CN1431716A - 半导体装置及半导体装置的制造方法 - Google Patents
半导体装置及半导体装置的制造方法 Download PDFInfo
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- CN1431716A CN1431716A CN03101048A CN03101048A CN1431716A CN 1431716 A CN1431716 A CN 1431716A CN 03101048 A CN03101048 A CN 03101048A CN 03101048 A CN03101048 A CN 03101048A CN 1431716 A CN1431716 A CN 1431716A
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Abstract
提供一种半导体装置及其制造方法,可以提高其特性和可靠性。该半导体装置,包括:半导体衬底;在该半导体衬底上形成的,包含含有金属元素的硅氧化膜的栅绝缘膜;以及在上述栅绝缘膜上形成的电极。上述含有金属元素的硅氧化膜具有下表面附近的第一区、上表面附近的第二区、以及第一区和第二区之间的第三区;上述硅氧化膜中含有的金属元素在厚度方向上的浓度分布在上述第三区中有最大点。
Description
技术领域
本发明涉及半导体装置及半导体装置的制造方法,尤其涉及半导体装置中采用的绝缘膜。
背景技术
随着MOSFET的微细化,要求栅绝缘膜的薄膜化。现在使用的硅氧化膜和硅氮氧化膜,通过增加直隧道电流,可达到约2nm的薄膜化的极限。
已提出含有金属的硅氧化膜(也称作金属硅酸盐膜或硅酸盐膜)在栅绝缘膜中的应用。该金属硅酸盐膜的介电率比硅氧化膜高,且结晶化温度较高,所以与多晶硅(多晶SiGe)栅电极工艺的整合性高。
为了抑制来自栅电极的硼扩散,提出了含氮的氮氧化金属硅膜(日本特开平2000-49349)。但是,不能得到具有良好的界面特性的氮氧化金属硅膜。另外,由于金属氮化物是导电的,泄露电流多,电荷捕获密度也高。而且,在栅电极界面上形成金属硅化物,损害绝缘特性。
作为金属硅酸盐膜的形成方法,有采用有机硅烷的CVD(化学汽相淀积)法。有机硅烷中可以使用四乙基原硅酸盐(Si(OC2H5)4∶TEOS)。由于TEOS的分解温度高,采用热CVD法时必须是700℃以上的温度。另外,由于在较低的温度下形成膜,可采用与TEOS同时使用臭氧(O3)的方法,或等离子体CVD法。
但是,使用臭氧或等离子体时,会在膜形成气氛中生成氧根或氧离子等的氧的活性种。由于活性的氧反应性高,会产生使基底氧化的问题。而使用等离子体时,会产生因等离子体损伤导致基底被损伤的问题。
作为与金属硅酸盐膜的形成方法有关的公知技术,有以下的情况。
在日本特开平5-239650号公报中,公开了在以硅氧烷为源气体的CVD法中,添加钛族元素的醇盐或烷基胺化合物的方法。但是,由于使用了臭氧或等离子体,基本上是使用氧的活性种的方法。
日本特开6-160657号公报也是使用臭氧的方法,是使用氧的活性种的方法。
在日本特开平11-111715号公报中公开了向源气体添加通过使具有烷氧基的化合物热分解生成的生成物的方法。但是,没有记载与硅源和金属源混合有关的内容。
在日本特开平5-226608号公报中公开了作为金属硅酸盐膜中含有的金属,使用钛的内容。但是,存在含有钛的金属硅酸盐膜难以得到良好的特性,难以在半导体装置上适用的问题。
发明内容
如上所述,现在存在不能得到具有优良特性的金属硅酸盐膜的问题,和对基底有恶劣影响的问题。因此,难以得到特性和可靠性优良的半导体装置。
本发明正是鉴于上述现有的问题而提出的,目的在于在具有含有金属元素的硅氧化膜的半导体装置中提高其特性和可靠性。
根据本发明的半导体装置,包括:
半导体衬底;
在上述半导体衬底上形成的,包含含有金属元素的硅氧化膜的栅绝缘膜;以及
在上述栅绝缘膜上形成的电极,
上述含有金属元素的硅氧化膜具有下表面附近的第一区、上表面附近的第二区、以及第一区和第二区之间的第三区;
上述硅氧化膜中含有的金属元素在厚度方向上的浓度分布,在上述第三区中有最大点。
根据本发明的半导体装置的制造方法,包括下列步骤:
在半导体衬底上形成含有金属元素的非晶态硅膜的步骤,该非晶态硅膜具有下表面附近的第一区、上表面附近的第二区、以及第一区和第二区之间的第三区,且金属元素在厚度方向上的浓度分布在第一区或第三区中有最大点;以及
使上述含有金属元素的非晶态硅膜氧化,形成含有上述金属元素的硅氧化膜的步骤。
根据本发明的半导体装置的制造方法,包括下列步骤:
向保持衬底的容器供给含有硅的有机化合物,和含有选自Zr、Hf、Al和La的金属元素的有机化合物的步骤;以及
用氧的活性种通过热CVD,在上述衬底上形成含有上述金属元素的硅氧化膜的步骤。
根据本发明的半导体装置的制造方法,包括通过CVD在半导体衬底上形成含金属元素的硅氧化膜的步骤,其特征在于还包括:
向保持半导体衬底的容器开始供给含有硅的有机化合物的步骤;
在开始供给上述含有硅的有机化合物之后,开始向上述容器供给含有金属元素的有机化合物的步骤;以及
增加向上述容器供给的上述含有金属元素的有机化合物的供给量的步骤。
附图说明
图1是示意性地展示根据本发明的实施方式1的金属硅酸盐膜中的金属元素在膜厚方向上的浓度分布的图;
图2是示意性地展示根据本发明的实施方式1的金属硅酸盐膜中的金属元素和氮在膜厚方向上的浓度分布的图;
图3是展示根据本发明的实施方式1的半导体装置的制造方法的剖面图;
图4是展示根据本发明的实施方式2的CVD装置的结构的图;
图5是展示根据本发明的实施方式2的金属硅酸盐膜的成膜速度与衬底温度的关系的图;
图6是展示根据本发明的实施方式2的比较例的金属硅酸盐膜的成膜速度与衬底温度的关系的图;
图7展示根据本发明的实施方式2的、HTB和TEOS的流量变化时的金属硅酸盐膜的测量结果的图;
图8是展示根据本发明的实施方式2的半导体装置的结构的剖面图;
图9是展示根据本发明的实施方式2的界面位错密度的减少效果的图;
图10是展示根据本发明的实施方式3的气体供给系统的图。
具体实施方式
下面,参照附图说明本发明的实施方式。(实施方式1)
下面,参照附图说明本发明的实施方式1。
图1是在根据实施方式1的MIS(MOS)型场效应晶体管中,作为栅绝缘膜使用的金属硅酸盐膜(含硅的硅氧化膜)中的金属元素在膜厚度方向上的浓度分布的示意图。在此,作为金属元素使用Zr(锆),但也可以向硅氧化膜添加比硅氧化膜介电率高的元素如Hf(铪)、Al(铝)、La(镧)等,可得到与Zr的场合同样的效果。
如图1所示,在金属硅酸盐膜的中央附近Zr的浓度最大。另外,浓度峰不必一定在金属硅酸盐膜的中央,也可以是在靠近金属硅酸盐膜下表面的区域(金属硅酸盐膜与硅衬底的界面附近的区域)、和靠近金属硅酸盐膜上表面的区域(金属硅酸盐膜与栅电极的界面附近的区域)夹着的区域(内部区域)。
通过这样构成,可以得到特性和可靠性优良的MIS型场效应晶体管。即,在半导体衬底侧的界面上,界面的固定电荷密度低,可抑制沟道迁移率的降低。另外,栅电极侧的界面上,作为栅电极使用多晶Si或多晶SiGe时,可抑制界面处的硅化物反应,可防止可靠性的降低。
图2展示了对上述构成,进而在栅电极侧导入氮(N)时,Zr和N的浓度分布的示意图。如图2所示,栅电极侧的界面附近N浓度最大。
这样地,由于在金属硅酸盐膜的上表面侧有陡峭的N浓度的峰,作为栅电极使用多晶Si或多晶SiGe时,可有效地抑制作为掺杂剂使用的硼等杂质向栅绝缘膜中甚至向半导体衬底扩散。另外,由于抑制了Zr与氮的反应,可以抑制泄露电流的增加和可靠性的下降。而且,由于在上表面侧存在氮,可以抑制衬底侧界面附近的固定电荷密度的增加,可以抑制沟道迁移率的降低。
另外,金属硅酸盐膜中含有的金属元素,不必一定是一种,也可以含有Zr、Hf、Al及La中的两种以上元素,
下面,参照图3(a)~3(e)说明本实施方式的制造方法。
首先,如图3(a)所示,准备常用的设置了元件分离区(图中未示出)的半导体衬底11。
然后,如图3(b)所示,在半导体衬底11的表面上堆积约2nm的含有Zr的非晶态硅膜12。该非晶态硅膜12可通过例如使用ZrCl4、SiH4和H2的LPVCD法形成。典型的成膜条件为500℃、0.5乇。控制ZrCl4和SiH4的流量比,可以使含有Zr的非晶态硅膜12中的Zr浓度的峰在膜厚方向的中央附近。
非晶态硅膜12也可以通过采用Zr靶和Si靶的溅射法堆积形成,此时,控制Zr靶和Si靶的功率比,可以使Zr浓度的峰在膜厚方向的中央附近。
另外,Zr浓度的峰不必一定在非晶态硅膜12的中央,也可以是夹在非晶态硅膜12的下表面附近的区域与上面附近的区域之间的区域(内部区域)。另外,Zr浓度的峰也可以在非晶态硅膜12的下表面附近的区域中。
然后,如图3(C)所示,使衬底温度为400℃,用O2等离子体氧化法使含有Zr的非晶态硅膜12氧化形成Zr硅酸盐膜(含有Zr的硅氧化膜)13。Zr硅酸盐膜13反映非晶态硅膜12的Zr浓度分布,具有图1所示的Zr浓度分布。在此,通过使用可以在较低温度下氧化的等离子体氧化法,可以抑制氧化时的结晶化,防止与结晶化伴随的表面不光洁。
另外,在Zr的浓度峰位于非晶态硅膜12的下表面附近的区域的场合下也是,由于在上述氧化步骤中半导体衬底11的表面区域被氧化,Zr的浓度峰位于Zr硅酸盐膜13的内部。
然后,如图3(d)所示,使晶片温度为400℃,用N2等离子体氮化法使Zr硅酸盐膜13的表面氮化,形成表面被氮化的Zr硅酸盐膜14。该表面被氮化的Zr硅酸盐膜14成为图2所示的氮浓度分布。
然后,如图3(e)所示,用LPCVD法堆积约150nm的作为栅电极的多晶SiGe膜(也可以是多晶Si膜)15。在此,在堆积多晶SiGe膜15之前,进行例如900℃、10秒的退火,使导入的氮稳定化。
之后,经过光刻步骤,栅电极蚀刻步骤,离子注入步骤,活性化退火步骤等,形成MIS型场效应晶体管(图中未示出)。最后,经过布线步骤,完成半导体装置(图中未示出)。
如上所述,根据本实施方式,通过使金属硅酸盐膜中的金属元素的浓度分布最优化,可获得良好的界面特性,同时抑制栅电极界面的反应。另外,通过氮的浓度分布最优化,可以抑制金属硅酸盐膜中的捕获物的增加,同时可以抑制来自栅电极的杂质的扩散。因此,可以实现高性能且可靠性高的半导体装置。
另外,通过用Zr、Hf、Al或La作为金属元素,可以增加金属硅酸盐膜的有效介电率。因此,可以用物理上膜厚厚的金属硅酸盐膜作为栅绝缘膜,可以实现高性能且可靠性高的半导体装置。
另外,根据本实施方式,通过金属和硅的二元堆积形成非晶态硅膜,可以使组成的控制变得容易,可以以低成本制造高性能的半导体装置。另外,抑制了部分的金属氧化物结晶的形成,可以实现特性偏差小的半导体装置。而且,通过与金属元素独立地导入氮,可以容易地实现最优的膜组成。
另外,通过使用金属源和硅源的CVD法形成非晶态硅膜,在例如局部有凹凸的半导体表面上也可以均匀地形成膜,可以实现可靠性高的半导体装置。另外,通过在金属源中使用金属元素的卤化物,硅源中使用硅的氢化物,可以在确保极薄膜的控制性的较低温度下形成膜,可以提高生产率。
另外,通过用O2等离子体氧化等,用活性的氧化种对非晶态硅膜氧化,可以抑制金属硅酸盐膜的多晶化。而且,通过用等离子体氮化金属硅酸盐膜的表面,可以在低温下向金属硅酸盐膜导入具有陡峭的浓度分布的氮。(实施方式2)
下面,参照附图说明本发明的实施方式2。本实施方式中,不用氧的活性种,而是通过热CVD法形成金属硅酸盐膜,气体源中使用含硅的有机化合物和含金属元素(Zr、Hf、Al或La)的有机化合物。(实施方式2-A)
本实施方式是用四乙基原硅酸盐膜(Si(OC2H5)4∶TEOS)和四叔丁氧基锆(Zr(Ot-C4H9)4∶ZTB),通过热CVD法堆积金属硅酸盐膜的例子。
图4是本实施方式中使用的LPCVD装置的一例。下面,参照图4说明制造方法。
首先,准备8英寸硅衬底,利用用纯水稀释后的氢氟酸,除去在硅衬底表面上形成的自然氧化膜。在稀氢氟酸处理后,把硅衬底103搬送到在反应容器101内设置的隔板104上。并用真空泵从反应容器101中排气。
反应容器101内的压力到达10-2乇以下后,把借助于质流控制器124、125把流量设定到300sccm的Ar气导入反应容器内。然后,通过与压力计108连动的压力调整阀106把反应容器101内的压力控制到10乇。反应容器101内的压力稳定后,用衬底加热器105开始加热衬底103。用与隔板104相接地配置的热电偶和温度调节器(图中未示出) 把衬底103的温度控制到595℃。
衬底温度稳定后,用质流控制器123把氧气流量控制到200SCCM,通过阀143,不通过反应容器101,流通氧气(O2)。另外,用质流控制器121和122分别把氩气控制到100Sum,向原料容器111和112流入氩气,开始原料的发泡。这些气体也可以通过阀141和142,不通过反应容器101流动。
分别向原料容器111内填充TEOS,向原料容器112内填充ZTB。原料容器111和112都控制到70℃。另外,用压力计151、152和压力调整阀131、132把原料容器111和112内的压力分别调整到100乇。在这样的条件下,推定TEOS的流量为56sccm、ZTB的流量为1.6sccm。
由于原料的温度为70℃,比室温高,把向反应容器101输送原料气体的配管和阀收存在烘箱内加热到200℃左右,防止凝结。另外,喷射头102也用油加热到200℃左右,防止喷射头内的原料凝结。至此为开始成膜的前阶段。
通过同时把阀141、142和143切换成阀144、145和146,通过喷射头向反应容器101内导入预先流入的氧气和原料气体,开始形成膜。成膜时间为10分钟。
10分钟后,通过把阀144、145和146切换成阀141、142和143,停止向反应容器内供应TEOS、ZTB和氧气。停止供气后,立即停止向衬底加热器105的通电,使衬底103冷却。衬底温度降到200℃后从反应容器101中取出衬底103。
用椭圆计测量这样形成的薄膜的厚度,发现形成了237nm厚的Zr硅酸盐膜。另外,在衬底温度为550℃、570℃时进行同样的膜形成。除衬底温度变化以外,与上述条件相同。结果,550℃下为191nm,570℃下为176nm。图5展示了把这些数据变换成成膜速度后的情况。
为了比较,只用TEOS进行膜的形成。形成膜的顺序与上述完全相同,但不进行ZTB的供给。衬底温度为570℃和590℃。结果,衬底温度为570℃时膜厚为0.7nm,在590℃时为0.9nm。图6展示了把这些数据变换成成膜速度后的情况。
另外,只用ZTB在595℃下形成膜的结果为,成膜速度0.1nm/分钟以下。
由上述这些结果可知,仅在同时供给TEOS和ETB这两者时,成膜速度增加。
如上所述,通过同时供给占TEOS流量(供给量)的1/10以下的ZTB,与只用TEOS的场合相比,可以得到100倍以上的成膜速度,可以以实用的成膜速度形成金属硅酸盐膜。
另外,即使不用对下层衬底造成不良影响的等离子体或臭氧等的化学上活跃的氧,也可以在600℃以下的较低温度下用热CVD法形成金属硅酸盐膜。这是因为ZTB促进TEOS的分解反应。
用荧光X射线测量分析Zr硅酸盐膜中含有的Zr原子数对Zr原子数和Si原子数的和的比率。上述比率用Zr/(Zr+Si)表示。结果,同时供给ZTB和TEOS进行膜的形成的试料为Zr/(Zr+Si)=12~30%。另外,已确认通过控制ZTB和TEOS的流量,可以把Zr/(Zr+Si)控制在5~30%的范围内。
如果Zr/(Zr+Si)太大,得到的Zr硅酸盐膜的介电率高。换言之,通过控制Zr和Si的比率,可以控制Zr硅酸盐膜的介电率。这一点在应用到半导体装置上时很重要。即,在层间绝缘膜和间隔膜的介电率小为优选的场合,调整ZTB和TEOS的供给量使Zr/(Zr+Si)减小。另一方面,在诸如栅绝缘膜之类的介电率大为优选的场合,调整ZTB和TEOS的供给量使Zr/(Zr+Si)增大。(实施方式2-B)
本实施方式是用TEOS和四叔丁氧基铪(Hf(Ot-C4H9)4∶HTB),通过热CVD法堆积金属硅酸盐膜的例子。本实施方式与上述实施方式2-A一样,使用图4所示的LPVCD装置。
首先,准备8英寸硅衬底,利用用纯水稀释后的氢氟酸,除去在硅衬底表面上形成的自然氧化膜。在稀氢氟酸处理后,把硅衬底103搬送到在反应容器101内设置的隔板104上。并用真空泵对反应容器101中排气。
反应容器101内的压力到达10-2乇以下后,把借助于质流控制器124、125把流量设定到300sccm的Ar气导入反应容器内。然后,通过与压力计108连动的压力调整阀106把反应容器101内的压力控制到10乇。反应容器101内的压力稳定后,用衬底加热器105开始加热衬底103。用与隔板104相接地配置的热电偶和温度调节器(图中未示出)把衬底103的温度控制到595℃。
衬底温度稳定后,用质流控制器123把氧气流量控制到200sccm,通过阀143,不通过反应容器101流通氧气(O2)。另外,用质流控制器121和122分别把氩气控制到100sccm,向原料容器111和112流入氩气,开始原料的发泡。这些气体也可以分别通过阀141和142,不通过反应容器101流动。
分别向原料容器111内填充TEOS,向原料容器112内填充HTB。反料容器111和112分别控制到40℃和45℃。另外,用压力计151、152和压力调整阀131、132把原料容器111和112内的压力分别调整到100乇。在这样的条件下,推定TEOS的流量为12sccm、HTB的流量为0.31sccm。
由于原料的温度比室温高,把向反应容器101输送原料气体的配管和阀收存在烘箱内加热到200℃左右,防止凝结。另外,喷射头102也用油加热到200℃左右,防止喷射头内的原料凝结。至此为开始成膜的前阶段。
通过同时把阀141、142和143切换成阀144、145和146,通过喷射头向反应容器101内导入预先流入的氧气和原料气体,开始形成膜。成膜时间为10分钟。
10分钟后,通过把阀144、145和146切换成阀141、142和143,停止向反应容器内供应TEOS、HTB和氧气。停止供气后,立即停止向衬底加热器105的通电,使衬底103冷却。衬底温度降到200℃后从反应容器103中取出衬底103。
用椭圆计测量这样形成的薄膜的厚度,发现形成了40nm厚的Hf硅酸盐膜。
为了比较,只用TEOS进行膜的形成。形成膜的顺序与上述完全相同,但不进行HTB的供给。膜厚为0nm。认为没形成金属硅酸盐膜。
另外,只用HTB在570℃下形成膜的结果为,成膜速度0.1nm/分钟以下。
由上述这些结果可知,仅在同时供给TEOS和HTB这两者时,成膜速度增加。
如上所述,通过同时供给占TEOS流量(供给量)的1/10以下的HTB,与只用TEOS的场合相比,可以大幅度增加成膜速度,可以以实用的成膜速度形成金属硅酸盐膜。
另外,即使不用对下层衬底造成不良影响的等离子体或臭氧等的化学上活跃的氧,也可以在600℃以下的较低温度下用热CVD法形成金属硅酸盐膜。这是因为HTB促进TEOS的分解反应。
用荧光X射线测量分析Hf硅酸盐膜中含有的Hf原子数对Hf原子数和Si原子数的和的比率。上述比率用Hf/(Hf+Si)表示。结果,同时供给HTB和TEOS进行膜的形成的试料为Hf/(Hf+Si)=23%。另外,已确认通过控制HTB和TEOS的流量,可以把Hf/(Hf+Si)控制在5~30%的范围内。
如果Hf/(Hf+Si)太大,得到的Hf硅酸盐膜的介电率高。换言之,通过控制Hf和Si的比率,可以控制Hf硅酸盐膜的介电率。这一点在应用到半导体装置上时很重要。即,在层间绝缘膜和间隔膜的介电率小为优选的场合,调整HTB和TEOS的供给量使Hf/(Hf+Si)减小。另一方面,在诸如栅绝缘膜之类的介电率大为优选的场合,调整HTB和TEOS的供给量使Hf/(Hf+Si)增大。
图7示出本实施方式中进行成膜的结果,衬底温度都是570℃,反应室内的压力为1乇,成膜时间为10分钟。(实施方式2-C)
本实施方式涉及具有用实施方式2-B的方法形成的金属硅酸盐膜的MOS电容器。
如图8所示,在n型硅衬底21上用实施方式2-B的方法形成4nm厚的金属硅酸盐膜22。通过改变成膜时间进行膜厚的控制。形成的金属硅酸盐膜22用荧光X射线测量确认,Hf/(Hf+Si)为10%。而且,在金属硅酸盐膜22上形成铂电极23。铂电极23通过遮蔽掩模用溅射法形成。
通过电容-电压法(C-V法)对由此制作的MOS电容器测量界面位错密度。结果,硅的带隙中形成的界面位错密度的最低值为2×1011cm-2eV-1。
为了比较,通过采用TEOS和氧的等离子体CVD法形成金属硅酸盐膜22。使衬底温度为400℃,采用13.56MHz的RF等离子体。膜厚为4nm。电极23上采用通过溅射形成的铂。这样形成的MOS电容器的界面位错密度的测定结果为1×1013cm-2eV-1。
作为另一比较例,通过采用TEOS-O3的热CVD法形成金属硅酸盐膜22,制作与前面相同的MOS电容器。用热壁型CVD装置在常压、400℃下形成金属硅酸盐膜22。膜厚为4nm。上部电极23是铂。用该MOS电容器测得的结果为界面位错密度5×1012cm-2eV-1。
图9汇总了上述各测量结果。
用等离子体CVD法形成金属硅酸盐膜时,界面位错密度高,因为在形成金属硅酸盐膜时等离子体会对硅衬底表面造成损伤。用使用TEOS-O3的热CVD法形成金属硅酸盐膜时,界面位错密度高,因为O3的化学反应性强,硅衬底表面不能维持良好的状态。
与此不同,由于本实施方式中不使用氧的活性种,可以形成缺陷少的氧化膜/硅表面。结果,得到低的界面位错密度。
如上所述,根据本实施方式,通过硅源和金属源的相互作用,促进源气体的分解。因此,即使在600℃以下的低温下,不用氧的活性种,也可以用热CVD法形成良好质量的金属硅酸盐膜。而且,由于不用氧的活性种,可以在金属硅酸盐膜和半导体衬底之间的界面上得到优良的界面特性。
另外,作为金属元素,除了上述Zr和Hf以外,还可以用Al或La。通过使用这些金属元素,可以增加金属硅酸盐膜的有效介电率。因此,可以用物理上膜厚厚的金属硅酸盐膜作为栅绝缘膜,可以实现高性能且可靠性高的半导体装置。另外,金属硅酸盐膜中含有的金属元素,不必一定是一种,也可以含有Zr、Hf、Al及La中的两种以上元素,可以得到同样的效果。
另外,作为硅源,可使用含有硅的有机化合物;作为金属源,可使用含有Zr、Hf、Al及La中的至少一种金属元素的有机化合物。
更具体地,作为含有硅的有机化合物,可优选使用TEOS等硅的烷氧基化合物。而含有金属元素的有机化合物可优选使用由(M(Ot-C4H9)4,其中M为Zr、Hf、Al及La)等的金属元素的烷氧基化合物。这些化合物的蒸气压高,所以CVD的控制性高。结果,可以形成膜厚均匀和组成控制性优良的金属硅酸盐膜。
另外,如果向反应容器供给的金属源的流量(供给量)比硅源的流量(供给量)的1/10大,则难以得到金属硅酸盐膜的成膜速度增大效果。但在1/10以下可以使成膜速度大幅度增加。
另外,若金属硅酸盐膜中含有的金属元素的原子数为NM、硅的原子数为NSi,优选地,
0<NM/(NM+NSi)<0.5。因为若金属元素的比率太高,则金属硅酸盐膜热不稳定,尤其是比率在0.5以上时,这种倾加更加显著。(实施方式3)
下面,参照附图说明本发明的实施方式3。本实施方式涉及使金属硅酸盐膜中含有的金属元素(Zr、Hf、Al或La)具有浓度分布的方法。
图10展示了用例如实施方式2说明的CVD装置形成金属硅酸盐膜时的气体供给系统。在此,硅源用TEOS,金属源用ZTB(或HTB)。另外,基本的成膜条件等与实施方式2相同,在此省略说明。
首先,开始向收存硅衬底的反应容器内供给TEOS。TEOS的供给稳定后,开始ZTB的供给,慢慢地增加ZTB的供给量。之后,保持ZTB的供给量恒定,经过预定时间后,慢慢地减少ZTB的供给量。然后,停止ZTB的供给,并停止TEOS的供给。这样地,在硅衬底上形成金属硅酸盐膜。而且,用氮等离子体使金属硅酸盐膜的表面氮化。
这样地得到的金属硅酸盐膜中,金属元素和氮的浓度分布成为如实施方式1所示的图2那样。因此,通过削减图3(a)~图3(e)中说明的步骤,可以得到具有与实施方式1所述的相同的效果的半导体装置。
另外,硅源和金属源除了TEOS和ZTB之外,也可以同样地适用实施方式2中详述的情况。因此,与例如实施方式2同样地,通过采用不用氧的活性种的热CVD法,可以得到具有与实施方式2所述的相同的效果的半导体装置。
如上所述,根据本实施方式,可以使金属硅酸盐膜中的金属元素和氮的浓度分布最佳化,可以实现高性能且可靠性高的半导体装置。另外,通过采用使用氧的活性种的热CVD法可以实现更高性能且可靠性高的半导体装置。
以上说明了本发明的实施方式,但本发明不限于上述实施方式,在不脱离其主要的构思的前提下可以进行种种变更。而且,上述各实施方式中包含了各个阶段的发明,可以通过公开的构成要件适当组合而得到各种发明。例如,即使从公开的构成要件中删除某一构成要件,只要能得到预定的效果,就可以作为一个发明抽出来。
根据本发明,可以提高具有含有金属元素的硅氧化膜的半导体装置的特性和可靠性。
Claims (23)
1.一种半导体装置,包括:
半导体衬底;
在上述半导体衬底上形成的,包含含有金属元素的硅氧化膜的栅绝缘膜;以及
在上述栅绝缘膜上形成的电极,
上述含有金属元素的硅氧化膜具有下表面附近的第一区、上表面附近的第二区、以及第一区和第二区之间的第三区;
上述硅氧化膜中含有的金属元素在厚度方向上的浓度分布,在上述第三区中有最大点。
2.如权利要求1所述的半导体装置,其特征在于:
上述硅氧化膜还含有氮;
上述硅氧化膜中含有的氮在厚度方向上的浓度分布在上述第二区中有最大点。
3.如权利要求1所述的半导体装置,其特征在于:
上述硅氧化膜中含有的金属元素从Zr、Hf、Al和La中选择。
4.如权利要求1所述的半导体装置,其特征在于:
上述硅氧化膜还含有其它的金属元素;
上述其它的金属元素从Zr、Hf、Al和La中选择。
5.一种半导体装置的制造方法,包括下列步骤:
在半导体衬底上形成含有金属元素的非晶态硅膜的步骤,该非晶态硅膜具有下表面附近的第一区、上表面附近的第二区、以及第一区和第二区之间的第三区,且金属元素在厚度方向上的浓度分布在第一区或第三区中有最大点;以及
使上述含有金属元素的非晶态硅膜氧化,形成含有上述金属元素的硅氧化膜的步骤。
6.如权利要求5所述的半导体装置的制造方法,其特征在于:还包括使上述硅氧化膜的表面氮化的步骤。
7.如权利要求5所述的半导体装置的制造方法,其特征在于:上述非晶态硅膜采用金属源和硅源通过CVD形成。
8.如权利要求7所述的半导体装置的制造方法,其特征在于:上述金属源是上述金属元素的卤化物,上述硅源是硅的氢化物。
9.如权利要求5所述的半导体装置的制造方法,其特征在于:上述非晶态硅膜用活性的氧化种进行氧化。
10.如权利要求6所述的半导体装置的制造方法,其特征在于:用等离子体氮化上述硅氧化膜的表面。
11.一种半导体装置的制造方法,包括下列步骤:
向保持衬底的容器供给含有硅的有机化合物,和含有选自Zr、Hf、Al和La的金属元素的有机化合物的步骤;以及
用氧的活性种通过热CVD,在上述衬底上形成含有上述金属元素的硅氧化膜的步骤。
12.如权利要求11所述的半导体装置的制造方法,其特征在于:还向上述容器供给氧气,
13.如权利要求11所述的半导体装置的制造方法,其特征在于:上述含有金属元素的硅氧化膜是栅绝缘膜。
14.如权利要求11所述的半导体装置的制造方法,其特征在于:上述含有金属元素的有机化合物还含有其它的金属元素,上述其它的金属元素从Zr、Hf、Al和La中选择。
15.如权利要求11所述的半导体装置的制造方法,其特征在于:向上述容器供给的上述含有金属元素的有机化合物的供给量为向上述容器供给的上述含有硅的有机化合物的供给量的1/10以下。
16.如权利要求11所述的半导体装置,其特征在于:设上述硅氧化膜中含有的金属元素的原子数为NM,硅的原子数为NSi则O<NM/NSi<0.5。
17.一种半导体装置的制造方法,包括通过CVD在半导体衬底上形成含金属元素的硅氧化膜的步骤,其特征在于还包括:
向保持半导体衬底的容器开始供给含有硅的有机化合物的步骤;
在开始供给上述含有硅的有机化合物之后,开始向上述容器供给含有金属元素的有机化合物的步骤;以及
增加向上述容器供给的上述含有金属元素的有机化合物的供给量的步骤。
18.如权利要求17所述的半导体装置的制造方法,其特征在于,还包括:
增加上述含有金属元素的有机化合物的供给量之后,减少向上述容器供给的上述含有金属元素的有机化合物的供给量的步骤;
停止向上述容器供给上述含有金属元素的有机化合物的步骤;以及
在停止供给上述含有金属元素的有机化合物之后,停止向上述容器供给上述含有硅的有机化合物的步骤。
19.如权利要求18所述的半导体装置的制造方法,其特征在于,还包括:使停止供给上述含有硅的有机化合物之后得到的上述含有为的硅氧化膜的表面氮化的步骤。
20.如权利要求11或17所述的半导体装置的制造方法,其特征在于:上述含有硅的有机化合物是硅的烷氧化物。
21.如权利要求20所述的半导体装置的制造方法,其特征在于:上述硅的烷氧化物是四乙氧基原硅酸盐膜。
22.如权利要求11或17所述的半导体装置的制造方法,其特征在于:上述含有金属元素的有机化合物是上述金属元素的烷氧化物。
23.如权利要求22所述的半导体装置的制造方法,其特征在于:上述金属元素的烷氧化物是叔丁氧基化合物。
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US7101775B2 (en) | 2006-09-05 |
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KR100512824B1 (ko) | 2005-09-07 |
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