JP2002181745A - Quantitative analysis method for sample analyzing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a quantitative analysis method for a sample analyzing device capable of improving accuracy in simplified quantitative analysis based on spectrum intensity obtained in qualitative analysis even on a sample in which elements such as Na, K, etc., with large changes with time are present. SOLUTION: Simplified quantitative analysis is performed in a step for determining the constituent elements of the sample by first qualitative analysis, a step for displacing the irradiation location of an electron beam to the sample in the case that it is determined that elements such as Na, K, etc., with large changes with time are present by the qualitative analysis and sequentially performing second qualitative analysis on the elements with large changes with time, and a step for performing quantitative analysis on the basis of energy spectrum intensity obtained as the result of the second qualitative analysis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simple quantitative analysis method based on qualitative analysis in a sample analyzer, and more particularly, to a sample analyzer which improves the accuracy of quantitative analysis in which the quantitative analysis value varies depending on the analysis measurement time. For a quantitative analysis method.

[0002]

2. Description of the Related Art Generally, in an X-ray microanalyzer using a wavelength dispersive spectrometer and an energy dispersive spectrometer, a spectrum obtained based on the qualitative analysis of various samples such as a glass sample and a steel sample is obtained. X
Simple quantitative analysis is performed based on the line intensity.

In recent years, in order to improve the efficiency of analysis,
When using a wavelength dispersive spectrometer, by collecting the spectrum by changing the diffraction angle of the spectroscopic element in a certain step, by comparing the detected peak position with the energy position in the literature stored in advance, The element is identified. At this time, the net X-ray intensity of the main peak is calculated and compared with the X-ray intensity of the standard sample stored in advance, corrected and calculated to obtain a simple quantitative result. I'm trying to get it.

[0004]

However, when a simple quantitative analysis is performed on the basis of the X-ray intensity of the spectrum obtained as a result of the qualitative analysis as described above, the time required to form a spectrum in the qualitative analysis is as follows. In some cases, the measurement is affected by the change with time of the sample, and the analysis and measurement time may be a factor that deteriorates the accuracy of the quantitative analysis result based on the spectrum obtained by the qualitative analysis. Specifically, for example, in a glass sample, ions of Na and K move by irradiation of an electron beam. This changes depending on the acceleration voltage, the irradiation electron beam diameter, and time. Further, in the analysis of carbon in iron and steel, the amount of carbon increases with time, depending on the degree of vacuum, depending on the degree of vacuum. For these reasons, the accuracy of the quantitative analysis result based on the spectrum obtained by the qualitative analysis is deteriorated.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in a simple quantitative analysis based on a spectrum obtained by a conventional qualitative analysis, and it is an element sensitive to electron beam irradiation damage such as Na and K. Analysis of the sample in which is present,
Alternatively, it is an object of the present invention to provide a quantitative analysis method in a sample analyzer capable of improving the accuracy of simple quantitative analysis based on a spectrum obtained by qualitative analysis also in the analysis of carbon in steel.

[0006]

In order to solve the above problems, the invention according to claim 1 comprises an electron beam source for irradiating a sample with an electron beam, and a characteristic X which is emitted from the sample to which the electron beam is irradiated. It has an X-ray spectrometer that detects X-rays, and a control unit that controls the operation of each unit, irradiates the sample with an electron beam, detects characteristic X-rays emitted from the sample surface, and performs quantitative analysis of the sample. A step of determining an element on the sample surface by a first qualitative analysis in the quantitative analysis method in the sample analyzer to be performed; and, as a result of the first qualitative analysis, an element sensitive to electron beam irradiation damage such as Na and K. If it is determined that does not exist, a step of performing a quantitative analysis based on the energy spectrum intensity obtained as a result of the first qualitative analysis, and a step of executing an electron beam of Na, K, etc., as a result of the first qualitative analysis. Some elements are sensitive to irradiation damage If it is determined that the sample is present, the electron beam irradiation analysis position on the sample is shifted to a position at least several times the beam diameter of the electron beam, and in the first sequence, an element sensitive to electron beam irradiation damage such as Na, K, etc. A second qualitative analysis step of automatically performing a qualitative analysis of the other elements and then automatically performing a qualitative analysis of other elements after the second sequence;
Performing a quantitative analysis based on the energy spectrum intensity obtained as a result of the second qualitative analysis.

In the thus constituted quantitative analysis method, if the first qualitative analysis reveals that elements such as Na and K are sensitive to electron beam irradiation damage, the X-ray intensity In order to avoid attenuation of the electron beam, the electron beam is shifted from the first qualitative analysis position to a position which is at least several times the electron beam diameter,
First, a second qualitative analysis is performed on elements sensitive to electron beam irradiation damage, and then a second qualitative analysis is automatically performed on other elements under the control of the control unit. For elements that are sensitive to electron beam irradiation damage such as Na and K, quantitative analysis is performed based on the qualitative analysis result obtained by short-time analytical measurement, thereby being sensitive to electron beam irradiation damage such as Na and K. Quantitative analysis is performed based on the qualitative analysis results at the stage where the transfer of ions of various elements is small,
A simple and accurate quantitative analysis result can be obtained.

According to a second aspect of the present invention, there is provided an electron beam source for irradiating a sample with an electron beam, an X-ray spectroscope for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, Having a control unit for controlling the operation, irradiating the sample with an electron beam,
In a quantitative analysis method in a sample analyzer for performing quantitative analysis of a sample by detecting characteristic X-rays emitted from the surface of the sample, elements such as Na and K are present in the sample that are sensitive to electron beam irradiation damage. If it is known in advance, the first
Automatically performing a qualitative analysis of elements sensitive to electron beam irradiation damage such as Na and K in the sequence, and then automatically performing a qualitative analysis of other elements in the second and subsequent sequences; Performing quantitative analysis of each element based on the energy spectrum intensity obtained as a result of the analysis.

In the quantitative analysis method configured as described above, when it is known in advance that elements sensitive to electron beam irradiation damage, such as Na and K, are present, Na, K is used in the first sequence. Since qualitative analysis of elements sensitive to electron beam irradiation damage such as K is performed, and qualitative analysis of elements other than those described above is automatically performed under the control of the control unit in the second and subsequent sequences, Na , K, etc., which are sensitive to electron beam irradiation damage, are subjected to quantitative analysis based on the qualitative analysis results obtained by short-time analytical measurement, thereby being sensitive to electron beam irradiation damage, such as Na, K, etc. Quantitative analysis is performed based on the qualitative analysis result at a stage where the movement of elemental ions is small, and a simple process with high accuracy and a simple quantitative analysis result can be obtained.

According to a third aspect of the present invention, there is provided an electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and Having a control unit for controlling the operation, irradiating the sample with an electron beam,
In a quantitative analysis method in a sample analyzer for performing quantitative analysis of a sample by detecting characteristic X-rays emitted from the sample surface, a step of determining an element on the sample surface by a first qualitative analysis; Performing a quantitative analysis based on the energy spectrum intensity obtained as a result of the first qualitative analysis, when the qualitative analysis reveals that there are no elements sensitive to electron beam irradiation damage, such as Na and K; If the first qualitative analysis reveals that elements sensitive to electron beam irradiation damage, such as Na and K, are present, elements such as Na and K, which are sensitive to electron beam irradiation damage, are used in the qualitative analysis. Measuring the effect of the electron beam irradiation analysis measurement time on the detected X-ray intensity, creating and registering an analysis measurement time effect curve;
a, the energy obtained from the second qualitative analysis result based on the analytical measurement time effect curve registered in advance according to the analytical measurement time required for each element sensitive to electron beam irradiation damage such as K. Performing a quantitative correction on the result of the quantitative analysis based on the spectrum intensity.

In the quantitative analysis method configured as described above, the influence of the elapsed time of electron beam irradiation on the detected X-ray intensity for elements sensitive to electron beam irradiation damage such as Na and K is measured in advance, and the measurement time effect curve is obtained. If qualitative analysis shows that there is an element sensitive to electron beam irradiation damage such as Na, K, etc., it is sensitive to electron beam irradiation damage during qualitative analysis. In accordance with the analysis and measurement time required for each element, based on the analysis and measurement time effect curve registered in advance, quantitative correction is performed on the quantitative analysis result based on the energy spectrum intensity obtained from the qualitative analysis result. Therefore, a simple and accurate quantitative analysis result can be obtained.

According to a fourth aspect of the present invention, there is provided an electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and Having a control unit for controlling the operation, irradiating the sample with an electron beam,
In a quantitative analysis method in a sample analyzer for detecting a characteristic X-ray emitted from the sample surface and performing a quantitative analysis of the sample, an influence of an electron beam irradiation time required for analysis of carbon on a detected X-ray intensity in qualitative analysis of steel is Measuring, analyzing and measuring time effect curve, and registering, and qualitative analysis of steel, according to the analysis and measurement time required for carbon analysis, based on the previously registered analysis and measurement time effect curve And performing a quantitative correction on the quantitative analysis result of carbon based on the energy spectrum intensity obtained as a result of the qualitative analysis.

In the quantitative analysis method configured as described above, the influence of the electron beam irradiation time on the detected X-ray intensity required for the qualitative analysis of carbon in steel is measured in advance, and an analysis measurement time influence curve is created and registered. In the qualitative analysis of steel, according to the analytical measurement time required for the analysis of carbon, based on the analytical measurement time effect curve registered in advance, based on the quantitative analysis results by energy spectrum intensity obtained qualitative analysis results Since the quantitative correction is performed for this, it is possible to obtain a highly accurate and simple quantitative analysis of carbon in steel.

[0014]

Next, an embodiment will be described. FIG. 1 is a schematic configuration diagram showing an X-ray microanalyzer used for performing a quantitative analysis method in a sample analyzer according to the present invention. In FIG. 1, 1 is an electron gun, 2 is Wehnelt, 3 is a deflection coil, 4 is an X-ray spectrometer driving motor, 5 is an X-ray spectroscopy element, 6 is an X-ray detector, and an X-ray spectrometer driving motor. 4, X-ray spectroscopy element 5, and X-ray detector 6
A DS (wavelength dispersive X-ray spectrometer) is configured. 7 is a backscattered electron detector, 8 is a secondary electron detector, 9 is an EDS (energy dispersive X-ray spectrometer), 10 is an analysis sample, 11 is a sample stage, 12 is a stage driving motor, and 13 is a deflection coil control. Device, 14 is a motor control device for driving the X-ray spectroscope, 15 is a motor control device for driving the stage, 16 is a secondary electron / reflected electron signal data acquisition device, 17 is a WDSX-ray signal data acquisition device, 18 is an EDSX-ray signal Reference numeral 19 denotes a control unit (CPU), and reference numeral 20 denotes a mass storage device.

The X-ray micronarizer comprising such components has the following functions by automatic control using a CPU, in addition to a normal X-ray micronarizer function. That is, digital control of electron beam scanning, scanning magnification, electron beam diameter, and the like can be performed, and drive measurement control of a plurality of WDSs and EDS measurement control of one can be performed. In addition, it is possible to measure and control the intensity of electron signals such as secondary electrons / reflected electrons, and to control the drive of the sample stage in each direction (X, Y, and Z axis directions). It is possible to collect surface analysis data of X-ray signals and electronic signals by beam scanning.

Next, a first embodiment of the quantitative analysis method according to the present invention, which is performed using the X-ray microanalyzer configured as described above, will be described with reference to the flowchart shown in FIG. In this embodiment, a simple quantitative analysis is performed on a sample whose constituent elements are unknown.
First, the first qualitative analysis is performed by the usual method using the WDS of the X-ray microanalyzer shown in FIG.
1). The constituent elements of the sample were determined by the first qualitative analysis (step S2), and it was found that there were no elements sensitive to electron beam irradiation damage such as Na and K (hereinafter referred to as elements having a large change with time). In the case, based on the X-ray intensity of the spectrum obtained as a result of the first qualitative analysis,
A simple quantitative analysis is performed by comparing with the standard sample data intensity stored in the control unit (step S3).

On the other hand, if it is determined by the first qualitative analysis that the constituent elements of the sample are present, such as Na, K, etc., that have large changes with time, the analysis position by electron beam irradiation is set to the beam diameter. Several times to 10 times (several tens to 100μ)
m) Shift (step S4) and perform a second qualitative analysis. At this time, a quantitative analysis of glass will be described as an example. In the first sequence, a spectroscopic element (TAP, PET, LiF) for analyzing Na, K, and Si which has the largest change with time, that is, which is likely to fluctuate quantitatively. ) And a peak analysis scan range are set to perform qualitative analysis. In the second sequence, for example, Al, Mg, O, C
qualitative analysis is performed by setting an analysis spectroscopic element such as a and a peak analysis scan range, and then a qualitative analysis is performed by setting an analysis spectroscopic element such as P and Cr and a peak analysis scan range in the third sequence with the least fluctuation. The analysis is performed to detect the constituent elements of the glass (step S5).

Table 1 shows the spectroscopic elements and the peak analysis scan range (wavelength, unit の) of the above analysis sequence for glass. In Table 1, TAP is a spectral element for Na, PET is a spectral element for Si, LiF is a spectral element for other elements in the first sequence, and TAP in the second sequence.
Is a spectral element for Al and Mg, PET is a spectral element for elements such as Cr and Ca, and TAP is a spectral element for P and O in the second sequence.

[0019]

[Table 1]

A second qualitative analysis is performed as described above.
Based on the X-ray intensity of the spectrum obtained as a result, simple quantitative analysis is performed by comparing with the standard sample data intensity stored in the storage device connected to the control unit (step S6). The operation of each unit in each of the above steps is configured to be automatically performed by a control unit (CPU) without human intervention.

As described above, when it is found in the first qualitative analysis that an element such as Na, K or the like which has a large change with time exists in the sample, the electron beam irradiation position on the sample is shifted to perform the second qualitative analysis. At that time, since the qualitative analysis is performed in the order of the element having a large change with time, that is, in the order of the element having a large variation quantitatively, the qualitative analysis is performed in a short time for the element having a large variation, and therefore, the accuracy is improved. Good simple quantitative analysis results can be obtained.

FIG. 3 shows the qualitative spectrum and the simplified quantitative results obtained in Table 1 together with the qualitative spectrum according to the conventional example for comparison. In FIG. 3, a dotted line is a qualitative spectrum obtained by the present embodiment, which is obtained by a qualitative analysis performed using a TAP spectroscopy element with a peak analysis scan range of 11.733-12.099 °, and a solid line obtained by a conventional example. The qualitative spectrum was obtained by qualitative analysis using a TAP spectroscopy element with a scan range of 6.439-21.192 °. As is clear from this figure, in the case of the conventional example, the attenuation of Na with the passage of the analysis time is remarkable, and a considerable error occurs in the simple quantitative result.

Next, a second embodiment will be described with reference to a flowchart shown in FIG. This embodiment is applied to a case where it is known in advance that the sample contains Na, K and the like which change greatly with time. Therefore, the quantitative analysis method according to this embodiment eliminates the first qualitative analysis for determining the presence / absence of an element whose change with time is large among the steps in the first embodiment shown in FIG. Process.

That is, in the case of a sample which is known to contain Na and K whose change with time is large, for example, a glass sample, Na as a first sequence is likely to fluctuate in quantitative amount.
, Qualitative analysis by setting the analysis spectroscopic element and peak analysis scan range for K, Si and other main elements,
Then, in each of the subsequent sequences, the spectroscopic element for analysis and the scan range for peak analysis are set in the order of the elements whose change over time becomes smaller sequentially, and the qualitative analysis is sequentially performed (step S11). Then, X of the spectrum obtained as a result of these qualitative analyzes was
Based on the line intensity, simple quantitative analysis is performed by comparison with the standard sample data intensity (step S12). Also in this embodiment, the operation of each unit in each step is automatically performed by the control unit (CPU).

As described above, when it is known that there is an element having a large change over time in a sample, the qualitative analysis is performed from the element having a large change over time, that is, the element having a large variation quantitatively. The qualitative analysis is performed in a short time on an element having a large value, and an accurate and simple quantitative analysis result can be obtained as in the first embodiment.

Next, a third embodiment will be described with reference to a flowchart shown in FIG. When the number of WDSs arranged in the X-ray microanalyzer shown in FIG. 1 is small, it may not be possible to analyze a plurality of elements at the same time. That is, for example, Si using the same PET spectroscopic element cannot be measured simultaneously during the analysis and measurement of K by PET.
Therefore, in such a case, a case arises in which the quantitative analysis methods according to the first and second embodiments cannot cope. The third embodiment is adapted to cope with such a case.

That is, in this embodiment, first, a first qualitative analysis is performed by a normal method to determine the presence or absence of an element which greatly changes with time in the constituent elements of the sample (steps S21 and S22). If it is found that there are no elements that change greatly with time, based on the X-ray intensity of the spectrum obtained in the first qualitative analysis, a simple quantitative analysis thereof is performed (step S23). Is the same as in the first embodiment.

Next, if it is determined by the first qualitative analysis that the constituent elements of the sample are present, such as Na, K, etc., if there is an element having a large change with time, the spectrum of the element having a large change with time is determined. The temporal change in the peak X-ray intensity is plotted to determine the rate of the time change (step S2).
Four). The rate of this time change is determined by approximating it with a higher-order curve, and is used as an influence curve of X-ray intensity due to the analysis measurement time. This influence curve becomes a decay curve for Na and K, and becomes an increase curve for other elements such as Si. For example, a decay curve of Na with time and an increase curve of Si of glass are illustrated in FIG.

Then, the influence curve of the X-ray intensity obtained by the analysis and measurement time of the spectrum peaks of the elements having large fluctuations such as Na and K is registered in the storage device connected to the control unit (step S25). ).

Next, a second qualitative analysis is performed under normal settings to identify each element, and an analysis measurement time until a main peak of each element is detected is measured (step S26). This analysis measurement time is calculated by the number of drive steps of the spectroscopic element (spectral crystal) and the measurement unit time. Then, the main spectrum intensities of the respective elements obtained by the above qualitative analysis are converted and corrected into net X-ray intensities based on the influence curves of the X-ray intensities due to the previously measured and registered analysis measurement times. . Then, simple quantitative analysis is performed based on the converted and corrected X-ray intensity (step S27).

As described above, in this embodiment, the analysis measurement time until the spectral peak of each element is detected in the qualitative analysis is measured, and the influence curve of the X-ray intensity based on the analysis measurement time determined in advance is obtained. Since the spectral peak intensities of the respective elements obtained by the qualitative analysis are converted and corrected based on the qualitative analysis, a highly accurate and simple quantitative analysis result can be obtained.

The method of the third embodiment can be applied to the analysis of carbon in steel. In other words, during the analysis and measurement of carbon in steel, the amount of carbon due to contamination increases depending on the degree of vacuum, resulting in a quantitative result larger than that of actual carbon. The influence curve of the X-ray intensity due to the measurement time is measured in advance and registered. Then, the measurement time until the spectral peak of carbon is detected in the qualitative analysis of the actual steel is measured, and the qualitative analysis is performed based on the influence curve of the X-ray intensity based on the previously determined analysis measurement time. By converting and correcting the spectral peak intensity of the carbon thus obtained, a highly accurate and simple quantitative analysis result of carbon in steel can be obtained.

[0033]

As described above with reference to the embodiment, according to the first aspect of the present invention, if it is found by the first qualitative analysis that an element having a large change with time is present, The second qualitative analysis is automatically performed in the order of the element having a large change with time by shifting the qualitative analysis position of 1 and the quantitative analysis is performed based on the result of the qualitative analysis. However, simple and accurate quantitative analysis can be obtained. According to the second aspect of the present invention, when it is previously known that an element having a large change with time is present in the sample, the first qualitative analysis is omitted, and the qualitative analysis is automatically performed in the order of the element with the largest change with time. , And quantitative analysis is performed based on the qualitative analysis result. Therefore, a simple quantitative analysis result can be obtained with a simple process even for an element that changes greatly with time. According to the third aspect of the present invention, the influence of the elapsed time of electron beam irradiation on the detected X-ray intensity is measured in advance for an element having a large change with time, and an analytical measurement time influence curve is created and registered. As a result, if it is found that there is an element that changes greatly with time, qualitative analysis is performed based on the analytical measurement time influence curve registered in advance according to the analysis measurement time required for each element that changes greatly with time during qualitative analysis. Quantitative correction is performed on the quantitative analysis result based on the energy spectrum intensity obtained as a result of the above, so that a highly accurate and simple quantitative analysis result can be obtained even for an element that changes greatly with time. According to the invention of claim 4, the influence of the electron beam irradiation time required for the qualitative analysis of carbon in the steel on the detected X-ray intensity is measured in advance, and an analysis measurement time influence curve is created and registered. According to the analysis measurement time required for the analysis of carbon at the time of qualitative analysis, the quantitative analysis result based on the energy spectrum intensity obtained as a result of the qualitative analysis is determined based on the previously registered analysis measurement time influence curve. Since the correction is performed, a highly accurate and simple quantitative analysis result of carbon in steel can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an X-ray microanalyzer used for performing a quantitative analysis method in a sample analyzer according to the present invention.

FIG. 2 is a flowchart for explaining a first embodiment of a quantitative analysis method in the sample analyzer according to the present invention.

FIG. 3 is a diagram showing a quantitative analysis result according to the first embodiment in comparison with a quantitative analysis result according to a conventional example.

FIG. 4 is a flowchart for explaining a second embodiment of the present invention.

FIG. 5 is a flowchart for explaining a third embodiment of the present invention.

FIG. 6 is a curve diagram showing the change over time in the X-ray intensity of Na and Si during qualitative analysis.

[Explanation of symbols]

 Reference Signs List 1 electron gun 2 Wehnelt 3 deflection coil 4 motor for driving X-ray spectroscope 5 X-ray spectroscopy element 6 X-ray detector 7 backscattered electron detector 8 secondary electron detector 9 EDS 10 analysis sample 11 sample stage 12 motor for stage drive 13 Deflection coil controller 14 X-ray spectroscope drive motor controller 15 Stage drive motor controller 16 Secondary / reflected electron signal data capture device 17 WDSX-ray signal data capture device 18 EDSX-ray signal data capture device 19 Controller (CPU) 20 Mass storage device

Claims (4)

[Claims] An electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and a control unit for controlling the operation of each unit. A sample analyzer that irradiates the sample with an electron beam, detects characteristic X-rays emitted from the sample surface, and performs a quantitative analysis of the sample. And if the first qualitative analysis shows that there is no element sensitive to electron beam irradiation damage, such as Na or K, the energy obtained as a result of the first qualitative analysis Performing a quantitative analysis based on the spectrum intensity; and, as a result of the first qualitative analysis, determining that an element sensitive to electron beam irradiation damage, such as Na or K, is present. Electron beam position Slide the remote location several times a beam diameter, automatically perform qualitative analysis of the sensitive elements Na, the radiation damage of the electron beam K such in the first sequence,
Next, a second qualitative analysis step of automatically performing qualitative analysis of other elements in the second and subsequent sequences, and a step of performing quantitative analysis based on the energy spectrum intensity obtained as a result of the second qualitative analysis are provided. A quantitative analysis method in a sample analyzer. 2. An electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and a control unit for controlling the operation of each unit. A sample analyzer that irradiates the sample with an electron beam, detects characteristic X-rays emitted from the sample surface, and performs a quantitative analysis of the sample. If it is known in advance that an element sensitive to irradiation damage is present, a qualitative analysis of elements sensitive to electron beam irradiation damage such as Na and K is automatically performed in the first sequence, and then the first sequence is performed. Automatically performing qualitative analysis of elements other than the above in the second and subsequent sequences; and performing quantitative analysis of each element based on the energy spectrum intensity obtained as a result of the qualitative analysis. Sample analyzer Quantitative analysis method that definitive. 3. An electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and a control unit for controlling the operation of each unit. A sample analyzer that irradiates the sample with an electron beam, detects characteristic X-rays emitted from the sample surface, and performs a quantitative analysis of the sample. And if the first qualitative analysis shows that there is no element sensitive to electron beam irradiation damage, such as Na or K, the energy spectrum obtained as a result of the first qualitative analysis Performing a quantitative analysis based on the intensity and, as a result of the first qualitative analysis, determining that there is an element sensitive to electron beam irradiation damage such as Na, K, Elements sensitive to irradiation damage Measuring the effect of the electron beam irradiation analysis measurement time on the detected X-ray intensity during qualitative analysis, creating and registering an analysis measurement time effect curve, and irradiating electron beams such as Na and K during the second qualitative analysis. Based on the analysis measurement time effect curve registered in advance according to the analysis measurement time required for each element sensitive to damage, the second qualitative analysis result is used to obtain a quantitative analysis result based on the energy spectrum intensity obtained. Performing a quantitative correction. A quantitative analysis method in the sample analyzer. 4. An electron beam source for irradiating a sample with an electron beam, an X-ray spectrometer for detecting characteristic X-rays emitted from the sample irradiated with the electron beam, and a control unit for controlling the operation of each unit. In a quantitative analysis method in a sample analyzer for irradiating a sample with an electron beam and detecting characteristic X-rays emitted from the surface of the sample to perform quantitative analysis of the sample, it is necessary to analyze carbon during qualitative analysis of steel. Measuring the effect of the electron beam irradiation time on the detected X-ray intensity, creating and registering an analytical measurement time effect curve, and performing qualitative analysis of steel and pre-registering according to the analytical measurement time required for carbon analysis Performing a quantitative correction on the quantitative analysis result of carbon based on the energy spectrum intensity obtained from the qualitative analysis result, based on the analyzed measurement time influence curve. A quantitative analysis method in a sample analyzer.