CN100352017C - 半导体装置和半导体装置的制造方法 - Google Patents

半导体装置和半导体装置的制造方法 Download PDF

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CN100352017C
CN100352017C CNB038205173A CN03820517A CN100352017C CN 100352017 C CN100352017 C CN 100352017C CN B038205173 A CNB038205173 A CN B038205173A CN 03820517 A CN03820517 A CN 03820517A CN 100352017 C CN100352017 C CN 100352017C
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gas
semiconductor device
film
silicon substrate
insulating film
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CN1679151A (zh
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山口正臣
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Fujitsu Ltd
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Fujitsu Ltd
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Abstract

本发明提供可形成Hf1-xAlx(0＜x＜0.3)氧化膜的半导体装置的制造方法，该氧化膜具有作为栅绝缘膜所期望的特性。所述半导体装置的制造方法包括如下步骤：(a)在反应室内加热硅基板的步骤；和(b)向上述硅基板的表面供给含有原料气、氮化气和促氮化气的成膜气体，从而以热化学气相沉积在上述加热了的硅基板上堆积相对介电常数比氧化硅大的Hf1-xAlxO:N(0.1＜x＜0.3)膜的步骤。

Description

半导体装置和半导体装置的制造方法
技术领域
本发明涉及半导体装置和半导体装置的制造方法，特别是涉及具有介电常数大的绝缘膜的半导体装置和半导体装置的制造方法。
背景技术
作为用于半导体集成电路装置中的代表性半导体元件，广泛使用以金属氧化物半导体(MOS)晶体管为代表的绝缘栅型场效应晶体管(IG-FET)。为了半导体集成电路装置的高集成化，而根据缩放规则对绝缘栅型场效应晶体管进行微细化。微细化使栅绝缘膜变薄、栅长度缩短等，缩小了绝缘栅型场效应晶体管的各种尺寸，可以正常地保持微细化后的元件的性能，并可以提高性能。
金属氧化物半导体晶体管在栅氧化膜上具有硅制栅电极。硅制栅电极掺杂有作为n型杂质的磷(P)和砷(As)或者作为p型杂质的硼(B)。如果栅氧化膜变薄，会产生栅电极的杂质穿透栅氧化膜并扩散至下方的通道区域的现象。要是栅电极的杂质扩散至通道区域，会降低晶体管的阈值，导致击穿。特别是p通道晶体管中的硼的穿透成为问题。
已知，如果在栅氧化膜中引入氮，对于防止硼的穿透是有效的。例如，通过进行热氮化可以在以热氧化形成栅氧化膜后在栅氧化膜引入氮。
第二代的金属氧化物半导体晶体管的栅氧化膜的厚度要求薄至小于等于2nm。该厚度是隧道电流开始流动的厚度，不能控制栅漏电流，也不能避免消耗电力的增大。只要使用氧化硅作为栅绝缘膜，微细化就会受到限制。为了抑制贯通栅绝缘膜的隧道电流，可以使用厚的栅绝缘膜。
为了使栅绝缘膜换算成氧化硅膜时的有效膜厚小于等于2nm同时又增大物理膜厚，提出了在栅绝缘膜中使用相对介电常数比氧化硅大的高相对介电常数绝缘材料的方案。
特开2001-274378号公报提出了采用相对介电常数比氧化硅大的钛酸钡(Ba(Sr)TiO3)、氧化钛(TiO2)、氧化钽(Ta2O5)、氧化锆(ZrO2)、氧化铪(HfO2)、氮化硅(Si3N4)、氧化铝(Al2O3)作为栅绝缘膜的方案。而且还提出了在这些相对介电常数大的绝缘材料膜和硅基板之间夹有氧化硅膜的结构。
如果采用相对介电常数大的新型材料作为绝缘栅场效应晶体管的栅绝缘膜，也会产生新的问题。为了促进新型材料的实用化，期望解决新的问题。
发明内容
本发明的目的是提供具有栅绝缘膜的半导体装置，所述栅绝缘膜使用了相对介电常数比氧化硅大的高相对介电常数绝缘材料。
本发明的另一目的是提供能以相对介电常数高于氧化硅的高相对介电常数绝缘材料为栅绝缘膜来形成半导体装置的制造方法。
本发明的又一目的是提供将引入了氮的Hf1-xAlx(0＜x＜0.3)的氧化膜用作栅绝缘膜的半导体装置。
本发明的又一目的是提供可形成引入了氮的Hf1-xAlx(0＜x＜0.3)的氧化膜作为栅绝缘膜的半导体装置的制造方法。
根据本发明的一个发明点，提供半导体装置的制造方法，其包括如下步骤：(a)在反应室内加热硅基板的步骤；和(b)向上述硅基板的表面供给含有原料气、氮化气和促氮化气的成膜气体，从而在上述加热了的硅基板上以热化学气相沉积(CVD)堆积相对介电常数比氧化硅大的绝缘膜。
根据本发明的另一发明点，提供半导体装置，其包括具有有源区域的硅基板、栅绝缘膜、栅电极和源极/漏极区域；所述栅绝缘膜是在上述硅基板的有源区域表面上形成的栅绝缘膜，且实质上由Hf1-xAlx(0＜x＜0.3)的氧化物构成，含有大于等于0.5at％的N，并含有相对介电常数比氧化硅大的高介电常数绝缘膜；所述栅电极形成在上述栅绝缘膜上，并含有添加了杂质的硅层；所述源极/漏极区域是在上述栅电极的两侧并在上述硅基板的有源区域内添加杂质而形成的。
向金属氧化物中引入氮不一定是容易的。通过使用了氮化气和促氮化气的化学气相沉积可以促进氮的引入。作为氮化气，优选使用氨、二叔丁基氨基硅烷、三乙胺中的至少一种。作为促氮化气，优选使用含氢的气体。
附图说明
图1A-1G是用于说明在硅基板上以化学气相沉积形成高相对介电常数绝缘膜的方法的截面图；
图2是表示热化学气相沉积装置的结构的简要截面图；
图3A-3C是表示有机铝原料、有机铪原料的例子的化学结构式；
图4A-4C是表示氮化气的例子的化学结构式；
图5是表示实验结果的表格；
图6A、6B是表示绝缘栅型场效应晶体管及半导体装置的结构的简要截面图。
具体实施方式
氧化铪是可以显示出相对介电常数比氧化硅高几倍至十几倍的绝缘体，具有较大可能性用作绝缘栅型场效应晶体管的栅绝缘膜。氧化铪是易于结晶的物质，不容易形成薄且具有均一厚度的致密膜。如果在硅基板上仅以氧化铪形成栅绝缘膜，则容易形成泄漏多的结晶性绝缘膜。
如果在氧化铪(HfO2)中混合氧化铝(Al2O3)，则可以抑制结晶化。要是抑制了结晶化，就可以减小漏电流。氧化铝具有比氧化铪低的相对介电常数。为了尽量得到大的相对介电常数，在氧化铪中混合的氧化铝的量优选限定为Hf1-xAlxO(0＜x＜0.3)。从抑制结晶化的目的考虑，优选为Hf1-xAlxO(0.1＜x＜0.3)。
这样的相对介电常数大的氧化绝缘膜不会形成硅基板的热氧化。作为不会对基板产生不良影响、可形成良好的高相对介电常数氧化绝缘膜的方法，有热化学气相沉积(CVD)。
为了防止来自栅电极的杂质的穿透，优选在栅绝缘膜中引入氮。已尝试了向HfAlO中引入氮。首先尝试了分别向HfO2和Al2O3中引入氮，接着尝试了向HfAlO中引入氮。以下，遵循发明人进行的实验予以说明。
如图1A所示，用H2SO4∶H2O2＝50∶1的H2SO4和H2O2清洗硅基板1的表面。在硅基板1表面形成有自然氧化膜2。清洗自然氧化膜2表面附着的污垢。
如图1B所示，用纯水对硅基板流水清洗10分钟。H2SO4和H2O2清洗的残留物被纯水冲洗掉。
如图1C所示，将硅基板1浸入HF∶H2O＝1∶20的稀HF水溶液中约1分钟，除去硅基板表面的自然氧化膜2。
如图1D所示，用纯水对硅基板流水清洗10分钟。HF和H2O的氧化膜除去工序的残留物被纯水冲洗掉。
如图1E所示，对硅基板进行SC2清洗(HCl∶H2O2∶H2O＝1∶1∶5)，在硅表面形成由SC2产生的化学氧化物膜3。形成比自然氧化膜2清洁的氧化硅膜3。
如图1F所示，用纯水对硅基板流水清洗10分钟。SC2的氧化膜形成工序的残留物被纯水冲洗掉。接着，通过热氮干燥，对基板表面进行干燥。随后，将硅基板移入化学气相沉积成膜装置中。
如图1G所示，在硅基板1的化学氧化物膜3上通过热化学气相沉积形成Al2O3、HfO2或者HfAlO的高相对介电常数绝缘膜4。作为HfAlO做成Hf0.8Al0.2O。化学氧化物膜3和高相对介电常数绝缘膜4形成复合绝缘膜5。
在厚度约1nm的氧化硅膜3上成长厚度约为3nm的HfO2膜，电容等价氧化硅膜厚(CET)为1.6nm。同样，在厚度约1nm的氧化硅膜3上成长厚度约为3nm的Al2O3膜，电容等价氧化硅膜厚(CET)为2.3nm。通过形成厚度大于等于3nm的HfAlO绝缘膜，可以使换算成氧化硅时的膜厚(CET)小于2nm。
如果考虑杂质由栅电极向通道区域的穿透，期望在高相对介电常数绝缘膜中引入氮。尝试了在热化学气相沉积的成膜气体中混入氮化气而向高相对介电常数绝缘膜4中引入氮。
图2简要表示热化学气相沉积成膜装置的结构。在反应室6中配置有喷头8，在喷头8的下方配置有基座7，所述基座7配备有加热器H。在喷头8中设有独立的配管9A、9B。由这些配管供给HfO2、Al2O3的原料气和氮化气。如果使氮化气的NH3和原料气等一起流动会发生反应，因而NH3和原料气需要彼此独立地流动。
图3A、3B表示作为Al的有机金属原料使用的Al(t-C4H9)3(三叔丁基铝，TTBAl)和Al(C2H5)3(三乙基铝，TEAl)的化学结构式。
图3C表示作为Hf的有机金属原料使用的Hf[N(CH3)2]4(四二甲氨基铪，TDMAHf)的化学结构式。这些有机金属原料在常温为液体，通过鼓入氮气而做成原料气。
图4A、4B、4C表示作为氮化气使用的NH3(氨)以及作为氮化气可以使用的SiH2(NHt-C4H9)2(二叔丁基氨基硅烷，BTBAS)、N(C2H5)3(三乙基胺，TEN)的化学结构式。以下，主要说明使用NH3作为氮化气的情况。
另外，作为成膜气体使用O2、H2、N2。根据基座的温度，将成膜中的硅基板的温度设定为500℃。成膜中的气氛压力设定为65Pa。成膜气体的总流量设定为1100sccm。NH3与有机金属原料气不进行混合，由二个系统的配管9A、9B供给。
图5表示进行实验的5种成长方法。以热化学气相沉积成长高相对介电常数膜，成长后通过俄歇电子分光(AES)调查N的存在。AES的检测灵敏度为百分级。检测精度并不太高，要是可以检测出则可以知道N确实存在。通过该AES检测出氮是指至少存在0.5at％的氮。
第一种成长方法以300sccm的Al或Hf的有机金属原料气R和100sccm的O2作为原料气，流动有余量700sccm的载运气体N2，进行热化学气相沉积。Al、Hf的有机金属原料气为三叔丁基铝、三乙基铝、四二甲氨基铪。三叔丁基铝、三乙基铝、四二甲氨基铪在基板表面发生热分解，包含在原料气中的Al或Hf和氧结合，形成Al2O3或者HfO2。虽然成膜气体中存在氮，但是用AES从已成膜的Al2O3膜、HfO2膜检测不出氮。
第二种成长方法是从第一种成长方法的成膜气体中除去O2，并加入300sccm的NH3作为氮化气。余量的载运气体N2为500sccm。即使在成膜气体中不存在氧，氧化膜也可以成膜。认为可能是从高相对介电常数绝缘膜下的氧化硅膜或者作为成膜后的氛围气的空气中供给了氧。
作为Al原料气使用三叔丁基铝时，用AES从已成膜的Al2O3膜中可以明确地检测出氮。可以确认向Al2O3膜中引入了氮。作为Al原料气使用三乙基铝时，用AES从已成膜的Al2O3膜检测出少许氮。作为Hf原料使用四二甲氨基铪时，用AES从HfO2膜检测不出氮。
第三种成长方法是在第二种成长方法的成膜气体中进一步加入300sccm的H2。载运气体的N2流量减少至200sccm。用AES从已成膜的Al2O3膜、HfO2膜均可以明确检测出氮。在以三叔丁基铝作为Al原料的Al2O3膜中可以进一步引入较多量的氮。在以三乙基铝作为Al原料的Al2O3膜中也可以引入氮。在以四二甲氨基铪作为Hf原料的HfO2膜中也可以引入氮。可以断定新加入的H2促进了氮化。
第四种成长方法相当于交替进行下述两种供给：第一种成长方法的不含氮化气的成膜气体的供给和从第二种成长方法的成膜气体中除去原料气而仅为氮化气(和载运气体)的供给。例如以周期为20秒进行交替供给。可以检测出在以三叔丁基铝作为Al原料的Al2O3膜中引入了氮。在以三乙基铝作为Al原料的Al2O3膜中也可以引入氮。从以四二甲氨基铪作为Hf原料的HfO2膜中也可以检测出少许的氮。
如果和第二种成长方法比较，则氮的引入量均得到提高。认为是，与同时供给氮化气和原料相比，交替供给氮化气和原料的情况下，其氮的引入量高。也可以使原料和氮化气的组成比(成膜气体的组成)随时间变化以代替交替供给。
第五种成长方法是在第四种成长方法的原料气、氮化气两者中均加入300sccm的H2。为了使总流量为1100sccm，减小了载运气体的流量。对于以三叔丁基铝作为Al原料的Al2O3膜、以三乙基铝作为Al原料的Al2O3膜、以四二甲氨基铪作为Hf原料的HfO2膜的任意一种，其氮的引入量均得到提高。
进而，在作为原料气R同时供给30sccm的三叔丁基铝和300sccm的四二甲氨基铪，并成长了Hf0.8Al0.2O的情况下，也可以确认良好的氮引入效果。从而可以成长相对介电常数大、渗漏电流少的HfAlO:N栅绝缘膜。
以氨作为氮化气、以氢作为促氮化气时，通过Al2O3、HfO2、HfAlO的热化学气相沉积可以引入氮。如果交替供给原料气和氢气，则可以进一步提高氮的引入量。作为氮化气使用二叔丁基氨基硅烷、三乙基胺时，也可以用AES进行氮的检测。
以上是在成膜温度均为500℃时进行化学气相沉积。使成膜温度为400℃时也可以引入氮。在400℃～600℃的成膜温度可以向Al2O3、HfO2、HfAlO中引入氮。
如果成膜中增大氛围气压力，会看到高相对介电常数膜的面内分布变差的倾向。成膜中氛围气压力优选为10Pa～100Pa。
交替供给原料和氮化气时，周期可以进行各种变更。优选10秒～120秒的周期。
作为Hf的有机金属原料也试着使用了Hf(OtC4H9)4，但是每一种成长方法均检测不出氮。认为是，在分子中含有O，容易生成HfO4，从而氮的引入变得困难。一旦形成HfO4，则由于Hf-O的解离能高，Hf-O键分离而形成Hf-N键是困难的。为了引入氮，优选在金属原料中不含有O。
已说明了热化学气相沉积Al2O3、HfO2、HfAlO的情况，而对于以热化学气相沉积成长其他的可氮化的高相对介电常数绝缘膜的情况，通过使用氮化气和促氮化气，也可以引入氮。原料气并不限于有机金属，但是特别是使用有机金属原料的情况，引入氮的可能性高。
图6A表示p通道绝缘栅型场效应晶体管的结构。在硅基板11上形成有通过浅槽隔离(STI)产生的元件分离区域12，在有源区域形成有n型阱13n。在其他地方也形成有p型阱。在有源区域表面上形成有栅绝缘膜14。栅绝缘膜14由化学氧化物膜和引入了氮的高相对介电常数绝缘膜层积而构成。
例如，在形成有化学氧化物膜的硅基板表面上供给含有规定比例的四二甲氨基铪、三叔丁基铝和氧的原料气，氮化气和促氮化气，并以热化学气相沉积形成Hf0.8Al0.2O:N膜。也可以形成引入了氮的高相对介电常数绝缘膜的单层来代替氧化硅膜和引入了氮的高相对介电常数绝缘膜的层积。
在栅绝缘膜14上形成有掺杂了硼的p型多结晶硅的栅电极15p。在栅电极的两侧的基板表面形成有p型伸展区域16p。在栅电极的侧壁上形成有氧化硅等侧壁隔离片17，在侧壁隔离片17的外侧的基板内形成有高浓度的p型源极/漏极区域18p。在栅电极15p、源极/漏极区域18p上形成有CoSi等的硅化物层19。由此，形成p通道绝缘栅型场效应晶体管20p。
根据上述结构，由于采用高相对介电常数绝缘膜而形成栅绝缘膜，即使等价氧化硅膜厚变薄，也可以增加物理膜厚，并可以抑制隧道电流。由于在栅绝缘膜中引入了氮，可以防止在栅电极中掺杂的杂质穿透通道区域。
图6B表示半导体集成电路装置的结构。在硅基板11上同时形成有n型阱13n和p型阱13p。在n型阱13n中形成有上述的p通道绝缘栅型场效应晶体管20p。在p型阱13p中形成有n通道绝缘栅型场效应晶体管20n。参考符号后的p、n表示导电型。n通道绝缘栅型场效应晶体管20n具有将p通道绝缘栅型场效应晶体管的各半导体区域的导电型反转后的结构。
栅绝缘膜14采用p通道绝缘栅型场效应晶体管、n通道绝缘栅型场效应晶体管均引入同样氮的Hf0.8Al0.2O:N高相对介电常数绝缘膜而形成。引入氮的高相对介电常数绝缘膜不仅有效防止p型杂质的硼的穿透，而且有效防止作为n型杂质的P或者As的穿透。
为了覆盖栅电极，形成有层间绝缘膜21，在层间绝缘膜中形成有多层配线24。各配线24是采用阻隔金属层22和铜、铜合金、铝等的主配线层23构成的。
根据上述实施例说明了本发明，但是本发明并不限定于这些实施例。例如，HfAlO:N的组成并不限于Hf0.8Al0.2O:N。进而，也可以使用其他的引入了氮的金属氧化物。
产业上利用的可能性
可利用于含有微细化的绝缘栅型场效应晶体管的半导体集成电路装置等。

Claims (14)

1、半导体装置的制造方法，其包括如下步骤：(a)在反应室内加热硅基板的步骤；和(b)向所述硅基板的表面供给含有原料气、氮化气和促氮化气的成膜气体，从而在所述加热了的硅基板上以热化学气相沉积堆积相对介电常数比氧化硅大的绝缘膜的步骤，其中，所述原料气为在载运气体中含有金属化合物的气体，所述金属化合物含有Hf和Al中的至少一种元素，所述促氮化气为含有氢的气体。
2、根据权利要求1所述的半导体装置的制造方法，其中，所述原料气为在载运气体中含有Hf的有机金属化合物和Al的有机金属化合物的气体。
3、根据权利要求1所述的半导体装置的制造方法，其中，在所述步骤(a)之前，还包括(x)在硅基板表面形成化学氧化物层的步骤。
4、根据权利要求1所述的半导体装置的制造方法，其中，所述成膜气体还含有氧。
5、根据权利要求1所述的半导体装置的制造方法，其中，所述硅基板在表面具有小于等于1nm厚度的氧化硅膜，并且所述成膜气体不含有氧。
6、根据权利要求1所述的半导体装置的制造方法，其中，所述氮化气为含有氨、二叔丁基氨基硅烷、三乙胺中至少一种的气体。
7、根据权利要求1所述的半导体装置的制造方法，其中，所述步骤(a)中，将硅基板加热至400℃～600℃的温度。
8、根据权利要求1所述的半导体装置的制造方法，其中，所述步骤(b)中，在10Pa～100Pa的压力下进行热化学气相沉积。
9、根据权利要求1所述的半导体装置的制造方法，其中，所述步骤(b)中，使成膜气体的成分比例随时间变化。
10、根据权利要求9所述的半导体装置的制造方法，其中，所述步骤(b)中，交替供给原料气和氮化气。
11、根据权利要求10所述的半导体装置的制造方法，其中，所述交替供给的周期在10秒～120秒的范围内。
12、半导体装置，其包括具有有源区域的硅基板、栅绝缘膜、栅电极和源极/漏极区域；
所述栅绝缘膜是在所述硅基板的有源区域表面上形成的栅绝缘膜，且由Hf1-xAlx的氧化物构成，所述栅绝缘膜含有大于等于0.5at％的N并含有相对介电常数比氧化硅大的高介电常数绝缘膜，其中0＜x＜0.3；
所述栅电极形成在所述栅绝缘膜上，并含有添加了杂质的硅层；
所述源极/漏极区域是在所述栅电极的两侧并在所述硅基板的有源区域内添加杂质而形成的。
13、根据权利要求12所述的半导体装置，其中，所述栅绝缘膜含有氢。
14、根据权利要求12所述的半导体装置，其中，所述栅绝缘膜由在硅基板上形成的含有化学氧化物的氧化硅膜和在其上形成的高介电常数绝缘膜层积而构成。
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