CN114264646B - Device and method for detecting NO by using photodiode with temperature compensation - Google Patents
Device and method for detecting NO by using photodiode with temperature compensation Download PDFInfo
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Abstract
The invention discloses a device and a method for detecting NO by using a photodiode with temperature compensation. The device comprises: the device comprises a measuring optical cavity, a compensating optical cavity, a measuring photodiode, a compensating photodiode and a signal amplifying temperature compensating circuit. The NO gas and ozone generate chemiluminescence reaction in the measuring optical cavity to generate weak optical signals, and the compensating optical cavity obtains background signals. The two paths of signals are collected by the measuring photodiode and the compensating photodiode, and the two paths of signals are subjected to differential processing by the differential amplifying circuit after passing through the current amplifying circuit with the same amplification factor to obtain compensated signals. By this means, NO detection concentration is obtained, while temperature and noise compensation is automatically performed, eliminating baseline drift. The device is particularly suitable for miniaturized and batch production.
Description
Technical Field
The invention belongs to the technical field of photoelectric detection of chemiluminescent reaction, and particularly relates to a device and a method for detecting low-concentration NO by using a photodiode with automatic temperature compensation.
Background
In the field of photo detection, photodiodes may be used as detectors for weak light signal detection, such as low concentration NO detection. The working principle of the photodiode is that the photoelectric effect is utilized, when the light irradiates, the energy of photons is absorbed, and carriers have the capacity of breaking loose valence bands, but if the energy of photons is insufficient, the carriers are not emitted but are transited to conduction bands, so that the electrochemical characteristics of the material are changed. When an electric field is externally applied, a self-built electric field is generated in the material, and a photovoltage is generated under the action of the self-built electric field, so that a photocurrent signal is output.
The small size of the photodiode is an ideal choice for miniaturized NO detection instruments, the spectral response range of the photodiode can meet the requirements of projects, and the photodiode has the advantages of good linear characteristics, small applied voltage, small dark current, small size, good stability, low price and the like.
When the illumination is zero, the photodiode also has a current output, and the output current is dark current. In general, in photoelectric precision measurement, a measured signal is weak, and thus the influence of dark current is very remarkable. In theory, the intensity of carrier movement is different at different temperatures, and the carrier movement speed is increased along with the temperature rise, so that the dark current is increased, therefore, the temperature is an important factor influencing the dark current, which leads to the deterioration of the output signal to noise ratio and is unfavorable for the detection of weak light signals, so that the research on the influence of temperature change on the static characteristics of the photodiode is very important, and the dark current changes along with the temperature change, because electrons in a valence band become more active along with the temperature rise and are excited to a conduction band. As the temperature increases, the dark current increases significantly.
The temperature characteristic of the photodiode dark current can be expressed by the following formula:
Wherein T CID is the temperature coefficient of the dark current of the photodiode, I D1 is the dark current at T 1 ℃, I D2 is the dark current at T 2 ℃,
Photodiodes, like diodes, have a relatively large negative temperature coefficient, and temperature fluctuations can lead to a baseline temperature drift of the detector, for which purpose compensation of the detector temperature effects or control of the temperature of the environment in which the detector is used is required for photoelectric detection. Such as: the patent CN103674914A and the patent CN109283172A, which are made by the article "design of a temperature control system of an optical signal detection module in an automatic analyzer for the concentration of nitrogen oxides in the atmosphere by a chemiluminescence method" (Korea, et al, optical and photoelectric technology, 21 volume 1, pages 80-84), adopt a semiconductor refrigeration mode to control a detector to be below room temperature, thereby realizing low temperature and low temperature drift. However, the method has the defects of complex structure design of the detector, heat insulation problem of front optical cavity heating and rear detector cooling, large volume, large power consumption and the like, and is not suitable for a micro instrument. The research paper (Wang Tao, yan Shanda, 2019) and the research of embedded intelligent photoelectric sensor (Yuanqiang, daqing petroleum institute, 2008) adopt a software compensation algorithm to perform temperature compensation, firstly, a temperature correction function or curve of a sensor needs to be drawn, and then concentration correction is performed according to the use temperature. The method requires placing the sensor in a calibration box with adjustable temperature, and a great deal of time, manpower and material resources are required for carrying out a great deal of experiments on the temperature. The temperature correction experiment needs to be carried out again after the sensor is replaced, and the sensor is not suitable for mass production.
In order to overcome the defects of temperature compensation, the invention adopts hardware to automatically carry out temperature compensation on the photodiode detector, thereby realizing the detection of NO, eliminating baseline drift and inhibiting the temperature drift and noise of the detector.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a temperature automatic compensation device and a method for detecting low-concentration NO by utilizing a photodiode, which are applied to the field of chemiluminescence reaction, so as to achieve the aims of eliminating signal baseline drift and inhibiting detector temperature drift.
The technical scheme of the invention is as follows:
in one aspect, the present invention provides a photodiode NO detection device with temperature compensation, comprising: the device comprises a measuring optical cavity, a compensating optical cavity, a measuring photodiode, a compensating photodiode and a signal amplifying temperature compensating circuit;
The measuring optical cavity is a hollow cavity with an opening of the base, two side surfaces of the hollow cavity are respectively provided with an ozone measuring air inlet and a gas measuring air outlet, and the top of the hollow cavity is provided with an NO air inlet; ozone enters the measuring light cavity through the measuring ozone air inlet, NO gas enters the measuring light cavity through the NO air inlet, chemiluminescent reaction occurs in the measuring light cavity, and the reacted gas flows out from the gas outlet;
The compensation optical cavity is a hollow cavity with an opening of the base, and two side surfaces of the hollow cavity are respectively provided with a compensation ozone inlet and a compensation ozone outlet; the compensation ozone outlet of the compensation optical cavity is communicated with the measurement ozone inlet of the measurement optical cavity;
The measuring photodiode and the compensating photodiode are respectively positioned on the cavity base of the measuring optical cavity and the cavity base of the compensating optical cavity, and the bases of the two hollow cavities are respectively sealed;
The signal amplification temperature compensation circuit performs the same-multiple amplification on the signals detected by the measurement photodiode and the compensation photodiode respectively to obtain an amplified detection signal and a compensation signal, and performs differential processing on the amplified detection signal and the compensation signal to obtain a compensated output signal.
Preferably, the signal amplification temperature compensation circuit includes two current amplification circuits and one differential amplification circuit; the two current amplifying circuits respectively comprise an operational amplifier with the same model number, a feedback resistor with the same value and a feedback capacitor, and the weak currents generated by the measurement photodiode and the compensation photodiode are amplified in the same proportion; the differential amplifying circuit comprises an operational amplifier and four resistors, and is used for carrying out differential amplification on signals output by the two current amplifying circuits and outputting signals after temperature compensation.
Preferably, the signal amplification temperature compensation circuit further comprises another software differential temperature compensation circuit, and the software differential temperature compensation circuit comprises an analog switch, a weak current amplification circuit and a microcontroller. The signal output ends of the compensation photodiode and the detection photodiode are respectively connected with two signal input ends of the analog switch, and the output end of the analog switch is connected with the micro controller. The analog switch can realize that the output end of the analog switch is respectively and independently connected with the output ends of the compensation photodiode and the detection photodiode under the control of the micro controller. The software differential temperature compensation method of the signal amplification temperature compensation circuit comprises the following steps: the micro controller firstly acquires the background signal of the compensation photodiode before detection, and then acquires the photochemical reaction signal of the detection photodiode. And carrying out differential operation on the photochemical reaction signal and the background signal to obtain a signal after temperature compensation.
Preferably, the measuring optical cavity and the compensating optical cavity are rectangular cavities with hemispherical cavities inside; the inner and outer structures of the compensating optical cavity are the same as the measuring optical cavity except different gas inlets and outlets.
Preferably, the measuring optical cavity and the compensating optical cavity are either integrated or split. The two cavities are in the same working environment: the same temperature, humidity and air pressure.
Preferably, the inside of the measuring optical cavity and the compensating optical cavity is subjected to mirror polishing or coating treatment.
Preferably, the measurement photodiode and the compensation photodiode are selected from the same model and the same batch of devices.
Preferably, the signal amplification temperature compensation circuit, the measurement photodiode, and the compensation photodiode are subjected to shielding processing.
Preferably, the current amplifying circuit has an amplifying power of 0.1-100G, and the post differential amplifying circuit has an amplifying power of 1-100.
In another aspect, the present invention provides a method for detecting NO using the above device, the method comprising: ozone enters the compensation optical cavity through the compensation ozone air inlet, the compensation photodiode detects a background signal without mixed NO gas, then the ozone flows out from the compensation ozone air outlet, enters the measurement optical cavity through the measurement ozone air inlet, carries out chemiluminescence reaction with the NO gas entering through the NO air inlet, at the moment, the measurement photodiode detects a chemiluminescent signal, the two paths of signals are amplified by the signal amplifying temperature compensation circuit in the same multiple way, and the amplified detection signal and compensation signal output NO detection concentration after baseline correction and temperature and noise compensation after differential processing.
Preferably, the concentration of ozone is much greater than the concentration of NO gas.
Advantageous effects
The invention adopts the design of double optical cavities and double photodiodes, one optical cavity and the photodiode are used for detecting NO, the other optical cavity and the photodiode are used as reference and compensation, weak signals are amplified by the same current amplifying circuit, and the differential amplifying circuit is used for differentiating the detection signals and the compensation signals, so that the compensated useful output signals are obtained.
Due to the large temperature coefficient of the photodiode, the dark current is different at different temperatures, and temperature compensation is necessary when detecting NO with the photodiode. When the measuring optical cavity and the compensating optical cavity are under the same environmental condition, the dark current of the photodiodes of the same type is the same. After passing through the same current amplifying circuit, the signals amplified by the same times are subjected to differential processing by utilizing a differential amplifying circuit to obtain the required signals. By the device, the temperature and noise compensation of the photodiode which can automatically perform chemiluminescence reaction at the same time of obtaining the NO detection concentration can be realized, and baseline drift can be eliminated. The huge temperature control device of semiconductor refrigeration is omitted, and the volume of the device is reduced. And a great deal of time, manpower and material resources are not required to be spent, and temperature correction experiments are carried out on each device. Is especially suitable for miniaturized and batch production.
Drawings
Fig. 1 is a schematic diagram of a photodiode NO detection device with temperature compensation according to embodiment 1.
Fig. 2 is a schematic diagram of a photodiode NO detection device with temperature compensation according to embodiment 2.
In the figure, 1-measuring the optical cavity; a 2-NO inlet; 3-measuring ozone inlet; 4-compensating an ozone outlet; 5-compensating the optical cavity; 6-compensating ozone inlet; 7-compensating photodiodes; 8-measuring a gas outlet; 9-measuring a photodiode; 10-a signal amplification temperature compensation circuit; 11-a software differential signal amplification temperature compensation circuit.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
Example 1
Fig. 1 is a schematic diagram of a photodiode NO detection device with temperature compensation according to embodiment 1, which mainly includes: a measuring optical cavity 1, a compensating optical cavity 5, a measuring photodiode 9, a compensating photodiode 7 and a signal amplifying temperature compensating circuit 10.
The measuring optical cavity 1 is a rectangular cavity with a hemispherical cavity inside, and the hemispherical cavity base is open. The two sides of the rectangular cavity are respectively provided with an ozone measuring air inlet 3 and an air measuring outlet 8. The top of the rectangular cavity is provided with an NO air inlet 2. The internal and external structures of the compensation optical cavity 5 are the same as those of the measurement optical cavity. Only two sides of the rectangular cavity are respectively provided with a compensation ozone inlet 6 and a compensation ozone outlet 4. The compensating ozone outlet 4 of the compensating optical cavity 5 is communicated with the measuring ozone inlet 3 of the measuring optical cavity 1.
The two photodiodes, the measuring photodiode 9 and the compensating photodiode 7 are respectively positioned on the hemispherical cavity base of the measuring optical cavity 1 and the hemispherical cavity base of the compensating optical cavity 5, and the two hemispherical cavities are respectively sealed. The measurement photodiode 9 serves to detect a weak light signal generated by the chemiluminescent reaction. The compensation photodiode 7 plays a role in compensating for temperature, noise and baseline.
The signal amplification temperature compensation circuit 10 is composed of two weak current amplification circuits and a differential amplification circuit. U1, R1 and C1 constitute a current amplifying circuit of the compensation photodiode. U2, R2 and C2 constitute a current amplifying circuit of the measurement photodiode. The two amplifier circuits have the same operational amplifier model, r1=r2, c1=c2, and thus have the same amplification factor. The differential amplifying circuit is composed of one operational amplifier U3 and four resistors R3, R4, R5, and R6, wherein r3=r5, r4=r6. Signals of the measuring amplifying circuit and the compensating amplifying circuit are input into the differential amplifying circuit for differential amplification, and then the detected NO signal after temperature compensation can be obtained.
The detection process using the device comprises the following steps:
ozone firstly enters the compensation optical cavity 5 through the compensation ozone air inlet 6, NO mixed NO gas background signal is detected by the compensation photodiode 7, then the ozone exits from the compensation ozone air outlet 4, and then enters the measurement optical cavity 1 through the measurement ozone air inlet 3 to carry out chemiluminescence reaction with NO gas. At this point the measurement photodiode 9 detects the chemiluminescent signal. The two signals output the detected NO concentration signal after baseline correction and temperature and noise compensation after passing through the signal amplification temperature compensation circuit 10.
In order to better realize the temperature compensation function, the measuring optical cavity 1 and the compensating optical cavity 5 are positioned in the same working environment: the same temperature, humidity and air pressure. The two can be designed as a whole or in a split structure.
The measuring photodiode 9 and the compensating photodiode 7 are selected from the same model and the same batch of devices.
In order to reduce the disturbance from the outside, the signal amplification temperature compensation circuit 10, the measurement photodiode 9, and the compensation photodiode 7 perform shielding processing.
The signal amplifying circuit and the differential amplifying circuit may form a multi-stage amplifying circuit, for example: the current amplification circuit has an amplification factor of 0.1G, the differential amplification circuit has an amplification factor of 10, and the final signal amplification factor is 1G.
In order to improve the detection sensitivity, the inside of the optical cavity is subjected to mirror polishing or plating treatment.
Example 2
Fig. 2 is a schematic diagram of a photodiode NO detection device with temperature compensation provided in embodiment 2, and the other components and connection relationships are the same as those in embodiment 1 except for a signal amplification temperature compensation circuit. The temperature compensation method adopts software differential temperature compensation.
In embodiment 2, the software differential signal amplification temperature compensation circuit 11 includes an analog switch U3, a weak current amplification circuit, and a microcontroller U2. Wherein U1, R1 and C1 constitute a current amplifying circuit of the compensation photodiode. The signals output by the compensation photodiode 7 and the detection photodiode 9 are respectively connected with two signal input ends S1 and S2 of the analog switch U3, and an output end D is connected with the micro controller U2. The two control ends C1 and C2 and the enabling end ENB of the analog switch U3 are connected with the pin of the micro controller U2.
The detection process of the device comprises the following steps:
When detection is needed, ozone firstly enters the compensation optical cavity 5 through the compensation ozone air inlet 6, firstly the micro controller U2 controls the analog switch U3 to enable the S1 to be communicated with the D, the compensation photodiode 7 enters the micro controller U2 after being amplified by the weak current amplifying circuit U1, background signals at the current temperature are collected, and then NO gas enters the measurement optical cavity 1 to carry out chemiluminescence reaction with ozone. At this time, the micro controller U2 controls the analog switch U3 to enable the S2 to be communicated with the D, the measurement photodiode 9 enters the micro controller U2 after being amplified by the weak current amplifying circuit U1, and chemiluminescent signals at the current temperature are collected. The two paths of signals are subjected to differential operation in the MCU, and the result is the detected NO concentration signal subjected to baseline correction, temperature and noise compensation.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.
Claims (8)
1. A photodiode NO detection device, the device comprising: the device comprises a measuring optical cavity, a compensating optical cavity, a measuring photodiode, a compensating photodiode and a signal amplifying temperature compensating circuit;
The measuring light cavity is a hollow cavity with an opening of the base, two side surfaces of the hollow cavity are respectively provided with an ozone measuring air inlet and a gas measuring air outlet, and the top of the hollow cavity is provided with an NO air inlet;
the compensating light cavity is a hollow cavity with an opening of the base, and two side surfaces of the hollow cavity are respectively provided with a compensating ozone inlet and a compensating ozone outlet; the compensation ozone outlet of the compensation optical cavity is communicated with the measurement ozone inlet of the measurement optical cavity;
the measuring photodiode and the compensating photodiode are respectively positioned on the cavity base of the measuring optical cavity and the cavity base of the compensating optical cavity, and the bases of the two hollow cavities are respectively sealed;
The signal amplification temperature compensation circuit is used for amplifying the signals detected by the measurement photodiode and the compensation photodiode by the same multiple to obtain amplified detection signals and compensation signals, and carrying out differential processing on the amplified detection signals and the compensation signals to obtain compensated output signals;
The signal amplification temperature compensation circuit comprises two current amplification circuits and a differential amplification circuit; the two current amplifying circuits respectively comprise an operational amplifier with the same model number, a feedback resistor with the same value and a feedback capacitor, and the weak currents generated by the measurement photodiode and the compensation photodiode are amplified in the same proportion; the differential amplifying circuit comprises an operational amplifier and four resistors, and is used for carrying out differential amplification on signals output by the two current amplifying circuits and outputting signals after temperature compensation;
Or the signal amplification temperature compensation circuit comprises a software differential temperature compensation circuit, and the software differential temperature compensation circuit comprises an analog switch, a weak current amplification circuit and a micro controller; the two signal input ends of the analog switch are respectively connected with the signal output ends of the compensation photodiode and the detection photodiode, the output end of the analog switch is connected with the micro controller, and the input end of the micro controller for controlling the analog switch is respectively and independently connected with the output ends of the compensation photodiode and the detection photodiode.
2. The NO detection apparatus according to claim 1, wherein: the measuring optical cavity and the compensating optical cavity are integrated or split; the measuring optical cavity and the compensating optical cavity are positioned in the same working environment: the same temperature, humidity and air pressure.
3. The NO detection apparatus according to claim 1, wherein: the measuring optical cavity and the compensating optical cavity are rectangular cavities with hemispherical cavities inside; and the inner cavities of the measuring optical cavity and the compensating optical cavity are subjected to mirror polishing or film coating treatment.
4. The NO detection apparatus according to claim 1, wherein: the measuring photodiode and the compensating photodiode are of the same model, and devices produced in the same batch are selected.
5. The NO detection apparatus according to claim 1, wherein: the signal amplification temperature compensation circuit, the measurement photodiode and the compensation photodiode are subjected to shielding treatment.
6. The NO detection apparatus according to claim 1, wherein: the amplification factor of the current amplifying circuit is 0.1-100G; the differential amplifying circuit has an amplifying multiple of 1-100.
7. A method of detecting NO using the device of any one of claims 1 to 6, characterized in that: the method comprises the following steps:
Ozone enters the compensation optical cavity through the compensation ozone air inlet, the compensation photodiode detects a background signal without mixed NO gas, then the ozone flows out from the compensation ozone air outlet, enters the measurement optical cavity through the measurement ozone air inlet, carries out chemiluminescence reaction with the NO gas entering through the NO air inlet, at the moment, the measurement photodiode detects a chemiluminescent signal, the two paths of signals are amplified by the signal amplifying temperature compensation circuit in the same multiple way, and the amplified detection signal and compensation signal output NO detection concentration after baseline correction and temperature and noise compensation after differential processing.
8. The method for detecting NO according to claim 7, wherein: the concentration of ozone is greater than the concentration of NO gas.
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