CN107643228B - Preparation method of chip for measuring mercury vapor and use method of sensor - Google Patents
Preparation method of chip for measuring mercury vapor and use method of sensor Download PDFInfo
- Publication number
- CN107643228B CN107643228B CN201710770984.5A CN201710770984A CN107643228B CN 107643228 B CN107643228 B CN 107643228B CN 201710770984 A CN201710770984 A CN 201710770984A CN 107643228 B CN107643228 B CN 107643228B
- Authority
- CN
- China
- Prior art keywords
- layer
- thin film
- electrode
- sensor
- film layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a chip for measuring mercury vapor, which comprises a silicon substrate layer; the middle layer comprises a Bragg acoustic reflection layer, a seed layer and a piezoelectric film layer which are sequentially stacked from bottom to top, and the Bragg acoustic reflection layer is arranged on the silicon substrate layer; each electrode assembly comprises a grounding electrode and a signal electrode which are arranged on the piezoelectric film layer, the grounding electrode is C-shaped and forms a containing area, and the signal electrode is contained in the containing area; the mercury reversible adsorption film layer is arranged on the signal electrode of one group of electrode assemblies, so that the electrode assemblies and the mercury reversible adsorption film layer form a signal electrode of the measurement unit together, and the other group of electrode assemblies form a signal electrode of the reference unit. The invention also provides a preparation method of the chip, a sensor assembled with the chip and a use method of the sensor. The invention has simple structure, high precision, strong anti-interference capability and easy mass production, and can be widely applied to various industrial emission detection systems.
Description
Technical Field
The invention relates to the field of mercury vapor measurement, in particular to a preparation method of a chip for measuring mercury vapor and a use method of a sensor thereof.
Background
Mercury is an element that is extremely harmful to the environment and humans. Commercial scale production results in about 2400 tons of mercury being emitted into the atmosphere each year, then through the soil, the ocean, and into the food chain. Mercury entering the human body can generate a bio-accumulation effect by forming methyl mercury, and further cause irreversible damage to the nervous system, the brain and the fetus. It has been reported that exposure of the human body to 0.1-0.2ppm mercury vapor results in chemical bronchitis, chemical pneumonia and pulmonary fibrosis for only a few hours. The method aims at main industrial activities, such as coal-fired smoke emission of a thermal power plant, mining and smelting emission, waste incineration emission and the like, and is important for controlling environmental mercury pollution.
At present, the widely used mercury vapor measuring device is mostly based on the fluorescence effect, and because the fluorescence absorption frequency of mercury is near 253.7nm, and the wavelength can cause photochemical reaction in high-temperature combustion flue gas, fluorescence quenching and photocatalytic oxidation of mercury are easily caused, and further the measuring precision is influenced, therefore, the measuring device is not suitable for monitoring the mercury emission in the combustion flue gas. In addition, the mercury vapor measuring device based on the fluorescence effect still has the shortcomings of large volume, high cost, frequent maintenance and unsuitability for low-cost networking monitoring.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a chip for measuring mercury vapor, which is miniaturized, low in cost, high in precision and free of maintenance, and can be widely applied to various industrial emission monitoring systems.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows: a chip for measuring mercury vapor, comprising:
a silicon substrate layer;
the middle layer comprises a Bragg acoustic reflection layer, a seed layer and a piezoelectric film layer which are sequentially stacked from bottom to top, and the Bragg acoustic reflection layer is arranged on the silicon substrate layer;
each group of electrode assemblies comprises a grounding electrode and a signal electrode which are arranged on the piezoelectric film layer, the grounding electrode is C-shaped and forms a containing area and an opening, and the signal electrode is contained in the containing area;
the mercury reversible adsorption film layer is arranged on the signal electrodes of one group of the electrode assemblies, so that the electrode assemblies and the mercury reversible adsorption film layer form signal electrodes of a measuring unit together, and the other group of the electrode assemblies form signal electrodes of a reference unit.
Further, the mercury reversible adsorption film layer is a Ni-Au nano film.
Further, the grounding electrode and the signal electrode respectively comprise a laminated Ni film and a laminated Ti film, the Ti film is arranged on the piezoelectric film layer, and the Ni film and the mercury reversible adsorption film layer of the signal electrode of the measuring unit are mutually attached.
Further, the thickness of the Ni film is 100-200nm, and the thickness of the Ti film is 40-70 nm.
Further, the Bragg acoustic reflection layer comprises three layer groups which are arranged in a stacked mode, and the layer groups are SiO from top to bottom2The structure of the/Mo double-layer film.
Further, the SiO2The film and the thickness of the Mo film are both 1/4 of the resonant sound wave at the respective middle wavelength.
Further, the seed layer comprises a Pt thin film and a Ti thin film which are stacked, the Pt thin film is arranged below the piezoelectric thin film layer, and the Ti thin film is arranged on the Bragg acoustic reflection layer.
Further, the thickness of the Pt thin film is 100-150nm, and the thickness of the Ti thin film is 40-70 nm.
Further, the piezoelectric thin film layer is an AlN layer with the preferred C-axis orientation.
Further, the thickness of the piezoelectric film layer is 1-2 um.
The invention also provides a preparation method of the chip for measuring mercury vapor, which comprises the following steps:
s1: depositing the Bragg acoustic reflection layer on the silicon substrate layer;
s2: depositing the seed layer on the Bragg acoustic reflection layer;
s3: depositing the piezoelectric thin film layer on the seed layer;
s4: depositing two grounding electrodes and two signal electrodes on the piezoelectric film layer;
s5: and preparing the mercury reversible adsorption film layer on one signal electrode by an ion displacement method.
Further, the crystalline orientation of the seed layer surface layer is an orientation.
Further, S4 includes a step of forming a protective layer in a region other than the predetermined region on the surface of the piezoelectric thin film layer.
Further, the mercury reversible adsorption film layer prepared by the ion replacement method in the S5 is specifically as follows:
putting the sample obtained in the S4 into a dialysis bag with the molecular weight cutoff of 8000-14000, injecting deionized water into the dialysis bag, and clamping and sealing an opening of the dialysis bag by using a dialysis bag clamp; placing the dialysis bag into a container, and pouring 1.5 × 10 concentration into the container-4 mol/L～2.5×10-4mol/L HAuCl4Solution to HAuCl4The solution was immersed in the dialysis bag top and HAuCl was stirred4And reacting the solution at room temperature for 6-10 hours.
The present invention also provides a sensor for measuring mercury vapor, comprising:
the packaging structure comprises a packaging tube shell and a detection device, wherein the packaging tube shell comprises a packaging base and a packaging top cover, the middle part of the packaging base is provided with a groove, the packaging top cover covers the packaging base, three terminals are arranged on two sides of the packaging base, and the packaging top cover is provided with a detection window;
the chip is accommodated in the groove, and the mercury reversible adsorption film layer is positioned right below the detection window; at the same time, the user can select the desired position,
the two ends of the grounding electrode of the two groups of electrode assemblies are electrically connected to two of the three terminals on the corresponding side of the packaging base, and the signal electrodes of the two groups of electrode assemblies are respectively and electrically connected to the other of the three terminals on the corresponding side of the packaging base.
The invention also provides a use method of the sensor for measuring mercury vapor, which comprises the following steps:
s1: the sensor is connected to a network analyzer;
s2: putting the sensor into a mercury vapor sensor calibration device to measure the frequency peak difference between the signal electrode of the measurement unit and the signal electrode of the reference unit so as to obtain a calibration fitting curve;
s3: placing the sensor in a gas environment to be measured to measure the frequency peak difference between the signal electrode of the measurement unit and the signal electrode of the reference unit;
s4: and (5) calculating the concentration of the mercury vapor in the gas to be measured by using an interpolation method by using the calibration fitting curve obtained in the step S2 and combining the frequency difference measured in the step S3.
Compared with the prior art, the invention has the advantages that:
(1) the invention has simple structure, high precision, strong anti-interference capability and easy mass production, and can be widely applied to various industrial emission detection systems.
(2) The invention can realize high-resolution monitoring of the concentration of trace mercury vapor in the gas to be detected by utilizing the reversible combination characteristic of the Ni-Au nano film to mercury vapor and the advantage of high sensitivity of the transverse excitation thickness shear mode film bulk acoustic resonator to acoustic load detection.
(3) The Ni-Au nano film has the characteristics of looseness and porosity, and the contact area with gas to be detected is increased. The Ni film hardly generates amalgam reaction with mercury, the nano-gold particles in the Ni-Au nano film have extremely strong compatibility with mercury, and the interface effect of Ni and Au effectively inhibits the mercury from generating irreversible combination with the adsorption layer, thereby having the advantage of maintenance-free.
Drawings
Fig. 1 is an exploded view of a sensor for measuring mercury vapor according to an embodiment of the present invention;
FIG. 2 is a schematic view of an electrode assembly according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a Bragg acoustic reflection layer provided by an embodiment of the present invention;
FIG. 4 is a schematic diagram of a seed layer structure provided in an embodiment of the invention;
fig. 5 is a schematic diagram of a sensor according to an embodiment of the present invention.
In the figure, 1-silicon substrate layer, 2-interlayer, 20-Bragg acoustic reflection layer, 200-layer group, 21-seed layer, 22-piezoelectric thin film layer, 3-electrode assembly, 30-grounding electrode, 300-housing region, 301-opening, 31-signal electrode, 310-body part, 311-extension part, 4-mercury reversible adsorption thin film layer, 5-measuring unit signal electrode, 6-reference unit signal electrode, 7-packaging shell, 70-groove, 71-packaging base, 72-packaging top cover, 73-terminal, 73 a-terminal, 73 b-terminal, 73 c-terminal, 73 d-terminal, 73 e-terminal, 73 f-terminal, 74-detection window, A-sensor, the system comprises a B-network analyzer, a C-mercury vapor sensor calibration device and a D-mercury vapor concentration regulating valve.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Referring to fig. 1 and 2, an embodiment of the present invention provides a chip for measuring mercury vapor, including:
the silicon substrate layer 1 is used for providing support, and the silicon substrate layer 1 adopts a (001) type P-type doped silicon substrate;
the middle layer 2 comprises a Bragg acoustic reflection layer 20, a seed layer 21 and a piezoelectric thin film layer 22 which are sequentially stacked from bottom to top, and the Bragg acoustic reflection layer 20 is arranged on the silicon substrate layer 1;
two sets of electrode assemblies 3, each set of electrode assemblies 3 including a ground electrode 30 and a signal electrode 31 disposed on the piezoelectric thin film layer 22, the ground electrode 30 being C-shaped and forming a receiving area 300 and an opening 301, the signal electrode 31 being received in the receiving area 300, and the signal electrode 31 including a main portion 310 and an extension portion 311 extending from the main portion 310, the extension portion 311 extending to the opening 301;
the Bragg acoustic reflection layer 20 is used for reflecting piezoelectric excitation sound waves transmitted in a direction perpendicular to the silicon substrate layer 1, so that the piezoelectric resonance quality factor Q is improved, and finally, the sensitivity of the sensor is improved;
the seed layer 21 is used for guiding the piezoelectric thin film layer 22 growing thereon to grow preferentially in the (001) orientation;
the piezoelectric thin film layer 22 is a hexagonal piezoelectric thin film material, and the polarization axis of the piezoelectric thin film material is perpendicular to the direction of the silicon substrate layer 1;
preferably, the two ground electrodes 30 are arranged in parallel, the openings are both outward and oppositely arranged, and the two ends of the openings are not communicated;
the shape of the signal electrode 31 matches the receiving area 300 of the ground electrode 30, for example, if the receiving area 300 is square, the signal electrode 31 has a square structure, and if the receiving area 300 is circular, the signal electrode 31 has a circular structure, and the signal electrode 31 is received in the receiving area 300 of the corresponding ground electrode 30;
and the mercury reversible adsorption film layer 4 is arranged on the signal electrode 31 of one group of the electrode assemblies 3, so that the group of the electrode assemblies 3 and the mercury reversible adsorption film layer 4 jointly form a measuring unit signal electrode 5, and the other electrode assembly 3 forms a reference unit signal electrode 6.
The middle layer 2, the two groups of electrode assemblies 3 and the mercury reversible adsorption film layer 4 form a transverse excitation thickness shear mode film bulk acoustic resonator, the acoustic load detection sensitivity is high, and high-resolution monitoring of concentration of trace mercury vapor in gas to be detected can be achieved.
The principle of the invention is as follows: the mercury is adsorbed on the mercury reversible adsorption film layer 4 in a dynamic equilibrium state, when the adsorption occurs, the weight of the mercury reversible adsorption film layer 4 is changed, so that the pressure applied to the signal electrode 5 of the measuring unit is changed, and a pressure difference signal between the signal electrode 5 of the measuring unit and the signal electrode 6 of the reference unit is transmitted to a detection instrument through the middle layer 2.
The invention has simple structure, high precision, strong anti-interference capability and easy mass production, and can be widely applied to various industrial emission detection systems.
Further, the mercury reversible adsorption film layer 4 is a Ni-Au nano film. The Ni-Au nano film generated by the ion replacement reaction has the function of adsorbing a trace amount of elemental mercury in the gas to be detected. The Ni-Au thin film generated by the ion replacement reaction has the characteristics of looseness and porosity, and the contact area with the gas to be detected is increased. Ni hardly generates amalgam reaction with mercury, nano gold particles in the Ni-Au nano film have extremely strong melting property with mercury, and the interface effect of Ni and Au effectively inhibits the irreversible combination of mercury and the adsorption layer.
Further, the ground electrode 30 and the signal electrode 31 both include a stacked Ni thin film and a Ti thin film, the Ti thin film is disposed on the piezoelectric thin film layer 22, and the Ni thin film of the measurement unit signal electrode 5 and the mercury reversible adsorption thin film layer 4 are attached to each other. The Ti film functions as an adhesion layer for reducing the growth stress between the Ni film and the piezoelectric thin film layer 22 and preventing the Ni film from peeling off during the heat treatment.
Further, the thickness of the Ni film is 100-200nm, the thickness of the Ti film is 40-70nm, preferably, the thickness of the Ni film is 150nm, and the thickness of the Ti film is 50 nm.
Referring to FIG. 3, further, the Bragg acoustic reflector layer 20 includes three layer sets 200 arranged in a stack, the layer sets 200 being SiO from top to bottom2The layer set 200 can be selected from a plurality of layers to be laminated according to actual needs.
Further, the SiO2The film and the thickness of the Mo film are both 1/4 of the resonant sound wave at the respective middle wavelength.
Referring to fig. 4, further, the seed layer 21 includes a Pt thin film and a Ti thin film stacked, the Pt thin film is disposed below the piezoelectric thin film layer 22, and the Ti thin film is disposed on the Bragg acoustic reflection layer 20. The Pt film is (111) preferred orientation and can guide the film growth thereon.
Further, the thickness of the Pt thin film is 100-150nm, the thickness of the Ti thin film is 40-70nm, preferably, the thickness of the Pt thin film is 100nm, and the thickness of the Ti thin film is 50 nm.
Further, the piezoelectric thin film layer 22 is an AlN layer with a preferred C-axis orientation, and the polarization axis is perpendicular to the silicon substrate layer 1.
Further, the thickness of the piezoelectric film layer 22 is 1-2um, preferably 1.2 um.
The invention also provides a preparation method of the chip for measuring mercury vapor, which comprises the following steps:
s1: depositing said Bragg acoustic reflector layer 20 on said silicon substrate layer 1;
s2: depositing the seed layer 21 on the Bragg acoustic reflection layer 20;
s3: depositing the piezoelectric thin film layer 22 on the seed layer 21;
s4: depositing two ground electrodes 30 and two signal electrodes 31 on the piezoelectric thin film layer 22;
s5: the mercury reversible adsorption film layer 4 is prepared on one of the signal electrodes 31 by an ion displacement method.
The method comprises the following specific implementation steps:
a. selecting the silicon substrate layer 1 with double-sided polishing, P-type doping and (001) type, and adopting Mo metal target and SiO2Ceramic target material, and SiO is deposited on the ceramic target material by respectively adopting direct current magnetron sputtering and alternating current magnetron sputtering processes2/Mo/SiO2/Mo/SiO2The Bragg acoustic reflector layer 20 of a/Mo sandwich structure.
b. Depositing the Pt thin film with the thickness of 100-150nm and the Ti thin film with the thickness of 40-70nm on the Bragg acoustic reflection layer 20 in the step a by adopting a magnetron sputtering method to serve as the seed layer 21, then carrying out rapid annealing on the obtained sample by adopting a rapid annealing furnace of a tungsten-iodine lamp, wherein the annealing temperature is 600-700 ℃, the annealing time is 2-5min, the preferred annealing temperature is 650 ℃, the annealing time is 2min, and finally confirming that the Pt thin film crystal orientation on the surface of the obtained sample is (111) orientation, which can be confirmed by adopting an XRD method.
c. Depositing a hexagonal AlN thin film with the thickness of 1-2um on the sample obtained in the step b by using an AlN ceramic target and an alternating current magnetron sputtering process to be used as the piezoelectric thin film layer 22, wherein the preferred thickness is 1.2 um; and (3) carrying out rapid annealing on the generated sample, wherein when the sample is annealed by using a rapid annealing furnace, the annealing temperature is slightly higher than the crystallization temperature of the piezoelectric thin film layer 22 of the hexagonal system, the annealing time is 2-5min, preferably 750 ℃, and the annealing time is 5 min. In the deposition and annealing processes of the piezoelectric thin film layer 22 of the hexagonal system, the polarization axis direction of the piezoelectric thin film layer 22 of the hexagonal system is made to be perpendicular to the surface of the silicon substrate layer 1 by adjusting process parameters, and confirmed by using XRD.
d. And (c) sequentially using processes of coating photoresist, exposing, developing and the like to form patterns of the two grounding electrodes 30 and the two signal electrodes 31 on the surface of the sample obtained in the step c, wherein the photoresist is positive photoresist.
e. And d, respectively using a Ti metal target, a Ni metal target and a direct current magnetron sputtering method to deposit the Ti film with the thickness of 40-70nm and the Ni film with the thickness of 100-200nm, preferably to deposit the Ti film with the thickness of 50nm and the Ni film with the thickness of 150nm on the sample obtained in the step d.
f. And (e) removing the photoresist on the sample generated in the step (e) and the Ti film and the Ni film on the photoresist by using a positive photoresist stripping process to form two grounding electrodes 30 and two signal electrodes 31.
g. And (3) forming a protective layer on the surface of the sample obtained in the step (f) except the signal electrode 31 contained in the signal electrode 5 of the measuring unit by using processes of coating photoresist, exposing, developing and the like, so that the region where the signal electrode 31 contained in the signal electrode 5 of the measuring unit is located is exposed.
h. Putting the sample obtained in the step g into a dialysis bag with the molecular weight cutoff of 8000-14000, clamping the lower end of the dialysis bag by using a dialysis clamp, pouring deionized water from an opening at the upper end of the dialysis bag, and clamping the upper end of the dialysis bag by using a dialysis bag clamp; the dialysis bag was placed in a beaker and poured into a flask at a concentration of 1.5X 10-4mol/L～2.5×10-4mol/L HAuCl4Solution, ensuring that the solution is immersed in the top of the dialysis bag, preferably at a concentration of 2X 10-4mol/L HAuCl4A solution; and (3) putting a magnetic stirrer into the beaker, putting the beaker on a magnetic stirrer, turning on a switch of the magnetic stirrer, and stirring for 6-10 hours, preferably 8 hours at room temperature.
i. And (4) taking the sample in the step (h) out of the dialysis bag, washing the sample with deionized water, removing the photoresist on the obtained sample by adopting a dry method or wet method photoresist removing process, and confirming that a Ni-Au nano alloy film is formed on the signal electrode 31 contained in the signal electrode 5 of the measurement unit on the sample by using XRD (X-ray diffraction), namely the chip is successfully prepared.
Further, the crystal orientation of the surface layer of the seed layer 21 is (111) orientation.
Further, S4 includes a step of forming a protective layer on the surface of the piezoelectric thin film layer 22 in a region other than the predetermined region. The preset area is an area where the signal electrode 31 contained in the signal electrode 5 of the measurement unit is located, and is preset to perform an ion exchange reaction to generate the reversible mercury adsorption film layer 4, and specifically includes: and forming a protective layer on the surface of the piezoelectric film layer 22 except for the signal electrode 31 contained in the signal electrode 5 of the measuring unit, so that the region where the signal electrode 31 contained in the signal electrode 5 of the measuring unit is located is exposed.
Further, the mercury reversible adsorption film layer 4 is prepared by an ion exchange method in S5 as follows:
putting the sample obtained in the S4 into a dialysis bag with the molecular weight cutoff of 8000-14000, injecting deionized water into the dialysis bag, and clamping and sealing an opening of the dialysis bag by using a dialysis bag clamp; placing the dialysis bag into a container, and pouring 1.5 × 10 concentration into the container-4 mol/L～2.5×10-4mol/L HAuCl4Solution to HAuCl4The solution was immersed in the dialysis bag top and HAuCl was stirred4And reacting the solution at room temperature for 6-10 hours. In the reaction, the concentration is preferably 2X 10-4mol/L HAuCl4A solution; the stirring time is preferably 8 hours, and a glass apparatus commonly used in laboratories such as a beaker and a flask may be used, and a magnetic stirrer may be used for the stirring, specifically, a magnetic stirrer is added to the beaker, and the beaker is placed on the magnetic stirrer to set the stirring time.
Referring to fig. 1, the present invention also provides a sensor for measuring mercury vapor, comprising:
the package tube 7 comprises a package base 71 and a package top cover 72, wherein the middle part of the package base 71 is provided with a groove 70, the package top cover 72 covers the package base 71, two sides of the package base 71 are respectively provided with three terminals 73, the package top cover 72 is provided with a detection window 74, the middle part of the package top cover 72 is also provided with a groove to form an inner cavity, the detection window 74 is provided with the groove, and the package top cover 72 is buckled with the package base 71 so as to contain a chip;
a chip as described above, wherein the chip is accommodated in the groove 70, and the mercury reversible adsorption film layer 4 is located right below the detection window 74; at the same time, the user can select the desired position,
both end legs of the ground electrodes 30 of the two sets of electrode assemblies 3 are electrically connected to two of the three terminals 73 on the corresponding side of the package base 71, and the signal electrodes 31 of the two sets of electrode assemblies 3 are electrically connected to the other of the three terminals 73 on the corresponding side of the package base 71, respectively.
The following is an embodiment, and for convenience of description, we mark the terminals 73 on both sides of the package base 71 as 73a, 73b, 73c, 73d, 73e and 73f, respectively, the signal electrode 31 of the measurement unit signal electrode 5 is connected to the terminal 73c through a gold wire, and both end pins of the ground electrode 30 of the measurement unit signal electrode 5 are connected to the terminal 73a and the terminal 73b through a gold wire, respectively; the signal electrode 31 of the reference cell signal electrode 6 is connected to the terminal 73f by a gold wire, and both end legs of the ground electrode 30 of the reference cell signal electrode 6 are connected to the terminal 73d and the terminal 73e by gold wires, respectively.
During assembly, the package top cover 72 is right-hand-held on the package base 71, and the detection window 74 is aligned with the mercury reversible adsorbing film layer 4, so as to seal the joint between the package base 71 and the package top cover 72.
The package base 71 and the package top cover 72 are made of ceramic.
Referring to fig. 5, the present invention also provides a method for using the sensor for measuring mercury vapor, which comprises the following steps:
s1: the sensor A is connected to a network analyzer B;
s2: putting the sensor A into a mercury vapor sensor calibration device C to measure the frequency peak difference between the signal electrode 5 of the measurement unit and the signal electrode 6 of the reference unit so as to obtain a calibration fitting curve;
s3: putting the sensor A into a gas environment to be measured to measure the frequency peak difference between the signal electrode 5 of the measurement unit and the signal electrode 6 of the reference unit;
s4: and (5) calculating the concentration of the mercury vapor in the gas to be measured by using an interpolation method by combining the frequency difference measured in the step S3 in the calibration fitting curve obtained in the step S2.
The following is an embodiment, and for convenience of description, we mark terminals 73 on both sides of the package base 71 as 73a, 73b, 73c, 73d, 73e and 73f respectively, and specifically, the following steps can be performed:
(1) connecting said terminal 73a and said terminal 73B of said sensor a to the ground terminal of channel 1 of network analyzer B, respectively, and connecting said terminal 73c of said sensor a to the signal terminal of channel 1 of said network analyzer B;
(2) the terminal 73d and the terminal 73e of the sensor a are connected to the ground terminal of the channel 2 of the network analyzer B, respectively, and the terminal 73f of the sensor a is connected to the signal terminal of the channel 2 of the network analyzer B.
(3) Placing the sensor A into a mercury vapor sensor calibration device C, adjusting a mercury vapor concentration adjusting valve D, respectively setting a channel 1 and a channel 2 to respectively measure reflection parameters in a frequency sweep mode under different mercury vapor concentrations, recording frequency differences of frequencies corresponding to peak values of the channel 1 and the channel 2, and taking a corresponding relation between the mercury vapor concentration and the frequency differences as a calibration fitting curve;
(4) and placing the sensor A into a gas environment to be measured, setting the network analyzer B to measure the reflection parameters of the channel 1 and the channel 2 in a frequency scanning mode, and calculating the frequency difference of the frequency corresponding to the peak value of the channel 1 and the channel 2.
(5) And (4) calculating the concentration of mercury vapor in the gas to be measured by using an interpolation method by combining the frequency difference measured in the step (4) in the calibration fitting curve obtained in the step (3).
The present invention is not limited to the above-described embodiments, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Claims (5)
1. A preparation method of a chip for measuring mercury vapor is characterized by comprising the following steps:
s1: depositing a Bragg acoustic reflection layer (20) on a silicon substrate layer (1), wherein the Bragg acoustic reflection layer (20) comprises three layer groups (200) which are arranged in a stacked mode, and the layer groups (200) are of SiO2/Mo double-layer thin film structures from top to bottom;
s2: depositing a seed layer (21) on the Bragg acoustic reflection layer (20), wherein the seed layer (21) comprises a Pt thin film and a Ti thin film which are stacked, the Ti thin film is arranged on the Bragg acoustic reflection layer (20), and the crystallization orientation of the surface layer of the seed layer (21) is (111) orientation;
s3: depositing a piezoelectric thin film layer (22) on the seed layer (21), wherein the Pt thin film is arranged below the piezoelectric thin film layer (22);
s4: depositing two grounding electrodes (30) and two signal electrodes (31) on the piezoelectric thin film layer (22);
s5: and preparing a mercury reversible adsorption film layer (4) on one of the signal electrodes (31) by an ion replacement method, wherein the mercury reversible adsorption film layer (4) is a Ni-Au nano film.
2. The method for manufacturing a chip for measuring mercury vapor according to claim 1, wherein: s4 further includes a step of forming a protective layer on the surface of the piezoelectric thin film layer (22) in a region other than the predetermined region.
3. The method for manufacturing a chip for measuring mercury vapor according to claim 1, wherein the mercury reversible adsorbing film layer (4) is manufactured by an ion exchange method in S5 as follows:
putting the sample obtained in the S4 into a dialysis bag with the molecular weight cutoff of 8000-14000, injecting deionized water into the dialysis bag, and clamping and sealing an opening of the dialysis bag by using a dialysis bag clamp; placing the dialysis bag into a container, and pouring 1.5 × 10 concentration into the container-4mol/L～2.5×10-4mol/L HAuCl4Solution to HAuCl4The solution was immersed in the dialysis bag top and HAuCl was stirred4And reacting the solution at room temperature for 6-10 hours.
4. The method for manufacturing a chip for measuring mercury vapor according to claim 1, wherein: the thickness of the piezoelectric film layer (22) is 1-2 um.
5. A method of using a sensor for measuring mercury vapor, comprising: the sensor for measuring mercury vapor includes:
the packaging structure comprises a packaging tube shell (7), wherein the packaging tube shell (7) comprises a packaging base (71) and a packaging top cover (72), the middle of the packaging base (71) is provided with a groove (70), the packaging top cover (72) covers the packaging base (71), three terminals (73) are arranged on two sides of the packaging base (71), and a detection window (74) is formed in the packaging top cover (72);
the chip of claim 1, wherein the chip is accommodated in the groove (70), and the mercury reversible adsorption film layer (4) is positioned right below the detection window (74); at the same time, the user can select the desired position,
the two ends of the grounding electrode (30) of the two groups of electrode assemblies (3) are electrically connected to two of the three terminals (73) on the corresponding side of the packaging base (71), and the signal electrodes (31) of the two groups of electrode assemblies (3) are respectively and electrically connected to the other of the three terminals (73) on the corresponding side of the packaging base (71);
the use method of the sensor for measuring mercury vapor comprises the following steps:
s1: the sensor (A) is connected to a network analyzer (B);
s2: putting the sensor (A) into a mercury vapor sensor calibration device (C) to measure the frequency peak difference between a signal electrode (5) of a measurement unit and a signal electrode (6) of a reference unit so as to obtain a calibration fitting curve;
s3: placing the sensor (A) in a gas environment to be measured to measure the frequency peak difference between the signal electrode (5) of the measurement unit and the signal electrode (6) of the reference unit;
s4: and (5) calculating the concentration of the mercury vapor in the gas to be measured by using an interpolation method by using the calibration fitting curve obtained in the step S2 and combining the frequency difference measured in the step S3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710770984.5A CN107643228B (en) | 2017-08-31 | 2017-08-31 | Preparation method of chip for measuring mercury vapor and use method of sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710770984.5A CN107643228B (en) | 2017-08-31 | 2017-08-31 | Preparation method of chip for measuring mercury vapor and use method of sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107643228A CN107643228A (en) | 2018-01-30 |
| CN107643228B true CN107643228B (en) | 2021-04-27 |
Family
ID=61111333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710770984.5A Expired - Fee Related CN107643228B (en) | 2017-08-31 | 2017-08-31 | Preparation method of chip for measuring mercury vapor and use method of sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107643228B (en) |
Citations (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4893161A (en) * | 1987-09-24 | 1990-01-09 | United Technologies | Quantum-well acoustic charge transport device |
| CN101013082A (en) * | 2007-02-01 | 2007-08-08 | 厦门大学 | Piezo-electric type harmonic oscillation cartridge quality sensing unit |
| CN101349639A (en) * | 2008-09-10 | 2009-01-21 | 中国烟草总公司郑州烟草研究院 | Method for measuring mercury content in loading paper for cigarette |
| JP2009054409A (en) * | 2007-08-27 | 2009-03-12 | Harison Toshiba Lighting Corp | Metal halide lamp, and metal halide lamp lighting device |
| CN101841313A (en) * | 2009-03-19 | 2010-09-22 | 太阳诱电株式会社 | Piezoelectric thin film resonator, filter, communication module and communication device |
| CN101871164A (en) * | 2010-06-17 | 2010-10-27 | 浙江大学 | Preparation method of mercury ion colorimetric sensing cellulose material |
| CN101900709A (en) * | 2010-07-22 | 2010-12-01 | 重庆大学 | Method for improving resolution of single-piezoelectric layer thin film acoustic wave sensor |
| CN101973713A (en) * | 2010-09-25 | 2011-02-16 | 东华大学 | Manufacturing method of polyaniline composite nano fiber membrane optical sensor and detection method thereof |
| CN102226752A (en) * | 2011-04-08 | 2011-10-26 | 常熟舒茨电子科技发展有限公司 | Method for detecting concentration of sulfur dioxide by using photoacoustic spectrometry |
| CN102430325A (en) * | 2011-11-14 | 2012-05-02 | 江苏大学 | Method for mercury removal of coal-fired flue gas |
| CN102565287A (en) * | 2012-01-05 | 2012-07-11 | 上海电力学院 | Evaluation device for coal-fired flue gas pollutant sorbent and application thereof |
| WO2012128131A1 (en) * | 2011-03-23 | 2012-09-27 | 株式会社Ihi | Ultraviolet absorbent and cosmetic preparation using same |
| CN102706862A (en) * | 2012-04-23 | 2012-10-03 | 宁波大学 | Electrogenerated chemiluminescence analysis detector with new added functions |
| CN102980872A (en) * | 2012-11-29 | 2013-03-20 | 太原理工大学 | Optical biological detection method based on tri-doped lithium niobate crystal |
| CN103233397A (en) * | 2013-04-18 | 2013-08-07 | 湖北中烟工业有限责任公司 | Reversible temperature-sensitive cigarette packing paper preparation method |
| CN103236823A (en) * | 2013-04-19 | 2013-08-07 | 山东科技大学 | Thin film bulk acoustic wave resonator capable of efficiently exciting shear wave resonance |
| CN103336039A (en) * | 2013-07-15 | 2013-10-02 | 长沙理工大学 | Sensing chip method for detecting mercury ions based on L-cysteine |
| CN103427778A (en) * | 2013-08-27 | 2013-12-04 | 张家港恩达通讯科技有限公司 | Method for preparing thin film bulk acoustic resonator based on ferroelectric materials and resonator |
| CN103439289A (en) * | 2013-09-02 | 2013-12-11 | 刘永宁 | Multichannel and multi-point-location gas detection system based on second harmonic detection technique |
| CN104316996A (en) * | 2014-11-03 | 2015-01-28 | 东南大学 | Waveguide Bragg grating refractive index sensor based on integrated polymers |
| CN104677399A (en) * | 2014-11-24 | 2015-06-03 | 麦克思智慧资本股份有限公司 | Ultrasonic sensor |
| CN104833610A (en) * | 2015-04-23 | 2015-08-12 | 电子科技大学 | Liquid property measurement method based on piezoelectric bulk acoustic wave resonant sensor |
| CN105189630A (en) * | 2013-03-15 | 2015-12-23 | 伯斯有限公司 | Three-dimensional air-adsorbing structure |
| CN105435659A (en) * | 2014-09-02 | 2016-03-30 | 中国科学院上海高等研究院 | Acid, alkali and organic solvent resisting diaphragm material, and preparation method and application thereof |
| CN106061373A (en) * | 2011-01-28 | 2016-10-26 | 巴伊兰大学 | Method and system for non-invasively monitoring biological or biochemical parameters of individual |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB322729A (en) * | 1928-07-31 | 1929-12-02 | Gramophone Co Ltd | Improved method of photographically recording acoustic frequency oscillations |
| US5759493A (en) * | 1996-04-30 | 1998-06-02 | Arizona Instrument Corporation | Apparatus for detecting a specified gas within a mixture |
| CN1513809A (en) * | 2002-12-31 | 2004-07-21 | 中国科学技术大学 | Preparation method of high performance lead zirconium titanate thin film |
| KR100455127B1 (en) * | 2003-01-24 | 2004-11-06 | 엘지전자 주식회사 | Field emission device and manufacturing method thereof |
| JP4222513B2 (en) * | 2003-08-19 | 2009-02-12 | 日本碍子株式会社 | Mass measuring apparatus and method |
| CN100410657C (en) * | 2004-09-13 | 2008-08-13 | 中国科学院电子学研究所 | Electric heating double parameter detecting chip and its preparing method |
| JP2007180201A (en) * | 2005-12-27 | 2007-07-12 | Yamaha Corp | Semiconductor device |
| JP4226003B2 (en) * | 2005-12-28 | 2009-02-18 | 日本電波工業株式会社 | Sensing device |
| CN100570356C (en) * | 2006-07-14 | 2009-12-16 | 中国科学院声学研究所 | A kind of micro-mass sensor based on difference frequency type film acoustic wave resonator |
| CN100547396C (en) * | 2007-05-08 | 2009-10-07 | 中国科学院上海微系统与信息技术研究所 | A kind of silicon based piezoelectricity thin film sensor and method for making that is applied to biological little quality testing |
| CN100432018C (en) * | 2007-05-23 | 2008-11-12 | 哈尔滨工业大学 | Method for fabricating film of aluminum zirconate titanate with high orientating (111) |
| CN101246162A (en) * | 2008-03-12 | 2008-08-20 | 浙江大学 | Immune body detecting biochip using piezo-electricity thin film acoustic wave device |
| JP4662084B2 (en) * | 2008-07-25 | 2011-03-30 | セイコーエプソン株式会社 | Liquid ejection head and liquid ejecting apparatus |
| CN101465628B (en) * | 2009-01-15 | 2011-05-11 | 电子科技大学 | Film bulk acoustic wave resonator and preparation method thereof |
| CN101846653B (en) * | 2010-04-30 | 2011-09-14 | 湖北大学 | Piezoelectric film bulk acoustic wave sensor with polygonal electrodes |
| CN102650616A (en) * | 2012-02-13 | 2012-08-29 | 湖北大学 | Gold nano porous sensitive film body type acoustic biosensor |
| CN102621025A (en) * | 2012-03-12 | 2012-08-01 | 山东科技大学 | Thin film bulk acoustic resonance biochemical sensor with annular electrodes |
| CN103359677B (en) * | 2012-03-29 | 2015-11-25 | 比亚迪股份有限公司 | A kind of Infrared Detectors encapsulating structure and preparation method thereof |
| CN102838079B (en) * | 2012-09-24 | 2015-04-22 | 江苏物联网研究发展中心 | Open-type packaging structure used for sensor chip and manufacturing method thereof |
| CN102937607B (en) * | 2012-11-09 | 2016-08-10 | 西安交通大学 | A kind of series-connection flexible vibration piezoelectric diaphragm type biosensor and preparation method thereof |
| JP2016516184A (en) * | 2013-03-14 | 2016-06-02 | ユニバーシティ・オブ・ウィンザー | Ultrasonic sensor microarray and manufacturing method thereof |
| CN103336053B (en) * | 2013-06-18 | 2015-11-04 | 电子科技大学 | A kind of surface acoustic wave gas sensors array of private reference |
| CN104038177A (en) * | 2014-06-04 | 2014-09-10 | 江苏艾伦摩尔微电子科技有限公司 | Thin film bulk acoustic resonator for ultraviolet detection and preparation method thereof |
| US10196678B2 (en) * | 2014-10-06 | 2019-02-05 | ALVEO Technologies Inc. | System and method for detection of nucleic acids |
| CN204495981U (en) * | 2014-11-28 | 2015-07-22 | 瑞声光电科技(常州)有限公司 | Based on the surface acoustic wave Magnetic Sensor of magnetoelectric effect |
| CN104764511A (en) * | 2015-04-22 | 2015-07-08 | 厦门大学 | C-axis tilt gallium nitride FBAR piezoelectric mass sensor |
| CN106405446B (en) * | 2016-11-28 | 2023-08-18 | 中国船舶重工集团公司第七一九研究所 | Magnetic sensor array integrated structure and manufacturing method thereof |
| CN207248668U (en) * | 2017-08-31 | 2018-04-17 | 中国船舶重工集团公司第七一九研究所 | Measure the chip of mercury vapour and be equipped with the sensor of the chip |
-
2017
- 2017-08-31 CN CN201710770984.5A patent/CN107643228B/en not_active Expired - Fee Related
Patent Citations (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4893161A (en) * | 1987-09-24 | 1990-01-09 | United Technologies | Quantum-well acoustic charge transport device |
| CN101013082A (en) * | 2007-02-01 | 2007-08-08 | 厦门大学 | Piezo-electric type harmonic oscillation cartridge quality sensing unit |
| JP2009054409A (en) * | 2007-08-27 | 2009-03-12 | Harison Toshiba Lighting Corp | Metal halide lamp, and metal halide lamp lighting device |
| CN101349639A (en) * | 2008-09-10 | 2009-01-21 | 中国烟草总公司郑州烟草研究院 | Method for measuring mercury content in loading paper for cigarette |
| CN101841313A (en) * | 2009-03-19 | 2010-09-22 | 太阳诱电株式会社 | Piezoelectric thin film resonator, filter, communication module and communication device |
| CN101871164A (en) * | 2010-06-17 | 2010-10-27 | 浙江大学 | Preparation method of mercury ion colorimetric sensing cellulose material |
| CN101900709A (en) * | 2010-07-22 | 2010-12-01 | 重庆大学 | Method for improving resolution of single-piezoelectric layer thin film acoustic wave sensor |
| CN101973713A (en) * | 2010-09-25 | 2011-02-16 | 东华大学 | Manufacturing method of polyaniline composite nano fiber membrane optical sensor and detection method thereof |
| CN106061373A (en) * | 2011-01-28 | 2016-10-26 | 巴伊兰大学 | Method and system for non-invasively monitoring biological or biochemical parameters of individual |
| WO2012128131A1 (en) * | 2011-03-23 | 2012-09-27 | 株式会社Ihi | Ultraviolet absorbent and cosmetic preparation using same |
| CN102226752A (en) * | 2011-04-08 | 2011-10-26 | 常熟舒茨电子科技发展有限公司 | Method for detecting concentration of sulfur dioxide by using photoacoustic spectrometry |
| CN102430325A (en) * | 2011-11-14 | 2012-05-02 | 江苏大学 | Method for mercury removal of coal-fired flue gas |
| CN102565287A (en) * | 2012-01-05 | 2012-07-11 | 上海电力学院 | Evaluation device for coal-fired flue gas pollutant sorbent and application thereof |
| CN102706862A (en) * | 2012-04-23 | 2012-10-03 | 宁波大学 | Electrogenerated chemiluminescence analysis detector with new added functions |
| CN102980872A (en) * | 2012-11-29 | 2013-03-20 | 太原理工大学 | Optical biological detection method based on tri-doped lithium niobate crystal |
| CN105189630A (en) * | 2013-03-15 | 2015-12-23 | 伯斯有限公司 | Three-dimensional air-adsorbing structure |
| CN103233397A (en) * | 2013-04-18 | 2013-08-07 | 湖北中烟工业有限责任公司 | Reversible temperature-sensitive cigarette packing paper preparation method |
| CN103236823A (en) * | 2013-04-19 | 2013-08-07 | 山东科技大学 | Thin film bulk acoustic wave resonator capable of efficiently exciting shear wave resonance |
| CN103336039A (en) * | 2013-07-15 | 2013-10-02 | 长沙理工大学 | Sensing chip method for detecting mercury ions based on L-cysteine |
| CN103427778A (en) * | 2013-08-27 | 2013-12-04 | 张家港恩达通讯科技有限公司 | Method for preparing thin film bulk acoustic resonator based on ferroelectric materials and resonator |
| CN103439289A (en) * | 2013-09-02 | 2013-12-11 | 刘永宁 | Multichannel and multi-point-location gas detection system based on second harmonic detection technique |
| CN105435659A (en) * | 2014-09-02 | 2016-03-30 | 中国科学院上海高等研究院 | Acid, alkali and organic solvent resisting diaphragm material, and preparation method and application thereof |
| CN104316996A (en) * | 2014-11-03 | 2015-01-28 | 东南大学 | Waveguide Bragg grating refractive index sensor based on integrated polymers |
| CN104677399A (en) * | 2014-11-24 | 2015-06-03 | 麦克思智慧资本股份有限公司 | Ultrasonic sensor |
| CN104833610A (en) * | 2015-04-23 | 2015-08-12 | 电子科技大学 | Liquid property measurement method based on piezoelectric bulk acoustic wave resonant sensor |
Non-Patent Citations (3)
| Title |
|---|
| 《Piezoelectric Sorption Detector 》;WILLIAM H.等;《ANALYTICAL CHEMISTRY》;19640831;第36卷(第9期);第1735-1739页 * |
| 《不同电极结构的纯横向场激励压电传感器性能研究》;张志甜等;《仪表技术与传感器》;20091231;第28-30页 * |
| 《张应力对准同形相界Pb ( Zr, Ti) O3薄膜相变和铁电性能影响》;闻心怡等;《物理学报》;20111231;第60卷(第09期);第097701页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107643228A (en) | 2018-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Van Hieu | Comparative study of gas sensor performance of SnO2 nanowires and their hierarchical nanostructures | |
| JP4789281B2 (en) | Surface acoustic wave filter and manufacturing method thereof | |
| KR101495422B1 (en) | Hydrogen sensor based on zinc oxide and method of fabricating the same | |
| Wang et al. | A ZnO nanorod-based SAW oscillator system for ultraviolet detection | |
| JPS584986B2 (en) | Oxygen concentration measuring device | |
| CN100422730C (en) | Nano-structure ordered porous film type gas sensor and preparation method thereof | |
| US9522827B2 (en) | Piezoelectric material, piezoelectric member, piezoelectric element, and pressure sensor | |
| KR20050050539A (en) | Lithium niobate substrate and method of producing the same | |
| JP2015065408A (en) | Metal nitride material for thermistor, method for manufacturing the same, and film-type thermistor sensor | |
| JP5966683B2 (en) | Piezoelectric material, piezoelectric member, piezoelectric element and pressure sensor | |
| CN107643228B (en) | Preparation method of chip for measuring mercury vapor and use method of sensor | |
| US20040132202A1 (en) | Ammonia sensor | |
| Yu et al. | Self-powered thermoelectric hydrogen sensors based on low-cost bismuth sulfide thin films: quick response at room temperature | |
| US20220359812A1 (en) | Piezoelectric material, piezoelectric member, piezoelectric element, and pressure sensor | |
| Barbi et al. | High temperature water electrolysis: Cathodic behaviour of Pt/yttria stabilized zirconia (ysz) interface | |
| US20090178925A1 (en) | Chemical Sensor Based on Zinc Oxide Nanostructures for Detection of Hydrazine | |
| JP6245269B2 (en) | Solid electrolyte, all-solid secondary battery using the same, solid electrolyte manufacturing method, and all-solid secondary battery manufacturing method | |
| JP4090148B2 (en) | Method for producing lithium ion conductive glass ceramics | |
| EP1114207B1 (en) | Pellistor | |
| JP2011069705A (en) | Ammonia sensor element and manufacturing method of proton conductive solid electrolyte | |
| KR100316389B1 (en) | A NOx Sensor And A Producting Methode of NOx Sensor | |
| CN114280111A (en) | Cerium-doped tungsten oxide composite material, hydrogen sulfide sensor and preparation method | |
| JP2007101536A (en) | Gas sensor and method for manufacturing the same | |
| JP3550674B2 (en) | Nitrogen oxide sensor | |
| KR20140015554A (en) | Manufacturing method for oxygen sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210427 Termination date: 20210831 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |