JP6313984B2 - Glow discharge spectroscopic analyzer, sample support and sample pressing electrode - Google Patents

Description

  The present invention relates to a glow discharge spectroscopic analysis apparatus and a sample support, in which an analysis surface of a planar sample and a curved sample is sputtered by ions generated by glow discharge and the emission of atoms knocked out of the analysis surface is spectrally analyzed. And a sample pressing electrode.

  A glow discharge spectrometer is used for elemental analysis in the depth direction of a sample. The glow discharge spectroscopic analyzer is provided with, for example, a Marcus glow discharge tube. The glow discharge tube has a hole formed in the flat portion of the disk and includes a sample support that supports the sample so as to seal the hole. The hole of the sample support leads to the internal space of the glow discharge tube, and a cylindrical electrode is disposed in the hole so as to face the sample. The glow discharge tube includes a sample pressing electrode that presses the sample into the hole. The sample support is sealed with the sample pressed into the hole. An inert gas such as argon is supplied between the cylindrical electrode and the sample, and a high frequency voltage is applied to the sample pressing electrode. Glow discharge occurs between the sample to which the high frequency voltage is applied by the sample pressing electrode and the cylindrical electrode. Ions generated by glow discharge collide with the analysis surface of the sample, and atoms on the analysis surface are knocked out. When the atoms are excited in the plasma and return to the ground state, they emit light having a wavelength unique to the element (hereinafter referred to as glow discharge light). The glow discharge spectroscopic analyzer spectroscopically analyzes glow discharge light with a spectroscope to identify elements on the analysis surface.

However, in the conventional glow discharge spectroscopic analyzer, since it is necessary to seal the hole by pressing the sample against the hole formed in the flat part of the sample support, the shape of the sample to be analyzed is flat. It was limited to the shape.
Patent Document 1 discloses a glow discharge spectroscopic analysis apparatus that solves such a problem and enables spectroscopic analysis of a curved sample. The glow discharge spectroscopic analyzer according to Patent Literature 1 includes an annular groove that holds an annular seal member on the outer periphery of a hole of a sample support, and a curved convex portion that extends outward in the circumferential direction of the annular groove. According to Patent Document 1, even if the sample has an analysis surface curved in a concave shape, the hole is sealed by supporting the sample on the sample support so that the analysis surface is along the convex portion. A sample having a concave analysis surface can be spectroscopically analyzed.

JP 2010-236979 A

However, in the glow discharge spectroscopic analyzer according to Patent Document 1, a sample having a concave analysis surface can be spectroscopically analyzed, but a sample having a flat analysis surface and a sample having a convex curved analysis surface There was a problem that it could not be spectroscopically analyzed. For this reason, it was necessary to replace the sample support in accordance with the shape of the analysis surface of the sample.
Further, in order to obtain a quantitative value of spectroscopic analysis, it is necessary to spectroscopically analyze a standard sample for a calibration curve. However, since the standard sample is flat, a sample support for preparing a calibration curve and a sample support for a curved sample are prepared and exchanged each time for quantitative spectroscopic analysis of a curved sample. There was a need to do.

  The present invention has been made in view of such circumstances, and the object thereof is to support a sample having a flat surface and a sample whose analysis surface is curved in a convex shape or a concave shape without exchanging the sample support. To provide a glow discharge spectroscopic analysis apparatus capable of sealing a hole in a body and performing spectroscopic analysis of the sample, and a sample support and a sample pressing electrode constituting the glow discharge spectroscopic analysis apparatus .

  A glow discharge spectroscopic analyzer according to the present invention includes a cylindrical electrode, a sample support that coaxially accommodates the cylindrical electrode, a sample support that supports a sample at an end of the cylindrical portion, and the sample And a sample pressing electrode for supplying power for generating glow discharge between the cylindrical electrode and the sample, and a glow generated between the cylindrical electrode and the sample. In the glow discharge spectroscopic analyzer for analyzing light emission by discharge, the outer peripheral side and inner peripheral edge of the end portion are curved, and the sample pressing electrode has a rod-shaped electrode portion in contact with the sample.

In the present invention, when the concave analysis surface of the curved sample is pressed against the end of the cylindrical portion, the analysis surface of the sample and the curved portion on the outer peripheral side of the cylindrical portion come into contact with each other, and the opening of the cylindrical portion The part is sealed.
When the convex analysis surface of the curved sample is pressed against the end portion of the tube portion, the analysis surface of the sample and the curved portion of the inner peripheral edge of the tube portion come into contact with each other, and the opening of the tube portion is sealed.
When the analysis surface of the flat sample is pressed against the end portion of the cylindrical portion, the end portion of the cylindrical portion and the analysis surface of the sample come into contact with each other, and the opening portion of the cylindrical portion is sealed. That is, the portion between the curved portion on the outer peripheral side of the end portion and the curved portion on the inner peripheral edge comes into contact with the analysis surface of the sample, and the opening of the cylindrical portion is sealed.

  In the glow discharge spectroscopic analyzer according to the present invention, the cylindrical portion has an annular flat end surface between a curved portion on the outer peripheral side of the end portion and a curved portion on the inner peripheral edge.

  In the present invention, when the analysis surface of the flat sample is pressed against the end portion, the analysis surface of the sample and the annular flat end surface of the tube portion come into contact with each other, and the opening portion of the tube portion is sealed.

  The glow discharge spectroscopic analysis apparatus according to the present invention includes a seal member that is fitted on an end portion of the cylindrical portion and seals between the end portion and the sample.

  In the present invention, the opening of the cylinder is more effectively sealed by the seal member that seals between the end of the cylinder and the sample.

  In the glow discharge spectroscopic analyzer according to the present invention, the sample support includes a conical cylinder part, and the cylinder part protrudes from the apex part of the conical cylinder part.

  In the present invention, since the cylindrical portion is provided at the apex portion of the conical cylindrical portion, the shape, size, etc. of the sample that can be supported by the cylindrical portion are compared with the case where the cylindrical portion is provided on the flat plate. High degree of freedom.

  In the glow discharge spectroscopic analysis apparatus according to the present invention, the end of the rod-shaped electrode portion has a spherical shape.

  In the present invention, since the end portion of the rod-shaped electrode portion is spherical, the end portion of the rod-shaped electrode portion can be brought into contact with the curved portion of the sample, and the sample can be pressed against the cylindrical portion. .

  In the glow discharge spectroscopic analysis apparatus according to the present invention, the apex portion of the rod-shaped electrode portion on the tube portion side has a planar shape.

  In the present invention, a voltage for generating a glow discharge is applied to the sample by reliably connecting the sample and the sample pressing electrode by bringing the planar apex portion of the rod-shaped electrode portion into contact with the sample. can do. Since the apex portion is planar, heat is easily conducted from the sample to the rod-shaped electrode portion, and heat can be efficiently radiated. In addition, the sample can be reliably held without displacement of the sample sandwiched between the cylindrical portion of the sample support and the rod-shaped electrode portion.

  A glow discharge spectroscopic analysis apparatus according to the present invention includes a power supply terminal for supplying power and a flat plate electrode to which the power supply terminal is detachably connected, and the sample pressing electrode is electrically conductively fitted on the flat plate electrode. An external fitting member and a conductive terminal connection portion projecting from the external fitting member to the cylindrical electrode side, to which the feeding terminal is detachably connected, and the rod electrode portion is connected to the terminal Provided in the department.

  In the present invention, it is possible to attach the sample pressing electrode having the rod-shaped electrode portion to the flat plate electrode by fitting the external fitting member to the flat plate electrode for spectroscopic analysis of the flat sample. In addition, the power supply terminal can be detachably connected to the terminal connection portion provided with the rod-shaped electrode portion.

  In the glow discharge spectroscopic analysis apparatus according to the present invention, the terminal connection portion has an electrode insertion hole into which the rod-shaped electrode portion is detachably inserted and electrically connected to the terminal connection portion.

  In this invention, a rod-shaped electrode part can be attached to a terminal connection part by inserting a rod-shaped electrode part in the electrode insertion hole of a terminal connection part. Therefore, the rod-shaped electrode portion can be easily replaced.

  In the glow discharge spectroscopic analyzer according to the present invention, the flat plate electrode has a disk shape, a water supply pipe and a drain pipe for water cooling are connected to the side of the flat plate electrode, and the outer fitting member is the flat plate A cylindrical portion that is externally fitted to the electrode is formed, and a concave portion for externally fitting to the flat plate electrode is formed in the cylindrical portion while avoiding the water supply pipe and the drain pipe.

  In this invention, even if it is a flat plate electrode to which the water supply pipe and the drain pipe were connected, an external fitting member can be externally fitted to this flat plate electrode, and a rod-shaped electrode part can be attached. Further, the outer fitting member can be indirectly cooled by the flat plate electrode.

  The sample support according to the present invention has a cylindrical portion that coaxially accommodates the cylindrical electrode, and in the sample support that supports the sample at the end of the cylindrical portion, the outer peripheral side and the inner peripheral edge of the end are It is curved.

In the present invention, when the concave analysis surface of the curved sample is pressed against the end of the cylindrical portion, the analysis surface of the sample and the curved portion on the outer peripheral side of the cylindrical portion come into contact with each other, and the opening of the cylindrical portion The part is sealed.
When the convex analysis surface of the curved sample is pressed against the end portion of the tube portion, the analysis surface of the sample and the curved portion of the inner peripheral edge of the tube portion come into contact with each other, and the opening of the tube portion is sealed.
When the analysis surface of the flat sample is pressed against the end portion of the cylindrical portion, the end portion of the cylindrical portion and the analysis surface of the sample come into contact with each other, and the opening portion of the cylindrical portion is sealed. That is, the portion between the curved portion on the outer peripheral side of the end portion and the curved portion on the inner peripheral edge comes into contact with the analysis surface of the sample, and the opening of the cylindrical portion is sealed.

  The sample pressing electrode according to the present invention presses the sample against the end of the cylindrical portion that coaxially accommodates the cylindrical electrode of the glow discharge spectroscopic analyzer, and generates glow discharge between the cylindrical electrode and the sample. In the sample pressing electrode for supplying electric power, a conductive outer fitting member fitted on the flat plate electrode of the glow discharge spectroscopic analyzer, and protruding from the outer fitting member to the cylindrical electrode side to supply electric power A conductive terminal connection portion to which a power supply terminal to be detachably connected and a rod-shaped electrode portion provided in the terminal connection portion are provided.

  In the present invention, the sample can be pressed against the sample support constituting the glow discharge spectroscopic analysis apparatus without interfering with the curved sample, and power necessary for the glow discharge spectroscopic analysis can be supplied to the sample. .

  According to the present invention, it is possible to seal a hole in a sample support by supporting a flat sample and a sample whose analysis surface is curved convexly or concavely without replacing the sample support. Spectroscopic analysis can be performed.

It is a schematic diagram which shows the structure of the glow discharge spectroscopy analyzer which concerns on this Embodiment 1. FIG. It is a sectional side view which shows the sample support body and sample press electrode which concern on this Embodiment 1. It is a perspective view which shows the sample support body and sample press electrode which concern on this Embodiment 1. FIG. It is a sectional side view which shows a sample support body. It is a sectional side view which shows the edge part of the cylinder part which comprises a sample support body. It is a side view etc. which show the external fitting member which comprises a sample press electrode. It is a sectional side view etc. which show the external fitting member which comprises a sample press electrode. It is a side view which shows the example of 1 structure of a rod-shaped electrode. It is a sectional side view which shows the edge part of the cylinder part by which the sample was pressed. It is a graph which shows the spectroscopic analysis result of the sample supported by the sample support body concerning this Embodiment 1. It is a graph which shows the spectroscopic analysis result of the sample supported by the conventional flat sample support. It is a graph which shows the surface state after the spectroscopic analysis of the sample supported by the sample support body concerning this Embodiment 1. FIG. It is a graph which shows the surface state after the spectroscopic analysis of the sample supported by the conventional flat sample support. It is a graph which shows the spectral-analysis result of the other sample supported by the sample support body which concerns on this Embodiment 1. FIG. It is a graph which shows the spectroscopic analysis result of the other sample supported by the conventional flat sample support. It is a graph which shows the spectral-analysis result of the sample which the analysis surface curved in convex shape. It is a graph which shows the spectroscopic analysis result of the sample which the analysis surface curved in the concave shape. 6 is a side sectional view showing a sample support according to Embodiment 2. FIG.

Hereinafter, the present invention will be described in detail with reference to the drawings illustrating embodiments thereof.
(Embodiment 1)

  FIG. 1 is a schematic diagram showing a configuration of a glow discharge spectroscopic analyzer 1 according to the first embodiment, FIG. 2 is a side sectional view showing a sample support 31 and a sample pressing electrode 4 according to the first embodiment, and FIG. 3 is a perspective view showing a sample support 31 and a sample pressing electrode 4 according to Embodiment 1. FIG. A glow discharge spectroscopic analysis apparatus 1 according to the first embodiment includes a Marcus glow discharge tube 2 having an anode 3. The anode 3 has a truncated cone shape with an opening at the tip and a ridge formed on the bottom side. Further, the glow discharge spectroscopic analyzer 1 presses the sample S against the tip of the anode 3 when performing the glow discharge spectroscopic analysis, and supplies the power for generating the glow discharge in the vicinity of the analysis surface of the sample S. An electrode 4 is provided. The anode 3 and the sample pressing electrode 4 are connected to a power supply unit 6, and the power supply unit 6 applies a high-frequency voltage to the sample pressing electrode 4. The glow discharge spectroscopic analysis apparatus 1 includes a water cooling unit 7 that cools the sample pressing electrode 4 with water. Details of the configuration relating to water cooling will be described later. The sample pressing electrode 4 is pressed by the pressing piston 5. The pressing piston 5 has a pressing rod 51 that can reciprocate in a direction in which it moves toward and away from the anode 3 of the glow discharge tube 2. The pressing rod 51 moved by the pressing piston 5 presses the sample pressing electrode 4 toward the anode 3 side. The opening of the anode 3 is sealed by the analysis surface of the sample S. The sample S is pressed against the tip portion of the anode 3 so as to be sandwiched between the tip portion of the anode 3 and the sample pressing electrode 4, and the opening is sealed by the analysis surface of the sample S.

  The glow discharge tube 2 includes an anode support block 21 that supports the anode 3. The anode support block 21 has a plate shape having a circular optical path hole penetrating in the thickness direction in the center portion, and an annular recess in a side view in which a flange of the anode 3 is fitted is formed at a substantially central portion of one end surface. The anode 3 fitted in the concave portion of the anode support block 21 is fixed to the anode support block 21 with screws by a fixing ring 22. On the other end surface side of the anode support block 21, a lens 23 that closes the optical path hole and guides the glow discharge light generated in the glow discharge tube 2 to the spectrometer 8 is provided.

  The anode support block 21 includes an inert gas introduction path 21d that supplies an inert gas to the anode 3, and an inert gas exhaust path that exhausts the inert gas that has flowed through the tip side and the inside of the anode 3, as will be described later. 21a, 21b. Moreover, it has the communicating hole 21c which connects the anode 3 inside and the inert gas exhaust passages 21a and 21b. The inert gas introduced into the anode support block 21 through the inert gas introduction path 21d flows through the optical path hole, the tip of the anode 3, and the inside thereof, and the inert gas flowing through the inside of the anode 3 communicates therewith. It is discharged to the outside of the glow discharge tube 2 through the hole 21c and the inert gas exhaust passages 21a and 21b.

  An inert gas is supplied between the facing anode 3 and the sample S, and a high-frequency voltage is applied. By applying the high frequency voltage, glow discharge is generated between the anode 3 and the sample S, and ions generated by the glow discharge collide with the analysis surface of the sample S, and atoms of the sample S are knocked out. When the atoms are excited in the plasma and return to the ground state, they emit a glow discharge light L having a wavelength unique to the element. The glow discharge light L enters the spectroscope 8 and is configured to be spectrally analyzed by the calculation unit 91.

  The spectroscope 8 is a device that splits the glow discharge light L emitted from the glow discharge tube 2, and is disposed at a position where the glow discharge light L emitted from the lens 23 of the glow discharge tube 2 is incident. The spectroscope 8 includes an incident slit 81, a diffraction grating 82, an exit slit 83, and a photodetector 84 such as a photomultiplier tube. The glow discharge light L incident on the lens 23 is focused at the entrance slit 81. The light that has passed through the entrance slit 81 is diffracted by the diffraction grating 82, and the spectrum light divided into the element-specific spectrum by diffraction passes through the exit slit 83 and is detected by the photodetector 84.

  Information on the spectrum light detected by the photodetector 84 is output to the calculation unit 91. The computing unit 91 performs spectral analysis based on the information and outputs the spectral analysis result to the display unit 92 or the printer unit 93. For example, the computing unit 91 identifies the light emitting element from the wavelength distribution of the spectrum light, and identifies the intensity of light emission from each element for each measurement time. And the graph which shows the time change of the emitted light intensity from each element is produced | generated, and the produced | generated graph is output to the display part 92 or the printer part 93. FIG.

The anode 3 includes an anode body 32 and a sample support 31.
FIG. 4 is a side sectional view showing the sample support 31. The anode main body 32 includes an annular conductive base portion 32a that fits into the concave portion of the anode support block 21, and a conductive conical cylinder portion 32b that protrudes from the inner peripheral edge of the conductive base portion 32a so that the center lines coincide with each other. It is provided on the conductive base 32a. A space between the conductive base portion 32 a and the anode support block 21 is sealed with an O-ring 24. Further, a cylindrical electrode 32c protrudes from the apex of the conductive conical cylinder portion 32b so that the center line coincides with the conductive conical cylinder portion 32b.
The sample support 31 is made of insulating ceramics. The sample support 31 has the same shape as the anode main body 32 and has a dimension that covers the anode main body 32. Specifically, the sample support 31 has an annular flange 31a having an outer diameter substantially the same as that of the conductive base 32a. The inner diameter of the collar portion 31a is larger than that of the conductive base portion 32a. A conical cylinder portion 31b that protrudes from the inner peripheral edge of the flange portion 31a so as to coincide with the center line is provided on the flange portion 31a. A gap is provided between the conical cylinder part 31b and the conductive conical cylinder part 32b to allow the inert gas to flow therethrough. Further, the cylindrical portion 31c protrudes from the apex portion 43d of the conical cylindrical portion 31b so that the central line coincides with the conical cylindrical portion 31b. The cylindrical part 31c accommodates the cylindrical electrode 32c coaxially, and supports the sample S at the end of the cylindrical part 31c. A predetermined gap is provided between the cylindrical portion 31c and the cylindrical electrode 32c. Further, the distal end of the cylindrical electrode 32c is located on the far side from the distal end of the cylindrical portion 31c. For this reason, when the sample S is pressed against the cylindrical portion 31c, a gap is generated between the analysis surface of the sample S and the cylindrical electrode 32c, and between the cylindrical electrode 32c and the analysis surface. Glow discharge occurs. A space between the conductive base portion 32 a and the flange portion 31 a of the sample support 31 is sealed with an O-ring 33. An annular groove is formed in the conductive base portion 32a, and an O-ring 33 is fitted in the groove.
Further, the conductive base portion 32a is provided with a through hole 32d through which the gas flowing through the gap between the conductive conical cylinder portion 32b and the conical cylinder portion 31b flows from the tip side of the anode 3. The through hole 32d is a hole penetrating in the thickness direction of the conductive base 32a. Further, on the surface of the conductive base portion 32a on the sample support 31 side, a flow groove 32e is formed to communicate the gap between the conductive cone tube portion 32b and the cone tube portion 31b with the flow hole 32d. According to the anode 3 configured in this way, the inert gas introduced into the glow discharge tube 2 is supplied to the tip side of the anode 3, that is, between the cylindrical electrode 32 c and the sample S. The active gas flows from the tip of the anode 3 to the inert gas exhaust paths 21a and 21b through the gap between the conductive conical cylinder part 32b and the conical cylinder part 31b, the flow groove 32e, and the communication hole 21c.

  FIG. 5 is a side sectional view showing an end portion of the cylindrical portion 31 c constituting the sample support 31. The inner peripheral edge of the end portion of the cylindrical portion 31c is curved. Hereinafter, the curved portion of the inner peripheral edge is referred to as an inner peripheral curved portion 31d. In addition, an outer peripheral curved portion 31e is formed on the outer peripheral side of the cylindrical portion 31c so that the length in the center line direction of the cylindrical portion 31c is shorter on the outer peripheral side than on the inner peripheral side. The curvature of the outer circumferential curved portion 31e is smaller than that of the inner circumferential curved portion 31d and is gently curved. An annular flat end surface 31f is formed between the inner peripheral curved portion 31d and the outer peripheral curved portion 31e. The annular flat end surface 31f is a plane that is substantially perpendicular to the center line of the cylindrical portion 31c.

  The sample pressing electrode 4 is an electrode for pressing the sample S against the end of the cylindrical portion 31c of the sample support 31 and supplying electric power for generating glow discharge between the cylindrical electrode 32c and the sample S. The glow discharge spectroscopic analysis apparatus 1 includes a disk-shaped flat plate electrode 40 to which a power supply terminal 61b for supplying power for generating glow discharge is detachably connected as shown by a broken line in FIG. A power supply plug 61 is provided at the tip of the power supply cable 61 a connected to the power supply unit 6, and a power supply terminal 61 b protrudes from the power supply plug 61. Electric power for generating glow discharge between the cylindrical electrode 32 c and the sample S is supplied from the power supply unit 6 to the plate electrode 40 to which the power supply terminal 61 b is connected. For example, a high frequency voltage of about 100 Hz is applied to the plate electrode 40, for example. The flat plate electrode 40 has a water channel (not shown) for cooling the flat plate electrode 40 with water. A water supply pipe 71 a and a drain pipe 72 a for cooling the flat plate electrode 40 with water, and a water supply pipe connection plug 71 and a drain pipe connection plug 72 for connecting the water channel are attached to the side of the flat plate electrode 40. The water supply pipe 71a and the drain pipe 72a are connected to the water cooling section 7, and the water cooling section 7 supplies water for cooling to the water supply pipe 71a. Cooling water flows into the water channel from the water cooling section 7 through the water supply pipe 71a, and cools the plate electrode 40 with water. The water flowing through the water channel is discharged to the outside through the drain pipe 72a.

The sample pressing electrode 4 includes a conductive outer fitting member 41 that is fitted on the flat plate electrode 40.
FIG. 6 is a side view showing the outer fitting member 41 constituting the sample pressing electrode 4, and FIG. 7 is a side sectional view showing the outer fitting member 41 constituting the sample pressing electrode 4. 6A is a plan view of the outer fitting member 41 (viewed from the front side in FIG. 3), FIG. 6B is a side surface of the outer fitting member 41 (viewed from the upper side in FIG. 3), and FIG. 6C is an outer fitting member. FIG. 6D is a partially cutaway side view of the external fitting member 41 (viewed from the lower side in FIG. 3). The outer fitting member 41 has a bottomed cylindrical shape, and is formed of a cylindrical portion 41 a that is fitted on the flat plate electrode 40 and a disc portion 41 b that covers the disc surface of the flat plate electrode 40. The cylindrical portion 41a is formed with recesses 41d and 41e for fitting to the flat plate electrode 40 while avoiding the water supply pipe 71a and the drain pipe 72a, and the water supply pipe connection plug 71 and the drain pipe connection plug 72. Further, a screw hole 41c for screwing the outer fitting member 41 to the flat plate electrode 40 is provided at an appropriate location of the cylindrical portion 41a. Further, a conductive terminal connection portion 42 that protrudes from the disc portion 41b and to which the power supply terminal 61b is detachably connected is formed at a substantially central portion of the disc portion 41b of the outer fitting member 41. . The terminal connection portion 42 is a conductive member formed integrally with the outer fitting member 41 and has a rectangular parallelepiped shape. As shown by the solid lines in FIGS. 2 and 3, the power supply terminal 61 b is detachably inserted in the side surface of the terminal connection portion 42, and a power supply terminal insertion hole 42 a electrically connected to the terminal connection portion 42 is formed. ing. In addition, a rod-like electrode portion 43 that comes into contact with the sample S is detachably inserted into the surface of the terminal connection portion 42 on the anode 3 side, that is, a surface substantially parallel to the disc portion 41 b, and is electrically connected to the terminal connection portion 42. An electrode insertion hole 42b to be connected is formed. For example, a female screw is formed in the electrode insertion hole 42b.

FIG. 8 is a side view showing a configuration example of the rod-shaped electrode portion 43. FIG. 8A shows an example of the rod-shaped electrode portion 43. As shown in FIG. 8A, a male screw 43b corresponding to the female screw of the electrode insertion hole 42b is formed at one end of the rod-like electrode portion 43. On the male screw 43b side of the cylindrical portion 43a of the rod-shaped electrode portion 43, a non-slip portion 43e is formed. The non-slip portion 43e is, for example, a mesh knurl. A spherical portion 43c is formed at the other end portion of the rod-shaped electrode portion 43, and a vertex portion 43d of the spherical portion 43c is planar.
FIG. 8B shows another example of the rod-shaped electrode portion 43. The rod-shaped electrode portion 143 shown in FIG. 8B has the same configuration as the rod-shaped electrode portion 43 shown in FIG. 8A, and only the length of the columnar portion 143a is different. The columnar portion 143a of the rod-shaped electrode portion 43 shown in FIG. 8B is shorter than the columnar portion 43a of the rod-shaped electrode portion 43 shown in FIG. 8A. The rod-shaped electrode portion 43 shown in FIG. 8A is suitable when the curvature of the curved sample S is large, and the rod-shaped electrode portion 143 shown in FIG. 8B is suitable when the curvature of the curved sample S is small.
FIG. 8C shows another example of the rod-shaped electrode portion 43. A male screw 43b similar to the rod-shaped electrode portion 43 shown in FIG. 8A is formed at one end of the rod-shaped electrode portion 243 shown in FIG. 8C, and a spherical surface portion 243c is formed at the other end. The apex portion 243d of the spherical portion 243c is planar. 8C has a truncated cone portion 243a in the middle in the center line direction. The truncated cone portion 243a has a large diameter on the male screw 43b side and a small diameter on the spherical surface portion 43c side. An anti-slip portion 243e is formed on the male screw 43b side of the truncated cone portion. The non-slip portion 43e is, for example, a mesh knurl. The rod-shaped electrode portion 243 shown in FIG. 8C has the diameter of the anti-slip portion 243e larger than the diameter of the anti-slip portions 43e and 143e of the rod-like electrode portions 43 and 143 shown in FIGS. 8A and 8B. It is easy to attach to the connection part 42.
FIG. 8D shows another example of the rod-shaped electrode portion 43. The rod-shaped electrode portion 343 shown in FIG. 8D includes a truncated cone portion having a non-slip portion 343e, like the rod-shaped electrode portion 243 shown in FIG. 8C, and the length of the truncated cone portion in the center line direction is different. The rod-shaped electrode portion 343 shown in FIG. 8D is formed with a male screw 43b similar to the rod-shaped electrode portion 243 shown in FIG. 8C at one end of the rod-like electrode portion 343 shown in FIG. 343c is formed. The apex portion 343d of the spherical surface portion 343c is planar.
In addition, the structure of the rod-shaped electrode part 43 shown to FIG. 8A-FIG. 8D is an example, and is not limited to these shapes. For example, the intermediate shape in the center line direction of the rod-shaped electrode portion 43 is not particularly limited, and a concave portion may be formed in part, or may be formed in a truncated cone shape. Further, when the rod-shaped electrode portion 43 is fixed to the terminal connection portion 42 by press-fitting into the electrode insertion hole 42b of the terminal connection portion 42, the male screw 43b is unnecessary. Further, if there is no problem with the attachment of the rod-shaped electrode portion 43, the anti-slip portion 43e may not be provided.

Next, the operation of the glow discharge spectroscopic analyzer 1, the sample support 31 and the sample pressing electrode 4 according to the first embodiment will be described.
FIG. 9 is a side sectional view showing an end portion of the cylindrical portion 31c where the sample S is pressed.
FIG. 9A shows a state in which the analysis surface of the concavely curved sample S is pressed against the end of the cylindrical portion 31 c of the sample support 31. As shown in FIG. 9A, when the analysis surface of the sample S curved in a concave shape is pressed against the end of the cylindrical portion 31c, the analysis surface of the sample S and the outer peripheral curved portion 31e of the cylindrical portion 31c come into contact with each other. The opening of the part 31c is sealed.
FIG. 9B shows a state in which the analysis surface of the sample S curved in a convex shape is pressed against the end of the cylindrical portion 31 c of the sample support 31. As shown in FIG. 9B, when the analysis surface of the sample S curved in a convex shape is pressed against the end of the cylindrical portion 31c of the sample support 31, the analysis surface of the sample S and the inner peripheral curved portion of the cylindrical portion 31c 31d abuts and the opening of cylinder part 31c is sealed.
FIG. 9C shows a state in which the analysis surface of the flat sample S is pressed against the end of the cylindrical portion 31 c of the sample support 31. As shown in FIG. 9C, when the analysis surface of the flat sample S is pressed against the end of the cylindrical portion 31c of the sample support 31, the analysis surface of the sample S and the annular flat end surface 31f of the cylindrical portion 31c are formed. It abuts and the opening of the cylinder part 31c is sealed.

FIG. 10 is a graph showing the spectroscopic analysis result of the sample S supported by the sample support 31 according to the first embodiment, and FIG. 11 shows the spectroscopic analysis result of the sample S supported by the conventional flat sample support. It is a graph. In the glow discharge spectroscopic analysis, the argon ions generated by the glow discharge collide with the analysis surface of the sample S, and the light contained in the analysis surface is analyzed to identify the atoms contained in the analysis surface. To do. 10 and 11, the horizontal axis indicates the depth of the sample S, and the vertical axis indicates the ratio of each element contained in the sample S. Since glow discharge spectroscopic analysis proceeds while excavating the analysis surface of the sample S, elements contained in the sample S can be spectroscopically analyzed in the depth direction. 10 and 11 show the spectral analysis results of the analysis surface of a planar silicon wafer having a thermal oxide film of about 1 μm. Details of the experimental conditions are as follows. Argon gas is supplied to the glow discharge tube 2 and the atmospheric pressure in the glow discharge tube 2 is maintained at 500 Pa. A pulsed high-frequency voltage of 20 W, duty 0.5, 100 Hz is applied to the sample pressing electrode 4.
However, the distance between the cylindrical electrode 32c of the first embodiment and the analysis surface of the sample S is about 110 μm, and the distance between the conventional cylindrical electrode and the analysis surface of the sample S is about 150 μm.
As shown in the graphs of FIGS. 10 and 11, oxygen (O) and silicon (Si) are detected on the surface of the sample S, and silicon (Si) is mainly detected in a portion deeper than the oxide film of the sample S. Has been. Thus, even when the sample support 31 according to the first embodiment was used, the same spectroscopic analysis results as those obtained using the conventional sample support that was confirmed to operate normally were obtained.

  FIG. 12 is a graph showing a surface state after spectroscopic analysis of the sample S supported by the sample support 31 according to the first embodiment, and FIG. 13 is spectroscopic analysis of the sample S supported by the conventional flat sample support. It is a graph which shows the surface state after. As shown in FIGS. 12 and 13, the excavation state of the analysis surface after the spectroscopic analysis using the sample support 31 according to the first embodiment and the spectroscopic analysis using the conventional sample support in which normal operation is confirmed. When compared with the excavation state of the analysis surface after the analysis, it was confirmed that the same excavation state was formed only in the depth of the recess formed on the analysis surface. Since the shapes of the anode main body 32 and the sample support 31 are different, there are some differences in the excavation shapes.

  FIG. 14 is a graph showing the results of spectroscopic analysis of another sample S supported by the sample support 31 according to the first embodiment, and FIG. 15 is a spectrum of another sample S supported by a conventional flat sample support. It is a graph which shows an analysis result. 14 and 15 show experimental results obtained by performing the above-described glow discharge spectroscopic analysis using different samples S. FIG. The graph shown in FIG.14 and FIG.15 has shown the spectral-analysis result of the analysis surface of the silicon steel plate which has a chromate film. The horizontal axis indicates the depth of the sample S, and the vertical axis indicates the ratio of each element contained in the sample S. As shown in the graphs of FIGS. 14 and 15, chromium (Cr), oxygen (O), and iron (Fe) are detected on the surface of the sample S, and iron is mainly used in a portion deeper than the oxide film of the sample S. Has been detected. Thus, even when another sample S was used, a normal spectroscopic analysis result was obtained.

  The above-described experimental results are experimental results performed using the planar sample S, but similar experimental results can be obtained using the curved sample S. FIG. 16 is a graph showing the spectroscopic analysis result of a sample whose analysis surface is curved in a convex shape, and FIG. 17 is a graph showing the spectroscopic analysis result of a sample whose analysis surface is curved in a concave shape. The graph shown in FIG.16 and FIG.17 has shown the spectral-analysis result of the analysis surface of the silicon steel plate which has a chromate film. 16 and 17, the horizontal axis indicates the depth of the sample S, and the vertical axis indicates the ratio of each element contained in the sample S. Chromium (Cr), oxygen (O), and iron (Fe) are detected on the surface of the sample S, and iron is mainly detected in a portion deeper than the oxide film of the sample S. Thus, even when the sample S whose analysis surface is curved in a convex shape or a concave shape is used, the same spectral analysis result as that obtained when the flat sample S is used is obtained.

  According to the first embodiment, the hole of the sample support 31 is sealed by supporting the flat sample S and the sample S whose analysis surface is convex or concave without exchanging the sample support 31. And spectroscopic analysis of the sample S can be performed.

  Further, since the cylindrical portion 31c that supports the sample S is provided at the apex portion 43d of the conical cylindrical portion 31b, the cylindrical portion 31c can support the cylindrical portion 31c as compared with the case where the cylindrical portion 31c is provided on a flat plate-like member. The degree of freedom such as the shape and size of the sample S that can be improved.

  Furthermore, since the end portion of the rod-shaped electrode portion 43 is spherical, the end portion of the rod-shaped electrode portion 43 can be brought into contact with the curved portion of the sample S and the sample S can be pressed against the cylindrical portion 31c. . Further, since the apex portion 43d of the rod-shaped electrode portion 43 is planar, the sample S and the sample pressing electrode 4 are securely connected by causing the apex portion 43d to contact the sample S, and glow discharge is generated. The voltage for making it apply can be applied to the sample S. Further, since the apex portion 43d is planar, heat is easily conducted from the sample S to the rod-shaped electrode portion 43, and heat can be efficiently radiated. Further, the sample S sandwiched between the cylindrical portion 31c of the sample support 31 and the rod-shaped electrode portion 43 can be reliably held without being displaced.

  Furthermore, the sample pressing electrode 4 according to the first embodiment can be detachably attached to the conventional flat plate electrode 40 of the glow discharge spectroscopic analyzer 1. Therefore, the spectroscopic analysis of the curved sample S can be performed without replacing the plate electrode 40 with the rod-shaped electrode portion 43.

  Furthermore, since the rod-shaped electrode portion 43 can be detachably attached to the terminal connection portion 42, the rod-shaped electrode portion 43 can be replaced according to the shape of the sample S.

  Furthermore, since the outer fitting member 41 is provided with the recesses 41d and 41e, even if the water cooling mechanism is provided in the flat plate electrode 40 of the glow discharge spectroscopic analyzer 1, the present embodiment is applied to the flat plate electrode 40. The sample pressing electrode 4 according to the first embodiment can be attached. Further, even if the sample pressing electrode 4 is heated during the spectroscopic analysis, heat is conducted from the sample pressing electrode 4 to the flat plate electrode 40, so that the sample pressing electrode 4 can be cooled with water using the water cooling mechanism of the flat plate electrode 40. it can. Further, since the sample pressing electrode 4 according to the first embodiment is provided with a separate water cooling mechanism and it is not necessary to replace the water supply pipe 71a and the drain pipe 72a connected to the flat plate electrode 40, the conventional glow discharge spectroscopic analyzer 1 is provided. In addition, the sample pressing electrode 4 according to the first embodiment can be introduced.

(Embodiment 2)
The glow discharge spectroscopic analysis apparatus 1 according to the second embodiment has the same configuration as that of the first embodiment, and only the configuration of the sample support 31 is different from that of the first embodiment. Therefore, the differences will be mainly described below. .
FIG. 18 is a side sectional view showing a sample support 31 according to the second embodiment. The sample support 31 according to the second embodiment includes a seal member 31g that is fitted on the end of the cylindrical portion 31c and seals between the end of the cylindrical portion 31c and the sample S. When the sample S is pressed against the cylindrical portion 31c of the sample support 31, the analysis surface of the sample S comes into contact with the seal member 31g and the end of the cylindrical portion 31c, and the opening of the cylindrical portion 31c is sealed.

  According to the second embodiment, the opening of the cylindrical portion 31c is more effectively sealed by sealing the end portion of the cylindrical portion 31c and the sample S with the sealing member 31g. Therefore, even when the curvature of the curved sample S is large, the opening of the sample support 31 can be more reliably sealed, and the sample S can be spectroscopically analyzed.

  The embodiment disclosed this time is to be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the meanings described above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

DESCRIPTION OF SYMBOLS 1 Glow discharge spectroscopic analyzer 2 Glow discharge tube 3 Anode 4 Sample press electrode 5 Press piston 6 Power supply part 7 Water cooling part 8 Spectrometer 21 Anode support block 22 Fixed ring 23 Lens 31 Sample support body 31a Girder part 31b Conical cylinder part 31c Cylinder Portion 31d inner curved portion 31e outer curved portion 31f annular flat end surface 31g sealing member 32 anode body 32a conductive base 32b conductive conical cylindrical portion 32c cylindrical electrode 40 flat plate electrode 41 external fitting member 41a cylindrical portion 41b disc portion 41c screw Hole 41d, 41e Concave part 42 Terminal connection part 42a Terminal insertion hole 42b Electrode insertion hole 43 Rod-like electrode part 43a Columnar part 43b Male screw 43c Spherical surface part 43d Vertex part 43e Non-slip part 61 Power supply plug 61a Power supply cable 61b Power supply terminal 71 Water supply pipe connection plug 71a Water supply pipe 72 Drain pipe connection plug Grayed 72a drainage pipe 81 entrance slit 82 diffraction grating 83 exit slit 84 photodetector 91 calculation unit 92 display unit 93 the printer unit S samples L glow discharge light

Claims (12)

A cylindrical electrode and a cylindrical portion that coaxially accommodates the cylindrical electrode, a sample support that supports the sample at the end of the cylindrical portion, and the sample is pressed against the end of the cylindrical portion, A glow discharge spectroscopic analysis apparatus comprising: a cylindrical electrode and a sample pressing electrode that supplies electric power for generating a glow discharge between the samples, and analyzing light emitted by the glow discharge generated between the cylindrical electrodes and the sample In
The outer peripheral side and the inner peripheral edge of the end of the cylindrical part are curved in a cross section including the center line of the cylindrical part ,
Furthermore, when the concave analysis surface of the curved sample is pressed against the end portion of the cylindrical portion, the analytical surface of the sample comes into contact with the curved portion on the outer peripheral side of the cylindrical portion, and the opening of the cylindrical portion When the convex analysis surface of the sample that is sealed and curved is pressed against the end of the tube portion, the sample analysis surface and the curved portion of the inner peripheral edge of the tube portion abut, It is configured so that the opening of the tube portion is sealed,
The sample pressing electrode has a rod-shaped electrode portion that comes into contact with the sample.   The curvature of the curved portion on the outer peripheral side of the cylindrical portion is smaller than the curvature of the curved portion on the inner peripheral edge of the cylindrical portion.
  The glow discharge spectroscopic analyzer according to claim 1. The cylindrical portion is
The glow discharge spectroscopic analyzer according to claim 1, further comprising an annular flat end surface between a curved portion on an outer peripheral side of the end portion and a curved portion on an inner peripheral edge. The glow discharge spectroscopic analyzer according to any one of claims 1 to 3, further comprising: a seal member that is externally fitted to an end portion of the cylindrical portion and seals between the end portion and the sample. The sample support comprises a conical cylinder;
The glow discharge spectroscopic analyzer according to any one of claims 1 to 4 , wherein the cylindrical portion protrudes from an apex portion of the conical cylindrical portion. The glow discharge spectroscopic analyzer according to any one of claims 1 to 5, wherein an end portion of the rod-shaped electrode portion has a spherical shape. The glow discharge spectroscopic analyzer according to claim 6 , wherein an apex portion of the rod-shaped electrode portion on the cylindrical portion side has a planar shape. A power supply terminal for supplying power;
A plate electrode to which the power supply terminal is detachably connected,
The sample pressing electrode is
A conductive outer fitting member fitted on the plate electrode;
Projecting from the outer fitting member toward the cylindrical electrode, and having a conductive terminal connection portion to which the power supply terminal is detachably connected,
The glow discharge spectroscopic analyzer according to any one of claims 1 to 7, wherein the rod-shaped electrode portion is provided in the terminal connection portion. The terminal connection portion is
The glow discharge spectroscopic analyzer according to claim 8 , wherein the rod-shaped electrode portion is detachably inserted and has an electrode insertion hole electrically connected to the terminal connection portion. The plate electrode has a disk shape, and a water supply pipe and a drain pipe for water cooling are connected to the side of the plate electrode,
The outer fitting member is
The plate electrode has a cylindrical portion which is fitted to, claim 8 or claim the cylindrical portion recess for fitted on the flat plate electrode to avoid the water supply pipe and drain pipe are formed 9 The glow discharge spectroscopic analyzer described in 1. In the sample support that has a cylindrical portion that accommodates the cylindrical electrode coaxially and supports the sample at the end of the cylindrical portion,
The outer peripheral side and the inner peripheral edge of the end of the cylindrical part are curved in a cross section including the center line of the cylindrical part ,
Furthermore, when the concave analysis surface of the curved sample is pressed against the end portion of the cylindrical portion, the analytical surface of the sample comes into contact with the curved portion on the outer peripheral side of the cylindrical portion, and the opening of the cylindrical portion When the convex analysis surface of the sample that is sealed and curved is pressed against the end of the tube portion, the sample analysis surface and the curved portion of the inner peripheral edge of the tube portion abut, A sample support configured to be hermetically sealed in an opening of a cylindrical portion . In a sample pressing electrode that presses a sample against an end of a cylindrical portion that coaxially accommodates a cylindrical electrode of a glow discharge spectrometer, and supplies electric power for generating glow discharge between the cylindrical electrode and the sample ,
A conductive outer fitting member fitted on the plate electrode of the glow discharge spectrometer;
A conductive terminal connecting portion protruding from the outer fitting member toward the cylindrical electrode, to which a power supply terminal for supplying power is detachably connected;
A sample pressing electrode comprising: a rod-shaped electrode portion provided at the terminal connection portion.

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