WO2019072034A1 - Selective electrochemical deposition method for nano-scale prussian blue thin film - Google Patents
Selective electrochemical deposition method for nano-scale prussian blue thin film Download PDFInfo
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- WO2019072034A1 WO2019072034A1 PCT/CN2018/102439 CN2018102439W WO2019072034A1 WO 2019072034 A1 WO2019072034 A1 WO 2019072034A1 CN 2018102439 W CN2018102439 W CN 2018102439W WO 2019072034 A1 WO2019072034 A1 WO 2019072034A1
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- the invention belongs to the technical field of electrochemistry, and in particular relates to a selective electrochemical deposition method of a nano-scale Prussian blue film.
- Prussian blue is widely used in biosensing because it can react with hydrogen peroxide at low voltages and is therefore called “artificial catalase.” Therefore, it is used for glucose detection, lactic acid detection, and the like. Prussian blue has electrochromic properties and can therefore be used in the manufacture of color-changing glass and color-changing windows. There are various methods for the preparation of Prussian blue, in which electrochemical deposition is the most convenient and fastest, and at the same time, a better quality of deposited film can be obtained. Parameters such as deposition potential, deposition current, and deposition time during electrochemical deposition control the thickness, quality, and adhesion to the deposited substrate.
- the nano-scale Prussian blue film can reduce the response time in biomonitoring, reduce the ion diffusion resistance, and increase the reaction response current.
- the nano-scale film needs to reduce the deposition time, and in order to ensure the quality of the deposited film, it is necessary to increase the deposition speed, and thus the film may not be dense, the strength is low, the adhesion to the substrate is poor, and the problem of cracking and debonding is easily caused.
- Most of the existing research content increases the deposition success rate and film quality by adding other substances such as polymers to the Prussian blue electrodeposition liquid, and at the same time achieving lower electrochemical impedance of the film. The consequence of this is that it affects the quality of Prussian Blue itself, while increasing the difficulty of preparing experimental materials.
- the use of polymers reduces the reliability and performance stability of long-term use.
- the present invention proposes a selective electrochemical deposition method of a nano-scale Prussian blue film, which is prepared by treating the surface of the metal electrode to improve the surface microstructure and improve the electrochemical deposition of Prussian blue. Efficiency and effectiveness, and selective electrodeposition of Prussian blue films at nanometer thickness.
- the electrochemical deposition reaction device for electrochemical deposition of Prussian blue film comprises: micro electrochemical reaction cell, electrochemical deposition solution, electrochemical deposition counter electrode, electrochemical deposition working electrode, electrochemical deposition reference electrode and electrochemical a workstation; wherein a chemical deposition solution is deposited in a microelectrochemical reaction cell; an electrochemical deposition counter electrode, an electrochemical deposition working electrode, and an electrochemical deposition reference electrode are inserted into the electrochemical deposition solution; electrochemical deposition of the counter electrode, electrochemical The deposition working electrode and the electrochemical deposition reference electrode are respectively connected to the electrochemical workstation by a cable.
- the selective electrochemical deposition method of the nano-scale Prussian blue film of the invention comprises the following steps:
- the electrochemical workstation performs electrochemical deposition reaction on the pattern of the working electrode of the sensor, and forms a Prussian blue film on the pattern of the working electrode of the sensor.
- the pattern of the working electrode of the sensor and the Prussian blue film on the sensor constitute the working electrode of the sensor, and the electrode of the sensor The pattern acts as a sensor counter electrode;
- the activated sensor working electrode is cleaned to obtain a sensor working electrode with a nano-scale Prussian blue film.
- preparing the metal electrode specifically comprises the following steps:
- the substrate is one of a polymer film in a silicon wafer or a glass wafer.
- the thickness of the bonding layer is on the order of nanometers to increase the adhesion of the deposited metal film.
- step c) of step 1) the metal film is patterned by means of semiconductor processing, including the following steps:
- the shape of the metal electrode is a sheet shape, a filament shape, a rod shape or a film shape.
- the material of the metal thin film is one of platinum, gold, and silver.
- step 2) the insulation between the pattern of the sensor working electrode and the pattern of the sensor counter electrode is performed, including the following steps:
- the metal electrode in order to prepare the surface microstructure, the metal electrode is immersed in the metal etching solution, and after a certain time, the surface is taken out and washed, and the time of immersing the etching liquid is 5 seconds to 8 seconds; or, by using roughness
- the surface friction metal electrode forms a surface microstructure on the surface of the metal electrode by adding metal nanoparticles on the surface of the metal electrode or by scanning the surface of the metal electrode by laser.
- step 6 the chemical deposition reaction is performed by means of constant potential deposition; or by cyclic voltammetric scanning deposition.
- the deposition reaction time was set to 5 seconds to 25 seconds.
- the stability scan uses a cyclic voltammetric scan; the stable scan solution removes the solution containing the iron ions and the ferricyanide ion species from the electrochemical deposition solution.
- the heating device is a heating plate, the heating temperature is 120 to 200 ° C, and the heating time is more than 1 hour.
- step 9 the activation treatment is carried out in a constant potential manner, the potential is -1 V to 1 V (relative to the electrochemical deposition reference electrode) activation time is greater than 0.5 hours; the solution used for activation is a phosphate buffer.
- step 10 the activated sensor working electrode is cleaned with deionized water or an organic solvent such as acetone or ethanol.
- the invention firstly prepares a metal electrode, which comprises a pattern of a sensor working electrode and a pattern of a sensor counter electrode, and performs surface treatment on the metal electrode to prepare a surface microstructure of a nanometer or a micrometer, a pattern of a working electrode of the sensor and a counter electrode of the sensor.
- FIG. 1 is a schematic view of a metal electrode obtained by a selective electrochemical deposition method of a nanoscale Prussian blue film according to the present invention
- FIG. 2 is a cross-sectional view of a sensor working electrode having a Prussian blue film obtained by a selective electrochemical deposition method of a nanoscale Prussian blue film according to the present invention
- Figure 3 is an electrochemical deposition reaction apparatus for electrochemical deposition of a Prussian blue film.
- the selective electrochemical deposition method of the nano-scale Prussian blue film of the present embodiment includes the following steps:
- the electrochemical deposition solution is a mixed solution of KCl, K 3 [Fe(CN) 6 ], FeCl 3 and HCl, and the working electrode of the sensor
- the pattern is connected to the electrochemical workstation via a cable.
- Electrochemical workstation performs electrochemical deposition reaction on the pattern of the working electrode of the sensor.
- the deposition reaction time is set to 10 seconds to 15 seconds by means of constant potential deposition.
- the Prussian blue film 5 is formed on the pattern of the working electrode of the sensor.
- the pattern of the electrodes and the Prussian blue film thereon constitute the sensor working electrode, and the pattern of the sensor counter electrode serves as the sensor counter electrode.
- the stability scanning solution removes a solution containing iron ions and light ferrite ion species.
- the sensor working electrode is taken out from the micro electrochemical reaction cell and dried by a heating device.
- the heating device is a heating plate, the heating temperature is 170 ° C, and the heating time is 1.5 hours.
- the dried working electrode of the sensor is activated in a micro-electrochemical reaction cell, and the activation treatment is performed by a constant potential method, the potential is -0.1 V, and the activation time is 1 hour with respect to the electrochemical deposition reference electrode.
- the activated sensor working electrode is cleaned with deionized water to obtain a sensor working electrode with a nano-scale Prussian blue film.
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Abstract
A selective electrochemical deposition method for a nano-scale Prussian blue thin film, comprising: firstly preparing a metal electrode, the metal electrode comprising a pattern of a sensor working electrode and a pattern of a sensor counter electrode; subjecting the metal electrode to surface treatment to prepare a nanoscale or micron-scale surface microstructure; insulating the pattern of the sensor working electrode from the pattern of the sensor counter electrode; performing electrochemical deposition on the pattern of the sensor working electrode, and obtaining a Prussian blue thin film on the pattern of the sensor working electrode by controlling the deposition time, so as to form the sensor working electrode; and then performing stability scanning, heating, activation treatment and cleaning to obtain the sensor working electrode having a nanoscale Prussian blue thin film. The present invention performs surface treatment on the metal electrode to prepare a nano-scale or micron-scale surface microstructure, and improves the efficiency and effect of electrochemical deposition of Prussian blue.
Description
本发明属于电化学技术领域，具体涉及一种纳米级普鲁士蓝薄膜的选择性电化学沉积方法。The invention belongs to the technical field of electrochemistry, and in particular relates to a selective electrochemical deposition method of a nano-scale Prussian blue film.
普鲁士蓝被广泛应用于生物传感，因为其可以在低电压下与过氧化氢发生反应，因此被称为“人工过氧化氢酶”。因此被用于葡萄糖检测，乳酸检测等。普鲁士蓝具有电致变色特性，因此可以用于变色玻璃、变色窗的制造。普鲁士蓝的制备有多种方法，其中电化学沉积是最方便最快捷的，同时可以得到较好的沉积薄膜质量。电化学沉积过程中沉积电位、沉积电流和沉积时间等参数控制被沉积薄膜的厚度、质量和与被沉积基底的粘附力。纳米级的普鲁士蓝薄膜可以降低生物监测中的响应时间，减少离子扩散阻力，提高反应响应电流。但是纳米级薄膜需要降低沉积时间，同时为了保证沉积薄膜的质量，需要提高沉积速度，因此可能会导致薄膜不致密，强度低和与基底粘附力差，容易破裂脱粘等问题。现有的研究内容大多以向普鲁士蓝电沉积液中添加其他物质例如聚合物的方式提高沉积成功率和薄膜质量质量，同时实现较低的薄膜电化学阻抗。这样做的后果是影响普鲁士蓝本身的品质，同时增加了实验材料准备难度，聚合物的使用降低了长期使用的可靠性和性能稳定性。Prussian blue is widely used in biosensing because it can react with hydrogen peroxide at low voltages and is therefore called "artificial catalase." Therefore, it is used for glucose detection, lactic acid detection, and the like. Prussian blue has electrochromic properties and can therefore be used in the manufacture of color-changing glass and color-changing windows. There are various methods for the preparation of Prussian blue, in which electrochemical deposition is the most convenient and fastest, and at the same time, a better quality of deposited film can be obtained. Parameters such as deposition potential, deposition current, and deposition time during electrochemical deposition control the thickness, quality, and adhesion to the deposited substrate. The nano-scale Prussian blue film can reduce the response time in biomonitoring, reduce the ion diffusion resistance, and increase the reaction response current. However, the nano-scale film needs to reduce the deposition time, and in order to ensure the quality of the deposited film, it is necessary to increase the deposition speed, and thus the film may not be dense, the strength is low, the adhesion to the substrate is poor, and the problem of cracking and debonding is easily caused. Most of the existing research content increases the deposition success rate and film quality by adding other substances such as polymers to the Prussian blue electrodeposition liquid, and at the same time achieving lower electrochemical impedance of the film. The consequence of this is that it affects the quality of Prussian Blue itself, while increasing the difficulty of preparing experimental materials. The use of polymers reduces the reliability and performance stability of long-term use.
发明内容Summary of the invention
针对以上现有技术中存在的问题，本发明提出了一种纳米级普鲁士蓝薄膜的选择性电化学沉积方法，通过对金属电极表面进行处理，制备出表面微结构，提高普鲁士蓝电化学沉积的效率和效果，并实现纳米级厚度的普鲁士蓝薄膜的选择性电沉积。In view of the above problems in the prior art, the present invention proposes a selective electrochemical deposition method of a nano-scale Prussian blue film, which is prepared by treating the surface of the metal electrode to improve the surface microstructure and improve the electrochemical deposition of Prussian blue. Efficiency and effectiveness, and selective electrodeposition of Prussian blue films at nanometer thickness.
本发明进行普鲁士蓝薄膜电化学沉积采用的电化学沉积反应装置包括：微型电化学反应池、电化学沉积溶液、电化学沉积对电极、电化学沉积工作电极、电化学沉积参比电极以及电化学工作站；其中，在微型电化学反应池中盛放电化学沉积溶液；电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极插入电化学沉积溶液中；电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别通过电缆连接至电化学工作站。The electrochemical deposition reaction device for electrochemical deposition of Prussian blue film comprises: micro electrochemical reaction cell, electrochemical deposition solution, electrochemical deposition counter electrode, electrochemical deposition working electrode, electrochemical deposition reference electrode and electrochemical a workstation; wherein a chemical deposition solution is deposited in a microelectrochemical reaction cell; an electrochemical deposition counter electrode, an electrochemical deposition working electrode, and an electrochemical deposition reference electrode are inserted into the electrochemical deposition solution; electrochemical deposition of the counter electrode, electrochemical The deposition working electrode and the electrochemical deposition reference electrode are respectively connected to the electrochemical workstation by a cable.
本发明的纳米级普鲁士蓝薄膜的选择性电化学沉积方法，包括以下步骤：The selective electrochemical deposition method of the nano-scale Prussian blue film of the invention comprises the following steps:
1)制备金属电极，金属电极包括传感器工作电极的图案和传感器对电极的图案；1) preparing a metal electrode comprising a pattern of a sensor working electrode and a pattern of a sensor counter electrode;
2)将传感器工作电极的图案和传感器对电极的图案之间进行绝缘处理；2) insulating the pattern between the sensor working electrode and the pattern of the sensor counter electrode;
3)在金属电极的表面制备出特征尺寸为纳米或者微米级的表面微结构；3) preparing a surface microstructure having a feature size of nanometer or micrometer on the surface of the metal electrode;
4)配置普鲁士蓝的电化学沉积溶液，添加入微型电化学反应池中，电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别插入电化学沉积溶液中，电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别通过电缆连接至电化学工作站；4) Disposing the electrochemical deposition solution of Prussian blue into the micro-electrochemical reaction cell, and inserting the electrochemical deposition counter electrode, the electrochemical deposition working electrode and the electrochemical deposition reference electrode into the electrochemical deposition solution, respectively, and electrochemical deposition The electrode, the electrochemical deposition working electrode and the electrochemical deposition reference electrode are respectively connected to the electrochemical workstation through a cable;
5)将金属电极中的传感器工作电极的图案沉浸在电化学沉积溶液中，并将传感器工作电极的图案连接至电化学沉积工作电极；5) immersing the pattern of the sensor working electrode in the metal electrode in the electrochemical deposition solution, and connecting the pattern of the sensor working electrode to the electrochemical deposition working electrode;
6)电化学工作站对传感器工作电极的图案进行电化学沉积反应，在传感器工作电极的图案上形成普鲁士蓝薄膜，传感器工作电极的图案及其上的普鲁士蓝薄膜构成传感器工作电极，传感器对电极的图案作为传感器对电极；6) The electrochemical workstation performs electrochemical deposition reaction on the pattern of the working electrode of the sensor, and forms a Prussian blue film on the pattern of the working electrode of the sensor. The pattern of the working electrode of the sensor and the Prussian blue film on the sensor constitute the working electrode of the sensor, and the electrode of the sensor The pattern acts as a sensor counter electrode;
7)电化学沉积反应完成后，更换微型电化学反应池内的溶液，加入稳定性扫描溶液，对传感器工作电极进行稳定性扫描；7) after the electrochemical deposition reaction is completed, the solution in the micro electrochemical reaction cell is replaced, and the stability scanning solution is added to perform stability scanning on the working electrode of the sensor;
8)将传感器工作电极从微型电化学反应池中取出，利用加热装置烘干；8) taking the sensor working electrode from the micro electrochemical reaction cell and drying it with a heating device;
9)更换微型电化学反应池内的溶液，加入用于活化的溶液，将烘干后的传感器工作电极在微型电化学反应池内做活化处理；9) replacing the solution in the micro electrochemical reaction cell, adding a solution for activation, and performing activation treatment on the dried working electrode of the sensor in the micro electrochemical reaction cell;
10)将活化后的传感器工作电极清洗干净，得到具有纳米级普鲁士蓝薄膜的传感器工作电极。10) The activated sensor working electrode is cleaned to obtain a sensor working electrode with a nano-scale Prussian blue film.
其中，在步骤1)中，制备金属电极具体包括以下步骤：Wherein, in step 1), preparing the metal electrode specifically comprises the following steps:
a)在清洁干燥的基底上旋涂转印层；a) spin coating a transfer layer on a clean, dry substrate;
b)在转印层上通过旋涂或者刮膜的方式，或者使用现成的薄膜绝缘材料粘贴固定在转印层的表面，制备绝缘支持层；b) preparing an insulating support layer on the transfer layer by spin coating or scraping, or by using an off-the-shelf thin film insulating material adhered to the surface of the transfer layer;
c)在绝缘支持层上溅射粘结层；c) sputtering a bonding layer on the insulating support layer;
d)在粘结层上通过电镀、电化学沉积、气相沉积或磁控溅射的方式制备金属薄膜，金属薄膜的厚度为纳米级或者微米级；d) preparing a metal film on the bonding layer by electroplating, electrochemical deposition, vapor deposition or magnetron sputtering, the thickness of the metal film being nanometer or micron;
e)将沉积过金属薄膜的基底切片或者剪裁成所需要的尺寸，然后通过半导体加工的方式对金属薄膜图形化，制备出所需要的金属电极，金属电极包括传感器工作电极的图案和传感器对电极的图案。e) slicing or trimming the substrate on which the metal film has been deposited into a desired size, and then patterning the metal film by means of semiconductor processing to prepare a desired metal electrode including a pattern of the sensor working electrode and a sensor counter electrode pattern.
在步骤1)的a)中，基底采用硅片、玻璃片中聚合物膜中的一种。粘结层的厚度为纳米级，以增加沉积的金属薄膜的沾附能力。In a) of step 1), the substrate is one of a polymer film in a silicon wafer or a glass wafer. The thickness of the bonding layer is on the order of nanometers to increase the adhesion of the deposited metal film.
在步骤1)的c)中，通过半导体加工的方式对金属薄膜图形化，包括以下步骤：In step c) of step 1), the metal film is patterned by means of semiconductor processing, including the following steps:
i.在金属薄膜上旋涂光刻胶；i. spin coating a photoresist on a metal film;
ii.采用掩膜在光刻机下对光刻胶进行曝光；Ii. exposing the photoresist under a lithography machine using a mask;
iii.在显影液中显影；Iii. developing in a developing solution;
iv.在刻蚀液中刻蚀金属薄膜至绝缘支持层的上表面，从而形成包括传感器对电极的图案和传感器工作电极的图案的金属电极。Iv. etching the metal film in the etching solution to the upper surface of the insulating support layer, thereby forming a metal electrode including a pattern of the sensor counter electrode and a pattern of the sensor working electrode.
金属电极的形状为片状、丝状、棒状或薄膜状。金属薄膜的材料为铂、金和银中的一种。The shape of the metal electrode is a sheet shape, a filament shape, a rod shape or a film shape. The material of the metal thin film is one of platinum, gold, and silver.
在步骤2)中，对传感器工作电极的图案和传感器对电极的图案之间进行绝缘处理，包括以下步骤：In step 2), the insulation between the pattern of the sensor working electrode and the pattern of the sensor counter electrode is performed, including the following steps:
a)将光刻金属薄膜的掩膜版设计成为多个不互相连接的金属电极的形状；a) designing a mask of the lithographic metal film into a shape of a plurality of metal electrodes that are not connected to each other;
b)利用光刻-显影-刻蚀的方式将金属电极之间的区域的金属完全刻蚀掉，使不同的金属电极之间无法互联。b) The metal in the region between the metal electrodes is completely etched by photolithography-developing-etching so that different metal electrodes are not interconnected.
在步骤3)中，为了制备表面微结构，将金属电极浸入金属的刻蚀液，在一定时间后取出并洗净表面，浸入刻蚀液的时间为5秒～8秒；或者，通过用粗糙的表面摩擦金属电极，通过在金属电极的表面添加金属纳米颗粒，或者通过激光扫描金属电极的表面的方式在金属电极的表面形成表面微结构。In the step 3), in order to prepare the surface microstructure, the metal electrode is immersed in the metal etching solution, and after a certain time, the surface is taken out and washed, and the time of immersing the etching liquid is 5 seconds to 8 seconds; or, by using roughness The surface friction metal electrode forms a surface microstructure on the surface of the metal electrode by adding metal nanoparticles on the surface of the metal electrode or by scanning the surface of the metal electrode by laser.
在步骤6)中，化学沉积反应采用恒电位沉积的方式；或者采用循环伏安扫描沉积的方式。沉积反应时间设置为5秒～25秒。In step 6), the chemical deposition reaction is performed by means of constant potential deposition; or by cyclic voltammetric scanning deposition. The deposition reaction time was set to 5 seconds to 25 seconds.
在步骤7)中，稳定性扫描使用循环伏安扫描的方式；稳定性扫描溶液为电化学沉积溶液去掉含有铁离子以及氰铁酸根离子物质的溶液。In step 7), the stability scan uses a cyclic voltammetric scan; the stable scan solution removes the solution containing the iron ions and the ferricyanide ion species from the electrochemical deposition solution.
在步骤8)中，加热装置为加热板，加热温度为120～200℃，加热时间为大于1小时。In the step 8), the heating device is a heating plate, the heating temperature is 120 to 200 ° C, and the heating time is more than 1 hour.
在步骤9)中，活化处理采用恒电位的方式，电位为-1V～1V(相对于电化学沉积参比电极)活化时间大于0.5小时；用于活化的溶液为磷酸缓冲液。In step 9), the activation treatment is carried out in a constant potential manner, the potential is -1 V to 1 V (relative to the electrochemical deposition reference electrode) activation time is greater than 0.5 hours; the solution used for activation is a phosphate buffer.
在步骤10)中，用去离子水或丙酮、乙醇等有机溶剂，将活化后的传感器工作电极清洗干净。In step 10), the activated sensor working electrode is cleaned with deionized water or an organic solvent such as acetone or ethanol.
本发明的优点：Advantages of the invention:
本发明首先制备金属电极，金属电极包括传感器工作电极的图案和传感器对电极的图案，对金属电极进行表面处理，制备出纳米或微米级的表面微观结构，传感器工作电极的图案与传感器对电极的图案之间进行绝缘处理，对传感器工作电极的图案进行选择性电化学沉积，通过控制沉积的时间在传感器工作电极的图案得到普鲁士蓝薄膜，形成传感器工作电极，然后再进行稳定性扫描、加热、活化处理和清洗，得到具有纳米级普鲁士蓝薄膜的传感器工作电极；本发明对金属电极进行表面处理，制备出纳米或微米级的表面微观结构，提高普鲁士蓝电化学沉积的效率和效果。The invention firstly prepares a metal electrode, which comprises a pattern of a sensor working electrode and a pattern of a sensor counter electrode, and performs surface treatment on the metal electrode to prepare a surface microstructure of a nanometer or a micrometer, a pattern of a working electrode of the sensor and a counter electrode of the sensor. Insulation treatment between the patterns, selective electrochemical deposition of the pattern of the working electrode of the sensor, obtaining a Prussian blue film by patterning the working electrode of the sensor to form a working electrode of the sensor, and then performing stability scanning, heating, Activation treatment and cleaning to obtain a sensor working electrode with a nano-scale Prussian blue film; the invention performs surface treatment on the metal electrode to prepare a nano- or micro-scale surface microstructure, and improves the efficiency and effect of electrochemical deposition of Prussian blue.
图1为根据本发明的纳米级普鲁士蓝薄膜的选择性电化学沉积方法得到的金属电极的示意图；1 is a schematic view of a metal electrode obtained by a selective electrochemical deposition method of a nanoscale Prussian blue film according to the present invention;
图2为根据本发明的纳米级普鲁士蓝薄膜的选择性电化学沉积方法得到的具有普鲁士蓝薄膜的传感器工作电极的剖面图；2 is a cross-sectional view of a sensor working electrode having a Prussian blue film obtained by a selective electrochemical deposition method of a nanoscale Prussian blue film according to the present invention;
图3为进行普鲁士蓝薄膜电化学沉积采用的电化学沉积反应装置。Figure 3 is an electrochemical deposition reaction apparatus for electrochemical deposition of a Prussian blue film.
下面结合附图，通过具体实施例，进一步阐述本发明。The invention will be further illustrated by the following examples in conjunction with the accompanying drawings.
如图1所示，本实施例的纳米级普鲁士蓝薄膜的选择性电化学沉积方法，包括以下步骤：As shown in FIG. 1, the selective electrochemical deposition method of the nano-scale Prussian blue film of the present embodiment includes the following steps:
1)制备金属电极：1) Preparation of metal electrodes:
a)在清洁干燥的硅基底上旋涂PMMA形成转印层；a) spin coating PMMA on a clean and dry silicon substrate to form a transfer layer;
b)在转印层上旋涂旋涂PI形成绝缘支持层1，固化；b) spin-coating PI on the transfer layer to form an insulating support layer 1 and curing;
c)在绝缘支持层上溅射铬形成粘结层2，以增加金属薄膜与绝缘支持层之间的粘附能力；c) sputtering chromium on the insulating support layer to form the bonding layer 2 to increase the adhesion between the metal film and the insulating support layer;
d)放入磁控溅射设备的真空腔内，在粘结层上沉积金形成金属薄膜，沉积的厚度为纳米级或者微米级；d) placing in a vacuum chamber of a magnetron sputtering apparatus, depositing gold on the bonding layer to form a metal thin film, and depositing a thickness of nanometer or micrometer;
e)将沉积过金属薄膜的基底切片成所需要的尺寸，然后通过半导体加工的方式对金属薄膜图形化，制备出所需要的金属电极，金属电极包括传感器工作电极的图案3和传感器对电极的图案4，通过半导体加工的方式对金属薄膜图形化，包括以下步骤：e) slicing the substrate on which the metal film has been deposited into a desired size, and then patterning the metal film by means of semiconductor processing to prepare a desired metal electrode including the pattern 3 of the sensor working electrode and the pattern of the sensor counter electrode 4. Patterning the metal film by means of semiconductor processing, including the following steps:
i.在金属薄膜上旋涂光刻胶；i. spin coating a photoresist on a metal film;
ii.采用掩膜在光刻机下对光刻胶进行曝光；Ii. exposing the photoresist under a lithography machine using a mask;
iii.在显影液中显影；Iii. developing in a developing solution;
iv.在刻蚀液中刻蚀金属薄膜至绝缘支持层的上表面，从而形成包括传感器对电极的图案4和传感器工作电极的图案3的金属电极，形状为片状、丝状、棒状或薄膜状，如图2所示。Iv. etching the metal film in the etching solution to the upper surface of the insulating support layer, thereby forming a metal electrode including the pattern 4 of the sensor counter electrode and the pattern 3 of the sensor working electrode, which is in the form of a sheet, a filament, a rod or a film. Shape, as shown in Figure 2.
2)对传感器工作电极的图案和传感器对电极的图案之间进行绝缘处理：2) Insulate between the pattern of the working electrode of the sensor and the pattern of the sensor and the electrode:
a)将光刻金属薄膜的掩膜版设计成为多个不互相连接的金属电极的形状；a) designing a mask of the lithographic metal film into a shape of a plurality of metal electrodes that are not connected to each other;
b)利用光刻-显影-刻蚀的方式将金属电极之间的区域的金属完全刻蚀掉，使不同的 金属电极之间无法互联。b) The metal in the region between the metal electrodes is completely etched by photolithography-developing-etching so that different metal electrodes are not interconnected.
3)在金属电极的表面制备出特征尺寸为纳米或者微米级的表面微结构。3) Surface microstructures having a feature size of nanometers or micrometers are prepared on the surface of the metal electrode.
4)配置普鲁士蓝的电化学沉积溶液9，添加入微型电化学反应池10中，电化学沉积对电极11、电化学沉积工作电极13和电化学沉积参比电极12插入电化学沉积溶液中，电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别通过电缆连接至电化学工作站，如图3所示。4) Configuring the electrochemical deposition solution 9 of Prussian blue, adding it to the microelectrochemical reaction cell 10, and inserting the electrochemical deposition counter electrode 11, the electrochemical deposition working electrode 13 and the electrochemical deposition reference electrode 12 into the electrochemical deposition solution, The electrochemical deposition counter electrode, the electrochemical deposition working electrode, and the electrochemical deposition reference electrode are respectively connected to the electrochemical workstation through a cable, as shown in FIG.
5)将金属电极中的传感器工作电极的图案沉浸在电化学沉积溶液，电化学沉积溶液为KCl、K
3[Fe(CN)
6]、FeCl
3和HCl的混合溶液，并将传感器工作电极的图案通过电缆连接至电化学工作站。
5) immersing the pattern of the sensor working electrode in the metal electrode in an electrochemical deposition solution, the electrochemical deposition solution is a mixed solution of KCl, K 3 [Fe(CN) 6 ], FeCl 3 and HCl, and the working electrode of the sensor The pattern is connected to the electrochemical workstation via a cable.
6)电化学工作站对传感器工作电极的图案进行电化学沉积反应，采用恒电位沉积的方式，沉积反应时间设置为10秒～15秒，在传感器工作电极的图案上形成普鲁士蓝薄膜5，传感器工作电极的图案和其上的普鲁士蓝薄膜构成传感器工作电极，传感器对电极的图案作为传感器对电极。6) Electrochemical workstation performs electrochemical deposition reaction on the pattern of the working electrode of the sensor. The deposition reaction time is set to 10 seconds to 15 seconds by means of constant potential deposition. The Prussian blue film 5 is formed on the pattern of the working electrode of the sensor. The pattern of the electrodes and the Prussian blue film thereon constitute the sensor working electrode, and the pattern of the sensor counter electrode serves as the sensor counter electrode.
7)电化学沉积反应完成后，更换微型电化学反应池内的溶液，加入稳定性扫描溶液，对传感器工作电极进行稳定性扫描，稳定性扫描使用循环伏安扫描的方式；稳定性扫描溶液为电化学沉积溶液去掉含有铁离子以及轻铁酸根离子物质的溶液。7) After the electrochemical deposition reaction is completed, the solution in the micro electrochemical reaction cell is replaced, the stability scanning solution is added, the stability of the working electrode of the sensor is scanned, and the stability scanning is performed by cyclic voltammetry; the stability scanning solution is electricity. The chemical deposition solution removes a solution containing iron ions and light ferrite ion species.
8)将传感器工作电极从微型电化学反应池中取出，利用加热装置烘干，加热装置为加热板，加热温度为170℃，加热时间为1.5小时。8) The sensor working electrode is taken out from the micro electrochemical reaction cell and dried by a heating device. The heating device is a heating plate, the heating temperature is 170 ° C, and the heating time is 1.5 hours.
9)将烘干后的传感器工作电极在微型电化学反应池内做活化处理，活化处理采用恒电位的方式，电位为-0.1V相对于电化学沉积参比电极，活化时间为1小时。9) The dried working electrode of the sensor is activated in a micro-electrochemical reaction cell, and the activation treatment is performed by a constant potential method, the potential is -0.1 V, and the activation time is 1 hour with respect to the electrochemical deposition reference electrode.
10)将活化后的传感器工作电极用去离子水清洗干净，得到具有纳米级普鲁士蓝薄膜的传感器工作电极。10) The activated sensor working electrode is cleaned with deionized water to obtain a sensor working electrode with a nano-scale Prussian blue film.
最后需要注意的是，公布实施例的目的在于帮助进一步理解本发明，但是本领域的技术人员可以理解：在不脱离本发明及所附的权利要求的精神和范围内，各种替换和修改都是可能的。因此，本发明不应局限于实施例所公开的内容，本发明要求保护的范围以权利要求书界定的范围为准。It is to be understood that the present invention is intended to be a further understanding of the invention, and it is understood by those skilled in the art that various modifications and changes can be made without departing from the spirit and scope of the invention and the appended claims It is possible. Therefore, the invention should not be limited by the scope of the invention, and the scope of the invention is defined by the scope of the claims.
Claims (7)
- 一种纳米级普鲁士蓝薄膜的选择性电化学沉积方法，其特征在于，所述选择性电化学沉积方法，包括以下步骤：A selective electrochemical deposition method for a nano-scale Prussian blue film, characterized in that the selective electrochemical deposition method comprises the following steps:1)制备金属电极，金属电极包括传感器工作电极的图案和传感器对电极的图案；1) preparing a metal electrode comprising a pattern of a sensor working electrode and a pattern of a sensor counter electrode;2)将传感器工作电极的图案和传感器对电极的图案之间进行绝缘处理；2) insulating the pattern between the sensor working electrode and the pattern of the sensor counter electrode;3)在金属电极的表面制备出特征尺寸为纳米或者微米级的表面微结构；3) preparing a surface microstructure having a feature size of nanometer or micrometer on the surface of the metal electrode;4)配置普鲁士蓝的电化学沉积溶液，添加入微型电化学反应池中，电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别插入电化学沉积溶液中，电化学沉积对电极、电化学沉积工作电极和电化学沉积参比电极分别通过电缆连接至电化学工作站；4) Disposing the electrochemical deposition solution of Prussian blue into the micro-electrochemical reaction cell, and inserting the electrochemical deposition counter electrode, the electrochemical deposition working electrode and the electrochemical deposition reference electrode into the electrochemical deposition solution, respectively, and electrochemical deposition The electrode, the electrochemical deposition working electrode and the electrochemical deposition reference electrode are respectively connected to the electrochemical workstation through a cable;5)将金属电极中的传感器工作电极的图案沉浸在电化学沉积溶液中，并将传感器工作电极的图案连接至电化学沉积工作电极；5) immersing the pattern of the sensor working electrode in the metal electrode in the electrochemical deposition solution, and connecting the pattern of the sensor working electrode to the electrochemical deposition working electrode;6)电化学工作站对传感器工作电极的图案进行电化学沉积反应，在传感器工作电极的图案上形成普鲁士蓝薄膜，传感器工作电极的图案及其上的普鲁士蓝薄膜构成传感器工作电极，传感器对电极的图案作为传感器对电极；6) The electrochemical workstation performs electrochemical deposition reaction on the pattern of the working electrode of the sensor, and forms a Prussian blue film on the pattern of the working electrode of the sensor. The pattern of the working electrode of the sensor and the Prussian blue film on the sensor constitute the working electrode of the sensor, and the electrode of the sensor The pattern acts as a sensor counter electrode;7)电化学沉积反应完成后，更换微型电化学反应池内的溶液，加入稳定性扫描溶液，对传感器工作电极进行稳定性扫描；7) after the electrochemical deposition reaction is completed, the solution in the micro electrochemical reaction cell is replaced, and the stability scanning solution is added to perform stability scanning on the working electrode of the sensor;8)将传感器工作电极从微型电化学反应池中取出，利用加热装置烘干；8) taking the sensor working electrode from the micro electrochemical reaction cell and drying it with a heating device;9)更换微型电化学反应池内的溶液，加入用于活化的溶液，将烘干后的传感器工作电极在微型电化学反应池内做活化处理；9) replacing the solution in the micro electrochemical reaction cell, adding a solution for activation, and performing activation treatment on the dried working electrode of the sensor in the micro electrochemical reaction cell;10)将活化后的传感器工作电极清洗干净，得到具有纳米级普鲁士蓝薄膜的传感器工作电极。10) The activated sensor working electrode is cleaned to obtain a sensor working electrode with a nano-scale Prussian blue film.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤2)中，对传感器工作电极的图案和传感器对电极的图案之间进行绝缘处理，包括以下步骤：The selective electrochemical deposition method according to claim 1, wherein in step 2), insulating the pattern between the pattern of the sensor working electrode and the pattern of the sensor counter electrode comprises the steps of:a)将光刻金属薄膜的掩膜版设计成为多个不互相连接的金属电极的形状；a) designing a mask of the lithographic metal film into a shape of a plurality of metal electrodes that are not connected to each other;b)利用光刻-显影-刻蚀的方式将金属电极之间的区域的金属完全刻蚀掉，使不同的金属电极之间无法互联。b) The metal in the region between the metal electrodes is completely etched by photolithography-developing-etching so that different metal electrodes are not interconnected.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤3)中，将金属电极浸入金属的刻蚀液，在一定时间后取出并洗净表面，浸入刻蚀液的时间为5秒～8秒；或者，通过用粗糙的表面摩擦金属电极，通过在金属电极的表面添加金属纳米颗粒，或者通过激光扫描金属电极的表面的方式在金属电极的表面形成表面微结构。The selective electrochemical deposition method according to claim 1, wherein in step 3), the metal electrode is immersed in the etching solution of the metal, and after a certain time, the surface is taken out and washed, and the time of immersing in the etching liquid is performed. It is 5 seconds to 8 seconds; alternatively, a surface microstructure is formed on the surface of the metal electrode by rubbing the metal electrode with a rough surface, by adding metal nanoparticles on the surface of the metal electrode, or by scanning the surface of the metal electrode by laser.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤6)中，化学沉积反应采用恒电位沉积的方式；或者采用循环伏安扫描沉积的方式；沉积反应时间设置为5秒～25秒。The selective electrochemical deposition method according to claim 1, wherein in the step 6), the chemical deposition reaction is performed by a potentiostatic deposition method; or the cyclic voltammetric scanning deposition method is employed; and the deposition reaction time is set to 5 Seconds to 25 seconds.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤7)中，稳定性扫描使用循环伏安扫描的方式；稳定性扫描溶液为电化学沉积溶液去掉含有铁离子以及氰铁酸根离子物质的溶液。The selective electrochemical deposition method according to claim 1, wherein in the step 7), the stability scan uses a cyclic voltammetric scan; the stable scan solution removes the iron ion and the cyanide from the electrochemical deposition solution. A solution of ferrite ionic species.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤8)中，加热装置为加热板，加热温度为120～200℃，加热时间为大于1小时。The selective electrochemical deposition method according to claim 1, wherein in the step 8), the heating means is a heating plate, the heating temperature is 120 to 200 ° C, and the heating time is more than 1 hour.
- 如权利要求1所述的选择性电化学沉积方法，其特征在于，在步骤9)中，活化处理采用恒电位的方式，电位为-1V～1V；活化时间大于0.5小时。The selective electrochemical deposition method according to claim 1, wherein in the step 9), the activation treatment is performed by a constant potential, the potential is -1 V to 1 V; and the activation time is greater than 0.5 hours.
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