CN114624301B - Enzyme-free glucose sensor electrode, preparation method thereof and detection device - Google Patents

Enzyme-free glucose sensor electrode, preparation method thereof and detection device Download PDF

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CN114624301B
CN114624301B CN202210250630.9A CN202210250630A CN114624301B CN 114624301 B CN114624301 B CN 114624301B CN 202210250630 A CN202210250630 A CN 202210250630A CN 114624301 B CN114624301 B CN 114624301B
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transition layer
diamond
carbon film
gradient
metal
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CN114624301A (en
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林松盛
王桓
苏一凡
石倩
郭朝乾
韦春贝
唐鹏
代明江
黄淑琪
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Institute of New Materials of Guangdong Academy of Sciences
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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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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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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    • 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
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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    • 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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
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    • 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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles

Abstract

The application discloses an enzyme-free glucose sensor electrode, a preparation method thereof and a detection device, and belongs to the technical field of bioelectrode sensors. The enzyme-free glucose sensor electrode comprises a sensor substrate and a diamond-like carbon film deposited on the surface of the substrate; the diamond-like carbon film is doped with metal; the doping amount of the metal in the diamond-like carbon film is 10-30at%. The method innovatively takes the diamond-like carbon film as the electrode coating of the enzyme-free glucose sensor, has the characteristics of wide potential window, low background current, good biocompatibility and high cycle performance, and is further doped with specific metals on the basis, so that the conductivity of the electrode and the catalytic activity to glucose are effectively improved. The corresponding preparation method is simple and rapid, has high efficiency, and the obtained electrode has the advantages of high sensitivity, low detection lower limit, quick response time and good anti-interference performance on glucose, and has great application potential.

Description

Enzyme-free glucose sensor electrode, preparation method thereof and detection device
Technical Field
The application relates to the technical field of bioelectrode sensors, in particular to an enzyme-free glucose sensor electrode, a preparation method thereof and a detection device.
Background
Diabetes has become a common chronic disease in recent decades, almost 17.1 million people worldwide are suffering from diabetes, and the number of people suffering from diabetes is increasing year by year. Up to now, no thorough treatment of diabetes has been found, and diabetics can only control by monitoring their own blood glucose concentration in real time.
Conventional glucose sensors are based on the electrochemical reaction of glucose molecules with immobilized glucose oxidase on an electrode, glucose being oxidized to glucose lactone: however, oxidase has the disadvantages of easy inactivation, difficult fixation, large influence of temperature and pH value, etc., so that in-situ monitoring of blood glucose concentration and manufacturing of implant equipment cannot be performed.
In view of this, the present application has been made.
Disclosure of Invention
An object of the present application is to provide an electrode for an enzyme-free glucose sensor, which solves the above-mentioned problems.
The second object of the present application is to provide a method for producing the electrode of the enzyme-free glucose sensor.
A third object of the present application is to provide a glucose sensor comprising the enzyme-free glucose sensor electrode.
The application can be realized as follows:
in a first aspect, the present application provides an enzyme-free glucose sensor electrode comprising a sensor substrate and a diamond-like carbon film deposited on the surface of the substrate; the diamond-like carbon film is doped with metal;
the doping amount of the metal in the diamond-like carbon film is 10-30at%.
In an alternative embodiment, the doped metal includes at least one of Ag, ni, and Cu.
In an alternative embodiment, the diamond-like carbon film has a thickness of 200-1000nm.
In an alternative embodiment, a mixed transition layer is arranged between the sensor matrix and the diamond-like carbon film, the mixed transition layer comprises a gradient transition layer deposited on the surface of the sensor matrix and a compound transition layer deposited on the surface of the gradient transition layer, and the diamond-like carbon film doped with metal is deposited on the surface of the compound transition layer;
the gradient transition layer is a metal layer formed by at least one metal element of Ti, cr and Zr, and the content of metal in the gradient transition layer is reduced in a gradient manner from one side close to the sensor matrix to one side close to the compound transition layer;
the compound transition layer is a metal carbide layer, and the carbon content in the compound transition layer is increased in a gradient manner from one side close to the gradient transition layer to one side far from the gradient transition layer.
In an alternative embodiment, the gradient transition layer has a thickness of 50-200nm and the compound transition layer has a thickness of 50-150nm.
In a second aspect, the present application provides a method for preparing an enzyme-free glucose sensor electrode according to any one of the preceding embodiments, comprising the steps of: and depositing a diamond-like carbon film on the surface of the sensor matrix by adopting a magnetron sputtering mode.
In an alternative embodiment, a mixed transition layer for improving the bonding force between the sensor substrate and the diamond-like carbon film is prepared between the sensor substrate and the diamond-like carbon film by adopting a magnetron sputtering mode.
In an alternative embodiment, in the preparation process of the diamond-like carbon film, the target material is disposed in a manner that includes: the graphite carbon target is inlaid with metal or the graphite carbon single-substance target and the metal single-substance target are opened simultaneously.
In an alternative embodiment, the diamond-like carbon film is produced at a temperature of 50-250 ℃.
In an alternative embodiment, the conditions for preparing the diamond-like carbon film further include: the power of the magnetron sputtering is 15-30kW, the vacuum degree is kept at 0.3-1.0Pa, the bias voltage is-50V to-150V, and the deposition time is 60-180min.
In an alternative embodiment, the mixed transition layer is prepared by starting a metal target material under different bias to prepare a gradient transition layer, and then starting the metal target and a high-purity carbon target to prepare a compound transition layer simultaneously.
In an alternative embodiment, the preparation of the hybrid transition layer comprises: setting 1-5 equal gradient difference biases in the range of-100V to-800V under the condition that the argon flow is 100-200sccm, and respectively depositing for 1-4min under each equal gradient difference bias to obtain a gradient transition layer;
and then setting 1-5 equal gradient difference biases within the range of-50V to-200V, and respectively depositing for 1-4min under each equal gradient difference bias to obtain the compound transition layer.
In a third aspect, the present application provides a glucose sensor comprising the enzyme-free glucose sensor electrode according to any one of the preceding embodiments.
The beneficial effects of the application include:
by depositing the diamond-like carbon film on the surface of the matrix, the sensor electrode has the characteristics of wide potential window, low background current, good biocompatibility and high cycle performance, avoids the problems of easy inactivation, difficult fixation and large influence by temperature and pH value, and can be used for in-situ monitoring of blood glucose concentration and implant equipment. By doping metal in the diamond-like carbon film, the conductivity of the electrode and the catalytic activity to glucose can be effectively improved.
The magnetron sputtering method provided by the application can effectively improve the binding force of metal particles while improving the preparation efficiency, and is simple and efficient in preparation. The enzyme-free glucose sensor electrode is used for preparing a glucose detection device, so that the corresponding device hasHas good biocompatibility, circularity and high catalytic activity, and also has high sensitivity (such as 796 mu AmM) -1 cm -2 ) The detection limit is wide (for example, the detection lower limit is 0.5 mu M), the response time is short (for example, 5 s), the anti-interference performance is good, and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the structure of an electrode of an enzyme-free glucose sensor provided by the application;
FIG. 2 is a graph showing the current response of the Ni-DLC film electrode of example 1 to glucose solutions of different concentrations;
FIG. 3 is a graph showing the response time of the Ni-DLC film electrode to glucose in example 1;
FIG. 4 is a graph showing the anti-interference result of the Ni-DLC film electrode in example 1;
FIG. 5 is a graph showing the surface morphology of the glucose sensor electrode of comparative example 3 and that of example 1, and a graph showing the effect of catalyzing glucose.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The enzyme-free glucose sensor electrode provided by the application and the preparation method and application thereof are specifically described below.
Based on the existing glucose sensor, which is usually an enzyme-containing sensor, and has the defects of easy inactivation, difficult fixation and large influence of temperature and pH value, the problems that the in-situ monitoring of blood glucose concentration and the manufacturing of implant equipment cannot be carried out, the inventor creatively proposes an electrode of the enzyme-free glucose sensor, and the problems can be effectively overcome.
The application provides an enzyme-free glucose sensor electrode (shown in figure 1), which comprises a sensor matrix and a diamond-like carbon film deposited on the surface of the matrix.
The substrate may be, for example, a T i substrate, but also other commonly used sensor substrates.
By depositing the diamond-like carbon film on the surface of the matrix, the sensor electrode has the characteristics of wide potential window, low background current, good biocompatibility and high cycle performance, avoids the problems of easy inactivation, difficult fixation and large influence by temperature and pH value, and can be used for in-situ monitoring of blood glucose concentration and implant equipment.
Further, the diamond-like carbon film is doped with a metal.
For reference, the doped metal may illustratively include at least one of Ag, ni, and Cu. The doping amount of the metal in the diamond-like carbon film is 10 to 30at%, such as 10at%, 12at%, 15at%, 18at%, 20at%, 22at%, 25at%, 28at% or 30at%, etc., and may be any other value within the range of 10 to 30at%.
By doping specific metals in the diamond-like carbon film, the conductivity of the electrode and the catalytic activity to glucose can be effectively improved. However, no strong carbon compound is formed between the doped metal and carbon.
The thickness of the diamond-like carbon film deposited on the surface of the substrate in the present application may be 200 to 1000nm, such as 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and may be any other value within the range of 200 to 1000nm.
If the thickness of the diamond-like carbon film is larger than 1000nm, the excessive internal stress of the carbon film is easy to cause, the bonding strength is reduced, and meanwhile, the conductivity of the carbon film is reduced, so that the conductivity of the electrode is influenced; if the particle diameter is less than 200nm, the carbon film is easy to fail too fast, and the service life of the electrode is insufficient.
The electrode with the characteristics has the advantages of high sensitivity, low detection lower limit, quick response time and good anti-interference performance for glucose.
Further, a mixed transition layer is further arranged between the sensor matrix and the diamond-like carbon film, the mixed transition layer comprises a gradient transition layer deposited on the surface of the sensor matrix and a compound transition layer deposited on the surface of the gradient transition layer, and the metal-doped diamond-like carbon film is deposited on the surface of the compound transition layer.
The gradient transition layer is a metal layer formed by at least one metal element of Ti, cr and Zr, and the content of metal in the gradient transition layer is reduced in a gradient manner from one side close to the sensor matrix to one side close to the compound transition layer.
The compound transition layer is a metal carbide layer, and the carbon content in the compound transition layer is increased in a gradient manner from one side close to the gradient transition layer to one side far from the gradient transition layer.
The transition from the graded transition layer to the metal carbide layer is essentially a transition between a metal rich layer to a carbon rich layer. The metal element in the gradient transition layer can form a strong carbon compound with carbon, so that the conductivity of the diamond-like carbon film is improved. The carbon-rich layer may further improve the conductivity.
By arranging the mixed transition layer, the contact resistance of the coating and the matrix is effectively reduced, the good conductivity of the electrode is ensured, and the effect of improving the combination force of the diamond-like carbon film and the matrix is also achieved.
In some alternative embodiments, the thickness of the gradient transition layer may be 50-200nm, such as 50nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, or the like, and may be any other value in the range of 50-200 nm.
The thickness of the compound transition layer may be 50-150nm, such as 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm, etc., or any other value within the range of 50-150nm.
By controlling the respective thicknesses of the gradient transition layer and the compound transition layer in the above-described ranges, the effects of reducing the contact resistance of the coating layer and the substrate and improving the binding force of the diamond-like carbon film and the substrate can be simultaneously satisfied.
It should be noted that even though the total thickness of the mixed transition layer is in the range of 100-350nm, the gradient transition layer has a thickness of less than 50nm, and the compound transition layer has a thickness of more than 150nm; or the thickness of the gradient transition layer is larger than 200nm, and the thickness of the compound transition layer is smaller than 50nm, namely the thickness difference between the gradient transition layer and the compound transition layer is larger, so that the growth stress between the two transition layers is suddenly changed easily, the gradient change of the stress cannot be formed, and the bonding strength between the matrix and the diamond-like carbon film is reduced.
Correspondingly, the application also provides a preparation method of the electrode of the enzyme-free glucose sensor, which comprises the following steps: and depositing a diamond-like carbon film on the surface of the sensor matrix by adopting a magnetron sputtering mode.
Further, the method also comprises the step of preparing a mixed transition layer for improving the binding force of the sensor matrix and the diamond-like carbon film between the sensor matrix and the diamond-like carbon film by adopting a magnetron sputtering mode.
It is worth noting that the conventional glucose sensor in the prior art is prepared by a two-step method, namely, depositing a film and then electrochemically modifying metal particles. However, the above method has problems of low preparation efficiency and poor binding force of metal particles. The magnetron sputtering mode provided by the application can effectively improve the binding force of metal particles while improving the preparation efficiency.
In an alternative embodiment, in the preparation process of the diamond-like carbon film, the target material is disposed in a manner that includes: the graphite carbon target is inlaid with metal or the graphite carbon single-substance target and the metal single-substance target are opened simultaneously.
By adopting the target setting mode, the diamond-like carbon film uniformly doped with metal can be prepared. And the magnetron sputtering deposition can be used for carrying out metal doping by a one-step method, so that the preparation time is greatly saved, and the binding force of metal particles is greatly improved.
The diamond-like carbon film may be prepared at a temperature of 50 to 250 ℃, such as 50 ℃, 100 ℃, 150 ℃, 200 ℃, or 250 ℃, or the like, or any other value within the range of 50 to 250 ℃.
The conditions for preparing the diamond-like carbon film also comprise: the power of the magnetron sputtering is 15-30kW, the vacuum degree is kept at 0.3-1.0Pa, the bias voltage is-50V to-150V, and the deposition time is 60-180min.
The power may be 15kW, 15.5kW, 17kW, 17.5kW, 19kW, 19.5kW, 21kW, 21.5kW, 23kW, 23.5kW, 25kW, 25.5kW or 30kW, etc., and may be any other value within the range of 15 to 30 kW.
The vacuum degree may be 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, or 1Pa, or any other value within the range of 0.3 to 1.0 Pa.
The bias voltage may be-50V, -60V, -70V, -80V, -90V, -100V, -110V, -120V, -130V, -140V, or-150V, etc., or any other value in the range of-50 to-150V.
The deposition time may be 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, etc., or any other value within the range of 60-180min.
The substrate bias voltage has great influence on the structure and performance of the diamond-like carbon film and can obviously influence sp in the carbon film 2 Bond and sp 3 Proportion of bonds. If the substrate bias is lower than-50V, sp in the carbon film is liable to be caused 2 The bond content is too low, and the resistance of the carbon film is too high, so that the electrode performance is affected; if the matrix bias voltage is higher than-150V, the phenomenon of self-sputtering is easy to cause serious and the internal stress is too high, and the binding force of the carbon film is seriously insufficient.
In the application, the mixed transition layer is prepared by adopting a mode of firstly starting a metal target material to prepare the gradient transition layer under different bias voltages and then simultaneously starting the metal target and a high-purity carbon target to prepare the compound transition layer.
For reference, the preparation of the hybrid transition layer may include: setting 1-5 equal gradient difference biases in the range of-100V to-800V under the condition that the argon flow is 100-200sccm, and respectively depositing for 1-4min under each equal gradient difference bias to obtain a gradient transition layer;
and then setting 1-5 equal gradient difference biases within the range of-50V to-200V, and respectively depositing for 1-4min under each equal gradient difference bias to obtain the compound transition layer.
The argon flow may be 100sccm, 110sccm, 120sccm, 130sccm, 140sccm, 150sccm, 160sccm, 170sccm, 180sccm, 190sccm, 200sccm, or any other value within the range of 100 to 200 sccm.
Any equal gradient difference bias voltage can be set in the range of-100V to-800V in the process of preparing the gradient transition layer, and the equal gradient difference bias voltage can be specifically 1, 2, 3, 4 or 5. As an illustration, in certain embodiments, the arrangement may be at a gradient of-100V to-450V and-450V to-800V; in certain embodiments, the arrangement may be at a gradient of-100V to-300V, -300V to-500V, and-500V to-800V; in some embodiments, the arrangement may be at a gradient of-100V to-275V, -275V to-450V, -450V to-625V, and-625V to-800V; in some embodiments, the arrangement may be in a gradient of-100V to-240V, -240V to-380V, -380V to-520V, -520V to-660V, and-660V to-800V. In other embodiments, 1-5 isophase differential biases may be provided in any bias voltage range from-100V to-800V, such as a gradient in the range from-200V to-800V or-100V to-600V or-500V to-800V.
The deposition time corresponding to each gradient can be 1min, 1.5min, 2min, 2.5min, 3min, 3.5min or 4min, etc., or can be any other value within the range of 1-4 min.
Accordingly, 1, 2, 3, 4, or 5 isophase differential biases can be provided in the range of-50V to-200V during the preparation of the compound transition layer. As an illustration, in certain embodiments, the arrangement may be at a gradient of-50V to-125V and-125V to-200V; in certain embodiments, the arrangement may be at a gradient of-50V to-100V, -100V to-150V, and-150V to-200V; in certain embodiments, the arrangement may be at a gradient of-50V to-87.5V, -87.5V to-125V, -125V to-162.5V, and-162.5V to-200V; in certain embodiments, the arrangement may be in a gradient of-50V to-80V, -80V to-110V, -110V to-140V, -140V to-170V, and-170V to-200V. In other embodiments, 1-5 isophase differential biases may be provided in any bias voltage range from-50V to-200V, such as a gradient in the range from-100V to-200V or-100V to-150V or-50V to-150V.
The deposition time corresponding to each gradient may be 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, or 4min, or may be any other value within the range of 1-4min, respectively.
Further, ultrasonic cleaning of the substrate and ion etching of the substrate and the planet carrier are included before depositing the gradient transition layer.
For reference, ultrasonic cleaning comprises sequentially cleaning matrix in cleaning solution, deionized water, and ethanol for 15-20min, oven drying, placing in a chamber with a fixture, and vacuumizing to 1.0X10 -3 Pa to 5.0X10 -3 Pa。
The ion etching of the substrate and the planet carrier can be performed by glow discharge, wherein in the ion etching process, the argon flow can be set to 100-200sccm, the bias voltage can be set to-700V to-900V, and the cleaning time can be set to 20-30min.
On the other hand, the method has simple and efficient preparation, and can prepare the glucose-sensitive material with high sensitivity (such as 796 mu AmM) - 1 cm -2 ) Low detection limit (e.g., 0.5 μm), fast response time (e.g., 5 s), and good immunity to interference.
In addition, the application also provides a glucose detection device containing the enzyme-free glucose sensor electrode, which is used for detecting the content of glucose (blood sugar), and has the advantages of good biocompatibility, cyclicity, higher catalytic activity, high sensitivity, wide detection limit, short response time, good anti-interference performance and the like.
It should be noted that the above detection does not relate to disease treatment or diagnosis.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The present example provides an enzyme-free glucose sensor electrode prepared by:
(1) Placing Ti matrix into cleaning solution, deionized water and ethanol, sequentially cleaning for 15min, oven drying, placing into a chamber with a fixture, and vacuumizing to 5.0X10 s -3 Pa (i.e. 5.0X10) -3 Pa, the smaller the number, the better the vacuum, the same as below).
(2) And (3) carrying out ion etching treatment on the substrate and the planet carrier by glow discharge, wherein in the ion etching process, the argon flow is 100sccm, the bias voltage is 700V, and the cleaning time is 30min.
(3) After the ion etching is finished, starting Cr targets under the bias voltages of-800V, -500V and-200V respectively, and preparing gradient transition layers (Cr layers) by performing magnetron sputtering on each gradient and depositing for 1 min.
(4) After the gradient Cr transition layer was prepared, the Cr target and the C target were simultaneously turned on under bias voltages of-200V, -150V and-100V, respectively, and each gradient was deposited for 1min, to prepare a compound transition layer (CrC layer).
(5) After the compound CrC transition layer is prepared, closing the Cr target, opening the C-Ni embedded target, and preparing the Ni metal doped diamond-like carbon (Ni-DLC) film by magnetron sputtering, wherein the technological parameters are as follows: the bias voltage was-50V, the vacuum degree was 0.4Pa, the target power was 15kW, the deposition time was 60 minutes, and the deposition temperature was 50 ℃.
In the Ni-DLC film electrode prepared as described above, the gradient transition layer (Cr layer) had a thickness of 50nm, the compound transition layer (CrC layer) had a thickness of 50nm, the total thickness of the mixed transition layer was 100nm, the Ni-DLC film had a thickness of 200nm, and the Ni metal doping amount was 10at%.
The current response results of the Ni-DLC film electrode to glucose solutions of different concentrations (1 mM to 5 mM) are shown in FIG. 2, the response time results to glucose are shown in FIG. 3, and the anti-interference results are shown in FIG. 4.
Specific conditions for the above measurement test are as follows: the performance of the Ni-DLC film electrode was measured by an Autolab three electrode electrochemical workstation. A reference potential of saturated glycerolMercury electrode (SCE), counter electrode is platinum sheet electrode, working electrode is Ni-DLC film electrode, working area of electrode is 1cm 2 . The solution reagents involved are mixed solutions of glucose solutions (1-5 mM) with 0.5mol/L NaOH solution, uric acid and ascorbic acid solutions of different concentrations.
The test steps are as follows:
(1) The Ni-DLC film electrode is packaged into an enzyme-free glucose sensing device through conductive silver paste and K-704 glue, and the structure is shown in figure 1.
(2) The sensor device is placed in a mixed solution of glucose solution and NaOH solution, and the current response of the Ni-DLC film electrode to glucose solutions with different concentrations (1 mM to 5 mM) is measured by adopting a cyclic voltammetry method, as shown in FIG. 2; the sensor is placed in a mixed solution of glucose solution, naOH solution, uric acid solution and ascorbic acid solution, and the anti-interference performance of the Ni-DLC film electrode is measured by adopting a chronoamperometry method, as shown in figure 4.
From fig. 2 to 4, it can be derived that: the sensitivity of the Ni-DLC film electrode to glucose is 796 mu AmM -1 cm -2 The detection lower limit is 0.5 mu M, the response time is 5s, and the anti-interference performance is good.
Example 2
The present example provides an enzyme-free glucose sensor electrode prepared by:
(1) Placing pure Ti matrix into cleaning solution, deionized water and ethanol, sequentially cleaning for 20min, oven drying, placing into a chamber with a fixture, and vacuumizing to 5.0X10 s -3 Pa。
(2) And (3) carrying out ion etching treatment on the substrate and the planet carrier by glow discharge, wherein in the ion etching process, the argon flow is 150sccm, the bias voltage is-800V, and the cleaning time is 25min.
(3) After the ion etching is finished, starting Ti targets under the bias voltages of-800V, -600V, -400V and-200V respectively, and preparing gradient transition layers (Ti layers) by magnetron sputtering for 4min each deposition of each gradient.
(4) After the gradient Ti transition layer is prepared, the Ti target and the C target are simultaneously started under the bias voltage of-200V, -125V and-50V respectively, and each gradient is deposited for 4min to prepare the compound transition layer (TiC layer).
(5) After the preparation of the compound TiC transition layer, closing the Ti target, simultaneously opening the C and Cu simple substance targets, and preparing the Cu metal doped diamond-like carbon (Cu-DLC) film by magnetron sputtering, wherein the technological parameters are as follows: the substrate bias voltage is-100V, the vacuum degree is 0.6Pa, the target power is 23kW, the deposition time is 120min, and the deposition temperature is 150 ℃.
In the Cu-DLC film electrode prepared as described above, the thickness of the gradient transition layer (Ti layer) was 100nm, the thickness of the mixed transition layer (TiC layer) was 100nm, the total thickness of the mixed transition layer was 200nm, the thickness of the Cu-DLC film was 500nm, and the Cu metal doping amount was 20at%.
The Cu-DLC film electrode obtained in this example was examined in the same manner as in example 1, and the results showed that: the sensitivity of the Cu-DLC film electrode to glucose is 648 mu AmM -1 cm -2 The detection lower limit is 0.8 mu M, the response time is 7s, and the anti-interference performance is good.
Example 3
The present example provides an enzyme-free glucose sensor electrode prepared by:
(1) Placing high-purity Ti matrix into cleaning solution, deionized water and ethanol, sequentially cleaning for 20min, oven drying, placing into a chamber with a fixture, and vacuumizing to 5.0X10 s -3 Pa。
(2) And (3) carrying out ion etching treatment on the substrate and the planet carrier by glow discharge, wherein in the ion etching process, the argon flow is 200sccm, the bias voltage is 900V, and the cleaning time is 20min.
(3) After the ion etching is finished, starting a Zr target under the bias voltages of-800V, -625V, -450V, -275V and-100V respectively, and preparing a gradient transition layer (Zr layer) by magnetron sputtering each gradient and depositing for 3 min.
(4) After the preparation of the gradient Zr transition layer, the Zr target and the C target were simultaneously turned on under the bias voltages of-200V, -175V, -150V, -125V, -100V, respectively, and each gradient was deposited for 3min, to prepare a compound transition layer (ZrC layer).
(5) After the compound transition layer is prepared, closing the Zr target, and starting the magnetron sputtering C-Ag embedded target to prepare the Ag metal doped diamond-like carbon (Ag-DLC) film, wherein the technological parameters are as follows: the bias voltage was-150V, the vacuum degree was 1.0Pa, the target power was 30kW, the deposition time was 180min, and the deposition temperature was 250 ℃.
The thickness of the gradient transition layer (Zr layer) of the prepared Ag-DLC film electrode is 200nm, the thickness of the compound transition layer (ZrC layer) is 150nm, the total thickness of the mixed transition layer is 350nm, the thickness of the Ag-DLC film is 1000nm, and the doping amount of Ag metal is 30at%.
The Cu-DLC film electrode obtained in this example was examined in the same manner as in example 1, and the results showed that: the sensitivity of the Ag-DLC film electrode to glucose is 712 mu AmM -1 cm -2 The detection lower limit is 0.6 mu M, the response time is 6s, and the anti-interference performance is good.
Comparative example 1
Comparative example 1 is similar to example 1, except that: comparative example 1 without active metal atom doping, the prepared diamond-like carbon film had poor catalytic effect on glucose, and the electrode had sensitivity to glucose of 0.574. Mu. AmM -1 cm -2 The lower limit of detection was 1.37mM and the response time was 10s. The overall performance of the electrode is significantly lower than that of examples 1-3.
Comparative example 2
Comparative example 2 is similar to example 1, except that: comparative example 2 did not employ a mixed transition layer, and only employed a metal transition layer, and the results showed that: the coating is poorly bonded, and the diamond-like carbon film is fallen off, so that the subsequent detection is not performed.
Comparative example 3
Comparative example 3 is similar to example 1, except that: comparative example 3 is a glucose sensor electrode prepared by a two-step process, where a diamond-like carbon film is deposited first and then modified by electrochemical deposition of metal particles.
In FIG. 5 (a) 1 ) Example 1 surface topography after Metal doping of glucose sensor electrode, (a) 2 ) The surface topography of the electrode of the glucose sensor prepared in the two-step method in comparative example 3 was shown.
From FIG. 5 (a 1 ) And (a) 2 ) It can be seen that: sensor electrode surface Metal particle distribution of example 1More uniform and dense means more active reaction sites.
In FIG. 5 (b) 1 ) FIG. 1 shows the effect of the glucose sensor electrode on glucose catalysis, (b) 2 ) The effect of the glucose sensor electrode on glucose catalysis is shown in comparative example 3.
From FIG. 5 (b 1 ) And (b) 2 ) It can be seen that: the sensor electrode in example 1 exhibited a more pronounced redox peak position and the catalytic effect on glucose was far superior to that of the electrode in comparative example 3.
In summary, the novel enzyme-free glucose sensor electrode provided by the application adopts the embedded target or the simple substance target, and the metal doped diamond-like carbon film is prepared by a magnetron sputtering one-step method, so that the preparation time is greatly saved, the metal particles exist in the diamond-like carbon film in a doped form, the binding force of active particles is greatly improved, and the prepared metal doped diamond-like carbon film electrode has high sensitivity, wide detection limit, short response time and good anti-interference performance on glucose detection.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (9)

1. An enzyme-free glucose sensor electrode is characterized by comprising a sensor matrix and a diamond-like carbon film deposited on the surface of the sensor matrix; the diamond-like carbon film is doped with metal;
the doping amount of the metal in the diamond-like carbon film is 10-30at%;
the doped metal comprises at least one of Ag, ni and Cu;
a mixed transition layer is arranged between the sensor matrix and the diamond-like carbon film, the mixed transition layer comprises a gradient transition layer deposited on the surface of the sensor matrix and a compound transition layer deposited on the surface of the gradient transition layer, and the metal-doped diamond-like carbon film is deposited on the surface of the compound transition layer;
the gradient transition layer is a metal layer formed by at least one metal element of Ti, cr and Zr; in the gradient transition layer, the content of metal is gradually reduced from one side close to the sensor matrix to one side close to the compound transition layer;
the compound transition layer is a metal carbide layer; in the compound transition layer, the carbon content is increased in a gradient from the side close to the gradient transition layer to the side far from the gradient transition layer.
2. The enzyme-free glucose sensor electrode according to claim 1, wherein the diamond-like carbon film has a thickness of 200-1000nm, the gradient transition layer has a thickness of 50-200nm, and the compound transition layer has a thickness of 50-150nm.
3. The method for preparing an electrode for an enzyme-free glucose sensor according to claim 1 or 2, comprising the steps of: depositing the diamond-like carbon film on the surface of the sensor matrix by adopting a magnetron sputtering mode;
and preparing a mixed transition layer between the sensor matrix and the diamond-like carbon film by adopting a magnetron sputtering mode, wherein the mixed transition layer is used for improving the binding force between the sensor matrix and the diamond-like carbon film.
4. The method according to claim 3, wherein in the preparation of the diamond-like carbon film, the target is disposed in a manner comprising: the graphite carbon target is inlaid with metal or the graphite carbon single-substance target and the metal single-substance target are opened simultaneously.
5. The method according to claim 3, wherein the diamond-like carbon film is produced at a temperature of 50 to 250 ℃.
6. The method of producing a diamond-like carbon film according to claim 3, wherein the conditions for producing the diamond-like carbon film further comprise: the power of the magnetron sputtering is 15-30kW, the vacuum degree is kept at 0.3-1.0Pa, the bias voltage is-50V to-150V, and the deposition time is 60-180min.
7. The method according to claim 3, wherein the mixed transition layer is prepared by starting a metal target material under different bias to prepare a gradient transition layer and then starting a metal target and a high-purity carbon target to prepare a compound transition layer simultaneously.
8. The method of preparing according to claim 7, wherein the preparing of the mixed transition layer comprises: setting 1-5 equal gradient difference biases in the range of-100V to-800V under the condition that the argon flow is 100-200sccm, and respectively depositing for 1-4min under each equal gradient difference bias to obtain the gradient transition layer;
and then setting 1-5 equal gradient difference biases within the range of-50V to-200V, and respectively depositing for 1-4min under each equal gradient difference bias to obtain the compound transition layer.
9. A glucose sensor comprising the enzyme-free glucose sensor electrode according to claim 1 or 2.
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