CN103008910A - 用于将电子部件连接到基板上的膏和方法 - Google Patents
用于将电子部件连接到基板上的膏和方法 Download PDFInfo
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- CN103008910A CN103008910A CN2012103509739A CN201210350973A CN103008910A CN 103008910 A CN103008910 A CN 103008910A CN 2012103509739 A CN2012103509739 A CN 2012103509739A CN 201210350973 A CN201210350973 A CN 201210350973A CN 103008910 A CN103008910 A CN 103008910A
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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
- B23K35/36—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
- B23K35/3618—Carboxylic acids or salts
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- 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
- H05K1/18—Printed circuits structurally associated with non-printed electric components
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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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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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
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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
- 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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
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Abstract
本发明提供可用于通过接触区将至少一个电子部件连接到至少一个基板上的膏,由此至少一个所述接触区含有非贵金属。所述膏含有(a)金属颗粒、(b)至少一种在分子中带有至少两个羧酸单元的活化剂和(c)分散介质。
Description
本发明涉及用于将电子部件(electronic component)连接到基板(substrate)上的膏(paste)和用于将电子部件连接到基板上的方法。
在电力电子学领域中,在基板上固定电子部件是一项特殊挑战。
在终端设备运行过程中出现的机械应力要求电子部件与基板之间的连接具有足够强度以使电子部件不会脱离基板。因此,通常使用含铅焊膏,其在焊接工艺中产生对连接技术而言在其强度方面表现出高可靠性的连接层。由于铅的毒性和相关健康危害,寻求对所述含铅焊膏的合适替代品。目前作为铅焊料的替代品论述了无铅焊膏非常适合生成电子部件与基板之间的具有高强度的连接层。但是,所述焊料具有不比电子部件在工作中承受的温度高很多的低熔点。因此,所述连接层的强度的可靠性在电子部件运行过程中显著变差。
可以用许多连接剂和连接方法实现电子部件与基板之间的连接强度的高可靠性。但是,这些通常要求高工艺温度和高工艺压力,它们对要连接的部件造成破坏并在大规模生产中产生高废品率。
这是旨在降低所述连接方法所需的工艺温度和工艺压力的原因。因此在一些用途中使用粘合剂连接所述部件。通过使用粘合剂,在一些情况下可获得连接电子部件与基板的高强度连接层。但是,粘合剂技术的一个缺点在于,由此生成的电子部件与基板之间的接触位点通常在热导率和电导率方面通常不足。
为了满足对连接位置的可靠性、热导率和电导率的要求,一段时间之前已提出通过烧结连接电子部件与基板(参见例如DE 10 2007 046 901 A1)。烧结技术是以稳定的方式连接部件的非常简单的方法。使用所述烧结方法,通常相当成功地将电子部件连接到基板上,只要这些各自包含含贵金属的接触区。但是,通常必须通过至少一个非贵金属接触区连接电子部件与基板。使用常规烧结方法,通过所述非贵金属接触区制造稳定接点通常不可行。
此外,早先已提出使用基于粒度不大于100纳米的纳米颗粒的膏连接电子部件与基板。但是,纳米颗粒的操作与健康危害相关,因此出于职业安全的原因常常避免。
因此本发明的一个目的是提供能通过接触区将至少一个电子部件连接到至少一个基板上的膏,其中至少一个所述接触区含有非贵金属。所述膏优选应用于制造确保在电子部件在工作中承受的温度下高可靠性的电子部件与基板之间的连接。此外,所述膏应优选还克服从现有技术中已知的其它缺点。
本发明的一个目的还提供通过接触区将至少一个电子部件连接到至少一个基板上的方法,其中至少一个所述接触区含有非贵金属。
通过独立权利要求的主题实现所述目的。
相应地,本发明提供膏,其含有(a)金属颗粒、(b)至少一种在分子中带有至少两个羧酸单元的活化剂和(c)分散介质。
此外,本发明提供通过接触区将至少一个电子部件连接到至少一个基板上的方法,其中至少一个所述接触区含有非贵金属,该方法包含以下步骤:
(i) 提供具有第一接触区的基板和具有第二接触区的电子部件,其中至少一个所述接触区含有非贵金属;
(ii) 提供膏,其含有
(a) 金属颗粒;
(b) 至少一种在分子中带有至少两个羧酸单元的活化剂;和
(c) 分散介质;
(iii) 形成结构,其中该基板的第一接触区通过膏接触该电子部件的第二接触区;和
(iv) 烧结所述结构,同时产生至少包含通过该烧结膏相互连接的该基板和该电子部件的模件。
本发明基于绝对令人惊讶的发现,如果所述膏含有在分子中带有至少两个羧酸单元的活化剂,通过借助膏的烧结能够通过至少一个包含非贵金属的接触区将电子部件连接到基板上,这迄今一直是不可能的。
根据本发明,提供膏。
对该术语“膏”的定义没有限制。但是,优选将膏理解为是指可通过普通施加技术,例如印刷技术(例如丝网印刷或模板印刷)、分配技术、喷涂技术、针板转移(pin transfer)或浸渍施加并具有足够高的粘度和内聚力以便施加的膏能在后继步骤中加工的任何分散体。
本发明的膏含有(a)金属颗粒。
金属颗粒优选被理解为是指含金属的颗粒。
根据一个优选实施方案,该金属选自铜、银、镍和铝。根据一个特别优选的实施方案,该金属是银。
该金属可以作为纯金属存在于金属颗粒中,例如具有至少99重量%的纯度、至少99.9重量%的纯度、至少99.99重量%的纯度或至少99.999重量%的纯度。另一方面,该金属颗粒同样可含有多种金属。该金属颗粒也可以含有由多种金属构成的合金或金属间相。
根据一个优选实施方案,该金属颗粒包含选自银、铜、镍和铝的元素作为它们的主要组分。在本发明的范围内,主要组分被理解为是指以比所述金属颗粒中存在的任何其它元素大的比例存在于相关金属颗粒中的元素。
根据一个特别优选的实施方案,该金属颗粒是银颗粒、铜颗粒、镍颗粒或铝颗粒。任选地,所述颗粒可以在它们的表面部分或完全氧化。
根据一个特别优选的实施方案,该金属颗粒是银颗粒。
对所述金属颗粒的形状没有限制。该金属颗粒优选呈薄片形、椭圆形或圆形。该金属颗粒同样可以是多种形状的混合物。
根据一个特别优选的实施方案,该金属颗粒呈薄片形。相对于金属颗粒的总重量,薄片的百分比在所述实施方案中优选为至少70重量%,更优选至少80重量%,再更优选至少90重量%,特别优选至少99重量%。
根据另一优选实施方案,该金属颗粒具有大于1.0的长度比,更优选大于1.2的长度比,再更优选大于1.5的长度比,特别优选大于2.0的长度比。该金属颗粒优选具有不大于20的长度比,更优选不大于15的长度比,再更优选不大于10的长度比。在这方面,长度比应被理解为是指贯穿金属颗粒横截面的最宽位置的距离(a)与贯穿沿垂直于距离(a)的线的所述横截面的最宽位置的距离(b)的比率。在这种情况中,横截面是具有最大表面积的穿过金属颗粒的截面。在金属颗粒具有例如矩形横截面时,长度比是该横截面的长宽比。例如具有2微米长和1微米宽的矩形横截面的金属颗粒具有2的长度比。
根据再一优选实施方案,长度比大于1.0的金属颗粒的百分比,更优选长度比大于1.2的金属颗粒的百分比,再更优选长度比大于1.5的金属颗粒的百分比为至少70重量%,更优选至少80重量%,再更优选至少90重量%,各自相对于金属颗粒的总重量。
该膏中存在的金属颗粒具有不同的粒度分布。
根据一个优选实施方案,金属颗粒的平均粒度(d50值)为至少500纳米,更优选至少650纳米,再更优选至少1微米。平均粒度(d50值)优选不大于20微米,更优选不大于15微米,再更优选不大于10微米。因此,平均粒度(d50值)优选为500纳米 - 20微米,更优选650纳米 - 15微米,再更优选1 - 10微米。平均粒度(d50值)优选被理解为是指50体积%的金属颗粒没达到而50体积%的金属颗粒超过的粒度。
根据另一优选实施方案,金属颗粒的粒度d10(d10值)为至少150纳米,更优选至少200纳米,再更优选至少250纳米。粒度d10(d10值)优选不大于5微米,更优选不大于4微米,再更优选不大于3微米。因此,粒度 d10(d10值)优选为150纳米 - 5微米,更优选200纳米 - 4微米,再更优选250纳米 - 3微米。粒度d10(d10值)优选被理解为是指10体积%的金属颗粒没达到而90体积%的金属颗粒超过的粒度。
根据再一优选实施方案,金属颗粒的粒度d90(d90值)为至少1.75微米,更优选至少2微米,再更优选至少2.25微米。粒度d90(d90值)优选不大于100微米,更优选不大于50微米,再更优选不大于25微米。因此,粒度d90(d90值)优选为1.75 - 100微米,更优选2 - 50微米,再更优选2.25 - 25微米。粒度d90(d90值)优选被理解为是指90体积%的金属颗粒没达到而10体积%的金属颗粒超过的粒度。
前述粒度规格适用于通过根据ISO 13320 (2009)的LALLS(低角度激光散射)方法的粒度测定分析。在这方面,Mastersizer 2000 (Malvern Instruments Ltd., Worcestershire, United Kingdom)优选充当测量仪器。在合适的条件(例如:标样:折光指数为0.14、吸收为3.99的银;分散介质:折光指数为1.36的乙醇;程序:将200毫升乙醇添加到0.5克粉末中并将所得悬浮液声处理5分钟,然后将用于测量的悬浮液等分试样转移到Mastersizer 2000的Hydro配件(Hydro Accessory)中;分析用的光学模型:Mie理论)下进行测量和分析。
该金属颗粒优选具有1–5平方米/克,更优选1–4平方米/克的根据BET(Brunauer, Emett, Teller)的比表面积。优选根据DIN ISO 9277:2003-05进行这种BET测量。
任选地,该金属颗粒同样可作为多个金属颗粒部分(fractions)的混合物存在。这些部分可例如在金属颗粒的组成、形状或尺寸方面不同。
优选地,相对于膏的总重量, 金属颗粒的百分比为至少50重量%,更优选至少60重量%,再更优选至少70重量%,特别优选至少80重量%。相对于膏的总重量,金属颗粒的百分比优选不大于95重量%,更优选不大于93重量%,再更优选不大于90重量%。因此,相对于膏的总重量,金属颗粒的百分比[优选]为50 - 95重量%,更优选60 - 93重量%,再更优选70 - 90重量%。
该金属颗粒可包含涂层。
在本发明的范围内,金属颗粒的涂层被理解为是指在金属颗粒表面上的牢固粘合层。牢固粘合层优选是指该层在重力作用下不简单地从金属颗粒脱离。
金属颗粒的涂层通常含有至少一种涂层化合物。
所述至少一种涂层化合物优选是有机化合物。
该涂层化合物优选选自饱和化合物、单不饱和化合物、多不饱和化合物及其混合物。
该涂层化合物优选选自支化化合物、非支化化合物及其混合物。
该涂层化合物优选具有8 - 28,再更优选12 - 24,特别优选12–18个碳原子。
根据一个优选实施方案,该涂层化合物选自脂肪酸、脂肪酸盐和脂肪酸酯。
可想到的脂肪酸盐优选是其阴离子组分是脱质子脂肪酸且其阳离子组分选自铵离子、单烷基铵离子、二烷基铵离子、三烷基铵离子、锂离子、钠离子、钾离子、铜离子和铝离子的盐。
优选的脂肪酸酯衍生自相应的脂肪酸,其中羧酸单元的羟基被烷基,特别是甲基、乙基、丙基或丁基替代。
根据一个优选实施方案,所述至少一种涂层化合物选自羊脂酸(辛酸)、羊蜡酸(癸酸)、月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕榈酸(十六烷酸)、硬脂酸(十八烷酸)、它们的混合物,以及相应的酯和盐及其混合物。
根据一个特别优选的实施方案,所述至少一种涂层化合物选自月桂酸(十二烷酸)、硬脂酸(十八烷酸)、硬脂酸钠、硬脂酸钾、硬脂酸铝、硬脂酸铜、棕榈酸钠和棕榈酸钾。
优选使用的涂布金属颗粒可购得。相应的涂层化合物可通过此领域中常见的技术施加到金属颗粒表面。
可以例如在溶剂中将该涂层化合物,特别是上文提到的硬脂酸盐或棕榈酸盐制浆并在球磨机中与金属颗粒一起研制该制浆的涂层化合物。在研制后,将届时被该涂层化合物涂布的金属颗粒干燥,然后去除灰尘。
优选地,相对于涂层总重量,所述至少一种选自脂肪酸、脂肪酸盐和脂肪酸酯的涂层化合物的百分比为至少80重量%,更优选至少90重量%,特别优选至少95重量%,再更特别优选至少99重量%,特别是100重量%。
根据一个优选实施方案,相对于涂布的金属颗粒的总重量,涂层化合物的总百分比为0.05 - 3重量%,更优选0.07 - 2.5重量%,再更优选0.1 - 2.2重量%。
涂布程度——被定义为涂层化合物的质量与金属颗粒表面积的比率,优选为0.00005 – 0.03克,更优选0.0001 – 0.02克,再更优选0.0005 – 0.02克涂层化合物/平方米金属颗粒表面积。
令人惊讶地发现,在金属颗粒上存在涂层显著改进电子部件与基板之间的连接强度的可靠性。
根据本发明,该膏还含有至少一种活化剂(b)。
该活化剂在分子中带有至少两个羧酸单元。因此,该活化剂可以在分子中带有多于2个,多于3个或多于4个羧酸单元。
羧酸单元在该分子中的位置不受限制。但是,该活化剂的羧酸单元优选位于末端位置。
此外,该活化剂的羧酸单元通过不多于5个碳原子,更优选不多于4个碳原子,再更优选不多于3个碳原子,特别优选不多于2个碳原子,再更特别不多于1个碳原子相互连接经证实是有利的。此外,该活化剂的羧酸单元优选通过至少一个碳原子相互连接。在确定该活化剂的羧酸单元经此相互连接的碳原子数时,在根据本发明范围的计算中不应包括羧酸单元本身的碳原子。因此,例如在丙二酸(HOOCCH2COOH)的情况下,羧酸单元通过一个碳原子相互连接,而在马来酸(HOOC(CH)2COOH)的情况下,羧酸单元通过两个碳原子相互连接。
根据一个优选实施方案,该活化剂包含至少2个碳原子,更优选至少3个碳原子。该活化剂优选包含不多于18个碳原子,更优选不多于14个碳原子,再更优选不多于12个碳原子,特别优选不多于10个碳原子,再更特别优选不多于8个碳原子,特别是不多于6个碳原子。因此,该活化剂优选包含2 – 18个碳原子,更优选2 – 14个碳原子,再更优选2 – 12个碳原子,特别优选2 – 10个碳原子,更特别优选2 – 8个碳原子,特别是2 – 6个碳原子或3 – 6个碳原子。
该活化剂可以是饱和或不饱和化合物。
不饱和活化剂优选在分子中包含至少一个碳-碳双键。此外,顺式-异构体经证实是特别有利的活化剂。
该活化剂可以是支化或非支化化合物。
支化活化剂的侧链的长度、类型和位置不受任何限制。支化活化剂优选包含至少一个长度为1 – 8个碳原子的侧链。通常,所述侧链是烷基,任选地,其可以被取代。
该活化剂可以是芳族或脂族化合物。但是,该活化剂优选是脂族化合物。
除羧酸单元中存在的氧原子外,本发明的活化剂还可带有其它杂原子。但是,该活化剂优选不含除羧酸单元中的氧原子外的杂原子。
该活化剂的羧酸单元优选以非质子化形式存在于膏中。因此可以有利地选择不会使羧酸单元发生离解的分散介质。
活化剂具有低于300℃的温度,更优选低于270℃的温度,再更优选低于240℃的温度,特别优选低于200℃的温度的分解点在许多情况下经证实有利。在这些情况下,活化剂的分解点优选为100℃ - 300℃,更优选110℃ - 270℃,再更优选120℃ - 240℃,特别优选130℃ - 200℃。
此外,活化剂的熔点为至少80℃,更优选至少90℃,再更优选至少100℃在许多情况下经证实有利。在这些情况下,熔点优选不大于200℃,更优选不大于180℃,再更优选不大于160℃。因此,活化剂的熔点优选为80℃ - 200℃,更优选90 - 180℃,再更优选100℃ - 160℃。
活化剂可以以非络合形式存在。另一方面,活化剂同样可以以络合形式,优选作为包括元素周期表的副族元素的络合物存在。如果活化剂以络合形式存在,这特别可以是络合的二羧酸。
根据一个优选实施方案,该活化剂选自草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、顺式-丁烯二酸(马来酸)、反式-丁烯二酸(富马酸)、顺式-2-戊烯酸、反式-2-戊烯酸和二甲基丙二酸。
根据一个特别优选的实施方案,该活化剂选自草酸、丙二酸、马来酸和二甲基丙二酸。
根据一个更特别优选的实施方案,该活化剂选自草酸、丙二酸、马来酸和二甲基丙二酸。
相对于膏的总重量,活化剂的百分比优选为至少0.1重量%,更优选至少0.3重量%,再更优选至少0.5重量%,特别优选至少1重量%,更特别优选至少2重量%。相对于膏的总重量,活化剂的百分比优选不大于30重量%,更优选不大于20重量%,再更优选不大于10重量%,特别优选不大于7重量%,更特别优选不大于5重量%。因此,相对于膏的总重量,活化剂的百分比为0.1 - 30重量%,更优选0.3 - 20重量%,再更优选0.5 - 10重量%,特别优选1 - 7重量%,更特别优选2 - 5重量%。
此外,本发明的膏含有分散介质(c)。
金属颗粒(a)优选可分散在分散介质(c)中。所述至少一种活化剂(b)也可分散在分散介质(c)中。但是,活化剂(b)同样也可溶解在分散介质(c)中。
该分散介质可以是此领域中常见的分散介质。
因此,该分散介质可含有一种或多种溶剂。
有机化合物例如是在这方面可想到的溶剂。
所述有机化合物优选含有5 – 50个碳原子,更优选8 – 32个碳原子,再更优选18 – 32个碳原子。
该有机化合物可以是支化或非支化的。该有机化合物同样可以是环状化合物。
该有机化合物也可以是脂族或芳族性质的。
此外,用作溶剂的有机化合物可以是饱和或单-或多-不饱和的化合物。
该有机化合物还可包含杂原子,特别是氧原子或氮原子。所述杂原子可以是官能团的一部分。可想到的官能团包括,例如,羧酸基团、酯基团、酮基(keto group)、醛基、羟基、氨基、酰胺基团、偶氮基团、酰亚胺基团、氰基或腈基。
因此,例如,α-萜品醇((R)-(+)-α-萜品醇、(S)-(-)-α-萜品醇或外消旋物)、β-萜品醇、γ-萜品醇、δ-萜品醇、前述萜品醇的混合物、N-甲基-2-吡咯烷酮、乙二醇、二甲基乙酰胺、醇,特别是包含具有5-9个碳原子的直链或支链的那些、1-己醇、1-辛醇、1-十二烷醇、1-十三烷醇、2-十三烷醇、3-十三烷醇、4-十三烷醇、5-十三烷醇、6-十三烷醇、异十三烷醇、二元酸酯(优选为戊二酸、己二酸或丁二酸的二甲酯或其混合物)、甘油、二乙二醇、三乙二醇或其混合物可用作溶剂。
根据另一优选实施方案,该分散介质含有至少一种非质子溶剂。相对于在25℃的温度和1.1013巴的压力下为液体的膏的所有组分的总重量,所述至少一种非质子溶剂的百分比也可有利地为至少70重量%,更优选至少80重量%,再更优选至少90重量%,特别优选至少95重量%,更特别优选至少99重量%。
该非质子溶剂优选选自脂族烃化合物、羧酸酯和醚。
根据一个特别优选的实施方案,该分散介质含有至少一种脂族烃化合物。所述脂族烃化合物优选包含5 – 50个碳原子,更优选8 – 32个碳原子,再更优选18 – 32个碳原子。
因此,该脂族烃化合物同样可以是石蜡。
相对于膏的总重量,分散介质的百分比优选为至少5重量%,更优选至少8重量%,再更优选至少10重量%。相对于膏的总重量,分散介质的百分比优选不大于40重量%,更优选不大于30重量%,再更优选不大于20重量%,特别优选不大于15重量%。因此,相对于膏的总重量,分散介质的百分比优选为5 - 40重量%,更优选8 - 30重量%,再更优选10 - 20重量%。
任选地,除金属颗粒(a)、所述至少一种活化剂(b)和分散介质(c)外,本发明的膏还可含有其它物质。
可想到的其它物质是此领域中常见的稀释剂、增稠剂和稳定剂。
优选地,相对于膏的总重量,除(a)金属颗粒、(b)所述至少一种在分子中带有至少两个羧酸单元的活化剂和(c)分散介质外的物质的百分比不大于20重量%,更优选不大于15重量%,再更优选不大于10重量%,特别优选不大于5重量%,再更特别优选不大于3重量%,特别是不大于1重量%。
本发明的膏可通过此领域中常见的方式制造。
可以例如通过金属颗粒(a)、所述至少一种在分子中带有两个羧酸单元的活化剂(b)和分散介质(c)的混合制造膏。
根据一个特别优选的实施方案,在多个步骤中制造膏。
在这方面,所述至少一种活化剂(b)在第一步骤中研制。研制可以在磨机中进行并用于改进活化剂在分散介质(c)中的可分散性。
研制的活化剂(b)可随后在第二步骤中与分散介质(c)合并。在此步骤中通常产生活化剂(b)在分散介质(c)中的均匀悬浮液。为了制造所述均匀悬浮液,任选地,可以用混合器,例如Ultraturax混合器处理该混合物。
最后,来自第二步骤的悬浮液可以在第三步骤中与金属颗粒(a)合并。随后,任选地,所得混合物例如手动均化。随后,该混合物可以反复输送通过辊磨机,及任选地,进一步均化。所得膏随后可用于预期用途。
本发明的膏优选用于将至少一个电子部件连接到至少一个基板。
在这种方法中,优选将所述至少一个电子部件固定在基板上。
通过烧结实现所述固定。在本发明的范围内,烧结被理解为是指通过加热(但不产生液相)连接两个或更多个部件。因此,烧结优选产生所述至少一个电子部件与基板之间的牢固粘合的连接。
如该领域中常见的那样,电子部件被理解为是可作为电子装置的一部分的物体。根据一个优选实施方案,电子部件被理解为是指不能进一步拆开并可充当电子电路的部件的单个部件。任选地,作为一个单元,该电子部件可以由多个部件构成。该电子部件可以例如是有源元件或无源元件。根据具体实施方案,该电子部件用在高功率电子装置中。该电子部件优选选自二极管(例如LED,发光二级管)、晶体管(例如IGBT,绝缘栅双极晶体管,具有绝缘栅极的双极晶体管)、集成电路、半导体芯片、裸片(dies)、电阻器、传感器、电容器、线圈和散热器。
通常,基板被理解为是指可连接到电子部件上的物体。根据一个优选实施方案,基板选自引线框、DCB基板(直接覆铜基板)和陶瓷基板。
根据一个优选实施方案,下列电子部件和基板对相互连接:LED/引线框、LED/陶瓷基板、裸片/引线框、裸片/陶瓷基板、裸片/DCB基板、二极管/引线框、二极管/陶瓷基板、二极管/DCB基板、IGBT/引线框、IGBT/陶瓷基板、IGBT/DCB基板、集成电路/引线框、集成电路/陶瓷基板、集成电路/DCB基板、传感器/引线框、传感器/陶瓷基板、散热器(优选铜或铝散热器)/DCB、散热器(优选铜或铝散热器)/陶瓷基板、散热器/引线框、电容器(优选钽电容器,更优选在未包封状态下)/引线框。
根据另一优选实施方案,多个电子部件可连接到基板上。此外,优选在基板的相反面上布置电子部件。
无论如何,电子部件和基板都包含至少一个接触区。
在本发明的范围内,接触区被理解为是指基板通过本发明的膏接触的电子部件区或电子部件通过本发明的膏接触的基板区。因此,电子部件的接触区优选包含一旦基板连接到其上就被基板覆盖的接触表面。同样地,基板的接触区优选包含一旦电子部件连接到其上就被电子部件覆盖的接触表面。优选地,电子部件的接触区具有由电子部件的接触区的接触表面(通过接触表面的宽度和长度限定)和50纳米厚度限定的体积。同样地,基板的接触区优选具有由基板的接触区的接触表面(通过接触表面的宽度和长度限定)和50纳米厚度限定的体积。电子部件和基板的接触区的所述体积具有一定重量。可以例如通过借助俄歇能谱法经溅射除去接触区、然后测定除去的区域的重量来测定所述重量。
该接触区可以是施加到电子部件上或施加到基板上的区域。例如,在许多情况下,对要连接的电子部件的表面施加金属化(metallisation)。所述金属化在许多情况下占100 - 400纳米的厚度。这种类型的金属化或其区域可代表本发明的接触区。
另一方面,该接触区同样可以是电子部件或基板的整体部件。例如,根据本发明,由铜制成的引线框可用作基板。这种引线框可具有几毫米的厚度。在这种情况中,所述引线框的区域(其不必在物质或结构方面不同于所述引线框的其它区域)可代表本发明的接触区。
电子部件和基板的至少一个接触区含有至少一种非贵金属。
根据一个优选实施方案,电子部件和基板的至少一个包含非贵金属的接触区含有(i) 至少一种选自铜、铝、锌和镍的元素、(ii) 包含至少一种选自铜、铝、锌和镍的元素的合金和(iii) 包含至少一种选自铜、铝、锌和镍的元素的金属间相。
相对于包含非贵金属的接触区的重量,所述至少一种非贵金属,例如选自铜、铝、锌和镍的非贵金属的百分比优选为至少5重量%,更优选至少7重量%,再更优选至少10重量%,特别优选至少15重量%,再更特别优选至少50重量%,特别是至少90重量%。
优选地,非贵金属,更优选选自铜、铝、锌和镍的非贵金属是接触区的主要成分。在本发明的范围内,接触区的主要成分被理解为是指以比所述接触区中存在的任何其它元素大的比例存在于所述接触区中的元素。
在本发明的范围内,所述包含非贵金属的接触区还可包含其它元素,特别包括贵金属。
当所述包含非贵金属的接触区含有包含至少一种选自铜、铝、锌和镍的元素的合金时,该合金可以例如是基本由铜、镍、锌和常见杂质构成的合金或基本由锡、金和常见杂质构成的合金。
在本发明的方法的第一步骤中,提供具有第一接触区的基板和具有第二接触区的电子部件,其中至少一个所述接触区含有非贵金属。
相应地,基板的接触区、电子部件的接触区、或基板的接触区和电子部件的接触区可含有非贵金属。
根据定义,基板包含第一接触区且电子部件包含第二接触区。此外,任选地,基板或电子部件可包含另外的接触区。当例如使用引线框作为基板时,所述引线框通常含有旨在连接至多个电子部件以形成子配件(subassembly)的多个(相邻)接触区。
在本发明的方法的下一步骤中,提供根据上文提供的定义的膏。
因此,所述膏含有(a)金属颗粒、(b)至少一种在分子中带有至少两个羧酸单元的活化剂和(c)分散介质。
在本发明的方法的进一步步骤中形成结构。
所述结构含有至少基板、电子部件和膏。在这方面,所述膏位于基板的第一接触区与电子部件的第二接触区之间。因此,基板的第一表面经由膏接触电子部件的第二表面。
可以例如通过将该膏施加到基板的第一接触区的接触表面上并将电子部件经第二接触区的接触表面放置在施加的膏上来形成该结构。通常地,也可以例如通过将该膏施加到电子部件的第二接触区的接触表面上并将基板经第一接触区的接触表面放置在施加的膏上来形成该结构。膏的施加可优选借助此领域中常见的施加技术,例如借助印刷法(例如丝网印刷或模板印刷)、分配技术、喷涂技术、针板转移或浸渍进行。
在刚形成该结构后,基板的第一表面与电子部件的第二表面之间的距离(其基本取决于该膏的厚度)优选为20 - 200微米,更优选50 - 100微米。
一旦形成该结构,任选地,可将其干燥。该结构优选在80 - 200℃的温度下,更优选在100 - 150℃的温度下干燥。干燥优选进行2 – 20分钟,更优选5 – 10分钟。任选地,或者或另外,也可以在形成该结构的同时(例如在将电子部件置于施加在基板上的膏上之前或在将基板置于施加在电子部件上的膏上之前)优选在上述条件下进行干燥。
在本发明的方法的进一步步骤中,对含有基板、电子部件和膏的结构施以烧结。
在烧结时,膏中存在的金属颗粒与至少一部分接触区烘烤在一起。膏中存在的其余组分通常在此过程中从膏中除去,例如通过蒸发它们,任选地,在发生化学转化后除去。该烧结基于扩散过程进行,其中膏的金属颗粒中存在的元素扩散到接触区中,接触区中存在的元素扩散到由膏的金属颗粒形成的居间空间中。由于这一过程中主导的温度和扩散速率,形成稳定的牢固粘合的连接。
优选通过加热至至少150℃的温度,更优选至少175℃的温度,再更优选至少200℃的温度实施该结构的烧结。优选通过加热至不大于350℃的温度,再更优选不大于300℃的温度实施该结构的烧结。因此,优选将该结构加热至150℃ - 350℃的温度,更优选150℃ - 300℃的温度,再更优选175℃ - 300℃的温度,特别优选200℃ - 300℃的温度。
该加热优选在不施加任何工艺压力的情况下,即在0 kbar的工艺压力下进行,但同样可以在升高的工艺压力下,例如在1 kbar或更大的工艺压力下进行。
该加热优选进行1 - 60分钟,更优选2 - 45分钟。
对实施加热时的气氛没有限制。但是,优选在含氧气氛中进行加热。
在此领域中常见的并在其中优选可设定上述工艺参数的合适的烧结用装置中进行烧结。
在烧结后,获得包含至少通过烧结膏相互连接的基板和电子部件的模件。
根据一个特别优选的实施方案,用于将至少一个电子部件连接到至少一个基板的本发明的方法通过接触区进行,其中至少一个所述接触区含有铜作为非贵金属。使用含有(a)金属颗粒、(b)作为活化剂的至少一种选自丙二酸、马来酸和草酸的化合物和(c)分散介质的膏在这种情况中经证实特别有利。
根据另一特别优选的实施方案,用于将至少一个电子部件连接到至少一个基板的本发明的方法通过接触区进行,其中至少一个所述接触区含有镍作为非贵金属。使用含有(a)金属颗粒、(b)作为活化剂的至少一种选自二甲基丙二酸和草酸的化合物和(c)分散介质的膏在这种情况中经证实特别有利。
下面基于不限制本发明的范围的实施例例证本发明。
实施例:
如下以根据下表1的组成制备根据本发明的膏1 - 3和参比膏1 – 3:
膏 1 | 膏 2 | 膏 3 | 参比膏1 | 参比膏2 | 参比膏3 | |
银颗粒 | 85重量% | 85重量% | 85重量% | 85重量% | 85重量% | 85重量% |
石蜡 | 12重量% | 12重量% | 12重量% | 12重量% | 12重量% | 12重量% |
活化剂: | ||||||
丙二酸 | 3重量% | - | - | - | - | - |
马来酸 | - | 3重量% | - | - | - | - |
二甲基丙二酸 | - | - | 3重量% | - | - | - |
乳酸银 | - | - | - | 3重量% | - | - |
丙酸 | - | - | - | - | 3重量% | - |
脲 | - | - | - | - | - | 3重量% |
表1:膏1 - 3和参比膏1 - 3的组成。
在六个不同样品(膏1 - 3和参比膏1 - 3)中,相应的活化剂首先在咖啡磨机中精细研制,然后添加到分散介质中。使用Ultraturax混合器由所述混合物制造均匀悬浮液。然后将所述均匀悬浮液添加到银粉中。所得混合物首先使用抹刀手动均化,然后经过辊磨机3次并再次均化以获得膏1 - 3和参比膏1 - 3。
膏1-3和参比膏1-3用于将引线框连接到半导体芯片。
为此目的使用由铜或镍制成的引线框和具有银金属化的半导体芯片。
在六个样品中将膏1-3和参比膏1-3施加到相应的引线框上。然后在施加的膏上放置半导体芯片。引线框与半导体芯片的相对表面之间的距离为80微米。由此获得的结构在150℃温度下预干燥5分钟。随后,由此获得的该结构在无压力下在250℃的温度下烧结。
在烧结过程后,进行分析以评估半导体芯片与引线框之间的连接的存在以及所述连接的可靠性。
这种分析的结果概括在表2中。
接触区的非贵金属 | 半导体芯片与引线框之间的连接 | 连接的可靠性 | |
膏 1 | 铜 | 稳定连接 | 极高 |
膏 2 | 铜 | 稳定连接 | 极高 |
膏 3 | 镍 | 稳定连接 | 极高 |
参比膏1 | 铜 | 无连接, 半导体芯片不粘附到引线框 | - |
参比膏2 | 铜 | 无连接, 半导体芯片不粘附到引线框 | - |
参比膏3 | 镍 | 无连接, 半导体芯片不粘附到引线框 | - |
表2:使用膏1 - 3和参比膏1 - 3的试验的结果。
试验表明,仅用本发明的膏1-3形成稳定连接,而在使用参比膏1 – 3时没有形成稳定连接。
Claims (10)
1.膏,所述膏含有
(a) 金属颗粒;
(b) 至少一种在分子中带有至少两个羧酸单元的活化剂;和
(c) 分散介质。
2.根据权利要求1的膏,其特征在于所述金属颗粒是银颗粒。
3.根据权利要求1或2的膏,其特征在于所述活化剂具有100-300℃的分解点。
4.根据权利要求1-3任一项的膏,其特征在于所述活化剂选自二羧酸和络合二羧酸。
5.根据权利要求1-4任一项的膏,其特征在于所述活化剂选自丙二酸、马来酸、二甲基丙二酸和草酸。
6.根据权利要求1-5任一项的膏,其特征在于所述分散介质含有脂族烃化合物。
7.通过接触区将至少一个电子部件连接到至少一个基板的方法,其中至少一个所述接触区含有非贵金属,所述方法包括以下步骤:
(i) 提供具有第一接触区的基板和具有第二接触区的电子部件,其中至少一个所述接触区含有非贵金属;
(ii) 提供膏,其含有
(a) 金属颗粒;
(b) 至少一种在分子中带有至少两个羧酸单元的活化剂;和
(c) 分散介质;
(iii) 形成结构,其中所述基板的第一接触区通过该膏接触所述电子部件的第二接触区;和
(iv) 烧结所述结构,同时产生包含至少通过该烧结膏相互连接的所述基板和所述电子部件的模件。
8.根据权利要求7的方法,其特征在于至少一个所述接触区是所述电子部件或所述基板的整体部件。
9.根据权利要求7或8的方法,其特征在于所述非贵金属是铜且所述活化剂选自丙二酸、马来酸和草酸。
10.根据权利要求7或8的方法,其特征在于所述非贵金属是镍且所述活化剂选自二甲基丙二酸和草酸。
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EP11007634.6 | 2011-09-20 | ||
EP11007634.6A EP2572814B1 (de) | 2011-09-20 | 2011-09-20 | Paste und Verfahren zum Verbinden von elektronischem Bauelement mit Substrat |
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EP (1) | EP2572814B1 (zh) |
JP (2) | JP2013069687A (zh) |
KR (1) | KR101419126B1 (zh) |
CN (1) | CN103008910A (zh) |
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JP2020520410A (ja) | 2017-05-12 | 2020-07-09 | ヘレウス ドイチェラント ゲーエムベーハー ウント カンパニー カーゲー | 金属ペーストの手段によりコンポーネントを接続する方法 |
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Also Published As
Publication number | Publication date |
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HUE028880T2 (en) | 2017-01-30 |
KR20130031213A (ko) | 2013-03-28 |
KR101419126B1 (ko) | 2014-07-11 |
EP2572814B1 (de) | 2016-03-30 |
TWI478178B (zh) | 2015-03-21 |
TW201320106A (zh) | 2013-05-16 |
EP2572814A1 (de) | 2013-03-27 |
JP2016171085A (ja) | 2016-09-23 |
SG188764A1 (en) | 2013-04-30 |
US20130068373A1 (en) | 2013-03-21 |
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