TWI406810B - Carbon nanotube film and method for making the same - Google Patents
Carbon nanotube film and method for making the same Download PDFInfo
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本發明涉及一種奈米碳管膜及其製備方法，尤其涉及一種透光性較好的奈米碳管膜及其製備方法。 The invention relates to a carbon nanotube film and a preparation method thereof, in particular to a carbon nanotube film with better light transmittance and a preparation method thereof.
奈米碳管(Carbon Nanotube,CNT)係一種由石墨烯片卷成的中空管狀物，其具有優異的力學、熱學及電學性質，因此具有廣闊的應用領域。由於單根奈米碳管的直徑只有幾個奈米至幾十奈米，難於進行加工，為便於實際應用，人們嘗試將大量奈米碳管作為原材料，製成具有較大尺寸的宏觀結構。奈米碳管膜(Carbon Nanotube Film,CNT Film)即為此種宏觀結構的具體形式之一。 Carbon Nanotube (CNT) is a hollow tube made of graphene sheets. It has excellent mechanical, thermal and electrical properties and therefore has a wide range of applications. Since the diameter of a single carbon nanotube is only a few nanometers to several tens of nanometers, it is difficult to process. For practical application, a large number of carbon nanotubes are used as raw materials to form a macrostructure having a large size. Carbon Nanotube Film (CNT Film) is one of the specific forms of such a macro structure.
馮辰等人在2008年8月16日公開的中華民國專利申請第200833862號中揭露了一種從奈米碳管陣列中直接拉取獲得的奈米碳管膜，這種奈米碳管膜具有宏觀尺度且能够自支撑，其包括多個在凡德瓦爾力作用下首尾相連的奈米碳管。由於在這種直接拉取獲得的奈米碳管膜中奈米碳管基本平行於奈米碳管膜表面，且相互並排的奈米碳管間存在一定間隙，因此該奈米碳管膜較為透明。另外，由於該奈米碳管膜中奈米碳管基本沿同一方向排列，因此該奈米碳管膜能够較好的發揮奈米碳管軸向具有的導電及導熱等各種優異性質，具有極為廣泛的應用前景。 A carbon nanotube film obtained by directly pulling from a carbon nanotube array is disclosed in the Chinese Patent Application No. 200833862, published on Aug. 16, 2008, which has a carbon nanotube film having It is self-supporting on a macro scale and includes a number of carbon nanotubes connected end to end under the action of Van der Valli. Since the carbon nanotube film obtained in the direct drawing is substantially parallel to the surface of the carbon nanotube film and there is a gap between the carbon nanotubes arranged side by side, the carbon nanotube film is relatively Transparent. In addition, since the carbon nanotubes in the carbon nanotube film are arranged substantially in the same direction, the carbon nanotube film can exhibit various excellent properties such as conductivity and heat conduction in the axial direction of the carbon nanotube. Wide application prospects.
然而，該直接拉取獲得的奈米碳管膜中，相鄰且並排的奈米碳管之間由於凡德瓦爾力的作用會聚集接觸從而形成較大直徑的奈米碳管束，該奈米碳 管束具有較大密度，使奈米碳管膜的透光性受到影響。 However, in the carbon nanotube film obtained by direct drawing, the adjacent and side-by-side carbon nanotubes are brought into contact due to the action of the van der Waals force to form a larger diameter carbon nanotube bundle, the nanometer. carbon The tube bundle has a large density, which affects the light transmittance of the carbon nanotube film.
有鑒於此，提供一種具有較好透光性的奈米碳管膜及其製備方法實為必要。 In view of the above, it is necessary to provide a carbon nanotube film having good light transmittance and a preparation method thereof.
一種奈米碳管膜的製備方法，其包括以下步驟：提供一奈米碳管初級膜，該奈米碳管初級膜由若干奈米碳管組成，所述若干奈米碳管為沿同一方向擇優取向排列；採用一雷射束沿平行於該若干奈米碳管擇優取向的方向逐行掃描該奈米碳管初級膜，從而在該奈米碳管初級膜中的局部位置形成多個减薄區域，該多個减薄區域沿該若干奈米碳管擇優取向的方向排列成至少一行。 A method for preparing a carbon nanotube film, comprising the steps of: providing a carbon nanotube primary membrane, the primary carbon nanotube membrane consisting of a plurality of carbon nanotubes, wherein the plurality of carbon nanotubes are in the same direction Aligning the preferred orientation; scanning the primary film of the carbon nanotubes line by line with a laser beam in a direction parallel to the preferred orientation of the plurality of carbon nanotubes, thereby forming a plurality of reductions in local locations in the primary film of the carbon nanotubes In the thin region, the plurality of thinned regions are arranged in at least one row along a direction in which the plurality of carbon nanotubes are preferentially oriented.
一種奈米碳管膜，該奈米碳管膜由若干奈米碳管組成，所述若干奈米碳管為沿同一方向擇優取向排列，該奈米碳管膜中定義有多個减薄區域，該多個减薄區域沿該若干奈米碳管擇優取向的方向排列成至少一行。 A carbon nanotube film consisting of a plurality of carbon nanotubes arranged in a preferred orientation in the same direction, wherein a plurality of thinned regions are defined in the carbon nanotube film And the plurality of thinned regions are arranged in at least one row along a direction in which the plurality of carbon nanotubes are preferentially oriented.
相較於先前技術，由於奈米碳管初級膜經雷射掃描後部分奈米碳管被氧化形成减薄區域，其中减薄區域的奈米碳管分佈密度降低，使該奈米碳管膜透光性增強。該雷射掃描沿奈米碳管初級膜中奈米碳管擇優取向的方向，使兩個相鄰的掃描行間的部分奈米碳管初級膜不致被破壞，從而使該奈米碳管膜在奈米碳管軸向的方向上具有較好的導電性，提高該奈米碳管膜的各向異性。 Compared with the prior art, since the carbon nanotubes are partially scanned by the laser, a portion of the carbon nanotubes are oxidized to form a thinned region, wherein the carbon nanotube distribution density in the thinned region is lowered to make the carbon nanotube film The light transmission is enhanced. The laser scanning is oriented along the preferred orientation of the carbon nanotubes in the primary membrane of the carbon nanotubes, so that the partial carbon nanotubes between the two adjacent scanning lines are not destroyed, so that the carbon nanotube membrane is The carbon nanotubes have good electrical conductivity in the axial direction, which improves the anisotropy of the carbon nanotube film.
100‧‧‧奈米碳管膜 100‧‧‧Nano carbon nanotube film
120‧‧‧奈米碳管初級膜 120‧‧‧Nanocarbon tube primary membrane
150‧‧‧奈米碳管陣列 150‧‧‧Nano Carbon Tube Array
110‧‧‧拉伸工具 110‧‧‧ stretching tools
143‧‧‧奈米碳管片段 143‧‧‧Nano carbon nanotube fragments
145‧‧‧奈米碳管 145‧‧・Nano carbon tube
140‧‧‧基底 140‧‧‧Base
130‧‧‧黏結劑層 130‧‧‧Binder layer
170‧‧‧雷射束 170‧‧‧Ray beam
126‧‧‧减薄區域 126‧‧‧Thinning area
124‧‧‧掃描行 124‧‧‧ scan line
128‧‧‧長條形區域 128‧‧‧Long strip area
180‧‧‧光斑 180‧‧‧ spot
160‧‧‧雷射裝置 160‧‧‧ Laser device
圖1係本發明實施例奈米碳管初級膜製備過程示意圖。 1 is a schematic view showing a preparation process of a primary film of a carbon nanotube according to an embodiment of the present invention.
圖2係本發明實施例奈米碳管初級膜掃描電鏡照片。 2 is a scanning electron micrograph of a primary film of a carbon nanotube according to an embodiment of the present invention.
圖3係圖2的奈米碳管初級膜中奈米碳管片段的結構示意圖。 3 is a schematic view showing the structure of a carbon nanotube segment in the primary membrane of the carbon nanotube of FIG. 2.
圖4係將圖2的奈米碳管初級膜鋪設於一基底的過程示意圖。 4 is a schematic view showing the process of laying the primary film of the carbon nanotube of FIG. 2 on a substrate.
圖5係本發明實施例一種具有間隔的减薄區域的奈米碳管膜的俯視示意圖。 Figure 5 is a top plan view of a carbon nanotube film having spaced apart thinned regions in accordance with an embodiment of the present invention.
圖6係本發明實施例一種具有連續的减薄區域的奈米碳管膜的俯視示意圖。 6 is a top plan view of a carbon nanotube film having a continuous thinned region in accordance with an embodiment of the present invention.
圖7係雷射减薄法製備本發明實施例奈米碳管膜的正視示意圖。 Fig. 7 is a front elevational view showing the preparation of a carbon nanotube film of the embodiment of the present invention by a laser thinning method.
圖8係雷射光斑在奈米碳管初級膜表面的一種移動路線示意圖。 Figure 8 is a schematic diagram of a movement path of a laser spot on the surface of the primary membrane of the carbon nanotube.
圖9係本發明實施例雷射减薄後形成的减薄區域的掃描電鏡照片。 Figure 9 is a scanning electron micrograph of a thinned region formed after laser thinning in accordance with an embodiment of the present invention.
圖10係本發明實施例另一種具有間隔的减薄區域的奈米碳管膜的俯視示意圖。 Figure 10 is a top plan view of another carbon nanotube film having spaced apart thinned regions in accordance with an embodiment of the present invention.
圖11係本發明實施例另一種具有連續的减薄區域的奈米碳管膜的俯視示意圖。 Figure 11 is a top plan view of another carbon nanotube film having a continuous thinned region in accordance with an embodiment of the present invention.
以下將結合附圖詳細說明本發明實施例奈米碳管膜及其製備方法。 Hereinafter, a carbon nanotube film of an embodiment of the present invention and a method for preparing the same will be described in detail with reference to the accompanying drawings.
本發明實施例提供一種具有較好透光性的奈米碳管膜100的製備方法，其包括以下步驟： The embodiment of the invention provides a method for preparing a carbon nanotube film 100 with better light transmittance, which comprises the following steps:
步驟一：提供一奈米碳管初級膜120。 Step 1: A carbon nanotube primary membrane 120 is provided.
請參閱圖1，該奈米碳管初級膜120可以從一奈米碳管陣列150中直接拉取獲得，其具體包括以下步驟： Referring to FIG. 1, the carbon nanotube primary film 120 can be directly drawn from a carbon nanotube array 150, which specifically includes the following steps:
(一)提供一奈米碳管陣列150。 (1) Providing a carbon nanotube array 150.
該奈米碳管陣列150通過化學氣相沈積法形成於一生長基底表面，優選為超順排的奈米碳管陣列150。該奈米碳管陣列150包括多個奈米碳管，該多個奈米碳管基本彼此平行且垂直於生長基底表面。通過控制生長條件，該奈 米碳管陣列150中基本不含有雜質，如無定型碳或殘留的催化劑金屬顆粒等。所述奈米碳管陣列150的製備方法可參閱馮辰等人在2008年8月16日公開的中華民國專利申請第200833862號。 The carbon nanotube array 150 is formed by chemical vapor deposition on a surface of a growth substrate, preferably a super-sequential carbon nanotube array 150. The carbon nanotube array 150 includes a plurality of carbon nanotubes that are substantially parallel to each other and perpendicular to the surface of the growth substrate. By controlling growth conditions, the nai The carbon nanotube array 150 contains substantially no impurities such as amorphous carbon or residual catalyst metal particles. The preparation method of the carbon nanotube array 150 can be referred to the Republic of China Patent Application No. 200833862, which was published on August 16, 2008 by Feng Chen et al.
該奈米碳管陣列150中的奈米碳管可以至少包括單壁奈米碳管、雙壁奈米碳管及多壁奈米碳管中的一種。所述奈米碳管的直徑為1奈米~50奈米，長度為50奈米~5毫米。本實施例中，奈米碳管的長度優選為100微米~900微米。 The carbon nanotubes in the carbon nanotube array 150 may include at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube. The carbon nanotubes have a diameter of 1 nm to 50 nm and a length of 50 nm to 5 mm. In this embodiment, the length of the carbon nanotubes is preferably from 100 micrometers to 900 micrometers.
可以理解，本發明實施例提供的奈米碳管陣列150不限於通過上述方法製備，也可為石墨電極恒流電弧放電沈積法、雷射蒸發沈積法等。 It can be understood that the carbon nanotube array 150 provided by the embodiment of the present invention is not limited to being prepared by the above method, and may be a graphite electrode constant current arc discharge deposition method, a laser evaporation deposition method, or the like.
(二)採用一拉伸工具110從該奈米碳管陣列150中拉取獲得該奈米碳管初級膜120。其具體包括以下步驟：(a)從所述奈米碳管陣列150中選定一奈米碳管片段，本實施例優選為採用具有一定寬度的膠帶或黏性基條接觸該奈米碳管陣列150以選定具有一定寬度的一奈米碳管片段；(b)通過移動該拉伸工具110，以一定速度拉取該選定的奈米碳管片段，從而首尾相連的拉出多個奈米碳管片段，進而形成一連續的奈米碳管初級膜120。該拉伸工具110基本沿平行於生長基底表面的方向移動。 (b) The carbon nanotube primary film 120 is obtained by pulling from the carbon nanotube array 150 using a stretching tool 110. Specifically, the method comprises the following steps: (a) selecting a carbon nanotube segment from the carbon nanotube array 150, and in this embodiment, preferably contacting the carbon nanotube array with a tape or a viscous strip having a certain width. 150 to select a carbon nanotube segment having a certain width; (b) pulling the selected carbon nanotube segment at a certain speed by moving the stretching tool 110, thereby pulling out a plurality of nanocarbons end to end The tube segments, in turn, form a continuous carbon nanotube primary membrane 120. The stretching tool 110 moves substantially in a direction parallel to the surface of the growth substrate.
在上述步驟(二)中，該通過拉伸工具110選定的奈米碳管片段可僅為一奈米碳管，也可由多個基本相互平行的奈米碳管組成。該多個奈米碳管相互並排使該奈米碳管片段具有一定寬度。當該被選定的一個或多個奈米碳管在拉力作用下沿拉取方向逐漸脫離基底的同時，由於凡德瓦爾力作用，與該選定的奈米碳管相鄰的其它奈米碳管首尾相連地相繼地被拉出，從而形成一連續、均勻且具有一定寬度的奈米碳管初級膜120。 In the above step (2), the carbon nanotube segments selected by the stretching tool 110 may be only one carbon nanotube or may be composed of a plurality of substantially parallel carbon nanotubes. The plurality of carbon nanotubes are arranged side by side such that the carbon nanotube segments have a certain width. When the selected one or more carbon nanotubes are gradually separated from the substrate in the pulling direction under the pulling force, other carbon nanotubes adjacent to the selected carbon nanotubes due to the van der Waals force They are successively pulled out end to end to form a continuous, uniform, and wide width of the carbon nanotube primary membrane 120.
請參閱圖2，所述奈米碳管初級膜120係由若干奈米碳管組成的自支撑結構 。所述若干奈米碳管為沿同一方向擇優取向排列。所述擇優取向係指在奈米碳管初級膜120中大多數奈米碳管的整體延伸方向基本朝同一方向。而且，所述大多數奈米碳管的整體延伸方向基本平行於奈米碳管初級膜120的表面。進一步地，所述奈米碳管初級膜120中多數奈米碳管係通過凡德瓦爾力首尾相連。具體地，所述奈米碳管初級膜120中基本朝同一方向延伸的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡德瓦爾力首尾相連。當然，所述奈米碳管膜中存在少數偏離該延伸方向的奈米碳管，這些奈米碳管不會對奈米碳管初級膜120中大多數奈米碳管的整體取向排列構成明顯影響。所述自支撑為奈米碳管初級膜120不需要大面積的載體支撑，而只要相對兩邊提供支撑力即能整體上懸空而保持自身膜狀狀態，即將該奈米碳管初級膜120置於(或固定於)間隔一定距離設置的兩個支撑體上時，位於兩個支撑體之間的奈米碳管初級膜120能够懸空保持自身膜狀狀態。所述自支撑主要通過奈米碳管初級膜120中存在連續的通過凡德瓦爾力首尾相連延伸排列的奈米碳管而實現。 Referring to FIG. 2, the carbon nanotube primary membrane 120 is a self-supporting structure composed of a plurality of carbon nanotubes. . The plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. The preferred orientation means that the majority of the carbon nanotubes in the primary membrane 120 of the carbon nanotubes extend substantially in the same direction. Moreover, the overall direction of extension of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube primary membrane 120. Further, most of the carbon nanotubes in the carbon nanotube primary membrane 120 are connected end to end by Van der Waals force. Specifically, each of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube primary membrane 120 and the carbon nanotubes adjacent in the extending direction pass through the van der Waals force. Connected. Of course, there are a few carbon nanotubes in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the primary membrane 120 of the carbon nanotubes. influences. The self-supporting carbon nanotube primary film 120 does not require a large-area carrier support, but can maintain a self-membrane state as long as the supporting force is provided on both sides, that is, the carbon nanotube primary film 120 is placed. When (or fixed to) two support bodies disposed at a distance apart, the carbon nanotube primary film 120 located between the two supports can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of continuous carbon nanotubes arranged in an end-to-end extension by van der Waals force in the primary carbon nanotube film 120.
具體地，所述奈米碳管初級膜120中基本朝同一方向延伸的多數奈米碳管，並非絕對的直線狀，可以適當的彎曲；或者並非完全按照延伸方向上排列，可以適當的偏離延伸方向。因此，不能排除奈米碳管初級膜120的基本朝同一方向延伸的多數奈米碳管中並列的奈米碳管之間可能存在部分接觸。 Specifically, the majority of the carbon nanotubes in the primary film 120 of the carbon nanotubes are substantially in a straight line shape and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately extended. direction. Therefore, partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes of the carbon nanotube primary membrane 120 extending substantially in the same direction cannot be excluded.
具體地，請參閱圖3，每一奈米碳管初級膜120包括多個連續且定向排列的奈米碳管片段143。該多個奈米碳管片段143通過凡德瓦爾力首尾相連。每一奈米碳管片段143由多個相互平行的奈米碳管145組成，該多個相互平行的奈米碳管145通過凡德瓦爾力緊密結合。該奈米碳管片段143具有任意的長度、厚度、均勻性及形狀。 Specifically, referring to FIG. 3, each of the carbon nanotube primary membranes 120 includes a plurality of continuous and aligned carbon nanotube segments 143. The plurality of carbon nanotube segments 143 are connected end to end by Van der Waals force. Each of the carbon nanotube segments 143 is composed of a plurality of mutually parallel carbon nanotubes 145 which are tightly bonded by van der Waals forces. The carbon nanotube segments 143 have any length, thickness, uniformity, and shape.
所述奈米碳管初級膜120的厚度為0.5奈米~100微米，長度及寬度與奈米碳 管陣列的面積有關。當該奈米碳管陣列150的直徑為4英寸時，該奈米碳管初級膜120的寬度約為0.5奈米~10厘米。該奈米碳管初級膜120的比表面積大於100平方米每克。 The carbon nanotube primary film 120 has a thickness of 0.5 nm to 100 μm, and has a length and a width and a nano carbon. The area of the tube array is related. When the carbon nanotube array 150 has a diameter of 4 inches, the carbon nanotube primary film 120 has a width of about 0.5 nm to 10 cm. The carbon nanotube primary membrane 120 has a specific surface area greater than 100 square meters per gram.
在上述選定奈米碳管並拉取的步驟中，由於難以通過拉伸工具110控制選定的奈米碳管片段的厚度，且並排的奈米碳管之間易通過凡德瓦爾力的吸引而相互聚集接觸，形成直徑較大的奈米碳管束，使拉取獲得的奈米碳管初級膜120厚度均勻性不佳。該奈米碳管束包含的奈米碳管數量較多，使奈米碳管束密度較大，因此透光性差，從而使得該奈米碳管初級膜120具有較差的透光性。經測試，該奈米碳管初級膜120的可見光透過率最大為75%。 In the step of selecting and drawing the carbon nanotubes described above, it is difficult to control the thickness of the selected carbon nanotube segments by the stretching tool 110, and the side-by-side carbon nanotubes are easily attracted by the van der Waals force. The mutually aggregated contact forms a bundle of carbon nanotubes having a larger diameter, so that the thickness of the carbon nanotube primary film 120 obtained by the drawing is not uniform. The carbon nanotube bundle contains a large number of carbon nanotubes, so that the carbon nanotube bundle has a large density, and thus the light transmittance is poor, so that the carbon nanotube primary membrane 120 has poor light transmittance. The carbon nanotube primary film 120 has been tested to have a visible light transmission of at most 75%.
請參閱圖4，該從奈米碳管陣列150中拉取獲得的奈米碳管初級膜120可通過其自身的自支撑性懸空設置，也可進一步設置於一基底140表面，其具體包括以下可選擇步驟：提供一基底140；將該奈米碳管初級膜120鋪設於該基底140一表面。由於本實施例中奈米碳管陣列150非常純淨，且由於奈米碳管本身的比表面積非常大，所以該奈米碳管初級膜120本身具有較強的黏性。因此，該奈米碳管初級膜120可直接通過自身的黏性固定在所述基底140表面。 Referring to FIG. 4 , the carbon nanotube primary film 120 taken from the carbon nanotube array 150 can be disposed by its own self-supporting suspension or can be further disposed on a surface of the substrate 140 , which specifically includes the following An optional step of: providing a substrate 140; laying the carbon nanotube primary film 120 on a surface of the substrate 140. Since the carbon nanotube array 150 is very pure in this embodiment, and since the specific surface area of the carbon nanotube itself is very large, the carbon nanotube primary film 120 itself has a strong viscosity. Therefore, the carbon nanotube primary film 120 can be directly fixed to the surface of the substrate 140 by its own viscosity.
該基底140可以為一透明或不透明的硬性或柔性基底，該基底140的材料不限，能够為保護該奈米碳管初級膜120並為該奈米碳管初級膜120提供一定支撑即可。該基底140的材料可以為玻璃、石英、塑膠或樹脂。本實施例中，該基底140為一聚對苯二甲酸乙二醇酯(PET)透明平板基底。 The substrate 140 can be a transparent or opaque rigid or flexible substrate. The material of the substrate 140 is not limited, and can protect the carbon nanotube primary film 120 and provide some support for the carbon nanotube primary film 120. The material of the substrate 140 may be glass, quartz, plastic or resin. In this embodiment, the substrate 140 is a polyethylene terephthalate (PET) transparent flat substrate.
進一步地，將該奈米碳管初級膜120鋪設於該基底140表面前可進一步包括在該基底140表面塗覆一黏結劑層130的步驟。該黏結劑層130均勻的塗覆在該基底140表面。該黏結劑層130的材料不限，可以將該奈米碳管初級膜120與該基底140更為牢固地結合即可，如一壓敏膠、熱敏膠或光敏膠等。 本實施例中，該黏結劑層130的材料可以為丙烯酸丁酯、丙烯酸-2-乙基已酯、醋酸乙烯、甲基丙烯酸縮水甘油酯、丙烯酸、過氧化苯甲醯及甲苯及醋酸乙酯的混合物。 Further, the step of coating the carbon nanotube primary film 120 on the surface of the substrate 140 may further include the step of coating a surface of the substrate 140 with a layer of adhesive 130. The adhesive layer 130 is uniformly coated on the surface of the substrate 140. The material of the adhesive layer 130 is not limited, and the carbon nanotube primary film 120 may be more firmly bonded to the substrate 140, such as a pressure sensitive adhesive, a heat sensitive adhesive or a photosensitive adhesive. In this embodiment, the material of the adhesive layer 130 may be butyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, glycidyl methacrylate, acrylic acid, benzamidine peroxide, toluene and ethyl acetate. mixture.
步驟二：採用一雷射束170沿該若干奈米碳管擇優取向的方向逐行掃描該奈米碳管初級膜120從而在該奈米碳管初級膜120中的局部位置形成多個减薄區域126，該多個减薄區域126沿該若干奈米碳管擇優取向方向排列成至少一行。 Step 2: scanning the carbon nanotube primary film 120 in a direction along the preferred orientation of the plurality of carbon nanotubes by using a laser beam 170 to form a plurality of thinning portions in the local portion of the carbon nanotube primary film 120. The region 126, the plurality of thinned regions 126 are arranged in at least one row along the preferred orientation direction of the plurality of carbon nanotubes.
定義所述大多數奈米碳管的整體延伸方向為x。該多個减薄區域126可以沿方向x排列形成一個掃描行124或多個掃描行124。該多個减薄區域126係以一定順序在該奈米碳管初級膜120中依次形成。請參閱圖5，當該多個减薄區域沿方向x排列成多行時，可先採用雷射束沿方向x在該奈米碳管初級膜120中形成一掃描行124，該掃描行124包括多個沿平行於該擇優取向的方向x排列的减薄區域126；再在與該掃描行124相間隔的位置以同樣的方式形成另一掃描行124，最後以上述方式基本均勻的在整個奈米碳管初級膜120中形成多個間隔的掃描行124。該多個掃描行124可等間隔排列或不等間隔排列，但應防止某一區域的掃描行124分佈過於密集。優選地，該多個掃描行124等間隔且基本平行的分佈於該奈米碳管初級膜120中。相鄰的兩個掃描行124的間距d為1微米~5毫米，優選為10微米~100微米，本實施例為20微米。在一個實施例中，d遠大於位於同一掃描行124中减薄區域126的間距。 It is defined that the overall extension direction of most of the carbon nanotubes is x. The plurality of thinned regions 126 may be arranged in a direction x to form one scan line 124 or a plurality of scan lines 124. The plurality of thinned regions 126 are sequentially formed in the carbon nanotube primary film 120 in a certain order. Referring to FIG. 5, when the plurality of thinned regions are arranged in a plurality of rows along the direction x, a scanning line 124 may be formed in the carbon nanotube primary film 120 by using a laser beam in the direction x. The scanning line 124 is formed. A plurality of thinned regions 126 arranged in a direction x parallel to the preferred orientation are included; and another scan line 124 is formed in the same manner at a location spaced from the scan line 124, and finally substantially uniform throughout the manner described above A plurality of spaced scan lines 124 are formed in the carbon nanotube primary film 120. The plurality of scan lines 124 may be arranged at equal intervals or at different intervals, but the scan lines 124 of a certain area should be prevented from being too densely distributed. Preferably, the plurality of scan lines 124 are equally spaced and substantially parallel distributed in the carbon nanotube primary film 120. The pitch d of the adjacent two scanning lines 124 is from 1 micrometer to 5 millimeters, preferably from 10 micrometers to 100 micrometers, and is 20 micrometers in this embodiment. In one embodiment, d is much larger than the pitch of the thinned regions 126 located in the same scan line 124.
該每一掃描行124的形成方法具體可以係沿方向x依次形成多個减薄區域126。請參閱圖5及圖6，該多個减薄區域126可相互間隔設置或連續設置形成一長條形區域128。當該多個减薄區域126間隔設置時，該多個减薄區域126可相互等間隔。當該多個减薄區域126連續設置時，該一個掃描行124 中的多個减薄區域126可相互連續地沿方向x從奈米碳管初級膜120一端延伸至另一端。該掃描行124的寬度D，即該减薄區域126的直徑，亦即由該多個减薄區域126組成的長條形區域128的寬度為1微米~5毫米，優選為10微米~100微米，本實施例為20微米。優選地，每個减薄區域126的面積基本相同，多個掃描行124中，每掃描行124的减薄區域126的數量基本相同。 The forming method of each scanning line 124 may specifically form a plurality of thinned regions 126 in sequence along the direction x. Referring to FIGS. 5 and 6, the plurality of thinned regions 126 may be spaced apart from each other or continuously disposed to form an elongated region 128. When the plurality of thinned regions 126 are spaced apart, the plurality of thinned regions 126 may be equally spaced from each other. When the plurality of thinned regions 126 are continuously disposed, the one scan line 124 The plurality of thinned regions 126 may extend continuously from one end of the carbon nanotube primary film 120 to the other end in the direction x. The width D of the scanning line 124, that is, the diameter of the thinned region 126, that is, the elongated region 128 composed of the plurality of thinned regions 126 has a width of 1 micrometer to 5 millimeters, preferably 10 micrometers to 100 micrometers. This embodiment is 20 microns. Preferably, the area of each of the thinned regions 126 is substantially the same, and of the plurality of scan lines 124, the number of thinned regions 126 per scan line 124 is substantially the same.
通過上述依次的在整個奈米碳管初級膜120表面間隔的局部减薄的方法，可降低該减薄區域126中奈米碳管的分佈密度或基本去除該减薄區域126中的奈米碳管，從而减小該奈米碳管初級膜120的奈米碳管的分佈密度，得到的奈米碳管膜100具有較好的透光性。可定義單位面積的奈米碳管膜中奈米碳管的質量為分佈密度。優選地，該减薄區域126內奈米碳管的分佈密度比未减薄前下降50%至100%，從而使該减薄區域126內的透光度從原來的75%提高到85%以上，比减薄區域126外的透光度提高10%至20%。該形成的奈米碳管膜100宏觀仍為一膜狀結構。由於該减薄區域126係沿方向x逐行形成，且相鄰的掃描行124之間具有一定間距，因此可以保證該奈米碳管膜100在相鄰的兩個掃描行124之間具有完整的首尾相連的奈米碳管，不致因减薄降低該奈米碳管膜100沿方向x的導電性，相反地，因减薄使該奈米碳管膜100在垂直於x方向且位於奈米碳管膜100內的y方向上的導電性顯著降低，從而提高該奈米碳管膜100在x方向上和y方向上導電性的差異。 The distribution density of the carbon nanotubes in the thinned region 126 can be reduced or the nanocarbon in the thinned region 126 can be substantially removed by the above-described sequential local thinning of the surface of the entire carbon nanotube primary film 120. The tube, thereby reducing the distribution density of the carbon nanotubes of the carbon nanotube primary film 120, provides the carbon nanotube film 100 with good light transmittance. The mass of the carbon nanotubes in the carbon nanotube film per unit area can be defined as the distribution density. Preferably, the distribution density of the carbon nanotubes in the thinned region 126 is reduced by 50% to 100% before the thinning, so that the transmittance in the thinned region 126 is increased from 75% to over 85%. The transmittance outside the thinned region 126 is increased by 10% to 20%. The formed carbon nanotube film 100 is still macroscopically a film-like structure. Since the thinned regions 126 are formed row by row in the direction x and have a certain spacing between adjacent scan lines 124, it is ensured that the carbon nanotube film 100 is intact between two adjacent scan lines 124. The carbon nanotubes connected end to end do not reduce the conductivity of the carbon nanotube film 100 in the direction x due to thinning. Conversely, the carbon nanotube film 100 is perpendicular to the x direction and located in the The conductivity in the y direction in the carbon nanotube film 100 is remarkably lowered, thereby improving the difference in conductivity between the carbon nanotube film 100 in the x direction and the y direction.
可以理解，上述將奈米碳管初級膜120鋪設於基底140的步驟可以在步驟二之前或之後進行。該奈米碳管初級膜120可預先鋪設於所述基底140表面後被雷射束170掃描减薄，也可懸空設置的被雷射束170掃描减薄，减薄後具有多個减薄區域126的奈米碳管膜100可進一步被鋪設於所述基底140表面。 It can be understood that the step of laying the carbon nanotube primary film 120 on the substrate 140 can be performed before or after the second step. The carbon nanotube primary film 120 may be pre-laid on the surface of the substrate 140 and scanned and thinned by the laser beam 170, or may be scanned and thinned by the laser beam 170, and has a plurality of thinned regions after being thinned. The carbon nanotube film 100 of 126 may be further laid on the surface of the substrate 140.
請一並參閱圖5至圖8，步驟二具體包括以下步驟。 Please refer to FIG. 5 to FIG. 8 together. Step 2 specifically includes the following steps.
(一)提供一雷射裝置160，從該雷射裝置160發射雷射束170至該奈米碳管初級膜120表面形成一光斑180。 (a) A laser device 160 is provided from which the laser beam 170 is emitted to the surface of the carbon nanotube primary film 120 to form a spot 180.
該雷射裝置160可發射一脉衝雷射束170，該雷射束170的功率不限，可為1瓦至100瓦。該雷射束170具有較好的定向性，因此在奈米碳管初級膜120表面可形成一光斑180。該雷射束170在奈米碳管初級膜120表面具有的功率密度可大於0.053×1012瓦特/平方米。本實施例中，該雷射裝置160為一個二氧化碳雷射器，該雷射器的功率為12瓦特。可以理解，該雷射裝置160也可以選擇為能够發射連續雷射的雷射器。 The laser device 160 can emit a pulsed laser beam 170 having an unlimited power ranging from 1 watt to 100 watts. The laser beam 170 has a good orientation, so that a spot 180 can be formed on the surface of the carbon nanotube primary film 120. The laser beam 170 can have a power density on the surface of the carbon nanotube primary film 120 of greater than 0.053 x 10 12 watts per square meter. In this embodiment, the laser device 160 is a carbon dioxide laser having a power of 12 watts. It will be appreciated that the laser device 160 can also be selected as a laser capable of emitting continuous lasers.
該光斑180基本為圓形，直徑為1微米~5毫米，優選為20微米。可以理解，該光斑180可為將雷射束170聚焦後形成或由雷射束170直接照射在奈米碳管初級膜120表面形成。聚焦形成的光斑180可具有較小的直徑，如20微米。將雷射束170不經過聚焦直接照射形成的光斑180具有較大的直徑，如3毫米。 The spot 180 is substantially circular and has a diameter of from 1 micron to 5 mm, preferably 20 microns. It can be understood that the spot 180 can be formed by focusing the laser beam 170 or directly irradiated by the laser beam 170 on the surface of the carbon nanotube primary film 120. The spot 180 formed by focusing may have a smaller diameter, such as 20 microns. The spot 180 formed by direct irradiation of the laser beam 170 without focusing is of a large diameter, such as 3 mm.
所述雷射裝置160也可包括多個雷射器。當該雷射裝置160包括多個雷射器時，該光斑可以為條狀或其他形狀，該條狀光斑的寬度為1微米~5毫米，優選為20微米。 The laser device 160 can also include a plurality of lasers. When the laser device 160 includes a plurality of lasers, the spot may be in the form of a strip or other shape having a width of from 1 micrometer to 5 millimeters, preferably 20 micrometers.
(二)使該奈米碳管初級膜120與該雷射束170相對運動，從而使該光斑180沿該奈米碳管初級膜120的方向x移動，形成至少一掃描行124，該掃描行包括多個沿方向x排列的减薄區域126。 (2) moving the carbon nanotube primary film 120 relative to the laser beam 170 such that the spot 180 moves along the direction x of the carbon nanotube primary film 120 to form at least one scan line 124. A plurality of thinned regions 126 arranged in the direction x are included.
該光斑180沿該奈米碳管初級膜120中方向x移動，以沿方向x减薄該奈米碳管初級膜120。為使該光斑180與奈米碳管初級膜120相對運動，可保持該雷射束170固定不動，通過移動該奈米碳管初級膜120實現；或者固定該奈 米碳管初級膜120不動，通過移動該雷射束170實現。該雷射裝置160可整體相對於該奈米碳管初級膜120平移，或者僅通過改變雷射裝置160出光部的出光角度，實現發射的雷射束170形成的光斑180在該奈米碳管初級膜120的位置變化。 The spot 180 moves in the direction x in the carbon nanotube primary film 120 to thin the carbon nanotube primary film 120 in the direction x. In order to move the spot 180 relative to the carbon nanotube primary film 120, the laser beam 170 can be kept stationary, by moving the carbon nanotube primary film 120; or fixing the nanosphere The carbon nanotube primary membrane 120 does not move and is achieved by moving the laser beam 170. The laser device 160 can be translated integrally with respect to the carbon nanotube primary film 120, or by changing the light exit angle of the light exit portion of the laser device 160, the spot 180 formed by the emitted laser beam 170 can be realized in the carbon nanotube. The position of the primary film 120 changes.
該同一掃描行124中的多個减薄區域126可以間隔或連續設置。由於該脉衝雷射束170由多個不連續的雷射脉衝組成，當雷射束170與奈米碳管初級膜120相對運動的速度較大，該多個不連續的雷射脉衝能够照射在該奈米碳管初級膜120表面的不同位置，從而實現對奈米碳管初級膜120不連續的局部减薄，形成多個不連續的圓形减薄區域126。當該雷射束170與奈米碳管初級膜120相對運動速度小於光斑180的直徑與雷射脉衝頻率的乘積(相對運動速度<光斑直徑×雷射脉衝頻率)時，該多個不連續的雷射脉衝照射在奈米碳管初級膜120表面的位置相互連接或部分重合，使該多個减薄區域126呈連續分佈。由於該光斑沿該奈米碳管初級膜120中方向x移動，該連續分佈的减薄區域126的長度方向與方向x平行。本實施例中，同一掃描行中相鄰的兩個减薄區域126間的距離小於100微米。 The plurality of thinned regions 126 in the same scan line 124 may be spaced or continuously disposed. Since the pulsed laser beam 170 is composed of a plurality of discontinuous laser pulses, when the laser beam 170 and the carbon nanotube primary film 120 relatively move at a relatively high speed, the plurality of discontinuous laser pulses Different locations on the surface of the carbon nanotube primary film 120 can be illuminated to achieve a discontinuous localized thinning of the carbon nanotube primary film 120, forming a plurality of discrete circularly thinned regions 126. When the relative movement speed of the laser beam 170 and the carbon nanotube primary film 120 is smaller than the product of the diameter of the spot 180 and the laser pulse frequency (relative motion speed < spot diameter × laser pulse frequency), the plurality of The continuous laser pulse irradiation is connected or partially overlapped at the position of the surface of the carbon nanotube primary film 120, so that the plurality of thinned regions 126 are continuously distributed. Since the spot moves along the direction x in the carbon nanotube primary film 120, the length direction of the continuously distributed thinned region 126 is parallel to the direction x. In this embodiment, the distance between two adjacent thinned regions 126 in the same scan line is less than 100 microns.
可以理解，當採用一連續雷射作為雷射束170時，可通過程序設定雷射器的開關，與奈米碳管初級膜120的運動相配合，從而形成間隔或連續的减薄區域126。 It will be appreciated that when a continuous laser is employed as the laser beam 170, the switch of the laser can be programmed to cooperate with the movement of the carbon nanotube primary film 120 to form a spaced or continuous thinned region 126.
可以理解，由於奈米碳管吸收能量後溫度升高並與氧氣反應，只需確保使足够能量的雷射在較短的時間內照射至奈米碳管表面，即可達到减薄該奈米碳管初級膜120的目的。因此，可通過採用不同功率、波長或脉衝頻率的雷射裝置160，並相應調整雷射束170與奈米碳管初級膜120的相對運動速度以及光斑180的大小達到局部减薄奈米碳管初級膜120的目的。可以理解，該雷射裝置160也不限於脉衝雷射器，只要能够發射雷射使奈米碳管局部 减薄即可。如圖9所示，該减薄區域126的奈米碳管的分佈密度减小或該减薄區域126的奈米碳管全部被刻蝕。 It can be understood that since the carbon nanotubes absorb the energy and the temperature rises and reacts with the oxygen, it is only necessary to ensure that the laser of sufficient energy is irradiated to the surface of the carbon nanotube in a short time, thereby thinning the nanometer can be achieved. The purpose of the carbon tube primary membrane 120. Therefore, localized thinning of nanocarbon can be achieved by using laser devices 160 of different power, wavelength or pulse frequency, and correspondingly adjusting the relative motion speed of the laser beam 170 and the carbon nanotube primary film 120 and the size of the spot 180. The purpose of the tube primary membrane 120. It can be understood that the laser device 160 is not limited to a pulse laser, as long as it can emit a laser to partially localize the carbon nanotube. Thinning can be done. As shown in FIG. 9, the distribution density of the carbon nanotubes of the thinned region 126 is reduced or the carbon nanotubes of the thinned region 126 are all etched.
進一步地，可以在所述奈米碳管初級膜120中間隔的形成多個掃描行124。 Further, a plurality of scan lines 124 may be formed spaced apart in the carbon nanotube primary film 120.
為形成多個掃描行124，可將奈米碳管初級膜120沿垂直於大多數奈米碳管整體延伸的方向y相對於雷射束170平移一定距離，再將奈米碳管初級膜120沿平行方向x相對於雷射束170運動；也可將雷射束170沿垂直於方向y相對於奈米碳管初級膜120移動一定距離，再使雷射束170沿方向x相對於奈米碳管初級膜120運動。本實施例中，該光斑180在該奈米碳管初級膜120表面移動的路線如圖8所示。 To form a plurality of scan lines 124, the carbon nanotube primary film 120 can be translated a certain distance relative to the laser beam 170 in a direction y extending perpendicular to the entirety of the majority of the carbon nanotubes, and then the carbon nanotube primary film 120 is transferred. Moving in a parallel direction x relative to the laser beam 170; the laser beam 170 can also be moved a certain distance relative to the carbon nanotube primary film 120 in a direction perpendicular to the direction y, and the laser beam 170 is oriented in the direction x relative to the nanometer. The carbon tube primary membrane 120 moves. In this embodiment, the route of the spot 180 moving on the surface of the carbon nanotube primary film 120 is as shown in FIG.
可以理解，為通過雷射减薄該奈米碳管初級膜120，所述步驟(二)中，該奈米碳管初級膜120放置於一具氧氣的環境中，如一空氣中，從而使被雷射束170照射的奈米碳管中的碳與氧氣反應生成二氧化碳。 It can be understood that, in order to reduce the carbon nanotube primary film 120 by laser, in the step (2), the carbon nanotube primary film 120 is placed in an oxygen environment, such as an air, so as to be The carbon in the carbon nanotubes irradiated by the laser beam 170 reacts with oxygen to form carbon dioxide.
為盡可能除去該奈米碳管初級膜120中存在的較大直徑的奈米碳管束，該雷射束170應盡可能均勻的掃描該奈米碳管初級膜120的整個表面，從而在該奈米碳管初級膜120表面形成多個均勻且間隔分佈的掃描行124。 In order to remove as much as possible the larger diameter carbon nanotube bundle present in the carbon nanotube primary membrane 120, the laser beam 170 should scan the entire surface of the carbon nanotube primary membrane 120 as uniformly as possible, thereby A plurality of uniform and spaced scan lines 124 are formed on the surface of the carbon nanotube primary film 120.
由於奈米碳管對雷射具有較好吸收特性，該奈米碳管初級膜120中具有較大直徑的奈米碳管束將會吸收較多的熱量，從而被燒蝕去除，使形成的奈米碳管膜100的透光性大幅度上升。本實施例中的奈米碳管膜100整體的光透過率可以大於75%。優選地，該奈米碳管膜100光透過率為95%。 Since the carbon nanotube has good absorption characteristics for the laser, the carbon nanotube bundle having a larger diameter in the primary membrane 120 of the carbon nanotube will absorb more heat, thereby being ablated and removed, so that the formed naphthalene is formed. The light transmittance of the carbon nanotube film 100 is greatly increased. The light transmittance of the carbon nanotube film 100 in the present embodiment as a whole may be greater than 75%. Preferably, the carbon nanotube film 100 has a light transmittance of 95%.
請參閱圖10，由於在步驟(二)中，該光斑180沿該奈米碳管初級膜120中方向x移動，使該雷射束170沿奈米碳管初級膜120中大多數奈米碳管整體延伸方向减薄奈米碳管束，因此，當奈米碳管初級膜120的一個掃描行124减薄完畢，需要减薄下一個掃描行124時，無須使兩個掃描行124中的减薄 區域126在y方向上對準。 Referring to FIG. 10, since the spot 180 moves in the direction x in the primary film 120 of the carbon nanotube in step (2), the laser beam 170 is along the majority of the nanocarbon in the primary film 120 of the carbon nanotube. The tube extends in a thinner direction, so that when a scan line 124 of the carbon nanotube primary film 120 is thinned, it is necessary to thin the next scan line 124 without subtracting the two scan lines 124. thin Region 126 is aligned in the y-direction.
如圖10所示，當光斑180沿該奈米碳管初級膜120中方向x移動時，即使兩掃描行124中的减薄區域126交錯排列，也不會影響該兩掃描行124間的奈米碳管145。因此，形成的奈米碳管膜100在兩個相鄰的掃描行124之間的奈米碳管145可以保持完整地首尾相連狀態而不受破壞，使該奈米碳管膜100在方向x上的導電性不受影響。 As shown in FIG. 10, when the spot 180 moves in the direction x in the carbon nanotube primary film 120, even if the thinned regions 126 in the two scanning lines 124 are staggered, the between the two scanning lines 124 will not be affected. Carbon tube 145. Therefore, the carbon nanotube film 145 of the formed carbon nanotube film 100 between the two adjacent scanning rows 124 can remain intact and end-to-end without being damaged, so that the carbon nanotube film 100 is in the direction x. The conductivity on the top is not affected.
可以理解，當該减薄區域126連續時，沿方向x進行减薄的優點尤為明顯。請參閱圖11，當沿方向x形成連續的减薄區域126時，相鄰的兩個掃描行124之間的奈米碳管145不會被减薄，從而使奈米碳管膜100在方向x的電導率及強度基本不受影響；相鄰兩掃描行之間沿方向x首尾相連的奈米碳管145不會被切斷，避免使奈米碳管膜100在方向x的電導率及強度大幅下降。 It will be appreciated that the advantage of thinning in the direction x is particularly pronounced when the thinned regions 126 are continuous. Referring to FIG. 11, when a continuous thinned region 126 is formed along the direction x, the carbon nanotubes 145 between the adjacent two scanning rows 124 are not thinned, thereby causing the carbon nanotube film 100 to be in the direction. The conductivity and strength of x are not affected at all; the carbon nanotubes 145 connected end to end in the direction x between adjacent scan lines are not cut, and the conductivity of the carbon nanotube film 100 in the direction x is avoided. The intensity has dropped dramatically.
為盡可能除去該奈米碳管初級膜120中的奈米碳管束，該相鄰的兩個掃描行124之間的間距不宜太大，為不影響奈米碳管膜100的導電性，該相鄰的兩個掃描行124之間的間距不宜太小。優選地，該兩個相鄰的掃描行124之間的間距為1微米~5毫米，優選為20微米。 In order to remove the carbon nanotube bundle in the carbon nanotube primary film 120 as much as possible, the spacing between the adjacent two scanning lines 124 is not too large, so as not to affect the conductivity of the carbon nanotube film 100, The spacing between adjacent scan lines 124 should not be too small. Preferably, the spacing between the two adjacent scan lines 124 is from 1 micron to 5 mm, preferably 20 microns.
可以理解，該通過雷射减薄後得到的奈米碳管膜100宏觀仍為一自支撑的膜狀結構，透光性在减薄後得到提升，而由於沿方向x進行减薄，奈米碳管膜100在方向x上的導電性得到一定程度的保持，在方向y上的導電性降低，從而使該奈米碳管膜100具有較好的各向異性。 It can be understood that the carbon nanotube film 100 obtained by laser thinning is still a self-supporting film-like structure, and the light transmittance is improved after thinning, and the nanometer is thinned in the direction x, and the nanometer is thinned. The conductivity of the carbon nanotube film 100 in the direction x is maintained to some extent, and the conductivity in the direction y is lowered, so that the carbon nanotube film 100 has good anisotropy.
請參閱表1，表1為通過雷射减薄的方法形成具有多個减薄區域126的奈米碳管膜100的具體參數，使用的雷射功率為3.6瓦，脉衝頻率為100kHz，該奈米碳管膜100的長度及寬度均為約30毫米。 Referring to Table 1, Table 1 shows specific parameters for forming a carbon nanotube film 100 having a plurality of thinned regions 126 by laser thinning, using a laser power of 3.6 watts and a pulse frequency of 100 kHz. The carbon nanotube film 100 has a length and a width of about 30 mm.
另外，可在該基底140表面先塗附一層絕緣的高分子材料溶液，將該奈米碳管膜100覆蓋該高分子溶液，使該奈米碳管膜100嵌入該高分子溶液後，使該高分子溶液固化，從而形成一複合膜。固化後的高分子材料能起到黏結劑層130的作用。另外，由於高分子材料阻隔Y方向奈米碳管之間的接觸，該複合膜比單一的奈米碳管膜100的各向異性進一步提高。 In addition, an insulating polymer material solution may be first coated on the surface of the substrate 140, and the carbon nanotube film 100 is covered with the polymer solution, and the carbon nanotube film 100 is embedded in the polymer solution. The polymer solution is solidified to form a composite film. The cured polymer material can function as the binder layer 130. Further, since the polymer material blocks contact between the Y-direction carbon nanotubes, the anisotropy of the composite film is further improved than that of the single carbon nanotube film 100.
請參閱圖5，6，10及11，所述具有較好透光性的奈米碳管膜100由若干奈米碳管組成，所述若干奈米碳管為沿同一方向擇優取向排列，該奈米碳管膜100中定義有多個减薄區域126及减薄區域126外的非减薄區域。該多個减薄區域126沿該若干奈米碳管擇優取向的方向x排列成至少一行，形成至少一掃描行124，該掃描行124中的减薄區域126沿方向x排列。該奈米碳管膜100可包括多個相互間隔的掃描行124，該多個掃描行124為依次分別形成。 Referring to FIGS. 5, 6, 10 and 11, the carbon nanotube film 100 having better light transmittance is composed of a plurality of carbon nanotubes, and the plurality of carbon nanotubes are arranged in a preferred orientation along the same direction. A plurality of thinned regions 126 and non-thinned regions outside the thinned regions 126 are defined in the carbon nanotube film 100. The plurality of thinned regions 126 are arranged in at least one row along the direction x of the preferred orientation of the plurality of carbon nanotubes to form at least one scan line 124, and the thinned regions 126 in the scan line 124 are aligned in the direction x. The carbon nanotube film 100 can include a plurality of mutually spaced scan lines 124 that are formed separately in sequence.
所述奈米碳管膜100由所述奈米碳管初級膜120形成，具有與奈米碳管初級膜120基本相同的結構，然而該奈米碳管膜100進一步定義多個减薄區域126。 The carbon nanotube film 100 is formed of the carbon nanotube primary film 120 and has substantially the same structure as the carbon nanotube primary film 120, however, the carbon nanotube film 100 further defines a plurality of thinned regions 126. .
該多個减薄區域126可以陣列方式分佈於該非减薄區域中，或以交錯排列的方式分佈於該非减薄區域中。具體地，該掃描行124均與方向x平行，該同一掃描行124中的多個减薄區域126在方向x基本對準，多個掃描行124的减薄區域126在方向y上可對準或不對準的交錯設置。該兩個相鄰的掃描行124間具有沿方向x從奈米碳管膜100的一端延伸至另一端的完整的部分奈米碳管初級膜120。該相鄰的兩個掃描行124之間的距離為1微米~5毫米，優選為20微米。所述排列成多行的多個减薄區域126相互平行且等間距設置。該同一掃描行124的多個减薄區域126可間隔設置或連續設置。所述同一掃描行124的多個减薄區域126可進一步相互等間隔設置，間隔優選小於100微米。該連續設置的减薄區域126的長度方向與該方向x平行。所述多個减薄區域126優選具有基本相同的面積。所述每一掃描行124優選具有基本相同數量的减薄區域126。 The plurality of thinned regions 126 may be distributed in the non-thinned region in an array manner or distributed in the non-thinned region in a staggered manner. In particular, the scan lines 124 are all parallel to the direction x, the plurality of thinned regions 126 in the same scan line 124 are substantially aligned in the direction x, and the thinned regions 126 of the plurality of scan lines 124 are aligned in the direction y Or misaligned staggered settings. The two adjacent scan lines 124 have a complete partial carbon nanotube primary film 120 extending from one end of the carbon nanotube film 100 to the other end in the direction x. The distance between the adjacent two scanning lines 124 is from 1 micrometer to 5 millimeters, preferably 20 micrometers. The plurality of thinned regions 126 arranged in a plurality of rows are arranged parallel to each other and equally spaced. The plurality of thinned regions 126 of the same scan line 124 may be spaced apart or continuously disposed. The plurality of thinned regions 126 of the same scan line 124 may be further spaced from one another, preferably less than 100 microns apart. The longitudinal direction of the continuously disposed thinned region 126 is parallel to the direction x. The plurality of thinned regions 126 preferably have substantially the same area. Each of the scan lines 124 preferably has substantially the same number of thinned regions 126.
該减薄區域126通過雷射照射的方式使奈米碳管發熱並氧化形成。該减薄區域126具有較為稀少的奈米碳管，該减薄區域126中奈米碳管的分佈密度可以為非减薄區域奈米碳管的分佈密度的50%以下，從而使該减薄區域126的可見光透過率從原先的約75%提高到85%以上，比非减薄區域的可見光透過率高10%以上。該雷射掃描沿奈米碳管整體延伸方向，使兩個相鄰的掃描行124間的部分奈米碳管初級膜120不致被破壞，從而使該奈米碳管膜100在奈米碳管整體延伸方向上的具有較好的導電性，提高該奈米碳管膜100的各向異性。該奈米碳管膜100可應用於透明電極、薄膜電晶體、觸摸屏等領域。 The thinned region 126 heats and oxidizes the carbon nanotube by laser irradiation. The thinned region 126 has a relatively rare carbon nanotube, and the distribution density of the carbon nanotube in the thinned region 126 may be less than 50% of the distribution density of the non-thinned region carbon nanotube, thereby making the thinning The visible light transmittance of the region 126 is increased from about 75% to 85% or more, and is higher than the visible light transmittance of the non-thinned region by 10% or more. The laser scanning extends along the entire extending direction of the carbon nanotubes so that the partial carbon nanotube primary film 120 between the two adjacent scanning lines 124 is not destroyed, so that the carbon nanotube film 100 is in the carbon nanotubes. The conductivity in the overall extension direction is good, and the anisotropy of the carbon nanotube film 100 is improved. The carbon nanotube film 100 can be applied to fields such as a transparent electrode, a thin film transistor, a touch panel, and the like.
綜上所述，本發明確已符合發明專利之要件，遂依法提出專利申請。惟，以上所述者僅為本發明之較佳實施例，自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化， 皆應涵蓋於以下申請專利範圍內。 In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Any person skilled in the art will be able to make equivalent modifications or variations in accordance with the spirit of the invention. All should be covered by the following patent application.
100‧‧‧奈米碳管膜 100‧‧‧Nano carbon nanotube film
120‧‧‧奈米碳管初級膜 120‧‧‧Nanocarbon tube primary membrane
124‧‧‧掃描行 124‧‧‧ scan line
126‧‧‧减薄區域 126‧‧‧Thinning area
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| US20080170982A1 (en) * | 2004-11-09 | 2008-07-17 | Board Of Regents, The University Of Texas System | Fabrication and Application of Nanofiber Ribbons and Sheets and Twisted and Non-Twisted Nanofiber Yarns |
| CN1903715B (en) * | 2005-07-29 | 2010-06-16 | 索尼株式会社 | Aggregation for manufacturing carbon nanometer tube and thin film, electronic component and method for destroying carbon nanometer tube and carbon nanometer tube selective reaction |
| CN101239712A (en) * | 2007-02-09 | 2008-08-13 | 清华大学 | Carbon nano-tube thin film structure and preparation method thereof |
| CN101585533A (en) * | 2008-05-23 | 2009-11-25 | 清华大学 | Transparent carbon nanotube membrane preparing method |
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| TW201125816A (en) | 2011-08-01 |
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