JP2022058178A - Sample manufacturing method and sample observation method - Google Patents

Abstract

To provide a new production method of a sample capable of suppressing deformation of a material over time or diffusion of elements of the material by electron beam radiation while preventing contamination caused by sample changes.SOLUTION: A production method of a sample includes: a first treatment step of forming a layer of a metal compound by adhering a gaseous metal compound to a surface of a material; and a second treatment step of forming a metal oxide or a metal layer from the metal compound layer by reacting the metal compound with a gaseous oxidant. The material contains a first component, and the sample contains the first component observation accuracy of which decreases or which deforms over time when receiving an electron beam from an electron microscope.SELECTED DRAWING: Figure 2

Description

The present invention relates to a method for producing a sample and a method for observing a sample.

For example, Patent Document 1 describes a detection kit in which a material is coated with a protective agent containing at least one selected from a surfactant-containing solution, an amphipathic compound, oils and fats, an ionic liquid, and osmium.

Further, Patent Document 2 describes an observation method including a step of applying a protective agent for electron microscope observation containing a saccharide and an electrolyte to a biological sample in a water-containing state.

Japanese Unexamined Patent Publication No. 2017-201289 (published on November 9, 2017) International Publication No. 2015/115502 (International Release on August 6, 2015)

Although the observation method using the detection kit described in Patent Document 1 and the observation method described in Patent Document 2 can be a means for preventing the diffusion of elements and the deformation of the material brought to the sample, the organic compound contained in the protective agent. However, there is a problem that the hydrocarbon gas is decomposed by the observation method to generate a hydrocarbon gas, and the generated hydrocarbon gas adheres to the sample or the observation device, thereby contaminating the observation environment. Therefore, it is possible to suppress the material from being deformed over time and the diffusion of the elements of the material due to electron beam irradiation, and to prevent the contamination caused by the change of the sample, and to manufacture a new sample. A method is required.

In order to solve the above problems, the production method according to one aspect of the present invention is a method for producing a sample for observation with an electron microscope, and a gaseous metal compound is formed on the surface of the material for producing the sample. In the first treatment step of forming a layer of the metal compound by adhering the metal compound, and by reacting the metal compound with a gaseous oxidizing agent, a metal oxide or a metal layer is formed from the layer of the metal compound. The material includes a first component that reduces observation accuracy or is deformed over time by receiving an electron beam from an electron microscope.

According to one aspect of the present invention, it is possible to prevent the material from being deformed over time and the elements of the material from being diffused by electron beam irradiation, and to prevent contamination caused by changes in the sample. It is possible to provide a new method for producing a sample and related technology thereof.

It is a figure explaining the outline of the atomic layer deposition (ALD) apparatus 10 for carrying out the manufacturing method which concerns on one aspect of this invention. It is a scanning transmission electron microscope (STEM) photograph in the flakes sample of Example 1, and the EDX spectrum of the scanning transmission electron microscope (STEM) in a corresponding region. It is the EDX spectrum of the transmission electron microscope (TEM) photograph in the flakes of Comparative Example 1 and the scanning transmission electron microscope (STEM) in the corresponding region. It is a scanning transmission electron microscope (STEM) photograph in the sample of Example 2 and Comparative Example 2. It is a scanning transmission electron microscope (STEM) photograph in the sample of Example 3 and Comparative Example 3.

In the present specification, when the term "sample" is simply referred to, the term "sample" means a layer of a metal oxide on the surface of an object as a material by the production method according to one aspect of the present invention, unless otherwise specified. Or it means the whole object in which a layer of metal is formed. Further, in the present specification, when the term "material" is simply used, the "material" means the entire object to be observed and is included in the "sample". The surface state of the "material" can be observed by an observation method such as an electron microscope via a layer of metal oxide or a layer of metal formed on the "sample".

<Sample manufacturing method>
The method for producing a sample according to one aspect of the present invention is a method for producing a sample for observation with an electron microscope, and the metal is formed by adhering a gaseous metal compound to the surface of a material for producing the sample. A first treatment step of forming a layer of a compound and a second treatment step of forming a metal oxide or a metal layer from the metal compound layer by reacting the metal compound with a gaseous oxidizing agent. , The material comprises a first component in which the observation accuracy of the sample is reduced over time or the observation accuracy of the observation sample is reduced by receiving an electron beam irradiated by an electron microscope. The method for producing a sample according to one embodiment may include a step of cutting out the material to obtain flakes of the material, depending on the form of the material.

〔material〕
The observation sample contains the first component in the material and may contain the second component. The first component is a material that causes the observation accuracy of the observation sample to be reduced by receiving an electron beam from an electron microscope, and the second component is at least the observation of the observation sample than the first component. It is a component that does not affect the accuracy. The first component may be a component that diffuses, deforms, and disappears when irradiated with an electron beam having an acceleration voltage of 30 kV or more in electron microscope observation. Further, the first component may be, for example, a component that is deformed, diffused, or disappears over time by about 10 days at the latest after cutting out the material. That is, the first component has the property of diffusing, deforming, and disappearing when irradiated with an electron beam, or the property of being deformed, diffused, or disappearing over time after cutting out the material, or both. Has the properties of.

[First component]
The reduction in observation accuracy caused by the first component is caused by the diffusion, deformation, and / or disappearance of the first component caused by irradiating the flakes of the material with an electron beam, or occurs over time.

Diffusion includes the meaning that the first component contained as a dopant in the inorganic component is diffused by an electron beam, that is, the element is diffused as an impurity in an inorganic material such as a so-called semiconductor. Further, diffusion means that a part of the first component contained in the flaked material is disintegrated by an electron beam (also referred to as fragmentation), and the fragment generated by the disintegration is diffused inside or outside the material. Also includes. Diffusion also includes the meaning of diffusion of gas released to the outside of the material by electron beam irradiation or not by electron beam irradiation, and diffusion of fine particles generated by disintegration in the material.

The deformation includes the meaning that the inorganic particles as the first component are made finer or the first component is fragmented by the electron beam irradiation or not by the electron beam irradiation, and as a result, the fine particles are made. The crystallized (collapsed) inorganic particles, or fragmented components, can diffuse inside or outside the material. That is, deformation can be one aspect of diffusion with collapse.

Further, the disappearance means that the unfragmented component or the fragmented first component is diffused by heat and disappears from the sliced material. That is, disappearance can be an aspect of diffusion.

However, the reduction in observation accuracy can occur due to the diffusion, deformation, and disappearance of the first component. In addition, due to the diffusion, deformation, and disappearance of the first component, there may be a problem that the material containing the first component cannot be observed in an appropriate state.

The material to be observed may have a fine structure even in its flakes. Here, the microstructure may be a multi-layer structure or a sea-island structure including a continuous phase and a dispersed phase. The material to be observed may include a layer having a sea-island structure having a continuous phase and a dispersed phase in one layer of the multilayer structure.

When the microstructure of the material flakes is a multi-layer structure, at least one of the plurality of layers in the multi-layer structure may contain the first component. The multi-layer structure of the material flakes may have a thickness of about 0.001 μm to 10 μm for each layer.

When the microstructure of the material flakes is a sea-island structure, one or both of the continuous phase and the dispersed phase in the sea-island structure may contain the first component. The sea-island structure of the material flakes may have an average particle size of the dispersed phase of about 1 nm to 1000 nm.

(halogen)
The first component may be a halogen or a component containing a halogen. Examples of the halogen itself include halogens doped with inorganic components as impurities.

As the first component, the halogen-containing material comprises the diffusion of halogen as a dopant, the diffusion of halogen gas, or the halogen generated by fragmentation of the first component, or halogen when the halogen is irradiated with an electron beam. It can result in the spread of containing fragments.

Examples of the component containing a halogen include silver halide, and the silver halide may be silver chloride, silver bromide, silver iodide, silver fluoride, and various silver halides having photosensitivity.

It should be noted that the fluororesin can also be a component that diffuses halogen by deforming. The fluorine-based resin is not particularly limited as long as it can be used for various devices, and examples of the halogen-based resin include a fluorine-based resin and a chlorine-based resin. Examples of the fluororesin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and tetra. Fluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-trichloroethylene copolymer, vinylidene fluoride-vinyl fluoride Examples thereof include polymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers, and ethylene-tetrafluoroethylene copolymers. Examples of the chlorine-based resin include polyvinyl chloride and polyvinylidene chloride.

Further, the fluorine-based resin may also contain a fluorine-based ionomer. Fluorine-based ionomer is a resin used as a material for a proton-conducting polymer membrane, and in a membrane / electrode junction, a binder similar to the ionomer used for a polymer membrane joins a catalyst layer and a polymer membrane. Has been adopted as. Specific examples of the fluoroionomer include ion-exchange type polymers having a sulfonic acid group, and among them, materials having excellent proton conductivity, strength, and chemical stability, such as perfluoro. It can be a fluoropolymer having a sulfonic acid group, such as a sulfonic acid polymer. Specific examples of the fluoropolymer having a sulfonic acid group include Nafion (registered trademark), Flexion (registered trademark), and Aciplex (registered trademark).

(Silver)
The first component includes silver, which is silver particles, for example, silver used as a metal catalyst and a transparent electrode material. After the material is flaky, which contains silver particles as the first component, it is deformed into finer particles than before the flaky sample was prepared due to temporal factors, and as a result, it diffuses inside the material. There is.

(lead)
The first component includes lead and lead-tin alloys, which may be in the form of particles, for example, lead-tin alloys contained in solder. Lead and lead-tin alloys can be diffused and deformed by electron beam irradiation.

(Organic compound)
Examples of the organic compound as the first component include resins, surfactants, organic solvents, and plasticizers. Organic compounds can be deformed and diffused by electron beam irradiation. Further, the organic compound may include a compound that diffuses to the outside of the thin piece of the material without being deformed by electron beam irradiation. If the flakes of the material contain an organic compound, the organic compound may decompose to produce hydrocarbon gas. The hydrocarbon gas generated as a fragment and the organic solvent vaporized without deformation diffuse and reattach to the sample surface or the observation device, causing contamination that contaminates the observation environment. If the organic compound has a hydrocarbon chain containing a carbon atom and a hydrogen atom and / or an aromatic ring, for example, a halogen atom, a nitrogen atom, a sulfur atom, and an oxygen atom have a molecular structure thereof. It may be included.

Examples of the resin include resins used as binders for inorganic particles, and for example, the above-mentioned fluorine-based resin and fluorine-based ionomer may be examples of the resin.

The resin may be a non-fluoropolymer selected from, for example, polyarylene ether such as polystyrene and polyetheretherketone, aromatic polyimide, polyphosphazene, and polybenzoimidazole. Examples thereof include sulfonated aromatic rings in the above, which may be configured as a copolymer with an olefin. Further, examples of the cellulosic resin include crosslinked sulfoethyl cellulose obtained by sulfoethylizing cellulose, and these can be contained in the membrane electrode.

Other examples of the resin include rosin, modified rosin, terpene resin, polystyrene, polyvinyl, styrene-divinylbenzene copolymer and the like, which may be contained in, for example, a solder material.

Examples of the surfactant include dispersants, wetting agents, defoaming agents, plasticizing agents, leveling agents and the like, which are used when inorganic particles are dispersed and mixed in a resin, and include anionic surfactants and cations. It may be any of a system-based surfactant, an amphoteric surfactant, and a nonionic-based surfactant.

More specifically, the surfactants include glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, trimethylolpropane fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, and polyoxy. Ethylene alkyl ether, polyoxyethylene alkyl phenyl ether, N, N-bis (2-hydroxyethyl) alkyl amide, condensate of fatty acid and diethanolamine, alkyl sulfonate, sodium dicyclohexylsulfosuccinate, polyoxyethylene alkyl phosphate , Tertiary ammonium chloride, alkyl betaine, alkyl imidazoline, alkyl alanine and the like. Surfactants are contained in solder materials and can cause contamination.

Examples of the organic solvent include alcohols such as ethanol and i-propanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dibutyl ethers, ethers such as 1,4-dioxane, pyridine, chlorobenzene, toluene, and the like. Examples thereof include aromatic solvents such as xylene and hydrocarbon solvents such as hexane and cyclohexane. The organic solvent is contained in the solder material as a diluent and can be a component that can cause contamination, diffuse, deform and disappear.

Examples of the plasticizer include a phosphoric acid ester-based plasticizer, a terephthalic acid-based plasticizer, an adipic acid-based plasticizer, and the like.

(Sulfur compound)
Examples of the first component include sulfur compounds. Sulfur atoms contained in the sulfur compound can be diffused by electron beam irradiation, which can cause a decrease in observation accuracy. Examples of the sulfur compound containing a sulfur atom include sulfur alone, sulfur oxide (SOx), hydrogen sulfide, and an organic sulfur compound.

[Second component]
The material and the flakes of the material may contain a second component. The second component is a material that itself does not substantially diffuse, deform, and disappear by electron beam irradiation or by temporal factors. The second component may be a component that does not substantially diffuse, deform, and disappear even when irradiated with an electron beam having an acceleration voltage of 30 kV to 300 kV in electron microscope observation. In addition, the second component may be, for example, a component that does not deform, diffuse, or disappear over time by about 10 days at the latest after cutting out the material.

When the microstructure of the material flakes is a multi-layer structure, at least one of the plurality of layers in the multi-layer structure may contain the second component. When the fine structure of the material flakes is a sea island structure, at least one of the continuous phase and the dispersed phase in the sea island structure may contain the second component.

The second component is one or more selected from glass, metal oxides, metals, metal alloys, preferably glass. Examples of the glass include quartz glass, soda-lime glass, silicic acid glass, organic glass and the like. Examples of the metal oxide include aluminum oxide, magnesium oxide, hafnium oxide and the like. Further, the second component may be a compound semiconductor such as silicon, sapphire, or GaAs (gallium arsenide), or may be a particulate semiconductor exhibiting fluorescence characteristics.

The second component may be, for example, a metal oxide such as titanium oxide, tin oxide, lead oxide, yttrium oxide, indium oxide, etc., and these metal oxides are used, for example, as a transparent electrode material and are layered into flakes. , Or may be included in the form of particles.

The second component includes a noble metal-based catalyst, and examples of the noble metal-based catalyst include metal particles containing a platinum group metal (PGM) such as a platinum catalyst, a ruthenium catalyst, and a ruthenium-platinum alloy catalyst.

Further, the second component may be a porous carbon carrier.

The second component may be an alloy containing tin and an element selected from the group consisting of gold, silver, silicon, bismuth and antimony, which may be included as an alloy in the solder material.

Second components include, for example, aluminum alloys, magnesium alloys, brass, bronze, armco iron, carbonyl iron, and white metal, which are contained in flakes of material in layered or particulate form. It may be.

The second component is aluminum oxide (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), silicon oxide-aluminum oxide (SiO ₂ -Al ₂ O ₃ ), titanium oxide (TIO ₂ ), magnesium oxide (MgO). ), Cerial, ceria-zirconia composite oxide, zirconia, activated carbon, graphite, boron nitride, and carbon nitride can be at least one selected. These may be included as catalyst carriers in the gas adsorption catalyst.

The type of the second component is not limited as long as it does not substantially diffuse, deform, or disappear by electron beam irradiation.

〔material〕
The material is, for example, a glass substrate including a layer of a transparent electrode material used for a touch panel or the like, a film electrode used for a fuel cell, a semiconductor constituting a part of a semiconductor chip or the like, and solder, a photosensitizer, and semiconductor particles. A dispersion liquid and the like can be mentioned. Depending on whether the material is a solid or a liquid, a part of the material may be cut out to produce a sample, or a sample may be produced without cutting out. The material may contain the first component in at least a portion thereof in a state prepared to be sized for observation, and may contain the second component.

The material for producing the sample may contain the first component and is not limited to the material such as a touch panel, and may be cut out as a thin piece from a solar cell, an organic EL material, a lens or the like. That is, the material can be, for example, the electrical and electronic device itself and a part of various composite materials used in the manufacture of the electrical and electronic device, and the observation accuracy is reduced by receiving a thinning process and / or an electron beam by an electron microscope. Contains the first component that causes the problem.

(Glass substrate)
The material used in the method for producing a sample according to one embodiment has a multilayer structure including a plurality of layers, and the first component is, for example, a fluororesin such as vinylidene fluoride or a fluorine-doped tin oxide film (a fluorine-doped tin oxide film). It may be a multi-layer structure including a layer such as FTO) and a layer of a transparent electrode and a layer of a glass substrate having a plurality of layers as a second component in the structure. Further, the glass substrate may contain metal oxides such as titanium oxide, tin oxide, lead oxide, yttrium oxide and indium oxide in the layer of the transparent electrode material contained as the second component.

When the glass substrate is a glass substrate for a touch panel, vinylidene fluoride resin may be contained as the piezo element as the fluororesin. Further, the glass substrate for a touch panel may be provided with fluorine-doped tin oxide as a layer of a transparent electrode. Further, the glass substrate may be a glass substrate provided with a fluorine-doped tin oxide film (FTO) as a layer of a transparent electrode. When such a glass substrate is irradiated with an electron beam, there is a problem that the fluorine doped in the transparent electrode material or the fluorine contained in the fluororesin diffuses toward the glass substrate. According to the method for producing a sample according to one aspect of the present invention, by performing ALD treatment on a thin piece of a glass substrate, the doped fluorine or the fluorine contained in the fluororesin diffuses toward the glass substrate by electron beam irradiation. Can be suitably prevented.

(P-type semiconductor)
The material used in the method for producing a sample according to one embodiment may be, for example, a P-type semiconductor in which nitrogen, phosphorus, arsenic, and antimon are doped in silicon, and the P-type semiconductor is further doped with fluorine as an impurity. ing. Such a P-type semiconductor may be a polyclonal metal oxide semiconductor (P-channel) and may form a part of CMOS (complementary metal-oxide semiconductor). When accelerating voltage is applied to the P-type semiconductor when observing the microstructure in the polyclonal, the doped fluorine atom diffuses in the P-type semiconductor. Therefore, there is a problem that it is not easy to observe the state of the polyclonal after doping with fluorine more accurately with an electron microscope. According to the method for producing a sample according to one aspect of the present invention, it is possible to suitably prevent the diffusion of fluorine atoms doped in a P-type semiconductor due to electron beam irradiation by performing ALD treatment on a slice of polyclonal. ..

(Membrane / electrode assembly)
The material used in the method for producing a sample according to one embodiment contains silver particles (dispersed phase) and a fluorine-based resin (continuous phase) as a first component, and the fluorine-based resin is a fluorine-based ionomer. It can be a catalyst layer (sea island structure) containing a carbon carrier as a component of the above, and can be a membrane / electrode assembly provided with the catalyst layer (multilayer structure). Instead of the fluorinated ionomer, the non-fluorinated ionomer may be contained in the catalyst layer of the membrane / electrode assembly together with the silver particles. The membrane / electrode assembly (MEA) is used as a membrane / electrode assembly having a polymer film and a catalyst layer in a solid fuel cell, and catalyst layers (also referred to as gas diffusion layers) are provided on both sides of the polymer film. Be done. One of the catalyst layers functions as a cathode and the other as an anode. The catalyst layer may contain a carbon material as the second component.

Ionomer is a resin used as a material for a proton-conducting polymer membrane, and in a membrane / electrode junction, an ionomer similar to the ionomer used for a polymer membrane forms a catalyst layer containing a porous material and a polymer film. It is used as a binder to join.

As the noble metal-based catalyst as the second component, metal particles containing a platinum group metal (PGM) such as a platinum catalyst, a ruthenium catalyst, and a ruthenium-platinum alloy catalyst are preferably used in the catalyst layer of the anode. In the catalyst layer on the cathode side, for example, metal particles such as a platinum catalyst are preferably used. These are included in the catalyst layer.

When the catalyst layer provided in the membrane / electrode assembly contains silver particles as the first component, the silver particles are deformed and diffused due to a temporal factor after the catalyst layer is sliced. There's a problem. Further, the catalyst layer contains a resin such as a fluorine-based ionomer, and when the resin is irradiated with an electron beam, there is a problem that the resin is deformed by heat and diffuses. According to the method for producing a sample according to one aspect of the present invention, by performing ALD treatment on the flakes of the catalyst layer, the silver particles (dispersed phase) are deformed by electron beam irradiation, and the resin such as fluoroionomer is deformed. Diffusion can be suitably prevented.

(Solder material)
Also, the material can be a solder material. The solder material is a solder material containing an organic compound as a first component and an alloy containing tin as an element selected from the group consisting of gold, silver, silicon, bismuth, and antimony as a second component. It can be a solder material that is present or contains a lead-tin alloy as the first component.

The solder material may be a solder paste used when mounting a semiconductor chip on a printed circuit board, or may be thread solder. Such a solder material may be subjected to electron microscope observation, for example, after being reflowed, in order to evaluate the relationship between the structure and the rust preventive performance, the current-carrying performance, and the like. The solder material may contain a large amount of a resin, which is also called a flux, a surfactant for adjusting the coating and leveling performance, and an organic solvent. According to the method for producing a sample according to one aspect of the present invention, by performing an ALD treatment on a thin piece of a solder material, it is possible to suitably prevent deformation and diffusion of an organic compound contained in the solder material, whereby electrons can be suitably prevented. By beam irradiation, it is possible to prevent a large amount of fragments of an organic compound or an organic solvent from diffusing into the electron microscope and contaminating the electron microscope itself and the sample.

(Photosensitive agent)
The material used in the method for producing a sample according to one embodiment may be a photosensitive agent. The photosensitizer contains silver halide and an organic compound as a first component, and is applied to a substrate by a known method to form a layered film. Even in such a photosensitive agent, when observing the state of silver halide by electron microscope observation, there is a problem that silver is reduced by electron beam irradiation and halogen gas is diffused. According to the method for producing a sample according to one aspect, it is possible to prevent the halogen gas from diffusing from the photosensitizer by electron beam irradiation by subjecting the flakes of the material containing the photosensitizer to ALD treatment.

(Dispersion)
The material used in the method for producing a sample according to one embodiment may be a dispersion liquid in which the above-mentioned second component is dispersed in an organic solvent. Examples of such a dispersion liquid include a dispersion liquid of a particulate semiconductor exhibiting fluorescent characteristics.

(Gas adsorption catalyst)
The material used in the method for producing a sample according to one embodiment may be, for example, a gas adsorption catalyst. The gas adsorption catalyst may contain an organic compound containing a sulfur atom as a first component, and as a second component, alumina (Al ₂ O ₃ ), silica (SiO ₂ ), silica-alumina (SiO ₂ -Al). It may contain at least one selected from _{2O 3} ), titania (TIO ₂ ), magnesia (MgO), zeolites, ceria-zirconia composite oxides, zirconia, activated carbon, graphite, boron nitride, and carbon nitride.

Electron microscopy may be used to evaluate how the gas molecules adsorbed in the gas adsorption catalyst are distributed in the catalyst. However, since the sulfur compound containing a sulfur atom may be diffused by electron beam irradiation, it may be difficult to observe the distribution of the adsorbed gas molecules in the original state. According to the method for producing a sample according to one aspect, it is possible to prevent sulfur atoms from diffusing from the gas adsorption catalyst by electron beam irradiation by subjecting the flakes of the material containing the gas adsorption catalyst to ALD treatment.

[Process of cutting out flakes from material]
The production method according to one aspect of the present invention may include a step of cutting out flakes from the material according to the form of the material before performing the first step described later. The step of cutting out the flakes from the material can be performed by a method known in the art. Examples of the pretreatment method include cutting by a focused ion beam method (FIB), cutting by a microtome method, polishing by an electrolytic polishing method or a chemical polishing method, and slicing by an Ar ion milling method, more preferably. , Focused ion beam method (FIB method) can be used.

The thickness of the flakes obtained by the step of cutting out the flakes from the material by the FIB (Focused Ion Beam) treatment is preferably 100 nm or less, more preferably 70 nm or less. Further, the vertical width × horizontal width of the thin section may be in the range of 5 μm ² to 100 μm ² .

For example, in the FIB treatment, a part of the material is cut into thin pieces by irradiating the material with a gallium (Ga) ion beam accelerated to several tens of kV. The slices cut out are picked up by a manipulator.

Further, in the FIB treatment, a thin piece cut out by irradiating a gallium (Ga) ion beam may be subjected to a treatment such as argon milling.

Prior to the FIB treatment, for example, a part of the material may be cut out in advance to a size capable of the FIB treatment with a diamond blade.

As described above, the flakes cut out by the FIB treatment are subjected to the ALD treatment.

[Atom Layer Deposition (ALD)]
The production method according to one aspect of the present invention is a method of producing a sample from a material by an atomic layer deposition method (ALD), and a layer of the metal compound is formed by adhering a gaseous metal compound to the surface of the material. This includes a first treatment step of forming a metal oxide or a metal layer from the metal compound layer by reacting the metal compound with a gaseous oxidizing agent. As will be described later, the first treatment step and the second treatment step may be repeated a plurality of times as a series of steps, and the series of steps may further include a step of supplying purge gas.

The material may be subjected to, for example, the production method according to one embodiment in a state of being supported by a support. Here, the support is not limited as long as it can support the material, and examples thereof include a plate made of glass, metal, and resin, a petri dish, a mesh, a grid for FIB, and the like. If the material is liquid, the mesh is preferable. If it is cut out in a flaky shape, it is preferably a grid for FIB. The FIB grid and mesh are preferably FIB grids generally used in electron microscope observation, and are metal FIB grids such as gold, copper, nickel, molybdenum and SUS (stainless steel), or metal meshes. It is more preferable to have. In addition, a film may be formed on the mesh and the grid for FIB.

(ALD device)
The method for producing a sample based on the atomic layer deposition method can be preferably performed by the ALD apparatus 10 exemplified in FIG. The ALD device 10 includes a reaction chamber 11, a decompression unit 12, a precursor gas supply unit 13, an oxidant gas supply unit 14, and a purge gas supply unit 15.

One aspect of the manufacturing method is a step of depositing a metal compound on the surface of a piece of material (first treatment step) and a step of oxidizing the metal compound deposited on the surface with an oxidizing agent to form a layer of metal oxide. It is preferable that the first treatment step and the second treatment step are performed in the reaction chamber 11 provided in the ALD apparatus 10, including the steps to be performed (second treatment step).

The reaction chamber 11 communicates with the decompression unit 12, the precursor gas supply unit 13, the oxidant gas supply unit 14, and the purge gas supply unit 15 separately. Further, the reaction chamber 11 is provided with a heating unit (not shown) such as an infrared heater, whereby the temperature in the chamber can be adjusted. In the manufacturing method according to one aspect, a layer of a metal oxide is formed on the surface of a material by performing a first treatment step and a second treatment step.

The decompression unit 12 includes, for example, a pump such as a turbo molecular pump and a rotary pump. As a result, the decompression unit 12 adjusts the air pressure in the reaction chamber 11 and discharges the unreacted metal compound gas, the oxidant gas, the purge gas, or the like remaining in the reaction chamber 11 to the outside of the reaction chamber 11. Or something.

The precursor gas supply unit 13 includes a mass flow controller (MFC) that controls the flow rate and temperature of the metal compound gas that is the precursor gas, whereby the flow rate of the metal compound gas supplied into the reaction chamber 11 can be controlled.

Like the precursor gas supply unit 13, the oxidant gas supply unit 14 includes a mass flow controller (MFC), whereby the flow rate of the oxidant gas supplied into the reaction chamber 11 can be controlled.

The purge gas supply unit 15 can supply the purge gas into the reaction chamber 11 and control the flow rate of the purge gas.

In addition, the ALD device 10 includes a control unit (not shown), and has a reaction chamber 11, a decompression unit 12, a precursor gas supply unit 13, an oxidant gas supply unit 14, and an oxidant gas supply unit 14 so as to continuously repeat a series of steps. It is preferable to control each of the purge gas supply units 15.

[A series of processes]
It is preferable that the production method according to one embodiment includes the first treatment step and the second treatment step as a series of steps, and repeats the series of steps a plurality of times in the reaction chamber 11. Thereby, the film thickness of the layer of the metal oxide deposited on the surface of the thin piece of the material can be suitably adjusted.

Further, the production method according to one aspect is a step of purging unreacted precursor gas from the reaction chamber after the first treatment step and before the second treatment step (first purge) in the reaction chamber 11. Step) and a step of purging the unreacted oxidant gas from the inside of the reaction chamber 11 (second purging step) after the second treatment step and before the first treatment step which follows. Is more preferable. This can prevent the deposition of unreacted material on the surface of the material and form a more homogeneous layer of metal oxide on the surface of the material.

That is, from the viewpoint of the film thickness of the metal oxide layer and the homogeneity of the layer, the production method according to one aspect is the first treatment step, the first purge step, and the second treatment in the reaction chamber 11. It is preferable to include the step and the second purging step as a series of steps, and repeat the series of steps a plurality of times.

When a series of steps are carried out in the reaction chamber 11, the temperature in the reaction chamber 11 is preferably maintained in the range of 20 ° C. to 200 ° C. in order to suitably react the metal compound with the oxidizing agent. It is more preferable that the temperature is maintained in the range of 80 ° C to 150 ° C. At this time, the atmospheric pressure in the reaction chamber 11 is preferably maintained in the range of 200 mPa to 300 mPa.

Further, it is preferable that the series of steps is repeated 10 to 30 times in order to form a metal oxide layer or a metal layer having a sufficient film thickness.

(First processing step)
The first treatment step is a step of depositing a metal compound on the surface of the material, whereby the surface of the material is coated with the metal compound. The first processing step can be performed by placing the FIB grid 20 in the reaction chamber 11 with the material S placed on the FIB grid 20 which is a support (FIG. 1). Prior to performing the first first treatment step, the FIB grid 20 may be placed in the reaction chamber 11 and then the air in the reaction chamber 11 may be purged with a purge gas.

The metal compound used in the first treatment step is a precursor of a metal oxide, and is supplied from the precursor gas supply unit 13 into the reaction chamber 11 in a vaporized state. The metal compound as a precursor may be any metal compound that can be vaporized (gasified) in a heated environment or a heated reduced pressure environment and reacts with an oxidizing agent to form a metal oxide, for example, hafnium (Hf). , Aluminum (Al), Silicon (Si), Zirconium (Zr), Titanium (Ti) and other metals, the metal having an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, and chlorine. , And a metal compound having a functional group selected from the group consisting of halogens such as bromine and hydrogen.

Specific examples of these metal compounds include hafnium compounds such as tetrakishafnium, diethylaluminum ethoxide, tris (ethylmethylamide) aluminum, aluminum sec-butoxide, aluminum tribromid, aluminum trichloride, triethylaluminum, and triisobutylaluminum. , Aluminum compounds such as trimethylaluminum (TMA) and tris (diethylamide) aluminum, silicon compounds such as tetramethoxysilane and _SiH4 , and titanium compounds such as tetraethoxytitanium. Among them, trimethylaluminum (TMA) is a more preferable metal compound because it can be suitably gasified in the reaction chamber 11 and can be rapidly reacted with an oxidizing agent. These metal compounds may be supplied into the reaction chamber 11 together with an inert gas such as nitrogen.

The above-mentioned metal compound may form a metal instead of a metal oxide depending on the type and production conditions. Therefore, the "metal oxide layer" described below can be interpreted by replacing it with the "metal layer", but for convenience, unless otherwise specified, only the "metal oxide layer" is used in the present application. The invention will be described.

In the first treatment step, when the metal compound gas which is the precursor gas is supplied to the reaction chamber 11, the OH group existing on the surface of the material reacts with the metal compound. The hydrogen atom of the OH group and one functional group of the metal compound are bonded to each other to form a by-product, while the oxygen atom derived from the OH group and the metal atom are bonded. At this time, the functional group derived from the metal compound as a raw material is not completely removed, and the metal compound is chemically bonded to the surface of the material in a partially oxidized state. The by-product varies depending on the type of the metal compound, but may be, for example, an alkane such as methane or ethane, an alcohol such as ethanol, a halogen, a hydrogen gas, or the like.

The supply amount of the metal compound gas in one first treatment step may be appropriately adjusted according to the type of material to be used in the production method and the amount of material, but the flow rate is within the range of 0.5 to 1 SCCM. This allows the metal compound in an amount that can sufficiently consume the hydroxyl group existing on the surface of the material by the reaction to be supplied into the reaction chamber 11. Further, it is preferable that one first treatment step is performed for 1 to 5 seconds. This makes it possible to sufficiently supply the metal compound to the surface of the material.

(First purging step)
The production method according to one embodiment is a step of purging an unreacted metal compound gas as an unreacted product from the inside of the reaction chamber 11 after the first treatment step and before the second step (first purging step). It is more preferable to include. The first purging step can be performed by supplying the purge gas from the purge gas supply unit 15 to the reaction chamber 11 and purging the purge gas from the decompression unit 12. As a result, the unreacted product of the metal compound gas supplied into the reaction chamber 11 in the first treatment step and the by-products produced by the reaction can be discharged to the outside of the reaction chamber 11. Thereby, the oxide gas supplied by the subsequent second treatment step can be suitably prevented from reacting with the unreacted metal compound gas remaining in the reaction chamber 11 and accumulating on the surface of the material.

Examples of the purge gas include nitrogen and rare gases such as argon and helium.

Further, the supply amount of the purge gas in one first purge step is preferably a flow rate in the range of 90 to 100 SCCM, and preferably 5 to 50 seconds.

(Second processing step)
In the production method according to one embodiment, the oxidant gas is supplied from the oxidant gas supply unit 14 into the reaction chamber 11 to react the metal compound chemically bonded to the surface of the fragment of the material with the oxidant gas. This forms a layer of metal oxide on the surface of the material.

The oxidant gas supplied into the reaction chamber 11 in the second treatment step is typically at least one selected from the group consisting of water vapor, ozone, and oxygen plasma. The oxidizing agent gas may be supplied into the reaction chamber 11 together with the inert gas such as nitrogen, for example.

The supply amount of the oxidant gas in one second treatment step may be appropriately adjusted according to the type of the material to be used in the manufacturing method and the amount of the material, but the flow rate is within the range of 0.5 to 1 SCCM. This allows the metal compound in an amount that can sufficiently consume the hydroxyl group existing on the surface of the material by the reaction to be supplied into the reaction chamber 11. Further, it is preferable that one first treatment step is performed for 1 to 5 seconds. This makes it possible to sufficiently supply the oxidant gas to the surface of the material.

In the second treatment step, when the oxidant gas is supplied to the reaction chamber 11, the metal compound deposited on the surface of the material reacts with the oxidant gas. As a result, the functional group of the metal compound is replaced with the OH group, and a layer of the metal oxide is formed. At this time, the same by-products as those in the first processing step are produced.

(Second purging step)
After the second treatment step and before the subsequent first treatment step, it is preferable to purge the oxidant gas and the by-products remaining in the reaction chamber 11 with an inert gas. Since the conditions for supplying the purge gas into the reaction chamber 11 in the second purge step are the same as the conditions for supplying the purge gas in the first purge step, the description thereof will be omitted.

In the manufacturing method according to one aspect, it is preferable that the series of steps is completed with the second purging step as the final step.

〔sample〕
The sample produced by the production method according to one aspect of the present invention includes a layer containing metal oxides such as HfO ₂ , Al ₂ O ₃ , SiO ₂ , ZrO ₂ , and TiO ₂ , and a metal such as Ti and Si. A layer selected from the layers containing the above is a sample obtained by covering the surface of the material.

Here, the film thickness of the metal oxide layer formed on the sample is preferably in the range of 0.5 to 2 nm. Thereby, it can be used as a sample whose surface state can be clearly observed by an electron microscope.

As described above, the sample produced by the production method according to one embodiment is suitably used as, for example, an observation sample.

<Observation method>
The surface structure of the observation sample produced by the production method according to one embodiment can be observed in detail with an electron microscope. As the electron microscope adopted in the observation method according to one embodiment, a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM) is preferable, and a scanning transmission electron microscope (STEM) is more preferable. The scanning transmission electron microscope may be a high-angle scattering dark-field scanning transmission electron microscope (HAADF-STEM) from the viewpoint that the type of atom can be confirmed based on the spectrum of the electron beam.

The transmission electron microscope irradiates a sample with an electron beam in parallel, and forms an image of the electron beam transmitted through the sample on a fluorescent screen using a magnetic field lens. The contrast of the image is the diffraction contrast or absorption contrast that utilizes the fact that the scattering angle of the electron beam differs depending on the density and crystal orientation of the substance, and the phase obtained by interfering the electron beam whose phase has changed due to the internal potential in the sample. Contrast can be mentioned.

When observing a sample with a scanning transmission electron microscope (STEM) or a transmission electron microscope (TEM), the acceleration voltage is preferably in the range of 30 to 300 kV. This makes it possible to suitably observe the state of the flaky material while preventing the components contained in the material from diffusing, deforming, and disappearing.

In addition, in the observation method according to one aspect, elemental analysis can be performed by combining energy dispersive X-ray light method (EDX method), electron energy loss spectroscopy (EELS method), etc. with electron microscope observation.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

[Evaluation of halogen diffusion]
Fragments were collected from a glass substrate for a touch panel by FIB treatment, and the flaky sample of Example 1 subjected to ALD treatment and the flakes of Comparative Example 1 were observed with an electron microscope to evaluate halogen diffusion.

[Example 1]
The flaky sample of Example 1 was obtained by ALD-treating the flakes of the multilayer composite material cut out from the glass substrate.

(FIB processing)
Obtain a glass substrate (metal layer / fluorine-based resin layer / glass substrate laminate) for a touch panel, and first use a diamond blade (product name: Isomet, manufactured by Buehler) with a size of 10 mm x 10 mm in length x width. The glass substrate was cut out so as to be. Subsequently, the cut out glass substrate was further cut out by a FIB device to obtain flakes of a multilayer composite material including a transparent electrode (metal layer). The processing conditions and the size of the slices cut out in the FIB apparatus (product name Helios600, manufactured by FEI) were as follows.
Ga ion beam irradiation conditions: Acceleration voltage: 30 kV
Cut out slice size: width 7 μm x length 3 μm x thickness 0.0007 μm

(ALD processing)
A thin section of the multilayer composite material obtained by FIB treatment was attached to a grid for FIB (diameter 3 mm, copper grid, manufactured by Ohken Shoji Co., Ltd.), and the mesh for TEM observation was attached to the reaction chamber of the ALD device AT-400 (manufactured by Anric Technologies). Was fixed and subjected to ALD treatment to obtain a flaky sample of Example 1. The conditions for ALD processing were as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidizing agent gas: H ₂ O
Purge gas: N ₂
Reaction chamber temperature: 150 ° C
A series of steps of continuously performing the precursor gas treatment step, the precursor gas purge step, the steam gas treatment step, and the steam gas purge step was set as one cycle, and the treatment was performed 20 times for a total of 30 minutes.
Precursor gas treatment: 0.5 seconds, TMA flow rate 0.75SCCM
Purge gas treatment: 8 seconds, purge gas flow rate 96SCCM
Steam treatment: 0.5 seconds, steam flow rate 0.75SCCM
Purge gas treatment: 10 seconds, purge gas flow rate 96SCCM
This series of treatments was carried out in a reaction chamber having a temperature of 150 ° C. and a degree of vacuum of 225 mPa, repeated for 20 cycles, and the total reaction time was about 30 minutes. By ALD treatment, an observation sample coated with a metal film of about 2 nm was obtained.

[Comparative Example 1]
From the same glass substrate as the glass substrate used for preparing the flaky sample of Example 1, flakes of the multilayer structure material were cut out by a FIB device under the same conditions as in Example 1 to obtain flakes of Comparative Example 1. The flakes of Comparative Example 1 were different from the flakes of Example 1 in that they were not subjected to ALD treatment.

(STEM observation)
Using a transmission electron microscope ARM200F (manufactured by JEOL Ltd.), STEM observation was performed on the flaky sample of Example 1 and the flakes of Comparative Example 1. The acceleration voltage in STEM observation was 200 kV, the observation magnification was set to 1,000,000 times, and each observation sample was photographed. 2 and 3 show STEM photographs of flaky samples subjected to ALD treatment under these conditions and element distribution spectra (EDX spectra). Regions 1 and 2 shown by dotted lines in FIGS. 2 and 3, respectively, are regions of a part of the glass substrate constituting the flakes, and are shown on the right side of the sample photograph in FIGS. 2 and 3, respectively. The spectrum is a spectrum in each region 1 or region 2.

As shown in Region 1 and Region 2 of the thin-section sample of Example 1 in FIG. 2, in the thin-section sample of Example 1 observed by ALD treatment, fluorine atoms were also detected from parts other than the film of the fluororesin. I didn't. On the other hand, as shown in the flakes 1 and 2 of Comparative Example 1 in FIG. 3, the flakes of Comparative Example 1 observed without ALD treatment are from regions 1 and 2 other than the film of the fluororesin. Fluorine atom was also detected. From this, it was confirmed that the diffusion of fluorine atoms can be suppressed when observing a thin section sample having a multi-layer structure by the ALD treatment.

[Evaluation of silver diffusion]
A film was formed from the conductive resin material used for the film electrode material for fuel cells, and then the flakes were collected by FIB treatment and subjected to ALD treatment, and the flakes sample of Example 2 was not subjected to ALD treatment. The flakes of Comparative Example 2 were observed with an electron microscope.

[Example 2]
First, an Ag paste (trade name: conductive resin material, manufactured by ThreeBond Co., Ltd.) is applied and dried to form a catalyst layer, and then a part of the catalyst layer is cut out by a FIB device to form a catalyst layer. I got a slice of. The obtained flakes were subjected to ALD treatment to obtain a flaky sample of Example 2.

(FIB processing)
The processing conditions and the size of the slices cut out in the FIB apparatus (product name: Helios600, manufactured by FEI) were as follows.
Ga ion beam irradiation conditions: Acceleration voltage: 30 kV
Cut out slice size: width 7 μm x length 3 μm x thickness 0.0007 μm

(ALD processing)
Place a thin piece of catalyst layer material obtained by FIB treatment on a grid for FIB (diameter 3 mm, copper grid, manufactured by Ohken Shoji Co., Ltd.), and place the grid for FIB in the reaction chamber of the ALD device AT-400 (manufactured by Anric Technologies). By fixing and performing ALD treatment, a flaky sample of Example 2 was obtained. The conditions for ALD processing are as follows.

The FIB grid on which the sample was placed was fixed in the reaction chamber of the ALD apparatus AT-400 (manufactured by Anric Technologies), and the ALD treatment was performed. The conditions for ALD processing are as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidizing agent gas: H ₂ O
Purge gas: N ₂
Reaction chamber temperature: 150 ° C
A series of steps of continuously performing the precursor gas treatment step, the precursor gas purge step, the steam gas treatment step, and the steam gas purge step was set as one cycle, and the treatment was performed 20 times for a total of 30 minutes.
Precursor gas treatment: 0.5 seconds, TMA flow rate 0.75SCCM
Purge gas treatment: 8 seconds, purge gas flow rate 96SCCM
Steam treatment: 0.5 seconds, steam flow rate 0.75SCCM
Purge gas treatment: 10 seconds, purge gas flow rate 96SCCM
This series of treatments was carried out in a reaction chamber having a temperature of 150 ° C. and a degree of vacuum of 225 mPa, repeated for 20 cycles, and the total reaction time was about 30 minutes. By ALD treatment, an observation sample coated with a metal film of about 2 nm was obtained.

[Comparative Example 2]
(Making flakes)
The flakes prepared under the same conditions as the flaky sample of Example 2 except that the ALD treatment was not performed were used as the flakes of Comparative Example 2.

(STEM observation)
STEM observation was performed on the day of thinning of each of the flaky sample of Example 2 and the flaky sample of Comparative Example 2 and 10 days later.

Using a scanning transmission electron microscope ARM200F (manufactured by JEOL Ltd.), STEM observation was performed on the slice sample of Example 1 and the slice of Comparative Example 1. The acceleration voltage in STEM observation was 200 kV, the observation magnification was set to 1,000,000 times, and the observation sample was photographed.

FIG. 4 shows STEM photographs taken on the day and 10 days after the flakes of Example 2 and the flakes of Comparative Example 2, respectively. As shown in FIG. 4, in the flaky sample of Example 2 (with ALD), the deformation and diffusion of the silver particles were not confirmed, whereas the silver particles contained in the flakes of Comparative Example 2 were deformed after 10 days. It was confirmed that the diffusion was progressing.

[Evaluation of contamination]
A sample was dropped onto a mesh for a STEM electron microscope, and then ALD treatment was performed together with the mesh to prepare an observation sample of Example 3 and a sample of Comparative Example 3.

[Example 3]
ZnCuInS / ZnS Quantum Dots (manufactured by PlasmaChem) was dropped as a sample onto a 150 mesh for STEM electron microscope (diameter 3 mm, copper mesh, manufactured by Oken Shoji Co., Ltd.) covered with a carbon thin film as an organic film, and then the mesh was dropped. Each ZnCuInS / ZnS was subjected to ALD treatment.

(ALD processing)
The sample for Example 3 was obtained by fixing the TEM observation mesh in the reaction chamber of the ALD apparatus AT-400 (manufactured by Anric Technologies) and performing the ALD treatment. The conditions for ALD processing were as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidizing agent gas: H ₂ O
Purge gas: N ₂
Reaction chamber temperature: 150 ° C
A series of steps of continuously performing the precursor gas treatment step, the precursor gas purge step, the steam gas treatment step, and the steam gas purge step was set as one cycle, and the treatment was performed 20 times for a total of 30 minutes.
Precursor gas treatment: 0.5 seconds, TMA flow rate 0.75SCCM
Purge gas treatment: 8 seconds, purge gas flow rate 96SCCM
Steam treatment: 0.5 seconds, steam flow rate 0.75SCCM
Purge gas treatment: 10 seconds, purge gas flow rate 96SCCM
This series of treatments was carried out in a reaction chamber having a temperature of 150 ° C. and a degree of vacuum of 225 mPa, repeated for 20 cycles, and the total reaction time was about 30 minutes. By ALD treatment, an observation sample coated with a metal film of about 2 nm was obtained.

(STEM observation)
A scanning transmission electron microscope ARM200F (manufactured by JEOL Ltd.) was used to perform STEM observation of the sample of Example 3. The acceleration voltage in STEM observation was 200 kV, and the observation magnification was set to 5,000,000 times. The observation sample was photographed. FIG. 5 shows STEM photographs of the observation sample of Example 3 that has been ALD-treated under these conditions and the sample of Comparative Example 3 that has not been ALD-treated.

As shown in FIG. 5, the observation sample formed from the ALD-treated Quantum Dots (manufactured by PlasmaChem) has a clear electron micrograph image, whereas the non-ALD-treated Quantum Dots (PlasmaChem). The image of the electron micrograph was not clear. From this, it was confirmed that the contamination of the STEM apparatus due to contamination can be suppressed by the ALD treatment, and the image of the electron micrograph can be clearly taken.

Claims (18)

It is a method of manufacturing a sample for observation with an electron microscope.
The first treatment step of forming a layer of the metal compound by adhering a gaseous metal compound to the surface of the material for producing the sample, and
A second treatment step of forming a metal oxide or a metal layer from the metal compound layer by reacting the metal compound with a gaseous oxidizing agent is included.
A method for producing a sample, wherein the material contains a first component whose observation accuracy is reduced by receiving an electron beam from an electron microscope or which is deformed over time. The method for producing a sample according to claim 1, wherein the first component is selected from silver, halogen, silver halide, lead, lead-tin alloy, fluororesin, sulfur compound, and organic compound. The material is
It further contains a second component other than the first component.
The second component includes a layer of a transparent electrode material, a layer of a glass substrate, and the first component includes a layer containing the fluororesin.
The fluorine-based resin is vinylidene fluoride-based resin,
The method for producing a sample according to claim 2, wherein the transparent electrode material is selected from tin oxide and indium oxide. The material is
It further contains a second component other than the first component.
The first component contains the silver particles and the fluororesin.
The second component contains a carbon carrier and contains.
The method for producing a sample according to claim 2, wherein the fluorine-based resin is a fluorine-based ionomer. The material is
It further contains a second component other than the first component.
The organic compound is contained as the first component, and the organic compound is contained.
The second component comprises an alloy containing tin and an element selected from the group consisting of gold, silver, silicon, bismuth, and antimony.
The method for producing a sample according to claim 2, wherein the organic compound contains at least one organic compound selected from a resin, a surfactant, and an organic solvent. The material is
The lead-tin alloy and the organic compound are contained as the first component.
The method for producing a sample according to claim 2, wherein the organic compound contains at least one organic compound selected from a resin, a surfactant, and an organic solvent. The material is a dispersion liquid containing the first component.
The organic compound is contained as the first component, and the organic compound is contained.
The method for producing a sample according to claim 2, wherein the organic compound contains at least one organic compound selected from a resin, a plasticizer, a surfactant, and an organic solvent. The material is
It further contains a second component other than the first component.
The sulfur compound is contained as the first component, and the sulfur compound is contained.
As the second component, alumina (Al ₂ O ₃ ), silica (SiO ₂ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ), titania (TIO ₂ ), magnesia (MgO), zeolite, ceria-zirconia. The method for producing a sample according to claim 2, which comprises at least one selected from composite oxide, zirconia, activated carbon, graphite, boron nitride, and carbon nitride. The method for producing a sample according to any one of claims 1 to 8, which comprises a step of cutting out a part of the material with a focused ion beam to obtain flakes of the material before the first treatment step. .. The method for producing a sample according to any one of claims 1 to 9, wherein the metal contained in the metal compound is any one metal selected from the group consisting of hafnium, zirconium, aluminum, silicon, and titanium. .. The method for producing a sample according to claim 10, wherein the metal compound is trimethylaluminum. The method for producing a sample according to any one of claims 1 to 11, wherein the gaseous oxidizing agent is at least one selected from the group consisting of water vapor, ozone, and oxygen plasma. The item according to any one of claims 1 to 12, wherein in the first treatment step and the second treatment step, the metal compound and the oxidizing agent are reacted at a temperature in the range of 20 ° C to 200 ° C. The method for producing the described sample. The method for producing a sample according to any one of claims 1 to 13, wherein the first treatment step and the second treatment step are repeated a plurality of times as a series of steps. The series of steps is carried out between after the first treatment step and before the second treatment step, and between after the second treatment step and before the first treatment step, respectively, with an inert gas. The method for producing a sample according to claim 14, further comprising a purging step of purging the unreacted substance of the gaseous metal compound and the unreacted substance of the gaseous oxidizing agent. A manufacturing process for manufacturing a sample by performing the method for manufacturing a sample according to any one of claims 1 to 15.
A method for observing a sample, which comprises an observation step of observing the sample with an electron microscope. The method for observing a sample according to claim 16, wherein the electron microscope is a scanning transmission electron microscope or a transmission electron microscope. The method for observing a sample according to claim 16 or 17, wherein the sample is observed by the electron microscope with an acceleration voltage in the range of 30 to 300 kV.

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