CN1208818C - A kind of preparation method of arrayed carbon nanotube thin film transistor - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000010409 thin film Substances 0.000 title claims description 26
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- 238000002360 preparation method Methods 0.000 title claims description 9
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
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Abstract
Description
技术领域：Technical field:
本发明涉及一种阵列碳纳米管薄膜晶体管的制备方法。The invention relates to a method for preparing an array carbon nanotube thin film transistor.
背景技术：Background technique:
薄膜晶体管是现代微电子技术的一种关键性元器件，它可以用于显示器、交易卡和身份识别器，易于制造，成本低等优点。薄膜晶体管主要由源极、漏极、栅极、栅极绝缘层以及半导体组成。当器件在积累模式时，电荷从源极注入半导体，在源漏之间移动形成电流。目前，用于薄膜晶体管的半导体材料主要是硅基材料，但是随着微电子器件尺寸的不断缩小，硅基电子器件的尺寸已接近其极限。因此开发新的、优良的、可制备更小尺寸器件的半导体材料尤为重要。Thin-film transistors are a key component of modern microelectronics technology. They can be used in displays, transaction cards and identification devices. They are easy to manufacture and low in cost. A thin film transistor is mainly composed of a source, a drain, a gate, a gate insulating layer and a semiconductor. When the device is in the accumulation mode, charge is injected into the semiconductor from the source, and moves between the source and drain to form a current. At present, the semiconductor materials used for thin film transistors are mainly silicon-based materials, but as the size of microelectronic devices continues to shrink, the size of silicon-based electronic devices is approaching its limit. Therefore, it is particularly important to develop new and excellent semiconductor materials that can be used to manufacture smaller-sized devices.
碳纳米管由于其独特的力学和电学性能，已经成为科学家广泛关注的极具潜力的特殊功能材料和器件材料。目前，碳纳米管被用于制备不同的电子元器件，尤其是具有半导体性能的碳纳米管是制备场效应晶体管的最有前途的材料。已有许多研究小组利用单根碳纳米管制成了晶体管(1：Derycke，V.；Martel，R.；Appenzeller，J.；Avouris，Ph.Nano.Lett.2001，1，453.2：Martel，R.；Schmidt，T.；Shea，H.R.；Hertel，T.；Avouris，Ph.Appl.Phys.Lett.1998，73，2447.3：Fuhrer，M.S.；Kim，B.M.；Durkop，T.；Brintlinger，T.Nano.Lett.2002，2，755.4：Choi，W.B.；Chu，J.U.；Jeong，K.S.；Bae，E.J.；Lee，J.W.；Kim，J.J.；Lee，J.O.Appl.Phys.Lett.2001，79，3696.)。但是这些方法都离不开电子束光刻等仪器来制备，因为要想在宏观层次上测量碳纳米管的电学性能，淀积电极是非常困难的。目前的方法繁杂而且设备昂贵，这给碳纳米管在器件方面的应用带来了极大的困难和复杂性。因而如何有效、简单、方便地测量碳纳米管的电学性能，成为许多科研和工程技术专家追求的目标。Due to its unique mechanical and electrical properties, carbon nanotubes have become a potential special functional material and device material that has been widely concerned by scientists. At present, carbon nanotubes are used to prepare different electronic components, especially carbon nanotubes with semiconductor properties are the most promising materials for the preparation of field effect transistors. Many research groups have made transistors using single carbon nanotubes (1: Derycke, V.; Martel, R.; Appenzeller, J.; Avouris, Ph. Nano. Lett. 2001, 1, 453.2: Martel, R. ; Schmidt, T.; Shea, H.R.; Hertel, T.; Avouris, Ph. Appl. Phys. Lett. 1998, 73, 2447.3: Fuhrer, M.S.; Lett. 2002, 2, 755.4: Choi, W.B.; Chu, J.U.; Jeong, K.S.; Bae, E.J.; Lee, J.W.; Kim, J.J.; Lee, J.O. However, these methods are inseparable from the preparation of electron beam lithography and other instruments, because it is very difficult to deposit electrodes in order to measure the electrical properties of carbon nanotubes at the macroscopic level. The current methods are complicated and the equipment is expensive, which brings great difficulty and complexity to the application of carbon nanotubes in devices. Therefore, how to effectively, simply and conveniently measure the electrical properties of carbon nanotubes has become the goal pursued by many scientific research and engineering experts.
阵列碳纳米管薄膜具有许多优良的电学性能，它的物理和化学性能具有高度的各项异性。目前阵列碳纳米管薄膜已经广泛用于场发射器件的研究(Nilsson，L.；Groening，O.；Emmenegger，C.；Kuettel，O.；Schaller，E.；Schlapbach，L.；Kind，H.；Bonard，J.M.；Kern，K.Appl.Phys.Lett.2000，76，2071)。王贤保等人用四探针方法测量了阵列碳纳米管膜的不同方向的电子传输性能，发现其径向和横向表现为不同的半导体性能(Wang，X.B.；Liu，Y.Q.；Yu，G.；Xu，C.Y.；Zhang，J.B.；Zhu，D.B.J.Phys.Chem.B 2001，105，9422.)。因此，阵列碳纳米管膜可以应用于许多半导体器件，尤其是作为制备薄膜晶体管的半导体材料。Arrayed carbon nanotube films have many excellent electrical properties, and their physical and chemical properties are highly anisotropic. At present, arrayed carbon nanotube films have been widely used in the research of field emission devices (Nilsson, L.; Groening, O.; Emmenegger, C.; Kuettel, O.; Schaller, E.; Schlapbach, L.; Kind, H. ; Bonard, J.M.; Kern, K. Appl. Phys. Lett. 2000, 76, 2071). Wang Xianbao et al. measured the electron transport properties of arrayed carbon nanotube films in different directions with a four-probe method, and found that the radial and lateral directions showed different semiconductor properties (Wang, X.B.; Liu, Y.Q.; Yu, G.; Xu , C.Y.; Zhang, J.B.; Zhu, D.B.J. Phys. Chem.B 2001, 105, 9422.). Therefore, the arrayed carbon nanotube film can be applied to many semiconductor devices, especially as a semiconductor material for preparing thin film transistors.
发明内容：Invention content:
本发明利用一种阵列碳纳米管膜作为半导体材料，制备了薄膜晶体管器件。通过一种简单的方法，无需任何复杂的预处理过程，直接在栅极绝缘层上大面积生长出阵列规整、结构均匀的碳纳米管薄膜。然后在膜上用真空蒸镀的方法淀积金电极作为源、漏电极，并在室温下发现这种材料具有优良的场效应性能，其迁移率很高，可与硅电子器件相媲美。The invention uses an array carbon nanotube film as a semiconductor material to prepare a thin film transistor device. Through a simple method, without any complicated pretreatment process, a large-area carbon nanotube film with regular array and uniform structure is directly grown on the gate insulating layer. Then gold electrodes were deposited on the film by vacuum evaporation as source and drain electrodes, and it was found that this material has excellent field effect performance at room temperature, and its mobility is very high, which is comparable to silicon electronic devices.
本发明使用的阵列碳纳米管薄膜是按照文献(1：Wang，X.B.；Liu，Y.Q.；Zhu，D.B.Appl.Phys.A.2000，71，347.2：刘云圻，王贤保，朱道本，申请号：01124300.7)合成的，只是将n-型单晶硅片换为SiO2/高掺杂Si基片，其由直径为20到200纳米，长度为1到100微米的结构均匀、阵列规整的碳纳米管阵列组成。The arrayed carbon nanotube film used in the present invention is synthesized according to the literature (1: Wang, XB; Liu, YQ; Zhu, DBAppl.Phys.A.2000, 71, 347.2: Liu Yunqi, Wang Xianbao, Zhu Daoben, application number: 01124300.7) , just replace the n-type monocrystalline silicon wafer with SiO 2 /highly doped Si substrate, which is composed of carbon nanotube arrays with a uniform structure and a regular array with a diameter of 20 to 200 nanometers and a length of 1 to 100 microns.
本发明的一种阵列碳纳米管薄膜晶体管的制备方法，依如下顺序步骤进行：以高掺杂硅作为栅电极，其上氧化一层200-400纳米的SiO2作为栅极绝缘层，将此SiO2/高掺杂硅基片放入石英管中部，通入氢气或氩气中的一种气体，气体的流量控制一般为每分钟10-100毫升，将控温仪设置到800-1200℃，开始加热，当炉心温度达到设置温度时，将盛有金属酞菁的石英舟放入炉口温度为500-600℃的区域，金属酞菁的用量一般为石英舟体积的1/6-2/3，恒温1-60分钟后，停止加热，继续通氢气使电炉冷至10-40℃，在基片上得到列阵碳纳米管薄膜，将其放入真空镀膜机，利用叉指电极模板真空蒸镀金作为薄膜晶体管的源、漏极，薄膜晶体管的沟道长度为0.1-0.5毫米，宽度为50-66毫米。利用HP4140B半导体测试仪，在源漏电压和栅极电压为0--1V的范围内扫描，从而得出其迁移率和开关比。A kind of preparation method of arrayed carbon nanotube thin film transistor of the present invention, carry out according to the following sequential steps: use highly doped silicon as gate electrode, SiO of oxidized layer 200-400 nanometers on it as gate insulating layer, this SiO 2 /highly doped silicon substrate is placed in the middle of the quartz tube, and a gas in hydrogen or argon is introduced. The flow control of the gas is generally 10-100 ml per minute, and the temperature controller is set to 800-1200 ° C. , start heating, when the furnace core temperature reaches the set temperature, put the quartz boat filled with metal phthalocyanine into the area where the temperature of the furnace mouth is 500-600 ° C, the amount of metal phthalocyanine is generally 1/6-2 of the volume of the quartz boat /3, after 1-60 minutes at constant temperature, stop heating, continue to pass hydrogen to cool the electric furnace to 10-40°C, get arrayed carbon nanotube film on the substrate, put it into a vacuum coating machine, and use the interdigitated electrode template to vacuum Evaporated gold is used as the source and drain of the thin film transistor, and the channel length of the thin film transistor is 0.1-0.5 mm and the width is 50-66 mm. Use HP4140B semiconductor tester to scan the source-drain voltage and gate voltage in the range of 0--1V, so as to obtain its mobility and switch ratio.
本发明的器件是由碳纳米管膜制备的P沟道薄膜晶体管，其空穴的场效应迁移率高达79.5cm2/Vs.另外，本发明的P沟道器件的开关比大于100。而且，这些性能都是在空气中测量得到的。The device of the present invention is a P-channel thin film transistor prepared by carbon nanotube film, and the field-effect mobility of the hole is as high as 79.5 cm 2 /Vs. In addition, the on-off ratio of the P-channel device of the present invention is greater than 100. Moreover, these properties are measured in air.
本发明制备的碳纳米管薄膜晶体管具有下述特征和优点：The carbon nanotube thin film transistor prepared by the present invention has the following characteristics and advantages:
1.本发明制备的阵列碳纳米管薄膜晶体管器件在室温下具有比较高的空穴迁移率，是一种理想的薄膜晶体管半导体材料。1. The arrayed carbon nanotube thin film transistor device prepared by the present invention has relatively high hole mobility at room temperature, and is an ideal semiconductor material for thin film transistors.
2.通过改变反应条件，可以控制碳纳米管的结构，从而影响器件的空穴传输性能。2. By changing the reaction conditions, the structure of carbon nanotubes can be controlled, thereby affecting the hole transport performance of the device.
3.利用本发明的方法制备的薄膜晶体管与传统的硅晶体管相比，工艺简单，成本低廉。3. Compared with traditional silicon transistors, the thin film transistor prepared by the method of the present invention has simple process and low cost.
4.本发明制备的阵列碳纳米管薄膜晶体管与有机薄膜晶体管相比，有机薄膜晶体管的场效应迁移率的并且在高温下性能降低。而碳纳米管在高温下其结构性能没有大的影响，一般多壁碳纳米管在空气中600℃才开始氧化。因此阵列碳纳米管薄膜晶体管在高温时也具有优良的性能和可靠性。4. Compared with the organic thin film transistor, the arrayed carbon nanotube thin film transistor prepared by the present invention has lower field effect mobility and lower performance at high temperature. However, carbon nanotubes have no great influence on their structural properties at high temperatures. Generally, multi-walled carbon nanotubes do not start to oxidize until 600°C in air. Therefore, the arrayed carbon nanotube thin film transistor also has excellent performance and reliability at high temperature.
附图说明Description of drawings
图1阵列碳纳米管薄膜晶体管的结构图。1，高掺杂硅栅极；2，二氧化硅绝缘层；3，碳纳米管膜；4，源极；5，漏极。Fig. 1 Structural diagram of arrayed carbon nanotube thin film transistor. 1, highly doped silicon gate; 2, silicon dioxide insulating layer; 3, carbon nanotube film; 4, source; 5, drain.
图2扫描电子显微镜拍摄的阵列碳纳米管薄膜的照片Figure 2 Photographs of arrayed carbon nanotube films taken by scanning electron microscope
图3透射电子显微镜拍摄碳纳米管薄膜的形貌。Fig. 3 Morphology of carbon nanotube film taken by transmission electron microscope.
图4扫描电子显微镜拍摄的阵列碳纳米管薄膜晶体管的照片。Figure 4 is a photograph of arrayed carbon nanotube thin film transistors taken by a scanning electron microscope.
图5碳纳米管薄膜晶体管的输出特性曲线Figure 5 output characteristic curve of carbon nanotube thin film transistor
图6碳纳米管薄膜晶体管的转移特性曲线Figure 6 Transfer characteristic curve of carbon nanotube thin film transistor
具体实施方式Detailed ways
下面结合附图和实施实例对本发明进行详细说明。但本发明并不限于此例。The present invention will be described in detail below in conjunction with the accompanying drawings and implementation examples. However, the present invention is not limited to this example.
实施例1如图1所示，本发明的一种阵列碳纳米管薄膜晶体管结构依次包括高掺杂硅为栅极1，二氧化硅2为绝缘层，阵列碳纳米管膜3作为半导体材料，金电极4，5为源、漏电极。将一块20×20mm大小的SiO2/Si基片，放入石英管中部，连接好配气系统，以每分钟20毫升的流量通入氢气，设置温度950℃，使电炉升温，当炉心温度达到900℃时，将盛有0.5克酞菁铁的石英舟(5毫升)放入炉口温度为550℃的区域恒温5分钟后停止加热。冷却至室温。制得直径为40纳米，长度6微米的阵列规整、尺寸均匀的碳纳米管。纳米管的长度有扫描电子显微镜照片测得(图2)和估算，直径由透射电子显微镜照片(图3)测得。然后在镀膜机中用叉指电极模板真空蒸镀金为源漏电极，沟道长度和宽度分别为0.4毫米和66毫米。器件的结构示意图如图1所示，器件的形貌可由扫描电子显微镜照片(图4)看到。最后，用HP4140B半导体测试仪测量器件的输出特性曲线(图5)和转移特性曲线(图6)，源漏电压和栅极电压在0--1V扫描。在空气中测量器件的空穴场效应迁移率为～79.3cm2/Vs，开关比大于～100。Embodiment 1 As shown in Figure 1, a structure of an arrayed carbon nanotube thin film transistor according to the present invention includes highly doped silicon as a gate 1, silicon dioxide 2 as an insulating layer, and an arrayed carbon nanotube film 3 as a semiconductor material. Gold electrodes 4 and 5 are source and drain electrodes. Put a 20×20mm SiO 2 /Si substrate into the middle of the quartz tube, connect the gas distribution system, feed hydrogen at a flow rate of 20 ml per minute, set the temperature at 950°C, and heat up the electric furnace. When the temperature of the furnace core reaches At 900° C., put a quartz boat (5 milliliters) filled with 0.5 gram of iron phthalocyanine into a zone with a furnace mouth temperature of 550° C. and stop heating after 5 minutes. Cool to room temperature. Carbon nanotubes with a diameter of 40 nanometers and a length of 6 micrometers with regular array and uniform size were prepared. The length of the nanotubes was measured (Fig. 2) and estimated from scanning electron micrographs, and the diameter was measured from transmission electron micrographs (Fig. 3). Then, the interdigitated electrode template was used to vacuum-deposit gold as the source and drain electrodes in a coating machine, and the channel length and width were 0.4 mm and 66 mm, respectively. The schematic diagram of the device structure is shown in Figure 1, and the morphology of the device can be seen from the scanning electron microscope photo (Figure 4). Finally, use the HP4140B semiconductor tester to measure the output characteristic curve (Figure 5) and the transfer characteristic curve (Figure 6) of the device, and the source-drain voltage and gate voltage are scanned at 0--1V. The hole field-effect mobility of the device measured in air is ~79.3 cm 2 /Vs, and the on/off ratio is greater than ~100.
实施例2按实施例1的制备方法，只是将沟道长度和宽度改变为0.2毫米和53毫米，在室温下测量所得的器件的空穴场效应迁移率为～48.9cm2/Vs，开关比大于～75。Example 2 According to the preparation method of Example 1, except that the length and width of the channel were changed to 0.2 mm and 53 mm, the hole field-effect mobility of the device measured at room temperature was ~48.9 cm 2 /Vs, and the on-off ratio Greater than ~75.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100367480C (en) * | 2005-03-17 | 2008-02-06 | 上海交通大学 | Method for manufacturing multi-channel field-effect transistor with channel formed of carbon nanotubes |
| CN100427388C (en) * | 2005-11-25 | 2008-10-22 | 清华大学 | A large-area ultra-thin carbon nanotube film and its preparation process |
| CN100488865C (en) * | 2006-09-11 | 2009-05-20 | 厦门大学 | Method for preparing Nano getter |
| CN101497437B (en) * | 2008-02-01 | 2012-11-21 | 清华大学 | Preparation method of carbon nanotube composite film |
| CN101599495B (en) * | 2008-06-04 | 2013-01-09 | 清华大学 | Thin-film transistor panel |
| CN101582449B (en) | 2008-05-14 | 2011-12-14 | 清华大学 | Thin film transistor |
| CN101582450B (en) | 2008-05-16 | 2012-03-28 | 清华大学 | Thin film transistor |
| CN101587839B (en) | 2008-05-23 | 2011-12-21 | 清华大学 | Method for producing thin film transistors |
| CN101593699B (en) | 2008-05-30 | 2010-11-10 | 清华大学 | Fabrication method of thin film transistor |
| CN101582382B (en) | 2008-05-14 | 2011-03-23 | 鸿富锦精密工业（深圳）有限公司 | Preparation method of thin film transistor |
| CN101582446B (en) | 2008-05-14 | 2011-02-02 | 鸿富锦精密工业（深圳）有限公司 | Thin film transistor |
| CN101582444A (en) | 2008-05-14 | 2009-11-18 | 清华大学 | Thin film transistor |
| CN101582448B (en) | 2008-05-14 | 2012-09-19 | 清华大学 | Thin film transistor |
| CN101582445B (en) | 2008-05-14 | 2012-05-16 | 清华大学 | Thin film transistor |
| CN101582381B (en) | 2008-05-14 | 2011-01-26 | 鸿富锦精密工业（深圳）有限公司 | Thin film transistor and method for manufacturing same |
| CN101625466B (en) * | 2008-07-09 | 2012-12-19 | 清华大学 | Touch liquid crystal display screen |
| CN101997035B (en) * | 2009-08-14 | 2012-08-29 | 清华大学 | Thin film transistor |
| CN105609636B (en) * | 2016-02-17 | 2018-05-08 | 上海交通大学 | Directional single-wall carbon nanotube array is the field-effect transistor and production method of raceway groove |
| CN108962759B (en) * | 2018-07-15 | 2019-07-30 | 吉林建筑大学 | A kind of preparation method of zinc oxide thin-film transistor |
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