CN1125836C - 用于化学放大抗蚀剂的共聚物 - Google Patents
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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Abstract
本发明提供了一种应用于化学放大抗蚀剂的光敏聚合物。光敏聚合物为式(I)：其中R1选自氢和C1至C20脂烃，n为整数。特别地，R1选自甲基、乙基、正丁基和环己基或R1选自含C7至C20脂环脂烃，如金刚烷基、降冰片基和异冰片基。本发明还提供了包含光酸引发剂和聚合物的化学放大抗蚀组合物。聚合物为式(II)：其中R1选自氢和C1至C20脂烃；R2选自氢或甲基；R3选自叔丁基或四氢吡喃基；n和m各自为整数，其中n/(m+n)比例为0.1至0.5。本发明化学放大抗蚀组合物对干蚀工艺具有强的抗蚀性，对膜材料具有优良的粘合性，可利用常规显影剂显影。
Description
本发明涉及用于化学放大抗蚀剂的共聚物及包含此共聚物的抗蚀组合物。
随着半导体装置集成化的提高，在光刻法中能够形成八分之一微米容量的精细结构的抗蚀剂需求急剧增大。使用ArF激发物激光(例如：λ＝193nm)的光刻法对设备提出超出10亿容量的要求。这种技术试图应用更远的紫外光(λ＝248nm)代替传统的KrF激发物光。因此需要发展新的化学放大抗蚀组合物。
一般地，对于使用ArF激发物激光，能够使用的化学放大抗蚀组合物的必要条件如下：
(1)在193nm下具有优良的反射度；
(2)优良的热特性，例如，在高玻璃化转变温度(Tg)下；
(3)优良的膜材料粘合力；
(4)优良的抗干蚀工艺；
(5)能够利用常规碱性显影剂显影的能力，所述显影剂如2.38wt％的四甲基铵氢氧化物(TMAH)。
一个已知可具有以上性能的聚合物实例为三元共聚物，命名为聚(MMA-tBMA-MAA)，其通式为：
上述聚合物不能令人满意。特别地，此三元共聚物对蚀刻工艺具有很弱的抵抗性，且具有弱的粘合性能。另外，需要特殊的显影剂来完成三元聚合物的显影。为了解决以上的问题，提出了一类脂环化合物，例如异冰片基、金刚烷基或三环癸烷基基团。
然而，这些脂环化合物仍然存在潜在的缺陷。特别地，脂环化合物具有弱的粘合性，结果会造成抗蚀剂向上移动；而且，脂环化合物对干蚀工艺具有弱的抵抗性，需要特殊的显影剂，该显影剂需要单独制备，且应当以特殊的浓度范围代替一般显影剂与上述脂环化合物一起使用。
基于以上原因，本发明目的在于提供用于化学放大抗蚀剂的光敏聚合物，该聚合物可暴露于ArF激光下，对干蚀工艺具有强的抵抗性，对膜材料具有优良的粘合性，且可使用常规显影剂。
本发明的进一步目的在于提供了含有光敏聚合物的化学放大抗蚀剂。
应用于化学放大抗蚀剂的光敏聚合物是本发明的目的、特点和优点。一方面，本方面涉及应用于化学放大抗蚀剂的共聚物，该共聚物通式(I)为：
在上式(I)中，R1选自氢和C1至C20的脂烃，n代表整数。特别地，R1选自甲基、乙基、正丁基和环己基或R1选自含有金刚烷基、降冰片基或异冰片基之C7到C20的脂环脂烃基。共聚物的平均分子量为3,000到100,000。
另一方面，本方面提供了含有三元聚合物和光酸引发剂的抗蚀组合物。该三元聚合物通式(II)为：
在上式(II)中，R1选自氢和C1至C20脂烃；R2为氢或甲基；R3为叔丁基或四氢吡喃基；n和m各自代表整数，n和n+m的比例是0.1至0.5。特别地，R1选自甲基、乙基、正丁基和环己基或R1选自含C7至C20脂环脂烃，如金刚烷基、降冰片基或异冰片基。三元聚合物的平均分子量为3,000到200,000。基于三元聚合物重量的光酸引发剂含量大约为1.0wt％至20.0wt％。光酸引发剂选自三芳基锍盐，二芳基碘鎓盐和磺酸盐。含三芳基锍盐的光酸引发剂选自三氟甲磺酸三苯基锍、碲酸三苯基锍、2，6-二硝基苄基磺酸盐、焦棓酚三(烷基磺酸酯)。含二芳基碘鎓盐的光酸引发剂选自三氟甲磺酸二苯基碘鎓、碲酸二苯基碘鎓、三氟甲磺酸甲氧基二苯基碘鎓和三氟甲磺酸二叔丁基二苯基碘鎓。
通过参考如下的附图，本领域的普通技术人员可以明显地理解本发明和本发明的目的。
图1代表根据本发明具有tBMA的三聚物的傅里叶变换红外光谱(FTIR)；和
图2为本发明抗蚀剂的0.3μm线性和立体图案的横截面照片。
参照本发明优选实施方案所示的附图，本发明的优选实施方案作出了完整和具体描述。然而，本发明描述可以不同的形式来表达，所以不会因为这里的描述而限制本发明；而且这些描述使得本发明公开得清楚完整，本领域技术人员可以完全理解本发明。
下面的实施例是为了说明而不是限制本发明。
实施例1
合成单体
(a)合成5-降冰片烯-2-环己基甲醇
本实施例中，0.1摩尔环己基溴化镁溶解在乙醚中，形成反应液，13克(0.1摩尔)5-降冰片烯-2-甲醛慢慢滴到上述溶液中，形成反应产物。该反应产物回流约12小时，接着倒入水。然后加入乙醚到产物溶液中分离出反应产物。用硫酸镁干燥，减压蒸发产物周围的水分，得到5-降冰片烯-2-环己基甲醇，产率为75％。
(b)合成5-降冰片烯-2-降冰片基甲醇
本实施例中，0.1摩尔2-降冰片基溴化镁溶解在四氢呋喃(THF)溶剂中，形成反应液，13克(0.1摩尔)5-降冰片烯-2-甲醛慢慢滴到上述溶液中，形成反应产物。反应产物回流约20小时，接着用转动蒸发器蒸发THF，接着倒入水。然后加入乙醚到产物溶液中分离出反应产物。用硫酸镁干燥，减压蒸发产物周围的水分，得到5-降冰片烯-2-将冰片基甲醇，产率为60％。
(c)合成四氢吡喃基异丁烯酸酯
本实施例中，在150毫升二氯甲烷中，0.1摩尔异丁烯酸和8.6克(0.11摩尔)3，4-二氢-2H-吡喃反应。少量的对甲苯磺酸加入到溶液中，在室温下放置4小时，形成了反应产物。加乙醚到产物溶液中，然后从溶液中分离出产物。用硫酸镁干燥后，减压蒸发产物周围的水分，得到四氢呋喃基异丁酸酯，产率为85％。实施例2
合成共聚物
本实施例中的共聚物合成反应可以下面的反应式表示：
合成聚(降冰片烯-2-环己基甲醇-alt-马来酸酐)
本实施例中，20克(0.1摩尔)5-降冰片烯-2-环己基甲醇和10克(0.1摩尔)马来酸酐溶解在100毫升的四氢呋喃中，加入0.32克AIBN(2，2′-偶氮二异丁腈)。混合物用氮气净化，形成产物。
反应产物回流约24小时，接着反应产物在稀释10次的正己烷中沉淀。然后，将沉淀再溶解在四氢呋喃中，再在正己烷中沉淀。过滤反应沉淀，在真空和50℃下，干燥约24小时，得到聚(降冰片烯-2-环己基甲醇-alt-马来酸酐)。产率为60％。所得聚合物的平均分子量为5,000，多分散指数(重均分子量/数均分子量)为2.1。聚合物的FTIR图谱分析结果如下：
FTIR(溴化钾)：3400至3600cm-1(-O-H)，1782cm-1(C＝O)。
(b)合成聚(降冰片烯-2-降冰片基甲醇-alt-马来酸酐)
本实施例中，21克(0.1摩尔)5-降冰片烯-2-降冰片基甲醇和10克(0.1摩尔)马来酸酐溶解在100毫升的四氢呋喃中，加入0.32克AIBN(2，2′-偶氮二异丁腈)。混合物用氮气净化，形成产物。
反应产物回流约24小时，接着反应产物在稀释10次的正己烷中沉淀。然后，将沉淀再溶解在四氢呋喃中，再在正己烷中沉淀。过滤反应沉淀，在真空和50℃下，干燥约24小时，得到聚(降冰片烯-2-降冰片基甲醇-alt-马来酸酐)。产率为65％。所得共聚物的平均分子量为4,700，多分散指数(重均分子量/数均分子量)为2.0。共聚合物的FTIR图谱分析结果如下：
FTIR(溴化钾)：3400至3600cm-1(-O-H)，1780cm-1(C＝O)。
实施例3
合成三聚物
本实施例三聚物的合成反应为下式：
(a)合成其中R3为叔丁基的三聚物
本实施例中，20克(0.1摩尔)5-降冰片烯-2-环己基甲醇、10克(0.1摩尔)马来酸酐和14克(0.1摩尔)异丁烯酸酯(t-MBA)溶解在150毫升四氢呋喃中，加入0.49克AIBN。混合物用氮气彻底净化，形成产物。
反应产物回流约24小时，接着反应产物在稀释10次的正己烷中沉淀。然后，将沉淀再溶解在四氢呋喃中，再在正己烷中沉淀。过滤反应沉淀，在真空和50℃下，干燥约24小时。得到聚(降冰片烯-2-降冰片基甲醇-alt-马来酸酐)。产率为75％。所得共聚物的平均分子量为5,500，多分散指数(重均分子量/数均分子量)为2.1。图1代表根据本实施例具有tBMA的三聚物的傅里叶变换红外光谱(FTIR)。FTIR图谱分析结果如下：
FTIR(溴化钾)：3400至3600cm-1(-O-H)，2789cm-1(C-H)，1780cm-1(C＝O)。
(b)合成其中R3为四氢吡喃基的三聚物
本实施例中，20克(0.1摩尔)5-降冰片烯-2-环己基甲醇、10克(0.1摩尔)马来酸酐和17克(0.1摩尔)四氢吡喃基异丁烯酸酯(THPMA)溶解在150毫升四氢呋喃中，加入0.49克AIBN。混合物用氮气彻底净化，形成产物。
反应产物回流约24小时，接着反应产物在稀释10次的正己烷中沉淀。然后，将沉淀再溶解在四氢呋喃中，再在正己烷中沉淀。过滤反应沉淀，在真空和50℃下，干燥约24小时。得到聚(降冰片烯-2-降冰片基甲醇-alt-马来酸酐)。产率为75％。所得共聚物的平均分子量为5,000，多分散指数(重均分子量/数均分子量)为2.0。
得到的共聚物FTIR图谱分析结果如下：
FTIR(溴化钾)：3400至3600cm-1(-O-H)，2957cm-1(C-H)，1780cm-1(C＝O)，1720cm-1(C＝O)。
实施例4
合成抗蚀组合物
(a)利用具有叔丁基的三聚物合成抗蚀组合物。
本实施例中，1.0克实施例3制备的具有T-MBA的三聚物和0.05克三氟甲磺酸三苯基锍完全溶解在6.0克丙二醇单甲基醚乙酸酯(PGMEA)中。彻底搅拌混合物。混合物首先用0.45μm的滤膜过滤，然后再用0.2μm的滤膜过滤制得抗蚀剂。硅胶片用六甲基二硅氮烷(HMDS)处理，然后把制得的抗蚀剂涂到胶片上形成约0.5μm的薄膜。
具有涂层的胶片在约130℃下预烘烤90秒，然后暴露在具有0.45光圈的KrF激发物激光下，然后在约140℃下再次烘烤约90秒。
然后，胶片用约2.38wt％的四甲基铵氢氧化物(TMAH)溶液显影约60秒。
附图2为本实施例抗蚀剂0.3μm线性和立体图案的横截面照片。关于图2，当曝光能量大约为20mJ/cm2时，得到了0.3μm的线性和立体图案。
(b)利用具有四氢吡喃基的三聚物合成抗蚀组合物
本实施例中，1.0克实施例3制备的具有THPMA的三聚物和0.05克三氟甲磺酸三苯基锍完全溶解在6.0克丙二醇单甲基醚乙酸酯(PGMEA)中。彻底搅拌混合物。混合物首先用0.45μm的滤膜过滤，然后再用0.2μm的滤膜过滤制得抗蚀剂。硅胶片用六甲基二硅氮烷(HMDS)处理，然后把制得的抗蚀剂涂到胶片上形成约0.5μm的薄膜。
具有涂层的胶片在约130℃下预烘烤约90秒，然后暴露在具有0.45光圈的KrF激发物激光下，然后在约140℃下再次烘烤90秒。
然后，胶片用约2.38wt％的四甲基铵氢氧化物(TMAH)溶液显影约60秒。
本实施例中，当曝光能量大约为13mJ/cm2时，得到了抗蚀剂的0.3μm的线性和立体图案。
(c)利用具有四氢吡喃基的三聚物合成抗蚀组合物
本实施例中，1.0克实施例3制备的具有THPMA的三聚物和0.05克三氟甲磺酸三苯基锍完全溶解在6.0克丙二醇单甲基醚乙酸酯(PGMEA)中。彻底搅拌混合物。混合物首先用0.45μm的滤膜过滤，然后再用0.2μm的滤膜过滤制得抗蚀剂。硅胶片用六甲基二硅氮烷(HMDS)处理，然后把制得的抗蚀剂涂到胶片上形成约0.5μm的薄膜。
具有涂层的胶片在约130℃下预烘烤约90秒，然后暴露在具有0.45光圈的KrF激发物激光下，然后在约140℃下再次烘烤约90秒。
然后，胶片用约2.38wt％的四甲基铵氢氧化物(TMAH)溶液显影60秒。
本实施例中，当曝光能量大约为18mJ/cm2时，得到了抗蚀剂的0.3μm的线性和立体图案。
尽管优选实施例已经详细描述了本发明，但是一些形式和细节的改变对于本领域的技术人员来说，不会脱离本发明的主题和范围。
Claims (3)
1.一种用于化学放大抗蚀剂的共聚物，所述共聚物具有式(I)：
其中R1选自氢和C1至C20脂烃，n为整数，所述共聚物的平均分子量为3,000到100,000。
2.根据权利要求1的共聚物，其中R1选自甲基、乙基、正丁基和环己基。
3.根据权利要求1的共聚物，其中R1选自含有金刚烷基、降冰片基或异冰片基之C7至C20脂环脂烃基。
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| KR65115/1997 | 1997-12-02 | ||
| KR65115/97 | 1997-12-02 | ||
| KR1019970065115A KR100245410B1 (ko) | 1997-12-02 | 1997-12-02 | 감광성 폴리머 및 그것을 이용한 화학증폭형 레지스트 조성물 |
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| CN98125176A Expired - Fee Related CN1125836C (zh) | 1997-12-02 | 1998-12-02 | 用于化学放大抗蚀剂的共聚物 |
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| EP (1) | EP0921439B1 (zh) |
| JP (1) | JP4291905B2 (zh) |
| KR (1) | KR100245410B1 (zh) |
| CN (2) | CN100335971C (zh) |
| DE (1) | DE69822091T2 (zh) |
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| KR19990049068A (ko) * | 1997-12-11 | 1999-07-05 | 우재영 | 신규한 노보넨 알콜 화합물 및 그의 제조방법 |
| KR100520148B1 (ko) * | 1997-12-31 | 2006-05-12 | 주식회사 하이닉스반도체 | 신규한바이시클로알켄유도체와이를이용한포토레지스트중합체및이중합체를함유한포토레지스트조성물 |
| KR100274119B1 (ko) * | 1998-10-08 | 2001-03-02 | 박찬구 | 감방사선성 레지스트 제조용 중합체 및 이를 함유하는 레지스트조성물 |
| ATE315245T1 (de) * | 1999-09-17 | 2006-02-15 | Jsr Corp | Strahlungsempfindliche harzzusammensetzung |
| US6517990B1 (en) | 2000-01-19 | 2003-02-11 | Samsung Electronics Co., Ltd. | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same |
| US6833230B2 (en) | 2000-01-19 | 2004-12-21 | Samsung Electronics Co., Ltd. | Photosensitive polymers containing adamantylalkyl vinyl ether, and resist compositions including the same |
| US6673513B2 (en) | 2000-01-19 | 2004-01-06 | Samsung Electronics Co., Ltd. | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same |
| KR100413756B1 (ko) * | 2000-01-19 | 2003-12-31 | 삼성전자주식회사 | 알킬 비닐 에테르의 공중합체를 포함하는 감광성 폴리머및 이를 포함하는 레지스트 조성물 |
| KR100510488B1 (ko) * | 2002-06-21 | 2005-08-26 | 삼성전자주식회사 | 아다만틸알킬 비닐 에테르의 공중합체를 포함하는 감광성폴리머 및 이를 포함하는 레지스트 조성물 |
| US6406828B1 (en) * | 2000-02-24 | 2002-06-18 | Shipley Company, L.L.C. | Polymer and photoresist compositions |
| CN1310090C (zh) * | 2001-02-25 | 2007-04-11 | 希普雷公司 | 新共聚物及光致抗蚀组合物 |
| US6696216B2 (en) * | 2001-06-29 | 2004-02-24 | International Business Machines Corporation | Thiophene-containing photo acid generators for photolithography |
| JP4545500B2 (ja) * | 2004-07-01 | 2010-09-15 | 東京応化工業株式会社 | 化学増幅型レジスト組成物およびレジストパターン形成方法 |
| US8748074B2 (en) * | 2010-11-24 | 2014-06-10 | Promerus, Llc | Self-imageable film forming polymer, compositions thereof and devices and structures made therefrom |
| KR101704474B1 (ko) | 2011-12-28 | 2017-02-09 | 금호석유화학 주식회사 | 레지스트용 첨가제 및 이를 포함하는 레지스트 조성물 |
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| EP0789278A2 (en) * | 1996-02-09 | 1997-08-13 | Japan Synthetic Rubber Co., Ltd. | Radiation-sensitive resin composition |
| EP0794458A2 (en) * | 1996-03-08 | 1997-09-10 | Lucent Technologies Inc. | An energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
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| KR970028828A (ko) * | 1995-11-10 | 1997-06-24 | 김광호 | 화학 증폭형 레지스트용 네거티브 베이스 수지 및 그 제조 방법 |
| KR970028829A (ko) * | 1995-11-10 | 1997-06-24 | 김광호 | 화학 증폭형 레지스트용 베이스 수지 및 그 제조 방법 |
| KR100261022B1 (ko) * | 1996-10-11 | 2000-09-01 | 윤종용 | 화학증폭형 레지스트 조성물 |
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- 1998-12-02 DE DE69822091T patent/DE69822091T2/de not_active Expired - Fee Related
- 1998-12-02 CN CNB021524890A patent/CN100335971C/zh not_active Expired - Fee Related
- 1998-12-02 JP JP35846898A patent/JP4291905B2/ja not_active Expired - Fee Related
- 1998-12-02 EP EP98309875A patent/EP0921439B1/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0789278A2 (en) * | 1996-02-09 | 1997-08-13 | Japan Synthetic Rubber Co., Ltd. | Radiation-sensitive resin composition |
| EP0794458A2 (en) * | 1996-03-08 | 1997-09-10 | Lucent Technologies Inc. | An energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
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| Publication number | Publication date |
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| JP4291905B2 (ja) | 2009-07-08 |
| DE69822091T2 (de) | 2005-01-20 |
| JPH11269234A (ja) | 1999-10-05 |
| KR100245410B1 (ko) | 2000-03-02 |
| EP0921439B1 (en) | 2004-03-03 |
| CN1224728A (zh) | 1999-08-04 |
| DE69822091D1 (de) | 2004-04-08 |
| KR19990046940A (ko) | 1999-07-05 |
| TW452676B (en) | 2001-09-01 |
| CN100335971C (zh) | 2007-09-05 |
| CN1515961A (zh) | 2004-07-28 |
| EP0921439A1 (en) | 1999-06-09 |
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