CN115555234B - 一种基于近场电纺制造100nm以下聚合物喷针的方法 - Google Patents

一种基于近场电纺制造100nm以下聚合物喷针的方法 Download PDF

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CN115555234B
CN115555234B CN202211232844.XA CN202211232844A CN115555234B CN 115555234 B CN115555234 B CN 115555234B CN 202211232844 A CN202211232844 A CN 202211232844A CN 115555234 B CN115555234 B CN 115555234B
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邹赫麟
徐良
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Abstract

本发明公开了一种基于近场电纺的纳米喷针制造方法，属于微机电研究领域。该方法通过采用近场电纺聚氧化乙烯溶液在硅片上获得纳米线条，然后以聚氧化乙烯纳米线条为掩膜，电感耦合等离子体刻蚀硅获得硅纳米凸模具；在硅纳米凸模具上，旋涂SU‑8胶紫外光刻出喷针微通道部分，形成硅‑SU‑8复合喷针模具；再通过PDMS浇筑，即可获得未键合PDMS喷针；最后通过氧等离子体键合将未键合PDMS喷针与盖板键合，获得PDMS聚合物喷针。本发明工艺简单，成本低，生产效率高并且易于实现。

Description

一种基于近场电纺制造100nm以下聚合物喷针的方法
技术领域
本发明属于微机电研究领域，涉及一种基于近场电纺制造100nm以下聚合物喷针的方法。
背景技术
随着纳米科学技术的不断进步，纳米器件在灵敏性、选择性和能量密度等方面获得了极大的提高，在电子信息、生物医疗、环境能源等领域具有广泛的应用前景。当前，纳米尺度结构的制造主要依赖于具有纳米分辨率的设备，如电子束光刻、聚焦离子束直写、激光直写等高精度设备，但是这些设备昂贵，制造成本高。电液动力射流打印是一种高分辨、高效率、低成本的增材制造技术。研究表明，电液动力射流打印具有尺度效应，在低粘度、小分子墨水的沉积中表现的愈加显著。因此，进一步减小喷针内径到纳米尺度是实现低成本、纳米分辨率电液动力打印的有效方法。
当前，Sutter型热拉仪能可靠拉制300nm～2μm尺度的石英喷针，但是当喷针尺度减小到100nm以下时，因拉制原理导致尺寸难以控制，同时拉制过程中喷针容易碎裂，成品率较低。近年来，聚合物以其高机械稳定性和加工灵活性被用于喷针制造上，如用于电喷雾质谱发射器的喷针即采用聚合物材料。但受限于光衍射极限，尺度仅为微米级。在聚合物纳米级通道的制造方面，有基于裂纹法和变形法等方法，虽然这些方法实现了低成本、简便的纳米通道制造，但制造过程难以控制，重复率低，难以实现批量制造。
发明内容
为解决上述问题，本发明提出一种基于近场电纺制造100nm以下聚合物喷针的方法。该方法通过采用近场电纺聚氧化乙烯溶液在硅片上获得纳米线条，然后以聚氧化乙烯纳米线为掩膜，电感耦合等离子体刻蚀硅获得硅纳米凸模具；在硅纳米模具上，旋涂SU-8胶紫外光刻出喷针微通道部分，形成硅-SU-8复合喷针模具；再通过PDMS浇筑，即可获得未键合PDMS喷针；最后通过氧等离子体键合将未键合PDMS喷针与盖板键合，获得PDMS聚合物喷针。
本发明采用的技术方案如下：
一种基于近场电纺制造100nm以下聚合物喷针的方法，包括以下三个步骤：制造硅纳米模具、制造硅-SU-8复合喷针模具、制造聚合物纳米喷针。
第一步，制造硅纳米模具，包括步骤(1)和(2)；
(1)利用近场电纺在硅片上制造聚氧化乙烯(PEO)纳米线条
对近场电纺基底硅片依次使用丙酮、乙醇和去离子水清洗。电纺墨水选用含1.0～2.0wt％PEO(分子量为5×106)的去离子水溶液。采用内径为110μm的不锈钢喷针进行电纺，硅片安装在移动台上，喷针到硅片之间距离为1～1.3mm，同时注射泵注入的流量为1～1.5μL/h；连续调控电压在180～420V变化，控制基板的运动速度在2.5～5mm/s，控制移动台的单步进给量在10～30μm，获得间距为10～30μm的纳米级PEO阵列线条。
(2)利用电感耦合等离子体硅刻蚀方法获得硅纳米凸模具
在步骤(1)获得的硅片上进行电感耦合等离子体刻蚀。刻蚀参数为：刻蚀上电极功率为400W，下电极功率为50W，刻蚀气体为SF6，刻蚀时间控制在10～30s，控制刻蚀深度为60～100nm。刻蚀过程中，PEO纳米线条覆盖的硅被保护而不会被刻蚀，未被PEO纳米线条覆盖的硅被刻蚀掉。刻蚀完成后，放置在去离子水中浸泡5min去除残留的PEO。完成后放置在120℃的热板上烘干得到硅纳米凸模具。
第二步，制造硅-SU-8复合喷针凸模具，包括步骤(3)；
(3)紫外光刻SU-8胶获得硅-SU-8复合喷针凸模具
在步骤(2)获得的硅纳米凸模具上进行氧等离子体处理以提高其与SU-8胶的结合力，处理参数为20W，20s。处理完成后旋涂一层40～50μm厚的SU-8胶。旋涂参数为，首先在600r/min的条件下旋涂9s，然后在3000～4000r/min的条件下旋涂30s。完成后，对SU-8胶4进行阶梯前烘固化，即65℃时烘30min，70℃时烘10min，75℃时烘10min，80℃时烘10min，最后在85℃烘30min。烘干后，采用含有喷针微通道图形的掩膜版进行紫外曝光，曝光剂量为528～650mJ/cm2。曝光后放置在85℃的热板后烘2min。后烘完成后，在SU-8胶显影液中显影70～80s，获得喷针的微米通道。硅纳米凸台与SU-8微通道凸台的联通构成硅-SU-8复合喷针模具。
第三步，聚合物纳米喷针制造，包括步骤(4)和(5)；
(4)浇筑获得PDMS喷针
将1～2mL三甲基氯硅烷TMCS放入干燥塔中，静置3～5min，使干燥塔内充满TMCS蒸汽。将步骤(3)获得的硅-SU-8复合喷针模具放入干燥塔内20～40min进行TMCS处理，以形成PDMS反粘层。完成后，将体积比为4:1～12:1的PDMS和固化剂混合后倒入到喷针模具上，置于压力为10Pa的真空箱中抽真空1h以保证液态PDMS完全地填充在喷针模具上。然后，将带有PDMS的喷针模具放置到65℃的烘箱中4h以固化。最后，将烘干的PDMS从喷针模具中缓慢剥离获得未键合的PDMS喷针。
(5)氧等离子体键合封装PDMS喷针
将比例为10:1的PDMS和固化剂混合后浇筑在PMMA平基底上，并放置在85℃的烘箱中2h以固化，固化后获得PDMS平盖板。对平盖板采用1mm打孔器打出储液池的孔。然后对步骤(4)获得的PDMS喷针和打完孔的平盖板进行氧等离子体处理，处理功率为15W,处理时间为15～25s。处理完成的将PDMS在常温下贴合，镊子轻轻按压键合，完成PDMS聚合物喷针的封装与制造。
本发明采用成本低廉的近场电纺和电感耦合等离子体硅刻蚀即可获得小于100nm的硅纳米凸模具，同时，该方法制造的喷针模具可多次重复浇筑。采用本发明的方法制造纳米喷针具有操作简单、价格低廉，生产效率高等有益效果。
附图说明
图1是本发明基于近场电纺的硅纳米模具制造流程图。
图2是本发明硅-SU8复合喷针凸模具制造流程图。
图3是本发明聚合物纳米喷针制造流程图。
图4是本发明键合后聚合物纳米喷针结构示意图。
图中：1硅片；2聚氧化乙烯(PEO)纳米线条；3硅纳米凸模具；
4SU-8胶；5紫外光；6光刻掩膜版；7硅-SU-8复合喷针凸模具；8PDMS；
9未键合的聚合物PDMS微纳跨尺度喷针芯片；10PMMA；11PDMS盖板；
12PDMS聚合物纳米喷针。
具体实施方式
下面结合附图对本发明的实施例作详细说明。
如图1所示，硅纳米模具制造流程步骤如下：
(a)采用硅片1作为近场电纺的沉积基底，墨水选用含1.0～2.0wt％PEO(分子量为5×106)的去离子水溶液。电纺前，作为沉积衬底的硅片1依次经过丙酮、乙醇和去离子水的清洗。采用内径为110μm的不锈钢喷针进行电纺，硅片1安装在移动台上，保持喷针到硅片1之间的距离为1～1.3mm，同时注射泵注入的流量为1～1.5μL/h。调整电纺电压在180～420V变化，移动台速度在2.5～5mm/s变化，实现PEO纳米线条2的连续可调控沉积。
(b)控制步骤(a)中的步进量在10～30μm，获得大面积、间距为10～30μm均匀的阵列式PEO纳米线2。
(c)将沉积有PEO纳米线条2的硅片1置于电感耦合等离子体刻蚀系统中刻蚀硅。刻蚀参数为：刻蚀上电极功率为400W，下电极功率为50W，刻蚀气体为SF6，刻蚀时间控制在10～30s，刻蚀深度为60～100nm。
(d)步骤(c)中刻蚀完的硅片1置于去离子水中浸泡5min去除残留的PEO，完成后放置在120℃的热板上烘干，即可获得不同深度的硅纳米凸模具3。
如图2所示，硅-SU-8复合喷针凸模具制造流程步骤如下：
(a)将尺寸在100nm以下的硅纳米凸模具3进行氧等离子体处理以提高其与胶的结合力，处理功率为20W，处理时间为20s，处理完后接触角可达15°。
(b)对步骤(a)氧等离子体处理后的硅纳米凸模具3高速旋涂一层40～50μm厚的负性SU-8胶4。首先在600r/min的条件下旋涂9s，然后在3000～4000r/min条件下旋涂30s。旋涂完成后，对SU-8胶4进行阶梯前烘固化，即65℃时烘30min，70℃时烘10min，75℃时烘10min，80℃时烘10min，最后在85℃时烘30min。
(c)采用含有喷针微通道图形的光刻掩膜版6，对固化的SU-8胶4进行紫外光5曝光，曝光剂量为528～650mJ/cm2。曝光后放置在85℃的热板后烘2min。
(d)后烘完成后，在SU-8胶4显影液中显影70～80s，获得微米通道。硅纳米通道与SU-8微通道的联通获得硅-SU-8复合喷针凸模具7。
如图3所示，聚合物纳米喷针制造流程步骤如下：
(a)对硅-SU-8复合喷针凸模具7进行TMCS气氛处理以保证PDMS浇筑过程中无损脱模。首先将1～2mL三甲基氯硅烷TMCS放入干燥塔中，静置3～5min，使干燥塔内充满TMCS蒸汽。然后，将模具7放入干燥塔内20～40min，以形成PDMS反粘层。TMCS气氛处理后，将体积比为4:1～12:1的PDMS和固化剂混合，倒入在模具7上，然后置于10Pa以下的真空环境中1h，去除PDMS 8内部气泡，同时确保PDMS 8能高精度的复制喷针模具中的纳米结构。真空完成后，再放置到65℃的烘箱中4h以固化PDMS 8。
(b)冷却至室温后，将PDMS 8缓慢从硅-SU-8复合喷针模具7上揭除，揭除后得到未键合的聚合物PDMS微纳跨尺度喷针芯片9。
(c)浇筑PDMS纳米喷针的平盖板。在PMMA10基板上倒入1mm厚的混合比例为10:1的PDMS 8，然后置于10Pa以下的真空环境中20min，去除PDMS 8内部气泡。真空后，再放置到85℃的烘箱中2h以固化PDMS 8。
(d)冷却至室温后，揭除PDMS 8，得到PDMS平盖板11。
(e)对步骤(d)获得的PDMS盖板11采用1mm的打孔器打出供液孔，然后与步骤(b)获得的未键合的聚合物PDMS微纳跨尺度喷针芯片9一起进行氧等离子体处理，处理功率为15W，处理时间为15～25s。处理完成后将盖板11与芯片9贴合，镊子轻轻按压键合，完成PDMS聚合物纳米喷针12制作(如图3)。
凡是利用本发明及附图内容的等效结构或等效工艺流程，或直接或间接运用在其它相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (7)

1.一种基于近场电纺制造100 nm以下聚合物喷针的方法，包括三部分：硅纳米模具制造、硅-SU-8复合喷针模具制造和聚合物纳米喷针制造；
第一步，制造硅纳米模具，包括步骤（1）和（2）；
（1）利用近场电纺在硅片上制造聚氧化乙烯（PEO）纳米线条
对近场电纺基底硅片依次使用丙酮、乙醇和去离子水清洗；采用不锈钢喷针进行电纺；连续调控电压在180 ~ 420V变化，获得间距为10~ 30μm的纳米级PEO阵列线条；
（2）利用电感耦合等离子体硅刻蚀方法获得硅纳米凸模具
在步骤（1）获得的硅片上进行电感耦合等离子体刻蚀，将PEO纳米线条转移至硅基底；刻蚀完成后，放置在去离子水中浸泡5 min去除残留的PEO；完成后放置在120℃的热板上烘干得到硅纳米凸模具；
第二步，制造硅-SU-8复合喷针凸模具，包括步骤（3）；
（3）紫外光刻SU-8胶获得硅-SU-8复合喷针凸模具
在步骤（2）获得的硅纳米凸模具上进行氧等离子体处理以提高其与SU-8胶的结合力，处理参数为20W，20 s；处理完成后旋涂一层40 ~ 50 μm厚的SU-8胶；
完成后，对SU-8胶4进行阶梯前烘固化，即65 ℃时烘30 min，70℃时烘10min，75℃时烘10min，80 ℃时烘10 min，最后在85 ℃烘30 min；
烘干后，采用含有喷针微通道图形的掩膜版进行紫外曝光，曝光剂量为 528 ~650 mJ/cm2；
曝光后放置在85℃的热板后烘2 min；后烘完成后，在SU-8胶显影液中显影 70~80 s，获得喷针的微米通道；硅纳米凸台与SU-8微通道凸台的联通构成硅-SU-8复合喷针模具；
第三步，聚合物纳米喷针制造，包括步骤（4）和（5）；
（4）浇筑获得PDMS喷针
将1~2 mL三甲基氯硅烷TMCS 放入干燥塔中，静置3~5 min，使干燥塔内充满TMCS蒸汽；将步骤（3）获得的硅-SU-8复合喷针模具放入干燥塔内20~40 min进行TMCS处理，以形成PDMS反粘层；完成后，将体积比为4:1~12:1的PDMS和固化剂混合后倒入到喷针模具上，置于压力为10 Pa的真空箱中抽真空1 h以保证液态PDMS完全地填充在喷针模具上；然后，将带有PDMS的喷针模具放置到65 ℃的烘箱中4 h以固化；最后，将烘干的PDMS从喷针模具中缓慢剥离获得未键合的PDMS喷针；
（5）氧等离子体键合封装PDMS喷针
将比例为10:1的PDMS和固化剂混合后浇筑在PMMA平基底上，并放置在85 ℃的烘箱中2h以固化，固化后获得PDMS平盖板；对平盖板采用1 mm打孔器打出储液池的孔；然后对步骤（4）获得的PDMS喷针和打完孔的平盖板进行氧等离子体处理，处理功率为15 W,处理时间为15 ~25s；处理完成的将PDMS 在常温下贴合，镊子轻轻按压键合，完成PDMS聚合物喷针的封装与制造。
2.根据权利要求1所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，步骤（1）中，选用的墨水为PEO的去离子水溶液，其中PEO的分子量为5×106，PEO的质量分数为1~2 wt%。
3.根据权利要求1所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，步骤（1）中，采用内径为110 μm的不锈钢喷针进行电纺，硅片安装在移动台上，喷针到硅片之间距离为1~ 1.3mm，同时注射泵注入的流量为1~1.5μL/h；连续调控电压在180 ~420V变化，控制基板的运动速度在2.5 ~ 5 mm/s，控制移动台的单步进给量在10~ 30 μm，获得间距为10~ 30μm的纳米级PEO阵列线条。
4.根据权利要求1-3任一所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，步骤（2）中，刻蚀参数为：刻蚀上电极功率为400 W，下电极功率为50 W，刻蚀气体为SF6，刻蚀时间控制在10 ~30 s，控制刻蚀深度为60~100 nm。
5.根据权利要求4所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，步骤（3）中，旋涂参数为，首先在600 r/min的条件下旋涂9 s，然后在3000 ~4000r/min的条件下旋涂30 s。
6.根据权利要求1或2或3或5所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，近场电纺的墨水可替换为以PEO 为本体的掺杂墨水，其中PEO的分子量为5×106，PEO的质量分数为1~2wt%。
7.根据权利要求6所述的一种基于近场电纺制造100 nm以下聚合物喷针的方法，其特征在于，所述的掺杂墨水为掺纳米银粒子或锆钛酸铅凝胶的PEO溶液。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003138393A (ja) * 2001-08-23 2003-05-14 Kanagawa Prefecture 金属部品の製造方法及び金属部品
CN103895345A (zh) * 2014-03-27 2014-07-02 华中科技大学 一种多功能电流体喷墨打印系统及方法
CN104849957A (zh) * 2015-04-29 2015-08-19 大连理工大学 一种带有纳米尺度通道的su-8胶电液动力射流喷针制造方法
CN111438944A (zh) * 2020-04-02 2020-07-24 吉林大学 一种基于su-8胶电解法制备纳米尺度电射流喷头的方法
CN111977611A (zh) * 2020-08-31 2020-11-24 大连理工大学 一种微纳跨尺度聚合物喷针的制造方法
CN113351268A (zh) * 2021-06-18 2021-09-07 华南理工大学 一种基于3d打印的同轴微流控芯片及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI367857B (en) * 2007-05-09 2012-07-11 Nat Univ Tsing Hua Fluidic nano/micro array chip and chipset thereof
KR101686716B1 (ko) * 2014-12-24 2016-12-29 포항공과대학교 산학협력단 유도성장을 이용한 나노선 어레이 제조방법
US11078093B2 (en) * 2017-06-30 2021-08-03 University Of Iowa Research Foundation Surfactant-assisted synthesis of surface-functionalized nanoparticle-polymer electrospun composites

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003138393A (ja) * 2001-08-23 2003-05-14 Kanagawa Prefecture 金属部品の製造方法及び金属部品
CN103895345A (zh) * 2014-03-27 2014-07-02 华中科技大学 一种多功能电流体喷墨打印系统及方法
CN104849957A (zh) * 2015-04-29 2015-08-19 大连理工大学 一种带有纳米尺度通道的su-8胶电液动力射流喷针制造方法
CN111438944A (zh) * 2020-04-02 2020-07-24 吉林大学 一种基于su-8胶电解法制备纳米尺度电射流喷头的方法
CN111977611A (zh) * 2020-08-31 2020-11-24 大连理工大学 一种微纳跨尺度聚合物喷针的制造方法
CN113351268A (zh) * 2021-06-18 2021-09-07 华南理工大学 一种基于3d打印的同轴微流控芯片及其制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Fabrication of Si-nozzles for parallel mechano-electrospinning direct writing;Pan,YQ et al;《JOURNAL OF PHYSICS D-APPLIED PHYSICS》;第46卷(第25期);第255301页 *
SU-8微纳流控芯片制造方法及相关理论研究;孙蕾;《中国博士学位论文全文数据库 信息科技辑》(第7期);第I135-10页 *
基于静电纺丝技术的多级结构聚合物纳米纤维复合材料的研究进展;缪月娥等;《高分子学报》(第8期);第16-26页 *
脉冲电射流打印喷头设计制造技术研究;方旭;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》(第4期);第B022-594页 *

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