CN1937180A - 富硅氧化物的制造方法及半导体器件的制造方法 - Google Patents

富硅氧化物的制造方法及半导体器件的制造方法 Download PDF

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CN1937180A
CN1937180A CNA2006101001100A CN200610100110A CN1937180A CN 1937180 A CN1937180 A CN 1937180A CN A2006101001100 A CNA2006101001100 A CN A2006101001100A CN 200610100110 A CN200610100110 A CN 200610100110A CN 1937180 A CN1937180 A CN 1937180A
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silicon
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李正贤
房想奉
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Samsung Electronics Co Ltd
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Abstract

提供了一种用在非易失性存储器件中的富硅氧化物(SRO)的制造方法以及使用该SRO的半导体器件。所述制造SRO的方法包括如下步骤：向所述衬底上吸收不含氧的第一硅源气体并通过含氧反应气体和所述第一硅源气体之间的氧化反应形成SiO2层；以及通过不含氧的第二硅源气体和对应于所述第二硅源气体的反应气体之间的还原反应形成Si层。所述制造方法方便了SRO中O浓度的调节并提供了出色的台阶覆盖，于是允许制造高质量的半导体器件。

Description

富硅氧化物的制造方法及半导体器件的制造方法
技术领域
本发明涉及一种制造富硅氧化物(SRO)的方法，尤其涉及一种制造SRO以及使用该SRO的半导体器件的方法。
背景技术
使用SRO的电荷存储器件最近得到了关注。该电荷存储器件具有许多优点。充当电荷俘获层的SRO具有适当比例的Si和SiO2，于是和常规动态随机存取存储器(DRAM)相比提供了非常优异的电特性。具有高Si/O比的SRO在高于预定温度的温度下被退火，SRO中的Si和SiO2彼此分离。于是有可能形成与SiO2分开的Si点(Si dots)。曾经提出过利用由Si点形成技术产生的Si纳米晶体的存储器件(美国专利No.6690059)。
通常，能够通过化学气相淀积(CVD)或原子层淀积(ALD)形成SRO。CVD提供的台阶覆盖由于等离子体屏蔽效应而变差。由于用作硅源的诸如四乙氧基硅烷(tetra-ethoxy-silane，TEOS)的前体与用作氧化剂的H2O之间的置换反应，ALD使得调节氧(O)的量，即调节Si和O(Si/O比)之比困难。
发明内容
本发明提供了一种台阶覆盖优异并能够容易地调节硅浓度的制造富硅氧化物(SRO)的方法以及使用该SRO的半导体器件。
根据本发明的一方面，提供了一种在衬底上制造具有SiO2和富余Si(extra Si)的SRO的方法，包括如下步骤：向所述衬底上吸收不含氧的第一硅源气体并通过含氧反应气体和所述第一硅源气体之间的氧化反应形成SiO2层；以及通过不含氧的第二硅源气体和对应于所述第二硅源气体的反应气体之间的还原反应形成Si层。
根据本发明的另一方面，提供了一种制造半导体器件的方法，所述半导体器件包括在其两侧具有源极和漏极的硅有源层、覆盖所述有源层的具有SRO的栅极绝缘层、以及覆盖所述栅极绝缘层并在所述有源层上生成电场的栅极，其中制造SRO的方法包括如下步骤：向所述衬底上吸收不含氧的第一硅源气体并通过含氧反应气体和所述第一硅源气体之间的氧化反应形成SiO2层；以及通过不含氧的第二硅源气体和对应于所述第二硅源气体的反应气体之间的还原反应形成Si层。
以预定周期交替地重复所述SiO2层的形成和所述Si层的形成步骤，以通过氧化和还原反应形成交替的SiO2和Si层的多层堆体。所述SiO2层和Si层均可以具有单层或多层结构。在形成所述SiO2层的步骤期间供应氧等离子体，且在形成所述Si层的步骤期间供应氢等离子体。所述第一和第二硅源是同样的前体。所述第一和第二硅源可以是SiCl基的前体，比如六氯二硅烷(HCDS)。用于所述第一硅源的反应气体为H2O，用于所述第二硅源的反应气体为H2。
附图说明
通过参考附图详细描述其示范性实施例，本发明的以上和其他特征和益处将变得更加显见，附图中：
图1A和1B示出了根据本发明实施例制造富硅氧化物(SRO)的方法的原理；
图2为示出根据本发明实施例制造SRO的方法的流程图；
图3为利用四乙氧基硅烷(TEOS)和六氯二硅烷(hexa-chloro-di-silane，HCDS)作为源制造的薄膜的X射线光电子光谱(XPS)曲线；
图4为曲线图，示出了在相同的淀积条件下使用TEOS、SiH4和HCDS作为源100次循环后淀积的薄膜相对于淀积温度的厚度；
图5A-5C为示出根据本发明制造的SRO样品的电特性的曲线图；
图6A和6B示出了根据本发明制造的非易失性存储器件的堆叠结构；以及
图7A-7J示出了根据本发明实施例制造鳍型晶体管的方法的步骤。
具体实施方式
在根据本发明实施例的制造富硅氧化物(SRO)的方法中，如图1A和1B所示，使用原子层淀积(ALD)形成SiO2层和Si层。更具体地说，在前体被吸收到衬底上之后，将反应气体引入反应室内。然后，将高的RF功率施加到反应气体以生成等离子体。当反应气体是H2O时，生成氧等离子体。当反应气体是H2时，生成氢等离子体。在通过氧等离子体和氢等离子体把反应能量供应给前体时，在前体和反应气体之间发生氧化反应和还原反应，形成SiO2层和Si层。通过利用等离子体的ALD交替地堆叠SiO2层和Si层，形成具有多层结构的SRO。
在形成SRO之前可以在衬底上形成另一个材料层。还要理解的是，当称SRO在诸如衬底或其他堆叠结构的结构“上”时，它可以直接在该结构上，或者还可以存在中间层。例如，当把根据本发明的SRO用于非易失性存储器时，它充当着作为存储器的基本结构的晶体管的栅极绝缘层，可以在栅极绝缘层之下形成硅有源层。此外，以下将通过举例而非限制的方式给出堆叠次序或堆叠层数。
图2为示出根据本发明实施例使用ALD制造SRO的方法的流程图。
a)在将衬底载入ALD室后，供应第一Si源气体以将Si吸收到衬底上，然后将诸如Ar的吹扫气体引入ALD室中(步骤10到12)。
b)将诸如H2O的氧化剂供应到ALD室中以产生等离子体，并利用氧等离子体氧化被吸收到衬底上的Si源，以在衬底上形成SiO2层(步骤13)。
c)必要时有选择地重复步骤a)和b)超过一次，以形成多个具有原子层厚度的SiO2层。
d)供应Si源以将Si源吸收到覆盖衬底的SiO2层上，然后利用Ar作为吹扫气体进行吹扫(步骤14和15)。
e)将H2供应到反应室中以产生等离子体，并在SiO2层上形成Si层(步骤16)。
f)必要时有选择地重复步骤d)和e)超过一次，以形成多个具有原子层厚度的Si层。
g)必要时有选择地重复步骤a)到f)超过一次。
重复上述工序以调节Si/O比，如有必要可以在衬底上重复堆叠多个SiO2层和Si层。
在当前实施例中，在25℃的温度、约10Torr以上的压强下从蒸发器向反应室供应硅源气体。该硅源可以是六氯二硅烷(HCDS)。利用等离子体增强的原子层淀积(PEALD)执行该工艺。
图3为使用本发明中所用的常规四乙氧基硅烷(TEOS)和HCDS制造的薄膜的X射线光电子光谱(XPS)曲线。从图3明显看出，利用HCDS获得的薄膜比利用TEOS源获得的薄膜展现出更清晰的Si峰。
图4为曲线图，示出了在相同的淀积条件下使用TEOS、SiH4和HCDS作为源100次循环后淀积的薄膜相对于淀积温度的厚度。如图4所明显示出的，因为利用HCDS获得的薄膜具有类似于利用TEOS源获得的薄膜的淀积速率，所以能够将HCDS用于典型的半导体工艺。
图5A-5C为曲线图，示出了根据本发明制造的SRO样品#1、#2和#3的电特性。
样品#1是通过以1∶6的堆叠比在10次循环中淀积Si和SiO2形成的。样品#2是通过以2∶12的堆叠比在5次循环中淀积Si和SiO2形成的。样品#3是通过以4∶24的堆叠比在3次循环中淀积Si和SiO2形成的。
如从图5A-5C所明显看出的，通过在10次循环中淀积由单个Si层和六个SiO2层构成的单位堆叠结构而形成的SRO样品1表现出最佳的电压-电容特性。作为在10V的应力电压下的测量结果，本发明能够提供高于3.2V的存储窗口。
本发明的制造方法使用ALD获得具有最佳台阶覆盖的SRO。该制造方法提供了优异的台阶覆盖和出众的电气性能，同时使得调节SRO中所含的O浓度容易。
图6A和6B示出了根据本发明制造的非易失性存储器件的堆叠结构。
参考图6A，首先，在p衬底上形成栅极氧化物层并在栅极氧化物层上形成多晶Si栅极。如在典型SRO存储器中那样，栅极氧化物层具有三层结构，包括最下的隧穿氧化物层、最上的控制氧化物层和中间的SRO层。
本发明的新颖方面在于SRO层，其由交替的SiO2和Si层的重复堆体构成。每个堆体包括至少一个原子层厚度的SiO2层和Si层。
具有上述结构的晶体管能够使用能够从常规方法推论得到的SRO制造技术容易地制造。
图6B为包括典型SRO的晶体管的纵向剖面图。图6B中所示的晶体管具有鳍形结构，其中有源层在衬底上垂直地立起。如上所述，晶体管包括：包括多层结构的SRO的栅极氧化物层以及覆盖栅极氧化物层的栅极。与鳍型晶体管相关的背景技术能够在韩国专利申请No.2004-0008598中找到。现在将参考图7A-7J简单描述制造鳍型晶体管的方法。将不给出公知工艺的详细解释。为了清晰起见放大了层和区域的厚度且仅示出了主要部分。
参考图7A，制备绝缘体上硅(SOI)衬底10，其具有下部Si衬底10a、中间绝缘层10b和上部Si衬底10c。如图7B所示，在上部Si衬底10c上形成第一光致抗蚀剂掩模11，用于形成鳍型晶体管的焊盘。参考图7C，未被第一光致抗蚀剂掩模11覆盖的上部Si衬底10c的暴露部分被干法蚀刻至预定深度，然后剥离第一光致抗蚀剂掩模11，由此获得在上部Si衬底10c的两侧突出的焊盘10d。如图7D所示，形成具有H形状的第二光致抗蚀剂图案12，覆盖两个焊盘10d，并构图焊盘10d之间的薄鳍形有源层。可以使用电子束光刻法构图第二光致抗蚀剂掩模。参考图7E，未被第二光致抗蚀剂掩模12覆盖的上部Si衬底10c的暴露部分被蚀刻，以获得鳍形有源层10e，然后使用剥离剂去除第二光致抗蚀剂掩模12。
参考图7F，在焊盘10d、有源层10e和绝缘层10b的暴露部分上形成栅极绝缘层13，栅极绝缘层13包括通过根据本发明的SRO制造工艺形成的SRO层和控制氧化物层以及分别在绝缘层10b上方和下方的隧穿氧化物层。更具体地说，在形成SRO层之前使用诸如淀积技术的常规技术形成SiO2隧穿氧化物层。然后，使用常规淀积技术在SRO层上形成SiO2控制氧化物层。
参考图7G，在所得的堆叠结构上淀积将被用作栅极14的材料的多晶Si。如图7H所示，形成第三光致抗蚀剂图案15以便构图栅极14。参考图7I，未被第三光致抗蚀剂掩模15覆盖的一部分所得结构被蚀刻，以形成栅极14，随后使用剥离剂除去第三光致抗蚀剂掩模15。如图7J所示，执行离子注入，以便使未被栅极14和焊盘10d覆盖的有源层10e具有导电性。
根据形成SRO的方法，使用含氧的源材料形成SiO2层和Si层，于是方便了O浓度的调节。通过调节形成于堆体中的分立的SiO2和Si层的数量和堆叠循环的数量容易调节O浓度。
利用表现出出色台阶覆盖的ALD的制造方法适于应用到具有复杂表面轮廓的结构，例如鳍晶体管，尤其是作为电荷储存存储器的非易失性存储器件。
尽管已经参考其示范性实施例特别展示和描述了本发明，但是仅以举例的方式，而非是限制的方式给出实施例。本发明不局限于以上描述和示出的结构和设置。亦即，本领域的普通技术人员应当理解，在不背离权利要求所述的本发明的精神和范围的情况下，可以在其中做出许多形式和细节上的变化。

Claims (20)

1.一种在衬底上制造具有SiO2和富余Si的富硅氧化物的方法，所述方法包括：
向所述衬底上吸收不含氧的第一硅源气体并通过含氧反应气体和所述第一硅源气体之间的氧化反应形成SiO2层；以及
通过不含氧的第二硅源气体和对应于所述第二硅源气体的反应气体之间的还原反应形成Si层。
2.如权利要求1所述的方法，其中以预定周期交替地重复所述SiO2层的形成和所述Si层的形成，以通过氧化和还原反应形成交替的SiO2和Si层的多层堆体。
3.如权利要求1所述的方法，其中所述SiO2层和Si层均具有多层结构。
4.如权利要求1所述的方法，其中在形成所述SiO2层期间供应氧等离子体，且在形成所述Si层期间供应氢等离子体。
5.如权利要求1所述的方法，其中所述第一和第二硅源是同样的前体。
6.如权利要求1所述的方法，其中所述第一和第二硅源为SiCl基的前体。
7.如权利要求1所述的方法，其中所述第一和第二硅源为六氯二硅烷。
8.如权利要求6所述的方法，其中用于所述第一硅源的反应气体为H2O，用于所述第二硅源的反应气体为H2。
9.如权利要求3所述的方法，其中所述第一和第二硅源为六氯二硅烷。
10.如权利要求9所述的方法，其中用于所述第一硅源的反应气体为H2O，用于所述第二硅源的反应气体为H2。
11.一种制造半导体器件的方法，所述半导体器件包括在其两侧具有源极和漏极的硅有源层、覆盖所述有源层的具有富硅氧化物的栅极绝缘层、以及覆盖所述栅极绝缘层并在所述有源层上生成电场的栅极，其中制造所述富硅氧化物的方法包括：
向所述衬底上吸收不合氧的第一硅源气体并通过含氧反应气体和所述第一硅源气体之间的氧化反应形成SiO2层；以及
通过不含氧的第二硅源气体和对应于所述第二硅源气体的反应气体之间的还原反应形成Si层。
12.如权利要求11所述的方法，其中以预定周期交替地重复所述SiO2层的形成和所述Si层的形成，以通过氧化和还原反应形成交替的SiO2和Si层的多层堆体。
13.如权利要求11所述的方法，其中所述SiO2层和Si层均具有多层结构。
14.如权利要求11所述的方法，其中在形成所述SiO2层期间供应氧等离子体，且在形成所述Si层期间供应氢等离子体。
15.如权利要求11所述的方法，其中所述第一和第二硅源是同样的前体。
16.如权利要求11所述的方法，其中所述第一和第二硅源为SiCl基的前体。
17.如权利要求11所述的方法，其中所述第一和第二硅源为六氯二硅烷。
18.如权利要求16所述的方法，其中用于所述第一硅源的反应气体为H2O，用于所述第二硅源的反应气体为H2。
19.如权利要求13所述的方法，其中所述第一和第二硅源为六氯二硅烷。
20.如权利要求19所述的方法，其中用于所述第一硅源的反应气体为H2O，用于所述第二硅源的反应气体为H2。
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