CN102294852B - Nano wire film and manufacturing method thereof - Google Patents

Abstract

Translated fromChinese

一种纳米线薄膜，其中，该纳米线薄膜包括第一基板以及依次层迭于该第一基板上的纳米线层、热塑性高分子膜层及第二基板，其中该纳米线层由多个纳米线组成，该纳米线的延伸方向平行于该第一基板。与现有技术相比，本发明所提供的纳米线薄膜具有大面积规则排列的纳米线，适合规模化生产。本发明还涉及该纳米线薄膜的制造方法。

A nanowire film, wherein the nanowire film includes a first substrate, a nanowire layer, a thermoplastic polymer film layer and a second substrate sequentially laminated on the first substrate, wherein the nanowire layer is composed of a plurality of nanowire layers composed of wires, the extension direction of the nanowires is parallel to the first substrate. Compared with the prior art, the nanowire thin film provided by the invention has a large area of regularly arranged nanowires and is suitable for large-scale production. The invention also relates to a manufacturing method of the nanowire thin film.

Description

Translated fromChinese

纳米线薄膜及其制造方法Nanowire thin film and its manufacturing method

技术领域technical field

本发明涉及一种纳米线薄膜及其制造方法。The invention relates to a nanowire thin film and a manufacturing method thereof.

背景技术Background technique

在高度集成化浪潮的推动下，现代技术对纳米尺度功能器件的需求将越来越迫切。纳米线具有极高的表面积对体积比，此一维结构在表面特征、机械性质、量子效应等方面皆有不俗的表现，因此根据不同材料的特性，其纳米线结构也相应的衍生了各种不同的应用，诸如：气体传感器、场效晶体管以及发光组件等。Driven by the wave of high integration, the demand for nanoscale functional devices in modern technology will become more and more urgent. Nanowires have a very high surface area to volume ratio. This one-dimensional structure has excellent performance in surface characteristics, mechanical properties, quantum effects, etc. Therefore, according to the characteristics of different materials, its nanowire structure is also derived from various different applications, such as: gas sensors, field effect transistors, and lighting components.

然而，在利用纳米线制作组件的难度在于，如何克服其尺寸问题并加以对位、控制是一个难点。倘若能够控制纳米线使之大量规则排列，将会使得纳米线能够顺利的导入量产制程。目前已知的制备纳米线薄膜方法大致有：介电泳(Dielectrophoresis)、微流道(Micro-fluid channel)、吹膜(Blown filmextrusion)等方法，而以上制程皆需将纳米线自成长基板取下，再均匀分散至溶剂中，属于湿式制程，其在准备或排列上需耗费较长时间，并且在将纳米线自成长基板上取下的过程中，很容易损坏纳米线的结构而影响了其功能性。However, the difficulty in using nanowires to make components lies in how to overcome the size problem and how to align and control them. If the nanowires can be controlled to make a large number of regular arrangements, the nanowires can be successfully introduced into the mass production process. Currently known methods for preparing nanowire thin films generally include: Dielectrophoresis, Micro-fluid channel, Blown filmextrusion and other methods, all of which require the removal of the nanowire self-growth substrate , and then uniformly dispersed into the solvent, which belongs to the wet process, which takes a long time to prepare or arrange, and in the process of removing the nanowires from the growth substrate, it is easy to damage the structure of the nanowires and affect its Feature.

发明内容Contents of the invention

有鉴于此，提供一种制程简单并且成本较低的纳米线薄膜及其制造方法实为必要。In view of this, it is necessary to provide a nanowire thin film with simple manufacturing process and low cost and its manufacturing method.

一种纳米线薄膜，其中，该纳米线薄膜包括第一基板以及依次层叠于该第一基板上的纳米线层、热塑性高分子膜层及第二基板，其中该纳米线层由多个纳米线组成，该纳米线的延伸方向平行于该第一基板。A nanowire film, wherein the nanowire film comprises a first substrate and a nanowire layer, a thermoplastic polymer film layer and a second substrate sequentially stacked on the first substrate, wherein the nanowire layer is composed of a plurality of nanowires Composition, the extension direction of the nanowire is parallel to the first substrate.

一种纳米线薄膜的制造方法，其包括如下步骤：提供一第一基板，该第一基板具有第一表面，该第一表面上垂直生长有纳米线阵列；提供一第二基板，该第二基板具有第二表面，在该第二表面上涂覆一层溶解有热塑性高分子材料的溶液；加热该第二基板以蒸发该溶液的溶剂以使该热塑性高分子材料析出成膜，进一步加热以软化该热塑性高分子膜；将该第二基板与该第一基板相互盖合以使该第二基板上被软化后的该热塑性高分子膜与生长于该第一基板上的纳米线阵列相互贴合；滚轮压合该相互盖合的第一基板与第二基板。A method for manufacturing a nanowire thin film, which includes the following steps: providing a first substrate, the first substrate has a first surface, and a nanowire array is vertically grown on the first surface; providing a second substrate, the second The substrate has a second surface, and a layer of solution in which a thermoplastic polymer material is dissolved is coated on the second surface; the second substrate is heated to evaporate the solvent of the solution so that the thermoplastic polymer material is deposited to form a film, and further heated to softening the thermoplastic polymer film; covering the second substrate with the first substrate so that the softened thermoplastic polymer film on the second substrate and the nanowire array grown on the first substrate are attached to each other close; the roller presses the first substrate and the second substrate that are covered with each other.

与现有技术相比，本发明提供的该纳米线薄膜具有大面积规则排列的纳米线，便于后续的使用。该纳米线薄膜的制造方法操作简单，能够对生长于基板上的纳米线阵列直接进行加工，无须将纳米线阵列由生长基板上取下，从而不但避免了纳米线阵列在由生长基板上取下的过程中受到损伤，而且可以实现纳米线薄膜的规模化生产。Compared with the prior art, the nanowire film provided by the invention has a large area of regularly arranged nanowires, which is convenient for subsequent use. The manufacturing method of the nanowire thin film is easy to operate, and can directly process the nanowire array grown on the substrate without removing the nanowire array from the growth substrate, thus not only avoiding the removal of the nanowire array from the growth substrate The process is damaged, and the large-scale production of nanowire films can be realized.

附图说明Description of drawings

图1是本发明实施例所提供的该纳米线薄膜的结构示意图。FIG. 1 is a schematic structural view of the nanowire film provided by an embodiment of the present invention.

图2是图1所示的该纳米线薄膜的制造流程示意图。FIG. 2 is a schematic diagram of the manufacturing process of the nanowire film shown in FIG. 1 .

图3是图1所示的该纳米线薄膜中纳米线的电镜照片。FIG. 3 is an electron micrograph of the nanowires in the nanowire film shown in FIG. 1 .

主要元件符号说明Description of main component symbols

纳米线薄膜        100Nanowire film 100

第一基板          10First Substrate 10

第一表面          11First Surface 11

纳米线阵列        12Nanowire Array 12

纳米线层          20Nanowire layer 20

热塑性高分子膜层  30Thermoplastic polymer film layer 30

第二基板          40Second Substrate 40

第二表面          41Second Surface 41

具体实施方式Detailed ways

下面将结合附图对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings.

请参见图1，本发明实施例所提供的纳米线薄膜100，其包括第一基板10以及依次层叠于该第一基板10上的纳米线层20、热塑性高分子膜层30以及第二基板40。Please refer to FIG. 1 , the nanowire film 100 provided by the embodiment of the present invention includes a first substrate 10 and a nanowire layer 20 , a thermoplastic polymer film layer 30 and a second substrate 40 sequentially stacked on the first substrate 10 .

该纳米线层20由多个平行排列的纳米线组成，并且该纳米线的延伸方向平行于该第一基板10。在本实施例中，该纳米线层20为碳纳米线层，可以理解的，该纳米线层20还可以是其它材料的纳米线层，例如硅纳米线层、氧化锌纳米线层等，并且该多个纳米线也可以不相互平行。The nanowire layer 20 is composed of a plurality of nanowires arranged in parallel, and the extension direction of the nanowires is parallel to the first substrate 10 . In this embodiment, the nanowire layer 20 is a carbon nanowire layer. It can be understood that the nanowire layer 20 can also be a nanowire layer of other materials, such as a silicon nanowire layer, a zinc oxide nanowire layer, etc., and The plurality of nanowires may not be parallel to each other.

如图2所示，本发明还提供了上述纳米线薄膜100的制造方法，其包括如下步骤。As shown in FIG. 2 , the present invention also provides a method for manufacturing the aforementioned nanowire thin film 100 , which includes the following steps.

(1)提供一第一基板10，该第一基板10具有第一表面11，该第一表面11上垂直生长有纳米线阵列12。(1) A first substrate 10 is provided. The first substrate 10 has a first surface 11 on which a nanowire array 12 is vertically grown.

在本实施例中，该第一基板10为硅基板，该纳米线阵列12为直接生长在该硅基板上的碳纳米线阵列，优选的，该碳纳米线阵列为超顺排列的碳纳米线阵列。In this embodiment, the first substrate 10 is a silicon substrate, and the nanowire array 12 is a carbon nanowire array directly grown on the silicon substrate. Preferably, the carbon nanowire array is a superparallel carbon nanowire array. array.

可以理解的，该第一基板10还可以是其它的刚性基板或者可挠性基板，该纳米线阵列12可以是通过移植等方法由其它适合于纳米线生长的基板上移植到该第一基板10上的。It can be understood that the first substrate 10 can also be other rigid substrates or flexible substrates, and the nanowire array 12 can be grafted onto the first substrate 10 from other substrates suitable for nanowire growth by methods such as transplantation. Up.

可以理解的，该纳米线阵列12可以是由其它材料所形成的纳米线阵列，例如硅纳米线阵列、氧化锌纳米阵列等。It can be understood that the nanowire array 12 may be a nanowire array formed of other materials, such as a silicon nanowire array, a zinc oxide nanowire array, and the like.

(2)提供一第二基板40，该第二基板具有第二表面41，采用旋转涂布的方式在该第二表面41上涂覆一层溶解有热塑性高分子材料的溶液。(2) A second substrate 40 is provided, the second substrate has a second surface 41 , and a solution in which a thermoplastic polymer material is dissolved is coated on the second surface 41 by means of spin coating.

该第二基板40可以是刚性基板或者可挠性基板，在本实施例中该第二基板40是聚对苯二甲酸乙二醇酯(PET)基板，而该热塑性高分子材料是聚甲基丙烯酸甲酯(PMMA)。The second substrate 40 can be a rigid substrate or a flexible substrate. In this embodiment, the second substrate 40 is a polyethylene terephthalate (PET) substrate, and the thermoplastic polymer material is polymethyl Methyl acrylate (PMMA).

需要注意的是，在选择该热塑性高分子材料的溶剂时需要考虑该第二基板40的材料，以使使用的溶剂适合于该第二基板40。在本实施例中，该第二基板40为亲水性的PET基板，故选择极性较低的甲苯作为PMMA的溶剂。It should be noted that the material of the second substrate 40 needs to be considered when selecting the solvent for the thermoplastic polymer material, so that the used solvent is suitable for the second substrate 40 . In this embodiment, the second substrate 40 is a hydrophilic PET substrate, so toluene with low polarity is selected as the PMMA solvent.

在该第二基板40上进行旋转涂布时，该PMMA溶液的浓度与旋转涂布的速度设定则依据实际所需进行调整控制，只要使得最后涂覆于该第二基板40上的可塑性高分子膜层30的厚度满足使用需要即可。When performing spin coating on the second substrate 40, the concentration of the PMMA solution and the speed setting of the spin coating are then adjusted and controlled according to actual needs, as long as the plasticity of the final coating on the second substrate 40 is high. The thickness of the molecular film layer 30 only needs to be satisfied.

(3)加热该第二基板40以蒸发该PMMA溶液的溶剂以使PMMA析出成膜，进一步加热以软化该PMMA膜。(3) Heating the second substrate 40 to evaporate the solvent of the PMMA solution to precipitate the PMMA to form a film, and further heating to soften the PMMA film.

优选的，在对该第二基板40加热时采用两段式加热，首先以较低的温度对该第二基板40进行加热使该PMMA溶液中的溶剂完全挥发，此时PMMA全部析出成膜并贴覆在该第二基板40的第二表面41上，然后升温至该PMMA玻璃化转变温度或以上以软化该PMMA膜。这样可以避免由于溶剂蒸发过快而使得生成的PMMA膜的均匀度受到影响。Preferably, when the second substrate 40 is heated, two-stage heating is adopted. First, the second substrate 40 is heated at a lower temperature so that the solvent in the PMMA solution is completely volatilized. At this time, all the PMMA is separated into a film and formed into a film. paste on the second surface 41 of the second substrate 40, and then heat up to the PMMA glass transition temperature or above to soften the PMMA film. In this way, the uniformity of the generated PMMA film can be prevented from being affected due to too fast evaporation of the solvent.

(4)将该第二基板40盖向该第一基板10，并使得该第二基板40上被软化后的PMMA膜与生长于该第一基板10上的纳米线阵列12相互贴合。(4) Cover the second substrate 40 to the first substrate 10 , and make the softened PMMA film on the second substrate 40 adhere to the nanowire array 12 grown on the first substrate 10 .

(5)滚轮压合该相互贴合的第一基板10与第二基板40。(5) The roller presses the first substrate 10 and the second substrate 40 that are attached to each other.

在滚轮压合过程中，滚轮会提供一侧向压力来推倒垂直生长于该第一基板10上的纳米线阵列12，并且同时在压合过程中藉由该软化后的PMMA膜所产生的黏滞力来带动该纳米线阵列12发生侧向倾倒，最后可以获得大面积规则排列的纳米线薄膜100，图3为依照上述方法所制备出来的纳米线薄膜的微观照片，图中黑色背景为纳米线薄膜的基板，白色条状物为平行于该基板排列的纳米线群。During the roller bonding process, the rollers will provide lateral pressure to push down the nanowire arrays 12 vertically grown on the first substrate 10, and at the same time, the softened PMMA film will produce a sticky layer during the bonding process. The hysteresis force drives the nanowire array 12 to dump sideways, and finally a large-area regularly arranged nanowire film 100 can be obtained. FIG. 3 is a microscopic photo of the nanowire film prepared according to the above method. The black background in the figure is nano The substrate of the wire film, and the white strips are nanowire groups arranged parallel to the substrate.

可以理解的是，本领域技术人员还可于本发明精神内做其它变化等用于本发明的设计，只要其不偏离本发明的技术效果均可。这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。It can be understood that those skilled in the art can also make other changes within the spirit of the present invention for the design of the present invention, as long as they do not deviate from the technical effects of the present invention. These changes made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims (6)

1. a manufacture method for nano wire film, is characterized in that comprising the steps:

One first substrate is provided, and this first substrate has first surface, and on this first surface, vertical-growth has nano-wire array;

One second substrate is provided, and this second substrate has second surface, applies one deck and be dissolved with the solution of thermoplastic macromolecule material on this second surface;

First heat this second substrate to evaporate the solvent of this solution so that this thermoplastic macromolecule material is separated out film forming with lower temperature, and then be warming up to the glass transition temperature of this thermoplastic macromolecule material or above to soften this thermal plastic high polymer film;

This second substrate and this first substrate are covered mutually so that this thermal plastic high polymer film after being softened on this second substrate with to grow in nano-wire array on this first substrate bonded to each other;

Roller pressing this first substrate mutually covering and second substrate.

2. the manufacture method of nano wire film as claimed in claim 1, is characterized in that: this nano-wire array is the nano-wire array of super in-line arrangement row.

3. the manufacture method of nano wire film as claimed in claim 1, is characterized in that: this nano-wire array is the carbon nanocoils array of super in-line arrangement row.

4. the manufacture method of nano wire film as claimed in claim 1, is characterized in that: this second substrate is pliability transparency carrier.

5. the manufacture method of nano wire film as claimed in claim 1, is characterized in that: this thermoplastic macromolecule material is polymethyl methacrylate.

6. the manufacture method of nano wire film as claimed in claim 1, is characterized in that: this solution that is dissolved with thermoplastic macromolecule material is to adopt the mode of rotary coating to be coated on the second surface of this second substrate.