CN1860590A - 室温共价粘结的方法 - Google Patents
室温共价粘结的方法 Download PDFInfo
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- CN1860590A CN1860590A CNA2004800181251A CN200480018125A CN1860590A CN 1860590 A CN1860590 A CN 1860590A CN A2004800181251 A CNA2004800181251 A CN A2004800181251A CN 200480018125 A CN200480018125 A CN 200480018125A CN 1860590 A CN1860590 A CN 1860590A
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Abstract
一种粘结方法,包括使用具有氟化氧化物的粘结层。通过暴露于含氟溶液、蒸汽或者气体下或者通过植入,可将氟引入到粘结层内。也可使用其中在粘结层的形成过程中将氟引入其内的方法,从而形成粘结层。粘结层的表面用所需物种,优选NH2物种终止。这可通过将粘结层暴露于NH4OH溶液来实现。在室温下获得高的粘结强度。该方法也可包括一起粘结两层粘结层并在粘结层之间的界面附近处生成具有峰值的氟浓度。粘结层之一可包括在彼此上形成的两层氧化物层。在两层氧化物层之间的界面处,氟的浓度也可具有第二峰值。
Description
发明背景
发明领域
本发明涉及室温下晶片的直接粘结领域,和更特别地,涉及利用氟和铵的效果和组合效果制造工程基底用基底的粘结,包封,和在电介质中,特别是在氧化硅层中三维器件整合。
相关领域的说明
由于逼近常规CMOS器件的物理极限,和对高性能电子系统需求急切,因此,芯片上系统(system-on-a chip)(SOC)成为半导体工业的自然解决方法。对于芯片上系统的制备来说,要求在芯片上的各种功能。尽管硅技术是加工大量器件的主要支持技术,但现在可由除了硅以外的材料制造的单独的器件和/或电路最佳地获得许多所需的电路和光电功能。因此,将非硅基器件与硅基器件整合的杂化系统具有提供独特的SOC功能的潜力,这种独特的功能不可能获自于单独的纯硅或者纯的非硅器件。
混杂器件整合的一种方法是在硅上不相类似的材料的异质外延生长(hetero-epitaxial)。迄今为止,认识到这种异质外延生长在异质外延生长的膜内的高密度缺陷,这主要是由于在非硅膜和基底之间晶格常数的错配所致。
混杂器件整合的另一方法是晶片粘结技术。然而,在升高的温度下热膨胀系数不同的不相类似的材料的晶片粘结引入热应力,所述热应力可导致错位生成、解粘结或龟裂。因此,希望低温粘结。对于粘结不相类似的材料来说,若不相类似的材料包括具有低分解温度的材料或者温敏器件,例如InP异质结双极晶体管或具有超浅源极和漏极曲线(profile)的加工过的Si器件,低温粘结也是所需的。
在含有不同材料的相同芯片上生产不同功能所需的工艺设计是困难的,且难以优化。确实,许多所得SOC芯片(特别是较大的整合尺寸的那些)显示出低的产率。一种方法是通过晶片粘合剂粘结和层的转移,互连充分加工的IC。参见,例如Y.Hayashi,S.Wada,K.Kajiyana,K.Oyama,R.Koh,S.Takahashi和T.Kunio,Symp.VLSI Tech.Dig.95(1990)和美国专利5563084,这两篇参考文献的全部内容在此通过参考引入。然而,晶片粘合剂粘结通常在升高的温度下操作,且缺点是,产生热应力、脱气、气泡形成和粘合剂的不稳定,从而导致在该工艺中降低的产率和随着时间流逝可靠度差。粘合剂也可与典型的半导体制造工艺不兼容。此外,粘合剂粘结通常不是气密的。
室温晶片直接粘结是使得在没有使用任何粘合剂的情况下,可在室温下粘结晶片,从而导致气密粘结的技术。在这种粘合剂粘结内不容易引入应力和不均匀度。此外,若低温粘结的晶片对可耐受修磨(thinning)的话,则对于特定的材料组合来说,当粘结对(bonded pair)中的一块晶片被修磨到小于相应临界值的厚度时,避免了在该层内生成不匹配位错和在随后的热处理步骤期间粘结对的滑动或龟裂。参见,例如Q.-Y.Tong和U.Gsele,Semiconductor Wafer Bonding:Scienceand Technology,John Wiley & Sons,New York,(1999),其全文内容在此通过参考引入。
发明概述
本发明涉及粘结方法,其中包括在相应的第一和第二元件上形成第一和第二粘结层,其中至少一层粘结层包括氟化氧化物层,使第一和第二粘结层在室温下在环境中接触,并在室温下,在所述第一和第二层之间形成粘结。
形成所述至少一层含氟化氧化物层的粘结层可包括形成氧化物层并将该层暴露于含氟溶液、蒸汽或者气体下。
形成本发明粘结结构的方法也可包括粘结第一和第二粘结层,并在第一和第二粘结层之间的界面附近处,形成具有第一峰值的氟浓度,和独立于第一峰值并且远离第一峰值处,在至少一层所述第一和第二层内形成第二峰值。粘结层之一可以是氧化物层,该方法进一步包括将氟引入到氧化物层内,并在引入步骤之后,在第一氧化物层上形成第二氧化物层。
本发明还涉及具有第一和第二元件的粘结结构体,其中分别在第一和第二元件上形成第一和第二粘结层,第一粘结层以非粘合剂的方式粘结到第二粘结层上,和第一粘结层包括氟化氧化物。在该结构体中,第一粘结层可包括在第二氧化物层上形成的第一氧化物层,其中在第一粘结层内的氟浓度具有位于第一和第二粘结层之间的界面附近的第一峰值,和第二峰值位于第一和第二氧化物层之间的界面处。
本发明的目的是在室温下,在空气中,在氧化硅覆盖的各种材料的晶片的表面上,实现非常高密度的共价粘结。
本发明进一步的目的是降低厚度为纳米到微米的表面氧化硅层的密度。
本发明再一目的是提高杂质和/或吸收的湿气离开粘结界面的扩散速度。
本发明另一目的是获得在表面上氟浓度大于1×1017cm-3的粘结层(厚度为纳米到微米)。
本发明额外的目的是使用标准半导体方法,在集成电路或器件图案的表面上改变共价粘结体的密度。
本发明另一目的是通过标准半导体方法,采用氟化处理,在氧化硅表面上局部或全部形成低-k电介质。
本发明再进一步的目的是生成其表面可用所需基团在原子水平上终止的材料,以便当两个这样的表面在室温下接触时形成共价粘结体。
附图简述
可容易获得本发明的更全面理解和许多附带的优点,这是因为通过参考下述详细说明,当与附图结合考虑时,可更好地理解它们,其中:
图1是根据本发明实施方案的流程图;
图2A是具有相应粘结层的一对解粘结基底的示意图;
图2B是一对彼此接触的解粘结基底的示意图;
图2C是在除去一部分基底之后,在图2B中的一对基底的示意图;
图2D是在粘结第三基底之后,在图2C中的一对基底的示意图;
图3是在粘结晶片对的气氛中,在有和无含氟与铵的粘结层的情况下,室温粘结能作为储存时间函数的图表;
图4是对于有和无等离子处理处理情况下加工的粘结晶片来说,粘结能作为储存时间函数的图表;
图5是对于有和无铵情况下处理的晶片对来说,在室温下,粘结能作为储存时间函数的图表;
图6是室温粘结能作为后-HF处理烘烤温度函数的图表;
图7是说明所测量的粘结能和储存时间的均方根之间线性关系的图表;
图8A-8C说明了其中在粘结层内形成氟化层的本发明的实施方案;
图9A-9E图示了在粘结晶片对内局部充分地共价粘结的区域;
图10是描述在本发明的粘结界面下方断裂的Si基底表面下的显微照片;
图11是包埋的低-k氧化物结构体的示意图;
图12是SIMS(次级离子质谱)测量结果;
图13说明了将多个器件粘结到较大的基底上;
图14A-14C图示了本发明粘结方法在金属对金属粘结上的应用;
图15说明了多个器件金属对金属地粘结到较大基底上;和
图16A-16E说明了本发明的气密封装应用。
优选实施方案的详细说明
现参考附图,其中在数幅附图中,类似的参考标记表示类似或者相应的部分,和更特别地描述图1和图2A-2B,其说明了本发明粘结方法的第一个实施方案。图1用通用的术语说明了本发明的方法。在待粘结的元件,例如基底或者晶片上形成粘结层(步骤10)。通过例如将粘结层的表面暴露于氟或氟植入剂下,从而氟化至少一层粘结层(步骤11)。使各层直接接触,从而形成粘结界面(步骤12),并通过化学反应导致形成共价键(步骤13)。随着额外共价键形成和/或来自所述化学反应的副产物扩散离开所述粘结界面,粘结强度会增加。优选地,粘结工艺在室温下,例如在约20-25℃下进行。
图2A示出了具有相应粘结层201、204和相应的相对表面202、205的两块晶片200、203。粘结层201和204由通过许多技术,其中包括,但不限于溅射、等离子加强的气相沉积中的任何一种或其结合形成的氧化硅,或由热氧化物形成。材料201和204的表面可以相对粗糙(>20埃RMS)且要求在直接接触之前变光滑。该膜也可具有足够低的表面粗糙度,在没有变光滑的情况下粘结。可使用申请WO01/61734、WO01/26137和WO01/71797中所述的技术制备表面202和205,产生光滑、活化的表面。
层201和204可以是使用化学气相沉积(CVD)或者等离子加强的CVD(PECVD)、溅射或者通过气化形成的绝缘体,例如SiO2、氮化硅、无定形硅。也可使用其它材料,例如聚合物,半导体或者烧结材料。层201和204的厚度应当大于相应基底201和203的表面形貌。
使用例如化学-机械抛光,平面化层201和204的表面202和205并使之变光滑。优选抛光表面202和205到约不大于3nm的粗糙度,和优选不大于约0.1nm,且基本上是平坦的。表面粗糙度值典型地以均方根(RMS)值的形式给出。此外,表面粗糙度可以以平均值形式给出,它几乎与RMS值相同。在抛光之后,清洗表面202和205,并干燥,以便从抛光步骤中除去任何残渣。抛光的表面201和205优选然后用溶液漂洗。
在抛光粘结层的表面到(如上所述的)小的表面粗糙度之后,视需要,将粘结层暴露于氟化处理下,例如稀释的含水HF、CF4或SF6等离子处理、F+植入下,视需要,加热,以氟化所有或所需部分的粘结层。如下所述,活化该层,并用所需基团在表面上终止。活化和终止步骤可一起进行。可如此处理粘结表面中的仅仅一个或者两个。
表面201和205然后进行活化工艺。这一活化工艺是蚀刻工艺,且优选是非常轻微的蚀刻(VSE)工艺。术语VSE是指非常轻微蚀刻的表面的均方根微粗糙度(micro-roughness)(RMS)保持接近于未蚀刻的数值,典型地<0.5nm,和优选在0.1nm-3nm范围内。所除去的材料的最佳量取决于除去所使用的材料和方法。所除去的典型量从数埃变化到数纳米。还可除去更多的材料。VSE还包括使在处理表面上的粘结断裂,和可在没有大量除去材料的情况下发生。VSE不同于通过例如在表面上引入电荷或者破坏表面层的简单的表面改性。在本发明方法的第一个实施例中,VSE方法由在特定的功率电平下,经特定时间的气体或者混合气体(例如氧气、氩气、氮气、CF4、NH3)的等离子工艺组成。等离子工艺的功率和持续时间将随获得所需粘结能所使用的材料而变化。以下给出了实例,但一般来说,根据经验确定功率和持续时间。
可以按照不同模式进行等离子工艺。可使用反应性离子蚀刻(RIE)和等离子体模式这二者,以及电感耦合等离子体模式(ICP)。也可使用溅射。以下给出了RIE和等离子体模式中的数据和实例。
VSE工艺通过物理溅射和/或化学反应非常轻微地蚀刻表面,且优选控制VSE工艺,使粘结表面的表面粗糙度不劣化。取决于VSE和所蚀刻的材料,可甚至改进表面粗糙度。对于本发明的室温粘结方法来说,不过度蚀刻表面34的任何气体或者气体混合物可用于本发明的室温粘结方法。
VSE起到清洗表面的作用并使晶片表面上的氧化物化学键断裂。CSE方法因此可显著提高表面活性。通过合适设计VSE,所需的粘结物种可用于在VSE过程中终止表面表面201和205。或者,可使用后VSE处理,其中在后VSE工艺过程中,用所需的终止物种活化并终止表面。
所需的物种进一步优选与表面原子层形成临时粘结,从而有效地终止原子层,直到随后这一表面可与通过相同或者另一粘结物种终止的表面结合在一起。在表面上的所需物种当它们足够接近时,进一步优选彼此反应,从而使得在低温或者室温下在表面201和205之间提供化学粘结,其中所述化学粘结通过已反应的所需物种扩散或者解离并扩散远离粘结界面来加强。
后VSE工艺优选包括在含选择化学品的溶液内浸渍,产生表面反应,所述表面反应导致用所需物种终止粘结表面34。浸渍优选就在VSE工艺之后进行。后VSE工艺可在与进行VSE工艺相同的装置内进行。如果VSE和后VSE工艺二者是或者干燥工艺,即等离子体、RIE、ICP、溅射等工艺,或者湿工艺,即,溶液浸渍的话,这可最容易进行。所需物种优选由一层单层或数层单层原子或分子组成。
后VSE工艺也可由等离子体、RIE或者其它干燥工艺组成,其中合适的气体化学品被引入,导致用所需物种终止该表面。后VSE工艺也可以是第二VSE工艺。终止工艺也可包括清洗工艺,其中在没有VSE的情况下除去表面污染物。在此情况下,类似于以上所述的后VSE工艺的后清洗工艺导致所需的表面终止。
若通过清洗或者VSE工艺活化的表面粘结随后足够弱地表面再构,且在粘结之前,可充分维持清洁,以便随后与类似表面的粘结可形成化学键的话,则后VSE或者后清洗工艺可以需要或者可以不需要用所需的物种终止表面。
任选地漂洗晶片,然后干燥。(视需要)通过校准两块晶片,并使之结合在一起,形成粘结界面,从而粘结它们。
如图2B所示,表面202和205彼此直接接触,形成粘结的结构体。在室温下,在两个表面202和205之间的界面206上发生共价键合。然后典型地在粘结界面内的一些位置处发生自发粘结,并在晶片上生长。随着起始的化学键开始生长,当表面足够接近时,在终止表面202和205所使用的物种之间发生导致化学键的化学反应,例如聚合。粘结能定义为在通过插入楔子(wedge)部分解粘结的粘结界面处独立的表面之一的特定表面能。在所述粘结表面彼此接触之后,随着时间流逝,当共价键的数量增加和/或来自于所述终止表面结合在一起形成的反应副产物扩散离开所述粘结表面时,在所述粘结的结构体内的粘结强度增加。反应副产物扩散离开粘结界面到晶片边缘上或者被晶片吸收,典型地被周围材料内的晶片被吸收。该副产物也可转化成扩散离开晶片或者被晶片吸收的其它副产物。可通过除去转化的物种,来增加共价和/或离子键的数量,从而导致粘结强度的进一步增加。
实施例
在第一个实施方案的第一个实施例中,在200-250℃下,PECVD(等离子加强的化学清洗沉积)二氧化硅沉积在单侧抛光的硅片上。PECVD氧化物的厚度不是关键的,和任意地选择为~1.0微米。抛光用PECVD氧化物层覆盖的晶片,使表面变光滑。使用AFM(原子力显微术),测定表面微粗糙度的RMS(均方根)数值为1-3埃。通过改性的RCA1(H2O∶H2O2∶NH4OH=5∶1∶0.25)溶液清洗晶片并旋转干燥。
将晶片任意地分成数组,其中在粘结之前,在一组内的每一晶片对以特定方式处理。在第I组中,在100mTorr下,氧化物覆盖的晶片对在氧气等离子体内以反应性离子蚀刻模式(RIE)处理30秒。等离子处理的晶片浸渍在含有35%氨水的CMOS级的氢氧化铵水溶液(下文称为“NH4OH”)中,之后旋转干燥,并在室温下,在空气中粘结。在第II组中,氧化物覆盖的晶片浸渍在0.025%HF水溶液中30秒,并旋转干燥。可根据所使用的氧化硅的类型改变HF浓度,和可以是0.01%-0.5%。然后在空气中,在250℃下加热晶片2-10小时。再次在RCA1中清洗晶片,氧气等离子体处理,在NH4OH中浸渍,并旋转干燥,之后在室温下在空气中粘结。
图3分别示出了在室温下,在空气中,第I组和第II组的粘结的晶片对的粘结能作为储存时间的函数。在笫II组内的晶片对的粘结能在3小时内快速增加到1000mJ/m2,并在空气中,在室温下,~40小时储存之后,达到本体硅的断裂能(2500mJ/m2)且显著高于第I组晶片对。这通过图3上部的曲线示出。在室温粘结之前,HF浸渍和随后加热在笫I组和第II组粘结晶片之间产生室温粘结能的巨大差别。
为了测定氧气等离子处理在提高室温粘结能方面的效果,制备另一组(第III组)晶片。在与第II组晶片对相同的工艺条件下处理,所不同的是省去氧气等离子处理步骤,之后在室温下粘结第III组内氧化物覆盖的晶片对。对于有和无等离子处理的晶片对来说,在室温下实现类似的粘结能,如图4所示。图4表明,若通过HF含水浸渍和烘烤,之后进行晶片粘结,则对于在室温下的充分化学键合来说,氧气等离子处理不是重要的。
在进一步的组,第IV组中,在与第II组晶片对相同的工艺条件下处理,所不同的是省去NH4OH浸渍并用去离子水漂洗替代,之后在室温下粘结该氧化物覆盖的晶片对。图5表明,对于不含NH4OH浸渍的晶片对来说,在室温下的粘结能下降60%,1051mJ/m2相对于2500mJ/m2。因此NH4OH浸渍显著增加室温下的粘结能。
NH4OH处理,用NH2基终止表面。因此,优选在本发明的方法中,在表面上终止NH2基。这可通过暴露于含NH4OH的气体下,暴露于含NH4OH的等离子体下,暴露于含NH4OH的液体蒸汽下或者暴露于含NH4OH的液体或者上述处理的结合,从而实现NH4OH处理。
与第II组中的那些一样处理晶片对,但改变后-HF烘烤。当不使用烘烤,且在空气中,在室温下储存粘结晶片时,获得~1000mJ/m2的粘结能。图6示出了对于这些晶片对来说,作为10小时后-HF烘烤温度函数室温粘结能的增加。对于后-HF、预粘结烘烤来说,存在其中实现最大室温粘结能的温度范围。对于在约250℃下的烘烤来说,获得最佳结果。因此,在本发明的方法中,优选在约250℃下进行加热。
上述结果表明,根据所得高的粘结强度,氧化物覆盖的晶片的HF浸渍、后HF烘烤、和NH4OH浸渍有助于室温下的化学键合。
本领域已知,添加氟到二氧化硅内可降低氧化物密度且在氧化物网络内产生微孔隙(参见,例如Lee和J-W.Park,J.Appl.Phys.80(9)(1996)5260,其全文内容在此通过参考引入)。最近,V.Pankov等,J.Appl.Phys.86(1999)275,和A.Kazor等,J.Phys.Lett.65(1994)1572(其全文内容在此通过参考引入)报道了掺入氟引起Si-O-Si环断裂且通过下述反应,将二氧化硅网络结构朝具有较低密度的大尺寸的环改变:
这一改性结构有助于杂质较高的扩散速度和提高的湿气吸收。此外,公知当氟化二氧化硅(SiOF)暴露于潮湿氛围下时,它有效地吸收水。V.Pankov,J.C.Alonso和A.Ortiz,J.Appl.Phys.86(1999),p.275(其全文内容在此通过参考引入)。
在HF浸渍,如在本发明的0.025%HF水溶液中浸渍的过程中,除了在二氧化硅表面上形成Si-F和Si-OH基以外,还如下所述生成一些F离子:
参见,例如H.Nielsen和D.Hackleman,J.Electrochem.Soc.Vol.130(1983)p.708(其全文内容在此通过参考引入)。在升高的温度下后HF烘烤有助于除去通过上述反应生成的水并提高氟的扩散。氟原子扩散到氧化物内,并根据方程式(1)与Si-O-Si键反应,形成SiOF。
较高温度的后HF烘烤可在氧化物表面上产生较厚的SiOF层,由于较高效率的吸水从而导致较高的室温粘结能。然而,对于最多350℃的烘烤来说,图6的结果表明,当后HF烘烤温度高于300℃时,所得粘结能实际上低于在较低温度下的烘烤。Chang等,Appl.Phys.Lett.vol.69(1996)p.1238(其全文内容在此通过参考引入)报道了若SiOF沉积温度高于300℃,则由于在氧化物内氟原子的损失导致该层的耐湿性开始增加。因此,对于在粘结之前,在350℃下后HF退火的晶片对来说,室温粘结能的下降可归因于下述事实:在粘结界面处的SiOF层吸收的湿气小于250℃退火的层,尽管SiOF层可能较厚。
在本发明的优选工艺中,根据下述交换反应,二氧化硅的最外层的表面终止从后HF退火的Si-F转化成RCA1溶液清洗之后的Si-OH:
在例如含水NH4OH浸渍(含有约65%的H2O)之后,大多数Si-OH基然后转化成Si-NH2:
然而,在NH4OH浸渍之后,由于在NH4OH内的H2O含量导致表面仍部分OH基终止。
Si-NH2和Si-OH终止的表面在室温下粘结,且当两种表面足够接近时,发生下述反应:
例如,Q.-Y.Tong和U.Goesele,J.Electroch.Soc.,142(1995),p.3975报道了可在室温下,在氢键键合到相反键合的亲水表面上的两个Si-OH之间形成Si-O-Si共价键。然而,上述聚合反应在小于~425℃的温度下是可逆的。参见,例如M.L.Hair,in SiliconChemistry,E.R.Corey,J.Y.Corey和P.P.Gaspar,Eds.,Wiley,NewYork(1987),p.482(其全文内容在此通过参考引入)。
若可在没有加热的情况下,除去通过上述反应生成的水和氢气,则根据上述反应,共价键不具有可逆性,且导致室温下永久的共价键合。根据本发明,通过在粘结之前,氟化氧化物,在远离粘结表面处氟掺入到氧化物内,且上述聚合反应的副产物可通过从粘结界面扩散到远离粘结界面的低密度的氟化氧化物内,从而导致在室温下在界面处高度的共价键合。图7示出了对于使用与第II组中的那些相同的工艺条件下,在室温下粘结的氧化物覆盖的晶片对来说,在室温下,作为储存时间的均方根函数的粘结能。对于水的恒定总量S来说,在粘结界面Cs1处的水浓度与均方根时间t和水的扩散系数D1成反比,和在粘结界面处的氢气浓度Cs2与均方根时间t和氢气的扩散系数D2成反比:
Cs1=S(πD1t)1/2 (7.1)
Cs2=S(πD2t)1/2 (7.2)
参见,例如J.C.C.Tsai,VLSI Technology,S.M.Sze,Ed.,McGraw-Hill,Auckland,(1983),p.147(其全文内容在此通过参考引入)。
当在粘结界面处,粘结能γ与水和氢气浓度成反比时,粘结能应当与氢气和水浓度的倒数成正比:
γ~(Cs1+Cs2)-1 (8)
尽管NH2终止的浓度可大于OH终止浓度,从而导致在粘结之后H2浓度比H2O高,但认为氢气的扩散性显著高于水,这是因为其尺寸小得多(2.5埃相对于3.3埃)。粘结能的增加可能主要由水的扩散支配,且如果扩散系数恒定,则与时间的均方根成正比:
γ~1/Cs1=(πD1t)1/2/S (9)
与这一结论一致的是,如图7所示,观察到所测量的粘结能与时间的均方根之间接近线性的关系,这与水(和氢气)扩散远离粘结界面进入氟化氧化物层内一致。因此,水(和氢气)扩散远离粘结界面可能是在本发明中观察到的粘结能提高的原因,但本发明不限于导致水副产物的反应和所述水(和氢气)副产物扩散远离所述粘结表面。
对于主要用OH基终止的粘结表面,例如与第IV组内的晶片一样的没有用NH4OH处理的粘结表面来说,存在显著较高浓度的水扩散离开该界面。因此,用NH4OH浸渍的晶片对的粘结能随储存时间快速增加,且与图5所示的不用NH4OH浸渍处理的晶片对相比,达到高得多的数值。
图8A-8C示出了在随后的粘结中使用的氟化氧化物层的方法。在于待粘结的基底90上形成氧化物层81(图9A)之后,或者通过湿法或者通过气体法,将氧化物暴露于HF下。气体工艺的实例是没有在HF溶液中浸渍的情况下,将晶片表面暴露于HF蒸汽下,可以以许多方式形成氧化物,其中包括,但不限于,溅射、等离子加强的气相沉积(PECVD)和热生长。基底可以是有或无在其内形成的器件的硅片。或者,F可以采用20-30keV的能量,通过1×1015到1×1016/cm2的氟离子植入,从而引入到氧化物层内。
在于~250℃下退火之后,在层81的表面82内形成厚度约0.5微米的SiOF表面粘结层83(图8B)。注意,层83的尺寸没有按比例画出。基底备用于粘结到具有第二粘结层85(其也具有在表面内形成的SiOF层86)的另一基底84上,粘结能在环境中,在室温下进行,如图8C所示。在室温下在基底之间形成非常高密度的共价粘结,其比没有使用HF浸渍和烘烤的晶片对高最多2.5倍(通过所测量的粘结强度来推导)。
还可将SiOF表面层粘结到不具有SiOF表面层的另一粘结层上。还可通过F+植入和/或蚀刻(例如,使用SF6和/或CF4的干燥蚀刻)氧化硅,接着在升高的温度下烘烤,形成SiOF表面层。另外,可通过PECVD(等离子加强的化学气相沉积)形成SiOF表面层。例如,在室温下,电子-共振PECVD氧化物沉积使用SiF4/Ar/N2O(S.P.Kim,S.K.Choi,Y.Park和I Chung,Appl.Phys.Lett.79(2001),p.185,PECVD oxide deposition using Si2H6/CF4/N2O at 120℃,J.Song,P.K.Ajmera和G.S.Lee,Appl.Phys.Lett.69(1996),p.1876or SiF4/O2/Ar at 300℃ S.Lee和J.Park,Appl.Phys.Lett.80(1996),p.5260)。
HF浸渍和退火,以便在二氧化硅表面上形成SiOF表面粘结层具有独特的应用。图9A-E图示了可使用本发明生产局部变化的共价粘结,和因此局部变化的在表面上的粘结能。图9A示出了在硅片上,在暴露的二氧化硅的选择区域内,在此情况下,硅器件区域内,使用稀释的HF(或缓冲的HF)溶液,从表面上蚀刻掉小量的氧化物。基底90具有二氧化硅层91和器件部分92。器件部分可以是离散的器件,电路或者集成电路。在具有孔隙94的氧化物91上形成光致抗蚀剂或掩膜层93。稀释的HF溶液蚀刻通过孔隙94暴露的二氧化硅,生成下凹的区域95。下凹的区域可具有非常宽范围的深度,从数纳米到许多微米,但较厚的吹塑也是可能的(图9B)。光致抗蚀剂或者掩膜层抗HF蚀刻。除去层93,接着如图9C所示,在~250℃下在整个表面上沉积二氧化硅。250℃再沉积工艺模拟后HF烘烤处理的效果且包埋稀释的HF处理过的表面。
CMP工艺步骤然后可用于平面化下凹的区域并改进表面粗糙度。第I组表面处理然后用到层96上,和硅片在室温下粘结到另一晶片,例如覆盖晶片98的二氧化硅层97上,如图9D所示。沿着本发明的粘结界面,在HF的蚀刻区域内,室温粘结能显著高于非HF蚀刻的区域。
当如此形成的粘结对被迫分离时,所得分离典型地不在HF浸渍的器件区域的粘结界面处。确实,一部分硅片或者硅片本身可在粘结界面下方处断裂并从基底上剥离,如图9D所图示。基底90的部分99连接到器件或电路92上。层91的部分100和层96的部分101因断裂而分离(图9E)。
在图10的显微照片中示出了图9图示的实际实例,其表明,来自粘结对的晶片残余物被迫分离。这一残余物表明在其中表面暴露于HF下的粘结界面下方硅片内的断面。这与在这些位置内氧化硅层之间的粘结能高于本体硅的断裂能一致。在晶片对的粘结界面的其它位置上,同样如图10所示,表面没有暴露于HF下。在这些位置内,认为粘结能低于本体硅的断裂能。这与在这些区域内缺少硅的剥离一致。
这种局部的氟化由于将F引入到氧化物内,降低该材料的介电常数,也可导致形成较低k的电介质。可利用本发明的这一特征,在集成电路或其它结构体的设计中发挥优势。例如,可在VLSI器件内,在金属线之间,而不是在多层互连体的通路电平内,通过蚀刻工艺,例如暴露于HF下,在其中希望低k电介质的区域内,形成低k电介质,接着在~250℃下沉积氧化物。图11示出了包埋的低k结构体的一个实例。在图11中,在氧化物层,例如SiO2,110、112和114之间形成低k材料层部分111和113。金属层115和117通过通路116和118连接。
实施例
使用图8A-8C再次描述本发明方法的第二个实施例。在基底80上形成第一氧化物层81(图8A)。通过以上所述的工序之一,亦即,暴露于HF下或者暴露于含氟气体下,将氟引入到膜81内。例如,在膜81上通过PECVD形成第二氧化物膜82(图8B)。也可通过使用沉积所述氧化物膜82用的合适的含氟前体,将它引入到第二膜内。注意,在该实施例中,膜81和82的尺寸没有按比例画出,这是因为该附图还用于描述其中在膜81内形成膜82的实施例,但该附图确实准确地代表了膜81和82的位置。在该实施例中,由于沉积温度和/或与所述氧化物膜82有关的含氟前体导致不需要烘烤基底,以生成辅助除去反应副产物的氟化层。然后将该用品备用于粘结另一晶片,如图8C所示。
在图10所示的样品上,在其中形成氧化硅层,并暴露于HF溶液,接着在250℃下沉积氧化物这样处理的样品的HF暴露表面积内,进行SIMS(次级离子质谱)测量。然后将该样品浸渍在NH4OH溶液内。图12示出了测量结果。图12所示的SIMS测量结果证明在粘结之前在NH4OH内浸渍的粘结晶片的粘结界面处Si-N共价键的存在。此外,SIMS断面测量清楚地证明在氧化物沉积的界面附近,在HF蚀刻的凹处存在高的氟浓度。由于在氧化物沉积之前,该样品仅仅暴露于HF下,因此合理地将在粘结界面处的F信号归因于F通过沉积的氧化物扩散并在250℃氧化物沉积过程中在氧化物表面处累积。在粘结界面处的氟浓度为约2×1018/cm3,和峰值氮浓度为~3.5×1020/cm3。远离粘结界面处的F有助于除去反应副产物,例如HOH,从而导致增加浓度的永久共价键和粘结强度。
在250℃下后HF含水浸渍烘烤10小时可与反复PECVD氧化物沉积的温度与持续时间相当。因此在HF浸渍之后,通过在HF处理的表面上沉积PECVD氧化物,可避免独立的退火步骤。这一优点的实例是在晶片粘结的制备中,在非平面晶片的平面化中。例如,对于集成电路(IC)的粘结来说,室温粘结可能非常有用。然而,IC典型地具有非平面表面,这不利于对于室温直接晶片粘结来说优选的平坦和光滑表面。改进这一平坦度的方法是沉积氧化物层,接着CMP。这类似于以上提供的实施例,所不同的是,非平坦度可以是1微米或者更大。在非平坦度增加的这一情况下,沉积较厚的氧化物或者大于一次地反复沉积氧化物,并使用CMP实现所需的平坦度。在这一平面化工艺中,若在(最后)的氧化物沉积之前,采用HF处理,则随后的氧化物沉积将具有增加的F浓度,和在氧化物沉积之后在其表面处具有F的累积。与若不使用HF处理所获得的粘结能相比,例如如上所述,采用第I组预粘结处理,且没有任何后氧化物生长热处理的情况下,这一F浓度可导致较高的粘结能。
可在环境条件下,而不是限制到高或超高真空(UHV)条件下,进行本发明的方法。因此,本发明的方法是成本低,可批量生产的制造技术。该方法也不限于晶片的类型、待粘结的基底或元件。晶片可以是本体材料,例如硅,具有在其内形成的器件的晶片,处理器基底、散热片等。
尽管图2A和2B示出了粘结在一起的两种器件,但该方法不限于粘结两种器件。可除去基底200和203之一并反复处理,正如图2C和2D所示。在图2C中,通过包括粉碎、搭接、抛光和化学蚀刻中的一种或多种工艺在内的工序,对图2B所示结构的基底203进行基底除去,得到部分207。可基于进行该方法的材料或者结构体的类型决定合适的一种或多种方法。在其中基底203在其表面上含有器件或其它元件的情况下,除了其中器件或其它元件驻留的区域以外,可除去所有或基本上所有的基底203。基于材料、材料的蚀刻特征或者特定应用的细节,可改变除去的量。
在部分207(如图2C所示)上形成相同或者不同材料的另一粘结层208,例如沉积的氧化硅材料,和如上所述制备具有粘结层2-7的基底209,亦即,使层210的表面变光滑到以上所述范围内的表面粗糙度,并以与以上所述相同的方式在界面211处,粘结到层108上。图2D示出了所得结构体。该工艺可进行N次,视需要产生(N+1)集成结构体。
本发明可局部粘结到全部晶片表面积上或者可粘结在整个全部晶片表面积上。换句话说,较小的小片可粘结到较大的小片上。这在图13中示出,其中具有相应粘结层134、136和138的数个较小的小片133、135和137粘结到粘结层131的表面132上。
本发明还可用于室温金属的直接粘结,正如在申请序列号10/359608中所述(其内容在此通过参考引入)。正如图14A所示,两个基底140和143具有各自的粘结层141和144以及金属垫142和145。间隙146隔开垫片,和垫片的上表面在层141和144的上表面上延伸。制备层141和144的表面以供如上所述的粘结,然后使基底的金属垫片接触(图14B)。至少一个基底弹性变形,且粘结层141和144接触,并开始在层141和144之间的一个或多个点处粘结(图14C)。粘结生长形成粘结体147。在室温下,形成强的粘结(例如共价粘结)。
图15示出了较小的器件或小片151和152对较大基底150的金属粘结。在器件151和152内的结构体153和154分别可以是有源器件或者接触结构体。在基底150内,还可以是有源器件或者含有有源器件的结构体156,具有接触结构体155。在基底150上的粘结层157和在较小器件151和152上的粘结层158之间的界面159处形成粘结。
金属直接粘结提供许多优点,其中包括省去磨光(grinding)和修磨小片,藉助蚀刻和金属沉积形成电连接,如参考的现有技术中所述一样互连相连的晶片。这消除了因这些小片磨光和修磨而引起的任何机械破坏。此外,省去深的通路蚀刻避免了台阶式覆盖问题,使得该方法可按比例缩小到较小尺寸,从而导致较小的通路插塞(plug)接触粘结的晶片。该方法与其它标准的半导体工艺兼容,且与VLSI兼容。
在进一步的实施例中,本发明的方法可用于气密封装,如图16A-16E所示。在载体上形成氟化的粘结层162,并在形成器件161,例如MEMS的过程中受到保护。图16A示出了在载体160上形成粘结层162,接着在粘结层162上形成保护膜163,和在载体160上形成器件161的步骤。作为实例,载体160可以是硅基底,和粘结层162可以是具有合适的表面粗糙度和平坦度特征的沉积的氧化物层,以促进室温粘结。如图16B所示,在形成器件161之后除去膜163,和在将粘结层162粘结到表面164上的位置处,制备具有合适的表面粗糙度和平坦度特征的覆盖层165,所述覆盖层165具有带表面167的部分166。使表面167与表面164直接接触并粘结,形成粘结体169,如图16C所示。图16D代表图16A-16C所示的方法的改性,其中在部分166上形成具有合适的表面和平坦度特征的粘结层170。使膜170的表面与膜162的表面接触并粘结,形成粘结体171。图16E示出了图16A-16C所示的方法的另一改性,其中覆盖层由板172和在该板172上形成的部分173组成。如上所述制备部分173的表面,并粘结162形成粘结体174。图16E的右手部分示出了进一步的改性,其中采用膜174,将部分173粘结到板172上,并粘结到层162上,形成粘结体175。在任何一种情况下,部分173可以是氧化物或硅材料,和板172可以是硅板。
根据本发明,通过任何方法,例如沉积、溅射、热或化学氧化,和玻璃上旋涂形成的二氧化硅可以以纯或者掺杂的状态使用。
在本发明的优选实施方案中,在水化之后和在粘结之前,通过氟化表面二氧化硅层覆盖的晶片的氨水溶液浸渍显著增加室温粘结能,这是由于形成Si-N键和氢键所致。
HF-浸渍和后HF烘烤可在晶片上的所需位置处,例如在二氧化硅层内的蚀刻窗处产生局部的共价键合。或者F的植入和随后退火可在所需位置处产生局部的共价键合。
根据本发明,HF-浸渍和后HF烘烤可在二氧化硅层内局部形成低k电介质。例如,可在VLSI器件内,在多层互连体内的金属线之间,但不是在通路电平处形成低k电介质。
本发明的方法可用于任何类型的基底,例如散热片、处理器或代用基底,具有有源器件的基底,具有集成电路的基底等。不同技术的基底,即硅、III-V材料,II-VI材料等可在本发明中使用。
本发明的应用包括,但不限于,用于3-D SOC的加工集成电路的垂直整合,微垫片封装、倒装片结合的低成本和高性能替代品,晶片级封装,热处理和独特的器件结构体,如金属基础器件。
鉴于上述教导,本发明的许多改性和改变是可能的。因此,要理解,可在此处具体地所述的以外在所附权利要求的范围内实践本发明。
Claims (48)
1.一种粘结方法,它包括:
在相应的第一和第二元件上形成第一和第二粘结层,其中至少一层所述粘结层包括氟化层;
使所述第一和第二粘结层在室温下在环境中接触;和
在室温下,在所述第一和第二层之间形成粘结。
2.权利要求1的方法,包括:
在室温下形成至少600mJ/m2的结合力。
3.权利要求1的方法,包括:
在室温下形成至少1000mJ/m2的结合力。
4.权利要求1的方法,包括:
在室温下形成至少2500mJ/m2的结合力。
5.权利要求1的方法,包括:
所述第一和第二粘结层各自形成具有约0.1到1.5nm RMS范围内的表面粗糙度。
6.权利要求5的方法,包括:
激活所述第一和第二粘结层。
7.权利要求1的方法,包括:
激活所述第一和第二粘结层。
8.权利要求1的方法,其中形成所述氟化层包括:
形成氧化物层;和
将所述氧化物层暴露于含氟溶液下。
9.权利要求8的方法,包括:
烘烤所述至少一层含氟化氧化物的所述层。
10.权利要求9的方法,包括:
在所述烘烤之后,将所述至少一层所述层暴露于RCA溶液下。
11.权利要求9的方法,包括:
在约100-300℃范围内的温度下,烘烤所述至少一层含氟化氧化物的所述层。
12.权利要求9的方法,包括:
在约250℃的温度下,烘烤所述至少一层含氟化氧化物的所述层。
13.权利要求9的方法,包括:
在所述烘烤之后,将所述至少一层所述层暴露于RCA溶液下。
14.权利要求8的方法,包括:
将所述层暴露于含HF的溶液下。
15.权利要求8的方法,包括:
将所述层暴露于含0.025%HF的溶液下。
16.权利要求1的方法,其中形成至少一层含氟化氧化物层的所述粘结层包括:
形成氧化物层;和
将所述氧化物层暴露于含氟气体下。
17.权利要求16的方法,包括:
将所述氧化物层暴露于HF蒸汽下。
18.权利要求16的方法,包括:
将所述氧化物层暴露于含SF6和CF4之一的等离子体下。
19.权利要求1的方法,其中形成至少一层含氟化氧化物层的所述粘结层包括使用含F的气体沉积氧化物。
20.权利要求1的方法,其中形成至少一层含氟化氧化物层的所述粘结层包括使用含SiF4、CF4和Si2H6之一的气体,沉积PECVD氧化物。
21.权利要求1的方法,其中形成至少一层含氟化氧化物层的所述粘结层包括:
形成氧化物层;和
将含氟的物种植入到所述氧化物层内。
22.权利要求21的方法,包括:
将含氟的物种以约1×1015-1×1016/cm2的剂量范围植入到所述氧化物层内。
23.权利要求1的方法,包括:
通过暴露于RIE工艺下蚀刻所述第一和第二粘结层。
24.权利要求1的方法,包括:
将所述粘结层暴露于NH4OH溶液和蒸汽之一下。
25.权利要求1的方法,包括:
覆盖所述第一粘结层的第一部分;和
氟化在所述覆盖步骤中没有被覆盖的所述第一粘结层的第二部分;和
将所述第二部分粘结到所述第二粘结层上。
26.权利要求1的方法,其中在所述第一和第二粘结层之一内形成所述氟化氧化物包括:
将第一氧化物层暴露于氟下;和
在所述暴露步骤之后,在所述第一氧化物层上形成第二氧化物层。
27.权利要求26的方法,包括:
在约100-300℃的温度范围内形成所述第二氧化物层。
28.权利要求26的方法,包括:
在约250℃的温度下形成所述第二氧化物层。
29.权利要求1的方法,包括:
形成氟浓度为至少1017/cm3的至少一层所述第一和第二粘结层。
30.权利要求1的方法,包括:
在所述第一和第二粘结层之间的界面附近,形成具有第一峰值的氟浓度,和独立于所述第一峰值并在远离所述第一峰值的位置处,在至少一层所述第一和第二层内形成具有第二峰值的氟浓度。
31.权利要求30的方法,其中形成所述第一和第二粘结层之一包括:
形成第一氧化物层;
将氟引入到所述氧化物层内;和
在所述引入步骤以后,在所述第一氧化物层上形成第二氧化物层。
32.权利要求31的方法,包括:
氟从所述第一氧化物层扩散到所述第二氧化物层内。
33.权利要求31的方法,包括:
将所述第一氧化物层暴露于各自含有氟的溶液、蒸汽和气体之一下。
34.权利要求31的方法,其中:
形成所述第一氧化物层包括使用含氟气体,沉积氧化物。
35.权利要求31的方法,其中:
将所述第一氧化物层暴露于含SF6和CF4之一的等离子体下。
36.权利要求31的方法,其中形成所述第一氧化物层包括使用含F气体,沉积氧化物。
37.权利要求31的方法,其中形成所述第一氧化物层包括使用含SiF4、CF4和Si2H6之一的气体,沉积PECVD氧化物。
38.一种粘结的结构体,包括:
第一和第二元件;
分别在第一和第二元件上形成第一和第二粘结层;
所述第一粘结层以非粘合剂的方式粘结到所述第二粘结层上;和
所述第一粘结层包括氟化氧化物。
39.权利要求38的结构体,其中:
所述第一粘结层包括在第二氧化物层上形成的第一氧化物层;和
在所述第一粘结层内的氟浓度具有位于所述第一和第二粘结层之间的界面附近的第一峰值,和位于所述第一和第二氧化物层之间的界面处的第二峰值。
40.权利要求38的结构体,其中所述第一粘结层包括植入氟的层。
41.权利要求38的结构体,其中所述第一粘结层包括具有用氟溶液蚀刻的表面的层。
42.权利要求38的结构体,其中所述第一粘结层包括具有用含HF溶液蚀刻的表面的层。
43.权利要求38的结构体,其中所述第一粘结层包括在含氟的第二氧化物层上,在约100-250℃的温度范围内形成的第一氧化物层。
44.权利要求38的结构体,其中所述第一粘结层包括在含氟的第二氧化物层上,在约250℃下形成的第一氧化物层。
45.权利要求38的结构体,其中所述第一粘结层包括植入剂量范围为约1×1015-1×1016/cm2的含F物种的氧化物层。
46.权利要求38的结构体,其中所述第一粘结层包括具有多个含氟的离散区域的层。
47.权利要求38的结构体,其中所述第一粘结层包括用Si-NH2和Si-OH中至少一个终止的表面。
48.权利要求38的结构体,其中所述第一粘结层包括用Si-NH2和Si-OH终止的表面。
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-
2003
- 2003-05-19 US US10/440,099 patent/US7109092B2/en not_active Expired - Lifetime
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- 2004-05-19 CN CN2008101340522A patent/CN101359605B/zh not_active Expired - Lifetime
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- 2004-05-19 JP JP2006532508A patent/JP5570680B2/ja not_active Expired - Lifetime
- 2004-05-19 CA CA 2526481 patent/CA2526481A1/en not_active Abandoned
- 2004-05-19 EP EP04750940A patent/EP1631981A4/en not_active Withdrawn
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108766873A (zh) * | 2011-01-25 | 2018-11-06 | Ev 集团 E·索尔纳有限责任公司 | 用于永久接合晶片的方法 |
CN108766873B (zh) * | 2011-01-25 | 2023-04-07 | Ev 集团 E·索尔纳有限责任公司 | 用于永久接合晶片的方法 |
CN108511332A (zh) * | 2017-02-28 | 2018-09-07 | Imec 非营利协会 | 半导体基材直接结合的方法 |
CN108511332B (zh) * | 2017-02-28 | 2023-06-20 | Imec 非营利协会 | 半导体基材直接结合的方法 |
CN110676164A (zh) * | 2019-10-14 | 2020-01-10 | 芯盟科技有限公司 | 半导体工艺部件及其形成方法、以及半导体工艺设备 |
CN110767541A (zh) * | 2019-10-28 | 2020-02-07 | 苏师大半导体材料与设备研究院(邳州)有限公司 | 一种晶圆键合方法 |
CN114975501A (zh) * | 2022-07-28 | 2022-08-30 | 晶芯成(北京)科技有限公司 | 晶圆键合方法以及背照式图像传感器的形成方法 |
CN115376966A (zh) * | 2022-08-09 | 2022-11-22 | 长春长光圆辰微电子技术有限公司 | 一种石英常温键合方法 |
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US20060216904A1 (en) | 2006-09-28 |
EP1631981A2 (en) | 2006-03-08 |
US20190344533A1 (en) | 2019-11-14 |
US20110143150A1 (en) | 2011-06-16 |
US20080187757A1 (en) | 2008-08-07 |
IL205212A0 (en) | 2011-07-31 |
US7109092B2 (en) | 2006-09-19 |
US7862885B2 (en) | 2011-01-04 |
JP5570680B2 (ja) | 2014-08-13 |
SG185826A1 (en) | 2012-12-28 |
US20040235266A1 (en) | 2004-11-25 |
US7335996B2 (en) | 2008-02-26 |
CN101359605A (zh) | 2009-02-04 |
CA2526481A1 (en) | 2004-12-02 |
JP5571227B2 (ja) | 2014-08-13 |
US10434749B2 (en) | 2019-10-08 |
WO2004105084A3 (en) | 2006-01-05 |
WO2004105084A2 (en) | 2004-12-02 |
JP2013219370A (ja) | 2013-10-24 |
EP1631981A4 (en) | 2010-01-20 |
US20150064498A1 (en) | 2015-03-05 |
US20190344534A1 (en) | 2019-11-14 |
CN100468639C (zh) | 2009-03-11 |
US8841002B2 (en) | 2014-09-23 |
KR20060028391A (ko) | 2006-03-29 |
CN101359605B (zh) | 2010-10-13 |
US20120183808A1 (en) | 2012-07-19 |
US11760059B2 (en) | 2023-09-19 |
JP2007515779A (ja) | 2007-06-14 |
KR101154227B1 (ko) | 2012-06-07 |
IL171996A0 (en) | 2009-02-11 |
US8163373B2 (en) | 2012-04-24 |
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