CN113804734A - Diamond particle doped sensor and preparation method and application thereof - Google Patents
Diamond particle doped sensor and preparation method and application thereof Download PDFInfo
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- CN113804734A CN113804734A CN202111078508.XA CN202111078508A CN113804734A CN 113804734 A CN113804734 A CN 113804734A CN 202111078508 A CN202111078508 A CN 202111078508A CN 113804734 A CN113804734 A CN 113804734A
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- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
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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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- C30B28/00—Production of homogeneous polycrystalline material with defined structure
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Abstract
The invention discloses a doped diamond particle sensor and a preparation method and application thereof, wherein the doped diamond particle sensor comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode consists of a glass tube, a copper wire packaged in the glass tube and doped diamond particles which are connected with the copper wire and are exposed outside; the doped diamond particles comprise carrier particles and a coating layer, wherein the carrier particles are boron-containing diamond particles or pure diamond particles, the coating layer is a doped diamond film, and doping elements are selected from one or more of boron, nitrogen and phosphorus.
Description
Technical Field
The invention belongs to the technical field of diamond electrode preparation, and particularly relates to a diamond particle doped sensor and a preparation method and application thereof.
Background
The artificial diamond is a superhard material, but the application in other aspects is very little, and the resistance of the diamond can be greatly reduced after the artificial diamond is doped with boron. At present, boron-doped diamond mainly comprises single crystal and polycrystalline boron-containing diamond particles and a boron-doped diamond film, wherein the boron-containing diamond particles are mainly prepared by a high-temperature high-pressure method, the particles prepared by the method are mainly single crystal diamond, and the problems of nonuniform B concentration distribution and low B concentration exist.
Although the doped diamond (BDD) thin film has the advantages of wide potential window, good chemical stability, weak surface adsorption and the like, the existing BDD material mostly uses metal or silicon wafers as a substrate, but has some fatal defects as a substrate material of the BDD. The metal substrate has advantages of high strength, good toughness and strong plasticity, but the substrate as an electrode has problems of poor corrosion resistance and high thermal expansion coefficient. In addition, the existing doped diamond (BDD) electrode has the defects of low electrocatalytic activity, poor selectivity and sensitivity, difficulty in large-scale production and the like, so that the application of the BDD electrode is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a doped diamond particle sensor and a preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical solutions.
The invention relates to a doped diamond particle sensor which comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode consists of a glass tube, a copper wire packaged in the glass tube and doped diamond particles which are connected with the copper wire and exposed outside; the doped diamond particles comprise carrier particles and a coating layer, wherein the carrier particles are boron-containing diamond particles or pure diamond particles, the coating layer is a doped diamond film, and doping elements are selected from one or more of boron, nitrogen and phosphorus, preferably boron.
In a preferred embodiment, the carrier particles have a single crystal structure, and the doped diamond film has a polycrystalline structure.
The inventor finds that the conductivity of the boron-containing diamond particles or diamond particles can be greatly improved by taking the boron-containing diamond particles or diamond particles with single crystal structures as carrier particles and then depositing the boron-doped diamond film with polycrystalline structures on the surfaces of the boron-containing diamond particles or diamond particles.
In the invention, the carrier particles can be natural or artificial, and are preferably prepared at high temperature and high pressure, so that the cost is reduced.
Preferably, the concentration of the doping element in the doped diamond film is more than 1021cm-3Preferably 1021cm-3～1022cm-3。
When the content of the doped diamond film is controlled to the above range, finallyThe resulting doped diamond particles perform optimally because the doping concentration is greater than 1018cm-3When the insulating diamond has a semiconductor property, it is more than 1021cm-3In this case, a metalloid property is obtained, however, too much doping causes the diamond lattice to be damaged due to the difference in the doping element and the lattice coefficient of diamond, resulting in an impurity phase (e.g., sp)2) Leading to the loss of some of the excellent properties of diamond such as high hardness, high strength, inert surface, and controlling the doping concentration in the doped diamond film within the above range will achieve optimum performance in cooperation with the carrier particles.
Preferably, the particle size of the carrier particles is 100nm to 500 μm, preferably 100nm to 300 μm, and more preferably 100nm to 100 μm, and the thickness of the doped diamond film is 5 μm to 20 μm.
The inventor finds that when the size of the carrier particles is less than 100 mu m, the microelectrode effect can be realized, the detection sensitivity is higher, but when the size of the electrode is more than 100 mu m and less than 300 mu m, the preparation method can be simple and convenient to a certain extent while the detection performance is better. The size may thus be chosen according to the actual application.
The inventors have found that by setting the thickness of the doped diamond film within the above range, it is possible to obtain doped diamond particles in which the coating is completely uniform and which are most excellent in performance.
Preferably, the doping mode of the doped diamond film comprises one or more combinations of constant doping, multi-layer variable doping and gradient doping.
Preferably, the diameter of the copper wire is 100-300 μm. The inventor finds that the copper wire is controlled within the range, so that the mounting of the copper wire and the doped diamond particles is convenient, and the detection sensitivity is high.
Preferably, the doped diamond film is a porous doped diamond film, and the aperture of the hole in the doped diamond film is 10nm-200 nm.
The specific surface area of the particles can be further improved by arranging the micropores on the surface of the doped diamond film, and the performance of the particles can be improved.
Preferably, the surface of the coating layer is provided with a modification layer, and the modification layer is selected from one or more of a metal modification layer, an organic modification and an end group modification.
The modification layer is arranged on the surface of the coating layer, so that the electrocatalytic activity of the modification layer particles can be further improved.
Further preferably, a metal modification layer is arranged on the surface of the coating layer, and the metal in the metal modification layer is selected from at least one of iron, copper, platinum, silver and gold.
The inventor finds that not only can the electrochemical catalytic performance be further improved by introducing metal modification, but also different metals have different electrochemical activities on different substances. Therefore, different metal modifications, such as Au detection-DA molecules, such as modified Ni detection of glucose, can be selected according to different applications.
The invention relates to a preparation method of a doped diamond particle sensor, which comprises the following steps:
step one preparation of doped diamond particles
Firstly planting nano diamond seed crystals on the surfaces of carrier particles, and then carrying out chemical vapor deposition on the carrier particles planted with the diamond seed crystals to grow a doped diamond film so as to obtain doped diamond particles, wherein during the chemical vapor deposition, the mass flow ratio of gas is hydrogen: methane: doping gas source 98: 2: 0.3-0.6, the growth pressure is 2-5Kpa, the growth temperature is 800-850 ℃, the growth frequency is 2-6 times, preferably 5 times, the carrier particles are taken out after each growth, the growth is continued after the carrier particles are shaken, the time of single growth is 3-6h, and the doping gas source is selected from at least one of ammonia gas, phosphine and hydrogen boride.
Step two working electrode encapsulation
Connecting the diamond-doped particles prepared in the step one with a metal wire by conductive silver adhesive, drying, inserting a copper wire into a glass tube, drawing the glass tube by a microelectrode drawing instrument, sealing the copper wire and the conductive silver adhesive into the obtained glass tube, exposing the diamond-doped particles outside the glass tube, dripping adhesive into the glass tube to fill the front section of the glass tube with the adhesive, drying to obtain a working electrode,
step three
And combining the working electrode, the reference electrode and the counter electrode to obtain the doped diamond particle sensor.
In the invention, in the first step, in the preparation process of the doped diamond particles, because the carrier particles and the doped diamond film have similar structures and are easy to nucleate, the excellent doped diamond film can be grown by adopting a conventional chemical vapor deposition method, but the inventor finds that the carrier particles are taken out after being cooled for 3-6h of growth, then the temperature is raised to the target temperature, the carrier particles can be better coated after being grown for multiple times, and finally the performance of the obtained boron-doped diamond particles is optimal.
Preferably, in the step one, the process of planting the nano-diamond seed crystals on the surfaces of the carrier particles comprises: and immersing the carrier particles into a suspension containing the nano-diamond, wherein the mass fraction of the nano-diamond in the suspension containing the nano-diamond is 0.01-0.1 wt%, and carrying out ultrasonic oscillation for more than or equal to 30min, and finally cleaning and drying.
Preferably, in the step one, the chemical vapor deposition is hot-wire chemical vapor deposition, and the temperature of the hot wire is 2500-.
In the preferred scheme, in the first step, etching treatment is carried out on the doped diamond particles to obtain a doped diamond film with a porous structure; the etching treatment process comprises the following steps: firstly, sputtering metallic nickel on the surface of the doped diamond film by adopting a magnetron sputtering method, and then carrying out heat treatment.
In addition, according to the practical application condition, after the heat treatment is finished, boiling nitric acid solution is adopted to remove nickel particles in the holes.
Further preferably, the process parameters of the sputtering metal nickel are as follows: introducing argon to adjust the air pressure to be 1-3 Pa, sputtering current to be 250-350 mA, and sputtering time to be 10-30 s; the thickness of the sputtered Ni layer is 5-10nm, and the air pressure is maintained at 7-15 kpa.
Further preferably, the heat treatment temperature is 800-900 ℃, and the heat treatment is carried out at the time of heat treatmentThe time is 3-5H, and the mass flow ratio of the introduced atmosphere is H2:Ar＝1.5。
Further preferably, the nitric acid solution is prepared by mixing concentrated nitric acid and water according to the weight ratio of 1-4: mixing at 4 volume ratio.
In the second step of the invention, the temperature of the secondary drying is 60 ℃ for 3 h.
In the second step of the present invention, the adhesive is preferably 502 glue, and the 502 glue is dropped into the glass tube to fill the front section of the glass tube, thereby preventing the exposure of the conductive silver glue and enabling the connection between the particles and the glass tube to be more compact.
Preferably, in the second step, metal particles are modified on the surfaces of the doped diamond particles exposed by the obtained working electrode.
Further preferably, when the modified metal particles are selected from Au, the modified metal particles are deposited on the particle electrode by using an electrochemical workstation and a selective pulse multi-potential deposition method by taking a sodium acetate buffer solution containing 5-50mM chloroauric acid and having a pH value of 4.5-5.5 as a deposition solution, wherein the conduction time is 0.6-0.8s, the conduction potential is-0.5V-1V, the disconnection time is 0.4-0.2s, and the disconnection voltage is 0V, namely, 10-500nm Au nanoparticles are obtained by modifying the surfaces of the doped diamond particles.
Preferably, in the second step, end group modification is carried out on the surfaces of the doped diamond particles exposed by the obtained working electrode, wherein the modification process is that the doped diamond particles exposed by the obtained working electrode are placed into 0.1-1MH2SO4And (3) applying a voltage of-3 to-3.5V to the solution, and reacting for 2-10min to obtain the H end group modification.
Preferably, in the second step, end group modification is carried out on the surfaces of the doped diamond particles exposed by the obtained working electrode, wherein the modification process is that the doped diamond particles exposed by the obtained working electrode are placed into 0.1-1MH2SO4In the solution, 3-3.5V voltage is applied, reaction is carried out for 2-10min, and O end group modification is carried out.
The invention also provides application of the doped diamond particle sensor, and the doped diamond particle sensor is used for electrochemical detection.
Advantageous effects
The invention is initiated at high temperatureThe diamond particles with single crystal structures or the boron-containing diamond particles synthesized by high pressure are used as carrier particles, and a polycrystalline doped diamond film grows on the surface of the carrier particles, so that the finally obtained doped diamond particles have excellent conductivity, high specific surface area, no toxicity to the environment and high signal-to-noise ratio. Further, since commercial particle electrodes are composed of impurities such as Fe and Ni, they tend to adsorb substances. And the polycrystalline thin film produced has a composition of sp as a main component3The diamond phase of the saturated structure, therefore, has a chemically inert surface and does not readily adsorb other substances. The BDD particle microelectrode is a polycrystalline BDD film on the surface, does not contain metal impurity phases, is low in capacitance and high in signal-to-noise ratio, and the manufactured sensor has good linear response and high detection sensitivity.
The invention adopts a vapor deposition mode in the growth process, taking boron-doped diamond film as an example, the vapor deposition is used for preparing polycrystalline diamond by mixing methane (CH)4) Hydrocarbon such as acetylene, hydrogen (H)2) The boron-doped diamond particles and borane are introduced into the reaction chamber, the gas concentration is adjustable, and the proportion is uniform, so that the B doping uniformity of the boron-doped diamond film prepared by the vapor deposition method is higher, and the preparation of the high-doping film is easy to realize.
The preparation method is simple and controllable, and the used carrier particles are commercialized diamond particles with single crystal structures synthesized at high temperature and high pressure or boron-containing diamond particles which are used as the carrier particles, so that the cost is low and the cost is low.
Drawings
Fig. 1 is a microscopic structure view of boron-doped diamond particles prepared in example 1, in which fig. 1(a) is an SEM image of a boron-containing diamond of a single crystal structure coated with a polycrystalline B-doped diamond film. (b) An enlarged view of the polycrystalline boron-doped diamond film. (c) Is the Raman spectrum of the polycrystalline diamond film.
Fig. 2 is a microscopic structure view of the boron-doped diamond particles prepared in example 2, in which fig. 1(a) is an SEM image of a single-crystal structure boron-containing diamond coated with a polycrystalline B-doped diamond film. (b) An enlarged view of the polycrystalline boron-doped diamond film. (c) Is the Raman spectrum of the polycrystalline diamond film.
Fig. 3 is a microscopic structure view of the prepared boron-doped diamond particles of the comparative example.
FIG. 4 is a schematic view of a doped diamond particle sensor of the present invention, wherein 1, the carrier particle; 2. doping a diamond film; 3. a copper wire; 4. a glass tube; 5. and (3) copper wires.
Detailed Description
Example 1
Preparation of boron-doped diamond particles
(1) Firstly, the boron-containing diamond particles with the average particle size of 150 mu m are cleaned.
(2) Immersing in suspension containing nano diamond, ultrasonic vibrating for 30min, cleaning and drying. Putting the suspension into the suspension containing the nano-diamond, wherein the mass fraction of the nano-diamond is 0.01 wt%.
(3) Depositing a boron-doped diamond film by adopting hot filament CVD, wherein the deposition process parameters are as follows: the distance of the hot wire is 6mm, the growth temperature is 800-850 ℃, the temperature of the hot wire is 2200 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 50 mu m by controlling the deposition time; during the chemical vapor deposition, the mass flow ratio of the passing gas is hydrogen: methane: borane 98: 2: 0.3, the growth pressure is 2Kpa, the growth times is 2 times, the carrier particles are taken out once for each growth, the growth is continued after the carrier particles are shaken, the time of single growth is 6h,
fig. 1(a) is an SEM image of single crystal B-doped diamond coated polycrystalline B-doped diamond film. (b) Enlargement of the polycrystalline thin film. (c) The Raman peak of the polycrystalline diamond film has higher B-doped degree, and a typical B peak (479 cm)-1And 1200cm-1) The graphite phase is relatively small (G peak: 1530cm-1) And B concentration is fitted to be greater than 1021cm-1It is shown as heavily doped B material.
Encapsulation of electrodes
Dipping conductive silver paste with copper wire (diameter is 100 μm), connecting the cleaned boron-doped diamond particles with the copper wire through the conductive silver paste, putting the boron-doped diamond particles into a drying oven, and drying for 3h at 60 ℃. After drying, inserting the copper wire into the glass tube, drawing the glass tube by using a microelectrode drawing instrument, sealing the copper wire and the conductive silver adhesive part into the glass tube, and only exposing the doped diamond particles outside the glass tube. The 502 glue is dripped into the glass tube to fill the front section part of the glass tube, so that the exposure of the conductive silver glue is prevented, and meanwhile, the particles are connected with the glass tube more tightly. Putting into an oven, and drying at 60 ℃ for 1 h.
Modification of electrodes
Sputtering nickel nano particles on a sample on physical vapor deposition equipment by a magnetron sputtering method, introducing argon to adjust the air pressure to be about 1Pa, sputtering current to be 200mA, and sputtering time to be 15 s.
The electrochemical potential window of the Ni-modified boron-doped diamond particle microelectrode obtained in the embodiment is up to 3.1V; detection with glucose: has good linear response in the concentration range of 0.05-15 MuM, and the detection sensitivity is as high as 140 MuA.mu.M-1. cm-2.
Example 2
(1) Firstly, the boron-containing diamond particles with the average particle size of 300 mu m are cleaned.
(2) Immersing in suspension containing nano diamond, ultrasonic vibrating for 30min, cleaning and drying. Putting the suspension into the suspension containing the nano-diamond, wherein the mass fraction of the nano-diamond is 0.1 wt%.
(3) Depositing a boron-doped diamond film by adopting hot filament CVD, wherein the deposition process parameters are as follows: the distance of the hot wire is 6mm, the growth temperature is 800-: methane: borane 98: 2: 0.5, obtaining the thickness of the diamond film by controlling the deposition time to be 10 mu m; the growth times is 4 times, the carrier particles are taken out every time of growth, the growth is continued after the carrier particles are shaken, the time of single growth is 4 hours,
fig. 2(a) is an SEM image of single crystal B-doped diamond coated polycrystalline B-doped diamond film. (b) Enlargement of the polycrystalline thin film. (c) Is a Raman peak of the polycrystalline diamond film, and a typical B peak (479 cm) appears at the peak-1And 1200cm-1) The graphite phase is relatively small (G peak: 1530cm-1) and B concentration is fitted to be greater than 1021cm-1It is shown as heavily doped B material.
Encapsulation of electrodes
Dipping conductive silver paste with copper wire (diameter is 200 μm), connecting the cleaned boron-doped diamond particles with the copper wire through the conductive silver paste, putting the boron-doped diamond particles into a drying oven, and drying for 3h at 60 ℃. After drying, inserting the copper wire into the glass tube, drawing the glass tube by using a microelectrode drawing instrument, sealing the copper wire and the conductive silver adhesive part into the glass tube, and only exposing the doped diamond particles outside the glass tube. The 502 glue is dripped into the glass tube to fill the front section part of the glass tube, so that the exposure of the conductive silver glue is prevented, and meanwhile, the particles are connected with the glass tube more tightly. Putting into an oven, and drying at 60 ℃ for 1 h.
And performing Au deposition on the particle electrode by using an electrochemical deposition workstation. The resulting mixture was placed in a 0.5mM chloroauric acid solution and deposited at-0.5V for 120 seconds by pulse electrodeposition.
The electrochemical potential window of the Au-modified boron-doped diamond particle microelectrode obtained in the embodiment is up to 3V; detection with dopamine: has good linear response in the concentration range of 0.05-16 mu M, and the detection sensitivity is as high as 205 mu A.mu M-1. cm-2.
Example 3
(1) Firstly, the boron-containing diamond particles with the average particle size of 300 mu m are cleaned.
(2) Immersing in suspension containing nano diamond, ultrasonic vibrating for 30min, cleaning and drying. Putting the suspension into the suspension containing the nano-diamond, wherein the mass fraction of the nano-diamond is 0.1 wt%.
(3) Depositing a boron-doped diamond film by adopting hot filament CVD, wherein the deposition process parameters are as follows: the distance of the hot wire is 6mm, the growth temperature is 800-: methane: borane 98: 2: 0.6, obtaining the thickness of the diamond film by controlling the deposition time to be 10 mu m; the growth times are 5 times, the carrier particles are taken out once for each growth, the growth is continued after the carrier particles are shaken, and the time of single growth is 3 hours.
(4) Etching the boron-doped diamond particles to obtain a boron-doped diamond film with a porous structure; the etching treatment process comprises the following steps: sputtering metallic nickel on the surface of the boron-doped diamond film by adopting a magnetron sputtering method, wherein the technological parameters of the sputtering metallic nickel are as follows: argon is introduced to adjust the air pressure to be 3Pa, the sputtering current is 350mA,sputtering time is 10 s; sputtering Ni layer with thickness of 7nm, heat treating at 900 deg.C under pressure of 12kpa for 3 hr, and introducing gas at mass flow rate of H2Ar is 1.5. And (5) after the heat treatment is finished.
Encapsulation of electrodes
Dipping conductive silver paste by using a copper wire (the diameter is 300 mu m), connecting the cleaned boron-doped diamond particles with the copper wire through the conductive silver paste, putting the boron-doped diamond particles into a drying oven, and drying for 3h at 60 ℃. After drying, inserting the copper wire into the glass tube, drawing the glass tube by using a microelectrode drawing instrument, sealing the copper wire and the conductive silver adhesive part into the glass tube, and only exposing the doped diamond particles outside the glass tube. The 502 glue is dripped into the glass tube to fill the front section part of the glass tube, so that the exposure of the conductive silver glue is prevented, and meanwhile, the particles are connected with the glass tube more tightly. Putting into an oven, and drying at 60 ℃ for 1 h.
And performing Au deposition on the particle electrode by using an electrochemical deposition workstation. The resulting mixture was placed in a 0.5mM chloroauric acid solution and deposited at-0.5V for 120 seconds by pulse electrodeposition.
The electrochemical potential window of the Au-modified boron-doped diamond particle microelectrode obtained in the embodiment is up to 3V; detection with dopamine: has good linear response in the concentration range of 0.1-1000 muM, and the detection sensitivity is as high as 390 muA.muM-1. cm-2.
Comparative example 1
(1) The diamond particles having an average particle diameter of 150 μm were washed.
(2) Immersing in suspension containing nano diamond, ultrasonic vibrating for 30min, cleaning and drying. Putting the suspension into the suspension containing the nano-diamond, wherein the mass fraction of the nano-diamond is 0.01 wt%.
(3) Depositing a boron-doped diamond film by adopting hot filament CVD, wherein the deposition process parameters are as follows: the distance of the hot wire is 7mm, the growth temperature is 800-900 ℃, the temperature of the hot wire is 2200 ℃, the deposition pressure is 3KPa, and the mass flow ratio of the passing gas is hydrogen: methane: borane 98: 2: 0.3, the growth pressure is 2Kpa, and the growth is continuously carried out for 6 h.
Fig. 3 is an SEM image of diamond particles coated with a polycrystalline B-doped diamond film. Some areas of the surface are not completely coated because of the lack of continuous growth.
Claims (10)
1. A doped diamond particle sensor, comprising: the device comprises a working electrode, a counter electrode and a reference electrode, wherein the working electrode consists of a glass tube, a copper wire packaged in the glass tube and doped diamond particles which are connected with the copper wire and exposed outside; the doped diamond particles comprise carrier particles and a coating layer, wherein the carrier particles are boron-containing diamond particles or pure diamond particles, the coating layer is a doped diamond film, and doping elements are selected from one or more of boron, nitrogen and phosphorus, preferably boron.
2. A doped diamond particle sensor according to claim 1, wherein: the carrier particles are of a single crystal structure, and the doped diamond film is of a polycrystalline structure; the particle size of the carrier particles is 100nm-500 mu m, and the thickness of the doped diamond film is 5 mu m-20 mu m;
the doping mode of the doped diamond film comprises one or more combinations of constant doping, multi-layer variable doping and gradient doping.
3. A doped diamond particle sensor according to claim 1, wherein: the diameter of the copper wire is 100-300 μm.
4. A doped diamond particle sensor according to claim 1, wherein: the concentration of doping elements in the doped diamond film is more than 1021cm-3。
5. A doped diamond particle sensor according to claim 1, wherein:
the doped diamond film is a porous doped diamond film, and the aperture of a hole in the doped diamond film is 10nm-200 nm;
the surface of the coating layer is provided with a modification layer, and the modification layer is selected from one or more of a metal modification layer, an organic modification and an end group modification.
6. A method of manufacturing a doped diamond particle sensor according to any one of claims 1 to 5, wherein: the method comprises the following steps:
step one preparation of doped diamond particles
Firstly planting nano diamond seed crystals on the surfaces of carrier particles, and then carrying out chemical vapor deposition on the carrier particles planted with the diamond seed crystals to grow a doped diamond film so as to obtain doped diamond particles, wherein during the chemical vapor deposition, the mass flow ratio of gas is hydrogen: methane: doping gas source 98: 2: 0.3-0.6, the growth pressure is 2-5Kpa, the growth temperature is 800-850 ℃, the growth frequency is 2-6 times, preferably 5 times, the carrier particles are taken out after each growth, the growth is continued after the carrier particles are shaken, the time of single growth is 3-6h, and the doping gas source is selected from at least one of ammonia gas, phosphine and borane.
Step two working electrode encapsulation
Connecting the diamond-doped particles prepared in the step one with a metal wire by conductive silver adhesive, drying, inserting a copper wire into a glass tube, drawing the glass tube by a microelectrode drawing instrument, sealing the copper wire and the conductive silver adhesive into the obtained glass tube, exposing the diamond-doped particles outside the glass tube, dripping adhesive into the glass tube to fill the front section of the glass tube with the adhesive, drying to obtain a working electrode,
step three
And combining the working electrode, the reference electrode and the counter electrode to obtain the doped diamond particle sensor.
7. The method of claim 6, wherein the sensor further comprises: in the first step, the process of planting the nano-diamond seed crystals on the surfaces of the carrier particles comprises the following steps: immersing carrier particles into suspension containing nano-diamond, and performing ultrasonic oscillation for more than or equal to 30min, and finally cleaning and drying to obtain the nano-diamond-containing suspension, wherein the mass fraction of the nano-diamond in the suspension containing the nano-diamond is 0.01-0.1 wt%;
in the first step, the chemical vapor deposition is hot wire chemical vapor deposition, and the temperature of the hot wire is 2500-.
8. The method of claim 6, wherein the sensor further comprises: in the first step, etching treatment is carried out on the doped diamond particles to obtain a doped diamond film with a porous structure; the etching treatment process comprises the following steps: firstly, sputtering metallic nickel on the surface of the doped diamond film by adopting a magnetron sputtering method, and then carrying out heat treatment;
the technological parameters of the sputtering metallic nickel are as follows: introducing argon to adjust the air pressure to be 1-3 Pa, sputtering current to be 250-350 mA, and sputtering time to be 10-30 s; the thickness of the sputtered Ni layer is 5-10nm, and the air pressure is maintained at 7-15 kpa
The heat treatment temperature is 800-900 ℃, the heat treatment time is 3-5H, and the mass flow ratio of the introduced atmosphere is H2:Ar＝1.5。
9. The method of claim 6, wherein the sensor further comprises: in the second step, metal particles are modified on the surfaces of the doped diamond particles exposed by the obtained working electrode,
when the modified metal particles are selected from Au, taking a sodium acetate buffer solution with the pH value of 4.5-5.5 and containing 5-50mM chloroauric acid as a deposition solution, using an electrochemical workstation, and selecting a pulse multi-potential deposition method to deposit the particle electrodes, wherein the on-time is 0.6-0.8s, the on-potential is-0.5V-1V, the off-time is 0.4-0.2s, and the off-voltage is 0V, namely, the Au nanoparticles with the particle size of 10-500nm are obtained by modifying the surfaces of the doped diamond particles;
or
In the second step, end group modification is carried out on the surfaces of the doped diamond particles exposed by the obtained working electrode, and the modification process is that the doped diamond particles exposed by the obtained working electrode are put into 0.1-1M H2SO4Applying a voltage of-3 to-3.5V in the solution, and reacting for 2-10min to obtain H end group modification;
or
In the second step, end group modification is carried out on the surfaces of the doped diamond particles exposed by the obtained working electrode, and the modification process is that the doped diamond particles exposed by the obtained working electrode are put into 0.1-1M H2SO4In the solution, 3-3.5V voltage is applied, reaction is carried out for 2-10min, and O end group modification is carried out.
10. Use of a doped diamond particle sensor according to any one of claims 1 to 5, wherein: the doped diamond particle sensor was used for electrochemical detection.
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