CN114149001B - Self-assembled carbon nano tube array preparation, transfer and orientation determination method for terahertz - Google Patents

Self-assembled carbon nano tube array preparation, transfer and orientation determination method for terahertz Download PDF

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CN114149001B
CN114149001B CN202111578685.4A CN202111578685A CN114149001B CN 114149001 B CN114149001 B CN 114149001B CN 202111578685 A CN202111578685 A CN 202111578685A CN 114149001 B CN114149001 B CN 114149001B
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谢丽娟
尹吉帆
应义斌
李麟
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Zhejiang Kaipu Technology Co ltd
Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing, transferring and determining orientation of a self-assembled carbon nano tube array for terahertz. The method prepares the high-density carbon nanotube array on the filter membrane by a vacuum filtration device, and can realize the preparation of the horizontally arranged directional arranged carbon nanotube film by combining the assistance of the gold electrode, wherein the conducting direction of the gold electrode is the arrangement direction of the carbon nanotubes. The method can prepare the carbon nanotube array (directional/non-directional arrangement) with the nano-scale thickness, realizes the rapid transfer of the carbon nanotube array in a simple and environment-friendly mode, and simultaneously determines the orientation of the directional arrangement carbon nanotubes by a rapid and nondestructive method, thereby having higher application value in the field of preparation of terahertz devices based on the carbon nanotubes.

Description

太赫兹用自组装碳纳米管阵列制备、转移及测定取向方法Preparation, transfer and orientation determination of self-assembled carbon nanotube arrays for terahertz

技术领域technical field

本发明涉及自组装碳纳米管阵列领域的一种碳纳米管制备和处理方法,具体为一种太赫兹用自组装碳纳米管阵列制备、转移及测定取向方法。The invention relates to a method for preparing and processing carbon nanotubes in the field of self-assembled carbon nanotube arrays, in particular to a method for preparing, transferring and measuring orientation of self-assembled carbon nanotube arrays for terahertz.

背景技术Background technique

碳纳米管是一种具有高电导率的一维纳米材料,其表现出奇特的的光电效应被广泛应用于制备太赫兹光电器件,如光电探测器、偏振器、吸收器。Carbon nanotubes are one-dimensional nanomaterials with high electrical conductivity, which exhibit unique photoelectric effects and are widely used in the preparation of terahertz optoelectronic devices, such as photodetectors, polarizers, and absorbers.

与气相沉积法制备碳纳米管相比,自组装排列碳纳米管技术能够获得高纯度、单一手性、纳米级厚度的碳纳米管,能够更好的发挥碳纳米管光电性能。目前针对自组装碳纳米管薄膜,转移方法为化学湿法刻蚀,即利用滤膜溶于氯仿的性质而目标基底与碳纳米管不溶于氯仿的原理,实现自组装碳纳米管到目标基底的转移。该方法使用的有机溶剂氯仿对人体具有一定的毒性,是一种环境不友好试剂,同时氯仿溶解滤膜需要一定的时间,通常整个转移步骤耗费20分钟;此外,由于氯仿与高分子聚合物会发生溶胀现象,因此不能通过该方法实现碳纳米管至聚二甲基硅氧烷类以及会与氯仿发生溶胀现象的柔性基底的转移;湿法转移还会由于碳纳米管与目标基底范德华力结合不紧密,导致转移后的碳纳米管出现空洞、不均一的现象;此外,对于定向排列碳纳米管,目前获取碳纳米管排列方向的方法主要有拉曼光谱技术、太赫兹光谱技术和扫描电镜,但这些方法步骤繁琐、破损样品。Compared with the preparation of carbon nanotubes by vapor deposition, self-assembled carbon nanotube technology can obtain carbon nanotubes with high purity, single chirality and nanometer thickness, which can better exert the photoelectric performance of carbon nanotubes. At present, for self-assembled carbon nanotube films, the transfer method is chemical wet etching, which uses the principle that the filter membrane is soluble in chloroform and the target substrate and carbon nanotubes are insoluble in chloroform, so as to realize the transfer of self-assembled carbon nanotubes to the target substrate. transfer. The organic solvent chloroform that this method uses has certain toxicity to human body, is a kind of environment unfriendly reagent, simultaneously chloroform dissolves filter membrane and needs certain time, usually whole transfer step takes 20 minutes; Swelling occurs, so the transfer of carbon nanotubes to polydimethylsiloxanes and flexible substrates that swell with chloroform cannot be achieved by this method; wet transfer is also due to van der Waals binding of carbon nanotubes to the target substrate The carbon nanotubes are not compact, resulting in voids and inhomogeneity in the transferred carbon nanotubes; in addition, for the alignment of carbon nanotubes, the current methods to obtain the arrangement direction of carbon nanotubes mainly include Raman spectroscopy, terahertz spectroscopy and scanning electron microscopy. , but these methods are cumbersome and damage the sample.

发明内容Contents of the invention

本发明的目的是为了通过自组装技术实现碳纳米管阵列的制备,克服现有湿法转移自组装碳纳米管的不足,提出了一种将自组装碳纳米管阵列通过绿色友好、简单快速的方式转移至柔性基底,同时能通过简单、快速和无损的方法确定定向排列碳纳米管的排列方向,进而制备太赫兹功能器件。The purpose of the present invention is to realize the preparation of carbon nanotube arrays through self-assembly technology, overcome the shortcomings of existing wet transfer self-assembled carbon nanotubes, and propose a method of self-assembled carbon nanotube arrays through a green, friendly, simple and fast method The method can be transferred to a flexible substrate, and at the same time, the arrangement direction of aligned carbon nanotubes can be determined by a simple, fast and non-destructive method, and then terahertz functional devices can be prepared.

本发明实现碳纳米管自组装,克服有机溶剂与柔性基底发生溶胀现象,通过绿色友好的方法在更短时间内将均一、无空洞的自组装碳纳米管阵列转移至柔性基底,并通过简单、快速和无损的方法确定定向排列碳纳米管的排列方向。The invention realizes the self-assembly of carbon nanotubes, overcomes the swelling phenomenon of organic solvents and flexible substrates, and transfers uniform and void-free self-assembled carbon nanotube arrays to flexible substrates in a shorter time through a green and friendly method. Rapid and non-destructive method for determining the alignment direction of aligned carbon nanotubes.

本发明的技术方案是:Technical scheme of the present invention is:

一、一种太赫兹用自组装碳纳米管阵列制备装置:1. A preparation device for self-assembled carbon nanotube arrays for terahertz:

装置包括玻璃瓶、真空泵、真空瓶、橡胶塞、连接管件、滤膜、导管;玻璃瓶置于真空瓶的上方,玻璃瓶底部开口,开口经连接管件连通到真空瓶内部,连接管件在和玻璃瓶底部开口连接处布置滤芯,滤芯上覆盖布置滤膜,滤膜上覆盖布置碳纳米管溶液,真空瓶和真空泵通过导管连通;连接管件的管道与真空瓶通过橡胶塞连接,连接管件的管道内装填橡胶塞。The device includes a glass bottle, a vacuum pump, a vacuum bottle, a rubber stopper, a connecting pipe, a filter membrane, and a catheter; the glass bottle is placed above the vacuum bottle, the bottom of the glass bottle is opened, and the opening is connected to the inside of the vacuum bottle through the connecting pipe, and the connecting pipe is connected to the glass A filter element is arranged at the opening connection at the bottom of the bottle, and a filter membrane is arranged on the filter element, and a carbon nanotube solution is arranged on the filter membrane, and the vacuum bottle and the vacuum pump are connected through a catheter; Fill the rubber stopper.

还包括一对金电极和可调电源,在滤膜上间隔布置一对金电极,一对金电极分别经导线后连接到可调电源的两端。It also includes a pair of gold electrodes and an adjustable power supply, a pair of gold electrodes are arranged at intervals on the filter membrane, and the pair of gold electrodes are respectively connected to two ends of the adjustable power supply through wires.

所述的可调电源的输出电压可调。The output voltage of the adjustable power supply is adjustable.

所述的一对金电极的连线方向平行于滤膜中的纳米级凹槽方向。The connection direction of the pair of gold electrodes is parallel to the direction of the nanoscale grooves in the filter membrane.

所述的玻璃瓶用于放置碳纳米管溶液。The glass bottle is used to place the carbon nanotube solution.

所述的连接管件包括位于上部的盘体和下部的管体,盘体嵌装在玻璃瓶底端的开口中,盘体表面从下到上层叠布置滤芯和滤膜,管体上端同心连接到盘体的中心通孔中,管体下端伸入到真空瓶中。The connecting pipe includes an upper disc body and a lower tube body, the disc body is embedded in the opening at the bottom of the glass bottle, the filter elements and filter membranes are stacked on the surface of the disc body from bottom to top, and the upper end of the tube body is concentrically connected to the disc In the central through hole of the body, the lower end of the tube body extends into the vacuum bottle.

所述的滤膜孔径小于单根碳纳米管长度。所述的滤膜具体采用WhatmanNuclepore Track-Etched膜,型号为111106产品或者系列或者型号。The pore diameter of the filter membrane is smaller than the length of a single carbon nanotube. The filter membrane is specifically WhatmanNuclepore Track-Etched membrane, the model is 111106 product or series or model.

二、一种太赫兹用自组装碳纳米管阵列制备方法,所述的制备方法包括:2. A method for preparing a self-assembled carbon nanotube array for terahertz, the preparation method comprising:

而对于非定向排列碳纳米管,采用所述的装置,通常是将去离子水浸润后的滤膜覆盖在连接管件上;将碳纳米管溶液加入玻璃瓶中,然后将真空泵打开,玻璃瓶的碳纳米管溶液中的非碳纳米管物质流入真空瓶中,碳纳米管阵列在滤膜上逐渐沉积,在无液体流入真空瓶后一段时间停止抽滤,在滤膜上获得自组装碳纳米管阵列。For non-aligned carbon nanotubes, using the device, usually the filter membrane soaked in deionized water is covered on the connecting pipe; the carbon nanotube solution is added to the glass bottle, and then the vacuum pump is opened, and the glass bottle The non-carbon nanotube substances in the carbon nanotube solution flow into the vacuum bottle, and the carbon nanotube array is gradually deposited on the filter membrane. After no liquid flows into the vacuum bottle, the suction filtration is stopped for a period of time, and self-assembled carbon nanotubes are obtained on the filter membrane. array.

对于水平排列的定向排列碳纳米管,采用所述的装置,将去离子水浸润后的滤膜覆盖在连接管件上,将一对金电极固定在滤膜上,且一对金电极之间的连线方向与滤膜上面的纳米级凹槽方向平行,用导线将一对金电极与可调电源的两端电连接;将碳纳米管溶液加入玻璃瓶中,打开可调电源并设置电压,使得定向排列碳纳米管阵列在滤膜上逐渐沉积,当玻璃瓶内溶液体积还剩加入体积的10%-20%时,再打开真空泵,玻璃瓶的碳纳米管溶液中的非碳纳米管物质流入真空瓶中,碳纳米管阵列继续在滤膜上逐渐沉积,在无液体流入真空瓶后一段时间停止抽滤,在滤膜上获得自组装碳纳米管阵列。For the aligned carbon nanotubes arranged horizontally, the device is used to cover the filter membrane soaked in deionized water on the connecting pipe, and a pair of gold electrodes are fixed on the filter membrane, and the gap between the pair of gold electrodes is The connection direction is parallel to the direction of the nanoscale groove on the filter membrane, and a pair of gold electrodes are electrically connected to both ends of the adjustable power supply with a wire; the carbon nanotube solution is added to the glass bottle, the adjustable power supply is turned on and the voltage is set. The array of aligned carbon nanotubes is gradually deposited on the filter membrane. When the volume of the solution in the glass bottle is 10%-20% of the added volume, the vacuum pump is turned on again, and the non-carbon nanotube substances in the carbon nanotube solution in the glass bottle Flowing into the vacuum bottle, the carbon nanotube array continues to be gradually deposited on the filter membrane, and the suction filtration is stopped for a period of time after no liquid flows into the vacuum bottle, and the self-assembled carbon nanotube array is obtained on the filter membrane.

本发明仅针对制备水平排列的定向排列碳纳米管,而不针对制备垂直排列的定向排列碳纳米管。The present invention is only aimed at preparing aligned carbon nanotubes arranged horizontally, but not directed at preparing aligned carbon nanotubes aligned vertically.

本发明通过在滤膜上设置了金电极,通过电压排列和膜上纳米级凹槽引导,控制碳纳米管沉积位置,进而实现了碳纳米管定向排列的效果/结果。In the present invention, gold electrodes are arranged on the filter membrane, and the deposition position of carbon nanotubes is controlled through voltage arrangement and nanoscale groove guidance on the membrane, thereby realizing the effect/result of directional arrangement of carbon nanotubes.

三、一种太赫兹用自组装碳纳米管阵列转移方法:3. A self-assembled carbon nanotube array transfer method for terahertz:

所述的转移方法为:The transfer methods described are:

将滤膜和滤膜上的自组装碳纳米管阵列取下,将附着在滤膜上的自组装碳纳米管阵列平行颠倒向下覆盖在目标柔性基底上,使得自组装碳纳米管阵列直接接触目标柔性基底的表面;然后从滤膜的上方向下滴加溶剂,使用工具向滤膜并向下施加均匀压力2-10N,改变能量释放率,施加压力5s-20s后,撕下滤膜,则将自组装碳纳米管阵列转移至目标柔性基底上,实现转移,该过程可通过机械自动化实现。Remove the filter membrane and the self-assembled carbon nanotube array on the filter membrane, and cover the self-assembled carbon nanotube array attached to the filter membrane on the target flexible substrate in parallel and upside down, so that the self-assembled carbon nanotube array directly contacts The surface of the target flexible substrate; then drop the solvent from the top of the filter membrane, use a tool to apply a uniform pressure of 2-10N to the filter membrane and downward, change the energy release rate, after applying pressure for 5s-20s, tear off the filter membrane, Then transfer the self-assembled carbon nanotube array to the target flexible substrate to realize the transfer, and this process can be realized by mechanical automation.

本发明实现了首次将自组装制备的碳纳米管阵列加水压印后实现从滤膜到目标柔性基底的转换,实现了绿色环保、快速转移的效果/优势。The invention realizes the conversion from the filter membrane to the target flexible substrate after adding water embossing to the carbon nanotube array prepared by self-assembly for the first time, and realizes the effect/advantage of green environmental protection and rapid transfer.

所述的溶剂为纯水、乙醇或者其他水溶剂。Described solvent is pure water, ethanol or other water solvents.

所述的目标柔性基底包括聚二甲基硅氧烷、聚酰亚胺、聚氯乙烯、聚对苯二甲酸乙二醇酯类介电材料。The target flexible substrate includes dielectric materials such as polydimethylsiloxane, polyimide, polyvinyl chloride, and polyethylene terephthalate.

四、太赫兹用自组装碳纳米管阵列的测定取向方法:4. Orientation determination method of self-assembled carbon nanotube arrays for terahertz:

对于水平排列的定向排列碳纳米管,定向排列碳纳米管的取向方向与一对金电极间的连线方向一致,即与滤膜上面的纳米级凹槽方向排列一致,具体实施中凹槽方向通过显微镜观察标记。以一对金电极间的连线方向或者滤膜上面的纳米级凹槽方向作为定向排列碳纳米管的取向方向。For the aligned carbon nanotubes arranged horizontally, the orientation direction of the aligned carbon nanotubes is consistent with the connection direction between a pair of gold electrodes, that is, it is aligned with the direction of the nanoscale grooves on the filter membrane, and the direction of the grooves in the specific implementation Observe the markers through a microscope. The alignment direction of the aligned carbon nanotubes is taken as the direction of the connection line between a pair of gold electrodes or the direction of the nanoscale grooves on the filter membrane.

所述自组装碳纳米管阵列中的碳纳米管是单壁碳纳米管、多壁碳纳米管中的一种或两种碳纳米管的组合。The carbon nanotubes in the self-assembled carbon nanotube array are one of single-walled carbon nanotubes and multi-walled carbon nanotubes, or a combination of two types of carbon nanotubes.

自组装碳纳米管阵列的厚度低至150nm,高至2μm。Self-assembled carbon nanotube arrays have thicknesses as low as 150 nm and as high as 2 μm.

碳纳米管转移至目标基底后,进一步加工为太赫兹功能器件。After the carbon nanotubes are transferred to the target substrate, they are further processed into terahertz functional devices.

本发明的创新方案包括自组装碳纳米管阵列制备方法、自组装碳纳米管阵列转移方法和自组装碳纳米管阵列取向测定方法。The innovative scheme of the invention includes a method for preparing the self-assembled carbon nanotube array, a method for transferring the self-assembled carbon nanotube array and a method for determining the orientation of the self-assembled carbon nanotube array.

本发明方法通过真空抽滤装置在滤膜上制备出高密度碳纳米管阵列,结合金电极辅助可实现定向排列(水平)碳纳米管薄膜的制备,且金电极导通方向即为碳纳米管排列方向。The method of the present invention prepares a high-density carbon nanotube array on the filter membrane through a vacuum filtration device, and the preparation of an aligned (horizontal) carbon nanotube film can be realized with the aid of a gold electrode, and the conduction direction of the gold electrode is the carbon nanotube alignment direction.

本发明能制备纳米级厚度的碳纳米管阵列(定向/非定向排列),通过简单、绿色环保的方式实现碳纳米管阵列的快速转移,同时通过快速无损的方法测定定向排列碳纳米管取向,在基于碳纳米管的太赫兹器件制备领域中有着较高的应用价值。The present invention can prepare carbon nanotube arrays (orientation/non-orientation arrangement) with nanoscale thickness, realize the rapid transfer of carbon nanotube arrays in a simple, green and environment-friendly way, and measure the orientation of orientation arrangement carbon nanotubes by a fast and nondestructive method at the same time, It has high application value in the field of preparation of terahertz devices based on carbon nanotubes.

本发明的优点及有益效果是:Advantage of the present invention and beneficial effect are:

1.本发明通过真空抽滤的方式实现了碳纳米管阵列自组装,同时通过金电极辅助实现了定向排列碳纳米管自组装。1. The present invention realizes the self-assembly of carbon nanotube arrays through vacuum filtration, and simultaneously realizes the self-assembly of aligned carbon nanotubes with the aid of gold electrodes.

2.本发明通过金电极导通方向即可获取定向排列碳纳米管排列方向,是一种快速、简单且无损获取取向度的方式。2. In the present invention, the arrangement direction of aligned carbon nanotubes can be obtained through the conduction direction of the gold electrode, which is a fast, simple and non-destructive way to obtain the degree of orientation.

3.本发明通过简单的加水按压方式增大碳纳米管与目标基底之间的能量释放率即可实现自组装碳纳米管到目标柔性基底的转移,克服了化学湿法转移自组装碳纳米管环境不友好、膜均一性差、操作时间长、与高分子聚合物柔性基底不相容的问题,避免了危险试剂(氯仿)对人体的危害。3. The present invention can realize the transfer of self-assembled carbon nanotubes to the target flexible substrate by simply adding water and pressing to increase the energy release rate between carbon nanotubes and the target substrate, which overcomes the chemical wet transfer of self-assembled carbon nanotubes The problems of unfriendly environment, poor membrane uniformity, long operation time, and incompatibility with flexible substrates of high molecular polymers avoid the harm of dangerous reagents (chloroform) to the human body.

4.本发明可以实现纳米级的自组装碳纳米管阵列,厚度可低至150nm,突破了直接生长碳纳米管只能转移微米级阵列的技术瓶颈。4. The present invention can realize nanoscale self-assembled carbon nanotube arrays, the thickness of which can be as low as 150nm, breaking through the technical bottleneck that the direct growth of carbon nanotubes can only transfer micron-scale arrays.

5.本发明转移的自组装碳纳米管均一性高于湿法刻蚀方法转移自组装碳纳米管,转移后的薄膜完整无空洞。5. The uniformity of the self-assembled carbon nanotubes transferred by the present invention is higher than that of the self-assembled carbon nanotubes transferred by the wet etching method, and the transferred film is complete without voids.

6.本发明转移至目标基底的碳纳米管阵列可用于制备太赫兹功能器件。6. The carbon nanotube array transferred to the target substrate of the present invention can be used to prepare terahertz functional devices.

附图说明Description of drawings

图1为非定向排列碳纳米管自组装示意图;Figure 1 is a schematic diagram of the self-assembly of non-aligned carbon nanotubes;

图2为定向排列(水平)碳纳米管自组装示意图;Figure 2 is a schematic diagram of the self-assembly of aligned (horizontal) carbon nanotubes;

图3为自组装碳纳米管薄膜光学照片;Fig. 3 is the optical photo of self-assembled carbon nanotube film;

图4为滤膜凹槽扫描电镜图;Fig. 4 is the scanning electron micrograph of filter membrane groove;

图5为自组装碳纳米管薄膜扫描电镜照片,包括(a)非定向排列碳纳米管和(b)定向排列碳纳米管(水平排列);Figure 5 is a scanning electron micrograph of a self-assembled carbon nanotube film, including (a) non-aligned carbon nanotubes and (b) aligned carbon nanotubes (horizontal arrangement);

图6为自组装碳纳米管加水按压转移至柔性基底流程图;Fig. 6 is a flowchart of transfer of self-assembled carbon nanotubes to flexible substrates by adding water;

图7为自组装碳纳米管转移至聚二甲基硅氧烷柔性基底后的光学照片;Figure 7 is an optical photo of self-assembled carbon nanotubes transferred to polydimethylsiloxane flexible substrate;

图8为自组装碳纳米管转移至聚氯乙烯柔性基底后的光学照片;Figure 8 is an optical photo of self-assembled carbon nanotubes transferred to a polyvinyl chloride flexible substrate;

图9为结构为碳纳米管-聚二甲基硅氧烷-金的太赫兹吸收器实物图Figure 9 is a physical picture of a terahertz absorber with a structure of carbon nanotubes-polydimethylsiloxane-gold

图中:玻璃瓶(1)、导管(2)、真空泵(3)、真空瓶(4)、橡胶塞(5)、连接管件(6)、滤膜(7)、碳纳米管溶液(8)、金电极(9)、金电极(15)、导线(16)、可调电源(17)、导线(18)。In the figure: glass bottle (1), catheter (2), vacuum pump (3), vacuum bottle (4), rubber stopper (5), connecting pipe fittings (6), filter membrane (7), carbon nanotube solution (8) , gold electrode (9), gold electrode (15), wire (16), adjustable power supply (17), wire (18).

具体实施方式Detailed ways

在具体实施过程中,本发明自组装碳纳米管阵列制备、转移及测定取向方法,利用真空抽滤制备自组装碳纳米管阵列,同时利用金电极辅助实现碳纳米管定向排列。金电极导通方向、滤膜凹槽方向即为碳纳米管排列方向。将附着在滤膜上的自组装碳纳米管阵列平行向下盖在目标柔性基底上,从上方滴加溶剂,人工或使用工具施加均匀压力后,人工或使用工具撕下滤膜,自组装碳纳米管阵列则转移至柔性基底上。In the specific implementation process, the self-assembled carbon nanotube array preparation, transfer and orientation determination method of the present invention uses vacuum filtration to prepare the self-assembled carbon nanotube array, and at the same time uses gold electrodes to assist in realizing the alignment of carbon nanotubes. The conduction direction of the gold electrode and the groove direction of the filter membrane are the arrangement directions of the carbon nanotubes. Cover the self-assembled carbon nanotube array attached to the filter membrane on the target flexible substrate in parallel, drop the solvent from above, apply uniform pressure manually or with tools, tear off the filter membrane manually or with tools, and the self-assembled carbon The nanotube arrays are then transferred to a flexible substrate.

下面,通过实施例和附图进一步详述本发明。Below, the present invention is further described in detail through examples and accompanying drawings.

实施例1Example 1

如图1所示,具体实施的装置包括玻璃瓶1、导管2、真空泵3、真空瓶4、橡胶塞5、连接管件6、滤膜7、碳纳米管溶液8;玻璃瓶1置于真空瓶4的上方,玻璃瓶1底部开口,开口经连接管件6连通到真空瓶4内部,连接管件6在和玻璃瓶1底部开口连接处布置滤芯,滤芯上覆盖布置滤膜7,真空瓶4和真空泵3的连通;连接管件6的管道内装填橡胶塞5。As shown in Figure 1, the device of concrete implementation comprises glass bottle 1, conduit 2, vacuum pump 3, vacuum bottle 4, rubber stopper 5, connecting pipe fitting 6, filter membrane 7, carbon nanotube solution 8; Glass bottle 1 is placed in vacuum bottle Above 4, the bottom of the glass bottle 1 is open, and the opening is connected to the inside of the vacuum bottle 4 through the connecting pipe 6. The connecting pipe 6 is arranged at the connection with the bottom opening of the glass bottle 1. The filter element is covered with a filter membrane 7, the vacuum bottle 4 and the vacuum pump. 3; rubber plug 5 is filled in the pipeline connecting pipe fitting 6.

连接管件6包括位于上部的盘体和下部的管体,盘体嵌装在玻璃瓶1底端的开口中,盘体表面从下到上层叠布置滤芯和滤膜7,管体上端同心连接到盘体的中心通孔中,管体下端伸入到真空瓶4中。The connecting tube 6 includes an upper disc body and a lower tube body. The disc body is embedded in the opening at the bottom of the glass bottle 1. The filter elements and filter membranes 7 are stacked on the surface of the disc body from bottom to top, and the upper end of the tube body is concentrically connected to the disc. In the central through hole of the body, the lower end of the tube body extends into the vacuum bottle 4.

滤膜是孔径为200nm的聚碳酸酯膜,将去离子水浸润后的滤膜7覆盖在连接管件6上,;配制浓度为421ug/mL碳纳米管溶液6mL加入玻璃瓶1中,然后将真空泵3打开,真空瓶4内压力小于玻璃瓶1内的压力,使得玻璃瓶1内物质被抽取到真空瓶4中,玻璃瓶1的碳纳米管溶液中的非碳纳米管物质流入真空瓶4中,碳纳米管阵列在聚碳酸酯滤膜7上逐渐沉积,在无液体流入真空瓶4后1小时停止抽滤,在滤膜7上自组装制备获得非定向排列碳纳米管的自组装碳纳米管阵列,自组装碳纳米管阵列如图3所示为膜状,厚度为2021nm,扫描电镜结果如图5(a)所示。The filter membrane is a polycarbonate membrane with a pore size of 200nm, and the filter membrane 7 soaked with deionized water is covered on the connecting pipe 6; the prepared concentration is 421ug/mL carbon nanotube solution 6mL is added to the glass bottle 1, and then the vacuum pump 3 open, the pressure in the vacuum bottle 4 is lower than the pressure in the glass bottle 1, so that the material in the glass bottle 1 is extracted into the vacuum bottle 4, and the non-carbon nanotube substances in the carbon nanotube solution in the glass bottle 1 flow into the vacuum bottle 4 , the carbon nanotube array is gradually deposited on the polycarbonate filter membrane 7, and the suction filtration is stopped 1 hour after no liquid flows into the vacuum bottle 4, and self-assembled on the filter membrane 7 is prepared to obtain a self-assembled carbon nanotube with non-aligned carbon nanotubes. Tube array, the self-assembled carbon nanotube array is shown in Figure 3 as a film with a thickness of 2021nm, and the scanning electron microscope results are shown in Figure 5(a).

实施例2Example 2

如图2所示,具体实施的装置包括玻璃瓶1、真空泵3、真空瓶4、橡胶塞5、连接管件6、滤膜7;玻璃瓶1置于真空瓶4的上方,玻璃瓶1底部开口,开口经连接管件6连通到真空瓶4内部,连接管件6在和玻璃瓶1底部开口连接处布置滤芯,滤芯上覆盖布置滤膜7,真空瓶4和真空泵3的连通;连接管件6的管道内装填橡胶塞5。As shown in Figure 2, the device of concrete implementation comprises glass bottle 1, vacuum pump 3, vacuum bottle 4, rubber stopper 5, connecting pipe fitting 6, filter membrane 7; Glass bottle 1 is placed on the top of vacuum bottle 4, glass bottle 1 bottom opening , the opening is connected to the inside of the vacuum bottle 4 through the connecting pipe fitting 6, the connecting pipe fitting 6 is arranged with a filter element at the connection with the bottom opening of the glass bottle 1, the filter element is covered with a filter membrane 7, and the vacuum bottle 4 and the vacuum pump 3 are connected; the pipeline of the connecting pipe fitting 6 Inner packing rubber stopper 5.

连接管件6包括位于上部的盘体和下部的管体,盘体嵌装在玻璃瓶1底端的开口中,盘体表面从下到上层叠布置滤芯和滤膜7,管体上端同心连接到盘体的中心通孔中,管体下端伸入到真空瓶4中。The connecting tube 6 includes an upper disc body and a lower tube body. The disc body is embedded in the opening at the bottom of the glass bottle 1. The filter elements and filter membranes 7 are stacked on the surface of the disc body from bottom to top, and the upper end of the tube body is concentrically connected to the disc. In the central through hole of the body, the lower end of the tube body extends into the vacuum bottle 4.

还包括一对金电极9、15和可调电源17,在滤膜7上间隔布置一对金电极9、15,一对金电极9、15分别经导线16、18后连接到可调电源17的两端,一对金电极9、15的连线方向平行于滤膜7中的纳米级凹槽方向。It also includes a pair of gold electrodes 9, 15 and an adjustable power supply 17, a pair of gold electrodes 9, 15 are arranged at intervals on the filter membrane 7, and a pair of gold electrodes 9, 15 are respectively connected to the adjustable power supply 17 through wires 16, 18 The direction of the pair of gold electrodes 9 and 15 is parallel to the direction of the nanoscale grooves in the filter membrane 7 .

滤膜是孔径为200nm的聚碳酸酯膜,将去离子水浸润后的滤膜7覆盖在连接管件6上,将一对金电极9、15平行固定在滤膜7上,且一对金电极9、15之间的连线方向与滤膜7上面的纳米级凹槽方向平行,凹槽方向通过显微镜观察并标记,如图4为滤膜凹槽扫描电镜图。,用导线16、18将一对金电极9、15与可调电源17的两端电连接;The filter membrane is a polycarbonate membrane with a pore size of 200nm. The filter membrane 7 soaked with deionized water is covered on the connecting pipe 6, and a pair of gold electrodes 9 and 15 are fixed on the filter membrane 7 in parallel, and a pair of gold electrodes The direction of the line between 9 and 15 is parallel to the direction of the nanoscale groove on the filter membrane 7, and the direction of the groove is observed and marked through a microscope, as shown in FIG. 4 is a scanning electron microscope image of the groove of the filter membrane. , a pair of gold electrodes 9,15 are electrically connected to the two ends of the adjustable power supply 17 with wires 16,18;

配制浓度为10ug/mL碳纳米管溶液20mL,将碳纳米管溶液加入玻璃瓶1中,打开可调电源17并设置电压,使得定向排列碳纳米管阵列在滤膜7上逐渐沉积生长,当玻璃瓶1内溶液体积还剩1ml时,再打开真空泵11,真空瓶4内压力小于玻璃瓶1内的压力,使得玻璃瓶1内物质被抽取到真空瓶4中,玻璃瓶1的碳纳米管溶液中的非碳纳米管物质流入真空瓶4中,碳纳米管阵列继续在滤膜7上逐渐沉积,在无液体流入真空瓶4后1小时停止抽滤,在滤膜7上自组装制备获得了水平排列的定向排列碳纳米管的自组装碳纳米管阵列,自组装碳纳米管阵列如图3所示为膜状,厚度为146nm,扫描电镜结果如图5(b)所示。Prepare 20 mL of a carbon nanotube solution with a concentration of 10 ug/mL, add the carbon nanotube solution into the glass bottle 1, turn on the adjustable power supply 17 and set the voltage, so that the array of aligned carbon nanotubes is gradually deposited and grown on the filter membrane 7, when the glass When the volume of the solution in the bottle 1 is 1ml, turn on the vacuum pump 11 again, the pressure in the vacuum bottle 4 is lower than the pressure in the glass bottle 1, so that the substance in the glass bottle 1 is extracted into the vacuum bottle 4, and the carbon nanotube solution in the glass bottle 1 The non-carbon nanotube substances in the flow into the vacuum bottle 4, the carbon nanotube array continues to be deposited on the filter membrane 7 gradually, and the suction filtration is stopped 1 hour after no liquid flows into the vacuum bottle 4, and the self-assembled preparation on the filter membrane 7 has obtained The self-assembled carbon nanotube array of aligned carbon nanotubes arranged horizontally, the self-assembled carbon nanotube array is shown in Figure 3 as a film with a thickness of 146nm, and the scanning electron microscope results are shown in Figure 5(b).

实施例3Example 3

如图6所示,将获得的自组装碳纳米管阵列平行向下盖在聚二甲基硅氧烷柔性基底上,与其黏附的聚碳酸酯滤膜朝上,滴加10uL超纯水,并垂直向自组装碳纳米管阵列表面均匀施加5N的力,待10s后,用镊子沿薄膜一边揭开聚碳酸酯滤膜,实现自组装碳纳米从聚碳酸酯薄膜至聚二甲基硅氧烷柔性基底的转移。As shown in Figure 6, the obtained self-assembled carbon nanotube arrays were covered in parallel downwards on the polydimethylsiloxane flexible substrate, and the polycarbonate filter membrane adhered to it was facing upwards, 10uL of ultrapure water was added dropwise, and Apply a force of 5N uniformly vertically to the surface of the self-assembled carbon nanotube array. After 10s, use tweezers to uncover the polycarbonate filter membrane along one side of the film to realize self-assembled carbon nanotubes from polycarbonate film to polydimethylsiloxane Transfer of flexible substrates.

2cm×2cm自组装碳纳米管转移至聚二甲基硅氧烷柔性基底后的结果如图7所示,转移后的薄膜均一完整。The result of transferring 2cm×2cm self-assembled carbon nanotubes to polydimethylsiloxane flexible substrate is shown in Figure 7, and the transferred film is uniform and complete.

将聚二甲基硅氧烷不接触碳纳米管阵列的一面溅射200nm金层,制备柔性太赫兹吸收器,如图9所示。A 200nm gold layer was sputtered on the side of the polydimethylsiloxane not in contact with the carbon nanotube array to prepare a flexible terahertz absorber, as shown in FIG. 9 .

实施例4Example 4

将本发明实施例3的方法制备自组装碳纳米管平行向下盖在聚氯乙烯柔性胶性面上,与其黏附的聚碳酸酯滤膜朝上,滴加10uL超纯水,并垂直碳纳米管施加2N的力,待2s后,用镊子沿薄膜一边揭开聚碳酸酯滤膜,实现自组装碳纳米从聚碳酸酯薄膜至聚氯乙烯柔性基底的转移。Cover the self-assembled carbon nanotubes prepared by the method of Example 3 of the present invention in parallel downwards on the flexible surface of polyvinyl chloride, with the polycarbonate filter membrane adhering to it facing up, add 10uL of ultrapure water dropwise, and vertically A force of 2N was applied to the tube, and after 2s, the polycarbonate filter membrane was uncovered along one side of the film with tweezers to realize the transfer of self-assembled carbon nanometers from the polycarbonate film to the flexible polyvinyl chloride substrate.

1cm×1.2cm自组装碳纳米管转移至聚氯乙烯柔性基底后的结果如图8所示,转移后的薄膜均一完整。Figure 8 shows the result of transferring 1cm×1.2cm self-assembled carbon nanotubes to the flexible polyvinyl chloride substrate, and the transferred film is uniform and complete.

本发明通过简单的加水按压方式增大碳纳米管与目标基底之间的能量释放率即可实现自组装碳纳米管到目标柔性基底的转移,克服了化学湿法转移自组装碳纳米管环境不友好、膜均一性差、操作时间长、与高分子聚合物柔性基底不相容的问题,可以实现纳米级的自组装碳纳米管阵列,厚度可低至150nm,突破了直接生长碳纳米管只能转移微米级碳纳米管阵列的技术瓶颈,能够获取均一性高于湿法刻蚀方法转移的自组装碳纳米管,转移后的薄膜完整无空洞。In the present invention, the transfer of self-assembled carbon nanotubes to the target flexible substrate can be realized by increasing the energy release rate between carbon nanotubes and the target substrate by simply adding water and pressing the method, which overcomes the environmental problems of chemical wet transfer of self-assembled carbon nanotubes. Friendly, poor film uniformity, long operating time, and incompatibility with polymer flexible substrates, nanoscale self-assembled carbon nanotube arrays can be realized, and the thickness can be as low as 150nm, breaking through the direct growth of carbon nanotubes. The technical bottleneck of transferring micron-scale carbon nanotube arrays can obtain self-assembled carbon nanotubes whose uniformity is higher than that transferred by wet etching method, and the transferred film is complete and void-free.

以上所述,仅为本发明的较佳实施例,并不用以限制本发明,凡是依据本发明的技术实质对以上实施例所做的任何细微修改、等同替换和改进,均应包含在本发明技术方案的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any minor modifications, equivalent replacements and improvements made to the above embodiments according to the technical essence of the present invention shall be included in the present invention. within the protection scope of the technical solution.

Claims (8)

1. A self-assembled carbon nanotube array preparation device for terahertz is characterized in that,
the device comprises a glass bottle (1), a vacuum pump (3), a vacuum bottle (4), a rubber plug (5), a connecting pipe fitting (6), a filter membrane (7) and a catheter (2); the glass bottle (1) is arranged above the vacuum bottle (4), the bottom of the glass bottle (1) is provided with an opening, the opening is communicated to the inside of the vacuum bottle (4) through a connecting pipe fitting (6), a filter element is arranged at the joint of the connecting pipe fitting (6) and the bottom opening of the glass bottle (1), a filter membrane (7) is covered on the filter element, a carbon nano tube solution (8) is covered on the filter membrane, and the vacuum bottle (4) is communicated with the vacuum pump (3) through a guide pipe (2); the pipeline of the connecting pipe fitting (6) is connected with the vacuum bottle (4) through a rubber plug (5);
the filter membrane (7) is provided with a pair of gold electrodes (9, 15) at intervals, the pair of gold electrodes (9, 15) are respectively connected to two ends of the adjustable power supply (17) after being connected with wires (16, 18);
the filter membrane (7) is provided with a nanoscale groove.
2. The device for preparing a terahertz self-assembled carbon nanotube array according to claim 1, wherein: the output voltage of the adjustable power supply (17) is adjustable.
3. The device for preparing a terahertz self-assembled carbon nanotube array according to claim 1, wherein: the connecting line direction of the pair of gold electrodes (9, 15) is parallel to the nano-scale groove direction in the filter membrane (7).
4. The device for preparing a terahertz self-assembled carbon nanotube array according to claim 1, wherein: the connecting pipe fitting (6) comprises a tray body positioned at the upper part and a pipe body positioned at the lower part, wherein the tray body is embedded in an opening at the bottom end of the glass bottle (1), the surface of the tray body is provided with a filter element and a filter membrane (7) in a stacking way from bottom to top, the upper end of the pipe body is concentrically connected into a central through hole of the tray body, and the lower end of the pipe body extends into the vacuum bottle (4).
5. The method for preparing the self-assembled carbon nano tube array for terahertz applied to the device of claim 1, which is characterized by comprising the following steps: for the horizontally arranged directional carbon nanotubes, the device of claim 2 is adopted, a filter membrane (7) soaked by deionized water is covered on a connecting pipe fitting (6), a pair of gold electrodes (9, 15) are fixed on the filter membrane (7), the connecting line direction between the pair of gold electrodes (9, 15) is parallel to the nano-scale groove direction on the filter membrane (7), and the pair of gold electrodes (9, 15) are electrically connected with two ends of an adjustable power supply (17) by leads (16, 18); adding a carbon nano tube solution into a glass bottle (1), opening an adjustable power supply (17) and setting voltage to enable the carbon nano tube array to be deposited on a filter membrane (7) gradually in an oriented arrangement mode, when the volume of the solution in the glass bottle (1) is 10-20% of the added volume, opening a vacuum pump (11), enabling non-carbon nano tube substances in the carbon nano tube solution in the glass bottle (1) to flow into a vacuum bottle (4), enabling the carbon nano tube array to continue to be deposited on the filter membrane (7) gradually, stopping suction filtration for a period of time after no liquid flows into the vacuum bottle (4), and obtaining the self-assembled carbon nano tube array on the filter membrane (7).
6. The transfer method of the self-assembled carbon nano tube array for terahertz is characterized by comprising the following steps of: the self-assembled carbon nano tube array attached to the filter membrane is covered on the target flexible substrate in a parallel and upside down mode, so that the self-assembled carbon nano tube array is in direct contact with the surface of the target flexible substrate; and then dropwise adding a solvent from the upper part of the filter membrane to the lower part of the filter membrane, applying uniform pressure to the filter membrane for 2-10N, and tearing off the filter membrane after applying the pressure for 5-20 s, so as to transfer the self-assembled carbon nano tube array onto a target flexible substrate to realize transfer.
7. The method for transferring a terahertz self-assembled carbon nanotube array according to claim 6, wherein the target flexible substrate comprises polydimethylsiloxane, polyimide, polyvinyl chloride, and polyethylene terephthalate dielectric materials.
8. The method for measuring orientation of the self-assembled carbon nanotube array for terahertz prepared by the preparation method of claim 5 is characterized in that for the horizontally arranged and oriented carbon nanotubes, the direction of a connecting line between a pair of gold electrodes or the direction of a nanoscale groove on the filter membrane is used as the orientation direction of the oriented carbon nanotubes.
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