WO2022163141A1 - 電子部品 - Google Patents

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Publication number
WO2022163141A1
WO2022163141A1 PCT/JP2021/044983 JP2021044983W WO2022163141A1 WO 2022163141 A1 WO2022163141 A1 WO 2022163141A1 JP 2021044983 W JP2021044983 W JP 2021044983W WO 2022163141 A1 WO2022163141 A1 WO 2022163141A1
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WO
WIPO (PCT)
Prior art keywords
insulating film
segregation
electronic component
element body
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/044983
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English (en)
French (fr)
Japanese (ja)
Inventor
悠太 星野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
Original Assignee
Murata Manufacturing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to JP2022578103A priority Critical patent/JP7552739B2/ja
Priority to DE212021000485.7U priority patent/DE212021000485U1/de
Priority to CN202180089173.3A priority patent/CN116745870A/zh
Publication of WO2022163141A1 publication Critical patent/WO2022163141A1/ja
Priority to US18/352,937 priority patent/US20240021360A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H01F27/32—Insulating of coils, windings, or parts thereof
    • H01F27/324—Insulation between coil and core, between different winding sections, around the coil; Other insulation structures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F17/00—Fixed inductances of the signal type
    • H01F17/0006—Printed inductances
    • H01F17/0013—Printed inductances with stacked layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F17/00—Fixed inductances of the signal type
    • H01F17/04—Fixed inductances of the signal type with magnetic core
    • H01F17/045—Fixed inductances of the signal type with magnetic core with core of cylindric geometry and coil wound along its longitudinal axis, i.e. rod or drum core
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H01F27/2823—Wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F27/00—Details of transformers or inductances, in general
    • H01F27/28—Coils; Windings; Conductive connections
    • H01F27/29—Terminals; Tapping arrangements for signal inductances
    • H01F27/292—Surface mounted devices

Definitions

  • the present invention relates to electronic components.
  • a laminated coil component in which an insulating film containing glass is formed on the surface of an element made of a ferrite sintered body.
  • Patent Document 1 an element body made of a ferrite sintered body and a coil configured by electrically connecting a plurality of internal conductors arranged side by side in the element body are provided, and the surface of the element body contains glass.
  • a laminated coil component covered with an insulating layer is disclosed.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide an electronic component having high adhesion between the base body and the insulating film.
  • One embodiment of the electronic component of the present invention includes a ceramic element body containing Cu element, an insulating film containing glass covering at least part of the surface of the element body, and a Cu segregation containing Cu element.
  • the Cu segregation is in contact with the element body and the insulating film at the interface between the element body and the insulating film.
  • FIG. 1 is a perspective view schematically showing an example of an electronic component according to an embodiment of the invention.
  • FIG. 2 is a sectional view taken along line II-II in FIG.
  • FIG. 3 is a perspective view schematically showing another example of the electronic component according to the embodiment of the invention.
  • FIG. 4 is a sectional view along line IV-IV in FIG.
  • FIG. 5 is a cross-sectional view schematically showing an example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • FIG. 6 is a cross-sectional view schematically showing another example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • FIG. 1 is a perspective view schematically showing an example of an electronic component according to an embodiment of the invention.
  • FIG. 2 is a sectional view taken along line II-II in FIG.
  • FIG. 3 is a perspective view schematically showing another example of the electronic component according to the
  • FIG. 7 is a cross-sectional view schematically showing still another example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • 8 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • FIG. 9 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • FIG. FIG. 10 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • the present invention is not limited to the following configurations, and can be appropriately modified and applied without changing the gist of the present invention.
  • One embodiment of the electronic component of the present invention includes a ceramic element body containing Cu element, an insulating film containing glass covering at least part of the surface of the element body, and a Cu segregation containing Cu element.
  • the Cu segregation is in contact with the element body and the insulating film at the interface between the element body and the insulating film.
  • FIG. 1 is a perspective view schematically showing an example of an electronic component according to an embodiment of the invention.
  • the element body 10 has a first end face 10a and a second end face 10b facing in the length direction L, a first side face 10c and a second side face 10d facing in the width direction W perpendicular to the length direction L, and a length direction L and a substantially rectangular parallelepiped shape having a top surface 10e and a bottom surface 10f facing each other in a thickness direction T orthogonal to the width direction W.
  • the insulating film 20 covers the entire second side surface 10d of the element body 10, the first end surface 10a, the second end surface 10b, the top surface 10e and the bottom surface 10f partially, and the first side surface 10c of the element body 10. and part of the first end surface 10a, the second end surface 10b, the top surface 10e and the bottom surface 10f.
  • the insulating films 20a and 20b are provided so as to partially overlap each other.
  • the number of insulating films covering the surface of the element body may be one, or three or more.
  • the entire surface of the element may be covered with one or more insulating films, except for a portion where a conductor layer, which will be described later, is exposed on the surface of the element.
  • An external electrode 50 is provided on the surface of the element body 10 .
  • the external electrodes 50 are provided so as to cover the first end surface 10a and the second end surface 10b of the base body 10, respectively.
  • a part of the external electrode 50 covering the first end surface 10a of the element body 10 is formed around a part of the first side surface 10c, the second side surface 10d, the upper surface 10e and the bottom surface 10f of the element body 10.
  • a part of the external electrode 50 covering the second end surface 10b of the element body 10 is formed around a part of the first side surface 10c, the second side surface 10d, the top surface 10e, and the bottom surface 10f of the element body 10. .
  • a portion of the surface of the element body 10 is covered with an insulating film 20 (20a, 20b), and a portion of the surface of the element body 10 that is not covered with the insulating film 20 is covered with an external electrode 50. As shown in FIG. Therefore, the surface of the element body 10 is not exposed. However, part of the surface of the element may be exposed without being covered with the insulating film and the external electrodes.
  • FIG. 2 is a sectional view taken along line II-II in FIG.
  • the element body 10 has a conductor layer 40 inside.
  • the conductor layer 40 is exposed on the first end surface 10 a and the second end surface 10 b of the element body 10 and electrically connected to the external electrode 50 .
  • the conductor layer 40 forms a coil as a whole.
  • the coil axis of the coil formed by the conductor layer 40 is parallel to the length direction L. As shown in FIG.
  • FIG. 3 is a perspective view schematically showing another example of the electronic component according to the embodiment of the invention.
  • the electronic component 2 shown in FIG. 3 includes an element body 11 and an insulating film 20 that partially covers the surface of the element body 11 .
  • the shape of the element body 11 is a barbell shape having a columnar winding core portion 60 around which the winding wire 43 is wound and flange portions 61 connected to both ends of the winding core portion 60 in the length direction L, respectively.
  • the winding 43 is wound around the winding core portion 60 of the element body 11 .
  • FIG. 4 is a sectional view along line IV-IV in FIG.
  • the insulating film 20 covers the entire collar portion 61 of the element body 11 and the entire winding core portion 60 . Since the entire surface of the element body 11 is covered with the insulating film 20 , the windings 43 are not in contact with the element body 11 . Although not shown, the ends of the windings 43 are connected to the external electrodes 50 . In the electronic component 2 shown in FIGS. 3 and 4 , the entire surface of the element body 11 is covered with the insulating film 20 and the windings 43 are not in contact with the element body 11 .
  • the number of insulating films covering the surface of the element is not particularly limited, and the surface of the element may be covered with two or more insulating films.
  • the element body is a ceramic containing Cu element.
  • Ceramics containing Cu elements include, for example, known ceramics such as ferrite, alumina, barium titanate, and Zn-based ceramics containing Cu elements.
  • the ceramic containing Cu element may contain additives such as Mn 3 O 4 , Co 3 O 4 , SnO 2 , Bi 2 O 3 and SiO 2 .
  • the content of Cu element in the element is preferably 6 mol % or more and 10 mol % or less.
  • the content of the Cu element in the element excludes from consideration the Cu element that constitutes the Cu segregation material segregated on the surface of the element.
  • the content of Cu element in the element body is measured by wavelength dispersive X-ray fluorescence (WD-XRF) with a spot diameter of ⁇ 1 ⁇ m or more by exposing a cross section that is 10 ⁇ m or more inside the element body from the surface of the element body by polishing. Therefore, it is possible to measure as a value excluding the influence of segregation.
  • the WD-XRF measurement may be performed on about five samples.
  • the Fe element content in the element body is preferably 40 mol % or more and 49.5 mol % or less in terms of Fe 2 O 3 .
  • Ni/Zn molar ratio in the element is not particularly limited, it is preferably 1.8 or more and 2.8 or less.
  • the shape of the element is not particularly limited, and examples thereof include a cubic shape, a rectangular parallelepiped shape, a barbell shape, an H shape, an I shape, and an annular shape.
  • the outer dimensions of the element are preferably length 5.7 mm or less x width 5.0 mm or less x height 5.0 mm or less, and length 1.6 mm or less x width 0.8 mm or less x height 0. 0.8 mm or less is particularly preferred.
  • the element body may have a conductor layer inside.
  • the conductor layers formed inside the element body may form passive elements such as coils, capacitors, resistors, and thermistors.
  • a plurality of passive elements may be formed inside the base body.
  • the orientation of the passive elements formed in the element body is arbitrary. Therefore, the coil axis of the coil formed in the base body may be horizontal or vertical to the mounting surface of the electronic component. Also, the number of coils formed in the element body may be one or plural.
  • An example of the electronic component of the present invention in which a coil is formed in the element body is a laminated coil component. It may be a part or the like.
  • the body may not have a conductor layer inside.
  • the element can also be used as a winding core by winding a wire around it.
  • An example of the electronic component of the present invention in which a wire is wound around the base includes a wound coil component.
  • the number of coils formed by winding a wire around the element body may be one or plural.
  • the insulating film covers at least part of the surface of the element.
  • the insulating film contains glass.
  • the glass constituting the insulating film include B--Si-based glass, Ba--B--Si-based glass, B--Si--Zn-based glass, B--Si--Zn--Ba-based glass, and B--Si--Zn--Ba--Ca.
  • -Al-based glass or the like can be used.
  • alkali metal glasses such as Na—Si glasses, K—Si glasses, Li—Si glasses, Mg—Si glasses, Ca—Si glasses, Ba—Si glasses, Sr— Alkaline earth metal glass such as Si glass, Ti—Si glass, Zr—Si glass, Al—Si glass, and the like can also be used.
  • the glass may be crystallizable glass.
  • the weight ratio of the glass in the insulating film is not particularly limited, but is preferably 90% by weight or more.
  • the thickness of the insulating film is not particularly limited, it is preferably 0.005 ⁇ m or more and 10.000 ⁇ m or less, and more preferably 0.030 ⁇ m or more and 1.500 ⁇ m or less.
  • the thickness of the insulating film can be measured by observing a cross section obtained by cutting the insulating film in the thickness direction with a scanning electron microscope (SEM).
  • the insulating film may contain pigments, silicone-based flame retardants, silane coupling agents, surface treatment agents such as titanate coupling agents, antistatic agents, and the like.
  • the Cu segregation containing Cu element is in contact with the element and the insulating film at the interface between the element and the insulating film.
  • the presence of Cu segregation at the interface between the element and the insulating film increases the adhesion between the element and the insulating film.
  • the Cu segregates may exist anywhere on the element, but preferably exist on the grain boundary of the ceramic of the element. Since the grain boundary of the ceramic of the element body has a concave shape on the surface of the element body, the presence of the Cu segregation on the grain boundary forming the concave shape causes an anchor effect, and the Cu segregation and The adhesion of the element is further improved.
  • composition of the Cu segregation is not particularly limited, it may contain at least Cu element, and examples thereof include Cu, CuO, Cu 2 O, and the like. Also, the Cu segregants may contain glass.
  • a plurality of Cu segregants may exist at the interface between the element and the insulating film. If a plurality of Cu segregants are present at the interface between the element and the insulating film, the adhesion between the element and the insulating film can be further enhanced.
  • Whether or not Cu segregation exists at the interface between the element and the insulating film is determined by scanning electron microscope-energy dispersive X-ray spectroscopic analysis of the interface between the element and the insulating film on the cut surface of the electronic component. It can be confirmed by observing with (SEM-EDX). By confirming the concentration distribution of the Cu element from the element mapping image near the interface between the element body and the insulating film obtained by SEM-EDX, the shape of the Cu segregation present near the interface between the element body and the insulating film can be specified.
  • the element is ferrite
  • the element is mainly composed of Fe element
  • the Cu segregation is mainly composed of Cu element
  • the insulating film is mainly composed of Si element.
  • the concentrations of the Fe element, the Cu element and the Si element in the elemental mapping image it is possible to distinguish between the elemental body, the Cu segregate and the insulating film in the elemental mapping image.
  • the element body is a ceramic other than ferrite
  • concentrations of the main component elements of the ceramic, the Cu element, and the Si element, the element, the Cu segregation, and the insulating film in the element mapping image can be determined. can be distinguished.
  • Each element may be the main component of the ceramic.
  • the shape of the Cu segregates is not particularly limited, but may be granular, wedge-shaped, or layered.
  • the shape of the Cu segregates can be determined by the value of the aspect ratio and whether or not the Cu segregates protrude toward the element body.
  • the aspect ratio of the Cu segregation is defined as the length of the Cu segregation in the direction in which the interface between the element body and the insulating film extends, and the length of the Cu segregation in the direction orthogonal to La as Lb. It is represented by the ratio [La/Lb] of length La to Lb (hereinafter also referred to as aspect ratio).
  • the length Lb passes through the point closest to the element body and the point farthest from the element body of the Cu segregation, and the interface between the element body and the insulating film extends. It corresponds to the distance between two line segments when each line segment is assumed to be parallel to the direction.
  • the shape of the Cu segregation is wedge-shaped regardless of the aspect ratio of the Cu segregation.
  • the shape with an aspect ratio of 3 or less is granular, and the shape with an aspect ratio of more than 3 is layered.
  • the shape of the Cu segregation except for the portion protruding toward the element may be granular or layered. Note that the layered Cu segregation exists only in a portion of the interface between the element and the insulating film, and does not cover the entire interface between the element and the insulating film.
  • FIG. 5 is a cross-sectional view schematically showing an example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • Cu segregants 30 ( 31 , 32 ) are present at the interface between the element 10 and the insulating film 20 and are in contact with the element 10 and the insulating film 20 .
  • the thickness of the insulating film 20 in the portion where the Cu segregation 30 does not exist is the length indicated by the double arrow T0 . Note that the thickness T0 of the insulating film 20 may differ from place to place.
  • the length of the Cu segregants 31 in the direction in which the interface between the base body 10 and the insulating film 20 extends (hereinafter also referred to as the lateral direction) is the length indicated by the double arrow La1.
  • the length of the Cu segregants 31 in the direction orthogonal to the horizontal direction (hereinafter also referred to as the vertical direction) is the length indicated by the double arrow Lb1 .
  • the aspect ratio [La 1 /Lb 1 ] of the Cu segregants 31 is approximately 1.4. Therefore, the shape of the Cu segregation material 31 is granular.
  • the thickness of the Cu segregants 31 has a length indicated by a double - headed arrow Lb1, and the thickness of the insulating film 20 immediately above and in contact with the Cu segregates 31 has a length indicated by a double - headed arrow T1.
  • the Cu segregants 31 have a shape that does not protrude toward the element body 10 side.
  • the sum of the thickness Lb1 of the Cu segregants 31 and the thickness T1 of the insulating film 20 directly in contact with the Cu segregates 31 matches the thickness T0 of the insulating film 20.
  • the thickness T0 of the insulating film 20 is thicker than the thickness T1 of the insulating film 20 directly above and in contact with the Cu segregation 31 .
  • the thickness T0 of the insulating film 20 is thicker than the thickness T1 of the insulating film 20 directly in contact with the Cu segregants 31, the irregularities on the surface of the insulating film caused by the presence of the Cu segregates are reduced. The smoothness of the surface of the insulating film is improved.
  • the Cu segregants 32 have protrusions 32a that protrude toward the element body 10 side. Therefore, it can be said that the shape of the Cu segregants 32 is wedge-shaped regardless of the aspect ratio. Whether or not the Cu segregation protrudes toward the element body can be determined from the shape of the element surface at the portion where the Cu segregation does not exist on the surface of the element. Estimate the shape of the element surface when there is no substance, and when the Cu segregation is located inside (element side) the estimated element surface, the Cu segregation protrudes toward the element. assume that The Cu segregation may protrude toward the insulating film instead of toward the element body. However, the Cu segregation protruding only on the insulating film side, not on the element body side, is determined whether it corresponds to a granular or layered shape depending on the aspect ratio.
  • FIG. 6 is a cross-sectional view schematically showing another example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • the Cu segregants 33 have a horizontal length indicated by a double - headed arrow La3 and a vertical length indicated by a double - headed arrow Lb3.
  • the aspect ratio [La 3 /Lb 3 ] is about 10. Therefore, the shape of the Cu segregants 33 is layered. Note that the layered Cu segregation exists only in a portion of the interface between the element and the insulating film, and does not cover the entire interface between the element and the insulating film.
  • the thickness of the Cu segregants 33 has a length indicated by a double - headed arrow Lb3
  • the thickness of the insulating film 20 directly above and in contact with the Cu segregates 33 has a length indicated by a double-headed arrow T3.
  • the Cu segregation material 33 has a shape that does not protrude toward the element body 10 side.
  • the sum of the thickness Lb3 of the Cu segregants 33 and the thickness T3 of the insulating film 20 immediately above and in contact with the Cu segregates 33 coincides with the thickness T0 of the insulating film 20 .
  • the thickness T0 of the insulating film 20 is thicker than the thickness T3 of the insulating film 20 directly above and in contact with the Cu segregation 33 .
  • the shape of the Cu segregates is related to the thickness of the insulating film directly above and in contact with the Cu segregates.
  • the thickness of the insulating film directly on and in contact with the Cu segregants is less than 0.5 ⁇ m, the shape of the Cu segregates tends to be granular or wedge-shaped.
  • the thickness of the insulating film directly on and in contact with the Cu segregation is 0.5 ⁇ m or more, the shape of the Cu segregation tends to be layered.
  • the part where the Cu segregation is mixed with the glass forming the insulating film is also regarded as part of the Cu segregation.
  • the shape is specified as one Cu segregation including the portion where the Cu segregation is mixed with the glass forming the insulating film.
  • the boundary between the Cu segregation and the insulating film can be confirmed by element mapping of Si element and Cu element by SEM-EDX.
  • the shape and aspect ratio of the Cu segregates, and the thickness of the insulating film immediately above and in contact with the Cu segregates can be measured by SEM-EDX.
  • the shape and aspect ratio of Cu segregates are determined for each individual Cu segregate. From the SEM-EDX image taken so that the Cu segregation and the insulating film are in one field of view, the thickness of the insulating film in contact with the Cu segregation is the upper surface of the Cu segregation for each Cu segregation. It is the minimum value of the length from one point to one point on the top surface of the insulating film directly above in the vertical direction.
  • the thickness of the insulating film in the portion where Cu segregation does not exist is the average value of the lengths from the surface of the element body to the top surface of the insulating film measured at three points. For the above three points, visually select the point where the length from the surface of the element to the top surface of the insulating film is the longest, the point where the length is the shortest, and the point where the length is between these.
  • the surface of the element body may be covered with a plurality of insulating films.
  • Both the element body 10 shown in FIGS. 1 and 2 and the element body 11 shown in FIGS. 3 and 4 are examples covered with a plurality of insulating films.
  • the plurality of insulating films may have different compositions or may have the same composition.
  • Cu segregation may exist at the interface between each insulating film and the element. Moreover, part of the Cu segregation does not have to be covered with the insulating film. Such Cu segregates are exposed on the surface of the element.
  • FIG. 7 is a cross-sectional view schematically showing still another example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • Two insulating films 20a and 20b are provided on the surface of the element body 10 shown in FIG.
  • Cu segregates 34a and 34b are present at the interfaces between the insulating films 20a and 20b and the element body 10, respectively.
  • the surface of the element body 10 has a portion not covered with the insulating film 20, and the surface of the element body 10 is exposed in this portion.
  • the Cu segregation 34c exists in the portion where the surface of the element body 10 is not covered with the insulating film 20. As shown in FIG. Therefore, the Cu segregants 34c are exposed on the surface of the element body 10.
  • FIG. 7 is a cross-sectional view schematically showing still another example of the state of the interface between the element body and the insulating film in one embodiment of the electronic component of the present invention.
  • an insulating film covering the Cu segregation is formed around the external electrodes to be plated.
  • an insulating film is formed around the external electrodes to be plated, it is possible to suppress the formation of plating in the region where the insulating film is formed.
  • External electrode One embodiment of the electronic component of the present invention has an external electrode, but its form is not particularly limited.
  • external electrodes include a combination of a base electrode layer and a coating layer formed on the surface thereof, a metal plate, lead terminals, and the like.
  • the base electrode layer may be an electrode formed by applying a glass paste containing glass and a conductor to the surface of the element and baking it, or an electrode formed directly on the surface of the element by sputtering or plating. There may be.
  • the underlying electrode layer preferably has a conductor portion containing a conductor and a glass portion containing glass.
  • the conductor portion preferably contains at least one metal element selected from the group consisting of Ni elements, Sn elements, Pd elements, Au elements, Ag elements, Pt elements, Bi elements, Cu elements and Zn elements. .
  • the conductor portion preferably contains Ag element as a conductor. Ag element has high conductivity. Further, the base electrode layer containing Ag element as a conductor is easy to form.
  • the average particle size of the conductive particles is not particularly limited, it is preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the weight ratio of the conductive particles in the base electrode layer is not particularly limited, it is preferably 71% by weight or more and 98% by weight or less.
  • the weight ratio of the glass in the base electrode layer is preferably 2% by weight or more and 15% by weight or less.
  • the weight ratio of the glass in the underlying electrode layer is 15% by weight or less, the resistance value of the underlying electrode layer does not become too large.
  • the weight ratio of the glass in the underlying electrode layer is 2% by weight or more, the denseness of the underlying electrode layer can be increased, preventing the plating solution and moisture from penetrating into the underlying electrode layer and preventing the plating from entering. Liquid and moisture can be prevented from penetrating into the body through the base electrode layer.
  • the coating layer is preferably, for example, a plated layer provided on the surface of the underlying electrode layer.
  • the plated layer preferably contains at least one metal selected from the group consisting of Cu, Ni, Sn, Pd, Au, Ag, Pt, Bi and Zn.
  • the plating layer may be one layer, or two or more layers.
  • the plating layer is more preferably a layer having a Ni plating layer and a Sn plating layer provided on the base electrode layer. The Ni-plated layer prevents water from entering the base body, and the Sn-plated layer can improve the mountability of the electronic component.
  • Cu segregation may exist at the interface between the element and the underlying electrode layer (preferably, the interface between the element and the glass portion).
  • the presence of Cu segregation at the interface between the element and the underlying electrode layer enhances the adhesion between the element and the underlying electrode layer.
  • the electronic component of this embodiment has excellent adhesion between the element body and the insulating film.
  • the electronic component of the present embodiment is not limited to a laminated coil component or a wound coil component, and may be any component as long as a ceramic containing Cu element is used as an element body.
  • a first embodiment of the method for manufacturing an electronic component according to the present invention comprises a ceramic sheet preparation step of preparing a ceramic sheet formed by forming a ceramic raw material containing Cu element into a sheet shape, and forming conductor patterns to be via holes and coil patterns on the ceramic sheet.
  • a step of forming a conductor pattern to be formed a step of preparing a laminate in which ceramic sheets are laminated, a step of firing the laminate to obtain a ceramic element, and an insulating film containing glass on the surface of the element. and a step of forming an insulating film.
  • Ceramic sheet preparation process In the ceramic sheet preparation step, a ceramic raw material containing Cu element is formed into a sheet.
  • the powdered ferrite raw material is prepared by weighing Fe 2 O 3 , ZnO, CuO, and NiO so as to have a predetermined ratio, wet-mixing them, and then pulverizing them. It can be obtained by drying and calcining.
  • a ceramic slurry is prepared by mixing a ceramic raw material, an organic binder such as polyvinyl butyral resin, an organic solvent such as ethanol or toluene, and the like, and pulverizing the mixture.
  • the ceramic slurry is formed into a sheet having a predetermined thickness by a doctor blade method or the like, and then punched into a predetermined shape to produce a ceramic sheet.
  • the content of Cu element in the ceramic raw material is preferably 6 mol % or more and 10 mol % or less. The higher the content of Cu element in the ceramic raw material, the easier it is for Cu segregation to occur on the surface of the element.
  • the content of the organic binder contained in the ceramic sheet is preferably 25% by weight or more and 35% by weight or less. Since the organic binder contained in the ceramic sheet contains carbon, it combines with oxygen in the atmosphere during firing to reduce the oxygen concentration. Therefore, as the content of the organic binder increases, the oxygen concentration tends to decrease in the firing process, and as a result, Cu segregation tends to occur on the surface of the element.
  • the thickness of the ceramic sheet is not particularly limited, it is preferably 15 ⁇ m or more and 50 ⁇ m or less.
  • a conductor pattern is formed by coating each ceramic sheet with a conductive paste such as Ag paste by a screen printing method or the like.
  • a via hole is formed in advance by irradiating a predetermined portion of the ceramic sheet with a laser, and the via hole is filled with a conductive paste.
  • Laminate preparation step After laminating the ceramic sheets, a laminated body is produced by crimping them by warm isostatic pressing (WIP) or the like.
  • WIP warm isostatic pressing
  • the number of laminated ceramic sheets is not particularly limited, it is preferably 30 or more and 100 or less.
  • the laminate is sintered to obtain an element body.
  • the firing conditions are such that Cu segregation is precipitated on the surface of the element. Whether or not Cu segregation occurs on the surface of the element body depends not only on the composition of the ceramic raw material, but also on the amount of carbon contained in the laminate, the firing temperature (maximum temperature), the rate of temperature increase, the firing atmosphere, the material of the firing furnace, etc. affects. When these conditions are appropriately selected, Cu segregates are precipitated on the surface of the element. That is, if the firing conditions are not appropriate, Cu segregation will not precipitate on the surface of the element even if the composition of the ceramic raw material is the same.
  • the firing temperature (maximum temperature) in the firing step is preferably 1000° C. or higher and 1300° C. or lower. If the firing temperature (maximum temperature) in the firing step is 1000° C. or higher, Cu segregation is likely to occur on the surface of the element.
  • the oxygen concentration in the firing step is preferably 15% by volume or less, more preferably 5% by volume or less. If the oxygen content in the firing atmosphere is 15% by volume or less, Cu segregation is likely to occur on the surface of the element.
  • the balance gas in the firing step is preferably nitrogen or argon.
  • the heating rate in the firing step is preferably 10° C./min or less. The shorter the time it takes to reach the sintering temperature, the more easily Cu segregation occurs on the surface of the element.
  • the furnace material that constitutes the firing furnace for firing the laminate in the firing step is preferably a high-density material such as a mixture of alumina and silicon. If the furnace material that constitutes the firing furnace is made of a high-density material, Cu segregation is likely to occur.
  • the insulating film can be formed by applying a paste containing glass (hereinafter referred to as glass paste) to the surface of the element and firing (baking) it.
  • glass paste a paste containing glass
  • the glass paste may contain a resin and a dispersion medium in addition to the glass.
  • glass examples include B--Si-based glass, Ba--B-Si-based glass, B--Si--Zn-based glass, B--Si--Zn--Ba-based glass, and B--Si--Zn--Ba-Ca--Al-based glass.
  • alkali metal glasses such as Na—Si glasses, K—Si glasses, Li—Si glasses, Mg—Si glasses, Ca—Si glasses, Ba—Si glasses, Sr— Alkaline earth metal glass such as Si glass, Ti—Si glass, Zr—Si glass, Al—Si glass, and the like can also be used.
  • the glass may be crystallizable glass.
  • the average particle size of the glass constituting the glass paste is not particularly limited, it is preferably 0.01 ⁇ m or more and 4.00 ⁇ m or less.
  • the glass paste applied to the surface of the element is dried. Although the drying conditions are not particularly limited, it may be heated at 150° C. for about 30 minutes. When the glass paste is applied to the surface of the element multiple times, it is preferable to repeat the application and drying of the glass paste. In addition to the application and drying of the glass paste, the insulating film can also be formed by repeating one or more sets of baking, which will be described later, as one set.
  • the temperature (baking temperature) for forming the insulating film is not particularly limited, it is preferably 750° C. or higher and 900° C. or lower.
  • the baking temperature is 750° C. or higher and 900° C. or lower, Cu segregation is more likely to occur on the surface of the element.
  • the Cu segregation and the glass contained in the insulating film can easily form a mixture, and the adhesion between the element body and the insulating film can be improved.
  • baking is preferably performed in a non-oxidizing atmosphere. By performing the baking at 825° C. or higher in a non-oxidizing atmosphere, the segregation of Cu on the surface of the element body can be promoted. Therefore, the adhesion between the element body and the insulating film can be further improved.
  • the method of forming an insulating film on the surface of the element is not limited to the method of applying and baking the glass paste described above, and examples thereof include sputtering, electron beam evaporation, thermal CVD, plasma CVD, spraying, and dipping. , a dip spin coating method, a sol-gel method, and the like, and two or more of these may be combined.
  • the method for manufacturing the base body may be a method other than the sheet lamination method described above.
  • Methods other than the sheet lamination method include, for example, a print lamination method (build-up method).
  • a method using photolithography can also be used as a method for forming wiring and vias on the surface of the sheet.
  • An external electrode forming step for forming external electrodes on the surface of the element body may be performed following the above steps.
  • External electrode forming process external electrodes are formed on the surface of the element body.
  • the external electrode forming step for example, a method of forming a Ni/Sn plating layer by performing Ni plating and Sn plating on the surface of the element in this order can be mentioned.
  • a glass paste containing glass and conductive particles is applied to the surface of the element and fired (baking) to form an underlying electrode layer.
  • a Ni/Sn plating layer serving as a coating layer may be formed on the surface of the .
  • a second embodiment of the method for manufacturing an electronic component according to the present invention includes an element body preparation step of forming a ceramic raw material containing Cu element to prepare a ceramic element body, and an insulating film of forming an insulating film on the surface of the element body.
  • the same ceramic raw material as used in the first embodiment of the method for manufacturing an electronic component according to the present invention can be preferably used.
  • a method for molding the ceramic raw material into a predetermined shape a conventionally known powder molding method can be used. At this time, a resin, a binder, or the like may be added to the ceramic raw material, if necessary. A body is obtained by firing a molded body obtained by molding a ceramic raw material. At this time, the compact is fired under the conditions that Cu segregation occurs on the surface of the element.
  • the element obtained by the above method is an element containing no conductor layer inside.
  • the insulating film forming step an insulating film is formed on the surface of the element obtained by the firing step.
  • the insulating film forming step in the second embodiment of the electronic component manufacturing method of the present invention is the same as the insulating film forming step in the first embodiment of the electronic component of the present invention.
  • the electronic component according to the embodiment of the present invention is manufactured.
  • an external electrode forming step of forming external electrodes on the surface of the element body may be performed.
  • the external electrode forming step in the second embodiment of the electronic component manufacturing method of the present invention is the same as the external electrode forming step in the first embodiment of the electronic component manufacturing method of the present invention.
  • the external electrode forming process may be performed before the coil forming process, and both ends of the winding to be the coil may be connected to the external electrodes in the coil forming process.
  • the method of connecting the windings to be the coil and the external electrodes is not particularly limited, for example, a method of bonding by thermocompression bonding can be used.
  • Example 1 [Body preparation process] A ferrite raw material prepared so that the Fe content is constant, the Ni/Zn molar ratio is 2.3, and the Cu content is 8 mol%, is shaped into a barbell having a winding portion and a flange portion. to obtain a molded body.
  • a ceramic body was obtained by firing the compact at 1100° C. for 1 hour.
  • the atmosphere during firing was normal pressure and oxygen partial pressure was 10% by volume.
  • the shape of the obtained element body includes first and second end surfaces opposed in the length direction, first and second side surfaces opposed in the width direction, and a thickness It had a substantially rectangular parallelepiped shape with a top surface and a bottom surface in opposite directions.
  • a glass paste is prepared by mixing a glass frit (borosilicate glass) and a solvent (terpineol), and the first side of the element is immersed in the glass paste up to a half position in the width direction of the element. , and dried at 150° C. for 30 minutes. After that, the orientation of the element is changed so that it is turned upside down, the element is immersed in the glass paste up to a half position in the width direction with the second side of the element facing downward, and then the element is heated at 150° C. for 30 minutes. dried. Finally, baking was performed at 650° C. for 10 minutes to form an insulating film, and the electronic component according to Example 1 was manufactured.
  • the baking temperature is preferably 750° C. or higher. By setting the temperature to 850° C. or higher, the fluidity of the Cu segregation itself is improved.
  • the first end face, the second end face, the upper surface and the bottom surface of the element body in addition to the entire first side surface of the element body, the first end face, the second end face, the upper surface and the bottom surface of the element body. and an insulating film covering part of the first end surface, the second end surface, the upper surface and the bottom surface of the element in addition to the entire second side surface of the element.
  • Example 2 Comparative Examples 1 to 3
  • Example 2 was carried out in the same manner as in Example 1, except that the Cu content was changed to 6 mol%, 4 mol%, 1 mol%, and 0 mol% without changing the Fe content and Ni/Zn molar ratio in the ferrite raw material.
  • electronic parts according to Comparative Examples 1 to 3 were manufactured.
  • the sintered densities of the bodies of each example and comparative example were about the same as that of the first example.
  • Comparative Example 4 An electronic component according to Comparative Example 4 was manufactured in the same manner as in Example 1 except that the firing temperature (maximum temperature) of the compact was changed to 950° C. or less without changing the composition of the ferrite raw material.
  • the sintered density of the element body of Comparative Example 4 was about the same as that of Example 1.
  • FIG. 8 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • the aspect ratio of the Cu segregants 31 was 2.0. Therefore, it was confirmed that granular Cu segregation 31 was present in the SEM-EDX elemental mapping image shown in FIG.
  • the thickness of the insulating film 20 immediately above and in contact with the Cu segregants 31 was 0.03 ⁇ m.
  • FIG. 9 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • FIG. The position for measuring SEM-EDX in FIG. 9 is different from the position for measuring SEM-EDX in FIG. From the results of FIG. 9, it was confirmed that in the electronic component according to Example 2, a region (Cu segregation 32) with a high concentration of Cu element was present at the interface between the element body 10 and the insulating film 20. The Cu segregants 32 protrude toward the element body 10 side. Therefore, it was confirmed that a wedge-shaped Cu segregation 32 was present in the SEM-EDX elemental mapping image shown in FIG. The thickness of the insulating film 20 immediately above and in contact with the Cu segregation 32 was 0.13 ⁇ m.
  • FIG. 10 is an elemental mapping image of Cu at the interface between the element body and the insulating film of the electronic component according to Example 2.
  • FIG. The position for measuring SEM-EDX in FIG. 10 is different from the position for measuring SEM-EDX in FIG. 8 and the position for measuring SEM-EDX in FIG. From the results of FIG. 10, it was confirmed that the layered Cu segregation 33 was present at the interface between the element body 10 and the insulating film 20 in the electronic component according to Example 2.
  • FIG. The thickness of the insulating film 20 immediately above and in contact with the Cu segregation 33 was 0.5 ⁇ m. Further, from the results of FIGS. 8, 9 and 10, it was confirmed that a plurality of Cu segregants with different shapes were present at the interface between the insulating film and the element in the same electronic component.
  • the electronic parts according to the embodiments of the present invention can be suitably used as parts such as inductors, antennas, noise filters, radio wave absorbers, LC filters combined with capacitors, and winding cores.
  • Reference Signs List 1, 2 Electronic component 10, 11 Base body 10a First end face of the base body 10b Second end face of the base body 10c First side face of the base body 10d Second side face of the base body 10e Upper surface of the base body 10f Bottom surface of the base body 20, 20a, 20b insulating film 30, 31, 32, 33, 34a, 34b, 34c Cu segregation 32a Protruding portion where Cu segregation protrudes toward the base 40 Conductor layer 43 Winding 50 External electrode 60 Winding core 61 Flange L Length direction La 1 , La 3 Cu segregation material lateral length Lb 1 , Lb 3 Cu segregation material longitudinal length T Thickness direction T 0 Insulating film thickness T 1 , T 3 Cu segregation Thickness of insulating film in contact with object directly W width direction

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