WO2014069530A1 - Dispositif d'analyse d'éléments - Google Patents

Dispositif d'analyse d'éléments Download PDF

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WO2014069530A1
WO2014069530A1 PCT/JP2013/079428 JP2013079428W WO2014069530A1 WO 2014069530 A1 WO2014069530 A1 WO 2014069530A1 JP 2013079428 W JP2013079428 W JP 2013079428W WO 2014069530 A1 WO2014069530 A1 WO 2014069530A1
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Prior art keywords
pyroelectric crystal
sample
insulator member
needle
electron beam
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PCT/JP2013/079428
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English (en)
Japanese (ja)
Inventor
潤 河合
晋 今宿
朗 今西
一誓 大谷
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国立大学法人京都大学
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Priority to JP2014544557A priority Critical patent/JP6179994B2/ja
Publication of WO2014069530A1 publication Critical patent/WO2014069530A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
    • G01N23/2252—Measuring emitted X-rays, e.g. electron probe microanalysis [EPMA]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/60—Specific applications or type of materials
    • G01N2223/624—Specific applications or type of materials steel, castings

Definitions

  • the present invention relates to a small elemental analyzer excellent in portability.
  • Non-patent Document 1 an element analyzer using pyroelectric crystals.
  • This elemental analyzer generates a high voltage between the pyroelectric crystal and the sample (object to be measured) by heating or cooling the pyroelectric crystal with a Peltier device, and accelerates electrons between the two to cause the sample to The element contained in the sample is detected from the spectrum of characteristic X-rays generated by irradiation.
  • This elemental analyzer is driven by a battery as small as a dry cell used for driving and controlling the Peltier device, and the entire size of the device is smaller than that of the trunk case, so that it is excellent in portability.
  • a pyroelectric crystal is a crystal in which the magnitude of spontaneous polarization changes with changes in temperature.
  • the equilibrium state charged particles floating around the surface adhere to the surface, so that the charge on the pyroelectric crystal surface due to polarization is canceled out, and an electrically neutral state is maintained in which no electric field appears outside (center of FIG. 13).
  • Figure 1 A pyroelectric crystal is a crystal in which the magnitude of spontaneous polarization changes with changes in temperature.
  • the equilibrium state charged particles floating around the surface adhere to the surface, so that the charge on the pyroelectric crystal surface due to polarization is canceled out, and an electrically neutral state is maintained in which no electric field appears outside (center of FIG. 13).
  • the state of polarization of the pyroelectric crystal changes, and the surface is charged positively or negatively (the right or left diagram in FIG. 13).
  • the temperature is kept constant, surface charge is eliminated by floating charged particles (not shown). Since there are a lot of floating charged particles in the atmosphere, the charge on the pyroelectric crystal surface
  • Non-Patent Document 1 a sample is placed on a conductive sample stage, and a pyroelectric crystal is arranged so that one polarization surface faces the sample (see FIG. 14).
  • the other polarization surface of the pyroelectric crystal is electrically connected to the sample stage and grounded.
  • Each charged particle is accelerated toward the pyroelectric crystal (the middle diagram in FIG. 14).
  • electrons irradiated on the sample contribute to emission of characteristic X-rays.
  • characteristic X-rays In the atmosphere, electrons collide with air molecules and lose energy, but in a vacuum of several Pa, most of the electrons collide with the sample on the sample stage without losing energy.
  • characteristic X-rays are emitted from the sample (the right figure in FIG. 14), and the characteristic X-ray spectrum is obtained by detecting the emitted characteristic X-rays with an energy dispersive X-ray detector (EDX) or the like. It is done.
  • EDX energy dispersive X-ray detector
  • a peak of an element that should not be included in the sample may appear in the obtained X-ray spectrum. It has been found that X-rays are not emitted only from the sample, that is, X-rays are emitted from other than the sample. When X-rays not derived from the sample are emitted, the X-ray spectrum becomes disturbance noise with respect to the sample, and thus the amount of elements contained in the sample cannot be accurately analyzed. In addition, when there is such disturbance noise, it is difficult to detect an element with a small content, and a high sensitivity analysis cannot be performed.
  • the problem to be solved by the present invention is to provide an elemental analyzer using pyroelectric crystals that can perform highly sensitive analysis with little disturbance noise even with an element having a small content in a sample. It is.
  • An elemental analyzer which has been made to solve the above problems, A vacuum vessel; A pyroelectric crystal disposed in the vacuum vessel; Temperature changing means for changing the temperature of the pyroelectric crystal; An insulator member covering one of the polarization planes of the pyroelectric crystal and having a low dielectric constant compared to the pyroelectric crystal; A conductive needle standing on the one polarization surface of the pyroelectric crystal and having a protruding end protruding from the insulator member; A conductive surface that is disposed in the vacuum vessel and has a sample placement surface that intersects with the extension line of the protruding end of the needle, is electrically connected to the other polarization surface of the pyroelectric crystal, and is grounded Sex sample stage, X-ray detection means for detecting characteristic X-rays emitted from the sample placed on the sample placement surface; It is characterized by providing.
  • the present inventor since the peak of an element not derived from the sample is included in the X-ray spectrum obtained by a conventional elemental analyzer using a pyroelectric crystal, the present inventor has examined the origin of the element. It was determined that it is a constituent element such as a vacuum vessel or a sample stage. From this, it is considered that negative suspended charged particles are irradiated not only to the sample but also to the inner wall of the vacuum vessel, the sample stage, etc., and a method for reducing the negative suspended charged particles that are directed to other than the sample was examined. .
  • the present inventor speculates that there is a site where a strong electric field is formed that gives sufficient energy to the negative suspended charged particles other than between the metal needle and the sample, and weakens the electric field at that site. Thought.
  • a relatively strong electric field is formed between the sample side polarization surface of the pyroelectric crystal and the inner wall or sample stage of the vacuum vessel. If the distance between the edge part) and the inner wall of the vacuum vessel is equal to or shorter than the distance between the metal needle and the sample, the gap between the peripheral part of the sample side polarization surface and the vacuum vessel is between the metal needle and the sample. We found that an electric field with the same or higher strength than the electric field is generated.
  • disturbance noise is generated between the time when the electric field is induced between the metal needle and the sample until the time when the electric field is induced between the surface of the insulator member and the inner wall of the vacuum vessel. Can be suppressed. For this reason, by using the X-ray spectrum obtained from the X-rays detected during this time, qualitative and quantitative analysis of the elements contained in the sample can be performed accurately. Since the needle has conductivity, when an electric charge is generated on the sample side polarization surface of the pyroelectric crystal, the same voltage is generated on the sample side polarization surface and the needle almost simultaneously.
  • the charge hardly moves in the insulator member, even if the charge is generated on the sample-side polarization surface of the pyroelectric crystal, the charge does not immediately appear on the surface of the insulator member. For this reason, it takes time until an electric field is induced between the surface of the insulator member and the inner wall of the vacuum vessel, and the time (hereinafter referred to as “induction time”) is the dielectric of the insulator member. The lower the rate, the longer. For this reason, the use of a material having a sufficiently low dielectric constant for the insulator member can extend the time effective for analysis (less disturbance noise).
  • Non-Patent Document 3 the total integrated intensity of X-rays generated from a sample is constant during one cycle from the start of heating or cooling of the pyroelectric crystal to the neutralization of the pyroelectric crystal. It is described.
  • the neutralization time depends on the size of the pyroelectric crystal, the contact area between the conductor layer and the pyroelectric crystal, and the like. If these are determined appropriately so that the neutralization time is shorter than the induction time, the irradiation of the electron beam to the sample is terminated before the high voltage is induced in the insulator member. Can be suppressed.
  • the insulator member may be not only a solid material such as glass, plastic or rubber, but also a gel material such as vacuum grease.
  • a gel material such as vacuum grease.
  • the vacuum grease for example, an insulating silicone grease having a low dielectric constant and electrical insulation is preferable.
  • vacuum grease it may be applied to the sample-side polarization surface of the pyroelectric crystal (or the surface of the conductor layer if a conductor layer is provided). Further, an insulating film may be formed on the sample-side polarization surface of the pyroelectric crystal or the surface of the conductor layer by vapor deposition or the like.
  • a material having a dielectric constant as low as possible for example, a low-k material
  • the same effect can be obtained even if the insulator member is made thick, for example. be able to.
  • the X-ray detection unit is an essential configuration, but when used as an electron beam irradiation apparatus, the X-ray detection unit is not necessary.
  • the electron beam irradiation apparatus is A vacuum vessel; A pyroelectric crystal disposed in the vacuum vessel; Temperature changing means for changing the temperature of the pyroelectric crystal; An insulator member covering one of the polarization planes of the pyroelectric crystal and having a low dielectric constant compared to the pyroelectric crystal; A conductive needle standing on the one polarization surface of the pyroelectric crystal and having a protruding end protruding from the insulator member; A conductive material disposed in a vacuum vessel and having an electron beam irradiation surface intersecting with an extension line of the protruding end of the needle, and electrically connected to the other polarization surface of the pyroelectric crystal and grounded An electron beam irradiation stand, It is characterized by having.
  • a conductor layer is provided between the insulator member and the sample-side polarization surface of the pyroelectric crystal, as in the element analysis apparatus.
  • the sample is approximately the same size as the irradiation range of the electron beam or larger than the irradiation range, it is possible to irradiate only the sample with an electron beam by arranging the sample in the irradiation range. Generation of X-rays from the sample placement surface can be suppressed.
  • the sample is smaller than the irradiation range of the electron beam, since the electron beam is applied to both the sample and the sample mounting surface, generation of X-rays from the sample mounting surface that causes disturbance noise is inevitable. . Therefore, in order to analyze minute substances, it is necessary to make the irradiation range of the electron beam as narrow as possible.
  • the needle is erected on the sample side polarization surface which is one of the polarization surfaces of the pyroelectric crystal, an electric field is induced between the tip of the needle and the sample placement surface.
  • the electron beam can be irradiated in a concentrated manner on a narrow area of the sample mounting surface. Therefore, fine substances such as aerosols present in the air, inclusions such as oxides (Al 2 O 3 , SiO 2 , MnO 2 etc.) and sulfides (MnS, CaS etc.) present in steel, It is possible to analyze fine particles such as aerosols present in the water.
  • Factors that affect the size of the electron beam irradiation range include the degree of vacuum in the vacuum vessel, the distance from one polarization surface of the pyroelectric crystal to the other polarization surface, and the needle protruding from the insulator member. Examples include the length of the tip, the size of the diameter of the tip of the needle, the distance from the tip of the needle to the sample, and the like. Therefore, it is preferable to set the size of the electron beam irradiation range by appropriately adjusting these factors according to the size of the sample to be measured. For example, the irradiation range of the electron beam can be increased by increasing the distance from the tip of the needle to the sample or increasing the length of the tip of the needle.
  • the sample-side polarization surface of the pyroelectric crystal is covered with an insulator member having a dielectric constant lower than that of the pyroelectric crystal, and the tip of the needle is protruded from the insulator member. For this reason, the time from when the electric charge is generated on the sample-side polarization surface of the pyroelectric crystal to the time when the electric field is induced elsewhere than the time from when the electric field is induced between the needle and the sample mounting surface. The time is longer.
  • the sample-side polarization surface of the pyroelectric crystal is covered with the insulator member, the electric field induced between the tip of the needle and the sample placement surface is not covered with the insulator member. It becomes weaker than the electric field induced between the polarization surface and the sample mounting surface, and as a result, the intensity of characteristic X-rays generated from the sample mounted on the sample mounting surface decreases.
  • highly sensitive qualitative / quantitative analysis of elements contained in a sample can be performed even if the intensity of characteristic X-rays is low.
  • the schematic block diagram which shows one Example of the elemental analyzer which concerns on this invention.
  • the figure which shows the voltage of the pyroelectric crystal vicinity of the elemental analyzer of a present Example.
  • the graph which shows the time change of the voltage in the surface of an insulator member.
  • the experimental results of using a tungsten needle and a Ti plate as a sample are shown.
  • (A) shows no needle, conductor layer, and insulator member
  • (b) shows needle and conductor layer. When the insulator member is not provided
  • (c) shows the characteristic X-ray spectrum when the needle, the conductor layer, and the insulator member are all provided.
  • the experimental results of using a gold needle and a Ti plate as a sample are shown.
  • (A) shows no needle, conductor layer, and insulator member; (b) shows needle and conductor layer When the insulator member is not provided, (c) is a graph showing characteristic X-ray spectra when the needle, the conductor layer, and the insulator member are all provided.
  • Measurement results of the elemental analyzer according to the present embodiment of the sample specimen were painted on the entire one surface of the carbon double-sided tape comprising a powder of MnO 2 (characteristic X-ray spectrum).
  • Measurement results of the elemental analysis apparatus according to the embodiment of one of the TiO 2 particles shown in FIG. 8 characteristic X-ray spectrum.
  • Measurement results of the elemental analysis apparatus according to the embodiment of one of the MnO 2 particles shown in FIG. 8 characteristic X-ray spectrum.
  • Explanatory drawing which shows the principle by which a sample on a sample stand is irradiated with electrons by a pyroelectric crystal.
  • FIG. 1 is a schematic configuration diagram of an elemental analyzer according to the present embodiment.
  • the + z direction in the figure is “up” and the ⁇ z direction is “down”.
  • a grounded conductive vacuum vessel 10 includes a grounded conductive vacuum vessel 10, a pyroelectric crystal 11 made of a single crystal of 3 mm ⁇ 3 mm ⁇ 5 mm LiTaO 3, and a Peltier element for heating / cooling the pyroelectric crystal 11. 12, a conductive sample stage 13 on which the sample S is placed, and a Si-PIN type X-ray detector 14 that detects characteristic X-rays emitted from the sample S when the sample S is irradiated with electrons. And a processing device 141 for processing the detection signal of the Si-PIN type X-ray detector 14.
  • the processing device 141 has a function of creating an X-ray spectrum from a detection signal of the Si-PIN type X-ray detector 14, a function of displaying the created X-ray spectrum, and the like.
  • the vacuum container 10 of the present example has a T-shaped flange 10A, which is a stainless steel T-shaped tube, and a flat blank flange 10B that seals the T-shaped flange 10A (the standards are NW25).
  • a vacuum pump (not shown) is connected to a pipe extending downward in the “T” of the T-shaped flange 10A (a pipe extending in the ⁇ x direction in FIG. 1).
  • a first rod 16 and a second rod 17 made of copper are inserted from both ends of a tube extending in the lateral direction of “T” (a tube extending in the z direction in FIG. 1).
  • the first rod 16 and the second rod 17 are bonded to the blank flange 10B with an epoxy adhesive, silver paste, or the like, and are then electrically connected to the blank flange 10B with a conductive carbon tape.
  • a through hole having a diameter of 10 mm is provided in the center of the tube extending in the z direction of the T-shaped flange 10A, and a Kapton tape (registered trademark) is attached to the through hole to form the window portion 15.
  • the Si-PIN type X-ray detector 14 is installed toward the window 15.
  • the pyroelectric crystal 11 is joined to the upper surface of the first rod 16 via the Peltier element 12.
  • the Peltier element 12 heats / cools the pyroelectric crystal 11 when power is supplied from the power supply unit 18. That is, the Peltier element 12 and the power supply unit 18 correspond to the temperature changing means of the present invention.
  • the upper surface of the pyroelectric crystal 11 is a ⁇ z plane (a surface that is negatively polarized), and the lower surface is a + z plane (a surface that is positively polarized).
  • the Peltier element 12 cools the pyroelectric crystal 11, and as shown in FIG. Thus, the upper surface of the pyroelectric crystal 11 is negatively charged and the lower surface is positively charged.
  • the pyroelectric crystal 11 may be turned upside down (that is, the upper surface is the + z plane and the lower surface is the ⁇ z plane). In this case, if the pyroelectric crystal 11 is heated by the Peltier element 12, the upper surface (+ z surface) of the pyroelectric crystal 11 is negatively charged and the lower surface ( ⁇ z surface) is positively charged (see the left diagram of FIG. 13). reference).
  • a 3 mm ⁇ 3 mm ⁇ 3 mm conductor layer 21 is bonded to the upper surface of the pyroelectric crystal 11, and a conductive needle 20 is erected on the conductor layer 21.
  • a conductive metal such as tungsten or gold can be used.
  • Insulating vacuum grease (silicone) is applied to the surfaces of the pyroelectric crystal 11 and the conductor layer 21 as the insulator member 22. At this time, the insulator material 22 is applied so that the distal end portion of the needle 20 protrudes to the outside of the insulator material 22 and the base end portion is thick enough to be buried in the insulator material 22.
  • the relative dielectric constant of silicone is about 3, which is sufficiently smaller than LiTaO 3 (relative dielectric constant is about 50).
  • the sample stage 13 is joined to the lower surface of the second rod 17.
  • the sample stage 13 is preferably made of a conductive material that does not emit characteristic X-rays of the element to be analyzed.
  • a graphite stage is used.
  • the lower surface of the sample stage 13 is a sample placement surface 13a.
  • the sample placement surface 13a intersects the extension line of the tip of the needle 20.
  • the sample mounting surface 13a has a 45 ° gradient with respect to the ⁇ z plane of the pyroelectric crystal 11 in order to make it easy to extract X-rays emitted from the sample S mounted thereon from the window portion 15. have.
  • the sample S is fixed to the sample mounting surface 13a with a carbon double-sided tape.
  • the lower surface (+ z surface) of the pyroelectric crystal 11 is electrically connected to the first rod 16 by a conducting wire or the like (not shown).
  • the bottom surface of the sample stage 13 is electrically connected to the second rod 17.
  • the first rod 16 and the second rod 17 are electrically connected to the vacuum vessel 10 by carbon tape.
  • the power supply unit 18 has a function of flowing a current through the Peltier element 12 and a function of periodically switching the direction of the current flowing through the Peltier element 12 every several minutes. Thereby, the upper surface of the Peltier element 12 repeats heating and cooling periodically. Accordingly, the pyroelectric crystal 11 bonded to the upper surface of the Peltier element 12 is periodically heated and cooled.
  • the sample S is affixed to the sample stage 13, the T-shaped flange 10A is sealed, and then the vacuum vessel 10 is exhausted through the exhaust pipe 16 by a rotary pump (not shown).
  • the vacuum chamber 10 is evacuated until the internal pressure reaches about several Pa (for example, 1 Pa to 5 Pa).
  • the pyroelectric crystal 11 is cooled in this state, an electric field is formed in the direction from the sample stage 13 toward the needle 20. Thereby, the stray electrons in the vicinity of the needle 20 are accelerated toward the sample stage 13, collide with the sample S fixed on the sample stage 13, and characteristic X-rays are emitted from the sample S.
  • the pyroelectric crystal 11 continues to be cooled by the Peltier element 12 and the temperature difference between the pyroelectric crystal 11 and the Peltier element 12 on the low temperature side (endothermic side) disappears, heat transfer from the pyroelectric crystal 11 to the Peltier element 12 (Endothermic action) is saturated and the temperature of the pyroelectric crystal 11 does not decrease, that is, the temperature does not change.
  • the pyroelectric crystal 11 is neutralized by floating charged particles in a vacuum, and the electric field disappears.
  • the pyroelectric crystal 11 is once heated, then the pyroelectric crystal is cooled again, and the sample is repeatedly irradiated with floating electrons, thereby detecting the Si-PIN X-ray. What is necessary is just to repeat the X-ray detection by the instrument 14 a plurality of times.
  • Fig. 2 shows that when the pyroelectric crystal is cooled, the sample-side polarization plane (-z plane) is negatively charged and a voltage of -H [V] (generally a high voltage of several tens [kV]) is generated. The voltage at each part in the vicinity of the pyroelectric crystal is shown.
  • V the voltage at the sample side polarization surface of the pyroelectric crystal 11 actually changes with time, in order to simplify the explanation, a constant voltage is assumed below.
  • the insulator member (grease) 22 provided on the conductor layer 21 has a low dielectric constant and is insulative, so that immediately after a voltage of ⁇ H [V] is applied to the conductor layer 21. No voltage is induced.
  • the insulator member 22 is not charged when a voltage is applied, and then slowly becomes negatively charged over time, and accordingly, the absolute value of the voltage on the surface of the insulator member 22 gradually increases ( FIG. 3).
  • FIG. 3 is a graph showing a schematic change in the voltage induced on the surface of the insulator member 22.
  • the horizontal axis in FIG. 3 represents time, and the vertical axis represents voltage.
  • shaft of FIG. 3 represents the negative numerical value, and it is located upward, so that a voltage value is small.
  • the voltage on the surface of the insulator member 22 is 0 [V] when a voltage of ⁇ H [V] is applied, and 0 [V] until a negative charge appears on the surface. It remains unchanged. When a negative charge appears on the surface of the insulator member 22, a negative voltage is generated.
  • the power supply unit 18 is controlled to switch between cooling and heating of the pyroelectric crystal 11 at an appropriate timing according to the length of the neutralization time and the induction time.
  • the insulator member 22 Since the insulator member 22 is not directly supplied with electric charges from the conductor layer 21, actually, even when the surface voltage of the insulator member 22 becomes higher than the threshold voltage, the surface voltage becomes the threshold voltage due to the emission of electrons. It becomes smaller and the emission of electrons stops. Therefore, even if the neutralization time slightly exceeds the induction time, if the cooling and heating of the Peltier element 12 are switched before and after the emission of electrons from the surface of the insulator member 22 repeatedly occurs, the disturbance noise generated thereby is reduced. It can be made sufficiently smaller than the peak of the sample element.
  • the experimental result by the elemental analyzer of a present Example is shown.
  • the following experimental results show that a voltage of 3 V is applied to the Peltier element 12, the pyroelectric crystal 11 is heated for about 120 seconds, and then cooled for 90 seconds by reversing the direction of the current. It is obtained by detecting X-rays with a PIN type X-ray detector 14. A 1 cm ⁇ 1 cm Ti plate was used as the sample S.
  • FIG. 4 shows (a) a characteristic X-ray spectrum (a spectrum of “(a) no needle” in FIG. 4) when none of the needle 20, the conductor layer 21, and the insulator member 22 is provided, and (b ) The characteristic X-ray spectrum (the spectrum of “(b) with needle / without grease” in FIG. 4) when the needle 20 and the conductor layer 21 are provided and the insulator member 22 is not provided; and (c) the needle 20.
  • Characteristic X-ray spectrum when the conductor layer 21 and the insulator member 22 are all provided (that is, by the elemental analyzer of the present embodiment) ("(c) Needle / Grease" spectrum in FIG. 4) Is shown.
  • a gold-plated tungsten needle 20 having a length of about 8 mm and a tip radius of curvature of several ⁇ m to several tens of ⁇ m was used. Moreover, the thickness of the insulator member 22 was about 3 mm.
  • FIG. 5 shows the experimental results using a gold (Au) needle as the needle 20. This gold needle is not subjected to electropolishing, and the radius of curvature at the tip is about several hundred ⁇ m. Other experimental conditions are the same as when the characteristic X-ray spectrum of FIG. 4 was acquired.
  • FIG. 6 shows a photograph (a) in the vicinity of a fluorescent plate when a fluorescent plate (5 mm ⁇ 6 mm) is placed on the sample mounting surface 13a as the sample S using the gold needle 20, and an electron beam on the fluorescent plate. It is the photograph (b) which image
  • FIGS. 7A to 7C are photographs and images corresponding to FIGS. 6A to 6C when none of the needle 20, the conductor layer 21, and the insulator member 22 is provided. From the image of FIG. 7C, it can be seen that the entire fluorescent plate emits light and the electron beam is irradiated over a wide range. In addition, it can be seen from the spectra of FIGS. 4 and 5 that the electron beam is applied to the inner wall of the vacuum vessel, for example, other than the fluorescent plate.
  • FIG. 8 is a photograph taken by an electron microscope (SEM) of this sample. As can be seen from this photograph, TiO 2 has a size of about 200 ⁇ m, and MnO 2 particles have a size of about 100 ⁇ m. Further, the MnO 2 particles and the TiO 2 particles are attached to the carbon double-sided tape in a state of being separated by about 500 ⁇ m.
  • FIG. 9 and 10 show a sample obtained by rubbing a powder of only MnO 2 or TiO 2 on one side of a carbon double-sided tape, using the elemental analyzer according to the present embodiment (with needle and with grease). The measured spectrum is shown. Therefore, this sample contains many particles of MnO 2 or TiO 2 .
  • FIG. 11 and FIG. 12 show measured spectra obtained by measuring one TiO 2 particle or one MnO 2 particle in the photograph shown in FIG. 8 with the elemental analyzer according to the present example (with needle and with grease). Indicates. In this experiment, a gold wire having a diameter of 0.2 mm was used as the needle 20.
  • the characteristic X-ray spectra of FIGS. 11 and 12 are much lower in intensity than the characteristic X-ray spectra of FIGS. 9 and 10, and therefore the background is relatively high.
  • the same tendency as in FIGS. 9 and 10 was shown. From this, it was found that fine particles having a size of about 100 ⁇ m to 200 ⁇ m can be analyzed with high sensitivity using the elemental analyzer according to the present example.
  • the needle 20 only needs to have a needle shape when viewed macroscopically, and there is no need to sharpen the tip like a needle used in a scanning tunneling microscope. Rather, the shape of the sample side is important, and only the sample is excited more efficiently by sticking the sample on as small a protrusion as possible.
  • the material of the needle 20 is more conductive than the pyroelectric crystal. Accordingly, graphite other than metal, for example, has sufficient conductivity and can be used for the needle 20.
  • a solid insulator material such as rubber, silicon oxide, glass or the like with a low dielectric constant (relative dielectric constant of about 1 to 10) can be used. If the dielectric constant of the insulator member 22 is about 1/5 or less of that of the pyroelectric crystal 11, the time during which the pyroelectric crystal 11 is neutralized is longer than the time during which a high voltage is induced on the surface of the insulator member 22. Can be shortened.
  • the elemental analyzer of FIG. 1 can be used also as an electron beam irradiation apparatus.
  • the X-ray detector 14 is not essential and may be added as necessary.
  • the sample stage 13 and the sample placement surface 13a of the elemental analyzer of FIG. 1 become an electron beam irradiation table and an electron beam irradiation surface, respectively.
  • Such an electron beam irradiation apparatus can also be used, for example, for cathodoluminescence analysis.
  • a visible light detector may be provided toward the window 15.
  • a Peltier device may be used for cooling and a heating wire may be used for heating.
  • a temperature change means is comprised from the Peltier element and a heating wire, and the power supply part which supplies electric power to these Peltier devices and a heating wire.

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Abstract

La présente invention concerne un dispositif d'analyse d'éléments comprenant un récipient sous vide ; un cristal pyroélectrique disposé à l'intérieur du récipient sous vide ; un moyen de variation de la température permettant de faire varier la température du cristal pyroélectrique ; un élément isolant destiné à recouvrir une face polarisée du cristal pyroélectrique et présentant une constante diélectrique inférieure à celle du cristal pyroélectrique ; une aiguille électroconductrice se dressant sur une face polarisée du cristal pyroélectrique et possédant une extrémité en saillie qui fait saillie depuis l'élément isolant ; une platine porte-objet disposée à l'intérieur du récipient sous vide ; et un moyen de détection des rayons X permettant de détecter un rayon X caractéristique émis depuis un échantillon monté sur la platine porte-objet. Le platine porte-objet comporte une surface de montage des échantillons qui est orthogonale à une ligne se prolongeant depuis l'extrémité en saillie de l'aiguille et est en connexion électrique avec l'autre face polarisée du cristal pyroélectrique et mise à la terre.
PCT/JP2013/079428 2012-10-30 2013-10-30 Dispositif d'analyse d'éléments WO2014069530A1 (fr)

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JP2012-238534 2012-10-30
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