CN113943321B - 用于薄膜沉积的第5族金属化合物和使用该化合物形成含第5族金属的薄膜的方法 - Google Patents

用于薄膜沉积的第5族金属化合物和使用该化合物形成含第5族金属的薄膜的方法 Download PDF

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CN113943321B
CN113943321B CN202110693956.4A CN202110693956A CN113943321B CN 113943321 B CN113943321 B CN 113943321B CN 202110693956 A CN202110693956 A CN 202110693956A CN 113943321 B CN113943321 B CN 113943321B
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李太荣
池成俊
白善英
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EGTM Co Ltd
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Abstract

根据本公开的实施方案的第5族金属化合物由以下<化学式1>和<化学式2>中的任一个表示:在<化学式1>和<化学式2>中,M是选自第5族金属元素中的任意一种,n是选自1至5的整数中的任意一个,R1是选自具有3至6个碳原子的直链烷基基团和具有3至6个碳原子的支链烷基基团中的任意一种,并且R2和R3各自独立地为选自氢、具有1至4个碳原子的直链烷基基团和具有1至4个碳原子的支链烷基基团中的任意一种。

Description

用于薄膜沉积的第5族金属化合物和使用该化合物形成含第5 族金属的薄膜的方法
对相关申请的交叉引用
本申请要求于2020年6月30日向韩国知识产权局提交的韩国专利申请号10-2020-0080284的优先权,该韩国专利申请的公开内容通过引用并入本文。
技术领域
本公开涉及第5族金属化合物和使用该化合物形成金属薄膜的方法,更具体地,涉及用作前体的第5族金属前体化合物和使用该化合物形成含第5族金属的薄膜的方法。
背景技术
随着电子技术的发展,对用于各种电子设备中的电子元件的小型化和轻量化的需求正在迅速增加。为了形成精细的电子元件,已经提出了各种物理和化学气相沉积方法,并且已经对通过这种沉积方法制造诸如金属薄膜、金属氧化物薄膜和金属氮化物薄膜之类的各种电子元件进行了各种研究。
在半导体元件的制造中,通常使用金属有机化学气相沉积(MOCVD)或原子层沉积(ALD)工艺形成含第5族金属化合物的薄膜。
然而,与MOCVD工艺相比,由于ALD工艺进行自限反应,因此其具有优异的阶梯覆盖性,并且由于ALD工艺是相对低温的工艺,因此其可以避免因热扩散导致的元件特性劣化。
含第5族金属化合物的薄膜中的氧化锆(ZrO2)薄膜已被用作电容器结构中绝缘层的高k材料。最近,已发现介于两个ZrO2介电层之间的氧化铌(Nb2O5)薄膜可显著降低漏电流并有助于稳定ZrO2的立方晶系/四方晶系相。所产生的ZrO2/Nb2O5/ZrO2层压板在动态随机存取存储器(DRAM)的当前金属-绝缘体-金属(MIM)电容器中提供更高的k值(文件[Alumina,J.Vac.Sci.Technol A 4(6),1986和Microelectronic Engineering 86(2009)1789-1795])。
选择适合于沉积工艺的前体化合物以沉积含铌(Nb)的薄膜是非常重要的。已知能够形成含第5族金属的薄膜的代表性有机金属前体化合物包括五(二甲基酰氨基)钽(PDMAT)、(叔丁基酰亚胺)三(二乙基酰氨基)钽(TBTDET)、(叔丁基酰亚胺)三(二乙基酰氨基)铌(TBTDEN)等。然而,由于PDMAT是固体,因此难以通过持续升华PDMAT来供给,通过将液体容纳在圆柱形容器中而使液体蒸发,或蒸发以恒定流速注入的液体的直接液体注入(DLI)装置等已广泛应用于半导体元件制造工艺中。另外,由于PDMAT、TBTDET、TBTDEN等都具有较差的热稳定性,在高温下使用它们是不利的。因此,难以在原子层沉积(ALD)工艺中使用这些化合物来于300℃在不平坦表面上形成具有均匀厚度的氧化膜。
因此,适用于原子层沉积(ALD)工艺的前体化合物应该在低温下具有高蒸气压,应该足够热稳定,并且应该是具有低粘度的液体化合物,以便它可以容易转移到反应室而不被分解。
[相关技术文件]
[专利文件]
(专利文件1)韩国早期公开专利公开号2020-0008048(2020.01.22.)
发明内容
本公开的目的是通过解决常规使用的金属前体化合物的缺点,提供一种在室温下为液体、具有高挥发性且热稳定的第5族金属化合物,以及用于包括该第5族金属化合物的用于薄膜沉积的前体组合物。此外,本公开的目的是提供一种使用包括第5族金属化合物的用于薄膜沉积的前体组合物来沉积高质量薄膜的薄膜形成方法。
根据以下详细描述,本公开的其他目的将变得更加明显。
根据本公开的实施方案的第5族金属化合物可以由以下化学式1和2中的任一个表示:
在<化学式1>和<化学式2>中,M为选自第5族金属元素[钒(V)、铌(Nb)和钽(Ta)]中的任意一种,n为选自1至5的整数,并且R1为选自具有3至6个碳原子数的直链烷基基团和具有3至6个碳原子数的支链烷基基团中的任意一种。例如,R1可以是选自正丙基基团、异丙基基团、正丁基基团、叔丁基基团、异丁基基团、仲丁基基团、正戊基基团、叔戊基基团、异戊基基团、仲戊基基团、新戊基基团和3-戊基基团中的任意一种。R2和R3各自独立地为选自氢、具有1至4个碳原子的直链烷基基团和具有1至4个碳原子的支链烷基基团中的任意一种。例如,R2和R3可以各自独立地为选自氢、甲基基团、乙基基团、正丙基基团、异丙基基团、正丁基基团、仲丁基基团、异丁基基团和叔丁基基团中的任意一种,并且R2和R3可以具有彼此相同的结构。
根据本公开实施方案的形成含第5族金属的薄膜的方法包括通过金属有机化学气相沉积(MOCVD)工艺或原子层沉积(ALD)工艺,使用由化学式1和化学式2中的任一个表示的第5族金属化合物作为前体在衬底上沉积薄膜。
当将根据本公开的实施方案的第5族金属化合物与作为代表性铌前体的(叔丁基酰亚胺)三(二乙氨基)铌(V)(TBTDEN)进行比较时,第5族金属化合物可以通过具有环戊二烯(CP)结构的优势为金属提供更多的电子。由于稳定的结构,增加了化合物的热稳定性,通过作为现有均配配体的金属-胺结构中的杂配配体结构(金属-醇盐、金属-胺、金属-烷基)有效减少沉积工艺中的残留物的量,并且由于将该化合物作为具有高挥发性的液体应用到该工艺中是有利的,因此有可能在原子层沉积(ALD)工艺中稳定地沉积单个原子层,并且ALD工艺的窗口范围可以扩展。
由于本公开的上述效果,当使用含第5族金属化合物的组合物在衬底上沉积薄膜时,可以改进沉积在衬底上的薄膜的质量。
附图说明
从结合附图的以下详细描述中,将更清楚地理解本公开的上述和其他方面、特征和其他优点,其中:
图1是示出了根据实施例1的((η-C5H5)C5H9)(tBuN)Nb(OiPr)2、根据实施例2的(η-C5H5)(tBuN)Nb(OiPr)2和根据对比例的TBTDEN的热量(差示扫描量热法)分析结果的表;以及
图2是示出了根据实施例1的((η-C5H5)C5H9)(tBuN)Nb(OiPr)2、根据实施例2的(η-C5H5)(tBuN)Nb(OiPr)2和根据比较例的TBTDEN的热重分析(TGA)结果的图。
具体实施方式
在下文中,将参照图1和2更详细地描述本公开的优选实施方案。本公开的实施方案可以以各种形式修改,并且本公开的范围不应被解释为限于以下描述的实施方案。提供本实施方案是为了向本公开所属领域的普通技术人员更详细地解释本公开。因此,附图中所示的每个元件的形状可能被夸大以着重进行更清楚的解释。
在本公开的整个说明书中,术语“烷基”或“烷基基团”包括具有1至12个碳原子、1至10个碳原子、1至8个碳原子、1至5个碳原子、1至3个碳原子、3至8个碳原子或3至5个碳原子的直链或支链烷基基团。例如,尽管烷基基团可选自甲基基团、乙基基团、正丙基基团(nPr)、异丙基基团(iPr)、正丁基基团(nBu)、叔丁基基团(tBu)、异丁基基团(iBu)、仲丁基基团(sBu)、正戊基基团、叔戊基基团、异戊基基团、仲戊基基团、新戊基基团、3-戊基基团、己基基团、异己基基团、庚基基团、4,4-二甲基戊基基团、辛基基团、2,2,4-三甲基戊基基团、壬基基团、癸基基团、十一烷基基团、十二烷基基团及其异构体,但其不限于此。
根据本公开的实施方案的第5族金属化合物可以由以下化学式1和化学式2中的任一个表示:
在<化学式1>和<化学式2>中,M为选自第5族金属元素中的任意一种,n为选自1至5的整数,R1为选自具有3至6个碳原子数的直链烷基基团和具有3至6个碳原子数的支链烷基基团中的任意一种,并且R2和R3各自独立地为选自氢、具有1至4个碳原子的直链烷基基团和具有1至4个碳原子的支链烷基基团中的任意一种。
更具体地,M可以是选自钒(V)、铌(Nb)和钽(Ta)中的任意一种。此外,R1可以是选自正丙基基团、异丙基基团、正丁基基团、叔丁基基团、异丁基基团、仲丁基基团、正戊基基团、叔戊基基团、异戊基基团、仲戊基基团、新戊基基团和3-戊基基团中的任意一种。此外,R2和R3可以各自独立地为选自氢、甲基基团、乙基基团、正丙基基团、异丙基基团、正丁基基团、仲丁基基团、异丁基基团和叔丁基基团中的任意一种,并且R2和R3可以具有相同的结构。
更具体地,由化学式1表示的第5族金属化合物可以是由以下化学式3表示的第5族金属化合物:
<化学式3>
在化学式3中,M为选自第5族金属元素中的任意一种,并且与化学式1中描述的相同。
此外,由化学式2表示的第5族金属化合物可以是由以下化学式4表示的第5族金属化合物:
<化学式4>
根据本公开的实施方案的第5族金属化合物具有其中第5族金属和环戊二烯直接连接的结构。根据本公开的实施方案的第5族金属化合物具有优异的热稳定性,因为第5族金属化合物可以通过使电子能够更容易地从环戊二烯提供给金属而保持结构更稳定的状态。因此,当使用根据本公开的实施方案的第5族金属化合物来形成薄膜时,有可能减少沉积工艺中生成的残留物的量。此外,由于第5族金属化合物易于应用于液体工艺,因此其可用于原子层沉积(ALD)工艺。
此外,在根据本发明的实施方案的第5族金属化合物中,第5族金属与一个氮原子形成双键,并分别与两个氧原子形成单键。第5族金属,例如铌(Nb)和氧原子(O)之间的键能大于铌(Nb)和氮原子(N)之间的键能。因此,与其中通过允许第5族金属与一个氮原子形成双键并与两个氮原子中的每一个形成单键而使第5族金属和三个氮原子连接的化合物相比,根据本公开的实施方案的第5族金属化合物具有更优异的热稳定性。
在下文中,将通过以下实施例更详细地描述根据本公开的第5族金属化合物。然而,这仅是为了帮助理解本公开而提出,并且本公开不限于以下实施例。
实施例1:((η-C5H5)C5H9)(tBuN)Nb(OiPr)2的制备
在将20g(0.0453mol,1当量)的双(二乙基酰胺基)(叔丁基酰亚胺)(环戊基环戊二烯)铌((η-C5H5)C5H9)(tBuN)Nb(NEt2)2和150mL的己烷(正己烷)注入到火焰干燥的500mLSchlenk烧瓶中后,将注入的材料在室温下搅拌。在于-20℃以下向烧瓶中滴加5.99g(0.0997mol,2.2当量)的异丙醇(C3H7OH)后,将反应液在室温下搅拌12小时。通过在减压下从反应溶液中除去溶剂并在减压下蒸馏除去了溶剂的反应溶液而获得18.73g(产率98%)的由((η-C5H5)C5H9)(tBuN)Nb(OiPr)2表示的淡黄色液体化合物。
实施例2:(η-C5H5)(tBuN)Nb(OiPr)2的制备
在将11g(0.029mol,1当量)的双(二乙基酰胺)(叔丁基酰亚胺)(环戊二烯)铌((η-C5H5)(tBuN)Nb(NEt2)2和150mL的己烷(正己烷)注入到火焰干燥的500mL Schlenk烧瓶中后,将注入的材料在室温下搅拌。在于-20℃以下向烧瓶中滴加3.8g(0.063mol,2.2当量)的异丙醇(C3H7OH)后,将反应液在室温下搅拌12小时。通过在减压下从反应溶液中除去溶剂并在减压下蒸馏除去了溶剂的反应溶液而获得9g(产率90%)的由((η-C5H5)(tBuN)Nb(OiPr)2表示的淡黄色液体化合物。
实验实施例:热分析
为了找出根据比较例的(t-丁基酰亚胺)三(二乙氨基)铌(V))(TBTDEN)、根据实施例1的((η-C5H5)C5H9)(tBuN)Nb(OiPr)2和根据实施例2的(η-C5H5)(tBuN)Nb(OiPr)2在类似条件下的热性能,进行了差示扫描量热法(DSC)分析和热重分析(TGA)。热重装置储存在其中水分和氧气含量保持在1ppm以下的氮气手套箱中。通过将15mg的样品放入坩埚中进行热重分析。此后,以10℃/min的温度梯度将样品从35℃加热到350℃。监测质量损失作为坩埚温度的函数。根据DSC分析,比较例、实施例1和实施例2的分解温度(Td)示于图1中。另外,根据TGA的图表结果示于图2中。参考图1和图2,可以证实,根据实施例1制备的((η-C5H5)C5H9)(tBuN)Nb(OiPr)2和根据实施例2制备的(η-C5H5)(tBuN)Nb(OiPr)2比根据对比例制备的TBTDEN更具热稳定性。由此可以看出,根据实施例1的((η-C5H5)C5H9)(tBuN)Nb(OiPr)2和根据实施例2的(η-C5H5)(tBuN)Nb(OiPr)2更有效地用作气相前体。
在下文中,将描述根据本公开的实施方案的形成含第5族金属的薄膜的方法。
根据本公开的实施方案的形成含第5族金属的薄膜的方法使用根据本公开的实施方案的第5族金属化合物作为前体通过沉积工艺在衬底上沉积薄膜。
沉积工艺可以包括原子层沉积(ALD)工艺或化学气相沉积(CVD)工艺,例如金属有机化学气相沉积(MOCVD)工艺。沉积工艺可于50至700℃进行。
首先,将由化学式1和化学式2中的任一个表示的第5族金属化合物转移到衬底上。例如,虽然可以通过鼓泡法、气相质量流量控制器法、直接气体注入(DGI)法、直接液体注入(DLI)法、液体转移法(其中液体溶解在有机溶剂中并转移等)将第5族金属化合物供应到衬底上,但是本公开不限于此。
更具体地,将第5族金属化合物与载气或稀释气体混合,该载气或稀释气体包含选自氩气(Ar)、氮气(N2)、氦气(He)和氢气(H2)中的一种或多种,从而使第5族金属化合物与载气或稀释气体的混合物通过鼓泡法或DGI法转移到衬底上。
同时,沉积工艺可包括在形成含第5族金属的薄膜时供应选自水蒸气(H2O)、氧气(O2)、臭氧(O3)和过氧化氢(H2O2)的一种或多种反应气体的步骤。此外,沉积工艺可以包括在形成含第5族金属的薄膜时,供应选自氨(NH3)、肼(N2H4)、一氧化二氮(N2O)和氮(N2)的一种或多种反应气体的步骤。由此,在衬底上形成的含金属的薄膜可以是第5族金属氧化物膜或第5族金属氮化物膜。
在上文中,已经通过示例详细描述了本公开,但是与其不同的其他类型的示例也是可能的。因此,下面阐述的权利要求的技术精神和范围不限于这些示例。

Claims (8)

1.一种第5族金属化合物,其由以下<化学式3>表示:
<化学式3>
其中M是选自所述第5族金属元素中的任意一种。
2.一种用于沉积含第5族金属的薄膜的前体组合物,所述前体组合物包含根据权利要求1所述的第5族金属化合物。
3.一种形成含第5族金属的薄膜的方法,所述方法包括使用根据权利要求1所述的第5族金属化合物作为前体,通过金属有机化学气相沉积(MOCVD)工艺或原子层沉积(ALD)工艺在衬底上沉积薄膜。
4.如权利要求3所述的方法,其中所述沉积工艺在50至700℃的温度范围内进行。
5.如权利要求3所述的方法,其中所述沉积工艺包括通过选自鼓泡法、气相质量流量控制器(MFC)法、直接气体注入(DGI)法、直接液体注入(DLI)法和其中所述第5族金属化合物溶解在有机溶剂中并移动的有机溶液供给法中的一种方法将所述第5族金属化合物移动到所述衬底上。
6.如权利要求5所述的方法,其中通过所述鼓泡法或所述DGI法将所述第5族金属化合物与载气一起移动到所述衬底上,并且所述载气为包含选自氩气(Ar)、氮气(N2)、氦气(He)和氢气(H2)的一种或多种的混合物。
7.如权利要求3所述的方法,其中所述沉积工艺包括在形成所述含第5族金属的薄膜时供应选自水蒸气(H2O)、氧气(O2)、臭氧(O3)和过氧化氢(H2O2)的一种或多种反应气体的步骤。
8.如权利要求3所述的方法,其中所述沉积工艺包括在形成所述含第5族金属的薄膜时供应选自氨(NH3)、肼(N2H4)、一氧化二氮(N2O)和氮气(N2)的一种或多种反应气体的步骤。
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