# US 11,442,039 B2 · Sample support body, production method for sample support body, and sample ionization method

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- Number: US 11,442,039 B2
- Document ID: US11442039B2
- Status: Granted
- Kind: B2
- Application number: 16/967,266
- Filed: 2019-01-08
- Published: 2020-12-10
- Granted: 2022-09-13
- Earliest claimed: 2018-02-09
- Assignees: Hamamatsu Photonics K.K.
- Applicants: Hamamatsu Photonics K.K.
- Inventors: Yasuhide Naito; Takayuki Ohmura; Masahiro Kotani
- Web page: https://patentgrep.com/patent/US11442039B2

## CPC

- G01N 27/623: combined with mass spectrometry
- H01J 49/0409: {Sample holders or containers (containers for retaining a material to be analyzed, B01L3/50, for DNA, C12Q1/6834, for biological materials, G01N33/543)}
- G01N 27/62: by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N 27/628: {and a beam of energy, e.g. laser enhanced ionisation}
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)

## Abstract

Provided is a sample support body that includes: a substrate having a first surface and a second surface opposite to each other; and a conductive layer provided on at least the first surface. A plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer. At least one of the second surface and the third surface is subjected to surface treatment for providing a difference in an affinity with water between a surface close to the second surface and a surface close to the third surface.

## Claims

### Claim 1

A sample support body for ionization of a sample comprising:
a substrate having a first surface and a second surface opposite to each other; and
a conductive layer provided on at least the first surface,
wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer, and
at least one of the second surface and the third surface is subjected to surface treatment for providing a difference in an affinity with water between a surface close to the second surface and a surface close to the third surface.

### Claim 2 (depends on 1)

The sample support body according to claim 1, wherein a hydrophobic coating layer is provided on the second surface such that the surface close to the third surface has a higher affinity with water than the surface close to the second surface.

### Claim 3 (depends on 1)

The sample support body according to claim 1, wherein:
surface treatment for improving the affinity with water is performed on the third surface and an inner surface of a portion including an edge of each through-hole which is close to the third surface such that the surface close to the third surface has a higher affinity with water than the surface close to the second surface; and
the surface treatment for improving the affinity with water includes at least one of, providing a hydrophilic coating layer on the third surface and the inner surface of the portion, and performing excimer application or plasma application on the third surface and the inner surface of the portion.

### Claim 4 (depends on 1)

The sample support body according to claim 1, wherein:
surface treatment for improving the affinity with water is performed on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that the surface close to the second surface has a higher affinity with water than the surface close to the third surface; and
the surface treatment for improving the affinity with water includes at least one of, providing a hydrophilic coating layer on the second surface and the inner surface of the portion, and performing excimer application or plasma application on the second surface and the inner surface of the portion.

### Claim 5 (depends on 1)

The sample support body according to claim 1, wherein a hydrophobic coating layer is provided on the third surface such that the surface close to the second surface has a higher affinity with water than the surface close to the third surface.

### Claim 6 (depends on 1)

The sample support body according to claim 1, wherein the substrate is formed by anodizing a valve metal or silicon.

### Claim 7 (depends on 1)

The sample support body according to claim 1, wherein widths of the through-holes are 1 nm to 700 nm.

### Claim 8 (depends on 1)

The sample support body according to claim 1, wherein a material of the conductive layer is platinum or gold.

### Claim 9

A sample support body for ionization of a sample comprising
a substrate which has conductivity and is formed with a plurality of through-holes which open to a first surface and a second surface opposite to each other,
wherein at least one of the first surface and the second surface is subjected to surface treatment for providing a difference in an affinity with water between a surface close to the first surface and a surface close to the second surface,
the surface treatment is
treatment that includes at least one of, providing a hydrophilic coating layer on the first surface and an inner surface of a portion including an edge of each through-hole which is close to the first surface such that a surface close to the first surface has a higher affinity with water than a surface close to the second surface, and performing excimer application or plasma application on the first surface and the inner surface of the portion including the edge of each through-hole which is close to the first surface, or
treatment that includes at least one of, providing a hydrophilic coating layer on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that the surface close to the second surface has a higher affinity with water than the surface close to the first surface, and performing excimer application or plasma application on the second surface and the inner surface of the portion including the edge of each through-hole which is close to the second surface.

### Claim 10 (depends on 3)

The sample support body according to claim 3, wherein the hydrophilic coating layer is a layer formed by forming a film of titanium oxide or zinc oxide.

### Claim 11 (depends on 2)

The sample support body according to claim 2, wherein the hydrophobic coating layer is a layer formed by vapor deposition of a metal, or a layer formed of a self-assembled monolayer.

### Claim 12

A production method for a sample support body for ionization of a sample comprising:
a first process of preparing a substrate having a first surface and a second surface opposite to each other and a conductive layer provided on at least the first surface, wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer; and
a second process of performing surface treatment, for providing a difference in an affinity with water between a surface close to the second surface and a surface close to the third surface, on at least one of the second surface and the third surface.

### Claim 13 (depends on 12)

The production method according to claim 12, wherein the second process includes a process of providing a hydrophobic coating layer on the second surface such that the surface close to the third surface has a higher affinity with water than the surface close to the second surface.

### Claim 14 (depends on 12)

The production method according to claim 12, wherein:
the second process includes a process of performing surface treatment for improving the affinity with water on the third surface and an inner surface of a portion including an edge of each through-hole which is close to the third surface such that the surface close to the third surface has a higher affinity with water than the surface close to the second surface; and
the surface treatment for improving the affinity with water includes at least one of, providing a hydrophilic coating layer on the third surface and the inner surface of the portion, and performing excimer application or plasma application on the third surface and the inner surface of the portion.

### Claim 15 (depends on 12)

The production method according to claim 12, wherein:
the second process includes a process of performing surface treatment for improving the affinity with water on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that the surface close to the second surface has a higher affinity with water than the surface close to the third surface; and
the surface treatment for improving the affinity with water includes at least one of, providing a hydrophilic coating layer on the second surface and the inner surface of the portion, and performing excimer application or plasma application on the second surface and the inner surface of the portion.

### Claim 16 (depends on 12)

The production method according to claim 12, wherein the second process includes a process of providing a hydrophobic coating layer on the third surface such that the surface close to the second surface has a higher affinity with water than the surface close to the third surface.

### Claim 17

A production method for a sample support body for ionization of a sample comprising:
a first process of preparing a substrate which has conductivity and is formed with a plurality of through-holes which open to a first surface and a second surface opposite to each other; and
a second process of performing surface treatment, for providing a difference in an affinity with water between a surface close to the first surface and a surface close to the second surface, on at least one of the first surface of the substrate and the second surface of the substrate,
wherein the surface treatment is
treatment that includes at least one of, providing a hydrophilic coating layer on the first surface and an inner surface of a portion including an edge of each through-hole which is close to the first surface such that a surface close to the first surface has a higher affinity with water than a surface close to the second surface, and performing excimer application or plasma application on the first surface and the inner surface of the portion including the edge of each through-hole which is close to the first surface, or
treatment that includes at least one of, providing a hydrophilic coating layer on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that the surface close to the second surface has a higher affinity with water than the surface close to the first surface, and performing excimer application or plasma application on the second surface and the inner surface of the portion including the edge of each through-hole which is close to the second surface.

### Claim 18 (depends on 14)

The production method according to claim 14, wherein, in the second process, the hydrophilic coating layer is formed by forming a film of titanium oxide or zinc oxide.

### Claim 19 (depends on 13)

The production method according to claim 13, wherein, in the second process, the hydrophobic coating layer is formed by vapor deposition of a metal, or is formed of a self-assembled monolayer.

### Claim 20

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has a first surface and a second surface opposite to each other, and a conductive layer provided on at least the first surface, wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer;
a second process of mounting the sample support body on a mounting surface of a mount such that the second surface faces the mounting surface;
a third process of dropping a solution including a sample onto the plurality of through-holes from a side of the third surface; and
a fourth process of applying an energy beam to the third surface while applying a voltage to the conductive layer and thus ionizing components of the sample,
wherein a hydrophobic coating layer is provided on the second surface of the substrate such that a surface close to the third surface has a higher affinity with water than a surface close to the second surface.

### Claim 21 (depends on 20)

The sample ionization method according to claim 20, wherein surface treatment for improving the affinity with water is performed on the third surface and an inner surface of a portion including an edge of each through-hole which is close to the third surface.

### Claim 22

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has a first surface and a second surface opposite to each other, and a conductive layer provided on at least the first surface, wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer;
a second process of mounting the sample support body on a mounting surface of a mount such that the second surface faces the mounting surface;
a third process of dropping a solution including a sample onto the plurality of through-holes from a side of the third surface; and
a fourth process of applying an energy beam to the third surface while applying a voltage to the conductive layer and thus ionizing components of the sample,
wherein surface treatment for improving an affinity with water is performed on the third surface and an inner surface of a portion including an edge of each through-hole which is close to the third surface such that a surface close to the third surface has a higher affinity with water than a surface close to the second surface.

### Claim 23

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has conductivity and is formed with a plurality of through-holes that open to a first surface and a second surface opposite to each other;
a second process of mounting the sample support body on a mounting surface of a mount such that the second surface faces the mounting surface;
a third process of dropping a solution including a sample onto the plurality of through-holes from a side of the first surface; and
a fourth process of applying an energy beam to the first surface while applying a voltage to the substrate and thus ionizing components of the sample,
wherein a hydrophobic coating layer is provided on the second surface such that a surface close to the first surface has a higher affinity with water than a surface close to the second surface.

### Claim 24

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has a first surface and a second surface opposite to each other, and a conductive layer provided on at least the first surface, wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer;
a second process of disposing the sample support body on a sample such that the second surface faces the sample mounted on a mounting surface of a mount; and
a third process of applying an energy beam to the third surface while applying a voltage to the conductive layer in a state in which components of the sample move toward the third surface via the plurality of through-holes due to a capillary phenomenon, and thus ionizing the components of the sample,
wherein surface treatment for improving an affinity with water is performed on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that a surface close to the second surface has a higher affinity with water than a surface close to the third surface.

### Claim 25 (depends on 24)

The sample ionization method according to claim 24, wherein a hydrophobic coating layer is provided on the third surface such that the surface close to the second surface has a higher affinity with water than the surface close to the third surface.

### Claim 26

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has a first surface and a second surface opposite to each other, and a conductive layer provided on at least the first surface, wherein a plurality of through-holes, which open to the second surface and a third surface of the conductive layer which is located on a side opposite to the substrate, are formed in the substrate and the conductive layer;
a second process of disposing the sample support body on a sample such that the second surface comes into contact with the sample mounted on a mounting surface of a mount; and
a third process of applying an energy beam to the third surface while applying a voltage to the conductive layer in a state in which components of the sample move toward the third surface via the plurality of through-holes due to a capillary phenomenon, and thus ionizing the components of the sample,
wherein a hydrophobic coating layer is provided on the third surface such that a surface close to the second surface has a higher affinity with water than a surface close to the third surface.

### Claim 27

A sample ionization method comprising:
a first process of preparing a sample support body that includes a substrate which has conductivity and is formed with a plurality of through-holes that open to a first surface and a second surface opposite to each other;
a second process of disposing the sample support body on a sample such that the second surface faces the sample mounted on a mounting surface of a mount; and
a third process of applying an energy beam to the first surface while applying a voltage to the substrate in a state in which components of the sample move toward the first surface via the plurality of through-holes due to a capillary phenomenon, and thus ionizing the components of the sample,
wherein surface treatment for improving an affinity with water is performed on the second surface and an inner surface of a portion including an edge of each through-hole which is close to the second surface such that a surface close to the second surface has a higher affinity with water than a surface close to the first surface.

### Claim 28 (depends on 24)

The sample ionization method according to claim 24, wherein:
the sample is a dry sample; and
the sample ionization method further comprises a process of adding a solution for reducing a viscosity of the sample to the sample mounted on the mounting surface before the third process.