CN114433261B - Nano-fluidic chip processing method based on carbon nanotube channel - Google Patents
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Abstract
Description
技术领域technical field
本发明涉及纳流控芯片加工技术领域,尤其涉及一种基于碳纳米管通道等低维材料的纳流控芯片加工方法。The invention relates to the technical field of nanofluidic chip processing, in particular to a nanofluidic chip processing method based on low-dimensional materials such as carbon nanotube channels.
背景技术Background technique
纳流控技术是研究尺度分子、离子、颗粒等物质在纳米尺度空间(1~100nm)的传输、操控和应用的科学。纳流控技术的发展关键在于纳流控芯片的加工,其中包括构建纳米尺度流体控制系统。碳纳米管内径可控(几十纳米至几纳米)且与分子的尺寸相当,这为检测和操纵单个纳米尺寸的物体,如阳离子、脱氧核糖核酸、有机小分子和固体纳米粒子提供了一个极好的平台。碳纳米管的均匀性可有效促进了纳米空间特有的传输机制,如碳纳米管的超疏水内表面和纳米管中水的特殊相变而导致的分子超快传输;其TPa级的杨氏模量和高化学惰性可有效防止其在应用过程中发生机械变形和化学变质;此外,通过化学气相沉积等方法合成超长碳纳米管比制备其它纳米孔的生产效率高,成本低;和生物纳米孔对温度、酸碱度和盐浓度比较敏感相比,基于碳纳米管的纳流控器件更加稳定;最后碳纳米管孔的化学性质可以通过共价或非共价分子键合来改变,特别是对碳纳米管端的修饰可以用来监测特定的目标。基于这些优点,越来越多的研究聚焦于基于碳纳米管的纳流控装置的研究。Nanofluidic technology is a science that studies the transmission, manipulation and application of scale molecules, ions, particles and other substances in the nanoscale space (1-100nm). The key to the development of nanofluidic technology lies in the processing of nanofluidic chips, including the construction of nanoscale fluid control systems. The inner diameter of carbon nanotubes is controllable (tens of nanometers to several nanometers) and is comparable to the size of molecules, which provides a pole for detecting and manipulating single nanometer-sized objects, such as cations, deoxyribonucleic acid, small organic molecules and solid nanoparticles. good platform. The uniformity of carbon nanotubes can effectively promote the unique transport mechanism of nanospace, such as the ultra-fast transport of molecules caused by the superhydrophobic inner surface of carbon nanotubes and the special phase transition of water in nanotubes; its TPa-level Young's mode Quantity and high chemical inertness can effectively prevent mechanical deformation and chemical deterioration during application; in addition, the production efficiency and cost of synthesizing ultra-long carbon nanotubes by chemical vapor deposition and other methods are higher than those of other nanopores; and bionano Nanofluidic devices based on carbon nanotubes are more stable than the pores sensitive to temperature, pH and salt concentration; finally, the chemical properties of carbon nanotube pores can be changed by covalent or non-covalent molecular bonding, especially for Modifications of carbon nanotube ends can be used to monitor specific targets. Based on these advantages, more and more researches focus on the research of nanofluidic devices based on carbon nanotubes.
已经报道的具有单个碳纳米管或多个碳纳米管作为流体通道的纳米流体装置,这些系统大致可以分为两个方向,即垂直型碳纳米管通道和水平型碳纳米管通道。制作垂直型碳纳米管芯片的路径是将分离的碳纳米管嵌入环氧树脂中并进行切片,这些具有相同纳米孔的切片被进一步安装到独立的膜支架上,以形成最终的装置。这种方式可以一次制造许多相同的芯片,然而这种方式的缺点在于这些芯片不方便进行芯片上集成,而且芯片的入口和出口在通道的两侧,芯片呈立体型,不便操作;制造垂直碳纳米管通道的另一种方法是将分散良好的超短碳纳米管插入脂质膜中,但是超声辅助切割过程会破坏碳纳米管壁的完整性,并且使得脂质层的机械稳定性不如固态器件和环氧树脂芯片。一种基于平面型的碳纳米管纳流控器件的开发,在制造过程中将碳纳米管水平定位在衬底上,并旋涂一层光刻胶将其覆盖,而后通过电子束进行光刻,但该方法需要随后通过高功率等离子体对碳纳米管进行剪切,然而等离子体切割碳纳米管或去除碳纳米管盖的效率并不高,尤其对于多壁碳纳米管来说,剪切效果较差。同时,以上基于碳纳米管构建的纳米流体芯片虽然可以同时进行光学和电学探测,但上述大多数芯片不是光学透明,不便于特种场合下光学测试需求。基于上述加工方法在技术上的不足,本专利提出了一种利用热转移法结合机械剪切方案进行平面布置碳纳米管纳流控芯片加工的新方法。Nanofluidic devices with a single carbon nanotube or multiple carbon nanotubes as fluid channels have been reported, and these systems can be roughly divided into two directions, namely, vertical carbon nanotube channels and horizontal carbon nanotube channels. The route to fabricate vertical CNT chips is to embed isolated CNTs in epoxy resin and slice them, and these slices with the same nanopores are further mounted on independent membrane scaffolds to form the final device. This method can manufacture many identical chips at one time, but the disadvantage of this method is that these chips are not convenient for on-chip integration, and the inlet and outlet of the chip are on both sides of the channel, and the chip is three-dimensional, which is inconvenient to operate; manufacturing vertical carbon Another approach for nanotube channeling is to insert well-dispersed ultrashort carbon nanotubes into lipid membranes, but the ultrasonic-assisted cleavage process destroys the integrity of the carbon nanotube walls and makes the lipid layer less mechanically stable than the solid state. devices and epoxy chips. Development of a planar-based carbon nanotube nanofluidic device, in which the carbon nanotubes are horizontally positioned on the substrate during the fabrication process, covered with a layer of photoresist by spin coating, and then photolithography is carried out by electron beam , but this method requires subsequent shearing of the carbon nanotubes by high-power plasma, however, the efficiency of plasma cutting carbon nanotubes or removing the caps of carbon nanotubes is not high, especially for multi-walled carbon nanotubes, shearing The effect is poor. At the same time, although the above-mentioned nanofluidic chips based on carbon nanotubes can perform optical and electrical detection at the same time, most of the above-mentioned chips are not optically transparent, which is not convenient for optical testing requirements in special occasions. Based on the technical deficiencies of the above-mentioned processing methods, this patent proposes a new method for processing planarly arranged carbon nanotube nanofluidic chips using a thermal transfer method combined with a mechanical shearing scheme.
发明内容Contents of the invention
根据上述提出的技术问题,而提供一种基于碳纳米管通道的纳流控芯片加工方法。本发明采用的技术手段如下:According to the technical problems raised above, a method for processing nanofluidic chips based on carbon nanotube channels is provided. The technical means adopted in the present invention are as follows:
一种基于碳纳米管通道的纳流控芯片加工方法,包括如下步骤:A nanofluidic chip processing method based on a carbon nanotube channel, comprising the following steps:
S1、在除水的基底上旋涂一薄层光刻胶并加热使其固化;S1. Spin-coat a thin layer of photoresist on the dehydrated substrate and heat it to cure;
S2、将碳纳米管薄层通过热释法转移至光刻胶薄层表面的预定位置;S2, transferring the carbon nanotube thin layer to a predetermined position on the surface of the photoresist thin layer by pyrolysis;
S3、在光刻胶薄层表面旋涂另一层光刻胶将碳纳米管嵌入其中;S3, spin coating another layer of photoresist on the surface of the photoresist thin layer to embed carbon nanotubes therein;
S4、加热使光刻胶溶剂挥发,之后进行光刻操作,在基底上加工开式微米通道系统,光刻操作后碳纳米管部分暴露在微流通道中;S4. Heating to volatilize the photoresist solvent, and then performing a photolithography operation to process an open micro-channel system on the substrate. After the photolithography operation, the carbon nanotubes are partially exposed in the microfluidic channel;
S5、将通道中倒入液态PDMS将暴露在通道中的碳纳米管嵌入PDMS,将PDMS固化并剥离,获得带有碳纳米管通道的纳流控芯片基底;S5. Pour liquid PDMS into the channel, embed the carbon nanotubes exposed in the channel into PDMS, solidify and peel off the PDMS, and obtain a nanofluidic chip substrate with carbon nanotube channels;
S6、对PDMS表面进行等离子氧化处理,将其和S5中所述碳纳米管通道的纳流控芯片基底进行等离子表面氧化处理,最终进行芯片键合,获得基于碳纳米管构建的纳流控芯片。S6. Perform plasma oxidation treatment on the PDMS surface, perform plasma surface oxidation treatment on it and the nanofluidic chip substrate of the carbon nanotube channel described in S5, and finally perform chip bonding to obtain a nanofluidic chip based on carbon nanotubes. .
进一步地,所述步骤S1中,基底为可提供平整且稳定的表面特征的材料,包括玻璃材质、硅基材质、二氧化硅,所述的除水过程可采用常压下加热至140~160℃并保持25~35分钟实现。Further, in the step S1, the substrate is a material that can provide flat and stable surface features, including glass materials, silicon-based materials, and silicon dioxide. The water removal process can be heated to 140-160 °C under normal pressure. ℃ and maintain for 25 to 35 minutes to achieve.
进一步地,所述步骤S2具体包括如下步骤:首先从碳纳米管束阵列中分离出一薄层碳纳米管,并将该层碳纳米管转移至一层柔性聚二甲基硅氧烷平板(Polydimethylsiloxane,PDMS)表面,而后将粘有碳纳米管的PDMS贴附在薄层光刻胶的预定位置,排除贴附过程中引入的气泡,将基底进行加热使光刻胶融化,而后将基底冷却至室温,去除PDMS层,完成碳纳米管的转移。Further, the step S2 specifically includes the following steps: first, separate a thin layer of carbon nanotubes from the array of carbon nanotube bundles, and transfer the layer of carbon nanotubes to a layer of flexible polydimethylsiloxane flat plate (Polydimethylsiloxane , PDMS) surface, and then attach the PDMS with carbon nanotubes on the predetermined position of the thin layer of photoresist, remove the air bubbles introduced during the attachment process, heat the substrate to melt the photoresist, and then cool the substrate to At room temperature, the PDMS layer was removed to complete the transfer of carbon nanotubes.
进一步地,所采用的PDMS为杨氏模量较低的PDMS且表面具有一定粘性,采用的PDMS通过本体和固化剂比例为10:1~15:1的液态混合物在70~80℃条件下加热约2小时获得。Further, the PDMS used is PDMS with a low Young's modulus and has a certain viscosity on the surface, and the PDMS used is heated at 70-80°C through a liquid mixture with a ratio of bulk and curing agent of 10:1-15:1. About 2 hours to get.
进一步地,所采用的碳纳米管为单根碳纳米管或者碳纳米管阵列薄膜,碳纳米管阵列薄膜的厚度小于1μm;单根碳纳米管或者碳纳米管阵列薄膜可通过粘性胶带多次粘贴和分离获得。Further, the carbon nanotubes used are a single carbon nanotube or a carbon nanotube array film, and the thickness of the carbon nanotube array film is less than 1 μm; a single carbon nanotube or a carbon nanotube array film can be pasted multiple times by adhesive tape and separation obtained.
进一步地,所述S3中的光刻胶为正胶或负胶,且应与S1中所选光刻胶为同一种类光刻胶,所旋涂的光刻胶的厚度大于碳纳米管薄膜的厚度,将碳纳米嵌入其中。Further, the photoresist in said S3 is a positive or negative resist, and should be the same type of photoresist as the selected photoresist in S1, and the thickness of the photoresist that is spin-coated is greater than that of the carbon nanotube film. thickness, into which carbon nanometers are embedded.
进一步地,所述步骤S4具体包括如下步骤:光刻过程所采用的光刻掩膜应该根据步骤S1和S3中所采用的光刻胶进行设计;光刻显影后,设计的碳纳米管流道部分应嵌入光刻胶中,其它部分应暴露在通道中。Further, the step S4 specifically includes the following steps: the photolithography mask used in the photolithography process should be designed according to the photoresist used in steps S1 and S3; after the photolithography is developed, the designed carbon nanotube flow channel Some parts should be embedded in the photoresist, other parts should be exposed in the channel.
进一步地,所述步骤S5,将PDMS本体和固化剂的比例为10:1~15:1的液态混合物浇筑在S4所述的微流通道中,进行真空除气,将暴露在通道中的碳纳米管完全嵌入PDMS中,PDMS固化后将PDMS剥离实现碳纳米管的机械剪切,获得碳纳米管微纳流控系统基底。Further, in the step S5, the liquid mixture of the PDMS body and the curing agent at a ratio of 10:1 to 15:1 is poured into the microfluidic channel described in S4, and vacuum degassing is performed, and the carbon nanometers exposed in the channel The tubes are completely embedded in PDMS, and after the PDMS is cured, the PDMS is peeled off to realize the mechanical shearing of the carbon nanotubes, and the substrate of the carbon nanotube micro-nanofluidic system is obtained.
进一步地,所述步骤S6键合过程中采用光学透明的粘合膜和等离子体处理方法;具体地,将一块PDMS平板进行等离子表面处理后并将一层聚丙烯酸粘合膜贴附在在其表面,而后在相应的位置打孔,为微流通道提供样品池,而后将该PDMS平板和S5所述的碳纳米管微纳流控系统基底一同进行等离子体氧化处理,通过将PDMS平板基底和碳纳米管微纳流控系统基底进行对准贴合实现基于碳纳米管通道的纳流控芯片的加工。Further, an optically transparent adhesive film and a plasma treatment method are used in the bonding process of the step S6; specifically, a PDMS plate is subjected to plasma surface treatment and a layer of polyacrylic acid adhesive film is attached to it. surface, and then punch holes in the corresponding positions to provide sample pools for the microfluidic channels, and then perform plasma oxidation treatment on the PDMS plate and the carbon nanotube micro-nanofluidic system substrate described in S5, by combining the PDMS plate substrate and The carbon nanotube micro-nanofluidic system substrate is aligned and bonded to realize the processing of the nanofluidic chip based on the carbon nanotube channel.
进一步地,所述的碳纳米管的内径在纳米数量级,使得加工的纳流控芯片能够实现分子级别的物质可控操作检测,同时使用超长的碳纳米管可实现平面上复杂纳流控系统的构建。Furthermore, the inner diameter of the carbon nanotubes is on the order of nanometers, so that the processed nanofluidic chip can realize the controllable operation detection of substances at the molecular level, and at the same time, the use of ultra-long carbon nanotubes can realize complex nanofluidic systems on the plane build.
本发明具有以下优点:The present invention has the following advantages:
1、完整性好。本发明采用的机械剪切力包裹切割碳纳米管的方法,不会破坏通道中碳纳米管的结构,实现了碳纳米管通道完整性。1. Good integrity. The method of wrapping and cutting carbon nanotubes by mechanical shearing force adopted in the present invention will not destroy the structure of carbon nanotubes in the channels, and realizes the integrity of the carbon nanotube channels.
2、制作效率高。相对于常用的等离子体切割碳纳米管的工艺,本发明所使用的工艺一次可以完成整个芯片所有碳纳米管的切割(剪切效率近100%),具有更高的切割效率。2. High production efficiency. Compared with the commonly used process of plasma cutting carbon nanotubes, the process used in the present invention can complete the cutting of all carbon nanotubes in the whole chip at one time (shearing efficiency is nearly 100%), and has higher cutting efficiency.
3、经济性好。本发明采用的方法在保证了通道功能的情况下,实现了更低成本的碳纳米管通道的切割,制备过程简单,对高端设备要求少,在实际应用中更易操作和普及。3. Good economy. The method adopted in the present invention realizes cutting of carbon nanotube channels at lower cost while ensuring channel functions, has a simple preparation process, requires less high-end equipment, and is easier to operate and popularize in practical applications.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图做以简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动性的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained according to these drawings without any creative effort.
图1为本申请方法流程图。Figure 1 is a flow chart of the method of the present application.
图2表示为碳纳米管通道的纳流控芯片加工方法流程说明图,其中:(a)在基底上旋涂光刻胶;(b)采用热释法将碳纳米管转移至光刻胶表面;(c)再次旋涂光刻胶将碳纳米管嵌入光刻胶层中;(d)紫外线曝光在光刻胶层构建微流通道;(e)显影后碳纳米管两端暴露在微流通道中;(f)采用PDMS浇筑、固化、剥离实现碳纳米管的精确剪切;(g)具有碳纳米管通道的纳流控芯片基底;(h)对PDMS平板表面进行等离子氧化处理;(i)在PDMS表面贴附双面胶层并打孔;(j)对PDMS平板和碳纳米管纳流控芯片基底表面进行等离子氧化处理;(k)芯片的键合。Fig. 2 is an explanatory diagram of the nanofluidic chip processing method for carbon nanotube channels, in which: (a) spin-coating photoresist on the substrate; (b) transferring carbon nanotubes to the photoresist surface by pyrolysis ; (c) spin-coat photoresist again to embed carbon nanotubes in the photoresist layer; (d) build microfluidic channels in the photoresist layer by ultraviolet exposure; (e) expose both ends of carbon nanotubes to microfluidic (f) Precise shearing of carbon nanotubes using PDMS pouring, curing, and peeling off; (g) Nanofluidic chip substrate with carbon nanotube channels; (h) Plasma oxidation treatment on the surface of the PDMS plate; (i ) attaching a double-sided adhesive layer on the surface of PDMS and punching holes; (j) performing plasma oxidation treatment on the surface of the PDMS flat plate and the substrate of the carbon nanotube nanofluidic chip; (k) bonding the chip.
图3表示为基于碳纳米管的纳流控芯片加工过程中的照片实例,其中,(a)紫外曝光后嵌入光刻胶层的碳纳米管;(b)显影后的微流通道,碳纳米管端口暴露在微流通道中;(c)通过PDMS机械剪切的碳纳米管;(d)键合后的芯片。Figure 3 shows an example of photos during the processing of nanofluidic chips based on carbon nanotubes, in which (a) carbon nanotubes embedded in the photoresist layer after ultraviolet exposure; (b) microfluidic channels after development, carbon nanotubes Tube ports exposed in microfluidic channels; (c) carbon nanotubes mechanically sheared by PDMS; (d) chip after bonding.
图4为基于碳纳米管芯片加工方法构建的碳纳米管通道结合电化学检测技术的纳流控芯片实例,其中,(a)通过剥离并转移到PDMS表面的碳纳米管薄膜;(b)和电化学检测技术结合的碳纳米管纳流控芯片;(c)芯片碳纳米管处放大图片。Figure 4 is an example of a nanofluidic chip with carbon nanotube channels combined with electrochemical detection technology based on the carbon nanotube chip processing method, in which (a) is stripped and transferred to the carbon nanotube film on the PDMS surface; (b) and Carbon nanotube nanofluidic chip combined with electrochemical detection technology; (c) Enlarged picture of carbon nanotubes on the chip.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
如图1所示,本发明实施例公开了一种基于碳纳米管通道的纳流控芯片加工方法,本发明为微纳流控领域提供一种基于碳纳米管的高效、可靠的纳流控芯片加工技术,包括如下步骤:As shown in Figure 1, the embodiment of the present invention discloses a nanofluidic chip processing method based on carbon nanotube channels. The present invention provides an efficient and reliable nanofluidic chip based on carbon nanotubes for the field of micro-nanofluidics Chip processing technology, including the following steps:
S1、在除水的基底上旋涂一薄层光刻胶并加热使其固化;S1. Spin-coat a thin layer of photoresist on the dehydrated substrate and heat it to cure;
S2、将碳纳米管薄层通过热释法转移至光刻胶薄层表面的预定位置;S2, transferring the carbon nanotube thin layer to a predetermined position on the surface of the photoresist thin layer by pyrolysis;
S3、在光刻胶薄层表面旋涂另一层光刻胶将碳纳米管嵌入其中;S3, spin coating another layer of photoresist on the surface of the photoresist thin layer to embed carbon nanotubes therein;
S4、加热使光刻胶溶剂挥发,之后进行光刻操作,在基底上加工开式微米通道系统,光刻操作后碳纳米管部分暴露在微流通道中;S4. Heating to volatilize the photoresist solvent, and then performing a photolithography operation to process an open micro-channel system on the substrate. After the photolithography operation, the carbon nanotubes are partially exposed in the microfluidic channel;
S5、将通道中倒入液态PDMS,将暴露在通道中的碳纳米管嵌入PDMS,将PDMS固化并剥离,实现碳纳米管精确机械剪切,获得带有碳纳米管通道的纳流控芯片基底;S5. Pour liquid PDMS into the channel, embed the carbon nanotubes exposed in the channel into PDMS, solidify and peel off the PDMS, realize precise mechanical shearing of carbon nanotubes, and obtain a nanofluidic chip substrate with carbon nanotube channels ;
S6、对PDMS表面进行等离子氧化处理,贴附一层双面胶,打孔后再次和S5中所述碳纳米管通道的纳流控芯片基底进行等离子表面氧化处理,最终进行芯片键合,获得基于碳纳米管构建的纳流控芯片。S6. Perform plasma oxidation treatment on the surface of PDMS, attach a layer of double-sided adhesive, perform plasma surface oxidation treatment with the nanofluidic chip substrate of the carbon nanotube channel described in S5 after drilling, and finally perform chip bonding to obtain Nanofluidic chips based on carbon nanotubes.
所述步骤S1中,基底为可提供平整且稳定的表面特征的材料,包括玻璃材质、硅基材质、二氧化硅,所述的除水过程可采用常压下加热至140~160℃并保持25~35分钟实现,本实施例中,除水过程可采用常压下加热至150℃并保持30分钟实现。In the step S1, the substrate is a material that can provide flat and stable surface features, including glass materials, silicon-based materials, and silicon dioxide. The water removal process can be heated to 140-160°C under normal pressure and kept It takes 25 to 35 minutes to realize. In this embodiment, the water removal process can be realized by heating to 150° C. under normal pressure and maintaining it for 30 minutes.
所述步骤S2具体包括如下步骤:首先从碳纳米管束阵列中分离出一薄层碳纳米管,并将该层碳纳米管转移至一层柔性聚二甲基硅氧烷(Polydimethylsiloxane,PDMS)平板表面,而后将粘有碳纳米管的PDMS贴附在薄层光刻胶的预定位置,排除贴附过程中引入的气泡,将基底进行加热使光刻胶融化,而后将基底冷却至室温,去除PDMS层,完成碳纳米管的转移。The step S2 specifically includes the following steps: first, separate a thin layer of carbon nanotubes from the array of carbon nanotube bundles, and transfer the layer of carbon nanotubes to a layer of flexible polydimethylsiloxane (Polydimethylsiloxane, PDMS) flat plate surface, and then attach the PDMS with carbon nanotubes on the predetermined position of the thin layer of photoresist, remove the air bubbles introduced during the attachment process, heat the substrate to melt the photoresist, and then cool the substrate to room temperature to remove PDMS layer to complete the transfer of carbon nanotubes.
所采用的PDMS为杨氏模量较低的PDMS且表面具有一定粘性,采用的PDMS通过本体和固化剂比例为10:1~15:1的液态混合物在70~80℃条件下加热约2小时获得,本实施例中,采用的PDMS通过本体和固化剂15:1的比例混合后在75℃条件下加热2小时获得。The PDMS used is PDMS with a low Young's modulus and the surface has a certain viscosity. The PDMS used is heated at 70-80°C for about 2 hours through a liquid mixture with a ratio of 10:1 to 15:1 of the bulk and curing agent. Obtained, in this example, the PDMS used is obtained by mixing the bulk and the curing agent at a ratio of 15:1 and then heating at 75°C for 2 hours.
所采用的碳纳米管为单根碳纳米管或者碳纳米管阵列薄膜,碳纳米管阵列薄膜的厚度小于1μm;单根碳纳米管或者碳纳米管阵列薄膜可通过粘性胶带多次粘贴和分离获得。作为可选方案,S2所述的热释转移方法可拓展用于其他通道材料的转移方法,具体地,可拓展用于其它纳米材料的操作、转移和纳流控芯片制作,如石墨烯、氧化石墨烯、MoS2、TiO2等纳米材料。The carbon nanotubes used are a single carbon nanotube or a carbon nanotube array film, and the thickness of the carbon nanotube array film is less than 1 μm; a single carbon nanotube or a carbon nanotube array film can be obtained by pasting and separating multiple times with an adhesive tape . As an alternative, the thermal release transfer method described in S2 can be extended to the transfer method of other channel materials, specifically, it can be extended to the operation, transfer and nanofluidic chip fabrication of other nanomaterials, such as graphene, oxide Graphene, MoS2, TiO2 and other nanomaterials.
所述S3中的光刻胶和碳纳米管层表面旋涂另一层光刻胶,所选旋涂光刻胶和第一层光刻胶为同一种类光刻胶,光刻胶为正胶或负胶,所旋涂的光刻胶的厚度大于碳纳米管薄膜的厚度,将碳纳米嵌入其中。The surface of the photoresist and the carbon nanotube layer in S3 is spin-coated with another layer of photoresist, the selected spin-coated photoresist and the first layer of photoresist are the same type of photoresist, and the photoresist is a positive photoresist Or negative resist, the thickness of the spin-coated photoresist is greater than the thickness of the carbon nanotube film, and the carbon nanometers are embedded in it.
所述步骤S4具体包括如下步骤:在光刻操作在光刻胶层制作微流通道,微流通道系统连接碳纳米管道,光刻过程所采用的光刻掩膜应该根据步骤S1和S3中所采用的光刻胶进行设计;光刻显影后,设计的碳纳米管流道部分应嵌入光刻胶中,其它部分应暴露在通道中。The step S4 specifically includes the following steps: in the photolithography operation, a microfluidic channel is made on the photoresist layer, and the microfluidic channel system is connected to the carbon nanopipe. The photoresist is used for design; after the photolithography is developed, the part of the designed carbon nanotube flow channel should be embedded in the photoresist, and the other part should be exposed in the channel.
所述步骤S5,将PDMS本体和固化剂的比例为10:1~15:1的液态混合物浇筑在S4所述的微流通道中,进行真空除气,将暴露在通道中的碳纳米管完全嵌入PDMS中,PDMS固化后将PDMS剥离实现碳纳米管的机械剪切,获得碳纳米管微纳流控系统基底。In the step S5, pouring the liquid mixture of the PDMS body and the curing agent at a ratio of 10:1 to 15:1 in the microfluidic channel described in S4, performing vacuum degassing, and completely embedding the carbon nanotubes exposed in the channel In PDMS, after the PDMS is cured, the PDMS is peeled off to realize the mechanical shearing of the carbon nanotubes, and the substrate of the carbon nanotube micro-nanofluidic system is obtained.
所述步骤S6键合过程中采用光学透明的粘合膜和等离子体处理方法;碳纳米管纳流控芯片的键合过程,为了获得密封的纳米流体装置,在结合过程中采用光学透明的粘合膜(聚丙烯酸)和等离子体处理方法;具体地,将一块PDMS平板进行等离子表面处理后并将一层聚丙烯酸粘合膜贴附在在其表面,而后在相应的位置打孔,为微流通道提供样品池,而后将该PDMS平板和S5所述的碳纳米管微纳流控系统基底一同进行等离子体氧化处理,通过将PDMS平板基底和碳纳米管微纳流控系统基底进行对准贴合实现基于碳纳米管通道的纳流控芯片的加工。In the bonding process of step S6, an optically transparent adhesive film and a plasma treatment method are used; in the bonding process of the carbon nanotube nanofluidic chip, in order to obtain a sealed nanofluidic device, an optically transparent adhesive film is used in the bonding process. Composite film (polyacrylic acid) and plasma treatment method; Specifically, a PDMS plate is subjected to plasma surface treatment and a layer of polyacrylic acid adhesive film is attached to its surface, and then holes are punched in corresponding positions to provide micro The flow channel provides a sample pool, and then the PDMS plate and the carbon nanotube micro-nanofluidic system substrate described in S5 are subjected to plasma oxidation treatment together, by aligning the PDMS plate substrate and the carbon nanotube micro-nanofluidic system substrate Bonding realizes the processing of nanofluidic chips based on carbon nanotube channels.
所述的碳纳米管的内径在纳米数量级,使得加工的纳流控芯片能够实现分子级别的物质可控操作检测,如进行离子的可控传输,对大分子进行计数检测等,同时使用超长的碳纳米管可实现平面上复杂纳流控系统的构建。The inner diameter of the carbon nanotubes is on the order of nanometers, so that the processed nanofluidic chip can realize the controllable operation and detection of substances at the molecular level, such as the controllable transmission of ions, and the counting and detection of macromolecules. The carbon nanotubes can realize the construction of complex nanofluidic systems on the plane.
实施例1Example 1
本实施例具体方法如下:The concrete method of this embodiment is as follows:
如图2(a),在除水基底上旋涂一薄层光刻胶并加热使其固化。所采用的基底为1mm厚度硅片,将硅片在常压下加热至150℃并保持30分钟进行除水,而后待硅片冷却立即在该硅片上进行旋涂,旋涂光刻胶为SU8-3005,旋涂厚度为5μm,旋涂后在95℃下加热2分钟使溶剂完全挥发;As shown in Figure 2(a), a thin layer of photoresist is spin-coated on a water-removing substrate and heated to cure it. The substrate used is a silicon wafer with a thickness of 1mm. The silicon wafer is heated to 150°C under normal pressure and kept for 30 minutes to remove water, and then spin-coated on the silicon wafer immediately after the silicon wafer is cooled. The spin-coated photoresist is SU8-3005, spin-coated with a thickness of 5 μm, heated at 95°C for 2 minutes after spin-coating to completely evaporate the solvent;
将碳纳米管薄层通过热释法转移至光刻胶薄层表面的预定位置。具体步骤和参数如下:如图4(a),采用胶带从竖直生长在硅片上的碳纳米管束中分离出一束碳纳米管,所述的碳纳米管的内径在纳米数量级,长度为约为5mm,厚度小于1μm;然后将该层碳纳米管转移至一片柔性聚二甲基硅氧烷(Polydimethylsiloxane,PDMS)平板表面,所采用的PDMS为杨氏模量较低的PDMS,该PDMS的加工过程采用本体和固化剂的比例为15:1,预固化PDMS加热温度为75℃,加热时间为2小时,其表面具有一定粘度;如图2(b),而后将粘有碳纳米管的PDMS贴附在薄层光刻胶的预定位置,贴附过程中保持碳纳米管朝向光刻胶一侧同时排除贴附过程中引入的气泡;而后将基底90℃条件下进行加热并保持1分钟使光刻胶融化,使碳纳米管嵌入融化的光刻胶层;而后将样该样品冷却至室温;随后去除PDMS层,完成碳纳米管的转移;The carbon nanotube thin layer is transferred to a predetermined position on the surface of the photoresist thin layer by a pyrolysis method. Concrete steps and parameters are as follows: as Fig. 4 (a), adopt adhesive tape to separate a bunch of carbon nanotubes from the carbon nanotube bundle that vertically grows on the silicon wafer, the internal diameter of described carbon nanotubes is on the order of nanometers, and length is It is about 5mm and the thickness is less than 1 μm; then transfer this layer of carbon nanotubes to the surface of a flexible polydimethylsiloxane (Polydimethylsiloxane, PDMS) flat plate, the PDMS used is PDMS with a low Young’s modulus, the PDMS The processing process adopts the ratio of body and curing agent as 15:1, the heating temperature of pre-cured PDMS is 75°C, and the heating time is 2 hours. The surface has a certain viscosity; as shown in Figure 2(b), and then carbon nanotubes will be stuck The PDMS is attached to the predetermined position of the thin layer of photoresist, and the carbon nanotubes are kept facing the side of the photoresist during the attachment process while eliminating the air bubbles introduced during the attachment process; then the substrate is heated at 90 ° C and kept for 1 The photoresist is melted in a few minutes, so that the carbon nanotubes are embedded in the melted photoresist layer; then the sample is cooled to room temperature; then the PDMS layer is removed to complete the transfer of the carbon nanotubes;
如图2(c),在第一层光刻胶薄层表面旋涂另一层光刻胶将碳纳米管嵌入其中。所旋涂光刻胶为SU8-3050,旋涂厚度为50μm,所旋涂的光刻胶的可完全将碳纳米管薄膜的覆盖;As shown in Figure 2(c), another layer of photoresist is spin-coated on the surface of the first photoresist thin layer to embed carbon nanotubes therein. The spin-coated photoresist is SU8-3050, the spin-coating thickness is 50 μm, and the spin-coated photoresist can completely cover the carbon nanotube film;
加热样品使光刻胶中溶剂挥发后进行光刻操作,在基底上加工开式微米通道系统,光刻操作过程中通过光刻掩膜的对准将被嵌入光刻胶层的碳纳米管两端暴露在通道中。如图2(d),图3(a),光刻操作在光刻胶层制作微流通道的具体参数为,将样品在65℃加热5分钟后转至95℃加热15分钟,待其冷却后进行紫外线曝光,曝光剂量为430mJ/cm2,曝光后进行后烘加热,具体为65℃加热1分钟后转至95℃加热6分钟而后再再转至65℃加热1分钟以减小光刻胶薄膜热应力;如图2(e),图3(b),对冷却后的样品进行显影操作,显影时间为5分钟;光刻显影后,碳纳米管的部分嵌入光刻胶中,碳纳米管的其它部分暴露在通道中以便在后续步骤中进行剪切;After heating the sample to volatilize the solvent in the photoresist, perform a photolithography operation, and process an open micron channel system on the substrate. During the photolithography operation, the two ends of the carbon nanotubes that will be embedded in the photoresist layer are aligned through the photolithography mask exposed to the channel. As shown in Figure 2(d) and Figure 3(a), the specific parameters of the photolithography operation to make microfluidic channels in the photoresist layer are: heat the sample at 65°C for 5 minutes, then turn it to 95°C for 15 minutes, and wait for it to cool Afterwards, UV exposure is carried out, the exposure dose is 430mJ/cm 2 , post-baking heating is carried out after exposure, specifically heating at 65°C for 1 minute, then heating at 95°C for 6 minutes, and then heating at 65°C for 1 minute to reduce the photolithography The thermal stress of the adhesive film; as shown in Figure 2(e) and Figure 3(b), the cooled sample was developed for 5 minutes; after photolithographic development, the carbon nanotubes were partially embedded in the photoresist, and the carbon Other parts of the nanotubes are exposed in the channel for shearing in subsequent steps;
如图2(f)-(g),图3(c),图4(b)-(c),将通道中倒入液态PDMS将暴露在通道中的碳纳米管嵌入PDMS,而后将PDMS固化并剥离,实现碳纳米管精确机械剪切,获得带有碳纳米管通道的纳流控芯片基底。在碳纳米管的剪切过程,液态PDMS的制备配方为PDMS本体和固化剂的比例为10:1,将液态PDMS预固化混合物浇筑在上述的微流通道中,进行真空除气,将暴露在通道中的碳纳米管完全嵌入PDMS中,将PDMS 90℃加热2小时经固化,而后将PDMS剥离实现碳纳米管的机械剪切,获得碳纳米管微纳流控系统基底;As shown in Figure 2(f)-(g), Figure 3(c), Figure 4(b)-(c), pour liquid PDMS into the channel to embed the carbon nanotubes exposed in the channel into PDMS, and then cure the PDMS And peel off, realize the precise mechanical shearing of carbon nanotubes, and obtain the nanofluidic chip substrate with carbon nanotube channels. In the shearing process of carbon nanotubes, the preparation formula of liquid PDMS is that the ratio of PDMS body and curing agent is 10:1, and the liquid PDMS pre-cured mixture is poured in the above-mentioned microfluidic channel, and vacuum degassing is performed, and the exposed The carbon nanotubes in the medium are completely embedded in PDMS, and the PDMS is heated at 90°C for 2 hours to be cured, and then the PDMS is peeled off to realize the mechanical shearing of the carbon nanotubes, and the substrate of the carbon nanotube micro-nanofluidic system is obtained;
如图2(h)-(k),图3(d),基于碳纳米管的纳流控芯片的键合。键合的具体步骤和参数为:将PDMS平板的表面进行等离子氧化处理,处理时间90s,处理功率30W;而后在处理后的PDMS表面贴附一层聚丙烯酸双面胶,胶层的厚度为25μm;对贴有胶层的PDMS平板进行打孔为纳流控芯片提供储液池;而后再次将碳纳米管通道的纳流控芯片基底和该PDMS平板进行等离子表面氧化处理,处理时间为90s,处理功率为30W;最终将PDMS平板和带有碳纳米管通道的纳流控芯片基底进行贴合进行芯片键合,获得基于碳纳米管的纳流控芯片。As shown in Figure 2(h)-(k) and Figure 3(d), the bonding of nanofluidic chips based on carbon nanotubes. The specific steps and parameters of the bonding are: plasma oxidation treatment is performed on the surface of the PDMS plate, the treatment time is 90s, and the treatment power is 30W; then a layer of polyacrylic double-sided adhesive is attached to the treated PDMS surface, and the thickness of the adhesive layer is 25μm ; Punch the PDMS plate with the adhesive layer to provide a liquid storage pool for the nanofluidic chip; and then perform plasma surface oxidation treatment on the nanofluidic chip substrate of the carbon nanotube channel and the PDMS plate again, and the treatment time is 90s. The processing power is 30W; finally, the PDMS plate and the nanofluidic chip substrate with carbon nanotube channels are bonded for chip bonding to obtain a nanofluidic chip based on carbon nanotubes.
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than limiting them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the various embodiments of the present invention. scope.
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