CN1619820A - 氧化铬及氧化铝合成介电层及其制造方法 - Google Patents
氧化铬及氧化铝合成介电层及其制造方法 Download PDFInfo
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Abstract
本发明涉及一种氧化铪及氧化铝合成介电层及其制造方法。所述介电层通过采用原子层沉积技术沉积形成。制造氧化铪及氧化铝合成介电层的方法包含下列步骤:通过重复进行原子层沉积技术的第一循环沉积氧化铪单原子层;通过重复进行原子层沉积技术的第二循环沉积氧化铝单原子层;及通过重复进行包含混合第一与第二循环的第三循环,沉积氧化铪单原子层与氧化铝单原子层的介电层。
Description
技术领域
本发明涉及一种半导体装置,具体地,涉及一种电容的介电层及其制造方法。
背景技术
通常,通过热处理或快速热处理生长的二氧化硅(SiO2)被用作动态随机存储器(DRAM)装置与逻辑装置的栅极氧化层。由于半导体装置的设计规则已转向最小化,用于产生隧道效应的所述栅极氧化层的有效厚度已减至约25~30,此为发生隧道效应的最小厚度。在利用约0.1μm设计规则的装置中,所述栅极氧化层的期望的厚度范围为约25至约30。然而,注意到由直接的隧道效应而引起的关闭电流的增加会对该装置的操作产生负面影响。具体的,主要焦点在于电流存储装置降低泄漏电流。
作为解决上述问题的一种尝试,已对由具有高介电常数的材料,即高k值介电材料构成的栅极氧化层进行了积极的研究。所述高k值介电例如氧化钽(Ta2O5)、氧化钛(TiO2)、氧化铝(Al2O3)与氧化铪(HfO2)。另外,半导体存储装置加速的集成度已导致单位单元面积的急剧下降。而且,操作电压也已被降低至一低电平。
然而,虽然单元面积已减少,但操作记存储装置所需的最小电容仍要大于25fA/单元,用以防止发生软错误与缩短更新时间。因此,已对用作电容器介电层的高介电材料进行了积极的研究,以期大规模集成半导体装置所需的有效的电容,其中所述高介电材料例如Ta2O5、TiO2、Al2O3或HfO2,它们的介电常数高于例如以下材料的介电常数:二氧化硅(SiO2)、氮化硅(Si3N4)与一氧化氮(NO)。具体的,HfO2与Al2O3的堆叠式介电层因其兼具HfO2层带来的良好的介电特性与Al2O3层带来的良好的泄漏电流特性,目前已被视为栅极氧化层与电容器最可能应用的介电层。
图1为一电容器结构的示图,包括氧化铪及氧化铝的堆叠式介电层。
如图所示,电容器包括一由多晶硅制成的下电极11、一堆叠式介电层12及一由多晶硅制成的上电极13。在此,所述堆叠式介电层12通过顺序层叠氧化铝层12A与氧化铪层12B而形成。
在所述堆叠式介电层12中,所述氧化铝层12A接触所述下电极11,而所述氧化铪层12B接触所述氧化铝层12A。在此,所述氧化铝层12A所需的厚度为大于约20埃(),以改善泄漏电流特性。
具有所述堆叠式介电层12的电容器在低电压时会显现出极好的泄漏电流特性。但是,在高电压时,泄漏电流会陡然增加而导致低的击穿电压。结果,会进一步降低所述电容器的可靠度。
图2为显示一具有堆叠式介电层的传统电容器的泄漏电流特性的曲线图,其中所述堆叠式介电层通过层叠氧化铪层与氧化铝层而形成。在图2中,水平轴与垂直轴分别代表所施加的偏压与泄漏电流。为测量所述泄漏电流,在对所述上电极施加正电压并确定所述下电极为接地的情况下,可得到曲线CI。另一方面,在对所述上电极施加一负电压并确定所述下电极为接地的情况下,则可获得曲线CII。
如图所示,在低电源电压VL的情况下,所述泄漏电流特性呈现出一渐减坡度。另一方面,在高电源电压VH的情况下,所述泄漏电流特性呈现出一突增坡度。由于在所述高电源电压VH的情况下所述泄漏电流的陡然增加增,所以电容器会有一低击穿电压。
而且,在所述氧化铝层上形成所述氧化铪层,以确保所述介电特性。然而,所述氧化铪对热是不稳定的,因此在所述上电极形成后随后的热处理会使所述泄漏电流与所述介电特性降级。
图3A为显示在实施所述随后的热处理时一传统电容器的泄漏电流特性的曲线图,其中所述传统电容器仅具有一氧化铝层。图3B为显示在实施所述随后的热处理时一传统电容器的泄漏电流特性的曲线图,其中所述传统电容器具有氧化铪与氧化铝的堆叠式介电层。在图3A与图3B中,水平轴与垂直轴分别代表所施加的偏压与泄漏电流。曲线C1与C3显示在所述随后热处理前所述泄漏电流特性,其中所述随后热处理是在所述上电极形成后进行的,而曲线C2与C4显示在所述热处理实施后所述泄漏电流特性。在此,所述随后热处理在大约750℃进行约20分钟,并在大约675℃下进行约70分钟。
参考图3A,仅具有所述氧化铝层的电容器不管是在所述随后热处理实施前还是实施后,在泄漏电流特性方面是一致的。然而,具有所述氧化铪与氧化铝的堆叠式介电层的电容器在所述随后热处理实施前和实施后则有不同的泄漏电流特性。更具体地,在施加相同偏压的情况下,在所述随后热处理之后所获得的泄漏电流会大于在所述随后热处理之前所获得的泄漏电流。如图3B所示,所述泄漏电流会突然增加,穿过由所述随后热处理而结晶的氧化铪的晶界。
发明内容
因此,本发明的一个目的在于提供一种半导体装置的介电层及其制造方法,在通过顺序层叠氧化铪(HfO2)层与氧化铝(Al2O3)层形成介电层时,其能够防止击穿电压在高电源电压下被降低。
本发明的另一目的在于提供一种半导体装置的介电层,其能够防止在后续的热处理期间由氧化铪(HfO2)与氧化铝(Al2O3)叠层介电层引起的漏电流的增加。
根据本发明的一方面,提供一种半导体装置的介电层,其包含通过利用原子层沉积技术而形成的氧化铪与氧化铝合成介电层。
根据本发明的另一方面,还提供一种制造半导体装置的介电层的方法,其包含下列步骤:通过重复进行原子层沉积技术的第一循环,沉积一氧化铪单原子层;通过重复进行原子层沉积技术的第二循环,沉积一氧化铝单原子层;及通过重复进行包含混合第一与第二循环的第三循环,沉积由氧化铪单原子层与氧化铝单原子层形成的合成介电层。
根据本发明的又一方面,还提供一种制造氧化铪与氧化铝合成介电层的方法,包含重复进行一单位循环,所述单位循环包括顺序提供铪与铝的单分子源气体、净化气体、氧化剂与净化气体。
附图说明
通过以下结合附图对优选实施例进行的描述,本发明的所述和其他的目的和特点将会更加容易了解,在所述附图中,
图1为显示一电容器结构的示图,其中所述电容器结构包括传统的氧化铪及氧化铝的堆叠式介电层;
图2为显示一具有传统的氧化铪及氧化铝堆叠式介电层的电容器的泄漏电流特性的曲线图;
图3A为显示在一后续热处理期间一电容器的泄漏电流特性的曲线图,其中所述电容器只具有一传统的氧化铝介电层;
图3B为显示在一后续热处理期间一电容器的泄漏电流特性的曲线图,其中所述电容器具有一传统的氧化铪及氧化铝的堆叠式介电层;
图4为显示依据本发明第一优选实施例的一氧化铪与氧化铝合成介电层的示图;
图5为显示在依据本发明第一优选实施例通过采用原子层沉积技术形成所述氧化铪及氧化铝合成介电层时将气体供应至一反应室的时序图;
图6为显示依据本发明第二优选实施例的一氧化铪与氧化铝合成介电层的图示;
图7A为显示在依据本发明第二优选实施例通过采用ALD技术形成所述氧化铪及氧化铝合成介电层时将气体供应至一反应室的时序图;
图7B为显示由Hf-Al单分子源气体和臭氧反应气体之间的反应形成的(HfO2)1-X(Al2O3)X的合成状态的示图;
图8为显示一电容器的氧化铪及氧化铝堆叠式介电层、一[A/H/A/H/A/H/A/H/A]叠层介电层及一[HOAOAO]合成介电层的泄漏电流特性的曲线图,其中“A”、“H”及“O”代表原子或分子。
具体实施方式
以下将结合附图详细说明本发明的优选实施例。
图4为显示依据本发明第一优选实施例的一氧化铪及氧化铝合成介电层的图示。
如图所示,所述介电层20通过使氧化铝21与氧化铪22一起形成合金而形成,以便所述介电层20的分子结构为(HfO2)1-X(Al2O3)X,其中x代表分子组成系数。
具体地,通过使用原子层沉积(ALD)技术沉积介电层20。例如,在一原子层单位内重复进行沉积Al2O321的循环,然后在一原子层单位内重复进行沉积HfO222的循环。其后,连续重复进行该二循环的混合循环,直到达到氧化铪(HfO2)与氧化铝(Al2O3)所需的厚度。
还有,如图4所示,Al2O321与HfO222形成于一层内。所述Al2O321与HfO222在一层内同时形成的原因是原子层沉积技术的特性,其通过控制循环的次数而允许单原子层不连续地形成。即,如果该循环重复进行的次数较少,则不连续地沉积形成Al2O321单原子层。以下,分别将在原子层的单位内形成的每个Al2O321与HfO222称作Al2O3层与HfO2层。
对于形成结构为(HfO2)1-X(Al2O3)X的介电层20的方法,更详细的是利用ALD技术可在单层内形成Al2O3层21与HfO2层22。此时,控制重复单独形成Al2O3层21与HfO2层22的每一循环的次数,以使所获得的Al2O3层21与HfO2层22的期望厚度在约1至10的范围。这里,所述厚度为每一个不连续生成的Al2O321与HfO222单层的厚度。若每一单层的厚度大于10,则形成连续单层,因而形成叠层结构而不是合成结构。
图5为显示在依据本发明第一优选实施例通过采用原子层沉积技术形成分子结构为(HfO2)1-X(Al2O3)X的介电层20时将气体供应至一反应室的时序图。
如已知的,首先将源气体供应至一反应室,以使所述源气体分子被化学地吸收到一基板的表面。然后,通过供应一净化气体来清除那些被物理吸收的源气体分子。将一反应气体供应至所述基板,以便使所述经化学吸收的源气体分子与所述反应气体进行反应。依此化学反应,可沉积一单原子层。之后,通过使用一净化气体来清除所述未反应的反应气体。上述连续步骤构成该单原子层沉积的一个循环。上述原子层沉积技术采用一表面反应机制来提供一稳定且均匀的薄层。同样地,与化学汽相沉积(CVD)技术相比,因为所述源气体与所述反应气体是分别依序提供及在随后清除,所以所述原子层沉积技术可通过汽相反应以有效地防止粒子产生。
以下将更详细说明用以沉积分子结构为(HfO2)1-X(Al2O3)X的介电层20的单位循环。
所述单位循环可表示成为如下:
[(Hf/N2/O3/N2)y(Al/N2/O3/N2)z]n 单位循环1
这里,铪及铝是用以分别形成所述氧化铪层22及所述氧化铝层21的源气体。所述下标“y”及“z”代表重复(Hf/N2/O3/N2)及(Al/N2/O3/N2)的各自循环的次数。另一下标“n”代表重复[(Hf/N2/O3/N2)y(Al/N2/O3/N2)z]的循环的次数。在此,“y”、“z”及“n”为自然数。
对所述单位循环1来说,更具体的是,(Hf/N2/O3/N2)y循环表示顺序提供铪源气体、氮净化气体、臭氧氧化剂及氮净化气体的步骤,且所述循环被重复进行y次。同样地,(Al/N2/O3/N2)z循环表示顺序提供铝源气体、氮净化气体、臭氧氧化剂及氮净化气体的步骤,且所述循环被重复进行z次。重复所述循环y次及z次,以分别沉积具有所需厚度的氧化铪22及氧化铝21的单层。
针对所述氧化铝21的单原子层沉积,首先使维持在室温的三甲基铝合金(Al(CH3)3)的源气体流入一反应室大约0.1秒至3秒的时间。以下将所述三甲基铝合金简称为TMA。在此时,使所述反应室的温度保持在大约200℃至350℃之间,且使其压力保持在大约0.1托至10托之间。所述TMA源气体分子被吸收到所述下电极21上。之后,使一氮净化气体流入所述反应室大约0.1秒至约5秒的时间,以去除未被化学吸收的TMA源气体分子。然后,使作为反应气体的臭氧氧化剂流入所述反应室大约0.1秒至3秒的时间,以引起所述被吸收的TMA源气体分子与所述臭氧气体分子间的反应。所述反应会造成一氧化铝21原子层的沉积。接下来,使一氮净化气体流入所述反应室大约0.1秒至5秒的时间,以清除未反应的臭氧分子及所述反应的副产物。
上述顺序提供TMA源气体、氮净化气体、臭氧反应气体及氮净化气体的步骤构成一个单位循环,该单位循环被重复进行z次,以沉积所述具有所需厚度的氧化铝层21。在此,除了所述TMA之外,可使用改进的TMA(MTMA;Al(CH)3N(CH2)5CH3)来做为铝源气体。除了臭氧气体之外,可使用水及氧气等离子体来作为氧化剂。亦可使用如氩气的惰性气体做为所述净化气体。
针对所述氧化铪22的单原子层沉积,在一汽化器中汽化一选自由HfCl4、Hf(NO3)4、Hf(NCH3C2H5)4、Hf(N(CH3)2)4及Hf(N(C2H5)2)4所组成的组的源气体,并使所述汽化的源气体流入一反应室中,由此使该铪源气体分子被吸收,其中所述反应室的温度维持在200℃至400℃之间,压力保持在0.1托至10托之间。然后,使一氮净化气体流入所述反应室大约0.1秒至5秒的时间,以清除未被吸收的铪源气体分子。使一臭氧反应气体流入所述反应室大约0.1秒至3秒的时间,以引导所述被吸收的铪源气体分子与所述臭氧气体分子间的反应。从所述化学反应可沉积一氧化铪22的单原子层。接下来,使一氮净化气体流入所述反应室大约0.1秒至5秒的时间,以清除未反应的臭氧气体分子及所述反应的副产物。
所述顺序提供铪源气体、氮净化气体、臭氧反应气体及氮净化气体的步骤构成一个单位循环,该单位循环被重复进行y次,以沉积具有所需厚度的氧化铪层22。除了所述臭氧气体之外,可使用水及氧等离子体来做为所述氧化剂。也可使用如氩气的惰性气体来做为所述净化气体。
众所皆知,所述原子层沉积技术是以脉冲样单元(pulse-like unit)来进行。重复所述单位循环1,以形成分子结构为(HfO2)1-x(Al2O3)x的介电层20,其中以一预定分子组成系数均匀地形成所述氧化铪层22与所述氧化铝层21。
形成所述具有(HfO2)1-x(Al2O3)x分子结构的介电层20需要有下列条件。首先,重复n次所述单位循环1,其中所述单位循环1包括重复进行y次(Hf/N2/O3/N2)的循环以及重复进行z次(Al/N2/O3/N2)的循环。但是,特别控制重复这两个循环中每一循环的次数,即y及z,使得由所述(Hf/N2/O3/N2)的循环所形成的氧化铪层22的厚度以及由所述(Al/N2/O3/N2)的循环所形成的氧化铝层21的厚度大约在1埃至10埃的范围内,以便最有效地使氧化铪及氧化铝均匀地在一起形成合金。如果每一单原子层的厚度大于约10埃,则每一单原子层会显示出连续特性,进而导致相同于传统氧化铪及氧化铝堆叠式介电层的介电特性或者更差的介电特性。
第二,必须适当控制重复所述两个循环的次数(亦即y及z)的比率,以使所述氧化铝层21占大约30%至60%的比率,以便通过使所述氧化铪层22及氧化铝层21形成合金来形成一非晶形薄介电层,进而获得一极好的电特性。
图6为显示根据本发明第二优选实施例的HfO2与Al2O3合成介电层的示图。
如图所示,通过使Al2O331与HfO232一起均匀形成合金而形成介电层30,使得介电层30具有(HfO2)1-X(Al2O3)x的分子结构,其中x表示分子组成比例。此处,通过利用ALD技术沉积介电层30。
与图4中的介电层20不同,因为使用Al与Hf的单分子源气体进行介电层30的沉积,所以介电层30具有不同的Al2O3与HfO2的合金结构。还进行另一种形式的单位循环来形成介电层30,该单位循环使用上述A1与Hf的单分子源气体。此单位循环可以下式表示:
[(Hf-Al)/N2/O3/N2]w 单位循环2
这里,Hf-Al代表一单分子源气体,其中,Hf及Al混合存在于一单分子中。如HfAl(MMP)2(OiPr)5的物质是所述铪与铝单分子源气体的一个例子。在此,MMP及OiPr分别代表甲基硫丙醛(methylthiopropionaldehyde)及异丙氧化物(isopropoxides)
在第一优选实施例中,分别供应所述铪源气体及铝源气体,如在图5的单位循环1中所述。然而,在第二优选实施例中,使用如单位循环2中所示的铪及铝的单分子源气体。所述单分子源气体的使用简化了供应所述源气体的步骤并进一步缩短了所述整个循环的全部周期。在混合铪及铝以形成一单分子时,可通过控制每一铪及铝的比率来控制所述铪及铝的组成系数。
图7A为显示在依据本发明第二优选实施例通过采用原子层沉积技术形成所述分子结构为(HfO2)1-X(Al2O3)X的合成介电层32时将气体供应至一反应室的时序图。图7B图为显示基于Hf-Al单分子源气体与O3反应气体之间的反应形成上述(HfO2)1-X(Al2O3)X分子结构的示图。
参见图7A,所述(Hf-Al/N2/O3/N2)w的单位循环涉及顺序提供一Hf-Al单分子源气体、氮净化气体、作为反应气体的臭氧氧化剂及氮净化气体的步骤。重复所述循环w次,直到分子结构为(HfO2)1-X(Al2O3)X的合成介电层32达到一所需厚度为止。在此,“w”为自然数。
以下将更详细描述原子层沉积技术的上述循环。首先,使维持在室温的源气体,例如HfAl(MMP)2(OiPr)5)流入一反应室大约0.1秒至约3秒的时间,以使所述HfAl(MMP)2(OiPr)5源气体被吸收。在此时,使所述反应室的温度保持在大约200℃至350℃之间,压力保持在大约0.1托至10托之间。接下来,使所述氮净化气体流入所述反应室大约0.1秒至5秒的时间,以清除未被吸收的HfAl(MMP)2(OiPr)5分子。之后,使所述臭氧反应气体流入所述反应室大约0.1秒至3秒的时间,以引导所述被吸收的HfAl(MMP)2(OiPr)5分子与所述所供应的臭氧气体之间的反应。依所述反应,可沉积一由所述氧化铪层32及所述氧化铝层31所构成的(HfO2)1-x(Al2O3)x原子层。使所述氮净化气体再次流入所述反应室约0.1秒至5秒的时间,以清除所述未反应的臭氧及所述反应的副产物。图7B中示出上述结构(HfO2)1-x(Al2O3)x。
重复w次所述单位循环2,直到所述氧化铪及氧化铝合成介电层32达到所需厚度为止,其中,所述单位循环2包括顺序提供所述HfAl(MMP)2(OiPr)5源气体、所述氮净化气体、所述臭氧反应气体及所述氮净化气体的步骤。同时,除了所述臭氧气体之外,可使用水及氧等离子体作为氧化剂。也可使用如氩的惰性气体作为所述净化气体。
图8为显示一HfO2/Al2O3堆叠式介电层、一[A/H/A/H/A/H/A/H/A]叠层介电层及一[HOAOAO]合成层的泄漏电流特性的曲线图。当上述所列的层被用作一电容器的介电层时,可获得所述泄漏电流特性。在此,“A”、“H”及“O”代表被用作形成所述所需层的一特定结构的原子或分子。
如图所示,通过堆叠厚度分别为约20埃和约25埃的氧化铪及氧化铝形成所述氧化铪及氧化铝堆叠式介电层。所述[A/H/A/H/A/H/A/H/A]叠层是通过交替层叠每个厚度约10埃的氧化铝及氧化铪而形成的。所述[HOAOAO]合成层是通过依据本发明第一优选实施例实施所述(Hf/N2/O3/N2)1(Al/N2/O3/N2)2的单位循环而形成的。
对图8中所述层的泄漏电流特性来说,更具体地,如同所述氧化铪及氧化铝堆叠式介电层,由于所述氧化铝层的接触特性,基于所述第一优选实施例所形成的[HOAOAO]合成层在一低电源电压VL情况下显示出一低泄漏电流特性。同样地,在所述低电源电压VL情况下,所述[HOAOAO]合成层显示出一高起升电压(take-off voltage)特性。在此,所述起升电压是指一泄漏电流突然增加的电压。然而,由于所述氧化铪的接触特性明显优于所述氧化铝的接触特性,所以在一高电源电压VH情况下,所述[HOAOAO]合成层显示出一高击穿电压特性。亦即,在所述高电源电压VH的情况下,所述[HOAOAO]合成层的泄漏电流以平缓斜率来增加。与所述[HOAOAO]合成层相比,所述氧化铪及氧化铝堆叠式介电层及所述[A/H/A/H/A/H/A/H/A]叠层的泄漏电流以陡峭斜率急剧地增加。同样地,在所述相同高电源电压VH的情况下,所述[HOAOAO]合成层与其它层相比具有一低泄漏电流密度。
所述[HOAOAO]合成层即使在所述高电源电压VH的情况下仍表现出具有所述特征的泄漏电流特性是因为通常存在于所述氧化铝层中的负电荷的缺陷及通常存在于所述氧化铪层中的正电荷的缺陷会彼此补偿。因此,与所述氧化铪及氧化铝堆叠式介电层相比,所述[HOAOAO]合成介电层在所述低电源电压VL情况下与所述高电源电压VH情况下均显示出极好的泄漏电流特性。
同样地,在所述[HOAOAO]合成层中,所述氧化铪层与上电极及下电极的直接接触被最小化,由此抑制由在所述上电极形成后进行的热处理所造成的泄漏电流及介电特性的降级。
根据本发明的第一优选实施例和第二优选实施例,可以制造具有高介电系数、高击穿电压特性与良好漏电流特性的高品质的介电层。
应注意的是,根据本发明的第一和第二优选实施例所形成的介电层仅可应用于作为电容器的栅极氧化层或介电层。
本申请包含与韩国专利申请KR 2003-0083398相关的主题,该申请于2003年11月22日向韩国专利局提出申请,在此参考引用其整个内容。
虽然已以有关优选实施例对本发明进行了说明,但是对本专业技术人员来说很明显的是可在不脱离权利要求所限定的本发明的范围的情况下进行不同的变化和改进。
Claims (19)
1.一种半导体装置的介电层,包含通过采用原子层沉积技术而形成氧化铪与氧化铝合成介电层。
2.如权利要求1所述的介电层,其中,所述氧化铪与氧化铝分别为HfO2与Al2O3,且所述氧化铪与氧化铝合成介电层所具有的分子结构为(HfO2)1-X(Al2O3)X,其中,x表示分子组成比例。
3.如权利要求2所述的介电层,其中,所述HfO2层与所述Al2O3层的每一层的厚度范围在约1至10的范围。
4.如权利要求2所述的介电层,其中,在所述(HfO2)1-X(Al2O3)X分子结构中,表示Al2O3层的分子组成比例的下标x在约0.3至约0.6的范围。
5.一种制造半导体装置的介电层的方法,包含下列步骤:
通过重复进行原子层沉积技术的第一循环,沉积一氧化铪单原子层;
通过重复进行原子层沉积技术的第二循环,沉积一氧化铝单原子层;及
通过重复进行包含混合所述第一与第二循环的第三循环,沉积一由所述氧化铪单原子层与所述氧化铝单原子层形成的合成介电层。
6.如权利要求5所述的方法,其中,所述氧化铪单原子层与氧化铝单原子层分别为HfO2层与Al2O3层,且所述氧化铪与氧化铝合成介电层所具有的分子结构为(HfO2)1-X(Al2O3)X,其中,x表示分子组成比例。
7.如权利要求6所述的方法,其中,所述HfO2层与Al2O3层的每一层的厚度在约1至10的范围。
8.如权利要求6所述的方法,其中,控制所述第一循环与所述第二循环的比例使表示Al2O3层分子比例的下标x在约0.3至约0.6的范围。
9.如权利要求5所述的方法,其中,所述第一循环为一单位循环,其包含顺序提供铪源气体、净化气体、氧化剂与净化气体的步骤。
10.如权利要求6所述的方法,其中,所述第一循环为一单位循环,其包含顺序提供铪源气体、净化气体、氧化剂与净化气体的步骤。
11.如权利要求9所述的方法,其中,所述铪源气体选自包含HfCl4、Hf(NO3)4、Hf(NCH3C2H5)4、Hf[N(CH3)2]4与Hf[N(C2H5)2]4的组;所述氧化剂为O3、H2O与O2等离子体中的一种;且所述净化气体为N2与Ar中的一种。
12.如权利要求10所述的方法,其中,所述铪源气体选自包含HfCl4、Hf(NO3)4、Hf(NCH3C2H5)4、Hf[N(CH3)2]4与Hf[N(C2H5)2]4的组;所述氧化剂为O3、H2O与O2等离子体中的一种;且所述净化气体为N2与Ar中的一种。
13.如权利要求5所述的方法,其中,所述第二循环为一单位循环,其包含顺序提供铝源气体、净化气体、氧化剂与净化气体的步骤。
14.如权利要求6所述的方法,其中,所述第二循环为一单位循环,其包含顺序提供铝源气体、净化气体、氧化剂与净化气体的步骤。
15.如权利要求13所述的方法,其中,所述铝源气体为三甲基铝(TMA)与改良的TMA(MTMA)中的一种;所述氧化剂为O3、H2O与O2等离子体中的一种;所述净化气体为N2与Ar中的一种。
16.如权利要求14所述的方法,其中,所述铝源气体为三甲基铝(TMA)与改良的TMA(MTMA)中的一种;所述氧化剂为O3、H2O与O2等离子体中的一种;所述净化气体为N2与Ar中的一种。
17.一种制造由氧化铪与氧化铝形成的合成介电层的方法,其包含重复进行一单位循环的步骤,所述单位循环包括顺序提供铪与铝的单分子源气体、净化气体、氧化剂与净化气体。
18.如权利要求17所述的方法,其中,所述氧化铪层与氧化铝的命名分别为HfO2与Al2O3,且所述氧化铪与氧化铝合成介电层所具有的分子结构为(HfO2)1-X(Al2O3)X,其中x表示分子组成比例。
19.如权利要求17所述的方法,其中,所述铪与铝的单分子源气体为HfAl(MMP)2(OiPr)5;所述氧化剂为O3、H2O与O2等离子体中的一种;且所述净化气体为N2与Ar中的一种。
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CN102452797A (zh) * | 2010-10-19 | 2012-05-16 | 英作纳米科技(北京)有限公司 | 药用玻璃瓶内壁涂层的制备方法 |
CN102452797B (zh) * | 2010-10-19 | 2014-08-20 | 英作纳米科技(北京)有限公司 | 药用玻璃瓶内壁涂层的制备方法 |
CN102477541A (zh) * | 2010-11-25 | 2012-05-30 | 英作纳米科技(北京)有限公司 | 紧固件表面三氧化二铝薄膜的制备方法及其产品 |
CN102477542A (zh) * | 2010-11-25 | 2012-05-30 | 英作纳米科技(北京)有限公司 | 紧固件表面二氧化铪薄膜的制备方法及其产品 |
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US20050110069A1 (en) | 2005-05-26 |
TW200517521A (en) | 2005-06-01 |
KR20050049700A (ko) | 2005-05-27 |
KR100550641B1 (ko) | 2006-02-09 |
TWI278529B (en) | 2007-04-11 |
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