CN102943247B - A method for preparing an inorganic proton conducting membrane - Google Patents

A method for preparing an inorganic proton conducting membrane Download PDF

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CN102943247B
CN102943247B CN201210477098.0A CN201210477098A CN102943247B CN 102943247 B CN102943247 B CN 102943247B CN 201210477098 A CN201210477098 A CN 201210477098A CN 102943247 B CN102943247 B CN 102943247B
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proton conducting
conducting membrane
phosphorus
inorganic proton
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CN102943247A (en
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万青
郭立强
竺立强
周菊枚
张洪亮
吴国栋
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中国科学院宁波材料技术与工程研究所
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Abstract

本发明公开了一种无机质子导电膜的制备方法,包括:采用化学气相沉积技术,将反应源通入沉积体系中,通过调节工艺参数,在衬底上制备出磷掺杂二氧化硅无机质子导电膜。 The present invention discloses a method for preparing an inorganic proton conducting membrane, comprising: a chemical vapor deposition reaction into the deposition source through the system, by adjusting the process parameters, the preparation of phosphorus-doped silicon dioxide on the substrate an inorganic proton a conductive film. 本发明还提供了一种基于该方法制备的导电膜,及用所述导电膜制成的制品。 The present invention also provides a conductive film prepared by the method based on, and made of the conductive film article. 本发明原材料来源丰富、价格便宜;制备工艺与现有设备相容,适于大面积连续生产;前景广阔、用途广泛,可在薄膜晶体管、聚合物电解质膜燃料电池、电化学传感器、水/蒸汽电解、生物系统等领域得到广泛应用。 The present invention is a rich source of raw materials, inexpensive; Preparation compatible with existing equipment, adapted to large-scale continuous production; prospects, widely used, can be a thin film transistor, a polymer electrolyte membrane fuel cell, an electrochemical sensor, the water / steam fIELD electrolysis, biological systems have been widely used.

Description

一种无机质子导电膜的制备方法 A method for preparing an inorganic proton conducting membrane

技术领域 FIELD

[0001] 本发明涉及材料领域,具体地涉及新的无机质子导电膜及其制法和应用。 [0001] The present invention relates to the field of materials, and in particular relates to a novel inorganic proton conducting membrane preparation method and application.

背景技术 Background technique

[0002] 质子传导和质子导电材料在电池、电化学传感器、水/蒸汽电解以及生物系统中起着越来越重要的作用。 [0002] The proton conductive material and a proton conducting plays an increasingly important role in the cell, an electrochemical sensor, the water / steam electrolyzer and biological systems. 例如,质子导电膜是聚合物电解质膜燃料电池的"心脏"。 For example, proton conducting membrane is a polymer electrolyte membrane fuel cell of the "heart." 它不同于一般化学电源中的隔膜,因为它不但起着隔离燃料和氧化剂,防止它们直接发生反应的作用,更起着电解质的作用。 It is different from the general chemical power sources diaphragm isolation because it not only plays a fuel and oxidant, into direct effect of preventing the reaction thereof, but acts as an electrolyte. 它应对质子导通,对电子绝缘,是一种选择透过性的功能高分子膜。 It deals with proton conduction, electron insulating, it is a function of the polymer film permeable choice. 因此聚合物电解质膜燃料电池的输出功率、电池效率、成本及应用前景强烈地依赖于质子交换膜。 Therefore, the output power of the polymer electrolyte membrane fuel cell, the cell efficiency, costs and application prospect is strongly dependent on the proton exchange membrane.

[0003] Yoshitaka Aoki (Adv. Mater. 2008, 20, 4387-4393)等人成功研制出基于娃的一种双氧化物非晶态质子导电膜,这种质子导电膜可在300~400°C范围内展现出良好的质子交换效果,但是在制作中,他们发现薄膜中同时存在一些缺陷,这将制约其大规模工业应用。 [0003] Yoshitaka Aoki (Adv. Mater. 2008, 20, 4387-4393), who successfully developed a double oxide based amorphous baby proton conducting membrane, the proton conducting membrane may be 300 ~ 400 ° C within the range of proton exchange show a good effect, but in the production, they found that while there are some flaws in the film, which will restrict its large-scale industrial applications. 2008年,法国托马斯•贝特洛等人(申请号:2008801108961)通过放射性接枝技术制备出用于燃料电池的质子导电膜,该技术属于化学溶液合成。 In 2008, Thomas France • Berthelot et al. (Application number: 2008801108961) preparing a proton conducting membrane for a fuel cell by radiation grafting technique belongs to the chemical solution synthesis. 此外,Abe等发现某些磷酸盐玻璃,如Ba〇-和Sr〇-P 205体系中质子以0H键基团形式存在,与其它玻璃系统相比(SiO 2玻璃)具有较高的质子导电率,而且氧化物玻璃的化学稳定性好、容易制成各种形状。 Further, Abe found that certain phosphate glass, such as Ba〇- Sr〇-P 205, and the system key protons present in the form 0H group, compared to other systems of glass (SiO 2 glass) having high proton conductivity and chemical stability of the oxide glass is easily formed into various shapes.

[0004] 介孔二氧化硅(Si02)具有很大的比表面积,能够吸附大量水分子,这些水分子能在介孔通道中发生毛细凝结作用,使通道可以像"小水池" 一样存储大量水分子,同时介孔状Si02的通道还可以充当质子移动通道,如图1所示,由此可以避免有机复合质子导电膜或有机无机杂化复合质子导电膜中因添加大量细微颗粒而造成的导电能力下降问题。 [0004] The mesoporous silica (Si02) having a large surface area, can adsorb a large amount of water molecules, the water molecules capillary coagulation can occur in the mesoporous channels, so that the same channel can store a large amount of water as "small pool" molecules, while the shape Si02 mesoporous channels also act as proton transfer channel, as shown in FIG. 1, whereby the electrically conductive organic compound can be avoided proton conducting membrane or composite organic-inorganic hybrid proton conducting membrane due to adding a large amount of fine particles caused by decreased ability problem.

[0005] 中国专利申请号200810035587. 4和200810035586中公开制备质子导电膜的方法,其中,通过在酸性或碱性聚合物中引入磺酸基团制备获得了无机二氧化硅中空微球(hso3-hss),从而在化学成分组成和空间结构两方面同时提高了体系对质子化助剂的保持能力。 [0005] Chinese Patent Application No. 200810035586 discloses a method and a proton conducting membrane was prepared 200810035587.4, wherein, by introducing a sulfonic acid group in an acidic or a basic polymer obtained in the preparation of inorganic silica hollow microspheres (HSO3- hss), so that the spatial structure and chemical composition of both systems while increasing the retention aid is protonated. 其制备的质子导电膜,在100°c以上仍有优良的质子导电性能,制备的质子导电膜可以作为中温(100-200°C )燃料电池的质子交换膜和膜电极。 Proton conducting membrane prepared in excellent proton conductivity is still above 100 ° c, may be prepared proton conducting membrane and a membrane electrode exchange membrane as a proton temperature (100-200 ° C) of the fuel cell. 然而,该质子导电膜的制备工艺和性能还难以令人满意。 However, the preparation and properties of the proton conducting membrane is also unsatisfactory.

[0006] Haibin Li (Adv. Mater. 2002, 14(12) : 912-914)等人以(CH3(CH2)15N+(CH3) 3Bi〇和C16E01(l等表面活性剂作为结构定向剂,在IT0玻璃上利用溶胶-凝胶技术成功制备出了可控孔状结构硅质子导电膜,研宄了膜中孔的沟道平行于衬底与膜中孔的沟道垂直于衬底两种情况下的导电特性。 [0006] Haibin Li (Adv Mater 2002, 14 (12):.. 912-914) et al., In (CH3 (CH2) 15N + (CH3) 3Bi〇 and C16E01 (l surfactant such as a structure directing agent, in IT0 glass by the sol - gel method successfully prepared silica controlled pore structure sub-conductive film, a study based on the channel parallel to the substrate pores in the membrane pores and channels perpendicular to the substrate film in both cases conductive properties.

[0007] 肖凯军等人采用溶胶-凝胶法成功制备了介孔Si(V薄膜,探讨了介孔状膜制备过程中溶胶液配方、溶胶液制备搅拌强度和成膜时间与其分离透过特性之间的关系,发现涂胶液粘度最好控制在30~40mPa *S范围内,并且经过高温灼烧之后,其介孔结构不会遭到破坏,最终得到纯水通量为4215L/m2 • h的介孔状Si02。 [0007] Xiao Kaijun et al sol - gel process mesoporous Si (V films were discussed during the film-like mesoporous sol liquid formulation, sol was stirred for strength and film-forming characteristics of the transmission time separated therefrom the relationship between, the viscosity of the liquid adhesive is preferably controlled found in the range of 30 ~ 40mPa * S, and the burning temperature after which the mesoporous structure is not destroyed, pure water flux finally obtained 4215L / m2 • h like mesoporous Si02.

[0008] 上海交通大学李海滨等人(中国专利申请号:201010134580)利用水热工艺技术, 发现磷酸中质子的离子性更强且每个磷原子附有3个0H,能够作为质子源提供更多质子, 从而获得高质子传导率的导电玻璃体材料。 [0008] Shanghai Jiaotong Haibin et al (China patent application number: 201010134580) using hydrothermal technology, found that the ionic phosphate and more protons per phosphorus atom with 3 0H, as the proton source can be more proton to obtain a conductive high proton conductivity of vitreous material.

[0009] 目前,现有的常规制备质子导电膜的方法大多采用化学溶液合成法、离子交换法、 溶胶-凝胶法等,这些方法的共同特点是均匀性相对较差,而且工艺不易用于规模化生产等缺点,尤其是制备的介孔Si0 2由于其介孔通道过大、且分布不够均匀,从而导致其质子的导电能力有限。 [0009] Currently, conventional methods proton conducting membrane conventionally prepared mostly chemical solution synthesis method, ion exchange method, a sol - gel method, a common feature of these methods is relatively poor uniformity, and the process is difficult for large-scale production and other shortcomings, especially in the preparation of the mesoporous mesoporous Si0 2 due to its passage too large, and the distribution is not uniform enough, resulting in the proton conductivity is limited.

[0010] 因此,本领域迫切需要开发制备介孔通道小、分布均匀、具有优异的质子导电性能的无机质子导电膜及相应的制备工艺。 [0010] Thus, the present art is urgent to develop a small hole prepared via channels, evenly distributed, with the corresponding preparation process of inorganic proton conducting membrane excellent in proton conductivity properties.

发明内容 SUMMARY

[0011] 本发明的目的是提供一种操作简便,适于大面积连续生产,产品介孔通道小、分布均匀、具有优异的质子导电性能的无机质子导电膜制备方法。 [0011] The object of the present invention is to provide a simple, suitable for large-scale continuous production, the product of small mesopores channels, evenly distributed, with preparation of an inorganic proton conducting membrane excellent in proton conductivity properties.

[0012] 本发明的第一方面,提供了一种无机质子导电膜的制备方法,包括步骤: The first aspect of the [0012] present invention, there is provided a method for preparing an inorganic proton conducting membrane, comprising the steps of:

[0013] 将反应源通入反应腔室,并进行化学气相沉积,从而形成具有介孔结构的磷掺杂二氧化硅无机质子导电膜,其中,所述的反应源包括硅源、磷源和氧源。 [0013] The reaction source into the reaction chamber, and chemical vapor deposition, thereby forming a mesostructure having a phosphorus doped silicon dioxide inorganic proton conducting membrane, wherein said reactive source comprises a silicon source, a phosphorus source, and oxygen source.

[0014] 在另一优选例中,所述的化学气相沉积选自下组:等离子体化学气相沉积、大气压化学气相沉积。 [0014] In another preferred embodiment, the chemical vapor deposition is selected from the group consisting of: plasma chemical vapor deposition, atmospheric pressure chemical vapor deposition.

[0015] 在另一优选例中,所述的化学气相沉积是大气压化学气相沉积。 [0015] In another preferred embodiment, the chemical vapor deposition is atmospheric pressure chemical vapor deposition.

[0016] 在另一优选例中,所述硅源、磷源和氧源的比例满足以下关系:磷源:硅源=1 : 100 ~20 :100;硅源:氧源=1 :1 ~1 :6。 [0016] In another preferred embodiment, the ratio of the silicon source, a phosphorus source and an oxygen source satisfy the following relationship: phosphorus source: silicon source = 1: 100 to 20: 100; silicon source: oxygen source = 1: 1 1: 6.

[0017] 在另一优选例中,所述方法还具有一个或多个以下特征: [0017] In another preferred embodiment, the method further comprises one or more of the following features:

[0018] 所述的硅源选自下组:三氯氢硅、四氯化硅、乙硅烷、硅烷,或其组合; [0018] The silicon source is selected from the group consisting of: trichlorosilane, tetrachlorosilane, disilane, silane, or combinations thereof;

[0019] 所述的磷源选自下组:三氯氧磷和/或磷烷(如磷化三氢PH3); [0019] The phosphorus source is selected from the group consisting of: phosphorus oxychloride and / or phosphorus alkyl (e.g., hydrogen phosphide of PH3);

[0020] 所述的氧源选自下组:氮气或氩气携带去离子水和/或氧气,且所述去离子水为气态。 [0020] The oxygen source is selected from the group consisting of: nitrogen or argon carrying deionized water and / or oxygen, and the gaseous deionized water.

[0021] 在另一优选例中,所述的硅烷为甲硅烷(SiH4)。 [0021] In another preferred embodiment, the silane is monosilane (SiH4).

[0022] 在另一优选例中,所述反应腔室内充有惰性气体(如氩气等)。 [0022] In another preferred embodiment, the reaction chamber filled with an inert gas (e.g., argon, etc.).

[0023] 在另一优选例中,所述化学气相沉积是沉积于衬底表面,从而形成沉积于衬底上的无机质子导电膜。 [0023] In another preferred embodiment, the chemical vapor deposition is deposited on the substrate surface, thereby forming an inorganic proton conducting membrane deposited on the substrate.

[0024] 在另一优选例中,其特征在于,所述衬底选自下组:玻璃衬底、塑料衬底、纸衬底、 陶瓷衬底、或其组合。 [0024] In another preferred embodiment, wherein the substrate is selected from the group: a glass substrate, a plastic substrate, a paper substrate, a ceramic substrate, or a combination thereof.

[0025] 在另一优选例中,所述的化学气相沉积过程中,所述衬底的温度为100~400°C。 [0025] In another preferred embodiment, the chemical vapor deposition process, the temperature of the substrate is 100 ~ 400 ° C.

[0026] 在另一优选例中,所述的等离子体化学气相沉积技术中,腔室压强为20~200Pa。 [0026] In another preferred embodiment, the plasma chemical vapor deposition, the chamber pressure of 20 ~ 200Pa.

[0027] 在另一优选例中,当采用等离子体化学气相沉积技术时,所述的衬底温度为0°C~ 100 °c〇 [0027] In another preferred embodiment, when a plasma chemical vapor deposition, the substrate temperature is 0 ° C ~ 100 ° c〇

[0028] 在另一优选例中,当采用大气压化学气相沉积技术时,所述的腔室压强为0. 1~ L 0atm〇 [0028] In another preferred embodiment, when using atmospheric pressure chemical vapor deposition technique, the chamber pressure of 0. 1 ~ L 0atm〇

[0029] 在另一优选例中,当采用大气压化学气相沉积技术时,所述的衬底温度100~ 400。 [0029] In another preferred embodiment, when using an atmospheric pressure chemical vapor deposition techniques, a substrate temperature of 100 to 400. . .

[0030] 在另一优选例中,所述反应过程中磷源与硅源的混合比例为1%~20%。 [0030] In another preferred embodiment, the ratio of the reaction mixture during the silicon source and the phosphorus source is 1 to 20%.

[0031] 本发明的第二方面,提供了一种无机质子导电膜,所述的无机质子导电膜是通过化学气相沉积形成的。 [0031] The second aspect of the invention, there is provided an inorganic proton conducting membrane, said inorganic proton conducting membrane is formed by chemical vapor deposition.

[0032] 本发明的第三方面,提供了一种无机质子导电膜,所述的无机质子导电膜是磷掺杂的介孔Si(V薄膜,并且所述无机质子导电膜具有以下导电特性:在环境湿度为80%和室温(如25°C )时,其质子电导率为1 X 10_2S/cm~l(T4S/cm,且在环境湿度为85%~100%和50°C~80°C时,质子电导率为lXl(T2S/cm ~lXl(T4S/cm。 [0032] The third aspect of the present invention, there is provided an inorganic proton conducting membrane, the proton conducting membrane is inorganic phosphorous doped mesoporous Si (V film, and the inorganic proton conducting membrane having the conductive properties: when the ambient humidity of 80% and room temperature (e.g. 25 ° C), proton conductivity was 1 X 10_2S / cm ~ l (T4S / cm, and ambient humidity of 85% to 100% and 50 ° C ~ 80 ° C, the proton conductivity of lXl (T2S / cm ~ lXl (T4S / cm.

[0033] 在另一优选例中,随环境湿度和温度变化,质子电导率将不同程度地增加或减小。 [0033] In another preferred embodiment, with the ambient humidity and temperature, the proton conductivity will be increased or decreased to varying degrees.

[0034] 在另一优选例中,所述的无机质子导电膜是通过化学气相沉积形成的。 [0034] In another preferred embodiment, the inorganic proton conducting membrane is formed by chemical vapor deposition.

[0035] 在另一优选例中,所述的无机质子导电膜是用如本发明第一方面所述的制备方法制备的。 [0035] In another preferred embodiment, the inorganic proton conducting membrane was prepared by the method of the first aspect of the present invention is prepared.

[0036] 在另一优选例中,所述的无机质子导电膜具有如下组分:磷、硅和氧。 [0036] In another preferred embodiment, the inorganic proton conducting membrane has the following components: phosphorus, silicon, and oxygen.

[0037] 在另一优选例中,所述的Si02薄膜的孔径为2~50nm。 [0037] In another preferred embodiment, the aperture of the Si02 film is 2 ~ 50nm.

[0038] 在另一优选例中,所述的薄膜的厚度为50nm~50 ym。 [0038] In another preferred embodiment, the thickness of the film is 50nm ~ 50 ym.

[0039] 在另一优选例中,所述的无机质子导电膜具有如下结构特征: [0039] In another preferred embodiment, the inorganic proton conducting membrane structure having the following characteristics:

[0040] 二氧化硅颗粒堆积组成具有介孔结构的膜骨架,和 [0040] The composition of the film deposited silica particles having mesoporous structure of the skeleton, and

[0041] 为质子提供输运通道的微介孔。 [0041] The micro-mesoporous provide proton transport channel.

[0042] 在另一优选例中,所述的微介孔通道的平均直径< 20nm。 [0042] In another preferred embodiment, the average diameter of the micro-mesoporous channels <20nm.

[0043] 在另一优选例中,所述的无机质子导电膜的厚度为100nm~20 ym。 [0043] In another preferred embodiment, the thickness of the inorganic proton conducting membrane is 100nm ~ 20 ym.

[0044] 在另一优选例中,所述的导电膜还可包括衬底材料。 [0044] In another preferred embodiment, the conductive film may further comprise a substrate material.

[0045] 本发明的第四方面,提供了一种制品,所述制品含有如本发明第二方面和第三方面所述的无机质子导电膜,或所述制品由如本发明第二方面和第三方面所述的无机质子导电膜制成。 [0045] The fourth aspect of the present invention, there is provided an article of manufacture comprising the second and inorganic proton conducting membrane as a third aspect of the present invention, or the article by a second aspect of the present invention and as the third aspect is made of said inorganic proton conducting membrane.

[0046] 在另一优选例中,所述的制品选自下组:具有所述导电膜的玻板、以玻璃为基体的微纳元器件(如:透明氧化物薄膜晶体管、燃料电池),以塑料为基体的微纳元器件(如:柔性薄膜晶体管、柔性传感器等),以纸为基体的柔性微纳元器件(如柔性薄膜晶体管)。 [0046] In another preferred embodiment, the article is selected from the group consisting of: glass plate having the conductive film, as a glass matrix micro-nano components (such as: a transparent oxide thin film transistor, a fuel cell), plastic matrix as micro-nano components (such as: a flexible thin film transistor, a flexible sensor, etc.), the flexible micro-nano components (e.g., flexible film transistor) paper as the substrate.

[0047] 应理解,在本发明范围内中,本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合,从而构成新的或优选的技术方案。 [0047] It should be understood, in the range of the present invention, can be combined with each other between the technical features of the invention and in the following technical features (as described in Example) specifically described, thereby constituting a new or preferred technique Program. 限于篇幅,在此不再一一累述。 Due to space limitations, which is not eleven tired.

附图说明 BRIEF DESCRIPTION

[0048] 图1为本发明制备的磷掺杂二氧化硅无机质子导电膜结构示意图; [0048] FIG 1 prepared in the present invention, the phosphorus-doped silica, a schematic structure of an inorganic proton-conductive film;

[0049] 图2为本发明制备的磷掺杂二氧化硅无机质子导电膜的扫描电子显微镜照片实例; [0049] FIG 2 prepared in the present invention, the phosphorus doped silicon dioxide inorganic proton conducting membrane of Example scanning electron micrograph;

[0050] 图3为本发明制备的磷掺杂二氧化硅无机质子导电膜阻抗分析图实例图,其中, Z'表示阻抗分析图谱中的实部,Z"表示阻抗分析图谱中的虚部。 [0050] FIG. 3 prepared in the present invention, the phosphorus doped silicon dioxide inorganic proton conducting membrane impedance analysis example of FIG. FIG, wherein, Z 'represents the impedance spectra analysis of the real part, Z "represents the imaginary part of the impedance spectra analysis.

具体实施方式 Detailed ways

[0051] 本发明人经过长期而深入的研宄,意外地发现,采用化学气相沉积方法可高效率、 大规模地制造性能优异的无机质子导电膜制备方法简单,制作原材料来源丰富,价格便宜, 制备工艺与微电子加工工艺兼容,不需改变其他现有生产设备,重复性和均匀性高,适于大面积连续生产;通过本发明方法制备的无机质子导电膜质量高,电阻小,可在薄膜晶体管、 聚合物电解质膜燃料电池、电化学传感器、水/蒸汽电解、生物系统等领域得到广泛应用。 [0051] The present invention after long-term and intensive study based, surprisingly been found that using a chemical vapor deposition method of high efficiency, high performance large-scale manufacturing an inorganic proton conducting membrane preparation method is simple, a rich source of raw material production, cheap, preparation process is compatible with microelectronic, other without changing existing production equipment, high uniformity and repeatability, suitable for large area continuous production; high inorganic proton conducting membrane produced by the process of the present invention, quality, low resistance, can be field of the thin film transistor, a polymer electrolyte membrane fuel cell, an electrochemical sensor, the water / steam electrolyzer, biological systems have been widely used.

[0052] 化学气相沉积法 [0052] The chemical vapor deposition method

[0053] 化学气相沉积(CVD)是用来沉积多种材料的技术,包括大范围的绝缘材料,大多数金属材料和金属合金材料。 [0053] Chemical vapor deposition (CVD) techniques are used to deposit a variety of materials, including a wide range of insulating materials, most metallic materials and metallic alloy materials. 通用的化学气相沉积法的操作方法为:将两种或两种以上的气态原材料导入到一个反应室内,所述原材料之间发生化学反应,形成的产物沉积到衬底表面上。 General method of operation of a chemical vapor deposition method is: introducing two or more gaseous starting material into a reaction chamber, a chemical reaction takes place between the starting material, the product formed is deposited onto the substrate surface.

[0054] 在本发明中,所述的化学气相沉积系统采用射频辉光放电使反应发生,并通过控制沉积体系温度、压强的方法控制吸附、成核和生长的过程。 [0054] In the present invention, the chemical vapor deposition system using radio frequency glow discharge reaction occurs, and by controlling the temperature of the deposition system, a method of controlling pressure adsorption, nucleation and growth process. 较佳地,本发明所用的化学气相沉积法可为等离子体化学气相沉积法或大气压化学气相沉积法。 Preferably, the chemical vapor deposition method may be used in the present invention is a plasma chemical vapor deposition or atmospheric pressure chemical vapor deposition.

[0055] 反应源 [0055] reaction source

[0056] 如本文所用,术语"反应源"指化学气相沉积法所用的原料,通常为气态,或通过一定方式(如高温,射频辉光放电等)转化为气态并在气相沉积系统中发生反应。 [0056] As used herein, the term "reactive source" refers to material chemical vapor deposition method used, normally gaseous, or converted to gaseous by a certain way (e.g., temperature, radio frequency glow discharge or the like) and reacted in a vapor deposition system, .

[0057] 用于本发明的质子导电膜制备的反应源包括(但不限于):硅源、氧源和/或磷源。 [0057] The reaction of the proton source conductive film production for the present invention include (but are not limited to): a silicon source, an oxygen source and / or a phosphorus source. 各反应源试剂可通过常规方法制备、或通过市售途径得到。 Each reaction reagent sources may be prepared by conventional methods, or obtained through a commercial route.

[0058] 其中,所述的硅源包括:三氯氢硅、四氯化硅、乙硅烷、硅烷,或其组合;所述的磷源包括:三氯氧磷、磷烷,或其组合;所述的氧源包括:载气携带的去离子水和/或氧气。 [0058] wherein the silicon source comprises: trichlorosilane, silicon tetrachloride, disilane, silane, or combinations thereof; said phosphorus source comprises: phosphorus oxychloride, phosphorus chloride, or combinations thereof; the oxygen source comprises: a carrier gas deionized water and / or oxygen carried. 较佳地,载气为惰性气体或氮气等不与反应源发生化学反应的组分,更佳地,载气为氩气。 Preferably, the carrier gas does not chemically react with the components of the reaction gas source, inert nitrogen or, more preferably, the carrier gas is argon.

[0059] 在本发明中,各反应源宜按一定比例通入腔室并发生反应。 [0059] In the present invention, each of the reaction should be a certain proportion of the source into the chamber and react. 在本发明中,所述的磷源和硅源混合比例为1%~20%,所述氧源的比例没有特别限制,较佳地,所述的氧源通入量大于磷源和/或硅源的通入量(以摩尔数计)。 In the present invention, the phosphorus source and a silicon source mixing ratio of 1% to 20%, the proportion of the source of oxygen is not particularly limited, preferably, the oxygen source into an amount greater than the phosphorus source and / or silicon source into an amount (in number of moles).

[0060] 制备方法 [0060] Preparation

[0061] 本发明提供了一种无机质子导电膜的制备方法,其采用化学气相沉积技术(如等离子体化学气相沉积技术、大气压化学气相沉积技术)。 [0061] The present invention provides a method for preparing an inorganic proton conducting membrane, the chemical vapor deposition techniques (e.g., plasma chemical vapor deposition, atmospheric pressure chemical vapor deposition).

[0062] 为了便于理解本发明,提供以下机理。 [0062] In order to facilitate understanding of the present invention, the following mechanism. 然而,应理解,本发明的保护范围并不受所述机理的限制。 However, it should be understood that the scope of the present invention is not limited to the mechanism.

[0063] 在本发明中,将所述反应源通入腔室后,可在合适的条件(衬底温度、压强)下发生反应,在衬底上沉积形成导电薄膜。 [0063] In the present invention, after the source into the reaction chamber, the reaction can take place under suitable conditions (substrate temperature, pressure), depositing a conductive thin film formed on a substrate. 无机质子导电膜中硅原子、磷原子与水分子结合,形成Si_OH+和P-OH+等基团;在电场作用下,H+从OH+基团分离,提供可导电的质子,介孔通道可以储存水分子和提供质子的运输途径。 Inorganic proton conducting membrane of silicon atom, a phosphorus atom with water molecules, forming Si_OH + and P-OH + like groups; in the electric field, H + from OH + radical separation, an electrically conductive protons, mesoporous channels can store water molecules and provide means of transport protons.

[0064] 在本发明中,通常将反应源按一定比例通入腔室,并进行化学气相沉积,就可形成具有介孔结构的磷掺杂二氧化硅无机质子导电膜。 [0064] In the present invention, the reaction is generally a certain proportion of the source into the chamber, and chemical vapor deposition, silicon dioxide can be formed via an inorganic proton conducting membrane having a pore structure of the phosphorus doping.

[0065] 此外,为了进一步提高质子导电膜的质量,宜利用氩气等惰性气体作为保护气体。 [0065] In order to further improve the quality of the proton conducting membrane, should be inert gas such as argon gas as the shielding gas.

[0066] 在优选例中,在三种反应源中宜先通入氧源,再通入硅源和磷源(后二种可同时通入)。 [0066] In a preferred embodiment, the three reaction advised source into a source of oxygen, and then into the silicon and phosphorus sources (the latter two may simultaneously fed).

[0067] 在本发明中,宜在衬底上进行化学气相沉积。 [0067] In the present invention, suitable for chemical vapor deposition on a substrate. 在本发明中,适用的衬底没有特别限制,代表性的衬底包括(但并不限于):硅片、玻璃、塑料、纸、陶瓷。 In the present invention, suitable substrates are not particularly limited, typical substrates include (but are not limited to): silicon, glass, plastic, paper, ceramics. 利用这些衬底,通过本发明化学气相沉积法,可制备带有衬底的磷掺杂二氧化硅无机质子导电膜。 Using these substrates, by chemical vapor deposition method of the present invention, the substrate may be prepared with a phosphorus doped silicon dioxide inorganic proton conducting membrane.

[0068] 在本发明中,可使用常规的化学气相沉积设备,也可使用微电子加工中所用的其他生产设备。 [0068] In the present invention, a conventional chemical vapor deposition apparatus, may also be used in other production equipment used in microelectronics processing.

[0069] 在一优选例中,所述的等离子体化学气相沉积技术中,反应压强为20~200Pa;所述的衬底温度为室温至l〇〇°C。 [0069] In a preferred embodiment, the plasma chemical vapor deposition technique, a reaction pressure of 20 ~ 200Pa; the substrate temperature is room temperature to l〇〇 ° C.

[0070] 在另一优选例中,所述的气压化学气相沉积技术中,反应压强为常压;所述的衬底温度为1〇〇~400 °C。 [0070] In another preferred embodiment, the pressure chemical vapor deposition technique, a reaction pressure of atmospheric pressure; 1〇〇 the substrate temperature is ~ 400 ° C.

[0071] 通过本发明方法制作的无机质子导电膜具有介孔通道小、分布均匀的特点,在一优选例中,所述薄膜具有直径小于20纳米的介孔通道。 [0071] The inorganic proton conducting membrane produced by the method of the present invention has a small hole via the channel, the characteristics of uniformly distributed, in a preferred embodiment, the film has a mesopore diameter of less than 20 nm channel.

[0072] 本发明提供的制备方法操作简便,适于大面积连续生产,因而非常适合用于工业化大规模生产磷掺杂的无机质子导电膜以及基于具备所述特征的导电膜加工制成的制品。 [0072] The present invention provides a method of preparation is simple, continuous production is suitable for large area, which makes it very suitable for industrial mass production of an inorganic proton conducting membrane comprising based on the phosphorus-doped and made of a conductive film is processed the characteristics of the article .

[0073] 无机质子导电膜 [0073] The inorganic proton conducting membrane

[0074] 本发明提供的无机质子导电膜为磷掺杂的具有介孔的Si(V薄膜。较佳地,本发明提供的无机质子导电膜具有如下结构:二氧化硅颗粒组成的具有介孔结构的膜骨架,且具有为质子提供输运通道的微介孔。 [0074] The inorganic proton conducting membrane of the present invention provides a phosphorus-doped Si (V film having mesopores Preferably, the inorganic proton conducting membrane of the present invention is provided having the structure: having the mesoporous silica particles membrane skeleton structure, and provided with micro-mesoporous proton transport channel.

[0075] 所述的用于掺杂的磷为P205的水溶液,较佳地为磷酸。 [0075] The phosphorus for doping aqueous solutions of P205, preferably a phosphate.

[0076] 在另一优选例中,本发明的无机质子导电膜具有如下组分:磷、硅和氧。 [0076] In another preferred embodiment, the inorganic proton conducting membrane of the present invention has the following components: phosphorus, silicon, and oxygen.

[0077] 本发明的无机质子导电膜的介孔通道直径为< 50nm,在一优选例中,所述的Si02 薄膜的孔径为2~50nm。 Mesoporous Channel [0077] The inorganic proton conducting membrane of the present invention having a diameter of <50nm, in a preferred embodiment, the aperture of the Si02 film is 2 ~ 50nm. 在另一优选例中,所述的微介孔通道的平均直径< 20nm。 In another preferred embodiment, the average diameter of the micro-mesoporous channels <20nm.

[0078] 本发明的导电薄膜的厚度为50nm~50ym,较佳地为100nm~20ym〇 [0078] The thickness of the conductive film of the present invention is 50nm ~ 50ym, preferably a 100nm ~ 20ym〇

[0079] 本发明的导电膜具有优异的质子导电性能,在一优选例中,在湿度为80%,和温度为室温(如25°C )的条件下,所述的无机质子导电膜的质子电导率可达到KT4S/cm以上。 [0079] The conductive film of the present invention has excellent proton conductivity, in a preferred embodiment, the humidity of 80% and a temperature of room temperature conditions (e.g. 25 ° C), the inorganic proton proton conducting membrane of the conductivity can be achieved KT4S / cm or more.

[0080] 无机质子导电膜制品 [0080] The inorganic proton conducting membrane preparation

[0081] 用本发明提供的无机质子导电膜,可以制备常用的通过导电膜制备的制品,如带有基体的微纳元器件。 [0081] The inorganic proton conducting membrane of the present invention provides the use, the article can be prepared by conventional preparation of the conductive film, as micro-nano Component having a base body. 优选的无机质子导电膜制品包括(但不限于):以玻璃为基体的微纳元器件(如:透明氧化物薄膜晶体管、燃料电池),以塑料为基体的微纳元器件(如:柔性薄膜晶体管、柔性传感器等),以纸为基体的柔性微纳元器件(如柔性薄膜晶体管)。 Preferred inorganic proton conducting membrane articles include (but are not limited to): In a glass matrix micro-nano components (such as: a transparent oxide thin film transistor, a fuel cell), as the plastic matrix micro-nano components (such as: a flexible film transistor, a flexible sensor, etc.), the flexible micro-nano components (e.g., flexible film transistor) paper as the substrate.

[0082] 本发明的主要优点包括: [0082] The main advantages of the present invention comprises:

[0083]1)本发明无机质子导电膜的制备方法简单、制作原材料来源丰富、价格便宜、获得的质子导电膜质量高,电阻小。 [0083] 1) preparing an inorganic proton-conductive film of the present invention is simple, making a rich source of raw materials, inexpensive, high quality of the obtained proton conducting membrane, a small resistance.

[0084] 2)本发明无机质子导电膜的制备工艺与微电子加工工艺兼容,不需改变其他现有生产设备,重复性和均匀性高,适于大面积连续生产; [0084] 2) Preparation process microelectronic inorganic proton-conductive film of the present invention is compatible with, the other without changing existing production equipment, high uniformity and repeatability, suitable for large area continuous production;

[0085] 3)本发明无机质子导电膜性能优异,因而具有极强的应用潜力,可在薄膜晶体管、 聚合物电解质膜燃料电池、电化学传感器、水/蒸汽电解、生物系统等领域得到广泛应用。 [0085] 3) of the present invention is excellent in proton-conductive inorganic film properties, and thus has a strong potential applications, can be widely used in the field of thin film transistors, a polymer electrolyte membrane fuel cell, an electrochemical sensor, the water / steam electrolysis, and other biological systems .

[0086] 下面结合具体实施例,进一步阐述本发明。 [0086] The following embodiments with reference to specific embodiments, further illustrate the present invention. 应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。 It should be understood that these embodiments are illustrative only and the present invention is not intended to limit the scope of the invention. 下列实施例中未注明具体条件的实验方法,通常按照常规条件,或按照制造厂商所建议的条件。 Experimental methods without specific conditions in the examples below, are performed under routine conditions, or in accordance with the conditions recommended by the manufacturer. 除非另外说明,否则百分比和份数按重量计算。 Unless otherwise indicated, percentages and parts are by weight.

[0087] 通用方法 [0087] General Procedure

[0088] 原料:硅烷:浓度为99. 9% ;磷烷:浓度为99. 9% ;氧气:浓度为99. 95% ;氩气:浓度为99. 95%,氮气浓度为99. 95%。 [0088] Starting material: Silane: a concentration of 99.9%; phosphane: a concentration of 99.9%; oxygen: a concentration of 99.95%; argon: 99.95% concentration, nitrogen concentration of 99.95% .

[0089] 在化学气相沉积系统中,采用射频辉光放电产生等离子体,在近真空环境中,控制腔室压强、衬底温度等工艺参数,使硅源、磷源、氧源等混合成分发生分解,并在衬底表面发生吸附、成核、生长等一系列化学反应生长磷掺杂二氧化硅无机质子导电膜,为提高无机质子导电膜的导电质量,制备完成后将无机质子导电膜在高氯酸锂溶液中浸泡半小时以上。 [0089] In a chemical vapor deposition system using a radio frequency glow discharge plasma is generated in a near vacuum environment, the control chamber pressure, substrate temperature and other process parameters, the silicon source, a phosphorus source ingredients are mixed, the oxygen source like occurs decomposition occurs at the substrate surface and the adsorption, nucleation, growth and a series of chemical reactions phosphorus-doped silicon dioxide grown inorganic proton conducting membrane, to improve the quality of the conductive inorganic proton conducting membrane was prepared after the completion of an inorganic proton conducting membrane in lithium perchlorate solution soak for half an hour.

[0090] 导电性能的测定 Determination of [0090] Conductivity of

[0091] 采用半导体阻抗仪对产品的阻抗特性进行测试,得到质子电阻;利用SEM等设备对薄膜的厚度进行表征,最后利用公式 [0091] The impedance characteristics of the semiconductor impedance meter for testing the product, proton resistance; film thickness were characterized by SEM and other equipment, and finally using the formula

Figure CN102943247BD00081

•计算薄膜的质子电导率, • calculate the proton conductivity of the film,

[0092] 式中:1为薄膜厚度;R为薄膜的质子阻抗,A为薄膜面积。 [0092] wherein: a film thickness is 1; R & lt impedance of a thin film of a proton, A is membrane area.

[0093] 实施例1 :等离子体化学气相沉积法在玻璃衬底上制备导电膜 [0093] Example 1: Plasma CVD conductive film was prepared on glass substrates

[0094] 1)对玻璃衬底进行严格清洗。 [0094] 1) the glass substrates stringency wash. 依次将玻璃衬底浸入酒精、去离子水超声清洗10分钟;再用去离子水反复冲洗;最后用氮气枪吹干。 Sequentially immersing the glass substrate alcohol, ultrasonic cleaning in deionized water, 10 minutes; rinse with deionized water repeatedly; and finally blown dry with a nitrogen gun.

[0095] 2)同时开启等离子体化学气相沉积设备,将腔室打开,为避免腔室对衬底以及生长的质子导电膜污染,首先用吸尘器抽出腔室内可能存在的细微颗粒,再分别依次经过丙酮、酒精反复擦拭腔室周围,最后立即将清洗好的衬底放入反应腔室; [0095] 2) while turning plasma chemical vapor deposition apparatus, the chamber is opened, the chamber in order to avoid substrate contamination and growth of proton conducting membrane, first with a vacuum chamber out of fine particles that may be present, and then sequentially, through acetone, alcohol repeatedly wipe around the chamber, and finally immediately cleaned substrate into a reaction chamber;

[0096] 3)依次开启机械泵将反应腔室本低真空抽至IPa左右; [0096] 3) sequentially turned mechanical pump of the present low vacuum reaction chamber is evacuated to about IPa;

[0097] 4)通入氩气,流量为45sccm(standard_statecubiccentimeterperminute,标况毫升每分),调节腔室压强至30Pa;开启射频电源,设定射频功率100W; [0097] 4) into an argon gas flow rate of 45sccm (standard_statecubiccentimeterperminute, superscript sccm), chamber pressure adjusted to 30 Pa; RF power is turned on, to set the RF power 100W;

[0098]5)通入氧源,流量为60sccm;待压强稳定后,通入硅烷和磷烧,总流量为lOsccm; 最后重新调整反应压强为30Pa; [0098] 5) into the oxygen source, the flow rate of 60 sccm; After the pressure became stable, the silane and phosphorus into burning, total flow lOsccm; and finally re-adjusting the reaction pressure of 30 Pa;

[0099] 6)控制生长时间50分钟,制备磷掺杂二氧化硅无机质子导电膜; [0099] 6) controlling the growth time of 50 minutes to prepare a phosphorus-doped silicon dioxide inorganic proton conducting membrane;

[0100] 7)为防止过量硅烷和磷烷自发反应生成二氧化硅粉末,造成污染,反应结束后,首先停止通入硅烷和憐烧混合气体,等待硅烷和憐烧混合气体质量流量显不为0时,等待2分钟,停止通入氧气; [0100] 7) to prevent excess phosphorus alkoxy silane and silica powder spontaneous reaction, pollution, after the completion of the reaction, first of all stopping the flow of a mixed gas of silane and Rei burn, wait, and Rei burning a mixed gas of silane mass flow rate is not significant 0, wait 2 minutes, stopping the flow of oxygen;

[0101] 8)氧气被抽完之后关闭射频;停止通入氩气保护气体; [0101] 8) Close radio oxygen after being smoked; stopping the flow of argon protective gas;

[0102] 9)全部打开分子泵与腔室之间的插板阀,将腔室真空抽至实验前本底真空以下; [0102] 9) all the flapper valve is opened between the molecular pump chamber, the vacuum chamber is evacuated to a vacuum prior to the experiment the background;

[0103] 10)关闭分子泵与腔室之间的插板阀,通入高纯氮气,开启腔室,取出样品,并保存,或应用于以玻璃为基体的微纳元器件中。 [0103] 10) between the closed flapper valve molecular pump chamber, into high purity nitrogen, the opening chamber, samples were removed and stored, or applied to a glass substrate in the micro-nano components.

[0104] 结果:制得的无机质子导电膜的结构示意图如图1所示,扫描电子显微镜照片如图2所示,从图中可以看出,该质子导电膜的厚度约为700nm,其剖面结构呈现竖状连接的条纹,这是由于微介孔道被剖开所致,说明质子导电膜的内部存在微介孔,其直径在20nm 以下。 [0104] Results: The structure of the inorganic proton conducting membrane was obtained in the schematic diagram shown in Figure 1, a scanning electron microscope photograph shown in FIG., It can be seen from Figure 2, the thickness of the proton conducting membrane of about of 700 nm, which is a sectional a stripe-shaped structure presentation vertical connection, which is broken away because microvia channels caused by the presence of micro-mesoporous described internal proton conducting membrane having a diameter of less than 20nm.

[0105] 实施例2 :等离子体化学气相沉积法在塑料衬底上制备导电膜 [0105] Example 2: conducting a plasma chemical vapor deposition on a plastic substrate film prepared

[0106] 1)对塑料衬底进行严格清洗。 [0106] 1) on a plastic substrate is stringency wash. 依次将塑料衬底浸入酒精、去离子水超声清洗10分钟;再用去离子水反复冲洗;最后用氮气枪吹干。 The plastic substrate is immersed successively alcohol, ultrasonic cleaning in deionized water, 10 minutes; rinse with deionized water repeatedly; and finally blown dry with a nitrogen gun.

[0107] 2)同时开启等离子体化学气相沉积设备,将腔室打开,为避免腔室对衬底以及生长的质子导电膜污染,首先用吸尘器抽出腔室内可能存在的细微颗粒,再分别依次经过丙酮、酒精反复擦拭腔室周围,最后立即将清洗好的衬底放入反应腔室; [0107] 2) while turning plasma chemical vapor deposition apparatus, the chamber is opened, the chamber in order to avoid substrate contamination and growth of proton conducting membrane, first with a vacuum chamber out of fine particles that may be present, and then sequentially, through acetone, alcohol repeatedly wipe around the chamber, and finally immediately cleaned substrate into a reaction chamber;

[0108] 3)依次开启机械泵将反应腔室本低真空抽至IPa左右; [0108] 3) sequentially turned mechanical pump of the present low vacuum reaction chamber is evacuated to about IPa;

[0109] 4)通入氩气,流量为6〇SCCm ;调节腔室压强至30Pa,开启射频电源,设定射频功率50W; [0109] 4) introduction of argon gas at a flow 6〇SCCm; chamber pressure adjusted to 30 Pa, RF power is turned on, to set the RF power 50W;

[0110] 5)通入氧气,流量为45sccm ;待压强稳定后,通入硅烷和磷烧,总流量为7sccm ; [0110] 5) through the oxygen gas flow rate of 45 sccm; After the pressure became stable, the silane and phosphorus into burning, 7 sccm total flow rate;

[0111] 6)控制生长时间45分钟,制备磷掺杂二氧化硅无机质子导电膜; [0111] 6) controlling the growth time of 45 minutes to prepare a phosphorus-doped silicon dioxide inorganic proton conducting membrane;

[0112] 7)为防止过量硅源与氧源自发反应生成二氧化硅粉末,造成污染,反应结束后,首先停止通入硅烷和憐烧混合气体,等待硅烷和憐烧混合气体质量流量显不为0时,等待2分钟,停止通入氧源; [0112] 7) to prevent excess fat from the silicon source and oxygen react to form silica powder, pollution, after the completion of the reaction, first of all stopping the flow of a mixed gas of silane and Rei burn, wait, and Rei burning a mixed gas of silane mass flow significantly is not zero, wait 2 minutes, stopping the flow of oxygen source;

[0113] 8)氧气被抽完之后关闭射频;停止通入氩气保护气体; [0113] 8) Close radio oxygen after being smoked; stopping the flow of argon protective gas;

[0114] 9)全部打开分子泵与腔室之间的插板阀,将腔室真空抽至实验前本底真空以下; [0114] 9) all the flapper valve is opened between the molecular pump chamber, the vacuum chamber is evacuated to a vacuum prior to the experiment the background;

[0115] 10)关闭分子泵与腔室之间的插板阀,通入高纯氮气,开启腔室,取出样品,并保存;或应用于以塑料为基体的柔性微纳元器件中,如:柔性薄膜晶体管、柔性传感器等。 [0115] 10) between the closed flapper valve molecular pump chamber, into high purity nitrogen, the opening chamber, samples were removed and stored; or applied to a flexible plastic components for the micro-nano matrix, as : a flexible thin film transistor, the flexible sensor.

[0116] 实施例3 :等离子体化学气相沉积法在纸衬底上制备导电膜 [0116] Example 3: a plasma chemical vapor deposition a conductive membrane on a paper substrate

[0117] 1)以纸作为衬底,用氮气枪吹去表面附着的颗粒。 [0117] 1) In a paper as a substrate, adhered to the surface of the particles blown off with a nitrogen gun.

[0118] 2)同时开启等离子体化学气相沉积设备,将腔室打开,为避免腔室对衬底以及生长的质子导电膜污染,首先用吸尘器抽出腔室内可能存在的细微颗粒,再分别依次经过丙酮、酒精反复擦拭腔室周围,最后立即将清洗好的衬底放入反应腔室; [0118] 2) while turning plasma chemical vapor deposition apparatus, the chamber is opened, the chamber in order to avoid substrate contamination and growth of proton conducting membrane, first with a vacuum chamber out of fine particles that may be present, and then sequentially, through acetone, alcohol repeatedly wipe around the chamber, and finally immediately cleaned substrate into a reaction chamber;

[0119] 3)依次开启机械泵依次开启机械泵将反应腔室本低真空抽至IPa左右。 [0119] 3) sequentially turned on sequentially turned mechanical pump mechanical pump of the present low vacuum reaction chamber is evacuated to about IPa.

[0120] 4)通入氩气,流量为2〇SCCm,调节腔室压强至35Pa ;开启射频电源,设定射频功率50W; [0120] 4) purged with argon, 2〇SCCm flow, chamber pressure adjusted to 35Pa; RF power is turned on, to set the RF power 50W;

[0121] 5)通入氮气携带去离子水,流量为40sccm ;待压强稳定后,通入三氯氢娃和三氯氧磷,总流量为5sCCm;最后重新调整反应压强为35Pa; [0121] 5) into a nitrogen gas carrying deionized water a flow rate of 40 sccm; After the pressure became stable, the baby into trichlorosilane and phosphorus oxychloride, the total flow rate of 5 sccm; and finally re-adjusting the reaction pressure of 35Pa;

[0122] 6)控制生长时间60分钟,制备磷掺杂二氧化硅无机质子导电膜; [0122] 6) controlling the growth time of 60 minutes to prepare a phosphorus doped silicon dioxide inorganic proton conducting membrane;

[0123]7)反应结束后,首先停止通入三氯氢硅和三氯氧磷混合气体,等待三氯氢硅和三氯氧磷混合气体质量流量显示为〇时,等待2分钟,停止通入氮气携带去离子水; After the [0123] 7) The reaction, stop silicon and phosphorus oxychloride hydrogen mixed gas into trichloroethyl, waiting trichlorosilane and phosphorus oxychloride mixed gas mass flow rate is displayed as square, wait 2 minutes, was stopped nitrogen carrying deionized water;

[0124] 8)通入氮气携带去离子水被抽完之后关闭射频;停止通入氩气保护气体; [0124] 8) nitrogen gas carrying off RF deionized water after being smoked; stopping the flow of argon protective gas;

[0125]9)全部打开分子泵与腔室之间的插板阀,将腔室真空抽至实验前本底真空以下; [0125] 9) all the flapper valve is opened between the molecular pump chamber, the vacuum chamber is evacuated to a vacuum prior to the experiment the background;

[0126] 10)关闭分子泵与腔室之间的插板阀,通入高纯氮气,开启腔室,取出样品,并保存,或应用于以纸为基体的柔性微纳元器件中,如:柔性薄膜晶体管。 [0126] 10) between the closed flapper valve molecular pump chamber, into high purity nitrogen, the opening chamber, samples were removed and stored, or applied to a flexible micro-nano Component paper as substrate, as : a flexible thin film transistor.

[0127] 实施例4 :大气压化学气相沉积法在玻璃衬底上制备导电膜 [0127] Example 4: Atmospheric pressure chemical vapor deposition of conductive films were prepared on glass substrates

[0128] 1)对玻璃衬底进行严格清洗。 [0128] 1) the glass substrates stringency wash. 依次将玻璃衬底浸入酒精、去离子水超声清洗10分钟;再用去离子水反复冲洗;最后用氮气枪吹干。 Sequentially immersing the glass substrate alcohol, ultrasonic cleaning in deionized water, 10 minutes; rinse with deionized water repeatedly; and finally blown dry with a nitrogen gun.

[0129] 2)同时开启大气压化学气相沉积设备,将腔室打开,为避免腔室对衬底以及生长的质子导电膜污染,首先用吸尘器抽出腔室内可能存在的细微颗粒,再分别依次经过丙酮、 酒精反复擦拭腔室周围,最后立即将清洗好的衬底放入反应腔室; [0129] 2) while turning atmospheric pressure chemical vapor deposition apparatus, the chamber is opened, the chamber in order to avoid substrate contamination and growth of proton conducting membrane, first with a vacuum chamber out of fine particles that may be present, and then successively through each of acetone , alcohol repeatedly wipe around the chamber, and finally immediately cleaned substrate into a reaction chamber;

[0130] 3)依次开启机械泵、分依次开启机械泵将反应腔室本低真空抽至IPa左右,设定衬底温度为300°C,并对衬底预热5分钟。 [0130] 3) sequentially turned mechanical pump, a mechanical pump will be divided sequentially turned present low vacuum reaction chamber evacuated to about IPa, the substrate temperature was set to 300 ° C, and the substrate is preheated for 5 minutes.

[0131] 4)通入氩气,流量为6〇SCCm ;在常压下,开启射频电源,设定射频功率300W ; [0131] 4) introduction of argon gas at a flow 6〇SCCm; under atmospheric pressure, RF power is turned on, to set the RF power 300W;

[0132] 5)通入氧气,流量为lOOsccm ;等待压强稳定后,通入硅烷和磷烧,总流量为15sccm; [0132] 5) feeding oxygen flow lOOsccm; waiting pressure became stable, the silane and phosphorus burn through, the total flow of 15 sccm;

[0133] 6)控制生长时间30分钟,制备可用于透明氧化物薄膜晶体管的磷掺杂二氧化硅无机质子导电膜; [0133] 6) controlling the growth time of 30 minutes to prepare a transparent oxide thin film can be used for a phosphorus doped silicon dioxide transistor inorganic proton conducting membrane;

[0134] 7)为防止过量硅烷与氧气自发反应生成二氧化硅粉末,造成污染,反应结束后,首先停止通入磷烧和硅烷混合气体,待磷烧和硅烷混合气体质量流量显示为0时,等待2分钟,停止通入氧气; [0134] 7) to prevent excess spontaneous reaction of silane with oxygen to form a silica powder, pollution, after the completion of the reaction, first stop burning phosphorus and silane gas mixture into, and to be burned phosphorus mixed gas of silane mass flow rate is displayed as 0 , wait 2 minutes, stopping the flow of oxygen;

[0135] 8)氧气被抽完之后关闭射频;停止通入氩气保护气体; [0135] 8) Close radio oxygen after being smoked; stopping the flow of argon protective gas;

[0136] 9)全部打开分子泵与腔室之间的插板阀,将腔室真空抽至实验前本底真空以下; [0136] 9) all the flapper valve is opened between the molecular pump chamber, the vacuum chamber is evacuated to a vacuum prior to the experiment the background;

[0137] 10)关闭分子泵与腔室之间的插板阀,通入高纯氮气,开启腔室,取出样品,并保存。 [0137] 10) between the closed flapper valve molecular pump chamber, into high purity nitrogen, the opening chamber, samples were removed and stored.

[0138] 实施例5 :等离子体化学气相沉积法在陶瓷衬底上制备导电膜 [0138] Example 5: a plasma chemical vapor deposition a conductive film on a ceramic substrate was prepared

[0139] 1)对陶瓷衬底进行严格清洗。 [0139] 1) of the ceramic substrate rigorous cleaning. 依次将陶瓷衬底浸入去离子水超声清洗10分钟; 再用去离子水反复冲洗;最后用氮气枪吹干。 The ceramic substrate is immersed successively in deionized water, ultrasonic cleaning 10 minutes; rinse with deionized water repeatedly; and finally blown dry with a nitrogen gun.

[0140] 2)同时开启等离子体化学气相沉积设备,将腔室打开,为避免腔室对衬底以及生长的质子导电膜污染,首先用吸尘器抽出腔室内可能存在的细微颗粒,再分别依次经过丙酮、酒精反复擦拭腔室周围,最后立即将清洗好的衬底放入反应腔室; [0140] 2) while turning plasma chemical vapor deposition apparatus, the chamber is opened, the chamber in order to avoid substrate contamination and growth of proton conducting membrane, first with a vacuum chamber out of fine particles that may be present, and then sequentially, through acetone, alcohol repeatedly wipe around the chamber, and finally immediately cleaned substrate into a reaction chamber;

[0141] 3)依次开启机械泵、依次开启机械泵将反应腔室本低真空抽至IPa左右,设定衬底温度为100 °C,并对衬底预热5分钟。 [0141] 3) sequentially turned mechanical pump, a mechanical pump sequentially turned present low vacuum reaction chamber evacuated to about IPa, the substrate temperature was set to 100 ° C, and the substrate is preheated for 5 minutes.

[0142] 4)通入氩气,流量为6〇SCCm,调节腔室压强至200Pa;开启射频电源,设定射频功率300W; [0142] 4) purged with argon, 6〇SCCm flow, chamber pressure adjusted to 200Pa; RF power is turned on, to set the RF power 300W;

[0143]5)通入氧气,流量为lOOsccm;等待压强稳定后,通入硅烷和磷烧,总流量为15sccm;最后重新调整反应压强为200Pa; [0143] 5) feeding oxygen flow lOOsccm; waiting pressure became stable, the silane and phosphorus burn through, the total flow of 15 sccm; and finally re-adjusting the reaction pressure of 200Pa;

[0144] 6)控制生长时间20分钟,制备可用于电解质膜燃料电池的磷掺杂二氧化硅无机质子导电膜; [0144] 6) controlling the growth time of 20 minutes, it can be used for the preparation of the electrolyte membrane fuel cell phosphorus-doped silicon dioxide inorganic proton conducting membrane;

[0145] 7)为防止过量硅烷与氧气自发反应生成二氧化硅粉末,造成污染,反应结束后,首先停止通入磷烧和硅烷混合气体,待磷烧和硅烷混合气体质量流量显示为0时,等待2分钟,停止通入氧气; [0145] 7) to prevent excess spontaneous reaction of silane with oxygen to form a silica powder, pollution, after the completion of the reaction, first stop burning phosphorus and silane gas mixture into, and to be burned phosphorus mixed gas of silane mass flow rate is displayed as 0 , wait 2 minutes, stopping the flow of oxygen;

[0146]8)氧气被抽完之后关闭射频;停止通入氩气保护气体; [0146] 8) Close radio oxygen after being smoked; stopping the flow of argon protective gas;

[0147] 9)全部打开分子泵与腔室之间的插板阀,将腔室真空抽至实验前本底真空以下; [0147] 9) all the flapper valve is opened between the molecular pump chamber, the vacuum chamber is evacuated to a vacuum prior to the experiment the background;

[0148] 10)关闭分子泵与腔室之间的插板阀,通入高纯氮气,开启腔室,取出样品,并保存。 [0148] 10) between the closed flapper valve molecular pump chamber, into high purity nitrogen, the opening chamber, samples were removed and stored.

[0149] 实施例2-5的测试结果如下:以上实例中计算得到质子电导率为1(T2S/Cm~ 10 4S/cm〇 [0149] Example 2-5 The test results are as follows: The above examples proton conductivity was calculated 1 (T2S / Cm ~ 10 4S / cm〇

[0150] 实施例6导电膜阻抗分析 Impedance Analysis conductive film of Example 6 [0150] Embodiment

[0151]其中实施例1的测试结果如图3所示,由图3可以看出,磷掺杂质子导电膜的组成有一个半圆弧和一线直线组成,根据阻抗分析理论,其阻抗值取圆弧和直线在虚部为〇时的交点,87. 3 Q,根据公式 [0151] wherein the test results of Example 1 is shown in embodiment 3, it can be seen from Figure 3, the phosphorus-doped proton conducting membrane composed of a semi-circular line and straight lines, the impedance analysis theory, the resistance value takes at the intersection of the arc and a straight imaginary part of the square, 87. 3 Q, according to the formula

Figure CN102943247BD00101

计算薄膜的质子电导率为KT4S/cm,式中:1为薄膜厚度;R 为薄膜的质子阻抗,A为薄膜面积。 The proton conductivity of the film is calculated KT4S / cm, wherein: a film thickness is 1; R & lt impedance of a thin film of a proton, A is membrane area.

[0152] 实施例7无机质子导电膜制品的制备 Example 7 Preparation of an inorganic proton conductive membrane preparation [0152] Embodiment

[0153] 1、在上述制备质子导电膜的基础上,采用ITO玻璃为基体制备质子导电膜作为晶体管的栅层。 [0153] 1, on the basis of the above-mentioned proton conducting membrane was prepared on the ITO glass preparation using a proton conductive film as the base layer of a transistor gate.

[0154] 2、采用自组装绕射技术,一次完成晶体管的沟道、源极和漏极的生长。 [0154] 2, diffraction technique using self-assembly, a complete channel transistor, the source and drain of growth.

[0155] 3、采用ALD技术,制备A1203作为晶体管的钝化层。 [0155] 3, the ALD technology, be prepared as a passivation layer of the transistor A1203.

[0156] 在本发明提及的所有文献都在本申请中引用作为参考,就如同每一篇文献被单独引用作为参考那样。 [0156] The present application are incorporated in all documents mentioned herein incorporated by reference, as if each reference were individually incorporated by reference above. 此外应理解,在阅读了本发明的上述讲授内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。 Furthermore, it should be understood that, after reading the above teachings of the present invention, those skilled in the art that various changes or modifications may be made to the present invention, and these equivalents also fall within the present application as defined in the appended claims scope.

Claims (11)

1. 一种无机质子导电膜的制备方法,其特征在于,包括步骤: 将反应源通入反应腔室,并进行化学气相沉积,从而形成具有介孔结构的磷掺杂二氧化硅无机质子导电膜,其中,所述的反应源包括硅源、磷源和氧源; 且所述的氧源选自下组:氮气或氩气携带去离子水和/或氧气,且所述去离子水为气态; 并且在三种反应源中先通入氧源,再通入硅源和磷源,其中,硅源和磷源同时通入。 A method for producing an inorganic proton conducting membrane, characterized by comprising the steps of: a reaction source into the reaction chamber, and chemical vapor deposition, thereby forming a via hole structure is phosphorus doped silicon dioxide inorganic proton conducting film, wherein the reactive source comprises a silicon source, a phosphorus source and an oxygen source; and an oxygen source selected from the group according to: nitrogen or argon carrying deionized water and / or oxygen, and the deionized water gas; oxygen source and into the first three reactions in the source, and then passed through a phosphorus source and a silicon source, wherein the silicon and phosphorus sources simultaneously fed.
2. 如权利要求1所述的方法,其特征在于,所述的化学气相沉积选自下组:等离子体化学气相沉积、大气压化学气相沉积。 2. The method according to claim 1, wherein said chemical vapor deposition is selected from the group consisting of: plasma chemical vapor deposition, atmospheric pressure chemical vapor deposition.
3. 如权利要求1所述的方法,其特征在于,所述硅源、磷源和氧源的比例满足以下关系:磷源:娃源=1 :1〇〇~20 :100 ;娃源:氧源=1 :1~1 :6。 3. The method according to claim 1, wherein the ratio of the silicon source, a phosphorus source and an oxygen source satisfy the following relationship: phosphorus source: Wa = 1 Source: 1〇〇 to 20: 100; baby source: oxygen source = 1: 1 to 1: 6.
4. 如权利要求1所述的方法,其特征在于,所述方法还具有一个或多个以下特征: 所述的硅源选自下组:三氯氢硅、四氯化硅、硅烷,或其组合; 所述的磷源选自下组:三氯氧磷和/或磷烷。 4. The method according to claim 1, wherein said method further comprises one or more of the following features: said silicon source is selected from the group consisting of: trichlorosilane, silicon tetrachloride, silane, or combinations thereof; said phosphorus source is selected from the group consisting of: phosphorus oxychloride and / or phosphine.
5. 如权利要求4所述的方法,其特征在于,所述方法还具有一个或多个以下特征: 所述的硅源为甲硅烷或乙硅烷;和/或所述的磷源为PH3。 5. The method according to claim 4, characterized in that the method further comprises one or more of the following features: the source of silicon is monosilane or disilane; and / or the source of phosphorus is PH3.
6. 如权利要求1所述的方法,其特征在于,所述化学气相沉积是沉积于衬底表面,从而形成沉积于衬底上的无机质子导电膜。 6. The method according to claim 1, wherein said chemical vapor deposition is deposited on the substrate surface, thereby forming an inorganic proton conducting membrane deposited on the substrate.
7. 如权利要求6所述的方法,其特征在于,所述衬底选自下组:玻璃衬底、塑料衬底、纸衬底、陶瓷衬底、或其组合。 7. The method according to claim 6, wherein said substrate is selected from the group: a glass substrate, a plastic substrate, a paper substrate, a ceramic substrate, or a combination thereof.
8. -种无机质子导电膜,其特征在于,所述的无机质子导电膜是通过化学气相沉积形成的; 其中,所述的化学气相沉积中,所用的氧源选自下组:氮气或氩气携带去离子水和/或氧气,且所述去离子水为气态; 并且在三种反应源中先通入氧源,再通入硅源和磷源,其中,硅源和磷源同时通入。 8. - inorganic proton conducting membrane, wherein said inorganic proton conducting membrane is formed by chemical vapor deposition; wherein, the chemical vapor deposition, the oxygen source used is selected from the group consisting of: nitrogen or argon deionized water carrying gas and / or oxygen, and the gaseous deionized water; and a source of oxygen into the first three reactions in the source, and then passed through a phosphorus source and a silicon source, wherein the silicon and phosphorus sources while passing into.
9. 一种无机质子导电膜,其特征在于,所述的无机质子导电膜是用如权利要求1所述的方法制备的,且所述的无机质子导电膜是磷掺杂的介孔SiO 2薄膜,并且所述无机质子导电膜具有以下导电特性:在环境湿度为80%和25°C时,其质子电导率为1X1(T 2S/Cm~ 10、/〇11,且在环境湿度为85%~100%和501:~801:时,质子电导率为1\10-25/〇11~ IX l(T4S/cm〇 An inorganic proton conducting membrane, wherein said inorganic proton conducting membrane was prepared by the method according to claim 1, and the proton conducting membrane is inorganic phosphorous doped mesoporous SiO 2 film, and the inorganic proton conducting membrane has a conductive property: when the ambient humidity of 80% and 25 ° C, proton conductivity is 1X1 (T 2S / Cm ~ 10, / 〇11 and ambient humidity of 85 100% and 501% ~: ~ 801: when a proton conductivity of 1 \ 10-25 / 〇11 ~ IX l (T4S / cm〇
10. 如权利要求8所述的无机质子导电膜,其特征在于,所述的无机质子导电膜是用如权利要求1所述的制备方法制备的。 10. The inorganic proton conducting membrane according to claim 8, wherein said inorganic proton conducting membrane was prepared according to the method as claimed in claim 1 is prepared.
11. 一种制品,其特征在于,所述制品含有如权利要求8或9所述的无机质子导电膜,或所述制品由权利要求8或9所述的无机质子导电膜制成。 11. An article, wherein the article contains an inorganic proton conducting membrane of claim 8 or claim 9, or the article inorganic proton conducting membrane of claim 8 or 9 is made by the claims.
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