WO2024100941A1 - 電子部品 - Google Patents

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Publication number
WO2024100941A1
WO2024100941A1 PCT/JP2023/027445 JP2023027445W WO2024100941A1 WO 2024100941 A1 WO2024100941 A1 WO 2024100941A1 JP 2023027445 W JP2023027445 W JP 2023027445W WO 2024100941 A1 WO2024100941 A1 WO 2024100941A1
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WIPO (PCT)
Prior art keywords
glass film
element body
potassium
arithmetic mean
mean roughness
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/JP2023/027445
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English (en)
French (fr)
Japanese (ja)
Inventor
知也 大島
悠太 星野
耕市 山田
康次郎 時枝
美希 佐々木
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
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Publication date
Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to CN202380077960.5A priority Critical patent/CN120202517A/zh
Priority to JP2024519778A priority patent/JP7529183B1/ja
Publication of WO2024100941A1 publication Critical patent/WO2024100941A1/ja
Priority to US19/189,284 priority patent/US20250266189A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/02—Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points specially adapted for resistors; Arrangements of terminals or tapping points on resistors
    • H01C1/1413—Terminals or electrodes formed on resistive elements having negative temperature coefficient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points specially adapted for resistors; Arrangements of terminals or tapping points on resistors
    • H01C1/148—Terminals or tapping points specially adapted for resistors; Arrangements of terminals or tapping points on resistors the terminals embracing or surrounding the resistive element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008—Thermistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/18—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material comprising a plurality of layers stacked between terminals
    • 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
    • H01F27/02—Casings
    • 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
    • H01F27/02—Casings
    • H01F27/022—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G2/00—Details of capacitors not covered by a single one of groups H01G4/00-H01G11/00
    • H01G2/10—Housing; Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/224—Housing; Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors (thin- or thick-film circuits; capacitors without a potential-jump or surface barrier specially adapted for integrated circuits, details thereof, multistep manufacturing processes therefor)

Definitions

  • This disclosure relates to electronic components.
  • the electronic component described in Patent Document 1 comprises an element body, a glass film, and external electrodes.
  • the element body is made of ceramics.
  • the external electrodes cover both end faces of the element body.
  • the glass film covers the side faces of the element body.
  • the glass film is sufficiently thin, about 0.05 to 0.2 ⁇ m thick. Therefore, the surface roughness of the outer surface of the glass film is approximately the same as the surface roughness of the outer surface of the element body.
  • the glass film In electronic components such as those described in Patent Document 1, it is preferable for the glass film to be as thin as possible, for example, in order to ensure electrical continuity between internal and external electrodes and to reduce the dimensions of the electronic component. However, if the glass film is made thin, the glass film is prone to damage such as cracks and chips when the electronic component rubs against another object.
  • an electronic component comprises an element body and a glass film covering the outer surface of the element body, the glass film containing one or more elements selected from alkali metals and alkaline earth metals as additives, the average thickness of the glass film is 80 nm or more and 5000 nm or less, and the ratio of the arithmetic mean roughness of the outer surface of the glass film to the arithmetic mean roughness of the outer surface of the element body is 0.0002 or more and 0.85 or less.
  • the outer surface of the glass film is smooth relative to the outer surface of the element body. This reduces the frictional force that occurs on the outer surface of the glass film when it rubs against another object. This makes it less likely that the glass film will break or chip.
  • the outer surface of the element body is rougher than the outer surface of the glass film. This provides sufficient adhesion of the glass film to the element body.
  • FIG. FIG. 3 is a cross-sectional view taken along line 3-3 in FIG. 2. 3 is an enlarged cross-sectional view of the outer surface of the element body and the outer surface of the glass film.
  • FIG. FIG. 4 is an enlarged cross-sectional view of the vicinity of a recess of the electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 1A to 1C are explanatory diagrams illustrating a manufacturing method of an electronic component.
  • 11 is a table showing the results of comparing electronic components between an example and a comparative example.
  • the electronic component 10 is, for example, a surface-mount type negative temperature coefficient thermistor component that is mounted on a circuit board, etc. Note that a negative temperature coefficient thermistor component has a characteristic that its resistance value decreases as the temperature increases.
  • the electronic component 10 includes an element body 20.
  • the element body 20 is generally rectangular prism-shaped and has a central axis CA.
  • an axis extending along the central axis CA is defined as a first axis X.
  • One of the axes perpendicular to the first axis X is defined as a second axis Y.
  • An axis perpendicular to the first axis X and the second axis Y is defined as a third axis Z.
  • One of the directions along the first axis X is defined as a first positive direction X1
  • the direction along the first axis X opposite to the first positive direction X1 is defined as a first negative direction X2.
  • One of the directions along the second axis Y is defined as a second positive direction Y1, and the direction along the second axis Y opposite to the second positive direction Y1 is defined as a second negative direction Y2.
  • One of the directions along the third axis Z is defined as a third positive direction Z1, and the direction along the third axis Z opposite to the third positive direction Z1 is defined as a third negative direction Z2.
  • the outer surface 21 of the element body 20 has six flat surfaces 22.
  • the "surface” of the element body 20 here refers to a surface that can be observed when the entire element body 20 is observed. In other words, even if there are minute irregularities or steps that cannot be seen unless a part of the element body 20 is magnified and observed with a microscope, the surface is expressed as a flat surface or a curved surface.
  • the six flat surfaces 22 face in different directions.
  • the six flat surfaces 22 are broadly divided into a first end surface 22A facing the first positive direction X1, a second end surface 22B facing the first negative direction X2, and four side surfaces 22C.
  • the four side surfaces 22C are a surface facing the third positive direction Z1, a surface facing the third negative direction Z2, a surface facing the second positive direction Y1, and a surface facing the second negative direction Y2, respectively.
  • the boundary portion between two adjacent flat surfaces 22 and the boundary portion between three adjacent surfaces are curved.
  • the corners of the element body 20 are rounded and chamfered.
  • the outer surface 51 of the glass film 50 which will be described later, is identified with the outer surface 21 of the element body 20 and is given a reference number.
  • the element body 20 has a larger dimension along the first axis X than along the third axis Z. Also, as shown in FIG. 1, the element body 20 has a larger dimension along the first axis X than along the second axis Y.
  • the material of the element body 20 is a ceramic made by sintering a metal oxide containing one or more elements selected from Mn, Fe, Ni, Co, Ti, Ba, Al, and Zn.
  • the electronic component 10 has two first internal electrodes 41 and two second internal electrodes 42.
  • the first internal electrodes 41 and the second internal electrodes 42 are embedded inside the element body 20.
  • the material of the first internal electrode 41 is a conductive material.
  • the material of the first internal electrode 41 is palladium.
  • the material of the second internal electrode 42 is the same as the material of the first internal electrode 41.
  • the first internal electrode 41 has a rectangular plate shape.
  • the main surface of the first internal electrode 41 is perpendicular to the second axis Y.
  • the second internal electrode 42 has the same rectangular plate shape as the first internal electrode 41.
  • the main surface of the second internal electrode 42 is perpendicular to the second axis Y, similar to the first internal electrode 41.
  • the dimension of the first internal electrode 41 in the direction along the first axis X is smaller than the dimension of the element body 20 in the direction along the first axis X. Also, as shown in FIG. 1, the dimension of the first internal electrode 41 in the direction along the third axis Z is approximately two-thirds of the dimension of the element body 20 in the direction along the third axis Z. The dimensions of the second internal electrode 42 in each direction are the same as those of the first internal electrode 41.
  • the first internal electrode 41 and the second internal electrode 42 are positioned alternately in the direction along the second axis Y. That is, from the side surface 22C facing the second positive direction Y1 toward the second negative direction Y2, the first internal electrode 41, the second internal electrode 42, the first internal electrode 41, the second internal electrode 42 are arranged in this order. In this embodiment, the distance between each internal electrode in the direction along the second axis Y is equal.
  • the two first internal electrodes 41 and the two second internal electrodes 42 are both located at the center of the element body 20 in the direction along the third axis Z.
  • the first internal electrode 41 is located closer to the first positive direction X1.
  • the second internal electrode 42 is located closer to the first negative direction X2.
  • the end of the first internal electrode 41 on the first positive direction X1 side coincides with the end of the element body 20 on the first positive direction X1 side.
  • the end of the first internal electrode 41 on the first negative direction X2 side is located inside the element body 20 and does not reach the end of the element body 20 on the first negative direction X2 side.
  • the end of the second internal electrode 42 on the first negative direction X2 side coincides with the end of the element body 20 on the first negative direction X2 side.
  • the end of the second internal electrode 42 on the first positive direction X1 side is located inside the element body 20 and does not reach the end of the element body 20 on the first positive direction X1 side.
  • the electronic component 10 includes a glass film 50.
  • the glass film 50 covers the outer surface 21 of the element body 20. In this embodiment, the glass film 50 covers substantially the entire area of the outer surface 21 of the element body 20.
  • the main material of the glass film 50 is insulating glass. Therefore, the glass film 50 contains silicon dioxide.
  • the glass film 50 also contains one or more elements selected from alkali metals and alkaline earth metals as additives. Specifically, the glass film 50 contains potassium as an additive.
  • the value of "K/Si" which is the ratio of potassium to silicon contained in the glass film 50, is 0.5 atm% or more and 90 atm% or less. Specifically, the ratio of potassium to silicon contained in the glass film 50 is about 30 atm%.
  • the electronic component 10 includes a first external electrode 61 and a second external electrode 62.
  • the first external electrode 61 includes a first base electrode 61A and a first metal layer 61B.
  • the first base electrode 61A is laminated on the glass film 50 in a portion of the outer surface 21 of the element body 20, including the first end face 22A.
  • the first base electrode 61A is a five-sided electrode that covers the first end face 22A of the element body 20 and portions of the four side faces 22C in the first positive direction X1.
  • the material of the first base electrode 61A is silver and glass.
  • the first metal layer 61B covers the first base electrode 61A from the outside. Therefore, the first metal layer 61B is laminated on the first base electrode 61A. Although not shown in the figure, the first metal layer 61B has a two-layer structure consisting of, in order from the first base electrode 61A side, a nickel layer and a tin layer.
  • the second external electrode 62 has a second base electrode 62A and a second metal layer 62B.
  • the second base electrode 62A is laminated on the glass film 50 in a portion of the outer surface 21 of the element body 20, including the second end face 22B.
  • the second base electrode 62A is a five-sided electrode that covers the second end face 22B of the element body 20 and portions of the four side faces 22C in the first negative direction X2.
  • the material of the second base electrode 62A is the same as the material of the first external electrode 61, which is a mixture of silver and glass.
  • the second metal layer 62B covers the second base electrode 62A from the outside. In other words, the second metal layer 62B is laminated on the second base electrode 62A.
  • the second metal layer 62B has a two-layer structure, consisting of nickel plating and tin plating, in that order from the element body 20 side, just like the first metal layer 61B.
  • the second external electrode 62 does not reach the first external electrode 61 on the side surface 22C, and is disposed away from the first external electrode 61 in the direction along the first axis X.
  • the first external electrode 61 and the second external electrode 62 are not laminated, and the glass film 50 is exposed. Note that in Figures 1 to 3, the first external electrode 61 and the second external electrode 62 are illustrated by two-dot chain lines.
  • the first external electrode 61 and the end of the first internal electrode 41 on the first positive direction X1 side are connected via a first penetration portion 71 that penetrates the glass film 50.
  • the first penetration portion 71 is formed during the manufacturing process of the electronic component 10 when the palladium that constitutes the first internal electrode 41 extends toward the first external electrode 61.
  • the second external electrode 62 and the end of the second internal electrode 42 on the first negative direction X2 side are connected via a second penetration portion 72 that penetrates the glass film 50.
  • the second penetration portion 72 is formed by the palladium that constitutes the second internal electrode 42 extending toward the second external electrode 62 during the manufacturing process of the electronic component 10.
  • the first internal electrode 41 and the first penetration portion 71 are illustrated as separate members with a boundary, but in reality there is no clear boundary between the two. The same applies to the second penetration portion 72.
  • the first penetration portion 71 and the second penetration portion 72 are not illustrated in FIGS. 1 and 2.
  • the shortest distance from outer surface 21 of element body 20 to outer surface 51 of glass film 50 is defined as thickness TG of glass film 50.
  • the average value of thickness TG of glass film 50 is 80 nm or more and 5000 nm or less. Specifically, the average value of thickness TG of glass film 50 is 1200 nm.
  • the average value of thickness TG of glass film 50 is calculated as follows.
  • a location on the outer surface 21 of the element body 20 where there are no recesses 23 due to falling off of ceramic particles, cracks, or chips in the element body 20 is identified.
  • a cross-section of the element body 20 at that location is photographed with an electron microscope.
  • a range of at least 10 ⁇ m in the direction along the outer surface 51 of the glass film 50 is set as the measurement range.
  • image processing is used to calculate the cross-sectional area of the glass film 50 in that measurement range.
  • the cross-sectional area of the glass film 50 in that measurement range is then divided by the length of that measurement range in the direction along the outer surface 51 of the glass film 50 to calculate the average thickness TG of the glass film 50.
  • the average thickness TG of the glass film 50 is the average thickness TG in the measurement range.
  • the recesses 23 having a maximum depth H of 10 times or more the arithmetic mean roughness of the outer surface 21 of the element body 20 are considered to be recesses 23 caused by the above-mentioned falling off of ceramic particles, cracks and chips of the element body 20, etc.
  • the maximum depth H of the recesses 23 is calculated as follows. First, the element body 20 is ground in a direction perpendicular to the outer surface 21 by focused ion beam processing. An image of the ground cross section of the element body 20 is taken. Then, as shown in FIG. 5, a tangent line CL is drawn on this cross section, circumscribing both of the outer surfaces 21 on both sides of the recess 23.
  • a part of the tangent line CL may coincide with the outer surface 21.
  • the depth of the recess 23 is the length from the tangent line CL to the inner surface of the recess 23 in a direction perpendicular to the tangent line CL circumscribing the outer surface 21.
  • the element body 20 is ground by focused ion beam processing by a predetermined imaging pitch from the above-mentioned ground cross section.
  • the imaging pitch of focused ion beam processing is, for example, 10 nm.
  • a new ground cross section of the element body 20 is then imaged, and the maximum depth of the same recess 23 on the new cross section is measured. In this manner, grinding and measurement of the maximum depth of the recess 23 are repeated.
  • the largest value among the maximum depths on each ground cross section thus obtained is set as the maximum depth H of the entire recess 23.
  • the maximum depth H of the recess 23 here is the depth at the deepest point of the recess 23.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 is 0.1 nm or more and 5 nm or less. Specifically, the arithmetic mean roughness of the outer surface 51 of the glass film 50 is 5 nm.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 is calculated as follows. First, a location on the outer surface 21 of the element body 20 where there are no recesses 23 due to falling off of ceramic particles, cracks or chips of the element body 20, etc. is identified by the above-mentioned method.
  • a range of at least 10 ⁇ m or more in a linear direction along the outer surface 21 of the element body 20 is set as a measurement range in the location.
  • the arithmetic mean roughness of the glass film 50 is measured using a laser microscope for the measurement range.
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 is 5.9 nm or more and 500 nm or less. Specifically, the arithmetic mean roughness of the outer surface 21 of the element body 20 is 70 nm.
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 is calculated as follows. First, the glass film 50 is removed from the electronic component 10 using an alkaline aqueous solution or the like that dissolves the glass film 50 but does not dissolve the element body 20. Then, in the same manner as in measuring the arithmetic mean roughness of the outer surface 51 of the glass film 50, a location where there are no recesses 23 due to the falling off of ceramic particles, cracks and chips of the element body 20, etc.
  • a range of at least 10 ⁇ m or more in a linear direction along the outer surface 21 of the element body 20 is set as the measurement range.
  • the arithmetic mean roughness of the element body 20 is measured using a laser microscope for that measurement range.
  • the element body 20 is formed by barrel polishing in the R chamfering process S12 described later. Therefore, the entire outer surface 21 of the element body 20 has the same degree of roughness, except for the recesses 23 caused by falling ceramic particles, cracks, and chips in the element body 20.
  • the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is 0.0002 or more and 0.85 or less. Specifically, the above ratio in the above embodiment is about 0.07.
  • the method for producing electronic component 10 includes a laminate preparation step S11, an R-chamfering process step S12, a solvent introduction step S13, a catalyst introduction step S14, an element introduction step S15, a polymer introduction step S16, and a metal alkoxide introduction step S17.
  • the method for producing electronic component 10 further includes a film formation step S18, a first drying step S19, an immersion step S20, a second drying step S21, a conductor coating step S22, a curing step S23, and a plating step S24.
  • a laminate is prepared, which is a rectangular parallelepiped element body 20 having six planes 22. That is, the laminate at this stage is in a state before R-chamfering.
  • a plurality of ceramic sheets that will become the element body 20 are prepared. The sheets are thin plates. A conductive paste that will become the first internal electrode 41 is laminated on the sheets. A ceramic sheet that will become the element body 20 is laminated on the laminate paste. A conductive paste that will become the second internal electrode 42 is laminated on the sheet. In this manner, the ceramic sheet and the conductive paste are laminated. Then, the laminate is cut to a predetermined size to form an unfired laminate. The unfired laminate is then fired at a high temperature to prepare the laminate.
  • the R-chamfering process S12 is performed.
  • curved surfaces are formed at the boundary portions between two adjacent flat surfaces 22 of the laminate prepared in the laminate preparation process S11, and at the boundary portions between three adjacent flat surfaces 22.
  • the corners of the laminate are R-chamfered by barrel polishing, thereby forming curved surfaces at the above-mentioned boundary portions.
  • a solvent introduction step S13 is performed as shown in Fig. 6.
  • a solvent introduction step S13 2-propanol is introduced into a reaction vessel 81 as a solvent 82.
  • a catalyst introduction step S14 is performed as shown in Fig. 6.
  • the catalyst introduction step S14 first, stirring of the solvent 82 in the reaction vessel 81 is started. Then, ammonia water is introduced into the reaction vessel 81 as an aqueous solution 83 containing a catalyst.
  • the catalyst in this embodiment is a hydroxide ion, which functions as a catalyst for promoting hydrolysis of a metal alkoxide 85 described later.
  • the element introduction step S15 is performed. As shown in FIG. 9, in the element introduction step S15, a plurality of element bodies 20 that have been previously formed in the R chamfering step S12 as described above are introduced into a reaction vessel 81.
  • a polymer introduction step S16 is performed.
  • polyvinylpyrrolidone is introduced into the reaction vessel 81 as the polymer 84.
  • the polymer 84 introduced into the reaction vessel 81 is adsorbed onto the outer surface 21 of the element body 20.
  • a metal alkoxide introduction step S17 is performed.
  • liquid tetraethyl orthosilicate is introduced into the reaction vessel 81 as the metal alkoxide 85.
  • tetraethyl orthosilicate is also called tetraethoxysilane.
  • the amount of metal alkoxide 85 introduced in the metal alkoxide introduction step S17 is calculated based on the area of the outer surface 21 of the element body 20 introduced in the element introduction step S15. Specifically, the amount of metal alkoxide 85 required per element body 20 to form the glass film 50 covering the outer surface 21 of the element body 20 is multiplied by the number of element bodies 20 to calculate the amount.
  • the film formation step S18 is performed.
  • the stirring of the solvent 82 which was started in the above-mentioned solvent introduction step S13, is continued for a predetermined time after the metal alkoxide 85 is introduced into the reaction vessel 81 in the metal alkoxide introduction step S17.
  • the metal alkoxide 85 is hydrolyzed by the hydroxide ions, which serve as a catalyst.
  • the hydrolyzed metal alkoxide 85 adheres to the surface of the element body 20.
  • the metal alkoxides 85 attached to the surface of the element body 20 are dehydrated and condensed with each other to form the glass film 50.
  • a sol-like glass film 50 is formed by a liquid-phase reaction in the reaction vessel 81.
  • a first drying step S19 is performed.
  • the element body 20 is removed from the reaction vessel 81 and dried.
  • the sol-like glass film 50 is dried and becomes a gel-like glass film 50.
  • the immersion step S20 is performed.
  • a solution 87 containing at least one element selected from alkali metals and alkaline earth metals as an additive is placed in advance in a reaction vessel 86 different from the reaction vessel 81 used up to the film-forming step S18.
  • the solution 87 is an aqueous solution containing a potassium oxide precursor.
  • the element body 20 having the gelled glass film 50 is immersed in the solution 87.
  • the solution 87 adheres to the surface of the glass film 50.
  • a second drying step S21 is performed.
  • the element 20 immersed in the solution 87 in the immersion step S20 is removed from the reaction vessel 86 and dried. This causes the water in the solution 87 adhering to the surface of the glass film 50 to evaporate. Meanwhile, the potassium oxide precursor contained in the solution 87 precipitates on the outer surface 51 of the glass film 50.
  • the conductor application process S22 is performed.
  • conductor paste is applied to two locations on the surface of the glass film 50: a portion including a portion covering the first end face 22A of the element body 20, and a portion including a portion covering the second end face 22B of the element body 20.
  • the conductor paste is applied to cover the glass film 50 over the entire first end face 22A and parts of the four side faces 22C.
  • the conductor paste is also applied to cover the glass film 50 over the entire second end face 22B and parts of the four side faces 22C.
  • the hardening step S23 is performed. Specifically, in the hardening step S23, the glass film 50 and the element 20 on which the conductor paste has been applied are heated. As a result, the precipitated potassium oxide precursor becomes potassium oxide. The potassium oxide diffuses into the glass film 50 covering the outer surface 21 of the element 20. Then, water and polymer 84 evaporate from the gelled glass film 50, and the glass film 50 covering the outer surface 21 of the element 20 is baked and hardened. Furthermore, in the hardening step S23, the conductor paste applied in the conductor application step S22 is baked to form the first base electrode 61A and the second base electrode 62A.
  • the Kirkendall effect which arises from the difference in diffusion rate between the first internal electrode 41 and the first base electrode 61A, attracts palladium contained in the first internal electrode 41 to the first base electrode 61A, which contains silver.
  • the first penetration portion 71 extends from the first internal electrode 41 toward the first base electrode 61A through the glass film 50, connecting the first internal electrode 41 to the first base electrode 61A.
  • the second penetration portion 72 that connects the second internal electrode 42 to the second base electrode 62A.
  • the plating process S24 is performed. Electroplating is performed on the first base electrode 61A and the second base electrode 62A. As a result, a first metal layer 61B is formed on the surface of the first base electrode 61A. Also, a second metal layer 62B is formed on the surface of the second base electrode 62A. Although not shown in the figure, the first metal layer 61B and the second metal layer 62B are electroplated with two types of metal, nickel and tin, to form a two-layer structure. In this manner, the electronic component 10 is formed.
  • the electronic component 10 of Example 1 is the one described in the above embodiment. That is, the average thickness TG of the glass film 50 is 1200 nm.
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 is 70 nm.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 is 5 nm. Therefore, the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is approximately 0.07.
  • the structure of the electronic component 10 in Examples 2 and 3 is similar to that described in the above embodiment. However, the thickness TG of the glass film 50, the arithmetic mean roughness of the outer surface 21 of the element body 20, and the arithmetic mean roughness of the outer surface 51 of the glass film 50 are different.
  • the average thickness TG of the glass film 50 is 80 nm. Furthermore, the arithmetic mean roughness of the outer surface 21 of the element body 20 is 5.9 nm. The arithmetic mean roughness of the outer surface 51 of the glass film 50 is 5 nm. Therefore, the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is approximately 0.85.
  • the average thickness TG of the glass film 50 is 5000 nm.
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 is 500 nm.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 is 0.1 nm. Therefore, the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is approximately 0.0002.
  • the arithmetic mean roughness of the outer surface 21 of the base body 20 can be adjusted as in each embodiment.
  • the time conditions of the film-forming process S18 and the concentration of the additive in the immersion process S20 can be adjusted as in each embodiment.
  • the structure of the electronic component of the comparative example is similar to that described in the above embodiment. However, the thickness TG of the glass film 50, the arithmetic mean roughness of the outer surface 21 of the element body 20, and the arithmetic mean roughness of the outer surface 51 of the glass film 50 are different.
  • the average thickness TG of the glass film 50 is 80 nm. Furthermore, the arithmetic mean roughness of the outer surface 21 of the element body 20 is 10 nm. The arithmetic mean roughness of the outer surface 51 of the glass film 50 is 10 nm. Therefore, the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is 1.
  • the electronic component of the comparative example was manufactured by the above-mentioned manufacturing method without carrying out the immersion step S20 and the second drying step S21.
  • the glass film 50 of the electronic component of the comparative example does not contain alkali metals and alkaline earth metals as additives.
  • the durability of the glass film 50 was evaluated by a micro-scratch test for the electronic components 10 of Examples 1 to 3 and the electronic component of the comparative example. Evaluation by the micro-scratch test was performed by scanning 400 ⁇ m with a load of 100 mN using a diamond needle with a tip curvature radius of 25 ⁇ m. If no scratches were observed, the sample was judged as passing, and if scratches were observed, the sample was judged as failing. In FIG. 13, ⁇ indicates passing, and ⁇ indicates failing.
  • the electronic components 10 of Examples 1 to 3 passed the micro-scratch test.
  • the electronic component of the comparative example failed the micro-scratch test. From these test results, it was found that it is preferable in terms of the durability of the glass film 50 if the arithmetic mean roughness of the outer surface 51 of the glass film 50 is smaller than the arithmetic mean roughness of the outer surface 21 of the element body 20.
  • the micro-scratch test can be passed if the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is 0.0002 or more and 0.85 or less. It was also found that the micro-scratch test can be passed even if the average value of the thickness TG of the glass film 50 is considerably thin, less than 5000 nm, so long as the above arithmetic mean roughness conditions are satisfied.
  • the ratio of the arithmetic mean roughness of the outer surface 51 of the glass film 50 to the arithmetic mean roughness of the outer surface 21 of the element body 20 is 0.0002 or more and 0.85 or less.
  • the outer surface 51 of the glass film 50 is smoother than the outer surface 21 of the element body 20. This reduces the frictional force generated on the outer surface 51 of the glass film 50 when the outer surface 51 of the glass film 50 rubs against another object. Therefore, the glass film 50 is less likely to be damaged, such as cracked or chipped.
  • the outer surface 21 of the element body 20 is rougher than the outer surface 51 of the glass film 50. Therefore, a sufficient adhesion force is obtained as the adhesion force of the glass film 50 to the element body 20.
  • the thickness TG of the glass film 50 is 80 nm or more and 5000 nm or less. If the thickness TG of the glass film 50 is thus thin, interfacial stress between the element body 20 and the glass film 50 is less likely to occur. Therefore, the glass film 50 is less likely to peel off from the element body 20.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 is 0.1 nm or more and 5 nm or less.
  • the outer surface 51 of the glass film 50 is considerably smooth. This reduces the frictional force generated on the outer surface 51 of the glass film 50. Therefore, the outer surface 51 of the glass film 50 is less likely to be scratched.
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 is 5.9 nm or more and 500 nm or less.
  • the presence of a certain degree of unevenness on the outer surface 21 of the element body 20 in this manner creates an anchor effect between the element body 20 and the glass film 50. This improves the adhesion between the element body 20 and the glass film 50.
  • the glass components of the first base electrode 61A diffuse into the glass film 50 and are integrated therewith.
  • the outer surface 51 of the glass film 50 is smooth, while also ensuring adhesion to the first base electrode 61A.
  • the second base electrode 62A is the same.
  • the glass film 50 contains one or more elements selected from alkali metals and alkaline earth metals as additives, and the ratio of the additive to the Si contained in the glass film 50 is 0.5 atm% or more and 90 atm% or less.
  • the ratio of the additive to the Si contained in the glass film 50 is 0.5 atm% or more and 90 atm% or less.
  • the electronic component 10 is not limited to a negative characteristic thermistor component.
  • it may be a thermistor component other than a negative characteristic, or it may be a multilayer capacitor component or an inductor component.
  • the material of the element body 20 is not limited to the example in the above embodiment.
  • the material of the element body 20 may be a composite body of resin and metal powder.
  • the shape of the element body 20 is not limited to the example of the above embodiment.
  • the element body 20 may be a polygonal columnar shape other than a quadrangular columnar shape having a central axis CA.
  • the element body 20 may also be a core of a wire-wound inductor component.
  • the core may have a so-called drum core shape.
  • the core may have a columnar winding core portion and flange portions provided at each end of the winding core portion.
  • the boundary portion between adjacent flat surfaces 22 of the outer surface 21 of the element body 20 does not have to be chamfered. In this case, no curved surface exists at the boundary portion.
  • the shapes of the first internal electrode 41 and the second internal electrode 42 are not important as long as they can ensure electrical conduction with the corresponding first external electrode 61 and second external electrode 62.
  • the number of first internal electrodes 41 and second internal electrodes 42 is not important, and the number of internal electrodes may be one, or three or more.
  • the configuration of the first external electrode 61 is not limited to the example of the above embodiment.
  • the first external electrode 61 may be composed of only the first base electrode 61A, and the first metal layer 61B may not have a two-layer structure. The same applies to the second external electrode 62.
  • the first base electrode 61A need only be electrically conductive with the first internal electrode 41, and need not contain glass.
  • the second base electrode 62A need only be electrically conductive with the second internal electrode 42, and need not contain glass.
  • the combination of materials between the first internal electrode 41 and the first base electrode 61A is not limited to the combination of palladium and silver.
  • it may be a combination of copper and nickel, copper and silver, silver and gold, nickel and cobalt, or nickel and gold.
  • it may be a combination of one being silver and the other being silver and palladium.
  • it may be a combination of one being palladium and the other being silver and palladium, or it may be a combination of one being copper and the other being silver and palladium.
  • it may be a combination of one being gold and the other being silver and palladium.
  • the Kirkendall effect may not be obtained.
  • the first internal electrode 41 may be processed to be exposed before the external electrode formation process.
  • the first end surface 22A side of the element body 20 may be polished to physically remove a part of the glass film 50.
  • the base electrode formation process may then be performed to connect the first internal electrode 41 and the first base electrode 61A.
  • the glass film 50 may be formed including the surface of the first base electrode 61A, and the glass film 50 covering the surface of the first base electrode 61A may be removed. This also applies to the combination of materials for the second internal electrode 42 and the second base electrode 62A.
  • the location of the first external electrode 61 is not limited to the example of the above embodiment.
  • the first external electrode 61 may be disposed only on the first end surface 22A and one side surface 22C.
  • the glass film 50 does not have to cover substantially all of the area of the outer surface 21 of the element body 20.
  • the area covered by the glass film 50 may be changed as appropriate depending on the shape of the element body 20, the positions of the first external electrode 61 and the second external electrode 62, etc.
  • the glass in the glass film 50 may diffuse into the glass in the first base electrode 61A, so that the two become integrated.
  • the ratio of the additives to the Si contained in the glass film 50 may be less than 0.5 atm% or greater than 90 atm%.
  • the material of the glass film 50 is not limited to the example of the above embodiment.
  • the glass is not limited to silicon dioxide, but may be a multi-component oxide containing Si, such as B-Si, Si-Zn, Zr-Si, or Al-Si oxides.
  • the glass may also be a multi-component oxide containing an alkali metal and Si, such as Al-Si, Na-Si, or Li-Si oxides.
  • the glass may be a multi-component oxide containing an alkaline earth metal and Si, such as Mg-Si, Ca-Si, Ba-Si, or Sr-Si.
  • the glass may not contain Si, and may be a mixture of these.
  • the material of the glass film 50 may contain, in addition to glass, a pigment, a silicone-based flame retardant, a surface treatment agent such as a silane coupling agent or a titanate coupling agent, or an antistatic agent. More specifically, the glass film 50 may contain, in addition to glass, additives such as organic acid salts, oxides, inorganic salts, organic salts, and fine particles and nanoparticles of other metal oxides.
  • the additives contained in the solution 87 are not limited to the potassium oxide precursor.
  • organic acid salts include salts of oxoacids such as soda ash, sodium carbonate, sodium hydrogen carbonate, sodium percarbonate, sodium sulfite, sodium hydrogen sulfite, sodium sulfate, sodium thiosulfate, sodium nitrate, and sodium sulfite, and halogen compounds such as sodium fluoride, sodium chloride, sodium bromide, and sodium iodide.
  • oxoacids such as soda ash, sodium carbonate, sodium hydrogen carbonate, sodium percarbonate, sodium sulfite, sodium hydrogen sulfite, sodium sulfate, sodium thiosulfate, sodium nitrate, and sodium sulfite
  • halogen compounds such as sodium fluoride, sodium chloride, sodium bromide, and sodium iodide.
  • An example of the oxide is sodium peroxide
  • an example of the hydroxide is sodium hydroxide.
  • examples of inorganic salts include sodium hydride, sodium sulfide, sodium hydrogen sulfide, sodium silicate, trisodium phosphate, sodium borate, sodium borohydride, sodium cyanide, sodium cyanate, and sodium tetrachloroaurate.
  • Inorganic salts include calcium peroxide, calcium hydroxide, calcium fluoride, calcium chloride, calcium bromide, calcium iodide, calcium hydride, calcium carbide, and calcium phosphide.
  • Additives may be oxoacid salts such as calcium carbonate, calcium bicarbonate, calcium nitrate, calcium sulfate, calcium sulfite, calcium silicate, calcium phosphate, calcium pyrophosphate, calcium hypochlorite, calcium chlorate, calcium perchlorate, calcium bromate, calcium iodate, calcium arsenite, calcium chromate, calcium tungstate, calcium molybdate, calcium magnesium carbonate, and hydroxyapatite.
  • Other examples of additives include calcium acetate, calcium gluconate, calcium citrate, calcium malate, calcium lactate, calcium benzoate, calcium stearate, and calcium aspartate.
  • the additive may be lithium carbonate, lithium chloride, lithium titanate, lithium nitride, lithium peroxide, lithium citrate, lithium fluoride, lithium hexafluorophosphate, lithium acetate, lithium iodide, lithium hypochlorite, lithium tetraborate, lithium bromide, lithium nitrate, lithium hydroxide, lithium aluminum hydride, lithium triethylborohydride, lithium hydride, lithium amide, lithium imide, lithium diisopropylamide, lithium tetramethylpiperidide, lithium sulfide, lithium sulfate, lithium thiophenolate, or lithium phenoxide.
  • the additive may be boron triiodide, sodium cyanoborohydride, sodium borohydride, tetrafluoroboric acid, triethylborane, borax, or boric acid.
  • the additive may be barium sulfite, barium chloride, barium chlorate, barium perchlorate, barium peroxide, barium chromate, barium acetate, barium cyanide, barium bromide, barium oxalate, barium nitrate, barium hydroxide, barium hydride, barium carbonate, barium iodide, barium sulfide, or barium sulfate.
  • the additive may be sodium acetate or sodium citrate.
  • the additive may also be fine particles or nanoparticles of metal oxides, such as sodium oxide, calcium oxide, lithium oxide, boron oxide, barium oxide, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, and magnesium oxide.
  • metal oxides such as sodium oxide, calcium oxide, lithium oxide, boron oxide, barium oxide, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, and magnesium oxide.
  • the potassium oxide precursor may be, for example, potassium arsenide, potassium bromide, potassium carbonate, potassium chloride, potassium fluoride, potassium hydride, potassium iodide, potassium triiodide, potassium azide, potassium nitride, potassium superoxide, potassium ozonate, potassium peroxide, potassium phosphide, potassium sulfide, potassium selenide, potassium telluride, potassium tetrafluoroaluminate, potassium tetrafluoroborate, potassium tetrahydroborate, potassium methanide, potassium cyanide, potassium formate, or hydrogen fluoride.
  • potassium arsenide potassium bromide, potassium carbonate, potassium chloride, potassium fluoride, potassium hydride, potassium iodide, potassium triiodide, potassium azide, potassium nitride, potassium superoxide, potassium ozonate, potassium peroxide, potassium phosphide, potassium sulfide, potassium selenide, potassium telluride, potassium
  • Metal alkoxide 85 includes, for example, sodium methoxide, sodium ethoxide, calcium diethoxide, lithium isopropoxide, lithium ethoxide, lithium tert-butoxide, lithium methoxide, boron alkoxide, potassium t-butoxide, tetraethyl orthosilicate, allyltrimethoxysilane, isobutyl(trimethoxy)silane, tetrapropyl orthosilicate, tetramethyl orthosilicate, [3-(diethylamino)propyl]trimethoxysilane, triethoxy (octyl)silane, triethoxyvinylsilane, triethoxyphenylsilane, trimethoxyphenylsilane, trimethoxymethylsilane, butyltrichlorosilane, n-propyltriethoxysilane, methyltrichlorosilane, dimeth
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 may be less than 0.1 nm. That is, the outer surface 51 of the glass film 50 may be smoother than the example given in this embodiment.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 may be greater than 5 nm. According to the present invention, the arithmetic mean roughness of the outer surface 51 of the glass film 50 relative to the arithmetic mean roughness of the outer surface 21 of the base body 20 can be made smaller than when the glass film 50 does not contain any additives. This achieves the effect described in (1).
  • the arithmetic mean roughness of the outer surface 21 of the element body 20 may be less than 5.9 nm or greater than 500 nm. If the outer surface 51 of the glass film 50 is sufficiently smooth compared to the roughness of the outer surface 21 of the element body 20, the effect described in (1) can be obtained.
  • the method of measuring the arithmetic mean roughness of the outer surface 51 of the glass film 50 and the arithmetic mean roughness of the outer surface 21 of the element body 20 is not limited to the example of this embodiment.
  • the cross section of the element body 20 may be photographed with an electron microscope, and the arithmetic mean roughness may be obtained by performing image analysis on the photographed image in a range of at least 10 ⁇ m or more in the direction along the outer surface 51 of the glass film 50.
  • the measurement points of the outer surface 51 of the glass film 50 and the measurement points of the outer surface 21 of the element body 20 may be approximately the same, and the arithmetic mean roughness may be obtained by the above method.
  • an instrument such as a white light interferometer, an atomic force microscope, or a stylus profiling system may be used instead of a laser microscope.
  • the instrument for measuring the arithmetic mean roughness of the outer surface 51 of the glass film 50 and the instrument for measuring the arithmetic mean roughness of the outer surface 21 of the element body 20 do not have to be the same.
  • the arithmetic mean roughness of the outer surface 51 of the glass film 50 may be measured using a white light interferometer, and the arithmetic mean roughness of the outer surface 21 of the element body 20 may be measured using a laser microscope.
  • the present invention comprises an element body and a glass film covering an outer surface of the element body,
  • the glass film contains one or more elements selected from alkali metals and alkaline earth metals as an additive,
  • the average thickness of the glass film is 80 nm or more and 5000 nm or less,
  • An electronic component wherein a ratio of the arithmetic mean roughness of the outer surface of the glass film to the arithmetic mean roughness of the outer surface of the element body is 0.0002 or more and 0.85 or less.

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Publication number Priority date Publication date Assignee Title
WO2025249191A1 (ja) * 2024-05-31 2025-12-04 株式会社村田製作所 電子部品

Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH0696907A (ja) * 1992-09-11 1994-04-08 Murata Mfg Co Ltd チップバリスタの製造方法
JP2003151805A (ja) * 2001-11-15 2003-05-23 Murata Mfg Co Ltd チップ型電子部品およびその製造方法
JP2004128488A (ja) * 2002-09-10 2004-04-22 Murata Mfg Co Ltd チップ型電子部品
JP2010027730A (ja) * 2008-07-16 2010-02-04 Tdk Corp セラミック積層電子部品およびその製造方法
JP2018195760A (ja) * 2017-05-19 2018-12-06 Tdk株式会社 電子部品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0696907A (ja) * 1992-09-11 1994-04-08 Murata Mfg Co Ltd チップバリスタの製造方法
JP2003151805A (ja) * 2001-11-15 2003-05-23 Murata Mfg Co Ltd チップ型電子部品およびその製造方法
JP2004128488A (ja) * 2002-09-10 2004-04-22 Murata Mfg Co Ltd チップ型電子部品
JP2010027730A (ja) * 2008-07-16 2010-02-04 Tdk Corp セラミック積層電子部品およびその製造方法
JP2018195760A (ja) * 2017-05-19 2018-12-06 Tdk株式会社 電子部品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025249191A1 (ja) * 2024-05-31 2025-12-04 株式会社村田製作所 電子部品

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