JP3996817B2 - Glow discharge analyzer and analysis result display method of glow discharge analyzer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a glow discharge analyzer and an analysis result display method of the glow discharge analyzer.
[0002]
[Prior art]
Conventionally, glow discharge analyzers have been used to perform component analysis from the surface of a sample to a predetermined depth position.
[0003]
In general, in a glow discharge analyzer, a sample is arranged facing the cylindrical portion of the anode of a glow discharge tube, an inert gas is supplied to the sample surface under a low pressure, and, for example, about 13 MHz is provided between the sample and the anode. A high-frequency voltage or a DC voltage of 400 to 1200 V is applied to cause glow discharge to emit light, and analysis is performed with an emission spectrum. The glow discharge analyzer of the present invention includes not only the above-described glow discharge emission analyzer (GDS) but also a glow discharge mass spectrometer (GDMS) that performs mass analysis of ions generated by glow discharge.
[0004]
FIG. 6 is a diagram showing a display example of a result obtained by analyzing a vehicle body metal of a car as a measurement target sample using a glow discharge analyzer. In FIG. 6, the vertical axis indicates the concentration obtained from the light intensity corresponding to each component included in the sample, and the horizontal axis indicates the depth of the sample.
[0005]
From this analysis result, the user judged the ratio of each component at each depth position of the sample, and classified the layers A _{1 to} A ₆ by classifying the sample at appropriate depth positions p ₁ to p ₅ . In addition, the integration of each component is obtained in each of the classified layers A _{1 to} A ₆ and the component ratio is displayed for each layer.
[0006]
[Problems to be solved by the invention]
However, it is difficult to stratify in the depth direction based on the analysis results shown in FIG. 6, which requires a special skill from the user side. Moreover, although the component ratio of each separated layer is displayed by, for example, a pie chart, it is difficult to imagine the configuration of each part of the sample based on this, and lacks visibility.
[0007]
The present invention has been made in consideration of the above-mentioned matters, and its purpose is to provide a display function of an analysis result that can grasp the layer separation state of the sample and the component ratio for each layer at a glance. The present invention provides a glow discharge analyzer having an analysis result and an analysis result display method of the glow discharge analyzer.
[0008]
[Means for Solving the Problems]
That is, the glow discharge analysis apparatus of the present invention, in a glow discharge spectrometer for performing component analysis in the depth direction of the sample using the sputtering on the sample surface by glow discharge,
A storage unit for storing the average value of the component ratio of the sample is layering the layers separated state of the sample are classified into layers each as a layer separated data by Ingredient ratio, component ratio of the respective layers based on the layer separation data and graphs made shows the average value, that it has a display unit indicating the depth component ratio graph made by superimposing the graph in accordance with the depth position from the number and the surface of the layer thicknesses of the layers as the width It is a feature. (Claim 1)
[0009]
Therefore, the user only glance check the display section of the depth component ratio graph, the thickness and the component ratio of each layer can be intuitively grasped, excellent visibility to the state of the sample can be confirmed easily Display can be performed.
In the present invention, preferably configured to sample attached to each layer are classified into the layer number by Ingredient ratio is displayed in Table radical 113 to the depth component ratio graph co. (Claim 2)
Further, in the present invention, in the depth component ratio graph, the layers separated state of a sample classifying a sample into a layer by Ingredient ratio, preferably configured to be displayed in different colors for each layer. (Claim 3)
Furthermore, in the present invention, in addition to the depth component ratio graph, preferably configured to have a display unit for displaying a graph in which a shows the average value of the layering has been each single component ratio. (Claim 4)
[0010]
Further, in the present invention, a glow discharge analyzer that performs component analysis in the depth direction of the sample using sputtering on the sample surface by glow discharge, wherein the component ratio of each layer classified into layers according to the component ratio of each part of the sample A depth component ratio graph indicating the average value of each layer corresponding to the position in the depth direction, and the depth component ratio graph is a pie chart of the component ratio of each layer and the thickness of the layer. By superimposing a three-dimensional pie chart showing the thickness as a width according to the number of layers and the depth position, the component ratio at each depth position is shown by one three-dimensional view, and the display unit Provides a glow discharge analyzer characterized in that the component ratio in each layer can be confirmed by rotating the three-dimensional view. In this case, since the state of each layer of the sample expressed three-dimensionally can be displayed according to the shape of the sample, a more intuitive and easy-to-understand display can be performed. In addition, it is possible to confirm a portion that cannot be confirmed in a stationary state by rotating the three-dimensional view.
[0011]
[0012]
Although sample layer separation can be performed manually by the user, operability is improved by automatically dividing the sample according to the component ratio of each part. Note that the layer separation based on the component ratio may be performed based on the point where the second derivative of the concentration of the main component becomes 0 (that is, the inflection point).
[0013]
Further, in the present invention, in a glow discharge analyzer that performs component analysis in the depth direction of the sample using sputtering on the sample surface by glow discharge, the sample is classified into layers according to the component ratio of each part, and the component ratio of each layer is determined. When displaying the average value as a depth component ratio graph corresponding to the position in the depth direction, the depth component ratio graph is a three-dimensional graph showing the component ratio of each layer as a circle graph and the thickness of the layer as a width. By overlaying a typical pie chart according to the number of layers and the depth position, the component ratio at each depth position is displayed using one solid diagram, and by rotating this solid diagram, An analysis result display method for a glow discharge analyzer, characterized in that each component ratio can be confirmed. (Claim 6)
[0014]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a diagram showing an overall configuration of a glow discharge analyzer 1 according to the present invention, and FIG. 2 is a partially enlarged view of the glow discharge analyzer 1.
[0015]
In FIG. 1, 2 is a glow discharge tube for generating a glow discharge with respect to the sample S to be measured, 3 is a power supply unit for supplying high-frequency power to the glow discharge tube 2, and 4 is a gas necessary for measuring an inert gas or the like. A gas supply unit 5 supplies a spectroscope for measuring the intensity of the light L generated from the discharge light emitting unit 2a of the glow discharge tube 2 and measures its intensity, and 6 is used for measuring each component to be measured based on the measured value of the light L. An arithmetic processing unit 7 that obtains and outputs the density is a display of the arithmetic processing unit.
[0016]
The glow discharge tube 2 includes a condensing lens 2b, and the spectroscope 5 includes a slit 5a that transmits light L at a focal position of the condensing lens 2b, and a diffraction grating 5b that disperses the light L transmitted through the slit 5a. It has slits 5c for transmitting the light split to the wavelength corresponding to each component to be measured, and photomultiplier tubes (photomultiplexers) 5d for detecting the intensity of the light transmitted through the slits 5c.
[0017]
Since the power supply unit 3 supplies, for example, high-frequency AC power of 13 MHz, the sample S can be measured even if it is a non-conductive material. The gas supply unit 4 includes a cylinder 4a and an electromagnetic valve 4b for supplying, for example, argon gas Ar and oxygen gas O ₂ as inert gases.
[0018]
The present invention does not limit the configuration of the glow discharge tube 2, the power supply unit 3, the gas supply unit, and the spectrometer 5. In particular, when performing mass analysis using ions generated by cutting using the sputtering of the surface of the sample S by glow discharge, it goes without saying that the configuration of the glow discharge tube 2 and the configuration of the mass analyzer are greatly different from those described above. Yes. In any case, the glow discharge analyzer 1 of the present invention performs component analysis in the depth direction of the sample S by cutting the surface of the sample S using sputtering.
[0019]
FIG. 2 is an enlarged view showing the structure of the glow discharge tube 2, and the glow discharge tube 2 is configured as follows. That is, reference numeral 10 denotes a lamp body made of an appropriate metal material, and a through hole 11 is formed therein. The through-hole 11 is continuous with the discharge light emitting unit 2a, and one opening thereof is sealed by a window 12 that also serves as the optical lens 2b. The optical lens 2b condenses the light L generated in the discharge light emitting section 2a on the slit 5a of the spectroscope 5, and this light L is a photomultiplier tube (spectrum light divided into element-specific spectra). It is electrically measured through a photomultiplexer 5d.
[0020]
A state in which the anode 14 and the cathode 15 made of a conductive material are pressed by the pressing block 17 through the insulator 16 on the end surface 13 opposite to the side on which the window 12 of the lamp body 10 is provided. Is provided. In a state where the anode 14 is fitted in a recess formed in the end face 13, a disc portion 20 having a hole 18 in the center concentrically with the through-hole 11 and having a hole 19 around it, and a concentric shape with the hole 18. The anode 14 composed of the cylindrical portions 21 connected so as to be in contact with each other is brought into contact, and the open end portion of the anode cylindrical portion 21 is provided in a state of being recessed from the end face of the cathode 15. The anode 14 is connected to the power supply unit 3 through the lamp body 10 and is configured to have a ground potential.
[0021]
The cathode 15 has a through-hole 22 having a diameter slightly larger than that of the anode cylindrical portion 21 at the center. The anode cylindrical portion 21 is concentrically positioned in the through-hole 22, and is slightly between the anode cylindrical portion 21. This gap is formed so as to be electrically insulated from the anode 14. The insulator 16 interposed between the anode disk portion 20 and the cathode 15 is made of, for example, a heat resistant fluororesin.
[0022]
The pressing block 17 is fixed to the end face 13 of the lamp body 10 so as to press the cathode 15 from the outside through an annular insulator 23 made of the same material as the insulator 16. The sample S is provided so as to seal the open end of the anode cylindrical portion 22 and is pressed against the cathode 15 so as to seal the open end of the through hole 21 by a sample pressing member 24 that also serves as a voltage application electrode. . By setting the sample S in this way, a gap is formed between the anode cylindrical portion 21 and the sample S as the discharge light emitting portion 2a.
[0023]
Reference numeral 25 denotes an introduction path of an inert gas IG formed in the lamp body 10, which connects the gas supply source 4 and the through hole 11 to each other, thereby allowing the discharge light emitting unit 2 a to gas through the through holes 11 and 18. It is configured to be filled with gas supplied from the supply source 4.
[0024]
Reference numerals 26 and 27 denote vacuum exhaust passages formed in the lamp body 2. One vacuum exhaust passage 26 is connected to the through hole 11, and the other vacuum exhaust passage 27 is a hole formed in the anode disk portion 20. 19 is connected to the discharge light emitting unit 2 a through 19. These vacuum exhaust passages 26 and 27 are connected to an exhaust system (not shown), and are configured to bring a space in the lamp body 10 such as the discharge light emitting unit 2a into a desired vacuum state.
[0025]
In order to analyze, for example, elements contained in the steel S using the glow discharge tube 1 having the above-described configuration, the steel S is set so as to seal the open end of the anode cylindrical portion 22, and the exhaust system is operated. Then, the space in the lamp body 10 is evacuated. Thereafter, argon gas is filled in the space in the lamp body 10 from the gas supply source 4, and a high-frequency voltage from the power supply unit 3 is applied to the sample S via the pressing member 24 under reduced pressure of the argon gas flow.
[0026]
Thereby, preliminary discharge is generated between the anode 14 and the sample S, and argon ions are generated based on the preliminary discharge. The argon ions are accelerated by a high electric field and collide with the surface of the sample S to emit light. Further, predetermined sputtering is performed by collision of argon ions, and particles (including atoms and molecules) containing ions are ejected from the surface of the sample S, and the particles are excited in the plasma to return to the ground state. Intrinsic light emission occurs. These lights L are led out toward the spectroscope 5 connected to the glow discharge tube 10, and a desired analysis is performed.
[0027]
The arithmetic processing unit 6 is, for example, measured value data 30 indicating the relationship between the measured value and the measured time detected by the photomultiplier tubes 5d when a glow discharge is continuously generated for a predetermined time, and the measured value with respect to the sputtering time. (See FIG. 1) is stored in the storage unit 6m of the arithmetic processing unit 6.
[0028]
Further, the arithmetic processing unit 6 converts the intensity of light of each wavelength detected by the photomultiplier tubes 5d... Using the measured value data 30 into the concentration of the measurement target component. Further, this measured value (intensity or concentration) is calculated in consideration of the sputtering progress rate obtained from the magnitude of the electric power supplied to the glow discharge tube 10 and the measured concentration of each component. And the arithmetic processing part 6 memorize | stores the relationship between the depth position of the sample S and the density | concentration of each measuring object component in the memory | storage part 6m as the conversion value data 31 which shows the relative intensity change ratio with respect to sputtering depth.
[0029]
The measurement value data 30 needs to be stored simultaneously with the glow discharge, but the conversion value data 31 can be created and stored by calculation based on the measurement value data 30. Therefore, the conversion of the measured value can be performed according to the operation of the user after the series of glow discharges is completed.
[0030]
3 and 4 show an example of a display screen 32 that displays a result calculated by the arithmetic processing unit 6 when measuring a sample S in which nickel, copper, and nickel are coated on the surface of an iron plate as an example. Is. In FIGS. 3 and 4, reference numeral 33 denotes a display unit that graphs the converted value data 31 with the horizontal axis representing the depth position and the vertical axis representing the component concentration (%).
[0031]
Next, the arithmetic processing unit 6 stratifies the sample S based on the converted value data 31 (which may be the measured value data 30) stored in the storage unit 6m. The division of each layer can be, for example, a point at which the second derivative of the component concentration value corresponding to each depth position becomes 0 (a point at which the slope becomes maximum). Note that the present invention does not limit the depth position determination criteria for stratification to the second derivative of the component concentration value, and various determination criteria such as a position where the concentration gradient exceeds a predetermined threshold value can be considered. . In any case, the sample S is classified into layers according to the component ratio of each part.
[0032]
In the case of the sample S shown in this example, the arithmetic processing unit 6 makes the first layer from the surface to a depth position of 4 μm, the second layer from the depth position of 4 to 17 μm, and the third to the depth position of 17 to 20 μm. The layer, the part deeper than 20 μm, is classified as the fourth layer. Next, the arithmetic processing unit 6 calculates the integrated value of the measurement target component in each layer, divides this by the depth of each layer, calculates the average value of the component ratio of each layer, and calculates the average value of each layer as the layer separation data. 34 is stored in the storage unit 6m (see FIG. 1).
[0033]
In this example, the burden placed on the user by automatically performing the layering of the sample S by the calculation by the calculation processing unit 6 is reduced as much as possible. However, the present invention does not limit this point. That is, the layering of the sample S may be freely selected or changed according to the judgment of the user. Also in this case, the arithmetic processing unit 6 obtains the average value of the component ratio for each layer determined by the user and stores it as the layer separation data 34.
[0034]
In FIG. 3, reference numeral 35 denotes a display unit of a depth component ratio graph 36 created based on the layer separation data 34. Together shown the average value of the component ratio of each layer stored as the layer separation data 34 in a pie chart 37 on the display unit 35 indicates the thickness of the layer (height in this example) width as h ₁ to h ₄ By superimposing a three-dimensional pie chart in accordance with the number of layers and the depth position, the depth component ratio graph 36 is displayed as a disk in which the component ratio at each depth position is represented as one solid diagram. ing. (Hereinafter, the depth component ratio graph 36 of this example is expressed as a disk 36)
[0035]
The disk 36 is shown by an image obtained by hollowing out a part of the surface portion of the sample S, and a cylindrical hole 38 indicating a state cut by sputtering is displayed at the center. The outer surface 39 of the disk 36 is color-coded according to, for example, the component concentration of the layer, so that the operator can intuitively know the thickness h ₁ to h ₄ and the position of each layer of the sample S at a glance. The inner surface of the hole 38 displays a component ratio graph showing the component ratio of each layer. Reference numeral 40 denotes a number display button and a detail display button assigned to each layer.
[0036]
Further, by rotating the disk 36 in the direction of arrow R, the contents of each component shown in the component ratio graph on the inner surface of the pie chart 37 and the hole 38 can be confirmed evenly, and the disk 36 has a three-dimensional display. Is shown. In the present example, the outer surface 39 of the disk is shown in an example in which each layer is color-coded according to the component concentration. However, the present invention is not limited to this, and is shown, for example, on the inner surface of the hole 38. Similarly to the component ratio graph, the component ratio in each layer may be displayed on the outer surface 39.
[0037]
In any case, the glow discharge analyzer of the present invention displays the depth component ratio graph 36 in three dimensions in accordance with the position in the depth direction of the sample S, so that the result of the surface analysis can be intuitively viewed at a glance. I can know. That is, the visibility is excellent, and the operator can easily know the analysis result.
[0038]
Reference numeral 41 denotes a display unit for pie charts 42 (FIG. 3) and 43 (FIG. 4) showing component ratios for each layer. The pie charts 42, 43,... Respectively correspond to the first layer, the second layer,..., And the display can be switched by a scroll bar provided on the side of the display unit 41. Further, it can be performed in conjunction with the detail display button 40 in the display unit 35. The user can confirm the details of the component ratio in each layer by switching the display unit 41.
[0039]
The present invention does not limit details of the depth component ratio graph 36. That is, the point that the shape is a disk shape, the rotation in the direction indicated by the arrow R, and the provision of the detail display button 40 can be appropriately changed. Further, the display of the pie chart 37 of the depth component ratio graph 36 is adapted to the shape of the sample S and is easy to understand intuitively, but the present invention does not limit the pie chart display of the depth component ratio graph.
[0040]
FIG. 5 is a diagram showing another example of the depth component ratio graph. The depth component ratio graph 50 shown in FIG. 5 has a width corresponding to the thickness of each layer in the depth direction, and the bar graphs 51 to 54 indicating the component ratio in each layer are stacked in correspondence with the positions in the depth direction. It is the shown graph.
[0041]
As shown in FIG. 5, by indicating the depth component ratio graph 50 with bar graphs 51 to 54, not only the thicknesses h _{1 to} h _{4 of} each layer but also the component ratio can be confirmed at a glance. Moreover, in this example, each bar graph 51-54 is displayed in three dimensions, which indicates that this indicates the component ratio of each layer.
[0042]
The depth component ratio graph in each of the above examples shows an example that is displayed by performing arithmetic processing on the measurement value data 30 stored in the storage unit 6m after the sample S is sputtered by the glow discharge tube 2. However, the present invention does not limit this point.
[0043]
That is, the progress of cutting and analysis of the sample S by the glow discharge tube 2 can be displayed in real time on the display unit 35 of the depth component ratio graph. In this case, it is possible to simultaneously confirm the progress of sputtering and the analysis result from the display content of the display unit 35, and the glow discharge analyzer 1 becomes easier to handle.
[0044]
【The invention's effect】
As described above, the glow discharge analyzer of the present invention and the analysis result display method of the glow discharge analyzer of the present invention configure the sample by displaying the analysis result in the depth direction of the sample based on its component ratio in three dimensions. It is possible to grasp at a glance the configuration of each layer.
[Brief description of the drawings]
FIG. 1 is a configuration explanatory view showing an example of a glow discharge analyzer of the present invention.
FIG. 2 is an enlarged view showing a part of the glow discharge analyzer.
FIG. 3 is a diagram for explaining an analysis result display method of the glow discharge analyzer.
FIG. 4 is a diagram for explaining an analysis result display method of the glow discharge analyzer.
FIG. 5 is a diagram for explaining another analysis result display method;
FIG. 6 is a diagram showing an example of an analysis result display method of a conventional glow discharge analyzer.
[Explanation of symbols]
1 ... glow discharge spectrometer, a display unit 35 ... depth component ratio graph, 36, 50 ... depth component ratio graph 37 ... pie, h ₁ to h ₄ ... Width (height), S ... sample.

Claims (6)

In glow discharge spectrometer for performing component analysis in the depth direction of the sample using the sputtering on the sample surface by glow discharge,
A storage unit for storing the average value of the component ratio of the sample is layering the layers separated state of the sample are classified into layers each as a layer separated data by Ingredient ratio, component ratio of the respective layers based on the layer separation data and graphs made shows the average value, that it has a display unit indicating the depth component ratio graph made by superimposing the graph in accordance with the depth position from the number and the surface of the layer thicknesses of the layers as the width A characteristic glow discharge analyzer. Glow discharge spectrometer according to claim 1, characterized in that the number of attached to each classified sample the layer is displayed in Table radical 113 to the depth component ratio graph co by Ingredient ratio. In the depth component ratio graph, the layers separated state of a sample classifying a sample into a layer by Ingredient ratio, a glow discharge analysis according to claim 1 or 2, characterized in that it is displayed in different colors for each layer apparatus. In addition to the depth component ratio graph, according to any one of claims 1 to 3, characterized in that a display unit for displaying a graph in which a shows the average value of the layering has been each single component ratio Glow discharge analyzer.   A glow discharge analyzer that performs component analysis in the depth direction of a sample using sputtering on the sample surface by glow discharge, and calculates the average value of the component ratio of each layer classified into layers according to the component ratio of each part of the sample. A depth component ratio graph display unit corresponding to the position in the vertical direction, and the depth component ratio graph is a three-dimensional graph showing the component ratio of each layer as a pie chart and the thickness of the layer as a width. By overlaying a typical pie chart in accordance with the number of layers and the depth position, the component ratio at each depth position is shown as a single three-dimensional view, and the display unit rotates this three-dimensional view. By doing so, it is possible to confirm each component ratio in each layer, a glow discharge analyzer.   In a glow discharge analyzer that performs component analysis in the depth direction of the sample using sputtering on the sample surface by glow discharge, the sample is classified into layers according to the component ratio of each part, and the average value of the component ratio of each layer is determined in the depth direction When displaying as a depth component ratio graph corresponding to the position of, as the depth component ratio graph, a three-dimensional pie chart showing the component ratio of each layer as a pie chart and the thickness of the layer as a width, By overlaying according to the number of layers and the depth position, the component ratio at each depth position is displayed using one solid diagram, and by rotating this solid diagram, each component ratio in each layer can be confirmed. An analysis result display method for a glow discharge analyzer characterized by comprising:

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