WO2011160532A1 - 一维纳米材料植入金属电极表面的方法 - Google Patents

一维纳米材料植入金属电极表面的方法 Download PDF

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WO2011160532A1
WO2011160532A1 PCT/CN2011/074838 CN2011074838W WO2011160532A1 WO 2011160532 A1 WO2011160532 A1 WO 2011160532A1 CN 2011074838 W CN2011074838 W CN 2011074838W WO 2011160532 A1 WO2011160532 A1 WO 2011160532A1
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nano material
dimensional nano
implanting
metal
metal electrode
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PCT/CN2011/074838
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French (fr)
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丁桂甫
王艳
汪红
崔雪梅
邓敏
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上海交通大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/304—Field-emissive cathodes
    • H01J1/3042—Field-emissive cathodes microengineered, e.g. Spindt-type
    • H01J1/3044—Point emitters

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  • the invention relates to a method in the field of nano material technology, in particular to a method for implanting a one-dimensional nano material into a surface of a metal electrode.
  • One-dimensional nanomaterials include nanowires, nanorods, nanobelts, nanotubes, nanofibers and other structural forms. They are characterized by a large aspect ratio and many types of materials. They are the most characteristic and most concerned among nanomaterials. One of the varieties. Because it not only has the nano-effect properties of conventional nanomaterials, but also has a series of unique mechanical, electrical, optical, chemical and biological properties, it has a wide range of application potential, especially when it is assembled with conductors. After the formation of the electrode structure together, its use is extremely extensive, and related basic research in the early 21st century was listed as a major scientific breakthrough (RFService) by Science magazine.
  • RFService scientific breakthrough
  • One-dimensional nanomaterials come in many different types and different properties. There are many methods for researchers to implant one-dimensional nanomaterials on metal electrode surfaces. Just as carbon nanotubes are the prominent representative of one-dimensional nanomaterials, research on the handling and arrangement of carbon nanotubes is also the most important, but not all technologies based on carbon nanotube development can be applied to all one-dimensional Nanomaterials, after sorting out the literatures to date, believe that there are several typical processes for manipulating one-dimensional nanomaterials:
  • Direct growth method One-dimensional nanomaterials are directly grown on the surface of the electrode, and most of them can be patterned by pre-micromachining of the substrate.
  • the process has high requirements on the base material and is suitable when the growth process temperature is low, and the combined strength and electrical contact effect of the one-dimensional nano material and the substrate are not always ensured, and the scale manufacturing cost is high.
  • Screen printing method Dispersing a one-dimensional nano material in a specific slurry, printing it on an electrode by screen printing, then removing the solvent and sintering to remove the binder to make it and the slurry
  • the metal powder in the metal is attached to the surface of the electrode.
  • the one-dimensional nano material of the process is prepared separately, has high efficiency and few limiting factors, and is suitable for large-scale manufacturing, but the combination state of the one-dimensional nano material and the powder sintered layer is random, and the electrical contact condition is particularly dispersed, and is only suitable for partial non- The material affected by the sintering process.
  • a polymer-based one-dimensional nano material composite material was prepared and attached to the surface of a metal electrode to serve as an electrode.
  • the process is simple and easy to use, and most of the one-dimensional nanomaterials are used, but the one-dimensional nanomaterial is easily coated with the polymer, the state is not ideal, and the polymer matrix cannot be applied in many cases.
  • the metal-based one-dimensional nano-material composite film is prepared by electrodeposition, and the micro-machining process is used to partially expose the one-dimensional nano material to the metal matrix to form a one-dimensional nano material on the surface of the metal substrate, which is a one-dimensional nano material.
  • the process of reliable electrical contact and mechanical bonding with the metal substrate is also suitable for large-scale manufacturing, but it is necessary to develop a special composite plating process to achieve uniform compounding of the one-dimensional nano material and the metal material, which is quite difficult, and one of the composite materials
  • the content of vitamin nano materials is usually low and the application is limited.
  • the method of high temperature sintering, mechanical shearing and blowing has improved the surface morphology and field emission performance of the cathode to some extent.
  • this method is difficult to precisely control the size and thickness of the structure, the surface morphology is poor, and the high temperature sintering is easy to damage the substrate.
  • the mechanical shearing and blowing post-treatment processes can achieve certain improvement effects, there is a lack of reliable and reproducible and reliable work. Mechanism, it is difficult to guarantee the uniformity, consistency and reliability of batch processing.
  • the present invention provides a method for implanting a one-dimensional nano material into a surface of a metal electrode according to the above-mentioned deficiencies of the prior art, and based on a polymer-based one-dimensional nano material composite material, through the flexible use of a non-silicon surface micro-machining process, Realize the effect of one-dimensional nanomaterials reliably implanted into the metal matrix.
  • the invention is achieved by the following technical solutions, firstly forming a composite film into a composite film, and then planarizing the surface, and then selectively controlling the surface layer of the etched composite film to partially expose the one-dimensional nano material, and then through surface metallization and thickening The process exposes the exposed one-dimensional nano material into the metal film, and finally selectively etches away the remaining part of the composite film, leaving the one-dimensional nano material with the implanted metal fixed, and realizes the reliable implantation of the one-dimensional nano material into the metal substrate. Effect.
  • the composite film is prepared by the following method:
  • the liquid polymer refers to a polymer or polymer solution in a liquid state.
  • the thorough mixing means that the liquid polymer is sufficiently uniformly mixed with the one-dimensional nano material by one of a manual agitation, an ultrasonic vibration mixing or a ball milling or a combination thereof.
  • the manual stirring refers to: manually mixing the liquid polymer as a dispersion medium and the one-dimensional nano material in a container, and manually grinding the mixture to improve the mixing uniformity;
  • the ultrasonic vibration mixing means The mixture is placed in an ultrasonic generator to enhance the wetting ability of the liquid polymer dispersion medium to the one-dimensional nano material by ultrasonic vibration;
  • the ball milling means ball milling the mixture by a ball mill to make it fully mixed and make one-dimensional nanometer The material is well dispersed. This process also has the effect of shearing one-dimensional nanomaterials.
  • the substrate is a substrate of silicon wafer, glass, metal or ceramic texture.
  • the drying refers to a process of drying and solidifying a liquid polymer as a medium, and the drying temperature is from 50 ° C to 300 ° C.
  • the surface planarization means that the surface of the composite material film is flattened by a precision surface processing method.
  • the precision surface processing method includes cutting, grinding and polishing with a thickness or depth of 2 ⁇ m or less.
  • the selective control etching means that the etching liquid used only reacts to the polymer medium and has no influence on the one-dimensional nano material.
  • the surface of the etched composite film refers to: etching the surface layer portion of the polymer medium with a polymer etching solution, and the etching depth is controlled by the etching time, and the etching time is 5 to 600 seconds.
  • the surface metallization refers to depositing a metal bonding layer and a seed layer on the surface of the composite film to realize reliable metallization of the surface of the one-dimensional nano material.
  • the bonding layer is prepared by dry deposition or wet deposition, wherein:
  • the dry deposition bonding layer is completed by sputtering, evaporation or other vacuum coating process
  • the wet deposition bonding layer is completed by electroplating, electroless plating or the like.
  • the seed layer is on the bonding layer as a starting layer for the subsequent electroplating and electroless plating thickening process.
  • the material is any metal or alloy used for electroplating or electroless plating, using a dry deposition process and electroplating. Or chemical wet deposition process.
  • the thickening process refers to: further thickening the metal layer on the basis of the seed layer by electrodeposition, electroless plating, evaporation, sputtering or CVD to form a metal substrate, and then selectively etching with an etching solution
  • the polymer dispersion medium in the remaining composite material realizes the implantation of the one-dimensional nano material on the surface of the metal electrode.
  • the electrodeposition method can adopt a conventional process, and the typical parameters are as follows: current density 2-3A/dm 2 , pH value 4-5, temperature 30-50 ° C, plating time 120-400 min, plating solution composition: Ni (NH) 2 SO 3 ) 2 350-450 g/L, H 3 BO 3 13-16 g/L, NiCl 2 8-12 g/L, PA5000 1.5-2.5 g/L.
  • the present invention Compared with the existing one-dimensional nanomaterial electrode preparation techniques such as vapor phase chemical deposition, screen printing, micro-operation welding and physical chemical manipulation arrangement, the present invention has the following advantages:
  • the planting process of the invention only utilizes the essential characteristics of the one-dimensional nano material shape, the slender shape and the large aspect ratio, and the one-dimensional nano material is controlled to be exposed and implanted to the metal surface to some extent through film formation and controlled etching. It is not affected by the material properties of one-dimensional nanomaterials, so it can be applied to one-dimensional nanomaterials composed of various materials, and has wide applicability, which is difficult to achieve by various process technologies;
  • the planting process of the invention can not only effectively disperse the one-dimensional nano material by selecting the polymer dispersing agent matched with the one-dimensional nano material, but also can make the composite material have a good film forming ability, so that it can be in a uniform film form. Integration into the micromachining technology system to have the potential to be integrated and integrated with existing micromachining technology systems;
  • the whole process of the planting process of the invention has a low process temperature, and the maximum temperature is generally lower than 120 ° C, so that it has the potential to be compatible with more material types and process types for integrated manufacturing;
  • the invention can ensure that the one-dimensional nano material is reliably protected in the controlled etching process of the dispersant, and the exposed one-dimensional nano material has no influence on the functional characteristics, and can be realized. Highly clean;
  • the planting process of the invention realizes the reliable combination of the one-dimensional nano material and the metal layer by depositing a high-strength metal bonding layer on the clean surface of the exposed one-dimensional nano material, which has firm mechanical strength and can guarantee Reliable electrical contact;
  • the invention adjusts the content of the one-dimensional nano material in the polymer dispersion medium by adjusting the ratio of the polymer to the one-dimensional nano material, thereby indirectly regulating the planting density of the one-dimensional nano material on the electrode surface, and the adjustable range is large;
  • polymer materials as dispersion media are not the only choice, as long as they can satisfy the basic conditions of adequate mixing, effective film formation, easy flattening and alternative etchants, other inorganic materials can also be dispersed.
  • Use of media such as water glass.
  • the technology has low temperature technology, compatibility with various materials, compatibility with existing micromachining process systems, wide application to various 1D nano materials, strong and reliable combination with metal electrodes, and wide adjustment of planting density and other technical advantages. It has a wide range of applications and can be applied to devices with such a structure as a core functional unit, such as field emission devices, gas ionization sensors, electrochemical sensors, and the like.
  • Figure 1 is a schematic view of the present invention.
  • the preparation process of the nickel/carbon nanotube electrode is as follows:
  • the cured composite film is planarized by a surface polishing method using a smooth polishing. First, the cured composite film is smoothed with a sandpaper, and then polished by a polishing machine. After polishing, the average surface roughness of the film is about 200 nm.
  • the photoresist medium is selectively etched with a 0.5% by mass sodium hydroxide solution to expose the carbon nanotubes to the surface of the composite film. After etching, it is neutralized with dilute hydrochloric acid, washed with deionized water and dried.
  • a Cr (30 nm) bonding layer and a Cu (50 nm) seed layer are sputter deposited on the surface-etched composite film to achieve reliable metallization of the carbon nanotube surface.
  • Ni metal layer 50 ⁇ m was further electroplated to form a metal substrate.
  • the glass substrate is removed, and the remaining photoresist medium is removed with acetone to obtain a carbon nanotube metal electrode in which the carbon nanotube portion is exposed and partially rooted in the metal matrix.
  • the density of carbon nanotubes on the surface of the electrode prepared by field emission electron microscopy is about 5 / ⁇ m 2
  • Example 2 Preparation of a copper-based field emission electrode with a weight ratio of carbon nanofibers and polyimide of 1:10
  • the preparation process of the copper/carbon nanofiber electrode is as follows:
  • the above mixture of the ball-milled carbon nanofibers and the polyimide is spin-coated on a clean glass substrate and dried to form a composite film.
  • the polyimide curing parameters are as follows:
  • the cured composite film is planarized by a surface polishing method using a smooth polishing. First, the cured composite film is smoothed with a sandpaper, and then polished by a polishing machine. After polishing, the average surface roughness of the film is about 200 nm.
  • the polyimide medium was selectively etched with a mixture of Na 2 HPO 4 and NaOH having a pH of 11.4 to partially expose the carbon nanofibers to the surface of the composite film. After etching, it is neutralized with dilute hydrochloric acid, washed with deionized water and dried.
  • a Cu metal layer (50 ⁇ m) was further electroplated to form a metal substrate.
  • the density of the electrode carbon nanofibers prepared by field emission electron microscopy is about 10 / ⁇ m 2
  • the pure ZnO nanorods were mixed with polyimide at a mass of 1:3, mixed, and placed in a ball mill for 6 hours at 400 rpm.
  • the cured composite film is planarized by a surface polishing method using a smooth polishing. First, the cured composite film is smoothed with a sandpaper, and then polished by a polishing machine. After polishing, the average surface roughness of the film is about 200 nm.
  • the polyimide medium was selectively etched with a mixture of Na 2 HPO 4 and NaOH having a pH of 11.4 to expose portions of the ZnO nanorods outside the interface of the composite film. After etching, it is neutralized with dilute hydrochloric acid, washed with deionized water and dried.
  • an Ag metal layer (50 ⁇ m) was further electroplated to form a metal substrate.
  • the density of the prepared ZnO nanorods was about 7/ ⁇ m 2 as observed by field emission electron microscopy.

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Description

一维纳米材料植入金属电极表面的方法 技术领域
本发明涉及的是一种纳米材料技术领域的方法，具体是一种一维纳米材料植入金属电极表面的方法。
背景技术
一维纳米材料包括纳米线、纳米棒、纳米带、纳米管、纳米纤维等多种结构形式，以长径比大为典型特征，材料种类多，是纳米材料中最富特色和最受关注的品种之一。由于其不仅具有通常纳米材料所具有的纳米效应性质，而且还具有一系列独特的机械、电子、光学、化学和生物相关特性，使其具有广泛的应用潜力，特别是当将其与导体组装在一起形成电极架构之后，其用途极为广泛，二十一世纪初相关基础研究曾被《Science》杂志列为当年的重大科学突破（R.F.Service, Assembling Nanocircutes from the Bottom Up, Science, 2001, 293:782），如今一维纳米材料规模化应用研究已经成为纳米材料研究最活跃的领域之一。但是，如何规模化操控一维纳米材料并使之与导体材料（特别是金属）有效地结合而构成稳定的电极，一直是困扰其商业化的关键工艺难题。
一维纳米材料种类众多，性质各异，对一维纳米材料如何植入金属电极表面，研究者尝试的方法众多。正像纳米碳管是一维纳米材料的突出代表一样，关于纳米碳管的操控与排布技术的研究同样最受重视，但是并非所有基于纳米碳管开发的技术都能够推广应用于所有一维纳米材料，经过对迄今为止的文献资料归纳整理，认为目前存在以下几种操控一维纳米材料的典型工艺：
(1)直接生长法：在电极表面直接生长一维纳米材料，多数可通过基体预先微加工实现图形化生长。该工艺对基体材料的要求高，生长工艺温度较低时适用，并不总能够保证一维纳米材料与基体的结合强度和电接触效果，规模化制造成本较高。
(2)丝网印刷法：将一维纳米材料分散在特定的浆料中，用丝网印刷的方法将其印制在电极上，然后去除溶剂并烧结清除粘合剂，使之与浆料中的金属粉末一起附着在电极表面。 该工艺一维纳米材料单独制备，效率高，限制因素少，适于规模化制造，但是一维纳米材料与粉末烧结层的结合状况随机性强，电接触状况尤其分散，仅适用于部分不受烧结工艺影响的材料。
(3) 自组装法：对一维纳米材料进行表面改性，然后通过一定的物理、化学机制自组装至电极表面。该工艺需要针对具体的材料开发自组装技术，特异性强，不具有通用性，不能够确保一维纳米材料与基体的结合强度，电接触特性更难保证。
(4)聚合物基复合材料法：制备聚合物基一维纳米材料复合材料，附着于金属电极表面，用作电极。该工艺简单易行，多数一维纳米材料都运用，但是一维纳米材料容易被聚合物包覆，状态不够理想，聚合物基体在很多情况下不能够应用。
(5)复合电镀法。通过电沉积制备金属基一维纳米材料复合薄膜，采用微加工工艺使一维纳米材料部分露出金属基体，形成一维纳米材料在金属基体表面植布的效果，是一种能够确保一维纳米材料与金属基体可靠电接触和机械结合的工艺路线，也适合规模化制造，但是需要开发专门的复合电镀工艺以实现一维纳米材料与金属材料的均匀复合，其难度颇高，且复合材料中一维纳米材料的含量通常较低，应用受到一定局限。
Xiu-Xia Zhang等人在 《 Microelectronics Journal》Volume 40， Issue 8， August 2009， 1166-1169上发表的“Electron translocation and field emission in printed CNT film by high-temperature sintering and post-treatment”（通过高温烧结和后处理的印刷碳纳米管膜的电子移动和场发射性能），该文章指出目前场发射阴极碳管薄膜存在的主要问题是发射尖端分布不均匀，碳管被埋在介质材料中，无法形成发射端高度一致，分散均匀，扎根牢固的阴极。文章中通过高温烧结，机械剪切和吹气的方法，一定程度上改善了阴极表面形貌和场发射性能，但是此方法难以精确控制结构尺寸和厚度，表面形貌差，高温烧结容易破坏基底，虽然机械剪切和吹气的后处理工艺能够达到一定的改进效果，但缺乏获得稳定可重复改进的可靠工作机制，难以保证批量加工的均匀性、一致性和可靠性。
但仔细分析现有技术，发现还没有一种工艺既具有广泛适用性（针对各种一维纳米材料具有通用性），又能够确保一维纳米材料与电极基体良好结合（同时保证机械结合和电接触效果），同时具有发射尖端密度和长度的可控制性，以及适合规模化制造的工艺方法，因此，开发建立这样一种通用工艺，对于推动一维纳米材料应用具有关键作用。
 发明内容
本发明针对现有技术存在的上述不足，提供一种一维纳米材料植入金属电极表面的方法，以聚合物基一维纳米材料复合材料为基础，通过非硅表面微加工工艺的灵活运用，实现一维纳米材料可靠植入金属基体的效果。
本发明是通过以下技术方案实现的，首先使复合材料形成复合薄膜，再使之表面平整化，然后选择性控制刻蚀复合薄膜表层使一维纳米材料部分暴露，接着通过表面金属化和加厚工艺将暴露出的一维纳米材料植入金属膜中，最后选择性刻蚀掉复合薄膜剩余部分，留下已植入金属被固定的一维纳米材料，实现一维纳米材料可靠植入金属基体的效果。
所述的复合材料薄膜通过以下方式制备得到：
1）将一维纳米材料与液态聚合物充分混合，形成膏状混合物复合材料；
2）将膏状混合物复合材料涂覆在基片上烘干形成复合材料薄膜。
所述液态聚合物是指呈液体状态的聚合物或者聚合物溶液。
所述的充分混合是指：通过手工搅拌、超声振荡混合或球磨中的一种或其组合的方式将液态聚合物与一维纳米材料充分均匀混合。
所述的手工搅拌是指：将作为分散介质的液态聚合物与一维纳米材料在容器中按比例混合后人工搅拌，同时手工研磨以改进混合均匀性；所述的超声振荡混合是指：将混合物置于超声波发生器中通过超声振荡增强液态聚合物分散介质对一维纳米材料的浸润能力；所述的球磨是指：采用球磨机对混合物进行球磨，使之充分混合均匀，并且使一维纳米材料充分分散。该过程同时具有剪切一维纳米材料的作用。
所述的基片为硅片、玻璃、金属或陶瓷质地的基体。
所述的烘干是指：将作为介质的液态聚合物进行干燥固化的过程，烘干温度为50℃-300℃。
所述的表面平整化是指：采用精密表面加工方法使复合材料薄膜表面平整化。
所述的精密表面加工方法包括：切削、研磨和抛光，其厚度或深度小于等于2µm。
所述的选择性控制刻蚀是指：所用的刻蚀液仅对聚合物介质起反应，而对一维纳米材料无影响。
所述的刻蚀复合膜表层是指：用聚合物刻蚀液刻蚀聚合物介质表层部分，刻蚀深度由刻蚀时间来控制，刻蚀时间为5-600秒。
所述的表面金属化是指：在复合薄膜表面沉积金属粘结层和种子层，实现一维纳米材料表面可靠金属化.
所述的粘结层采用干法沉积或者湿法沉积制备得到，其中：
干法沉积粘结层采用溅射、蒸镀或者其它真空镀膜工艺完成；
湿法沉积粘结层采用电镀、化学镀等工艺完成。
所述的种子层是在粘结层之上，作为后续电镀、化学镀加厚工艺的起始层，材料是任何用作电镀、化学镀种子层的金属或者合金，采用干法沉积工艺、电镀或化学度湿法沉积工艺制备。
所述的加厚工艺是指：采用电沉积法、化学镀、蒸镀、溅射或CVD方法在种子层基础上，进一步加厚金属层，形成金属基体，再用刻蚀液选择性刻蚀剩余的复合材料中的聚合物分散介质，实现一维纳米材料植入金属电极表面。
所述的电沉积法可采用常规工艺，典型参数如下：电流密度2-3A/dm2，pH值4-5，温度30-50℃，电镀时间120-400min，镀液成份为：Ni(NH2SO3)2 350-450g/L、H3BO3 13-16 g/L、NiCl2 8-12 g/L、PA5000 1.5-2.5 g/L。
与现存的一维纳米材料电极的制备技术如气相化学沉积、丝网印刷法、微操作焊接和物理化学操控排布等方法相比，本发明具有以下优势：
本发明的植布工艺仅仅利用一维纳米材料外形细长、长径比大的本质特点，通过成膜与控制刻蚀实现一维纳米材料一定程度上有控制地暴露并植入金属表面，基本上不受一维纳米材料自身物质属性的影响，因此可以适用于各种物质构成的一维纳米材料，具有广泛适用性，这是此前各种工艺技术所难以企及的；
本发明的植布工艺通过选择与一维纳米材料匹配的聚合物分散剂，既能够使一维纳米材料有效分散，又可以使复合材料拥有较好的成膜能力，使之能够以均匀薄膜形态融入微加工技术体系，从而拥有与现有微加工技术体系兼容集成制造的潜力；
本发明的植布工艺全流程工艺温度很低，最高温度一般低于120℃，使其拥有兼容更多材料种类和工艺类型集成制造的潜力；
本发明通过选择合适的刻蚀剂，能够保证在对分散剂的可控刻蚀过程中，一维纳米材料得到可靠保护，是暴露出来的一维纳米材料功能特性不受任何影响，并且能够实现高度清洁；
本发明的植布工艺通过在暴露出的一维纳米材料的清洁表面沉积高强度金属粘结层的办法实现一维纳米材料与金属层的可靠结合，既具有牢固的机械结合强度，又可以保证可靠的电接触；
本发明通过调节聚合物与一维纳米材料的配比，调整聚合物分散介质中一维纳米材料的含量，从而间接调控电极表面一维纳米材料的植布密度，可调节范围很大；
从更广泛意义上，作为分散介质的聚合物材料并非唯一选择，只要能够满足充分混合、有效成膜，易于平整化加工和可供选择的刻蚀剂等基本条件，其它无机材料同样可以作为分散介质使用，如水玻璃等。
该技术具有低温工艺、多种材料兼容、与现有微加工工艺体系兼容集成、广泛适用于各种一维纳米材料、与金属电极结合牢固可靠并可以大范围调节植布密度等多方面技术优势，具有广泛应用价值，可适用于以这一类结构作为核心功能单元的器件，例如：场发射器件、气体离化传感器、电化学传感器等等。
 附图说明
图1为本发明示意图。
 具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例 1 碳纳米管和光刻胶重量配比为1:20的镍基场发射电极的制备
如图1所示，镍/碳纳米管电极的制备流程如下：
1. 将纯的碳纳米管与光刻胶混合后进行球磨。碳纳米管与光刻胶按 1:20 的重量比混合后，用行星球磨机以600rpm的转速对其球磨6h。
2. 将碳纳米管与光刻胶的均匀混合物流平在洁净的玻璃基片上，烘干固化，形成复合薄膜，烘胶固化参数如下:
温度（℃） 50 60 65 70 75 80 100 30
升温时间（ h ） 1 1 1 1 1 1 2 2
保温时间 (h) 2 1 1 1 1 1 1 24
3. 采用磨平抛光的表面加工方法使上述固化的复合薄膜平整化。首先将上述固化后的复合薄膜用砂纸磨平，然后用抛光机进行抛光，抛光后薄膜表面平均粗糙度在200nm左右。
4. 用质量浓度为0.5%的氢氧化钠溶液选择性刻蚀光刻胶介质，使碳纳米管部分暴露于复合膜表层。刻蚀后用稀盐酸中和，再用去离子水洗涤后烘干。
5．对上述表面刻蚀后的复合薄膜，溅射沉积Cr(30nm)粘结层和Cu(50nm)种子层，实现碳纳米管表面可靠金属化。
6. 在溅射沉积的的Cr粘结层和Cu种子层 上，进一步电镀Ni金属层（50μm），形成金属基体。
7.去除玻璃基片，用丙酮去除剩余的光刻胶介质，获得碳纳米管金属电极，其中碳纳米管部分裸露在外、部分根植于金属基体之中。
经场发射电子显微镜观察，制得的电极表面碳纳米管的密度约为：5根/µm2
实施例 2碳纳米纤维和聚酰亚胺重量配比为1:10的铜基场发射电极的制备
如图1所示，铜/碳纳米纤维电极的制备流程如下：
1. 将纯的碳纳米纤维与聚酰亚胺混合后球磨。碳纳米纤维与聚酰亚胺按 1:10的重量比例混合，混合后用行星球磨机以300rpm转速球磨8h。
2. 将上述球磨混合后的碳纳米纤维与聚酰亚胺的混合物旋涂在洁净的玻璃基片上，烘干，形成复合薄膜，聚酰亚胺固化参数如下:
温度（℃） 60 90 100 110 120 30
升温和降温时间（ min ） 60 30 20 60 60 180
保温时间 (min) 30 180 60 60 60 60
3. 采用磨平抛光的表面加工方法使上述固化的复合薄膜平整化。首先将上述固化后的复合薄膜用砂纸磨平，然后用抛光机进行抛光，抛光后薄膜表面平均粗糙度在200nm左右。
4. 用pH值为11.4的Na2HPO4和NaOH的混合液选择性刻蚀聚酰亚胺介质，使碳纳米纤维部分暴露于复合膜表层。刻蚀后用稀盐酸中和，再用去离子水洗涤后烘干。
5．对上述表面刻蚀后的复合薄膜，溅射沉积Cr(30nm)粘结层和Cu(50nm)种子层 ，实现碳纳米纤维表面可靠金属化。
6. 在溅射沉积的的Cr粘结层和Cu种子层 上，进一步电镀Cu金属层（50μm），形成金属基体。
7. 去除玻璃片，用6.7mol/L浓度的KOH和1.9mol/L浓度的K2CO3配比混合溶液去除铜金属基底背后聚酰亚胺介质，获得碳纳米纤维金属电极，其中碳纳米纤维部分裸露在外、部分根植于金属基体之中。
经场发射电子显微镜观察，制得的电极碳纳米纤维密度约为：10根/µm2
实施例 3 ZnO纳米棒/聚酰亚胺配比为1:3的银基场发射电极的制备
如图1所示，ZnO纳米棒场发射阴极制备流程如下：
1.将纯的ZnO纳米棒与聚酰亚胺按质量1:3混合，混合后放入球磨机以400rpm转速球磨6小时。
2. 将球磨后的ZnO纳米棒与聚酰亚胺的混合物滩涂在洁净的硅基片上，烘干，形成复合薄膜。聚酰亚胺固化参数如下：
温度（℃） 60 90 100 110 120 30
升温和降温时间（ min ） 60 60 60 30 30 180
保温时间 (min) 30 180 60 30 30 60
3. 采用磨平抛光的表面加工方法使上述固化的复合薄膜平整化。首先将上述固化后的复合薄膜用砂纸磨平，然后用抛光机进行抛光，抛光后薄膜表面平均粗糙度在200nm左右。
4. 用pH值为11.4的Na2HPO4和NaOH的混合液选择性刻蚀聚酰亚胺介质，使ZnO纳米棒部分暴露于复合薄膜界面之外。刻蚀后用稀盐酸中和，再用去离子水洗涤后烘干。
5．对上述表面刻蚀后的复合薄膜，溅射沉积Cr(30nm)粘结层和Cu(50nm)种子层 ，实现ZnO纳米棒表面可靠金属化。
6. 在溅射沉积的的Cr粘结层和Cu种子层上，进一步电镀Ag金属层（50μm），形成金属基体。
7. 去除硅基片，用6.7mol/L的KOH和1.9mol/L的K2CO3混合溶液去除剩余的聚酰亚胺分散介质，形成了ZnO纳米棒植布于银基体的效果，获得ZnO纳米棒金属电极，其中ZnO纳米棒部分裸露在外、部分根植于金属基体之中。
经场发射电子显微镜观察，制得的电极ZnO纳米棒密度约为：7根/µm2。

Claims (15)

  1. 一种一维纳米材料植入金属电极表面的方法，其特征在于，首先使复合材料形成复合薄膜，再使之表面平整化，然后选择性控制刻蚀复合薄膜表层使一维纳米材料部分暴露，接着通过表面金属化和加厚工艺将暴露出的一维纳米材料植入金属膜中，最后选择性刻蚀掉复合薄膜剩余部分，留下已植入金属被固定的一维纳米材料，实现一维纳米材料可靠植入金属基体的效果。
  2. 根据权利要求1所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的复合材料薄膜通过以下方式制备得到：
    1）将一维纳米材料与液态聚合物充分混合，形成膏状混合物复合材料；
    2）将膏状混合物复合材料涂覆在基片上烘干形成复合材料薄膜。
  3. 根据权利要求2所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的充分混合是指：通过手工搅拌、超声振荡混合或球磨中的一种或其组合的方式将液态聚合物与一维纳米材料充分均匀混合。
  4. 根据权利要求3所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的手工搅拌是指：将作为分散介质的液态聚合物与一维纳米材料在容器中按比例混合后人工搅拌，同时手工研磨以改进混合均匀性；所述的超声振荡混合是指：将混合物置于超声波发生器中通过超声振荡增强液态聚合物分散介质对一维纳米材料的浸润能力；所述的球磨是指：采用球磨机对混合物进行球磨，使之充分混合均匀，并且使一维纳米材料充分分散。该过程同时具有剪切一维纳米材料的作用。
  5. 根据权利要求2所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的基片为硅片、玻璃、金属或陶瓷质地的基体。
  6. 根据权利要求2所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的烘干是指：将作为介质的液态聚合物进行干燥固化的过程，烘干温度为50℃-300℃。
  7. 根据权利要求2所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的表面平整化是指：采用精密表面加工方法使复合材料薄膜表面平整化。
  8. 根据权利要求7所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的精密表面加工方法包括：切削、研磨和抛光，其厚度或深度小于等于2µm。
  9. 根据权利要求1所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的选择性控制刻蚀是指：所用的刻蚀液仅对聚合物介质起反应，而对一维纳米材料无影响。
  10. 根据权利要求1所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的刻蚀复合膜表层是指：用聚合物刻蚀液刻蚀聚合物介质表层部分，刻蚀深度由刻蚀时间来控制，刻蚀时间为5-600秒。
  11. 根据权利要求1所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的表面金属化是指：在复合薄膜表面沉积金属粘结层和种子层，实现一维纳米材料表面可靠金属化.
  12. 根据权利要求11所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的粘结层采用干法沉积或者湿法沉积制备得到，其中：
    干法沉积粘结层采用溅射、蒸镀或者其它真空镀膜工艺完成；
    湿法沉积粘结层采用电镀、化学镀等工艺完成。
  13. 根据权利要求11所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的种子层是在粘结层之上，作为后续电镀、化学镀加厚工艺的起始层，材料是任何用作电镀、化学镀种子层的金属或者合金，采用干法沉积工艺、电镀或化学度湿法沉积工艺制备。
  14. 根据权利要求1所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的加厚工艺是指：采用电沉积法、化学镀、蒸镀、溅射或CVD方法在种子层基础上，进一步加厚金属层，形成金属基体，再用刻蚀液选择性刻蚀剩余的复合材料中的聚合物分散介质，实现一维纳米材料植入金属电极表面。
  15. 根据权利要求14所述的一维纳米材料植入金属电极表面的方法，其特征是，所述的电沉积法的工艺参数如下：电流密度2-3A/dm2，pH值4-5，温度30-50℃，电镀时间120-400min，镀液成份为：Ni(NH2SO3)2 350-450g/L、H3BO3 13-16 g/L、NiCl2 8-12 g/L、PA5000 1.5-2.5 g/L。
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CN101880025A (zh) * 2010-06-26 2010-11-10 上海交通大学 一维纳米材料植入金属电极表面的方法

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CN111302653A (zh) * 2020-03-23 2020-06-19 天水师范学院 一种网状金银复合纳米薄膜的制备方法
CN111302653B (zh) * 2020-03-23 2022-04-05 天水师范学院 一种网状金银复合纳米薄膜的制备方法
CN115138230A (zh) * 2022-07-29 2022-10-04 江苏艾森半导体材料股份有限公司 一种厚膜负性光刻胶及配胶方法
CN115138230B (zh) * 2022-07-29 2023-06-13 江苏艾森半导体材料股份有限公司 一种厚膜负性光刻胶及配胶方法

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