JP2018129139A - X-ray transmission window member, x-ray detector, and method of manufacturing x-ray transmission window member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an X-ray transmission window member capable of improving X-ray transmittance while ensuring pressure resistance.SOLUTION: An X-ray transmission window member includes: a support frame 10 having an opening window; an X-ray transmission film 11 provided to close an opening window 10a; and a reinforcement pattern 12 being provided on a main surface S1 of the X-ray transmission film 11 and made of an organic material.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an X-ray transmission window member, an X-ray detector, and a method for manufacturing an X-ray transmission window member.

  In the analyzer using X-rays, an X-ray transmission window member that transmits X-rays is used as a partition member for isolating the X-ray detection element from the outside air or isolating the sample chamber from the reduced-pressure atmosphere. Yes.

  For example, in Patent Document 1 below, as a configuration for preventing breakage of an X-ray transmission window provided in a sample chamber in a vacuum vessel, a configuration in which a support that reinforces the X-ray transmission window is provided on the X-ray transmission window. X-ray transmissive window members are disclosed. The support protrudes in a lattice shape on the X-ray transmission window and is composed of, for example, Si, Au, Cr, Ti or the like.

  Patent Document 2 below relates to an X-ray transmission window using a beryllium foil having high X-ray transmittance and mechanical strength, and is heat-treated after an aluminum adhesive layer is vacuum-deposited on the beryllium foil. A configuration in which a treated adhesive layer is coated with a polyimide resin film is disclosed. With such a configuration, the adhesion between the beryllium foil and the resin film protecting the beryllium foil is improved.

JP-A-7-333399 JP-A-8-315759

  However, the X-ray transmission window member described above is desired to further improve the X-ray transmittance in order to improve the accuracy of X-ray analysis and the analysis speed.

  Therefore, the present invention provides an X-ray transmission window member capable of improving the X-ray transmittance while ensuring pressure resistance, an X-ray detector using the X-ray transmission window member, and an X-ray transmission window member It aims at providing the manufacturing method of.

  In order to achieve such an object, the present invention provides a support frame having an opening window, an X-ray transmission film provided by closing the opening window, and an organic film provided on the main surface of the X-ray transmission film. An X-ray transmission window member provided with a reinforcing pattern made of a material. Moreover, this invention is also an X-ray detector provided with the X-ray transmissive window member of such a structure, and a manufacturing method of such an X-ray transmissive window member.

  According to the present invention configured as described above, an X-ray transmission window member capable of improving the X-ray transmittance while ensuring pressure resistance, and an X-ray detector using the X-ray transmission window member And the manufacturing method of an X-ray transmissive window member can be provided.

It is a top view of the X-ray transmissive window member of 1st Embodiment. It is sectional drawing of the X-ray transmissive window member of 1st Embodiment. It is a top view which shows the modification 1 of 1st Embodiment. It is a top view which shows the modification 2 of 1st Embodiment. It is a graph which shows the relationship between the opening width of the transmission window part in a X-ray transmission window member, and the pressure difference at the time of destruction. It is sectional process drawing which shows the manufacturing method of the X-ray transmissive window member of 1st Embodiment. It is a figure explaining formation of the reinforcement pattern by the inkjet method. It is a graph for demonstrating the effect of the X-ray transmissive window member of 1st Embodiment. It is sectional drawing of the X-ray transmissive window member of 2nd Embodiment. It is a top view which shows the modification of 2nd Embodiment. It is sectional drawing which shows the modification of 2nd Embodiment. It is a block diagram of the X-ray detector of 3rd Embodiment.

Hereinafter, embodiments of the present disclosure will be described in the following order based on the drawings.
1. 1st Embodiment (X-ray transmissive window member which provided the reinforcement pattern in the one main surface side)
2. Second embodiment (X-ray transmission window member provided with reinforcing patterns on both sides)
3. Third Embodiment (X-ray detector provided with an X transmission window member)
In addition, the same code | symbol is attached | subjected to the same component in each embodiment and modification, and the overlapping description is abbreviate | omitted.

<< First Embodiment >>
FIG. 1 is a plan view of the X-ray transmissive window member of the first embodiment. FIG. 2 is a cross-sectional view of the X-ray transmissive window member of the first embodiment, and is a view corresponding to the AA cross section of FIG.

  The X-ray transmissive window member 1 shown in these drawings is used, for example, for isolating the X-ray detection element from the outside air, or for isolating the sample chamber for storing the sample to be analyzed in the X-ray analysis from the reduced-pressure atmosphere. It is used as a partition member. The X-ray transmission window member 1 includes a support frame 10, an X-ray transmission film 11, a reinforcing pattern 12, a mask film 13, a visible light shielding film 14 (shown only in FIG. 2), and a flange 15. Hereinafter, the structure of each of these members constituting the X-ray transmissive window member 1 will be described, and then the method for manufacturing the X-ray transmissive window member 1 will be described.

<Support frame 10>
The support frame 10 is a frame having an opening window 10a in the center, and supports an X-ray transmissive film 11 described below. The support frame 10 may be made of any material as long as it has an atmospheric pressure strength sufficient to withstand normal use, but is made of a material having a high etching selectivity with respect to the X-ray transmission film 11. Is preferred. As an example, when the X-ray transmissive film 11 described below is made of silicon nitride (SiN), the support frame 10 is made of a silicon substrate.

  Although the opening shape of the opening window 10a is not limited, the planar shape is assumed to be a substantially square as an example. Further, the side wall of the opening window 10 a has a tapered shape in which the opening diameter decreases toward the X-ray transmission film 11. The opening window 10a as described above has such a size that a necessary amount of X-ray transmission can be obtained, and is approximately 10 mm × 10 mm, for example, at a position where the opening width between opposing sides having a substantially square shape is substantially square. Suppose that

<X-ray permeable membrane 11>
The X-ray transmission film 11 is a film made of a material that transmits X-rays, and is provided on one main surface of the support frame 10 so as to close the opening window 10 a of the support frame 10. As such an X-ray transmissive film 11, a metal material such as silicon nitride (SiN), silicon carbide (SiC), thin film graphite, diamond, ceramic, and metal beryllium, and a polymer material are used. Among these, amorphous silicon nitride is preferably used from the viewpoint of radiation resistance, mechanical strength, and chemical stability by X-ray irradiation.

  The film thickness of the X-ray transmission film 11 is set in a range where a sufficiently large X-ray transmittance can be obtained by the energy of X-rays transmitted through the X-ray transmission film 11. For example, when the X-ray transmission window member 1 is provided in an X-ray detector, the film thickness of the X-ray transmission film 11 made of silicon nitride is about 50 nm.

<Reinforcement pattern 12>
The reinforcing pattern 12 is for preventing the X-ray permeable film 11 from being damaged by a pressure difference applied to both surfaces of the X-ray permeable film 11, and is provided on the main surface of the X-ray permeable film 11. In particular, the reinforcing pattern 12 is made of an organic material, and is provided on one main surface S <b> 1 of the X-ray transmission film 11. Here, as an example, a configuration in which the reinforcing pattern 12 is provided on one main surface S1 of the X-ray permeable membrane 11 toward the support frame 10 side is illustrated. However, the reinforcing pattern 12 is the X-ray permeable membrane 11. Of the main surfaces on both sides, it is preferably provided on one main surface S1 on the negative pressure side. Therefore, the reinforcing pattern 12 may be provided on the main surface opposite to the support frame 10 side of the X-ray permeable membrane 11.

[Material of reinforcing pattern 12]
The reinforcing pattern 12 as described above is made of an organic material, thereby preventing the X-ray transmission from being impaired. The organic material constituting the reinforcing pattern 12 is appropriately selected and used from among organic materials excellent in radiation resistance, mechanical strength, and chemical stability by X-ray irradiation, and in particular, a polymer organic material is used. It is done. An example of such an organic material is polyimide.

[Layout Structure of Reinforcement Pattern 12]
The layout structure of the reinforcing pattern 12 is preferably a lattice-like network structure on one main surface S1 of the X-ray transmissive film 11. Such reinforcing patterns 12 are arranged in a plurality of rows (here 5 rows) / a plurality of columns (here 5 columns) along the side wall of the opening window 10a having a substantially square shape, for example. The interval of 12 is assumed to be uniform. In addition, the reinforcement patterns 12 of the plurality of columns / rows are arranged so that both end portions thereof reach the side wall of the opening window 10a of the support frame 10 and overlap the tapered side wall. Moreover, in the position where the reinforcement pattern 12 of several rows and the reinforcement pattern 12 of several rows overlap, these reinforcement patterns 12 may be in the laminated | stacked state.

  Thereby, in the inner periphery of the opening window 10a, the X-ray transmission film 11 is partitioned into a plurality of transmission window portions 11a by the reinforcing pattern 12. Here, each divided transmission window portion 11a has a substantially square shape in plan view.

  FIG. 3 is a plan view showing Modification 1 of the first embodiment. As shown in FIG. 3, the layout structure of the reinforcement pattern 12 in the X-ray transmission window member 1a may be a configuration in which the reinforcement patterns 12 are arranged in a plurality of rows / columns so that the transmission window portion 11a is rectangular. Good. In the case of the rectangular transmission window portion 11a, the peripheral length with respect to the area of the transmission window portion 11a is larger than that of the substantially square transmission window portion 11a as shown in FIG. 1, and the pressure resistance of each transmission window portion 11a is increased. Is improved.

  FIG. 4 is a plan view showing a second modification of the first embodiment. As shown in FIG. 4, the layout structure of the reinforcing pattern 12 in the X-ray transmissive window member 1b may be a honeycomb structure. In this case, each transmission window portion 11a partitioned by the reinforcing pattern 12 has a regular hexagonal planar shape, and the strength of the reinforcing pattern 12 itself can be obtained. Moreover, the corner | angular part of the periphery of each permeation | transmission window part 11a becomes a more obtuse angle, and it becomes difficult to apply a stress to a corner | angular part, As a result, the improvement of the pressure | voltage resistance of each permeation | transmission window part 11a is achieved.

  In addition to Modification 1 and Modification 2 described above, the layout structure of the reinforcing pattern 12 may be concentric or other than the mesh structure, or may be a mesh structure combining these. It may be another structure.

[Opening width of reinforcing pattern 12]
The opening width of the reinforcing pattern 12, that is, the opening width of each transmission window portion 11 a partitioned by the reinforcing pattern 12 is, for example, horizontal opening when the layout of the reinforcing pattern 12 is the lattice-like mesh structure shown in FIGS. The width [Dh] and the vertical opening width [Dv]. In the case of the honeycomb structure shown in FIG. 4, the distance between diagonals, the distance between opposite sides, or the average distance thereof. Such an opening width is determined by pressure resistance required for each transmission window portion 11 a partitioned by the reinforcing pattern 12.

  For example, when the X-ray transmissive window member 1 is provided in an X-ray detector, the X-ray transmissive window member 1 is applied with an atmospheric pressure of 1 atmosphere or more. For this reason, each transmission window portion 11a is required to have a pressure resistance of 2.5 atm or more. Therefore, for the opening width of the transmission window portion 11a, for example, a pressure resistance simulation required when the opening width of the transmission window portion 11a is changed or a preliminary test is performed, and a required pressure resistance is obtained based on the result. It shall be set to a value.

  FIG. 5 is a graph showing the relationship between the opening width of the transmission window portion 11a in the X-ray transmission window member 1 and the pressure difference at break. This graph shows that when the transmission window portion 11a is broken by pressing the X-ray transmission film 11 from the side where the reinforcing pattern 12 is not provided for the transmission window portion 11a having a substantially square planar shape shown in FIG. The result of having actually measured the pressure difference of both sides of the X-ray permeable membrane 11 as the pressure difference at the time of destruction is shown. The pressing speed was about 0.2 atm / second. The horizontal axis of the graph is the average value of the horizontal opening width [Dh] (= vertical opening width [Dv]) of the transmission window portion 11a, and the vertical axis of the graph is the pressure difference at break.

  From this graph, it can be seen that pressure resistance of a pressure difference of 2.5 atm or more is obtained when the horizontal opening width [Dh] (= vertical opening width [Dv]) of the transmission window portion 11a is 600 μm or less. If the pressure resistance of 2.5 atm to 4.0 atm is required for each transmission window portion 11a, the horizontal opening width [Dh] (= vertical opening width [Dv]) of each transmission window portion 11a is , 220 μm or more and 600 μm or less.

[Pattern width of reinforcing pattern 12]
The pattern width of the reinforcing pattern 12 is, for example, the horizontal pattern width [Wh] and the vertical pattern width [Wv] when the layout of the reinforcing pattern 12 is the lattice-like mesh structure shown in FIGS. In the case of the honeycomb structure shown in FIG. 4, it may have a single pattern width [W]. Such a pattern width is set in a range in which each transmission window portion 11a of the X-ray transmission film 11 can have an opening width that can maintain a desired pressure resistance, and in a range that satisfies a required aperture ratio of the transmission window portion 11a. Is done. Here, the aperture ratio of the transmission window portion 11a is the total of the opening area of the transmission window portion 11a with respect to the opening area of the opening window 10a, and is set to 70% or more, for example. And the pattern width of the reinforcement pattern 12 set so that the opening width and opening ratio of such a transmission window part 11a may be satisfy | filled the range of about 1 micrometer or more and 100 micrometers or less.

[Height of reinforcing pattern 12]
The height [H] of the reinforcing pattern 12 is a value determined by the material and the pattern width of the reinforcing pattern 12, and may be any value as long as the pressure resistance required for the reinforcing pattern 12 is obtained. Here, the pressure resistance required for the reinforcing pattern 12 is approximately the same as the pressure resistance required for each transmission window portion 11a, for example, 2.5 atm or more.

  The pattern height [H] of the reinforcing pattern 12 is set in a range of approximately 10 μm to 300 μm. As an example, if the reinforcing pattern 12 is made of polyimide and has a pattern width of 40 μm, the height is set to about 50 μm.

<Mask film 13>
The mask film 13 is a film that becomes an etching mask in etching when the opening window 10 a is formed in the support frame 10. Such a mask film 13 may be made of the same material as that of the X-ray transmission film 11, and is configured using silicon nitride (SiN) when the support frame 10 is configured using a silicon substrate. .

<Visible light shielding film 14>
The visible light shielding film 14 is a film for preventing mixing of noise due to light in the visible light region. Such a visible light shielding film 14 is made of a material having a property of shielding light in the visible light region among materials that transmit X-rays, and is made of a metal material such as aluminum. The visible light shielding film 14 made of a metal material is formed on the transmission window portion 11a in a state of closing the opening window 10a of the support frame 10 by a film forming method such as a sputtering method. The visible light shielding film 14 may be provided as necessary, may be provided so as to cover the reinforcing pattern 12 as illustrated, or may be provided on the opposite surface.

<Flange 15>
The flange 15 is a member for attaching the X-ray transmissive window member 1 to an apparatus main body such as an X-ray detector, and is provided in a state where the support frame 10 is held and printed. It has a screw hole and so on. The flange 15 may be made of any material as long as it has an atmospheric pressure strength sufficient to withstand normal use, and is made of silicon, ceramic, metal, plastic, resin, or the like.

<The manufacturing method of the X-ray transmissive window member 1>
FIG. 6 is a cross-sectional process diagram illustrating the method for manufacturing the X-ray transmissive window member of the first embodiment described above. Hereinafter, the manufacturing method of the X-ray transmissive window member 1 will be described with reference to FIG.

  First, as shown in FIG. 6A, the X-ray transmission film 11 is formed on one surface of the substrate 100, and the mask film 13 is formed on the other surface. For example, a silicon substrate is used as the substrate 100, and an X-ray transmissive film 11 made of silicon nitride having a predetermined thickness is formed on one main surface by a CVD method. On the other main surface of the substrate 100, a mask film 13 made of silicon nitride having a predetermined film thickness necessary as an etching mask is formed by a CVD method.

  Next, as shown in FIG. 6B, a resist pattern 101 is formed on the mask film 13 by lithography. At this time, the resist pattern 101 is formed in a planar shape that covers the periphery of the substrate 100 and has a rectangular opening at the center. Thereafter, the shape of the resist pattern 101 is transferred to the mask film 13 by etching the mask film 13 using the resist pattern 101 as a mask.

  Thereafter, in the X-ray transmission film 11, a protective film 102 is formed on the main surface opposite to the support frame 10 as necessary. The protective film 102 is made of, for example, a coating agent or resist having resistance to an alkaline etching solution, and is formed by a spin coating method.

  Next, as shown in FIG. 6C, the substrate 100 is etched using the resist pattern 101 and the mask film 13 as a mask to expose the X-ray transmissive film 11 on the bottom surface of the etching. Etching may be wet etching or dry etching as long as it is isotropic. Thereby, the support frame 10 provided with the opening window 10a having a side wall taper shape and a rectangular planar shape is formed in the central portion of the substrate 100. Then, the opening window 10a of the support frame 10 is closed with the X-ray transmission film 11, and the X-ray transmission film 11 on the inner periphery of the opening window 10a is a single self-supporting film. In the etching of the substrate 100, the resist pattern 101 serving as a mask is removed by etching at an initial stage, and thereafter, the etching of the substrate 100 proceeds using the mask film 13 as a mask.

  Next, the adhesion between the X-ray transmissive film 11 and the reinforcement pattern to be formed next is improved with respect to one main surface S1 of the X-ray transmissive film 11 exposed inside the opening window 10a of the support frame 10. For the pre-processing. This pretreatment is, for example, a treatment in which a silane coupling agent is applied on one main surface S1 of the X-ray transmission film 11 and dried. By this pretreatment, one main surface S1 of the X-ray permeable film 11 is made an adhesion improving layer 10 '.

  Next, as shown in FIG. 6 (d), a reinforcing pattern made of an organic material is formed on one main surface S1 of the X-ray transmissive film 11 exposed on the inner periphery of the opening window 10a of the support frame 10 by a printing method. 12 are laminated by a bottom-up method. An ink jet method is preferably applied to the formation of the reinforcing pattern 12 by such a printing method.

  FIG. 7 is a diagram illustrating the formation of a reinforcing pattern by the ink jet method. As shown in this figure, in the formation of the reinforcing pattern by the ink jet method, the uncured organic material 104 is continuously ejected from the ink jet nozzle 103 onto one main surface S1 of the X-ray transmission film 11. At this time, the ink jet nozzle 103 having a discharge diameter [r] of 1 μm or less can form a reinforcing pattern having a pattern width in the range of approximately 1 μm to 100 μm as described above. In the case of forming the reinforcing pattern 12 made of polyimide, the ink jet nozzle 103 is made to discharge a polyimide varnish obtained by dissolving a polyimide precursor in an organic solvent as an ink.

  At this time, the tip of the inkjet nozzle 103 is moved relative to the main surface S1 of the X-ray transmission film 11, and the main surface of the X-ray transmission film 11 whose surface is covered with the adhesion improving layer 10 ′. An uncured organic material layer 104a is formed on the surface S1. The relative movement of the inkjet nozzle 103 is performed along the layout of the reinforcing pattern to be formed. Then, by controlling the relative movement of the inkjet nozzle 103, the material layer 104a is stacked in a plurality of layers so as to have a height necessary for the reinforcing pattern. For example, in the case of forming a reinforcing pattern having a height of 40 μm, the material layer 104a is laminated in a plurality of layers at a height of about 80 μm, which is higher than this. Each material layer 104a is preferably formed continuously until the side wall of the opening window 10a in the support frame 10 is reached. As a result, the height [H] of the reinforcing pattern 12 partially increases at the position where the reinforcing patterns 12 intersect, but the strength of the reinforcing pattern 12 can be ensured.

  As described above, after the uncured organic material layer 104a is stacked at a required height along the layout of the reinforcing pattern 12 by the ink jet method, the material layer 104a is cured. Here, for example, when polyimide is used as the organic material, pre-baking is performed at 90 ° C. for 1 hour as a curing process, and then post-baking is performed at 400 ° C. for 1 hour. As a result, as shown in FIG. 6D, the reinforcing pattern 12 made of an organic material and having a predetermined pattern width and height [H] is formed in a predetermined layout structure.

  Thereafter, as shown in FIG. 6E, the protective film 102 is removed by etching. Next, if necessary, a visible light shielding film 14 made of, for example, aluminum is formed in a state of covering the reinforcing pattern 12 by a sputtering method.

  As described above, the X-ray transmission window member 1 described with reference to FIGS. 1 and 2 is manufactured. Moreover, the manufacturing method of X-ray transmissive window member 1a, 1b demonstrated using FIG. 3 and FIG. 4 is implemented similarly to the above.

<Effects of First Embodiment>
The X-ray transmissive window member 1 of the first embodiment described above (including the X-ray transmissive window members 1a and 1b of Modifications 1 and 2) is made of an organic material on one principal surface S1 of the X-ray transmissive film 11. This is a configuration in which the configured reinforcing pattern 12 is provided. The X-ray transmission window member 1 having such a configuration has a configuration in which X-rays also pass through the reinforcing pattern 12 made of an organic material, and can improve the X-ray transmittance while maintaining pressure resistance. Become. In addition, compared to conventional silicon reinforcing grids, it is possible to prevent the constituent material of the reinforcing pattern 12 from being excited by X-rays and emitting noise wavelength components.

  Further, by forming the reinforcing pattern 12 by a bottom-up method by a printing method, a fine reinforcing pattern 12 made of an organic material can be easily formed with high accuracy as compared with, for example, an LB film formed by self-assembly. It is possible. In addition, since the reinforcing pattern 12 can be formed without applying excessive stress to the X-ray transmissive film 11 serving as the base, the reinforcing pattern 12 is not damaged without damaging the X-ray transmissive film 11 serving as a self-supporting film. Can be formed.

  FIG. 8 is a graph for explaining the effect of the X-ray transmission window member of the first embodiment. This graph is a diagram showing the result of simulating the relationship of the X-ray transmittance with respect to the incident X-ray energy for each of the X-ray transmissive window members of (1) to (3). The horizontal axis is the incident X-ray energy, and the vertical axis is the X-ray transmittance.

  The X-ray transmission window member of (1) to (3) has a silicon nitride film with a film thickness of 50 nm as an X-ray transmission film, and the aperture ratio of the reinforcement pattern is 76%. As the pressure resistance, a pressure difference at break of 2.5 atm or more is secured.

  Among these, (1) is a result of the X-ray transmissive window member of the first embodiment described above, and the reinforcing pattern is polyimide having a height of 40 μm. (2) is the result of the X-ray transmissive window member of Comparative Example 1, and the reinforcing pattern is silicon having a height of 15 μm. (3) is a result of the X-ray transmissive window member of Comparative Example 2, and the reinforcing pattern is silicon having a height of 200 μm.

  From the results shown in FIG. 8, the X-ray transmissive window member provided with the reinforcing pattern made of the organic material of the first embodiment of (1) is 3 keV to 10 keV as compared with those of (2) and (3). The effect of increasing the X-ray transmittance in the high energy region was confirmed.

<< Second Embodiment >>
FIG. 9 is a cross-sectional view of the X-ray transmissive window member of the second embodiment. The X-ray transmissive window member 2 of the second embodiment shown in this figure is different from the X-ray transmissive window member 1 of the first embodiment in that a reinforcing pattern made of an organic material on both sides of the X-ray transmissive film 11 12 and 12 'are provided. Other configurations include the constituent materials of the reinforcing patterns 12 and 12 ′, and are the same as the X-ray transmissive window member 1 of the first embodiment. Therefore, the layout structure of the reinforcing patterns 12, 12 ′ will be mainly described below.

<Reinforcement pattern 12>
The reinforcing pattern 12 is the same as the reinforcing pattern of the first embodiment, and is provided on one main surface S1 of the X-ray permeable membrane 11 toward the support frame 10 side. The layout structure of the reinforcing pattern 12 may be the same as that of any one of the first embodiment shown in FIG. 1, the first modification shown in FIG. 3, and the second modification shown in FIG. The reinforcing pattern 12 may be covered with the visible light shielding film 14 as necessary, as in the first embodiment.

<Reinforcement pattern 12 '>
The reinforcing pattern 12 ′ is provided on the other main surface S 2 of the X-ray permeable membrane 11. The layout structure of the reinforcing pattern 12 ′ may be the same as that of the reinforcing pattern 12, and is disposed so as to overlap the reinforcing pattern 12 with the X-ray transmissive film 11 interposed therebetween. In addition, when providing the visible light shielding film 14 as needed, this visible light shielding film 14 may be provided in a state of covering the reinforcing pattern 12 ′, or may cover both of the reinforcing patterns 12 and 12 ′. May be.

  FIG. 10 is a plan view showing a modification of the second embodiment. FIG. 11 is a cross-sectional view showing a modification of the second embodiment, corresponding to the AA cross section of FIG. 10 and FIG. 11, the X-ray transmissive window member 2a may be provided with the reinforcing patterns 12, 12 ′ on both surfaces of the X-ray transmissive film 11 being shifted from each other in plan view. . In this case, as shown in FIG. 10, the layout structure of the reinforcement patterns 12 and 12 ′ is configured such that the same layout structure is shifted as it is in plan view, so that the arrangement state of the reinforcement patterns 12 and 12 ′ is uniform. However, the present invention is not limited to this. For example, the layout structure of the reinforcing pattern 12 ′ has a configuration in which a plurality of rows / columns of reinforcing patterns 12 provided on the one principal surface S 1 side are thinned out every other line, or the reinforcing pattern of the layout structure of FIG. 12 may be combined with a reinforcing pattern 12 ′ having another layout structure, for example, the layout structure of FIG.

<The manufacturing method of the X-ray transmissive window member 2>
The manufacturing method of the X-ray transmissive window member 2 having such a configuration will be described with reference to FIG. 6D before and after any of the manufacturing procedures of the first embodiment described with reference to FIG. What is necessary is just to implement formation of reinforcement pattern 12 'by the inkjet method demonstrated using FIG.

<Effects of Second Embodiment>
According to the second embodiment described above (including modifications), the same effect as that of the first embodiment is obtained by providing the reinforcing patterns 12 and 12 ′ made of an organic material on both surfaces of the X-ray transmission film 11. Can be obtained. Further, since the heights [H] and [H ′] of the respective reinforcing patterns 12 and 12 ′ can be reduced, the pattern collapse of the reinforcing patterns 12 and 12 ′ hardly occurs, and pattern formation is easy.

«Third embodiment»
FIG. 12 is a configuration diagram of the X-ray detector of the third embodiment. An X-ray detector 3 shown in this figure is an energy dispersive detector mounted on, for example, an electron microscope or an analyzer using an electron beam. The X-ray detector 3 shown in FIG. Is characteristically provided with any of the X-ray transmission window members of the second embodiment and its modification. Here, as an example, the X-ray detector 3 will be described as including the X-ray transmission window member 1 of the first embodiment.

  The X-ray detector 3 includes, in order from the X-ray capturing direction, a magnet collimator 31, a case 32 having the X-ray transmission window member 1, an X-ray detection element 33 and a heat transfer unit housed in the case 32. 34, a detector body 35, a signal transmission unit 36, and a signal amplification processing unit 37.

  The housing 32 provided with the X-ray transmission window member 1 is configured as a cylindrical chamber whose inside is kept airtight, and is provided coaxially with the aperture 31 a provided in the magnet collimator 31. In such a casing 32, the X-ray transmission window member 1 is disposed on the bottom surface on the magnet collimator 31 side so as to face the aperture hole 31 a, and the X-ray transmission window member 1 allows one of the cylindrical casings 32 to be disposed. The bottom is sealed. From the viewpoint of ensuring the pressure resistance of the transmission window, the X-ray transmission window member 1 may be provided on the bottom surface of the casing 32 so that the reinforcing pattern is disposed toward the inside of the casing 32 that is at a negative pressure. preferable. The X-ray transmission window member 2 shown in FIGS. 9 to 11 is not limited to this because the reinforcing patterns 12 and 12 ′ are provided on both surfaces of the X-ray transmission film 11.

  The X-ray detection element 33 is disposed inside the housing 32 so as to face the X-ray transmission window member 1 and is cooled by a cooling element. The heat transfer section 34 is arranged so as to be drawn from the cooling element provided in the X-ray detection element 33 to the detector body 35 along the cylindrical casing 32. Further, a signal transmission unit 36 and a signal amplification processing unit 37 that processes a signal transmitted from the signal transmission unit 36 are arranged at the subsequent stage of the detector body 35.

  In the X-ray detector 3 having the above-described configuration, in order to prevent condensation of the cooled X-ray detection element 33 and maintain sensitivity, the internal environment of the housing 32 is isolated from the external environment to a constant vacuum environment. It has a configuration that can be maintained. On the other hand, a change in atmospheric pressure occurs outside the housing 32 due to, for example, taking a sample to be analyzed into and out of the analyzer. For this reason, in the X-ray transmissive window member 1 constituting the bottom surface of the housing 32, the external environment side of the housing 32 becomes positive pressure and the internal environment side of the housing 32 becomes negative pressure due to a change in atmospheric pressure of the external environment. Pressure is applied.

<Effect of the third embodiment>
The X-ray detector 3 of the third embodiment as described above has a configuration in which the bottom surface of the housing 32 provided with the X-ray detection element 33 is closed by the X-ray transmission window member 1 of the first embodiment. As described in the effect of the first embodiment, the X-ray transmissive window member 1 is intended to improve the X-ray transmittance while ensuring the pressure resistance. Therefore, in the X-ray detector 3 using such an X-ray transmission window member 1, the sensitivity is improved by improving the X-ray transmittance, the analysis accuracy is improved in the qualitative analysis and the quantitative analysis, and the analysis speed is further improved. It is possible to increase the speed.

  Moreover, the X-ray detector 3 is replaced with the X-ray transmissive window member 1 of 1st Embodiment, the modification 1 of the 1st Embodiment shown in FIG.3 and FIG.4, Modification 2, Furthermore, FIGS. Even when the X-ray transmissive window member of any one of the second embodiment shown in FIG. 10 and its modification is used, the same effect can be obtained.

  In the above third embodiment, as an example of an apparatus provided with an X-ray transmission window member, an X-ray having a configuration in which a casing 32 in which an X-ray detection element 33 is accommodated is sealed with an X-ray transmission window member. The detector 3 has been described. However, the X-ray transmissive window member described above is not limited to such application, and can be widely applied as an X-ray transmissive window member disposed in a portion where a pressure difference occurs. As an example, the X-ray transmission window member of each of the above-described embodiments and modifications can be used as the X-ray transmission window member provided in the sample chamber in the vacuum vessel in the X-ray analyzer, and the same effect can be obtained. Can be obtained.

DESCRIPTION OF SYMBOLS 1, 1a, 1b, 2, 2a ... X-ray transmissive window member 3 ... X-ray detector 10 ... Support frame 10a ... Opening window 11 ... X-ray permeable film 12, 12 '... Reinforcement pattern 100 ... Substrate

Claims (11)

A support frame having an open window;
An X-ray permeable membrane provided to close the opening window;
An X-ray transmission window member, comprising: a reinforcing pattern made of an organic material provided on a main surface of the X-ray transmission film. The X-ray transmissive window member according to claim 1, wherein the organic material is polyimide. The X-ray transmissive window member according to claim 1, wherein the reinforcing pattern has a mesh structure. The X-ray transmissive window member according to claim 1, wherein the reinforcing pattern has a honeycomb structure. The X-ray transmission window member according to any one of claims 1 to 4, wherein the reinforcing pattern is provided on main surfaces on both sides of the X-ray transmission film. The reinforcing pattern provided on one main surface of the X-ray permeable membrane and the reinforcing pattern provided on the other main surface of the X-ray permeable membrane are provided so as to be shifted in plan view. Item 6. The X-ray transmissive window member according to Item 5. An X-ray detector comprising the X-ray transmission window member according to any one of claims 1 to 6. Forming an X-ray transmission film on one main surface of the substrate;
Forming a support frame having an opening window by pattern etching the substrate, and closing the opening window with the X-ray transmission film;
Forming a reinforcing pattern made of an organic material by a printing method on a main surface of the X-ray transmissive film. The step of forming the reinforcing pattern includes:
The method for manufacturing an X-ray transmissive window member according to claim 8, wherein after the support frame is formed, the reinforcing pattern is formed on an inner periphery of an opening window of the support frame. The step of forming the reinforcing pattern includes:
The method for manufacturing an X-ray transmissive window member according to claim 8 or 9, wherein the reinforcing pattern is formed by an inkjet method. Before the step of forming the reinforcing pattern, a step of pretreating the main surface of the X-ray permeable membrane using a silane coupling agent is performed.
The X-ray transmission according to any one of claims 8 to 10, wherein, in the step of forming the reinforcement pattern, the reinforcement pattern is formed on the pretreated main surface of the main surface of the X-ray transmission film. The manufacturing method of a window member.

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