WO2017193415A1 - 石墨烯修饰的复合平板ph传感器制备方法 - Google Patents

石墨烯修饰的复合平板ph传感器制备方法 Download PDF

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WO2017193415A1
WO2017193415A1 PCT/CN2016/082578 CN2016082578W WO2017193415A1 WO 2017193415 A1 WO2017193415 A1 WO 2017193415A1 CN 2016082578 W CN2016082578 W CN 2016082578W WO 2017193415 A1 WO2017193415 A1 WO 2017193415A1
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graphene
graphene film
copper foil
sputtering
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张西良
徐坤
崔守娟
耿妙妙
李萍萍
张世庆
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Jiangsu University
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    • 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
    • G01N27/28—Electrolytic cell components
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • 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
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes

Definitions

  • the invention relates to the field of preparation of chemical sensors, and more particularly to a method for preparing a graphene modified composite flat pH sensor.
  • pH is an important physical and chemical parameter, and it is receiving more and more attention from scholars at home and abroad.
  • the electrochemical measurement method has the advantages of rapid measurement, light weight, low cost, and the like, and is the most commonly used pH measurement method.
  • the electrochemical pH test system consists of a reference electrode and a working electrode. In order to realize the rapid and accurate measurement of the in-situ system and the development of sensor miniaturization, high-performance composite pH sensor has become one of the research hotspots and focus, and has important promotion and application value for improving industrial and agricultural production efficiency.
  • a thick all-solid-state pH sensor was prepared using thick film printing technology combined with screen-printing yttrium oxide electrode and screen-printed Ag/AgCl reference electrode. Improve the durability of the electrode.
  • Libu Manjakkal et al. mentioned in their paper "Fabrication of thick film sensitive RuO2-TiO2 and Ag/AgCl/KCl reference electrodes and their application for pH measurements" that yttrium oxide based oxidation was prepared on a alumina substrate by screen printing.
  • the all-solid composite pH sensor of titanium pH sensitive membrane and Ag/AgCl/KCl reference electrode reduces the cost of the electrode, and the method is simple and easy to implement.
  • CN101236170A is based on an integrated solid-state pH electrochemical sensor of nano-tungsten oxide and a preparation method thereof, and discloses an integrated flat-plate all-solid-state pH electrochemical sensor, but the measurement accuracy is not High, long response time, poor adaptability to pH real-time testing of solids, semi-solids, pastes and solutions with a certain water content.
  • the invention aims at the deficiencies of the existing pH sensor technology, and proposes a method for preparing a graphene-modified composite flat pH sensor for realizing the pH test of soil, cultivation substrate and solution having a certain water content.
  • the present invention achieves the above technical objects by the following technical means.
  • a method for preparing a graphene-modified composite flat pH sensor comprising the steps of:
  • Making a working electrode depositing a first graphene film on the surface of the first copper foil by micro-mechanical stripping; then depositing a Sb layer on the surface of the first graphene film by RF magnetron sputtering; The Sb 2 O 3 layer is deposited on the surface of the Sb layer by spraying; finally, the Nafion layer is coated on the outer surface of the Sb 2 O 3 layer by a spin coating method; the first graphene film, the Sb layer, the Sb 2 O 3 layer and The Nafion layer constitutes a working electrode, wherein the first graphene film is electrically connected to the first copper foil;
  • Making a reference electrode depositing a second graphene film on the surface of the second copper foil by micro-mechanical stripping method, and then depositing an Ag layer on the surface of the second graphene film by RF magnetron sputtering; and further using FeCl 3 solution
  • the Ag layer is immersed to form an AgCl layer on the surface of the Ag layer; the AgCl layer does not completely cover the Ag layer, and finally a third graphene film is deposited on the surface of the AgCl layer by micromechanical stripping; the second graphene film, the Ag layer, the AgCl layer, and The third graphene film constitutes a reference electrode.
  • the Sb layer deposited in the S2 is subjected to RF magnetron sputtering using an Sb target and Ar as a shielding gas; sputtering conditions are sputtering at room temperature, sputtering time is 40 to 50 min, gas flow rate is 39 sccm, and vacuum degree is 3 ⁇ 10 -4 Pa, sputtering power was 65 W, and working pressure was 1 Pa.
  • the Sb 2 O 3 layer deposited by the RF magnetron sputtering in the S2 is made of Sb as a target, Ar as a shielding gas, and O 2 is introduced , and the concentration ratio of Ar to O 2 is 8:2, and the deposition time is 50min.
  • the deposited Ag layer in the S3 is performed by using Ag as a target and Ar as a shielding gas for RF magnetron sputtering.
  • the sputtering conditions are sputtering at room temperature, the sputtering time is 20-30 min, the gas flow rate is 30 sccm, and the degree of vacuum is 3 ⁇ 10 -4 Pa, sputtering power is 18 W, and working pressure is 1 Pa.
  • the concentration of the FeCl 3 solution in the S3 is 0.1 mol/L, and the soaking time is 30 s.
  • the Sb layer has a thickness of 230 to 250 nm
  • the Sb 2 O 3 layer has a thickness of 40 to 60 nm
  • the Nafion layer has a thickness of 1.5 to 1.9 ⁇ m.
  • the Ag layer has a thickness of 140 to 160 nm, and the AgCl layer has a thickness of 15 to 25 nm.
  • the composite flat panel pH sensor prepared by the invention uses graphene as a base material, and the conductivity is greatly enhanced, and the response time is reduced.
  • the reference electrode is surface-modified with graphene to isolate external interference and at the same time achieve the purpose of electron conduction and improve the sensitivity of the sensor.
  • the working electrode uses yttrium and yttrium oxide as sensing materials, and the anti-interference ability is greatly improved by Nafion modification.
  • 1 is a schematic view showing the structure of a graphene-modified composite flat pH sensor.
  • FIG. 2 is a schematic view showing the structure of a working electrode portion.
  • Figure 3 is a schematic view showing the structure of a portion of a reference electrode.
  • 1-working electrode 2-first copper foil, 3-lead, 4-substrate, 5-second copper foil, 6-reference electrode, 11-Nafion layer, 12-Sb 2 O 3 layer, 13-Sb layer , 14-first graphene film, 61-second graphene film, 62-Ag layer, 63-AgCl layer, 64-third graphene film.
  • the graphene-modified composite flat pH sensor of the present invention is composed of a working electrode 1, a reference electrode 6, and a substrate 4, as shown in FIG.
  • the bottom of the working electrode 1 is connected to the upper copper foil 2 through the first graphene film 14 and is turned on; the Sb layer 13 and the Sb 2 O 3 layer are sequentially deposited on the first graphene film 14. 12.
  • the outer surface of the Sb 2 O 3 layer 12 is coated with a Nafion layer 11.
  • the reference electrode 6 includes a second graphene film 61, and a second graphene film 61 is deposited on the surface of the second copper foil 5, and an Ag layer 62 is sequentially deposited on the surface of the second graphene film 61.
  • the AgCl layer 63, the third graphene film 64 is deposited on the outer surface of the AgCl layer 63.
  • the preparation method of the graphene modified composite flat pH sensor comprises the following steps:
  • Forming the substrate 4 respectively, grooves are formed on the front and back surfaces of the substrate 4, and the first copper foil 2 is respectively coated on the bottom of the groove
  • the second copper foil 5; the leads 3 are printed in the substrate 4, and the leads 3 are connected to the first copper foil 2 and the second copper foil 5, respectively.
  • Making the working electrode 1 depositing the first graphene film 14 on the surface of the first copper foil 2 by micro-mechanical stripping; then depositing the Sb layer 13 on the surface of the first graphene film 14 by radio frequency magnetron sputtering; The method of magnetron sputtering deposits the Sb 2 O 3 layer 12 on the surface of the Sb layer 13; finally, the Nafion layer 11 is coated on the outer surface of the Sb 2 O 3 layer by a spin coating method; the first graphene film 14 and the Sb layer 13.
  • the Sb 2 O 3 layer 12 and the Nafion layer 11 constitute a working electrode 1 in which the first graphene film 14 is electrically connected to the first copper foil 2.
  • the Sb layer 13 has a thickness of 230 to 250 nm
  • the Sb 2 O 3 layer 12 has a thickness of 40 to 60 nm
  • the Nafion layer 11 has a thickness of 1.5 to 1.9 ⁇ m.
  • Making a reference electrode 6 depositing a second graphene film 61 on the surface of the second copper foil 2 by a micromechanical stripping method, and then depositing an Ag layer 62 on the surface of the second graphene film 61 by radio frequency magnetron sputtering; The Ag layer 62 is immersed in the FeCl 3 solution to form an AgCl layer 63 on the surface of the Ag layer 62; finally, a third graphene film 64 is deposited on the surface of the AgCl layer 63 by micromechanical stripping; the second graphene film 61, the Ag layer 62, and the AgCl The layer 63 and the third graphene film 64 constitute a reference electrode 6.
  • the Ag layer 62 has a thickness of 140 to 160 nm, the AgCl layer 63 has a thickness of 15 to 25 nm, and the AgCl layer 63 does not completely cover the Ag layer 62.
  • Step 1 fabricating the substrate 4: respectively, grooves are formed on the front and back surfaces of the substrate 4, and the first copper foil 2 and the second copper foil 5 are respectively coated on the bottom of the groove, and the leads are printed on the substrate 4 to connect the leads respectively.
  • Step 2 Making the working electrode 1: depositing the first graphene film 14 on the surface of the first copper foil 2 by micro-mechanical stripping method; then, by means of RF magnetron sputtering, using Sb target, Ar as shielding gas, and Sb Deposited on the surface of the first graphene film 14 to obtain the Sb layer 13; sputtering conditions are sputtering at room temperature, sputtering time 45 min, gas flow rate 39 sccm, vacuum degree 3 ⁇ 10 -4 Pa, sputtering power 65 W, working pressure It is 1 Pa, and the Sb layer 13 has a thickness of 240 nm.
  • Sb is used as the raw material
  • Ar is used as the shielding gas
  • O 2 is introduced
  • Sb 2 O 3 layer 12 is deposited on the surface of Sb layer 13; the deposition time is 50 min, and the concentration ratio of Ar to O 2 is 8:2, Sb 2 O 3 layer 12 thickness ⁇ 50 nm.
  • a Nafion layer 11 having a thickness of 1.7 ⁇ m was coated on the outer surface of the Sb 2 O 3 layer by spin coating.
  • Step 3 fabricating the reference electrode 6: depositing a second graphene film 61 on the surface of the second copper foil 2 by micro-mechanical stripping method, and then using RF magnetron sputtering method, using Ag as a raw material and Ar as a shielding gas, Ag is deposited on the surface of the second graphene film 61 to obtain an Ag layer 62; sputtering conditions are sputtering at room temperature, sputtering time is ⁇ 25 min, gas flow rate is 30 sccm, vacuum degree is 3 ⁇ 10 ⁇ 4 Pa, and sputtering power is 18 W. The working gas pressure was 1 Pa, and the Ag layer 62 was 150 nm thick.
  • the Ag layer 62 was further immersed in FeCl 3 having a solution concentration of 0.1 mol/L for 30 s, and an AgCl layer 63 was formed on the surface of the Ag layer 62.
  • the AgCl layer 63 was 15 nm thick, and the AgCl layer 63 did not completely cover the Ag layer 62.
  • a graphene film is deposited on the surface of the AgCl layer 63 by micromechanical stripping to deposit a third graphene film 64.

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Abstract

一种石墨烯修饰的复合平板pH传感器制备方法，在正反面分别开槽并涂覆铜箔的基板上，通过与铜箔连线引出导线，通过微机械剥离法分别在上下铜箔表面沉积第一石墨烯膜和第二石墨烯膜；通过磁控溅射法，分别在第一石墨烯膜表面沉积Sb层和Sb 2O 3层，然后用旋涂法在Sb 2O 3层外表面涂覆Nafion层，制得工作电极；通过磁控溅射法，在第二石墨烯膜表面沉积Ag层，然后用FeCl 3溶液浸泡，在表面生成AgCl层；最后用微机械剥离法在AgCl层表面沉积第三石墨烯膜，制得参比电极。所述的石墨烯修饰的复合pH传感器制备方法制备的pH传感器，具有响应快，稳定性好，重现性好等优点，可用于具有一定含水量的固体、半固体、糊状物的pH测试，以及溶液的pH测试。

Description

[根据细则37.2由ISA制定的发明名称]　石墨烯修饰的复合平板pH传感器制备方法 技术领域
本发明涉及化学传感器的制备领域，更具体的说是涉及一种石墨烯修饰的复合平板pH传感器制备方法。
背景技术
不论是工农业生产还是日常生活，pH值都是一个重要的理化参数，而且越来越受到国内外学者的关注。目前，国内外对于pH测量方法的研究，主要分为电化学测量方法和非电化学测量方法两大类。电化学测量方法具有测量快速，设备轻便，成本低廉等优点，是最常用的pH值测量方法。电化学pH测试系统由参比电极和工作电极组成。为实现对被测体系的原位快速准确测量，及传感器微型化智能化的发展需求，高性能的复合pH传感器成为研究热点和焦点之一，对于提高工农业生产效率具有重要推广应用价值。
目前，对于复合pH传感器制备方法的研究有很多，如2012年吕广梅等在其论文《一种全固态pH传感器的研制》中提到了一种采用浸渍涂层法制备锑/氧化锑pH电极，压片法制备新型全固态参比电极，并结合制备一种新型固体填充的全固态复合锑/氧化锑pH电极，能够承受较大压力，完成对地下深井水的pH在线测量。2013年D.K.Maurya等在其论文《High-sensitivity pH sensor employing a sub-micron ruthenium oxide thin-film in conjunction with a thick reference electrode》中提到以氧化铝陶瓷为基底材料，采用磁控溅射技术制备了以Ag/AgCl为参比电极，次微米的氧化钌薄膜电极为工作电极的全固态复合pH电极，在水溶液中的响应斜率接近理论能斯特响应；M.Glanc-Gostkiewicz等在其论文《Performance of miniaturised thick-film solid state pH sensors》中提到采用厚膜印刷技术，结合丝网印刷氧化钌离子电极和丝网印刷Ag/AgCl参比电极，制备了一种小型的的全固态pH传感器，提高电极的耐用性。2014年Libu Manjakkal等在其论文《Fabrication of thick film sensitive RuO2-TiO2and Ag/AgCl/KCl reference electrodes and their application for pH measurements》中提到采用丝网印刷技术在氧化铝基底上制备了基于氧化钌氧化钛pH敏感膜和Ag/AgCl/KCl参比电极的全固态复合pH传感器，降低了电极成本，方法简单易实现。然而，以上研究主要针对溶液环境的pH测量，对于有一定含水量的固体、半固体或糊状物等的适应性并未涉及。又如中国专利公开号CN104007158A全固态一体式pH复合电极装置及其电极的制备方法，公开了一种全固态的pH复合电极，具有一定 的机械强度和穿刺能力，可用于对固体、半固体、糊状物，以及溶液的pH测试，但是其材料导电性能具有一定的局限性，且制备方法是粗放式的，重现性差，无法精确控制敏感材料的沉积过程；中国专利公开号CN101236170A基于纳米氧化钨的集成化全固态pH电化学传感器及其制备方法，公开了一种集成化的平板式全固态pH电化学传感器，但是测量精度不高，响应时间较长，对一定含水量的固体、半固体、糊状物和溶液的pH实时测试适应性差。
发明内容
本发明针对已有pH传感器技术的不足，提出一种石墨烯修饰的复合平板pH传感器制备方法，用于实现对有一定含水量的土壤、栽培基质，以及溶液的pH测试。
本发明是通过以下技术手段实现上述技术目的的。
一种石墨烯修饰的复合平板pH传感器的制备方法，其特征在于，包括如下步骤：
S1.制作基板：在基板正反面分别开槽，并在所述槽的底部分别涂覆第一铜箔和第二铜箔；在基板内印刷引线，使引线分别连接第一铜箔和第二铜箔；
S2.制作工作电极：通过微机械剥离法在第一铜箔表面沉积第一石墨烯膜；然后通过射频磁控溅射的方法，在第一石墨烯膜表面沉积Sb层；再通过磁控溅射的方法在Sb层表面沉积Sb2O3层；最后用匀胶机旋涂法在Sb2O3层外表面涂覆Nafion层；第一石墨烯膜、Sb层、Sb2O3层和Nafion层构成工作电极，其中第一石墨烯膜与第一铜箔导通；
S3.制作参比电极：通过微机械剥离法在第二铜箔表面沉积第二石墨烯膜，然后通过射频磁控溅射的方法在第二石墨烯膜表面沉积Ag层；再用FeCl3溶液浸泡Ag层，从而在Ag层表面生成AgCl层；AgCl层未完全覆盖Ag层，最后用微机械剥离法在AgCl层表面沉积第三石墨烯膜；第二石墨烯膜、Ag层、AgCl层和第三石墨烯膜构成参比电极。
进一步地，所述S2中沉积Sb层是以Sb靶材、Ar作为保护气进行射频磁控溅射；溅射条件为室温下溅射，溅射时间40～50min，气体流量39sccm，真空度3×10-4Pa，溅射功率为65W，工作气压为1Pa。
进一步地，所述S2中射频磁控溅射沉积Sb2O3层是以Sb为靶材、Ar作为保护气，通入O2，Ar与O2的浓度比为8:2，沉积时间为50min。
进一步地，所述S3中沉积Ag层是以Ag为靶材、Ar作为保护气进行射频磁控溅射，溅射条件为室温下溅射，溅射时间20～30min，气体流量30sccm，真空度3×10-4Pa，溅射功率为18W，工作气压为1Pa。
进一步地，所述S3中FeCl3溶液浓度0.1mol/L，浸泡时间30s。
进一步地，Sb层厚度230～250nm，Sb2O3层厚度40～60nm，Nafion层厚度1.5～1.9μm。
进一步地，Ag层厚度140～160nm，AgCl层厚度15～25nm。
本发明采用上述技术解决方案所能达到的有益效果是：
(1)本发明制备的复合平板pH传感器以石墨烯作为基底材料，导电性大大增强，减少响应时间。
(2)参比电极以石墨烯做表面修饰，隔绝外部干扰，同时达到电子传导的目的，提高传感器响应灵敏度。
(3)工作电极以锑和氧化锑作为传感材料，经过Nafion修饰，抗干扰能力大大提高。
附图说明
图1是石墨烯修饰的复合平板pH传感器结构示意图。
图2是工作电极部分结构示意图。
图3是参比电极部分结构示意图。
图中：
1-工作电极，2-第一铜箔，3-引线，4-基板，5-第二铜箔，6-参比电极，11-Nafion层，12-Sb2O3层，13-Sb层，14-第一石墨烯膜，61-第二石墨烯膜，62-Ag层，63-AgCl层，64-第三石墨烯膜。
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
本发明所述的石墨烯修饰的复合平板pH传感器如图1所示，由工作电极1、参比电极6和基板4组成。如图2所示，所述的工作电极1底部通过第一石墨烯膜14与上铜箔2连接，并导通；第一石墨烯膜14上方依次沉积有Sb层13和Sb2O3层12，Sb2O3层12外表面涂覆有Nafion层11。如图3所示，所述的参比电极6包括第二石墨烯膜61，第二石墨烯膜61沉积于第二铜箔5表面，第二石墨烯膜61表面依次沉积有Ag层62和AgCl层63，AgCl层63外表面沉积有第三石墨烯膜64。
所述的石墨烯修饰的复合平板pH传感器的制备方法包括以下步骤：
制作基板4：在基板4正反面分别开槽，并在所述槽的底部分别涂覆第一铜箔2和 第二铜箔5；在基板4内印刷引线3，使引线3分别连接第一铜箔2和第二铜箔5。
制作工作电极1：通过微机械剥离法在第一铜箔2表面沉积第一石墨烯膜14；然后通过射频磁控溅射的方法，在第一石墨烯膜14表面沉积Sb层13；再通过磁控溅射的方法在Sb层13表面沉积Sb2O3层12；最后用匀胶机旋涂法在Sb2O3层外表面涂覆Nafion层11；第一石墨烯膜14、Sb层13、Sb2O3层12和Nafion层11构成工作电极1，其中第一石墨烯膜14与第一铜箔2导通。Sb层13厚度230～250nm，Sb2O3层12厚度40～60nm，Nafion层11厚度1.5～1.9μm。
制作参比电极6：通过微机械剥离法在第二铜箔2表面沉积第二石墨烯膜61，然后通过射频磁控溅射的方法在第二石墨烯膜61表面沉积Ag层62；再用FeCl3溶液浸泡Ag层62，从而在Ag层62表面生成AgCl层63；最后用微机械剥离法在AgCl层63表面沉积第三石墨烯膜64；第二石墨烯膜61、Ag层62、AgCl层63和第三石墨烯膜64构成参比电极6。Ag层62厚度140～160nm，AgCl层63厚度15～25nm，且AgCl层63未完全覆盖Ag层62。
实施例1：
步骤一：制作基板4：在基板4正反面分别开槽，并在所述槽的底部分别涂覆第一铜箔2和第二铜箔5，在基板4内印刷引线，使引线分别连接第一铜箔2和第二铜箔5。
步骤二：制作工作电极1：通过微机械剥离法在第一铜箔2表面沉积第一石墨烯膜14；然后通过射频磁控溅射的方法，以Sb靶材、Ar作为保护气，将Sb沉积在第一石墨烯膜14表面，获得Sb层13；溅射条件为室温下溅射，溅射时间45min，气体流量39sccm，真空度3×10-4Pa，溅射功率为65W，工作气压为1Pa，Sb层13厚度240nm，。再通过磁控溅射的方法，以Sb为原料、Ar作为保护气，通入O2，在Sb层13表面沉积Sb2O3层12；沉积时间为50min，Ar与O2的浓度比为8:2，Sb2O3层12厚度～50nm。最后用匀胶机旋涂法在Sb2O3层外表面涂覆厚度为1.7μm的Nafion层11。所述的
步骤三：制作参比电极6：通过微机械剥离法在第二铜箔2表面沉积第二石墨烯膜61，然后通过射频磁控溅射的方法，以Ag为原料、Ar作为保护气，将Ag沉积在第二石墨烯膜61表面，获得Ag层62；溅射条件为室温下溅射，溅射时间～25min，气体流量30sccm，真空度3×10-4Pa，溅射功率为18W，工作气压为1Pa，Ag层62厚度150nm。再用溶液浓度为0.1mol/L的FeCl3浸泡Ag层62，浸泡时间30s，在Ag层62表面生成AgCl层63，AgCl层63厚度15nm，且AgCl层63未完全覆盖Ag层62。最后用微机械剥离法将石墨烯膜沉积在AgCl层63表面沉积第三石墨烯膜64。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。

Claims (7)

  1. 一种石墨烯修饰的复合平板pH传感器的制备方法，其特征在于，包括如下步骤：
    S1.制作基板(4)：在基板(4)正反面分别开槽，并在所述槽的底部分别涂覆第一铜箔(2)和第二铜箔(5)；在基板(4)内印刷引线，使引线分别连接第一铜箔(2)和第二铜箔(5)；
    S2.制作工作电极(1)：通过微机械剥离法在第一铜箔(2)表面沉积第一石墨烯膜(14)；然后通过射频磁控溅射的方法，在第一石墨烯膜(14)表面沉积Sb层(13)；再通过磁控溅射的方法在Sb层(13)表面沉积Sb2O3层(12)；最后用匀胶机旋涂法在Sb2O3层外表面涂覆Nafion层(11)；第一石墨烯膜(14)、Sb层(13)、Sb2O3层(12)和Nafion层(11)构成工作电极(1)，其中第一石墨烯膜(14)与第一铜箔(2)导通；
    S3.制作参比电极(6)：通过微机械剥离法在第二铜箔(2)表面沉积第二石墨烯膜(61)，然后通过射频磁控溅射的方法在第二石墨烯膜(61)表面沉积Ag层(62)；再用FeCl3溶液浸泡Ag层(62)，从而在Ag层(62)表面生成AgCl层(63)；AgCl层(63)未完全覆盖Ag层(62)，最后用微机械剥离法在AgCl层(63)表面沉积第三石墨烯膜(64)；第二石墨烯膜(61)、Ag层(62)、AgCl层(63)和第三石墨烯膜(64)构成参比电极(6)。
  2. 根据权利要求1所述的一种石墨烯修饰的复合平板pH传感器的制备方法，其特征在于：所述S2中沉积Sb层是以Sb靶材、Ar作为保护气进行射频磁控溅射；溅射条件为室温下溅射，溅射时间40～50min，气体流量39sccm，真空度3×10-4Pa，溅射功率为65W，工作气压为1Pa。
  3. 根据权利要求1所述的一种石墨烯修饰的复合平板pH传感器的制备方法，其特征在于：所述S2中射频磁控溅射沉积Sb2O3层是以Sb为靶材、Ar作为保护气，通入O2，Ar与O2的浓度比为8:2，沉积时间为50min。
  4. 根据权利要求1所述的石墨烯修饰的复合平板电极pH传感器的制备方法，其特征在于：所述S3中沉积Ag层(62)是以Ag为靶材、Ar作为保护气进行射频磁控溅射，溅射条件为室温下溅射，溅射时间20～30min，气体流量30sccm，真空度3×10-4Pa，溅射功率为18W，工作气压为1Pa。
  5. 根据权利要求1所述的石墨烯修饰的复合平板电极pH传感器的制备方法，其特 征在于：所述S3中FeCl3溶液浓度0.1mol/L，浸泡时间30s。
  6. 根据权利要求1所述的石墨烯修饰的复合平板电极pH传感器的制备方法，其特征在于：Sb层(13)厚度230～250nm，Sb2O3层(12)厚度40～60nm，Nafion层(11)厚度1.5～1.9μm。
  7. 根据权利要求1所述的石墨烯修饰的复合平板pH传感器的制备方法，其特征在于：Ag层(62)厚度140～160nm，AgCl层(63)厚度15～25nm，且AgCl层(63)未完全覆盖Ag层(62)。
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