Sample support and method for manufacturing the sample support

Abstract

To provide a sample support that enables highly sensitive mass spectrometry, and a method for manufacturing the sample support.SOLUTION: A sample support is a sample support used to ionize the component of a sample. The sample support 1 includes a substrate 2, a conductive layer 5, and a plurality of particles 71. The substrate 2 has a first main surface 2a and a plurality of holes 2c opening to the first main surface 2a. The conductive layer 5 is provided on the first main surface 2a such that the holes 2c are not blocked. The plurality of particles 71 are provided on the surface 5a of the conductive layer 5. The absorptance of the plurality of particles 71 with respect to the energy rays used for ionization is greater than or equal to the absorptance of the conductive layer 5 with respect to the energy rays.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a sample support and a method for manufacturing a sample support. [Background technology]

[0002] Conventionally, sample supports for ionizing components of a sample in mass analysis of the sample have been known (see, for example, Patent Document 1). Such sample supports include a substrate having a first main surface, a second main surface opposite to the first main surface, and a plurality of through-holes opening into the first and second main surfaces, and a conductive layer provided on the first main surface.

[0003] In such mass analysis, when an energy beam such as a laser beam is irradiated onto the first principal surface of the substrate, the energy is transmitted to the components of the sample on the first principal surface side via the conductive layer. As a result, the components of the sample are ionized, resulting in the generation of sample ions. The sample ions are then detected, and mass analysis of the sample is performed based on the detection results. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6093492 Summary of the Invention [Problem to be solved by the invention]

[0005] In the above-described mass spectrometry, energy is transferred to the sample components via the conductive layer, resulting in efficient ionization of the sample components. As a result, sample ions are also efficiently detected, ensuring improved sensitivity (signal intensity). However, in mass spectrometry, further improvement in sensitivity is sometimes desired.

[0006] An object of the present invention is to provide a sample support that enables highly sensitive mass analysis, and a method for manufacturing the sample support. [Means for solving the problem]

[0007] The sample support of the present invention is a sample support used for ionizing components of a sample, and comprises a substrate having a main surface and a plurality of holes opening into the main surface, a conductive layer provided on the main surface so that the holes are not blocked, and a plurality of particles provided on the surface of the conductive layer, wherein the absorptance of the plurality of particles for the energy beam used for ionization is equal to or greater than the absorptance of the conductive layer for the energy beam.

[0008] This sample support includes a substrate having a main surface and a plurality of holes opening to the main surface. When sample components are introduced into the plurality of holes, the components remain on the main surface side. When an energy beam is irradiated onto the main surface while a voltage is applied to the conductive layer, energy is transferred to the components on the main surface side. The components on the main surface side are ionized by this energy. Here, a plurality of particles are provided on the surface of the conductive layer. The absorption rate of the plurality of particles for the energy beam is equal to or greater than the absorption rate of the conductive layer for the energy beam. Therefore, the energy is efficiently transferred to the components on the main surface side, thereby efficiently ionizing the components on the main surface side. Therefore, the signal intensity of the sample ions generated by the ionization of the components is improved. Therefore, this sample support enables highly sensitive mass analysis.

[0009] The plurality of particles may be a plurality of nanoparticles deposited on the surface of the conductive layer, which allows the energy to be transferred more efficiently to the components on the main surface side, thereby enabling more sensitive mass analysis.

[0010] When viewed from a direction perpendicular to the main surface, the area corresponding to the plurality of particles may be smaller than the area corresponding to the conductive layer, thereby ensuring the functions of both the conductive layer and the particles and enabling the above-described highly sensitive mass analysis to be reliably achieved.

[0011] The surface of the conductive layer includes a plurality of first regions spaced apart from one another and a second region located between each of the first regions, and each of the first regions may be provided with a plurality of particles, while the second region may not be provided with a plurality of particles. This ensures the functions of both the conductive layer and the particles, and reliably achieves the above-described highly sensitive mass analysis.

[0012] The plurality of particles may have absorptivity for laser light, whereby the use of laser light as an energy beam makes it possible to realize the above-described highly sensitive mass analysis.

[0013] The particles may be ultraviolet absorbing, which broadens the wavelength band of the energy ray, thereby increasing the degree of freedom in selecting the type of energy ray.

[0014] The sensitization effect of the plurality of particles on the energy beam may be greater than the sensitization effect of the conductive layer on the energy beam, thereby ensuring the above-described highly sensitive mass analysis.

[0015] The material of the plurality of particles may be different from the material of the conductive layer, which allows for greater freedom in selecting the materials for the conductive layer and the particles while ensuring the functions of both the conductive layer and the particles.

[0016] The material of the plurality of particles may contain a metal element, which allows for greater freedom in selecting the material of the particles while ensuring the function of the particles having energy ray absorption properties.

[0017] The material of the particles may be gold, platinum, or titanium dioxide, which allows for greater freedom in selecting the material of the particles while ensuring the function of the particles having energy ray absorption.

[0018] The material of the plurality of particles may contain carbon, which allows for greater freedom in selecting the material of the particles while ensuring the function of the particles having energy ray absorption properties.

[0019] The material of the plurality of particles may be a compound containing a metal element or carbon, which allows for greater freedom in selecting the material of the particles while ensuring the function of the particles having energy ray absorption.

[0020] The particles may be formed by electrospraying, which can ensure the function of particles that are absorbent to energy rays at low cost.

[0021] The method for manufacturing a sample support of the present invention is a method for manufacturing a sample support used for ionizing components of a sample, and includes the following steps: a first step of preparing a substrate having a main surface and a plurality of holes opening into the main surface; a second step of providing a conductive layer on the main surface so as not to block the holes; and a third step of providing a plurality of particles on the surface of the conductive layer, wherein the absorptance of the plurality of particles for the energy beam used for ionization is equal to or greater than the absorptance of the conductive layer for the energy beam.

[0022] According to this manufacturing method, as described above, it is possible to manufacture a sample support that enables highly sensitive mass analysis.

[0023] In the third step, a plurality of particles may be provided by a wet process, which ensures the formation of particles that are absorptive of energy rays.

[0024] In the third step, a liquid containing a plurality of particles may be sprayed onto the surface of the conductive layer by electrostatic spraying, thereby forming particles that are absorptive of energy rays reliably and at low cost. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a sample support that enables highly sensitive mass analysis, and a method for manufacturing the sample support. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a plan view of an embodiment of a sample support. [Figure 2] FIG. 2 is a cross-sectional view taken along line II-II shown in FIG. [Figure 3] 2 is a magnified image of the substrate of the sample support shown in FIG. 1. [Figure 4] Figure 1 is a schematic diagram of the surface of the sample support shown. [Figure 5] FIG. 2 is a schematic cross-sectional view of the sample support shown in FIG. 1. [Figure 6] 2 is a magnified image of the surface of the sample support shown in FIG. 1. [Figure 7] 2 is a diagram showing steps of a mass spectrometry method using the sample support shown in FIG. 1. FIG. [Figure 8] FIG. 10 is a diagram showing the results of the mass spectrometry methods of the first comparative example and the first embodiment. [Figure 9] FIG. 10 is a diagram showing the results of the mass spectrometry methods of the second comparative example and the second embodiment. [Figure 10] 2A to 2C are diagrams showing steps in a method for manufacturing the sample support shown in FIG. 1. [Figure 11] FIG. 10 is a diagram showing the results of the mass spectrometry methods of the third comparative example and the third embodiment. [Figure 12] 10 is a magnified image of the surface of a modified sample support. [Figure 13] 10 is a magnified image of the surface of a modified sample support. [Figure 14] FIG. 10 is a schematic cross-sectional view of a modified sample support. [Figure 15] FIG. 10 is a cross-sectional view of a modified sample support. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In each drawing, the same or corresponding parts are designated by the same reference numerals, and redundant explanations will be omitted.

[0028] [Configuration of sample support] As shown in Figures 1 and 2, the sample support 1 includes a substrate 2, a frame 3, and a conductive layer 5. The sample support 1 has a substantially rectangular shape in a plan view. In this embodiment, the direction along the long side of the sample support 1 is represented as the X-axis direction, the direction along the short side of the sample support 1 is represented as the Y-axis direction, and the thickness direction of the sample support 1 is represented as the Z-axis direction. The length of the sample support 1 in the X-axis direction is, for example, about 3 cm. The length of the sample support 1 in the Y-axis direction is, for example, about 2 cm.

[0029] The substrate 2 has, for example, a rectangular plate shape. The substrate 2 has a first main surface 2a, a second main surface 2b opposite to the first main surface 2a, and a plurality of holes 2c. When viewed in the thickness direction D of the substrate 2 (a direction perpendicular to the first main surface 2a), the length of one side of the substrate 2 is, for example, about several centimeters. The thickness of the substrate 2 is, for example, about 1 μm to 50 μm. In this embodiment, the thickness of the substrate 2 is 5 μm to 50 μm.

[0030] The plurality of holes 2c are formed uniformly (with a uniform distribution) in the substrate 2. Each hole 2c extends along the thickness direction D of the substrate 2 and opens to the first main surface 2a and the second main surface 2b. In other words, each hole 2c is a through-hole that penetrates the substrate 2. The shape of the holes 2c when viewed from the thickness direction D is, for example, approximately circular. The sizes of the holes 2c may be uneven, or the holes 2c may be partially connected to each other. The substrate 2 is made of an insulating material.

[0031] As shown in FIG. 3, a plurality of holes 2c having a substantially uniform width are uniformly formed on the substrate 2. The substrate 2 shown in FIG. 3 is an alumina porous coating formed by anodizing aluminum (Al). For example, an anodizing treatment is performed on an Al substrate, whereby a surface portion of the Al substrate is oxidized and a plurality of pores (portions that will become the holes 2c) are formed in the surface portion of the Al substrate. Subsequently, the oxidized surface portion (anodized coating) is peeled off from the Al substrate, and the peeled anodized coating is subjected to a pore widening treatment to widen the pores, thereby obtaining the substrate 2. The substrate 2 may be formed by anodizing a valve metal other than Al, such as tantalum (Ta), niobium (Nb), titanium (Ti), hafnium (Hf), zirconium (Zr), zinc (Zn), tungsten (W), bismuth (Bi), or antimony (Sb), or by anodizing silicon (Si).

[0032] The width of the holes 2c is, for example, approximately 1 nm to 700 nm. The width of the holes 2c is a value obtained as follows. First, images of each of the first main surface 2a and the second main surface 2b of the substrate 2 are obtained. FIG. 3 shows an example of an SEM image of a portion of the first main surface 2a of the substrate 2. In the SEM image, the black parts are the holes 2c, and the white parts are the partitions between the holes 2c. Next, the obtained image of the first main surface 2a is subjected to, for example, binarization processing to extract multiple pixel groups corresponding to multiple first openings (openings of the holes 2c on the first main surface 2a side) in the measurement region R, and the diameter of a circle having an average area of ​​the first openings is obtained based on the size per pixel. Similarly, the obtained image of the second main surface 2b is subjected to, for example, binarization processing to extract multiple pixel groups corresponding to multiple second openings (openings of the holes 2c on the second main surface 2b side) in the measurement region R, and the diameter of a circle having an average area of ​​the second openings is obtained based on the size per pixel. Then, the average value of the diameter of the circle obtained for the first main surface 2a and the diameter of the circle obtained for the second main surface 2b is obtained as the width of the hole 2c.

[0033] The frame 3 is provided on the first main surface 2a of the substrate 2 and supports the substrate 2 on the first main surface 2a side. The frame 3 has a first surface 3h facing the first main surface 2a of the substrate 2 and a second surface 3g opposite to the first surface 3h. In this embodiment, the frame 3 is formed in the shape of a rectangular plate that is larger than the substrate 2 when viewed in the thickness direction D.

[0034] An opening 3a is formed in the approximate center of the frame 3, penetrating in the thickness direction of the frame 3 (i.e., thickness direction D). An opening 3b is formed in the corner of the frame 3, penetrating in the thickness direction of the frame 3. A recess 3d is provided in the center of an edge 3c of the frame 3 in the X-axis direction (i.e., an edge along the Y-axis direction), recessed inward in the X-axis direction.

[0035] The opening 3a is formed in a substantially circular shape. In this embodiment, the opening 3a has a shape obtained by cutting out a portion of a circle (portions facing each other in one direction) in an arched shape. Specifically, the opening 3a has a shape obtained by cutting out a portion of a circle in an arched shape so that both edges in the Y-axis direction are parallel to the X-axis direction. As an example, the width of the opening 3a in the Y-axis direction is approximately 1.5 cm. The portion of the substrate 2 corresponding to the opening 3a (i.e., the portion overlapping with the opening 3a when viewed from the thickness direction D) functions as a measurement region R for measuring the sample. That is, the measurement region R is defined by the opening 3a provided in the frame 3. In other words, the opening 3a opens on the first surface 3h and the second surface 3g so as to correspond to the measurement region R. That is, the frame 3 is formed to surround the measurement region R of the substrate 2 when viewed from the thickness direction D.

[0036] Opening 3b is formed in a circular shape that is smaller than opening 3a. For example, opening 3b has a diameter of about 1 mm. The portion of substrate 2 that corresponds to opening 3b (i.e., the portion that overlaps with opening 3b when viewed from the thickness direction D) functions as calibration area C for calibration.

[0037] As described above, a plurality of holes 2c are uniformly formed in the substrate 2, and therefore both the measurement region R and the calibration region C are regions that include a plurality of holes 2c. The aperture ratio of the holes 2c in the measurement region R (the proportion of the measurement region R that is occupied by the holes 2c when viewed from the thickness direction D) is practically 10 to 80%, and preferably 30 to 60%. The same applies to the calibration region C as to the measurement region R.

[0038] The frame 3 is made of, for example, a metal or ceramic. In this embodiment, the frame 3 is made of a non-magnetic and acid-resistant material. Examples of such materials include titanium and stainless steel (SUS). In this embodiment, the frame 3 is made of SUS. The outer shape of the sample support 1 is determined mainly by the frame 3. The length of the frame 3 in the X-axis direction is, for example, about 3 cm. The length of the frame 3 in the Y-axis direction is, for example, about 2 cm. The thickness of the frame 3 is, for example, 3 mm or less. As an example, the thickness of the frame 3 is 0.2 mm.

[0039] When viewed from the thickness direction D, the substrate 2 is fitted between a pair of edge portions 3e of the frame 3 along the X-axis direction, and is also fitted between the bottom portions 3f of a pair of recesses 3d of the frame 3. Portions of the substrate 2 other than the measurement region R and the calibration region C are bonded to the frame 3 by an adhesive layer 6. By bonding and supporting the substrate 2 to the frame 3 in this manner, handling of the sample support 1 is facilitated and deformation of the substrate 2 due to temperature changes and the like is suppressed.

[0040] The adhesive layer 6 is formed between the first main surface 2a of the substrate 2 and the first surface 3h of the frame 3, and bonds the substrate 2 and the frame 3 together. The adhesive layer 6 can be formed, for example, of an adhesive that emits little gas (e.g., low-melting-point glass, vacuum adhesive, etc.). The adhesive layer 6 may be formed of a conductive adhesive, or may be formed by applying a metal paste. The adhesive layer 6 may also be formed of a UV-curable adhesive (photo-curable adhesive), an inorganic binder, or the like. Examples of UV-curable adhesives include acrylic adhesives and epoxy adhesives. Examples of inorganic binders include Ceramabond (registered trademark) manufactured by Odec Corporation and Aron Ceramic (registered trademark) manufactured by Toagosei Co., Ltd. In this embodiment, as an example, the adhesive layer 6 is formed of a UV-curable adhesive.

[0041] The conductive layer 5 is provided on the first main surface 2a of the substrate 2. The conductive layer 5 is formed continuously (integrally) on a region of the first main surface 2a of the substrate 2 corresponding to the opening 3a of the frame 3, on the inner surface of the opening 3a, and on the second surface 3g of the frame 3 around the periphery of the opening 3a. In the measurement region R, the conductive layer 5 covers a portion of the first main surface 2a of the substrate 2 where no holes 2c are formed. The conductive layer 5 is provided so as not to block the holes 2c. In the measurement region R, the holes 2c are exposed to the opening 3a.

[0042] The conductive layer 5 is also formed continuously (integrally) on the first main surface 2a of the substrate 2 in an area corresponding to the opening 3b of the frame 3, on the inner surface of the opening 3b, and on the second surface 3g of the frame 3 around the periphery of the opening 3b. In the calibration region C, the conductive layer 5 covers the portion of the first main surface 2a of the substrate 2 where no holes 2c are formed. The conductive layer 5 is provided so as not to block the holes 2c. In the calibration region C, as in the measurement region R, the holes 2c are exposed to the opening 3b. Note that the conductive layer 5 is not shown in FIG. 1.

[0043] The conductive layer 5 is made of a conductive material. The conductive layer 5 is made of a material suitable for mass spectrometry of a sample. Specifically, the conductive layer 5 is made of, for example, Pt (platinum) or Au (gold). For the reasons described below, it is preferable to use, as the material for the conductive layer 5, a metal that has low affinity (reactivity) with the sample and high conductivity.

[0044] For example, if the conductive layer 5 is made of a metal such as Cu (copper) that has a high affinity for a sample such as a protein, the sample may be ionized in a state in which Cu atoms are attached to the sample molecules during the sample ionization process described below, and the detection results in the mass spectrometry method described below may be distorted by the amount of the added Cu atoms. Therefore, it is preferable to use a metal that has a low affinity for the sample as the material for the conductive layer 5.

[0045] On the other hand, the higher the conductivity of a metal, the easier and more stable the application of a constant voltage. Therefore, if the conductive layer 5 is made of a metal with high conductivity, it becomes possible to uniformly apply a voltage to the first main surface 2a of the substrate 2 in the measurement region R. Furthermore, the higher the conductivity of a metal, the higher the thermal conductivity tends to be. Therefore, if the conductive layer 5 is made of a metal with high conductivity, it becomes possible to efficiently transmit the energy of the energy beam irradiated onto the substrate 2 to the sample via the conductive layer 5. Therefore, it is preferable to use a metal with high conductivity as the material for the conductive layer 5.

[0046] From the above viewpoints, it is preferable to use, for example, Pt, Au, etc. as the material of the conductive layer 5. In this embodiment, the material of the conductive layer 5 is Pt. The conductive layer 5 is formed, for example, by a known general vapor deposition method. The conductive layer 5 is formed by vapor-depositing Pt onto the heated substrate 2. This ensures the flatness or uniformity of the surface 5a of the conductive layer 5. The vapor deposition of Pt is carried out, for example, in a vacuum chamber with a degree of vacuum of 10 -4The deposition is carried out under conditions of about Pa. The conductive layer 5 is a vapor-deposited film formed in a film shape. The thickness of the conductive layer 5 is, for example, about 1 nm to 350 nm. The thickness of the conductive layer 5 may be, for example, less than 30 nm. Note that, as the material of the conductive layer 5, for example, Cr (chromium), Ni (nickel), Ti (titanium), Ag (silver), etc. may be used. The conductive layer 5 may be formed by, for example, sputtering, etc.

[0047] The sample support 1 is fixed to a slide glass (reinforcing substrate) 8 by a conductive tape 4. The conductive tape 4 is made of a conductive material. The conductive tape 4 is, for example, an aluminum tape, a carbon tape, or the like. The thickness of the conductive tape 4 is, for example, about 50 μm.

[0048] The conductive tape 4 is attached to the second surface 3g of the frame 3. In this embodiment, the conductive tape 4 is provided on both sides of the frame 3 in the X-axis direction. Specifically, the conductive tape 4 has a conductive tape 41 provided on one side of the frame 3 in the X-axis direction (the left side in FIG. 1 ) and a conductive tape 42 provided on the other side of the frame 3 in the X-axis direction (the right side in FIG. 1 ).

[0049] The conductive tape 41 is provided on one side (the left side in FIG. 1 ) of the center of the frame 3 in the X-axis direction so as not to cover the measurement region R and the calibration region C. The conductive tape 41 is provided with a circular opening 41a for exposing the calibration region C. In this embodiment, the edges of the conductive tape 41 are slightly spaced apart from the edges 3c and 3e of the frame 3, the edge of the opening 3a of the frame 3, and the edge of the opening 3b of the frame 3. Meanwhile, the conductive tape 41 is also provided at a position overlapping with the space formed by the recess 3d of the frame 3 when viewed from the thickness direction D. That is, the conductive tape 41 has a portion 4b that does not overlap with the frame 3 when viewed from the thickness direction D (i.e., the portion overlapping with the space formed by the recess 3d).

[0050] The conductive tape 42 is provided on the other side of the center of the frame 3 in the X-axis direction (the right side in FIG. 1 ) so as not to cover the measurement region R. In this embodiment, the edges of the conductive tape 42 are slightly spaced from the edges 3c and 3e of the frame 3 and the edge of the opening 3a of the frame 3. Meanwhile, the conductive tape 42 is also provided at a position overlapping the recess 3d of the frame 3 when viewed from the thickness direction D. That is, the conductive tape 42 has a portion 4b that does not overlap the frame 3 when viewed from the thickness direction D (i.e., a portion that overlaps with the space formed by the recess 3d). The portions 4b of the conductive tapes 41 and 42 are attached to the mounting surface 8a of the slide glass 8, thereby fixing the sample support 1 to the slide glass 8.

[0051] The slide glass 8 is a glass substrate on which a transparent conductive film such as an ITO (Indium Tin Oxide) film is formed, and the surface of the transparent conductive film serves as the mounting surface 8a. The slide glass 8 is fixed to the substrate 2 so as to cover at least the entire second main surface 2b of the substrate 2 in the measurement region R. As an example, the slide glass 8 has a rectangular shape larger than the outer shape of the frame 3 when viewed from the thickness direction D (Z-axis direction). That is, when viewed from the thickness direction D, all elements constituting the sample support 1 described above (such as the substrate 2 and frame 3) are contained within the slide glass 8. That is, the slide glass 8 covers not only the measurement region R but also the entire substrate 2. The sample support 1 is reinforced by the slide glass 8. Note that a substrate other than the slide glass 8 may be used as the reinforcing substrate for the sample support 1.

[0052] 4 is an enlarged view of the measurement region R when viewed from the first main surface 2a side of the substrate 2. As shown in FIG. 4, the sample support 1 has a plurality of absorbing portions 7. The plurality of absorbing portions 7 are provided on the surface 5a of the conductive layer 5. The absorbing portions 7 are provided at least in the measurement region R and the calibration region C.

[0053] The absorbing portions 7 are scattered on the surface 5a of the conductive layer 5. Specifically, the surface 5a of the conductive layer 5 includes a plurality of first regions 51a and second regions 52a. The first regions 51a are spaced apart from one another. When viewed from the thickness direction D, the shapes of the first regions 51a are different from one another. When viewed from the thickness direction D, the first regions 51a are irregularly distributed. The second regions 52a are located between the first regions 51a. In this embodiment, the second regions 52a are regions of the surface 5a of the conductive layer 5 other than the first regions 51a.

[0054] The absorbing portions 7 are provided in the first regions 51a. In this embodiment, the absorbing portions 7 are provided in each of the first regions 51a, and the absorbing portions 7 are not provided in the second regions 52a. In other words, each of the first regions 51a is a region of the surface 5a of the conductive layer 5 where the absorbing portions 7 are provided. The second regions 52a are a region of the surface 5a of the conductive layer 5 where the absorbing portions 7 are not provided. The second regions 52a are exposed.

[0055] The first region 51a and the second region 52a are defined by the shape and distribution of the absorbing portions 7. Because the absorbing portions 7 are provided on a part of the surface 5a of the conductive layer 5, when viewed from the thickness direction D, the area corresponding to the plurality of absorbing portions 7 is smaller than the area corresponding to the conductive layer 5. Note that the absorbing portions 7 are not shown in FIGS. 1 and 2.

[0056] FIG. 5 is a cross-sectional view of a portion of the sample support 1 where the absorbing section 7 is present. As shown in FIG. 5, the conductive layer 5 is formed on the first main surface 2a of the substrate 2 and on a portion of the inner wall surface of each hole 2c on the first main surface 2a side. The absorbing section 7 has a plurality of particles 71. The plurality of particles 71 are deposited on the surface 5a of the conductive layer 5. The particles 71 are, for example, nanoparticles. Nanoparticles refer to particles with a particle size smaller than a predetermined value. In this embodiment, the average particle size of the particles 71 is approximately 5 nm to 1000 nm.

[0057] The average particle size of the particles 71 is a value obtained by a method of two-dimensionally observing the shape of the particles 71. The shape of the particles 71 is observed, for example, using a scanning electron microscope (SEM) or a scanning probe microscope (SPM). The average particle size of the particles 71 is obtained by performing image analysis on a two-dimensional image obtained using the microscope described above, or by directly measuring the length of an image observed using the microscope described above. In the case of image analysis, for example, a binarization process is performed on the obtained image of the absorbing portion 7 to extract multiple pixel groups corresponding to multiple particles 71, and the diameter of a circle having the average area of ​​the multiple particles 71 is obtained as the average particle size of the multiple particles 71 based on the size per pixel.

[0058] When measuring the length directly, the outer edge of the particle 71 is recognized based on the contrast difference of the particle boundary of the particle 71 in the image of the absorbing portion 7 to be observed, and then the particle diameter (actual size) of the particle 71 is obtained based on the length across the outer edge (pixel size). When measuring the length directly, both ends of the particle 71 may be recognized based on a one-dimensional profile representing the unevenness of the surface of the particle 71 in the image of the absorbing portion 7 to be observed, and then the particle diameter (actual size) of the particle 71 may be obtained based on the length between the ends (pixel size). When measuring the length directly, the particle diameters of multiple particles 71 are obtained as described above, and then a statistical average or median is obtained as the average particle diameter of the particles 71. Note that, when the shape observation shows that multiple particles 71 form an aggregate, the particle diameter of each particle 71 included in the aggregate is measured. In this embodiment, the average particle diameter (approximately 5 nm to 1000 nm) of the particles 71 is a value obtained by one of the above methods.

[0059] The plurality of particles 71 are distributed so as to partially cover the conductive layer 5. Specifically, the plurality of particles 71 are distributed on the surface 5a of the conductive layer 5 formed on the first main surface 2a, on the surface 5a of the conductive layer 5 formed on the inner wall surface of each hole 2c, and on the portion of the inner wall surface of each hole 2c that is exposed from the conductive layer 5. The plurality of particles 71 do not have to completely cover the conductive layer 5. A portion of the conductive layer 5 may be exposed from the plurality of particles 71. The plurality of particles 71 do not block each hole 2c. The plurality of particles 71 may block a portion of the hole 2c. The plurality of particles 71 may completely block some of the holes 2c. It is sufficient that the plurality of particles 71 do not block all of the holes 2c.

[0060] Fig. 6 shows an example of an SEM image of a part of the sample support 1 on which absorbing portions 7 are provided. In the SEM image, the black parts are holes 2c, the gray parts are conductive layers 5 formed on the surfaces of the partition walls between the holes 2c, and the white parts are absorbing portions 7. As shown in Fig. 6, a plurality of absorbing portions 7 are scattered on the surface 5a of the conductive layer 5. Each absorbing portion 7 is attached to the surface 5a of the conductive layer 5.

[0061] The plurality of particles 71 are absorptive of the energy rays used to ionize the components of the sample S. That is, the absorptivity of the plurality of particles 71 to the energy rays is relatively high. The absorptivity of the plurality of particles 71 to the energy rays is equal to or greater than the absorptivity of the conductive layer 5 to the energy rays. In this embodiment, the absorptivity of the plurality of particles 71 to the energy rays is greater than the absorptivity of the conductive layer 5 to the energy rays. The plurality of particles 71 exhibit a sensitizing effect to the energy rays. The sensitizing effect of the plurality of particles 71 to the energy rays is equal to or greater than the sensitizing effect of the conductive layer 5 to the energy rays. In this embodiment, the energy rays are laser light. That is, the plurality of particles 71 are absorptive of the laser light.

[0062] The plurality of particles 71 are conductive. This allows a voltage to be applied not only to the conductive layer 5 but also to the particles 71, thereby ensuring the transfer of energy to the components of the sample on the first principal surface 2a side. The material of the plurality of particles 71 is different from the material of the conductive layer 5. The material of the plurality of particles 71 contains a metal element. In this embodiment, the material of the plurality of particles 71 is Au.

[0063] The plurality of particles 71 are formed by electrostatic spraying. Specifically, first, a liquid (particle dispersion) containing the plurality of particles 71 is injected (sprayed) onto the surface 5a of the conductive layer 5. Then, the liquid attached to the surface 5a of the conductive layer 5 is dried. As a result, each absorbing portion 7 formed of the plurality of particles 71 is formed on the surface 5a of the conductive layer 5.

[0064] [Mass spectrometry method] Next, an example of a mass spectrometry method using the sample support 1 will be described.

[0065] First, the above-described sample support 1 is prepared in advance. Next, a sample is introduced into each hole 2c. The introduction of the sample into each hole 2c is performed, for example, by pressing the measurement area R against a sample applied to human skin. In other words, the sample is transferred to the measurement area R. The introduction of the sample into each hole 2c may also be performed, for example, by dropping the sample into the measurement area R.

[0066] When the sample is transferred to the measurement region R, the sample support 1 (particularly the substrate 2) can be effectively prevented from being damaged because the sample support 1 is reinforced by the slide glass 8. Next, as shown in Fig. 7, the sample support 1, which has been previously integrated with the slide glass 8, is placed on the support part 12 of the mass spectrometer 10. Note that in Fig. 7, the hole 2c, the conductive layer 5, the adhesive layer 6, and each absorbing part 7 are not shown.

[0067] The mass spectrometer 10 comprises a support unit 12, a sample stage 18, a camera 16, an irradiation unit 13, a voltage application unit 14, an ion detection unit 15, and a control unit 17. The support unit 12 is placed on the sample stage 18. The irradiation unit 13 irradiates an energy beam L onto the first main surface 2a of the sample support 1. The voltage application unit 14 applies a voltage to the first main surface 2a of the sample support 1. The ion detection unit 15 detects sample ions S2. The camera 16 acquires a camera image including the position irradiated with the energy beam L by the irradiation unit 13. The camera 16 is, for example, a small CCD camera attached to the irradiation unit 13.

[0068] The control unit 17 controls the operations of the sample stage 18, the camera 16, the irradiation unit 13, the voltage application unit 14, and the ion detection unit 15. The control unit 17 is, for example, a computer device including a processor (for example, a CPU, etc.) and a memory (for example, a ROM, a RAM, etc.).

[0069] Next, the voltage application unit 14 applies a voltage to the mounting surface 8a of the slide glass 8 and the conductive layer 5 (see FIG. 2) of the sample support 1 via the conductive tape 4. Next, the control unit 17 operates the irradiation unit 13 based on the image acquired by the camera 16. Specifically, the control unit 17 operates the irradiation unit 13 so that the energy beam L is irradiated onto the first principal surface 2a within the laser irradiation range (for example, a region of the measurement region R where the component S1 identified based on the image acquired by the camera 16 exists).

[0070] As an example, the control unit 17 moves the sample stage 18 and controls the irradiation operation (irradiation timing, etc.) of the energy beam L by the irradiation unit 13. That is, after confirming that the sample stage 18 has moved a predetermined distance, the control unit 17 causes the irradiation unit 13 to irradiate the energy beam L. For example, the control unit 17 repeats the movement (scanning) of the sample stage 18 and the irradiation of the energy beam L by the irradiation unit 13 so as to raster scan the laser irradiation range. Note that the irradiation position on the first main surface 2a may be changed by moving the irradiation unit 13 instead of the sample stage 18, or by moving both the sample stage 18 and the irradiation unit 13.

[0071] In this way, by applying a voltage to the conductive layer 5 and irradiating the first principal surface 2a within the laser irradiation range with an energy ray L, the component S1 attached to the measurement region R is ionized. As a result, sample ions S2 are emitted. Specifically, energy is transferred from the conductive layer 5 that has absorbed the energy of the energy ray L to the component S1 attached to the measurement region R, and the component S1 that has acquired the energy is vaporized and acquires an electric charge, becoming the sample ion S2. The above steps correspond to a method for ionizing the component S1 of a sample using the sample support 1 (here, as an example, laser desorption ionization as part of a mass spectrometry method).

[0072] The emitted sample ions S2 move while accelerating toward a ground electrode (not shown) provided between the sample support 1 and the ion detection unit 15. That is, the sample ions S2 move while accelerating toward the ground electrode due to the potential difference generated between the conductive layer 5 to which a voltage is applied and the ground electrode. The sample ions S2 are then detected by the ion detection unit 15.

[0073] The detection result of the sample ions S2 by the ion detection unit 15 is associated with the irradiation position of the energy beam L. Specifically, the ion detection unit 15 detects the sample ions S2 individually for each position within the laser irradiation range. This allows a distribution image (MS mapping data) showing the mass distribution of the sample S to be acquired. Furthermore, it is possible to image the two-dimensional distribution of the molecules that make up the sample S. In other words, it is possible to perform imaging mass analysis. Note that the mass spectrometer 10 here is a mass spectrometer that uses time-of-flight mass spectrometry (TOF-MS).

[0074] As described above, the sample support 1 includes a substrate 2 having a first principal surface 2a and a plurality of holes 2c opening to the first principal surface 2a. When sample component S1 is introduced into the plurality of holes 2c, the component S1 remains on the first principal surface 2a side. When an energy beam L is irradiated onto the first principal surface 2a while a voltage is applied to the conductive layer 5, energy is transferred to the component S1 on the first principal surface 2a side. The component S1 on the first principal surface 2a side is ionized by this energy. Here, a plurality of particles 71 are provided on the surface 5a of the conductive layer 5. The absorptivity of the plurality of particles 71 for the energy beam L is equal to or greater than the absorptivity of the conductive layer 5 for the energy beam L. Therefore, the energy is efficiently transferred to the component S1 on the first principal surface 2a side, thereby efficiently ionizing the component S1 on the first principal surface 2a side. This improves the signal intensity of the sample ions S2 generated by the ionization of the component S1. Therefore, the sample support 1 enables highly sensitive mass analysis.

[0075] The plurality of particles 71 are a plurality of nanoparticles deposited on the surface 5a of the conductive layer 5. This allows the energy to be more efficiently transmitted to the component S1 on the first principal surface 2a side, enabling more sensitive mass analysis.

[0076] When viewed from the thickness direction D, the area corresponding to the plurality of particles 71 is smaller than the area corresponding to the conductive layer 5. This ensures the functions of both the conductive layer 5 and the particles 71, and reliably achieves the highly sensitive mass analysis described above. Specifically, with this configuration, a portion of the conductive layer 5 is exposed, allowing the sample component S1 to come into contact with both the conductive layer 5 and the particles 71. This allows a voltage to be applied to the sample component S1 via the conductive layer 5, while energy is transmitted to the sample component S1 via the particles 71.

[0077] The surface 5a of the conductive layer 5 includes a plurality of first regions 51a that are spaced apart from one another and second regions 52a that are located between each of the plurality of first regions 51a. A plurality of particles 71 are provided in each of the plurality of first regions 51a. A plurality of particles 71 are not provided in the second region 52a. As a result, as described above, it is possible to reliably ensure the functions of both the conductive layer 5 and the particles 71, and to reliably achieve highly sensitive mass analysis.

[0078] The plurality of particles 71 have the ability to absorb laser light, and therefore, by using laser light as the energy ray L, it is possible to realize the above-described highly sensitive mass analysis.

[0079] The sensitizing effect of the plurality of particles 71 on the energy rays L is greater than the sensitizing effect of the conductive layer 5 on the energy rays L. This makes it possible to reliably achieve the above-described highly sensitive mass analysis.

[0080] The material of the plurality of particles 71 is different from the material of the conductive layer 5. This allows for greater freedom in selecting the materials for the conductive layer 5 and the particles 71 while ensuring the functions of both the conductive layer 5 and the particles 71.

[0081] The material of the plurality of particles 71 contains a metal element, which allows for greater freedom in selecting the material of the particles 71 while ensuring the function of the particles 71 having the ability to absorb the energy ray L.

[0082] The material of the plurality of particles 71 is Au. This allows for greater freedom in selecting the material of the particles 71 while ensuring the function of the particles 71 having the ability to absorb the energy ray L.

[0083] The plurality of particles 71 are formed by electrospraying. This allows the particles 71 to have the ability to absorb energy rays L at low cost. Furthermore, aggregation of the particles 71 can be suppressed, and the particles 71 formed on the surface 5a of the conductive layer 5 can be kept in a particle state. Furthermore, the plurality of particles 71 can be distributed evenly on the surface 5a of the conductive layer 5.

[0084] [Example] FIG. 8(a) shows a mass spectrum obtained by the mass spectrometry method of the first comparative example. FIGS. 8(b) and 8(c) each show a mass spectrum obtained by the mass spectrometry method of the first example. The sample support used in the mass spectrometry method of the first comparative example differs from the sample support 1 in that it does not include particles 71. In the mass spectrometry method of the first comparative example, the intensity of the laser light was set to 75%. In the first example, a sample support 1 (FIG. 8(b)) whose particles 71 are made of Pt and a sample support 1 (FIG. 8(c)) whose particles 71 are made of Au were used. In the first example, the intensity of the laser light was set to 50%. The rest of the mass spectrometry method of the first comparative example is the same as the mass spectrometry method of the first example. In the first comparative example and the first example, angiotensin II was used as the sample.

[0085] 8(a) to 8(c), although the intensity of the laser light in Example 1 is lower than that in Comparative Example 1, the detection intensity of ions in the mass spectrometry method of Example 1 is higher than that in the mass spectrometry method of Comparative Example 1 in the region of m / z approximately from 1050 to 1100. Thus, it was found that the sample support 1 enables highly sensitive mass analysis.

[0086] FIG. 9(a) shows a mass spectrum obtained by the mass spectrometry method of the second comparative example. FIG. 9(b) shows a mass spectrum obtained by the mass spectrometry method of the second example. The sample support used in the mass spectrometry method of the second comparative example differs from the sample support 1 in that it does not include particles 71. In the mass spectrometry method of the second comparative example, the intensity of the laser light was set to 80%. In the second example, a sample support 1 whose particles 71 were made of Pt was used. In the second example, the intensity of the laser light was set to 55%. The rest of the mass spectrometry method of the second comparative example is the same as the mass spectrometry method of the second example. In the second comparative example and the second example, angiotensin II was used as the sample.

[0087] 9(a) and 9(b), although the intensity of the laser light in Example 2 is lower than that in Comparative Example 2, the detection intensity of ions in the mass spectrometry method of Example 2 is higher than that in the mass spectrometry method of Comparative Example 2 in the region of m / z approximately 1050 to 1100. Thus, it was found that the sample support 1 enables highly sensitive mass analysis.

[0088] As shown in Figure 8 or 9, the sample support 1 enables highly sensitive mass analysis even when the intensity of the energy beam is relatively low. This makes it possible to perform highly sensitive mass analysis while suppressing damage to the sample component S1, which is the object to be measured, caused by irradiation with the energy beam. In other words, highly sensitive mass analysis is possible while realizing softer ionization of the sample component S1.

[0089] [Method of manufacturing the sample support] Next, a method for manufacturing the sample support 1 will be described.

[0090] As shown in FIG. 10, first, a substrate 2 is prepared (step S1, first process). The substrate 2 is prepared in a state where it is adhered to a frame 3 by an adhesive layer 6. Subsequently, a conductive layer 5 is provided on a first main surface 2a of the substrate 2 (step S2, second process). In step S2, the conductive layer 5 is formed by, for example, a known vapor deposition method. In step S2, Pt is vapor-deposited onto the heated substrate 2. This ensures the flatness of the surface 5a of the conductive layer 5. In step S2, for example, a vacuum of 10 -4 Pt is vapor-deposited under conditions of about Pa. In step S2, a conductive layer 5 is provided so as not to block the holes 2c.

[0091] Next, a plurality of absorbing portions 7 are provided on the surface 5a of the conductive layer 5 (step S3, third process). In step S3, a plurality of absorbing portions 7 are provided by a wet process. In step S3, a plurality of absorbing portions 7 are provided by, for example, an electrostatic spray method. Specifically, in step S3, an electrostatic spray is used to form a liquid containing a plurality of particles 71 into fine droplets and then spray (spray) them onto the surface 5a of the conductive layer 5. This makes it possible to provide a plurality of particles 71 on the surface 5a of the conductive layer 5 while suppressing aggregation of the plurality of particles 71.

[0092] In step S3, a liquid containing a plurality of particles 71 is sprayed onto the surface 5a of the conductive layer 5 provided in at least each of the measurement region R and the calibration region C. The electrostatic spraying method in step S3 uses, for example, an electrostatic spray film-forming device manufactured by Hamamatsu Nano Technology Co., Ltd. Next, the liquid adhered to the surface 5a of the conductive layer 5 is dried. As a result, each absorbing portion 7 containing the particles 71 is formed on the surface 5a of the conductive layer 5.

[0093] As explained above, according to the method for manufacturing the sample support 1, it is possible to manufacture the sample support 1 that enables highly sensitive mass analysis, as described above.

[0094] In step S3, a plurality of particles 71 are provided by a wet process. This makes it possible to reliably form the particles 71 that are absorbent to the energy ray L.

[0095] In step S3, a liquid containing a plurality of particles 71 is sprayed onto the surface 5a of the conductive layer 5 by electrostatic spraying. This makes it possible to reliably form the particles 71 that are absorbent to the energy ray L at low cost. Furthermore, it is possible to suppress aggregation of the particles 71, thereby ensuring that the particles 71 formed on the surface 5a of the conductive layer 5 remain in a particle state. Furthermore, it is possible to distribute the plurality of particles 71 evenly on the surface 5a of the conductive layer 5.

[0096] [Variations] Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. For example, the materials and shapes of the components are not limited to those described above, and various materials and shapes can be used.

[0097] The conductive layer 5 may be composed of, for example, a plurality of particles. In this case, the density of the plurality of particles in the conductive layer 5 is greater than the density of the plurality of particles 71 in the absorbing section 7. The density refers to the ratio of the volume of the particles to the volume of a space having a predetermined volume when the plurality of particles are present in the space. For example, the greater the number of particles present in the space, the greater the particle density tends to be. For example, the smaller the volume of the gaps between the particles present in the space, the greater the particle density tends to be. The plurality of particles in the conductive layer 5 are more densely packed than the plurality of particles 71 in the absorbing section 7. The average particle size of the plurality of particles 71 in the absorbing section 7 is greater than the average particle size of the plurality of particles in the conductive layer 5. The average particle size of the plurality of particles in the conductive layer 5 is obtained by the same method as the plurality of particles 71 in the absorbing section 7. With this configuration, the energy ray L can be efficiently absorbed without increasing the thickness of the conductive layer 5. Specifically, according to the sample supports 1, 1A, and 1B, the conductive layer 5 ensures the function of conductivity, and the absorbing portions 7 also ensure the function of absorbing the energy rays L, so the thickness of the conductive layer 5 can be set to the minimum value necessary to ensure conductivity. The total thickness of the conductive layer 5 and the thickness of the plurality of absorbing portions 7 may be less than 30 nm, for example.

[0098] In the embodiment, the material of the plurality of particles 71 is Au. However, the material of the plurality of particles 71 may be, for example, Pt. That is, the material of the plurality of particles 71 may be the same as the material of the conductive layer 5. In this case, the conductive layer 5 and the material of the plurality of particles 71 can be made of the same material, simplifying the configuration of the sample support 1. Furthermore, when a liquid containing a sample is dropped onto a region of the measurement region R where the absorption section 7 is provided, the visibility of the region of the measurement region R onto which the liquid is dropped can be improved. Furthermore, the material of the plurality of particles 71 may be Pd (palladium). The plurality of particles 71 may be capable of absorbing hydrogen. The absorption rate of Pd for the energy beam L is greater than the absorption rate of Pt for the energy beam L. When the material of the plurality of particles 71 is Pd, the plurality of particles 71 may be subjected to a treatment for absorbing hydrogen (treatment of exposing to a hydrogen gas atmosphere). The material of the plurality of particles 71 may be a material capable of absorbing hydrogen, such as Mg (magnesium), Al (aluminum), Ti (titanium), Fe (iron), Ni (nickel), Zr (zirconium), Nb (niobium), Mo (molybdenum), Ta (tantalum), La (lanthanum), Ce (cerium), Th (thorium), or an alloy containing any of these. Even in such a case, the plurality of particles 71 may be subjected to a treatment for absorbing hydrogen.

[0099] The material of the plurality of particles 71 may be, for example, TiO2 (titanium dioxide). In this case, the functionality of the particles 71 having the absorbency for the energy ray L is ensured, and the degree of freedom in selecting the material of the particles 71 can be improved.

[0100] FIG. 11(a) shows a mass spectrum obtained by the mass spectrometry method of the third comparative example. FIG. 11(b) shows a mass spectrum obtained by the mass spectrometry method of the third example. The sample support used in the mass spectrometry method of the third comparative example differs from the sample support 1 in that it does not include particles 71. In the third example, a sample support 1 was used in which the particles 71 were made of TiO2. The rest of the mass spectrometry method of the third comparative example was the same as the mass spectrometry method of the third example. In the third comparative example and the third example, a sunscreen cream applied to human skin was transferred to the measurement region R. The intensity of the laser light in the third comparative example was the same as that in the third example.

[0101] 11(a) and (b), the detection intensity of ions in the mass spectrometry method of the third embodiment is greater than the detection intensity of ions in the mass spectrometry method of the third comparative example in the region around m / z 630. Thus, it was found that the sample support 1 enables highly sensitive mass spectrometry.

[0102] The material of the plurality of particles 71 may contain carbon. The material of the plurality of particles 71 may be a compound containing a metal element or carbon. In the embodiment, an example has been shown in which the plurality of particles 71 are conductive, but the plurality of particles 71 may also be insulating. The plurality of particles 71 may also have semiconductor properties. In these cases, the functionality of the particles 71 that absorbs the energy ray L can be ensured while increasing the degree of freedom in selecting the material of the particles 71. The plurality of particles 71 only needs to absorb the energy ray L used to ionize the component S1 of the sample.

[0103] The plurality of particles 71 may have ultraviolet absorbing properties, which broadens the range of wavelength band of the energy rays L, thereby improving the degree of freedom in selecting the type of energy rays L.

[0104] In the embodiment, an example has been shown in which the absorbing portions 7 are scattered on the surface 5a of the conductive layer 5, but the plurality of particles 71 may cover the surface 5a of the conductive layer 5. In other words, the entire surface 5a of the conductive layer 5 provided at least in the measurement region R or the calibration region C may be covered with the plurality of particles 71. The surface 5a of the conductive layer 5 does not have to be exposed.

[0105] In the embodiment, the plurality of particles 71 are formed by electrostatic spraying as an example of a wet process, but the plurality of particles 71 may be formed by, for example, another wet process. The plurality of particles 71 may be formed by, for example, ultrasonic spraying. In this case, similar to the electrostatic spraying, the plurality of particles 71 can be evenly distributed on the surface 5a of the conductive layer 5.

[0106] The plurality of particles 71 may be formed by dripping or dip coating using a particle dispersion liquid containing the plurality of particles 71. In this case, the thickness of the absorbing section 7 can be ensured by performing the dripping or dip coating multiple times. Fig. 12 is an enlarged image of the absorbing section 7 formed by the dripping onto the surface 5a of the conductive layer 5. As shown in Fig. 12, the surface 5a of the conductive layer 5 has a plurality of absorbing sections 7 provided thereon.

[0107] The plurality of particles 71 may be formed by spin coating using a particle dispersion liquid containing the plurality of particles 71. Fig. 13 is an enlarged image of the absorbing portion 7 formed by the above-described spin coating on the surface 5a of the conductive layer 5. As shown in Fig. 13, the surface 5a of the conductive layer 5 has a plurality of absorbing portions 7 provided thereon.

[0108] The particles 71 may be formed by a dry process, such as magnetron sputtering, spark ablation, or pulsed vacuum arc deposition.

[0109] In the embodiment, an example has been shown in which the holes 2c extend along the thickness direction D of the substrate 2 and are uniformly formed in the substrate 2. However, the substrate 2 may have, for example, an irregular porous structure. Specifically, the sample support 1 may include a substrate 2A shown in FIG. 14 instead of the substrate 2. As shown in FIG. 14, the substrate 2A is, for example, a sintered body of glass beads. The sintered body of glass beads has a structure in which, for example, a large number of glass beads 21 are integrated by sintering. The shape and size of the glass beads 21 included in the substrate 2A may be uniform or irregular. The holes 2d in the substrate 2A are gaps formed between the glass beads. The holes 2d extend in irregular directions and are irregularly distributed in three dimensions. The holes 2d are irregularly connected to each other. Therefore, for example, a liquid that comes into contact with one main surface of the substrate 2A can move toward the other side of the substrate 2A by following multiple paths (holes 2d) formed inside the substrate 2A. Each hole 2d does not have to penetrate through the substrate 2A. Each hole 2d may be open to one main surface of the substrate 2A and not open to the other main surface of the substrate 2A.

[0110] In the embodiment, an example has been shown in which each hole 2c penetrates the substrate 2, but each hole 2c does not have to penetrate the substrate 2. Specifically, the sample support 1 may include a substrate 2B shown in FIG. 15 instead of the substrate 2. As shown in FIG. 15, the substrate 2B differs from the substrate 2 in that it has a plurality of holes 2e instead of the plurality of holes 2c. Each hole 2e does not penetrate the substrate 2B. Each hole 2e is open to the first main surface 2a but not to the second main surface 2b. The substrate 2B may be, for example, an anodized alumina porous coating used in SALDI. [Explanation of symbols]

[0111] 1...sample support, 2, 2A, 2B...substrate, 2a...first main surface, 2c...hole, 5...conductive layer, 5a...surface, 51a...first region, 52a...second region, 71...particle, L...energy ray, S1...component of sample.

Claims

1. 1. A sample support for use in ionizing components of a sample, comprising: a substrate having a main surface and a plurality of holes opening on the main surface; a conductive layer provided on the main surface so as not to block the hole; a plurality of particles provided on the surface of the conductive layer, The sample support, wherein the absorptivity of the plurality of particles for the energy beam used for the ionization is equal to or greater than the absorptivity of the conductive layer for the energy beam.

2. 2. The sample support of claim 1, wherein the plurality of particles is a plurality of nanoparticles deposited on the surface of the conductive layer.

3. 3. The sample support according to claim 1, wherein an area corresponding to the plurality of particles is smaller than an area corresponding to the conductive layer when viewed in a direction perpendicular to the main surface.

4. the surface of the conductive layer includes a plurality of first regions spaced apart from one another and second regions located between each of the plurality of first regions; the plurality of particles are provided in each of the plurality of first regions, The sample support of claim 3 , wherein the second region is free of the plurality of particles.

5. 5. The sample support according to claim 1, wherein the plurality of particles are absorptive of laser light.

6. 6. A sample support according to claim 1, wherein the plurality of particles are absorbent to ultraviolet light.

7. 7. The sample support according to claim 1, wherein the sensitizing effect of the plurality of particles to the energy ray is greater than the sensitizing effect of the conductive layer to the energy ray.

8. A sample support according to any one of claims 1 to 7, wherein the material of the plurality of particles is different from the material of the conductive layer.

9. A sample support according to any one of claims 1 to 8, wherein the material of the plurality of particles comprises a metal element.

10. 10. The sample support of claim 9, wherein the material of the plurality of particles is gold, platinum, or titanium dioxide.

11. A sample support according to any one of claims 1 to 8, wherein the material of the plurality of particles comprises carbon.

12. 9. The sample support according to claim 1, wherein the material of the plurality of particles is a compound containing a metal element or carbon.

13. 13. The sample support according to claim 1, wherein the plurality of particles are formed by electrospray deposition.

14. 1. A method for producing a sample support for use in ionizing components of a sample, comprising: A first step of preparing a substrate having a main surface and a plurality of holes opening on the main surface; a second step of providing a conductive layer on the main surface so as not to block the holes; and a third step of providing a plurality of particles on the surface of the conductive layer, The method for manufacturing a sample support, wherein the absorptivity of the plurality of particles for the energy beam used for the ionization is equal to or greater than the absorptivity of the conductive layer for the energy beam.

15. The method for manufacturing a sample support according to claim 14 , wherein in the third step, the plurality of particles are provided by a wet process.

16. 16. The method for manufacturing a sample support according to claim 15, wherein in the third step, the liquid containing the plurality of particles is sprayed onto the surface of the conductive layer by electrospraying.

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