CN103097394A - 钼(iv)酰胺前驱物和其在原子层沉积中的用途 - Google Patents
钼(iv)酰胺前驱物和其在原子层沉积中的用途 Download PDFInfo
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D1/60—Deposition of organic layers from vapour phase
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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Abstract
Description
相关申请案的交叉参考
本申请案主张2010年8月27日提交的美国专利申请案第61/377,692号的优先权,后者的全部揭示内容以引用的方式并入本文。
技术领域
本发明涉及钼(Mo)(IV)酰胺前驱物和采用此类前驱物通过原子层沉积(ALD)来制备MoO2膜的方法。
背景技术
ALD为已知的薄膜沉积方法。其为一种自限性、连续独特的膜生长技术,此项技术以表面反应为基础并且可提供原子层控制,并且将由前驱物所提供的材料的保形薄膜沉积到不同组成的衬底上。在ALD中,在反应期间分离前驱物。第一前驱物通过衬底并在所述衬底上形成单层。将任何过量的未反应前驱物泵出反应室。接着第二前驱物通过所述衬底并与第一前驱物反应,从而在所述衬底表面上形成单层膜。重复此循环以得到所需厚度的膜。
ALD方法可应用在纳米技术和半导体元件(例如电容器电极、栅电极、粘合剂扩散障壁以及集成电路)的制造中。此外,在微电子学和光电子学的许多子领域内需要具有高介电常数(电容率)的介电薄膜。随着微电子组件的尺寸持续缩小,使得使用此类介电膜的需求日益增加。
格林,J.(Green,J.)等人报道了Mo络合物Mo(C5H5)(NMe2)3的合成与分离。化学学会会志(J.Chem.Soc.),道耳顿会刊(Dalton Trans.),1997,第3219-3224页。
美国专利第5,064,686号报道了一种用于化学气相沉积(CVD)的Mo(IV)络合物。在CVD中尝试使用Mo[N(Me)(Me)]4。然而,在CVD中注意到热稳定性问题并且已发现虽然此前驱物在结构上类似,但它并不适合用于沉积MoO2层。
此外,发现Mo(NtBu)2(NMe2)2对通过ALD来形成MoO2膜并不能产生良好效果,原因在于其形成了不适于DRAM的MoO3膜。因此需要发现新的Mo前驱物,其能够通过ALD沉积MoO2膜,其具有改善的热稳定性、较高的挥发性或提高的沉积速率。
发明内容
在一个实施例中,提供一种络合物,其结构对应于式I:
其中L为--NR1R2;R1和R2为C1-C6烷基或氢;R为C1-C6烷基;并且n为0、1、2或3。
在另一实施例中,提供一种通过ALD形成MoO2膜的方法。所述方法包括将至少一种前驱物传送到衬底,其中所述至少一个前驱物结构对应于上述式I。
在另一实施例中,提供络合物Mo[N(Me)(Et)]4和其在ALD中形成MoO2膜的用途。
其它实施例(包括以上概述的实施例的特定方面)将从以下详细描述中获悉详情。
附图说明
图1为显示Mo[N(Me)(Et)]4的毫克数相对于温度/时间的热重量分析(TGA)数据的图示。
具体实施方式
在本发明的多个方面中,提供Mo(IV)酰胺前驱物,并且提供其使用方法以通过ALD来形成MoO2膜。
在一个实施例中,可使用本发明的方法来形成或生长出显示高介电常数的含Mo薄膜。如本文所使用的介电薄膜意指具有高电容率的薄膜。
如本文所使用,术语“前驱物”意指有机金属分子、络合物和/或化合物,其被传送到衬底用于沉积,以通过ALD形成薄膜。
术语“Cp”意指与过渡金属结合的环戊二烯基(C5H5)配体。如本文所使用,Cp配体的全部五个碳原子通过π键结以η5配位结合到金属中心,因此本发明的前驱物为π络合物。
术语“烷基”意指长度为1到约6个碳原子的饱和烃链,例如(但不限于)甲基、乙基、丙基以及丁基。烷基团可为直链或支链。举例来说,如本文所使用,丙基包含正丙基和异丙基;丁基包含正丁基、仲丁基、异丁基以及叔丁基。此外,如本文所使用,“Me”意指甲基,并且“Et”意指乙基。
术语“氨基”在本文中意指任选取代的单价氮原子(即,-NR1R1,其中R1和R2可相同或不同)。本发明所包含的氨基的实例包括(但不限于)以及此外,此氨基的氮原子以共价方式结合到金属中心,其一起可称为“酰胺”基团(即)。此又可称为“氨基(ammono)”基团或无机酰胺。
在第一实施例中,提供一种“琴凳”络合物,其结构对应于式I:
其中L为--NR1R2;R1和R2独立地为C1-C6烷基或氢;R为C1-C6烷基;并且n为0、1、2或3。
R1和R2可相同或不同。在一个特定实施例中,R1和R2均为甲基。在另一个特定实施例中,R1为甲基并且R2为乙基。
在又一实施例中,当n为0时,R1和R2彼此不同。
在一个实施例中,R1和R2独立地为甲基、乙基或丙基;R为甲基、乙基或丙基;并且n为0、1或2。
在另一实施例中,R1和R2相同;R为甲基;n为0、1或2。
在另一实施例中,R1为甲基并且R2为乙基;R为甲基;并且n为0、1或2。
结构对应于式I的络合物的实例为:
(环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NMe2)3;
(乙基环戊二烯基)Mo(NMe2)3;
(丙基环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NEt2)3;
(乙基环戊二烯基)Mo(NEt2)3;
(丙基环戊二烯基)Mo(NEt2)3;
(环戊二烯基)Mo(NMeEt)3;
(甲基环戊二烯基)Mo(NMeEt)3;
(乙基环戊二烯基)Mo(NMeEt)3;以及
(丙基环戊二烯基)Mo(NMeEt)3。
在另一实施例中,用另一酰胺基团取代Mo(IV)酰胺络合物上的环戊二烯基环,形成四酰胺:Mo[N(Me)(Et)]4。
将依据式I的络合物和Mo[N(Me)(Et)]4用作前驱物,以通过ALD形成MoO2膜。可以脉冲方式,与适当氧源(例如H2O、H2O2、O2、臭氧、iPrOH、tBuOH或N2O)脉冲交替将本文所揭示的前驱物传送到衬底以供沉积。
在一个实施例中,可通过独立传送或与一种共反应剂组合传送至少一种依据式I的前驱物,以供沉积,从而形成MoO2膜。此类共反应剂的实例包括(但不限于)氢、氢等离子体、氧气、空气、水、H2O2、氨、肼、烷基肼、硼烷、硅烷、臭氧或其任何组合。
在本发明的方法中可使用多种衬底。举例来说,可将依据式I的前驱物或Mo[N(Me)(Et)]4传送到衬底(例如(但不限于)硅、氧化硅、氮化硅、钽、氮化钽或铜)上以供沉积。
本发明的ALD方法包括多种类型的ALD方法。举例来说,在一个实施例中,采用传统的ALD来形成本发明的含金属膜。有关传统和/或脉冲注入的ALD方法可参见(举例来说)乔治S.M.(George S.M.)等人,物理化学杂志(J.Phys.Chem.)1996.100:13121-13131。
在又一实施例中,采用液体注入ALD来形成含金属膜,其中液体前驱物不采用利用(传统)鼓泡器的蒸汽牵引,而是以直接液体注入方式传送到反应室。有关液体注入ALD方法可参见(举例来说)R.J.等人,化学气相沉积(Chem.Vap.Deposition.)2005.11(3):159。
液体注入ALD生长条件的实例包括(但不限于):
(1)衬底温度:Si(100)上160-300℃
(2)蒸发器温度范围:约120-200℃
(3)反应器压力范围:约2-50毫巴
(4)溶剂:甲苯,或任何上述溶剂
(5)溶液浓度范围:约0.05到2M
(6)注入速率范围:每脉冲约1-10μl(每周期4个脉冲)
(7)惰性气体流动速率:约50-500cm3min-1
(8)脉冲顺序(秒)(前驱物/净化/H2O/净化):将依据腔室大小变化。
(9)循环次数:将依据所需膜厚度而变化。
前驱物可溶解在适当的烃或胺溶剂中。适当的烃溶剂包括(但不限于)脂肪族烃,例如己烷、庚烷和壬烷;芳香烃,例如甲苯和二甲苯;脂肪族和环醚,例如二甘醇二甲醚、三甘醇二甲醚和四甘醇二甲醚。适当的胺溶剂的实例包括(但不限于)辛胺和N,N-二甲基十二胺。举例来说,前驱物可溶解于甲苯中,以得到0.05到1M的溶液。
在另一实施例中,可将至少一种结构对应于式I的前驱物和/或Mo[N(Me)(Et)]4呈“纯物质”(未经运载气体稀释)传送到衬底。
在另一实施例中,采用光辅助ALD来形成含金属膜。有关光辅助ALD方法可参见(举例来说)美国专利第4,581,249号。
在另一实施例中,可采用液体注入和光辅助ALD两者,并且使用至少一种结构对应于式I的前驱物和/或Mo[N(Me)(Et)]4来形成含金属膜。
在另一实施例中,可采用等离子体辅助ALD,并且使用至少一种结构对应于式I的前驱物和/或Mo[N(Me)(Et)]4来形成含金属膜。
因此,在这些方法中所使用的结构对应于式I的有机金属前驱物和Mo[N(Me)(Et)]4可为液体、固体或气体。特定而言,前驱物在周围温度下为液体,且具有高蒸汽压力以不断地输送蒸汽到处理室。
ALD实质上依赖于化学反应而非热分解。因此,为适当前驱物所需的特征存在根本差异。所述前驱物在所采用的温度下必须为热稳定的,且应具有足够的挥发性,以允许沉积到衬底上。此外,当沉积金属氧化物膜时,在金属前驱物与氧化物源之间需要快速又完全的化学反应。然而,反应应仅在衬底表面发生,以免损害下层结构,且应可容易地自表面移除副产物(例如碳和氢)。
已发现Cp环的取代和连接到金属中心的三个相同配体的变化在ALD方法中展示有用且得到改善的性质。举例来说,式I的前驱物提高通过ALD沉积MoO2膜的能力,其生长速率接近采用简单金属酰胺时的生长速率,但由于提高了热稳定性而可在较高温度下操作,此使得产品品质得到改善。此外,使用琴凳型Mo(IV)酰胺络合物可通过使分子极化以容许与表面反应而增强ALD性能,所述表面的自限性膜生长可达饱和状态,以达到优良的保形控制。
在特定实施例中,本发明的方法被用于例如硅芯片的衬底上的应用,例如用于存储和逻辑应用的动态随机存取存储器(DRAM)和互补金属氧化物半导体(CMOS)。
在又一实施例中,提供通过ALD来形成“混合”金属膜的方法。本文所使用的术语“混合”金属膜指至少由两种不同金属构成所述膜。
在一个实施例中,通过传送至少一种依据式I的前驱物和/或Mo[N(Me)(Et)]4和至少一种具有不同金属中心的共前驱物通过ALD沉积来形成混合金属膜。举例来说,可将至少一种依据式I的Mo前驱物和/或Mo[N(Me)(Et)]4和至少一种适当的共前驱物(例如铅、钛、锶和/或钡前驱物)传送到衬底进行沉积,从而产生混合金属膜。
利用本发明方法所形成的薄膜具有介于10和250之间、优选为至少25到40且更优选为至少40到100的电容率。此外,高于100的值可被认为是超高电容率。所属领域的一般技术人员应了解,所得膜的电容率取决于许多因素,例如用于沉积的金属、所形成的膜的厚度、在生长以及随后的处理期间所采用的参数和衬底。
实例
以下实例仅为说明性的,并不以任何方式限制本发明。所有的操作均在惰性气氛中使用手套箱和史兰克管技术(Schlenk line technique)进行。使用布鲁克250MHz仪器(Bruker250MHz machine)进行NMR分析。
实例1-Mo(NMeEt)4的合成
使用标准技术从nBuLi和HNEtMe制备N-乙基,甲基胺化锂。在4小时时间内将N-乙基甲基胺(65.6g,1.1摩尔)逐滴滴加到nBuLi(680ml,1.6M己烷溶液,已用冰浴冷却到0℃)。在已添加所有胺后,立即加热所述混合物至室温,接着搅拌过夜。将THF(250ml)添加到此混合物中,且搅拌此混合物1小时,接着在冰浴中冷却到0℃。将MoCl5(50.2g,0.18摩尔,由于混合物会大量放热并且喷溅,所以应在8小时时间内以每小份约1-2g分次添加)添加到此混合物中。一旦所有的MoCl5添加完毕,就将此深褐色(近乎黑色)反应混合物加热到室温,接着回流1小时。冷却混合物并接着搅拌过夜。使用标准技术使所述混合物沉降(LiCl)并过滤。从反应混合物汽提出溶剂,接着将紫色液体从所述反应混合物升华/蒸馏出来,得到紫色液体。
蒸馏条件:压力范围3.5×10-2托(Torr)和油浴温度100-110℃。
Mo(NEtMe)4NMR | δ,ppm-(积分值) | 分布 |
1.17(12H) | 乙基CH3,即NCH2 CH 3 | |
3.22(8H) | 乙基CH2,即NCH 2CH3 | |
3.49(12H) | 氮上的甲基,即NCH 3 |
图1展示Mo(NMeEt)4的TGA数据。
实例2-[Mo(MeCp)(NEtMe)3]的合成
向已在冰浴中冷却到0℃的Mo(NEtMe)4(如上述制备,3.3g,0.01摩尔)的深紫色甲苯溶液(60ml)中添加新近裂化的MeCpH(4g,0.05摩尔,经由注射添加)。未立即观察到颜色变化,因此在室温下搅拌所述混合物2小时。仍未观察到颜色变化,因而让所述混合物回流3小时,以得到深绿色溶液。从反应混合物汽提出甲苯,得到深绿色液体。
Mo(MeCp)(NEtMe)3 | 1.00,(9H) | 乙基CH3,即CH2 CH 3 |
1.60,(3H) | Cp环上的甲基,即MeCp | |
2.95,(9H) | 氮上甲基,即NCH 3 | |
3.15,(6H) | 乙基CH2,即NCH 2CH3 | |
4.95(2H) | Cp环氢 | |
5.15,(2H) | Cp环氢 |
实例3-使用[Mo(MeCp)(NEtMe)3]的ALD
在定制的ALD反应器中沉积MoO2膜。Mo(MeCp)(NEtMe)3和臭氧用作前驱物。将MoO2膜沉积在硅晶片衬底上。在沉积之前,通过切割所述晶片(1英寸×1/2英寸)并用1%HF抛光来制备晶片衬底。
生长温度为200-350℃。生长压力为0.5-1.5托(Torr)。用30sccm的干氮连续净化所述反应器。所述反应器中的所有用计算机控制的阀均为购自卡洪(Cajon)的气动型ALDVCR阀。
将臭氧充分净化。将钼存储在不锈钢安瓿中。ALD阀直接与所述安瓿相连。此ALD阀的出口与用于氮气注入的另一ALD阀成T形。T形出口端管连接到500cm3不锈钢储槽。所述储槽的出口连接到称为注入阀的第三ALD阀,其出口直接通向所述反应器。注入氮气用于建立钼注入阀后面的总压力,以使所述压力高于反应器生长压力。使用30微米的针孔VCR垫片完成氮气注入。所有的阀和安瓿均置于炉形箱中,使安瓿、阀和导管均匀加热到50℃到250℃。
在ALD生长操作期间,阀以以下方式排序。将钼前驱物引至活化硅表面。接着进行氮气净化,其包括抽气以移除剩余的未附着到表面的反应剂分子。接着引入臭氧,随后再用氮气进行净化。接着注入臭氧以重新开始ALD循环。
循环的总数量一般为300次。
本文所引用的全部专利和公开案以全文引用方式并入到本申请案中。
用词“包括(comprise)”、“包括(comprises)”和“包括(comprising)”应解释为涵盖含义而非穷举含义。
Claims (21)
1.一种络合物Mo[N(Me)(Et)]4。
2.一种通过原子层沉积来形成MoO2膜的方法,所述方法包括将Mo[N(Me)(Et)]4传送到衬底。
4.根据权利要求3所述的络合物,其中
R1和R2独立地为甲基、乙基或丙基;
R为甲基、乙基或丙基;并且
n为0、1或2。
5.根据权利要求3所述的络合物,其中
R1和R2相同;
R为甲基;并且
n为0、1或2。
6.根据权利要求3所述的络合物,其中
R1为甲基并且R2为乙基;
R为甲基;并且
n为0、1或2。
7.根据权利要求3所述的络合物,其中所述结构对应于式I的络合物选自由以下所组成的群组:
(甲基环戊二烯基)Mo(NMe2)3;
(乙基环戊二烯基)Mo(NMe2)3;
(丙基环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NEt2)3;
(乙基环戊二烯基)Mo(NEt2)3;
(丙基环戊二烯基)Mo(NEt2)3;
(环戊二烯基)Mo(NMeEt)3;
(甲基环戊二烯基)Mo(NMeEt)3;
(乙基环戊二烯基)Mo(NMeEt)3;以及
(丙基环戊二烯基)Mo(NMeEt)3。
8.根据权利要求3所述的络合物,其中所述结构对应于式I的络合物选自由以下所组成的群组:
(甲基环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NMeEt)3;以及
(环戊二烯基)Mo(NMeEt)3。
10.根据权利要求9所述的方法,其中:
R1和R2独立地为甲基、乙基或丙基;
R为甲基、乙基或丙基;并且
n为0、1或2。
11.根据权利要求9所述的方法,其中
R1和R2相同;
R为甲基;并且
n为0、1或2。
12.根据权利要求9所述的方法,其中
R1为甲基并且R2为乙基;
R为甲基;并且
n为0、1或2。
13.根据权利要求9所述的方法,其中所述至少一种结构对应于式I的前驱物选自由以下所组成的群组:
(环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NMe2)3;
(乙基环戊二烯基)Mo(NMe2)3;
(丙基环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NEt2)3;
(乙基环戊二烯基)Mo(NEt2)3;
(丙基环戊二烯基)Mo(NEt2)3;
(环戊二烯基)Mo(NMeEt)3;
(甲基环戊二烯基)Mo(NMeEt)3;
(乙基环戊二烯基)Mo(NMeEt)3;以及
(丙基环戊二烯基)Mo(NMeEt)3。
14.根据权利要求9所述的方法,其中所述至少一种结构对应于式I的前驱物选自由以下所组成的群组:
(甲基环戊二烯基)Mo(NMe2)3;
(甲基环戊二烯基)Mo(NMeEt)3;
(环戊二烯基)Mo(NMeEt)3;以及
(环戊二烯基)Mo(NMe2)3。
15.根据权利要求9所述的方法,其中所述原子层沉积选自由光辅助原子层沉积、液体注入原子层沉积和等离子体辅助原子层沉积所组成的群组。
16.根据权利要求9所述的方法,其中将所述前驱物以脉冲方式与选自H2O、H2O2、O2、臭氧、iPrOH、tBuOH和N2O的氧源脉冲交替沉积到所述衬底上。
17.根据权利要求9所述的方法,其中将至少两种结构对应于式I的前驱物传送到所述衬底,以通过原子层沉积形成MoO2膜。
18.根据权利要求9所述的方法,其进一步包括将至少一种共前驱物传送到所述衬底,以通过原子层沉积形成混合金属膜。
19.根据权利要求9所述的方法,其中将所述至少一种结构对应于式I的前驱物在传送到所述衬底之前溶解于溶剂中。
20.根据权利要求19所述的方法,其中将所述至少一种结构对应于式I的前驱物呈纯物质传送到所述衬底。
21.根据权利要求9所述的方法,其中所述MoO2膜用于存储器和/或逻辑应用。
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CN109134546A (zh) * | 2017-06-15 | 2019-01-04 | 三星电子株式会社 | 钨前驱体及使用其形成含钨层的方法 |
CN109134546B (zh) * | 2017-06-15 | 2023-03-10 | 三星电子株式会社 | 钨前驱体及使用其形成含钨层的方法 |
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CN103097394B (zh) | 2016-03-02 |
IL224618A (en) | 2015-02-26 |
EP2609102B1 (en) | 2014-12-31 |
US9802220B2 (en) | 2017-10-31 |
TW201219405A (en) | 2012-05-16 |
SG187920A1 (en) | 2013-03-28 |
WO2012027575A1 (en) | 2012-03-01 |
EP2609102A1 (en) | 2013-07-03 |
US20130196065A1 (en) | 2013-08-01 |
JP5873494B2 (ja) | 2016-03-01 |
TWI549958B (zh) | 2016-09-21 |
KR20130139866A (ko) | 2013-12-23 |
JP2013540893A (ja) | 2013-11-07 |
KR101847953B1 (ko) | 2018-04-11 |
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