WO2023032519A1 - 電子部品 - Google Patents

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Publication number
WO2023032519A1
WO2023032519A1 PCT/JP2022/028463 JP2022028463W WO2023032519A1 WO 2023032519 A1 WO2023032519 A1 WO 2023032519A1 JP 2022028463 W JP2022028463 W JP 2022028463W WO 2023032519 A1 WO2023032519 A1 WO 2023032519A1
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WIPO (PCT)
Prior art keywords
plating film
plating
electronic component
plane
film
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/JP2022/028463
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English (en)
French (fr)
Japanese (ja)
Inventor
真聖 長友
慶伸 崎
佳祐 磯貝
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
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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 DE112022003373.8T priority Critical patent/DE112022003373T5/de
Priority to JP2023545156A priority patent/JP7663126B2/ja
Priority to CN202280057566.0A priority patent/CN117916832A/zh
Publication of WO2023032519A1 publication Critical patent/WO2023032519A1/ja
Priority to US18/420,936 priority patent/US20240161949A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01C1/00—Details
    • H01C1/14—Terminals or tapping points specially adapted for resistors; Arrangements of terminals or tapping points on resistors
    • H01C1/1406—Terminals or electrodes formed on resistive elements having positive 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
    • H01C1/1413—Terminals or electrodes formed on resistive elements having negative temperature coefficient
    • 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
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
    • H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
    • 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
    • H01G4/228—Terminals
    • H01G4/248—Terminals the terminals embracing or surrounding the capacitive element, e.g. caps
    • 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
    • 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
    • H01C7/022—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 mainly consisting of non-metallic substances
    • H01C7/023—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 mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025—Perovskites, e.g. titanates
    • 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
    • H01C7/042—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 mainly consisting of inorganic non-metallic substances
    • H01C7/043—Oxides or oxidic compounds
    • H01C7/045—Perovskites, e.g. titanates
    • 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
    • H01C7/10—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 voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/115—Titanium dioxide- or titanate type
    • 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
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • 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
    • H01G4/228—Terminals
    • H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor

Definitions

  • the present invention relates to electronic components.
  • An electronic component such as a positive temperature coefficient thermistor generally includes an external electrode that is configured by laminating a conductive layer provided at the end of a ceramic body and a metal plating film formed by electrolytic plating, electroless plating, or the like.
  • the plated film can be formed from one layer or multiple layers.
  • the first plating film in contact with the conductive layer is a nickel plating film for the purpose of improving heat resistance, etc.
  • the second plating film covering the first plating film is a solderability. It is a tin-plated film for the purpose of improvement.
  • Patent Document 1 a conductive epoxy-based thermosetting resin layer containing metal powder (hereinafter referred to as a "resin layer”) is provided between the baked electrode and the plating layer in the external electrode of the electronic component. It has been proposed to provide a The resin layer functions as a stress-absorbing layer and can suppress the occurrence of cracks in the ceramic body.
  • Patent Document 1 In an external electrode including a resin layer as disclosed in Patent Document 1, the plated film formed on the resin layer may peel off. If the plating film peels off, there is a risk that contact failure will occur inside the external electrode and that the electronic component will not operate normally. Patent Document 1 does not discuss peeling of the plating layer formed on the resin layer.
  • the present invention has been made against the background of the above circumstances, and an object of the present invention is to suppress peeling of the plating film in an electronic component provided with an external electrode having a plating film on a resin layer.
  • an electronic component comprising a ceramic body and external electrodes at the ends of the ceramic body
  • the external electrode includes a resin layer containing conductive powder and a plated film in direct contact with the resin layer,
  • the plating film is made of a metal having a face-centered cubic structure
  • An electronic component is provided in which the plated film has an F value of 0.20 or more and 0.50 or less, which is determined by the following formula (1).
  • F (P ⁇ P 0 )/(1 ⁇ P 0 ) (1)
  • P0 and P are determined by the following formulas (2) and (3).
  • I 0 (111), I 0 (200) and I 0 (220) are respectively the (111) plane obtained from known powder X-ray diffraction data for the metal constituting the plating film , are the diffraction intensities of the (200) and (220) planes,
  • I (111), I (200) and I (220) are the (111) plane, (200) plane and (220) plane obtained from the X-ray diffraction pattern of the plating film, respectively. is the diffraction intensity.
  • FIG. 1 is a schematic cross-sectional view of an electronic component according to Embodiment 1.
  • FIG. 2 is a schematic cross-sectional view of an electronic component according to Embodiment 2.
  • FIG. 1 is a schematic cross-sectional view of an electronic component according to Embodiment 1.
  • FIG. 2 is a schematic cross-sectional view of an electronic component according to Embodiment 2.
  • the inventors of the present invention have made intensive studies to suppress peeling of the plating film in an electronic component having an external electrode including a resin layer and a plating film in direct contact with the resin layer. Then, the inventors have found that peeling of the plating film can be suppressed by improving the orientation of the metal material that constitutes the plating film, and have completed the present invention. Although the reason why such an effect is obtained is not clear, it is presumed to be the following mechanism.
  • the plating film is formed while smoothing (flattening) the surface of the plating film by the impact force caused by rotation.
  • the plated film grows chaotically due to the flattening, and the plated film is formed in which the crystal orientations are not aligned (that is, the crystallographic consistency is not consistent).
  • the chaotic growth of the plated film may cause defects in metal bonding inside the plated film.
  • the adhesiveness at the interface between the resin layer and the plated film is low, and the strength of the plated film itself is low. It is believed that the internal destruction of the film causes the film to peel off easily.
  • the present inventors believe that the crystallographic consistency of the plating film, and further the crystallographic consistency between the plating film and the conductive powder in the resin layer, contributes to the suppression of peeling of the plating film.
  • Study was carried out.
  • the inventors optimized the plating bath and plating conditions to grow the plating film so as to be strongly oriented in a specific plane ((111) plane) and have a regular crystal structure.
  • a plating film was formed. With such a plated film, the adhesion between the resin layer and the plated film is improved, and the strength of the plated film itself is also improved, so that peeling of the plated film can be suppressed.
  • FIG. 1 is a schematic cross-sectional view of an electronic component 10A according to Embodiment 1 of the present invention.
  • An example of the electronic component 10A shown in FIG. 1 is a positive temperature coefficient (or positive temperature coefficient, PTC) thermistor.
  • the electronic component 10A includes a ceramic body 20A and external electrodes provided at the ends of the ceramic body 20A.
  • the electronic component 10A has at least one external electrode.
  • the positive temperature coefficient thermistor shown in FIG. 1 has a pair of external electrodes 30 and 40 provided at both ends of a ceramic body 20A.
  • the external electrodes 30 , 40 include at least resin layers 32 , 42 containing conductive powder and plated films 33 , 43 directly contacting the resin layers 32 , 42 .
  • the external electrodes 30, 40 are further composed of underlying layers 31, 41 provided between the end faces 21A, 22A of the ceramic body 20A and the resin layers 32, 42, and second plating films covering the plating films 33, 43. 34, 44 may be provided.
  • the plating films 33 and 43 formed on the resin layers 32 and 42 are formed from a metal having a face-centered cubic structure in order to suppress peeling of the plating films 33 and 43. Furthermore, it was found that it is effective to preferentially orient the (111) plane with respect to the orientation of the crystal structure of the plating films 33 and 43 .
  • the value of F defined by the following formula (1) serves as an index.
  • P0 and P are determined by the following formulas (2) and (3).
  • P 0 I 0 (111)/ ⁇ I 0 (111)+I 0 (200)+I 0 (220) ⁇
  • P I(111)/ ⁇ I(111)+I(200)+I(220) ⁇
  • I 0 (111), I 0 (200) and I 0 (220) are respectively the (111) plane obtained from known powder X-ray diffraction data for the metal constituting the plating film , are the diffraction intensities of the (200) and (220) planes
  • I (111), I (200) and I (220) are the (111) plane, (200) plane and (220) plane obtained from the X-ray diffraction pattern of the plating film, respectively. is the diffraction intensity.
  • I(111), I(200) and I(220) are obtained from diffraction patterns obtained by measuring the plating films 33 and 43 with an XRD diffractometer.
  • a two-dimensional X-ray diffraction image obtained using a two-dimensional detector is converted into a one-dimensional profile, and the obtained one-dimensional profile is used to determine the peak diffraction intensity value of each orientation plane.
  • the value of the diffraction intensity is obtained as a relative intensity with 100 being the highest intensity.
  • a micro X-ray diffraction device can be used.
  • a specific device for example, there is D8 DISCOVER manufactured by BRUKER axs.
  • the second plating film 34 , 44 are removed to expose the plating films 33 and 43, and then the XRD diffraction of the plating films 33 and 43 is measured.
  • the value of F obtained by formulas (1) to (3) is an index of the orientation of the (111) plane of the material forming the plating films 33 and 43 .
  • Formulas (1) to (3) will be described in detail below.
  • a Lotgering factor f is known as a definition of the "degree of orientation" of a predetermined orientation plane.
  • the Lotgering factor f is calculated by the following formula (4) using the intensity of X-rays diffracted from a predetermined orientation plane (denoted as (xyz) for convenience).
  • f (pp 0 )/(1 ⁇ p 0 ) (4)
  • p 0 is a value based on known powder X-ray diffraction data for the substance of interest
  • p is a value based on the X-ray diffraction pattern of the substance of interest, and is represented by the following formula (5 ) and (6).
  • h, k, and l are integers including zero.
  • ⁇ I 0 (hkl) is the diffraction intensity of the peaks of all planes obtained from known powder X-ray diffraction data for the target substance (usually, relative intensity with the highest intensity being 100) means the sum
  • I 0 (xyz) means the value of diffraction intensity (ditto) of the peak in a given orientation plane (xyz) obtained from known powder X-ray diffraction data for the substance of interest.
  • the value of F can take a value of ⁇ 1 or more and 1 or less, and the closer to 1, the higher the orientation of the (111) plane of the plating films 33 and 43.
  • the value of F of the plating films 33 and 43 is 0.20 or more and 0.50 or less. If the value of F is less than 0.20, the adhesion between the resin layers 32, 42 and the plating films 33, 43 is not sufficient. If the value of F exceeds 0.50, the adhesion between the resin layers 32, 42 and the plated films 33, 43 increases, but the plated films 33, 43 having high orientation must be formed. In order to realize this, severe restrictions are imposed on the production conditions, which increases the manufacturing cost.
  • the value of F is preferably 0.23 or more and 0.48 or less, more preferably 0.25 or more and 0.45 or less.
  • the metal having a face-centered cubic structure, which constitutes the plating films 33 and 43, is preferably at least one selected from the group consisting of Ni, Au, Cu, Ag, Pt, Pd, and Al. .
  • the thickness of the plating films 33 and 43 may be any film thickness that can protect the end faces 21A and 22A of the ceramic body 20A of the electronic component 10A from the reflow atmosphere. .
  • the second plating films 34, 44 are selected from the group consisting of Sn, Au, Cu, and Pd. At least one selected is preferred.
  • the thickness of the second plating films 34 and 44 may be any thickness that allows the solder material to wet and spread during reflow.
  • the film thicknesses of the plated films 33, 43 and the second plated films 34, 44 are obtained by performing fluorescent X-ray analysis on samples with the respective plated films exposed on the outermost surface, and applying the obtained X-ray intensities to a calibration curve. Measure.
  • a calibration curve is obtained by performing fluorescent X-ray analysis on a standard sample with a known film thickness and plotting the relationship between the resulting X-ray intensity and film thickness using a regression equation.
  • the film thickness of the plated film in a standard sample of known film thickness is measured by the following method.
  • the resin layers 32, 42 of the external electrodes 30, 40 function as stress absorption layers that suppress the occurrence of cracks in the ceramic body 20A due to external impact, thermal stress, and the like.
  • the resin layers 32, 42 contain conductive powder and a resin material.
  • the resin layers 32 and 42 have conductivity due to the conductive powder dispersed in the resin material.
  • the conductive powder contained in the resin layers 32, 42 is preferably metal powder.
  • at least one metal powder selected from the group consisting of Ag, Au, Ni, Cu, Pt, Pd and Al is preferred. Since these metals have the same face-centered cubic structure as the metals forming the plating films 33, 43, the metal powder exposed on the surfaces of the resin layers 32, 42 and the metal powder formed on the surfaces of the resin layers 32, 42 The crystallographic consistency with the plated films 33 and 43 to be applied is good. Therefore, it is expected that the oriented growth of the plating films 33 and 43 is promoted. In addition, an effect of improving adhesion between the plating films 33 and 43 and the resin layers 32 and 42 is expected.
  • thermosetting resin As the resin material contained in the resin layers 32 and 42, a thermosetting resin, an ultraviolet curable resin, or the like is preferable, and a thermosetting resin having excellent heat resistance is particularly preferable.
  • Suitable thermosetting resins include, for example, epoxy resins, phenol resins, urethane resins, silicone resins, and polyimide resins. Epoxy resins are particularly preferred because of their excellent heat resistance, moisture resistance, and adhesion.
  • the resin materials may be used singly or in combination of two or more.
  • a curing agent may be included together with the thermosetting resin.
  • an epoxy resin is used as the base resin, known compounds such as phenol-based, amine-based, acid anhydride-based, and imidazole-based curing agents can be used.
  • the present invention is particularly effective in the small chip-type electronic component 10A. This is because the contact areas between the resin layers 32, 42 and the plated films 33, 43 are small in the small chip-type electronic component 10A, so the adhesion therebetween is particularly important.
  • the present invention is suitable for an electronic component 10A having a length of 0.6 mm or more and 1.0 mm or less and a width of 0.3 mm or more and 0.5 mm or less (equivalent to sizes 0603 to 1005).
  • Electronic components 10A suitable for applying the first embodiment include chip-type ceramic electronic components such as negative characteristic (or negative temperature coefficient, NTC) thermistors, varistors, and capacitors, in addition to the positive characteristic thermistors described above.
  • the materials forming the ceramic body 20A are selected according to the required characteristics.
  • a method for manufacturing the electronic component 10A according to Embodiment 1 will be described by taking a positive temperature coefficient thermistor having the structure shown in FIG. 1 as an example.
  • the ceramic body 20A is made of, for example, BaTiO 3 , CaTiO 3 , SrTiO 3 , CaZrO 3 , (BaSr)TiO 3 , Ba(ZrTi)O 3 and (BiZn)Nb 2 O 7 .
  • ceramic raw materials such as BaCO 3 , TiO 2 , PbO, SrCO 3 and CaCO 3 , Sm 2 O 3 , Er 2 O 3 and the like are used as raw materials for the ceramic body 20A.
  • the weighed raw materials are put into a ball mill together with grinding media such as partially stabilized zirconia (PSZ) (hereinafter also referred to as PSZ balls) and pure water, and wet-mixed and ground.
  • PSZ partially stabilized zirconia
  • pure water wet-mixed and ground.
  • the obtained mixture is calcined at a predetermined temperature (for example, 1000 to 1200° C.) to obtain a calcined powder.
  • An organic binder, dispersing agent, and pure water are added to the obtained calcined powder, mixed, and then dried to granulate.
  • a compact is obtained by molding the obtained granules. The compact is subjected to degreasing treatment and binder removal treatment, and fired at a prescribed temperature (1200 to 1400° C.) and in a prescribed atmosphere to obtain the ceramic body 20A.
  • underlayers 31 and 41 may be formed to cover the end surfaces 21A and 22A of the ceramic body 20A after the ceramic body 20A is fabricated.
  • a material having ohmic properties with the ceramic body 20A is appropriately selected.
  • metal materials such as Ag, Zn, Cr, Ni, Cu, Ti, W, V, Au, and Al, and oxides.
  • the underlayers 31 and 41 are formed by various thin film forming methods (sputtering method, vapor deposition method, etc.), various printing methods, dipping methods, or the like.
  • the underlying layers 31 and 41 are obtained by baking a conductive paste.
  • the baking temperature of the conductive paste is, for example, 500-900.degree.
  • Resin layers 32 and 42 containing conductive powder are formed at the ends of the ceramic body 20A.
  • the resin layers 32 and 42 are provided by curing a fluid resin electrode paste.
  • the resin electrode paste contains a conductive powder and a resin raw material. After the resin electrode paste is applied to the ends of the ceramic body 20 so as to cover the base layers 31 and 41, the resin raw material in the resin electrode paste is cured.
  • the conductive powder contained in the resin electrode paste is preferably a metal powder, particularly at least one metal powder selected from the group consisting of Ag, Au, Ni, Cu, Pt, Pd and Al. preferable.
  • the resin raw material contained in the resin electrode paste a material capable of forming the resin material contained in the resin layers 32 and 42 of the electronic component 10A is used. That is, the resin raw material contained in the resin electrode paste is preferably a resin raw material such as a thermosetting resin before curing or an ultraviolet curable resin before curing. is preferred. Suitable resin raw materials for thermosetting resins include, for example, epoxy resins, phenol resins, urethane resins, silicone resins, polyimide resins, etc. Resin raw materials for epoxy resins are particularly preferred. The resin raw material is preferably a liquid resin raw material. The resin raw materials may be used singly or in combination of two or more. It is preferable to use a curing agent together with the resin raw material of the thermosetting resin. When an epoxy resin is used as the base resin, known compounds such as phenol-based, amine-based, acid anhydride-based, and imidazole-based curing agents can be used.
  • the blending amount of the conductive powder is preferably 70 parts by weight or more and 90 parts by weight or less for the resin material of 10 parts by weight or more and 30 parts by weight or less.
  • plating films 33 and 43 (Formation of plating films 33 and 43) Plating films (first plating films) 33 and 43 that are in direct contact with the resin layers 32 and 42 are formed.
  • the plating films 33 and 43 are made of metal having a face-centered cubic structure. As described above, the metal having a face-centered cubic structure is preferably at least one selected from the group consisting of Ni, Au, Cu, Ag, Pt, Pd, and Al.
  • the plating films 33 and 43 can be formed by a known plating method such as a method using centrifugal force or an electrolytic barrel plating method.
  • a known plating bath can be used.
  • the metal having a face-centered cubic structure is Ni, for example, there are a matte nickel bath, a Watt bath, a sulfamic acid bath, a Woodstrike bath, a total chloride bath, and the like.
  • Second plating films 34 and 44 may be formed to cover the plating films 33 and 43 .
  • the second plating films 34, 44 are preferably at least one selected from the group consisting of Sn, Au, Cu, and Pd.
  • the second plating films 34 and 44 are formed by a known plating method such as a method using centrifugal force or an electrolytic barrel plating method.
  • a known plating bath can be used.
  • an acidic bath and an alkaline bath can be used.
  • a sulfuric acid bath, a methanesulfonic acid bath, or the like can be used as the acidic bath.
  • Embodiment 2 The electronic component according to Embodiment 2 is different from Embodiment 1 in that internal electrodes are provided inside the ceramic body, and the rest of the configuration is the same as that of Embodiment 1. An electronic component according to the second embodiment will be described with a focus on differences from the first embodiment.
  • FIG. 2 is a schematic cross-sectional view of an electronic component 10B according to Embodiment 2 of the present invention.
  • An example of the electronic component 10B shown in FIG. 2 is a positive temperature coefficient thermistor having internal electrodes 71 and 72 .
  • the electronic component 10B includes a ceramic body 20B and external electrodes provided at the ends of the ceramic body 20B.
  • the electronic component 10B further includes internal electrodes 71 and 72 inside the ceramic body 20B. Since the configuration of the external electrodes is the same as that of the first embodiment, the description is omitted.
  • the ceramic body 20B is composed of a plurality of ceramic layers 200.
  • a plurality of ceramic layers 200 and internal electrodes 71 and 72 are alternately laminated to form a laminate 80 .
  • the internal electrode 71 is exposed from one end face 21B of the ceramic body 20B, and the internal electrode 72 is exposed from the other end face 22B of the ceramic body 20B.
  • the underlying layers 31, 41 of the external electrodes 30, 40 formed at the ends of the ceramic body 20B are in contact with the internal electrodes 71, 72 exposed from the end faces 21B, 22B of the ceramic body 20B.
  • Electronic components 10B suitable for applying the second embodiment are chip-type ceramic electronic components with negative characteristics (or negative temperature coefficient, NTC) thermistors, varistors, capacitors, etc., in addition to the positive temperature coefficient thermistors described above. , some have internal electrodes.
  • NTC negative temperature coefficient
  • a method for manufacturing the electronic component 10B according to the second embodiment will be described by taking a PTC thermistor having internal electrodes 71 and 72 as shown in FIG. 2 as an example.
  • the ceramic body 20B is made of, for example, BaTiO 3 , CaTiO 3 , SrTiO 3 , CaZrO 3 , (BaSr)TiO 3 , Ba(ZrTi)O 3 and (BiZn)Nb 2 O 7 .
  • the material forming the internal electrodes 71 and 72 is not particularly limited as long as it is conductive, and examples thereof include Ag, Cu, Pt, Ni, Al, Pd, and Au. preferable.
  • ceramic raw materials such as BaCO 3 , TiO 2 , PbO, SrCO 3 and CaCO 3 , semiconductor agents such as Sm 2 O 3 and Er 2 O 3 , sintering aids such as SiO 2
  • a predetermined amount of an agent, an agent for adjusting the properties of MnO 2 , and the like are weighed.
  • the weighed raw materials are put into a ball mill together with grinding media such as partially stabilized zirconia (PSZ) (hereinafter also referred to as PSZ balls) and pure water, and wet-mixed and ground.
  • PSZ partially stabilized zirconia
  • pure water pure water
  • An organic binder is added to the obtained calcined powder, mixed in a wet process to form a slurry, and then molded using a doctor blade method or the like to produce a ceramic green sheet with a desired thickness.
  • a conductive paste for internal electrodes is applied to the surfaces of the ceramic green sheets to form internal electrode patterns.
  • the conductive paste for internal electrodes can be prepared, for example, by dispersing metal powder and an organic binder in an organic solvent.
  • the internal electrode paste may be applied by, for example, screen printing. A predetermined number of ceramic green sheets having internal electrode patterns formed thereon are stacked, and then the ceramic green sheets having no internal electrode patterns formed thereon are sandwiched from the top and bottom and pressed together to form a laminate.
  • a laminated body 80 having a laminated structure including the internal electrodes 71 and 72 is obtained.
  • base layers 31 and 41 As shown in FIG. 2, after fabrication of the ceramic body 20B, base layers 31 and 41 may be formed to cover the end faces 21B and 22B of the ceramic body 20B (the end faces of the laminate 80).
  • the underlying layers 31, 41 are electrically connected to the internal electrodes 71, 72 exposed from the end faces 21B, 22B of the ceramic body 20B. Since the method of forming the underlying layers 31 and 41 is the same as that of the first embodiment, the description thereof is omitted.
  • Resin layers 32 and 42 containing conductive powder are formed on the ends of the ceramic body 20B.
  • the method of forming the resin layers 32 and 42 is the same as that of the first embodiment, so the explanation is omitted.
  • Plating films (first plating films) 33 and 43 that are in direct contact with the resin layers 32 and 42 are formed.
  • the method of forming the plated films 33 and 43 is the same as in the first embodiment, so the description is omitted.
  • Second plating films 34 and 44 may be formed to cover the plating films 33 and 43 .
  • the method of forming the second plated films 34 and 44 is the same as that of the first embodiment, so the description is omitted.
  • the method for manufacturing the electronic component 10B according to the second embodiment of the present invention has been described by taking the positive temperature coefficient thermistor having internal electrodes as an example. can be produced as appropriate.
  • Example 1 (Preparation of object to be plated) A “object to be plated” for forming a plating film was prepared.
  • a barium titanate-based semiconductor (hereinafter referred to as “element body”) having a size of 0.53 mm (L) ⁇ 0.27 (W) ⁇ 0.27 (T) was prepared.
  • An underlayer for obtaining an ohmic contact with the element was formed on the WT surface of the element by sputtering. The thickness of the underlying layer was 2.5 ⁇ m.
  • a resin layer made of epoxy resin and silver powder was formed on the WT surface so as to cover the underlayer. In this way, a "plating object” including the base body, base layer and resin layer was obtained.
  • a nickel plating film was formed on the surface of the resin layer of the object to be plated by electrolytic barrel plating.
  • a Watts bath (pH 4.5, bath temperature 55° C., nickel sulfate 240-300 g/L, nickel chloride 45-50 g/L, boric acid 30-40 g/L) was used as the plating bath.
  • metallic nickel was brought into contact with the anode electrode.
  • metal media for assisting electrical conduction between objects to be plated and insulating resin balls for stirring the contents of the barrel were used.
  • metal media conductive media
  • a conductive medium were put into the barrel container.
  • the cathode electrode was arranged at a position in contact with the object to be plated and the conductive medium inside the barrel container.
  • a resin ball for stirring was put into the barrel container.
  • a nickel plating film having a desired thickness is formed on the surface of the resin layer of the object to be plated by passing current between the anode and the cathode at a predetermined current density for a predetermined time while rotating or rocking the barrel. bottom.
  • the average film thickness of the nickel plating film was 6.74 ⁇ m.
  • a tin plating film (second plating film) was formed on the surface of the nickel plating film by electrolytic barrel plating.
  • a plating bath there are an acidic bath and an alkaline bath, and the acidic bath was selected.
  • a sulfuric acid bath or a methanesulfonic acid bath was used as the acid bath.
  • metallic tin was brought into contact with the anode electrode.
  • the same operations as those for forming the nickel plating film were performed.
  • the average film thickness of the tin-plated film was 4.37 ⁇ m.
  • the element was washed with pure water and dried in a constant temperature bath at 85°C for 20 minutes and then at 120°C for 6 hours to prepare a plated sample (measurement sample).
  • the tin plating film of the measurement sample was dissolved in a solvent and removed.
  • the solvent is not particularly limited as long as it can selectively dissolve tin, but in Example 1, a solvent containing boron fluoride as a main component was used.
  • the exposed nickel-plated film was subjected to micro X-ray diffraction measurement using D8 DISCOVER manufactured by BRUKER axs. A two-dimensional X-ray diffraction image obtained using a two-dimensional detector was converted into a one-dimensional profile.
  • the diffraction intensities I(111), I(200), and I(220) of the XRD diffraction peaks of the (111) plane, (200) plane, and (220) plane of the nickel plating film are obtained from the obtained one-dimensional profile
  • the value of the diffraction intensity area of each peak was used.
  • the value of the diffraction intensity was obtained as a relative intensity with the highest intensity I(111) set to 100.
  • F which is an index indicating the orientation of the (111) plane.
  • the F value of the nickel plating film of Example 1 was 47.7% (0.477).
  • P 0 and P were determined by the following formulas (2) and (3).
  • P 0 I 0 (111)/ ⁇ I 0 (111)+I 0 (200)+I 0 (220) ⁇
  • P I(111)/ ⁇ I(111)+I(200)+I(220) ⁇
  • I 0 (111), I 0 (200) and I 0 (220) are the (111) plane, (200), respectively, obtained from powder X-ray diffraction data for nickel obtained from the ICDD database. Diffraction intensity of plane and (220) plane.
  • I (111), I (200) and I (220) are the (111) plane, (200) plane and (220) plane obtained from the XRD diffraction measurement of the nickel plating film of the measurement sample. is the diffraction intensity of the surface.
  • F 2 (200) which indicates the orientation of the (200) plane, was calculated using the formulas (1-2), (2-2) and (3-2), and is shown in Table 1.
  • F (200) (P (200) - P 0 (200) )/(1-P 0 (200) ) (1-2)
  • P 0 (200) and P (200) were obtained by the following formulas (2-2) and (3-2).
  • F 2 (220) which indicates the orientation of the (220) plane, was determined using the formulas (1-3), (2-3) and (3-3), and is shown in Table 1.
  • F (220) (P (220) - P 0 (220) )/(1-P 0 (220) ) (1-3)
  • P 0 (220) and P (220) were determined by the following formulas (2-3) and (3-3).
  • Adhesion between the nickel plating film and the resin layer was evaluated based on the breaking strength determined by the lateral shear strength test method and the peeling mode at the time of breaking.
  • the plated sample (measurement sample) was mounted on a glass cloth-based epoxy resin substrate (JIS C 6484:2005) of a copper-clad laminate.
  • Sn-3Ag-0.5Cu solder paste was screen-printed on the substrate to a thickness of 200 ⁇ m. Place the measurement sample on the solder paste on the substrate with the WT surface (the surface on which the plating film is formed) facing the substrate, and circulate in a reflow furnace with a nitrogen gas atmosphere at a maximum temperature of 220 ° C at room temperature. and implemented reflow.
  • the mounted measurement sample was laterally pushed with a push-pull gauge to measure the strength when the measurement sample was peeled off from the substrate in the same manner as in JIS 62137-1-2:2010.
  • the soldered portion of the substrate was observed using a digital microscope and a scanning electron microscope. It was determined whether the failure was due to the element breaking and peeling) or the electrode breaking (the interface between the nickel plating film and the resin electrode was broken and peeling, or the nickel plating film itself was broken and peeling).
  • Example 2 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed to set the F value of the nickel plating film to 35.7% (0.357). , to evaluate the adhesion strength.
  • the average film thicknesses of the nickel plating film and the tin plating film were 5.32 ⁇ m and 3.16 ⁇ m, respectively.
  • the average breaking strength of 10 specimens was 6.85 N, and the number of peeling modes was 10 and 0, respectively.
  • Example 3 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed to set the F value of the nickel plating film to 25.8% (0.258). , to evaluate the adhesion strength.
  • the average film thicknesses of the nickel plating film and the tin plating film were 7.02 ⁇ m and 3.20 ⁇ m, respectively.
  • the average breaking strength of 10 specimens was 7.43 N, and the number of peeling modes was 10 and 0, respectively.
  • Example 1 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed to set the F value of the nickel plating film to 1.96% (0.0196). , to evaluate the adhesion strength.
  • the average film thicknesses of the nickel plating film and the tin plating film were 6.21 ⁇ m and 3.57 ⁇ m, respectively.
  • the average breaking strength of 10 specimens was 4.53 N, and the peeling modes were 3 ceramics and 7 electrodes, respectively.
  • Example 2 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed to set the F value of the nickel plating film to 5.02% (0.0502). , to evaluate the adhesion strength.
  • the average film thicknesses of the nickel plating film and the tin plating film were 5.78 ⁇ m and 3.34 ⁇ m, respectively.
  • the average breaking strength of 10 specimens was 3.97 N, and the number of peeling modes was 3 ceramics fractures and 7 electrode fractures, respectively.
  • Example 3 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed and the F value of the nickel plating film was set to -1.16% (-0.0116). Then, the adhesion strength was evaluated. The average film thicknesses of the nickel plating film and the tin plating film were 5.19 ⁇ m and 3.37 ⁇ m, respectively. The average breaking strength of 10 specimens was 5.04 N, and the number of peeling modes was 2 and 8, respectively.
  • Example 4 A post-plating sample (measurement sample) was prepared in the same manner as in Example 1 except that the plating conditions of the nickel plating film were changed and the F value of the nickel plating film was set to -10.9% (-0.109). Then, the adhesion strength was evaluated. The average film thicknesses of the nickel plating film and the tin plating film were 5.54 ⁇ m and 3.22 ⁇ m, respectively. The average breaking strength of 10 specimens was 4.67 N, and the peeling modes were 3 ceramics and 7 electrode fractures, respectively.
  • Example 1 The results of Examples 1-3 and Comparative Examples 1-4 are summarized in Table 1.
  • a post-plating sample having a value of F indicating the (111) orientation of the nickel plating film of 20.0% or more and 50.0% or less (0.20 or more and 0.50 or less) is The breaking strength after solder mounting was high, and in the evaluation of the peeling mode, there were no samples with electrode breakdown (the interface between the nickel plating film and the resin electrode was broken and peeled, or the nickel plating film itself was broken and peeled).

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JPH11162771A (ja) * 1997-11-25 1999-06-18 Kyocera Corp 積層セラミックコンデンサ
JP2004119798A (ja) * 2002-09-27 2004-04-15 Murata Mfg Co Ltd チップ型電子部品及びその製造方法
JP2013110363A (ja) * 2011-11-24 2013-06-06 Tdk Corp セラミック電子部品
JP2017197788A (ja) * 2016-04-25 2017-11-02 日本高純度化学株式会社 電子部品接点部材の製造方法及び電子部品接点部材

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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162771A (ja) * 1997-11-25 1999-06-18 Kyocera Corp 積層セラミックコンデンサ
JP2004119798A (ja) * 2002-09-27 2004-04-15 Murata Mfg Co Ltd チップ型電子部品及びその製造方法
JP2013110363A (ja) * 2011-11-24 2013-06-06 Tdk Corp セラミック電子部品
JP2017197788A (ja) * 2016-04-25 2017-11-02 日本高純度化学株式会社 電子部品接点部材の製造方法及び電子部品接点部材

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