CN1643674A - 使用氨基硅烷和臭氧的低温介电沉积 - Google Patents

使用氨基硅烷和臭氧的低温介电沉积 Download PDF

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CN1643674A
CN1643674A CN 03805832 CN03805832A CN1643674A CN 1643674 A CN1643674 A CN 1643674A CN 03805832 CN03805832 CN 03805832 CN 03805832 A CN03805832 A CN 03805832A CN 1643674 A CN1643674 A CN 1643674A
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千崎佳秀
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Abstract

本发明描述了通过使用氨基硅烷或烷基酰胺基硅作为硅前体以及使用包括臭氧的氧化剂，用CVD方法在低温下(20－400℃)沉积具有良好阶跃覆盖和填充高纵横比器件结构的能力的介电层或膜的方法。本发明还提供了通过使用氨基硅烷或烷基酰胺基硅作为硅前体以及使用包括臭氧和氨(NH3)的氧化剂，在低温下沉积氧氮化硅(SiOxNy)膜的方法。

Description

使用氨基硅烷和臭氧的低温介电沉积
相关申请的互相参考
本发明涉及并要求2002年7月19日申请的、名称为“Low TemperatureDielectric Deposition Using Aminosilane and Ozone”的美国临时专利申请60/396,746的优先权，在此引入其全部公开内容作为参考。
发明领域
本发明主要涉及半导体领域。更具体地，本发明涉及在半导体器件和晶片上的化学气相沉积。
发明背景
在半导体器件的制造中，低压热化学气相沉积(CVD)产生具有良好阶跃覆盖(step coverage)特性和可接受的隙缝填充(gapfill)纵横比(aspect ratio)的前金属介电膜(premetal dielectric film)。当一些前体，如双(四丁基氨)硅烷(BTBAS)和Et2SiH2在约400℃下通过化学气相沉积(CVD)与氧气O2反应时，这些前体产生SiO2。然而，未来的集成电路要求更低的温度加工前金属介电质(PMD)和分隔器应用(spacer application)。降低加工温度的可选方法是：使用高密度等离子体(HDP)化学气相沉积(HDPCVD)工艺。通过使用HDPCVD工艺，在300～500℃范围内沉积掺杂磷的玻璃(PSG)或未掺杂的硅酸盐玻璃(NSG)。然而，HDP化学气相沉积具有限制其有用性的缺陷。HDPCVD工艺将隙缝填充能力限制为约3∶1的纵横比，而较高温度的热CVD工艺获得更适合的6∶1的隙缝填充或者更高纵横比。因此，本领域需要在较低温度下在前金属介电质上运行化学气相沉积，并同时保留良好的阶跃覆盖的方法。
发明概述
本发明提供一种方法，该方法在约400℃的低温下，在硅基底上沉积SiO2和其它氧化物，并同时保持良好的阶跃覆盖和隙缝填充能力。
本发明的方法能够用于掺杂和未掺杂的SiO2沉积。该方法在IC制作种的经典应用是，但不限于前金属介电质(PMD)、浅槽隔离(shallow trenchisolation，STI)、槽形衬里(trench liner)和分隔器介电质。
通过使用O3和NH3的混合物作为反应物气体，本发明的沉积方法也能够用氧氮化硅(silicon oxynitride)进行。本发明的其它方面包括除硅之外的基底，如SiC、SOI、平板(flat panels)、钨或铝。
本发明的一个方面提供在加工室内的基底表面上沉积介电层的方法，所述方法包括：将基底暴露给包括氧化剂气体和硅前体的反应物气体，其中所述氧化剂气体包括臭氧，硅前体包括烷基酰胺基硅(silicon alkylamide)和氨基硅烷中的至少一种。该方法可在约20～400℃的温度范围内进行。
本发明的另一方面提供在加工室内的基底上沉积氧氮化硅层的方法，所述方法包括：将基底暴露给包括氧化剂气体、氨气和硅前体的反应物气体，其中氧化剂包括臭氧，硅前体包括烷基酰胺基硅和氨基硅烷中的至少一种。该方法可在约20～400℃的温度下进行。
附图说明
以下结合附图，详细描述本发明，其中：
图1说明了适合运行本发明方法的CVD装置。
发明详述
本发明提供新型低热预算方法(low thermal budget method)，即在低于或等于约400℃的温度下，通过化学气相沉积(CVD)在半导体基底上沉积介电层或膜的方法。在本发明的一个实施方案中，CVD反应可用下述方程概括：
                         (1)
其中硅前体是Si(NR1R2)4，R1或R2为H 、C1-C6烷基、环烷基、F取代的烷基，或者Si(NR1R2)4-xLx(X＝1、2或3)，其中L＝H或Cl。
在方程(1)中，氨基硅烷和烷基酰胺基硅化合物(以下简称“硅前体”)内的Si-N键是不稳定的。与其它含硅的前体相比，该键在较低温度下与氧化剂气体反应。这种类型的化合物中优选的硅前体具有较小的R基团，如甲基乙基酰胺基。在含有基底的反应器或室内，进行该反应。结合使用臭氧作为氧化剂气体的组分，SiO2 CVD工艺温度可降到低于400℃，同时保持低压热CVD工艺的良好阶跃覆盖和隙缝填充能力。臭氧气体在比气体氧化剂如氧气或水更低的温度下提供原子氧。该反应中，硅前体的氧化在约200℃或更低的温度下提供了良好的结果，20℃至300℃的温度范围为优选的范围。对前体气体流而言，过程气体流量在约1sccm至1000sccm范围内，优选在约10至500sccm的范围内。氧化剂气体流量在约10sccm至2000sccm范围内，优选在约100-2000sccm范围内。
在一些情况下，也可以使用稀释气体流以提高均匀性，但不是必需的。惰性气体，如氮气、氦气、氖气、氩气、氙气及它们的结合可以用作稀释气体。考虑到成本，氮气和氩气是优选的稀释气体。稀释气体流量在约1sccm至1000sccm的范围内。因为压力必须在所需的范围内，所以在所有情况下气体流量取决于室的大小和泵送的能力，并且本领域的普通技术人员可以用常规的实验方法确定这些变化。
在本发明的另一个方面，提供了氧氮化硅的形成。将放置在室内的基底暴露给下述反应物，并且用下述方程概括CVD反应：
                     (2)
其中，硅前体是Si(NR1R2)4，R1或R2为H、C1-C6烷基、环烷基、F取代的烷基或者Si(NR1R2)4-xLx(X＝1、2或3)，其中L为H或Cl。
在方程(2)中，使用NH3和O3气体混合物，在低温下沉积氧氮化硅(SiOxNy)。除半导体应用之外，SiOxNy是光学应用的重要材料，这是因为SiOxNy具有在1.45(对SiO2来说)和2.0(对氮化硅来说)之间的可变折光系数。如方程(1)的反应所示，氨基硅烷或烷基酰胺基硅化合物中的Si-N键相当不稳定，在低温下与臭氧反应，这允许低温CVD方法在低于400℃下进行。在本发明的该方面，氨气(NH3)的气体流量在约10sccm至2000sccm的范围内，优选在约100至2000sccm的范围内。这种新方法可用于形成掺杂的或未掺杂的SiO2。该方法在IC制造中的应用包括，但不限于，前金属介电质(PMD)、浅槽隔离(STI)、槽形衬里和分隔器介电质。
在本发明的另一方面，可改变压力，以优化工艺使其适合于不同的应用。参考方程(1)和(2)，这些反应可在常压下进行，并获得良好结果，或者这些反应可在约1毫托(milliToor)至800托范围内进行。例如，为在非平面基底上获得改进的阶跃覆盖，反应可在减压下进行。可选择地，可在对阶跃覆盖要求不是最严格的PMD应用中，使用较高的压力。通常，压力越高，反应速率和最终的沉积速率越快。
本发明中使用的基底通常是硅。然而，可替代的基底，如SiC、SOI、平板、钨或铝可用于取代硅，并且在本发明的范围和精神之内。基底的选择取决于具体的应用。
可以在公知的沉积***如通常使用的CVD、PECVD、喷洒热解(spraypyrolysis)、电弧喷射沉积(arc jet deposition)或者ALD***10中进行本发明。参考图1，图1显示进行适合本发明方法的CVD***的简化截面图。硅晶片100放置在沉积室101内，并用晶片支撑体或夹盘102支撑。可以在低于或者接近常压下，进行该工艺。在过程室101中，用加热器将晶片100加热至沉积温度，加热器优选位于支撑体102内。对CVD工艺而言，通过经注入器110将稀释气体103引入室101中，建立加工压力。接着，使用半导体和薄膜工业中常用的气体输送方法，引入硅前体104和氧化剂105(如果要沉积SiOxNy，也包括NH3 106)气体。在靠近晶片处，输送反应物气体。反应物气体混合并反应，在晶片表面上形成所需的材料层。在经过获得目标膜厚度所需的一段适宜时间后，关闭硅前体和氧化剂/NH3气体流量，并优选输送稀释惰性气体至室内，以吹洗除去残留的反应物至排气装置(exhaust)112。在经过一段适宜的吹洗时间后，完成该过程，然后从过程室中移去晶片。
尽管本发明示例性的实施方案是CVD沉积，但此处所述的反应和方法也对用其它沉积技术沉积介电膜有利，其它沉积技术包括等离子体增强CVD(PECVD)、喷洒热解、电弧喷射或者阴极电弧喷洒沉积和旋涂玻璃(spin-on glass)(湿化学法)沉积。本发明也使用于原子层沉积(ALD)，其中可独立输送反应物。
已经根据专利法的要求详细而又具体地描述了本发明，在权利要求书中说明了专利特许证要求和需要保护的内容。

Claims (17)

1.一种在室内的基底上沉积介电层的方法，所述方法包括：
将基底暴露给反应物气体，所述反应物气体包括氧化剂气体和硅前体，
其中所述氧化剂气体包括臭氧，所述硅前体包括烷基酰胺基硅和氨基硅烷中的至少一种，其中当所述反应物气体组存在于所述室内时，所述室的温度在约20℃至400℃之间。
2.如权利要求1所述的方法，其中当所述反应物气体组存在于所述室内时，所述室内的压力在约1毫托至760托之间。
3.如权利要求1所述的方法，其中通过使反应物气体组流过所述室内的基底之上，将所述基底暴露给反应物气体。
4.如权利要求3所述的方法，其中所述硅前体气体的流量在约1sccm至1000sccm之间，臭氧流量在约10至2000sccm之间。
5.如权利要求4所述的方法，还包括结合所述反应物气体一起流动稀释气体。
6.如权利要求1所述的方法，其中所述反应物气体还包括氨。
7.一种在室内的基底上沉积氧氮化硅的方法，所述方法包括：
将基底暴露给所述反应物气体，所述反应物气体包括氧化剂气体、氨和硅前体，
其中所述氧化剂气体包括臭氧，所述硅前体包括烷基酰胺基硅和氨基硅烷中的至少一种，其中当所述反应物气体组存在于所述室内时，所述室的温度在约20℃至400℃之间。
8.如权利要求7所述的方法，其中所述反应物气体组存在于所述室内时，所述室内的压力在约1毫托至760托之间。
9.如权利要求8所述的方法，其中通过使反应物气体组流过所述室内的基底之上，将所述基底暴露给反应物气体。
10.如权利要求9所述的方法，其中硅前体气体的流量在约1sccm至1000sccm之间，臭氧流量在约10至2000sccm之间。
11.如权利要求10所述的方法，还包括结合所述反应物气体一起流动稀释气体。
12.如权利要求11所述的方法，其中所述稀释气体是惰性气体。
13.如权利要求12所述的方法其中所述惰性气体是氩气或氮气。
14.一种在室内的基底上沉积氧化硅的方法，所述方法包括：
使臭氧和硅前体在室内存在基底的情况下反应，其中所述室的温度在400℃，所述硅前体包括烷基酰胺基硅和氨基硅烷中的至少一种，所述氧化剂气体包括臭氧。
15.如权利要去14所述的方法，还包括使氨与氧化剂气体和硅前体一起反应。
16.如权利要去14所述的方法，还包括在室内存在基底的情况下反应氧化剂气体和硅前体的步骤中，使稀释气体流过所述室。
17.如权利要求14所述的方法，其中所述温度在20至400℃的范围内。
CN 03805832 2002-07-19 2003-07-15 使用氨基硅烷和臭氧的低温介电沉积 Pending CN1643674A (zh)

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