Sample support

Abstract

The sample support body comprises: a substrate having a plurality of through holes opening on a first surface and a second surface; a first component having a plurality of first openings and arranged on the first surface; a second component having a plurality of second openings corresponding to the plurality of first openings in the thickness direction of the substrate and arranged on the second surface; an adhesive component arranged between the first component and the second component and bonding at least one of the first component and the second component to the substrate; and a conductive layer integrally provided on areas of the second surface corresponding to the plurality of second openings, a surface of the second component on the opposite side to the substrate, and inner surfaces of the plurality of second openings, wherein the plurality of through holes include: a plurality of first through holes located between each of the plurality of first openings and each of the plurality of second openings; and a plurality of second through holes located between the first component and the second component, wherein the plurality of second openings are connected to the plurality of first openings via the plurality of first through holes.

Description

Technical Field

[0001] The present disclosure relates to a sample support. Background Art

[0002] As a sample support for ionizing a component of a sample, there is known a sample support comprising: a substrate having a first surface, a second surface opposite to the first surface, and a plurality of through holes opened on the first surface and the second surface; a base bonded to the first surface of the substrate; and a conductive layer provided on the second surface of the substrate, with a plurality of openings formed on the base (for example, see Patent Document 1). In such a sample support, a plurality of regions corresponding to the plurality of openings in the substrate can be used as measurement regions.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent No. 6539801 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] In the case of manufacturing the sample support as described above, when bonding the first surface of the substrate and the base, if the adhesive component before curing reaches the second surface of the substrate through the through hole of the substrate, when the conductive layer is provided on the second surface of the substrate, outgassing is generated from the conductive layer and the adhesive component, and a mixed layer caused by the outgassing may be deposited on the substrate. If the mixed layer is deposited on the substrate, noise caused by the mixed layer may be generated in mass analysis.

[0008] Therefore, an object of the present disclosure is to provide a sample support capable of performing high-precision mass analysis.

[0009] Means for solving technical problems

[0010] The sample support disclosed in the present invention is a sample support for ionizing components of a sample, and comprises: a substrate having a first surface, a second surface on the opposite side of the first surface, and a plurality of through holes opening on the first surface and the second surface; a first component having a plurality of first openings and arranged on the first surface; a second component having a plurality of second openings corresponding to the plurality of first openings in the thickness direction of the substrate and arranged on the second surface; an adhesive component arranged between the first component and the second component to adhere at least one of the first component and the second component to the substrate; and a conductive layer integrally provided on areas of the second surface corresponding to the plurality of second openings, a surface of the second component on the opposite side of the substrate, and an inner surface of each of the plurality of second openings, the plurality of through holes comprising: a plurality of first through holes located between each of the plurality of first openings and each of the plurality of second openings; and a plurality of second through holes located between the first component and the second component, the plurality of second openings being connected to the plurality of first openings via the plurality of first through holes.

[0011] In the sample support, the plurality of second openings of the second component are connected to the plurality of first openings of the first component via the plurality of first through holes of the substrate. Thus, the plurality of regions corresponding to the plurality of second openings in the substrate can be used as measurement regions. Here, in the case of manufacturing the sample support, the substrate, the first component and the second component can be unitized using an adhesive component, and then a conductive layer is set from the second component side. Thus, when the conductive layer is set from the second component side, since the adhesive component is arranged between the first component and the second component, it is difficult to generate outgassing from the conductive layer and the adhesive component, and as a result, the mixed layer caused by the outgassing can be suppressed from being accumulated on the substrate. Therefore, according to the sample support, high-precision mass analysis can be performed.

[0012] In the sample support disclosed in the present invention, the adhesive component can also be arranged in the plurality of second through holes. According to this structure, when the plurality of areas corresponding to the plurality of second openings in the substrate are respectively used as measurement areas, the plurality of measurement areas are respectively isolated by the adhesive component. Therefore, when the sample is respectively arranged in the plurality of measurement areas, the movement of the sample between adjacent measurement areas is suppressed. Therefore, high-precision mass analysis can be performed on each measurement area.

[0013] In the sample support disclosed in the present invention, the adhesive member may bond the first member and the substrate between each of the plurality of first openings, and bond the second member and the substrate between each of the plurality of second openings. According to this structure, as described above, when the plurality of regions corresponding to the plurality of second openings in the substrate are used as measurement regions, respectively, the movement of the sample between adjacent measurement regions can be more reliably suppressed. Therefore, a higher-precision mass analysis can be performed on each measurement region.

[0014] In the sample support of the present disclosure, the first member and the second member may be formed of a metal material, respectively. According to this structure, a voltage can be stably applied to the conductive layer provided in the second surface of the substrate in the regions corresponding to the plurality of second openings.

[0015] In the sample support of the present disclosure, the adhesive member may have conductivity. According to this structure, a voltage can be stably applied to the conductive layer provided in the region corresponding to each of the plurality of second openings in the second surface of the substrate.

[0016] In the sample support disclosed herein, the adhesive component may also be formed of a photocurable material. For example, the adhesive component may also be formed of an acrylic material or an epoxy material. According to this structure, it is not necessary to perform a heat treatment in order to cure the adhesive component. Therefore, even if a material having a large difference in thermal expansion coefficient with the material of the substrate is used for at least one of the first component and the second component, the generation of deflection caused by the heat treatment can be avoided.

[0017] The sample support disclosed in the present invention may also include at least one of a plurality of first marks indicating a plurality of first openings when the first component is observed from the side opposite to the substrate, and a plurality of second marks indicating a plurality of second openings when the second component is observed from the side opposite to the substrate. According to this structure, when a plurality of regions corresponding to the plurality of second openings in the substrate are used as measurement regions, each of the plurality of measurement regions can be easily identified by identifying each of the plurality of first openings and at least one of each of the plurality of second openings.

[0018] In the sample support disclosed in the present invention, the first component may have a third surface on which a substrate is disposed, and a fourth surface on the outside of the substrate facing the same side as the third surface, and the distance between the surface on the opposite side of the substrate and the fourth surface in the conductive layer provided on the second surface is less than the thickness of the substrate. According to this structure, an adapter having a reference surface located on the same plane as the focus of energy lines such as laser light is used in a mass spectrometer, and when the sample support is mounted in the mass spectrometer, the first component is held on the adapter in such a manner that the reference surface of the adapter and the fourth surface of the first component are located on the same plane, thereby enabling the focus of the energy line to be aligned with the surface of the conductive layer at a level less than the thickness of the substrate. Therefore, high-precision alignment of the focus of the energy line can be performed in the mass spectrometer.

[0019] In the sample support disclosed herein, the fourth surface may extend in a manner surrounding the substrate when viewed from the thickness direction. According to this structure, the strength of the first component and thus the strength of the sample support can be improved. In addition, the first component can be easily and reliably held in the above-mentioned adapter.

[0020] In the sample support disclosed in the present invention, the outer edge of each of the plurality of second openings may be located inside the outer edge of each of the plurality of first openings when observed from the thickness direction. In the substrate, when the area where the first opening and the second opening overlap when observed from the thickness direction is used as the measurement area, for example, if the outer edge of the second opening is located outside the outer edge of the first opening, then when the second component is observed from the opposite side of the substrate, the area delimited by the outer edge of the second opening includes not only the measurement area but also other areas. Therefore, it may be difficult to grasp the scope of the measurement area. Here, according to the structure in which the outer edge of the second opening is located inside the outer edge of the first opening, when the second component is observed from the opposite side of the substrate, the area delimited by the outer edge of the second opening becomes the measurement area, and therefore, by grasping the outer edge of the second opening, the scope of the measurement area can be easily grasped.

[0021] In the sample support disclosed in the present invention, the thickness of the second component may be smaller than the thickness of the first component. According to this structure, when an adapter having a reference surface located on the same plane as the focus of the laser isoenergy line is used in a mass spectrometer, for example, when the sample support is mounted on the mass spectrometer, when the first component is held on the adapter, even if the second component protrudes from the reference surface of the adapter, interference between the sample support and the mass spectrometer can be suppressed.

[0022] Effects of the Invention

[0023] According to the present disclosure, it is possible to provide a sample support capable of performing high-precision mass analysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a top view of a sample support according to one embodiment.

[0025] Figure 2 It is along Figure 1 A cross-sectional view taken along line II-II is shown.

[0026] Figure 3 yes Figure 2 A partial enlarged view of the sample support is shown.

[0027] Figure 4 Yes means Figure 1 FIG. 1 is a SEM image of the surface of the substrate.

[0028] Figure 5 is a top view of a sample support and adapter according to one embodiment.

[0029] Figure 6 It is along Figure 5 A cross-sectional view taken along line VI-VI is shown.

[0030] Figure 7 It is a diagram showing a mass analysis method according to one embodiment.

[0031] Figure 8 It is a figure which shows the mass spectra obtained by the mass analysis method of each of the first example and the first comparative example.

[0032] Fig. 9 1 and 2 are diagrams showing mass spectra obtained by the mass analysis methods of the second comparative example and the second example, and the third comparative example and the third example, respectively.

[0033] Fig.10 It is a cross-sectional view of a sample support body according to a modified example.

[0034] Fig.11 It is a cross-sectional view of a sample support body according to a modified example.

[0035] Fig.12 It is a cross-sectional view of a portion of a sample support and an adapter according to a modified example.

[0036] Explanation of symbols

[0037] 1…sample support, 2…substrate, 2a…surface (first surface), 2b…surface (second surface), 2c…through hole, 2d…first through hole, 2e…second through hole, 3…base (first component), 3a…surface, 3b…surface (third surface), 3c…opening (first opening), 3d…surface (fourth surface), 4…cover (second component), 4a…surface, 4b…surface, 4c…opening (second opening), 5…adhesive component, 6…conductive layer, 6a…surface, 32…marker (first mark), 42…marker (second mark), D…direction (thickness direction), S…sample, S1…component. DETAILED DESCRIPTION

[0038] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be noted that in each of the drawings, the same or corresponding parts are denoted by the same reference numerals, and repeated descriptions are omitted.

[0039] [Structure of sample support]

[0040] Figure 1 to Figure 3The sample support 1 shown is used to ionize the components of the sample. The sample support 1 includes a substrate 2, a base (first component) 3, a cover (second component) 4, an adhesive component 5 and a conductive layer 6. The substrate 2 has a surface (first surface) 2a and a surface (second surface) 2b opposite to the surface 2a. A plurality of through holes 2c opening on the surface 2a and the surface 2b are formed in the substrate 2. Each through hole 2c extends along a thickness direction D (hereinafter referred to as "direction D") of the substrate 2. Direction D is a direction in which the surface 2a and the surface 2b are opposite to each other.

[0041] The substrate 2 is formed into a rectangular plate shape by, for example, an insulating material. The length of one side of the substrate 2 when viewed from the direction D is, for example, several centimeters, and the thickness of the substrate 2 is, for example, 1 to 50 μm. The shape of each through hole 2c when viewed from the direction D is, for example, roughly circular, and the width of each through hole 2c is, for example, 1 to 700 nm. A plurality of through holes 2c each having a roughly constant width are uniformly (uniformly distributed) formed on the substrate 2. The opening ratio of the through holes 2c in the measurement area R (described later) (the ratio of all the through holes 2c to the measurement area R when viewed from the direction D) is preferably 10 to 80% in practical terms, and particularly preferably 20 to 40%. It should be noted that, among the plurality of through holes 2c, the widths of the through holes 2c may not be consistent, and the through holes 2c may be partially connected to each other.

[0042] The width of the through hole 2 c is a value obtained as follows: First, images of each of the surface 2 a and the surface 2 b of the substrate 2 are obtained. Figure 4 : is a diagram showing an SEM image of the surface 2a of the substrate 2. In the SEM image, the black portion is the through hole 2c, and the white portion is the partition wall portion between the through holes 2c. Next, the image of the surface 2a obtained is subjected to, for example, binarization processing, thereby extracting a plurality of pixel groups corresponding to the plurality of openings in the measurement area R (the openings on the surface 2a side of the through holes 2c), and based on the size of each pixel, the diameter of a circle having the average area of ​​the opening is obtained. Similarly, the image of the surface 2b obtained is subjected to, for example, binarization processing, thereby extracting a plurality of pixel groups corresponding to the plurality of openings in the measurement area R (the openings on the surface 2b side of the through holes 2c), and based on the size of each pixel, the diameter of a circle having the average area of ​​the opening is obtained. Then, the average value of the diameter of the circle obtained for the surface 2a and the diameter of the circle obtained for the surface 2b is obtained as the width of the through hole 2c.

[0043] Figure 4The substrate 2 shown is an alumina porous membrane formed by anodizing Al (aluminum). Specifically, the Al substrate is anodized, and the oxidized surface portion is peeled off from the Al substrate, thereby obtaining the substrate 2. It should be noted that the substrate 2 can also be formed by anodizing a valve metal other than Al, such as Ta (tantalum), Nb (niobium), Ti (titanium), Hf (hafnium), Zr (zirconium), Zn (zinc), W (tungsten), Bi (bismuth), Sb (antimony), etc., or by anodizing Si (silicon).

[0044] like Figure 1 and Figure 2 As shown, the base 3 is in the shape of a rectangular plate. The base 3 has a surface 3a and a surface (third surface) 3b on the opposite side of the surface 3a. The length of one side of the base 3 when viewed from the direction D is, for example, about several centimeters. When viewed from the direction D, the outer edge of the base 3 is located outside the outer edge of the substrate 2. The thickness of the base 3 (the distance between the surface 3a and the surface 3b) is, for example, about 1 mm.

[0045] The base 3 is formed with a plurality of openings (first openings) 3c arranged in a two-dimensional shape (e.g., a matrix shape of 5 rows and 14 columns). The plurality of openings 3c are defined by partition walls 31 of the base 3. The shape of each opening 3c when viewed from the direction D is, for example, circular, and the diameter of each opening 3c in this case is, for example, several mm to several tens of mm. The diameter of each opening 3c is, for example, about 3 mm.

[0046] The base 3 includes a main body 33 and a protrusion 34. The main body 33 and the protrusion 34 are formed integrally. A plurality of openings 3c are formed in the main body 33. The protrusion 34 protrudes from the surface 3b at the periphery of the main body 33. The protrusion 34 is in a rectangular ring shape when viewed from the direction D. That is, a recess defined by the surface 3b and the protrusion 34 is formed in the base 3. When viewed from the direction D, the protrusion 34 extends in a manner surrounding the plurality of openings 3c. The protrusion 34 includes a surface (fourth surface) 3d facing the same side as the surface 3b. When viewed from the direction D, the surface 3d extends in a manner surrounding the plurality of openings 3c.

[0047] The base 3 is arranged on the surface 2a of the substrate 2. Specifically, the substrate 2 is arranged in the recess of the base 3 in such a manner that the protrusion 34 is located outside the substrate 2. The substrate 2 is arranged on the surface 3b of the base 3 in such a manner that the surface 2a faces the surface 3b of the base 3. The protrusion 34 extends in such a manner as to surround the substrate 2 when viewed from the direction D. The surface 3d extends in such a manner as to surround the substrate 2 when viewed from the direction D.

[0048] The base 3 has conductivity. The base 3 is formed of a metal material. For example, the base 3 is formed of a material having the same thermal expansion coefficient as that of the material of the substrate 2, or a material having a lower thermal expansion coefficient than that of the material of the substrate 2 (when the material of the substrate 2 is alumina, for example, an iron-nickel alloy (42 alloy), molybdenum, Kovar alloy, titanium, etc.). In the present embodiment, the material of the base 3 is an iron-nickel alloy.

[0049] The sample support 1 is provided with a plurality of marks (first marks) 32 respectively indicating a plurality of openings 3c when the base 3 is observed from the opposite side to the substrate 2. The plurality of marks 32 are provided on the surface 3a of the base 3 (the surface of the base 3 on the opposite side to the substrate 2). The plurality of marks 32 are provided in a manner corresponding to the plurality of openings 3c one-to-one. The plurality of marks 32 are provided next to each of the plurality of openings 3c when observed from the direction D. The plurality of marks 32 are, for example, numbers. The plurality of marks 32 have a width that can be recognized by the visual inspection of the measurer. The plurality of marks 32 are formed, for example, by making the surface 3a concave and convex. The plurality of marks 32 are provided, for example, by engraving using stamping or laser.

[0050] The cover 4 is in the shape of a rectangular plate. The cover 4 has a surface 4a and a surface 4b on the opposite side of the surface 4a. The length of one side of the cover 4 when viewed from the direction D is, for example, about several centimeters. When viewed from the direction D, the outer edge of the cover 4 is located outside the outer edge of the substrate 2. The thickness of the cover 4 is smaller than the thickness of the base 3. The thickness of the cover 4 is, for example, about 0.2 mm.

[0051] The cover 4 is formed with a plurality of openings (second openings) 4c arranged in a two-dimensional shape (e.g., a matrix shape of 5 rows and 14 columns). The plurality of openings 4c are defined by the partition wall portion 41 of the cover 4. The shape of each opening 4c when viewed from the direction D is, for example, circular, and the diameter of each opening 4c in this case is, for example, several mm to several tens of mm. The diameter of each opening 4c is smaller than the diameter of each opening 3c. The diameter of each opening 4c is, for example, about 2.5 mm.

[0052] The cover 4 is arranged on the surface 2b of the substrate 2. Specifically, the cover 4 is arranged in a manner that the surface 4a of the cover 4 is opposite to the surface 2b of the substrate 2. The plurality of openings 4c of the cover 4 correspond to the plurality of openings 3c of the base 3 in the direction D. Specifically, each of the plurality of openings 4c is opposite to each of the plurality of openings 3c in the direction D one-to-one. The center line of each of the plurality of openings 4c overlaps with the center line of each of the plurality of openings 3c. When viewed from the direction D, the outer edge of each of the plurality of openings 4c is located inside the outer edge of each of the plurality of openings 3c. The portions of the substrate 2 corresponding to the overlapping regions of each of the plurality of openings 4c and each of the plurality of openings 3c when viewed from the direction D function as measurement regions R for ionizing the sample. In the present embodiment, the portions of the substrate 2 corresponding to the plurality of openings 4c function as measurement regions R. When viewed from the direction D, the plurality of measurement regions R are demarcated by the outer edges of the plurality of openings 4c.

[0053] The cover 4 has conductivity. The cover 4 is formed of a metal material. For example, the cover 4 is formed of a material having the same thermal expansion coefficient as the material of the substrate 2, or a material having a lower thermal expansion coefficient than the material of the substrate 2 (when the material of the substrate 2 is alumina, for example, an iron-nickel alloy (42 alloy), molybdenum, Kovar alloy, titanium, etc.). In the present embodiment, the material of the cover 4 is an iron-nickel alloy.

[0054] It should be noted that by using a material having the same thermal expansion coefficient as that of the substrate 2 or a material having a lower thermal expansion coefficient than that of the substrate 2 for at least one of the base 3 and the cover 4, it is possible to suppress the substrate 2 from bending after bonding and firing, and to achieve sufficient close contact between the substrate 2 and the sample and improve sensitivity in mass analysis. When manufacturing the sample support 1, by firing the sample support 1 formed with the conductive layer 6, the crystallinity of the conductive layer 6 can be improved, and a sample support 1 more suitable for mass analysis can be obtained.

[0055] The sample support 1 is provided with a plurality of marks (second marks) 42 respectively indicating a plurality of openings 4c when the cover 4 is observed from the opposite side to the substrate 2. The plurality of marks 42 are provided on the surface 4b of the cover 4 (the surface of the cover 4 on the opposite side to the substrate 2). The plurality of marks 42 are provided in a manner corresponding to the plurality of openings 4c one-to-one. The plurality of marks 42 are provided next to each of the plurality of openings 4c when observed from the direction D. The plurality of marks 42 are, for example, numbers. The plurality of marks 42 are provided in a manner corresponding to the plurality of marks 32 one-to-one. Specifically, mutually corresponding marks 42 and marks 32 are provided next to each of the openings 4c and openings 3c corresponding to each other. The mutually corresponding marks 42 and marks 32 are the same numbers, respectively. The plurality of marks 42 have a width that can be recognized by the visual inspection of the measurer. The plurality of marks 42 are formed, for example, by making the surface 4b concave and convex. The plurality of marks 42 are provided, for example, by engraving using stamping or laser.

[0056] like Figure 3 As shown, the plurality of through holes 2c of the substrate 2 include a plurality of first through holes 2d and a plurality of second through holes 2e. The plurality of first through holes 2d are located between each of the plurality of openings 3c and each of the plurality of openings 4c. That is, the measurement area R of the substrate 2 includes a plurality of first through holes 2d. The plurality of second through holes 2e are located between the base 3 and the cover 4. The plurality of second through holes 2e are located between the partition wall portion 31 of the base 3 and the partition wall portion 41 of the cover 4. Each of the plurality of openings 3c corresponding to each other and each of the plurality of openings 4c are connected to each other via the plurality of first through holes 2d.

[0057] like Figure 2 and Figure 3 As shown, the adhesive component 5 is arranged between the base 3 and the cover 4. The adhesive component 5 adheres the base 3 to the substrate 2 between each of the plurality of openings 3c, and adheres the cover 4 to the substrate 2 between each of the plurality of openings 4c. The adhesive component 5 is integrally (continuously) arranged in the plurality of second through holes 2e, between the partition wall portion 31 of the base 3 and the substrate 2, between the partition wall portion 41 of the cover 4 and the substrate 2, and between the side surface of the substrate 2 and the protrusion 34 of the base 3. The adhesive component 5 is covered by the cover 4 when viewed from the direction D. When viewed from the direction D, the adhesive component 5 overlaps with the partition wall portion 41 of the cover 4. The adhesive component 5 is not exposed in each of the plurality of openings 4c.

[0058] The adhesive component 5 has conductivity. The adhesive component 5 can be formed by a conductive adhesive or by applying a metal paste. The adhesive component 5 is formed by a UV curable material (photocurable material). The adhesive component 5 is formed by an acrylic material or an epoxy material. As the material of the adhesive component 5, it is preferred to use an adhesive material that releases less gas (such as a vacuum adhesive, etc.).

[0059] The conductive layer 6 is integrally (continuously) provided on the surface 2b of the substrate 2 in the regions corresponding to the plurality of openings 4c of the cover 4 (i.e., the regions corresponding to the plurality of measurement regions R on the surface 2b of the substrate 2), the inner surfaces of the plurality of openings 4c, and the surface 4b of the cover 4. The conductive layer 6 covers the regions on the surface 2b of the substrate 2 where the plurality of through holes 2c are not formed in each measurement region R. The conductive layer 6 covers the mark 42 on the surface 4b of the cover 4. However, since the mark 42 is formed by making the surface 4b concave and convex, even if covered by the conductive layer 6, it does not hinder visual recognition.

[0060] In each measurement region R, the surface 6a on the opposite side of the substrate 2 and the surface 3d of the protrusion 34 of the conductive layer 6 provided on the surface 2b of the substrate 2 are located on the same plane (the same plane perpendicular to the direction D). That is, the distance between the surface 6a and the surface 3d in the direction D is 0 in the present embodiment, which is smaller than the thickness of the substrate 2.

[0061] The conductive layer 6 is formed of a conductive material. However, as the material of the conductive layer 6, it is preferred to use a metal having low affinity (reactivity) with the sample and high conductivity for the reasons described below. For example, if the conductive layer 6 is formed of a metal such as Cu (copper) having high affinity with a sample such as a protein, the sample is ionized in a state where Cu atoms are attached to the sample molecules during the ionization of the sample, and as a result, the ionized sample is detected as a Cu-attached molecule, and therefore, the detection result may be deviated. Therefore, as the material of the conductive layer 6, it is preferred to use a metal having low affinity with the sample.

[0062] On the other hand, the more conductive the metal is, the easier and more stable it is to apply a certain voltage. Therefore, if the conductive layer 6 is formed by a metal with high conductivity, a voltage can be uniformly applied to the surface 2b of the substrate 2 in the measurement area R. In addition, as the material of the conductive layer 6, it is preferably a metal that can effectively transfer the energy of the laser irradiated to the substrate 2 to the sample via the conductive layer 6. For example, when irradiated with a standard laser (such as a triple harmonic Nd or YAG laser with a wavelength of about 355nm or a nitrogen laser with a wavelength of about 337nm) used in MALDI (Matrix-Assisted Laser Desorption / Ionization), as the material of the conductive layer 6, Al, Au (gold) or Pt (platinum) with high absorption in the ultraviolet region are preferably used.

[0063] From the above viewpoints, Au, Pt, etc. are preferably used as the material of the conductive layer 6. The conductive layer 6 is formed to a thickness of about 1 nm to 350 nm by, for example, electroplating, atomic layer deposition (ALD: Atomic Layer Deposition), evaporation, sputtering, etc. It should be noted that, as the material of the conductive layer 6, Cr (chromium), Ni (nickel), Ti (titanium), etc. may also be used.

[0064] [Adapter structure]

[0065] Figure 5 and Figure 6 The adapter 10 shown is used to install the above-mentioned sample support 1 in a mass spectrometer. The adapter 10 includes a holding portion 11. The holding portion 11 includes a main body 12, a plurality of stoppers 13, a plurality of washers 14, and a bolt 15. The main body 12 is formed into a rectangular frame shape by a metal material, for example. A plurality of stoppers 13 are provided on the main body 12 in a manner protruding toward the inner side of the main body 12. The plurality of washers 14 and the bolt 15 can be attached and detached relative to a surface 12a of the main body 12. In a state where the plurality of washers 14 and the bolt 15 are fixed to the surface 12a of the main body 12, a portion of each washer 14 faces each stopper 13 at a predetermined distance in a direction D. The holding portion 11 has a reference surface 11a located on the same plane as the focus of the laser (the same plane parallel to the optical axis of the laser) in the mass spectrometer. In the present embodiment, the reference surface 11a is the surface 12a of the main body 12. The distance between the surface 3 a and the surface 3 d of the base 3 in the direction D may be substantially equal to a predetermined distance between a portion of each washer 14 and each stopper 13 .

[0066] The sample support 1 is arranged on a plurality of stoppers 13, and in this state, is held by the holding portion 11 by fixing a plurality of sets of washers 14 and bolts 15 to the surface 12a of the main body member 12. In the state where the sample support 1 is held by the holding portion 11, the reference surface 11a of the holding portion 11 and the surface 3d of the base 3 are located on the same plane (the same plane parallel to the direction D and the optical axis of the laser). That is, the holding portion 11 holds the base 3 in such a manner that the reference surface 11a of the holding portion 11 and the surface 3d of the base 3 are located on the same plane.

[0067] [Ionization method and mass analysis method]

[0068] Reference Figure 7The ionization method and mass spectrometry method using the above-mentioned sample support 1 and adapter 10 are described. First, the sample support 1 is prepared. Then, the sample S is arranged in each measurement area R of the sample support 1. In the present embodiment, for example, a solution containing the sample S is dripped from the surface 2b side of the substrate 2 to each measurement area R. As a result, in each measurement area R, the excess solution penetrates into the plurality of through holes 2c, and the component S1 of the sample S is appropriately maintained on the conductive layer 6. Next, the sample support 1 with the sample S arranged in each measurement area R is installed in the mass spectrometer 100 using the adapter 10.

[0069] Next, the voltage applying unit 101 of the mass spectrometer 100 is operated to apply a voltage to the conductive layer 6 of the sample support 1 via the adapter 10, and the laser irradiation unit 102 of the mass spectrometer 100 is operated to irradiate each measurement region R with laser light (energy line) L. Thus, the component S1 of the sample S is ionized. At this time, since the focus P of the laser light L and the reference surface 11a of the holding unit 11 are located on the same plane, the reference surface 11a of the holding unit 11 and the surface 3d of the base 3 are located on the same plane, and the surface 3d of the base 3 and the surface 6a of the conductive layer 6 are located on the same plane, the focus P of the laser light L is located on the surface 6a of the conductive layer 6 holding the component S1 of the sample S. The above steps correspond to the ionization method (laser desorption ionization method in this embodiment) using the sample support 1 and the adapter 10.

[0070] Next, the sample ions S2 (ionized component S1) released due to the ionization of the component S1 of the sample S are detected in the ion detection unit 103 of the mass spectrometer 100. Specifically, the released sample ions S2 are accelerated while moving toward the ground electrode (not shown) provided between the sample support 1 and the ion detection unit 103 by the potential difference generated between the conductive layer 6 to which the voltage is applied and the ground electrode (not shown), and are detected by the ion detection unit 103. In the present embodiment, the mass spectrometer 100 is a scanning mass spectrometer using a time-of-flight mass spectrometry method (TOF-MS). The above steps correspond to a mass spectrometry method using the sample support 1 and the adapter 10.

[0071] It should be noted that in Figure 1 and Figure 5 to Figure 7 In FIG. 6 , the conductive layer 6 is omitted. Figure 1 , Figure 2 and Figure 5 to Figure 7 In FIG. 1 , the illustration of the plurality of through holes 2c is omitted. Figure 1 , Figure 2 as well as Figure 5In the figure, a part of the opening 3c and a part of the opening 4c are omitted. Figure 1 , Figure 2 and Figure 5 In the example, the number of openings 3c and 4c is less than the actual number. Figure 3 In the figure, a part of the first through hole 2d and a part of the second through hole 2e are omitted. Figure 3 In the figure, the number of the first through holes 2d and the second through holes 2e is smaller than the actual number.

[0072] [Function and Effect]

[0073] As described above, in the sample support 1, the plurality of openings 4c of the cover 4 are connected to the plurality of openings 3c of the base 3 via the plurality of first through holes 2d of the substrate 2. Thus, the plurality of regions corresponding to the plurality of openings 4c in the substrate 2 can be used as the measurement regions R. Here, when manufacturing the sample support 1, the substrate 2, the base 3, and the cover 4 can be unitized using the adhesive member 5, and then the conductive layer 6 can be provided from the cover 4 side. Thus, when the conductive layer 6 is provided from the cover 4 side, since the adhesive member 5 is arranged between the base 3 and the cover 4, it is difficult to generate outgassing from the conductive layer 6 and the adhesive member 5, and as a result, it is possible to suppress the accumulation of a mixed layer caused by the outgassing on the substrate 2. Therefore, according to the sample support 1, high-precision mass analysis can be performed.

[0074] Figure 8 (a) and (b) are diagrams showing mass spectra obtained by the mass analysis method of the first embodiment. Figure 8 (c) and (d) are diagrams showing mass spectra obtained by the mass spectrometry method of the first comparative example. In the mass spectrometry method of the first embodiment, a sample support 1 is used. The sample support used in the mass spectrometry method of the first comparative example is different from the sample support 1 mainly in that the sample support 1 does not have a cover 4. Figure 8 As shown, in the first embodiment, the noise in the detected signal is less than that in the first comparative example.

[0075] Fig. 9 (a) is a diagram showing a mass spectrum obtained by the mass spectrometry method of the second comparative example. Fig. 9 (b) is a diagram showing a mass spectrum obtained by the mass analysis method of the second example. Fig. 9 (c) is a diagram showing a mass spectrum obtained by the mass spectrometry method of the third comparative example. Fig. 9(d) is a diagram showing a mass spectrum obtained by the mass spectrometry method of the third embodiment. In the mass spectrometry methods of the second embodiment and the third embodiment, the sample support 1 is used. The sample support used in the mass spectrometry methods of the second comparative example and the third comparative example is different from the sample support 1 mainly in that the cover 4 is not provided. Fig. 9 As shown in (a) and (b) of FIG. 1 , in the second embodiment, the noise in the detected signal is less than that in the second comparative example. Fig. 9 As shown in (c) and (d) of FIG. 3 , in the third embodiment, the noise in the detected signal is less than that in the third comparative example.

[0076] In addition, in the sample support 1, the adhesive member 5 is arranged in the plurality of second through holes 3e. According to this structure, when the plurality of regions corresponding to the plurality of openings 4c in the substrate 2 are respectively used as the measurement regions R, the plurality of measurement regions R are respectively isolated by the adhesive member 5. Therefore, when the sample S is respectively arranged in the plurality of measurement regions R, the movement of the sample S between adjacent measurement regions R can be suppressed. Therefore, high-precision mass analysis can be performed on each measurement region R.

[0077] In addition, in the sample support 1, the adhesive member 5 bonds the base 3 to the substrate 2 between each of the plurality of openings 3c, and bonds the cover 4 to the substrate 2 between each of the plurality of openings 4c. According to this structure, as described above, when the plurality of regions corresponding to the plurality of openings 4c in the substrate 2 are used as the measurement regions R, respectively, the movement of the sample S between the adjacent measurement regions R can be more reliably suppressed. Therefore, a higher-precision mass analysis can be performed on each measurement region R.

[0078] In the sample support 1, the base 3 and the cover 4 are each formed of a metal material. With this configuration, a voltage can be stably applied to the conductive layer 6 provided in the region corresponding to each of the plurality of openings 4c on the surface 2b of the substrate 2.

[0079] In addition, in the sample support 1, the adhesive member 5 has conductivity. According to this structure, a voltage can be stably applied to the conductive layer 6 provided in the region corresponding to each of the plurality of openings 4c in the surface 2b of the substrate 2.

[0080] In addition, in the sample support 1, the adhesive member 5 is formed of a UV curable material. The adhesive member 5 is formed of an acrylic material or an epoxy material. According to this structure, it is not necessary to perform a heat treatment in order to cure the adhesive member 5. Therefore, even if a material having a large difference in thermal expansion coefficient with the material of the substrate 2 is used for at least one of the base 3 and the cover 4, the generation of deflection caused by the heat treatment can be avoided.

[0081] In addition, the sample support 1 includes a plurality of marks 32 that indicate the plurality of openings 3c when the base 3 is viewed from the side opposite to the substrate 2, and a plurality of marks 42 that indicate the plurality of openings 4c when the cover 4 is viewed from the side opposite to the substrate 2. According to this structure, when a plurality of regions corresponding to the plurality of openings 4c in the substrate 2 are used as measurement regions R, each of the plurality of measurement regions R can be easily identified by identifying each of the plurality of openings 3c and each of the plurality of openings 4c. Depending on the type of solution containing the sample S, the solution may drip from the surface 2a side of the substrate 2 to the measurement region R. That is, when the substrate 2 has a higher affinity for the solution than the conductive layer 6, it is preferred to drip the solution from the surface 2a side of the substrate 2. As a result, the solution can flow more smoothly into the first through hole 2d than when the solution drips from the surface 2b side of the substrate 2. In this embodiment, the sample support 1 has both a plurality of marks 32 respectively representing a plurality of openings 3c, and a plurality of marks 42 respectively representing a plurality of openings 4c. Therefore, when the solution is dripped from the surface 2a side of the substrate 2, the openings 3c are identified by the marks 32, thereby identifying the measurement area R. Thereafter, when the laser L is irradiated, the measurement area R can be identified by identifying the openings 4c using the marks 42.

[0082] In addition, in the sample support 1, the base 3 has a surface 3b on which the substrate 2 is arranged, and a surface 3d on the outside of the substrate 2 facing the same side as the surface 3b, and the distance between the surface 6a of the conductive layer 6 and the surface 3d is smaller than the thickness of the substrate 2. According to this structure, in the mass spectrometer 100, the adapter 10 having the reference surface 11a located on the same plane as the focal point P of the laser L is used, and when the sample support 1 is mounted on the mass spectrometer 100, the base 3 is held on the adapter 10 in such a manner that the reference surface 11a of the adapter 10 and the surface 3d of the base 3 are located on the same plane, so that the focal point P of the laser L can be aligned with the surface 6a of the conductive layer 6 at a level smaller than the thickness of the substrate 2. Therefore, in the mass spectrometer 100, the focal point P of the laser L can be aligned with high precision.

[0083] In the sample support 1, the protrusion 34 of the base 3 extends to surround the substrate 2 when viewed from the direction D. This structure can improve the strength of the base 3 and thus improve the strength of the sample support 1. In addition, the base 3 can be easily and reliably held in the adapter 10 as described above.

[0084] In addition, in the sample support 1, the outer edge of each of the plurality of openings 4c is located inside the outer edge of each of the plurality of openings 3c when viewed from the direction D. In the substrate 2, when the region where the openings 3c and the openings 4c overlap when viewed from the direction D is used as the measurement region R, for example, if the outer edge of the opening 4c is located outside the outer edge of the opening 3c, when the cover 4 is viewed from the side opposite to the substrate 2, the region defined by the outer edge of the opening 4c includes not only the measurement region R but also other regions. Therefore, it may be difficult to grasp the range of the measurement region R. Here, according to the structure in which the outer edge of the opening 4c is located inside the outer edge of the opening 3c, when the cover 4 is viewed from the side opposite to the substrate 2, the region defined by the outer edge of the opening 4c becomes the measurement region R, and therefore, by grasping the outer edge of the opening 4c, the range of the measurement region R can be easily grasped.

[0085] In addition, in the sample support 1, the thickness of the cover 4 is smaller than the thickness of the base 3. According to this structure, for example, when the adapter 10 having the reference surface 11a located on the same plane as the focal point P of the laser light L is used in the mass spectrometer 100, when the sample support 1 is mounted on the mass spectrometer 100, when the base 3 is held on the adapter 10, even if the cover 4 protrudes from the reference surface 11a of the adapter 10, interference between the sample support 1 and the mass spectrometer 100 can be suppressed.

[0086] [Modifications]

[0087] The example in which the adhesive member 5 adheres the base 3 and the substrate 2 between each of the plurality of openings 3c, and adheres the cover 4 and the substrate 2 between each of the plurality of openings 4c is shown, but the present invention is not limited thereto. Fig.10 As shown, the adhesive component 5 may not adhere the base 3 and the substrate 2 between each of the plurality of openings 3c. That is, the adhesive component 5 may not be arranged between the partition wall portion 31 of the base 3 and the substrate 2 between each of the plurality of openings 3c. It should be noted that the adhesive component 5 may be arranged between the partition wall portion 31 of the base 3 and the substrate 2 on the outside of the plurality of openings 3c (the outer edge of the substrate 2), or may not be arranged. In addition, the adhesive component 5 may be arranged between the side surface of the substrate 2 and the protrusion 34 of the base 3, or may not be arranged. In addition, as Fig.11 As shown, the adhesive component 5 may not bond the cover 4 and the substrate 2 between each of the plurality of openings 4c. That is, the adhesive component 5 may not be arranged between the partition wall portion 41 of the cover 4 and the substrate 2 between each of the plurality of openings 4c. It should be noted that the adhesive component 5 may be arranged between the partition wall portion 41 of the cover 4 and the substrate 2 outside the plurality of openings 4c (outer edge portion of the substrate 2), or may not be arranged. As described above, the adhesive component 5 is arranged between the base 3 and the cover 4, and at least one of the base 3 and the cover 4 is bonded to the substrate 2.

[0088] In addition, if the distance between the surface 6a of the conductive layer 6 and the surface 3d of the base 3 is smaller than the thickness of the substrate 2, the surface 6a of the conductive layer 6 and the surface 3d of the base 3 may not be located on the same plane perpendicular to the direction D. In this case, by holding the base 3 with the adapter 10 in such a manner that the reference surface 11a of the adapter 10 and the surface 3d of the base 3 are located on the same plane, the focus P of the laser light L can be aligned with the surface 6a of the conductive layer 6 at a level smaller than the thickness of the substrate 2.

[0089] In addition, the retaining portion 11 of the adapter 10 is not limited to the above-mentioned structure (i.e., having a main body part 12, multiple stoppers 13, multiple sets of washers 14 and bolts 15) as long as it can retain the base 3 in a manner such that the reference surface 11a of the adapter 10 and the surface 3d of the base 3 are located on the same plane.

[0090] In addition, an example is shown in which the main body 33 and the protrusion 34 of the base 3 are formed integrally, but Fig.12 As shown, the main body 33 and the protrusion 34 may be formed separately. In this case, the protrusion 34 may be formed of, for example, an adhesive or a vapor-deposited metal.

[0091] In addition, an example is shown in which the protrusion 34 (including the surface 3d) extends to surround the substrate 2 when viewed from the direction D, but the present invention is not limited thereto. When viewed from the direction D, the base 3 may also have a plurality of protrusions arranged along the outer edge of the substrate 2. The plurality of protrusions correspond to each of the plurality of sets of washers 14 and bolts 15.

[0092] In addition, the base 3 may not include the protrusion 34. A recess (countersink) having a depth substantially equal to the thickness of the protrusion 34 may be formed on the surface 12a of the main body 12. In this case, the sample support 1 is arranged on a plurality of stoppers 13, and in this state, the sample support 1 is held by the holding portion 11 by fixing a plurality of sets of washers 14 and bolts 15 to the bottom surface of the recess formed in the main body 12. That is, the holding portion 11 holds the base 3 in such a manner that the bottom surface of the recess formed in the main body 12 and the surface 3b of the base 3 are located on the same plane. In this case, the focus P of the laser L can also be aligned with the surface 6a of the conductive layer 6 at a level smaller than the thickness of the substrate 2.

[0093] In addition, although the example in which the adhesive member 5 is formed of a UV curable material is shown, the adhesive member 5 may also be formed of an inorganic adhesive, etc. Examples of the inorganic adhesive include Ceramabond (registered trademark) manufactured by Odec Corporation and Aron Ceramic (registered trademark) manufactured by Toagosei Co., Ltd.

[0094] In addition, although an example is shown in which the plurality of identifiers 32 are numbers, the plurality of identifiers 32 may be various identifiers. The plurality of identifiers 32 may be, for example, at least one selected from numbers, symbols, and characters. Similarly, although an example is shown in which the plurality of identifiers 42 are numbers, the plurality of identifiers 42 may be various identifiers. The plurality of identifiers 42 may be, for example, at least one selected from numbers, symbols, and characters.

[0095] In addition, an example is shown in which the plurality of marks 32 are formed by making the surface 3a of the base 3 concave and convex, but the plurality of marks 32 may be formed by printing such as nanoimprinting, photolithography using EUV (Extreme Ultraviolet) exposure, writing based on paint, or black (oxidation) as an example of laser engraving. Similarly, an example is shown in which the plurality of marks 42 are formed by making the surface 4b of the cover 4 concave and convex, but the plurality of marks 42 may be formed by printing such as nanoimprinting, photolithography using EUV (Extreme Ultraviolet) exposure, writing based on paint, or black (oxidation) as an example of laser engraving. It should be noted that when the plurality of marks 42 are not formed by making the surface 4b of the cover 4 concave and convex, and are covered by the conductive layer 6 to hinder visibility, the conductive layer 6 is not formed in the area of ​​the surface 4b of the cover 4 where the plurality of marks 42 are formed.

[0096] In addition, an example is shown in which a plurality of marks 32 are respectively provided in a one-to-one correspondence with a plurality of openings 3c and are respectively provided next to the plurality of openings 3c when viewed from the direction D, but the plurality of marks 32 may be respectively arranged along the rows and columns of the plurality of openings 3c on the outside of the plurality of openings 3c when viewed from the direction D. The plurality of marks 32 may also constitute a coordinate system for respectively identifying the plurality of openings 3c. Similarly, an example is shown in which a plurality of marks 42 are respectively provided in a one-to-one correspondence with a plurality of openings 4c and are respectively provided next to the plurality of openings 4c when viewed from the direction D, but the plurality of marks 42 may be respectively arranged along the rows and columns of the plurality of openings 4c on the outside of the plurality of openings 4c when viewed from the direction D. The plurality of marks 42 may also constitute a coordinate system for respectively identifying the plurality of openings 4c.

[0097] In addition, an example is shown in which a plurality of marks 32 are provided on the surface 3a of the base 3, but when a conductive layer 6 is provided on the surface 3a of the base 3, for example, the plurality of marks 32 may be provided on the surface of the conductive layer 6 provided on the surface 3a. Although an example is shown in which a plurality of marks 42 are provided on the surface 4b of the cover 4, the plurality of marks 42 may be provided on the surface 6a of the conductive layer 6 or the surface 3d of the base 3, for example.

[0098] In addition, an example is shown in which a solution containing a sample S is dripped from the surface 2b side of the substrate 2 to each measurement area R, but the solution may also be dripped from the surface 2a side of the substrate 2 to each measurement area R. As described above, when the substrate 2 has a higher affinity for the solution than the conductive layer 6, it is preferred to drip the solution from the surface 2a side of the substrate 2. Specifically, in a state where the sample support 1 is supported in a manner such that the surface 2a is located on the upper side relative to the surface 2b, the solution is dripped from the surface 2a side to each measurement area R. Thereafter, by maintaining the state in which the surface 2a is located on the upper side relative to the surface 2b, the solution moves into the plurality of first through holes 2d due to gravity and capillary phenomena. Here, since the surface 2a has a higher affinity for the solution than the conductive layer 6, by dripping the solution on the surface 2a, the solution can flow into the first through holes 2d more smoothly than when the solution is dripped on the surface 2b (conductive layer 6). Next, the sample support 1 is turned over so that the surface 2b is located on the upper side relative to the surface 2a, and is mounted on the mass spectrometer 100 in a state where the surface 2b is located on the upper side relative to the surface 2a. Next, a voltage is applied to the conductive layer 6 and the surface 2b is irradiated with laser light L, thereby ionizing the component S1 of the sample S. Here, the sample support 1 is provided with both a plurality of marks 32 representing a plurality of openings 3c, and a plurality of marks 42 representing a plurality of openings 4c. Therefore, when the solution is dripped from the surface 2a side, the measurement region R is identified by identifying the openings 3c using the marks 32, and then, when the surface 2b is irradiated with laser light L, the measurement region R can be identified by identifying the openings 4c using the marks 42.

[0099] In addition, the example in which the sample support 1 includes the multiple marks 32 and the multiple marks 42 is shown, but the sample support 1 may not include either the multiple marks 32 or the multiple marks 42. That is, the sample support 1 only needs to include at least one of the multiple marks 32 and the multiple marks 42.

[0100] In addition, as long as the conductive layer 6 is provided at least on the surface 2b of the substrate 2, it may be provided on the surface 2a of the substrate 2 and the inner surface of each through hole 2c, or it may not be provided.

[0101] In addition, the use of the sample support 1 is not limited to ionization of the sample S by irradiation with the laser light L. The sample support 1 can be used for ionization of the sample S by irradiation with energy beams such as laser light, ion beams, and electron beams. In the above-mentioned ionization method and mass spectrometry method, the sample S can be ionized by irradiation with energy beams.

Claims

1. A sample support, wherein: The sample support is used for ionization of components of the sample and comprises: A substrate having a first surface, a second surface opposite to the first surface, and a plurality of through holes opened on the first surface and the second surface; A first component having a plurality of first openings and disposed on the first surface; A second component having a plurality of second openings respectively corresponding to the plurality of first openings in a thickness direction of the substrate and arranged on the second surface; an adhesive component disposed between the first component and the second component and bonding at least one of the first component and the second component to the substrate; as well as a conductive layer integrally provided on regions of the second surface corresponding to the plurality of second openings, a surface of the second member opposite to the substrate, and an inner surface of each of the plurality of second openings, The plurality of through holes include: a plurality of first through holes located between each of the plurality of first openings and each of the plurality of second openings, and a plurality of second through holes located between the first component and the second component. The plurality of second openings are respectively connected to the plurality of first openings via the plurality of first through holes. The first component has a third surface on which the substrate is arranged, and a fourth surface on the outer side of the substrate facing the same side as the third surface. A distance between a surface of the conductive layer disposed on the second surface on the opposite side to the substrate and the fourth surface is smaller than a thickness of the substrate.

2. The sample support according to claim 1, wherein: The adhesive member is disposed in the plurality of second through holes.

3. The sample support according to claim 2, wherein: The bonding member bonds the first member and the substrate between each of the plurality of first openings, and bonds the second member and the substrate between each of the plurality of second openings.

4. The sample support according to any one of claims 1 to 3, wherein The first member and the second member are respectively formed of a metal material.

5. The sample support according to any one of claims 1 to 3, wherein The adhesive member has conductivity.

6. The sample support according to any one of claims 1 to 3, wherein The adhesive member is formed of a photocurable material.

7. The sample support according to claim 6, wherein: The adhesive member is formed of an acrylic material or an epoxy material.

8. The sample support according to any one of claims 1 to 3, wherein The sample support body also includes: at least one of a plurality of first marks and a plurality of second marks, wherein the plurality of first marks respectively indicate the plurality of first openings when the first component is observed from the side opposite to the substrate, and the plurality of second marks respectively indicate the plurality of second openings when the second component is observed from the side opposite to the substrate.

9. The sample support according to claim 1, wherein: When viewed from the thickness direction, the fourth surface extends so as to surround the substrate.

10. The sample support according to any one of claims 1 to 3, wherein When viewed from the thickness direction, an outer edge of each of the plurality of second openings is located inside an outer edge of each of the plurality of first openings.

11. The sample support according to any one of claims 1 to 3, wherein The second member has a thickness smaller than that of the first member.

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