CN100468659C - 制造闪存器件的电介质膜的方法 - Google Patents

制造闪存器件的电介质膜的方法 Download PDF

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CN100468659C
CN100468659C CNB2005101362405A CN200510136240A CN100468659C CN 100468659 C CN100468659 C CN 100468659C CN B2005101362405 A CNB2005101362405 A CN B2005101362405A CN 200510136240 A CN200510136240 A CN 200510136240A CN 100468659 C CN100468659 C CN 100468659C
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朱光喆
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Abstract

本发明提供一种制造闪存器件的电介质膜的方法，包括步骤：提供形成有浮置栅极的半导体衬底；在减压状态下实施氧化工艺从而在所述包括浮置栅极的半导体衬底上形成第一氧化物膜的薄膜；在所述第一氧化物膜上顺序形成氮化物膜和第二氧化物膜从而形成具有第一氧化物膜、氮化物膜和第二氧化物膜的电介质膜。

Description

制造闪存器件的电介质膜的方法
技术领域
本发明涉及一种制造闪存器件的方法，更具体地，设计一种形成电介质膜的方法，所述电介质膜形成在闪存器件的浮置栅极和控制栅极之间。
背景技术
通常，闪存器件的栅极具有包括隧道氧化物膜11、浮置栅极12、电介质膜13和控制栅极14的结构，其全部形成在硅衬底10上，如图1所示。附图标记15表示隔离膜(isolation film)。
如上构造的闪存器件的编程、擦除和读操作以这样的方式进行，即通过施加适当的偏置电压到控制栅极14和硅衬底10，电子注入到浮置栅极12或从其取出。
电介质膜13具有氧化物-氮化物-氧化物(ONO)结构，其中堆叠第一氧化物膜13a、氮化物膜13b和第二氧化物膜13c。它们之中，第一和第二氧化物膜13a和13c借助二氯硅烷(SiH2Cl2)基的化学气相沉积(CVD)方法形成。然而，由CVD形成的CVD氧化物膜与借助普通干和湿氧化方法形成的氧化物膜相比具有低的膜质量。
电介质膜13极大地影响闪存器件的运行。更特别地，第一氧化物膜13a的厚度和膜质量对闪存器件的电荷泄漏和保持特性具有显著影响。
在70nm或更低的设计尺寸中，浮置栅极12之间的距离非常狭窄，即10nm或更低。如果电介质膜13形成为具有现有厚度，则由于浮置栅极12之间在后面的用于控制栅极的多晶硅沉积时没有被完全填充，所以在电介质膜13间导致空洞(void)A。这些空洞A在后面的栅极蚀刻工序中产生单元之间的多晶硅剩余物，导致单元之间的桥的产生。
为了防止这些空洞的产生，需要薄地沉积电介质膜13，因为必须保证浮置栅极12之间的空间。然而，如果第一氧化物膜13a的厚度减小，则会有数据保持特性退化的问题。
为了形成具有良好数据保持特性以及均匀且薄的厚度的氧化物膜，优选采用热氧化工艺。
热氧化工艺通常在大气压强下进行，其中充分提供氢(H2)气和氧(O2)气以引起火花反应(spark reaction)。在对未处理过的硅衬底进行热氧化工艺的情况中，可形成具有良好数据保持特性和薄的厚度的氧化物膜。如果对由掺杂的多晶硅制成的浮置栅极12而不是未处理的硅衬底进行热氧化工艺，沿着浮置栅极12的晶界(grain boundary)产生过氧化，其是热不稳定的。因此难以形成具有良好数据保持特性以及均匀且薄的厚度的氧化物膜。
发明内容
本发明的一个优点是提供一种制造闪存器件的电介质膜的方法，其中形成具有良好的电荷保持特性以及均匀且薄的厚度的电介质膜。
本发明的另一特性是防止在用于控制栅极的多晶硅膜中空洞的产生。
本发明的再一优点是防止单元之间桥的形成。
根据本发明，一种制造闪存器件的电介质膜的方法包括步骤:提供形成有浮置栅极的半导体衬底；以减压状态实施氧化工艺从而在包括所述浮置栅极的所述半导体衬底上形成第一氧化物膜的薄膜；随后在所述第一氧化物膜上形成氮化物膜和第二氧化物膜从而形成具有所述第一氧化物膜、所述氮化物膜和所述第二氧化物膜的电介质膜。
优选地，所述在减压状态的氧化工艺采用在减压状态的湿氧化工艺或游离基氧化工艺(radical oxidization process)。
优选地，如果采用所述在减压状态的湿氧化工艺，则可以使用采用催化剂的水汽生成器。
优选地，所述在减压状态的湿氧化工艺可以在200托(Torr)至700托的压强下在与O2相比包括大量H2的气氛下进行。
优选地，所述在减压状态的湿氧化工艺可以在0.1托至200托的压强下在与H2相比包括大量O2的气氛下进行。
更优选地，氧气对氢气的比值可以是1:1至15:1。
优选地，所述游离基氧化工艺可以在0.1托至1托的压强下进行。
优选地，所述游离基氧化工艺可以在与H2相比包括大量O2的气氛下进行。
更优选地，H2的量可以设置为低于全部气体的40％。
优选地，该方法还可包括步骤:在形成所述第一氧化物膜之前，进行除去形成在所述浮置栅极的表面上的本来的氧化物膜的预处理清洁工艺。
更优选地，进行预处理清洁工艺时，可以使用HF或缓冲氧化物蚀刻剂(BOE)。
优选地，该方法还可包括步骤:所述电介质膜形成之后进行蒸汽退火工艺。
附图说明
图1是现有技术闪存器件的剖视图；
图2A至2I是用于说明根据本发明一实施例制造闪存器件的方法的剖视图；
图3A和3B是用于说明根据本发明形成电介质膜的方法的剖视图。
具体实施方式
下面将参照附图描述根据本发明的优选实施例。因为提供优选实施例是为了使本领域普通技术人员能够理解本发明，所以它们可以以各种方式修改且本发明的范围不局限于下面描述的优选实施例。
图2A至2I是用于说明根据本发明一实施例制造闪存器件的方法的剖视图。
如图2A所示，屏蔽氧化物膜(screen oxide film)21形成在半导体衬底20上。然后实施离子注入工艺例如阱离子注入工艺和阈值电压离子注入工艺。
形成屏蔽氧化物膜21之前，可以利用以50:1的比值用蒸馏水稀释的SC-1(NH4OH/H2O2/H2O)和HF的混合物或者以100:1或300:1的比值用蒸馏水稀释的SC-1和BOE的混合物优选实施预处理清洁工艺。
屏蔽氧化物膜21可以借助湿或干氧化模式在750℃至800℃的温度下形成至50至80
Figure C200510136240D0005095102QIETU
的厚度。
然后衬垫氮化物膜(pad nitride film)22和硬掩模氧化物膜23形成在屏蔽氧化物膜21上。衬垫氮化物膜22借助于低压化学气相沉积(LPCVD)形成，且考虑到随后将形成的浮置栅极的高度，其具有1000
Figure C200510136240D0005095115QIETU
至2000
Figure C200510136240D0005095119QIETU
的厚度。
如图2B所示，为了定义隔离区域，硬掩模氧化物膜23借助于光刻工艺被构图。
然后利用图案化的硬掩模氧化物膜23作为蚀刻掩模蚀刻衬垫氮化物膜22、屏蔽氧化物膜21和半导体衬底20，形成沟槽(trench)24且除去硬掩模氧化物膜23。
其后，厚度100至200
Figure C200510136240D0006095138QIETU
的二氯硅烷(SiH2Cl2)高温氧化物(下文称为“DCS HTO”)膜通过LPCVD在0.1托至1托的压强和800℃至830℃的温度下沉积在形成有沟槽24的半导体衬底20上，形成侧壁氧化物膜(未示出)。
在形成侧壁氧化物膜之前，可以优选实施利用以50:1的比值用蒸馏水稀释的SC-1(NH4OH/H2O2/H2O)和HF的混合物或以100:1或300:1的比值用蒸馏水稀释的SC-1和BOE的混合物的预处理清洁工艺。
如图2C所示，隔离氧化物膜25沉积在半导体衬底20的整个表面上，使得沟槽24被完全填埋。自然产生在隔离氧化物膜25内的接缝(seam)和空洞借助高温蒸汽退火工艺被去除。
隔离氧化物膜25可以利用高密度等离子体(HDP)氧化物膜、O3-TEOS(HARP:高孔径比平坦化(High Aspect Ratio Planarization))氧化物膜和聚硅氮烷(polysilazane，PSZ)氧化物膜中的一种形成。
参照图2D，对隔离氧化物膜25实施利用衬垫氮化物膜22作为目标的化学机械抛光(CMP)工艺，从而形成在沟槽24内的隔离膜25a。CMP工艺期间，考虑浮置栅极的高度决定作为目标的衬垫氮化物膜22的厚度。
参照图2E，衬垫氮化物膜22利用磷酸(H3PO4)溶液被除去。隔离膜25a的凸出高于半导体衬底20的表面的一部分因为衬垫氮化物膜22的去除而被暴露。这样，隔离膜25a的凸出高于半导体衬底20的表面的该部分称为隔离膜突起(nipple)。
其后，屏蔽氧化物膜21借助利用以50:1的比值用蒸馏水稀释的SC-1(NH4OH/H2O2/H2O)和HF的混合物或者以100:1或300:1的比值用蒸馏水稀释的SC-1和BOE的混合物的清洁工艺被除去。此时，隔离膜突起也被蚀刻从而确保将形成浮置栅极的空间。
参照图2F，隧道氧化物膜26形成在半导体衬底20的通过屏蔽氧化物膜21的去除暴露的有源区上。
在该情况下，隧道氧化物膜26借助于湿氧化模式在750℃至800℃的温度形成。
在该情况下，为了最小化在半导体衬底20与隧道氧化物膜26之间的界面处的缺陷密度，形成隧道氧化物膜26之后，可优选实施在氮(N2)气气氛下在900℃至1000℃的温度持续20分钟至30分钟的退火工艺。
供选地，为了最小化在半导体衬底20与隧道氧化物膜26之间的界面处的缺陷密度，形成隧道氧化物膜26之后，可以在900℃至1000℃的温度实施利用N2O或NO气体的退火工艺5分钟至6分钟从而除去隧道氧化物膜26内的陷阱电荷(trap charge)，然后在900℃至1000℃的温度实施利用氮(N2)气的退火工艺。
利用N2O或NO气体的退火工艺可以与隧道氧化物膜26的形成工艺原位(in-situ)或离位(ex-situ)实施。
利用SiH4或Si2H6以及PH3通过LPCVD在0.1托至3托的压强和480℃至620℃的温度下沉积掺杂的多晶硅膜27。多晶硅膜27的掺杂浓度可以优选为约3E20至5E20原子/cc。
接着参照图2G，多晶硅膜27经历CMP，使得隔离膜25a被暴露，从而形成其间以隔离膜25a隔离的多个浮置栅极27a。
如图2H所示，为了提高耦合率(coupling ratio)且最小化单元间干扰，隔离膜25a突起被蚀刻。此时，优选隔离膜25a的表面不低于隧道氧化物膜26。
然后进行利用BON(H2SO4+H2O2+BOE+SC-1)的后清洁工艺。为了除去形成在浮置栅极27a上的本来的氧化物膜，实施利用HF或BOE溶液的预处理清洁工艺。
其后，如图2I所示，借助根据本发明的制造电介质膜的方法形成电介质膜28。
现在将描述根据本发明的制造电介质膜的方法。
图3A和3B是用于说明根据本发明的形成电介质膜的方法的剖视图。
如图3A所示，DCS HTO膜借助在减压气氛下的氧化工艺沉积在浮置栅极27a上从而形成第一氧化物膜28a。第一氧化物膜28a优选形成为20至180
Figure C200510136240D0007095220QIETU
的厚度。
减压气氛下的氧化工艺可采用减压气氛下的湿氧化工艺或者游离基氧化工艺。
在普通湿氧化工艺的情况下，利用加热器型(heater type)或者斜型(ramptype)喷灯(torch)产生H2O。在减压状态下H2和O2的量不够。因此由于未产生火花反应而不能引起氧化反应。
相反，本发明中，采用催化剂的水汽生成器(WVG)被用来以少量H2和O2引起火花反应，从而产生H2O。使得在减压状态的湿氧化工艺可行，从而能够引起火花反应，即使在0.1托至700托的低压下。
在减压状态的湿氧化工艺可以在200托至700托的压强在与O2相比包括大量H2的气氛下进行，或者可以在0.1托至200托的压强在与H2相比包括大量O2的气氛下进行，H2:O2的比值为1:1至1:15。
同时，在游离基氧化工艺的情况下，与利用火花反应的湿氧化工艺不同，在0.1托至1托的快速减压气氛下利用具有高活性的基团(O*、H*、OH*)形成氧化物膜。在该情况下，形成与H2相比包括大量O2的气氛。此时，H2的比例优选保持为全部气体的40％或更低。
这样，在以减压状态使用湿氧化工艺或者游离基氧化工艺的情况下，氧化物膜的厚度可被控制为比较薄，即使在高温下。因此可以形成具有良好电荷保持特性以及均匀且薄的厚度的第一氧化物膜28a，即使在浮置栅极27a的热不稳定的晶界。
其后，如图3B所示，具有20
Figure C200510136240D0008095302QIETU
至100
Figure C200510136240D0008095307QIETU
厚度的氮化物膜28b和具有20
Figure C200510136240D0008095313QIETU
至100
Figure C200510136240D0008095256QIETU
厚度的第二氧化物膜28c顺序形成在第一氧化物膜28a上，从而形成电介质膜28。
为了使电介质膜28致密且除去出现在氮化物膜28b中的针孔(pinhole)，实施湿退火工艺。
如图2I所示，用于控制栅极的多晶硅膜29通过LPCVD利用SiH4或Si2H6和PH3在0.1托至3托的压强和480℃至620℃的温度下形成在整个表面上。然后钨硅化物膜(未示出)形成在用于控制栅极的多晶硅膜29上。
在该情况下，钨硅化物膜可通过MS(SiH4)或DCS(SiH2Cl2)和WF6在300℃至500℃的反应形成，具有低氟(F)含量、低退火后应力和严密粘合性。
其后，尽管附图中未示出，但是钨硅化物膜、用于控制栅极的多晶硅膜29、电介质膜28和浮置栅极27a被选择性构图从而形成栅极。
本发明具有如下效果。
第一，可以形成具有良好电荷保持特性以及均匀且薄的厚度的电介质膜。
第二，因为可以形成具有良好电荷保持特性的电介质膜，所以可以提高器件的可靠性和产率。
第三，因为可以薄地形成电介质膜，所以可以确保其中将填埋用于控制栅极的多晶硅膜的空间。因此，可以防止用于控制栅极的多晶硅膜中空洞的产生。
第四，因为防止了用于控制栅极的多晶硅膜中空洞的产生，所以可以防止单元之间桥的产生。

Claims (12)

1.一种制造闪存器件的电介质膜的方法，包括步骤:
提供形成有浮置栅极的半导体衬底；
实施在减压状态的氧化工艺从而在包括所述浮置栅极的所述半导体衬底上形成第一氧化物膜的薄膜；以及
在所述第一氧化物膜上顺序形成氮化物膜和第二氧化物膜从而形成具有所述第一氧化物膜、所述氮化物膜和所述第二氧化物膜的电介质膜。
2.如权利要求1所述的方法，包括:所述在减压状态的氧化工艺采用在减压状态的湿氧化工艺或游离基氧化工艺。
3.如权利要求2所述的方法，包括:如果采用所述在减压状态的湿氧化工艺，则采用利用催化剂的水汽生成器。
4.如权利要求2所述的方法，包括:在200托至700托的压强在与O2相比包括大量H2的气氛下实施所述在减压状态的湿氧化工艺。
5.如权利要求2所述的方法，包括:在0.1托至200托的压强在与H2相比包括大量O2的气氛下实施所述在减压状态的湿氧化工艺。
6.如权利要求5所述的方法，其中所述氧气对氢气的比值为1:1至15:1。
7.如权利要求2所述的方法，包括在0.1托至1托的压强实施所述游离基氧化工艺。
8.如权利要求2所述的方法，包括:实施所述游离基氧化工艺在与H2相比包括过量O2的气氛下进行。
9.如权利要求8所述的方法，其中H2构成全部气体的小于40％。
10.如权利要求1所述的方法，还包括步骤:在形成所述第一氧化物膜之前，实施去除形成在所述浮置栅极的表面上的本来的氧化物膜的预处理清洁工艺。
11.如权利要求10所述的方法，包括:在预处理清洁工艺时使用HF或缓冲氧化物蚀刻剂(BOE)。
12.如权利要求1所述的方法，还包括步骤:在所述电介质膜形成之后实施蒸汽退火工艺。
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