CN108367994B - 铜陶瓷基板、制备铜陶瓷基板的铜半成品及制备铜陶瓷基板的方法 - Google Patents
铜陶瓷基板、制备铜陶瓷基板的铜半成品及制备铜陶瓷基板的方法 Download PDFInfo
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Abstract
本发明涉及一种铜陶瓷基板(1),其包括陶瓷支撑体(2)和连接至陶瓷支撑体(2)的表面的铜层(3,4),其中铜层(3,4)具有至少一个第一层(5,6)和第二层(7,8),所述第一层(5,6)朝向陶瓷支撑体并具有第一平均晶粒尺寸,所述第二层(7,8)布置在铜层(3,4)背离陶瓷支撑体(2)的一侧上并具有第二平均晶粒尺寸,其中第二晶粒尺寸小于第一晶粒尺寸。第一层(5,6)的平均晶粒尺寸大于100μm,优选约250μm至1000μm,并且第二层(7,8)的平均晶粒尺寸小于100μm,优选约50μm,或者,第一层(5,6)的平均晶粒尺寸大于150μm,优选约250μm至2000μm,并且第二层(7,8)的平均晶粒尺寸小于150μm,优选约50μm。优选使用Cu‑ETP和Cu‑OF或Cu‑OFE。
Description
本发明涉及具有权利要求1前序部分所述特征的铜陶瓷基板,涉及具有权利要求7或9前序部分所述特征的用于制备铜陶瓷基板的铜半成品,并且涉及具有权利要求13前序部分所述特征的用于制备的铜陶瓷基板的方法。
铜陶瓷基板(例如DCB、AMB)用于制造例如电力电子模块,并且是由陶瓷支撑体和布置在该陶瓷支撑体一个面上或两个面上的铜层制成的复合材料。铜层被预制成通常具有0.1mm至1.0mm厚度的铜片形式的铜半成品,并通过连接方法连接至陶瓷支撑体。这种连接方法也已知为DCB(直接铜键合)或AMB(活性金属钎焊法)。然而,如果陶瓷支撑体具有高强度,则还可以应用具有甚至更大厚度的铜层,这对于电性能和热性能而言是基本的优势。
图1中位于上方的图示出了现有技术的铜陶瓷基板1,其包括陶瓷支撑体2,所述陶瓷支撑体2具有布置在不同面上的两个铜层3和4,由导体路径形成的结构也被蚀刻到铜层3(图中的上层)中,而铜层4(图中的下层)则形成于整个表面上。
由例如莫来石、Al2O3、Si3N4、AlN、ZTA、ATZ、TiO2、ZrO2、MgO、CaO、CaCO3或这些材料中的至少两种的混合物制成的陶瓷板被用作陶瓷支撑体。
因此以DCB方法通过以下方法步骤将铜层连接至陶瓷基体:
-使铜层氧化,从而制备均匀的铜氧化物层;
-将铜层置于陶瓷支撑体上;
-将复合材料加热到1060℃至1085℃的处理温度。
这在铜层上产生共晶熔体,其产生与陶瓷支撑体的整体连接。这个过程称为键合(bonding)。如果使用Al2O3作为陶瓷支撑体,则连接产生薄Cu-Al尖晶石层。
在键合过程之后,通过蚀刻朝向外部的铜层表面,即自由表面,来构造必要的导体路径。然后通过应用焊线来钎焊芯片并产生连接,以在芯片上部的面上形成接触,为此,应该尽可能均匀且精细地构造铜层的自由表面的结构。为了制造电力模块,之后还可以将铜陶瓷基板连接至基板。
所描述的铜陶瓷基板的优点主要包括铜的高电流负载能力以及来自陶瓷支撑体的良好的电绝缘和机械支撑。通过DCB技术还可以实现铜层与陶瓷支撑体的高黏附性。此外,所使用的铜陶瓷基板在高环境温度下是稳定的,而高环境温度在使用所述基板时经常出现。
铜陶瓷基板的弱点在于所谓的抗热疲劳性,它是一种描述元件在确定数量的临时热诱导应力之后失效的材料特性。由于在模块工作期间产生极端的温度梯度,该参数对于电力模块的使用寿命很重要。由于所使用的陶瓷材料和铜材料的热膨胀系数不同,因此在使用期间铜陶瓷基板中热诱导机械应力,并且在经过一定次数的循环之后,这可以导致铜层与陶瓷层脱层和/或导致陶瓷层中产生裂纹和/或铜层中产生裂纹,从而导致元件失效。由热应力引起的铜陶瓷基板1的弯曲在图1的下部的图中夸大性地示出。由不同的铜量所导致的铜层3和4的不同膨胀导致铜陶瓷基板弯曲。由于铜陶瓷基板1的这种弯曲,在铜层3和4本身中,特别是在铜层3和4与陶瓷支撑体2的连接处产生剪切应力、压缩应力和拉伸应力,该应力可以导致铜层3和4与陶瓷支撑体2之间的连接处断裂以及在铜层3和4中和/或在陶瓷支撑体2中产生裂纹。
在这种背景下,本发明解决的问题是提供可以根据对铜层和基板的各种要求以改进的方式进行调整的铜陶瓷基板和铜半成品。本发明解决的另一个问题是提供一种用于制备这类铜陶瓷基板的具有成本效益的方法。
为了解决该问题,提出了具有权利要求1的特征的铜陶瓷基板,提出了具有权利要求5或权利要求7的特征的铜半成品,并提出了具有权利要求11的特征的方法。进一步优选的发展方案见于从属于上述权利要求的从属权利要求、附图和相关描述中。
根据本发明的基本构思,提出铜层包括至少一个第一层和第二层,所述第一层朝向陶瓷支撑体并具有第一平均晶粒尺寸,所述第二层布置在铜层背离陶瓷支撑体的面上并具有第二平均晶粒尺寸,第二晶粒尺寸小于第一晶粒尺寸,并且第一层中的铜层具有大于100μm的平均晶粒尺寸,优选约250μm至1000μm,并且第二层中的铜层具有小于100μm的平均晶粒尺寸,优选约50μm,或者第一层具有大于150μm的平均晶粒尺寸,优选约250μm至2000μm,并且第二层具有小于150μm的平均晶粒尺寸,优选约50μm。
所提出的解决方案的优点在于,由于所提出的两层结构的不同晶粒尺寸,铜层可以被设计以使其明显更符合对铜层的要求。其中一个特别的优点在于,铜层在第一层中具有更大的平均晶粒尺寸,铜层因更大的晶粒尺寸而具有改进的抗热疲劳性和由此产生的降低的屈服应力,从而降低产生脱层或裂纹的可能性。Hall-Petch关系式描述了屈服应力与晶粒尺寸之间的关系:
其中,σy是屈服应力,σ0和K是取决于材料的常数,dK是晶粒尺寸。
然而,铜层具有第二层,该第二层在朝向外部且背离陶瓷支撑体的面上具有更微细的晶粒尺寸,其结果是该面上的铜层具有更高的硬度水平、强度水平和屈服应力,这转而有利于涉及高负荷(如振动)的应用领域。此外,更微细的晶粒结构对于光学系统的进一步处理是有利的。在用于制备导体结构的处理程序(例如蚀刻过程)期间,微细晶粒尺寸也是优选的,因为其结果是可以更好地制备尖锐的边缘和更微细的结构。在这种情况下,粗晶粒会沿晶界的深蚀刻坑,这将增加铜表面的粗糙度。这也产生微细晶粒尺寸呈现均匀的视觉印象。此外,表面上的微细结构对于焊线是有利的。
总体而言,通过使用本发明的解决方案,可以制备具有高抗热疲劳性的铜陶瓷基板,该铜陶瓷基板同时具有良好的可加工性、高强度和拥有高质量视觉特性的铜层的自由表面。
在任何情况下,两层晶粒尺寸不同比目前为止使用具有一致晶粒尺寸的铜层可以明显更好地满足对铜层的要求。因此,可以通过在一定范围内选择两层的晶粒尺寸,对铜层进行单独地优化以满足所施加的要求,而无需进行针对必定对特性中的一个具有不利影响的另一种特性的优化。在实践中,晶粒尺寸被用作特征变量,借助于该特征变量,铜层的性能也可以通过针对要满足的不同要求刻意使用相同的材料而得以改善。
在这种情况下,在第一层和陶瓷支撑体之间当然也可以设置具有更微细颗粒结构的另外的第三薄层,而因此不偏离本发明的构思。唯一重要的是,朝向陶瓷支撑体的第一层相对于第二层具有更粗糙的晶粒结构。在这种情况下,第一层布置在第二层与第三层之间并且实际上形成铜层的核心,并且因此对于热应力下基板的变形特性是决定性的。在这种情况下,也利用了本发明的优点,因为由第一铜层的较粗糙的晶粒结构使得铜层弯曲减小,以及与此相关的铜层中的应力也减小,尽管第一层不直接安置在陶瓷支撑体上,而是通过第三层与陶瓷支撑体隔开。唯一重要的是,第一层足够厚,以致其积极地影响并且特别是减小由热应力引起的铜层中的材料应力。
铜层中的不同结构可以例如特别简单地通过铜层的特定热处理来获得。或者,具有不同晶粒尺寸的至少两种不同铜材料也可以例如通过覆盖彼此连接以形成铜层。在这种情况下,预制带形式的不同铜材料可以在之前的工艺步骤中彼此连接以形成铜半成品。或者,也可以首先将具有较大晶粒尺寸的第一层应用至陶瓷支撑体,之后可以将具有较微细晶粒尺寸的第二层应用至具有较大晶粒尺寸的第一层。
此外,具有相同晶粒尺寸或任何给定晶粒尺寸的两种不同的铜材料也可以彼此连接,其中材料的高温性能被调节成使得在热处理期间,在第一层中制备具有大晶粒尺寸的结构并且在第二层中制备具有较小晶粒尺寸的结构。理想地,DCB或AMB方法本身中的键合过程可用于高温处理。在这种情况下,可以通过将两种不同的铜材料与特定热处理结合使用来获得两个面上的不同结构。
在这种情况下,还提出,第一层的铜材料为Cu-ETP,第二层中朝向外部的面的铜材料为Cu-OF,更优选为Cu-OFE。在凝固相图上,Cu-OF和Cu-OFE尤其具有明显的阶梯熔点,即其在低于或高于熔融温度时突然凝固和熔融。Cu-ETP包含铜氧化物的部分,这导致凝固相图上Cu-ETP在向下倾斜的熔限内凝固或熔融。由于Cu-OF的熔点高于Cu-ETP的固相线温度,因此所有的Cu-OF在Cu-ETP熔融时仍然是凝固的。使用Cu-ETP作为第一层的优点在于,当超过Cu-ETP的固相线温度时,该温度对应于DCB方法的键合温度,铜层由此开始在第一层的区域中熔融以与陶瓷支撑体产生连接,而由Cu-OF形成的铜层的自由表面仍然完全凝固。由于铜氧化物在Cu-ETP上熔融,因此可以实现特别是第一铜层与陶瓷支撑体之间的连接和黏合强度的改善。此外,在之后的冷却期间,Cu-ETP形成比自由表面的Cu-OF更粗糙的晶粒结构,由此根据上述原理自动实现改善的抗热疲劳性。
下面参考优选实施方案更详细地描述本发明。在附图中,详细地:
图1示出了现有技术的铜陶瓷基板;
图2示出了包括由不同铜材料制成的两层的铜半成品;以及
图3是本发明的铜陶瓷基板的截面图。
电力模块是电力电子产品的半导体器件并用作半导体开关。它们在壳体中包含多个电力半导体(芯片),其与散热器电绝缘。这些模块通过钎焊或黏合应用至电绝缘板(例如,由陶瓷制成的电绝缘板)的金属化表面,以确保朝向基板的热输出同时确保电绝缘。由金属化层和绝缘板制成的复合材料被称为铜陶瓷基板,并且通过被称为DCB技术(直接铜键合)的方法以工业规模生产。
芯片之间的接触通过具有细焊线的连接物来建立。此外,具有不同功能的其他组装件(例如传感器、电阻器)可以存在并集成。
为了制备DCB基板,陶瓷支撑体(例如Al2O3、Si3N4、AIN、ZTA、ATZ)在键合工艺中在其上面和下面通过铜层彼此连接。在准备这一过程时,铜层可以在被置于陶瓷支撑体上之前在表面被氧化(例如化学氧化或热氧化),之后可以置于陶瓷支撑体上。该连接在1060℃至1085℃的高温过程中发生,在铜层的表面上产生共晶熔体,该熔体产生与陶瓷支撑体的连接部。例如,在铜(Cu)置于氧化铝(Al2O3)上的情况下,该连接部由薄的Cu-Al尖晶石层组成。
图1示出了现有技术的铜陶瓷基板1,其包括陶瓷支撑体2以及保持在陶瓷支撑体2的表面上的两个铜层3和4。
图3示出了根据本发明的发展的铜陶瓷基板1,其包括陶瓷支撑体2以及两个铜层3和4。根据本发明的发展的图3中的两个铜层3和4各自包括朝向陶瓷支撑体2并具有较粗糙的微结构的第一层5和6。第一层5和6优选为这样的层:其中铜层3和4在第一层5和6处贴靠陶瓷支撑体2并与陶瓷支撑体2形成连接部。
铜层3和4中的第一层5和6各自在外自由面上被第二层7和8覆盖,第二层7和8具有较微细的微结构,其平均较微细的晶粒尺寸为小于100μm或小于150μm、优选约50μm。然而,两个铜层3和4中的第一层5和6具有较粗糙的微结构,其平均较大晶粒尺寸大于100μm或大于150μm、优选约250μm至1000μm或约250μm至2000μm。因此铜层3和4的微结构呈现朝向陶瓷支撑体2的第一层5和6中的晶粒尺寸比朝向外的层7和8中的晶粒尺寸平均大10倍。第一层5和6可以比第二层7和8厚得多并形成铜层3和4的基层。第二层7和8可以薄得多,具有约50μm至100μm的厚度,并形成铜层3和4的自由表面。由于具有较大晶粒尺寸的第一层5和6的厚度明显更大,因此铜层3和4的机械性能得以改变,以致铜层3和4总体上具有更低的屈服应力,并因此具有更高的抗热疲劳性,而具有明显更微细的微结构的第二层7和8仅形成自由表面。
在开篇描述的DCB方法之后,铜层3和4例如可以连接至陶瓷支撑体2,使得两个铜层3和4的两个第一层5和6通过陶瓷支撑体2的相应表面边缘区9和10中的整体连接部而连接至陶瓷支撑体2。由于两个铜层3和4在第一层5和6中具有相当粗糙的微结构,其具有250μm至1000μm或250μm至2000μm的大晶粒尺寸,作为上述Hall-Petch关系式的结果,第一层5和6还具有比布置在外面上的第二层7和8更低的屈服应力,并因此以更高的抗热疲劳性连接至陶瓷支撑体2,所述更高的抗热疲劳性高于两个铜层3和4在该面与在外面具有相同的50μm晶粒尺寸的情况下的抗热疲劳性。因此,通过所提出的设计形成并在与陶瓷支撑体2连接的面上具有较大晶粒尺寸的铜层3和4被特别设计成在表面边缘区9和10之间的连接部具有高抗热疲劳性。相比之下,由于第二层7和8的较微细的微结构具有50μm的更细晶粒尺寸,因此铜层3和4在其外面被明显更简单且精确地处理以引入导体结构。此外,该面上的层具有更大的硬度、强度和屈服应力,使得铜陶瓷基板1的使用寿命对于外部影响也可以增加。此外,形成表面的第二层7和8的微细晶粒结构对于连接线是有利的。
铜层3和4在不同层5、6、7和8中的不同微结构可以通过特别进行的热处理或通过使用两种不同的铜材料或通过两种措施的组合来实现。根据优选的实施方案,通过使铜材料Cu-OF层、优选Cu-OFE层与铜材料Cu-ETP层相覆盖(如辊压接合)来制备两个铜层3和4,从而形成铜半成品11和12,如图2中所示。由Cu-ETP形成的第一层5,6和由Cu-OF形成的第二层7,8在此具有相同或至少相当的晶粒尺寸。在DCB方法过程中,将预氧化的铜半成品11或12例如置于陶瓷支撑体2上,然后加热至1060℃至1085℃的处理温度。通过这样的方式,在该情况下由Cu-ETP形成的第一层5,6中的铜氧化物在表面边缘区9和10中熔融并与陶瓷支撑体2形成连接。由于加热和两种铜材料的不同重结晶行为,结构得以改变以致Cu-ETP中的颗粒之后为粗糙的,而Cu-OF或Cu-OFE具有更微细的微结构。
Cu-OF或Cu-OFE和Cu-ETP是高度导电的铜材料并且具有大于或等于58MS/m的电导率。然而,具有较低电导率的材料也是可能的。此外,这两种铜材料还可以通过其他连接方法如焊接、钎焊、钉合、黏合或增材制造方法彼此连接。此外,如果需要,铜层3和4还可以补充以其他铜材料或铜层,条件是铜层3和4的材料性质旨在进一步精密改善。
两个铜层3和4优选地在每种情况下通过使两种铜材料相覆盖而被预制成铜半成品11和12。由于所提出的使用不同的铜材料并在键合期间加热,键合之后,铜半成品11和12已经在一个面上具有约50μm的更微细晶粒尺寸的微结构,并且在另一个面上具有250μm至1000μm的更大晶粒尺寸的微结构。在这种情况下,键合同时有意地构成热处理,期间,铜层3和4的朝向陶瓷支撑体2的第一层5和6的晶粒尺寸进一步增大,而这转而对铜层3和4,特别是对连接部9和10与陶瓷支撑体2的连接区域的抗热疲劳性的进一步增加具有积极意义。同时,热处理不导致铜层3和4或铜半成品11和12的背离陶瓷支撑体2的层7和8中晶粒尺寸的显著增加,从而使得铜层3和4在该面上的性能不会不利地改变。
根据一个实施方案,两种不同的铜材料通过覆盖彼此连接,使得可以特定地设定最终材料的高温特性,以在加热期间在铜层3和4中朝向陶瓷支撑体2的面上制备具有低屈服应力的粗糙结构,并在自由表面制备具有所需表面特性的更微细的结构。以这种方式,还可以在具有较粗糙结构的第一层5和6与陶瓷支撑体2之间存在同样具有更微细结构的其他层,条件是这对于特定应用是有利的。然而,由于在这种情况下铜层3和4的第一层5和6也形成屈服应力降低从而抗热疲劳性增强的核心,因此在热疲劳应力下减少裂纹形成和防止脱层的主要优势仍然存在。
此外,在这种情况下键合也用作热处理,优选连接部的形成同时进行,通过这种方式,特别容易实现本发明提出的铜层3和4的两个面上的不同晶粒尺寸,通过使用两种不同的铜材料有可能进一步提高效果。
铜层3和4优选地被预制成铜半成品11和12,铜半成品11和12通过两种提出的铜材料相覆盖得到。通过这种方式,朝向陶瓷支撑体2并由Cu-ETP形成的第一层5和6被设计成明显更厚并对由Cu-OF形成的明显更薄的第二层7和8形成一种支撑功能。
铜半成品11和12可以具有0.1mm至1.0mm的厚度,以大尺寸放置在陶瓷支撑体2上,并通过DCB方法连接至陶瓷支撑体2。然后,大表面积的铜陶瓷基板1被切割成更小的单元并进一步处理。
除了改进的铜陶瓷基板1和被预制成铜半成品11和12的铜片之外,本发明还提供了用于制备铜陶瓷基板1的优选的具有成本效益的方法。在该方法中,所提出的铜陶瓷基板1优选通过热处理制备,借助热处理,两层5和6或7和8中的不同晶粒尺寸得以自动调节。在这种情况下,铜层3和4可以在连接到陶瓷支撑体2之前经受热处理,或者可以在键合方法期间使用加热以影响微结构。此外,铜层3和4也可以通过使已经具有不同微结构或然后在热处理期间形成不同微结构的两种不同的铜材料相覆盖而组合。
Claims (20)
1.一种铜陶瓷基板(1),其包括
-陶瓷支撑体(2),和
-连接至所述陶瓷支撑体(2)的表面的铜层(3,4),
其特征在于,
-所述铜层(3,4)包括至少一个第一层(5,6)和第二层(7,8),所述第一层(5,6)朝向陶瓷支撑体并具有第一平均晶粒尺寸,所述第二层(7,8)布置在所述铜层(3,4)背离所述陶瓷支撑体(2)的面上并具有第二平均晶粒尺寸,
-所述第二平均晶粒尺寸小于所述第一平均晶粒尺寸,并且
-所述第一层(5,6)的平均晶粒尺寸大于100μm,并且
-所述第二层(7,8)的平均晶粒尺寸小于100μm,
或者
-所述第一层(5,6)的平均晶粒尺寸大于150μm,并且
-所述第二层(7,8)的平均晶粒尺寸小于150μm。
2.根据权利要求1所述的铜陶瓷基板(1),其特征在于,
-所述第一层(5,6)的平均晶粒尺寸为250μm至1000μm,并且
-所述第二层(7,8)的平均晶粒尺寸为50μm。
3.根据权利要求1所述的铜陶瓷基板(1),其特征在于,
-所述第一层(5,6)的平均晶粒尺寸为250μm至2000μm,并且
-所述第二层(7,8)的平均晶粒尺寸为50μm。
4.根据权利要求1所述的铜陶瓷基板(1),其特征在于,
-所述铜层(3,4)的第一层和第二层(5,6,7,8)由至少两种不同的铜材料形成。
5.根据权利要求4所述的铜陶瓷基板(1),其特征在于,
-所述第一层(5,6)的铜材料为Cu-ETP。
6.根据权利要求4或5所述的铜陶瓷基板(1),其特征在于,
-所述第二层(7,8)的铜材料为Cu-OF。
7.根据权利要求6所述的铜陶瓷基板(1),其特征在于,
-所述第二层(7,8)的铜材料为Cu-OFE。
8.根据权利要求1至5中任一项所述的铜陶瓷基板(1),其特征在于,
-所述第一层(5,6)具有比所述第二层(7,8)更低的屈服应力。
9.根据权利要求1至5中任一项所述的铜陶瓷基板(1),其特征在于,
-所述第一层(5,6)具有1060°C至1085°C的熔点。
10.一种用于制备铜陶瓷基板(1)的铜半成品(11,12),其特征在于,
-所述铜半成品(11,12)包括至少一个第一层(5,6)和第二层(7,8),所述第一层(5,6)具有第一平均晶粒尺寸,所述第二层(7,8)具有第二平均晶粒尺寸,两种平均晶粒尺寸不同,
-所述第一层(5,6)的平均晶粒尺寸大于100μm,所述第二层(7,8)的平均晶粒尺寸小于100μm,或者
-所述第一层(5,6)的平均晶粒尺寸大于150μm,并且
-所述第二层(7,8)的平均晶粒尺寸小于150μm。
11.根据权利要求10所述的铜半成品(11,12),其特征在于,
-所述第一层(5,6)的平均晶粒尺寸为250μm至1000μm,并且
-所述第二层(7,8)的平均晶粒尺寸为50μm。
12.根据权利要求10所述的铜半成品(11,12),其特征在于,
-所述第一层(5,6)的平均晶粒尺寸为250μm至2000μm,并且
-所述第二层(7,8)的平均晶粒尺寸为50μm。
13.根据权利要求10所述的铜半成品(11,12),其特征在于,
-两种层(5,6,7,8)由不同的铜材料形成。
14.一种用于制备根据权利要求1-9中任一项所述的铜陶瓷基板(1)的铜半成品(11,12),其特征在于,
-所述铜半成品(11,12)包括由第一铜材料制成的第一层(5,6)和由第二铜材料制成的第二层(7,8),
-所述第一铜材料和第二铜材料被设计成在加热之后具有不同的晶粒尺寸。
15.根据权利要求13或14所述的铜半成品(11,12),其特征在于,
-两种不同的铜材料通过覆盖彼此连接。
16.根据权利要求13或14所述的铜半成品(11,12),其特征在于,
-两种不同的铜材料为Cu-OF和Cu-ETP。
17.根据权利要求16所述的铜半成品(11,12),其特征在于,
-两种不同的铜材料为Cu-OFE和Cu-ETP。
18.根据权利要求10至14中任一项所述的铜半成品(11,12),其特征在于,
-所述铜半成品(11,12)在两种层(5,6,7,8)中经历不同的热处理。
19.一种用于制备具有权利要求1至9中任一项所述的特征的铜陶瓷基板(1)的方法,其特征在于,
-铜层(3,4)的两种层(5,6,7,8)的不同晶粒尺寸通过在将所述铜层(3,4)连接至陶瓷支撑体(2)的键合方法过程中进行加热来实现。
20.根据权利要求19所述的方法,其特征在于,所述铜层(3,4)由权利要求10或从属于权利要求10时的权利要求11至13中任一项所述的铜半成品(11,12)形成。
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DE102016203030A1 (de) | 2016-02-26 | 2017-08-31 | Heraeus Deutschland GmbH & Co. KG | Kupfer-Keramik-Verbund |
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DE102017128308B4 (de) | 2017-11-29 | 2020-04-23 | Rogers Germany Gmbh | Verfahren zur Herstellung eines Metall-Keramik-Substrats |
DE102017128316B4 (de) * | 2017-11-29 | 2019-12-05 | Rogers Germany Gmbh | Verfahren zur Herstellung eines Metall-Keramik-Substrats und Metall-Keramik-Substrat |
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