WO2015007005A1 - 一种有机单分子层薄膜场效应气体传感器及制备方法 - Google Patents

一种有机单分子层薄膜场效应气体传感器及制备方法 Download PDF

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WO2015007005A1
WO2015007005A1 PCT/CN2013/081606 CN2013081606W WO2015007005A1 WO 2015007005 A1 WO2015007005 A1 WO 2015007005A1 CN 2013081606 W CN2013081606 W CN 2013081606W WO 2015007005 A1 WO2015007005 A1 WO 2015007005A1
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layer
thin film
gas sensor
organic
active layer
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PCT/CN2013/081606
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French (fr)
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江潮
王嘉玮
莫扎⋅米斯巴
李德兴
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国家纳米科学中心
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4141—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for gases

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  • the invention relates to the technical field of gas sensors, and in particular to an organic monolayer film field effect gas sensor and a preparation method thereof.
  • OFT Organic Thin Film Transistor
  • FET Bay Area Transistor
  • New electronic devices It has the advantages of light weight, simple preparation process, low price and compatibility with flexible substrates, and has been widely concerned since its inception. At present, its performance is close to or exceeds that of amorphous silicon thin film transistors, and is widely used in organic light-emitting display OLED driving, organic RF tags and organic sensors.
  • a sensor is a device that, in a selective manner, responds to a particular analyte to be analyzed in a selective manner to qualitatively or quantitatively determine an analyte, and can be used to detect a particular substance or substances.
  • organic materials have better molecular recognition and specific selectivity than inorganic materials, and thus have higher response sensitivity to the gas to be detected. Moreover, the chemical modification of organic materials can also enhance their sensitivity to different gases, so organic gas sensors have shown good prospects in applications.
  • the preparation of gas sensors based on organic field effect transistors most of the methods used at home and abroad are to prepare tens of nanometers thick film or to apply crystalline organic crystals.
  • the active layer for gas detection the bulk material has the characteristics of simple preparation process and stable sensor performance.
  • the semiconductor active layer molecules interact with the gas to be detected, and the electrical properties of the active layer will change. These changes are reflected in the change of the electrical signal (such as leakage current or threshold voltage) of the device. Detection of gas molecules.
  • the above-mentioned gas sensor based on an organic field effect tube also has its drawbacks.
  • a conventional tens of nanometers thick active layer is used for gas detection, since gas molecules are mostly distributed on the surface of the active layer, the conductive channels participating in carrier transport in the active layer are located closest to the dielectric layer and organic.
  • the gas molecules to be measured are diffused from the surface (crossing the organic active layer of several tens of nanometers thick) to the channel to affect the conductance properties of the device, so that high response efficiency cannot be achieved. Make the response time of the sensor longer.
  • the object of the present invention is to provide a novel organic single molecule thin film field effect gas sensor structure, which directly acts on the active layer portion participating in the main carrier transport to improve the organic field effect transistor. Gas detector detection efficiency.
  • the invention also provides a preparation method of an organic single molecule thin film field effect gas sensor.
  • An organic monolayer thin film field effect gas sensor comprising a substrate, a gate electrode, a dielectric layer, an active layer and source and drain electrodes from bottom to top, wherein the active layer is an organic monomolecular film layer.
  • the main optimized structure of the gas sensor of the present invention is an airport effect transistor in contact with the bottom gate.
  • the organic monomolecular film layer is composed of 1 to 5 monomolecular layers, preferably 1 monolayer.
  • the substrate material is a silicon wafer, a glass, a polymer film or a metal foil, preferably a silicon wafer.
  • the gate electrode and the source and drain electrodes are independently selected from the group consisting of low resistance metals and alloy materials thereof, metal oxides or conductive composite materials.
  • a heavily doped silicon wafer can be selected as the gate electrode as a substrate.
  • the dielectric layer is made of a polymer or an oxide; the selected polymer or oxide dielectric layer causes the first monolayer to grow thereon in a two-dimensional layered mode; the dielectric layer is preferably A polystyrene layer of a certain thickness is modified on the silica.
  • the active layer is made of an acene-based small molecule material; the acene-based material is selected from the group consisting of pentacene, tetracene and the like.
  • the source/drain electrode is composed of a metal foil and a wire, and has a thickness of several tens of micrometers to several hundreds of micrometers.
  • the dielectric layer is 200-300 nm thermal oxidized silica, and a polystyrene layer of about several tens of nanometers is modified thereon.
  • the thickness of the silicon dioxide in the dielectric layer is 200 to 300 nm, and the thickness of the polystyrene PS layer is 30 to 40 nm, and further preferably 30 nm.
  • the invention also provides a preparation method of the gas sensor as described above, wherein the preparation method adopts a vacuum evaporation method to deposit an organic monomolecular film layer on the dielectric layer; when evaporating, the evaporation source is first heated to the target Temperature (such as 123 °C), after the deposition rate is stable, the beam baffle is turned on to start evaporation; the evaporation rate is selected appropriately (such as 1.5nm/mm), the purpose is to ensure that the vapor deposition layer grows in a two-dimensional growth mode.
  • the evaporation time (e.g., 1 mm) is controlled to obtain an organic monomolecular film layer as an active layer.
  • the source electrode electrode is directly attached to the surface of the organic monomolecular film layer by a mechanical method.
  • the reason why the direct vapor deposition electrode is not used here is that the monomolecular layer morphology is destroyed by the heat radiation introduced by direct vapor deposition, and a good electrical characteristic curve cannot be formed. This is because the monolayer structure is very fragile compared to the thick film active layer, and the gold is easily vapor-deposited. The atom (or the heat radiation of the high temperature source furnace) is destroyed.
  • the direct attachment method of the machine avoids destroying the structure and morphology of the monolayer while forming a good ohmic contact.
  • the present invention constructs an airport effect gas sensor with a single layer molecular film.
  • the sensor is grown on a heavily doped Si substrate (gate), 200-300 nm thick silicon dioxide and a polystyrene (PS) layer as a dielectric layer, and a growth layer is formed on the dielectric layer.
  • the single layer of pentacene monolayer has a thickness of about 1.5 nm, and the gold foil is directly attached to the surface of the active layer as a source/drain electrode by a mechanical method.
  • the present invention has the following beneficial effects:
  • all of the pentacene molecules in the active layer can be brought into contact with the outside by using the gas sensor of the pentacene monolayer as the active layer.
  • the gas sensor of the pentacene monolayer as the active layer.
  • FIG. 1 is a cross-sectional view showing the structure of an organic monolayer thin film field effect gas sensor of the present invention
  • FIG. 2 is a cross-sectional view showing the structure of a gas sensor according to an embodiment of the present invention
  • Figure 3 is a topographical view of a pentacene monolayer characterized by atomic force microscopy
  • Figure 4 is the response curve of organic monolayer thin film field effect gas sensor for different concentrations of ammonia
  • Figure 5 is the response curve of thick film sensor for different concentrations of ammonia
  • Figure 6 shows the relationship between the sensitivity of the organic monolayer and thick film field effect sensor and the ammonia concentration according to the equations 4 and 5 and the sensitivity R formula.
  • an organic monolayer thin film field effect gas sensor includes a substrate 5, a gate electrode 4, a dielectric layer 3, an active layer 2, and source and drain electrodes 1 from bottom to top,
  • the active layer 2 is an organic monomolecular film layer.
  • the organic monomolecular film layer may actually be composed of 1 to 5 monomolecular layers, preferably 1 monomolecular layer.
  • the material of the substrate 5 is a silicon wafer, a glass, a polymer film or a metal foil, preferably a silicon wafer.
  • the gate electrode 4 and the source/drain electrode 1 are independently selected from a low resistance metal and an alloy material thereof, a metal oxide or a conductive composite material.
  • the dielectric layer 3 is made of a polymer or an oxide; the selected polymer or oxide dielectric layer causes the first monolayer to be grown thereon in a two-dimensional layered mode; the dielectric layer 3 is preferably The polystyrene layer was modified on silica.
  • the active layer 2 is made of an acene-based material; the acene-based material is selected from pentacene or tetracene.
  • the source/drain electrode 1 is composed of a metal foil and a wire, and has a thickness of several tens of micrometers to several hundreds of micrometers.
  • the thickness of the silicon dioxide in the dielectric layer 3 is 200 to 300 nm, and the thickness of the polystyrene layer is 30. ⁇ 40nm, further one is preferably 30nm.
  • a method for preparing the gas sensor wherein the preparation method adopts a vacuum evaporation method to deposit an organic monomolecular film layer on the dielectric layer 3; during evaporation, the evaporation source is first heated to a target temperature (eg, 123 °) C), after the deposition rate is stable, the beam baffle is turned on to start evaporation; the evaporation rate is selected appropriately (eg 1.5nm/mm), the purpose is to ensure that the vapor deposition molecular layer is grown in a two-dimensional growth mode, and the evaporation time (for example, 1 mm) is controlled to obtain an organic monomolecular film layer as the active layer 2.
  • a target temperature eg, 123 °
  • the beam baffle is turned on to start evaporation
  • the evaporation rate is selected appropriately (eg 1.5nm/mm)
  • the purpose is to ensure that the vapor deposition molecular layer is grown in a two-dimensional growth mode, and the evaporation time (
  • the metal foil as the source/drain electrode 1 is directly attached to the surface of the organic monomolecular film layer by a mechanical method.
  • a main process for preparing an organic monolayer thin film field effect gas sensor as shown in Fig. 2 is as follows:
  • a layer of PS is spin-coated on the Si/Si0 2 sheet as a dielectric layer having a thickness of about 30 nm.
  • the sample was baked in a vacuum oven for 12 hours, and the baking temperature was 85 °C.
  • FIG. 3 is a characterization image of the sample by atomic force microscopy, and the polymorphic pentacene molecular layer can be clearly seen. It is almost exactly covered on the PS dielectric layer.
  • Si/S ⁇ film purchased from Hefei Kejing Material Technology Co., Ltd. was selected as the substrate, which was cut into about lx lcm size, and then ultrasonically cleaned with acetone, ethanol and deionized water for 10 min, then used at 100 °C. Bake for 2 hours. After drying, spin coating is applied. The spin coating process is completed on a laurell WS-400MZ-8NPP-LITE spin coater. The substrate is adsorbed on a spin coater, set at a speed of 6000/min, and a 1% PS toluene is used with a dropper. The solution was dropped on the surface of the substrate, and the solution was required to spread over the substrate, and spin coating was started.
  • the sample was placed in a vacuum drying oven, and the baking temperature was set to 85 ° C, and baked for 12 hours.
  • the key step of organic active layer evaporation is performed on BOC-Edwards's auto306 vacuum evaporation equipment.
  • the crucible containing pentacene powder loaded after evaporation source of the deposition chamber to seal the chamber and turn on the vacuum pump extraction, when the pressure chamber is lower than 4x 10- 7 Torr, the power source is turned on evaporation
  • the crucible is heated to a target temperature of 123 °C. As the temperature of the evaporation source increases, pentacene begins to sublimate.
  • the quartz oscillator is turned on to monitor the deposition thickness and deposition rate of pentacene.
  • the deposition rate of pentacene tends to be stable (at this time, the deposition rate is about 1.5 nm/min)
  • the baffle is opened, and pentacene will start to deposit on the PS-coated substrate at a rate of about 1.5 nm/min.
  • the baffle is turned off and the power is turned on.
  • the evaporation is finished, the evaporation thickness is about 1.5 nm, and the AFM characterization image shows exactly one layer of pentacene monolayer.
  • the gas sensor prepared in the manner described was tested for ammonia gas molecules.
  • the sensor is placed in a vacuum probe station, the transfer curve of the sensor is measured under a vacuum environment, and then an appropriate amount of ammonia gas is introduced to measure the transfer curve of the sensor at an ammonia concentration of 20 ppm, and then gradually increase the ammonia concentration.
  • the transfer curves at concentrations of 40, 60, 80, and 100 ppm were measured, and the entire test procedure is shown in Figure 4. It can be seen that the sensor has different transfer curves for ammonia gas at different concentrations. As the ammonia concentration increases, the source and drain currents will gradually decrease, and the threshold voltage will move toward the negative value, indicating the sensitivity of the sensor. When the sensor is placed back in a vacuum environment, its transfer curve is substantially restored to the level before exposure to ammonia, indicating the reversibility and repeatability of the sensor's operation.
  • a field effect gas sensor having an organic active layer thickness of 40 nm was prepared.
  • the preparation method was as described in the specific example 1, except that the vapor deposition time of pentacene was appropriately extended to obtain an active layer having a film thickness of 40 nm.
  • the prepared 40 nm thick film sensor was subjected to ammonia gas molecular test, and the test result was compared with that in Concrete Example 2.
  • the test results of the single-molecule sensor are compared.
  • the specific comparison method is as follows: Compare the changes of source and drain currents of the two sensors in different concentrations of ammonia. It is found that the source-drain current of the monolayer sensor has a more obvious change with the ammonia concentration, indicating that the monolayer sensor has higher sensitivity than the thick film sensor.
  • the overall test results are shown in Figure 5.

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Abstract

本发明涉及一种有机单分子层薄膜场效应气体传感器及制备方法。所述气体传感器组成结构由下至上包括衬底、栅电极、介电层、活性层及源漏电极，所述活性层为有机单分子薄膜层。所述制备方法采用真空蒸镀的方法在介电层上蒸镀有机单分子薄膜层；蒸镀时，首先将蒸发源加热至目标温度（如123°C），待沉积速率稳定后开启束流挡板开始蒸镀；控制蒸镀时间以得到有机单分子薄膜层作为活性层。根据本发明的技术方案，通过将并五苯单分子层作为活性层的气体传感器，使得活性层中所有的并五苯分子都能够与外界接触。传感器工作时，并五苯分子将不受阻挡地与被探测气体直接相互作用，并能灵敏地将这种相互作用反映在其薄膜晶体管输出曲线的变化中。

Description

一种有机单分子层薄膜场效应气体传感器及制备方法 技术领域
本发明涉及气体传感器技术领域， 尤其涉及一种有机单分子层薄膜场效应 气体传感器及制备方法。
背景技术
有机薄膜晶体管 （OTFT) 又名有机场效应晶体管， 是与传统无机场效应晶 体管（FET)结构类似， 但活性层是基于有机半导体（具有共轭 π电子结构的小 分子或聚合物） 的一类新型电子器件。 它具有重量轻、 制备工艺简单、 价格低 廉及可与柔性基底兼容等优点， 因而自问世以来就受到了人们广泛关注。 目前 它的性能已接近或超过非晶硅薄膜晶体管的水平， 并被广泛应用于有机发光显 示 OLED驱动， 有机射频标签及有机传感器等领域。
传感器是一种能够通过某种作用以选择性的方式对特定的待分析物质产生 响应从而对分析物质进行定性或定量测定的装置， 可以用于检测特定的一种或 多种物质。
目前， 气体传感器的发展趋势集中表现为： 1、 提高灵敏度和工作性能， 并 使其微型化， 并能够与应用整机相结合； 2、 增强可靠性， 具备多种功能， 发展 现场适用的变送器和智能型传感器。
在传感器的应用方面， 与无机材料相比， 有机材料具有更优的分子识别和 特异选择性， 因而对被探测气体具有更高的响应灵敏度。 而且通过对有机材料 进行化学修饰还可以增强其对不同气体的敏感选择性， 因此有机气体传感器在 应用方面展现出了良好的前景。 在基于有机场效应晶体管的气体传感器的制备 方面， 国内外采用的方法大多以制备数十纳米厚度薄膜或者应用结晶的有机晶 体材料作为气体探测的活性层部分， 具有制备工艺简易， 传感器性能稳定等特 点。 器件工作时， 半导体活性层分子与被探测气体相互作用， 活性层的电学特 性将会发生改变， 这些改变反映在该器件的电学信号 （如漏电流或阈值电压） 的改变中， 以此来完成对气体分子的探测。
但是， 上述基于有机场效应管的气体传感器也有它的不足之处。 例如， 采 用传统的几十纳米厚度的活性层作气体探测时， 因为气体分子大多分布于活性 层的表面， 而活性层中参与载流子输运的导电沟道位于最贴近介电层和有机半 导体的界面处的分子层中， 即被测气体分子要从表面扩散 （跨过几十纳米厚的 有机活性层） 到沟道才能影响器件的电导性质， 因此无法达到很高的响应效率， 也使传感器的响应时间变长。 综上， 目前亟需制备一种能使气体直接影响载流 子输运层的有机场效应晶体管气体传感器。
发明内容
本发明的目的在于针对现有技术的不足， 提出一种新的有机单分子薄膜场 效应气体传感器结构， 使气体与参与主要载流子输运的活性层部分直接作用， 来提高有机场效应晶体管气体探测器的探测效率。
本发明还提供了一种有机单分子薄膜场效应气体传感器的制备方法。
为达此目的， 本发明采用以下技术方案：
一种有机单分子层薄膜场效应气体传感器， 所述气体传感器由下至上包括 衬底、 栅电极、 介电层、 活性层及源漏电极， 所述活性层为有机单分子薄膜层。
本发明所述气体传感器的主要优化结构为底栅顶接触的有机场效应晶体 管。 其它组合结构， 如底栅底电极也有获得高灵敏度的可能。
所述有机单分子薄膜层由 1~5个单分子层组成， 优选为 1个单分子层。 所述衬底材料为硅片、 玻璃、 聚合物薄膜或金属箔， 优选为硅片。 所述栅电极及源漏电极独立地选自低电阻的金属及其合金材料、 金属氧化 物或导电复合材料。
在本发明中， 可以选用重掺杂硅片作为栅电极， 同时作为衬底。
优选地， 所述介电层由聚合物或氧化物制成； 所选聚合物或氧化物介电层 使首个单分子层在其上以二维层状模式生长； 所述介电层优选为二氧化硅上修 饰一定厚度聚苯乙烯层。
优选地， 所述活性层由并苯类小分子材料制成； 所述并苯类材料选自并五 苯、 并四苯等。
所述源漏电极由金属箔、 丝构成， 其厚度为几十微米至几百微米， 优选
50μπΐ;
所述介电层为 200~300nm热氧化二氧化硅， 及其上修饰约几十纳米聚苯乙 烯层。
优选地， 所述介电层中二氧化硅的厚度为 200~300nm， 聚苯乙烯 PS层的厚 度为 30~40nm， 进一歩优选 30nm。
本发明还提供了一种如上所述气体传感器的制备方法， 所述制备方法采用 真空蒸镀的方法在介电层上蒸镀有机单分子薄膜层； 蒸镀时， 首先将蒸发源加 热至目标温度 （如 123 °C )， 待沉积速率稳定后开启束流挡板开始蒸镀； 蒸镀速 率选取适当（如 1.5nm/mm)， 目的是保证蒸镀分子层以二维生长模式进行生长， 控制蒸镀时间 （如 lmm) 以得到有机单分子薄膜层作为活性层。
不同于传统的应用掩膜遮挡法热蒸镀源漏电极， 根据本发明， 将源漏电极 应用机械方法直接贴附于有机单分子薄膜层表面。 此处不采用直接蒸镀电极的 原因为单分子层形貌会被直接蒸镀引入的热辐射所破坏， 无法形成良好的电特 性曲线。 这是因为与厚膜活性层相比， 单分子层结构非常脆弱， 易被蒸镀的金 原子 （或高温源炉的热辐射） 所破坏。 机械直接贴附的方法可以避免破坏单分 子层的结构和形貌同时又可形成良好的欧姆接触。
具体地， 本发明以单层分子薄膜构建有机场效应气体传感器。 该传感器以 生长在重掺杂 Si 衬底 （栅极）， 200~300nm 厚的二氧化硅及修饰有聚苯乙烯 (Polystyrene, PS)层为介电层， 并在前述介电层上面生长一个单层的并五苯单 分子层，厚度约为 1.5nm，采用机械法将金箔直接贴于活性层表面作为源漏电极。
与已有技术方案相比， 本发明具有以下有益效果：
根据本发明的技术方案， 通过将并五苯单分子层作为活性层的气体传感器， 使得活性层中所有的并五苯分子都能够与外界接触。 传感器工作时， 并五苯分 子将不受阻挡地与被探测气体直接相互作用， 并能灵敏地将这种相互作用反映 在其薄膜晶体管输出曲线的变化中。
附图说明
图 1为本发明有机单分子层薄膜场效应气体传感器结构截面示图； 图 2为本发明具体实施例的气体传感器结构截面示图；
图 3为原子力显微镜表征的并五苯单分子层的形貌图；
图 4为有机单分子层薄膜场效应气体传感器对不同浓度的氨气的响应曲线； 图 5为厚膜传感器对不同浓度的氨气的响应曲线；
图 6为根据图 4和 5及灵敏度 R公式给出的有机单分子层和厚膜场效应传 感器灵敏度与氨气浓度间的关系。
图 6中的灵敏度 R定义为： R = (IN2-lNH3yiN2， 即一定栅压下氮气环境下（氨 气浓度为零）漏电流与特定氨气浓度下的漏电流之差除以氮气环境下的漏电流。
图中： 1-源漏电极； 2-活性层； 3-介电层； 4-栅电极； 5-衬底。
下面对本发明进一歩详细说明。 但下述的实例仅仅是本发明的简易例子， 并不代表或限制本发明的权利保护范围， 本发明的保护范围以权利要求书为准。 具体实施方式
为更好地说明本发明， 便于理解本发明的技术方案， 本发明的典型但非限 制性的实施例如下：
如图 1 所示， 一种有机单分子层薄膜场效应气体传感器， 所述气体传感器 由下至上包括衬底 5、 栅电极 4、 介电层 3、 活性层 2及源漏电极 1， 所述活性 层 2为有机单分子薄膜层。
所述有机单分子薄膜层实际可由 1~5个单分子层组成， 优选为 1个单分子 层。
所述衬底 5材料为硅片、 玻璃、 聚合物薄膜或金属箔， 优选为硅片。
所述栅电极 4及源漏电极 1独立地选自低电阻的金属及其合金材料、 金属 氧化物或导电复合材料。
所述介电层 3 由聚合物或氧化物制成； 所选聚合物或氧化物介电层使首个 单分子层在其上以二维层状模式生长； 所述介电层 3 优选为二氧化硅上修饰聚 苯乙烯层。
所述活性层 2由并苯类材料制成； 所述并苯类材料选自并五苯或并四苯。 所述源漏电极 1 由金属箔、 丝构成， 其厚度为几十微米至几百微米， 优选 所述介电层 3 中二氧化硅的厚度为 200~300nm， 聚苯乙烯层的厚度为 30~40nm, 进一歩优选 30nm。
一种所述气体传感器的制备方法， 所述制备方法采用真空蒸镀的方法在介 电层 3 上蒸镀有机单分子薄膜层； 蒸镀时， 首先将蒸发源加热至目标温度 （如 123 °C ) , 待沉积速率稳定后开启束流挡板开始蒸镀； 蒸镀速率选取适当 （如 1.5nm/mm) ,目的是保证蒸镀分子层以二维生长模式进行生长，控制蒸镀时间（如 lmm) 以得到有机单分子薄膜层作为活性层 2。
将作为源漏电极 1 的金属箔应用机械方法直接贴附于有机单分子薄膜层表 面。
具体地， 一种制备如图 2所示的有机单分子层薄膜场效应气体传感器的主 要过程如下：
( 1 ) 在 Si/Si02片上旋涂一层 PS作为介电层， 其厚度约为 30nm。
(2) 为了进一歩除去 PS溶液中的甲苯溶剂， 将样品在真空干燥箱内烘烤 12h， 烘烤温度为 85 °C。
(3 )进行蒸镀时， 首先对蒸发源设置温度， 并进行加热； 开启石英振荡器， 其作用是监测蒸镀的膜厚， 并计算出沉积速率， 沉积速率稳定后开始蒸镀， 蒸 镀速率约为 1.5nm/min， 蒸镀时间为 lmin, 最后得到膜厚为 1.5nm的薄膜。
(4) 通过原子力显微镜的表征， 可以确定， 以上述方法制备的并五苯薄膜 接近一个单分子层厚度， 图 3 为原子力显微镜对样品的表征图像， 可清晰看到 多晶并五苯分子层基本恰好铺满于 PS介电层上面。
( 5 ) 将两片金箔作为源漏电极直接贴附于有机单分子薄膜层表面。
具体实施例 1
选用购置于合肥科晶材料技术有限公司的 Si/S ^片作为衬底， 将其切割为 约 l x lcm大小， 依次使用丙酮、 乙醇、 去离子水超声清洗 10min， 之后使用热 台在 100 °C下烘烤 2h。 烘干之后进行旋涂， 旋涂过程在 laurell WS-400MZ-8NPP-LITE旋涂仪上完成， 将衬底吸附于旋涂仪上， 设置转速 6000/ 分， 用滴管将 1%的 PS甲苯溶液滴于衬底表面， 要求溶液铺满衬底， 开始旋涂。 旋涂完毕之后， 将样品置于真空干燥箱内， 设置烘烤温度为 85°C， 烘烤 12h。 样品烘干之后，进行有机活性层蒸镀这一关键歩骤，此过程在 BOC-Edwards 公司的 auto306真空蒸镀设备上完成。将装有并五苯粉末的坩埚加载于蒸发源之 后， 对蒸镀腔室进行密封并开启真空泵对腔室进行真空抽取， 当腔室的气压低 于 4x 10— 7托时， 开启蒸发源电源对坩埚进行加热， 所设目标温度为 123 °C。 随着 蒸发源温度升高， 并五苯开始升华， 当蒸发源温度到达 123 °C时， 开启石英振荡 器，监测并五苯的沉积厚度以及沉积速率。当并五苯的沉积速率趋于稳定时（此 时沉积速率约为 1.5nm/min)， 将挡板打开， 并五苯将以约 1.5nm/min的速率开 始沉积到涂有 PS的衬底上面， 沉积 lmm之后， 关闭挡板以及加热电源， 蒸镀 结束， 蒸镀厚度约为 1.5nm， AFM表征图像显示恰好为一层并五苯单分子层。
从腔室内取出样品之后，将两片厚度约为 ΙΟΟμπι,面积为 l x lmm2的金箔贴 于有机活性层表面， 形成良好的接触， 整个器件构建完毕。
将所述方式制备的气体传感器对氨气分子进行测试。 首先将传感器置于真 空探针台中， 在真空环境下测得传感器的转移曲线， 然后通入适量氨气， 测得 在氨气浓度为 20ppm下传感器的转移曲线， 之后逐渐增大氨气浓度， 分别测得 在浓度为 40、 60、 80以及 lOOppm下的转移曲线， 整个测试过程如图 4。 可见 传感器对不同浓度下的氨气有不同的转移曲线与之对应， 随着氨气浓度的增加， 源漏电流会逐渐减小， 阈值电压向负值方向移动， 说明了此传感器的灵敏度。 当将传感器重新置于真空环境时， 其转移曲线基本恢复到暴露氨气之前的水平， 说明了此传感器工作的可逆性和重复性。
具体实施例 2 (对比例）
制备有机活性层厚度为 40nm的场效应气体传感器，制备方式参照具体实施 例 1所述， 只是适当延长并五苯的蒸镀时间， 以得到膜厚度为 40nm的活性层。 将制备的 40nm厚膜传感器进行氨气分子测试，将测试结果与具体实施例 2中的 单分子层传感器的测试结果进行对比， 具体对比方式为： 将两种传感器在不同 浓度氨气中源漏电流的变化进行对比。 发现： 单分子层传感器的源漏电流随氨 气浓度具有更明显的变化， 说明了单分子层传感器比厚膜传感器有更高的灵敏 度。 整个测试结果如图 5。
申请人声明， 本发明通过上述实施例来说明本发明的详细结构特征以及制 备方法， 但本发明并不局限于上述详细结构特征以及制备方法， 即不意味着本 发明必须依赖上述详细结构特征以及制备方法才能实施。 所属技术领域的技术 人员应该明了， 对本发明的任何改进， 对本发明所选用部件的等效替换以及辅 助部件的增加、 具体方式的选择等， 均落在本发明的保护范围和公开范围之内。
另外需要说明的是， 在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾的情况下， 可以通过任何合适的方式进行组合， 为了避免不必要的重 复， 本发明对各种可能的组合方式不再另行说明。
此外， 本发明的各种不同的实施方式之间也可以进行任意组合， 只要其不 违背本发明的思想， 其同样应当视为本发明所公开的内容。

Claims

权 利 要 求 书
1、 一种有机单分子层薄膜场效应气体传感器， 所述气体传感器由下至上包 括衬底 （5)、 栅电极 （4)、 介电层 （3 )、 活性层 （2) 及源漏电极 （1 )， 其特征 在于， 所述活性层 （2) 为有机单分子薄膜层。
2、 如权利要求 1所述的气体传感器， 其特征在于， 所述有机单分子薄膜层 由 1~5个单分子层组成， 优选为 1个单分子层。
3、 如权利要求 1或 2所述的气体传感器， 其特征在于， 所述衬底 （5 ) 材 料为硅片、 玻璃、 聚合物薄膜或金属箔， 优选为硅片；
优选地， 所述栅电极 （4 ) 及源漏电极 （1 ) 独立地选自低电阻的金属及其 合金材料、 金属氧化物或导电复合材料；
优选地， 所述介电层 （3 ) 由聚合物或氧化物制成； 所选聚合物或氧化物介 电层使首个单分子层在其上以二维层状模式生长； 所述介电层 （3 ) 优选为二氧 化硅上修饰聚苯乙烯层；
优选地， 所述活性层 （2) 由并苯类小分子材料制成； 所述并苯类小分子材 料选自并五苯或并四苯。
4、 如权利要求 3 所述的气体传感器， 其特征在于， 所述源漏电极 （1 ) 由 金属箔、 丝构成， 其厚度为几十微米至几百微米， 优选 50μπι;
优选地， 所述介电层 （3 ) 中二氧化硅的厚度为 200~300nm， 聚苯乙烯层的 厚度为 30~40nm， 进一歩优选 30nm。
5、 一种如权利要求 1-4之一所述气体传感器的制备方法， 其特征在于， 所 述制备方法采用真空蒸镀的方法在介电层 （3 ) 上蒸镀有机单分子薄膜层； 蒸镀 时， 首先将蒸发源加热至目标温度， 待沉积速率稳定后开启束流挡板开始蒸镀; 控制蒸镀时间以得到有机单分子薄膜层作为活性层 （2)。
6、 如权利要求 5所述的制备方法， 其特征在于， 将作为源漏电极 （1 ) 的 金属箔应用机械方法直接贴附于有机单分子薄膜层表面 (
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