CN104661786A - 涂覆及接合衬底的方法 - Google Patents

涂覆及接合衬底的方法 Download PDF

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Publication number
CN104661786A
CN104661786A CN201280076109.2A CN201280076109A CN104661786A CN 104661786 A CN104661786 A CN 104661786A CN 201280076109 A CN201280076109 A CN 201280076109A CN 104661786 A CN104661786 A CN 104661786A
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Prior art keywords
substrate
diffusion bond
bond layer
layer
diffusion
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CN201280076109.2A
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CN104661786B (zh
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M.温普林格
B.雷班
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EV Group E Thallner GmbH
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EV Group E Thallner GmbH
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    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
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    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
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    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
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    • B23K20/023—Thermo-compression bonding
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Abstract

涂覆及接合衬底的方法。本发明涉及一种经由沉积第一材料而对第一衬底(1)涂覆第一扩散接合层(5)的方法，其在第一衬底(1)的第一表面(1o)上形成第一扩散接合层(5)，以使该第一扩散接合层(5)形成具有小于1μm的与该第一表面(1o)平行的平均粒直径H的粒表面。此外，本发明涉及一种采用以下步骤，尤其是以下流程将已如此涂覆的第一衬底(1)接合至具有第二扩散接合层(4)的第二衬底(3)的方法：-使第一衬底(1)的第一扩散接合层(5)与第二衬底(3)的第二扩散接合层接触，-将该衬底(1、3)压在一起而形成该第一及第二衬底(1、3)间的永久金属扩散接合。

Description

涂覆及接合衬底的方法
本发明涉及一种如权利要求1所述用于对第一衬底涂覆第一扩散接合层的方法及一种如权利要求6所述进行接合的方法。
将衬底永久或不可逆接合的目标是在该衬底的两个接触表面间制造尽量强力(并且尤其是尽量永久)的连结，因此获得高接合力。为达此目的，在现有技术中有各种不同方法及制造方法，尤其是较高温下的表面熔接。
所有类型的材料(但主要是指金属、半金属、半导体、聚合物和/或陶瓷)是永久地接合。永久接合的最重要系统之一为金属-金属系统。特别是，Cu-Cu系统在近些年来日益涌现。3D结构的开发大多明确要求不同功能层的连接。此连接越来越通常是经由所谓的TSV(硅穿孔(through silicon vias))完成。该TSV彼此间的接触极通常是经由铜接触部位进行。在接合的时间点极通常会有全值可使用结构(例如微芯片)位于衬底的一或多个表面上。由于在微芯片中使用具有不同热膨胀系数的不同材料，不希望在接合期间提高温度。提高温度可导致热膨胀且因而导致可破坏微芯片的部件或其周围的热应力和/或应力诱发空洞(SIV)。
已知制造方法及迄今一直遵循的方法通常会导致无法再生产或再生产不良的并且可能极难应用于已改变的条件的结果。特别地，目前所采用的制造方法通常会使用高温(尤其是>400℃)以确保重现结果。
诸如高能量消耗及存在于衬底上的结构可能会被破坏的技术问题是由迄今为高接合力所需要的高温及由于加载和/或卸载产生的快速和/或通常完全温度变化(部分远高于300℃)所导致。
其它要求由以下组成：
-线后端(back-end-of-line)兼容性。
此线后端兼容性定义为该过程在处理期间的兼容性。该接合过程因此必须设计成使一般由已经存在于结构晶圆上的电导体及低k电介质组成的线后端结构在处理期间既不受负面影响也不会受损坏。兼容性标准主要包括机械及热负载能力(主要对于热应力及应力诱发空洞(SIV))。
-线前端(front-end-of-line)兼容性。
此线前端兼容性定义为该过程于制造电主动组件期间的兼容性。该接合过程因此必须设计成使已经存在于结构晶圆上的主动组件(诸如晶体管)在处理期间既不受负面影响也不受损坏。兼容性标准主要包括某些化学元素(主要在CMOS结构中)的纯度、机械及热负载能力(主要对于热应力)。
-  低污染。
-  不施加力，或施加尽量低的力。
-  尽量低的温度，尤其针对于具有不同热膨胀系数的材料。
尤其当介于金属导体之间的绝缘层是由所谓的“低k”材料制成时，接合力的减小导致更无损伤地处理结构晶圆且因而导致降低因直接机械负载所造成的故障概率。
目前的接合方法主要设计用于高压及高温。特别是避免高温对于未来的半导体应用的熔接而言很重要，这是因为具有不同热膨胀系数的不同材料在加热和/或冷却过程期间产生不可忽视的热应力。另外，掺杂元素在温度升高的扩散日益成为难题。所掺杂元素在掺杂过程之后不应离开预期的空间区域。否则，电路的物理特性将基本上改变。在最优选情况中，这导致劣化，在最糟及最可能发生的情况中，会导致组件无法使用。特别是，存储器由于热过程期间电介质的降级及相关联的储存时间的缩短所致极易受影响。另一方面，存在其中3D技术的使用日益增加提高容量及性能的存储器。
因此，本发明的任务是设计一种在同时尽量低的温度和/或平均处理时间的情况下无损伤地制造具有尽量高的接合力的两个衬底间永久接合的方法。
利用权利要求1及6的特征实现此任务。本发明的有利改进方案在从属权利要求中给出。本说明书、权利要求书和/或附图所提供特征中至少两者的所有组合亦落在本发明的范围中。在给定值范围内，位于所指示边界内的值亦将被认为是作为边界值公开并且将以任何组合方式要求保护。
本发明的基本概念是至少在衬底之一上施加或建立具有微结构的材料的扩散接合层，该微结构具有尽量微细的晶粒，及因而具有尽量大的晶界表面。如本发明所主张，特别是，晶界以垂直于要接合的衬底表面为优选。这是如本发明所主张经由适宜地设定扩散接合层的层厚度实现，该层厚度构成晶粒的晶粒尺寸的限制准则。这两个衬底可(然非必需)彼此进行预接合。还可行的是，在不形成预接合情况下简单接触。如本发明所主张，术语“反应”应理解为固体扩散。在第一和/或第二衬底上形成/施加一或多层扩散接合层之前和/或之后，一般而言，尤其以冲洗步骤进行该一个或多个衬底的清洁。此清洁一般应确保表面上不存在将产生非接合部位的颗粒。理想地，如本发明所主张的所有沉积和/或接合步骤皆发生在优选填充惰性气体、更优选抽真空的封闭系统中以使可省略涂覆后的清洁步骤。
本发明的中心是至少在第一和第二衬底间接触面上形成具有小于1 μm的与该接触面或衬底表面平行的平均粒直径H的扩散接合层。
如此形成且具有小平均粒直径的该扩散接合层会产生导致较快速直接扩散于衬底间接触表面上且因而能达成主要在低温下的永久接合并且此外强化该接合并且提高接合速度的技术可能性。
后文中变形定义为表面和/或块体的由于扩散所致的变化。
周期表中的所有元素(主要是金属、半金属、镧系元素及锕系元素)可作为如本发明所主张用于扩散接合层的材料。
然而，本发明特别优选是用于Cu-Cu接合。
可设想将半导体的以下混合形式作为衬底：
-III-V：GaP、GaAs、InP、InSb、InAs、GaSb、GaN、AlN、InN、AlxGaI-xAs、InxGaI-xN
-IV-IV：SiC、SiGe，
-III-VI：InAlP，
-非线性光学器件：LiNbO3、LiTaO3、KDP (KH2PO4)
-太阳能电池：CdS、CdSe、CdTe、CuInSe2、CuInGaSe2、CuInS2、CuInGaS2
-导电氧化物：In2-xSnxO3-y
如本发明所主张，若衬底的接触在施加扩散接合层之后尽量接近同时(尤其在2小时内、优选在30分钟内、甚至更优选在10分钟内、理想地在5分钟内)发生则极为有利。通过此措施将可能的不期望反应(诸如，金属扩散接合层或衬底表面的氧化)减少至最低。
还可在实际接合过程之前进行氧化物的移除。氧化物可例如经由湿化学方法或以对应还原气体移除。可采用针对于氧化物还原的任何已知化学和/或物理方法。
如本发明所主张，可设置该装置，以在接触面的接触之前抑制金属扩散接合层和/或衬底表面的该反应，尤其是经由钝化衬底的表面，优选经由暴露于N2、合成气体或惰性氛围或在真空下，或经由非晶化。在此方面，已证实以包含合成气体(尤其大致上由合成气体组成)的等离子体进行处理是特别适宜。其中合成气体定义为含有至少2%、更优选4%、理想地10%或15%氢气的气体。该混合物的其余部分由诸如(例如)氮气或氩气的惰性气体所组成。优选地，具有惰性氛围或真空氛围的系统可实现作为其中衬底自处理腔室至下一处理腔室的转移是藉助可将衬底完全转移于受控可调氛围(尤其是真空氛围)中的衬底处理系统进行的系统。该系统为本领域技术人员所熟知。
扩散接合层是依以下方法中的一或多种方法施加：
-CVD，尤其是PECVD、LPCVD、MOCVD或ALD
-PVD，尤其是溅射或气相沉积
-磊晶法，尤其是MBE、ALE
-电化学沉积过程
-无电流沉积过程
因此本发明通过利用最上层(扩散接合层)的微结构特性的方式解决更优选地熔接已使的彼此接触的两个经涂覆衬底的表面的难题。本发明因而涉及一种用于经由化学和/或物理过程适宜地沉积薄层而调整最上沉积层的微结构以使其粒界面尽量地大的方法或方式。优选地，该晶界通常可垂直于衬底表面延伸。
如本发明所主张小的晶粒尺寸会获得极显著增加的晶界表面且因而获得相应较大的扩散通道；在接合期间此可促进两个材料层的熔接。本发明所主张的概念因此是由经由增加晶界表面来增加沿着晶界扩散的原子的流动组成。
根据本发明的另一有利实施例规定，永久接合的形成是在介于室温和400℃之间、尤其介于室温和300℃之间、优选介于室温和200℃之间、甚至更优选介于室温和100℃之间的温度下尤其于最大12天、优选最大1天、甚至更优选最大1小时、最佳最大15分钟期间发生。
其中，若不可逆接合具有大于1.5 J/m2、尤其大于2 J/m2、优选大于2.5 J/m2的接合强度则极为有利。可例如利用所谓的Maszara测试来测定接合强度。
接合强度可尤其通过下列方式有利地增加，使得这两个衬底具有具有如本发明所主张的极小晶粒尺寸及因而具有极大晶界表面的扩散接合层。由此可实现沿两个方向扩散流动的增加，该增加相应有助于接合过程。
若在施加/形成功能层之前尤其经由介于10和600 kHz之间的活化频率和/或介于0.075和0.2瓦/cm2之间的功率密度和/或经由施加介于0.1和0.6毫巴之间的压力进行衬底表面的等离子体活化，会引起额外效应(诸如接触表面的平滑化)。其中，压力的施加理解为工作氛围在等离子体活化期间的压力。
若在介于0.1 MPa和10 MPa之间的压力下挤压该衬底，可达成最优选结果。优选地，压力介于0.1和10 MPa之间，又更优选地，介于0.1和1 MPa之间，最优选地，介于0.1及0.3 MPa之间。该压力必须选择得越大，则不平整越大且层越薄。
有利地，根据本发明的一个实施例规定，扩散接合层的形成/施加是在真空中进行。因此，可避免扩散接合层受不期望材料或化合物污染。
若扩散接合层优选以介于0.1 nm和2500 nm之间、更优选介于0.1 nm和150 nm之间、甚至更优选介于0.1 nm和10 nm之间、最优选介于0.1 nm和5 nm之间的平均厚度R制成，则该方法的流程特别有效。
根据优选例示性实施例的以下说明及利用附图可知本发明的其它优点、特征及详细内容。
图1显示已如本发明所主张涂覆有层系统的两个衬底的横截面，
图2显示如本发明所主张的扩散接合层，
图3显示如本发明所主张的中间层，
图4显示施加至衬底的扩散接合层，
图5显示具有一个中间层及一个扩散接合层的施加至衬底上的层系统及
图6显示具有两个中间层及一个扩散接合层的施加至衬底上的层系统。
在附图中，相同或等效特征由相同附图标记表示。附图是非按比例的。特别是，更大多倍地显示中间层及扩散接合层能够更好理解地表示微结构。
本发明涉及一种经由两个层系统2、4将两个经涂覆衬底1、3彼此接合的方法。该层系统2、4可由任何数目的具有不同物理和/或化学特性及微结构的不同类型层5、5'、5"(中间层5'、5"及扩散接合层5)组成。如本发明所主张，此时位于各最上的层(介于该层系统2、4之间的接触面)为扩散接合层5，因此，为晶粒尺寸如本发明所主张受限制的层。
施加至第一衬底1的第一表面的扩散接合层5称为第一扩散接合层及施加至第二衬底3的第二表面3o则称为第二扩散接合层。
衬底1、3的表面1o、3o的平均粒直径H优选小于1 μm、更优选小于100 nm、又更优选小于10 nm、甚至更优选小于5 nm、最优选小于1 nm，该直径以与表面平行方式投影(平面图)。
与平均粒直径H或衬底表面正交测得的平均粒直径V优选小于1 μm、更优选小于100 nm、又更优选小于10 nm、甚至更优选小于5 nm、最优选小于1 nm。
所投影的粒直径H和V不一定相同。然而在极薄层厚度t的情况下，推测H和V具有相同数量级。在此情况中，V或t限制粒直径。原因在于防止晶粒扩大的表面能。在图2所显示的实施例中，规定垂直粒直径V以在此仅由单一扩散接合层5组成的层系统2的层厚度t限制。于是该层系统2的层厚度t等于粒直径V。
在图4所显示的实施例中，具有尽量大粒界面的该扩散接合层5是直接沉积在第一衬底1上。
在本发明所主张的如图5所显示的另一实施例中，具有尽量大粒界面(因此具有许多晶界)的扩散接合层5是沉积在任何其它中间层5'上。该中间层5'可为如在扩散接合层5中的具有视情况的不同晶粒尺寸分布的相同材料。在接触面(扩散接合层5的表面)上的微结构尤其仅受沉积过程影响。特别地，该中间层5'是经由电化学沉积过程(ECD)或PVD过程制得，反之，该扩散接合层5是经由PVD和/或CVD过程制得。
如图3所显示的中间层5'具有与表面1o或3o平行的较大平均粒直径H'及横向于表面1o或3o的较大平均粒直径V'。这里，若该中间层5'的层厚度t'大小比平均粒直径V更大、尤其大两倍、优选大3倍、更优选大5倍、又更优选大10倍、最优选大100倍、所有中最优选大1000倍，也极为有利。
在本发明所主张如图6所显示的另一实施例中，另一中间层5"是沉积在该扩散接合层5与该中间层5'之间。在此该中间层5"具有如本发明所主张防止该扩散接合层5和该中间层5'之间可能的相互扩散以使在实际接合过程之前会保持该扩散接合层5的微结构的任务。
通过两个衬底1、3透过其层系统2、4的后续接合过程，如本发明所主张通过至少一个扩散接合层的大粒界面(及因而大晶界数量)，发生原子自层系统2更为有效率地扩散至层系统4中并且反之亦然。
如本发明所主张，该扩散接合层5为形成接触面的层。原因在于该扩散接合层5具有极大数量的晶界7。因此平均扩散流动优选是在垂直方向(横向于表面1o、3o)中沿着该晶界7发生。
物质沿暴露表面的本质扩散比沿着晶界更大，但沿着晶界比在块体内更大。因此优选地，将通过如本发明所主张的大数量的晶界而发生两个层系统2和4的原子在晶界上“彼此相互扩散”。
此两个层系统2和4的接合优选发生在尽量低的温度下。就金属而言，接合优选发生在小于1.0的相当温度下，但高于室温且低于300℃温度。
本发明所主张的层系统将尤其为下述：
-Si衬底/薄扩散屏障/厚(ECD)Cu层/薄扩散屏障(例如Ti、Ta、...)/薄(PVD)Cu层
-Si衬底/薄扩散屏障/厚(ECD)Cu层/薄(PVD)Cu层
-Si衬底/薄扩散屏障/薄(PVD)Cu层
-Si衬底/薄扩散屏障/Cu层/薄Si层
-Si衬底/薄扩散屏障/Cu层/过渡金属(Ti、Ta、W、...)的薄层
-Si衬底/薄扩散屏障/Cu层/贵金属(Au、Pd、...)的薄层
-前述层系统的任何组合
接合过程可如本发明所主张经由将任一前述层系统接合至任何其它前述层系统进行。类似考虑适用于未明确述于本文但基于相同发明概念的任何其它层系统。
如本发明所主张优选的用于制造具有相当大晶粒尺寸(相较于扩散接合层5)的中间层5'、5"的方法为电化学沉积(ECD)。
如本发明所主张优选的用于制造具有相当小晶粒尺寸的扩散接合层5的方法为所有PVD和/或CVD方法。
附图标记
1               第一衬底
1o             表面
2               层系统
3               第二衬底
3o             表面
4               层系统
4o，4o'          表面
5               扩散接合层
5'     ，5"            中间层
6               晶粒
7               晶界
t，t'               层厚度
H，H'                 (平均)粒直径
V，V'                       (平均)粒直径

Claims (10)

1. 一种经由沉积第一材料而对第一衬底(1)涂覆第一扩散接合层(5)的方法，所述第一材料在所述第一衬底(1)的第一表面(1o)上形成所述第一扩散接合层(5)，以使所述第一扩散接合层(5)形成具有小于1 μm的与所述第一表面(1o)平行的平均粒直径H的粒表面。
2. 如权利要求1的方法，其中所述第一扩散接合层(5)在所述粒表面上横向于所述第一表面(1o)形成小于1 μm、尤其小于100 nm、优选小于10 nm、甚至更优选小于1 nm的平均粒直径V。
3. 如上述权利要求之一的方法，其中所述第一扩散接合层(5)是横向于第一表面(1o)以小于1 μm、尤其小于100 nm、优选小于10 nm、甚至更优选小于1 nm的平均厚度t施加。
4. 如上述权利要求之一的方法，其中在所述第一扩散接合层(5)与所述第一衬底(1)之间形成已尤其经由电化学沉积过程制得的至少一个另外的中间层(5'、5")。
5. 如上述权利要求之一的方法，其中所述第一扩散接合层(5)是经由物理气相沉积和/或化学气相沉积制得。
6. 一种用于将如权利要求1至5中任一项所述涂覆的第一衬底(1)与具有第二扩散接合层的第二衬底(3)或具有“标准层”的衬底接合的方法，其具有以下步骤，尤其是以下流程：
使所述第一衬底(1)的第一扩散接合层(5)与所述第二衬底(3)的第二扩散接合层或具有“标准层”的衬底接触，
将所述衬底(1、3)压在一起形成所述第一及第二衬底(1、3)间的永久金属扩散接合。
7. 如权利要求6的方法，其中所述永久接合具有大于1.5 J/m2、尤其大于2 J/m2、优选大于2.5 J/m2的接合强度。
8. 如权利要求6或7的方法，其中所述压在一起是在0.1和10 MPa之间的压力下进行。
9. 如权利要求6至8之一的方法，其中制成第一和/或第二扩散接合层(5)，以使所述扩散接合层作为固体扩散，尤其是至少大半作为晶界扩散而发生。
10. 如权利要求6至9之一的方法，其中永久接合的形成是在室温和500℃之间、尤其在室温和200℃之间、优选在室温和150℃之间、甚至更优选在室温及100℃之间、最优选在室温和50℃之间的温度下尤其在至多12天、优选至多1天、甚至更优选至多1小时、最佳至多15分钟期间发生。
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