CN110787361A - A hollow inclined metal microneedle array and its manufacturing method based on SU-8 mold - Google Patents
A hollow inclined metal microneedle array and its manufacturing method based on SU-8 mold Download PDFInfo
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- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
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- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
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Abstract
本发明公开了一种空心倾斜金属微针阵列及其基于SU‑8模具的制造方法,属于微纳制造工艺领域。该微针阵列,金属材料为可电镀金属,空心倾斜金属微针呈斜圆锥状,倾斜角度为50°~70°;垂直高度为500μm~650μm;空心倾斜金属微针底部到尖端为等壁厚结构,壁厚为8μm~10μm;空心倾斜金属微针底部外径为150μm~250μm;空心倾斜金属微针锥角为10°~15°,空心倾斜金属微针顶部带有尖端。本发明将SU‑8模具掩膜图形转移到玻璃片上,避免了传统接触式曝光存在气隙的问题,提高到达各层光刻胶的紫外线光强,微针模具与基底结合力更强。充分利用OmniCoat,提高了SU‑8模具与玻璃片的粘附性,同时工艺后期更容易去除SU‑8模具。倾斜圆台微针经过RIE刻蚀获得尖端,实现了金属微针尖端结构。
The invention discloses a hollow inclined metal microneedle array and a manufacturing method based on a SU-8 mold, belonging to the field of micro-nano manufacturing technology. In the microneedle array, the metal material is electroplatable metal, the hollow inclined metal microneedles are inclined conical shape, the inclination angle is 50°~70°; the vertical height is 500μm~650μm; the hollow inclined metal microneedles have equal wall thickness from the bottom to the tip The structure has a wall thickness of 8 μm to 10 μm; the outer diameter of the bottom of the hollow inclined metal microneedle is 150 μm to 250 μm; the cone angle of the hollow inclined metal microneedle is 10° to 15°, and the top of the hollow inclined metal microneedle has a tip. The invention transfers the SU-8 mold mask pattern to the glass sheet, avoids the problem of air gaps in traditional contact exposure, improves the intensity of ultraviolet light reaching each layer of photoresist, and has stronger bonding force between the microneedle mold and the substrate. Making full use of OmniCoat improves the adhesion of the SU-8 mold to the glass sheet, while making it easier to remove the SU-8 mold later in the process. The tip of the inclined circular truncated microneedle was etched by RIE, and the tip structure of the metal microneedle was realized.
Description
技术领域technical field
本发明属于微纳制造工艺领域,更具体的涉及一种空心倾斜金属微针阵列及其基于SU-8模具的制造方法。The invention belongs to the field of micro-nano manufacturing technology, and more particularly relates to a hollow inclined metal micro-needle array and a manufacturing method based on a SU-8 mold.
背景技术Background technique
微针皮下注射是医疗领域的重要发展方向,微米尺度微针能够极大减少注射痛苦和针头注射恐惧,为缓慢注射和定量药物注射带来了极大便利。微针长度通常为100至1000μm,能穿透外部皮肤角质层,直接将治疗材料注入组织层。通过控制微针的长度可以确保穿透深度,不会影响位于真皮层中的多数神经纤维和血管。目前微针主要包括实心微针、空心微针、可溶解微针、水凝胶微针等。实心微针通过在微针表面涂覆药物,或者是拔出微针后贴附药物实现药物注射。可溶解微针、水凝胶微针对微针的材料要求极高,且材料强度难以控制;空心微针更加适合缓慢持续注射,可以输送不同类型的药物制剂,如溶液,悬浮液,乳液,干粉和凝胶等。Micro-needle subcutaneous injection is an important development direction in the medical field. Micro-scale micro-needles can greatly reduce the pain of injection and the fear of needle injection, and bring great convenience to slow injection and quantitative drug injection. Microneedles, typically 100 to 1000 μm in length, penetrate the outer stratum corneum of the skin and directly inject the therapeutic material into the tissue layer. Controlling the length of the microneedles ensures a depth of penetration without affecting most of the nerve fibers and blood vessels located in the dermis. At present, microneedles mainly include solid microneedles, hollow microneedles, dissolvable microneedles, and hydrogel microneedles. The solid microneedle realizes drug injection by coating the drug on the surface of the microneedle, or by attaching the drug after pulling out the microneedle. Dissolvable microneedles and hydrogel microneedles require extremely high materials, and the material strength is difficult to control; hollow microneedles are more suitable for slow and continuous injection, and can deliver different types of pharmaceutical preparations, such as solutions, suspensions, emulsions, dry powders and gel, etc.
微制造空心微针可以实现药物注射速度和用药量的可控。此外,空心微针不仅可以提供治疗,还可以从皮肤中提取生物液体用于分析、监测和生物响应功能。空心微针需要刺破皮肤进入皮下组织实现药物释放,因此微针的头部结构和强度对微针的使用具有很重要的影响。Microfabricated hollow microneedles can achieve controllable drug injection speed and dosage. In addition, hollow microneedles can not only provide therapy, but also extract biological fluids from the skin for analysis, monitoring, and biological response functions. The hollow microneedle needs to pierce the skin and enter the subcutaneous tissue to achieve drug release, so the head structure and strength of the microneedle have an important influence on the use of the microneedle.
目前空心微针主要分为聚合物微针和金属微针两类。2007年H HUANG等人利用背面曝光技术制作了带倾角的中空的异平面微针阵列(Huang H,Fu C.Differentfabrication methods of out-of-plane polymer hollow needle arrays and theirvariations.Journal of Micromechanics and Microengineering,2007)。该法利用菲涅尔衍射效应和多掩模同时曝光制备得到带尖角的聚合物微针。2007年Kabseog Kim等利用背面曝光和菲涅尔衍射效应制作出垂直圆台状的SU-8模具,并用该模具和电镀工艺制作了中空金属微针结构(Kim K,Lee J B.High aspect ratio tapered hollow metallicmicroneedle arrays with microfluidic interconnector.Microsystem Technologies,2007)。分析目前的空心微针制备工艺可以发现:利用聚合物材料较易实现空心带尖端的微针阵列,但聚合物微针的强度不高;利用SU-8模具法可制备金属微针,但顶部尖端难以实现,后期脱模工艺中SU-8模具很难去除,极大限制了此法的应用。At present, hollow microneedles are mainly divided into two categories: polymer microneedles and metal microneedles. In 2007, H HUANG et al. used back exposure technology to fabricate hollow hetero-planar microneedle arrays with dip angles (Huang H, Fu C. Different fabrication methods of out-of-plane polymer hollow needle arrays and their variations. Journal of Micromechanics and Microengineering, 2007). The method utilizes Fresnel diffraction effect and simultaneous exposure of multiple masks to prepare polymer microneedles with sharp corners. In 2007, Kabseog Kim et al. used back exposure and Fresnel diffraction effect to produce a vertical truncated SU-8 mold, and used the mold and electroplating process to make a hollow metal microneedle structure (Kim K, Lee J B. High aspect ratio tapered hollow metallicmicroneedle arrays with microfluidic interconnector. Microsystem Technologies, 2007). Analysis of the current hollow microneedle preparation process shows that: it is easier to use polymer materials to realize hollow microneedle arrays with tips, but the strength of polymer microneedles is not high; the SU-8 mold method can be used to prepare metal microneedles, but the top The tip is difficult to achieve, and the SU-8 mold is difficult to remove in the later demoulding process, which greatly limits the application of this method.
发明内容SUMMARY OF THE INVENTION
针对现有技术的以上缺点或改进需求,本发明提供了一种基于SU-8模具的空心倾斜金属微针阵列制造方法,克服了目前SU-8模具制备空心金属微针中SU-8模具难以去除,微针尖端难以实现等不足,具有结构一致性良好,微针模具与基底的粘附性强等优势。In view of the above shortcomings or improvement needs of the prior art, the present invention provides a hollow inclined metal microneedle array manufacturing method based on a SU-8 mold, which overcomes the difficulty of SU-8 molds in the current SU-8 molds for preparing hollow metal microneedles. It has the advantages of good structural consistency and strong adhesion between the microneedle mold and the substrate.
本发明提供的一种空心倾斜金属微针阵列,金属材料为可电镀金属,空心倾斜金属微针呈斜圆锥状,倾斜角度为50°~70°;垂直高度为500μm~650μm;空心倾斜金属微针底部到尖端为等壁厚结构,壁厚为8μm~10μm;空心倾斜金属微针底部外径为150μm~250μm;空心倾斜金属微针锥角为10°~15°,空心倾斜金属微针顶部带有尖端。The invention provides a hollow inclined metal microneedle array, the metal material is electroplatable metal, the hollow inclined metal microneedle is in the shape of an oblique cone, the inclination angle is 50° to 70°, the vertical height is 500 μm to 650 μm; The bottom of the needle to the tip is of equal wall thickness, and the wall thickness is 8 μm to 10 μm; the outer diameter of the bottom of the hollow inclined metal microneedle is 150 μm to 250 μm; the cone angle of the hollow inclined metal microneedle is 10° to 15°, and the top of the hollow inclined metal microneedle is 10° to 15°. with tip.
本发明提出的一种基于SU-8模具的空心倾斜金属微针阵列制造方法,主要包括光刻、电镀、溅射等微加工工艺,由电镀在SU-8模具表面的金属层,再经顶部刻蚀、去除SU-8模具得到,具体制备方法包括以下步骤:The invention proposes a method for manufacturing a hollow inclined metal microneedle array based on SU-8 mold, which mainly includes micromachining processes such as photolithography, electroplating, and sputtering. It is obtained by etching and removing the SU-8 mold, and the specific preparation method includes the following steps:
步骤一:在玻璃基底上制备SU-8模具,包括以下子步骤:Step 1: Preparation of SU-8 mold on glass substrate, including the following sub-steps:
1.1玻璃基底上制备SU-8模具掩膜图形1.1 Preparation of SU-8 mold mask pattern on glass substrate
将厚度为500μm~1000μm玻璃片1充分热烘或氧等离子清洗,去除基底表面的有机物;然后在玻璃片表面溅射一层金属铬;在铬金属层上旋涂正胶,曝光、显影后露出需要腐蚀的铬,在金属铬腐蚀液中腐蚀后得到SU-8模具掩膜图形层4。Fully heat the glass sheet 1 with a thickness of 500 μm to 1000 μm or clean it with oxygen plasma to remove the organic matter on the surface of the substrate; then sputter a layer of metallic chromium on the surface of the glass sheet; spin-coat positive glue on the chromium metal layer, expose it after exposure and development Chromium that needs to be etched is etched in a metallic chromium etching solution to obtain the SU-8 mold
1.2在玻璃片表面制备SU-8模具底部牺牲层1.2 Preparation of the sacrificial layer at the bottom of the SU-8 mold on the surface of the glass sheet
将样件清洗并充分热烘,在样件无金属铬的一面旋涂OmniCoat作为SU-8模具底部牺牲层2并充分热烘。OmniCoat作为一种SU-8专用的增粘/去胶助剂,有利于增强SU-8模具与玻璃基底的粘附性,同时利于去除固化后的SU-8。The sample was cleaned and fully heat-baked, and OmniCoat was spin-coated on the chromium-free side of the sample as the
1.3背面倾斜曝光1.3 Back tilt exposure
在步骤1.2得到样件的OmniCoat面旋涂第一层SU-8光刻胶3,厚度为1μm~2μm,然后进行正面垂直无掩模曝光(图2a);在同一面上再旋涂第二层SU-8光刻胶5,厚度为500μm~650μm,第二层光刻胶5厚度决定SU-8模具上微针垂直高度及空心倾斜金属微针垂直高度H,第二层光刻胶层5经充分前烘后,将样件置于紫外曝光灯下,SU-8模具掩膜图形层4朝向紫外光灯,利用夹具使样件与紫外光夹角β为40°~90°(图2c),样件与紫外光夹角β决定SU-8模具上微针的倾斜角度及空心倾斜金属微针倾斜角度α,然后经后烘、显影得到SU-8模具6。Spin-coat the first layer of SU-8
由于紫外光在不同介质中的折射率不同,SU-8模具上微针的倾斜角度主要由入射角、SU-8光刻胶和入射介质的折射系数决定,在空气介质中倾斜曝光时,SU-8模具上微针的倾斜角度为54°~90°。因紫外线在甘油和SU-8光刻胶中的折射率接近,在甘油介质中进行背面倾斜曝光时,SU-8模具上微针的倾斜角度为19°~90°。因此在制备倾斜角度小于54°的微针模具时,需将前述样件浸没在甘油介质中,然后进行背面倾斜曝光(图2d)。Due to the different refractive indices of UV light in different media, the tilt angle of the microneedles on the SU-8 mold is mainly determined by the incident angle, the refractive index of the SU-8 photoresist and the incident medium. The inclination angle of the microneedles on the -8 mold is 54° to 90°. Because the refractive index of ultraviolet light in glycerol and SU-8 photoresist is close, when the backside oblique exposure is performed in glycerol medium, the inclination angle of the microneedles on the SU-8 mold is 19°-90°. Therefore, when preparing a microneedle mold with an inclination angle of less than 54°, it is necessary to immerse the aforementioned sample in glycerol medium, and then perform oblique exposure on the back side (Fig. 2d).
在得到的SU-8模具表面用喷胶机喷涂一层OmniCoat,然后置于恒温箱中热烘。SU-8模具微针表面OmniCoat作用与步骤(1.2)中SU-8模具结构底部牺牲层一样,利于去除固化后的SU-8。A layer of OmniCoat was sprayed on the surface of the obtained SU-8 mold with a glue sprayer, and then placed in an incubator for thermal drying. The function of OmniCoat on the surface of the SU-8 mold microneedle is the same as that of the sacrificial layer at the bottom of the SU-8 mold structure in step (1.2), which is beneficial to remove the cured SU-8.
在背面曝光中,与玻璃片接触的光刻胶能充分吸收紫外光,有助于提高SU-8模具与玻璃基底的粘附性;玻璃片上铬图形层与光刻胶底部之间的距离导致光刻中的菲涅尔衍射增强,曝光中与玻璃片接触的SU-8胶层向外,紫外光分布直径急剧收缩,紫外线光强迅速减小,最终SU-8模具上的微针呈斜圆台状;将SU-8模具掩模版图形复制到玻璃片上,消除了接触曝光中掩模版和玻璃片间存在的气隙,提高了SU-8模具的一致性。In back exposure, the photoresist in contact with the glass sheet can fully absorb ultraviolet light, which helps to improve the adhesion of the SU-8 mold to the glass substrate; the distance between the chrome pattern layer on the glass sheet and the bottom of the photoresist causes The Fresnel diffraction in lithography is enhanced, the SU-8 adhesive layer in contact with the glass sheet during exposure is outward, the diameter of the ultraviolet light distribution shrinks sharply, the ultraviolet light intensity decreases rapidly, and finally the microneedles on the SU-8 mold are inclined. Conesus-shaped; the SU-8 mold reticle pattern is copied to the glass sheet, eliminating the air gap that exists between the reticle and the glass sheet in contact exposure, improving the consistency of the SU-8 mold.
步骤二:在SU-8模具表面制备空心倾斜金属微针;包括以下子步骤:Step 2: Preparation of hollow inclined metal microneedles on the surface of the SU-8 mold; including the following sub-steps:
2.1在SU-8模具表面溅射沉积金属种子层2.1 Sputter deposition of metal seed layer on the surface of SU-8 mold
在步骤1.3得到喷涂OmniCoat的SU-8模具6上溅射沉积金属种子层7,厚度为100nm~200nm,溅射中需确保样件与金属沉积方向的夹角为180°-α,SU-8模具上微针与金属沉积方向平行(图2e),确保SU-8模具上微针外部完全被沉积的金属种子层7包裹。On the SU-8
2.2在金属种子层表面电镀金属层,形成倾斜金属微针结构层2.2 Electroplating a metal layer on the surface of the metal seed layer to form an inclined metal microneedle structure layer
将样件放入可电镀金属的电解质溶液中进行电镀,电镀金属层厚度为8μ~10μm,形成倾斜金属微针结构层8(图2f)。The sample is placed in an electroplating metal electrolyte solution for electroplating, and the thickness of the electroplated metal layer is 8 μm to 10 μm to form an inclined metal microneedle structure layer 8 ( FIG. 2 f ).
步骤三:制备倾斜金属微针顶部尖端,包括以下子步骤:Step 3: Prepare the top tip of the inclined metal microneedle, including the following sub-steps:
3.1制备SU-8模具上倾斜金属微针顶部尖端掩模3.1 Preparation of SU-8 mold on the top tip mask of inclined metal microneedles
在步骤2.2得到的倾斜金属微针结构层8表面涂覆SU-8光刻胶,然后将其置于热板上热烘,使SU-8胶层充分平坦,然后将样件置于显微镜下观察SU-8光刻胶面与SU-8模具微针顶部垂直距离d,重复前述旋涂和热烘,直至SU-8光刻胶面比SU-8模具微针顶部垂直距离d为50μm~70μm(图2g)。Coat the surface of the inclined metal
将样件涂胶面置于紫外光灯下进行无掩模垂直曝光,曝光量为标准曝光能量的1/4~1/3,然后进行正常的热烘,得到.SU-8模具上微针顶部倾斜尖端掩模9。光刻胶曝光后可耐受温度得到提升,不充分曝光有利于SU-8模具上微针顶部倾斜尖端掩模9的去除。The glued surface of the sample is placed under an ultraviolet lamp for maskless vertical exposure, and the exposure amount is 1/4 to 1/3 of the standard exposure energy, and then normal heat baking is performed to obtain the microneedles on the .SU-8 mold. Top sloped
3.2制备SU-8模具上倾斜金属微针顶部倾斜尖端3.2 Preparation of SU-8 molds on top of sloping metal microneedles with sloping tips
将步骤3.1处理后的样件进行第一次RIE刻蚀,刻蚀功率为80W~120W,氧气流量10cm3/min~40cm3/min,氧气气压0.5Pa~15Pa,刻蚀中样件与刻蚀方向的夹角γ为60°~70°,刻蚀掉倾斜金属微针结构层8顶部固化的SU-8胶层。The sample processed in step 3.1 is subjected to the first RIE etching, the etching power is 80W ~ 120W, the oxygen flow rate is 10cm 3 /min ~ 40cm 3 /min, and the oxygen pressure is 0.5Pa ~ 15Pa. The included angle γ of the etching direction is 60°˜70°, and the SU-8 adhesive layer cured on the top of the inclined metal
保持样件与刻蚀方向的夹角不变,将样件置于含氟气体(如CF4,O2)进行第二次RIE刻蚀,去除SU-8模具上微针顶部表面的倾斜金属微针结构层和电镀金属层,直至露出SU-8模具(图2h)。因为SU-8模具上的微针均为倾斜圆台,在进行第二次RIE刻蚀中,SU-8模具上的微针顶部正下方倾斜金属微针结构层被遮挡,无法被刻蚀,最终形成尖端结构(图2h)。样件与刻蚀方向的夹角γ可增大遮挡金属的面积,调整微针尖端的形貌。Keep the angle between the sample and the etching direction unchanged, place the sample in a fluorine-containing gas (such as CF 4 , O 2 ) to perform a second RIE etching to remove the inclined metal on the top surface of the microneedle on the SU-8 mold Microneedle structure layer and electroplated metal layer until the SU-8 mold is exposed (Fig. 2h). Because the microneedles on the SU-8 mold are all inclined circular truncated truncated cones, during the second RIE etching, the inclined metal microneedle structure layer directly below the top of the microneedles on the SU-8 mold is blocked and cannot be etched. A tip structure was formed (Fig. 2h). The angle γ between the sample and the etching direction can increase the area of the shielding metal and adjust the topography of the microneedle tip.
步骤四:去除SU-8模具Step 4: Remove the SU-8 mold
将步骤3得到的样件置于SU-8专用去胶液中,超声显影30min~50min,超声功率30W~50W,温度50℃~80℃,得到带尖端的空心倾斜金属微针阵列图(2i)。The sample obtained in
通过本发明所构思的以上技术方案与现有技术相比,能够取得以下明显进步。Compared with the prior art, the above technical solutions conceived by the present invention can achieve the following obvious progress.
1)将SU-8模具掩膜图形转移到玻璃片上,避免了传统接触式曝光存在气隙的问题,提高到达各层光刻胶的紫外线光强,微针模具与基底结合力更强。1) The SU-8 mold mask pattern is transferred to the glass sheet, which avoids the problem of air gaps in traditional contact exposure, increases the intensity of ultraviolet light reaching each layer of photoresist, and strengthens the bonding force between the microneedle mold and the substrate.
2)本发明充分利用OmniCoat,提高了SU-8模具与玻璃片的粘附性,同时工艺后期更容易去除SU-8模具。2) The present invention makes full use of OmniCoat to improve the adhesion between the SU-8 mold and the glass sheet, and at the same time, it is easier to remove the SU-8 mold in the later stage of the process.
3)倾斜圆台微针经过RIE刻蚀获得尖端,实现了金属微针尖端结构。3) The tip of the inclined circular truncated microneedle is obtained by RIE etching, and the tip structure of the metal microneedle is realized.
下面结合实施例和附图对本发明的技术方案做进一步描述,但并非对本发明技术方案限定。The technical solutions of the present invention will be further described below with reference to the embodiments and drawings, but the technical solutions of the present invention are not limited.
附图说明Description of drawings
图1:空心倾斜金属微针阵列示意图Figure 1: Schematic diagram of hollow inclined metal microneedle array
图2a:SU-8模具底部牺牲层、SU-8模具掩膜图形层、第一层SU-8光刻胶在玻璃片上的分布及第一层SU-8光刻胶正面曝光示意图Figure 2a: Schematic diagram of the sacrificial layer at the bottom of the SU-8 mold, the mask pattern layer of the SU-8 mold, the distribution of the first layer of SU-8 photoresist on the glass sheet, and the front exposure of the first layer of SU-8 photoresist
图2b:第二层SU-8光刻胶示意图Figure 2b: Schematic diagram of the second layer of SU-8 photoresist
图2c:背面倾斜曝光制备SU-8模具示意图Figure 2c: Schematic diagram of preparation of SU-8 mold by backside oblique exposure
图2d:丙三醇中背面倾斜曝光制备SU-8模具示意图Figure 2d: Schematic diagram of preparation of SU-8 mold by backside oblique exposure in glycerol
图2e:溅射沉积金属种子层示意图Figure 2e: Schematic diagram of sputter deposition of metal seed layer
图2f:电镀金属层示意图Figure 2f: Schematic diagram of electroplated metal layer
图2g:制备SU-8模具上微针顶部倾斜尖端掩模示意图Figure 2g: Schematic diagram of preparation of SU-8 mold on the top of the microneedle inclined tip mask
图2h:制备SU-8模具上微针顶部倾斜尖端示意图Figure 2h: Schematic diagram of the inclined tip on the top of the microneedle on the preparation of the SU-8 mold
图2i:带尖端的空心倾斜金属微针阵列剖面示意图Figure 2i: Schematic cross-section of a hollow inclined metal microneedle array with a tip
附图标记:Reference number:
1.玻璃片,2.SU-8模具底部牺牲层(前面为结构),3.第一层SU-8光刻胶,4.SU-8模具掩膜图形层,5.第二层SU-8光刻胶,6.SU-8模具,7.金属种子层,8.倾斜金属微针结构层,9.SU-8模具上微针顶部倾斜尖端掩模,d.SU-8光刻胶面与SU-8模具微针顶部垂直距离,H.空心倾斜金属微针垂直高度,α.SU-8模具上微针的倾斜角度及空心倾斜金属微针倾斜角度,β.样件与紫外光夹角,180°-α.样件与金属沉积方向的夹角1. Glass sheet, 2. The sacrificial layer at the bottom of the SU-8 mold (the front is the structure), 3. The first layer of SU-8 photoresist, 4. The SU-8 mold mask pattern layer, 5. The second layer of SU- 8 photoresist, 6. SU-8 mold, 7. metal seed layer, 8. slanted metal microneedle structure layer, 9. slanted tip mask on top of microneedles on SU-8 mold, d. SU-8 photoresist The vertical distance between the surface and the top of the SU-8 mold microneedle, H. The vertical height of the hollow inclined metal microneedle, α. The inclination angle of the microneedle on the SU-8 mold and the inclination angle of the hollow inclined metal microneedle, β. The sample and UV light Included angle, 180°-α. The included angle between the sample and the metal deposition direction
γ.刻蚀方向与样件夹角γ. The angle between the etching direction and the sample
具体实施方式Detailed ways
以下结合具体实施例对本发明做进一步的描述。The present invention will be further described below with reference to specific embodiments.
实施例1Example 1
参阅图2,本实施例针对的空心倾斜金属微针阵列,其微针垂直高度H为500μm;微针底部外径为150μm;微针倾斜角度α为70°;电镀金属层为镍,微针壁厚8μm;微针锥角为10°。Referring to FIG. 2 , the hollow inclined metal microneedle array in this embodiment has a vertical height H of the microneedles of 500 μm; the outer diameter of the bottom of the microneedles is 150 μm; the inclination angle α of the microneedles is 70°; The wall thickness is 8 μm; the taper angle of the microneedle is 10°.
该实施例的空心倾斜金属微针阵列制备过程如下:The preparation process of the hollow inclined metal microneedle array of this embodiment is as follows:
步骤一:在玻璃基底上制备SU-8模具,包括以下子步骤:Step 1: Preparation of SU-8 mold on glass substrate, including the following sub-steps:
1.1玻璃基底上制备SU-8模具掩膜图形1.1 Preparation of SU-8 mold mask pattern on glass substrate
将厚度为500μm石英玻璃片1氧等离子清洗;然后在石英玻璃片表面溅射一层60nm金属铬;在铬金属层上旋涂正胶,曝光、显影后露出需要腐蚀的铬,在金属铬腐蚀液中腐蚀后得到SU-8模具掩膜图形层4。The quartz glass sheet with a thickness of 500 μm is cleaned by oxygen plasma; then a layer of 60nm metal chromium is sputtered on the surface of the quartz glass sheet; After etching in liquid, the SU-8 mold
1.2在玻璃片表面制备SU-8模具底部牺牲层1.2 Preparation of the sacrificial layer at the bottom of the SU-8 mold on the surface of the glass sheet
将样件清洗并充分热烘,在样件无金属铬的一面旋涂3nm的OmniCoat作为SU-8模具底部牺牲层2,并进行充分热烘。The sample was cleaned and fully thermally baked, and 3nm OmniCoat was spin-coated on the chromium-free side of the sample as the
1.3背面倾斜曝光1.3 Back tilt exposure
在步骤1.2的OmniCoat面旋涂第一层SU-8光刻胶3,厚度为1μm,然后进行正面垂直无掩模曝光(图2a),曝光剂量为70mJ/cm2;在同一面上再旋涂第二层SU-8光刻胶5,厚度为500μm。第二层SU-8光刻胶5经充分前烘后,将样件置于紫外曝光灯下,SU-8模具掩膜图形层4朝向紫外光灯,利用夹具使样件与紫外光夹角β为55°(图2c),曝光剂量为200mJ/cm2,经后烘、显影得到SU-8模具6。A first layer of SU-8
在SU-8模具6表面用喷胶机喷涂一层OmniCoat,置于旋涂机上以3000转/分速甩胶,然后置于恒温箱中200℃热烘1分钟。Spray a layer of OmniCoat on the surface of SU-8
步骤二:在SU-8模具表面制备空心倾斜金属微针,包括以下子步骤:Step 2: Preparation of hollow inclined metal microneedles on the surface of SU-8 mold, including the following sub-steps:
2.1在SU-8模具表面溅射沉积金属种子层2.1 Sputter deposition of metal seed layer on the surface of SU-8 mold
在步骤1.3得到样件的SU-8模具6上溅射沉积金属种子层7,厚度为100nm,溅射中需确保样件与金属沉积方向的夹角为110°,SU-8模具上微针与金属沉积方向平行(图2e),确保SU-8模具上微针外部完全被沉积的金属种子层7包裹。On the SU-8
2.2在金属种子层表面电镀金属层,形成倾斜金属微针结构层2.2 Electroplating a metal layer on the surface of the metal seed layer to form an inclined metal microneedle structure layer
将样件放入金属镍的电解质溶液中进行电镀,电镀金属层厚度为8μm,形成倾斜金属微针结构层8(图2f)。The sample was placed in an electrolyte solution of metallic nickel for electroplating, and the thickness of the electroplated metal layer was 8 μm to form an inclined metal microneedle structure layer 8 (FIG. 2f).
步骤三:制备倾斜金属微针顶部尖端,包括以下子步骤:Step 3: Prepare the top tip of the inclined metal microneedle, including the following sub-steps:
3.1制备SU-8模具上倾斜金属微针顶部尖端掩模3.1 Preparation of SU-8 mold on the top tip mask of inclined metal microneedles
在步骤2.2得到样件的倾斜金属微针结构层8表面涂覆SU-8光刻胶,然后将其置于热板上热烘,使SU-8胶层充分平坦,然后将样件置于显微镜下观察SU-8光刻胶面与SU-8模具微针顶部垂直距离d,重复前述旋涂和热烘,直至SU-8光刻胶面比SU-8模具微针顶部垂直距离为50μm(图2g)。The surface of the inclined metal
将样件涂胶面置于紫外光灯下进行无掩模垂直曝光,曝光量为200mJ/cm2,然后进行正常的热烘,得到得到倾斜金属微针顶部尖端掩模9。The glue-coated surface of the sample is placed under an ultraviolet lamp for maskless vertical exposure, and the exposure amount is 200 mJ/
3.2制备SU-8模具上倾斜金属微针顶部倾斜尖端3.2 Preparation of SU-8 molds on top of sloping metal microneedles with sloping tips
将步骤3.1处理后的样件进行第一次RIE刻蚀,刻蚀功率为80W,氧气流量10cm3/min,氧气气压0.5Pa,刻蚀中样件与刻蚀方向的夹角γ为60°,刻蚀掉倾斜金属微针结构层8顶部固化的SU-8胶层。The sample processed in step 3.1 was subjected to the first RIE etching, the etching power was 80W, the oxygen flow rate was 10cm 3 /min, the oxygen pressure was 0.5Pa, and the included angle γ between the sample and the etching direction during the etching was 60° , and the SU-8 adhesive layer cured on the top of the inclined metal
保持样件与刻蚀方向的夹角不变,将样件置于含氟气体(CF4、O2)进行第二次RIE刻蚀,去除SU-8模具上微针顶部表面的倾斜金属微针结构层和电镀金属层,直至露出SU-8模具(图2h)。Keep the angle between the sample and the etching direction unchanged, place the sample in a fluorine-containing gas (CF4, O2) for the second RIE etching to remove the inclined metal microneedle structure on the top surface of the microneedle on the SU-8 mold layer and plated metal layers until the SU-8 mold is exposed (Figure 2h).
4去除SU-8模具4 Remove the SU-8 mold
将步骤3得到的样件置于SU-8专用去胶液中,超声显影30min,超声功率30W,温度50℃,得到带尖端的空心倾斜金属微针阵列(图2i)。The sample obtained in
实施例2Example 2
参阅图2,本实施例针对的空心倾斜金属微针阵列,其微针垂直高度H为650μm;微针底部外径为250μm;微针倾斜角度α为50°;电镀金属层为镍,微针壁厚10μm;微针锥角为15°。Referring to FIG. 2 , the hollow inclined metal microneedle array in this embodiment has a vertical height H of the microneedles of 650 μm; the outer diameter of the bottom of the microneedles is 250 μm; the inclination angle α of the microneedles is 50°; The wall thickness is 10 μm; the taper angle of the microneedle is 15°.
该实施例的空心倾斜金属微针阵列制备过程如下:The preparation process of the hollow inclined metal microneedle array of this embodiment is as follows:
步骤一:在玻璃基底上制备SU-8模具Step 1: Preparation of SU-8 mold on glass substrate
本步骤包括以下子步骤:This step includes the following sub-steps:
1.1玻璃基底上制备SU-8模具掩膜图形1.1 Preparation of SU-8 mold mask pattern on glass substrate
将厚度为1000μm石英玻璃片1氧等离子清洗;然后在石英玻璃片表面溅射一层60nm金属铬;在铬金属层上旋涂正胶,曝光、显影后露出需要腐蚀的铬,在金属铬腐蚀液中腐蚀后得到SU-8模具掩膜图形层4。The quartz glass sheet with a thickness of 1000 μm was cleaned by oxygen plasma; then a layer of 60nm metal chromium was sputtered on the surface of the quartz glass sheet; positive glue was spin-coated on the chromium metal layer, exposed and developed to expose the chromium to be corroded, and the chromium metal was corroded After etching in liquid, the SU-8 mold
1.2在玻璃片表面制备SU-8模具底部牺牲层1.2 Preparation of the sacrificial layer at the bottom of the SU-8 mold on the surface of the glass sheet
将样件清洗并充分热烘,在样件无金属铬的一面旋涂3nm的OmniCoat作为SU-8模具底部牺牲层2,并进行充分热烘。The sample was cleaned and fully thermally baked, and 3nm OmniCoat was spin-coated on the chromium-free side of the sample as the
1.3背面倾斜曝光1.3 Back tilt exposure
在步骤1.2的OmniCoat面旋涂第一层SU-8光刻胶3,厚度为2μm,然后进行正面垂直无掩模曝光(图2a),曝光剂量为80mJ/cm2;在同一面上再旋涂第二层SU-8光刻胶5,厚度为650μm。第二层SU-8光刻胶5经充分前烘后,将样件固定在石英玻璃容器中,置于紫外曝光灯下,SU-8模具掩膜图形层4朝向紫外光灯,利用夹具使样件与紫外光夹角β为48°(见图2d)。在石英玻璃容器中加入丙三醇,直到丙三醇将整个样件浸没为止。待丙三醇液面静止后曝光,曝光剂量为300mJ/cm2。经后烘、显影得到SU-8模具。Spin-coat the first layer of SU-8
在SU-8模具表面用喷胶机喷涂一层OmniCoat,旋涂机上3000转/分高速甩胶,然后置于恒温箱中200℃热烘1分钟。Spray a layer of OmniCoat on the surface of the SU-8 mold with a glue sprayer, spin the glue at a high speed of 3000 rpm on the spin coater, and then place it in an incubator at 200 °C for 1 minute.
步骤二:在SU-8模具表面制备空心倾斜金属微针,包括以下子步骤:Step 2: Preparation of hollow inclined metal microneedles on the surface of SU-8 mold, including the following sub-steps:
2.1在SU-8模具表面溅射沉积金属种子层2.1 Sputter deposition of metal seed layer on the surface of SU-8 mold
在步骤1.3得到样件的SU-8模具6上溅射沉积金属种子层7,厚度为200nm,溅射中需确保样件与金属沉积方向的夹角为130°,SU-8模具上微针与金属沉积方向平行(图2e),确保SU-8模具上微针外部完全被沉积的金属种子层7包裹。On the SU-8
2.2在金属种子层表面电镀金属层,形成倾斜金属微针结构层2.2 Electroplating a metal layer on the surface of the metal seed layer to form an inclined metal microneedle structure layer
将样件放入金属镍的电解质溶液中进行电镀,电镀金属层厚度为10μm,形成倾斜金属微针结构层8。The sample is placed in an electrolytic solution of metallic nickel for electroplating, and the thickness of the electroplated metal layer is 10 μm to form the inclined metal
步骤三:制备倾斜金属微针顶部尖端,包括以下子步骤:Step 3: Prepare the top tip of the inclined metal microneedle, including the following sub-steps:
3.1制备SU-8模具上倾斜金属微针顶部尖端掩模3.1 Preparation of SU-8 mold on the top tip mask of inclined metal microneedles
在步骤2.2得到样件的倾斜金属微针结构层8表面涂覆SU-8光刻胶,然后将其置于热板上热烘,使SU-8胶层充分平坦,然后将样件置于显微镜下观察SU-8光刻胶面与SU-8模具微针顶部垂直距离d,重复前述旋涂和热烘,直至SU-8光刻胶面比SU-8模具微针顶部垂直距离d为70μm。The surface of the inclined metal
将样件涂胶面置于紫外线灯下进行无掩模垂直曝光,曝光量为220mJ/cm2,然后进行正常的热烘,得到倾斜金属微针顶部尖端掩模9。The glued surface of the sample is placed under an ultraviolet lamp for maskless vertical exposure, and the exposure amount is 220 mJ/cm 2 , and then normal thermal baking is performed to obtain a
3.2制备SU-8模具上倾斜金属微针顶部倾斜尖端3.2 Preparation of SU-8 molds on top of sloping metal microneedles with sloping tips
将步骤3.1处理后的样件进行第一次RIE刻蚀,刻蚀功率为120W,氧气流量40cm3/min,氧气气压15Pa,刻蚀中样件与刻蚀方向的夹角γ为70°,刻蚀掉倾斜金属微针结构层8顶部固化的SU-8胶层。The sample processed in step 3.1 was subjected to the first RIE etching, the etching power was 120W, the oxygen flow rate was 40cm 3 /min, the oxygen pressure was 15Pa, and the included angle γ between the sample and the etching direction during the etching was 70°, The SU-8 adhesive layer cured on the top of the inclined metal
保持样件与刻蚀方向的夹角不变,将样件置于含氟气体(CF4、O2)进行第二次RIE刻蚀,去除SU-8模具上微针顶部表面的倾斜金属微针结构层和电镀金属层,直至露出SU-8模具(图2h)。Keep the angle between the sample and the etching direction unchanged, place the sample in a fluorine-containing gas (CF4, O2) for the second RIE etching to remove the inclined metal microneedle structure on the top surface of the microneedle on the SU-8 mold layer and plated metal layers until the SU-8 mold is exposed (Figure 2h).
4.去除SU-8模具4. Remove the SU-8 mold
将步骤3得到的样件置于SU-8专用去胶液中,超声显影50分,超声功率50W,温度80℃,得到带尖端的空心倾斜金属微针阵列(见图2i)。The sample obtained in
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