CN103208425B - 一种石墨烯调制的高K金属栅Ge基MOS器件的制作方法 - Google Patents
一种石墨烯调制的高K金属栅Ge基MOS器件的制作方法 Download PDFInfo
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- CN103208425B CN103208425B CN201310095306.5A CN201310095306A CN103208425B CN 103208425 B CN103208425 B CN 103208425B CN 201310095306 A CN201310095306 A CN 201310095306A CN 103208425 B CN103208425 B CN 103208425B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 238000005468 ion implantation Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 238000011056 performance test Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 8
- 239000012212 insulator Substances 0.000 abstract description 5
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910002616 GeOx Inorganic materials 0.000 description 1
- 229910003855 HfAlO Inorganic materials 0.000 description 1
- 229910004143 HfON Inorganic materials 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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Abstract
本发明提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,包括步骤:1)于Ge基衬底上引入石墨烯薄膜;2)对石墨烯薄膜进行氟化处理形成氟化石墨烯;3)采用臭氧等离子体活化氟化石墨烯表面,然后通过原子层沉积技术于氟化石墨烯表面形成高k栅介质;4)于高k栅介质表面形成金属电极。本发明利用石墨烯作为钝化层抑制Ge基衬底表面非稳定氧化物GeOx形成,同时阻挡栅介质与Ge基衬底间的互扩散,提高Ge与高k栅介质层之间的界面性质。氟化石墨烯能够在保持石墨烯优良特性的基础上使石墨烯变为质量较好的绝缘体,减少其对Ge 基器件电学性能的影响。采用臭氧等离子处理Ge基石墨烯,然后采用原子层沉积技术可以获得超薄的Hf基高k栅介质层。
Description
技术领域
本发明涉及一种MOS器件的制作方法,特别是涉及一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法。
背景技术
随着半导体器件的特征尺寸进入到45nm技术节点以后,为了减小栅隧穿电流,降低器件的功耗,并彻底消除多晶硅耗尽效应和P型金属-氧化物-半导体场效应晶体管(PMOSFET)中硼穿透引起的可靠性问题,缓解费米能级钉扎效应,高介电常数(k)/金属栅材料已经代替传统的SiO2/多晶硅(poly)结构成为了必然的选择。然而,根据国际半导体技术发展蓝图(international technology roadmap for semiconductor,ITRS),CMOS技术将于2015-2020年进入16nm技术节点。CMOS逻辑器件等比例缩小将面临更多的挑战。为了跨越尺寸缩小所带来的这些障碍,要求把最先进的工艺技术整合到产品制造过程中。根据现有的发展趋势,被引入到16nm节点的新的技术应用,涉及如下几个方面:浸入式光刻的延伸技术、迁移率增强衬底技术、超浅结(ultra-shallow junction,USJ)以及其他应变增强工程等方法。其中迁移率增强衬底技术得到了越来越广泛的关注。锗(Germanium,Ge)因其极高的载流子迁移率,且与半导体工艺兼容,被认为是最具潜力的高迁移率半导体材料。锗的带隙宽度为0.66eV,电子迁移率与空穴迁移率分别是Si的2.6与4.2倍,而且迁移率还可以通过应变增强技术得到进一步提高,是CMOS器件理想的沟道材料。然而,Ge的氧化物在性质上不同于Si的氧化物,GeO2在常温下很容易吸收水分子而变得不稳定。而且在温度升高时,GeO2会与Ge反应生成GeO,导致在MOS工艺下高k/Ge结构界面不稳定。此外,由于高k/Ge界面容易发生严重的互扩散还会导致介质层性能下降、器件栅极漏电流严重等问题。
针对高k/Ge界面结构所面临的挑战,石墨烯被认为是有机材料中最稳定的二维材料,而且具有超强的柔韧性以及超高的致密度。最新的研究表明,石墨烯不仅具有超高的载流子迁移率,同时也具有很好的钝化效果。研究发现,通过化学气相沉积的方法将石墨烯生长到铜或铜镍合金表面,能够很好的阻止金属材料被氧化。在Ni、Al、Au与Si衬底之间引入石墨烯,可以很好在较高温度条件下作为钝化层抑制不同薄层之间原子的扩散。另外,研究表明石墨烯的导体特性可以通过H、O或者F等离子体处理向半导体甚至绝缘体转变。因此,在高k栅介质材料与锗衬底之间引入等离子处理的石墨烯阻挡层,有望在不影响沟道特性的前提下解决不稳定GeOx生成和Ge与高k间的互扩散难题。该研究成果将拓展石墨烯材料的应用领域,推动微电子技术延续摩尔定律不断发展。
发明内容
鉴于以上所述现有技术的缺点,本发明的目的在于提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,用于解决现有技术中不稳定GeOx生成和Ge与高k金属栅间的互扩散的问题。
为实现上述目的及其他相关目的,本发明提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,至少包括以下步骤:
1)于Ge基衬底上引入石墨烯薄膜;
2)对所述石墨烯薄膜进行氟化处理形成氟化石墨烯绝缘薄层;
3)采用臭氧等离子体活化所述氟化石墨烯表面,然后通过原子层沉积技术于所述氟化石墨烯表面形成高k栅介质;
4)于所述高k栅介质表面形成金属电极。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,还包括以下步骤:
5)去除部分的金属电极、高k栅介质及氟化石墨烯,形成MOS器件的栅极结构;
6)通过离子注入工艺形成MOS器件的源区和漏区;
7)制作源区电极及漏区电极。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,步骤1)包括以下步骤:
1-1)于金属衬底上生长石墨烯薄膜;
1-2)将所述石墨烯薄膜转移至所述Ge基衬底上;
1-3)退火加固所述石墨烯薄膜及Ge基衬底的结合。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,步骤1)采用化学气相沉积法于所述Ge基衬底表面原位生长石墨烯薄膜。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,步骤2)中,采用XeF2气体对所述石墨烯薄膜进行等离子体氟化处理。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,所述高k栅介质的材料为Hf基介质。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,步骤4)采用物理气相沉积法形成所述金属电极,所述金属电极为Pt电极。
作为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法的一种优选方案,步骤4)后还包括于N2及O2气氛中退火并进行界面的扩散及电性能测试的步骤。
如上所述,本发明提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,包括步骤:1)于Ge基衬底上引入石墨烯薄膜;2)对所述石墨烯薄膜进行氟化处理形成氟化石墨烯;3)采用臭氧等离子体活化所述氟化石墨烯表面,然后通过原子层沉积技术于所述氟化石墨烯表面形成高k栅介质;4)于所述高k栅介质表面形成金属电极。本发明具有以下有益效果:1)采用石墨烯作为钝化层抑制GeOx中间层的产生,阻挡界面原子互扩散,调制HfO2/Ge堆叠结构的界面性质,同时利用石墨烯二维材料特性,有效控制MOS器件介质层的EOT;2)整合HfO2作为介质材料的优良性质以及Ge作为衬底材料所具有的超高迁移率特性;3)采用氟化处理石墨烯使石墨烯由导体转变为绝缘体,降低石墨烯钝化层对沟道特性的影响;采用臭氧等离子处理Ge基石墨烯,为超薄HfO2生长提供必要条件。
附图说明
图1a~图2b显示为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法步骤1)所呈现的结构示意图。
图3~图4显示为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法步骤2)所呈现的结构示意图。
图5~图6显示为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法步骤3)所呈现的结构示意图。
图7~图8显示为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法步骤4)所呈现的结构示意图。
图9显示为本发明的石墨烯调制的高k金属栅Ge基MOS器件的制作方法步骤5)~7)所呈现的结构示意图。
元件标号说明
具体实施方式
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。
请参阅1a~图9。需要说明的是,本实施例中所提供的图示仅以示意方式说明本发明的基本构想,遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制,其实际实施时各组件的型态、数量及比例可为一种随意的改变,且其组件布局型态也可能更为复杂。
如图1a~图9所示,本实施例提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,至少包括以下步骤:
如图1a~图2b所示,首先进行步骤1),于Ge基衬底101上引入石墨烯薄膜102。
如图1a~1b所示,在一具体的实施过程中,步骤1)包括以下步骤:
首先进行步骤1-1),于金属衬底上生长石墨烯薄膜102。
作为示例,所述金属衬底为铜或镍等。
然后进行步骤1-2),将所述石墨烯薄膜102转移至所述Ge基衬底101上。
作为示例,先将金属衬底上生长的石墨烯薄膜102转移至PMMA基底103上,然后藉由该PMMA基底103将石墨烯薄膜102贴合至Ge基衬底101表面,接着采用丙酮溶液清洗去除所述PMMA基底103。
最后进行步骤1-3),退火加固所述石墨烯薄膜102及Ge基衬底101的结合。
如图2a~图2b所示,在另一具体的实施过程中,步骤1)采用化学气相沉积法于所述Ge基衬底101表面原位生长石墨烯薄膜102。
作为示例,以H2105和CH4104作为反应气体,在较低的温度下采用化学气相沉积法于所述Ge基衬底101表面原位生长石墨烯薄膜102。
所述石墨烯薄膜102可以作为钝化层抑制Ge基衬底101中非稳定氧化物GeOx形成,同时阻挡后续高k栅介质107与Ge基衬底101之间的互扩散。
如图3~图4所示,然后进行步骤2),对所述石墨烯薄膜102进行氟化处理形成氟化石墨烯106绝缘薄层。
作为示例,将所述石墨烯薄膜102置于等离子设备中,采用离化的XeF2气体对所述石墨烯薄膜102进行等离子体氟化处理,形成氟化石墨烯106绝缘薄层。
氟化石墨烯106能够在保持石墨烯相关优良特性的基础上使石墨烯变为质量较好的绝缘体,利用等离子体氟化处理石墨烯可以减少其对Ge沟道材料电学性能的影响。
如图5~图6所示,接着进行步骤3),采用臭氧等离子体活化所述氟化石墨烯106表面,然后通过原子层沉积技术于所述氟化石墨烯106表面形成高k栅介质107。
作为示例,所述高k栅介质107的材料为Hf基介质,在本实施例中,所述高k栅介质107的材料为HfO2。当然,在其它的实施例中,所述高k栅介质107也可以为HfON、HfAlO、HfAlON、HfTaO、HfTaON、HfSiO、HfSiON、HfLaO或者HfLaON等。
由于石墨烯是二维材料,很难直接采用原子层沉积ALD技术在其上沉积高质量的金属氧化层,而采用臭氧等离子表面活化技术能够在石墨烯表面产生悬挂键,为后续ALD前驱体表面吸附提供必要的条件,获得高质量的超薄的高k栅介质107层。
如图7~图8所示,最后进行步骤4),于所述高k栅介质107表面形成金属电极108。
作为示例,采用物理气相沉积法形成所述金属电极108,所述金属电极108为Pt电极。当然,所述金属电极108也可以是如Au等其它的金属。
作为示例,步骤4)后还包括于N2及O2气氛中退火并进行界面的扩散及电性能测试的步骤。该步骤可以用于研究Hf基高k金属栅与Ge界面的扩散行为及相关电学性质,具体地,采用常规的MOS工艺退火后,可以采用高分辨透射电镜对样品界面状态进行表征,采用XPS深度分析研究退火前后的界面处元素分布情况等。
如图8所示,于高k金属栅及Ge基衬底101界面间增加一层氟化石墨烯106薄膜102,可以阻挡界面原子互扩散,调制HfO2/Ge堆叠结构的界面性质。同时利用石墨烯二维材料特性,有效控制MOS器件介质层的EOT。
如图9所示,作为示例,形成Ge基衬底101/氟化石墨烯106/高k金属栅堆叠结构后,还包括采用常规的MOS工艺形成MOS器件的步骤,具体地,至少还包括以下步骤:
首先进行步骤5),去除部分的金属电极108、高k栅介质107及氟化石墨烯106,形成MOS器件的栅极结构。
作为示例,采用干法刻蚀工艺形成所述栅极结构。
然后进行步骤6),通过离子注入工艺形成MOS器件的源区109和漏区110。
作为示例,可以先通过离子注入工艺及退火工艺形成浅掺杂漏LDD。
作为示例,可以于栅极结构侧壁形成保护如氧化硅、氮化硅等侧墙结构。
作为示例,所述MOS器件可以是PMOS、NMOS或CMOS器件,可以通过不同类型的离子注入实现不同类型的MOS器件。
最后进行步骤7),制作源区电极111及漏区电极112。
作为示例,所述源区电极111及漏区电极112可以通过直接溅射或电镀工艺形成,也可以通过沉积后退火形成金属锗化物作为电极。
综上所述,本发明提供一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,包括步骤:1)于Ge基衬底101上引入石墨烯薄膜102;2)对所述石墨烯薄膜102进行氟化处理形成氟化石墨烯106;3)采用臭氧等离子体活化所述氟化石墨烯106表面,然后通过原子层沉积技术于所述氟化石墨烯106表面形成高k栅介质107;4)于所述高k栅介质107表面形成金属电极108。本发明具有以下有益效果:1)采用石墨烯作为钝化层抑制GeOx中间层的产生,阻挡界面原子互扩散,调制HfO2/Ge堆叠结构的界面性质,同时利用石墨烯二维材料特性,有效控制MOS器件介质层的EOT;2)整合HfO2作为介质材料的优良性质以及Ge作为衬底材料所具有的超高迁移率特性;3)采用氟化处理石墨烯使石墨烯由导体转变为绝缘体,降低石墨烯钝化层对沟道特性的影响;采用臭氧等离子处理Ge基石墨烯,为超薄HfO2生长提供必要条件。所以,本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。
Claims (7)
1.一种石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于,至少包括以下步骤:
1)于Ge基衬底上引入石墨烯薄膜;
2)对所述石墨烯薄膜进行氟化处理形成氟化石墨烯绝缘薄层;
3)采用臭氧等离子体活化所述氟化石墨烯表面,然后通过原子层沉积技术于所述氟化石墨烯表面形成高k栅介质;
4)于所述高k栅介质表面形成金属电极;
5)去除部分金属电极、高k栅介质及氟化石墨烯,形成MOS器件的栅极结构;
6)通过离子注入工艺形成MOS器件的源区和漏区;
7)制作源区电极及漏区电极。
2.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于:步骤1)包括以下步骤:
1-1)于金属衬底上生长石墨烯薄膜;
1-2)将所述石墨烯薄膜转移至所述Ge基衬底上;
1-3)退火加固所述石墨烯薄膜及Ge基衬底的结合。
3.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于:步骤1)采用化学气相沉积法于所述Ge基衬底表面原位生长石墨烯薄膜。
4.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于:步骤2)中,采用XeF2气体对所述石墨烯薄膜进行等离子体氟化处理。
5.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于,所述高k栅介质的材料为Hf基介质。
6.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于:步骤4)采用物理气相沉积法形成所述金属电极,所述金属电极为Pt电极。
7.根据权利要求1所述的石墨烯调制的高k金属栅Ge基MOS器件的制作方法,其特征在于:步骤4)后还包括于N2及O2气氛中退火并进行界面的扩散及电性能测试的步骤。
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