CN111971803A - 用于原子层沉积的可聚合自组装单体 - Google Patents
用于原子层沉积的可聚合自组装单体 Download PDFInfo
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- CN111971803A CN111971803A CN201980021671.7A CN201980021671A CN111971803A CN 111971803 A CN111971803 A CN 111971803A CN 201980021671 A CN201980021671 A CN 201980021671A CN 111971803 A CN111971803 A CN 111971803A
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Images
Classifications
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Abstract
利用包含氢键合基团和可聚合二亚乙酰基的化合物在基底表面的部分上选择性地制备自组装单层(SAM)。使用紫外光光聚合该SAM。与缺乏这些官能团的类似化合物相比,预聚合和聚合的SAM是在原子层沉积过程中是更有效的金属沉积阻挡层。
Description
技术领域
本发明涉及用于原子层沉积(ALD)中的可聚合自组装单层(SAM),更具体来说,涉及通过区域选择性原子层沉积(AS-ALD)生成图案化层的方法,其中SAM充当阻挡层,并且沉积主要或仅限于除SAM的顶表面之外的表面。
背景技术
原子层沉积(ALD)是一种化学气相沉积技术,该技术甚至在高纵横比特征上产生原子平滑且共形的涂层。这种技术可以通过热工艺或等离子体增强工艺(通常用于沉积过渡金属)沉积宽范围的材料-金属、非金属及其相关氧化物和氮化物。
热沉积工艺通常每个沉积的原子层需要两个反应步骤(有机金属前体,然后是氧化剂)。在ALD工艺的半循环第一个半循环中,膜表面用有机金属前体饱和,有机金属前体与表面基团反应,与表面产生共价键。这种反应是自限制的,因为半循环将仅导致形成一层官能化的有机金属。第二个半循环涉及引入氧化剂,该氧化剂产生用于下一ALD循环的反应性表面基团。每个完整ALD循环(即,两个ALD半循环,本文中也简称为“ALD循环”),该方法将膜形成限制为一个原子层的沉积。使用多个ALD循环来建立薄膜厚度,直到达到所需的厚度为止。
在区域选择性ALD(AS-ALD)中,沉积仅发生在基底的选定表面区域上。选择性阻断ALD沉积的一种方法是区域失活。例如,可以使用光刻聚合物来阻断基底表面的特定反应位点。基于阻挡材料与比表面积的材料的反应性,可以选择性地将其他阻断材料施加到基底的特定表面区域。作为一个实例,有机小分子可以用于在多个ALD循环之后补充的ALD期间阻断所希望的表面位点。或者,由长链有机小分子组成的自组装单层(SAM)可选择性地吸附到表面上且提供朝向可能需要或可能不需要补充的ALD的阻挡层。用于SAM的材料的实例包括1)烷基硅烷,其保护SiO2和GeO2;2)炔/烯烃,其保护H封端的表面;3)硫醇,其保护裸金属;和4)羧酸/膦酸,其保护金属氧化物。特别地,膦酸SAM不沉积在SiO2或裸金属上。这允许在由一个或多个膦酸SAM保护的相邻金属氧化物位点的存在下,在裸露的金属位点上选择性沉积至SiO2。
已经将可光聚合的双烯键式部分结合到SAM形成材料中以改善SAM针对ALD沉积的稳健性(LI,Feng等人的“Photopolymerization of Self-Assembled Monolayers ofDiacetylenic Alkylphosphonic Acids on Group-III Nitride Substrates”(第1II族氮化物基底上的二乙酰基烷基膦酸的自组装单层的光聚合),Langmuir,2010,26(13),第10725–10730页)。在形成初始SAM之后,通常通过将初始SAM暴露于紫外光,二亚乙酰基允许局部化学聚合。例如,已将双烯属烷基膦酸用作III族氮化物表面上的SAM,并在暴露于紫外(UV)辐射后表现出改善的稳健性。然而,需要提供ALD沉积的甚至更大面积选择性的自组装材料。
发明内容
因而,根据本发明,一种方法包括:
将被称为SAM的自组装单层布置在基底的表面的一部分上,由此形成所述表面的掩蔽部分,同时使所述表面的一部分不被掩蔽,所述SAM包含式(1)的化合物的键合形式:
其中
a是1或2,
H’是包含能够通过静电相互作用和/或共价键结合至所述表面的所述部分的官能团的头基,
T’为与头基共价连接的尾基,尾基包括氢键形成官能团、可聚合基团和非极性外围端基,
将所述SAM暴露于辐射,由此形成聚合的SAM;和
使用原子层沉积工艺将材料选择性地沉积到所述表面的所述未被掩蔽部分上,从而形成分层结构。
此外,根据本发明,公开了通过上述方法形成的层状结构。
从另一方面来看本发明,一种方法包括:
将被称为SAM的自组装单层布置在基底的表面上,该SAM包含式(1)的化合物的键合形式:
其中
a是1或2,
H’是包含能够通过静电相互作用和/或共价键结合至表面的所述部分的官能团的头部基团,
T’为与头基共价连接的尾基,尾基包括氢键形成官能团、可聚合基团和非极性外围端基,
将所述SAM逐图案地暴露于辐射,由此形成包括曝光的SAM和未曝光的SAM的图案化的SAM,所述曝光的SAM包括所述化合物的聚合形式;
选择性地去除所述未曝光的SAM,由此形成所述基底的所述表面的未被掩蔽区域;和
使用原子层沉积工艺将材料选择性地沉积到所述基底的未被掩蔽区域上。
从又另一方面来看本发明,一种方法包括:
将自组装单层设置在基底的一部分上,从而形成所述基底的掩蔽部分,同时使所述基底的一部分未被掩蔽,其中所述自组装单层包括选自包括由以下各项组成的组中的部分:可光聚合部分、氢键形成部分和它们的组合;和
使用原子层沉积工艺将材料选择性地沉积到所述基底的所述未被掩蔽的部分上。
从以下详细描述、附图和所附权利要求中,本领域技术人员将理解并理解本发明的上述和其他特征和优点。
附图说明
图1A-1F是示出使用原子层沉积(ALD)形成分层结构的方法的横截面层图。
图2A-2E为显示使用ALD形成分层结构的第二方法的横截面层图。
图3是比较在铜表面上的氧化锌的阻挡原子层沉积中由UODPA、ODPA和PFDA形成的自组装单层(SAM)的性能的图。
图4是比较在阻断铜表面上的氧化锌的ALD中由DA和ODPA形成的SAM的性能的图。
图5是示出包含嵌入式Cu线图案的预图案化基底的横截面层图。
具体实施方式
本文公开的方法利用能够形成聚合的、交联的自组装单层(SAM)的化合物,该单层设置在层状基底(例如,硅晶片)或其一部分的顶表面上。这些化合物在本文中称为SAM形成化合物。SAM的顶表面可抵抗ALD前体的沉积,这意味着在ALD过程的前半个循环中传送的材料(例如,二甲基锌)。在第二个半循环中,ALD前体转化为ALD产物(例如ZnO)。因此,SAM用于在ALD膜形成过程中掩盖基底表面的区域。结果,ALD产物的成核主要或仅在基底的未被掩蔽区域(即,其上未设置SAM的基底表面)中发生。ALD工艺可涉及数百个ALD循环,以实现所需厚度的沉积材料。在此,更有效的SAM允许在掩模区域中形成不需要水平的ALD产物之前,允许更大数量的ALD循环。下面的示例进一步证明,使用所公开的方法和材料可以实现实质上更高数量的ALD循环,这是在半导体器件制造过程中使缺陷最小化以及潜在地提供具有较小临界尺寸的图案的重要属性。
这里,SAM是通过化合物的自组装形成的层。该化合物是可聚合的。单层的厚度对应于单层紧密堆积结构中化合物的一个分子的长度。化合物的官能团通过静电相互作用和/或一个或多个共价键结合到基质的表面基团上,从而辅助了紧密堆积。化合物与底物表面结合的部分在本文中称为化合物的“头部”。该化合物的其余部分称为“尾部”。尾部从化合物的头部延伸到SAM顶表面的大气界面。尾部在大气界面处具有非极性的外围端基。因此,在紧密堆积结构中几乎没有缺陷的结构良好的SAM可以显示高接触角。
SAM形成化合物的头部可以选择性地结合至包括不同组成区域的基底顶表面的一部分,而使基底顶表面的其他部分不具有或基本上不具有置于其上的SAM形成化合物置于其上。在这种情况下,可以通过将基材浸入溶解在合适溶剂中的给定SAM形成化合物的溶液中,在一个步骤中形成图案化的初始SAM。
在此,紫外线辐射可以具有大约4nm至450nm的波长。深紫外线(DUV)辐射的波长可以在124nm至300nm之间。极端紫外线(EUV)辐射的波长约为4nm至小于124nm。
SAM形成化合物具有根据式(1)的结构:
其中
a是1或2,
H'为头部基团,其包含能够通过静电相互作用和/或共价键结合至基材的给定选定顶表面的官能团,
T'是与头部基团共价连接的末端基团,该末端基团包括氢键形成官能团、可聚合基团和非极性外围端基。
SAM形成化合物可以具有1或2个尾基。每个尾基可包含一个或多个形成氢键的基团和一个或多个可聚合的基团。SAM形成化合物可以单独使用或结合使用。
在一个实施例中,SAM形成化合物具有一个尾基。这些化合物具有根据式(2)的结构:
H′-S′-B′-S″-P′-E′ (2),
其中
H'为头部基团,其包含能够通过静电相互作用和/或共价键结合至基材的给定选定顶表面的官能团,
S'-B'-S”-P'-E'是与H'共价连接的尾基,
S'是包含至少一个碳的第一间隔基,
B'是包含氢键形成官能团的部分,
S”是包含至少一个碳的第二间隔基,
P'是包含可聚合基团的部分,并且
E'是包含1-20个碳的非极性外围端基。
头基H’的非限制性示例性官能团包括:膦酸基(*-P(=O)(-OH)2及其盐、羧酸基(*-C=O)OH)及其盐、磺酸基(*-S=O)2OH)及其盐、亚磺酸基(*-S=O)OH)及其盐、醇(*-OH)、硫醇(*-SH)、二硫化物(*-S=S-*)、烯烃(*-C=C-*)、炔(*-C≡C-*)、硅烷以及杂环(例如,咪唑、噁唑、噻唑等)。其他非限制性头部基团包括氧化膦、亚磷酸酯、磷酸酯、膦嗪、叠氮化物、肼、硫化物、醛、酮、硅烷、锗烷、胂、腈、异氰化物、异氰酸酯、硫氰酸酯、异硫氰酸酯、酰胺、醇、硒醇、硝基、硼酸、醚、硫醚、氨基甲酸酯、硫代氨基甲酸酯、二硫代氨基甲酸酯、二硫代羧酸酯、黄原酸酯、硫代黄原酸酯、烷基硫代磷酸酯、二烷基二硫代磷酸酯、异羟肟酸。上述头部基团可以单独或组合使用。在一个实施例中,该头基包括由膦酸基(*-P(=O)(-OH)2及其盐、羧酸基(*-C(=O)OH)及其盐、磺酸基(*-S(=O)2OH)及其盐、亚磺酸基(*-S(=O)OH)及其盐、醇(*-OH)、硫醇(*-SH)、烯烃(*-C=C-*)、炔(*-C≡C-*)、硅烷、及其组合组成的组中的一个成员。
在本文中,具有至星号的键的原子中心是指原子中心共价连接至化学结构的另一个未指定的原子中心。
上述酸基团的盐包括带负电荷的基团(例如,膦酸酯基团(*-P(=O)(-O-)2、羧酸酯基团(*-C(=O)O-)、磺酸酯基团S(=O)2O-)、以及亚磺酸酯基团(*-S(=O)O-)),该带负电荷的基团与带正电荷的抗衡离子(例如像Li+、Na+、K+、Rb+、或Cs+)离子缔合。
间隔基团S”和S””是独立的二价非环状烃基,更确切地说是支链的和非支链的C1-C20非环状脂肪族烃基。示例性非限制性二价无环脂肪族基团包括亚甲基、乙-1,2-二基(*-CH2CH2-*)、丙-1,3-二基(*-CH2CH2CH2-*)、丙-1,2-二基(*-CH(CH3)CH2-*)、丁-1,4-二基(*-CH2(CH2)2CH2-*)、丁-1,3-二基(*-CH2CH2CH(CH3)-*)、戊-1,5-二基(*-CH2(CH2)3CH2-*)、以及己-1,6-二基(*-CH2(CH2)4CH2-*)、庚-1,8-二基(*-CH2(CH2)5CH2-*)、辛-1,8-二基(*-CH2(CH2)6CH2-*)、壬-1,9-二基(*-CH2(CH2)7CH2-*)、辛-CH2(CH2)8CH2-*、辛-CH2(CH2)9CH2-*、辛-CH2(CH2)10CH2-*、辛-CH2(CH2)11CH2-*、以及壬-CH2(CH2)12CH2-*)。
在本发明的一个实施例中,SAM形成化合物的尾部不包括环。在另一个实施例中,该尾基包含10至50个亚甲基(*-CH2-*)。
氢键形成基团B'包括氢供给部分(例如,*-NH-*和氢受体部分(例如,羰基))。非限制性的示例性氢键形成官能团包括酰胺(*-NH-C(=O)-*)、脲(*-NH-C(=O)-NH-*)、以及氨基甲酸酯(*-NH-C(=O)-O-*)。B'基团可以包括一个或多个前述官能团。
只要不对所得SAM的性能产生不利影响,对二价可聚合基团P'没有限制。优选的P'基团包含一个或多个选自下组的可聚合基团,该组由以下各项组成:乙烯-1,1-二基((*)2C=CH2)、乙烯-1,2-二基(*-C(H)=C(H)-*)、乙炔-1,2-二基(*-C≡C-*)、以及其组合。更具体的P'基团包含聚烯、聚炔及其组合。在一个实施例中,P'包括由1,3-丁二烯-1,4-二基(*-C=C(H)-C(H)=C-*)、丁二炔-1,4-二基(*-C≡C-C≡C-*)、以及它们的组合组成的组的成员。
端基E’包含碳和选自氢、氟及其组合的基团的成员。非限制性端基E’包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基、和其中一个或多个氢被氟取代的任何上述基团。在一个实施例中,E”是正十二烷基。
这里,全氟化基团是其分子式仅包含元素碳和氟的官能团。优选地,当存在氟时,E”的相邻碳通过单键连接(即,E”是全氟化的烷基,意指其中每个氢被氟取代的烷基)。示例性E”基团包括三氟甲基(*-CF3)、全氟乙基(*-CF2CF3)、全氟正丙基(*-CF2CF2CF3)、全氟异丙基(*-CF(CF3)2)、全氟正丁基(*-CF2CF2CF2CF3)、全氟异丁基(*-CF2CF(CF3)2)、全氟正戊基(*-CF2(CF2)3CF3)、全氟正己基、全氟正庚基、全氟正辛基、全氟正壬基、全氟正癸基、全氟正十一烷基、全氟正十二烷基等。
其他更具体的SAM形成化合物具有根据式(3)的结构:
其中
m是具有4至20的值的正整数,
n是具有0至19的值的正整数,
H’是头基,该头基包括能够通过静电相互作用和/或共价键结合至基底的给定的所选顶表面的官能团,
S’是包含至少一个碳的间隔基团,
B’是包含形成氢键的基团的部分,并且
每个X是选自氢和氟的独立取代基。
上面进一步提及的式(2)的S",P',和E'的实例在式(3)中标记。
在以上结构中,二乙炔基共价连接至两个独立的二价亚烷基链,每个独立的二价亚烷基链包含4-20个亚甲基。周围的亚烷基链被甲基封端。
更具体的SAM形成化合物具有根据式(4)的结构:
其中
k是具有1至10的值的正整数,
m是具有4至20的值的正整数,
n是具有4至20的值的正整数,
H’是头基,该头基包括能够通过静电相互作用和/或共价键结合至基底的给定的所选顶表面的官能团,
B'是包括选自下组的成员的部分,该组由以下各项组成:酰胺、脲、和氨基甲酸酯,并且
每个X是选自氢和氟的独立取代基。
上面进一步提及的式(2)的S',S",P'和E'的实例在式(4)中标记。
在一个实施例中,每个X是氢。在另一个实施例中,每个X是氟。
在以下每种方法中,SAM充当掩模以阻止ALD前驱体在SAM占据的基底表面部分上沉积。
方法1
在图1A-1F的截面层图中示出了通过ALD形成分层结构的第一种方法。该方法利用可聚合的SAM作为抗蚀剂,以在原子层沉积过程中掩盖表面。图1A的基底110可以包括一层或多层。为简单起见,示出的基底110具有一层,即层112(例如,铜箔)。层12具有能够与SAM形成化合物的头部基团离子或共价结合的顶表面114。
SAM形成化合物的头基的选择取决于顶表面114的表面基团。为了说明的目的,并不意味着限制,如果层112包含铜金属,则顶表面114可以包含在氧等离子清洗铜箔期间形成的铜的氧化物。在这种情况下,头基优选包含膦酸基团,其与氧化铜表面基团强烈地相互作用。对于其他金属氧化物,其他头基可能是优选的。
可以使用任何合适的涂覆技术将SAM形成化合物施加到顶面114上(例如,使用在合适溶剂中的SAM形成化合物的溶液浸涂基底,旋转浇铸在合适溶剂中的SAM形成化合物的溶液,蒸镀SAM形成化合物),从而生成结构120(图1B)。结构120包括设置在层112上的初始SAM层121。初始SAM层121是SAM形成化合物的单层,其头基通过静电和/或共价相互作用在界面123处与层112的表面基团结合(例如,SAM形成化合物的膦酸头基与层112的CuO/CuO2表面基团结合)。初始SAM层121包括顶表面122。初始SAM层121在界面123和顶表面122之间的区域中包括氢键形成基团,该氢键形成基团有助于稳定和紧密堆积结合的SAM形成化合物的尾部。初始SAM层121在界面123和顶表面122之间的区域中还包含可聚合基团。顶表面122是非极性的并且阻止由ALD传送的材料的沉积。
在逐图案地曝光之前,可以在适当的时间和温度条件下用任选的后施加烘烤(PAB)和/或任选的溶剂冲洗来处理SAM层121。任选的PAB处理通常是于50℃至250℃的温度进行1秒至10分钟,更具体为在惰性气氛(例如氮气、氦气或氩气)下于90℃至130℃进行约1分钟。PAB可用于干燥过量溶剂的膜、去除不想要的或过量的有机配体、和/或产生将头基连接至顶表面114的氧化物的共价键。经热处理的SAM层121具有1个单层的SAM形成化合物的厚度。
然后,使用能够诱导SAM层的可聚合P'基团聚合的高能辐射,通过具有期望图案的掩模,以图案方式曝光初始SAM层121或烘焙的初始SAM层(未示出),从而产生结构130(图1C)。结构130包括设置在层112上的曝光的SAM层135。曝光的SAM层135包括:i)曝光的SAM层135包括:i)曝光的SAM特征131,其包含聚合的结合的SAM形成化合物并且具有顶表面132;以及ii)未曝光的SAM特征133,其包含未聚合的结合的SAM形成化合物并且具有顶表面134。顶表面132和顶表面134是非极性的。
用于诱导SAM的聚合的高能辐射的非限制性示例包括深紫外(DUV)光、准分子激光、x射线或极紫外(EUV)光。紫外光暴露剂量优选为约1mJ/cm2至约500mJ/cm2,更优选约10mJ/cm2至约100mJ/cm2。可通过常规光刻或通过液体浸入光刻(例如,使用EUV曝光)来执行曝光。液体浸入曝光设备在光路中在掩模和SAM层之间使用诸如水、碳氢化合物液体和/或氟化液体之类的介质,这导致对高能辐射的较少吸收并且能够在数值孔径和有效波长方面实现更高效的精细处理。在这种情况下,可以预先向SAM层施加不溶于水的保护膜。在实施例中,使用在100nm与300nm之间的紫外波长进行曝光。
在选择性去除未曝光的SAM特征之前,可在合适的时间和温度条件下用任选的曝光后烘烤(PEB)和/或任选的溶剂清洗来处理曝光的SAM层135。任选的PEB可以在50℃至250℃的温度进行1秒至10分钟,更具体地在惰性气氛下在80℃至140℃的温度进行约1至5分钟。
SAM层可在暴露、PAB和/或PEB之前或之后用溶剂(例如,水、水溶液(包含水/醇混合物)和有机溶剂)冲洗。可以在室温或接近室温(例如,10℃至50℃)进行冲洗1秒至1小时。与未曝光的SAM特征相比,可选的烘烤(PAB和/或PEB)处理和/或可选的冲洗处理可以增强曝光的SAM特征的溶解度差异。
可使用任何合适的方法和材料来选择性地去除未曝光的SAM特征133(例如,在能够选择性地溶解未曝光的SAM特征133的有机溶剂中显影层135,留下曝光的SAM特征131),由此形成结构140(图1D)。结构140包括图案化层141,图案化层141包括曝光的SAM特征131和沟槽142。沟槽142具有底表面143和高度t的侧壁144,该高度t对应于聚合的SAM形成化合物的一个单层的厚度。
结构140随后经受ALD工艺,ALD工艺在底表面143上选择性地沉积ALD前体,而不留下或基本上不留下布置在顶表面132上的ALD前体。即,ALD前体对底表面143具有高亲合力,而对顶表面132具有低亲合力,或更优选地不具有亲合力。第一ALD循环在底表面143上形成ALD产物的一个单层,并且每个连续的ALD循环在先前的ALD单层上形成ALD产物的另一个单层。ALD工艺可根据需要重复多次循环以产生ALD产物的期望厚度t’,从而形成结构150(图1E)。结构150包括图案化层151和ALD特征152,图案化层151包括具有厚度t的曝光的SAM特征131,ALD特征152包含设置在沟槽区域142中的底表面143上的ALD产物。ALD特征152具有顶表面153和厚度t’,厚度t’可小于(示出)、大于(未示出)或等于(未示出)曝光的SAM特征131的厚度t。优选地,曝光的SAM特征131的顶表面132没有或基本上没有ALD产物布置在其上。
给定的ALD循环可以包括初始沉积的ALD前体的一个或多个化学转化。例如,ALD循环可涉及低沸点有机金属化合物(例如,二甲基锌,沸点46℃)的初始传送,其在ALD循环的第二阶段中使用水蒸气转化为金属氧化物(例如,ZnO)。给定的ALD前体可以是金属、有机金属化合物、无机化合物或有机化合物。ALD工艺的每个ALD循环可以形成相同的产品或不同的产品。
然后可以选择性地去除曝光的SAM特征131,留下结构160(图1F)。结构160包括图案化层161,图案化层161包括设置在基底110的层112上的ALD特征152。图案化层161还包括具有基底110的底表面163的沟槽162。可使用已知技术(包括但不限于溶剂剥离和氧等离子体蚀刻)来执行对曝光的SAM特征131的选择性去除。用于去除曝光的SAM特征131的蚀刻工艺还可选择性地去除SAM特征131下方的材料,由此在基底内形成浮雕图案(未示出)。
方法2
在该方法中,SAM形成化合物的头基对于基底的顶表面的一部分具有优先的亲和力,并且选择性地吸附该基底的顶表面的一部分包括具有不同化学组成的两个或更多个区域。
基底210(图2A)是包括与底层212接触的特征215的多层基底。底层212具有顶表面214。特征215可布置在顶表面214上(未示出),或延伸到底层212中(示出)。特征215具有顶表面216、底表面213和侧壁217。在该非限制性示例中,底面213和侧壁217与底层212接触。层212的顶表面216和顶表面214与大气接触并且在成分上是不同的。在该示例中,特征215被示为部分地嵌入在层212中,并且高度t小于特征215的厚度t。高度t’可以大于或等于零。高度t’可以大于t(未示出)、等于t(未示出)、或小于t(示出)。
作为非限制性示例,层212可以是具有包括SiO2的顶面214的硅层,并且特征215可以是铜线图案,其顶面216包括CuO和/或CuO2。在这个实例中,由于其与顶表面216的CuO和/或CuO2的强结合特性和与顶表面214的SiO2的弱结合特性,包含膦酸头基的SAM形成化合物将是优选的。
然后将SAM形成化合物施加到基底210,从而形成结构220(图2B)。结构220包括选择性地布置在特征215上的初始SAM特征221的图案。结构220还包括沟槽223,该沟槽223包括底表面214,该底表面214上未布置有或基本上未布置有SAM形成化合物。沟槽223将初始SAM特征221分开。初始SAM特征221的厚度等于SAM形成化合物的一个单层。如在先前的方法中的那样,初始SAM特征可被给予可选的施加后烘烤和/或施加后溶剂冲洗。
在可选的烘烤和/或冲洗之前或之后,结构220在高能辐射下的泛光照射产生结构230(图2C)。结构230包括具有顶表面232的曝光的SAM特征231,这些曝光的SAM特征231由具有底表面214的沟槽223分隔开。底表面214上没有布置SAM形成化合物或者基本上没有布置SAM形成化合物。曝光的SAM特征231包括聚合的SAM形成化合物。顶表面232是非极性的。曝光的SAM特征可被给予任选的曝光后烘烤和/或曝光后溶剂漂洗。
结构230然后经受ALD工艺,该ALD工艺在第一半循环中选择性地在沟槽223的底表面214上沉积ALD前体,从而形成结构240(图2D)。然后在半循环第二个半循环中将沉积的ALD前体转化为ALD产物。结构240不具有或基本上不具有设置在曝光的SAM特征231的顶表面232上的ALD产物。ALD前体对底表面214具有优先亲合力,而对顶表面232具有低亲合力,或更优选地无亲合力。ALD工艺可包括产生ALD产物的期望厚度h’所需的尽可能多的ALD循环。ALD特征241包括ALD产物并且具有顶表面242,顶表面242可以在顶表面232下方(示出)、上方(未示出)或者与顶表面232共面。ALD特征241的底表面243与层212接触。
然后可以选择性地去除曝光的SAM特征231,留下结构250(图2E)。在此实例中,结构250包括与层112接触的ALD特征241的图案,ALD特征241由基底210的特征215分离。结构250的特征215具有顶表面251,顶表面251可在ALD特征241的顶表面242下方(示出)、上方(未示出)或共面。对曝光的SAM特征231的选择性去除还可包括去除曝光的SAM特征231下方的材料,包括特征215和底层112(未示出)的材料。
基底
基底是包括一个或多个层的层状结构并且具有顶表面。该基底,并且更具体地该基底的表面,可以包括无机或有机材料,如金属、碳、和/或聚合物。更具体地,基底可以包括半导体材料,该半导体材料包括例如Si、SiGe、SiGeC、SiC、Ge合金、GaAs、InAs、InP、氮化硅、氮化钛、氧化铪以及其他III-V或II-VI化合物半导体。基底可以包括介电材料,诸如SiO2、TiO2、Al2O3、Ta2O5以及聚合物(例如,聚酰亚胺、聚酰胺、聚乙烯)。基底还可以包括诸如Si/SiGe的层状半导体或绝缘体上半导体(SOI)。特别地,基底可以包含含Si的半导体材料(即,包括Si的半导体材料)。半导体材料可以是掺杂的、非掺杂的或者在其中包含掺杂的和非掺杂的区域两者。
基底可具有抗反射控制层(ARC层)或底部ARC层(BARC层)以降低膜堆叠的反射率。许多合适的BARC在文献中是已知的,包括单层BARC、双层BARC、分级BARC和可显影BARC(DBARC)。基底还可包含硬掩模、转移层(例如,平面化层、旋涂玻璃层、旋涂碳层)及分层装置所需的其他材料。
SAM层的配方
还公开了用于制备SAM层的组合物。该组合物包含溶剂以及与溶剂接触的0.1-5重量%的SAM形成化合物,其中重量%是基于组合物的总重量。SAM形成化合物可以溶解或分散在溶剂中。该组合物适于形成包含SAM形成化合物的SAM层。示例性溶剂包括但不限于:甲苯、二甲苯、二氯甲烷(DCM)、氯仿、四氯化碳、乙酸乙酯、乙酸丁酯、乙酸戊酯、丙二醇单甲醚乙酸酯(PGMEA)、丙二醇单甲醚(PGME)、丙酸乙氧基乙酯、苯甲醚、乳酸乙酯、二乙醚、二噁烷、四氢呋喃(THF)、乙腈、乙酸、乙酸戊酯、乙酸正丁酯、γ-丁内酯(GBL)、丙酮、甲基异丁基酮、2-庚酮、环己酮、甲醇、乙醇、2-乙氧基乙醇、2-丁氧基乙醇、异丙醇、正丁醇、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺、吡啶、以及二甲亚砜(DMSO)。溶剂可以单独使用或组合使用。
可以使用任何合适的涂覆技术(例如,浸涂、旋涂)将溶液施加到基底的顶表面,随后去除溶剂,从而形成初始SAM层。SAM层具有与大气接触的顶表面和与基底的选定表面接触的底表面,SAM形成化合物对该基底具有优先的亲和力。
一般而言,SAM可具有约0.5至约20纳米、更具体地约0.5至约10纳米、并且甚至更具体地约0.5至约2纳米的厚度。
退火条件
SAM使给定基底表面对ALD沉积失活的选择性程度是SAM形成化合物的尾部的化学结构、头部基团结合到基底表面的性质(离子或共价)、SAM层中任何溶剂的存在、用于实现紧密堆积的退火条件(例如,温度、环境和退火时间)、实现的聚合度以及SAM界面性质(例如,SAM-空气界面)的函数。可调整这些参数以优化SAM对给定ALD前体的沉积的抗性。
SAM层的自组装可在SAM层形成期间和/或在施加后退火步骤(例如,后续热退火工艺或溶剂退火工艺)期间发生。热退火工艺包括在恒定温度下退火和热梯度退火。热退火步骤可在约80-350℃,更优选约120-350℃的温度下进行。热退火可以进行约1秒至约24小时的时间,并且更具体地,约1分钟至约20分钟的时间。
选择性去除
SAM特征的选择性去除可通过任何合适的工艺(例如,对可热分解材料的热烘烤、反应离子蚀刻工艺、在选择性溶剂中的溶解、紫外线暴露或前述各项的组合)来执行。选择性去除可以包括干法蚀刻,例如等离子体蚀刻和/或使用选择性溶剂和/或蒸汽的湿法蚀刻。通常,使用合适的气体(O2)的干法蚀刻工艺用于在亚50nm尺寸下蚀刻。选择性地去除SAM特征产生了可被转移到下层基底中的浮雕图案。
在选择性去除SAM特征和/或转移之前,SAM特征可任选地经化学修饰以改善选择性去除所需的属性,诸如耐蚀刻性或机械属性。可将抗蚀刻材料施加到基底表面、SAM特征的表面和/或ALD特征的表面以控制相对蚀刻速率。抗蚀材料可以通过包括化学气相沉积(CVD)、等离子体增强CVD、原子层沉积(ALD)、顺序渗透合成(SIS)、金属盐的顺序渗透、溅射、热蒸发、电子束蒸发、脉冲激光沉积或与微电子制造中使用的工艺和设备兼容的其他适当的沉积方法的工艺从气相沉积。
化学修饰可通过多种已知方法完成。例如,化学试剂可用于与SAM的官能团结合或化学偶联,以实现例如可有利地用于选择性地去除SAM特征的增加的溶解性特性差异。
SAM特征的选择性去除可去除基底和/或抗蚀剂的底层材料。
实用性
上述方法可用于形成包括金属、金属氧化物、氮化物或多晶硅的图案化层的层状结构。所述方法有利地提供具有减小的特征尺寸和良好的均匀性的结构特征。
以下实例说明SAM的制备以及它们在去活化氧等离子体清洁的铜表面对充当氧化锌的前体的有机锌化合物的ALD沉积的有效性。
实例
在以下实例中使用的材料列于表1中。
表1
合成
从可商购的(2-氰基乙基)膦酸二乙酯和10,12-二十五烷二炔酸以三个步骤合成(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸(DA)。
A.(3-氨基丙基)膦酸二乙酯(C-1)的制备。
在0℃下,在1:1THF/水混合物(65mL,0.1M)中,将(2-氰基乙基)膦酸二乙酯(3.24g,17.0mmol,1.0当量)用硼氢化钠(9.00g,237mmol,14.0当量)和氯化钴六水合物(0.81g,3.4mmol,20mol%)还原,并允许经24小时加热至23℃。添加NH4OH(1L,在H2O中28%)并且搅拌1小时。用DCM(4x200mL)萃取水相,将其经MgSO4干燥并在真空中浓缩,以给出(3-氨基丙基)膦酸二乙酯(C-1,1.51g,7.74mmol,46%粗收率)。C-1不经进一步纯化直接进行。1HNMR(400MHz,CDCl3):δ4.10(q,J=6.9,4H),2.77(t,J=6.6,2H),1.84–1.66(m,4H),1.32(t J=7.1,6H)。
B.(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸二乙酯(C-2)的制备。
使用EDCI(0.75g,4.8mmol,1.1当量)在DMAP(0.03g,0.22mmol,5mol%)的存在下在二氯甲烷(12mL,0.4M)中经24小时将C-1(0.85g,4.32mmol,1.0当量)与10,12-二十五烷二炔酸(1.62g,4.32mmol,1.0当量)偶联。将反应物用水(2x200mL)洗涤。将有机相经MgSO4干燥并且然后在真空中浓缩。将粗产物通过柱色谱法(50%EtOAc/己烷→5%MeOH/DCM)进行纯化以产生(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸二乙酯(C-2,0.63g,1.17mol,27%产率)。1HNMR(400MHz,CDCl3):δ6.05(s,1H),4.10(q,J=7.5,4H),3.35(q,J=6.3,2H),2.24(t,J=6.9,4H),2.16(t,J=7.4,2H),1.88–1.71(m,4H),1.56(m,37H),0.88(t,J=6.9,3H)。
C.(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸(DA)的制备。
通过用氯三甲基硅烷(3.89g,35.8mmol,60.0当量)在DMF(5ml,0.12M)中在90℃下经24小时原位形成三甲基甲硅烷基膦酸酯,使膦酸酯C-2(0.32g,0.60mmol,1.0当量)脱保护。用水水解三甲基甲硅烷基酯产生了所需产物DA(0.25g,0.50mol,84%产率)。通过过滤粗固体、用水(5mL)冲洗过滤的固体、并且用DCM(3x5mL)研磨,来纯化粗DA。1HNMR(400MHz,DMSO-d6):δ3.04(q,J=5.8,4H),2.27(t,J=6.8,4H),2.02(t,J=7.7,2H),1.63–1.07(m,36H),0.85(t,J=6.6,3H)。
由4-溴苯甲酸甲酯以四个步骤制备三芳香族膦酸化合物TP。
A.4-(二甲氧基磷酰基)苯甲酸甲酯(C-3)的制备。
将4-溴苯甲酸甲酯(5.0g,23mmol,1.0当量)与Pd(Ph3P)4(2.7g,2.3mmol,0.1当量)和碳酸铯(9.1g,28mmol,1.2当量)在四氢呋喃(116mL,0.2M)中合并,并且在80℃下加热18小时。将该反应混合物经硅藻土塞过滤并且将滤液在真空中浓缩。将该橙色固体通过柱色谱法(2%MeOH/DCM)进行纯化以获得C-3(1.95g,7.99mmol,34%产率)。1HNMR(400MHz,CDCl3):δ8.13(app dd,J=8.3,3.9,2H),7.88(app dd,J=13.0,8.3H),3.95(s,3H),3.79(d,J=11.1,6H).。
B.4-(二甲氧基磷酰基)苯甲酸(C-4)的制备。
将在水(0.1M)中的LiOH(0.35g,8.39mmol,1.05当量)缓慢添加至在1:1MeOH/H2O混合物(160mL,0.05M)中的4-(二甲氧基磷酰基)苯甲酸甲酯(C-3,1.95g,7.99mmol,1.0当量)中并且在23℃下搅拌2小时。将MeOH在真空中去除并且将水相用EtOAc(2x200mL)漂洗并且用1M HCl(100mL)酸化。用EtOAc(3x100mL)萃取有机相,经MgSO4干燥并在真空中浓缩,以获得产物C-4(1.0g,4.34mmol,54%产率)。1HNMR(400MHz,CDCl3):8.21(app dd,J=8.5,3.9,2H),7.93(1HNMR(400MHz,CDCl3):δ8.21(app dd,J=8.5,3.9,2H),7.93(app dd,J=13.0,8.5 2H),3.82(d,J=11.2,6H).。
C.(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸(DA)的制备。
将4-氨基苯甲酰胺(0.41g,1.9mmol,1.1当量)添加到4-(二甲氧基磷酰基)苯甲酸(C-4,0.4g,1.8mmol,1.0当量)、1-乙基-3-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDCI,0.4g,2.1mmol,1.2当量)、N-羟基苯并三唑(HOBZt,0.3g,2.1mmol,1.2当量)、以及三乙胺(Et3N,0.25g,2.5mmol,1.44当量)在DMF(29mL,0.06M)中的搅拌溶液中。将所得溶液在23℃下搅拌24小时。将溶剂在真空中去除并且将材料从H2O/MeOH中重结晶以获得C-5(0.13g,0.31mmol,18%产率)。HNMR(400MHz,DMSO-d6):δ10.72(s,1H),10.19(s,1H),8.26–7.00(m,13H),3.71(d,J=11.1,6H)。
D.TP的制备
通过在100℃下,在DMF(2mL,0.06M)中用氯三甲基硅烷(0.77g,7.09mmol,60.0当量)原位形成三甲基甲硅烷基膦酸酯1小时来使C-5脱保护,随后用水水解三甲基甲硅烷基酯。将所得沉淀物过滤并且用水(5mL)和Et2O(5mL)冲洗以得到所需产物TP(0.03g,0.08mmol,64%产率)。1HNMR(400MHz,DMSO-d6):δ10.58(s,1H),10.17(s,1H),8.08–7.04(m,13H)。
SAM形成材料列于下表2中。
表2
接触角
测量作为浸渍时间的函数并且在包括金属(Cu、Sn、Zn、V)和硅表面(天然SiO2、SiN)的各种表面上的各种SAM的接触角。在溶剂4-甲基-2-戊醇中按0.1重量%制备所有SAM溶液,然后通过0.2微米PTFE注射器式过滤器过滤。在涂覆之前立即用氧等离子体清洁表面。应当理解,当以这种方式清洁时,金属表面包含金属氧化物。除非另外指明,所有涂覆均在室温下进行。
表3列出了所获得的在室温下(即,在照射SAM层之前)在不同金属表面上形成的各种初始SAM层的接触角。较大的接触角是期望的,并且较大的接触角表明SAM形成材料结合至金属表面。
表3
表3中的结果显示ODPA、SA、DA和PFDA在铜和锡表面上选择性地形成SAM。SAM在这些表面上具有80-110度范围内的相似接触角。较低的接触角(例如,在SiO2和SiN表面上)表明在这些表面上SAM形成较差。
ALD研究
使用圆形阴影掩模将50nm厚的Cu膜蒸发到四英寸回收的硅晶片上,该掩模保护一部分天然SiO2表面免于Cu沉积。在破坏真空之后,Cu层在表面上生长自然氧化物层(即,CuO和/或Cu2O)。然后在65℃下将晶片在(3-(二十五烷-10,12-二炔酰氨基)丙基)膦酸(DA)的二甲亚砜(0.5mg/mL,试剂级)溶液中浸入24小时,然后用异丙醇冲洗并使用恒定氮气流干燥。SAM的接触角为104°,表明在Cu表面上形成组装良好的SAM。在氮气氛下将晶片加热至120℃以促进膦酸与金属氧化物的酯化。测得SAM的接触角为104°,表明SAM没有从Cu膜上解吸。
将晶片分成两半。一半用254nm紫外光照射5分钟(即,照射半个晶片的不具有SAM的区域和具有SAM的区域)。SAM辐照后的接触角为101°,表明SAM从Cu表面的解吸可忽略不计。然后将两个半晶片装载入ALD室中。ZnO沉积使用二甲基锌作为ZnO的有机金属前体。在此过程中,ALD工艺是在150℃的温度下连续不断地注入Ar,以实现140mT的基本压力。0.015秒的水脉冲后,停顿20秒,接着是0.0125秒的二甲基锌脉冲,再停20秒,然后抽空任何未反应的二甲基锌。该过程表示一个ALD循环。每个循环后获得的ZnO膜厚度为约0.12nm。在总共10个试样或1000个ALD循环的每100个循环之后,将每半的试样从ALD室去除。
然后,通过卢瑟福背散射光谱法(RBS)对试样进行表征,以测量不具有SAM的晶片部分的表面组分(即具有SiO2表面的区域)。在两种情况下,ZnO组分都直接在SiO2表面上方增加,这与ZnO膜的生长一致。在晶片的非光辐照和光辐照的两半的SiO2表面上观察到可以忽略不计的ZnO沉积差异,总结于表2中。
表2
在晶片两半的SAM部分上,使用PIXE(粒子诱导的X射线发射)分析来确定少量的ZnO成核。检测极限为0.1单层ZnO。DA的非光辐照SAM(下面的表3中的实例1)显示,直到800次ALD循环都未检测到ZnO。1000次循环后,检测到的ZnO。因此,DA的非光辐照SAM的最大ALD循环数在800-1000个循环之间。对于DA的光辐射SAM(下面的实施例8,表3),在1000次ALD循环后未检测到ZnO。因此,对于DA的光辐照SAM来说,最大ALD循环数为1000以上。DA的非光辐照SAM是很强的失活阻挡层,而DA的光辐照SAM对ZnO沉积的失活甚至更大。
包含嵌入的Cu线图案的预图案化基底
图4中示出用于形成SAM的这个基底。基底300包括具有顶表面314的Cu线图案312。Cu线图案312嵌入在电介质层316中,该电介质层由八甲基环四硅氧烷(OMCTS)制备并且具有包括SiO2的顶表面318。Cu线图案312的顶表面314含有铜的氧化物。Cu线图案312的顶表面314也与电介质层316的顶表面318共面。基底300的底层310是硅晶圆。
ALD结果
ZnO沉积的程序如上所述。
用于HfO2沉积的有机金属前体为TDHf四(二甲氨基)铪(IV)。在70℃下以Ar的连续流进行HfO2沉积的ALD过程,以实现200mT的基压。0.25秒的TDHf脉冲后暂停240秒,接着是0.06秒的水脉冲,接着是240秒的暂停,接着是排空任何未反应的TDHf。
用于TiO2沉积的有机金属前体是TDTi四(二甲氨基)钛(IV)。在150℃下以Ar的连续流进行用于TiO2沉积的ALD过程,以实现220mT的基础压力。在0.06秒的水脉冲之后,暂停10秒,接着是0.1秒的TDTi脉冲,接着是10秒的暂停,接着是排空任何未反应的TDTi。
使用上述通用过程筛选SAM形成化合物,用于氧等离子体清洁的Cu表面的失活。结果汇总于表3中。“最大ALD循环”是指在失活的铜表面上发生不需要的ALD沉积之前的循环数。期望有更高数目的最大ALD循环。
表3
注1:因为在照射之后观察到接触角的大幅减小,所以不执行ALD。
注2:使用OMCTS制备的预图案化基底。
表3中的结果表明,非光辐照的ODPA(实例2)和光辐照的ODPA(实例7)表现相当,各自具有最大ALD循环数600。与非光照射的DA(实例1,800-1000个循环)相比,ODPA实例2和7也较少失活。与非光照射的脲化合物UODPA(实例3,800个循环)相比,ODPA实例2和7也较少失活。UODPA实施例3与非光照射的DA(实施例1,800-1000个循环)相比失活稍少,表明UODPA的脲氢键形成基团和DA的酰胺氢键形成基团对SAM表面对ZnO沉积的失活具有类似影响。用不含膦酸头基、氢键形成基团和可聚合基团的SAM形成化合物获得了最低效的去活化(实例4-5)。最有效的化合物是光辐照的DA(实例6,>1000个循环)。
尽管DC(实例10)形成了初始SAM,但初始SAM在光辐照后并不保持高接触角。不希望受理论束缚,相信初始SAM的双烯键式基团不能适当地对准以用于聚合。此实例指出氢键基团对于提供可聚合基团的适当对准和稳定性的重要性。
当ALD产物是TiO2时,相对于SiO2表面,使用光辐照的DA(实施例10)和非光辐照的ODPA(实施例9)没有观察到Cu表面的失活。TiO2在两个表面上都形成。
图3是比较UODPA、ODPA和PFDASAM在阻断铜表面上的氧化锌的ALD中的性能的图。期望的Zn/(Zn+Cu)组成比为零。示出了最多600个ALD循环,超过这些循环,每个SAM在SAM上显示出不可接受的高水平的锌成核。
图4是比较由DA和ODPA形成的SAM在阻断铜表面上的氧化锌的ALD中的性能的图。DA的一个SAM仅在ALD之前被给予烘烤,另一个在ALD之前通过UV照射而聚合。经UV照射的DASAM在1000次ALD循环之后展示与经烘烤的DASAM相比实质上较少的锌沉积,所述经烘烤的DASAM允许最多800次ALD循环。ODPA允许最多600次ALD循环。结果表明,DA的氢键合基团相对于ODPASAM增强了DASAM的选择性(分别为800次循环对600次循环的最大值),并且当通过UV照射来聚合二亚乙酰基时获得了DASAM的选择性的进一步增强(≥1000次循环)。
在此使用的术语仅用于描述具体实施例的目的并且不旨在限制本发明。如在此使用的,单数形式“一”、“一个”、“该”,除非上下文另外明确指出,否则旨在也包括复数形式。将进一步理解,术语“包括”、“包含”,当在本说明书中使用时,指定所陈述的特征、整数、步骤、操作、元件和/或组件的存在,但不排除一个或多个其他特征、整数、步骤、操作、元件、组件和/或其群组的存在或添加。当一个范围被用来使用两个数值极限X和Y(例如,X ppm到Yppm的浓度)来表示一个可能的值时,除非另外说明,否则该值可以是X、Y、或X与Y之间的任何数字。
本发明的描述是出于说明和描述的目的而呈现的,但不旨在是穷尽性的或局限于所披露的形式的本发明。在不脱离本发明的范围的情况下,许多修改和变化对本领域的普通技术人员而言将是显而易见的。选择和描述实施例以便最好地解释本发明的原理及其实际应用,并且使得本领域普通技术人员能够理解本发明。
Claims (20)
2.如权利要求1所述的方法,其中,a是1。
3.如权利要求1所述的方法,其中,头基H’包括由以下项组成的组中的一个成员:膦酸基(*-P(=O)(-OH)2及其盐、羧酸基(*-C(=O)OH)及其盐、磺酸基(*-S(=O)2OH)及其盐、亚磺酸基(*-S(=O)OH)及其盐、醇(*-OH)、硫醇(*-SH)、烯烃(*-C=C-*)、炔(*-C≡C-*)、硅烷、以及它们的组合。
4.如权利要求1所述的方法,其中,所述氢键形成基团包括选自下组的一个官能团,该组由以下各项组成:酰胺、氨基甲酸酯、脲、以及它们的组合。
5.如权利要求1所述的方法,其中,所述尾部的可聚合基团包括由以下各项组成的组中的成员:1,3-丁二烯-1,4-二基(*-C=C(H)-C(H)=C-*)、丁二炔-1,4-二基、以及它们的组合。
6.如权利要求1所述的方法,其中,所述可聚合的基团包括丁二炔-1,4-二基(*-C≡C-C≡C-*)。
7.如权利要求1所述的方法,其中,所述化合物不包括环。
8.如权利要求1所述的方法,其中,所述SAM具有非极性顶表面。
9.如权利要求1所述的方法,其中,所述基底的所述表面的被掩蔽部分含有铜的氧化物。
10.如权利要求1所述的方法,其中,所述基底的所述表面的未被掩蔽部分含有SiO2。
11.如权利要求1所述的方法,其中,,所述非极性外围端基包括碳和选自包含以下各项的组的成员:氢、氟及其组合。
12.如权利要求1所述的方法,其中,所述SAM是通过使所述基底与包含溶解于溶剂中的所述化合物的溶液接触而形成的,其中,所述化合物选择性地吸附到所述基底的所述部分上。
14.如权利要求13所述的方法,其中,B’选自由以下各项组成的组:酰胺基团、氨基甲酸酯基团、以及脲基团。
15.由权利要求1所述的方法形成的层状结构。
17.如权利要求16所述的方法,其中,所述暴露所述SAM是使用紫外光来执行的。
18.一种方法,包括:
将自组装单层设置在基底的一部分上,从而形成所述基底的被掩蔽部分,同时使所述基底的一部分未被掩蔽,其中,所述自组装单层包括选自由以下各项组成的组中的部分:可光聚合部分、氢键形成部分以及它们的组合;和
使用原子层沉积工艺将材料选择性地沉积到所述基底的所述未被掩蔽部分上。
19.如权利要求18所述的方法,其中,所述单层包括可光聚合部分,所述方法包括光聚合所述自组装单层,从而在原子层沉积期间增强所述被掩蔽部分的选择性。
20.如权利要求18所述的方法,其中,所述单层包括氢键形成部分,所述氢键形成部分在原子层沉积期间增强所述被掩蔽部分的选择性。
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