CN104139249A - 焊膏 - Google Patents
焊膏 Download PDFInfo
- Publication number
- CN104139249A CN104139249A CN201410194323.9A CN201410194323A CN104139249A CN 104139249 A CN104139249 A CN 104139249A CN 201410194323 A CN201410194323 A CN 201410194323A CN 104139249 A CN104139249 A CN 104139249A
- Authority
- CN
- China
- Prior art keywords
- powder
- soldering paste
- copper
- weight
- flux
- 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.)
- Granted
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Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- 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
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- 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
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- 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
- B23K35/025—Pastes, creams, slurries
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- 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
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- 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
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- 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
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- 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
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- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
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- 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
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C13/00—Alloys based on tin
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- 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
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0425—Copper-based alloys
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- C22C1/0483—Alloys based on the low melting point metals Zn, Pb, Sn, Cd, In or Ga
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- H01L2224/274—Manufacturing methods by blanket deposition of the material of the layer connector
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- H—ELECTRICITY
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- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
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Abstract
本发明的实施方案涉及焊膏,其包含熔剂和与熔剂混合的粉末,所述粉末包含彼此混合的第一粉末和第二粉末。第一粉末包含锡(Sn)和溶于锡(Sn)中的至少一种金属,并且第二粉末包含其表面涂覆有银(Ag)的铜(Cu)粉。
Description
相关申请的交叉引用
本申请要求于2013年5月10日提交的韩国专利申请第10-2013-0053047号的优先权,其如同在本文中全部列出一样通过引用整体并入本文。
技术领域
实施方案涉及作为焊粉(solder powder)和焊接用熔剂(flux)的混合物的焊膏。
背景技术
考虑到精细的接合部,将回流焊(reflow soldering)用于电子元件的内部接合。用于回流焊的焊膏是焊粉和焊接用熔剂的混合物。
为了防止环境污染,将无铅焊料(称为“无Pb焊料”)广泛用于电子元件的内部接合。无Pb焊料是指不包含Pb并且使Sn、Ag、Sb、Cu、Zn、Bi、Ni、Cr、Fe、P、Ge、Ga等的两种或更多种元素与彼此组合的焊粉。
此外,其中Sn、Ag和Cu彼此混合的Sn-Ag基合金已被广泛用作无Pb焊料。因为在使用Sn-Ag基合金时焊接温度为约240℃至250℃,所以无Pb焊料需要至少250℃的高固相线温度。
发明内容
实施方案提供了可以增强可湿性并且限制空隙产生的焊膏。
在一个实施方案中,焊膏包含熔剂和与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,所述第一粉末包含锡和溶于锡中的至少一种金属,并且所述第二粉末包含其表面涂覆有银的铜粉。
所述至少一种金属可包括铜和银。
第一粉末可包含锡、银和铜的合金。
第二粉末的重量可以为混合粉末重量的5%至40%。
第二粉末中所含银涂层的重量可以为第二粉末中所含铜粉重量的10%至50%。
第二粉末中所含铜粉的直径可以为2μm至25μm。
第二粉末中所含银涂层的厚度可以为1μm或更小。
所述至少一种金属可包括银(Ag)、铜(Cu)、锑(Sb)、铋(Bi)、铟(In)和锌(Zn)中的至少一种。
第一粉末中所含锡与银与铜的重量百分比之比可以为96.5:3:0.5。
第一粉末可通过使锡、银和铜的合金块破碎来形成。
第二粉末的氧化起始温度可以为219℃或更高。
第二粉末的氧化起始温度可高于240℃至250℃的范围。
熔剂可以为液相、具有延展性的固体、或者固体。
熔剂可包含松香、稀释剂和活化剂。
活化剂可以以基于熔剂总重量30%至70%的量存在。
熔剂还可包含胶凝剂(gelant),并且胶凝剂可以以基于熔剂总重量0.1%至10%的量存在。
活化剂还可包含卤代化合物。
铜粉的直径可以为4μm至7μm。
在另一个实施方案中,焊膏包含熔剂和与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,其中所述第一粉末包含锡和溶于锡中的至少一种金属,并且所述第二粉末包含铜粉和涂覆在铜粉表面上的隔离涂膜,并且其中所述隔离涂膜的熔化温度等于或高于锡的熔化温度。
隔离涂膜可以是银涂膜。
第二粉末的氧化起始温度可高于第一粉末的低共熔点(eutecticpoint)。
在又一个实施方案中,焊膏包含熔剂和与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,其中所述第一粉末包含锡、银和铜,其中所述第二粉末包含铜粉和铜粉整个表面上的银涂膜,其中所述第二粉末的重量为混合粉末重量的5%至40%,并且其中第二粉末中所含银涂膜的重量为第二粉末中所含铜粉重量的10%至50%。
附图说明
可参照以下附图详细地描述布置和实施方案,其中相同的附图标记指相同的元件,并且其中:
图1示出了根据一个实施方案的焊膏的概念图;
图2示出了图1所示第一粉末的放大图;
图3示出了图1所示第二粉末的放大图;
图4示出了铜与锡反应的活化能和银与锡反应的活化能;
图5示出了第一粉末的锡和第二粉末的铜的第一相图;
图6示出了第一粉末的锡和第二粉末的银的第二相图;
图7A示出了根据第一个实施方案的第二粉末的热流量根据温度的变化;
图7B示出了图7A所示第二粉末的重量根据温度的变化;
图8A示出了根据第二个实施方案的第二粉末的热流量根据温度的变化;
图8B示出了图8A所示第二粉末的重量根据温度的变化;
图9A示出了根据第三个实施方案的第二粉末的热流量根据温度的变化;
图9B示出了图9A所示第二粉末的重量根据温度的变化;
图10A示出了根据第四个实施方案的第二粉末的热流量根据温度的变化;
图10B示出了图10A所示第二粉末的重量根据温度的变化;
图11A示出了根据第五个实施方案的第二粉末的热流量根据温度的变化;
图11B示出了图11A所示第二粉末的重量根据温度的变化;
图12A示出了使用一般焊膏的焊层;
图12B示出了使用根据实施方案的焊膏的焊层;以及
图13示出了使用根据实施方案的焊膏的包括接合部的发光器件封装件的截面图。
具体实施方案
下文中,将参照附图通过以下描述清楚地揭示实施方案。在实施方案的描述中,应理解,当每个层(膜)、区域、图案或结构被称为在另一层(膜)、区域、衬垫或图案“上”或“下”时,所述层(膜)、区域、图案或结构可直接在所述层(膜)、区域、衬垫或图案上/下,并且也可以存在一个或更多个插入元件。当元件被称为“在……上”或“在……下”时,基于元件可包括“在元件下”以及“在元件上”。另外,还应理解,可相对于附图描述在每个层“上/上方”或“下/下方”。
在附图中,为了清楚和方便起见,尺寸可被放大、省略或示意性说明。另外,每个构成元件的尺寸不完全反映实际尺寸。另外,在整个附图的描述中,相同的附图标记指示相同或同样的组件。下文中,将参照附图描述根据一个实施方案的焊膏。
图1示出了根据一个实施方案的焊膏100的概念图,图2示出了图1所示第一粉末10的放大图,并且图3示出了图1所示第二粉末20的放大图。
参照图1至图3,焊膏100可包含混合粉末5和熔剂30,并且可采取混合粉末5和熔剂30的混合物的形式。
混合粉末5可以是焊粉,并且可以是第一粉末10和第二粉末20的混合物。
熔剂30用来在回流焊期间防止基底金属(例如,衬底,参见图12A和12B中的105)或与基底金属相接触的组件(参见图12A和12B中的210)的表面处的氧化,从而增强焊接期间基底金属与组件之间的粘附性。
熔剂30可以是液相、具有延展性的固体、或者固体。熔剂30可包含松香、稀释剂、活化剂等。稀释剂具有挥发性并因此蒸发。松香和活化剂留下成为固体残余物。
松香可用作微酸性活化剂,并且可添加其以防止金属氧化。松香可以是选自歧化松香、氢化松香、脱氢松香和非改性松香的一种或更多种材料。
活化剂可用来分解或移除可存在于待焊接衬底部分上的氧化膜(例如,PCB衬底上氧化的铜或焊料氧化物)。
熔剂30还可选择性地包含在加热时排放卤化氢的卤代化合物。
例如,卤代化合物可选自反式-2,3-二溴-2-丁烯-1,4-二醇、中-2,3-二溴琥珀酸酯(meso-2,3-dibromosuccinate)、三-(2,3-二溴丙基)异氰脲酸酯及其组合。
熔剂30可通过使活化剂、胶凝剂、树脂等分散在溶剂中来形成。本文中,所用术语“树脂”可包括天然树脂,例如松香、化学改性松香和合成树脂。松香可以是从天然来源如松树树液中获得的天然材料,并且可包含松香酸的异构体。
熔剂30可包含以基于组成总重量30%至70%的量,更特别地以40%至60%的量存在的活化剂。
另外,熔剂30可包含以基于组成总重量0.1%至10%的量,更特别地以0.4%至1%的量存在的胶凝剂。
熔剂30的流变性可取决于熔剂30中存在的胶凝剂的水平,并且熔剂30可具有牛顿流变性。
第一粉末10可包含锡(Sn)作为主要组分并且可以是Sn和溶于Sn中的金属的合金。在这种情况下,溶于Sn中的金属可包括银(Ag)、铜(Cu)、锑(Sb)、铋(Bi)、铟(In)和锌(Zn)中的至少一种。
例如,第一粉末10可由锡(Sn)、银(Ag)和铜(Cu)构成,并且可通过将Sn、Ag和Cu的合金块转化成粉末形式获得。
例如,第一粉末10中Sn与Ag与Cu的重量百分比之比可以为96.5:3:0.5,但不限于此。
第二粉末20可以是其中Ag被涂覆在溶于Sn中的金属表面上的粉末。例如,第二粉末20可以是其表面涂覆有Ag的Cu粉。Ag可涂覆在Cu粉22的整个表面或者Cu粉22的整个周面(circumferential surface)上。
第二粉末20可通过在Cu粉22表面上形成Ag涂膜24获得。例如,Ag涂膜24可使用电镀、在水溶液中沉淀等形成。
在回流焊期间,Ag涂膜24可充当阻挡物以防止Sn扩散至Cu粉22的表面。
可如下实施回流焊工艺。
在将焊膏10施用至待焊接位置之后,将所施用焊膏100加热至240℃至250℃的温度。
因为Sn的熔点低于Ag的熔点和Cu的熔点,所以第一粉末10中所含Sn可熔化,并且熔化的Sn可通过与第一粉末10中所含Ag和Cu反应形成金属间化合物。
例如,熔化的Sn可通过与第一粉末10中所含Ag反应形成Ag3Sn,并且熔化的Sn可通过与第一粉末10中所含Cu反应形成Cu3Sn、Cu6Sn5等。
但是,熔化的Sn不能直接与第二粉末20的Cu粉22反应。也就是说,熔化的Sn由于Ag涂膜24而不能直接与Cu粉22反应,并且可通过与Ag涂膜24反应形成金属间化合物(例如,Ag3Sn)。熔化的Sn与Cu22的反应仅在通过上述反应移除Ag涂膜24使得Cu22从Ag涂膜24中暴露出来之后发生,从而形成金属间化合物。
如上所述,Ag涂膜24可用来限制或延迟第一粉末10的熔化的Sn与第二粉末20的Cu22之间的反应。
图4示出了Cu与Sn反应的活化能以及Ag与Sn反应的活化能。
参照图4,应理解,Cu与Sn反应的第一活化能为28kJ/mol并且Ag与Sn反应的第二活化能为52.6kJ/mol。也就是说,由于第二活化能是第一活化能的约两倍,所以Ag至Sn的扩散或者Ag与Sn的反应可比Cu至Sn的扩散或者Cu与Sn的反应进行得慢。
因此,在实施方案中,在Cu粉22表面上形成的Ag涂膜24限制了回流焊期间Sn至Cu粉22的扩散,其可为Sn待焊接位置提供足够的润湿时间,导致了增强的可湿性。
另外,由于熔化的Sn与Cu粉22的这种缓慢反应,所以可通过反应物料实现获得除去第一粉末10与第二粉末20之间的空隙足够的时间。因此,实施方案可限制焊接之后产生的焊层中的空隙产生。
图5示出了第一粉末10的Sn和第二粉末20的Cu22的第一相图,并且图6示出了第一粉末10的Sn和第二粉末20的Ag24的第二相图。
参照图5和图6,应理解,在200℃至300℃的温度下,随着重量百分比(%)增加,第二相图所绘Ag的液相线梯度比第一相图所绘Cu的液相线梯度增加得更缓慢。
参照如图5和图6示例性示出的第一相图和第二相图,在实施方案中,可调整Cu粉22的直径D1和Ag涂膜24的厚度D2以增强可湿性并且限制焊层中的空隙产生。
第二粉末20的重量可以为混合粉末5总重量的5%至40%。当第二粉末20的重量低于5%时,不能实现重熔预防(remelting prevention)。当第二粉末20的重量超过40%时,第二粉末20与第一粉末10的反应量过度增加,这可使得难以实现充足的可湿性,从而在焊层中产生大量空隙。
Ag涂膜24的重量可以为Cu粉22重量的10%至50%。
当Ag涂膜24的重量低于10%时,第二粉末20开始氧化的温度(下文中称为“氧化起始温度”)可低于第一粉末10的低共熔点(例如,约213℃)。当Ag涂膜24的重量超过50%时,焊膏100的价格提高并因此经济效率低下。
Cu粉22的直径D1可以为2μm至25μm,更特别地为4μm至7μm。
当Cu粉22的直径D1低于2μm时,大的比表面积可造成与第一粉末10的Sn进行的反应过分快速地进行,导致不良的可湿性。
另一方面,当Cu粉22的直径D1超过25μm时,与熔化的Sn进行的缓慢反应可使所添加Cu的量增加,从而使焊层的强度退化。另外,焊层强度的恶化可在以下过程中导致焊层的重熔。
Ag涂膜24的厚度D2可以为1μm或更小,但不限于此。虽然在另一个实施方案中Ag涂膜24的厚度D2可超过1μm,但是Ag涂膜24的过厚的厚度D2可使焊膏100的价格增加。因为当第二粉末20的氧化起始温度低于第一粉末10的低共熔点时在焊层中产生了大量空隙,所以必须确定第二粉末20的重量、Cu粉22的直径D1以及Ag涂膜24的厚度D2,使得第二粉末20的氧化起始温度高于第一粉末10的低共熔点。
图7A示出了根据第一实施方案的第二粉末20的热流量根据温度的变化,并且图7B示出了图7A所示第二粉末20的重量根据温度的变化。
图7A和图7B示出了其中Cu粉22的直径D1为4μm,第二粉末20的重量为混合粉末5重量的10%,并且Ag涂膜24的厚度D2为0.1μm的情况。
参照图7A,鉴于第二粉末20的热流量由约221℃快速增加,所以第二粉末20的氧化起始温度可估计为约221℃。
参照图7B,鉴于第二粉末20的重量由约219℃开始增加,所以第二粉末20的氧化起始温度可估计为约219℃。
鉴于图7A和图7B的实验结果,应理解,根据第一实施方案的焊膏100的第二粉末20的氧化起始温度至少高于第一粉末10的低共熔点(例如,约213℃)。
因为第二粉末20的氧化起始温度至少高于第一粉末10的低共熔点,所以在回流焊期间第一粉末10的Sn可以以液相存在。液相Sn防止了回流焊期间第一粉末10与氧的反应,因此根据第一实施方案的焊膏100的第二粉末20在回流焊期间没有被充分氧化。
图8A示出了根据第二实施方案的第二粉末20的热流量根据温度的变化,并且图8B示出了图8A所示第二粉末20的重量根据温度的变化。
图8A和图8B示出了其中Cu粉22的直径D1为4μm,第二粉末20的重量为混合粉末5重量的15%,并且Ag涂膜24的厚度D2为0.2μm的情况。
参照图8A,鉴于第二粉末20的热流量由约259.62℃快速增加,所以第二粉末20的氧化起始温度可估计为约259.62℃
参照图8B,鉴于第二粉末20的重量由约258.70℃开始增加,所以第二粉末20的氧化起始温度可估计为约258.70℃。
鉴于图8A和图8B的实验结果,应理解,根据第二实施方案的焊膏100的第二粉末20的氧化起始温度高于回流焊温度(例如,240℃至250℃),因此在回流焊温度(例如,240℃至250℃)下不发生第二粉末20的氧化。
图9A示出了根据第三实施方案的第二粉末20的热流量根据温度的变化,并且图9B示出了图9A所示第二粉末20的重量根据温度的变化。
图9A和图9B示出了其中Cu粉22的直径D1为7μm,第二粉末20的重量为混合粉末5重量的12%,并且Ag涂膜24的厚度D2为0.2μm的情况。
参照图9A,鉴于第二粉末20的热流量由约273.17℃快速增加,所以第二粉末20的氧化起始温度可估计为约273.17℃。
参照图9B,鉴于第二粉末20的重量由约260.72℃开始增加,所以第二粉末20的氧化起始温度可估计为约260.72℃。
鉴于图9A和图9B的实验结果,应理解,根据第三实施方案的焊膏100的第二粉末20的氧化起始温度高于回流焊温度(例如,240℃至250℃),因此在回流焊温度(例如,240℃至250℃)下不发生第二粉末20的氧化。
图10A示出了根据第四实施方案的第二粉末20的热流量根据温度的变化,并且图10B示出了图10A所示第二粉末20的重量根据温度的变化。
图10A和图10B示出了其中Cu粉22的直径D1为7μm,第二粉末20的重量为混合粉末5重量的20%,并且Ag涂膜24的厚度D2为0.4μm的情况。
参照图10A,在350℃或更小的温度下观察不到第二粉末20热流量的快速增加。
参照图10B,鉴于第二粉末20的重量由约286.24℃开始增加,所以第二粉末20的氧化起始温度可估计为约286.24℃。
鉴于图10A和图10B的实验结果,应理解,根据第四实施方案的焊膏100的第二粉末20的氧化起始温度高于回流焊温度(例如,240℃至250℃),因此在回流焊温度(例如,240℃至250℃)下不发生第二粉末20的氧化。
图11A示出了根据第五实施方案的第二粉末20的热流量根据温度的变化,并且图11B示出了图11A所示第二粉末20的重量根据温度的变化。
图11A和图11B示出了其中Cu粉22的直径D1为7μm,第二粉末20的重量为混合粉末5重量的30%,并且Ag涂膜24的厚度D2为0.6μm的情况。
参照图11A,在350℃或更小的温度下观察不到第二粉末20热流量的快速增加。
参照图11B,鉴于第二粉末20的重量由约299.88℃开始增加,所以第二粉末20的氧化起始温度可估计为约299.88℃。
鉴于图11A和图11B的实验结果,应理解,根据第五实施方案的焊膏100的第二粉末20的氧化起始温度至少高于回流焊温度(例如,240℃至250℃),因此在回流焊温度(例如,240℃至250℃)下不发生第二粉末20的氧化。
为了增强焊料的可湿性,可形成隔离涂膜用来防止第一粉末10的Sn扩散至第二粉末20的Cu粉22表面上的金属必须溶于Sn,其需要熔化温度等于或高于Sn的熔化温度,并且在溶于Sn中时不允许恶化可焊性。
满足上述条件的涂膜可如实施方案中的由Ag形成,并且镍(Ni)也可满足上述条件。但是,Ni在低于第一粉末10的低共熔点(例如,约213℃)的温度下被充分氧化,所以焊接之后可在焊层中产生大量空隙。
也就是说,由于Ni在等于或小于第一粉末10的低共熔点(例如,约213℃)的温度下已经被氧化,所以第二粉末20的Ni涂膜在回流焊期间已经被氧化,因此焊接之后可在焊层中产生大量空隙。
因此,当使用由Ni形成的隔离涂膜时,在焊层中产生的大量空隙可使焊层的电阻增加并恶化热辐射,因此回流焊可需要在氮环境下进行以防止氧化。
但是,在实施方案中,隔离涂膜可由氧化敏感性比Ni小的Ag形成。另外,根据上述实验结果,在实施方案中,通过调节第二粉末20的重量和Ag涂膜24的厚度,第二粉末20的氧化起始温度可变为约219℃或更高,这至少高于第一粉末10的低共熔点(例如,约213℃)。
如上所述,因为在回流焊温度(约240℃至250℃)下不发生第二粉末20的大量氧化,所以实施方案可限制焊层中空隙的产生并且防止由空隙造成的电阻增加和热辐射效率恶化。
另外,因为在回流焊期间不发生第二粉末20的大量氧化,所以实施方案在回流焊期间可不受氮环境和氧密度影响。
图12A示出了使用一般焊膏的焊层110,并且图12B示出了使用根据实施方案的焊膏的焊层120。
应理解,接合如图12A示例性示出的基底金属105和组件210的焊层110具有大量空隙,而在如图12B示例性示出的基底金属105与组件210之间的焊层120具有良好的可湿性,从而确保在其侧边光滑地形成圆角(fillet)220并且产生较少的空隙。
图13示出了使用根据实施方案的焊膏的包括接合部360的发光器件封装件300的截面图。
参照图13,发光器件封装件300可包括副安装座(sub-mount)301、发光器件302和接合部303。
副安装座301支承发光器件302,并且发光器件302安装在副安装座301上。
副安装座301可采取例如封装件体或印刷线路板的形式,并且可具有多种其他形状以使得发光器件302能够倒装接合。
副安装座301可包括第一导电层382和第二导电层384,其与发光器件302接合。第一导电层382和第二导电层384可彼此间隔开以与彼此电气绝缘。
发光器件302被设置在副安装座301上,并且通过接合部303与副安装座301电气连接。
发光器件302包括衬底310、发光结构体320、导电层330、第一电极342、第二电极344和绝缘层350。发光器件302可设置在副安装座301上使得第一电极342和第二电极344朝向副安装座301。
发光结构体320位于衬底310的一个表面上。
衬底310可以是光传播衬底,例如蓝宝石衬底、硅(silicone,Si)衬底、氧化锌(ZnO)衬底和氮化物半导体衬底中的任意一种;或者可以是GaN、InGaN、AlGaN、AlInGaN、SiC、GaP、InP、Ga2O3和GaAs中的至少一种堆叠在其上的模板衬底。
发光结构体320可包括多个第III-V族化合物半导体层。例如,发光结构体320可包括第一导电半导体层322、第二导电半导体层326以及第一导电半导体层322与第二导电半导体层326之间的有源层324。
发光结构体320的侧面可通过绝缘蚀刻倾斜,用于在每个单元芯片的基础上进行分割。例如,发光结构体320的侧面从衬底310的表面开始具有倾斜。
第一导电半导体层322可由第III-V族化合物半导体形成并且可掺杂有第一导电掺杂剂。第一导电半导体层322可由组成式为InxAlyGa1-x-yN(0≤x≤1,0≤y≤1,0≤x+y≤1)的半导体材料形成,并且例如可选自AlGaN、GaN、AlN、InGaN、InAl、InAlGaN、AlInN、AlGaAs、GaP、GaAs、GaAsP、AlGaInP等,并且可掺杂有n型掺杂剂,例如Si、Ge、Sn、Te等。
有源层324可使用在由第二导电半导体层326和第一导电半导体层322提供的电子与空穴复合期间产生的能量产生光。有源层324可由组成式为InxAlyGa1-x-yN(0≤x≤1,0≤y≤1,0≤x+y≤1)的半导体材料形成。有源层324可具有单量子阱结构、多量子阱结构、量子点结构或量子线结构中的至少一种。
在有源层324具有多量子阱结构的情况下,有源层324可采取多个阱层和多个势垒层的堆叠体的形式。例如,有源层324的阱层/势垒层可具有InGaN/GaN、InGaN/InGaN、GaN/AlGaN、InAlGaN/GaN、GaAs(InGaAs)/AlGaAs和GaP(InGaP)/AlGaP的至少一对构造,并且不限于此。在这种情况下,阱层可由能带间隙比势垒层的能带间隙小的材料形成。
第二导电半导体层326可由第III-V族化合物半导体形成并且可掺杂有第二导电掺杂剂。第二导电半导体层326可由组成式为InxAlyGa1-x-yN(0≤x≤1,0≤y≤1,0≤x+y≤1)的半导体材料形成,并且例如可选自AlGaN、GaN、AlN、InGaN、InAl、InAlGaN、AlInN、AlGaAs、GaP、GaAs、GaAsP、AlGaInP等,并且可掺杂有p型掺杂剂,例如Mg、Zn、Ca、Sr、Ba等。
可在有源层324与第一导电半导体层322之间或者在有源层324与第二导电半导体层326之间形成掺杂有n型或p型掺杂剂的覆层(未示出)。覆层可以是包含AlGaN或InAlGaN的半导体层。
虽然上述描述说明了第一导电半导体层322包括n型半导体层并且第二导电半导体层326包括p型半导体层,但是实施方案不限于此。第一导电半导体层322可包括p型半导体层并且第二导电半导体层326可包括n型半导体层。另外,在第二导电半导体层326之下还可提供n型或p型半导体层。
因此,发光结构体320可包括nn、pn、npn、和pnp接合构造中的至少一种。另外,第一导电半导体层322和第二导电半导体层326的掺杂剂可具有均匀或不均匀的掺杂密度。也就是说,发光结构体320的构造可以以多种方式变化,并且发光结构体320可发射具有多种波长的光。
导电层330可设置在第二导电半导体326上。
例如,导电层330可位于第二导电半导体层326与第二电极344之间,并且可与第二导电半导体层326欧姆接触。导电层330可降低总反射并且表现出高透光率,从而增加光从有源层324到第二导电半导体层326的提取效率。
导电层330可由与第二导电半导体层326欧姆接触的至少一种金属形成,例如Au、Pd、Pt、Ru、Re、Mg、Zn、Hf、Ta、Rh、Ir、W、Ti、Ag、Cr、Mo、Nb、Al、Ni、Cu、WTi、V或其合金中的至少一种。
另外,导电层330可使用在发射光波长表现出高透射率的透明氧化物基材料形成单层或多层,所述透明氧化物基材料例如,铟锡氧化物(ITO)、氧化锡(TO)、铟锌氧化物(IZO)、铟锌锡氧化物(IZTO)、铟铝锌氧化物(IAZO)、铟镓锌氧化物(IGZO)、铟镓锡氧化物(IGTO)、铝锌氧化物(AZO)、锑锡氧化物(ATO)、镓锌氧化物(GZO)、IrOx、RuOx、RuOx/ITO、Ni、Ag、Ni/IrOx/Au或Ni/IrOx/Au/ITO的一种或更多种。
发光结构体320可具有这样的区域,通过该区域暴露出第一导电半导体层322的一部分用于布置第一电极342。例如,发光结构体320可包括通过部分蚀刻第二导电半导体层326、有源层324和第一导电半导体层322形成的区域,以便暴露出第一导电半导体层322的一部分。
第一电极342可设置在第一导电半导体层322的暴露部分上以与第一导电半导体层322相接触。
第二电极344可设置在导电层330的上表面上以与导电层330相接触。
第一电极342和第二电极344可由导电金属形成,例如由Au、Pd、Pt、Ru、Re、Mg、Zn、Hf、Ta、Rh、Ir、W、Ti、Ag、Cr、Mo、Nb、Al、Ni、Cu、WTi、V或其合金中的至少一种形成。
绝缘层350可设置在发光结构体320的侧面上。例如,绝缘层350可覆盖发光结构体320的侧面。
另外,绝缘层350可设置在第一导电半导体层322中除第一电极342所设置的部分之外剩余暴露的部分上。
另外,绝缘层350可设置在导电层330上表面中除第二电极344所设置的部分之外的暴露部分上。
绝缘层350可暴露第一电极342上表面的至少一部分和第二电极344上表面的至少一部分。
副安装座301位于第一电极342和第二电极344下方。
副安装座301可包括例如由树脂(如聚邻苯二甲酰胺(PPA))、液晶聚合物(LCP)、聚酰胺9T(PA9T)等,金属,光敏玻璃,蓝宝石,陶瓷等形成的印刷线路板。但是,根据实施方案的副安装座301不限于上述材料。
第一导电层382和第二导电层384可设置在副安装座301的上表面上以与彼此间隔开。在这里,副安装座301的上表面可以是朝向发光器件302的表面。
第一导电层382和第一电极342可与彼此垂直对准,并且第二导电层384和第二电极344可与彼此垂直对准。在这里,垂直方向可以是副安装座301和发光器件302的对准方向。
接合部303可位于第一导电层382与第一电极342之间以及第二导电层384与第二电极344之间,以使其彼此接合。
例如,接合部303可包括使第一导电层382与第一电极342彼此接合的第一接合部362,以及使第二导电层384与第二电极344彼此接合的第二接合部364。
第一接合部362和第二接合部364可以是使用根据实施方案的焊膏100的焊料。第一接合部362和第二接合部364可具有图12B所述圆角220。也就是说,发光器件302可与副安装座301使用根据实施方案的焊膏100倒装接合。
如由以上描述所显而易见的,实施方案可提供增强的可湿性和受限的空隙产生。
虽然已参照本发明的多个说明性实施方案描述了实施方案,但是应理解,本领域技术人员可设计多种其他的修改方案和实施方案,其也在本公开原理的精神和范围内。更特别地,可以在本公开内容、附图和所附权利要求的范围内对主题组合布置的组成部件和/或布置进行多种变化和修改。除对组成部件和/或布置进行变化和修改之外,替代性用途对于本领域技术人员也是显而易见的。
Claims (22)
1.一种焊膏,其包含:
熔剂;和
与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,
其中所述第一粉末包含锡和溶于所述锡中的至少一种金属,并且所述第二粉末包含其表面涂覆有银的铜粉。
2.根据权利要求1所述的焊膏,其中所述至少一种金属包括铜和银。
3.根据权利要求1所述的焊膏,其中所述第一粉末包含锡、银和铜的合金。
4.根据权利要求1所述的焊膏,其中所述第二粉末的重量为所述混合粉末重量的5%至40%。
5.根据权利要求1所述的焊膏,其中所述第二粉末中所含银涂层的重量为所述第二粉末中所含铜粉重量的10%至50%。
6.根据权利要求1所述的焊膏,其中所述第二粉末中所含所述铜粉的直径为2μm至25μm。
7.根据权利要求1所述的焊膏,其中所述第二粉末中所含银涂层的厚度为1μm或更小。
8.根据权利要求1所述的焊膏,其中所述至少一种金属包括银(Ag)、铜(Cu)、锑(Sb)、铋(Bi)、铟(In)和锌(Zn)中的至少一种。
9.根据权利要求3所述的焊膏,其中所述第一粉末中所含锡与银与铜的重量百分比之比为96.5:3:0.5。
10.根据权利要求3所述的焊膏,其中所述第一粉末通过使锡、银和铜的合金块破碎形成。
11.根据权利要求1至10中任一项所述的焊膏,其中所述第二粉末的氧化起始温度为219℃或更高。
12.根据权利要求1至10中任一项所述的焊膏,其中所述第二粉末的氧化起始温度高于240℃至250℃的范围。
13.根据权利要求1至10中任一项所述的焊膏,其中所述熔剂为液相、具有延展性的固体、或者固体。
14.根据权利要求13所述的焊膏,其中所述熔剂包含松香、稀释剂和活化剂。
15.根据权利要求14所述的焊膏,其中所述活化剂以基于所述熔剂总重量的30%至70%的量存在。
16.根据权利要求14所述的焊膏,其中所述熔剂还包含胶凝剂,并且
所述胶凝剂以基于所述熔剂总重量的0.1%至10%的量存在。
17.根据权利要求14所述的焊膏,其中所述活化剂还包含卤代化合物。
18.根据权利要求1所述的焊膏,其中所述铜粉的直径为4μm至7μm。
19.一种焊膏,其包含:
熔剂;和
与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,
其中所述第一粉末包含锡和溶于所述锡中的至少一种金属,并且所述第二粉末包含铜粉和涂覆在所述铜粉表面上的隔离涂膜,并且
其中所述隔离涂膜的熔化温度等于或高于所述锡的熔化温度。
20.根据权利要求19所述的焊膏,其中所述隔离涂膜是银涂膜。
21.根据权利要求19所述的焊膏,其中所述第二粉末的氧化起始温度高于所述第一粉末的低共熔点。
22.一种焊膏,其包含:
熔剂;和
与所述熔剂混合的混合粉末,所述混合粉末包含彼此混合的第一粉末和第二粉末,
其中所述第一粉末包含锡、银和铜,
其中所述第二粉末包含铜粉和在所述铜粉的整个表面上的银涂膜,
其中所述第二粉末的重量为所述混合粉末重量的5%至40%,并且
其中所述第二粉末中所含所述银涂膜的重量为所述第二粉末中所含的所述铜粉重量的10%至50%。
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CN111571065A (zh) * | 2020-05-14 | 2020-08-25 | 深圳市唯特偶新材料股份有限公司 | 一种改善bga封装焊接性能的锡膏及其制备方法 |
CN114055008A (zh) * | 2021-11-18 | 2022-02-18 | 陕西众森电能科技有限公司 | 一种制备超细焊锡膏的金属粉、焊锡膏及其制备方法 |
CN114055007A (zh) * | 2021-11-16 | 2022-02-18 | 陕西众森电能科技有限公司 | 一种超细低温焊锡粉、锡膏及其制备方法与应用 |
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US9282638B2 (en) * | 2012-01-13 | 2016-03-08 | Zycube Co., Ltd. | Electrode, electrode material, and electrode formation method |
KR102101474B1 (ko) | 2015-12-15 | 2020-04-16 | 주식회사 엘지화학 | 금속 페이스트 및 열전 모듈 |
JP7145855B2 (ja) * | 2017-11-22 | 2022-10-03 | 深▲チェン▼市福英達工業技術有限公司 | マイクロ/ナノ粒子強化型複合はんだ及びその調製方法 |
CN109244686B (zh) * | 2018-07-26 | 2021-06-18 | 合德华厦安防科技有限公司 | 一种用于接地系统的芯棒及其制备方法 |
US11581239B2 (en) * | 2019-01-18 | 2023-02-14 | Indium Corporation | Lead-free solder paste as thermal interface material |
EP3782764A1 (de) * | 2019-08-19 | 2021-02-24 | Heraeus Deutschland GmbH & Co KG | Cu-pasten/lotkombination zur erzeugung bleifreier hochtemepraturstabiler lötverbindungen |
JP2023000704A (ja) * | 2021-06-18 | 2023-01-04 | パナソニックIpマネジメント株式会社 | 導電性ペーストおよびそれを用いて形成される導電膜 |
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CN114055007A (zh) * | 2021-11-16 | 2022-02-18 | 陕西众森电能科技有限公司 | 一种超细低温焊锡粉、锡膏及其制备方法与应用 |
CN114055007B (zh) * | 2021-11-16 | 2023-03-14 | 陕西众森电能科技有限公司 | 一种超细低温焊锡粉、锡膏及其制备方法与应用 |
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CN114055008B (zh) * | 2021-11-18 | 2023-09-05 | 陕西众森电能科技有限公司 | 一种制备超细焊锡膏的金属粉、焊锡膏及其制备方法 |
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US9610655B2 (en) | 2017-04-04 |
CN104139249B (zh) | 2017-01-18 |
KR102156373B1 (ko) | 2020-09-16 |
EP2801435A2 (en) | 2014-11-12 |
US20140332116A1 (en) | 2014-11-13 |
EP2801435A3 (en) | 2015-03-04 |
KR20140133221A (ko) | 2014-11-19 |
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