CN103940873A - Electrochemical and optoelectronic integrated chip for monitoring heavy metal and wireless buoy sensing system - Google Patents
Electrochemical and optoelectronic integrated chip for monitoring heavy metal and wireless buoy sensing system Download PDFInfo
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- CN103940873A CN103940873A CN201410186971.XA CN201410186971A CN103940873A CN 103940873 A CN103940873 A CN 103940873A CN 201410186971 A CN201410186971 A CN 201410186971A CN 103940873 A CN103940873 A CN 103940873A
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Abstract
The invention discloses an electrochemical and optoelectronic integrated chip for monitoring heavy metal and a wireless buoy sensing system. An electrochemical sensor, a light-addressable potentiometric sensor and a counter electrode array are integrated on a same chip, so that the microminiaturization and the integration of the sensor are achieved, and meanwhile, the data fusion and the calibration of different sensors are introduced, so that the detection accuracy and the anti-jamming capability of the integrated chip are improved. The wireless buoy sensing system comprises a buoy for carrying, a heavy metal detecting instrument fixed inside the buoy for carrying; the heavy metal detecting instrument comprises the electrochemical and optoelectronic integrated chip, a reference electrode, a pump valve waterway module, a signal collection circuit, a light source modulation circuit, an ARM control panel, a test cavity and an excitation light source. Thus, the automatic sampling, the discharging, the automatic detection and the data uploading in the system are achieved, the on-line and real-time monitoring on the heavy metal in lake water is achieved, and the electrochemical and optoelectronic integrated chip for monitoring the heavy metal has a great application prospect.
Description
Technical field
The present invention relates to chemical sensor and field of biosensors, relate in particular to galvanochemistry and photoelectricity integrated chip and the wireless buoy sensor-based system of a heavy metal species monitoring.
Background technology
Heavy metal uses by mining, metal smelting and processing, Chemical Manufacture, agriculture chemical and the various artificial pollution modes such as house refuse enter water body for main path, there is high toxicity, be difficult for metabolism, be easily bioaccumulation and have the features such as biological amplification, serious harm ecologic environment and human health, in the urgent need to setting up the heavy metal real time monitoring system of water environment.Up to now, rare domestic environmental monitoring center changes and monitors the content of beary metal of water body.
Be usually used in the method for heavy metal detection with atomic absorption spectrography (AAS) (Atomic absorption spectroscopy, AAS) and inductively coupled plasma mass spectrometry (Inductively-coupled plasma mass spectroscopy, ICP-MS) be main.Be generally used for laboratory measurement, and need complicated pre-treatment operation, cannot be used for on-the-spot Real-Time Monitoring.And, expensive, the complicated operation of instrument, expend time in long, detect when being difficult to realize various heavy.By contrast, stripping voltammetry by under constant potential to heavy metal accumulation, greatly improved the concentration of working electrode surface heavy metal, with after-applied by bearing to positive scanning voltage, make the heavy metal of enrichment again be oxidized to ionic state, carry out quantitative test by heavy metal characteristic of correspondence peak.Stripping voltammetry has very low detection lower limit, can detect various heavy simultaneously, and Measuring Time is short, highly sensitive, simple to operate, can be used as real-time online detection means.
Microelectrode array (Microelectrode array, MEA) reaches micron-sized electrod-array for certain one dimension size, because its size is little, is convenient to accurately location and analysis, has been widely used in the multiple fields such as biology, chemistry, environment.In electrochemical analysis, compare traditional large electrode, microelectrode array has the good electrochemical properties such as mass transfer rate is high, current density is large, time constant is little, signal to noise ratio (S/N ratio) is high, iR reduction, becomes one of important means of water environment heavy metal detection.The research that researcher detects for heavy metal at microelectrode array both at home and abroad, is only confined to the analysis and research in laboratory conventionally, cannot be applied to on-the-spot actual detection.
Light Addressable Potentiometric Sensor (Light addressable potentiometric sensor, LAPS) be the semiconductor chemical sensor of a kind of function class like chemFET, carry out the field effect of modulation device by light stimulus, this effect is to the sensitive membrane potential change sensitivity between device isolation layer and electrolytic solution, and the ion concentration of its response current and sample is linear, by the response current that obtains reaction zone sensitive membrane, testing sample is quantitatively detected.In the mensuration of pH, LAPS shows good sensitivity, the linearity and stability, has been widely used in biological and cell experiment.
Along with the progress of radio network technique and perfect, sensor is towards the future development of microminiaturized, integrated and networking, and increasing sensor network is applied to field monitoring.The present invention adopts the integrated chip based on galvanochemistry and Light Addressable Potentiometric Sensor, introduces data fusion and the calibration of different sensors, and the impact changing to solve on-the-spot lake Water pH improves accuracy and antijamming capability that integrated chip detects.Simultaneously, designed the wireless network sensor-based system that is installed on buoy and can be used for on-the-spot lake water heavy metal monitoring based on this integrated chip, can realize online, Real-Time Monitoring to lake water heavy metal, by multiple monitoring system composition sensor networks, there is great application prospect simultaneously.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, galvanochemistry and photoelectricity integrated chip and the wireless buoy sensor-based system of a heavy metal species monitoring is provided, the present invention can be for the monitoring real-time of on-the-spot lake water heavy metal ion.
The object of the invention is to be achieved through the following technical solutions: galvanochemistry and the photoelectricity integrated chip of a heavy metal species monitoring, it is by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, microelectrode array by silicon wafer-based at the bottom of, MEA region SiO
2oxide layer, Cr adhesion layer, MEA insulation course and MEA gold electrode composition, to electrod-array by silicon wafer-based at the bottom of, MEA region SiO
2oxide layer, Cr adhesion layer, MEA insulation course and electrode is formed.Light Addressable Potentiometric Sensor is by Al layer, LAPS weakened region, LAPS region SiO
2oxide layer and LAPS insulation course form; Galvanochemistry and the photoelectricity integrated chip of described heavy metal monitoring prepare by the following method:
(1), select 4 inches of silicon chips as silicon wafer-based at the bottom of 10, silicon wafer thickness is 450 μ m, cleans and dries through RCA standard cleaning technique; Reduction processing is carried out in silicon chip back side LAPS corresponding region, utilize photolithography plate to corrode, attenuate silicon wafer thickness to 100 μ m, forms LAPS weakened region, the intensity of response current when LAPS weakened region contributes to improve light stimulus;
(2), remove photoresist the SiO at silicon chip surface heat growth one deck 50nm thickness
2, form LAPS region SiO
2oxide layer;
(3), the Si of PECVD deposition 100nm thickness
3n
4as LAPS insulation course;
(4), two-sided etching SiO
2and Si
3n
4, generate corresponding LAPS shape, form the structure of Light Addressable Potentiometric Sensor;
(5), the impact that LAPS caused for fear of the processing of microelectrode array part, adopting thermal oxidation process is the MEA region SiO of 650 nm at corresponding region growth thickness
2oxide layer;
(6), sputter Cr adhesion layer and gold electrode layer, sputter thickness is respectively 30 nm and 300 nm, by photoetching process etching gold electrode layer, forms respectively MEA gold electrode, to electrode and gold electrode trace layer.
(7), make golden microelectrode array electrode pattern and pad, lead-in wire region by lithography;
(8), use PECVD deposition Si
3n
4insulation course, deposit thickness is 400 nm, as the insulation course of golden microelectrode array;
(9) Si that, etching has deposited
3n
4insulation course, exposes golden microelectrode array electrode pattern, pad lead-in wire region and perform region, LAPS surface;
(10), at silicon chip back side LAPS corresponding region evaporation of aluminum, thickness is 300 nm;
(11), the aluminium that covers of photoetching silicon chip back side, form Al layer.
Galvanochemistry and photoelectricity integrated chip and the wireless buoy sensor-based system of one heavy metal species monitoring, it forms by carrying with buoy and being fixed on the heavy metal detector device of lift-launch in buoy, and heavy metal detector device comprises: galvanochemistry and photoelectricity integrated chip, contrast electrode, pump valve water route module, signal acquisition circuit, modulation of source circuit, ARM control panel, test chamber and exciting light source; Wherein, described galvanochemistry and photoelectricity integrated chip are by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, galvanochemistry and photoelectricity integrated chip are fixed on the bottom of test chamber, contrast electrode inserts the top cover of test chamber, it is internal-filling liquid that contrast electrode uses saturated KCl solution, microelectrode array in contrast electrode and galvanochemistry and photoelectricity integrated chip, Light Addressable Potentiometric Sensor and electrod-array is formed to three-electrode system, as the sensor detecting unit of heavy metal; Galvanochemistry and photoelectricity integrated chip are encapsulated on pcb board by pad, are connected with signal acquisition circuit, carry out signals collecting; The pcb board that is packaged with galvanochemistry and photoelectricity integrated chip is packaged in test chamber bottom to detect; Exciting light source is packaged in the Light Addressable Potentiometric Sensor back in galvanochemistry and photoelectricity integrated chip, is connected with modulation of source circuit, makes Light Addressable Potentiometric Sensor produce photogenerated current by exciting light; Pump valve water route module, signal acquisition circuit are all connected with ARM control panel by serial ports, and modulation of source circuit and signal Acquisition Circuit connects.
The invention has the beneficial effects as follows, it is detecting element that the present invention adopts the photoelectricity integrated chip based on galvanochemistry and Light Addressable Potentiometric Sensor, by data fusion and the calibration of multiple sensors, improves accuracy in detection and the antijamming capability of system.The wireless buoy sensor-based system of design adopts compound circuit structure for designed integrated chip, so that sensor is carried out to modulation of source and signals collecting, realizes automatic analysis and the detection of system.The present invention adopts multi-position valve and syringe pump to build waterway structure, realizes the operation such as automatic sampling, cleaning, stock layout of system.Meanwhile, sensor-based system carries ARM control panel, realizes communicating by letter of wireless buoy sensor-based system and server, to ensure that system wireless control and testing result upload.System is equipped on buoy, can realize the real time monitoring of lake water heavy metal.
Brief description of the drawings
Fig. 1 is the structured flowchart of the wireless buoy sensor-based system of the present invention;
Fig. 2 is the structured flowchart of galvanochemistry of the present invention and photoelectricity integrated chip;
Fig. 3 is the testing circuit structural drawing of the wireless buoy sensor-based system of the present invention;
Fig. 4 is the waterway structure figure of the wireless buoy sensor-based system of the present invention;
Fig. 5 is the buoyage structural drawing that the present invention is carried;
Fig. 6 is that the present invention detects heavy metal Zn in lake water
2+the typical curve result figure of concentration;
Fig. 7 is the response curve result figure that the present invention detects pH value in lake water;
Fig. 8 is the typical curve result figure that the present invention detects pH value in lake water.
In figure, at the bottom of galvanochemistry and photoelectricity integrated chip 1, contrast electrode 2, pump valve water route module 3, signal acquisition circuit 4, modulation of source circuit 5, ARM control panel 6, test chamber 7, exciting light source 8, server 9, silicon wafer-based 10, the SiO of MEA region
2oxide layer 11, Al layer 12, LAPS weakened region 13, LAPS region SiO
2oxide layer 14, Cr adhesion layer 15, MEA insulation course 16, LAPS insulation course 17, MEA gold electrode 18, to electrode 19, gold electrode trace layer 20, MEA testing circuit 21, LAPS testing circuit 22, active shielding circuit 23, filtering zeroing and amplifying circuit 24, D/A converting circuit 25, analog to digital conversion circuit 26, level shifting circuit 27, level shifting circuit 28, serial interface chip 29, multichannel IV translation circuit 30, microprocessor 31, low-pass filter circuit 32, zeroing and amplifying circuit 33, multichannel IV translation circuit 34, four road LAPS commutation circuits 35, impedance chip 36, outer clock circuit 37, four paths of LEDs commutation circuits 38, LED drive circuit 39, three electrodes 40, operational amplifier 41, pure water pond 42, sample cell 43, plating mercury solution pond 44, buffer pool 45, mark liquid pool 46, six path multi-position valves 47, three-way syringe pump 48, waste liquid pool 49, buoy support 50, buoy main body 51, buoy chamber 52, fixation steel plate 53, communications rack 54, thief hole 55, heavy metal detector device 56.
Embodiment
The ultimate principle that the galvanochemistry that place of matchmakers is used in detail below and photoelectricity integrated chip detect for heavy metal.
Electrochemical sensor adopts microelectrode array, utilizes the feature oxidation-reduction potential of different heavy metals to detect.Microelectrode array is in the time applying a constant potential, and heavy metal ion, by electrolytic reduction, changes atomic state into by ionic state, and is deposited on microelectrode array surface.Subsequently, on microelectrode array, apply a reverse scan voltage, make the heavy metal again oxidation dissolution of reduction on microelectrode surface, produce obvious oxidation peak current.Different heavy metals are distinguished by specific oxidizing potential, and the amplitude of oxidation peak current and sample heavy metal concentration linear, for the quantitative test of heavy metal.
Light Addressable Potentiometric Sensor is utilized semi-conductive inner photoeffect, and, in the time that semiconductor is subject to the irradiation of certain wavelength, semiconductor absorbs photon, forms electron hole pair thereby produce forbidden band to the transition of conduction band.At sensor both sides applying bias voltage, in semiconductor, produce depletion layer, a part for photo-generated carrier centering can be at compound front arrival depletion layer again not, so electronics separates with the highfield of the depleted layer in hole, the movement of electron hole pair forms photocurrent.Light Addressable Potentiometric Sensor adopts the irradiation of intensity modulated on the surface of device, the photocurrent alternately changing in external circuit, just can be detected.The size of photocurrent is relevant to sensor two ends electromotive force extent, and its frequency equals to irradiate the frequency that light intensity changes.
Below in conjunction with drawings and Examples, the invention will be further described.
As shown in Figure 1, the present invention is for lake water heavy metal wireless monitor, wireless buoy sensor-based system forms by carrying with buoy and being fixed on the heavy metal detector device of lift-launch in buoy, and heavy metal detector device comprises: galvanochemistry and photoelectricity integrated chip 1, contrast electrode 2, pump valve water route module 3, signal acquisition circuit 4, modulation of source circuit 5, ARM control panel 6, test chamber 7 and exciting light source 8.Wherein, galvanochemistry and photoelectricity integrated chip 1 are by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, and detailed structure as shown in Figure 2.Galvanochemistry and photoelectricity integrated chip 1 are fixed on the bottom of test chamber 7, and contrast electrode 2 inserts the top cover of test chamber 7, and using saturated KCl solution is internal-filling liquid.Microelectrode array (working electrode) in contrast electrode 2 and galvanochemistry and photoelectricity integrated chip 1, Light Addressable Potentiometric Sensor (working electrode) and to electrod-array formation three-electrode system, as the sensor detecting unit of heavy metal.Galvanochemistry and photoelectricity integrated chip 1 are encapsulated on pcb board by pad, are connected with signal acquisition circuit 4, carry out signals collecting.Afterwards, the pcb board that is packaged with galvanochemistry and photoelectricity integrated chip 1 is packaged in test chamber 7 bottoms to detect.Exciting light source 8 is packaged in the Light Addressable Potentiometric Sensor back in galvanochemistry and photoelectricity integrated chip 1, is connected with modulation of source circuit 7, makes Light Addressable Potentiometric Sensor produce photogenerated current by exciting light.Pump valve water route module 3, signal acquisition circuit 4 are all connected with ARM control panel 6 by serial ports, and modulation of source circuit 5 is connected with signal acquisition circuit 4, are subject to the control chip control on signal acquisition circuit 4.
The detailed structure of galvanochemistry and photoelectricity integrated chip as shown in Figure 2.Signal acquisition circuit structural drawing as shown in Figure 3.Pump valve water route module 3 is used No. six multi-position valves and syringe pump design sample introduction pipeline and stock layout pipeline, uses the polyfluortetraethylene pipe of 2mm external diameter to connect water route, samples and stock layout control by detailed waterway structure design, and waterway structure as shown in Figure 4.ARM control panel 6, for detection of the control of circuit, water route module, has data buffer storage, data transmission and the function of ordering control.ARM control panel 6 is controlled with modulation of source circuit 5 and communicates by letter with pump valve water route control 3, signal acquisition circuit 4 by serial ports RS232.Meanwhile, built-in wireless network card in ARM control panel 6, communicates by letter with server 9 by Wi-Fi, detects data upload and reception server 9 is controlled.Buoy structure figure as shown in Figure 5.
As shown in Figure 2, be the detailed structure view of galvanochemistry and photoelectricity integrated chip.Galvanochemistry and photoelectricity integrated chip be by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, microelectrode array by silicon wafer-based at the bottom of 10, MEA region SiO
2oxide layer 11, Cr adhesion layer 15, MEA insulation course 16 and MEA gold electrode 18 form, to electrod-array by silicon wafer-based at the bottom of 10, MEA region SiO
2oxide layer 11, Cr adhesion layer 15, MEA insulation course 16 and electrode 19 is formed.Light Addressable Potentiometric Sensor is by Al layer 12, LAPS weakened region 13, LAPS region SiO
2oxide layer 14 and LAPS insulation course 17 form.Its concrete work flow is as follows:
1, select 4 inches of silicon chips as silicon wafer-based at the bottom of 10, silicon wafer thickness is 450 μ m, cleans and dries through RCA standard cleaning technique; Reduction processing is carried out in silicon chip back side LAPS corresponding region, utilize photolithography plate to corrode, attenuate silicon wafer thickness to 100 μ m, forms LAPS weakened region 13, the intensity of response current when LAPS weakened region 13 contributes to improve light stimulus;
2, remove photoresist the SiO at silicon chip surface heat growth one deck 50nm thickness
2, form LAPS region SiO
2oxide layer 14;
3, the Si of PECVD deposition 100nm thickness
3n
4as LAPS insulation course 17;
4, two-sided etching SiO
2and Si
3n
4, generate corresponding LAPS shape, form the structure of Light Addressable Potentiometric Sensor;
5, the impact for fear of the processing of microelectrode array part, LAPS being caused, adopts the MEA region SiO that thermal oxidation process is 650nm at corresponding region growth thickness
2oxide layer 11;
6, sputter Cr adhesion layer 15 and gold electrode layer, sputter thickness is respectively 30 nm and 300 nm, by photoetching process etching gold electrode layer, forms respectively MEA gold electrode 18, to electrode 19 and gold electrode trace layer 20.
7, make golden microelectrode array electrode pattern and pad, lead-in wire region by lithography;
8, use PECVD deposition Si
3n
4insulation course 16, deposit thickness is 400 nm, as the insulation course of golden microelectrode array;
9, the Si that etching has deposited
3n
4insulation course 16, exposes golden microelectrode array electrode pattern, pad lead-in wire region and perform region, LAPS surface;
10, at silicon chip back side LAPS corresponding region evaporation of aluminum, thickness is 300 nm;
11, the aluminium that photoetching silicon chip back side covers, forms Al layer 12.
As shown in Figure 3, be galvanochemistry of the present invention and photoelectricity integrated chip testing circuit structural drawing, formed by signal acquisition circuit 4 and 5 two modules of modulation of source circuit; Signal acquisition circuit 4 is divided into again MEA testing circuit 21 and 22 two modules of LAPS testing circuit, shares same microprocessor 31.The mixed-signal processor MSP426FG4619 that whole system adopts 16 super low-power consumptions, have reduced instruction set computer, as microcontroller 31, realizes the control to whole system testing process.Three electrodes 40 form reliable three-electrode system with operational amplifier 41, comprise the LED light source being integrated in wherein in system.MEA and LAPS signal that three-electrode system produces are gathered, are nursed one's health by signal acquisition circuit 4.Signal acquisition circuit 4 is made up of MEA testing circuit 21 and 22 two modules of LAPS testing circuit.
In figure, 21 is structured flowcharts of MEA testing circuit 21.MEA testing circuit has carried out the preliminary filtering of LC at front end to three electrode output signal, adopts coaxial wire to transmit, and adopts active shielding 23 to improve shield effectiveness for the screen layer of working electrode and contrast electrode simultaneously.Also taked the form of short-circuited conducting sleeve to improve signal to noise ratio (S/N ratio) for the signal lead on pcb board.Electrochemical signals converts faint current signal to stronger voltage signal by I/V change-over circuit 30.The voltage signal of changing out after filtering simultaneously, zeroing and amplifying circuit 24 carry out signal condition: utilize four different single order passive RC filters to carry out low-pass filtering to voltage signal, remove the high frequency noise that circuit system may be introduced; Introduce zeroing circuit the signal of sending into analog to digital conversion circuit 26 is carried out to pre-service, DC-offset correction, makes full use of the range of conversion chip; In addition also signal has been carried out to a homophase and amplified, object is also the range in order more to make full use of conversion chip, realizes At High Resolution conversion.What D/A converting circuit 25 used is the DAC712 chip of TI company, is 16 figure place weighted-voltage D/A converters of 16 bus interface, is used to provide the needed bias voltage of electrochemical reaction, have chance with screened circuit 23 voltages and the needed calibration current potential of circuit self-inspection.What analog to digital conversion circuit 26 adopted is the ADS8505 chip of TI company, and this chip is 16 250kHz CMOS analog to digital converters, has 16 bus interface and 2.5V internal reference voltage, is used for the electrochemical signals producing to gather.The bus interface of D/A converting circuit 25 and analog to digital conversion circuit 26 shares level shifting circuit 27 and level shifting circuit 28.Level shifting circuit is connected with the universaling I/O port of microprocessor 31, and controls its level conversion direction by microprocessor 31.Realize the core procedure differential pulse scanning stripping voltammetry in testing process by programming on microcontroller 31.Differential pulse scanning stripping voltammetry has been eliminated the impact of background current substantially, and detection limit is declined, and sensitivity greatly improves.On software, coordinate hardware to realize the automatic range function of system simultaneously, improved the precision detecting.
In figure, 22 is structured flowcharts of LAPS detection module 22.In LAPS signal detection process, microcontroller 31 is by the corresponding LAPS sensor passage of pilot relay gating.The ultra-weak electronic signal that LAPS produces converts photocurrent to voltage signal by I/V translation circuit 34.Then utilize zeroing and amplifying circuit 33 to carry out the conditioning of sensor signal: the direct current biasing error of removing system by zeroing circuit; Signal is carried out to homophase amplification, improve signal to noise ratio (S/N ratio), effectively utilize chip detection scope.Low-pass filter circuit 32 uses the LTC1569-7 chip of LINEAR company, and filter range is optional, and filtering low-frequency noise improves signal quality.Impedance chip 36 AD5933 are by providing a high-frequency ac driving source to carry out the detection of impedance to LED drive circuit 39.The result that impedance chip 36 detects passes to microprocessor 31 MSP426FG4619 for post-processed by I2C bus communication.Outer clock circuit 37 uses ADF4001 clock signal chip and the active crystal oscillator of 16M, is controlled and is provided reliable and stable clock signal for impedance chip 36 by microprocessor 31.
In order to realize optimized detection, signal acquisition circuit 4 is provided with the I/V translation circuit 25 of the different gears in four tunnels, utilize two electronic switches to switch complete whole current-to-voltage converting circuit, every group independently I/V translation circuit all carry out the compensation of corresponding amplitude versus frequency characte and phase propetry, ensure system stability; Two analog switches are not included in amplifier feedback control loop; Analog switch is controlled by microprocessor 31, synchronously connects a certain group of I/V translation circuit, is worked by this group I/V translation circuit, and working electrode Stripping Currents is converted to voltage signal.
Modulation of source circuit 5 is mainly made up of LED drive circuit 39 and four paths of LEDs commutation circuit 38 two parts.LED drive circuit 39 is constant current sources that size is adjustable that are made up of DAC8811 and operational amplifier, and DAC8811 provides a direct current biasing, the driving source acting in conjunction driving sensor LED light source providing with impedance chip 36.
Whole system utilizes serial interface chip 29 to realize communicating by letter between microcontroller 31 MSP426FG4619 and host computer by RS232 serial communication, realizes relevant control and data-transformation facility to slave computer.Also realize the function of startup self-detection in order to improve the stability of system, can carry out self-inspection and self calibration to circuit self and microelectrode array sensor by the control of circuit pathways, realized robotization, the intellectuality of the whole testing process of system.
As shown in Figure 4, be the detailed waterway structure figure of the present invention, for controlling sample introduction and the stock layout of testing process.Pump valve water route module 3 is mainly connected and is formed by six path multi-position valve 47Yu No. tri-syringe pumps 48.Six path multi-position valves 47 respectively with pure water pond 42, sample cell 43, plating mercury solution pond 44, buffer pool 45, mark liquid pool 46 and test chamber 7 is connected, and extracts or discharge various reagent by syringe pump 48.Syringe pump path is connected with test chamber, for the solution of emptying test chamber.And be connected with waste liquid pool 49, by extract solution from test chamber 7, finally enter waste liquid pool 49.
The water-flow chart that the present invention is complete is: syringe pump extracts pure water and enters test chamber 7 from pure water pond 42, and test chamber is cleaned.Subsequently the pure water in test chamber 7 is entered to waste liquid pool 49.Extracting reagent mercury solution pond 44 from plating enters test chamber 7 galvanochemistry and photoelectricity integrated chip is carried out to pre-treatment.Test chamber 7 is carried out to discharge opeing and cleaning.Extracting lake water sample to be measured from sample cell 43 again carries out test chamber 7 and detects for the first time.After detection completes, the standard solution extracting in mark liquid pool 46 enters test chamber 7, detects for the second time.After detection completes, test chamber 7 is carried out to discharge opeing and cleaning, and carry out heavy metal concentration analysis according to the testing result of twice.
As shown in Figure 5, be the sectional view of whole buoy monitoring system.System is by buoy support 50, and buoy main body 51 and buoy chamber 52 and heavy metal detector device 56 totally four parts form.Heavy metal detector device 56 is placed in buoy chamber 52, is fixed upper and lower by fixation steel plate 53, prevents that detecting instrument from rocking in the time of the Site Detection of lake.Fixation steel plate 53 is fixed on buoy by fixing threaded hole.The upper outside communications rack 54 that is equipped with of buoy, for the antenna of fixed test instrument, to ensure the stabilized communication distance of instrument.On buoy, be designed with thief hole 55, heavy metal detector device 56 extracts sample by conduit via thief hole 55 from lake water, realizes the sampling process of actual sample.
The workflow that the present invention is complete is: server 9 is sent and starts sense command to wireless buoy sensor-based system by Wi-Fi mode, and ARM control panel 6 receives also and starts to carry out sequential after resolve command.Six path multi-position valves 47 are started working with three-way syringe pump 48, extract on-the-spot lake water sample enter test chamber 7 through thief hole 55.Subsequently, ARM control panel 6 is controlled MEA testing circuit 21 and is started working with LAPS testing circuit 22, gathers the response signal of galvanochemistry and photoelectricity integrated chip.After detection completes, emptying and clean test chamber 7 by six path multi-position valves 47 and three-way syringe pump 48.The built-in program of ARM control panel 6 carries out uploading result to server 9 after concentration analysis, completes the field monitoring flow process of heavy metal.
Provide application case of the present invention below.
As shown in Figure 6, for the present invention is for heavy metal Zn
2+the typical curve result figure detecting.Adopt the ultrapure water (18.2M Ω cm) of Milipore company and the Klorvess Liquid that analytically pure potassium chloride compound concentration is 0.5M.Adopt the heavy metal Zn through the 100mg/L of standard substance certification
2+standard solution is for the demarcation of typical curve.Respectively solution is carried out to mark-on, heavy metal Zn in solution
2+concentration is 10 μ g/L, 20 μ g/L, and 30 μ g/L, 40 μ g/L, 50 μ g/L. use the wireless buoy sensor-based system of the present invention to detect sample.Accumulating potential is-1.35V, enrichment time 120s, and tranquillization time 15s, scanning voltage scope-1.3V is to-0.8V.Record its Stripping Voltammetry curve, the peak height value of getting its stripping curve is ordinate, and concentration value is that horizontal ordinate obtains its corresponding typical curve.
As shown in Figure 7, the response curve result figure detecting for sample pH for the present invention.Adopt the ultrapure water (18.2M Ω cm) of Milipore company and the Klorvess Liquid that analytically pure potassium chloride compound concentration is 0.5M.The HCl of the 1mol/L of employing purity assay and NaOH are for the adjustment of pH.Bias voltage is 1.4V, and optical frequency is 4000Hz.Under condition of different pH, obtain after response curve, curve is normalized, curve as shown in Figure 7.
As shown in Figure 8, the typical curve result figure detecting for sample pH for the present invention.By the characteristic response voltage of calculated response curve, adopting the voltage of second order number of plies zero point (flex point) of response curve is character voltage, and taking pH as horizontal ordinate, characteristic response voltage is ordinate, obtains the typical curve that system of the present invention detects for pH.
Claims (2)
1. galvanochemistry and the photoelectricity integrated chip of a heavy metal species monitoring, is characterized in that, it is by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, microelectrode array by silicon wafer-based at the bottom of (10), MEA region SiO
2oxide layer (11), Cr adhesion layer (15), MEA insulation course (16) and MEA gold electrode (18) composition, to electrod-array by silicon wafer-based at the bottom of (10), MEA region SiO
2oxide layer (11), Cr adhesion layer (15), MEA insulation course (16) and to electrode (19) composition, Light Addressable Potentiometric Sensor is by Al layer (12), LAPS weakened region (13), LAPS region SiO
2oxide layer (14) and LAPS insulation course (17) form; Galvanochemistry and the photoelectricity integrated chip of described heavy metal monitoring prepare by the following method:
(1), select 4 inches of silicon chips as silicon wafer-based at the bottom of (10), silicon wafer thickness is 450 μ m, cleans and dries through RCA standard cleaning technique; Reduction processing is carried out in silicon chip back side LAPS corresponding region, utilize photolithography plate to corrode, attenuate silicon wafer thickness to 100 μ m, forms LAPS weakened region (13), the intensity of response current when LAPS weakened region (13) contributes to improve light stimulus;
(2), remove photoresist the SiO at silicon chip surface heat growth one deck 50nm thickness
2, form LAPS region SiO
2oxide layer (14);
(3), the Si of PECVD deposition 100nm thickness
3n
4as LAPS insulation course (17);
(4), two-sided etching SiO
2and Si
3n
4, generate corresponding LAPS shape, form the structure of Light Addressable Potentiometric Sensor;
(5), the impact that LAPS caused for fear of the processing of microelectrode array part, adopting thermal oxidation process is the MEA region SiO of 650 nm at corresponding region growth thickness
2oxide layer (11);
(6), sputter Cr adhesion layer (15) and gold electrode layer, sputter thickness is respectively 30 nm and 300 nm, by photoetching process etching gold electrode layer, forms respectively MEA gold electrode (18), to electrode (19) and gold electrode trace layer (20);
(7), make golden microelectrode array electrode pattern and pad, lead-in wire region by lithography;
(8), use PECVD deposition Si
3n
4insulation course (16), deposit thickness is 400 nm, as the insulation course of golden microelectrode array;
(9) Si that, etching has deposited
3n
4insulation course (16), exposes golden microelectrode array electrode pattern, pad lead-in wire region and perform region, LAPS surface;
(10), at silicon chip back side LAPS corresponding region evaporation of aluminum, thickness is 300 nm;
(11), photoetching silicon chip back side cover aluminium, form Al layer (12).
2. galvanochemistry and photoelectricity integrated chip and the wireless buoy sensor-based system of a heavy metal species monitoring, it is characterized in that, it forms by carrying with buoy and being fixed on the heavy metal detector device of lift-launch in buoy, and heavy metal detector device comprises: galvanochemistry and photoelectricity integrated chip (1), contrast electrode (2), pump valve water route module (3), signal acquisition circuit (4), modulation of source circuit (5), ARM control panel (6), test chamber (7) and exciting light source (8); Wherein, described galvanochemistry and photoelectricity integrated chip (1) are by microelectrode array, form electrod-array and Light Addressable Potentiometric Sensor, galvanochemistry and photoelectricity integrated chip (1) are fixed on the bottom of test chamber (7), contrast electrode (2) inserts the top cover of test chamber (7), it is internal-filling liquid that contrast electrode (2) uses saturated KCl solution, microelectrode array in contrast electrode (2) and galvanochemistry and photoelectricity integrated chip (1), Light Addressable Potentiometric Sensor and to electrod-array formation three-electrode system, as the sensor detecting unit of heavy metal; Galvanochemistry and photoelectricity integrated chip (1) are encapsulated on pcb board by pad, are connected with signal acquisition circuit (4), carry out signals collecting; The pcb board that is packaged with galvanochemistry and photoelectricity integrated chip (1) is packaged in test chamber (7) bottom to detect; Exciting light source (8) is packaged in the Light Addressable Potentiometric Sensor back in galvanochemistry and photoelectricity integrated chip (1), is connected with modulation of source circuit (7), makes Light Addressable Potentiometric Sensor produce photogenerated current by exciting light; Pump valve water route module (3), signal acquisition circuit (4) are all connected with ARM control panel (6) by serial ports, and modulation of source circuit (5) is connected with signal acquisition circuit (4).
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