JPH0416754A - Analyzer - Google Patents

Abstract

PURPOSE:To sequentially and successively display a composition ratio of sample components along a scanning line on a sample surface together with scanning by dispersing secondary radiation irradiated from a sample while the sample surface is being scanned by an excitation beam. CONSTITUTION:A sample moving device 3 is driven by a constant distance along a scanning line to be analyzed by an irradiation point of an electron beam on a sample S to be measured, and spectrometers 41,42 corresponding sample components are sequentially positioned on three points on a scanning range per each measurement point on the scanning line to measure X-ray intensity at a characteristic X-ray wavelength position of each element. Then net characteristic X-ray intensity of each component element of the sample S to be measured and first approximate concentration of each element are used to calculate respective component element concentrations C1 to Cn by corrective calculation, and then the spectrometers are moved to the next measurement point. The obtained C1 to Cn are sequentially output to a display device 9 to draw a graph showing a relative change in concentrations of respective component elements along the scanning line.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is an analysis method for quantifying sample components by irradiating the sample surface with excitation radiation and spectroscopy of the secondary radiation emitted from the sample. The present invention relates to an analysis device that can display the quantitative component composition of a sample in real time when performing analysis while scanning a surface.

(Prior Art) Elemental analysis of the sample surface can be performed by irradiating the sample surface with an electron beam and spectrally analyzing the X-rays emitted from the sample. When performing quantitative analysis using this method, the characteristic X-ray intensity of each element is measured using a pure product or a standard sample of known concentration of each sample component element, and this is used as the denominator, and the characteristic Xv1 of each element of the sample to be measured is calculated. The concentration of each component element is determined proportionally with the intensity as the numerator, and this is taken as a first approximation. The characteristic X-ray intensity of each component element is affected by absorption by other coexisting elements, excitation by characteristic X-rays from other elements, etc., so the concentration of each element cannot be determined by simple proportional calculations as described above. First, the concentration of each element must be determined by performing a correction calculation on the concentration of the first approximation described above. The correction calculation itself in this case is well known. In addition, the characteristic X-ray intensity of each element cannot be directly determined for both the standard sample and the measured sample, and the peak of the characteristic X-ray of each element is on the baseline of the X-ray spectrum, so the true characteristic The ray intensity can only be determined by correcting this baseline to the directly measured X-ray intensity.

When performing quantitative analysis of a sample using X-ray spectroscopy in this way, it is not possible to immediately relate the measured values of characteristic X-rays of each element obtained from the sample to be measured with the concentration of each element, so it is necessary to excite the sample surface. There was no device that could scan a line and display changes in the composition ratio of elements along the scanning line in real time.

The same thing is not limited to X-ray spectroscopy; for example,
The same can be said for line photoelectron spectroscopy.

(Issues to be solved by the invention) The present invention scans the sample surface with an excitation line and spectrally spectra the secondary radiation emitted from the sample, thereby scanning the composition ratio of sample components along the scanning line of the sample surface. The present invention aims to provide an analysis device that can simultaneously display data sequentially and continuously.

(Means for solving the problem) A means for scanning the sample surface with an excitation line, a means for spectrally dispersing the secondary radiation emitted from the sample, and a means for determining the peak center and the peak center of the sample component element on the spectroscopic secondary radiation spectrum. means for determining the peak intensity of each element from the spectral intensities at background positions on both sides thereof; and means for storing the peak intensities of each element for standard samples obtained through the above-mentioned means for standard samples of each component element; The first approximate concentration of each component element is calculated proportionally from the peak intensity of the standard sample of each of the above elements and the peak intensity of each element obtained through each of the above devices for the ratio measurement sample, and the first approximate concentration of each component is calculated from the first approximate concentration. The analyzer was composed of a data processing device that performs correction calculations to determine the concentration of elements.

(Function) According to the above configuration, if the peak intensity of the net secondary radiation spectrum of each element with background correction is determined in advance for the standard sample of each component element constituting the sample, the result will be memorized. Therefore, when the sample surface of the sample to be measured is scanned with the excitation line, the concentration of each component element is calculated in real time for each measurement point on the scanning line. Since the concentration of each component is determined in real time, it is possible to sequentially display the component ratios along the scanning line of the sample surface simultaneously with the sample surface scanning.

(Example) FIG. 1 shows an example of the present invention. (2) is an electron gun, and (2) is an objective lens that focuses the electron beam onto the sample surface. Reference numeral 3 denotes a sample moving device which moves the electron beam irradiation point on the sample surface by moving the sample in a direction perpendicular to the electron beam. Electron gun 1. Objective lens 2. The sample moving device 3 constitutes means for scanning the sample surface with an excitation line. 41.
42 is a plurality of X-ray spectrometers arranged around the sample S,
Although only two are shown in the figure, they are arranged as many times as there are elements to be analyzed. 51 and 52 are X-ray detectors of each X-ray spectrometer. Each X-ray spectrometer is capable of scanning a small wavelength range centered around the state in which it detects the characteristic X-ray wavelength of the element it is trying to detect, and 61.62 is the scanning range for wavelength scanning with each X-ray spectrometer. It is a driving device. 7 is a data processing control device, and a sample transfer bag y13. Control of the wavelength scanning drive device of each X-ray spectrometer and each X-ray detector 51, . Data processing is performed on the output signal such as 52. 8 is a memory for storing data necessary for data processing, and 9 is a display device for displaying the results of data processing, which can be a CRT or a plotter.

A procedure for performing quantitative elemental analysis along one scanning line of a sample to be measured using the above-described apparatus will be described. It is assumed that the component elements of the sample are known in advance. If the component elements are unknown, wavelength scanning is performed using one X-ray spectrometer in the above-mentioned apparatus, and the entire X-ray spectrum is measured to qualitatively determine the component elements. Since the component elements of the sample are known, a plurality of X-ray spectrometers are made to correspond to the component elements of the sample one by one, and the center and scanning width of the wavelength scan of each X-ray spectrometer is set. Next, prepare standard samples for each component element. The standard sample is preferably a pure sample with a concentration of 100%, but it may be of any known concentration. Each standard sample is irradiated with an electron beam, and the X-ray intensity is measured at three points: the characteristic X-ray wavelength position of the element, and the background position at both ends of the peak (both end wavelength positions of the preset wavelength scanning width). Jsi, Bs11. Bs12. From these data, the data processing control device calculates Ts i=J s i −(Bs i 1+Bs i2
)/2'! 1 + 2 p...n) and store this in the memory 8 as the net characteristic X-ray intensity of the standard sample of the i-th element.The meaning of this calculation is clear in Figure 2. Thus, the average baseline level is subtracted from the peak height.

Next, for the sample to be measured, the sample moving device 3 is driven a certain distance at a time so that the irradiation point of the electron beam is along the scanning line to be analyzed. The X-ray intensity Jui, B at the characteristic X-ray wavelength position of each element is
uil, Bui2 are measured, Iu i=J u i −(・Bu i I+Bu i
2) /2 is calculated, and this is taken as the net characteristic X-ray intensity of each component element of the sample to be measured, and the first approximate concentration K i of each element is calculated by, and using 1 to Kn, ZAF correction is performed. The concentrations C1 to Cn of each component element are calculated by calculation, and the measurement point is moved to the next measurement point. C1 to Cn obtained as described above are sequentially outputted to the display device 1i9 to draw a display graph of the relative change in concentration of each component element along the scanning line as shown in FIG.

(Effects of the Invention) According to the present invention, changes in the composition ratio of component elements along the scanning line of the sample surface can be determined in real time, so it can be used to test the quality of materials that are prone to segregation or compositional unevenness, and to detect abnormal parts. etc. can be done quickly.

[Brief explanation of drawings]

FIG. 1 is a block diagram showing the configuration of an apparatus according to an embodiment of the present invention, FIG. 2 is an explanatory diagram of background correction, and FIG. 3 is a graph of measurement records obtained with the apparatus according to the embodiment. 1... Electron gun, 2... Objective lens, 3... Sample moving device, S... Sample, 41.42... X-ray spectrometer,
51°52...X-ray detector, 61.62...Scanning drive device, 7...Data processing, control device, 8...Memory, 9...Display device. Agent Patent Attorney Hiroshi Agata Procedural Amendment (Format) 1. Display of case 1990 Patent Application No. 122192 2
, Invention title analysis device 3, Relationship with the amended person case Patent applicant address Name: 1 Kuwabara-cho, Nishinokyo, Nakagyo-ku, Kyoto City (199
) Shimadzu Corporation Representative Minoru Nishihachijo 4, Agent Address Nakajin Building, 5-16 Yokobori, Higashi-ku, Osaka Name (7045) Patent attorney Kosuke Agata 5 Date of amendment order August 1990 28th -1'-6, Figure 3 subject to correction

Claims (1)

[Claims] means for scanning the sample surface with an excitation line; means for dispersing secondary radiation emitted from the sample; and spectral intensities at the peak center of the sample component element and background positions on both sides of the peak center on the separated secondary radiation spectrum. a means for determining the peak intensity of each element from the spectral intensity of the peak center position of each component element and the background positions on both sides thereof, and a standard sample of each component element obtained through the above means. A means for storing the peak intensity of each element in the above, and a means for storing the peak intensity of each component element in proportion to the peak intensity of the standard sample of each of the above elements and the peak intensity of each element obtained through each of the above devices for the sample to be measured. An analysis device comprising: a data processing device that calculates a first approximate concentration and performs a correction calculation to determine the concentration of each component element from the first approximate concentration.