are not limited thereto.

[0245] According to one aspect of the present disclosure, the vehicle interior material 850 may include one or more of metal, wood, rubber, plastic, glass, fiber, cloth, paper, mirror, leather, and carbon, but the aspects of the present disclosure are not limited thereto. The vehicle interior material 850 including a plastic material may be an injection molded material obtained by an injection molding process using a thermosetting resin or a thermoplastic resin, but the aspects of the present disclosure are not limited thereto. The vehicle interior material 850 including a fiber material may include one or more of synthetic fiber, carbon fiber (or aramid fiber), and natural fiber, but the aspects of the present disclosure are not limited thereto. The vehicle interior material 850 including a fiber material may be a fabric sheet, a knitted sheet, or a non-woven fabric, but the aspects of the present disclosure are not limited thereto. For example, the interior material 20c or the outer surface member including a fiber material may be a fabric member, but the aspects of the present disclosure are not limited thereto. For example, the paper may be cone paper. For example, the cone paper may be pulp or foam plastic, but the aspects of the present disclosure are not limited thereto. The vehicle interior material 850 including a leather material may be natural leather or artificial leather, but the aspects of the present disclosure are not limited thereto.

[0246] The vehicle interior material 850 according to one aspect of the present disclosure may include one or more of a flat portion and a curved portion. For example, the vehicle interior material 850 may have a structure corresponding to that of a corresponding vehicle structural material, or may have a structure different from that of a corresponding vehicle structural material.

[0247] According to one aspect of the present disclosure, the sound device 500 may be provided at the vehicle interior material 850. The sound device 500 may vibrate the vehicle interior material 850 to generate the sound S based on the vibration of the vehicle interior material 850. For example, the sound device 500 may directly vibrate the vehicle interior material 850 to generate the sound S based on the vibration of the vehicle interior material 850.

[0248] For example, the sound device 500 may be configured with the Figures 1 to 14 One of the piezoelectric devices of one or more aspects of the present disclosure is described.

[0249] For example, the sound device 500 can be configured to vibrate the vehicle interior material 850 to output sound S to the interior or indoor space IS of the vehicle 800. Thus, the vehicle interior material 850 can function as a sound vibration plate. The vehicle interior material 850 can be a vibration plate, a sound vibration plate, or a sound generating plate for outputting sound S. For example, the size of the vehicle interior material 850 can be larger than that of the sound device 500, but aspects of the present disclosure are not limited thereto.

[0250] For example, the sound device 500 can be set in one or more of the dashboard, pillar interior material, floor interior material, roof interior material, door interior material, handle interior material and seat interior material, or can be set in one or more of the rear package interior material, overhead console, rearview mirror, glove box and sun visor.

[0251] The sound device 500 according to one aspect of the present disclosure can vibrate the corresponding vehicle interior material 850 by at least one of the one or more sound devices 500 set at the vehicle interior material 850 to output real sound S including multi-channels and / or stereo sound to the interior space IS of the vehicle 800.

[0252] Figure 16 is a perspective view of a display device according to one aspect of the present disclosure. Figure 17 According to one aspect of the present disclosure Figure 16 A cross-sectional view taken along line II' in FIG.

[0253] refer to Figure 16 and Figure 17 , an apparatus according to one aspect of the present disclosure may include a vibration member 100 and a piezoelectric device 200 .

[0254] The vibration member 100 may be configured to display an image. The piezoelectric device 200 may be provided at a rear surface (or back surface) of the vibration member 100. For example, the piezoelectric device 200 may be configured to vibrate the vibration member 100.

[0255] For example, the vibration member 100 may output sound based on vibration of the piezoelectric device 200. For example, the vibration member 100 may be a vibration object, a display panel, a vibration plate, or a front member, but aspects of the present disclosure are not limited thereto.

[0256] For example, the vibration member 100 or the vibration object may include one or more of the following: a display panel including pixels configured to display an image, a screen panel that projects an image from a display device, a lighting panel, a signage panel, a vehicle interior material, a vehicle glass window (or a vehicle window), a vehicle exterior material, a building ceiling material, a building interior material, a building glass window (or a building window), an aircraft interior material, an aircraft glass window (or an aircraft window), wood, plastic, glass, metal, cloth, fiber, paper, rubber, leather, and a mirror, but aspects of the present disclosure are not limited thereto.

[0257] In the following description, it will be described that the vibration member 100 is the display panel 100 .

[0258] The display panel 100 may display electronic images, digital images, still images, or video images. For example, the display panel 100 may output light to display an image. The display panel 100 may be a curved display panel, or may be any type of display panel, such as a liquid crystal display panel, an organic light-emitting display panel, a quantum dot light-emitting display panel, a micro-light-emitting diode display panel, and an electrophoretic display panel. The display panel 100 may be a flexible display panel. For example, the display panel 100 may be a flexible light-emitting display panel, a flexible electrophoretic display panel, a flexible electrowetting display panel, a flexible micro-light-emitting diode display panel, or a flexible quantum dot light-emitting display panel, but aspects of the present disclosure are not limited thereto.

[0259] The display panel 100 according to one aspect of the present disclosure may include a display area AA (or active area) configured to display an image according to driving of a plurality of pixels. In addition, the display panel 100 may further include a non-display area IA surrounding the display area AA, but aspects of the present disclosure are not limited thereto.

[0260] The piezoelectric device 200 may vibrate the display panel 100 at the rear surface of the display panel 100, thereby providing sound and / or tactile feedback to the user (or viewer) based on the vibration of the display panel 100. The piezoelectric device 200 may be implemented at the rear surface of the display panel 100 to directly vibrate the display panel 100.

[0261] As one aspect of the present disclosure, the piezoelectric device 200 may vibrate according to a voice signal synchronized with an image displayed by the display panel 100 to vibrate the display panel 100. As another aspect of the present disclosure, the piezoelectric device 200 may be provided at the display panel 100, or may vibrate according to a tactile feedback signal (or tactile feedback signal) synchronized with a user's touch applied to a touch panel (or touch sensor layer) embedded in the display panel 100 to vibrate the display panel 100. Thus, the display panel 100 may vibrate based on the vibration of the piezoelectric device 200 to provide at least one of sound and tactile feedback to the user (or viewer).

[0262] The piezoelectric device 200 according to one aspect of the present disclosure can be implemented to have a size corresponding to the display area AA of the display panel 100. The size of the piezoelectric device 200 can be 0.9 to 1.1 times the size of the display area AA, but aspects of the present disclosure are not limited thereto. For example, the size of the piezoelectric device 200 can be the same as or smaller than the size of the display area AA. For example, the size of the piezoelectric device 200 can be the same or approximately the same as the display area AA of the display panel 100, so that the piezoelectric device 200 can cover most of the area of ​​the display panel 100, and the vibration generated by the piezoelectric device 200 can vibrate the entire area of ​​the display panel 100, so that the localization of the sound can be high and the user's satisfaction can be improved. In addition, the contact area (or panel coverage) between the display panel 100 and the piezoelectric device 200 can be increased, so that the vibration area of ​​the display panel 100 can be increased, thereby improving the sound of the mid- and low-pitched vocal cords generated based on the vibration of the display panel 100. Furthermore, the piezoelectric device 200 applied to a large-sized display device can vibrate the entire display panel 100 having a large size (or large area), thereby further enhancing the localization of the sound based on the vibration of the display panel 100, thereby achieving an improved sound effect. Therefore, the piezoelectric device 200 according to one aspect of the present disclosure can be provided at the rear surface of the display panel 100 to fully vibrate the display panel 100 in the vertical (or front-to-back) direction, thereby outputting the desired sound to the front area in front of the device or display device.

[0263] The piezoelectric device 200 according to one aspect of the present disclosure may be implemented as a membrane type. Since the piezoelectric device 200 may be implemented as a membrane type, it may have a thickness thinner than the display panel 100, and therefore, the thickness of the display device due to the arrangement of the piezoelectric device 200 may be minimized. For example, the piezoelectric device 200 may use the display panel 100 as a sound vibration plate. For example, the piezoelectric device 200 may be referred to as a sound generating module, a vibration generating device, a membrane actuator, a membrane-type piezoelectric composite actuator, a membrane speaker, a membrane-type piezoelectric speaker, or a membrane-type piezoelectric composite speaker using the display panel 100 as a vibration plate, but aspects of the present disclosure are not limited thereto. As another aspect of the present disclosure, the piezoelectric device 200 may not be provided at the rear surface of the display panel 100, but may be applied to a vibrating object instead of the display panel. For example, the vibrating object can be one or more of a non-display panel, wood, metal, plastic, glass, cloth, paper, mirror, fiber, rubber, leather, vehicle interior material, vehicle glass window (or car window), building interior ceiling, building glass window (or building window), building interior material, aircraft interior material and aircraft glass window (or aircraft window), etc., but aspects of the present disclosure are not limited thereto. For example, the non-display panel can be a light-emitting diode lighting panel (or device), an organic light-emitting lighting panel (or device) or an inorganic light-emitting lighting panel (or device), etc., but aspects of the present disclosure are not limited thereto. In this case, the vibrating object can be used as a vibration plate, and the piezoelectric device 200 can vibrate the vibrating object to output sound.

[0264] The piezoelectric device 200 according to one aspect of the present disclosure may further include a vibration structure 230 , and a connection member 210 disposed between the vibration structure 230 and the display panel 100 .

[0265] According to one aspect of the present disclosure, the connection member 210 may include at least one substrate, and may include an adhesive layer attached to one surface or both surfaces of the substrate, or may be configured as a single adhesive layer.

[0266] For example, the connection member 210 may include a foam pad, a double-sided foam pad, a double-sided tape, a double-sided foam tape, a double-sided adhesive, or an adhesive, but aspects of the present disclosure are not limited thereto. For example, the adhesive layer of the connection member 210 may include epoxy, acrylic, silicone, or polyurethane, but aspects of the present disclosure are not limited thereto.

[0267] The display panel 100 according to one aspect of the present disclosure may further include a support member 300 disposed at a rear surface of the display panel 100 .

[0268] The support member 300 may cover the rear surface of the display panel 100. For example, the support member 300 may cover the entire rear surface of the display panel 100 with a gap space GS therebetween. For example, the support member 300 may include at least one of a glass material, a metal material, and a plastic material. For example, the support member 300 may be a rear structure or a complete structure. For example, the support member 300 may be a cover bottom, a plate bottom, a back cover, a base frame, a metal frame, a metal chassis, a chassis base, or an m chassis, etc., but aspects of the present disclosure are not limited thereto. Therefore, the support member 300 may be implemented as any type of frame or plate-like structure provided at the rear surface of the display panel 100.

[0269] The apparatus according to one aspect of the present disclosure may further include a middle frame 400 .

[0270] The middle frame 400 may be disposed between the rear periphery of the display panel 100 and the front periphery of the support member 300. The middle frame 400 may support at least one of the rear periphery of the display panel 100 and the front periphery of the support member 300, respectively, and may surround one or more side surfaces of each of the display panel 100 and the support member 300. The middle frame 400 may define a gap space GS between the display panel 100 and the support member 300. The middle frame 400 may be referred to as an middle chassis, middle cover, middle chassis, etc., but aspects of the present disclosure are not limited thereto.

[0271] The middle frame 400 according to one aspect of the present disclosure may include a first supporting portion 410 and a second supporting portion 430 .

[0272] The first supporting portion 410 may be disposed between the rear periphery of the display panel 100 and the front periphery of the supporting member 300, and thus a gap space GS may be configured between the display panel 100 and the supporting member 300. The front surface of the first supporting portion 410 may be coupled or connected to the rear periphery of the display panel 100 via the first frame connecting member 401. The rear surface of the first supporting portion 410 may be coupled or connected to the front periphery of the supporting member 300 via the second frame connecting member 403. For example, the first supporting portion 710 may have a single picture frame structure having a square shape or a frame structure having a plurality of divided strips, but aspects of the present disclosure are not limited thereto.

[0273] The second supporting portion 430 may be vertically coupled to the outer surface of the first supporting portion 410 in parallel with the thickness direction Z of the device. The second supporting portion 430 may surround one or more of the outer surface of the display panel 100 and the outer surface of the support member 300, thereby protecting the outer surfaces of the display panel 100 and the support member 300. The first supporting portion 410 may protrude from the inner surface of the second supporting portion 430 toward the gap space GS between the display panel 100 and the support member 300.

[0274] Figure 18 According to one aspect of the present disclosure Figure 16 piezoelectric device.

[0275] refer to Figure 18 , the piezoelectric device 200 according to one aspect of the present disclosure may include a vibration structure 230 .

[0276] The vibration structure 230 may include a piezoelectric device layer 231 , a first electrode portion 233 , and a second electrode portion 235 .

[0277] The vibration structure 230 may include a first electrode portion 233 disposed at a first surface of the piezoelectric device layer 231 and a second electrode portion 235 disposed at a second surface of the piezoelectric device layer 231 opposite to (or different from) the first surface.

[0278] The piezoelectric device layer 231 may include a first material layer 231a and a second material layer 231b surrounded by the first material layer 231a. According to one aspect of the present disclosure, one first material layer 231a and one second material layer 231b may form a single crystal grain having the same or substantially the same crystal orientation, and a grain boundary (GB) may be formed at a portion where another first material layer 231a and second material layer 231b forming another adjacent crystal grain contact each other. In one or more aspects of the present disclosure, the crystal orientation is the +Z-axis direction defined in the drawings. However, aspects of the present disclosure are not limited thereto, and the crystal orientation may be any other applicable direction.

[0279] According to one aspect of the present disclosure, the grains of the first material layer 231a can grow based on the crystal direction of the second material layer 231b, and therefore, multiple first material layers 231a can have the same or substantially the same crystal direction, for example, can have a (001) crystal direction, but aspects of the present disclosure are not limited thereto.

[0280] According to one aspect of the present disclosure, the first electrode portion 233 may be disposed at a first surface of the piezoelectric device layer 231. The second electrode portion 235 may be disposed at a second surface of the piezoelectric device layer 231 opposite to (or different from) the first surface.

[0281] The first electrode portion 233 and the second electrode portion 235 may use metal electrodes, for example, silver electrodes, but aspects of the present disclosure are not limited thereto.

[0282] In addition, Figure 18 , the vibrating structure 230 is shown as a single layer, but may be configured as additional stacks based on the desired performance of the piezoelectric device.

[0283] The above aspects of the vibration structure 230 have been described as examples. The vibration structure 230 according to one aspect of the present disclosure is not limited to a specific structure or configuration, such as the amount and / or location of material layers.

[0284] According to an aspect of the present disclosure, the piezoelectric device can be applied to (or be included in) the vibration device (or sound device) arranged at the equipment. According to an aspect of the present disclosure, the device can be applied to mobile device, video phone, smart watch, watch phone, wearable device, foldable device, rollable device, bendable device, flexible device, bending device, sliding device, variable device, electronic organizer, e-book, portable multimedia player (PMP), personal digital assistant (PDA), MP3 player, mobile medical device, desktop personal computer (PC), laptop PC, netbook computer, workstation, navigation device, car navigation device, car display device, car device, theater equipment, theater display device, TV, wallpaper display device, signage device, gaming device, notebook computer, monitor, camera, camcorder or household appliances etc. In addition, according to some aspects of the present disclosure, the vibration device can be applied to (or be included in) organic light emitting lighting equipment or inorganic light emitting lighting equipment. When the vibration device is applied to (or included in) lighting equipment, the lighting equipment can serve as lighting and loudspeaker. In addition, when the vibration device of the present disclosure is applied to (or included in) a mobile device or the like, the vibration device may function as one or more of a speaker, a receiver, and a haptic device, but aspects of the present disclosure are not limited thereto.

[0285] Described below are piezoelectric material compositions, methods of manufacturing the same, piezoelectric devices, and apparatuses including the piezoelectric devices according to one or more aspects of the present disclosure.

[0286] A piezoelectric material composition according to one aspect of the present disclosure may be represented by Formula 1.

[0287] [Formula 1]

[0288] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0289] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0290] According to one or more aspects of the present disclosure, a piezoelectric material composition may include a first material and a second material surrounded by the first material.

[0291] According to one or more aspects of the present disclosure, the first material may be represented by Formula 2.

[0292] [Formula 2]

[0293] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A

[0294] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and

[0295] 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.00.

[0296] According to one or more aspects of the present disclosure, the piezoelectric material composition may have a piezoelectric charge constant of 400 pC / N to 1,000 pC / N.

[0297] According to one or more aspects of the present disclosure, the first material may include 3 mol % or less of CuO relative to the piezoelectric material composition.

[0298] According to one or more aspects of the present disclosure, the second material may include 7 volume % or less of BaTiO 3 relative to the piezoelectric material composition.

[0299] According to one or more aspects of the present disclosure, the first material may include a plurality of grains oriented in a single (001) direction, the second material may be disposed in the plurality of grains, and the plurality of grains may be grown by reacting the second material.

[0300] According to one or more aspects of the present disclosure, the piezoelectric material composition may have a Lotgering factor of 70% or more.

[0301] According to one or more aspects of the present disclosure, the piezoelectric material composition may have a relative density of 90% or more.

[0302] The method of manufacturing a piezoelectric material composition according to one aspect of the present disclosure may include mixing a matrix material and a seed material to prepare a slurry, shaping the slurry to prepare a green tape, and sintering the green tape to prepare a sinter. The sinter may be represented by Formula 1.

[0303] [Formula 1]

[0304] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0305] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0306] According to one or more aspects of the present disclosure, the matrix material may be represented by Formula 2.

[0307] [Formula 2]

[0308] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A

[0309] Where 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.00.

[0310] According to one or more aspects of the present disclosure, the seed material may include BaTiO 3 .

[0311] According to one or more aspects of the present disclosure, the seed material may be added in an amount of 7 volume % or less relative to the piezoelectric material composition.

[0312] According to one or more aspects of the present disclosure, sintering the green tape to prepare a sinter may be performed at a temperature of 950° C. to 1,250° C. for 9 to 10 hours.

[0313] A piezoelectric device according to one aspect of the present disclosure may include a piezoelectric device layer including a piezoelectric material composition including a first material and a second material surrounded by the first material; a first electrode portion disposed on a first surface of the piezoelectric device layer; and a second electrode portion disposed on a second surface different from the first surface of the piezoelectric device layer. The piezoelectric device layer may be represented by Formula 1.

[0314] [Formula 1]

[0315] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0316] A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24,

[0317] 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0318] According to one or more aspects of the present disclosure, the first material may include 3 mol % or less of CuO relative to the piezoelectric material composition.

[0319] According to one or more aspects of the present disclosure, the second material may include 7 volume % or less of BaTiO 3 relative to the piezoelectric material composition.

[0320] An apparatus according to one aspect of the present disclosure may include a vibration member and a piezoelectric device disposed on a rear surface of the vibration member. The piezoelectric device may include a piezoelectric device layer comprising a first material and a second material surrounded by the first material; a first electrode portion disposed on a first surface of the piezoelectric device layer; and a second electrode portion disposed on a second surface different from the first surface of the piezoelectric device layer. The piezoelectric device layer may be represented by Formula 1.

[0321] [Formula 1]

[0322] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3

[0323] wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.00.

[0324] According to one or more aspects of the present disclosure, the vibration component may include one or more of the following: a display panel including multiple pixels configured to display an image, a screen panel that projects an image from a display device, a light-emitting diode lighting panel, an organic light-emitting lighting panel, an inorganic light-emitting lighting panel, a signage panel, an interior material of a vehicle tool, an exterior material of a vehicle tool, a window (or glass window) of a vehicle tool, an interior material of a seat of a vehicle tool, a ceiling material of a building, an interior material of a building, a window (or glass window) of a building, an interior material of an aircraft, a window (or glass window) of an aircraft, wood, plastic, glass, metal, cloth, fiber, paper, rubber, leather, carbon, and a mirror.

[0325] It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the scope of the present disclosure. Therefore, it is intended that the present disclosure cover modifications and variations of the present disclosure that come within the scope of the appended claims and their equivalents.

Claims

1. A piezoelectric material composition represented by Formula 1, [Formula 1] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3 wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.

00.

2. The piezoelectric material composition according to claim 1, wherein the piezoelectric material composition comprises: First material; and A second material is surrounded by the first material.

3. The piezoelectric material composition according to claim 2, wherein the first material is represented by Formula 2, [Formula 2] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.

00. 4 . The piezoelectric material composition according to claim 1 , wherein the piezoelectric material composition has a piezoelectric charge constant of 400 pC / N to 1,000 pC / N. 5 . The piezoelectric material composition according to claim 2 , wherein the first material contains 3 mol % or less of CuO relative to the piezoelectric material composition. 6 . The piezoelectric material composition according to claim 5 , wherein the first material includes 1 mol % to 3 mol % of CuO relative to the piezoelectric material composition. 7 . The piezoelectric material composition according to claim 6 , wherein the first material includes 1 mol % to 2 mol % of CuO relative to the piezoelectric material composition.

8. The piezoelectric material composition according to claim 2, wherein the second material contains 7 volume % or less of BaTiO3 relative to the piezoelectric material composition. 9 . The piezoelectric material composition according to claim 8 , wherein the second material comprises 1 volume % to 7 volume % of BaTiO 3 relative to the piezoelectric material composition.

10. The piezoelectric material composition according to claim 2, wherein the first material comprises a plurality of grains oriented in a single direction (001), wherein the second material is disposed in the plurality of grains, and The plurality of grains are grown by reaction from the second material. 11 . The piezoelectric material composition according to claim 1 , wherein a Lotgering factor of the piezoelectric material composition is 70% or more. 12 . The piezoelectric material composition according to claim 1 , wherein a relative density of the piezoelectric material composition is 90% or more.

13. The piezoelectric material composition according to claim 1, wherein the dielectric constant ε of the piezoelectric material composition is T 33 / ε0 is 2700 to 4000. 14 . The piezoelectric material composition according to claim 1 , wherein the electromechanical coupling factor kρ of the piezoelectric material composition is 0.41 to 0.

62.

15. A method for manufacturing a piezoelectric material composition, the method comprising: mixing a matrix material with a seed material to prepare a slurry; forming the slurry to prepare a green tape; as well as sintering the green tape to produce a sintered product, The sintered product is represented by Formula 1: [Formula 1] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3 wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.

00.

16. The method according to claim 15, wherein the matrix material is represented by Formula 2, [Formula 2] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, Among them, 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35 and 0.00≤x≤3.

00.

17. The method of claim 15, wherein the seed material comprises BaTiO3. 18 . The method according to claim 15 , wherein the seed material is added at 7 volume % or less relative to the piezoelectric material composition.

19. The method of claim 15, wherein the matrix material comprises 3 mol% or less of CuO relative to the piezoelectric material composition.

20. The method of claim 15, wherein the step of mixing the matrix material with the seed material to prepare the slurry comprises preparing a slurry including the matrix material and mixing the seed material with the matrix material.

21. The method according to claim 20, wherein the step of preparing the slurry including the matrix material comprises performing primary slurry grinding by adding a dispersant and a solvent to the matrix material, and performing secondary slurry grinding by further adding a binder and a plasticizer after the primary slurry grinding.

22. The method of claim 20, wherein the step of mixing the seed material with the matrix material comprises mixing the seed material with the slurry including the matrix material prepared in the previous step and performing third slurry milling and fourth slurry milling.

23. The method of claim 15, wherein the step of shaping the slurry to produce a green tape comprises: The piezoelectric material in the form of a slurry is cast, the cast piezoelectric material is primarily molded, and the primarily molded piezoelectric material is secondarily molded.

24. The method of claim 15, wherein sintering the green tape to prepare the sintered product is performed at a temperature of 950°C to 1250°C for 9 hours to 10 hours.

25. The method according to claim 24, wherein sintering the green tape to prepare the sintered product is performed at a temperature of 1250°C for 10 hours.

26. A piezoelectric device comprising: a piezoelectric device layer comprising a piezoelectric material composition comprising a first material and a second material surrounded by the first material; a first electrode portion disposed at a first surface of the piezoelectric device layer; as well as a second electrode portion disposed at a second surface different from the first surface of the piezoelectric device layer, Wherein the piezoelectric device layer is represented by Formula 1, [Formula 1] aPbZrO3-bPbTiO3–(1-ab)Pb(Ni c Nb 1-c )O3+x mol%A+y volume%BaTiO3 wherein A is Fe2O3, Co2O3, Mn2O3, ZnO, GeO2, CuO or NiO, and 0.15≤a≤0.24, 0.29≤b≤0.38, 0.30≤c≤0.35, 0.00≤x≤3.00 and 0.00≤y≤7.

00. 27 . The piezoelectric device according to claim 26 , wherein the first material contains 3 mol % or less of CuO relative to the piezoelectric material composition.

28. The piezoelectric device according to claim 26, wherein the second material comprises 7 volume % or less of BaTiO3 relative to the piezoelectric material composition.

29. An apparatus comprising: Vibrating components; as well as The piezoelectric device according to any one of claims 26 to 28, wherein the piezoelectric device is provided at the rear surface of the vibration member.

30. The device of claim 29, wherein the vibration component comprises one or more of: a display panel comprising a plurality of pixels configured to display an image, a screen panel that projects an image from a display device, a light emitting diode lighting panel, an organic light emitting lighting panel, an inorganic light emitting lighting panel, a signage panel, an interior material of a vehicle tool, an exterior material of a vehicle tool, a window of a vehicle tool, an interior material of a seat of a vehicle tool, a ceiling material of a building, an interior material of a building, a window of a building, an interior material of an aircraft, a window of an aircraft, wood, plastic, glass, metal, cloth, fiber, paper, rubber, leather, carbon, and a mirror.

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