CN108269735A - 石墨烯膜的制造方法和使用它的表膜构件的制造方法 - Google Patents
石墨烯膜的制造方法和使用它的表膜构件的制造方法 Download PDFInfo
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Abstract
本发明的目的在于提供用于得到石墨烯膜的有效的制造方法和对EUV光表现出高透射率的表膜构件的制造方法。本发明的特征在于,包括:准备设置在衬底上的石墨烯的工序;用保护膜覆盖石墨烯的工序;通过湿式蚀刻除去衬底的工序;以及使用表面张力比湿式蚀刻所使用的湿式蚀刻液小的溶剂将保护膜溶解而除去的工序。
Description
技术领域
本发明涉及石墨烯膜的制造方法和将其用作表膜的表膜构件(Pellicle)的制造方法。
背景技术
在半导体制造工艺所使用的光刻技术中,作为提高分辨率的手段,已推进曝光用光源的短波长化。目前为止,曝光用光源已从水银灯的g线(436nm)、i线(365nm)转向KrF准分子激光(248nm)、ArF准分子激光(193nm),而且也在研究主波长为13.5nm的EUV(ExtremeUltra Violet:远紫外)光的使用。
在半导体和液晶显示器制造工艺的光刻工序中,对涂敷有抗蚀剂的半导体晶圆、液晶用原板照射光从而制作图案,但是如果此时使用的光刻用掩模和中间掩膜(以下,通称为“曝光原版”)上附着有异物,则除了由于该异物吸收光或使光弯折而导致所转印的图案变形或者边缘粗糙以外,还会存在基底污黑或者尺寸、质量、外观等受损的问题。
这些工序通常在无尘室内进行,但是即使如此也难以保证曝光原版总是清洁。因此,一般采用对曝光原版设置被称为表膜构件的除异物构件来进行曝光的方法。
该表膜构件一般包括:框状的表膜构件框架;张设于表膜构件框架的上端面的表膜;以及形成于表膜构件框架的下端面的气密用衬垫等,表膜对曝光用光表现出高的透射率。另外,气密用衬垫采用粘合剂等。
只要对曝光原版设置这种表膜构件,异物就不会直接附着于曝光原版,而会附着于表膜构件上。并且,在光刻中只要使焦点对准曝光原版的图案即可,表膜构件上的异物就会与转印无关,能抑制图案的变形等问题。
此外,表膜的材料要根据曝光用光的种类而现在透射率高的材料。例如,在g线(436nm)、i线(365nm)、KrF准分子激光(248nm)、ArF准分子激光(193nm)为曝光用光的情况下,将硝化纤维、醋酸纤维、氟系聚合物等用作表膜。
另一方面,在新推进开发的EUV曝光中,现有的表膜透射率低,难以使用。因此,作为EUV曝光所使用的表膜,已研究了对EUV光表现出高透射率的超薄硅、石墨烯的使用。
现有技术文献
专利文献
专利文献1:特表2013-534727号
专利文献2:特开2015-18228号
发明内容
发明要解决的问题
专利文献1记载了表膜采用石墨烯的技术方案。在此,将石墨烯片材(Graphenesheet)、石墨烯薄片(Graphene flake)、石墨烯片材与支护材料的层叠体等用作表膜,但是专利文献1没有记载它们的制造方法。
另外,专利文献2公开了包括将石墨烯膜与支撑网膜接合而成的复合膜的表膜,也记载了其制造方法。具体地说,是在催化剂金属衬底上形成石墨烯膜,将树脂作为保护膜紧贴到未与衬底紧贴的一面的石墨烯膜的表面。然后,将催化剂金属溶解而除去,将石墨烯膜转印、接合于支撑网膜表面,最后用溶剂将保护膜溶解而除去的方法等。
如专利文献2记载的方法那样,在表膜采用支护材料、支撑网膜的情况下,机械强度提高,但曝光用光的透射率受限,因此理想上希望使用单一的石墨烯膜作为表膜。
石墨烯能通过CVD(Chemical Vapor Deposition:化学气相沉积)法形成在Ni箔、Cu箔等基材上。另外,只要对形成的石墨烯贴附热剥离片,对基材进行蚀刻,再贴附到其它基材后,除去热剥离片,就也能将石墨烯转印于SiO2/Si等其它基材。
为了将这种石墨烯用作表膜,需要除去基材而得到单一的石墨烯膜。然而,本发明的发明人对此进行了尝试,发现在将设于基材上的石墨烯置于湿式蚀刻液而除去基材的情况下,当在湿式蚀刻后将石墨烯膜单独从液中提起时,石墨烯膜会发生破损。
并且,本发明的发明人进行进一步了研究,发现该石墨烯膜的破损是由湿式蚀刻液的表面张力引起的,另外还发现这是由于酸、碱的蚀刻液而致使石墨烯受到化学损伤。
因此,本发明的目的在于提供用于得到石墨烯膜的有效的制造方法和对EUV光表现出高透射率的表膜构件的制造方法。
用于解决问题的方案
即,本发明的特征在于,包括:准备设置在衬底上的石墨烯的工序;用保护膜覆盖石墨烯的工序;通过湿式蚀刻除去衬底的工序;以及使用表面张力比湿式蚀刻所使用的湿式蚀刻液小的溶剂将保护膜溶解而除去的工序。
另外,在本发明的制造方法中,优选保护膜是氟树脂,溶剂是氟系溶剂,能将通过该制造方法得到的石墨烯膜作为表膜来制造表膜构件。
发明效果
根据本发明的石墨烯膜的制造方法,能抑制制造工序中的石墨烯膜的破损、损伤。另外,如果将通过本发明得到的石墨烯膜用作表膜,则能制造适合于EUV曝光的表膜构件。
附图说明
图1是示出本发明的石墨烯膜的制造方法的一个实施方式的(A)~(H)的示意图。
图2是示出本发明的石墨烯膜的制造方法的一个实施方式的(I)~(K)的示意图。
附图标记说明
1 衬底
2 石墨烯(石墨烯膜)
3 保护膜
4 粘接剂
5、8 保持部件
6 湿式蚀刻液
7 粘接剂
9 溶剂。
具体实施方式
以下,参照附图说明本发明的一个实施方式。
在本发明中,首先,准备图1的(A)所示的设置在衬底1上的石墨烯2。将石墨烯2设置在衬底1上的方法没有特别限定,使用公知的方法即可。
作为石墨烯2的制造方法,例如能举出从石墨进行机械剥离、CVD法、SiC衬底的表面热分解法等,但是从量产性的观点出发优选CVD法。在该CVD法中,将烃类气体作为原料,在Ni箔、Cu箔等基材上形成石墨烯2。另外,只要对形成的石墨烯2贴附热剥离片,对基材进行蚀刻,再贴附于其它基材后,除去热剥离片,即能将石墨烯转印到Si/SiO2等其它基材。
该工序中使用的衬底1没有特别限定,能将上述Ni箔和Cu箔、这些金属箔与SiO2/Si等的衬底的复合衬底乃至将转印了石墨烯的SiO2/Si等用作衬底1。另外,从透射率的观点出发,优选该石墨烯2为单层,但是从机械强度的观点出发也可以是多层结构。优选为单层或者2~100层程度的多层结构。
接下来,如图1的(B)所示,用保护膜3覆盖设置在衬底1上的石墨烯2。此时,优选保护膜3对用于在后面的工序中除去衬底1的湿式蚀刻液具有耐性。另外,能将该保护膜3溶解而除去的溶剂的表面张力需要小于湿式蚀刻液的表面张力。
用保护膜3覆盖石墨烯2的方法根据用作保护膜3的材料而适当选择即可。例如,在保护膜3使用树脂的情况下,能通过旋涂、浸涂等公知的方法涂敷其溶液,除去溶剂从而用保护膜3覆盖石墨烯2。
在本发明中,如图1的(D)和(E)所示,在用保护膜3覆盖设置在衬底1上的石墨烯2后,通过湿式蚀刻除去衬底1。在该湿式蚀刻中,湿式蚀刻液6使用能对衬底1进行蚀刻的液体,但是该湿式蚀刻液6只要根据进行蚀刻的衬底1的种类而适当选择即可。在衬底1为SiO2/Si的情况下,例如湿式蚀刻液6能使用24%氢氧化钾水溶液等。该24%氢氧化钾水溶液的表面张力为72mN/m。
在该湿式蚀刻工序中,即使在除去衬底1后将石墨烯2从湿式蚀刻液6取出,由于保护膜3的存在,也能防止膜状的石墨烯2的破损。另外,也能利用保护膜3防止与衬底1相反的一侧的石墨烯2表面由于湿式蚀刻液6而受到损伤。
接下来,如图2的(I)和(J)所示,在通过湿式蚀刻除去衬底1后,使用表面张力比上述湿式蚀刻所使用的湿式蚀刻液6小的溶剂9将保护膜3溶解而除去。该溶剂9根据保护膜3和湿式蚀刻液6的种类而选择,保护膜3也根据该溶剂9的种类而选择。
例如,保护膜3能选择丙烯酸树脂,溶剂9能选择丙酮。另外,保护膜3能选择氟树脂,溶剂9能选择氟系溶剂。特别是,氟树脂的药品耐性高,因而作为保护膜3是优选的,而且氟系溶剂的表面张力小,因而作为该工序中使用的溶剂9是优选的。
在该工序中,即使在除去保护膜3后将石墨烯2从溶剂9取出,由于表面张力小而能降低对膜状的石墨烯2的应力,因此能抑制膜状的石墨烯2的破损。
能将这样得到的膜状的石墨烯2用作表膜,将其设置成覆盖框状的表膜构件框架开口部从而形成表膜构件。并且,也可以根据需要对该表膜构件设置用于将表膜构件设于曝光原版的粘合剂、用于调整气压的通气孔、用于防止异物从通气孔侵入的过滤器等,各材质、形状也没有限定。另外,该表膜构件由于是将对EUV光的透射率高的石墨烯膜用作表膜,因此适合作为EUV曝光用表膜构件。
此外,在本发明的石墨烯膜的制造方法中,也可以设置如图1的(C)所示的保持部件5。在此,将用保护膜覆盖的石墨烯2和保持部件5通过粘接剂4接合。该保持部件5能用于操纵等,例如能使用金属制的框架等。另外,粘接剂4没有特别限定,使用公知的粘接剂即可。
设置保持部件5的时机没有特别限定,例如可以如图1的(G)所示,在通过湿式蚀刻除去衬底1后,将其设于石墨烯2侧(与衬底1紧贴的一侧)。
在本发明中,也可以对石墨烯膜设置支撑网膜等支护材料。在设有支护材料的情况下,也能抑制制造工序中的石墨烯膜的破损。另外,还能使支撑网膜的开口率变大,能使曝光用光的透射率变高。
支护材料例如能在通过湿式蚀刻除去衬底1后,设于石墨烯2侧(与衬底1紧贴的一侧)。
另外,能将保持部件作为表膜构件框架。这样,能直接得到石墨烯膜和表膜构件框架接合的结构。
实施例
〈实施例1〉
首先,准备在表面具有SiO2层的Si(SiO2/Si)衬底1上设有100mm见方的石墨烯2(30~60层)的衬底(图1的(A))。接下来,通过旋涂对设置在衬底1上的石墨烯2涂敷作为保护膜3的氟树脂(旭硝子(株)制造的CYTOP CTX-S)使得干燥后的厚度为1μm,以180℃加热1分钟而使其固化(图1的(B))。接着,从作为该保护膜3的氟树脂上使用环氧树脂系粘接剂4(施敏打硬(株)制EP330)以包围石墨烯2的方式粘接兼作保持部件5的150mm见方的不锈钢(SUS)制框架(图1的(C))。
接下来,使其浸渍于24%氢氧化钾水溶液(表面张力:72mN/m)中,对SiO2/Si衬底1进行湿式蚀刻。在除去了SiO2/Si衬底1时,将石墨烯2从蚀刻液取出,能得到未破损而被保护膜3的氟树脂支撑的石墨烯膜2(图1的(D)、(E)、(F))。
接着,使用环氧树脂系粘接剂4(施敏打硬(株)制EP330)对被保护膜3的氟树脂支撑的石墨烯膜2粘接兼作保持部件8的100mm见方的SUS制框架(图1的(G))。此时,以机械方式除去了100mm见方的SUS制框架的外侧的保护膜3的氟树脂(图1的(H))。
接下来,将其垂直浸渍于氟溶剂9(住友3M(株)制NOVEC7300,表面张力:15mN/m)中,经过24小时后保护膜3的氟树脂被完全溶解而除去,因此将石墨烯膜2缓慢地提起,对得到的石墨烯膜2进行观察时,没有见到损伤、破损(图2的(I)、(J)、(K))。
〈比较例1〉
首先,准备在表面具有SiO2层的Si(SiO2/Si)衬底1上设有100mm见方的石墨烯2(30~60层)的衬底。接下来,不设置保护膜3而直接使用环氧树脂系粘接剂4(施敏打硬(株)制EP330)对石墨烯2粘接100mm见方的SUS制框架。
接着,使其浸渍于24%氢氧化钾水溶液(表面张力:72mN/m)中,对SiO2/Si衬底1进行湿式蚀刻。然后,在除去了SiO2/Si衬底1后,对石墨烯膜2的状态进行确认时,发现被湿式蚀刻液6侵蚀而在石墨烯膜2中开孔。另外,在将石墨烯膜2从湿式蚀刻液6取出时,石墨烯膜2由于蚀刻液6的表面张力而发生了破损。
Claims (3)
1.一种石墨烯膜的制造方法,其特征在于,包括:
准备设置在衬底上的石墨烯的工序;用保护膜覆盖该石墨烯的工序;通过湿式蚀刻除去上述衬底的工序;以及使用表面张力比上述湿式蚀刻所使用的湿式蚀刻液小的溶剂将上述保护膜溶解而除去的工序。
2.根据权利要求1所述的石墨烯膜的制造方法,其特征在于,
上述保护膜是氟树脂,上述溶剂是氟系溶剂。
3.一种表膜构件的制造方法,其特征在于,
将通过权利要求1或2所述的制造方法得到的石墨烯膜用作表膜。
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KR102532602B1 (ko) * | 2017-07-27 | 2023-05-15 | 삼성전자주식회사 | 포토마스크용 펠리클 조성물, 이로부터 형성된 포토마스크용 펠리클, 그 제조방법, 펠리클을 함유한 레티클 및 레티클을 포함하는 리소그래피용 노광장치 |
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