CN1072813C - 正性光致抗蚀剂的显影方法和所用的组合物 - Google Patents
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Abstract
说明了一种用于正性光致抗蚀剂显影的方法和组合物。本发明的显影剂包括氢氧化铵类的含水碱和最优选其含量为10至约30ppm的氟化烷基烷氧基化物类的表面活性剂。特别优选的表面活性剂包括磺酰基和胺部分。
Description
本发明一般涉及正性光致抗蚀剂基片的显影方法,更具体涉及适合于正性光致抗蚀剂的含有表面活性剂的含水碱类显影剂组合物的应用。用于本发明的显影剂组合物,特别是当用于适宜粘合剂体系中的重氮萘醌光敏化合物时,包括烷基烷氧基化物类的表面活性剂,以增进影像的形成。
光致抗蚀剂对本领域的技术人员而言是众所周知的。一般说来,它们必须是对光敏感的,以便能在其中形成图像,而且它们还必须选择性地耐随后的蚀刻或其他加工过程,以便能将图像转移到基片上。当前,在集成电路的生产中使用的主要光致抗蚀剂体系是线性酚醛清漆树脂/重氮萘醌组合物。在正性光致抗蚀剂中所用的这类萘醌,典型地是通过萘醌二叠氮化物磺酰氯与酚类化合物反应而形成的。这样形成的反应产物可能包括萘醌(1,2)二叠氮化物(5)-磺酰、萘醌(1,2)二叠氮化物(4)-磺酰、萘醌(2,1)二叠氮化物(5)-磺酰、或萘醌(2,1)二叠氮化物4-磺酰基团。当然,这样合成的磺酸酯类可能包括所有适宜的酚类化合物的残余物。这些二叠氮化物还算是可溶于有机溶剂但不易溶于水的非极性有机分子。
然而,简单地改变光敏化合物的溶解度是不够的,而必须改变整个光致抗蚀剂混合物的溶解度。因此,光敏化合物与粘合剂树脂的相互反应同样是重要的考虑因素,其吸收光谱也是如此。因此,正性光致抗蚀剂组合物通常包括线性酚醛清漆树脂类的酚醛树脂或有时包括羟基苯乙烯聚合物,例如聚(4-羟基苯乙烯)。其他聚合物组分,包括苯乙烯、甲基苯乙烯、苯乙烯-马来酐组分也可以与上述的组分配合使用。有关正性光致抗蚀剂的详细资料通常可参阅Hoechst Celanese Corporation,Somerville,NewJersey的美国专利4,732,836和4,863,827。
由于显影是集成电路生产过程的主要方面,显影剂组合物的选择对光致抗蚀剂的使用相当重要。总体生产的最优化通常是尝试法。显影是采用浸没法或采用搅拌法(Puddle)还是采用喷雾法就是如此。Cawston等人的美国专利4,628,023公开和申请保护一种包括无金属的碱和表面活性剂的含水无金属离子的显影剂组合物。据报道,所述显影剂可导致抗蚀剂曝光所需的能量降低而对影像质量和清晰度没有有害的影响。在Schwalm等人的美国专利5,039,595(以下简称为’539)中介绍了另一种带有杂环羟烷基化合物作为羟基源的含水显影剂。在’539专利中指出可以采用下列表面活性剂:壬基苯氧基聚(乙烯氧基)乙醇、辛基苯氧基聚(乙烯氧基)乙醇或市售氟化的表面活性剂(第4列第45-51行)。当然,市售的氟化表面活性剂可包括许多不同类型例如离子型或非离子型的候选表面活性剂化合物。
如J.M.Lewis和A.J.Blakeney的美国专利4,710,449(以下简称为’449)中所述,采用表面活性剂,在某些方面是需要的,经常使显影过程难以控制。在’449专利中说明在含水碱类显影剂中1%(10,000ppm,重量)的氟化烷基烷氧基化物简直是太具有侵蚀性,从而导致不良的壁角、反差以及不能接受的膜损耗。这些问题可以通过用含有阳离子表面活性剂的含水碱类显影剂溶液预浸的方法,预处理光致抗蚀剂基片而明显地排除。然而,从器材和供应的观点来看,增加处理步骤的数量是不合乎要求的。
在美国专利4,784,937中公开了一种采用含氟的表面活性剂的显影剂溶液。所提出的一些实施例表明,当采用100-2,000ppm(重量)的表面活性剂含量时,可获得A级质量的图像(均匀性良好)。当表面活性剂的含量为50ppm、以及没有表面活性剂且显影时间为40秒钟时,得到B级质量的图像(均匀性差)。该专利还公开称,当表面活性剂的含量太低时,不能完全获得所需的改进润湿性的效果。
本发明公开和要求保护一种曝光后的正性光致抗蚀剂薄膜的显影方法。本发明的方法主要包括涂覆包含氢氧化铵类的碱和含量为10-30ppm(重量)的氟化烷基烷氧基化物类的表面活性剂的含水碱类显影剂,随后将该显影剂组合物漂洗掉。本方法基本的和新颖的特点在于采用低浓度的表面活性剂且不像已报道的采用较高浓度表面活性剂的情况那样,需要对曝光后的光致抗蚀剂另外进行化学预处理的步骤。适宜的表面活性剂可以色括如下: 下文中将其统称为氟化烷基烷氧化物。特别优选的是下式的氟化烷氧化物:式中R1和R3是相同的或不同的且是C1-C10烷基,R2是C1-C10亚烷基,m和n独立为2-20的整数。
本发明的另一方面公开了优选的显影剂组合物,该组合物包括含水氢氧化铵类的碱和10-30ppm的氟化烷基烷氧基化物类表面活性剂。
下面,将参照为说明而提供的许多实施例对本发明作详细说明,但对本发明绝无限制。一般而言,在快速显影过程中约10至约30ppm(重量)的氟化烷基烷氧基化物类表面活性剂是实用的。该表面活性剂分散在包括氢氧化铵类组分的含水碱中。通常,该碱的氢氧化物类组分约为0.15至约0.5当量,更典型的是约0.2至约0.35当量,优选约为0.261当量作为工业标准。
氢氧化铵类组分可以是氢氧化四甲铵、氢氧化三甲基乙醇铵(胆碱)、氢氧化四(2-羟乙基)铵及其混合物,或类似的化合物。氢氧化四甲铵(TMAH)是特别优选的,如果需要,也可以采用其他氢氧化铵类化合物。虽然任何正性光致抗蚀剂基片都是适宜的,但是,本发明的方法通常采用包括称为线性酚醛清漆树脂的苯酚甲醛树脂和重氮萘醌类光敏化合物的组合物实施。
本文中所用的术语“主要包括”指的是本发明的显影方法除了涂覆显影剂并在适当的时间间隔后将其漂洗掉以外,不需要其他实质性的步骤。这与Lewis等人公开的在常规的显影之前要用阳离子表面活性剂和碱进行化学预处理的方法形成对照。
比较例1-12
这一系列的实施例详述了含水碱类组合物,特别是关于所用表面活性剂的浓度的筛选。一般而言,集成电路生产中重要的问题是,添加剂例如表面活性剂对生产过程或产品参数,例如景深(“DOF”)或最终产品中能达到的线宽、在给定的一组加工条件下使抗蚀剂充分溶解所需的光能(下文中称为“Eclear”)、在给定的加工方法下印制0.5μm(微米)线所需的光能(下文中称为“Enominal”)以及在以下实施例中是否能可靠地产生0.35μm(微米)的线(下文中称为“clear 0.35”),都不会产生不利的影响;这是主要性能的量度。在下述的实施例中,Eclear或为清除而需要的辐射剂量以及Enominal均以每平方厘米的毫焦耳数表示。DOF,即在0.5μm(微米)宽的图像品质变坏之前,按微米测量的离辐射源的距离可作多大的改变。本领域技术熟练的人员会容易地理解DOF是对形貌变化敏感度的量度,而Enominal则随感光速度成反比变化。
在以下的实施例中,用作显影剂的溶液包括添加到含水碱中的各种表面活性剂,这些表面活性剂包括可从许多来源买到的通常称之为环氧乙烷的乙二醇/丙二醇1∶2的共聚物。还使用过下文中称为“NPO”的(壬基苯氧基)聚氧化乙烯、下文中称为“OPE”的(对叔辛基苯氧基)聚乙氧基乙醇以及丁基卡必醇。
在比较例1-12的每一个实例中,将采用六甲基二硅氧烷蒸气预处理过的硅片旋转涂覆一层AZ7500正性光致抗蚀剂(从Hoechst CelaneseCorporation,Someville,New Jersey购得)薄膜。该光致抗蚀剂属于线性酚醛清漆树脂类,这种树脂是由间甲酚,3,5-二甲苯酚和甲醛合成的。该光敏组分由萘醌二叠氮化物磺酰氯和三(羟基苯基)乙烷制得。
然后,将涂覆过的基片在110℃下适度烘焙60秒钟,所生成的抗蚀剂薄膜的厚度约为1.29μm(微米)。将涂覆过的基片在Nikon0.54数值孔径(numerical aperture)(具有已知图像的清晰度中缩板(Resolutionrecticle))1-行步进器(1-line stepper)上曝光,同时,将该基片按X、Y和Z方向移位。曝光后再将该基片在110℃下烘焙60秒钟,显影的规程是采用Silicon Valley Group(SVG)的显影导向装置,在上述涂覆过的基片于300rpm下旋转的同时,通过鼓风喷雾3秒钟将显影剂分布在该基片上。停止该基片旋转,继续喷射显影剂2秒钟,继而保持47秒钟。然后,将该显影后的基片以鼓风喷雾的方式,在该基片于300rpm下旋转的同时,用去离子水漂洗15秒钟,随后在同一装置中于400rpm下干燥15秒钟。
以下比较例1-12即按此程序进行,除了含水显影剂组合物以外,材料和程序基本上相同,所述显影剂组合物在所有的情况下均包括0.261当量(2.38%,重量)电子级纯的TMAH溶液以及不同量的表面活性剂(ppm,重量),如表Ⅰ所示。对每个实施例都测定了Eclear、Enominal和DOF。将表面活性剂添加到显影剂溶液中的具体方法并不是关键的;可径直将其加到适宜碱的容器中,接着进行搅拌、摇动或类似操作。
表Ⅰ:表面活性剂性能与浓度的关系
比较例 | 表面活性剂 | 表面活性剂浓度ppm | Eclear | Enominal | Clear 0.35微米 | DOF,微米 |
1 | 0 | 97 | 180 | 是 | 1.2 | |
2 | NPO | 400 | 107 | 200 | 否 | 1.2 |
3 | NPO | 15 | 180 | 是 | 1.2 | |
4 | NPO | 75 | 190 | 是 | 1.2 | |
5 | NPO | 150 | 180 | 否 | 1.2 | |
6 | OPE | 250 | 180 | 是 | 1.2 | |
7 | OPE | 500 | 98 | 170 | 否 | <1.2 |
8 | OPE | 1000 | 102 | 165 | 否 | 1.2 |
9 | OPE | 1750 | 94 | 160 | 否 | 1.2 |
10 | OPE | 2500 | 140 | 否 | 1.0 | |
11 | 环氧乙烷 | 400 | 103 | 165 | 否 | 1.2 |
12 | 丁基 | 100 | 180 | 是 | 1.2 |
从以上可见,在这些方法中采用浓度低于250ppm的表面活性剂的含水碱类使光致抗蚀剂显影在大多数情况下是适宜的,采用浓度低于150ppm的表面活性剂更是特别优选的,在这种场合下显影过程主要包括涂覆显影剂组合物,接着将该基片漂洗和干燥,即,不像Lewis等人在美国专利4,710,449中所述的那样在涂覆显影剂溶液之前有明显的预处理步骤,例如用碱和表面活性剂预处理。
还进一步发现,可以使用很少量含有磺酰或胺的氟化烷基烷氧基化物类表面活性剂,如下面所述。
比较例13-15和16
按比较例1-12的涂覆、曝光和显影程序,制备了4块基片组。步进器仅在不用带有图像的中缩板或掩膜的情况下,按x-y模式对这些基片进行操作,且在所有情况下显影剂溶液均为含有0.261当量的TMAH以及表Ⅱ中列出的少量表面活性剂。因此,这些基片都具备未印制图像的均匀的抗蚀剂薄膜,在曝光和显影之前和之后均在5个位置测定其厚度,如表Ⅱ中所示。
除了对照(没有表面活性剂)和上述实施例的含有环氧乙烷的显影剂溶液以外,3号基片显影时采用称为FluoradTM FC143的表面活性剂(从3MCorporation,Minneapolis Minnesota购得),该表面活性剂是十五氟辛酸铵(“AO”),4号基片则采用FluoradTM FC171表面活性剂(也从3M购得)。FC171是以下通式的含磺酰和氨基的氟化烷基烷氧基化物类表面活性剂:式中n认为是约5至约15的整数,可能约为10。
从上式可以看出,FC-171更具体是含磺酰、氨基和氟化烷基的乙氧基化物,在表Ⅱ中缩写为SAE。为方便起见,该化合物可以命名为聚(氧-1,2-乙二基)-”-[2-[乙基[(十七氟辛基)磺酰基]氨基]乙基]-2-甲氧基以便于编目。
根据表Ⅱ,必须指出的是,只有氟化烷基烷氧基化物可以给出优良的结果,即均匀性优于不含表面活性剂的显影剂。
表Ⅱ具有低ppm表面活性剂含量的显影剂组合物
表面活性剂 | 基片# | 位置1 | 位置2 | 位置3 | 位置4 | 位置5 | 平均 | 标准偏差 | Eclear | |
无 | 1 | 之前 | 1.2831 | 1.2809 | 1.2792 | 1.2806 | 1.2799 | 1.28074 | 0.001318 | 103 |
之后 | 0.7814 | 0.7697 | 0.7457 | 0.7546 | 0.7657 | 0.76342 | 0.012326 | |||
相差 | 0.5017 | 0.5112 | 0.5335 | 0.536 | 0.5142 | 0.51732 | 0.01121 | |||
25ppmoxirane | 2 | 之前 | 1.2885 | 1.2873 | 1.2844 | 1.2866 | 1.2886 | 1.28658 | 0.001526 | 107 |
之后 | 0.766 | 0.7877 | 0.767 | 0.7471 | 0.8022 | 0.774 | 0.019076 | |||
相差 | 0.519 | 0.4996 | 0.5174 | 0.5395 | 0.4864 | 0.51238 | 0.018126 | |||
20ppmAO | 3 | 之前 | 1.2885 | 1.288 | 1.2889 | 1.2908 | 1.2878 | 1.2888 | 0.001071 | 106 |
之后 | 0.8803 | 0.9604 | 0.8844 | 0.8527 | 0.856 | 0.88676 | 0.038927 | |||
相差 | 0.4082 | 0.3276 | 0.4045 | 0.4381 | 0.4318 | 0.40204 | 0.039424 | |||
20ppmSAE | 4 | 之前 | 1.2906 | 1.2878 | 1.2905 | 1.2898 | 1.2844 | 1.28942 | 0.001129 | 104 |
之后 | 0.883 | 0.8584 | 0.8646 | 0.8645 | 0.8715 | 0.8684 | 0.008395 | |||
相差 | 0.4076 | 0.4294 | 0.4259 | 0.4253 | 0.4169 | 0.42102 | 0.007867 |
Claims (10)
1.一种正性光致抗蚀剂薄膜的基片的显影方法,该方法主要包括以下步骤:将包括含水氢氧化铵类的碱和氟化烷基烷氧基化物类的表面活性剂的含水碱类显影剂组合物涂覆到所述薄膜上,其中所述表面活性剂的含量为10至30ppm(重量),随后将该显影剂组合物从所述薄膜上漂洗掉。
2.根据权利要求1的方法,其中在所述显影剂组合物中的氢氧化铵类的碱的浓度为0.15至0.5当量。
3.根据权利要求1的方法,其中在所述显影剂组合物中的氢氧化铵类的碱的浓度为0.2至0.35当量。
4.根据权利要求1的方法,其中在所述显影剂组合物中的氢氧化铵类的碱的浓度为0.261当量。
5.根据权利要求1的方法,其中所述氢氧化铵类的碱选自氢氧化四甲铵、氢氧化三甲基乙醇铵、氢氧化四(2-羟乙基)铵及其混合物。
6.根据权利要求5的方法,其中所述氢氧化铵类的碱是氢氧化四甲铵。
7.根据权利要求1的方法,其中所述基片包括酚醛树脂和重氮萘醌类光敏化合物。
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TW527363B (en) * | 1999-09-08 | 2003-04-11 | Shinetsu Chemical Co | Polymers, chemical amplification resist compositions and patterning process |
US6120978A (en) * | 2000-01-06 | 2000-09-19 | Air Products And Chemicals, Inc. | Use of N,N-dialkyl ureas in photoresist developers |
US6136514A (en) * | 2000-01-31 | 2000-10-24 | Advanced Micro Devices, Inc. | Resist developer saving system using material to reduce surface tension and wet resist surface |
JP2002049161A (ja) * | 2000-08-04 | 2002-02-15 | Clariant (Japan) Kk | 被覆層現像用界面活性剤水溶液 |
US6613499B2 (en) * | 2001-06-12 | 2003-09-02 | Macronix International Co., Ltd. | Development method for manufacturing semiconductors |
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US20040091813A1 (en) * | 2002-11-05 | 2004-05-13 | Honeywell International Inc. | Fluorinated polymers |
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US20060008731A1 (en) * | 2004-07-09 | 2006-01-12 | Michael Van Der Puy | Novel photoresist monomers and polymers |
US20060008730A1 (en) * | 2004-07-09 | 2006-01-12 | Puy Michael V D | Monomers for photoresists bearing acid-labile groups of reduced optical density |
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US4784937A (en) * | 1985-08-06 | 1988-11-15 | Tokyo Ohka Kogyo Co., Ltd. | Developing solution for positive-working photoresist comprising a metal ion free organic base and an anionic surfactant |
US4710449A (en) * | 1986-01-29 | 1987-12-01 | Petrarch Systems, Inc. | High contrast low metal ion positive photoresist developing method using aqueous base solutions with surfactants |
US4732836A (en) * | 1986-05-02 | 1988-03-22 | Hoechst Celanese Corporation | Novel mixed ester O-quinone photosensitizers |
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TW353159B (en) | 1999-02-21 |
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