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US20140112710A1 - Solder Alloy for Power Devices and Solder Joint Having a High Current Density - Google Patents

Solder Alloy for Power Devices and Solder Joint Having a High Current Density Download PDF

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Publication number
US20140112710A1
US20140112710A1 US14/001,561 US201214001561A US2014112710A1 US 20140112710 A1 US20140112710 A1 US 20140112710A1 US 201214001561 A US201214001561 A US 201214001561A US 2014112710 A1 US2014112710 A1 US 2014112710A1
Authority
US
United States
Prior art keywords
solder
mass
alloy
electromigration
rem
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.)
Abandoned
Application number
US14/001,561
Other languages
English (en)
Inventor
Hans-Jurgen Albrecht
Klaus Wilke
Katsuaki Suganuma
Minoru Ueshima
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.)
Senju Metal Industry Co Ltd
Original Assignee
Senju Metal Industry 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 Senju Metal Industry Co Ltd filed Critical Senju Metal Industry Co Ltd
Assigned to SENJU METAL INDUSTRY CO., LTD. reassignment SENJU METAL INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SUGANUMA, KATSUAKI, UESHIMA, MINORU, ALBRECHT, HANS-JURGEN, WILKE, KLAUS
Publication of US20140112710A1 publication Critical patent/US20140112710A1/en
Abandoned legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3457—Solder materials or compositions; Methods of application thereof
    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1305—Bipolar Junction Transistor [BJT]
    • H01L2924/13055—Insulated gate bipolar transistor [IGBT]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1306—Field-effect transistor [FET]
    • H01L2924/13091—Metal-Oxide-Semiconductor Field-Effect Transistor [MOSFET]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0263—High current adaptations, e.g. printed high current conductors or using auxiliary non-printed means; Fine and coarse circuit patterns on one circuit board

Definitions

  • This invention relates to a solder alloy and a solder joint which can withstand a high current density without being damaged by electromigration.
  • the present invention also relates to an electronic element (electronic device) and particularly a power device using such a solder joint.
  • Soldering is the most commonly used method for electrically connecting electronic devices to circuit boards and similar substrates.
  • solder joints As electronic devices become increasingly small, the size of solder joints for connecting electronic devices to other members is similarly becoming smaller, and as their shape becomes smaller, the current density in each joint is becoming extremely large.
  • solder joints normally used for electronic devices do not have a considerably high current density.
  • current densities such as 5-100 kA/cm 2 .
  • Such a high current density is particularly anticipated in electrical equipment such as power devices used in hybrid electric vehicles, inverters, and the like.
  • solder paste containing a Bi-based solder power having a solidus temperature of at least 260° C. and a thermosetting adhesive Patent Document 1.
  • the inventors of the present invention found that the cause of the occurrence of electromigration is that due to the current which is generated by the operation of electronic devices or printed circuit boards of electronic equipment, electrons flow in the opposite direction from the current and the metal in a joint moves together with the movement of electrons, thereby causing voids and cracks to develop on the cathode side of the joint. They also found that electromigration is alleviated by controlling abrupt movement of metal atoms in the joints of printed circuit boards of electronic equipment, and they completed the present invention.
  • An electronic device in which a solder alloy and a solder joint according to the present invention are used and a solder joint which connects such an electronic device to a printed circuit board are effective at preventing electromigration.
  • a solder alloy according to the present invention has a Sn—Ag—In—Bi solder composition like that described in Patent Document 2 or Patent Document 3, and the solder composition falls into the range of a low-temperature solder.
  • solder alloy according to the present invention is used for a joint connecting the emitter and the collector of a power device, it is possible to maintain quality for long periods, which is desirable, even if there is a high current density between terminals.
  • a solder alloy for a power device according to the present invention has a so-called low-temperature solder composition containing Bi and In, it has heat resistance of around 150° C. even if it is used for joints for connection inside a power device. In addition, it is not damaged by electromigration even at a high current density of 5-100 kA/cm 2 . Accordingly, a power device made using a solder alloy according to the present invention can stably operate for long periods.
  • FIG. 2 is a schematic view of an IGBT (insulated gate bipolar transistor).
  • FIG. 3 is an explanatory view showing the state of solder connection in an example of the present invention.
  • a solder joint according to the present invention can be formed in various shapes. For example, inside a power device, methods such as wire bonding or flip clip bonding by reflow soldering using preforms, solder balls, or solder paste are conceivable.
  • the Ag content is determined from the standpoints of the melting temperature and resistance to thermal fatigue of the solder. If the Ag content is lower than 2%, thermal fatigue properties of the solder worsen. On the other, if it exceeds 4%, its liquidus temperature increases, so the number of voids increases and the quality of a solder joint decreases. Accordingly, the Ag content in the present invention is at least 2 mass % and at most 4 mass %.
  • a low melting point phase (low-temperature phase) which melts at 139° C. crystallizes out due to segregation at the time of soldering. Since a solder joint is sometimes is heated to a high temperature of 150° C., the formation of a liquid phase at that time due to the presence of such a low-temperature phase in a solder joint cannot be avoided. As a result, due to an increase in stress load caused by thermal fatigue, cracks suddenly develop. Therefore, the added amount of Bi is made at most 4%.
  • the added amount of Bi in the present invention is at least 2 mass % and at most 4 mass %.
  • the addition of Co also makes the surface of a (CuCo)6(SnIn)5 reaction phase smooth, and it forms a reaction layer with a uniform thickness. If the added amount of Co is less than 0.01%, severe surface irregularities form in the (CuCo)6(SnIn)5 reaction phase, and if current concentrates in portions where the reaction layer is thin, the reaction phase easily disappears by electromigration. After the reaction phase disappears, Cu electrodes and solder directly contact each other, and diffusion of Cu from the Cu electrodes into solder is accelerated, causing open circuits to occur in short period of time.
  • a small amount of Fe may be added to a Sn—Ag—Bi—In alloy according to the present invention.
  • its content is preferably 0.01-0.1%.
  • solder alloy powder is mixed with a suitable flux in a conventional manner.
  • the minimum bonding strength of a 3216-size part was made 15N.
  • the cumulative number of solder joints having a strength of 15N or less was calculated every 500 cycles. Failure was made the point at which the cumulative number exceeded 10%, and the previous 500 cycles was made the life span of the solder joints. The results are shown in Table 1.
  • FIG. 5 is an electron photomicrograph showing the state of a copper land when the resistance increased by 5% after carrying a current of 20 amperes at 125° C. in an example of the present invention.
  • FIG. 6 is an electron photomicrograph showing the state of a copper land when the resistance increased by 10% after carrying a current of 20 amperes at 125° C. in an example of the present invention.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
  • Contacts (AREA)
US14/001,561 2011-02-25 2012-02-27 Solder Alloy for Power Devices and Solder Joint Having a High Current Density Abandoned US20140112710A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2011-057183 2011-02-25
JP2011057183 2011-02-25
PCT/JP2012/054774 WO2012115268A1 (fr) 2011-02-25 2012-02-27 Alliage de brasure pour dispositif électrique et joint brasé de densité de courant élevée

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/054774 A-371-Of-International WO2012115268A1 (fr) 2011-02-25 2012-02-27 Alliage de brasure pour dispositif électrique et joint brasé de densité de courant élevée

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/010,990 Division US11331759B2 (en) 2011-02-25 2020-09-03 Solder alloy for power devices and solder joint having a high current density

Publications (1)

Publication Number Publication Date
US20140112710A1 true US20140112710A1 (en) 2014-04-24

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US14/001,561 Abandoned US20140112710A1 (en) 2011-02-25 2012-02-27 Solder Alloy for Power Devices and Solder Joint Having a High Current Density
US17/010,990 Active US11331759B2 (en) 2011-02-25 2020-09-03 Solder alloy for power devices and solder joint having a high current density

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Application Number Title Priority Date Filing Date
US17/010,990 Active US11331759B2 (en) 2011-02-25 2020-09-03 Solder alloy for power devices and solder joint having a high current density

Country Status (10)

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US (2) US20140112710A1 (fr)
EP (1) EP2679334B1 (fr)
JP (1) JP5418718B2 (fr)
KR (3) KR101773733B1 (fr)
CN (1) CN103501959B (fr)
BR (1) BR112013021668B1 (fr)
ES (1) ES2799421T3 (fr)
MY (1) MY157295A (fr)
TW (1) TWI565550B (fr)
WO (1) WO2012115268A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150328722A1 (en) * 2012-12-18 2015-11-19 Senju Metal Industry Co., Ltd. Lead-free solder alloy
US9931716B2 (en) 2014-06-24 2018-04-03 Harima Chemicals, Incorporated Solder alloy, solder composition, solder paste, and electronic circuit board
US12179291B2 (en) 2019-05-27 2024-12-31 Senju Metal Industry Co., Ltd. Method for step-soldering

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JP2013252548A (ja) * 2012-06-08 2013-12-19 Nihon Almit Co Ltd 微細部品接合用のソルダペースト
WO2014129258A1 (fr) * 2013-02-25 2014-08-28 ソニー株式会社 Composition de matériau de soudure, structure de connexion électrique, élément de connexion électrique, carte de câblage imprimée, et dispositif de circuit électronique
JP2016103530A (ja) * 2014-11-27 2016-06-02 新日鉄住金マテリアルズ株式会社 無鉛はんだバンプ接合構造
WO2017134974A1 (fr) * 2016-02-01 2017-08-10 株式会社村田製作所 Matériau de liaison, procédé de liaison mettant en œuvre celui-ci, et structure de liaison
JP6365653B2 (ja) * 2016-08-19 2018-08-01 千住金属工業株式会社 はんだ合金、はんだ継手およびはんだ付け方法
JP2018140427A (ja) * 2017-02-28 2018-09-13 千住金属工業株式会社 はんだ材料、はんだペースト、フォームはんだ及びはんだ継手
US11819955B2 (en) 2019-05-27 2023-11-21 Senju Metal Industry Co., Ltd. Solder alloy, solder paste, solder ball, solder preform, solder joint, on-board electronic circuit, ECU electronic circuit, on-board electronic circuit device, and ECU electronic circuit device
CN112317972B (zh) * 2020-09-30 2021-07-20 厦门大学 一种单向性耐高温焊接接头的低温快速制造方法
JP7481285B2 (ja) 2021-03-23 2024-05-10 株式会社デンソー 半導体装置およびその製造方法
KR102394475B1 (ko) 2021-09-14 2022-05-04 마이크로컴퍼지트 주식회사 저융점 고신뢰성 솔더 입자, 이를 포함하는 수지 조성물
JP2024035598A (ja) * 2022-09-02 2024-03-14 株式会社デンソー 半導体装置

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Publication number Priority date Publication date Assignee Title
US5658528A (en) * 1994-11-02 1997-08-19 Mitsui Mining & Smelting Co., Ltd. Lead-free solder
US5958333A (en) * 1996-08-29 1999-09-28 Mitsui Mining & Smelting Co., Ltd. Tin-silver-based soldering alloy
US20030015575A1 (en) * 2000-09-18 2003-01-23 Atsushi Yamaguchi Solder material and electric or electronic device in which the same is used
US20100297470A1 (en) * 2001-06-28 2010-11-25 Senju Metal Industry Co., Ltd. Lead-free solder alloy
US6822327B1 (en) * 2003-06-13 2004-11-23 Delphi Technologies, Inc. Flip-chip interconnected with increased current-carrying capability
US20100307823A1 (en) * 2007-07-18 2010-12-09 Yuji Kawamata Indium-containing lead-free solder for vehicle-mounted electronic circuits

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* Cited by examiner, † Cited by third party
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US20150328722A1 (en) * 2012-12-18 2015-11-19 Senju Metal Industry Co., Ltd. Lead-free solder alloy
US10343238B2 (en) 2012-12-18 2019-07-09 Senju Metal Industry Co., Ltd. Lead-free solder alloy
US9931716B2 (en) 2014-06-24 2018-04-03 Harima Chemicals, Incorporated Solder alloy, solder composition, solder paste, and electronic circuit board
US9956649B2 (en) 2014-06-24 2018-05-01 Harima Chemicals, Incorporated Solder alloy, solder paste, and electronic circuit board
US12179291B2 (en) 2019-05-27 2024-12-31 Senju Metal Industry Co., Ltd. Method for step-soldering

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KR20160086964A (ko) 2016-07-20
BR112013021668B1 (pt) 2019-04-02
MY157295A (en) 2016-05-20
KR20130118993A (ko) 2013-10-30
JPWO2012115268A1 (ja) 2014-07-07
US20210008670A1 (en) 2021-01-14
CN103501959B (zh) 2016-03-16
WO2012115268A1 (fr) 2012-08-30
JP5418718B2 (ja) 2014-02-19
CN103501959A (zh) 2014-01-08
EP2679334B1 (fr) 2020-05-27
EP2679334A1 (fr) 2014-01-01
US11331759B2 (en) 2022-05-17
KR101773733B1 (ko) 2017-08-31
EP2679334A4 (fr) 2016-06-01
KR20160101209A (ko) 2016-08-24
TW201302366A (zh) 2013-01-16
BR112013021668A2 (pt) 2016-11-01
TWI565550B (zh) 2017-01-11
KR101752616B1 (ko) 2017-06-29

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