JP5538840B2 - X-ray monochromator, manufacturing method thereof, and X-ray spectrometer - Google Patents

Description

  The present invention relates to an X-ray monochromator, a method of manufacturing the same, and an X-ray spectrometer using the X-ray monochromator.

  The X-ray monochromator is used in an X-ray spectrometer having a configuration as shown in FIG. As shown in FIG. 1, an X-ray monochromator 11, an X-ray source 12, and an X-ray detector 13 are arranged on the circumference of a Roland circle 14 having a radius R. The X-ray source 12 is a sample or the like that exhibits fluorescent X-rays. X-rays (incident X-rays 16) including various wavelength components emitted from the X-ray source 12 are reflected at each position of the X-ray monochromator 11, and reflected X-rays 17 are collected at the X-ray detector 13. It is illuminated and the X-ray intensity is measured. At this time, a diffraction phenomenon is used for reflection of X-rays, and only a specific wavelength satisfying the following Bragg condition (Equation 1) is measured by the X-ray detector 13. By moving the X-ray source 12 and the X-ray detector 13 on the circumference of the Roland circle 14 and changing the incident angle θ, the X-ray intensity of each wavelength corresponding to Equation 1 can be measured.

(Where d: structure period, θ: incident angle, diffraction angle (Bragg angle), n: order of diffraction, λ: wavelength of X-ray)

  Each reflection position of the X-ray monochromator 11 has a structure periodicity in the direction toward the point B so that Expression 1 is satisfied, and the structure period is d in Expression 1. In other words, the X-ray monochromator 11 is made of a material having a periodicity in the normal direction of the curved surface, curved with the diameter (2R) of the Roland circle as the radius of curvature.

  Furthermore, the surface shape of the X-ray monochromator 11 needs to be along the circumference of the Roland circle 14 so that the reflected X-rays 17 are collected at the position of the X-ray detector 13. The configuration is called the Johansson type monochromator. However, actually, in order to manufacture a Johansson type monochromator, it is necessary to polish the monochromator. Therefore, as reported in Patent Document 1, depending on the structural periodic material to be used, the shape of the monochromator surface is a circumference of a circle 15 having a Roland circle diameter (2R) as a radius without performing polishing. In many cases, a Johann monochromator as shown in FIG.

  The structural periodic material used for the X-ray monochromator has a structural period of several nanometers mainly composed of inorganic substances from the viewpoint that the structural period can be easily changed when the wavelength of the X-ray is relatively long. An artificial multilayer film is often used. Furthermore, in order to improve the X-ray spectral performance, it is preferable to use a material having a low electron density such as an organic substance for the artificial multilayer film. As an X-ray monochromator composed of an artificial multilayer film of a material having a low electron density, Patent Document 1 uses an arbitrary one as long as the interface between layers is clean and orderly at the atomic level, regardless of whether it is organic or inorganic. A possible X-ray monochromator is disclosed. Patent Document 2 discloses an X-ray monochromator using clay having a layered structure in which an organic cation is included in a layer space and a mica mineral for the structural periodic material.

JP-A-6-27300 JP-A-63-94200

  However, the above literature has a problem to be improved. The X-ray monochromator disclosed in Patent Document 1 makes X-rays incident at a minute angle (3 ° or less). Therefore, the width of the X-ray irradiated to the X-ray monochromator is increased, and the length of the monochromator and the Roland circle must be increased. Therefore, there has been a problem that the X-ray spectrometer using the X-ray monochromator has to be enlarged.

  In addition, the X-ray monochromator disclosed in Patent Document 2 produces an artificial multilayer film of an X-ray monochromator from a particulate sol solution of several μm or less. Therefore, the crystallite size of clay and mica mineral is relatively small, and unevenness having a film thickness larger than 100 nm is formed on the artificial multilayer film, which causes a problem that the spectral performance of X-rays may be limited.

The present invention has been made in view of such a background art, and provides an X-ray monochromator that has a good X-ray spectral performance and can be designed in a relatively small size, and a method for manufacturing the same.
The present invention also provides an X-ray spectrometer using the above X-ray monochromator.

An X-ray monochromator that solves the above-mentioned problem is an organic material composed of alkyl chains and an inorganic oxide composed of silica alternately formed on the concave surface of a substrate having a concave surface curved with the diameter of the Roland circle as the radius of curvature. An X-ray monochromator composed of laminated organic-inorganic layered films, wherein an incident angle of X-rays incident on the organic-inorganic layered film from the circumference of a Roland circle is 10 ° or more, and the organic- The maximum height Ry of the surface roughness of the inorganic layered film is 100 nm or less, and the organic substance and the inorganic oxide of the organic-inorganic layered film alternately have a structural period in the normal direction of the curved concave surface of the substrate. It is characterized by being laminated.

  An X-ray spectrometer that solves the above problems includes a substrate having a concave surface that is curved with the diameter of a Roland circle as a radius of curvature, the X-ray monochromator formed on the concave surface of the substrate, and the Roland circle. An X-ray source and an X-ray detector arranged on the circumference of

  An X-ray monochromator manufacturing method that solves the above problems includes a step of preparing a reaction liquid containing an organic substance and a precursor of an inorganic oxide, and a concave surface of a substrate that is curved with the diameter of a Roland circle as a radius of curvature. And a step of forming an organic-inorganic layered film using the reaction solution.

According to the present invention, it is possible to provide an X-ray monochromator having a good X-ray spectral performance and capable of being designed in a relatively small size, and a method for manufacturing the same.
Further, the present invention can provide an X-ray spectrometer using the above X-ray monochromator.

It is the schematic which shows an X-ray monochromator and an X-ray spectrometer. It is the schematic which shows the board | substrate used for an X-ray monochromator. It is the schematic which shows the board | substrate used by the Example and comparative example of this invention. It is the schematic which shows an example of the organic-inorganic layered film | membrane with which the organic substance and the inorganic oxide were laminated | stacked alternately in the X-ray monochromator of this invention.

Hereinafter, the present invention will be described in detail.
The X-ray monochromator according to the present invention is composed of an organic-inorganic layered film in which organic substances and inorganic oxides are alternately stacked, which are formed on the concave surface of a substrate having a concave surface curved with the diameter of a Roland circle as the radius of curvature. X-ray monochromator, wherein the incident angle of X-rays incident on the organic-inorganic layered film from the circumference of the Roland circle is 10 ° or more, and the maximum surface roughness of the organic-inorganic layered film is The height Ry is 100 nm or less, and the organic material and the inorganic oxide of the organic-inorganic layered film are alternately stacked with a structural period in the normal direction of the curved concave surface of the substrate. To do.

  The present invention will be described based on the X-ray monochromator and X-ray spectrometer shown in FIG. The X-ray monochromator 11 of the present invention is an organic-inorganic layered film in which organic substances and inorganic oxides are alternately stacked, which are formed on the concave surface of the substrate 18 having a concave surface curved with the diameter of the Roland circle as the radius of curvature. It is a configured X-ray monochromator. The organic-inorganic layered film of the X-ray monochromator has a structural period in the normal direction 19 of the concave surface of the substrate 18 (hereinafter referred to as a normal structural period). The Roland circle represents the circle 14 in FIG. That is, the X-ray source 12 such as a sample showing fluorescent X-rays, the X-ray detector 13 and the X-ray monochromator 11 are circles arranged on the circumference thereof.

  In FIG. 1, it can be seen that the smaller the incident angle θ, the larger the area where the incident X-ray 16 is irradiated to the X-ray monochromator. Therefore, when the incident angle θ of the X-ray is small, the diverging incident X-ray 16 is reflected by the X-ray monochromator 11 and the reflected X-ray 17 is collected by the X-ray detector 13 with a larger area. An X-ray monochromator must be used. Along with this, the diameter of the Roland circle must be increased. This means that the X-ray spectrometer using the X-ray monochromator becomes large.

  Therefore, the X-ray monochromator of the present invention is preferably designed so that the incident angle θ of incident X-rays is 10 ° or more. For this purpose, the area of the organic-inorganic layered film of the X-ray monochromator is reduced to a size capable of detecting X-rays incident at an angle of 10 ° or more, preferably 15 ° or more from the circumference of the Roland circle. Can do. By making X-rays incident at a wide angle of 10 ° or more, an X-ray monochromator that can be designed to be relatively small and an X-ray spectrometer using the X-ray monochromator can be provided.

  As will be described later, the organic-inorganic layered film can adjust the normal structure period by appropriately selecting an organic molecule or the like used as a precursor. Therefore, the normal structure period can be adjusted as appropriate according to the wavelength region of the target X-ray, and the X-ray incident angle θ can be designed to be 10 ° or more according to Equation 1.

  The organic-inorganic layered film in the present invention is a film having a structure in which inorganic oxides and organic substances are alternately stacked, and the stacking cycle is a normal structure cycle. These normal structure periods can be measured by θ-2θ scanning X-ray diffraction in a Bragg-Brentano configuration.

  FIG. 4 is a schematic view showing an example of an organic-inorganic layered film in which organic substances and inorganic oxides are alternately laminated in the X-ray monochromator of the present invention. In FIG. 4, reference numeral 41 denotes a substrate, 42 denotes an inorganic substance, 43 denotes an organic substance, and 44 denotes a structural period.

The thickness of the organic-inorganic layered film in the X-ray monochromator of the present invention is 50 nm to 1000 nm, preferably 100 nm to 600 nm.
The thickness of the normal structure period is 2 nm to 50 nm, preferably 3 nm to 20 nm.

  Moreover, the organic-inorganic layered film in the present invention is produced from a precursor reaction liquid through a chemical reaction, as will be described later. For this reason, the organic-inorganic layered film is produced by combining molecules or atoms, so that the crystallite size is large, and a uniform film is formed over the entire surface of the substrate. Therefore, the maximum height Ry of the surface roughness of the organic-inorganic layered film can be 100 nm or less, preferably 50 nm or less, and the X-ray spectral performance can be enhanced. The organic-inorganic layered film in the present invention is not a crystal in a strict sense, but is a crystalline film having a structural period, and hence the expression “crystallite” is used. Specifically, a crystallite is a local structure having crystallinity, and its size can be calculated by a Scherrer method in X-ray diffraction.

  The method for producing an X-ray monochromator according to the present invention includes a step of preparing a reaction liquid containing an organic substance and a precursor of an inorganic oxide, and the reaction liquid on a concave surface of a substrate that is curved with a diameter of a Roland circle as a radius of curvature. And a step of forming an organic-inorganic layered film using

  The X-ray monochromator manufacturing method according to the present invention includes a step of preparing a reaction solution containing an organic substance and a precursor of an inorganic oxide, and a concave surface of a substrate that is curved with the diameter of a Roland circle as a radius of curvature. It has the process of forming an organic-inorganic layered film | membrane using a reaction liquid, and the process of removing organic substance from the said organic-inorganic layered film | membrane.

  In the present invention, the organic-inorganic layered film can be produced using any conventionally known method. For example, a method of forming a film when a solution containing an organic surfactant, an inorganic oxide precursor, an acid, and a solvent is applied onto a substrate and the solvent evaporates can be used. Alternatively, a film can be formed by applying a reaction liquid containing an alkyl chain-containing siloxane oligomer or a silane coupling agent containing an organic moiety on a substrate. When the siloxane oligomer is used, it is possible to provide an X-ray monochromator having a narrower normal structure period distribution and good X-ray spectral performance.

  In the present invention, the organic-inorganic layered film is formed by applying the precursor liquid onto the substrate, whereby the film is formed by a relatively fast process. Therefore, the manufacturing time can be shortened and the X-ray can be produced at low cost. A monochromator can be provided. Furthermore, unlike the artificial multilayer film produced by the dry process, the organic-inorganic layered film in the present invention can be produced by the wet process as described above, and does not require precise control of the process, and is simple. An X-ray monochromator can be provided.

  In the present invention, examples of the inorganic oxide of the organic-inorganic layered film include silica, titania, zirconia, and the like. As long as reflected X-rays with sufficient intensity can be detected, it is preferable to use a material having a low electron density from the viewpoint of X-ray wavelength resolution. For example, the wavelength resolution of X-rays can be improved by using silica.

  Examples of the organic substance include amphiphilic molecules typified by surfactants, alkyl chain portions of siloxane oligomers, and the like. By appropriately selecting the organic substance to be used, the aggregate size of the organic substance in the film can be controlled, and the normal structure period of the film can be controlled. For example, when a nonionic surfactant having a hydrophilic part of polyethylene oxide is used as an organic molecule, the normal structure period of the film increases as the chain length of polyethylene oxide increases. That is, according to the wavelength region of X-rays to be dispersed, an appropriate organic molecule is appropriately selected, the normal structure period is adjusted, and an X-ray monochromator having an X-ray incident angle of 10 ° or more is manufactured. it can.

It is preferable that the organic-inorganic layered film has a structure in which an organic substance made of an alkyl chain and an inorganic oxide made of silica are alternately laminated.
In the present invention, the step of forming the organic-inorganic layered film is preferably a step of applying the reaction liquid to the concave surface of the substrate. Moreover, it is preferable that the said reaction liquid contains the precursor which consists of an organic inorganic oligomer or a silane coupling agent.

In the present invention, the material of the substrate is not particularly limited as long as it is not damaged in the film formation process. For example, glass or the like can be used.
In the present invention, the shape of the upper surface of the substrate is a concave surface curved with the diameter of the Roland circle as the radius of curvature. 2 is preferably a concave surface curved in the direction of the axis 24 in the cross-sectional direction in which the X-ray source 22 and the X-ray detector 21 are arranged. Furthermore, the X-ray can be detected with higher intensity by being curved also in the axis 25, that is, in the direction perpendicular to the cross section. The one formed on the concave surface curved only in the direction of the shaft 24 is called a cylindrical curved monochromator, and the one formed on the concave surface curved in the direction of the shaft 24 and the shaft 25 is called a spherical curved monochromator. .

  The upper surface of the substrate is a surface on which a film is formed, and surface treatment for improving the wettability of the reaction solution can be performed in order to produce a uniform and smooth film. For example, when a hydrophilic reaction solution is used, the organic substance on the surface can be removed by ozone ashing or the like to make the upper surface of the substrate hydrophilic.

Next, an X-ray spectrometer using the X-ray monochromator of the present invention will be described.
An X-ray spectrometer according to the present invention includes a substrate having a concave surface that is curved with the diameter of a Roland circle as a radius of curvature, the X-ray monochromator formed on the concave surface of the substrate, and a circle of the Roland circle. It has an X-ray source and an X-ray detector arranged on the circumference.

  In the X-ray spectrometer of the present invention, as shown in FIG. 1, an X-ray source, an X-ray detector, and an X-ray monochromator are arranged. By scanning the incident angle of the incident X-ray from the X-ray source and the reflection angle θ of the reflected X-ray to the X-ray detector, the X-ray having a wavelength corresponding to the Bragg condition (Equation 1) is converted to X Measured by line detector.

  When the wavelength of the X-ray is relatively long, it is also absorbed or scattered by a gas such as air in the spectroscopic device, depending on the optical path length of the X-ray. For this reason, it is preferable that the portion where the X-ray source, the X-ray detector, and the X-ray monochromator are disposed is covered with a chamber and the pressure is reduced as appropriate.

  According to the present invention, an organic material and an inorganic oxide, which are a material having a low electron density and can be smoothly formed, are alternately laminated on a substrate having a concave surface curved with the diameter of a Roland circle as a radius of curvature. An X-ray monochromator that has a good X-ray spectroscopic performance by forming an organic-inorganic layered film and that can enter X-rays at a wide angle of 10 ° or more and that can be designed in a relatively small size, and Can be provided.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to this.
In this example, a spherical curved monochromator with an organic-inorganic layered film in which organic layers and inorganic oxide layers are alternately stacked is prepared by applying a reaction solution onto a substrate, and its performance is examined. It is an example.

  First, a glass substrate (vertical 25 mm, width 25 mm, height 10 mm) having a curved concave surface shown in FIG. 3 is prepared. The concave surface of the substrate is curved in a spherical shape with a radius of curvature of 200 mm (diameter of a Roland circle) in two directions of an axis 31 and an axis 32. The glass substrate is cleaned with acetone, isopropyl alcohol, and pure water, and the surface is cleaned in an ozone apparatus.

  Next, an alkyl chain-containing siloxane oligomer that is a precursor of the layered film is synthesized. While dissolving 0.11 mol of decyltrichlorosilane in 250 mL of diethyl ether and stirring vigorously in an ice bath, a mixed solution of 350 mL of tetrahydrofuran, 365 mL of diethyl ether, 6.5 mL of pure water, and 33.0 mL of aniline is added dropwise. After stirring for 2 hours, the precipitate is removed by filtration, hexane is added to the filtrate and the solvent is evaporated to obtain a solid.

The solid is separated by suction filtration, washed thoroughly with cold acetone, and vacuum dried. When the solid after drying was dissolved in tetrahydrofuran and measured for ²⁹ Si NMR, it was found that the solid was an alkyl chain-containing siloxane oligomer having a structure of C ₁₀ H ₂₁ Si (OSi (OMe) ₃ ) _3. I can confirm.

  Next, siloxane oligomer, tetramethoxysilane, tetrahydrofuran, pure water, and hydrochloric acid are mixed and adjusted so that the molar ratio is 1: 2: 15: 14: 0.005 in order. The solid content is dissolved by stirring, and after 2.5 hours, tetrahydrofuran is added to adjust the molar ratio to 1: 2: 60: 14: 0.005.

  This solution is immersed in the reaction solution with the position of the surface 3R of the glass substrate shown in FIG. 3 facing down, pulled up from the position of the surface 3L at a speed of 2 mm per second, and the reaction solution is dip coated on the substrate. The substrate after dip coating is placed in a constant temperature and humidity chamber at 20 ° C. and a humidity of 40% and held for one day or more to produce an X-ray monochromator. The thickness of the formed film is 200 nm (average). When a part of the formed film is peeled off and observed with an electron microscope, it is confirmed by the electron microscope that a film having a layered structure is formed.

  Analysis of the produced X-ray monochromator by θ-2θ scanning X-ray diffraction measurement using an X-ray microbeam (3 μmφ, 8 keV) confirms that the normal structure period is 3.23 nm at each position of the film. it can. Further, the contact surface level difference meter shows that the surface roughness of the film is 50 nm at the maximum height Ry.

  Next, as shown in FIG. 1, an X-ray source 12 (X-ray fluorescence from a sample containing 30% carbon, 10% nitrogen and 60% hydrogen), an X-ray detector 13 and the produced X-ray monochromator 11 The X-ray spectroscope is manufactured by arranging the X-ray source 12 and the X-ray source in conjunction with each other on the circumference of a Roland circle having a radius of 100 mm. Cover the Roland circle with a vacuum chamber and measure under reduced pressure. When θ is scanned in the range of 15 ° to 45 °, an X-ray spectrum from a wavelength range of 1.67 nm to 4.56 nm can be measured, and the respective intrinsic X-rays of carbon and nitrogen are expressed as θ = 43.7 °. , And 29.3 °. Its spectral performance is 0.078 nm in half width.

(Comparative Example 1)
This comparative example is an example in which a spherical curved monochromator using synthetic mica is manufactured and its performance is examined.

  First, a glass substrate having a curved concave surface shown in FIG. 3 is prepared. The concave surface of the substrate is curved in a spherical shape with a radius of curvature of 200 mm (diameter of a Roland circle) in two directions of an axis 31 and an axis 32. The glass substrate is cleaned with acetone, isopropyl alcohol, and pure water, and the surface is cleaned in an ozone apparatus.

  Next, a coating solution to be applied to the substrate is adjusted. To 10 g of synthetic mica sodium teniolite, an aqueous solution of n-butylamine hydrochloride (0.4 M) is added to 50 mL and stirred for 2 hours. After washing with purified water several times and stirring, 200 mL of polyoxyethylene laurylamine hydrochloride aqueous solution (5 wt%) is added and ion exchange is performed for 24 hours. The resulting suspension is dewatered under reduced pressure with a Buchner funnel and washed several times with purified water. The washed product is dried at 80 ° C., then placed in benzene and dispersed with a homogenizer. This benzene suspension is applied onto the substrate, dried at room temperature, and then dried at 110 ° C.

  Analysis of the produced X-ray monochromator by θ-2θ scanning X-ray diffraction measurement using an X-ray microbeam (3 μmφ, 8 keV) confirms that the normal structure period is 3.48 nm at each position of the film. it can. Further, the contact surface level difference meter shows that the surface roughness of the film is 850 nm at the maximum height Ry.

  Next, as shown in FIG. 1, an X-ray source 12 (X-ray fluorescence from a sample containing 30% carbon, 10% nitrogen and 60% hydrogen), an X-ray detector 13 and the produced X-ray monochromator 11 The X-ray spectroscope is manufactured by arranging the X-ray source 12 and the X-ray source in conjunction with each other on the circumference of a Roland circle having a radius of 100 mm. Cover the Roland circle with a vacuum chamber and measure under reduced pressure. When θ is scanned in the range of 15 ° to 45 °, an X-ray spectrum from a wavelength range of 1.80 nm to 4.92 nm can be measured, and each intrinsic X-ray of carbon and nitrogen is expressed as θ = 40.0 °. , And 27.0 °. Its spectral performance is 0.12 nm in half width.

X-ray monochromator according to the present invention is relatively small in can designs, high X-ray performance, can be used for X-ray spectrometer.

11 X-ray monochromator 12 X-ray source 13 X-ray detector 14 Roland circle (center: A)
15 Circular arc with the radius of the Roland circle as the radius of curvature (center: B)
16 Incident X-ray 17 Reflected X-ray 18 Substrate

Claims (6)

X composed of an organic-inorganic layered film formed by alternately laminating an organic substance composed of an alkyl chain and an inorganic oxide composed of silica , which is formed on the concave surface of a substrate having a concave surface curved with the diameter of a Roland circle as a radius of curvature. A line monochromator, wherein an incident angle of X-rays incident on the organic-inorganic layered film from a circumference of a Roland circle is 10 ° or more, and a maximum surface roughness Ry of the organic-inorganic layered film X-ray, wherein the organic material and the inorganic oxide of the organic-inorganic layered film are alternately laminated with a structural period in the normal direction of the curved concave surface of the substrate Monochromator. A substrate having a concave surface for bending the diameter of the Rowland circle as the radius of curvature, is formed on the concave surface of the substrate, and the X-ray monochromator according to claim 1, which is arranged on the circumference of the Rowland circle An X-ray spectrometer comprising an X-ray source and an X-ray detector.   A step of preparing a reaction liquid containing an organic substance and a precursor of an inorganic oxide, and a step of forming an organic-inorganic layered film using the reaction liquid on a concave surface of a substrate that is curved with the diameter of a Roland circle as a radius of curvature. A method for manufacturing an X-ray monochromator, comprising: 4. The method of manufacturing an X-ray monochromator according to claim 3 , wherein the step of forming the organic-inorganic layered film is a step of applying the reaction liquid to the concave surface of the substrate. The method for producing an X-ray monochromator according to claim 3 or 4 , wherein the reaction solution contains a precursor composed of an organic inorganic oligomer or a silane coupling agent. The method for producing an X-ray monochromator according to claim 5, wherein the precursor is an alkyl chain-containing siloxane oligomer.

Images