CN101489954B - 制造陶瓷衬底的方法以及陶瓷衬底 - Google Patents

制造陶瓷衬底的方法以及陶瓷衬底 Download PDF

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CN101489954B
CN101489954B CN2007800266003A CN200780026600A CN101489954B CN 101489954 B CN101489954 B CN 101489954B CN 2007800266003 A CN2007800266003 A CN 2007800266003A CN 200780026600 A CN200780026600 A CN 200780026600A CN 101489954 B CN101489954 B CN 101489954B
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M·埃伯特
M·亨里克
A·劳尔
G·诺迪特
T·谢贝尔
R·韦斯
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Abstract

本发明涉及一种用于制造半导体组件的陶瓷衬底的方法,其特征在于以下方法步骤:制造至少含有纤维素纤维以及要碳化的填料和/或SiC的纸;将所制造的纸热解;和将所热解的纸渗硅。

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制造陶瓷衬底的方法以及陶瓷衬底
本发明涉及一种用于制造半导体组件的陶瓷衬底的方法。本发明还涉及一种作为半导体组件组成部分的载体形式的陶瓷衬底。 
在如太阳能技术的半导体技术中公知的是,将电活性层施加到如石墨衬底的衬底上。对于太阳能电池,相应的载体具有通常最大10×10cm的尺寸,使得需要将相应的太阳能电池费事地连接至面板。 
从DE-A-102004 043 985中公开了一种碳化物陶瓷材料和一种用于制造这种碳化物陶瓷材料的方法。碳化物陶瓷材料具有短碳纤维作为初始材料。在此可将碳化物陶瓷材料用作硅晶片或镜头载体的载体结构。 
在文献DE.Z.:cfi/Ber.DKG 82(2005),Nr.5,D 32中报导了,通过热解和随后的氧化,将用由硅和铝金属粉组成的填料所装载的纸转换成SiC纤维陶瓷体。该体在此具有由SiC组成的内骨干和由氧化物陶瓷组成的外层。WO-A-2005/049524也教导了相应的内容。 
从EP-A-1129578中可以获悉Si/SiC复合材料,该Si/SiC复合材料具有如纸浆的纤维素纤维作为主要的组成部分。为了制造反应管(Reaktorrohr)或晶片舟(Wafer-Schiffchen),可以用树脂来浸渍厚度为20μm的和长度为3mm的纤维素纤维,以便然后成型、热解和渗硅(silizieren)。 
本发明所基于的任务在于,提供一种陶瓷衬底以及一种用于制造半导体组件的陶瓷衬底的方法,该陶瓷衬底被构造为大面积的,并具有微小的重量。同时应通过该陶瓷衬底开启以下的可能性,方便构建要施加到陶瓷衬底上的活性层,并因此导致成本降低。 
根据本方法,主要通过以下的方法步骤解决该任务: 
-制造至少含有纤维素纤维以及要碳化的填料和/或SiC的纸,将碳黑、或由碳黑和SiC组成的混合物、或由碳黑、SiC和Si组成的混合物采用为填料, 
-热解所制造的纸,和 
-将所热解的纸渗硅。 
根据本发明使用用如碳黑的碳化的填料所装载的纸,使得可以制造大面积的陶瓷衬底。达1×1m或超出于此的尺寸毫无问题是可能的。同 时可以极其薄地构造陶瓷衬底,使得半导体组件具有微小的重量。除了碳黑和/或至少另一种碳化的或可碳化的填料之外,可以含有SiC或Si+SiC。也存在单独用SiC或SiC+Si装载纸的可能性。要热解的纸也可以附加地含有如酚醛树脂或纤维素的接合剂。与此无关地,填料的重量分量应为以由纸的纤维素纤维和填料组成的纸干物质为基准的50重量%至85重量%(Gew.-%)。 
渗硅本身应使用极纯硅来实现,其中,可以在超量或不足量下工作。在此可以用通常的方法执行渗硅。但是尤其是为了渗硅,例如通过芯子(Docht)、传输板或类似技术使所热解的纸与硅熔体(Siliziumschmelze)接触。 
在本发明的优选扩展方案中,按照所提及的方式在超量下使硅渗硅,其中,在被渗硅的陶瓷衬底的至少一个平侧面上构成硅层,然后尤其是以外延的方式例如通过CVD将半导体组件的活性层施加到该硅层上。 
优选在应位于50毫巴(mbar)至0.05毫巴范围中的、尤其位于0.1毫巴范围中的压力下,在反应室中对经热解的纸渗硅。在C与Si反应成SiC之后,然后用惰性气体气氛使反应室通风,使得不从反应室中排出过量的硅,而是可以在经渗硅的陶瓷衬底上构成为Si层。在此应优选如此控制该过程,使得Si层具有0.5μm≤d≤50μm、尤其是10μm≤d≤20μm的厚度d。随后应稍高于硅的熔点地熔化Si层,并然后再结晶,以便发现半导体组件的要以外延发方式施加的活性层的要使用的晶核层(Keimschicht),因此尤其是发现所希望的掺杂的Si层。 
渗硅本身应在1350℃≤T≤2000℃、尤其是在1650℃≤T≤1700℃范围中的温度T下来执行。 
作为半导体组件组成部分的载体形式的陶瓷衬底的特征在于,陶瓷衬底是转换成SiC且用可碳化的填料和/或SiC所装载的纸,其中,尤其是在陶瓷衬底的至少一个平侧面上存在在制造陶瓷衬底时随同构成的再结晶的Si层。 
载体的基础因此是陶瓷的纸。 
SiC陶瓷衬底本身应具有D≤2mm、优选D≤0.8mm的厚度D。厚度D优选总计为0.5mm≤D≤1mm。 
施加在陶瓷衬底的至少一个侧面上的Si层具有0.5μm≤d≤50μ m、尤其是10μm≤d≤20μm的厚度d。 
陶瓷衬底的面积F尤其是应为1600cm2≤F≤10000cm2或更大。 
在纸本身中SiC的容积分量V优选为25容积%≤V≤85容积%,尤其是60容积%≤V≤80容积%(Vol.-%)。 
本发明的特征还在于,将用要反应成SiC的填料和/或用SiC充填的含有纤维素的纸应用于制造作为半导体组件衬底的碳化物陶瓷。在此尤其是规定,填料的分量G为以纸的由纤维素纤维和填料所组成的干物质(Trockesubstanz)为基准的50重量%≤G≤重量%。 
优选是碳黑或含有碳黑的填料,还可以或替代地以所需要的化学计量比例含有SiC和Si。 
除了填料之外,还可以将如接合剂的其它添加剂增添到纸中。 
不仅从权利要求中、由所述权利要求可获得的特征(本身和/或组合地)中、而且也从实施例的以下说明以及附图中,得出本发明的其它细节、优点和特征。 
实例1
使用具有0.7mm厚度、约800g/m2重量和1m2面积的纸幅(Papierbahn),其用由碳黑组成的填料装载。填料的重量分量约为以纸的由纤维素纤维和填料所组成的干物质为基准的75%。于是在惰性气氛中,在800℃和1400℃之间的温度下,将如此装载的纸碳化。然后借助芯子利用硅熔体在1650℃和1700℃之间范围中的温度下,实现所碳化的纸的渗硅。在反应室本身中,笼罩着在0.1毫巴范围中的压力。在此用超量的硅来实现渗硅。在实现了硅与碳反应成SiC之后,用惰性气体使反应室通风,以便避免排出过量的硅。由此在陶瓷衬底上形成了Si层,其中,如此控制该过程,使得厚度处于10μm和20μm之间的范围中。于是稍高于硅熔点的温度下重新熔化和再结晶固化的层。将极纯硅使用于渗硅本身。 
产生薄壁的高稳定的结构。显微图显示出,衬底基本上由包围自由硅的SiC所组成。可能以极小的规模含有未反应的C。 
可以采用陶瓷作为太阳能电池的衬底。在此,以例如CVD的通常技术,将太阳能电池的电活性层以外延的方式施加到再结晶的Si层上。再结晶的Si层具有晶核层的功能。 
实例2
使用具有d为0.7mm的厚度d、约900g/m2重量和1m2面积的纸幅,其用由碳黑(Ruβ)和SiC组成的填料装载。填料的重量分量约为以纸的由纤维素纤维和填料所组成的干物质(Trockensubstanz)为基准 的75%。于是在惰性气氛中,在800℃和1400℃之间的温度下对如此装载的纸碳化。于是借助芯子利用硅熔体在1650℃和1700℃之间的范围中的温度下,实现所碳化的纸的渗硅。在反应室本身中,笼罩着在0.1毫巴范围中的压力。在此用超量的硅来实现渗硅。在实现了硅与碳反应成SiC之后,用惰性气体使反应室通风,以便避免排出过量的硅。由此在陶瓷衬底上形成Si层,其中,如此控制该过程,使得厚度处于10μm和20μm之间的范围中。于是在稍高于硅熔点的温度下,重新熔化和再结晶固化的层。将极纯硅采用于渗硅本身。 
产生薄壁的高稳定的结构。显微图显示出,衬底基本上由包围自由硅的SiC所组成。可能以极小的规模含有未反应的C。 
陶瓷可以被使用为太阳能电池的衬底。在此,以例如CVD的通常技术,将太阳能电池的电活性层以外延的方式施加到再结晶的Si层上。再结晶的Si层具有晶核层的功能。 
实例3
使用具有d为0.7mm的厚度d、约900g/m2重量和1m2面积的纸幅,其用由碳黑和SiC组成的填料装载。填料的重量分量约为以纸的由纤维素纤维和填料所组成的干物质为基准(bezogen auf)的75%。于是在惰性气氛中,在800℃和1400℃之间的温度下,对如此装载的纸碳化。于是借助芯子利用硅熔体在1650℃和1700℃之间的范围中的温度下,实现所碳化的纸的渗硅。在反应室本身中,笼罩着在0.1毫巴范围中的压力。用缺量的硅来实现渗硅,以便制造由于剩余的残余碳或残余多孔性而具有较小重量的陶瓷构件。在实现了毛细渗硅之后,在渗硅设备中使用剩余的Si蒸汽压力,以便在衬底表面上从汽相(Dampfphase)中析出Si。在此之后用惰性气体进行通风,其中,如此控制该过程,使得Si层的厚度处于10μm至20μm的范围中。于是在稍高于硅熔点的温度下,重新熔化和再结晶固化的层。将极纯硅采用于渗硅本身。 
产生一种薄壁的高稳定的结构。显微图显示出,衬底基本上由包围自由硅的SiC所组成。可能以极小的规模含有未反应的C。 
陶瓷可以被用作太阳能电池的衬底。在此,以例如CVD的通常技术,将太阳能电池的电活性层以外延的方式施加到再结晶的Si层上。再结晶的Si层具有晶核层的功能。 
借助图1还将再次阐述本发明方法。为了制造半导体组件的大面积 构造的和具有微小重量的陶瓷衬底,首先制造纸和用例如碳黑和SiC的填料来装载纸。在此,可以在一个方法流程中实现纸的制造和填料装载,正像方法步骤纸制造10和填料装载12的虚线边框所表示的那样。随后对用填料所装载的纸进行热解,其中,优选在800℃和1400℃之间范围的温度下,实现碳化(方法步骤14)。然后进行渗硅(方法步骤16)。这可以借助芯子利用硅熔体在1650℃和1700℃之间范围中的温度下在笼罩着0.1毫巴压力的反应室中来实现。在此将以超量的硅实现渗硅。在此在实现了硅与碳反应成SiC之后,用惰性气体使反应室通风,以便避免排出过量的硅。由此实现在如此制造的陶瓷衬底上构造Si层,其中,与过程控制有关地实现在10μm和20μm之间的厚度。具有硅层的相应陶瓷衬底,然后可以被使用为半导体组件的载体(方法步骤18)。尤其是设置在纯原理上可从图2中获知的太阳能电池作为半导体组件。 
太阳能电池20具有根据本发明所制造的陶瓷形式的载体或衬底22,其中,朝向光敏层的面,具有处于10μm和20μm之间的范围中的Si层24。载体22的厚度是如此的,使得电池是形式稳定的。 
硅层24可以用作为晶核层,具有在20μm和100μm之间范围中的厚度的例如p导电的SiC层26以外延的方式施加到晶核层上,该SiC层26用作为背面接触。然后将p导电层形式的和n导电层形式的光敏外延层28、30施加到SiC层26上。最后优选将条形的前接触(Frontkontakt)32、34、36施加到n导电层30上。 
图2中所示出的太阳能电池20在其构造上应该纯原理性地来理解,其中,也可以有pn构造来代替np构造。 
根据本发明的教导,可以制造足够稳定的、具有1m2或更大尺寸的面积的大面积太阳能电池。 

Claims (30)

1.用于制造半导体组件的陶瓷衬底的方法,其特征在于方法步骤:
-制造至少含有纤维素纤维以及要碳化的填料和/或SiC的纸,其中,将碳黑、或由碳黑和SiC组成的混合物、或由碳黑、SiC和Si组成的混合物采用为填料,
-将所制造的纸热解,和
-将所热解的纸渗硅。
2.按照权利要求1的方法,其特征在于,增添如酚醛树脂或纤维素的接合剂作为要热解的纸的添加剂。
3.按照权利要求1或2的方法,其特征在于,将具有以纸的由纤维素纤维和填料所组成的千物质为基准的50重量%≤G≤85重量%的重量分量G的填料放入到纸中。
4.按照权利要求3的方法,其特征在于,将具有以纸的由纤维素纤维和填料所组成的干物质为基准的60重量%≤G≤80重量%的重量分量G的填料放入到纸中。
5.按照权利要求1或2的方法,其特征在于,用极纯硅将所热解的纸渗硅。
6.按照权利要求1或2的方法,其特征在于,用超量或缺量的极纯硅将所热解的纸渗硅。
7.按照权利要求1或2的方法,其特征在于,借助硅熔体将所热解的纸渗硅。
8.按照权利要求1或2的方法,其特征在于,将过量的硅在渗硅的陶瓷衬底的至少一个平侧面上构造为硅层。
9.按照权利要求1或2的方法,其特征在于,在反应室中,在0.05毫巴≤p≤50毫巴的压力p下,将所热解的纸渗硅。
10.按照权利要求9的方法,其特征在于,在反应室中,在p≈0.1毫巴的压力p下,将所热解的纸渗硅。
11.按照权利要求1或2的方法,其特征在于,在惰性气体气氛中,在使反应室通风之前、期间或之后构造Si层。
12.按照权利要求1或2的方法,其特征在于,在1350℃≤T≤2000℃的温度T下,使所碳化的纸与Si反应成SiC。
13.按照权利要求12的方法,其特征在于,在1650℃≤T≤1700℃的温度T下,使所碳化的纸与Si反应成SiC。
14.按照权利要求1或2的方法,其特征在于,在构造Si层之后熔化所述Si层,并为了再结晶而将所述Si层冷却。
15.按照权利要求1或2的方法,其特征在于,将半导体组件的层以外延的方式施加到再结晶的Si层上。
16.按照权利要求1至15之一所述的方法所制造的作为半导体组件组成部分的载体形式的陶瓷衬底,其中,所述陶瓷衬底是纸,所述纸被转换成SiC并且用可碳化的填料和/或SiC装载。
17.按照权利要求16的陶瓷衬底,其特征在于,所述陶瓷衬底在至少一个平侧面上具有再结晶的Si层。
18.按照权利要求16或17的陶瓷衬底,其特征在于,所述陶瓷衬底具有D≤2.0mm的厚度D。
19.按照权利要求18的陶瓷衬底,其特征在于,所述陶瓷衬底具有D≤0.8mm的厚度D。
20.按照权利要求16或17的陶瓷衬底,其特征在于,所述陶瓷衬底具有0.5mm≤D≤1mm的厚度D。
21.按照权利要求16或17的陶瓷衬底,其特征在于,所述陶瓷衬底具有1600cm2≤F≤10000cm2的面积F。
22.按照权利要求16或17的陶瓷衬底,其特征在于,所述Si层具有0.5μm≤d≤50μm的厚度d。
23.按照权利要求22的陶瓷衬底,其特征在于,所述Si层具有10μm≤d≤20μm的厚度d。
24.按照权利要求16或17的陶瓷衬底,其特征在于,填料的分量以纸的由纤维素纤维和填料所组成的干物质为基准为50重量%至85重量%。
25.按照权利要求24的陶瓷衬底,其特征在于,填料的分量以纸的由纤维素纤维和填料所组成的干物质为基准为60重量%至80重量%。
26.用反应成SiC的填料和/或SiC所充填的含有纤维素的纸的用途,用于制造作为半导体组件衬底的碳化物陶瓷。
27.按照权利要求26的用途,其特征在于,填料的分量G以纸的由纤维素纤维和填料所组成的干物质为基准为50重量%≤G≤85重量%。
28.按照权利要求26或27的用途,其特征在于,除了所述填料之外,给要制造的纸增添接合剂。
29.按照权利要求26或27的用途,其特征在于,所述纸具有0.16m2≤F≤1m2的面积F。
30.按照权利要求26或27的用途,其特征在于,所述纸具有0.5mm≤D≤1mm的厚度D。
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