Sample detection system based on a glow discharge mass spectrometer

Abstract

The present application relates to the technical field of glow discharge mass spectrometer, and specifically discloses a sample detection system based on a glow discharge mass spectrometer, which comprises an optical receiving and detection module, is used for optical focusing, and transmits the light signal of a sample to an ion source, a mass analyzer and an ion detector module, and receives the light signal by using the detector, converts the light signal into an electric signal through signal amplification and transmission, and inputs and outputs through a signal transceiving communication module; the present application adds a GDMS sample ion calibration module, calibrates the ion beam generated by glow discharge and the mass spectrometer by using a standard sample with known components and content, obtains the relative sensitivity factor of each element, performs quantitative analysis on unknown samples, realizes the rapid prototyping and training function of a mixed quantum classical model by using a QUANTUM software processing module, optimizes a new quantum algorithm, and improves the quantitative analysis capability of the GDMS.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glow discharge mass spectrometer, and particularly relates to a sample detection system based on a glow discharge mass spectrometer. BACKGROUND

[0002] The glow discharge mass spectrometer is used for detecting the element composition, impurity content and purity contained in a solid sample. The low-pressure argon gas is filled in the glow discharge chamber, and the voltage is applied to the anode and cathode to form the glow discharge state. The ion and electron of the discharge gas collide with the atoms of the sample frequently, so that the sample is greatly sputtered and ionized. The light signal received is converted into the electric signal and transmitted to the computer for signal processing. The sample composition is analyzed, calculated and detected by using the detection software. However, the existing glow discharge mass spectrometer has the problems of fixed sample calibration, voltage, material, interference of cooling process and non-optimized software calculation model of electronic control, which affect the analysis result.

[0003] In the sample detection system of the existing glow discharge mass spectrometer, the sample is introduced and pretreated by using mechanical auxiliary equipment. The signal is collected, processed, analyzed and detected by the internal detection system of the glow discharge mass spectrometer. In order to improve the detection accuracy of the glow discharge mass spectrometer, the existing technology calibrates the sample before detection, so as to reduce the inevitable error of the detection instrument and the accidental error problem of the parameter condition in the detection process.

[0004] Therefore, the present application provides a sample detection system based on a glow discharge mass spectrometer. The performance index parameters, including the detector noise, resolution, sensitivity, detection limit, value error and repeatability, are calculated and analyzed by establishing a quantitative evaluation comprehensive model of performance index, so as to reduce the inevitable error of the detection instrument and the accidental error problem of the parameter condition in the detection process. SUMMARY

[0005] (I) Technical problems solved

[0006] In view of the deficiencies of the prior art, the present application provides a sample detection system based on a glow discharge mass spectrometer. The GDMS sample ion calibration module is added. The ion beam generated by the glow discharge is calibrated with the mass spectrometer by using the standard sample with known composition and content. The relative sensitivity factor of each element is obtained, and the unknown sample is quantitatively analyzed. The QUANTUM software processing module is used to realize the rapid prototyping and training function of the mixed quantum classical model, and the new quantum algorithm is optimized, so as to solve the problems in the background art.

[0007] (II) Technical solutions

[0008] To achieve the above object, the present application is realized by the following technical solutions: a sample detection system based on a glow discharge mass spectrometer, comprising an optical receiving and detection module, an ion source, a mass analyzer and an ion detector module, and a computer control display module; the optical receiving and detection module is used for optical focusing and transmitting light signals from a sample to the ion source, the mass analyzer and the ion detector module; the light signals received by the detector are converted into electrical signals through signal amplification and transmission; the input and output of the signal transceiver communication module are transmitted to the computer control display module for signal reprocessing;

[0009] The ion source, the mass analyzer and the ion detector module are modules that integrate instruments for separating and detecting different isotopes throughout the sample detection system; the ion source is an ionization device for ionizing and sputtering sample molecules under high vacuum conditions; the mass analyzer is a device for separating different mass ions entering the device simultaneously according to the mass-to-charge ratio; the ion detector receives the ions separated by the mass analyzer and transmits the amplified ion signals to the computer for collection, processing and drawing into a mass spectrum using QUANTUM software;

[0010] The signal transceiver communication module is used for receiving the light signals transmitted by the optical receiving and detection module and the ion source, the mass analyzer and the ion detector module; the light signals are converted into electrical signals in the photomultiplier tube, and the converted electrical signals are transmitted to the computer control display module for information reprocessing;

[0011] The GDMS sample ion calibration module is used for detecting a specific sample several times, comparing the metrological data according to the calibration parameters of the detector noise, resolution, sensitivity, detection limit, value error and repeatability, quantifying the calibration level that meets the glow discharge mass spectrometer, performing ion detection on the sample to be measured with the same calibration parameter value, and transmitting the data to the QUANTUM software processing module for calculation and analysis to output a spectrum;

[0012] The computer control display module receives the electrical signals output by the signal transceiver communication module, converts the received electrical signals into logical signals using the processor of the computer, transmits the data using binary representation, and communicates to other modules in the system through the OSI protocol from the physical layer, data link layer, network layer, transport layer, session layer, presentation layer and application layer;

[0013] The QUANTUM software processing module receives the logical signals from the computer control display module, brings the collected information into the machine learning algorithm of artificial intelligence in digital form, and uses the programs in the software to correct, smooth, integrate, fit and quantify the original data collected in the glow discharge mass spectrometer, so as to obtain the element composition and depth distribution information of the sample.

[0014] Further, the optical receiving detection module comprises a glow discharge light source unit and an optical mechanism detection unit. The glow discharge light source unit is used to display the glow discharge phenomenon of gas in low-pressure gas, which is the direct current glow discharge of the glow discharge lamp in the differential pressure provided by the vacuum pump. The light emitted by the plasma generated by the inert gas discharge is used to analyze the information of atomic interaction in the gas. The vacuum pump is used to provide a low-pressure gas environment to enable the glow discharge lamp to work normally. Specifically, the vacuum pump removes the gas in the discharge tube to reduce the gas pressure and removes the sputtered atoms to ensure that the element composition in the sample and the received spectral intensity always remain synchronized. The glow discharge lamp uses the light emitted by the plasma generated by the gas discharge to form a stable glow discharge area in low-pressure gas.

[0015] The optical mechanism detection unit uses lenses, slits, mirrors, and grating colorimeters to perform clear imaging of the monitored sample, collimation of the light beam, folding and adjustment of the optical path, separation and focusing of the spectrum, and screening and control of the wavelength. The lenses are used to focus and diffuse the ion beam, change the transmission efficiency and resolution of the ions, and the slits are used to limit the width and direction of the ion beam to improve the resolution and signal-to-noise ratio of the mass spectrometer. The mirrors are used to change the transmission direction of the ion beam to increase the sensitivity and dynamic range of the mass spectrometer. The grating colorimeter is used to disperse light of different wavelengths to form a spectrum, enabling wavelength selection and measurement.

[0016] Further, the sample detection of the ion source, mass analyzer, and ion detector module comprises the following steps:

[0017] A1. Introducing the sample into the inert gas vacuum ion source ionization chamber for ionization and separation of the sample;

[0018] A2. Providing a voltage to ionize the molecules into ions and enter the acceleration electric field to cause sputtering, for sample screening and detection;

[0019] A3. After secondary ionization, the mass-to-charge ratio is separated, and the amplified ion signal is transmitted to the signal receiver for charge conversion and signal conversion of the sample.

[0020] Further, the signal transceiver communication module is composed of a photomultiplier signal amplifier and a protocol communication receiver. The photomultiplier signal amplifier is composed of a photodetector and a signal amplifier. The photomultiplier signal amplifier is a vacuum electronic device that amplifies weak optical signals into detectable electrical signals by using external photoelectric effect and secondary electron emission effect, and is specifically composed of a photocathode, a multiplication stage and an anode. The photomultiplier signal amplifier has the characteristics of high gain, low noise, high frequency response and large signal receiving area. The protocol communication receiver is a device that converts electrical signals into protocol data packets. The protocol communication receiver encodes and decodes according to different communication standards and protocols, and is used for communication and interaction with other devices to realize data transmission and processing.

[0021] Further, the calibration method of the GDMS sample ion calibration module is to establish a quantitative evaluation comprehensive model of performance indicators. According to the calibration steps, a reference ion is selected. On the GDMS device, the detection conditions and the calibration sample ion calibration parameters are set. The signal intensities of the sample ion and the reference ion are monitored and recorded in real time. According to the signal ratio of the reference ion to the sample ion, a relative intensity ratio is obtained. Then, the calibrated sample ion signal intensity is obtained by multiplying the relative intensity ratio by the theoretical intensity of the sample ion. The code edited by MATLAB is as follows:

[0022] % Set the absorbance data of a set of standard solutions and samples

[0023] % Concentration of standard solution (mol / L)

[0024] c = [0.01, 0.02, 0.03, 0.04, 0.05];

[0025] % Absorbance of standard solution

[0026] A = [0.12, 0.25, 0.36, 0.47, 0.59];

[0027] % Absorbance of sample

[0028] As = [0.18, 0.32, 0.41];

[0029] % Draw the standard curve

[0030] plot(c, A, 'o'); % Draw scatter plot

[0031] hold on; % Keep graphics

[0032] p = polyfit(c, A, 1); % Fit a polynomial of degree 1

[0033] x = linspace(0, 0.06); % Generate points in the range of independent variable

[0034] y = polyval(p,x); % Calculate the value of the fitted polynomial at these points

[0035] plot(x,y); % Plot the fitted curve

[0036] xlabel('Concentration (mol / L)'); % Add x-axis label

[0037] ylabel('Absorbance'); % Add y-axis label

[0038] title('Standard Curve'); % Add title

[0039] % Calculate sample concentration

[0040] cs = (As - p(2)) / p(1); % Solve concentration from fitted polynomial

[0041] disp('Sample concentration is: ');

[0042] disp(cs);

[0043] % Calculate correlation coefficient and residual

[0044] r = corrcoef(c,A); % Calculate correlation coefficient matrix

[0045] r2 = r(1,2)^2; % Calculate determination coefficient

[0046] disp('Determination coefficient is: ');

[0047] disp(r2);

[0048] e = A - polyval(p,c); % Calculate residual

[0049] disp('Residual is: ');

[0050] disp(e); The quantitative evaluation comprehensive model for performance indicators is combined with quantitative evaluation to improve the accuracy of sample detection.

[0051] Further, the quantitative evaluation comprehensive model for performance indicators uses an exponential regression algorithm, with the formula y = ab x , where y is the response variable, x is the mean of the calculated variable, a and b are the quantitative regression coefficients describing the relationship between x and y, and a > 0, b ≠ 0, where the calculation process of a and b uses MATLAB code as follows: % Take the natural logarithm of the dependent variable y z = log(y);

[0052] % Linear regression analysis of z and x

[0053] p = polyfit(x,z,1); % fit a linear polynomial

[0054] alpha = p(2); % intercept of linear regression equation

[0055] beta = p(1); % slope of linear regression equation

[0056] % find regression coefficients a and b for exponential regression equation from linear regression equation

[0057] a = exp(alpha); b = exp(beta); % get exponential regression model

[0058] y = a*b.^x; %.^ means power operation between array elements.

[0059] Further, the quantitative evaluation value of the performance index is an evaluation result of quantifying the performance index by using mathematical methods and statistical analysis methods, which is used for objectively understanding the actual performance of the GDMS detection system, finding problems and improvement space of the system, optimizing the design and configuration of the system, and thereby improving the quality of the system and the accuracy of the to-be-tested sample, wherein the detector noise is ≤1 cps, the resolution is ≥8000, the sensitivity is ≥1 x 10 8 cps, the detection limit is ≤7 ng / g, the indication error is ≤±20%, and the repeatability is ≤10%.

[0060] Further, the QUANTUM software processing module includes establishing a standard curve, data processing, deep analysis of the test sample, and outputting a spectrum report; the calculation content of the QUANTUM software includes measuring and calibrating the sputtering rate and sputtering pit depth of the sample by using a differential interferometer and a standard sample; quantifying by using an internal standard method and an external standard method, and standardizing the element concentration of the sample by using a standard sample and a standard curve; calculating the element depth distribution of the sample by using integral method and fitting method by comprehensively considering the atomic mixing effect in the sputtering process; and eliminating the element interference of the sample by using the accurate mass number and relative sensitivity coefficient of a high-resolution mass spectrometer and a mathematical model; the QUANTUM software uses the fitting method of the atomic mixing effect to calculate the element depth distribution of the sample, which provides quantitative methods of internal standard method, external standard method, and semi-quantitative method, and has a friendly graphical user interface, which is convenient for importing, exporting, displaying, editing, saving data and results.

[0061] Further, the data processing is a correction, smoothing, integration, fitting and quantification operation on the raw data of the glow discharge spectrometer to obtain the element composition and depth distribution information of the sample, wherein the correction is to correct the mass number and relative sensitivity coefficient of the raw data to eliminate errors caused by instruments, samples or environmental factors.

[0062] Further, the depth analysis and detection of the sample is a process of detecting and analyzing the internal structure and composition of the sample to obtain the depth distribution information of the sample and reveal the physical, chemical, biological and other properties and characteristics of the sample, and the depth analysis and detection of the sample includes the stages of sample preparation, sample loading, sample scanning, sample etching and data processing.

[0063] (III) Beneficial effects

[0064] The present application provides a sample detection system based on a glow discharge mass spectrometer, which has the following beneficial effects:

[0065] The present application adds a GDMS sample ion calibration module, calibrates the ion beam generated by the glow discharge and the mass spectrometer by using standard samples with known composition and content, obtains the relative sensitivity factor of each element, and performs quantitative analysis on unknown samples, and uses the QUANTUM software processing module to realize the rapid prototyping and training function of the mixed quantum classical model and optimize the new quantum algorithm, improve the quantitative analysis ability of the GDMS, so that it can accurately determine the element content of different types and forms of samples; simplify the operation process of the GDMS, so that it does not need complex sample preparation and processing, only needs to put the sample into the GD source for analysis function, and prolongs the service life of the GDMS instrument, so that it does not need to frequently replace or clean the GD source and mass spectrometer, reduces the maintenance cost and time. BRIEF DESCRIPTION OF DRAWINGS

[0066] Figure 1 The sample detection system based on the glow discharge mass spectrometer of the present application is a block diagram.

[0067] Figure 2 The ion source, mass analyzer and ion detector module detection sample flowchart of the present application is a flowchart.

[0068] Figure 3 The optical receiving detection module schematic diagram of the present application is a schematic diagram.

[0069] Figure 4 The signal transceiver communication module schematic diagram of the present application is a schematic diagram.

[0070] Figure 5 The GDMS sample ion calibration module calibration method diagram of the present application is a calibration method diagram.

[0071] Figure 6 Flow chart of the QUANTUM software processing module of the present application. DETAILED DESCRIPTION

[0072] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0073] Embodiment 1

[0074] Please refer to Figures 1-6 The present application provides a sample detection system based on a glow discharge mass spectrometer, which comprises an optical receiving and detection module, an ion source, a mass analyzer and an ion detector module, and a computer control and display module. The optical receiving and detection module is used for optical focusing and transmission of light signals from a sample to the ion source, the mass analyzer and the ion detector module. The light signals received by the detector are converted into electrical signals through signal amplification and transmission. The input and output of the signal transceiver communication module are transmitted to the computer control and display module for signal reprocessing.

[0075] The ion source, the mass analyzer and the ion detector module are modules that integrate instruments for separating and detecting different isotopes throughout the sample detection system. The ion source is an ionization device for ionizing and sputtering sample molecules under high vacuum conditions. The mass analyzer is a device for separating different mass ions entering the device simultaneously according to the mass-to-charge ratio. The ion detector receives the ions separated by the mass analyzer and transmits the amplified ion signals to the computer for collection, processing and drawing of a mass spectrum using QUANTUM software.

[0076] The signal transceiver communication module is used for receiving the light signals transmitted by the optical receiving and detection module and the ion source, the mass analyzer and the ion detector module. The light signals are converted into electrical signals in the photomultiplier tube and transmitted to the computer control and display module for information reprocessing.

[0077] The GDMS sample ion calibration module is used for detecting a specific sample for several times, comparing the metrological data according to the calibration parameters of the detector noise, resolution, sensitivity, detection limit, value error and repeatability, quantifying the calibration level of the glow discharge mass spectrometer, ion detecting the sample to be measured with the same calibration parameter value, and transmitting the ion detection to the QUANTUM software processing module for calculation and analysis and outputting a spectrum.

[0078] The computer control display module is configured to receive the electrical signal output by the signal transceiver communication module, convert the received electrical signal into a logic signal by using a processor of a computer, transmit data by using a binary representation, and communicate the data to other modules in the system by using the OSI protocol from the physical layer, the data link layer, the network layer, the transport layer, the session layer, the presentation layer, and the application layer.

[0079] The QUANTUM software processing module is configured to receive the logic signal from the computer control display module, import the logic signal into the QUANTUM software in a digital form, import the collected information into a machine learning algorithm of artificial intelligence, correct, smooth, integrate, fit, and quantify the original data collected in the glow discharge mass spectrometer by using a program in the software, and obtain the element composition and depth distribution information of the sample.

[0080] In a preferred embodiment, the optical receiving detection module includes a glow discharge light source unit and an optical mechanism detection unit. The glow discharge light source unit is configured to display a gas discharge phenomenon of glow in a low-pressure gas, is a direct-current glow discharge of a glow discharge lamp in a differential pressure provided by a vacuum pump, and uses light emitted by plasma generated by inert gas discharge to analyze information of atomic interaction in the gas. The vacuum pump is configured to provide a low-pressure gas environment to enable the glow discharge lamp to work normally, specifically, the vacuum pump is configured to pump away gas in a discharge tube to reduce the gas pressure, and pump away sputtered atoms to ensure that the element composition in the sample and the received spectral intensity are always kept in synchronization. The glow discharge lamp uses light emitted by plasma generated by gas discharge, and needs to be in a low-pressure gas to form a stable glow discharge area.

[0081] The optical mechanism detection unit is configured to use a lens, a slit, a mirror, and a grating color instrument to clearly image the monitored sample, collimate the light beam, fold and adjust the light path, separate and focus the spectrum, and screen and control the wavelength. The lens is configured to focus and diffuse the ion beam to change the transmission efficiency and resolution of the ions. The slit is configured to limit the width and direction of the ion beam to improve the resolution and signal-to-noise ratio of the mass spectrometer. The mirror is configured to change the transmission direction of the ion beam to increase the sensitivity and dynamic range of the mass spectrometer. The grating color instrument is configured to disperse light of different wavelengths to form a spectrum to realize wavelength selection and measurement.

[0082] In a preferred embodiment, the sample detection of the ion source, the mass analyzer, and the ion detector module includes the following steps:

[0083] A1. Introducing the sample into an inert gas vacuum ion source ionization chamber to ionize and separate the sample;

[0084] A2. Providing a voltage to ionize molecules into ions to enter an acceleration electric field to occur sputtering, for screening and detecting the sample;

[0085] A3, after secondary ionization, mass-to-charge ratio separation is carried out, and the amplified ion signal is transmitted to the signal receiver for charge conversion and signal conversion of the sample.

[0086] In a preferred embodiment, the signal transceiver communication module is composed of a photomultiplier signal amplifier and a protocol communication receiver. The photomultiplier signal amplifier is composed of a photodetector and a signal amplifier, which uses the external photoelectric effect and secondary electron emission effect to amplify weak optical signals into detectable electrical signals. It is composed of a part of photocathode, multiplication stage and anode, and has the characteristics of high gain, low noise, high frequency response and large signal receiving area. The protocol communication receiver is a device that converts electrical signals into protocol data packets. It encodes and decodes according to different communication standards and protocols, and is used for communication and interaction with other devices to realize data transmission and processing.

[0087] In a preferred embodiment, the calibration method of the GDMS sample ion calibration module is to establish a quantitative evaluation comprehensive model of performance indicators. According to the calibration steps, reference ions are selected. The detection conditions and calibration sample ion calibration parameters are set on the GDMS device. The signal intensities of sample ions and reference ions are monitored and recorded in real time. According to the signal ratio of reference ions to sample ions, the relative intensity ratio is obtained. Then, the calibrated sample ion signal intensity is obtained by multiplying the theoretical intensity of the sample ion by the ratio. The code edited by MATLAB is as follows:

[0088] % Set a set of standard solution and sample absorbance data

[0089] % Standard solution concentration (mol / L)

[0090] c = [0.01, 0.02, 0.03, 0.04, 0.05];

[0091] % Standard solution absorbance

[0092] A = [0.12, 0.25, 0.36, 0.47, 0.59];

[0093] % Sample absorbance

[0094] As = [0.18, 0.32, 0.41];

[0095] % Draw standard curve

[0096] plot(c, A, 'o'); % Draw scatter plot

[0097] hold on; % Keep graphics

[0098] p = polyfit(c, A, 1); % Fit a polynomial of degree one

[0099] x = linspace(0, 0.06); % Generate points in the range of the independent variable

[0100] y = polyval(p, x); % Calculate the values of the fitted polynomial at these points

[0101] plot(x, y); % Plot the fitted curve

[0102] xlabel('Concentration (mol / L)'); % Add the x-axis label

[0103] ylabel('Absorbance'); % Add the y-axis label

[0104] title('Standard Curve'); % Add a title

[0105] % Calculate the sample concentration

[0106] cs = (As - p(2)) / p(1); % Solve for the concentration from the fitted polynomial

[0107] disp('Sample concentration is: ');

[0108] disp(cs);

[0109] % Calculate the correlation coefficient and residuals

[0110] r = corrcoef(c, A); % Calculate the correlation coefficient matrix

[0111] r2 = r(1, 2)^2; % Calculate the coefficient of determination

[0112] disp('Coefficient of determination is: ');

[0113] disp(r2);

[0114] e = A - polyval(p, c); % Calculate the residuals

[0115] disp('Residuals are: ');

[0116] The quantitative evaluation comprehensive model of the performance index is used to quantitatively and comprehensively calculate, and the precision of the detection sample is improved; wherein, the performance index includes detector noise, resolution, sensitivity, detection limit, indication error and repeatability; the detector noise refers to random fluctuation in the detector output signal irrelevant to the measured quantity, which will affect the sensitivity and resolution of the detector, reduce the signal-to-noise ratio of the detection signal, and the calculation formula of the root mean square method is as follows: T_x=\sqrt{\sum_{i=1}^{n}T_i^2}, wherein, T_x is the tolerance of the target size, T_i is the tolerance of the i th size in the size chain, and n is the number of sizes in the size chain; the resolution is the ability of the detector to distinguish two similar signals, which can reflect the response degree of the detector to the slight signal change; the sensitivity is the proportional relationship between the detector output signal and the input signal, which can reflect the amplification multiple or conversion efficiency of the detector to the input signal; the detection limit is the minimum input signal that can be reliably detected by the detector, which can reflect the recognition ability of the detector to the weak signal; the indication error is the deviation between the output indication value of the detector and the true value of the measured quantity, which can reflect the accuracy and reliability of the detector; the repeatability is the consistency degree between the several indication values obtained by repeatedly measuring the same measured quantity under the same or similar conditions, which can reflect the stability and repeatability of the detector.

[0117] In a preferred embodiment, the quantitative evaluation comprehensive model of the performance index adopts an exponential regression algorithm, and the formula is y=ab x , wherein, y is a response variable, x is the mean value of the calculation variable, a and b are quantitative regression coefficients describing the relationship between x and y, and a>0, b≠0, wherein the calculation process of a and b adopts the MATLAB code as follows: % take the natural logarithm of the dependent variable y z=log(y);

[0118] % linear regression analysis is performed on z and x

[0119] p=polyfit(x,z,1);%fit a first order polynomial

[0120] alpha=p(2);%intercept of the linear regression equation

[0121] beta=p(1);%slope of the linear regression equation

[0122] % obtain the regression coefficients a and b in the exponential regression equation from the linear regression equation

[0123] a=exp(alpha);b=exp(beta);%obtain the exponential regression model

[0124] y=a*b.^x;%.^represents the power operation between array elements.

[0125] In a preferred embodiment, the quantitative evaluation value of the performance index is an evaluation result of quantifying the performance index by mathematical methods and statistical analysis methods, which is used to objectively understand the actual performance of the GDMS detection system, find out the problems and improvement space of the system, optimize the design and configuration of the system, and thus improve the quality of the system and the accuracy of the sample to be detected, wherein the detector noise is ≤1 cps, the resolution is ≥8000, the sensitivity is ≥1×10 8 cps, the detection limit is ≤7 ng / g, the indication error is ≤±20%, and the repeatability is ≤10%.

[0126] In a preferred embodiment, the QUANTUM software processing module includes establishing a standard curve, data processing, deep analysis of the sample, and outputting a spectrum report; the calculation content of the QUANTUM software includes measuring and calibrating the sputtering rate and sputtering pit depth of the sample by a differential interferometer and a standard sample; quantifying by an internal standard method and an external standard method, and standardizing the element concentration of the sample by a standard sample and a standard curve; calculating the element depth distribution of the sample by comprehensively considering the atomic mixing effect in the sputtering process, using integral method and fitting method; and eliminating the element interference of the sample by the accurate mass number and relative sensitivity coefficient of a high-resolution mass spectrometer and a mathematical model; the QUANTUM software uses the fitting method of atomic mixing effect to calculate the element depth distribution of the sample, which provides quantitative methods of internal standard method, external standard method, and semi-quantitative method, and has a friendly graphical user interface, which is convenient for importing, exporting, displaying, editing, saving data and results.

[0127] In a preferred embodiment, the data processing is a process of correcting, smoothing, integrating, fitting and quantifying the raw data of the glow discharge spectrometer to obtain the elemental composition and depth distribution information of the sample, wherein the correction is to eliminate the errors caused by the instrument, sample or environment by correcting the mass number and relative sensitivity coefficient of the raw data, and the specific correction formula of sputtering rate and sputtering pit depth is d = \frac{V}{A} = \frac{V}{\pi r^2}, wherein d is the sputtering pit depth, V is the sputtering volume, A is the sputtering area, and r is the sputtering pit radius; the formula for correcting signal intensity and background noise is I_c = I_s - I_b, wherein I_c is the corrected signal intensity, I_s is the original signal intensity, and I_b is the background noise intensity; the formula for correcting the mass number and the relative sensitivity coefficient is C_i = \frac{I_i}{R_i}, wherein C_i is the concentration of element i, I_i is the signal intensity of element i, and R_i is the relative sensitivity coefficient of element i; the smoothing is to calculate the raw data by using the moving average method, median filtering method and wavelet transform method to reduce the influence of random noise or abnormal value, so that the data is more smooth and continuous; the integration is to perform numerical integration on the raw data or the smoothed data by using the trapezoidal method, Simpson method and Gauss-Legendre method to obtain the elemental concentration and elemental content of the sample; the fitting is to perform mathematical model fitting on the raw data and the smoothed data by using the least squares method, maximum likelihood method and Bayesian method to obtain the elemental depth distribution and elemental interference coefficient of the sample; and the quantification is to perform quantitative analysis on the integrated or fitted data by using the internal standard method, external standard method and semi-quantitative method to obtain the elemental composition and depth distribution information of the sample.

[0128] In a preferred embodiment, the depth analysis and detection of the sample is a process of detecting and analyzing the internal structure and composition of the sample to obtain the depth distribution information of the sample and reveal the physical, chemical, biological and other properties and characteristics of the sample, and the depth analysis and detection of the sample includes the stages of sample preparation, sample loading, sample scanning, sample etching and data processing.

[0129] Those skilled in the art can appreciate that the units and algorithm steps of each example described in combination with the embodiments disclosed herein can be realized by electronic hardware or a combination of computer software and electronic hardware. Whether the functions are realized in hardware or software depends on the specific application and design constraints of the technical solution. The skilled person can use different methods to realize the described functions for each specific application, but such implementation should not be considered beyond the scope of the present application.

[0130] Those skilled in the art can clearly understand that, for the convenience and brevity of description, the specific working process of the system, device and unit described above can refer to the corresponding process in the foregoing method embodiments, which will not be repeated here.

[0131] In several embodiments provided in the present application, it should be understood that the disclosed system, device and method can be implemented in other ways. For example, the device embodiments described above are only schematic, for example, the division of the units is only a logical function division, and actual implementation can have another division manner, for example, a plurality of units or components can be combined or integrated into another system, or some features can be ignored or not executed. In addition, the coupling or direct coupling or communication connection between the units shown or discussed can be indirect coupling or communication connection through some interface, device or unit, and can be electrical, mechanical or other forms.

[0132] The units described as separate components can or can not be physically separated, and the components shown as units can or can not be physical units, that is, they can be located in one place, or can be distributed on a plurality of network units. Part or all of the units can be selected according to actual needs to achieve the purpose of the embodiment scheme.

[0133] In addition, each functional unit in each embodiment of the present application can be integrated in one processing unit, or each unit can exist physically, or two or more units can be integrated in one unit.

[0134] If the functions are realized in the form of software function units and sold or used as independent products, they can be stored in a computer readable storage medium. Based on this understanding, the technical solutions of the present application or the essential part or part of the technical solutions that make contributions to the prior art can be embodied in the form of a software product. The computer software product is stored in a storage medium, and includes a plurality of instructions for causing a computer device (which can be a personal computer, a server, or a network device, etc.) to execute all or part of the steps of the method described in each embodiment of the present application. The foregoing storage medium includes: a U disk, a mobile hard disk, a read-only memory (ROM), a random access memory (RAM), a magnetic disk or an optical disk, and various program code storage media.

[0135] The above merely provides the specific implementation of the present application, but the protection scope of the present application is not limited to this. Any person skilled in the art can easily think of the changes or replacements within the technical range disclosed by the present application, which should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

[0136] Finally, the above merely provides the preferred embodiments of the present application, but is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A sample detection system based on a glow discharge mass spectrometer, characterized in that: The optical receiving detection module is used for optical focusing and transmitting light signals from a sample to an ion source, a mass analyzer and an ion detector module. The ion source, the mass analyzer and the ion detector module are modules that integrate instruments for separating and detecting different isotopes. The signal transceiver communication module is used for receiving optical signals transmitted by the optical receiving detection module and the ion source, the mass analyzer and the ion detector module, converting and processing the electrical signals, and transmitting the converted electrical signals to the computer control display module for information reprocessing. The GDMS sample ion calibration module is used for detecting a specific sample for several times, comparing metrological data according to calibration parameters such as detector noise, resolution, sensitivity, detection limit, value error and repeatability, quantifying and limiting the calibration level of the glow discharge mass spectrometer, detecting ions of the sample with the same calibration parameter value, and transmitting the ions to the QUANTUM software processing module for calculation and analysis to output a spectrum. The calibration method of the GDMS sample ion calibration module is to establish a quantitative evaluation comprehensive model of performance indicators, select reference ions according to the calibration steps, set detection conditions and calibration sample ion calibration parameters on the GDMS device, monitor and record the signal intensities of sample ions and reference ions in real time, obtain the relative intensity ratio according to the ratio of the reference ion signal to the sample ion signal, multiply the theoretical intensity of the sample ion by the ratio to obtain the calibrated sample ion signal intensity, and perform quantitative comprehensive calculation combined with the quantitative evaluation comprehensive model to improve the precision of the detected sample. The quantitative evaluation comprehensive model of the performance index adopts an exponential regression algorithm, and the formula is , , wherein y is a response variable, x is the mean of a calculation variable, a and b are quantitative regression coefficients describing the relationship between x and y, and a>0, b≠0, wherein the calculation process of a and b adopts the MATLAB code as follows: % take the natural logarithm of the dependent variable y z = log(y); Linear regression analysis is performed on z and x p = polyfit(x,z,1); % fitting a polynomial alpha = p(2); % intercept of the linear regression equation beta = p(1); % slope of the linear regression equation The regression coefficients a and b in the exponential regression equation are obtained from the linear regression equation a = exp(alpha); b = exp(beta); % get the exponential regression model y = a * b.^ x; %.^ represents the power operation between array elements The quantitative evaluation value of the performance indicators is the evaluation result of quantifying the performance indicators by mathematical methods and statistical analysis methods, which is used to objectively understand the actual performance of the GDMS detection system and find problems and improvement space of the system, and optimize the design and configuration of the system. The computer control display module receives the electrical signals output by the signal transceiver communication module, converts the received electrical signals into logic signals by the processor of the computer, and communicates the logic signals to other modules in the system. The QUANTUM software processing module receives the logic signals of the computer control display module and brings the collected information into the machine learning algorithm of artificial intelligence.

2. The glow discharge mass spectrometer based sample detection system of claim 1, wherein: The optical receiving detection module comprises a glow discharge light source unit and an optical mechanism detection unit. The glow discharge light source unit is used to display the glow discharge phenomenon of gas in low-pressure gas. The direct current glow discharge of the glow discharge lamp in the differential pressure provided by the vacuum pump utilizes the light emitted by the plasma generated by the inert gas discharge to analyze the information of atomic interaction in the gas. The optical mechanism detection unit utilizes lenses, slits, mirrors and grating colorimeters to perform clear imaging of the monitored sample, collimation of the light beam, folding and adjustment of the light path, separation and focusing of the spectrum, and screening and control of the wavelength.

3. The glow discharge mass spectrometer based sample detection system of claim 1, wherein: The sample detection of the ion source, mass analyzer and ion detector module comprises the following steps: A1. Introducing the sample into the inert gas vacuum ion source ionization chamber; A2. Providing a voltage to ionize the molecules into ions and enter the acceleration electric field to generate sputtering; A3. After secondary ionization, the mass-to-charge ratio is separated, and the amplified ion signal is transmitted to the signal receiver.

4. The glow discharge mass spectrometer based sample detection system of claim 1, wherein: The signal transceiver communication module is composed of a photomultiplier signal amplifier and a protocol communication receiver. The photomultiplier signal amplifier is composed of a photodetector and a signal amplifier. It is a vacuum electronic device that amplifies weak optical signals into detectable electrical signals using external photoelectric effect and secondary electron emission effect. The protocol communication receiver is a device that converts electrical signals into protocol data packets. It encodes and decodes according to different communication standards and protocols for communication and interaction with other devices.

5. The glow discharge mass spectrometer based sample detection system of claim 1, wherein: The QUANTUM software processing module includes establishing a standard curve, data processing, depth analysis of the sample, and outputting a spectrum report. The calculation content of the QUANTUM software includes measuring and calibrating the sputtering rate and sputtering pit depth of the sample through a differential interferometer and a standard sample. The element concentration of the sample is quantified by internal standard method and external standard method through standard samples and standard curves. By comprehensively considering the atomic mixing effect in the sputtering process, the integral method and the fitting method are used to calculate the element depth distribution of the sample. The accurate mass number and relative sensitivity coefficient of the high-resolution mass spectrometer and mathematical model are used to eliminate the element interference of the sample.

6. The glow discharge mass spectrometer based sample detection system of claim 5, wherein: The data processing is the correction, smoothing, integration, fitting and quantification of the original data of the glow discharge spectrometer to obtain the element composition and depth distribution information of the sample. The correction is performed by correcting the mass number and relative sensitivity coefficient of the original data to eliminate the errors caused by the instrument, sample or environmental factors.

7. The glow discharge mass spectrometer based sample detection system of claim 5, wherein: The depth analysis of the sample is the process of detecting and analyzing the internal structure and composition of the sample to obtain the depth distribution information of the sample and reveal the physical, chemical and biological properties and characteristics of the sample.

Images