CN103975418B - 用于平版印刷加工的旋涂碳组合物 - Google Patents
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- CN103975418B CN103975418B CN201280060464.0A CN201280060464A CN103975418B CN 103975418 B CN103975418 B CN 103975418B CN 201280060464 A CN201280060464 A CN 201280060464A CN 103975418 B CN103975418 B CN 103975418B
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- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
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- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
本文所述的发明涉及旋涂碳材料,其包括在溶剂系统中的聚酰胺酸组合物和交联剂。所述材料可用于三层照相平版印刷工艺。用发明性组合物制备的膜不溶于常用于平版印刷材料的溶剂,例如但不限于,PGME、PGMEA和环己酮。但是,所述膜可溶于照相平版印刷中常用的显影剂。在一种实施方式中,可在高温下加热膜,以改善用于高温加工的热稳定性。与实施方式无关,所述材料可施涂至平坦的/平面表面或者图案化表面。优选地,在使用氟碳蚀刻把图案转移至硅基片时,所述材料呈现抗扭曲性。
Description
发明背景
相关申请
本申请要求2011年10月10日提交的名为“用于平版印刷加工的旋涂碳组合物(SPIN-ON CARBON COMPOSITIONS FOR LITHOGRAPHIC PROCESSING)”的临时申请系列号第61/545,313号的优先权,该文通过引用纳入本文。
发明领域
本发明涉及从聚酰胺酸形成用于多层堆叠件及其微电子结构的富碳(旋涂碳)层的方法。
现有技术说明
随着半导体工业持续地缩小部件的尺寸,单层光刻胶的厚度不足以完全地把图案转移至基片。因此,通常使用三层堆叠件(光刻胶-硬掩模-碳层)来把由光刻胶制备的图案转移到基片。可通过化学气相沉积(CVD)或者旋涂来形成碳层。但是,CVD方法是昂贵的、具有低通量且把片暴露于苛刻的条件。目前,环氧甲酚酚醛是用于制造旋涂碳(“SOC”)层的最常见的材料,但这种材料热稳定性低且碳含量低,导致在把图案转移到硅基片时的高升华和不良的抗扭曲性。此外,这种层在固化后难以除去。已经形成的其它SOC可通过干蚀刻除去。但是,干蚀刻要求苛刻的加工条件和特种设备,使得这种方法更不那么理想。
本领域需要具有高热稳定性和光学常数、同时还可湿法除去的(可溶于显影剂的)的改善的SOC层。此外,这些层应阻止或者最小化许多现有技术方法中存在的线“扭曲(wiggling)”。
发明内容
本发明提供一种形成微电子结构的方法。所述方法包括提供具有表面的基片。任选地,在所述表面上形成一种或更多种中间层,如果存在一种或更多种中间层,那么在所述表面上有最上的中间层。如果存在中间层则把一种组合物施涂到所述最上的中间层,或者,如果不存在中间层则施涂至所述基片表面。所述组合物包含分散或溶解在溶剂体系中的聚酰胺酸。加热所述组合物来形成旋涂碳层或者富碳层,且所述富碳层是可溶于显影剂的,且在约400℃的温度下保持约10分钟时具有小于约10%的重量损失。
本发明还提供了一种新颖的微电子结构。所述结构包括微电子基片,该基片包括表面和在所述表面上的一种或更多种中间层。如果存在一种或更多种中间层,那么在所述表面上有最上的中间层。如果存在中间层则富碳层在所述最上的中间层上,如果不存在中间层则该富碳层在所述基片表面上。所述富碳层:包括交联的聚酰胺酸;是可溶于显影剂的;以及在约400℃的温度下保持约10分钟时,具有小于约10%的重量损失。
附图简述
图1是实施例26所演示的正性显影照相平版印刷(40L/80P,16.8mJ)的扫描电子显微镜(“SEM”)照片;
图2是实施例27中实施的负性显影照相平版印刷(53S/105P,19.6mJ)的SEM照片;
图3是实施例28中形成的蚀刻的旋涂碳层的SEM照片;
图4显示了来自实施例29的SOC制剂E-2的热重分析(“TGA”)曲线;
图5是如实施例30所述的SOC制剂E-2填充隔离的深接触孔的SEM照片;
图6是如实施例30所述的SOC制剂E-2填充致密深接触孔的SEM照片;
图7是显示如实施例32所述的C4F8/Ar蚀刻后的SOC110D图案的SEM照片;以及
图8是显示如实施例33所述的C4F8/Ar蚀刻后的制剂E-2图案的SEM照片。
优选实施方式详述
发明详述
发明方法
更具体地,本发明提供用于形成微电子结构的方法,且特别适于多层工艺。在发明性方法中,把一种或更多种任选的中间层施涂到基片表面。合适的中间层包括选自下组的那些:旋涂硬掩模、CVD硬掩模以及旋涂碳层(不含聚酰胺酸)。可以使用任意常规的微电子基片。优选的基片包括选自下组的那些:硅、SiGe、SiO2、Si3N4、SiON、铝、钨、硅化钨、砷化镓、锗、钽、氮化钽、珊瑚、黑金刚石、掺杂磷或硼的玻璃、Ti3N4、铪、HfO2、钌、磷化铟,以及上述材料的混合物。所述基片的表面可以是平坦的,或者它可以包括形貌特征(通孔、沟槽、接触孔、凸起特征、线条等)。在本文中,"形貌"表示基片表面之内或之上的结构的高度或深度。
如果存在中间层,则把聚酰胺酸组合物施涂到最上的中间层;如果不存在中间层,则把聚酰胺酸组合物施涂到基片表面,以在基片表面上形成层。所述组合物可通过任何已知的施涂方法施涂,优选的施涂方法是在约500转每分钟(rpm)-5000rpm的转速下旋涂所述组合物(优选转速为约1,000rpm-约2000rpm),旋涂持续时间为约5秒-120秒(优选为约30秒-约60秒)。组合物施涂之后,优选地加热到约200℃-约450℃以及更优选地约205℃-约400℃的温度,持续时间为约10秒-约120秒(优选地约30秒-约90秒),以蒸发溶剂。烘烤将引发交联反应来固化该层,由此形成富碳层,它将包括交联的聚酰胺酸。如本文所使用,术语“富碳层”指以所述层的重量作为100重量%为基准计,层包括大于约50重量%碳,优选地大于约60重量%碳,更优选地大于约70重量%碳,以及甚至更优选地约70%-99重量%碳。这些富碳层还优选地包括低氢含量(如以所述层的重量作为100重量%为基准计,小于约10重量%氢,优选地小于约5重量%氢,更优选地小于约3重量%氢,以及甚至更优选地约0.01%-约2重量%氢)。
烘烤之后测定的富碳层的平均厚度优选为约0.05微米-约10微米,更优选为约0.1微米-约5.0微米,以及甚至更优选地约0.1微米-约2.0微米。如果基片表面包括形貌,优选地以足以基本上覆盖基片形貌且取得在形貌之上的上述平均厚度的厚度,来形成富碳层。本发明的方法所用的组合物具有优异的间隙填充性质,且能很好地填充深接触孔。
取决于用于形成富碳层的具体聚酰胺酸组合物(下文将详细讨论),干燥或交联的富碳层在所用波长(如365纳米、248纳米、193纳米、157纳米或13.5纳米)处的折射率(n值)至少为约1.40,优选地为约1.45-约1.70,以及甚至更优选地为约1.50-约1.65。
干燥或交联的富碳保护层将基本上不溶于用来在多层堆叠件中形成后续层的常用有机溶剂,例如丙二醇甲基醚乙酸酯(PGMEA)、丙二醇单甲基醚(PGME)、乳酸乙酯、丙二醇正丙基醚、γ-丁内酯、环戊酮、环己酮、乙酸正丁酯、甲基异丁基甲醇((MIBC)及其混合物。因此,当进行剥落测试的时候,富碳层的剥落百分数小于约5%,优选小于约1%,以及更优选地为约0%。剥落测试包括首先测定厚度(取层的五个不同位置的测量值的平均值)。这是初始平均膜厚度。接下来,溶剂(例如乳酸乙酯)在膜上淋洗约30秒,然后在大约500-3,000rpm的转速下旋转干燥约20-60秒以除去溶剂。使用椭圆光度法再次测量在晶片上那五个不同的点的厚度,得到这些测量值的平均值。这是最终平均膜厚度。
剥落的量是初始平均膜厚度与最终平均膜厚度之间的差值。剥落百分数为:
尽管通常不溶于有机溶剂,但富碳层可溶于或能变得溶于常规水性显影剂(如,光刻胶显影剂)中。即,如本文所使用,术语“可溶于显影剂”指可用常规的水性显影剂(如氢氧化物和/或任意碱/碱性化学溶液)除去富碳层。特别优选地显影剂选自下组:氢氧化四甲铵(TMAH)、氢氧化钾(KOH)、氢氧化钠,及其混合物。因此,优选地可在加工时除去富碳层而无需干蚀刻(如,反应性离子蚀刻),且优选地在本发明的方法中,富碳层不进行任何干蚀刻。
富碳层优选地不是光敏的(即,当暴露于约1J/cm2时无法在层中形成图案),因此光敏组合物如光刻胶或其它成像层不适于用作本发明的富碳层。
优选地,富碳层具有高的热稳定性,使它特别适用于高温加工,例如通过CVD来沉积无机掩模。在本实施方式中,可在更高的温度下(即,从约300℃-约450℃,以及优选地约350℃-约400℃)加热所述交联的聚酰胺酸层来促进酰亚胺化。高的热稳定性可通过TGA来观察。具体来说,在约400℃的温度下保持约10分钟,富碳层将经历小于约10%、优选地小于约5%以及优选地约0%的重量损失。
富碳层将还具有低的升华。根据实施例31中所述的升华测试,在约205℃-约225℃的温度下,根据本发明的富碳层的升华小于约1,500纳克,优选地小于约1,000纳克,以及甚至更优选地小于约500纳克。
最后,富碳层形成SOC图案,该图案最小化或防止线变形或线“扭曲(wiggling)”。线扭曲是不利的,且妨碍图案良好地转移到下面的层和最终转移至基片。因此,用本发明取得了改善的图案化。
在基片表面上形成富碳层以后,任选的可在该富碳层附近(即在其顶部)形成一种或更多种额外的中间层。这种额外的中间层的示例包括选自下组的那些:蚀刻阻挡层、图案转移层和光刻胶。所述额外的中间层可通过任何已知的施涂方法来形成,一种优选的方法是在大约1,000-约5,000rpm的转速下旋涂所述组合物,优选转速为约1,250-约1,750rpm,持续时间为约30-约120秒,优选为约45-约75秒。
如果使用了中间蚀刻阻挡层,它优选地包括碳化合物、金属化合物或者硅化合物(如Si3N4、SiO2、SiC或SiON)。蚀刻阻挡层的厚度可变化,但优选地为约0.1纳米-约100纳米,更优选地为约1纳米-约20纳米,以及甚至更优选地为约5纳米-约10纳米。
最优选地的中间层是邻近富碳层形成的图案转移层(硬掩模)。可通过已知的任意施涂方法来形成图案转移层,一种优选的方法是以下述速度旋涂所述组合物:约1,000-约5,000rpm(优选地约1,000-约2,000rpm),并旋涂约30-约120秒(优选的约45-约60秒)的时段。还可使用化学气相沉积来形成图案转移层。然后,可把图案转移层加热至约100℃-约300℃,以及更优选地约160℃-约205℃的温度,并持续约30秒-约120秒(优选地约45秒-约60秒)的时段,以蒸发溶剂。图案转移层的厚度可变化,但优选地为约0.1纳米-约1,000纳米,更优选地为约20纳米-约100纳米,以及甚至更优选地为约30纳米-约50纳米。适用于形成图案转移层的组合物包括硬掩模材料(如含硅或金属硬掩模和混合硬掩模)或者旋涂玻璃材料(如硅酸盐、磷硅酸盐、硅氧烷)。
然后在堆叠件上形成成像层。可通过任意已知的施涂方法来形成成像层,一种优选地方法是以约500-约5,000rpm(优选地约1,000-约2,000rpm)的速度旋涂约30-约120秒(优选地约45-约60秒),如果存在额外的中间层,则把该成像层施涂到该额外的中间层上;如果不存在额外的中间层,则把该成像层施涂到富碳层上。成像层施涂后在至少约90℃,以及优选地约90℃-约130℃的温度下,烘烤约30秒-约120秒(优选地45-约60秒)的时段。合适的成像组合物包括可在市场上购得的光刻胶(例如购自日本川崎市神奈川县的TOK的TArFPi6-001;购自加利福尼亚州桑尼威尔的捷时雅迈科(JSR Micro)的ARX3001、ARX3340J、AM2073J和KrFM592Y;购自日本东京信越化学(Shin-Etsu)的SAIL-X-181或者任何其它的光敏性组合物。本发明的方法允许使用更薄的成像层。成像层的厚度小于约500纳米,优选地小于约300纳米,更优选地为约50纳米-约200纳米以及甚至更优选地为约100纳米-约180纳米。应理解,在堆叠件中的额外的中间层(或者富碳层,如果不存在额外的中间平面)和成像层之间,还可存在常规的减反射涂层,从而控制成像层暴露时的反射。
然后,可通过暴露于合适波长的光,来图案化成像层。具体来说,使用设置在成像层上方的掩模来曝光成像层。掩模具有开放区域,所述开放区域设计用来允许辐射(hν)穿过该掩模并接触成像层。掩模剩余的实心部分设计用来在某些区域阻止辐射与成像层相接触。本领域技术人员能够很容易地理解,开放区域和实心部分是根据将要在成像层上、最终在基片中形成的所需图案来设计的。曝光后,成像层优选地在约90℃-约150℃,更优选地约110℃-约130℃的温度下进行约30秒-约120秒的时段的曝光后烘烤。
曝光时,成像层中暴露于辐射的部分会变得可溶于水性显影剂。然后,使成像层中通过上述工艺变得可溶的曝光部分,与水性显影剂接触,从而除去该曝光的部分并在成像层中形成所需的图案。所述图案可以是通孔、沟槽、线条、间隔等,最终采用蚀刻法或离子注入法或金属沉积把它们转移到基片上。或者,成像层的曝光的部分可在曝光工艺中变得不可溶的,在这种情况下,去除过程与上述过程相反。即,在显影中除去未曝光的部分来形成图案。无论在哪种实施方式中,优选地通过显影剂除去成像层中至少约95%,更优选的是至少约99%,以及甚至更优选的是约100%的曝光的(或者有时是未曝光的)部分。合适的显影剂是有机或无机碱性溶液,例如KOH或者TMAH,以及优选是浓度为约0.26N的TMAH水性溶液。一些这样的显影剂是市售产品,商品名为PD523AD(购自美国华盛顿州,摩斯湖的摩斯湖工业有限公司(Moses Lake Industries,Inc.)),MF-319(购自美国马萨诸塞州的西普力(Shipley,Massachusetts)),MF-320(购自西普力)以及NMD3(购自日本的TOK)。
还应理解,还可使用其它图案化技术,包括新兴技术例如压印平版印刷(imprintlithography)、纳米压印平版印刷、热压印平版印刷,以及用来在成像层中形成图案的烫印图案转移。这些技术使用图案化的模具来转移图案,而不是如上所述的依赖照相平版印刷图案化。还可使用导向自组装(DSA)来图案化成像层。
不管成像层中的图案是怎样的形成的,随后使用蚀刻工艺把该图案从图案化的成像层转移进入图案转移层和/或一种或更多种其它额外的中间层(如果存在)。优选的是,通过使用CF4、CHF3、O2、HBr、Cl2、SF6、C2F6、C4F8、CO、CO2、N2、H2、C4H8、Ar、N2H2、He、CH2F2的反应性离子等离子体,利用RIE来转移图案。蚀刻突破一种或更多种额外的中间层,并曝光可溶于显影剂的富碳层。然后,把图案转移进入富碳层。
用于本发明的聚酰胺酸组合物
使用的富碳组合物包括分散或溶解于溶剂系统中的聚酰胺酸。以所述组合物中固体的总重量作为100重量%为基准计,聚酰胺酸以下述水平存在于该组合物中:优选地1%-约30重量%、优选地约2%-约20重量%,以及更优选地约5%-约15重量%。聚酰胺酸的重均分子量优选地小于约15,000道尔顿(Daltons)、更优选地约4,000道尔顿-约12,000道尔顿以及甚至更优选地约6,000道尔顿-约11,000道尔顿。
聚酰胺酸应选定成具有高度刚性的结构。理想地,聚酰胺酸具有平坦或平面的结构,其旋转的可能性有限,且具有大量π键。这些聚酰胺酸的合成包括这些聚合物的合适的可溶于显影剂的组合物参见美国专利No.7,261,997和7,364,835,以上各文的全部内容通过引用纳入本文。可通过调节二酸酐-对-二胺的比例、以及二酸酐和二胺的种类来形成聚酰胺酸。二酸酐可以是脂肪族或者芳香族的。典型的脂肪族二酸酐包括选自下组的那些:5-(2,5-二氧四氢呋喃(dioxotetrahydrol))-3-甲基-3-环己烯-1,2-二羧酸酸酐、环丁烷四羧酸二酸酐、1,2,3,4-环戊烷四羧酸二酸酐、四氢呋喃-2,3,4,5-四羧酸二酸酐、4-(2,5-二氧四氢呋喃-3-基)-1,2,3,4-四氢萘-1,2-二羧酸酸酐,以及双环(2,2,2)辛-7-烯-2,3,5,6-四羧酸二酸酐。芳香族二酸酐包括选自下组的那些:3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)、均苯四酸二酐(PMDA)、3,3',4,4'-联苯四羧酸二酐(S-BPDA)、2,2'-双-(3,4-二羧基苯基)六氟丙烷二酐(6FDA)、4,4'-氧双邻苯二甲酸酐(OPDA)、3,3',4,4'-二苯基砜四羧酸二酐(DSDA苯酚)、4,4'-双酚A二酐(BPADA)、氢醌双邻苯二甲酸酸酐(hydroquinonediphtatic anhydride)(HQDA)、3,4,9,10-苝-四羧酸二酐、1,4,5,8-萘四羧酸二酐和乙二醇二(偏苯三酸酐)。
二胺可以是脂肪族或者芳香族的。典型的脂肪族二胺包括选自下组的那些:1,3-二(氨基甲基)环己烷、1,4-二(氨基甲基)-环己烷、4,4'-亚甲基二(环己胺)、4,4'-亚甲基二(2-甲基环己基)胺。芳香族二胺包括选自下组的那些:3-氨基苄胺、1,3-双(3-氨基苯氧基)-苯、1,3-双(4-氨基苯氧基)-苯、1,4-双(4-氨基苯氧基)苯、4,4'-双(4-氨基苯氧基)联苯、2,2-双[4-4-氨基苯氧基)-苯基]六氟丙烷、双[4-(4-氨基苯氧基)-苯基]丙烷、双[4-(4-氨基苯氧基)苯基]砜、双[4-(4-氨基苯氧基)苯基]砜、1,1'-双(4-氨基苯基)-环己烷、9,9'-双(4-氨基苯基)-芴(FDA)、2,2'-双(4-氨基苯基)六氟丙烷、双(2-氨基苯基)硫醚、双(4-氨基苯基)硫醚、双(3-氨基苯基)砜、双(4-氨基苯基)砜、4,4'-二氨基-3,3'-二甲基二苯基甲烷、3,4'-二氨基二苯基醚、4,4'-二氨基二苯基醚、3,3'-二氨基二苯基甲烷、3,4'-二氨基二苯基甲烷、2,7-二氨基芴、1,5-二氨基萘、4,4'-二氨基八氟联苯、2,5-二甲基-1,4-苯二胺、4,4'-乙烯双苯胺(ethylenedianiline)、1,3-苯二胺、1,4-苯二胺、2,3,5,6-四甲基-1,4-苯二胺、间-苯二甲胺和对-苯二甲胺。
优选的聚酰胺酸包括具有下述通式的重复单体
和
其中和各自独立地选自下组:脂肪族基团和芳基。特别优选的X和Y包括选自下组的那些:取代的或未取代的苯基、联苯基、萘基和蒽基,以及取代的或未取代的C1-C12脂肪族基团(优选的烷基)。
用于所述组合物的特别优选的聚酰胺酸包括选自下组的重复单体
和
其中:
X选自下组:-O-、-S-、-CH2-、-C(CF3)2-和-C(CH3)2-;
n是2-8;以及
R4各自独立地选自下组:-H和-OH。
优选的二酸酐-对-二胺的摩尔比是约1.8:1-约1.05:1,更优选地为约1.6:1-约1.1:1以及甚至更优选地为约1.4:1-约1.2:1。
聚酰胺酸也选定成“富碳的”。如本文所使用,术语“富碳的聚酰胺酸”指以所述聚合物的总重量作为100重量%为基准计,聚酰胺酸包括大于约50重量%碳,优选地大于约60重量%碳,更优选地大于约70重量%碳原子以及甚至更优选地约70%-约99重量%碳。这些优选的富碳聚酰胺酸还优选地包括低氢含量(如以所述聚合物的总重量作为100重量%为基准计,小于约10重量%氢,优选地小于约5重量%氢,更优选地小于约3重量%氢,以及甚至更优选地约0.01%-约2重量%氢)。
用于本发明的富碳组合物优选地还包括交联剂,该交联剂将与羧酸和/或仲胺反应。环氧交联剂、乙烯基醚交联剂和氨基交联剂是特别优选的。环氧交联剂包括具有多个环氧基的小分子,例如选自下组的那些:N,N,N',N'-四缩水甘油基-4,4'-亚甲基二苯胺、4-缩水甘油基氧-N,N'-二缩水甘油基苯胺以及己二酸二(3,4-环氧基环己基甲基)酯,以及具有环氧基的聚合物,例如环氧甲酚酚醛、或者由具有环氧基作为侧链的甲基丙烯酸酯或丙烯酸酯制成的聚合物。乙烯基醚交联剂包括多官能度乙烯基醚,例如选自下组的那些:1,3,5-苯三羧酸三[4-(乙烯氧基)丁基]酯、间苯二甲酸双[4-(乙烯氧基)丁基]酯、1,6-己二基二氨基甲酸双[4-(乙烯氧基)丁基]酯、戊二酸双[4-(乙烯氧基甲基)环己基甲基]酯、琥珀酸双[4-(乙烯氧基)丁基]酯、三(乙二醇)二乙烯基醚、和聚(乙二醇)二乙烯基醚。氨基树脂交联剂包括选自下组的那些:三聚氰胺交联剂、脲交联剂、苯并胍胺交联剂和甘脲交联剂。
以所述组合物中固体的总重量作为100重量%为基准计,交联剂以下述水平存在于该组合物中:优选地0.1%-约30重量%、优选地约0.5%-约25重量%,以及更优选地约1%-约20重量%。
还可把多种任选的成分包括进入组合物(如催化剂、表面活性剂)。任选的催化剂可包括,但不限于:酸,如5-磺基水杨酸、热致生成的酸(TAG)、光致生成的酸(PAG),或者碱。合适的表面活性剂同时包括离子性表面活性剂和非离子性表面活性剂。
与实施方式无关,所述组合物通过简单地将聚酰胺酸分散或溶解在合适的溶剂体系中而形成所述组合物,优选在环境条件下进行足够时间的分散或混合,以形成基本均一的分散体。其它成分(如交联剂、任意催化剂和/或表面活性剂)优选地与化合物一起分散或溶解于溶剂系统中。
优选的溶剂体系包括选自下组的溶剂:PGMEA、PGME、丙二醇正丙基醚(PnP)、乳酸乙酯、环己酮、γ-丁内酯(GBL),及其混合物。以所述组合物的总重量作为100重量%为基准计,应使用约80-99重量%以及优选地约95-99重量%水平的溶剂系统。以所述组合物的总重量作为100重量%为基准计,所述组合物通常具有约1-20重量%以及优选地约1-5重量%的固含量。
所得聚酰胺酸组合物是富碳的。如本文所使用,术语“富碳的组合物”指以所述组合物的总重量作为100重量%为基准计,组合物包括大于约50重量%碳,优选地大于约60重量%碳,更优选地大于约70重量%碳以及甚至更优选地约70%-约99重量%碳。这些聚酰胺酸组合物还优选地包括低氢含量(如以所述组合物中的固体总量作为100重量%为基准计,小于约10重量%氢,优选地小于约5重量%氢,更优选地小于约3重量%氢,以及甚至更优选地约0.01%-约2重量%氢)。
实施例
以下实施例描述了根据本发明的优选方法。然而应理解,这些实施例通过举例的方式提供,其所含的任何内容都不应视作对本发明整体范围的限制。
实施例1
聚合物A的合成
在本实施例中,把16.99克(0.0643摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)、14.00克(0.0402摩尔)的4,4'-(9-亚芴基)二苯胺(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)和123.95克的丙二醇单甲醚("PGME,"超纯解决方案公司(Ultra PureSolutions),卡斯特罗维尔(Castroville),加利福尼亚州)添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。本实施例的反应方案如下所示。
实施例2
SOC制剂A-1
通过混合5.01克的来自实施例1的聚合物A与0.114克的50重量%的在PGME中的MY-720溶液(亨斯曼先进材料(Huntsman Advanced Materials),伍德兰兹,德克萨斯)、22.04克的PGME、和2.92克的环己酮制备固含量为3.5重量%的溶液,来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在225℃的热台上烘烤60秒。所得固化膜用椭圆光度法测定的厚度为1317埃,且不能用PGME或丙二醇甲基醚乙酸酯(“PGMEA”)除去。
实施例3
SOC制剂A-2
通过混合5.01克的来自实施例1的聚合物A与0.206克的50重量%的在PGME中的MY-720溶液、23.25克的PGME、和3.07克的环己酮制备固含量为3.5重量%的溶液,来制备SOC制剂。把溶液良好混合4小时,并随后通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在225℃的热台上烘烤60秒。所得固化膜用椭圆光度法测定的厚度为1,378埃,且不能用PGME或PGMEA除去。
实施例4
聚合物B的合成
在本实施例中,把15.92克(0.0603摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、15.00克(0.043摩尔)的4,4'-(9-亚芴基)二苯胺和123.95克的PGME(超纯解决方案公司(Ultra Pure Solutions),卡斯特罗维尔(Castroville),加利福尼亚州)添加到两颈圆底烧瓶。在氮气下搅拌内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例5
SOC制剂B-1
通过混合5.01克的来自实施例4的聚合物B与0.101克的50重量%的在PGME中的MY-720溶液、22.03克的PGME、和2.92克的环己酮制备固含量为3.5重量%的溶液,来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在225℃的热台上烘烤60秒。所得固化膜用椭圆光度法测定的厚度为1423埃,且不能用PGME和PGMEA除去。
实施例6
SOC制剂B-2
通过混合5.02克的来自实施例4的聚合物B与0.202克的50重量%的在PGME中的MY-720溶液、23.22克的PGME、和3.03克的环己酮制备固含量为3.5重量%的溶液,来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在225℃的热台上烘烤60秒。所得固化膜用椭圆光度法测定的厚度为1,422埃,且不能用PGME和PGMEA除去。
实施例7
聚合物C的合成
在本实施例中,把20.40克(0.0459摩尔)的4,4'-(六氟异亚丙基)邻苯二甲酸酸酐(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)、10.00克(0.0287摩尔)的4,4'-(9-亚芴基)二苯胺和121.70克的PGME添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热20小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例8
SOC制剂C-1
通过混合9.08克的来自实施例7的聚合物B与0.36克的50重量%的在PGME中的MY-720溶液、35.75克的PGME、和7.80克的环己酮制备固含量为3.5重量%的溶液,来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在225℃的热台上烘烤60秒。所得固化膜用椭圆光度法测定的厚度为1,578埃,且不能用PGME和PGMEA除去。
实施例9
聚合物D的合成
在本实施例中,把16.99克(0.0643摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、14.0克(0.0402摩尔)的4,4'-(9-亚芴基)二苯胺和99.2克的PGME和24.8克的环己酮(超纯解决方案公司(Ultra Pure Solutions),卡斯特罗维尔(Castroville),加利福尼亚州)添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例10
SOC制剂D-1
通过混合5.01克来自实施例9的聚合物D与0.15克的50重量%的在PGME中的MY-721溶液(亨斯曼先进材料(Huntsman Advanced Materials),伍德兰兹,德克萨斯),以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例11
聚合物E的合成
在本实施例中,把15.9克(0.0609摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、15.00克(0.0430摩尔)的4,4'-(9-亚芴基)二苯胺和98.8克的PGME、24.8克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例12
SOC制剂E-1
通过混合5.01克来自实施例11的聚合物E与0.15克的50重量%的在PGME中的MY-721溶液以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例13
SOC制剂E-2
通过混合5.01克来自实施例11的聚合物E与0.20克的1,3,5-苯三羧酸三[4-(乙烯氧基)丁基]酯交联剂(结构如下所示,布鲁尔科技公司(Brewer Science Inc.),罗拉(Rolla),密苏里州),以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在225℃的热台上烘烤60秒。
实施例14
SOC制剂E-3
通过混合5.01克来自实施例11的聚合物E与0.20克的Cymel1174交联剂(结构如下所示,氰特工业(Cytech Industries),伍德兰德园,新泽西州)、0.01克TAG2689(购自王者工业(King Industries)的热酸产生器,诺瓦克,康涅狄格州)、以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例15
聚合物F的合成
在本步骤中,把14.57克(0.0551摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、15.00克(0.0459摩尔)的4,4'-(9-亚芴基)二苯胺和98.8克的PGME、以及24.8克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例16
SOC制剂F-1
通过混合5.01克来自实施例15的聚合物F与0.15克的50重量%的在PGME中的MY-721溶液以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例17
聚合物G的合成
在本步骤中,把15.9克(0.0609摩尔)的5-(2,5'-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、15.00克(0.0430摩尔)的4,4'-(9-亚芴基)二苯胺、24.8克的PGME、以及98.8克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在60℃下加热24小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例1中所示的相同。
实施例18
聚合物H的合成
在本实施例中,把19.6克(0.0441摩尔)的4,4'-(六氟异亚丙基)邻苯二甲酸酸酐(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)、11.00克(0.0315摩尔)的4,4'-(9-亚芴基)二苯胺、85.79克的PGME和36.75克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在80℃下加热20小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案见下图所示。
实施例19
SOC制剂H-1
通过混合5.01克来自实施例18的聚合物H与0.05克的50重量%的在PGME中的MY-721溶液(亨斯曼先进材料(Huntsman Advanced Materials),伍德兰兹,德克萨斯),以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,时间为60秒,并随后在350℃的热台上烘烤60秒。根据下文所示的机理形成高度热稳定的碳层。
实施例20
聚合物I的合成
在本实施例中,把19.6克(0.0441摩尔)的4,4'-(六氟异亚丙基)邻苯二甲酸酸酐、11.00克(0.0315摩尔)的4,4'-(9-亚芴基)二苯胺和121.70克的γ-丁内酯(GBL)添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在80℃下加热20小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案与实施例18中所示的相同。
实施例21
聚合物J的合成
在本实施例中,把11.3克(0.0351摩尔)的3,3',4,4'-二苯甲酮四羧酸二酐(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)、8.71克(0.0251摩尔)的4,4'-(9-亚芴基)二苯胺、56.0克的PGME和24.0克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在80℃下加热20小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案如下图所示。
实施例22
SOC制剂J-1
通过混合5.01克来自实施例21的聚合物J与0.15克的50重量%的在PGME中的MY-721溶液以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1,500rpm,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例23
聚合物K的合成
在本实施例中,把7.93克(0.0363摩尔)的均苯四酸二酐(克里斯科夫公司(CHRISKEV),雷那克萨(Lenexa),堪萨斯州)、12.07克(0.0260摩尔)的4,4'-(9-亚芴基)二苯胺、56.0克的PGME和24.0克的环己酮添加到两颈圆底烧瓶。在氮气下搅拌烧瓶中的内容物,保持搅拌并在80℃下加热20小时,以完成反应。把混合物冷却至室温,并密封。固含量是20重量%。反应方案如下图所示。
实施例24
SOC制剂K-1
通过混合5.01克来自实施例23的聚合物K与0.15克的50重量%的在PGME中的MY-721溶液以及15.5克的PGME来制备SOC制剂。把溶液良好混合4小时,并通过孔径为0.1微米的PTFE滤膜过滤。把制剂旋涂到4英寸的硅片上,速度为1500rpm,时间为60秒,并随后在205℃的热台上烘烤60秒。
实施例25
SOC制剂的表征
用M2000椭圆光度仪(乌兰姆((J.A.Woollam),林肯市,内布拉斯加州)测量光学常数(n和k)和膜厚。对于溶剂阻抗测试,用溶剂将涂覆的片搅拌20秒,并旋涂干燥。比较溶剂接触前后的厚度,结果见表1。对于重做的测试,将涂覆的片在显影剂PD523AD(莫斯化学公司(Moses Chemicals),摩塞斯莱克,华盛顿州)中于不同温度下浸没5分钟,并随后用去离子水冲洗。
表1
实施例26
正性显影平版印刷
使用下述多层堆叠件(从顶部到底部)来进行平版印刷测试:AIM54B4(捷时雅迈科公司(JSR Micro),桑尼维尔,加利福尼亚州)光刻胶、HM9825(布鲁尔科技公司(Brewer Science Inc.),罗拉(Rolla),密苏里州)硬掩模,以及SOC制剂E-2(实施例13)作为碳层。用1900i分档器(stpper)(ASML,费尔德霍芬(Veldhoven),荷兰)曝光涂覆的片,并用水性碱性溶液OPD5262(富士胶片(FujiFilm),北金斯敦(North Kingstown),北卡罗来纳州)显影,以除去曝光的部分。图1显示了平版印刷结果。
实施例27
负性显影平版印刷
使用下述堆叠件(从顶部到底部)来进行平版印刷测试:FAIRS9521-V10K(富士胶片(FujiFilm),北金斯敦(North Kingstown),北卡罗来纳州)光刻胶;来自布鲁尔科技公司(Brewer Science Inc.),罗拉(Rolla),密苏里州的实验硬掩模;以及SOC制剂E-2(实施例13)作为碳层。使用1900i分档器曝光涂覆的片,并用有机显影剂FN-DP001(富士胶片(FujiFilm),北金斯敦(North Kingstown),北卡罗来纳州)显影,以除去未曝光的部分。图2显示了平版印刷结果。
实施例28
图案转移到SOC层
把来自实施例26的片切成小片,并随后装载在牛津等离子体实验室(OxfordPlasmalab)RIE上,在下述条件下蚀刻:CF4,35sccm(标准气体条件下立方厘米/分钟),55秒,50毫托,100W,然后Ar/CO2,25/25sccm,70秒,20毫托,300W。SEM照片(图3)表明光刻胶的图案成功转移到SOC层。
实施例29
SOC的热稳定性
在片上形成制剂E-2(实施例13)的膜,并随后从该片撕下,装载进入TGA坩锅中。以20℃/分钟的速度把样品加热到400℃,并保持10分钟。图4显示了重量损失随时间变化的曲线,它表明材料在该温度下具有极高的热稳定性,该温度类似于实施CVD过程来在SOC层上沉积硬掩模的温度。
实施例30
间隙填充
把SOC制剂E-2(实施例13)和E-3(实施例14)旋涂到从托普片(Topowafer)(赛马特科(SEMATECH),奥尔巴尼(Albany),纽约)切割的小片上,并在225℃下烘烤。SEM图像(图5和6)表明深接触孔(致密或隔开的)都填充得非常好,且无缺陷。
实施例31
升华测试
使用石英晶体微天平(QCM)来测试样品的升华。在该方法中,把石英晶体悬挂在加热区域正上方,它在那里可收集来自加热的片的除气材料。把排气管道连接到顶部,向上吸收气流并使除气材料在石英晶体表面冷凝。收集晶体上的冷凝物,共振频率的改变对应于冷凝物的质量单位。标准的过程包括用有机旋涂涂层涂覆的4英寸硅片。把该片在QCM之下的热区域放置120秒。收集数据。
把SOC110D(布鲁尔科技公司(Brewer Science Inc.),罗拉(Rolla),密苏里州)、制剂E-1(实施例12)和制剂E-2(实施例13)旋涂到4英寸硅片上并烘烤。把升华物收集120秒。数据见表2,它表明甚至当烘烤温度更高时,制剂具有可与现有标准物质相比拟的升华。
表2
实施例32
图案转移至硅基片以及抗扭曲性(测试1)
使用下述多层堆叠件(从顶部到底部)来进行平版印刷测试:AIM54B4光刻胶、HM825硬掩模和SOC110D作为碳层。使用1900i分档器曝光涂覆的片,并通过OPD5262显影以除去曝光的部分。把片切成小片,并随后装载进入牛津等离子体实验室(Oxford Plasmalab)RIE,在下述条件下蚀刻:CF4,35sccm,55秒,50毫托,100W,然后Ar/CO2,25/25sccm,70秒,20毫托,300W,以及随后C4F8/Ar,5/100sccm,70秒,20毫托,300W。图7表明SOC层的图案在C4F8/Ar蚀刻中扭曲,且不能良好的图案转移至硅基片。
实施例33
图案转移至硅基片以及抗扭曲性(测试2)
把来自实施例26的片切成小片,并随后装载进入牛津等离子体实验室(OxfordPlasmalab)RIE,在下述条件下蚀刻:CF4,35sccm,55秒,50毫托,100W,然后Ar/CO2,25/25sccm,70秒,20毫托,300W,以及随后C4F8/Ar,5/100sccm,70秒,20毫托,300W。图8表明SOC图案不扭曲,它比现有的标准材料(实施例32)具有更好的抗扭曲性。图案成功的转移至硅基片。
Claims (32)
1.一种形成微电子结构的方法,所述方法包括:
提供具有表面的基片;
任选的在所述基片表面上形成一种或更多种中间层,如果存在一种或更多种中间层,那么在所述基片表面上有最上的中间层;
如果存在中间层则把一种组合物施涂到所述最上的中间层,或者,如果不存在中间层则施涂至所述基片表面,所述组合物包含溶解或分散在溶剂体系中的聚酰胺酸;
加热所述组合物来形成富碳层,所述富碳层是可溶于显影剂的,且在400℃的温度下保持10分钟时具有小于10%的重量损失。
2.如权利要求1所述的方法,其特征在于,在所述基片表面上有至少一种中间层。
3.如权利要求1所述的方法,其特征在于,所述方法还包括在所述富碳层上形成成像层。
4.如权利要求1所述的方法,其特征在于,所述方法还包括在所述富碳层上形成至少一种额外的中间层。
5.如权利要求4所述的方法,其特征在于,所述方法还包括在所述至少一种额外的中间层上形成成像层。
6.如权利要求1所述的方法,其特征在于,以所述组合物中固体的重量作为100重量%为基准计,所述组合物包括大于50重量%碳。
7.如权利要求1所述的方法,其特征在于,以所述组合物中所有固体的总重量作为100重量%为基准计,所述组合物包括小于10重量%氢。
8.如权利要求1所述的方法,其特征在于,以所述层的重量作为100重量%为基准计,所述富碳层包括大于50重量%碳。
9.如权利要求1所述的方法,其特征在于,以所述层的总重量作为100重量%为基准计,所述富碳层包括小于10重量%氢。
10.如权利要求1所述的方法,其特征在于,所述聚酰胺酸包括具有下述通式的重复单体
其中和各自独立地选自下组:脂肪族基团和芳基。
11.如权利要求1所述的方法,其特征在于,所述聚酰胺酸是二酸酐和二胺的共聚物,其中:
所述二酸酐选自下组:5-(2,5-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、环丁烷四羧酸二酸酐、1,2,3,4-环戊烷四羧酸二酸酐、四氢呋喃-2,3,4,5-四羧酸二酸酐、4-(2,5-二氧四氢呋喃-3-基)-1,2,3,4-四氢萘-1,2-二羧酸酸酐、双环(2,2,2)辛-7-烯-2,3,5,6-四羧酸二酸酐、3,3',4,4'-二苯甲酮四羧酸二酐、均苯四酸二酐、3,3',4,4'-联苯四羧酸二酐、2,2'-双-(3,4-二羧基苯基)六氟丙烷二酐、4,4'-氧双邻苯二甲酸酐、3,3',4,4'-二苯基砜四羧酸二酐、4,4'-双酚A二酐、氢醌双邻苯二甲酸酸酐、3,4,9,10-苝-四羧酸二酐、1,4,5,8-萘四羧酸二酐和乙二醇二(偏苯三酸酐);以及
所述二胺选自下组:1,3-二(氨基甲基)环己烷、1,4-二(氨基甲基)-环己烷、4,4'-亚甲基二(环己胺)、4,4'-亚甲基二(2-甲基环己基)胺、3-氨基苄胺、1,3-双(3-氨基苯氧基)-苯、1,3-双(4-氨基苯氧基)-苯、1,4-双(4-氨基苯氧基)苯、4,4'-双(4-氨基苯氧基)联苯、2,2-双[4-4-氨基苯氧基)-苯基]六氟丙烷、双[4-(4-氨基苯氧基)-苯基]丙烷、双[4-(4-氨基苯氧基)苯基]砜、双[4-(4-氨基苯氧基)苯基]砜、1,1'-双(4-氨基苯基)-环己烷、9,9'-双(4-氨基苯基)-芴、2,2'-双(4-氨基苯基)六氟丙烷、双(2-氨基苯基)硫醚、双(4-氨基苯基)硫醚、双(3-氨基苯基)砜、双(4-氨基苯基)砜、4,4'-二氨基-3,3'-二甲基二苯基甲烷、3,4'-二氨基二苯基醚、4,4'-二氨基二苯基醚、3,3'-二氨基二苯基甲烷、3,4'-二氨基二苯基甲烷、2,7-二氨基芴、1,5-二氨基萘、4,4'-二氨基八氟联苯、2,5-二甲基-1,4-苯二胺、4,4'-乙烯双苯胺、1,3-苯二胺、1,4-苯二胺、2,3,5,6-四甲基-1,4-苯二胺、间-苯二甲胺和对-苯二甲胺。
12.如权利要求1所述的方法,其特征在于,所述聚酰胺酸的重均分子量小于15,000道尔顿。
13.如权利要求1所述的方法,其特征在于,所述组合物还包括交联剂。
14.如权利要求1所述的方法,其特征在于,所述加热导致所述聚酰胺酸交联。
15.如权利要求1所述的方法,其特征在于,所述基片是选自下组的微电子基片:硅、SiGe、SiO2、Si3N4、SiON、铝、钨、硅化钨、砷化镓、锗、钽、氮化钽、珊瑚、黑金刚石、磷或硼掺杂的玻璃、Ti3N4、铪、HfO2、钌、磷化铟,以及上述材料的混合物。
16.如权利要求1所述的方法,其特征在于,所述富碳层的n值至少为1.40。
17.如权利要求1所述的方法,其特征在于,所述方法还包括:
任选的在所述富碳层上形成一种或更多种中间层,如果所述富碳层上存在一种或更多种中间层,那么在所述富碳层上有最上的中间层;以及
如果存在中间层则在所述富碳层的所述最上的中间层上形成成像层,如果所述富碳层上不存在中间层则在所述富碳层上形成成像层。
18.如权利要求17所述的方法,其特征在于,所述方法还包括:
图案化所述成像层从而在它里面形成图案;以及
如果存在中间层则把所述图案转移到在所述富碳层上的所述中间层,并转移到所述富碳层,其中所述图案包括多种线,且所述线没有或只有少量扭曲。
19.如权利要求18所述的方法,其特征在于,所述图案化包括:
使所述成像层曝光,形成所述成像层的曝光部分;以及
曝光后使所述成像层与显影剂接触,从而除去所述曝光的部分。
20.如权利要求19所述的方法,其特征在于,所述接触导致除去部分的所述富碳层,由此形成所述线。
21.一种微电子结构,其包括:
具有表面的微电子基片;
任选的在所述基片表面上形成一种或更多种中间层,如果存在一种或更多种中间层,那么在所述基片表面上有最上的中间层;
一种富碳层,如果存在中间层则该富碳层在所述最上的中间层上,如果不存在中间层则该富碳层在所述基片表面上,所述富碳层:
包括交联的聚酰胺酸;
是可溶于显影剂的;以及
在400℃的温度下保持10分钟时,具有小于10%的重量损失。
22.如权利要求21所述的结构,其特征在于,在所述基片表面上有至少一种中间层。
23.如权利要求21所述的结构,其特征在于,所述结构还包括在所述富碳层上的成像层。
24.如权利要求21所述的结构,其特征在于,所述结构还包括在所述富碳层上的至少一种额外的中间层。
25.如权利要求24所述的结构,其特征在于,所述结构还包括在所述至少一种额外的中间层上的成像层。
26.如权利要求21所述的结构,其特征在于,以所述层的重量作为100重量%为基准计,所述富碳层包括大于50重量%碳。
27.如权利要求21所述的结构,其特征在于,以所述层的重量作为100重量%为基准计,所述富碳层包括小于10重量%氢。
28.如权利要求21所述的结构,其特征在于,所述微电子基片选自下组:硅、SiGe、SiO2、Si3N4、SiON、铝、钨、硅化钨、砷化镓、锗、钽、氮化钽、珊瑚、黑金刚石、磷或硼掺杂的玻璃、Ti3N4、铪、HfO2、钌、磷化铟,以及上述材料的混合物。
29.如权利要求21所述的结构,其特征在于,所述富碳层的n值至少为1.40。
30.如权利要求21所述的结构,其特征在于,所述交联的聚酰胺酸由聚酰胺酸形成,该聚酰胺酸包括具有下述通式的重复单体
其中和各自独立地选自下组:脂肪族基团和芳基。
31.如权利要求21所述的结构,其特征在于,所述交联的聚酰胺酸由聚酰胺酸形成,该聚酰胺酸包括二酸酐和二胺的共聚物,其中:
所述二酸酐选自下组:5-(2,5-二氧四氢呋喃)-3-甲基-3-环己烯-1,2-二羧酸酸酐、环丁烷四羧酸二酸酐、1,2,3,4-环戊烷四羧酸二酸酐、四氢呋喃-2,3,4,5-四羧酸二酸酐、4-(2,5-二氧四氢呋喃-3-基)-1,2,3,4-四氢萘-1,2-二羧酸酸酐、双环(2,2,2)辛-7-烯-2,3,5,6-四羧酸二酸酐、3,3',4,4'-二苯甲酮四羧酸二酐、均苯四酸二酐、3,3',4,4'-联苯四羧酸二酐、2,2'-双-(3,4-二羧基苯基)六氟丙烷二酐、4,4'-氧双邻苯二甲酸酐、3,3',4,4'-二苯基砜四羧酸二酐、4,4'-双酚A二酐、氢醌双邻苯二甲酸酸酐、3,4,9,10-苝-四羧酸二酐、1,4,5,8-萘四羧酸二酐和乙二醇二(偏苯三酸酐);以及
所述二胺选自下组:1,3-二(氨基甲基)环己烷、1,4-二(氨基甲基)-环己烷、4,4'-亚甲基二(环己胺)、4,4'-亚甲基二(2-甲基环己基)胺、3-氨基苄胺、1,3-双(3-氨基苯氧基)-苯、1,3-双(4-氨基苯氧基)-苯、1,4-双(4-氨基苯氧基)苯、4,4'-双(4-氨基苯氧基)联苯、2,2-双[4-4-氨基苯氧基)-苯基]六氟丙烷、双[4-(4-氨基苯氧基)-苯基]丙烷、双[4-(4-氨基苯氧基)苯基]砜、双[4-(4-氨基苯氧基)苯基]砜、1,1'-双(4-氨基苯基)-环己烷、9,9'-双(4-氨基苯基)-芴、2,2'-双(4-氨基苯基)六氟丙烷、双(2-氨基苯基)硫醚、双(4-氨基苯基)硫醚、双(3-氨基苯基)砜、双(4-氨基苯基)砜、4,4'-二氨基-3,3'-二甲基二苯基甲烷、3,4'-二氨基二苯基醚、4,4'-二氨基二苯基醚、3,3'-二氨基二苯基甲烷、3,4'-二氨基二苯基甲烷、2,7-二氨基芴、1,5-二氨基萘、4,4'-二氨基八氟联苯、2,5-二甲基-1,4-苯二胺、4,4'-乙烯双苯胺、1,3-苯二胺、1,4-苯二胺、2,3,5,6-四甲基-1,4-苯二胺、间-苯二甲胺和对-苯二甲胺。
32.如权利要求21所述的结构,其特征在于,所述富碳层是图案的形式,所述图案包括线,且所述线没有或只有少量的扭曲。
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- 2012-10-10 US US13/648,890 patent/US8895230B2/en not_active Ceased
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Patent Citations (2)
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US6927012B2 (en) * | 2001-07-26 | 2005-08-09 | Nissan Chemical Industries, Ltd. | Polyamic acid resin composition |
CN101370849A (zh) * | 2006-12-30 | 2009-02-18 | 第一毛织株式会社 | 具有抗反射性和高碳含量的聚合物及含有该聚合物的硬掩模组合物以及形成图案化材料层的方法 |
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WO2013055798A1 (en) | 2013-04-18 |
JP6295198B2 (ja) | 2018-03-14 |
SG10201607603VA (en) | 2016-11-29 |
SG11201401430RA (en) | 2014-09-26 |
EP2766920A1 (en) | 2014-08-20 |
TWI582134B (zh) | 2017-05-11 |
KR102058760B1 (ko) | 2019-12-23 |
US20130089716A1 (en) | 2013-04-11 |
USRE46841E1 (en) | 2018-05-15 |
CN103975418A (zh) | 2014-08-06 |
TW201331265A (zh) | 2013-08-01 |
EP2766920A4 (en) | 2015-05-27 |
US20140356593A1 (en) | 2014-12-04 |
US8895230B2 (en) | 2014-11-25 |
JP2014530386A (ja) | 2014-11-17 |
KR20140082782A (ko) | 2014-07-02 |
US9102129B2 (en) | 2015-08-11 |
EP2766920B1 (en) | 2020-12-02 |
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