JP2010164442A - Analysis method by energy dispersive x-ray spectrometer, and x-ray analyzer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To automatically stop measurement before a sample is damaged by electron beam irradiation, in an analysis method for detecting X-rays generated from the sample by electron beam irradiation. <P>SOLUTION: X-rays, secondary electrons or the like generated from the sample by electron beam irradiation are detected respectively by an X-ray detector 24 and an electron detector 23, and results are stored in a storage part 34 as time series data combined in time series together with elapsed time information and a coordinate position. While measuring, an X-ray signal is extracted from the storage part 34 at fixed time intervals from start of measurement, and an X-ray spectrum is reproduced. A fluctuation with elapse of time of X-ray intensity in the whole spectrum or in an optionally specified energy range is monitored, and when detecting an abnormality, measurement is stopped manually or automatically. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a transmission electron microscope (TEM), a scanning electron microscope (SEM), an electron equipped with an energy dispersive X-ray spectrometer (EDS) for detecting characteristic X-rays emitted by irradiating a sample with an electron beam. The present invention relates to an X-ray analyzer such as a probe microanalyzer (EPMA), and more particularly to a method for analyzing a sample that changes due to electron beam damage or the like with the measurement elapsed time.

  2. Description of the Related Art Elemental analysis methods and apparatuses for analyzing a sample by spectrally detecting characteristic X-rays emitted by irradiating the sample with an electron beam are widely used. Some samples cause changes in composition and shape when irradiated with an electron beam. Alkaline elements such as sodium (Na) and potassium (K) contained in soda glass are representative elements whose characteristic X-ray intensity is attenuated during analysis by irradiating a sample with an electron beam. In Japanese Patent No. 3950626 of Patent Document 1, an element sensitive to damage caused by electron beam irradiation such as Na and K is obtained in advance when performing a simple quantitative analysis using the characteristic X-ray peak intensity of the qualitative spectrum. A technique for improving the analysis accuracy by correcting the characteristic X-ray peak intensity with an analysis measurement time influence curve representing the relationship between the electron beam irradiation analysis measurement time and the detected X-ray intensity has been disclosed.

  Japanese Patent Application Laid-Open No. 2007-198749 of Patent Document 2 includes a tag representing a measurement elapsed time between energy data of detected X-ray signals in a surface analyzer equipped with an energy dispersive X-ray spectrometer (EDS). By placing a tag representing position (coordinate) information on the sample and storing all the X-ray signal data in the storage device in sequence, it is possible to reproduce the spectrum every arbitrary time by measuring the EDS spectrum once. A possible technique is disclosed.

Japanese Patent No. 3950626 JP 2007-198749 A

  In the technique disclosed in Japanese Patent No. 3950626 of Patent Document 1, an analysis measurement time influence curve must be created before analysis. However, if analysis conditions such as the irradiation current value of the electron beam and the electron beam diameter change, a curve corresponding to the analysis condition is required, which requires a lot of preparation.

  The technique disclosed in Japanese Patent Application Laid-Open No. 2007-198749 of Patent Document 2 can reproduce an X-ray spectrum at an arbitrary elapsed time after the start of measurement once data has been acquired. You can see how the composition has changed. Further, only the desired X-ray spectrum can be extracted from the state of the change and used for quantitative analysis or the like. However, a technique for stopping the electron beam irradiation (measurement) while measuring the data while the influence of the electron beam irradiation on the sample is small is not shown. In addition, there is also a technology that detects when a part of the analysis area changes due to electron beam irradiation during line analysis or surface analysis, and detects the change if necessary. Absent.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a transmission electron microscope (TEM) equipped with an X-ray analyzer using an energy dispersive X-ray spectrometer (EDS), a scanning electron. Provided are an X-ray analysis method and an electron beam apparatus capable of automatically stopping measurement of a sample before it is damaged by electron beam irradiation in an electron beam apparatus such as a microscope (SEM) or an electron probe microanalyzer (EPMA). There is to do.

To solve the above problem,
The invention according to claim 1 is an X-ray analysis method for analyzing a sample by irradiating a sample with an electron beam, detecting characteristic X-rays generated from the sample with an energy dispersive X-ray spectrometer,
A detection step of detecting characteristic X-rays generated from the sample by two-dimensionally controlling the sample irradiation position of the electron beam;
An analysis step of analyzing the energy of the characteristic X-ray detected by the detection step;
A data processing step for generating X-ray signal data of energy detected in the analysis step, generating characteristic X-ray measurement elapsed time information data, and generating position information data of the electron beam;
A data storage step of storing in a storage device as time-series data in which each data generated by the data processing step is combined in time series;
An extraction step for extracting X-ray signal data included in the specified measurement elapsed time range of the stored measurement elapsed time and / or the specified position information range of the position information data from the time-series data. In the line analysis method,
A fluctuation detecting step of detecting fluctuations with time of all or part of the X-ray signal data extracted by the extracting step;
The electron beam irradiation to the sample is stopped based on the fluctuation of the data detected in the fluctuation detecting step.

  According to a second aspect of the present invention, in the fluctuation detecting step, the X-ray signal of the X-ray signal is plotted on the horizontal axis using the X-ray signal data included in the range of the fixed time interval and / or the fixed position interval. A spectrum having an energy value and a vertical axis representing the accumulated number of the X-ray signals is constructed, and the electron beam irradiation to the sample is stopped based on the detected fluctuation of the spectrum.

  The invention according to claim 3 is characterized in that the fluctuation of the spectrum is a change in the integrated number of the X-ray signals included in a predetermined energy range.

  The invention according to claim 4 further includes a step of stopping the electron beam irradiation to the sample when the variation of the data accompanying the increase in the measurement elapsed time exceeds a predetermined threshold value. And

The invention according to claim 5 extracts, from the storage device, X-ray signal data repeatedly measured in a region determined by the fixed position interval,
The electron beam irradiation to the sample is stopped based on a variation accompanying an increase in the number of repeated measurements of the X-ray signal data that has been repeatedly measured.

  In the invention according to claim 6, X-ray intensity of a section constituting the region is obtained using all or part of the X-ray signal data repeatedly measured, and the X-ray intensity corresponding to the region is obtained. An image representing the distribution of the above is constructed for each repeated measurement, and the electron beam irradiation to the sample is stopped based on the fluctuation of the intensity distribution accompanying the increase in the number of repeated measurements.

  Further, in the invention according to claim 7, the fluctuation of the intensity distribution is determined by the average value of the X-ray intensity of the image constructed for each repeated measurement and the last image of the repeated measurement for an arbitrary section constituting the image. It is a difference from the X-ray intensity of the image used for construction.

  The invention according to claim 8 is characterized in that the fluctuation of the intensity distribution is a standard deviation of all the X-ray intensities used for the image constructed for each repeated measurement.

The invention described in claim 9 is an X-ray equipped with an energy dispersive X-ray spectrometer that analyzes the sample by irradiating the sample with an electron beam and spectrally detecting characteristic X-rays generated from the sample. An analyzer,
Detection means for two-dimensionally controlling the electron beam sample irradiation position to detect characteristic X-rays generated from the sample;
Analyzing means for analyzing energy of characteristic X-rays detected by the detecting means;
Data processing means for generating X-ray signal data of energy detected by the analyzing means, generating measurement elapsed time information data of characteristic X-rays, and generating position information data of the electron beam;
Data storage means for storing the data generated by the data processing means in a storage device as time-series data in a time-series combination;
X having extraction means for extracting X-ray signal data included in the specified measurement elapsed time range of the stored measurement elapsed time and / or the specified position information range of the position information data from the time series data In the line analyzer,
Fluctuation detecting means for detecting fluctuations with time of all or part of the X-ray signal data extracted by the extracting means,
The electron beam irradiation to the sample is stopped based on the fluctuation of the data detected by the fluctuation detecting means.

According to the present invention,
X-ray signal data included in a range of arbitrarily specified fixed time intervals and / or fixed position intervals is extracted from time-series data, and the time of all or part of the extracted X-ray signal data is extracted. It has a fluctuation detection process that detects fluctuations with progress,
Since the electron beam irradiation to the sample is stopped based on the fluctuation of the data detected in the variation detection step, the measurement can be automatically stopped before the sample is damaged by the electron beam irradiation.

Further, X-ray signal data included in a range of an arbitrarily specified constant time interval and / or a fixed position interval is extracted from time-series data, and all or a part of the extracted X-ray signal data is extracted. It is provided with a fluctuation detecting means for detecting fluctuation with the passage of time,
Since the electron beam irradiation to the sample is stopped based on the fluctuation of the data detected by the fluctuation detecting means, the measurement can be automatically stopped before the sample is damaged by the electron beam irradiation. A line analyzer can be provided.

The figure which shows the schematic structural example of SEM which implements this invention. The figure for demonstrating the method to extract the X-ray signal data contained in the desired time range from the stored data in this invention. In the present invention, an example of an X-ray spectrum obtained from X-ray signal data extracted from stored data. The graph which plotted the change of the X-ray intensity using the X-ray spectrum created by the X-ray signal extracted from the stored data at a fixed time interval in the present invention. The figure for demonstrating the case where a line analysis is performed for the division set on the sample as a unit of sample position information in this invention. The figure which shows the storage and extraction method of the line analysis data by this invention. The figure for demonstrating the case where surface analysis is performed for the division set on the sample as a unit of sample position information in this invention. The figure which shows the storage and extraction method of surface analysis data by this invention. The figure which shows the some image obtained by the X-ray signal extracted from the data which repeated the measurement in the same surface analysis area | region in this invention. The figure which shows the example which image-displays the fluctuation | variation of the X-ray intensity in the area | region to which attention is paid in this invention.

  Embodiments of the present invention will be described below with reference to the drawings. However, the technical scope of the present invention is not limited by this illustration. In each figure, the same reference numerals are given to those performing the same or similar operations, and detailed description is not repeated.

  FIG. 1 is a diagram showing a schematic configuration example of an SEM implementing the present invention. An electron optical system including an electron gun 11 that generates an electron beam 12, a focusing lens 13 that narrows the electron beam 12 and an objective lens 15, and a deflector 14 that deflects the electron beam 12 is disposed inside the lens barrel 10. . The electron optical system control unit 16 controls the acceleration voltage applied to the electron gun 11, the excitation current of the focusing lens 13 and the objective lens 15, the applied voltage of the deflector 14, and the like. The position where the electron beam 12 irradiates the sample 21 is determined by the applied voltage of the deflector 14.

  Inside the sample chamber 20, a sample stage 22 for moving the sample 21, an electron detector 23 for detecting electrons (secondary electrons, reflected electrons, etc.) generated from the sample by electron beam irradiation and X-ray detection are detected. An energy dispersive X-ray detector 24 is arranged.

Reference numeral 25 denotes an X-ray signal processing unit for analyzing an energy value by a multi-channel analyzer based on the pulse peak value of the X-ray signal detected by the X-ray detector 24 and assigning a corresponding channel. Reference numeral 26 denotes a sample stage control unit for moving the sample 21 and changing the irradiation position of the electron beam 12. Reference numeral 27 denotes an electronic signal processing unit for sending the electronic signal intensity detected by the electronic detector 23 to the computer 31 as a digital signal. The electronic signal intensity data from the electronic signal processing unit 27 is
It is sent to the computer 31 in association with the irradiation position of the electron beam 12 determined by the deflector 14.

  The electron optical system control unit 16, the X-ray signal processing unit 25, the sample stage control unit 26, and the electronic signal processing unit 27 are connected to a computer 31 via a bus 30. The computer 31 includes a display unit 32 such as a liquid crystal display that displays an electron beam image, an X-ray image, an operation screen, an input unit 33 such as a mouse and a keyboard, and a storage unit 34 such as a hard disk that stores analysis data. Connected through.

The passage of the electron beam 12 in the lens barrel 10 and the inside of the sample chamber 20 are maintained at a vacuum of about 10 ⁻³ Pa by a vacuum exhaust pump (not shown). In the actual apparatus, an electron beam shutter, a diaphragm, an astigmatism correction coil, etc. are arranged in addition to those described above, but the description thereof is omitted.

  Next, the structure of analysis data used for carrying out the present invention will be described. In the present invention, the deflector 14 for changing the irradiation position of the electron beam 12 is controlled by the electron optical system controller 16 to irradiate the electron beam 12 to a predetermined coordinate position of the sample 21. X-rays generated by electron beam irradiation are detected by an X-ray detector 24 and converted into an X-ray signal by an X-ray signal processing unit 25, secondary electrons and the like are detected by an electron detector 23, and an electronic signal processing unit 27 is detected. To convert it to an electronic signal. The data of these signals is stored in the storage unit 34 as time-series data that is time-series combined with the elapsed time information of measurement and the coordinate position.

  It is not essential for X-ray analysis to acquire an electronic signal together with acquisition of an X-ray signal. However, since the image formed by the electronic signal brings important knowledge for knowing the analysis location, it is greatly advantageous to capture it simultaneously with the X-ray signal.

The structure of the time-series data stored in the storage unit 34 is, for example, that the position information data is P, the X-ray signal data is D, the electronic signal data from the electron detector is I, and the elapsed time information data is T.
P, I, D, D, D, D, T, D, ..., D, P, I, D, D ... T, D, D ... D, P, I, D, ...・ It is expressed as D, D, T, D, D,. This data string is time-series data in which the respective data are arranged in series along the measurement elapsed time axis from the left side to the right side of the page.

  The position information (P) is a coordinate value representing the analysis position on the sample, and is one of the X and Y axes perpendicular to the electron beam, the Z axis parallel to the electron beam, the T axis of the sample tilt, the R axis of the sample rotation, and the like. Part or all data.

  The X-ray signal (D) represents energy value data (or a corresponding channel) obtained by analyzing each X-ray quantum incident on the X-ray detector 24, and preferably has a depth of about 13 bits, for example. .

  The electronic signal (I) means data of one or more electronic signals (secondary electrons, reflected electrons, transmitted electrons, etc.).

  The elapsed time information (T) is data indicating a part or all of the actual elapsed time (Real Time) or the effective time (Live Time). Here, the actual elapsed time is the time actually elapsed from the start of measurement, and the effective time is the net measurement time excluding the EDS dead time.

Since the data structure in the present invention is created so that various data are individually stacked and stored in order, it is possible to add signal data such as sample absorption current and cathode luminescence other than the above. is there.
(Embodiment 1)
FIG. 2 is a diagram for explaining a method of extracting X-ray signal (D) data included during a lapse of a desired time b from a desired elapsed time a from the start of measurement from time-series data stored in the storage unit 34. FIG. In FIG. 2A, when elapsed time information having data of elapsed time a is represented by Ta and elapsed time information when time b has elapsed from the elapsed time information Ta is represented by Ta + b, Ta and Ta + b If all of the X-ray signal (D) data included in between is extracted, the spectrum of X-rays collected within a certain time can be obtained. The elapsed time a and the time range b can be arbitrarily specified as a multiple of t _min if the minimum time interval for putting the elapsed time information T at the time of measurement into the data string is t _min .

  An example of the X-ray spectrum obtained from the X-ray signal (D) data extracted from the stored data is shown in FIG. In FIG. 3, the horizontal axis represents the energy of X-rays, and corresponds to each channel divided by 0.01 KeV intervals of the multichannel analyzer. The vertical axis represents the value obtained by integrating the number of X-ray signals (D) for each channel. This integrated value is usually called X-ray intensity.

  ROI (Region of Interest) means an energy range provided for selecting only an X-ray signal having a desired energy. The ROI range can be arbitrarily set by the operator, but there is also a device having a function of automatically setting an appropriate range when the operator designates an element.

  In FIG. 3, ROI (Si) and ROI (Ca) are set so as to include characteristic X-rays of silicon (Si-Kα) and calcium (Ca-Kα, Ca-Kβ), respectively. The setting range of ROI (Ca) may be set so that only Ca-Kα is included.

    Table 1 shows the relationship among X-ray energy, D value and channel. ROI (Si) is set in the range of 1.6 KeV to 1.9 KeV, and ROI (Ca) is set in the range of 3.55 KeV to 4.15 KeV. By integrating all the numbers of X-ray signal (D) data included between Ta and Ta + b, the X-ray intensity of the entire spectrum can be known. Moreover, if the number of D having a value between ROI (Si) and ROI (Ca) is integrated, the X-ray intensities of Si and Ca can be known separately.

  In Table 1, the X-ray energy is converted into the D value so that the D value corresponds to the channel number, but the present invention is not limited to this. For example, X-ray energy may be stored in units of 1 eV (1.6 KeV X-ray is “D = 1600”), and data may be extracted and converted according to the energy width of the channel when obtaining a spectrum. .

  FIG. 2B shows a case where the elapsed time information is read from the stored data string, the X-ray signal (D) data is extracted at arbitrary time intervals, and the X-ray spectrum is obtained in time series. Yes. In FIG. 2 (b), the elapsed time information Ta + 2b and Ta + nb means T having elapsed time data when the times of 2 times b and n times b have elapsed from the elapsed time a, respectively. Yes.

  Next, a method for monitoring whether there is a problem in the apparatus or the sample during analysis using the X-ray spectrum obtained in time series as described above will be described.

  During analysis, abnormalities may occur in measurement data due to various factors. For example, the brightness of the electron gun filament may fluctuate due to the filament breaking. In addition, the sample may be deformed due to heat damage due to electron beam irradiation, or the composition may change. When an abnormality occurs during measurement, not only is it time consuming to continue the measurement, but particularly when the sample is damaged, it is necessary to quickly stop the electron beam irradiation.

  FIG. 4 shows the X-ray intensity in the whole or arbitrarily specified energy range using the X-ray spectrum created by the X-ray signal extracted at a certain time interval from the start of measurement by the method shown in FIG. It is the graph which plotted the fluctuation | variation of. The horizontal axis represents the elapsed time, and the vertical axis represents the integrated value of the X-ray signal (D) included in a certain time interval. For example, when the sample surface is depressed by electron beam irradiation, X-rays emitted from the sample surface may be reduced due to excessive absorption. In that case, the progress of the sample damage can be known by monitoring the change in the X-ray intensity of the entire X-ray spectrum. If a graph as shown in FIG. 4 is displayed in real time during measurement, the operator can confirm the state of fluctuation and stop the measurement (stop the electron beam irradiation). Alternatively, a threshold value may be set in advance (95% of the start in the graph of FIG. 2), and the measurement may be automatically stopped when the X-ray intensity reaches the threshold value.

  As described above, since alkali elements such as sodium (Na) and potassium (K) contained in soda glass are particularly vulnerable to electron beam irradiation, ROI as shown in FIG. You may make it monitor the X-ray intensity change of these elements.

  Furthermore, after the measurement is completed, the state of fluctuation of the X-ray intensity may be confirmed, and only data in a range usable for analysis may be extracted.

(Embodiment 2)
Conventionally, there has been an analysis method in which an electron beam and a sample are moved relative to each other in an arbitrary line shape or strip shape, and profiles of intensity changes of various signals obtained from the sample are drawn (in the following explanation, this is referred to as “line analysis”). ). The relative movement between the electron beam and the sample is performed using the deflector 14 or the sample stage 22 or both.

  FIG. 5 is a diagram for explaining a case where line analysis is performed using a section set on a sample as a unit of sample position information. Sample irradiation with an electron beam starts from the section P1 and ends at Pe. FIG. 6 is a diagram showing a method for storing and extracting line analysis data according to the present invention. In FIG. 6A, P1 and Pe indicate data having position information on the beginning and end on the line, respectively. By extracting the X-ray signal (D) sandwiched between the position information (P), the X-ray intensity change of the specified element can be obtained as a profile for an arbitrary section on the line.

  FIG. 6B shows a method of extracting measurement data when repeatedly measuring on the line. The number of repetitions can be determined by counting the line end position information Pe. If X-ray signal (D) is integrated in order from Line_1 while performing X-ray intensity integration for each line, and a graph as shown in FIG. 4 is created, measurement data can be obtained even when the sample is thermally damaged. It is possible to quickly detect such abnormalities and to perform operations such as stopping electron beam irradiation.

  Even for data acquired by line analysis, measurement data in an arbitrary time range can be extracted independently of position information or in association with position information by adding measurement elapsed time information to the data string. Is possible.

(Embodiment 3)
Conventionally, there is an analysis method in which an electron beam and a sample are relatively moved two-dimensionally in an arbitrary region, and an X-ray intensity change obtained from the sample is displayed as a color image or the like (in the following explanation, this is referred to as “surface”). Analysis "). The relative movement between the electron beam and the sample is performed using the deflector 14 or the sample stage 22 or both simultaneously.

  FIG. 7 is a diagram for explaining a case where surface analysis is performed using a section set on a sample as a unit of sample position information. Sample irradiation with an electron beam starts from the section P11 and ends at Pxy.

  FIG. 8 is a diagram showing a method for storing and extracting surface analysis data according to the present invention. In FIG. 8A, P11 and Pxy mean data having position information at the beginning and end of the surface analysis area, respectively. In the data string shown in FIG. 8 (a), the relative movement between the electron beam and the sample starts from the upper left side of the paper and moves linearly in the right direction. It is an example of data stored when it is performed so that it may move linearly.

  If the X-ray signal (D) sandwiched between the position information (P) is extracted and integrated, the X-ray intensity of the specified element can be obtained for any section included in the surface analysis region. Therefore, the variation in the X-ray intensity in the surface analysis region can be obtained as a distribution image such as a color. For example, if you want to know the fluctuations in the block (Block) whose head and end position information is P27 and P39, respectively, and the line (Line) whose head and end position information is P61 and P612, respectively, see FIG. As shown, a region of interest can be extracted by specifying a range. If an ROI is set for a necessary element at this time, a distribution image of each element can be obtained.

  FIG. 8B shows a method of extracting data for each frame from the measurement data when the surface analysis region is repeatedly measured. Data from P11 to Pxy may be Frame_1, and each frame data may be extracted every time Pxy appears. The number of repetitions can be known by counting the position information Pxy at the end of the surface analysis area.

  FIG. 9 is an image obtained based on the X-ray signal (D) extracted by the method shown in FIG. 8B from data obtained by repeating measurement in the same surface analysis region. If an integrated value of all X-ray signals (D) sandwiched between position information at the beginning and end of each frame or an X-ray signal (D) included in the ROI set for a specific element is extracted, the distribution of X-ray intensity An image can be obtained.

  Extracting the X-ray signal (D) in order from Frame_1 while repeating the surface analysis for each frame, and creating a graph as shown in FIG. 4, even if the sample is damaged by heat, Abnormalities can be detected quickly, and operations such as stopping electron beam irradiation can be performed.

  Even in the case of data acquired by surface analysis, by adding measurement elapsed time information to a data string, measurement data in an arbitrary time range is extracted independently of position information or in association with position information. be able to.

(Embodiment 4)
In FIG. 9, it is possible to detect an abnormality in the measurement data by monitoring the fluctuation of the X-ray intensity of the block including the section Am or Am of interest. FIG. 10 is an example in which the variation C of the block including the section Am of interest is obtained and the distribution diagram of the variation C is displayed. Nothing is displayed in the block including Am until Frame_n, but the variation C is displayed in Frame_n + 1. That is, it means that the variation C of the data included in the block including Am exceeds a certain magnitude during the measurement of Frame_n + 1.

  As the variation C, for example, if the integrated value of a block including Am of Frame_i is fi, a deviation from the average value up to Frame_n calculated by the following equation (1) can be taken.

Further, for example, a standard deviation up to Frame_n as calculated by the following expression (2) may be displayed.

  In the above description, the data extracted from the stored data at an arbitrary time interval or position interval is the X-ray signal (D). However, even the electronic information (I) or other such as cathodoluminescence It may be data.

As described above, according to the present invention, by using an X-ray spectrum created from an X-ray signal extracted at a certain time interval from the start of measurement, a change in the X-ray intensity in the whole or arbitrarily designated energy range can be detected. By monitoring, the measurement can be stopped before the sample is damaged by the electron beam irradiation.

(Common reference numerals are used for the same or similar operations.)
DESCRIPTION OF SYMBOLS 10 ... Lens barrel 11 ... Electron gun 12 ... Electron beam 13 ... Condensing lens 14 ... Deflector 15 ... Objective lens 16 ... Electron gun control part 17 ... Electro-optic system control part 20 ... Sample chamber 21 ... Sample 22 ... Sample stage 23 ... Electron detector 24 ... X-ray detector 25 ... X-ray signal processing unit 26 ... Sample stage control unit 27 ... Electronic signal processing unit 30 ... Bus 31 ... Computer 32 ... Display unit 33 ... Input unit 34 ... Storage unit

Claims (9)

An X-ray analysis method for analyzing a sample by irradiating a sample with an electron beam and detecting characteristic X-rays generated from the sample with an energy dispersive X-ray spectrometer,
A detection step of detecting characteristic X-rays generated from the sample by two-dimensionally controlling the sample irradiation position of the electron beam;
An analysis step of analyzing the energy of the characteristic X-ray detected by the detection step;
A data processing step for generating X-ray signal data of energy detected in the analysis step, generating characteristic X-ray measurement elapsed time information data, and generating position information data of the electron beam;
A data storage step of storing in a storage device as time-series data in which each data generated by the data processing step is combined in time series;
An extraction step for extracting X-ray signal data included in the specified measurement elapsed time range of the stored measurement elapsed time and / or the specified position information range of the position information data from the time-series data. In the line analysis method,
A fluctuation detecting step of detecting fluctuations with time of all or part of the X-ray signal data extracted by the extracting step;
An X-ray analysis method characterized in that irradiation of an electron beam to a sample is stopped based on a variation in data detected in the variation detection step. In the variation detection step, using the X-ray signal data included in the fixed time interval and / or the range for each fixed position interval, the horizontal axis indicates the energy value of the X-ray signal, and the vertical axis indicates the X-ray signal. The X-ray analysis method according to claim 1, wherein a spectrum with an integrated number of is constructed and electron beam irradiation to the sample is stopped based on the detected fluctuation of the spectrum. 4. The X-ray analysis method according to claim 1, wherein the spectrum variation is a change in an integrated number of the X-ray signals included in a predetermined energy range. 5. 4. The method according to claim 1, further comprising a step of stopping the electron beam irradiation on the sample when the fluctuation of the data accompanying the increase in the measurement elapsed time exceeds a predetermined threshold value. 5. X-ray analysis method described in 1. Extracting X-ray signal data repeatedly measured in the region determined by the fixed position interval from the storage device;
2. The X-ray analysis method according to claim 1, wherein irradiation of the electron beam to the sample is stopped based on a variation accompanying an increase in the number of times of the repeated measurement of the X-ray signal data measured repeatedly. . Using all or part of the repeatedly measured X-ray signal data, the X-ray intensity of the section constituting the area is obtained, and an image representing the X-ray intensity distribution corresponding to the area is obtained for each repeated measurement. 6. The X-ray analysis method according to claim 5, wherein the electron beam irradiation to the sample is stopped based on the fluctuation of the intensity distribution accompanying the increase in the number of repeated measurements. The fluctuation of the intensity distribution is the average value of the X-ray intensity of the image constructed for each repeated measurement for an arbitrary section constituting the image and the X-ray intensity of the image used for the last image construction of the repeated measurement. The X-ray analysis method according to claim 6, wherein the X-ray analysis method is a difference between the two. The X-ray analysis method according to claim 6, wherein the fluctuation of the intensity distribution is a standard deviation of all the X-ray intensities used for the image constructed for each of the repeated measurements. An X-ray analyzer equipped with an energy dispersive X-ray spectrometer that analyzes a sample by irradiating the sample with an electron beam and spectrally detecting characteristic X-rays generated from the sample,
Detection means for two-dimensionally controlling the electron beam sample irradiation position to detect characteristic X-rays generated from the sample;
Analyzing means for analyzing energy of characteristic X-rays detected by the detecting means;
Data processing means for generating X-ray signal data of energy detected by the analyzing means, generating measurement elapsed time information data of characteristic X-rays, and generating position information data of the electron beam;
Data storage means for storing the data generated by the data processing means in a storage device as time-series data in a time-series combination;
X having extraction means for extracting X-ray signal data included in the specified measurement elapsed time range of the stored measurement elapsed time and / or the specified position information range of the position information data from the time series data In the line analyzer,
Fluctuation detecting means for detecting fluctuations with time of all or part of the X-ray signal data extracted by the extracting means,
An X-ray analyzer characterized in that the electron beam irradiation to the sample is stopped based on the fluctuation of the data detected by the fluctuation detecting means.

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