CN109422236A - 三维结构、制作三维结构的方法、及流体喷射装置 - Google Patents
三维结构、制作三维结构的方法、及流体喷射装置 Download PDFInfo
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- CN109422236A CN109422236A CN201810919939.6A CN201810919939A CN109422236A CN 109422236 A CN109422236 A CN 109422236A CN 201810919939 A CN201810919939 A CN 201810919939A CN 109422236 A CN109422236 A CN 109422236A
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Classifications
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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
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/02—Microstructural systems; Auxiliary parts of microstructural devices or systems containing distinct electrical or optical devices of particular relevance for their function, e.g. microelectro-mechanical systems [MEMS]
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- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1601—Production of bubble jet print heads
- B41J2/1603—Production of bubble jet print heads of the front shooter type
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- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1626—Manufacturing processes etching
- B41J2/1628—Manufacturing processes etching dry etching
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- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1631—Manufacturing processes photolithography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1637—Manufacturing processes molding
- B41J2/1639—Manufacturing processes molding sacrificial molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B3/00—Devices comprising flexible or deformable elements, e.g. comprising elastic tongues or membranes
- B81B3/0064—Constitution or structural means for improving or controlling the physical properties of a device
- B81B3/0067—Mechanical properties
- B81B3/0072—For controlling internal stress or strain in moving or flexible elements, e.g. stress compensating layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/0032—Packages or encapsulation
- B81B7/0035—Packages or encapsulation for maintaining a controlled atmosphere inside of the chamber containing the MEMS
- B81B7/0038—Packages or encapsulation for maintaining a controlled atmosphere inside of the chamber containing the MEMS using materials for controlling the level of pressure, contaminants or moisture inside of the package, e.g. getters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00047—Cavities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00134—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems comprising flexible or deformable structures
- B81C1/00142—Bridges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00261—Processes for packaging MEMS devices
- B81C1/00269—Bonding of solid lids or wafers to the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00261—Processes for packaging MEMS devices
- B81C1/00333—Aspects relating to packaging of MEMS devices, not covered by groups B81C1/00269 - B81C1/00325
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00388—Etch mask forming
- B81C1/00396—Mask characterised by its composition, e.g. multilayer masks
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Abstract
本发明提供一种用于处理流体的三维(“3D”)结构、一种包含所述三维结构的流体处理装置以及一种制作所述三维结构的方法。所述三维结构包括复合膜层。所述复合膜层包括第一光致抗蚀剂层,不具有疏水性试剂;以及至少一第二光致抗蚀剂层,包含所述疏水性试剂,其中所述复合膜层在所述第一光致抗蚀剂层与所述第二光致抗蚀剂层之间不具有粘附促进层。
Description
技术领域
本公开涉及一种微机电***装置及纳米装置,尤其涉及一种制作具有不同的疏水性程度及亲水性程度的三维感光成像结构的改善的方法、三维结构、及流体喷射装置。
背景技术
微机电***(micro-electromechanical systems,“MEMS”)及纳米装置通常包括由感光成像材料制作的三维(three-dimensional,“3D”)结构。在一些应用中,需要所述3D结构具有亲水性质和/或疏水性质。MEMS装置及纳米装置的实例包括但不限于:流体喷射头、微过滤器、微分离器、微筛以及其他微米及纳米级流体处理结构。这类结构可处理各种各样的流体。举例来说,流体喷射头是适用于喷射包括油墨、冷却流体、药物、润滑剂等在内的各种流体的3D纳米装置。广泛使用的流体喷射头是用于喷墨打印机中。然而,流体喷射头也可用于蒸气疗法用气化装置、电子烟等中。正持续不断地开发新技术,以对这类装置提供低成本、高度可靠的流体喷射头。
流体喷射头是看似简单的装置,其具有包含电路、油墨通道及精密组装的各种微小部件,以提供强大而多功能的流体喷射头的相对复杂的结构。喷射头的组件必须彼此协作,并适用于各种流体及流体配方。因此,使喷射头组件与被喷射的流体匹配非常重要。生产品质的轻微变化,可对产品良率及所得喷射头性能产生巨大影响。
流体喷射头的主要组件是半导体衬底、贴合到所述衬底的流动特征层、喷嘴板层以及柔性电路。半导体衬底优选地由硅制成,并包含沉积在半导体衬底的装置表面上的各种钝化层、导电金属层、电阻层、绝缘层及保护层。形成在衬底的装置表面上的流体喷射致动器,可为热致动器或压电致动器。对于热致动器,在电阻层中界定有单独的加热器电阻器,且每一加热器电阻器对应于喷嘴板中的喷嘴孔,以加热流体并从喷射头朝期望的衬底或目标喷射流体。
当前用于制作流体流动层及喷嘴板层的方法,涉及了使用旋涂光致抗蚀剂或干膜光致抗蚀剂与对每一层进行的多个成像、显影及烘烤步骤的组合。举例来说,在传统工艺中,将第一粘附促进层施加到半导体衬底,将感光成像材料所形成的流体流动层旋涂到粘附层上。流体流动层是进行了成像、固化及显影的负性光致抗蚀剂层。在施加喷嘴层之前,将第二粘附促进层施加到流体流动层。接下来,通过第二粘附促进层将喷嘴层作为干膜而积层到流体流动层。对喷嘴层进行成像、固化及显影。然后,对半导体衬底进行深度反应离子蚀刻(deep reactive ion etched,DRIE)以形成穿过衬底的通孔。由于流体流动层及喷嘴层已经贴合到衬底,因此DRIE工艺的工艺范围(process latitude)受到限制。
在替代工艺中,在将粘附促进层施加到半导体衬底之前或之后,首先利用DRIE工艺对所述衬底进行蚀刻以形成通孔。然后,将流体流动层及喷嘴层作为干膜施加到衬底,从而分别进行成像及显影。每一干膜均需要单独的粘附促进层。施加每一附加的粘附促进层,会在各层之间存在粘附损失的风险。
在替代工艺的变型中,DRIE工艺是在将流体流动层施加到衬底并进行成像及显影之后进行。在DRIE工艺之后,将喷嘴层积层到流体流动层并进行成像及显影。
无论所使用的工艺如何,使用需要多种粘附促进剂的多个层,增加了制作流体喷射头的工艺时间,并增大了因粘附层失败而造成损失的风险。此外,具有3D结构的MEMS装置或纳米级装置,可能需要具有亲水性的层及具有疏水性的层,来高效地处理流过所述装置的流体。因此,所需要的是一种3D结构以及一种制作能够控制所述3D结构的复合膜的特定层内的流体流动的所述结构的方法。
发明内容
本公开提供一种用于处理流体的三维(“3D”)结构、一种包含所述3D结构的流体处理装置以及一种制作所述3D结构的方法。在一个实施例中,所述三维结构包括复合膜层。所述复合膜层包括:第一光致抗蚀剂层,不具有疏水性试剂;以及至少一第二光致抗蚀剂层,包含所述疏水性试剂。所述复合膜层在所述第一光致抗蚀剂层与所述第二光致抗蚀剂层之间不具有粘附促进层。
在另一实施例中,提供一种由复合膜层制作三维结构的方法。所述方法包括:将第一光致抗蚀剂层施加到载体膜,所述第一光致抗蚀剂层不具有疏水性试剂;对所述第一光致抗蚀剂层进行干燥以提供经干燥的第一光致抗蚀剂层;将第二光致抗蚀剂层施加到所述经干燥的第一光致抗蚀剂层,所述第二光致抗蚀剂层包含疏水性试剂;对所述第二光致抗蚀剂层进行干燥以提供经干燥的第二光致抗蚀剂层,其中所述经干燥的第一光致抗蚀剂层与所述经干燥的第二光致抗蚀剂层形成不具有中间粘附层的所述复合膜层;将所述复合膜层积层到衬底的表面;将所述复合膜层曝光于曝光波长选自由e线、g线、h线、i线、中紫外线及深紫外线组成的群组的辐射;以及同时对所述复合膜层进行显影以提供所述三维结构。
本公开的另一实施例提供一种具有流体喷射头及控制器的流体喷射装置。所述流体喷射头包括:半导体衬底,包含位于所述半导体衬底的装置表面上的多个流体喷射致动器以及蚀刻穿过所述半导体衬底的一个或多个流体供应通孔;粘附促进层,施加到所述半导体衬底的所述装置表面;复合膜层,设置在所述粘附促进层上,其中所述复合膜层包含:第一光致抗蚀剂层,不具有疏水性试剂;以及至少一第二光致抗蚀剂层,包含疏水性试剂,其中所述复合膜层在所述第一光致抗蚀剂层与所述第二光致抗蚀剂层之间不具有粘附促进层。控制器用于激活所述流体喷射头。
在一些实施例中,所述复合膜层包括至少一第三光致抗蚀剂层,其中所述第三光致抗蚀剂层不具有疏水性试剂。
在一些实施例中,所述复合膜层具有介于约6μm到约150μm的范围的厚度。
在一些实施例中,所述复合膜层的所述第一光致抗蚀剂层是利用曝光波长选自由e线、g线、h线、i线、中紫外线及深紫外线组成的群组的第一辐射进行成像。
在一些实施例中,所述复合膜层的所述第二光致抗蚀剂层是利用曝光波长选自由e线、g线、h线、i线、中紫外线及深紫外线组成的群组的第二辐射进行成像。
操纵每一复合光致抗蚀剂材料层的表面条件的有益效果是能够形成疏水表面及亲水表面,从而可用于管理MEMS装置或纳米装置的性能。因此,本公开的实施例简化了MEMS结构及纳米结构并使得MEMS结构及纳米结构的多个层能够具有不同的表面能及表面张力,以便操纵水系流体的流动、分离、过滤及混合。
本公开所述的实施例的另一优点是制作3D MEMS装置及纳米装置的工艺步骤如以下更详细所述被大大简化,且因积层粘附失败的减少而以更高良率提供装置。
附图说明
通过结合各图式参照详细说明,所公开的实施例的更多特征及优点将明白易懂,所述图式未必按比例绘制,在全部的视图中,相同参考元件符号指示相同元件,其中:
图1到图2是制作流体喷射头的现有技术工艺步骤的流程图。
图3是根据本公开实施例的制作喷射头的工艺步骤的流程图。
图4A是根据本公开的流体喷射头的一部分的未按比例绘制的示意性剖视图。
图4B是沿着图4A的4B-4B线所示流体喷射头的一部分的未按比例绘制的平面示意图。
图5是根据本公开实施例的双层光致抗蚀剂材料的未按比例绘制的剖视图。
图6到图8是根据本公开实施例的制作流体喷射头的步骤的未按比例绘制的示意图。
图9是根据本公开实施例的三层光致抗蚀剂材料的未按比例绘制的剖视图。
[符号的说明]
10、50、60:方块流程图
12:DRIE工艺
14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、52、62、64、66、68、70、72、74:步骤
100:喷射头
110:半导体衬底
112:压电装置或加热器电阻器
114:装置表面
116:流体供应通孔
118:流体供应通道
120:流体腔室
122:部分
124、200、240:复合膜层
126:喷嘴孔
210:第一光致抗蚀剂层
212:载体膜
214、242:第二光致抗蚀剂层
220、224:e线、g线、h线、i线、中UV或深UV的辐射
222:掩模
226:第二掩模
228:未显影的流动特征
230:未显影的喷嘴特征
244:第三光致抗蚀剂膜层
具体实施方式
关于本公开的实施例,可制作具有期望流体流动性质的各种MEMS装置及纳米装置。这种装置的实例是流体喷射头。因此,为简化目的,所述说明具体来说涉及流体喷射头。然而,本公开所述的实施例可适用于制作以上所提到的各种各样的3D MEMS装置及纳米装置。
图1及图2以图示形式示出制作喷射头的现有技术工艺步骤的方块流程图10及50。参照图1,第一步骤是DRIE工艺12,以蚀刻穿过半导体衬底的流体通孔。接下来,在步骤14中对衬底进行等离子体清洁,且在步骤16中将粘附促进层(adhesion promotion layer)施加到衬底。在步骤18中将提供流体流动层的干膜层(dry film layer)施加到粘附层。在步骤20中通过掩模将流体流动层曝光于辐射,且在步骤22中进行烘烤以将所述层的被曝光区域固化。接下来,在步骤24中对流体流动层进行显影,以移除流体流动层的被遮蔽区域。然后,在步骤26中将流体流动层曝光于紫外线(UV)辐射,并在步骤28中又进行烘烤以移除任何残余的光酸产生剂、显影剂和/或未固化的树脂。在步骤30中对半导体衬底及流体流动层进行等离子体清洁,且在步骤32中施加第二粘附促进层。在步骤34中将第二干膜层积层到流体流动层以提供喷嘴层。在步骤36中将喷嘴层曝光于辐射,以在喷嘴层中形成喷嘴孔。在步骤38中执行第二后曝光烘烤,以将喷嘴层中的未遮蔽的材料固化。接下来,在步骤40中对喷嘴层进行显影,以形成喷嘴孔。在步骤42中将喷嘴层曝光于UV辐射,并在步骤44中进行后曝光烘烤。
方块流程图10与方块流程图50之间的主要差异在于:在方块流程图10中,在半导体衬底中形成通孔的DRIE工艺是在将流动层中的任一个施加到衬底之前进行,而在方块流程图50中,DRIE工艺是在将流体流动层施加到衬底、曝光于辐射并进行显影之后进行。由于半导体衬底尚不包含流体通孔,因此在步骤52中可将流体流动层旋涂到衬底上而非积层到粘附层。在其他方面,所述工艺步骤相似于参照图1所述的工艺步骤。
根据本公开实施例的简化工艺的方块流程图60示于图3中。所述方块流程图60的工艺的前三个步骤,相似于现有技术工艺的方块流程图10的前三个步骤。然而,代替将单个流体流动层积层到衬底,在步骤62中将复合干膜层(composite dry film layer)积层到粘附促进层。接下来,在步骤64中通过掩模将复合干膜层曝光于第一辐射源,以在复合干膜层中提供流体流动特征(fluid flow feature)。在对流体流动特征进行显影之前,在步骤66中通过第二掩模将复合干膜层曝光于第二辐射源,以在复合干膜层中提供喷嘴孔。然后,在步骤68中对复合干膜层进行烘烤,以将复合干膜层的被遮蔽区域固化。在步骤70中,对复合干膜层进行显影,以在复合干膜层中形成流体流动特征及喷嘴孔。如在现有技术工艺中一样,然后在步骤72中将复合膜层曝光于UV辐射,并在步骤74中进行烘烤。
通过前述工艺制成的喷射头100的一部分,示于图4A及图4B中。喷射头100包括半导体衬底110,半导体衬底110优选为硅半导体衬底,其包含:形成在半导体衬底110的装置表面114上的多个流体喷射致动器(例如压电装置或加热器电阻器112)。在激活加热器电阻器112时,通过半导体衬底110中的一个或多个流体供应通孔116而供应的流体,会通过流体供应通道118而流到复合膜层124(composite film layer)的一部分122中的流体腔室120,使流体通过复合膜层124中的喷嘴孔126而喷射出。流体喷射致动器(例如加热器电阻器112)是通过众所周知的半导体制造技术,而形成在半导体衬底110的装置表面114上。
半导体衬底110的尺寸为相对小,且半导体衬底110通常具有介于以下范围的总体尺寸:约2毫米(millimeter,mm)到约8毫米的宽度,约10毫米到约20毫米的长度,约0.4毫米到约0.8毫米的厚度。在传统的半导体衬底110中,流体供应通孔116是在半导体衬底110中经喷砂处理而得到。这类流体供应通孔116通常具有:约9.7毫米长、及约50微米到约400微米宽的尺寸。通过流体供应通孔116中的单个槽或者通过位于半导体衬底110中的多个开口,使流体可被提供到流体喷射致动器,其中,所述开口是利用选自于反应离子蚀刻(reactive ion etching,RIE)或深度反应离子蚀刻(DRIE)、电感耦合等离子体蚀刻等中的干式蚀刻工艺而制成的。复合膜层124可由以下更详细描述的一个或多个负性光致抗蚀剂材料层形成。复合膜层124可具有:介于约6μm到约150μm以上、例如约10μm到约80μm范围的厚度。
流体供应通孔116将流体从流体贮存器引导到包含加热器电阻器112的半导体衬底110的装置表面114,其中,喷射头100通过流体供应通孔116而附接到流体贮存器。半导体衬底110的装置表面114优选地也包含:从加热器电阻器112到用于将半导体衬底110连接到柔性电路或胶带自动接合(tape automated bonding,TAB)电路的接触垫的电迹线(electrical tracing),以从流体喷射控制器供应电脉冲,从而激活半导体衬底110上的一个或多个加热器电阻器112。
参照图5,示出附接到载体膜212的复合膜层200。复合膜层200包括第一光致抗蚀剂层210,第一光致抗蚀剂层210被配制成包含第一光酸产生剂,所述第一光酸产生剂具有至少一第一辐射曝光波长。第一光致抗蚀剂层210中的光酸产生剂的波长可选自于e线、g线、h线、i线、中UV及深UV辐射。第一辐射曝光波长在一些实施例中可大于350nm。第一光致抗蚀剂层210的厚度可介于约3μm到约50μm的范围。
复合膜层200也可包含第二光致抗蚀剂层214,第二光致抗蚀剂层214被配制成包含疏水性试剂以及第二光酸产生剂,所述第二光酸产生剂具有与第一辐射曝光波长不同的第二辐射曝光波长。第二辐射曝光波长可选自于e线、g线、h线、i线、中UV及深UV辐射。在一些实施例中,第二辐射曝光波长可小于350nm。第二光致抗蚀剂层214可具有介于约3μm到约100μm范围的厚度。
根据本公开实施例的由可使用的辐射源提供的波长如下:
e线=546nm
g线=435nm
h线=405nm
i线=365nm
中UV=310nm
深UV=254nm。
包含光酸产生剂的光致抗蚀剂材料,可被配制成包含:多官能环氧化合物、双官能环氧化合物、相对高分子量聚羟基醚、粘附增强剂(adhesion enhancer)及脂肪酮溶剂中的一种或多种。为了本公开,“双官能环氧”意指:在分子中仅具有两个环氧官能基的环氧化合物及材料。“多官能环氧”意指:在分子中具有多于两个环氧官能基的环氧化合物及材料。
制作根据本公开一个实施例的用于复合膜层200或复合膜层240(图9)的光致抗蚀剂配方的合适的多官能环氧组分,可选自芳香族环氧化物,例如多元苯酚的缩水甘油醚。示例性的第一多官能环氧树脂是:苯酚甲醛酚醛清漆树脂的多缩水甘油醚,例如酚醛环氧树脂,其环氧化物克当量重量介于约190到约250的范围,并且在130℃下的粘度介于约10到约60的范围。
光致抗蚀剂配方的多官能环氧组分可具有:通过凝胶渗透色谱法确定的约3000道尔顿到约5000道尔顿的重量平均分子量,以及大于3、优选为约6到约10的平均环氧基官能度。以经固化的厚膜层的重量计,示例性的光致抗蚀剂配方中的多官能环氧树脂的量,可介于约30重量百分比到约50重量百分比的范围。
双官能环氧组分可选自双官能环氧化合物,其包括:双酚A的二缩水甘油醚、3,4-环氧环己基甲基-3,4-环氧环-己烯羧酸酯、3,4-环氧-6-甲基环己基甲基-3,4-环氧-6-甲基环-己烯羧酸酯、双(3,4-环氧-6-甲基环己基甲基)己二酸酯及双(2,3-环氧环戊基)醚。
示例性的双官能环氧组分是:环氧化物当量大于约1000的双酚A/环氧氯丙烷环氧树脂。“环氧化物当量”是含有1克当量的环氧化物的树脂的克数。第一双官能环氧组分的重量平均分子量通常高于2500道尔顿,例如约2800重量平均分子量到约3500重量平均分子量。以经固化的树脂的重量计,光致抗蚀剂配方中的第一双官能环氧组分的量可介于约30重量百分比到约50重量百分比的范围。
示例性的光酸产生剂包括:能够产生阳离子的化合物或能够产生阳离子的化合物的混合物,例如芳香族络合盐,其可选自VA族元素的鎓盐、VIA族元素的鎓盐及芳香族卤鎓盐。芳香族络合盐在被曝光于紫外线辐射或电子束照射时,能够产生起始与环氧化物的反应的酸部分(acid moieties)。以经固化的树脂的重量计,光致抗蚀剂配方中可存在介于约5重量百分比到约15重量百分比的范围的量的光酸产生剂。
可使用当由活性射线照射时产生质子酸的化合物作为光酸产生剂,包括但不限于:芳香族碘鎓络合盐及芳香族锍络合盐。实例包括:二-(叔丁基苯基)碘鎓三氟甲磺酸盐、二苯基碘鎓四(五氟苯基)硼酸盐、二苯基碘鎓六氟磷酸盐、二苯基碘鎓六氟锑酸盐、二(4-壬基苯基)碘鎓六氟磷酸盐、[4-(辛氧基)苯基]苯基碘鎓六氟锑酸盐、三苯基锍三氟甲磺酸盐、三苯基锍六氟磷酸盐、三苯基锍六氟锑酸盐、三苯基锍四(五氟苯基)硼酸盐、4,4'-双[二苯基锍]二苯硫醚、双-六氟磷酸盐、4,4'-双[二([β]-羟乙氧基)苯基锍]二苯硫醚双-六氟锑酸盐、4,4'-双[二([β]-羟乙氧基)(苯基锍)二苯硫醚-双六氟磷酸盐、7-[二(对甲苯基)锍]-2-异丙基噻吨酮六氟磷酸盐、7-[二(对甲苯基)锍-2-异丙基噻吨酮六氟锑酸盐、7-[二(对甲苯基)锍]-2-异丙基四(五氟苯基)硼酸盐、苯基羰基-4'-二苯基锍二苯硫醚六氟磷酸盐、苯基羰基-4'-二苯基锍二苯硫醚六氟锑酸盐、4-叔丁基苯基羰基-4'-二苯基锍二苯硫醚六氟磷酸盐、4-叔丁基苯基羰基-4'-二苯基锍二苯硫醚六氟锑酸盐、4-叔丁基苯基羰基-4'-二苯基锍二苯硫醚四(五氟苯基)硼酸盐、二苯基[4-(苯基硫代)苯基]锍六氟锑酸盐等。
可用于复合光致抗蚀剂材料的一个或多个层的疏水性试剂包括:含有硅的材料,例如硅烷及硅氧烷。因此,疏水性试剂可选自十七氟-癸基三甲氧基硅烷、十八烷基二甲基氯硅烷、十八烷基三氯硅烷、甲基三甲氧基硅烷、辛基三乙氧基硅烷、苯基三甲氧基硅烷、叔丁基甲氧基硅烷、四乙氧基硅烷、甲基硅醇钠盐、乙烯基三甲氧基硅烷、N-(3-(三甲氧基硅烷基)丙基)乙二胺聚甲基甲氧基硅氧烷、聚二甲基硅氧烷、聚乙基含氢硅氧烷(polyethylhydrogensiloxane)及二甲基硅氧烷。以经固化的树脂的总重量计,经固化的复合膜中的疏水性试剂的量可为:约0.5重量百分比到约2重量百分比,例如约1.0重量百分比到约1.5重量百分比,包括其中所包含的所有范围。
用于光致抗蚀剂配方中的示例性溶剂为非光反应性的溶剂。非光反应性溶剂包括但不限于:γ-丁内酯、C1-6乙酸酯、四氢呋喃、低分子量酮、及其混合物等。以光致抗蚀剂配方的总重量计,在用于提供复合膜层124的配方混合物中,存在:介于约20重量百分比到约90重量百分比、例如约40重量百分比到约60重量百分比的范围的量的非光反应性溶剂。在示例性实施例中,非光反应性溶剂不残留在经固化的复合膜层中,且因此在复合膜层固化步骤之前或期间被移除。
光致抗蚀剂配方可视需要包含:有效量的粘附增强剂(adhesion enhancingagent),例如硅烷化合物。与光致抗蚀剂配方的组分相容的硅烷化合物通常具有:能够与选自于由多官能环氧化合物、双官能环氧化合物及光引发剂组成的群组中的至少一个进行反应的官能基。这种粘附增强剂可为具有环氧化物官能基的硅烷,例如3-(胍基)丙基三甲氧基硅烷及缩水甘油氧基烷基三烷氧基硅烷,例如γ-缩水甘油氧基丙基三甲氧基硅烷。当使用时,以经固化的树脂的总重量计,可存在介于约0.5重量百分比到约2重量百分比、例如约1.0重量百分比到约1.5重量百分比的范围(包括其中包含的所有范围)内的量的粘附增强剂。本公开所使用的粘附增强剂被定义为意指:可溶于光致抗蚀剂组合物中的有机材料,其有助于复合膜层200或复合膜层240的邻近于半导体衬底110的装置表面114的膜形成特性及粘附特性。
第一光致抗蚀剂层210及第二光致抗蚀剂层214的代表性配方,示于下表1及表2中。
表1
表2
为了提供复合膜层200,可将光致抗蚀剂树脂的含有光酸产生剂1的第一光致抗蚀剂层210涂布到载体膜212上并进行干燥。接下来,可将光致抗蚀剂树脂的含有疏水性试剂的第二光致抗蚀剂层214涂布到第一光致抗蚀剂层210上并进行干燥。然后可根据步骤62(图3)从载体膜212移除复合干膜层200,并将复合干膜层200积层到半导体衬底110的装置表面114,如图6所示。
参照图7,可通过掩模222,将第一光致抗蚀剂层210曝光于e线、g线、h线、i线、中UV或深UV的辐射220,以在复合膜层200的第一光致抗蚀剂层210中形成流动特征。接下来,如图8所示,通过第二掩模226,将复合膜层200的第二光致抗蚀剂层214曝光于e线、g线、h线、i线、中UV或深UV的辐射224,以在复合膜层200的第二光致抗蚀剂层214中提供喷嘴特征。图8示出复合膜层200中的未显影的流动特征228及未显影的喷嘴特征230。
在将复合膜层200曝光于辐射之后,对复合膜层200进行加热以交联复合膜层200的被曝光区域中的光致抗蚀剂材料。然后,将显影剂溶剂施加到半导体衬底110及复合膜层200以移除未固化的光致抗蚀剂材料,从而在其中形成流体供应通道118(图4A到图4B)、流体腔室120及喷嘴孔126。在一个实施例中,利用兆声波搅拌(megasonic agitation)将包含经辐射曝光的复合膜层200的半导体衬底110放置在显影剂浴中,以溶解第一光致抗蚀剂层210及第二光致抗蚀剂层214中的未交联的材料,从而通过先前形成的流体供应通孔116来溶解来自第一光致抗蚀剂层210的未交联的材料,且溶解来自第二光致抗蚀剂层214的未交联的材料以在第二光致抗蚀剂层214中形成喷嘴孔126。用于显影剂浴中的例示性的显影剂包括:例如丁基溶纤剂乙酸酯、环己酮、甲基乙基酮、二甲苯与丁基溶纤剂乙酸酯的混合物、以及C1-6乙酸酯(例如乙酸丁酯)、或前述中的两个或更多个的组合。可使用在约200℃的温度下历时约2小时的第三加热步骤,来移除可能位于复合膜层200中的任何残余光酸产生剂。
在图9所示的替代实施例中,复合膜层240可附接到载体膜212。复合膜层240包括第一光致抗蚀剂层210,第一光致抗蚀剂层210被配制成不具有疏水性试剂。第一光致抗蚀剂层210的厚度可介于约3μm到约50μm的范围。复合膜层240也可包含第二光致抗蚀剂层242,第二光致抗蚀剂层242被配制成包含疏水性试剂。第二光致抗蚀剂层242可具有介于约3μm到50μm的范围的厚度。在一个实施例中,可将不具有疏水性试剂的第三光致抗蚀剂层244施加到第二光致抗蚀剂层242。第三光致抗蚀剂层244可具有介于约3μm到约50μm的范围的厚度,且可通过掩模被曝光于e线、g线、h线、i线、中UV或深UV辐射,以在第三光致抗蚀剂层244中形成流动特征。
第一光致抗蚀剂层210、第二光致抗蚀剂层242及第三光致抗蚀剂层244的代表性配方,示于下表3及表4中。
表3
表4
通过使用上述复合膜层200及复合膜层240,可避免使用制作流体喷射头的多个粘附促进步骤。此外,如上所示,每一层可具有相同的或不同的光酸产生剂,且因此可利用不同的辐射曝光波长进行成像。由于除了光酸产生剂、少量的绿色染料及疏水性试或不含疏水性试剂外,每一层的配方是相似的,因此光致抗蚀剂材料将混合并在各层之间的界面处附着到彼此,而不需要粘附促进层。绿色染料的量在各个层中可为不同的,以进一步增强对所述层成像所需要的辐射波长。多个光酸产生剂干膜层也允许对干膜的上部层中的开放区域下方的结构进行成像。
每一层可依据疏水性试剂存在还是不存在,而对水性流体具有更高或更低的亲和力。因此,具有多个表面能的MEMS装置或纳米装置,可使得能够定制特定层的表面张力/能量,以有助于形成微过滤器、微分离器、微筛及其他微米及纳米级流体处理结构。各种流体的内部流速可在此种装置内进行调整及定制。因此,本公开的实施例可应用于若干领域,这是因为纳米级液体流动及有效粘度,可通过用作容器或流体管道的材料的类型进行显著地操纵。MEMS装置或纳米装置的尺寸越小,液体表面相互作用力的影响越大。因此,本公开将这类装置构造在特定芯片上。可为亲水的或疏水的例如氨基酸等材料,可在这种装置中进行组合及分离。
通过阐述本公开的各个方面及实施例以及其若干优点,本领域技术人员将认识到,在不背离权利要求的精神及范围内,所述实施例易于进行各种修改、替换及修正。
Claims (15)
1.一种三维结构,其特征在于,所述三维结构包括:
复合膜层,包括:
第一光致抗蚀剂层,不具有疏水性试剂;以及
至少一第二光致抗蚀剂层,包含所述疏水性试剂,
其中,所述复合膜层在所述第一光致抗蚀剂层与所述第二光致抗蚀剂层之间不具有粘附促进层。
2.根据权利要求1所述的三维结构,其特征在于,所述复合膜层还包括:
至少一第三光致抗蚀剂层,不具有所述疏水性试剂。
3.根据权利要求1或2所述的三维结构,其特征在于,
所述复合膜层具有介于约6μm到约150μm的范围的厚度。
4.根据权利要求1到3中任一项所述的三维结构,其特征在于,
所述复合膜层的所述第一光致抗蚀剂层是利用第一辐射进行成像,
所述第一辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
5.根据权利要求1到4中任一项所述的三维结构,其特征在于,
所述复合膜层的所述第二光致抗蚀剂层是利用第二辐射进行成像,
所述第二辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
6.一种由复合膜层制作三维结构的方法,其特征在于,所述方法包括:
将第一光致抗蚀剂层施加到载体膜,所述第一光致抗蚀剂层不具有疏水性试剂;
对所述第一光致抗蚀剂层进行干燥,以提供经干燥的第一光致抗蚀剂层;
将第二光致抗蚀剂层施加到所述经干燥的第一光致抗蚀剂层,所述第二光致抗蚀剂层包含所述疏水性试剂;
对所述第二光致抗蚀剂层进行干燥,以提供经干燥的第二光致抗蚀剂层,其中,所述经干燥的第一光致抗蚀剂层与所述经干燥的第二光致抗蚀剂层形成不具有中间粘附层的所述复合膜层;
将所述复合膜层积层到衬底的表面;
将所述复合膜层曝光于辐射,所述辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组;以及
同时对所述复合膜层进行显影,以提供所述三维结构。
7.根据权利要求6所述的方法,其特征在于,还包括:
将第三光致抗蚀剂层施加到所述经干燥的第二光致抗蚀剂层,以提供所述复合膜层,
其中,所述第三光致抗蚀剂层不具有所述疏水性试剂。
8.根据权利要求6或7所述的方法,其特征在于,
所述复合膜层具有介于约6μm到约150μm的范围的厚度。
9.根据权利要求6到8中任一项所述的方法,其特征在于,
所述复合膜层的所述第一光致抗蚀剂层被曝光于第一辐射,
所述第一辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
10.根据权利要求6到9中任一项所述的方法,其特征在于,
所述复合膜层的所述第二光致抗蚀剂层被曝光于第二辐射,
所述第二辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
11.一种流体喷射装置,其特征在于,所述流体喷射装置包括:
流体喷射头,所述流体喷射头包括:
半导体衬底,包含:位于所述半导体衬底的装置表面上的多个流体喷射致动器、以及蚀刻穿过所述半导体衬底的一个或多个流体供应通孔;
粘附促进层,施加到所述半导体衬底的所述装置表面;
复合膜层,设置在所述粘附促进层上,其中,所述复合膜层包括:
第一光致抗蚀剂层,不具有疏水性试剂;以及
至少一第二光致抗蚀剂层,包含所述疏水性试剂;且
其中,所述复合膜层在所述第一光致抗蚀剂层与所述第二光致抗蚀剂层之间不具有所述粘附促进层;以及
控制器,用于激活所述流体喷射头。
12.根据权利要求11所述的流体喷射装置,其特征在于,所述复合膜层还包括:
至少一第三光致抗蚀剂层,不具有所述疏水性试剂。
13.根据权利要求11或12所述的流体喷射装置,其特征在于,
所述复合膜层具有介于约6μm到约150μm的范围的厚度。
14.根据权利要求11到13中任一项所述的流体喷射装置,其特征在于,
所述复合膜层的所述第一光致抗蚀剂层是利用第一辐射进行成像,
所述第一辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
15.根据权利要求11到14中任一项所述的流体喷射装置,其特征在于,
所述复合膜层的所述第二光致抗蚀剂层是利用第二辐射进行成像,
所述第二辐射具有的曝光波长选自于由e线、g线、h线、i线、中紫外线及深紫外线组成的群组。
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