CN117769649A - Method for producing sample and method for observing sample - Google Patents
Method for producing sample and method for observing sample Download PDFInfo
- Publication number
- CN117769649A CN117769649A CN202280053357.9A CN202280053357A CN117769649A CN 117769649 A CN117769649 A CN 117769649A CN 202280053357 A CN202280053357 A CN 202280053357A CN 117769649 A CN117769649 A CN 117769649A
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- Prior art keywords
- component
- sample
- producing
- sample according
- metal
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims description 55
- 239000000463 material Substances 0.000 claims abstract description 143
- 238000011282 treatment Methods 0.000 claims abstract description 82
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- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 238000010926 purge Methods 0.000 claims description 55
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- 150000002894 organic compounds Chemical class 0.000 claims description 24
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- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002363 hafnium compounds Chemical class 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
- G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/40—Imaging
- G01N2223/418—Imaging electron microscope
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sampling And Sample Adjustment (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
Provided is a method for producing a novel sample, by which the deformation of a material with time and the diffusion of a material element due to electron beam irradiation can be suppressed and contamination due to the change of the sample can be prevented. The manufacturing method comprises the following steps: a 1 st treatment step of adhering a gaseous metal compound to the surface of a material to form a layer of the metal compound; and a 2 nd treatment step of reacting the metal compound with a gaseous oxidizing agent to form a metal oxide layer or a metal layer from the metal compound layer, wherein the material contains a 1 st component, and the 1 st component is subjected to electron beam from an electron microscope to cause a decrease in observation accuracy or is deformed with time.
Description
Technical Field
The present invention relates to a method for producing a sample and a method for observing a sample.
Background
For example, patent document 1 describes a detection kit in which a material is coated with a protective agent containing at least 1 selected from a surfactant-containing solution, an amphiphilic compound, oils and fats, an ionic liquid, and osmium.
Patent document 2 describes an observation method including the steps of: a protective agent for electron microscopic observation containing a saccharide and an electrolyte is applied to a biological sample in an aqueous state.
(prior art literature)
Patent document 1: japanese patent application laid-open No. 2017-201289
Patent document 2: international publication No. 2015/115502
Disclosure of Invention
(problem to be solved by the invention)
Regarding the method of observation using the detection kit described in patent document 1 and the observation method described in patent document 2, although these methods are possible to prevent the sample from being affected by element diffusion and material deformation, there are the following problems: the organic compound contained in the protective agent is decomposed by the observation method to generate hydrocarbon gas, and the generated hydrocarbon gas is attached to the sample and the observation device to pollute the observation environment. Therefore, there is a need for a method for producing a novel sample by which the deformation of a material with time and the diffusion of a material element due to electron beam irradiation can be suppressed and contamination due to the change of the sample can be prevented.
(means for solving the problems)
In order to solve the above-described problems, a method for manufacturing a sample observed by an electron microscope according to an embodiment of the present invention includes: a 1 st treatment step of forming a layer of a gaseous metal compound by adhering the metal compound to a surface of a material for producing the sample; and a 2 nd treatment step of reacting the metal compound with a gaseous oxidizing agent to form a metal oxide layer or a metal layer from the metal compound layer, wherein the material contains a 1 st component, and the 1 st component is subjected to electron beam from an electron microscope to cause a decrease in observation accuracy or is deformed with time.
(effects of the invention)
According to one embodiment of the present invention, a method for manufacturing a novel sample and a related technique thereof can be provided, by which a case where a material is deformed with time and a case where a material element is diffused due to electron beam irradiation can be suppressed, and contamination due to a change in the sample can be prevented.
Drawings
Fig. 1 is a schematic view of an Atomic Layer Deposition (ALD) apparatus 10 for performing a manufacturing method according to an embodiment of the present invention.
Fig. 2 is a Scanning Transmission Electron Microscope (STEM) photograph of the sheet sample of example 1 and an EDX spectrum of the result of Scanning Transmission Electron Microscope (STEM) observation of the corresponding region thereof.
Fig. 3 is a Transmission Electron Microscope (TEM) photograph of the sheet of comparative example 1 and an EDX spectrum of a Scanning Transmission Electron Microscope (STEM) observation result of the corresponding region thereof.
Fig. 4 is a Scanning Transmission Electron Microscope (STEM) photograph of the sample of example 2 and comparative example 2.
Fig. 5 is a Scanning Transmission Electron Microscope (STEM) photograph of the sample of example 3 and comparative example 3.
Detailed Description
In the present specification, the term "sample" refers to the whole of an object obtained by forming a metal oxide layer or a metal layer on the surface of a material object by the manufacturing method according to one embodiment of the present invention unless otherwise specified. In the present specification, the term "material" refers to the whole object to be observed, and is included in the "sample". The surface state of the "material" can be observed by an observation method using an electron microscope or the like through a layer of a metal oxide or a layer of a metal formed on the "sample".
< method for producing sample >
A method for producing a sample according to an aspect of the present invention is a method for producing a sample observed by an electron microscope, the method including: a 1 st treatment step of forming a layer of a gaseous metal compound by adhering the metal compound to a surface of a material for producing the sample; and a 2 nd treatment step of reacting the metal compound with a gaseous oxidizing agent to form a metal oxide layer or a metal layer from the metal compound layer, wherein the material contains a 1 st component, and the 1 st component causes a decrease in the observation accuracy of the sample with the passage of time or the 1 st component causes a decrease in the observation accuracy of the sample for observation by receiving an electron beam irradiated by an electron microscope. The method for producing a sample according to one aspect of the present invention may further include a step of cutting a material according to a form of the material to obtain a sheet of the material.
(Material)
The material of the observation sample may contain the 1 st component or the 2 nd component. The 1 st component is a material that receives an electron beam from an electron microscope and deteriorates the observation accuracy of the observation sample. The 2 nd component is a component having a smaller influence on the observation accuracy of the observation sample than at least the 1 st component. The 1 st component may be the following: a component that diffuses, deforms, and disappears when irradiated with an electron beam having an acceleration voltage of 30kV or more in electron microscope observation. The 1 st component may be, for example, the following: ingredients that deform, diffuse or disappear over time within up to 10 days after the material is cut out. That is, component 1 has either or both of the following properties: diffusion, deformation, and disappearance properties due to the irradiation of the electron beam; or the property of deforming, diffusing or disappearing over time after cutting out the material.
(component 1)
The reason for the decrease in the observation accuracy due to the 1 st component is that: irradiating a sheet of material with an electron beam to cause the 1 st component to diffuse, deform, and/or disappear; or, the passage of time.
The term diffusion includes the following meanings: the 1 st component contained in the inorganic component as a dopant diffuses by electron beams, that is, an element diffuses into an inorganic material such as a semiconductor as an impurity. In addition, diffusion also includes the following meanings: a part of the 1 st component contained in the sheet material is disintegrated (also referred to as fragmented) by the electron beam, and fragments generated by the disintegration are diffused in the material or diffused out of the material. In addition, diffusion also includes the following meanings: the gas released outside the material due to or independent of the electron beam irradiation diffuses, and the particles generated due to the disintegration diffuse within the material.
The term "modified" includes the following meanings: as a result of the electron beam irradiation or the independence of the electron beam irradiation, the inorganic particles as the 1 st component are miniaturized or the 1 st component is fragmented, and as a result, the miniaturized (disintegrated) inorganic particles or the fragmented components may be spread inside the material or spread outside the material. That is, in a sense, the deformation may be a diffusion accompanied by disintegration.
The term "vanishing" includes the following meanings: the non-fragmented component or the fragmented 1 st component diffuses by heat and disappears from the sheet material. That is, in a sense, the disappearance may be a kind of diffusion.
However, the diffusion, deformation, disappearance of the 1 st component may cause a decrease in the accuracy of observation. In addition, there is a problem that the material containing the 1 st component cannot be observed in an appropriate state due to the diffusion, deformation, and disappearance of the 1 st component.
The material as the object of observation may have a fine structure therein even if it is made into a sheet. Here, the microstructure may be a multilayer structure or an island structure including a continuous phase and a dispersed phase. The observation target material may have the following sea-island structure: 1 layer in the multi-layer structure of the sea-island structure has a continuous phase and a dispersed phase.
In the case where the fine structure of the sheet of material is a multilayer structure, at least 1 layer among the layers in the multilayer structure contains the 1 st component. The thickness of each layer of the multilayered structure of the sheet of material may be about 0.001 μm to 10 μm.
In the case where the fine structure of the sheet of material is an island-in-sea structure, it is sufficient that either one or both of the continuous phase and the dispersed phase in the island-in-sea structure contain the 1 st component. The average particle diameter of the dispersed phase of the island structure of the sheet of the material can be about 1nm to 1000 nm.
(halogen)
The 1 st component may be a halogen or a halogen-containing component. Examples of the halogen include halogen doped as an impurity in an inorganic component.
The halogen-containing material as the 1 st component may exhibit the following diffusion when halogen is irradiated with electron beams: diffusion of halogen as a dopant, diffusion of halogen gas, or diffusion of halogen or halogen-containing fragments generated by fragmentation of the 1 st component.
Examples of the halogen-containing component include silver halide, which may be silver chloride, silver bromide, silver iodide, or silver fluoride, and various kinds of silver halides having photosensitivity.
Note that the fluorine-based resin may be a component that causes halogen diffusion due to deformation. The fluorine-based resin is particularly limited as long as it can be used in various devices. Examples of the halogen-based resin include fluorine-based resin and chlorine-based resin. Examples of the fluorine-based resin include polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-trichloroethylene copolymer, vinylidene fluoride-fluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, and ethylene-tetrafluoroethylene copolymer. Examples of the chlorine-based resin include polyvinyl chloride and polyvinylidene chloride.
The fluorine-based resin may further contain a fluorine-based ionomer. The fluorine-based ionomer is a resin used as a proton-conductive polymer membrane material. In the membrane/electrode assembly, the same ionomer as that used in the polymer membrane is used as an adhesive for bonding the catalyst layer to the polymer membrane. More specifically, examples of the fluorine-based ionomer include ion-exchange polymers having sulfonic acid groups, which can be a raw material excellent in proton conductivity, strength and chemical stability, and examples thereof include fluorine-based polymers having sulfonic acid groups such as perfluorosulfonic acid polymers. Specific examples of the fluorine-based polymer having a sulfonic acid group include Nafion (registered trademark), flemion (registered trademark), and Aciplex (registered trademark).
(silver)
The 1 st component may be silver, and may be silver particles, for example, silver used as a metal catalyst or a transparent electrode material. After flaking, the material containing silver particles as the 1 st component is deformed into finer particles than before the flaking sample is produced due to the passage of time, and as a result, diffusion may occur in the sample.
(lead)
The 1 st component may be lead or a lead-tin alloy, and these may be in the form of particles, for example, lead-tin alloy contained in solder. Lead and lead-tin alloys may diffuse and deform as a result of irradiation by electron beams.
(organic Compound)
Examples of the organic compound as the 1 st component include resins, surfactants, organic solvents, and plasticizers. The organic compound may be deformed and diffused by being irradiated with the electron beam. The organic compound may contain a substance which is not deformed by the electron beam irradiation but may be diffused outside the material sheet. In the case where the sheet of material contains an organic compound, the organic compound may decompose to generate hydrocarbon gas. Hydrocarbon gas generated by fragmentation and organic solvents and the like which do not evaporate by deformation are diffused and attached to the sample surface or the observation device, and become contaminants which pollute the observation environment. In addition, if the organic compound has a hydrocarbon chain and/or an aromatic ring containing carbon atoms and hydrogen atoms, the molecular structure of the organic compound may contain, for example, halogen atoms, nitrogen atoms, sulfur atoms, and oxygen atoms.
As the resin, for example, a resin in which inorganic particles are used as a binder, and the above-mentioned fluorine-based resin and fluorine-based ionomer can be exemplified as the resin.
Specific examples of the resin include the following non-fluorinated polymers: the aromatic ring of the aromatic polymer selected from the group consisting of polyarylene ether such as polystyrene and polyether ether ketone, aromatic polyimide, polyphosphazene and polybenzimidazole is sulfonated, and the aromatic polymer may be a copolymer with an olefin. Examples of the cellulose-based resin include crosslinked sulfoethyl cellulose obtained by sulfoethylation of cellulose, and the crosslinked sulfoethyl cellulose can be contained in a membrane electrode.
Further, as the resin, rosin, modified rosin, terpene resin, polystyrene, polyethylene, styrene-divinylbenzene copolymer, and the like can be cited, and they can be contained in, for example, a solder material and the like.
Examples of the surfactant include a dispersant, a wetting agent, a defoaming agent, a plasticizer, a leveling agent, and the like used when inorganic particles are dispersed and mixed in a resin, and any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
More specifically, the surfactant may be exemplified by 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, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, N-bis (2-hydroxyethyl) alkylamide, condensate of fatty acid and diethanolamine, alkylsulfonate, sodium dicyclohexylsulfosuccinate, polyoxyethylene alkyl phosphate, quaternary ammonium chloride, alkyl betaine, alkyl imidazoline, and alkylalanine. Surfactants are included in the solder material and may become contaminants.
The organic solvents include: alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; ethers such as dibutyl ether and 1, 4-dioxane; aromatic solvents such as pyridine, chlorobenzene, toluene, and xylene; hydrocarbon solvents such as hexane and cyclohexane. The organic solvent contained in the solder material as a diluent may become a contaminant, and may be diffused, deformed, and vanished.
Examples of the plasticizer include phosphate plasticizers, terephthalic plasticizers, adipic plasticizers, and the like.
(sulfur Compound)
The 1 st component is, for example, a sulfur compound. The sulfur atoms contained in the sulfur compound may diffuse due to irradiation with an electron beam, and thus may cause a decrease in the observation accuracy. Examples of the sulfur compound containing a sulfur atom include elemental sulfur, sulfur oxides (SOx), hydrogen sulfide, and organic sulfur compounds.
(component 2)
The material and the sheet of material may comprise component 2. The 2 nd component is a material which itself does not substantially diffuse, deform and disappear due to electron beam irradiation or due to time passage. The 2 nd component may be a component which does not substantially diffuse, deform or disappear under electron microscope observation even when an electron beam having an acceleration voltage of 30kV to 300kV is irradiated thereto. The 2 nd component is, for example, a component which does not deform, spread or disappear with time within about 10 days after cutting of the material.
In the case where the fine structure of the sheet of material is a multilayer structure, at least 1 layer of the plurality of layers in the multilayer structure may contain the 2 nd component. In the case where the fine structure of the sheet of material is an island-in-sea structure, at least one of the continuous phase and the dispersed phase in the island-in-sea structure may contain the 2 nd component.
The 2 nd component is 1 or more selected from glass, metal oxide, metal, and metal alloy, preferably selected from glass. Examples of the glass include quartz glass, soda lime glass, borosilicate glass, and organic glass. Examples of the metal oxide include aluminum oxide, magnesium oxide, and hafnium oxide. The 2 nd component may be a compound semiconductor such as silicon, sapphire, gaAs (gallium arsenide), or the like, or may be a granular semiconductor showing fluorescence characteristics.
The 2 nd component may be, for example, a metal oxide such as titanium oxide, tin oxide, lead oxide, yttrium oxide, indium oxide, or the like, and these metal oxides are used as, for example, a transparent electrode material and may be contained in a sheet in a layered or particulate form.
The 2 nd component may be a noble metal catalyst, and the noble metal catalyst may be platinum-based catalyst, ruthenium-platinum alloy-based catalyst, or other metal particles containing Platinum Group Metal (PGM).
The 2 nd component may be a porous carbon support.
In addition, the 2 nd component may be an alloy containing tin and an element selected from gold, silver, silicon, bismuth, antimony, which may be contained in an alloy form in the solder material.
Examples of the 2 nd component include aluminum alloy, magnesium alloy, brass, bronze, armco (Armco) iron, carbonyl iron, and white metal, which may be contained in a lamellar or particulate form in a sheet of the material.
In addition, the 2 nd component may be selected from alumina (Al 2 O 3 ) Silicon dioxide (SiO) 2 ) Silica-alumina (SiO) 2 -Al 2 O 3 ) Titanium oxide (TiO) 2 )、At least 1 of magnesium oxide (MgO), zeolite, ceria-zirconia composite oxide, zirconia, activated carbon, graphite, boron nitride, and carbon nitride. They may be contained as catalyst carriers in gas adsorption catalysts.
The type of the 2 nd component is not limited as long as it does not substantially diffuse, deform or disappear by electron beam irradiation.
[ Material ]
Examples of the material include: a glass substrate including a layer of a transparent electrode material for a touch panel or the like; membrane electrode for fuel cell; a semiconductor constituting a part of a semiconductor chip or the like; solder; a sensitizer; and a dispersion of semiconductor particles. Depending on whether these materials are solid or liquid, a portion of the materials may be cut out to produce a sample, or the sample may be produced in an undivided manner. The material may contain the 1 st component or the 2 nd component in at least a part thereof in a state of being prepared to a size suitable for observation.
The material for producing the sample is not limited to the material such as a touch panel, and may be a sheet cut from a solar cell, an organic EL material, a lens, or the like, as long as the 1 st component is contained. That is, the material may be, for example, a part of an electric and electronic device itself or a part of various composite materials used in manufacturing an electric and electronic device, and may contain the 1 st component, wherein the 1 st component causes a decrease in the observation accuracy due to the flaking treatment and/or the reception of an electron beam from an electron microscope.
(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 multilayer structure may include a layer of a fluororesin such as vinylidene fluoride or a fluorine-doped tin oxide Film (FTO) as the 1 st component, a layer of a transparent electrode, and a layer of a glass substrate as the 2 nd component. The glass substrate may contain a metal oxide such as titanium oxide, tin oxide, lead oxide, yttrium oxide, or indium oxide in the layer of the transparent electrode material as the 2 nd component contained therein.
When the glass substrate is a glass substrate for a touch panel, a vinylidene fluoride resin may be contained as a fluororesin to be used as a piezoelectric element. The glass substrate for a touch panel may also include a layer in which fluorine-doped tin oxide is used as the transparent electrode. The glass substrate may also include a fluorine-doped tin oxide Film (FTO) as a layer of the transparent electrode. When such a glass substrate is irradiated with an electron beam, fluorine contained in fluorine or fluorine resin doped in a transparent electrode material diffuses toward the glass substrate. According to the method for producing a sample of one embodiment of the present invention, by performing ALD processing on a thin sheet of a glass substrate, it is possible to satisfactorily prevent fluorine contained in doped fluorine or fluorine resin from diffusing into the glass substrate due to irradiation with an electron beam.
(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 obtained by doping silicon with nitrogen, phosphorus, arsenic, or antimony, and fluorine may be further doped as an impurity into the P-type semiconductor. Such a P-type semiconductor can be a PMOS (P-channel metal oxide semiconductor: P-channel metal oxide semiconductor) or can form part of a CMOS (complementary metal-oxide semiconductor: complementary metal oxide semiconductor). When an acceleration voltage electron is applied to the P-type semiconductor in observing the microstructure of the PMOS, fluorine atoms doped in the P-type semiconductor are diffused. Therefore, there is a problem in that it is difficult to accurately observe the state of PMOS doped with fluorine under an electron microscope. According to the method for manufacturing a sample of one embodiment of the present invention, by performing ALD processing on a PMOS thin sheet, diffusion of fluorine atoms doped in a P-type semiconductor due to electron beam irradiation can be prevented well.
(Membrane/electrode combination)
The material used in the method for producing a sample according to one embodiment may be a catalyst layer (sea-island structure) containing silver particles (dispersed phase) and a fluorine-based resin (continuous phase) as the 1 st component, or may be a membrane/electrode assembly (multilayer structure) including the catalyst layer, wherein the fluorine-based resin is a fluorine-based ionomer and the catalyst layer contains a carbon support as the 2 nd component. Non-fluorine-based ionomers, instead of fluorine-based ionomers, may also be included in the catalyst layer of the membrane/electrode assembly along with the silver particles. A membrane-electrode assembly (MEA) is used as a membrane-electrode assembly including a polymer membrane having catalyst layers (also referred to as gas diffusion layers) on both surfaces thereof and a catalyst layer in a solid fuel cell. The catalyst layer on one side functions as a cathode, and the catalyst layer on the other side functions as an anode. The catalyst layer may contain a carbon material as the 2 nd component.
The ionomer is a resin used as a proton conductive polymer membrane material, and in the membrane/electrode assembly, the same ionomer as that used in the polymer membrane is used as an adhesive for bonding the catalyst layer containing the porous material to the polymer membrane.
The noble metal catalyst as the 2 nd component in the catalyst layer on the anode side is preferably a platinum group catalyst, a ruthenium-platinum alloy group catalyst, or other Platinum Group Metal (PGM) -containing metal particles, and the noble metal catalyst as the 2 nd component in the catalyst layer on the cathode side is preferably a platinum group catalyst, or other metal particles. These metal particles are contained in the catalyst layer.
If the catalyst layer provided in the membrane/electrode assembly contains silver particles as the 1 st component, there is a problem in that the silver particles deform and spread due to time after flaking the catalyst layer. In addition, if the catalyst layer contains a resin such as a fluorine-based ionomer and the resin is irradiated with an electron beam, there is a problem in that the resin is deformed and spread by heat. According to the method for producing a sample of one embodiment of the present invention, the ALD treatment of the thin sheet of the catalyst layer can satisfactorily prevent the deformation of silver particles (dispersed phase) and the deformation and diffusion of the resin such as fluorine-based ionomer due to the electron beam irradiation.
(solder material)
Further, the material may be a solder material. The solder material can be the following: contains an organic compound as component 1 and an alloy containing tin and an element selected from the group consisting of gold, silver, silicon, bismuth, and antimony as component 2. Alternatively, the solder material may be a solder material containing a lead-tin alloy as the 1 st component.
The solder material may be a solder paste used when mounting a semiconductor chip on a printed circuit board, or may be a wire solder. Such a solder material may be subjected to, for example, reflow treatment, and then observed by an electron microscope in order to evaluate the relationship between the structure and rust inhibitive performance, electrical conduction performance, and the like. The solder material can contain a plurality of: a resin called a flux; a surfactant for adjusting coating properties and leveling properties; an organic solvent. According to the method for producing a sample of one embodiment of the present invention, the ALD treatment is performed on the thin sheet of the solder material, whereby the deformation and diffusion of the organic compound contained in the solder material can be satisfactorily prevented, and thus the contamination of the electron microscope itself and the sample due to the diffusion of a large amount of fragments of the organic compound or the organic solvent in the electron microscope caused by the electron beam irradiation can be prevented.
(sensitizer)
The material used in the method for producing a sample according to one embodiment may be a sensitizer. The sensitizer contains silver halide and an organic compound as the 1 st component, and is coated on a substrate by a known method to form a layered coating. Such a sensitizer also has a problem that when the state of silver halide is observed by an electron microscope, the silver is reduced by electron beam irradiation, and thus halogen gas is diffused. According to the method for producing a sample of one embodiment, the ALD processing is performed on the thin sheet of the material containing the sensitizer, so that the diffusion of the halogen gas from the sensitizer due to the electron beam irradiation can be prevented.
(Dispersion liquid)
The material used in the method for producing a sample according to one embodiment may be a dispersion in which the component 2 is dispersed in an organic solvent. Such a dispersion liquid may be, for example, a dispersion liquid of a granular semiconductor exhibiting fluorescence characteristics.
(gas adsorption catalyst)
Material used in method for producing sample according to one embodimentThe material may be, for example, a gas adsorption catalyst. The gas adsorption catalyst can contain an organic compound containing sulfur atoms as the 1 st component, and can contain a catalyst selected from alumina (Al 2 O 3 ) Silicon dioxide (SiO) 2 ) Silica-alumina (SiO) 2 -Al 2 O 3 ) Titanium dioxide (TiO) 2 ) At least 1 of magnesium oxide (MgO), zeolite, ceria-zirconia composite oxide, zirconia, activated carbon, graphite, boron nitride and carbon nitride as the 2 nd component.
In order to evaluate how gas molecules adsorbed by the gas adsorption catalyst are distributed in the catalyst, observation by an electron microscope is sometimes used. However, sulfur compounds containing sulfur atoms may diffuse due to electron beam irradiation, and thus it may be difficult to observe the original distribution state of adsorbed gas molecules. According to the method for producing a sample of one embodiment, the ALD processing is performed on the thin sheet of the material containing the gas adsorption catalyst, whereby diffusion of sulfur atoms from the gas adsorption catalyst due to electron beam irradiation can be prevented.
[ procedure for cutting out sheet from Material ]
In the manufacturing method according to one embodiment of the present invention, a step of cutting out a sheet from a material according to the form of the material may be included before the step 1 described below. The step of cutting the sheet from the material may be performed by methods known in the art. Examples of the pretreatment include cutting by a Focused Ion Beam (FIB), cutting by a slicing method, grinding by an electrolytic grinding method or a chemical grinding method, and flaking by an Ar Ion cutting method, and more preferably, a Focused Ion Beam (FIB) method.
The thickness of the sheet obtained by the step of cutting out the sheet from the material by the treatment with FIB (Focused Ion Beam) is preferably 100nm or less, more preferably 70nm or less. In addition, the longitudinal width X transverse width of the sheet was 5 μm 2 ～100μm 2 Is within the range of (2).
In FIB processing, for example, a material is irradiated with a gallium (Ga) ion beam accelerated at several tens kV, whereby a part of the material is cut out as a sheet. The cut sheet is picked up by a robot.
In the FIB processing, a sheet cut out by irradiating a gallium (Ga) ion beam may be subjected to processing such as argon cutting.
In addition, a part of the material may be cut into a size suitable for FIB processing by a diamond blade, for example, before FIB processing.
As described above, the thin sheet cut by FIB processing is supplied to ALD processing.
(atomic layer deposition (Atom Layer Deposition: ALD))
A manufacturing method according to an embodiment of the present invention is a method for manufacturing a sample from a material by Atomic Layer Deposition (ALD), including: a 1 st treatment step of adhering a gaseous metal compound to the surface of a material to form a layer of the metal compound; and a 2 nd treatment step of reacting the metal compound with a gaseous oxidizing agent to form a metal oxide layer or a metal layer from the metal compound layer. As described later, the 1 st and 2 nd treatment steps may be repeated as a single set of steps. The set of steps may further include a step of supplying a purge gas.
The material may be supplied to one embodiment of the manufacturing method in a state supported by the support body, for example. The support is not limited as long as it can support the material, and examples thereof include a plate made of glass, metal, or resin, a petri dish, a mesh, a grid for FIB, and the like. The FIB grid and the mesh are preferably FIB grids generally used for observation by an electron microscope, and more preferably FIB grids made of metal such as gold, copper, nickel, molybdenum, and SUS (stainless steel), or metal meshes. The support and FIB grids may have a coating film formed thereon.
(ALD apparatus)
The method for producing the sample by the atomic layer deposition method can be preferably performed by the ALD apparatus 10 illustrated in fig. 1. The ALD apparatus 10 includes a reaction chamber 11, a pressure reducing section 12, a precursor gas supply section 13, an oxidizing gas supply section 14, and a purge gas supply section 15.
The production method according to one embodiment may include a step of depositing a metal compound on the surface of a thin sheet of material (step 1), and a step of oxidizing the metal compound deposited on the surface with an oxidizing agent to form a metal oxide layer (step 2), wherein the step 1 and the step 2 are performed in a reaction chamber 11 provided in the ALD apparatus 10.
The reaction chamber 11 communicates with each of the depressurization portion 12, the precursor gas supply portion 13, the oxidizing gas supply portion 14, and the purge gas supply portion 15. The reaction chamber 11 can be provided with a heating unit (not shown) such as an infrared heater, for example, to adjust the temperature in the chamber. In one embodiment, the metal oxide layer is formed on the surface of the material by performing the 1 st and 2 nd treatment steps.
The pressure reducing portion 12 includes, for example, a molecular turbine pump, a rotor pump, and the like. Thereby, the pressure reducing unit 12 adjusts the gas pressure in the reaction chamber 11, or discharges the unreacted metal compound gas, the oxidizing gas, the purge gas, or the like remaining in the reaction chamber 11 to the outside of the reaction chamber 11.
The precursor gas supply unit 13 includes a Mass Flow Controller (MFC) that controls the flow rate and temperature of the metal compound gas as the precursor gas, thereby controlling the flow rate of the metal compound gas supplied into the reaction chamber 11.
The oxidizing gas supply unit 14 is provided with a Mass Flow Controller (MFC) in the same manner as the precursor gas supply unit 13, and thus can control the flow rate of the oxidizing gas supplied into the reaction chamber 11.
The purge gas supply unit 15 can supply a purge gas into the reaction chamber 11 and control the flow rate of the purge gas.
The ALD apparatus 10 further includes a control unit (not shown) that preferably controls the reaction chamber 11, the pressure reducing unit 12, the precursor gas supply unit 13, the oxidizing gas supply unit 14, and the purge gas supply unit 15 so as to continuously repeat one set of steps.
(one set of procedures)
The production method according to one embodiment preferably includes the 1 st process and the 2 nd process as a set of processes, and the set of processes is repeated a plurality of times in the reaction chamber 11. This enables the film thickness of the metal oxide layer to be deposited on the surface of the sheet of material to be favorably adjusted.
Further, the manufacturing method according to one embodiment further preferably includes: a step (1 st purge step) of purging the reaction chamber of the unreacted precursor gas after the 1 st process step and before the 2 nd process step; and a step (2 nd purge step) of purging the unreacted oxidizing gas from the reaction chamber 11 after the 2 nd treatment step and before the next round of the 1 st treatment step. This prevents the unreacted material from accumulating on the surface of the material, and a more uniform metal oxide layer can be formed on the surface of the material.
That is, from the viewpoint of the film thickness of the metal oxide layer and the uniformity of the layer, the manufacturing method according to one embodiment preferably includes: a set of steps including the 1 st process step, the 1 st purge step, the 2 nd process step, and the 2 nd purge step is performed in the reaction chamber 11, and the set of steps is repeated a plurality of times.
In the case of performing one set of steps in the reaction chamber 11, the temperature in the reaction chamber 11 is preferably maintained in the range of 20 to 200 ℃, more preferably in the range of 80 to 150 ℃ in order to allow the metal compound to react with the oxidizing agent well. In this case, the air pressure in the reaction chamber 11 is preferably maintained in the range of 200 to 300 mPa.
In order to form a metal oxide layer or a metal layer having a sufficient thickness, this set of steps is preferably repeated 10 to 30 times.
(treatment step 1)
The 1 st treatment step is a step of depositing a metal compound on the surface of the material, thereby covering the surface with the metal compound. The 1 st process step may be performed by placing the material S on the FIB-use grid 20 as a support and loading the FIB-use grid 20 into the reaction chamber 11 (fig. 1) in this state. The FIB grid 20 may be loaded into the reaction chamber 11 before the 1 st treatment step 1 is performed, and then the air in the reaction chamber 11 may be purged with a purge gas.
The metal compound used in the 1 st process 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 the precursor may be any metal compound that can be gasified (gasified) in a heating environment or a heating and pressure reducing environment and that reacts with an oxidizing agent to form a metal oxide, and the metal compound may contain, for example, a metal such as hafnium (Hf), aluminum (Al), silicon (Si), zirconium (Zr), and titanium (Ti), and the metal may have a functional group selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, halogen such as chlorine and bromine, and hydrogen.
Specific examples of these metal compounds include: hafnium compounds such as hafnium; and aluminum compounds such as diethyl aluminum ethoxide, tris (ethylmethylamido) aluminum, sec-butoxyaluminum, aluminum tribromide, aluminum trichloride, triethylaluminum, triisobutylaluminum, trimethylaluminum (TMA) and tris (diethylamido) aluminum; tetramethoxysilane, siH 4 A silicon compound; titanium compounds such as tetraethoxytitanium. Among them, trimethylaluminum (TMA) is a more preferable metal compound because it can be well 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, for example.
The metal compound may be formed as a metal instead of a metal oxide depending on the kind and manufacturing conditions. Therefore, the "metal oxide layer" described below may be interchangeably construed as "metal layer", but for convenience of understanding, the present invention will be described by simply using "metal oxide layer" unless otherwise specified.
In the 1 st process step, when a metal compound gas is supplied to the reaction chamber 11 as a precursor gas, OH groups present on the surface of the material react with the metal compound. The hydrogen atom of the OH group is bonded to 1 functional group of the metal compound to form a by-product, and simultaneously, the oxygen atom derived from the OH group is bonded to the metal atom. At this time, the functional group derived from the raw metal compound is in a state of not being completely removed, and thus the metal compound is chemically bonded to the surface of the material in a partially oxidized state. The byproducts may vary depending on the type of the metal compound, and may be, for example, alkanes such as methane and ethane, alcohols such as ethanol, halogens, hydrogen, and the like.
The amount of the metal compound gas to be supplied in each 1 st treatment step is preferably in the range of 0.5 to 1SCCM, and the amount of the metal compound sufficient to consume the hydroxyl groups present on the surface of the material by reaction can be supplied into the reaction chamber 11 by appropriately adjusting the amount of the metal compound gas to be supplied in each 1 st treatment step, depending on the type of the material and the amount of the material to be supplied in the production method. Further, the 1 st treatment step is preferably performed every 1 st treatment step for 1 to 5 seconds. This makes it possible to sufficiently supply the metal compound to the surface of the material.
(purging step 1)
More preferably, the production method according to one embodiment includes a step of purging the unreacted metal compound gas from the reaction chamber 11 as an unreacted substance after the 1 st treatment step and before the 2 nd step (1 st purge step). The 1 st purge step may be performed by supplying the purge gas from the purge gas supply unit 15 to the reaction chamber 11 or by purging the purge gas from the pressure reduction unit 12. This can discharge the unreacted product of the metal compound gas supplied into the reaction chamber 11 in the 1 st process step and by-products generated by the reaction, out of the reaction chamber 11. This can satisfactorily prevent the oxide gas supplied in the subsequent processing step 2 from reacting with the unreacted metal compound gas remaining in the reaction chamber 11 and depositing on the surface of the material.
Examples of the purge gas include nitrogen gas, and rare gases such as argon gas and helium gas.
The purge gas is preferably supplied at a flow rate in the range of 90 to 100SCCM for 5 to 50 seconds in every 1 st purge step.
(treatment step 2)
In one embodiment of the production method, an oxidizing gas is supplied from the oxidizing gas supply unit 14 into the reaction chamber 11, and the oxidizing gas reacts with the metal compound chemically bonded to the surface of the sheet of material. Thereby, a layer of metal oxide is formed on the surface of the material.
The oxidizing gas supplied into the reaction chamber 11 in the 2 nd treatment step is typically at least 1 selected from the group consisting of water vapor, ozone, and oxygen plasma. These oxidizing gases may be supplied into the reaction chamber 11 together with an inert gas such as nitrogen, for example.
The amount of the oxidizing gas to be supplied in each 1 nd treatment step may be appropriately adjusted in accordance with the type of the material and the amount of the material to be supplied in the production method, and preferably the flow rate is in the range of 0.5 to 1SCCM, whereby a sufficient amount of the metal compound to be capable of reactively consuming the hydroxyl groups present on the surface of the material can be supplied into the reaction chamber 11. Further, the 1 st treatment step is preferably performed every 1 st treatment step for 1 to 5 seconds. This makes it possible to sufficiently supply the oxidizing gas to the surface of the material.
In the 2 nd process step, when the oxidizing gas is supplied to the reaction chamber 11, the metal compound deposited on the surface of the material reacts with the oxidizing gas. Thus, the functional group of the metal compound is substituted with an OH group, thereby forming a layer of the metal oxide. In this case, the same by-product as that after the 1 st treatment step is produced.
(purging step 2)
Preferably, the oxidizing gas and the by-products remaining in the reaction chamber 11 are purged by the inert gas after the 2 nd treatment step and before the next round of the 1 st treatment step. The condition for supplying the purge gas into the reaction chamber 11 in the 2 nd purge step is substantially the same as the condition for supplying the purge gas in the 1 st purge step, and therefore, the description thereof will be omitted.
In the manufacturing method according to one embodiment, the one set of steps is preferably terminated with the 2 nd purge step as the final step.
(sample)
The sample produced by the production method according to one embodiment of the present invention is a sample obtained by coating a material surface with a coating layer selected from the group consisting of: containing HfO 2 、Al 2 O 3 、SiO 2 、ZrO 2 TiO (titanium dioxide) 2 A layer of metal oxide, and a layer containing metals such as Ti and Si.
The thickness of the metal oxide layer formed on the sample is preferably in the range of 0.5 to 2 nm. This can be used as a sample in which the surface state can be clearly observed under an electron microscope.
As described above, the sample produced by the production method according to one embodiment can be used favorably as an observation sample, for example.
< observation method >
The observation sample manufactured by the manufacturing method according to one embodiment can observe the surface structure in detail under an electron microscope. The electron microscope used in the observation method according to one embodiment is preferably a Transmission Electron Microscope (TEM) or a Scanning Transmission Electron Microscope (STEM), and more preferably a Scanning Transmission Electron Microscope (STEM). 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 atoms can be confirmed based on an electron beam spectrum.
The transmission electron microscope irradiates the sample with electron beams in parallel, and images the electron beams transmitted through the sample on the fluorescent plate using a magnetic field lens. The contrast of the video may be: diffraction contrast or absorption contrast obtained according to the principle that the electron beam scattering angle varies with the density and crystal orientation of the substance; and a phase contrast obtained by interfering the electron beam whose phase has been changed by the internal potential of the sample.
In the case of observing a sample by Scanning Transmission Electron Microscopy (STEM) or Transmission Electron Microscopy (TEM), the acceleration voltage is preferably in the range of 30 to 300 kV. This makes it possible to prevent the diffusion, deformation, and disappearance of the components contained in the material and to observe the state of the flaked material satisfactorily.
In one embodiment of the observation method, the elemental analysis may be performed by combining electron microscopic observation with an energy dispersive X-ray method (EDX method), an electron energy loss spectroscopy (EELS method), or the like.
The present invention is not limited to the above embodiments, and various modifications can be made within the scope of the invention, and embodiments in which the technical means disclosed in the different embodiments are appropriately combined are also included in the technical scope of the present invention.
Examples
(evaluation of halogen diffusion)
The thin sheet was collected from the glass substrate for touch panel by FIB processing, and the thin sheet sample of example 1 and the thin sheet of comparative example 1 after ALD processing were observed by electron microscope, and halogen diffusion was evaluated.
[ example 1 ]
ALD processing was performed on a thin sheet of a multilayer composite material cut out from a glass substrate, thereby obtaining a thin sheet sample of example 1.
(FIB treatment)
After a glass substrate for a touch panel (laminate of metal layer/fluororesin layer/glass substrate) was obtained, a portion having a longitudinal width×a lateral width of 10mm×10mm was cut from the glass substrate by a diamond blade (product name Isomet, manufactured by Buehler corporation). Then, the glass substrate cut out by the FIB apparatus was further cut out, and a sheet of a multilayer composite material including a transparent electrode (metal layer) was obtained. The processing conditions of the FIB apparatus (product name: helios600; manufactured by FEI Co., ltd.) and the dimensions of the cut sheet were as follows.
Ga ion beam irradiation conditions: accelerating voltage of 30kV
Size of cut sheet: transverse 7 μm X longitudinal 3 μm X thickness 0.0007 μm
(ALD processing)
A thin sheet of the multi-layer composite material obtained by FIB treatment was set on a FIB grid (diameter: 3mm, copper grid, manufactured by Nippon Denshoku Co., ltd.) and the TEM observation carrying net was fixed in a reaction chamber of ALD apparatus AT-400 (manufactured by Anric Technologies Co., ltd.) and ALD treatment was performed to obtain a thin sheet sample of example 1. The ALD process conditions are as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidant gas: h 2 O
Purge gas: n (N) 2
Temperature in the reaction chamber: 150 DEG C
The set of steps for continuously performing the precursor gas treatment step, the precursor gas purge step, the vapor gas treatment step, and the vapor gas purge step was set to 1 cycle, and 20 cycles were performed, whereby the total 30 minutes of treatment was performed.
Precursor gas treatment: 0.5 second, TMA flow 0.75SCCM
And (3) purge gas treatment: 8 seconds, purge gas flow 96SCCM
And (3) water vapor treatment: 0.5 second, steam flow 0.75SCCM
And (3) purge gas treatment: 10 seconds, purge gas flow 96SCCM
The set of treatments was carried out in a reaction chamber at a temperature of 150℃and a vacuum of 225mPa, and repeated for 20 cycles, with a total reaction time of about 30 minutes. An observation sample covered with a metal film of about 2nm was obtained by ALD treatment.
Comparative example 1
Under the same conditions as in example 1, a sheet of a multilayered structure material was cut out from the same glass substrate as that used in the production of the sheet sample of example 1 by a FIB apparatus to obtain a sheet of comparative example 1. The sheet of comparative example 1 differs from the sheet of example 1 in that the ALD process is not performed.
(STEM observation)
STEM observations were performed on the sheet sample of example 1 and the sheet of comparative example 1 using a transmission electron microscope ARM200F (manufactured by japan electronics corporation). The acceleration voltage in STEM observation was set to 200kV, and the observation magnification was set to 1000000 times, whereby each observation sample was photographed. Fig. 2 and 3 show STEM photographs and element distribution spectra (EDX spectra) obtained by photographing the ALD-treated sheet sample under these conditions. The region 1 and the region 2 shown by the broken lines in fig. 2 and 3 are partial glass substrate regions constituting a sheet, and the spectra shown on the right side of the sample photograph in fig. 2 and 3 are the respective spectra of the region 1 and the region 2.
As shown in the areas 1 and 2 of the sheet sample of example 1 in fig. 2, no fluorine atom was detected in any part of the sheet sample of example 1 other than the fluorine-based resin film, which was observed after ALD treatment. On the other hand, as shown in the regions 1 and 2 of the sheet of comparative example 1 in fig. 3, fluorine atoms were detected from the regions 1 and 2 other than the fluorine-based resin film in the sheet of comparative example 1 observed without ALD treatment. As a result, it was found by observing the multilayered thin sheet sample that the diffusion of fluorine atoms can be suppressed by ALD processing.
[ evaluation of silver diffusion ]
A conductive resin material used as a membrane electrode material for a fuel cell was formed into a film, and then a thin sheet was collected by FIB processing, and electron microscopic observation was performed on a thin sheet sample of example 2 after ALD processing and a thin sheet of comparative example 2 without ALD processing.
[ example 2 ]
First, an Ag paste (trade name: conductive resin material; manufactured by threbond, inc.) was applied and dried to form a catalyst layer, and then a part of the catalyst layer was cut out by an FIB device to obtain a sheet of the catalyst layer. The obtained sheet was subjected to ALD treatment, whereby a sheet sample of example 2 was obtained.
(FIB treatment)
The processing conditions of the FIB apparatus (product name: helios600; manufactured by FEI Co., ltd.) and the dimensions of the cut sheet were as follows.
Ga ion beam irradiation conditions: accelerating voltage of 30kV
Size of cut sheet: transverse 7 μm X longitudinal 3 μm X thickness 0.0007 μm
(ALD processing)
A thin sheet of the catalyst layer material obtained by the FIB treatment was placed on a FIB grid (diameter: 3mm, copper grid, manufactured by Nippon Denshoku Co., ltd.) and the FIB grid was fixed in a reaction chamber of an ALD apparatus AT-400 (manufactured by Anric Technologies Co.) and ALD treatment was performed to obtain a thin sheet sample of example 2. The ALD process conditions are as follows.
An ALD process was performed by fixing a sample-mounted FIB grid in a reaction chamber of an ALD apparatus AT-400 (manufactured by Anric Technologies). The ALD process conditions are as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidant gas: h 2 O
Purge gas: n (N) 2
Temperature in the reaction chamber: 150 DEG C
The set of steps for continuously performing the precursor gas treatment step, the precursor gas purge step, the vapor gas treatment step, and the vapor gas purge step was set to 1 cycle, and 20 cycles were performed, whereby the total 30 minutes of treatment was performed.
Precursor gas treatment: 0.5 second, TMA flow 0.75SCCM
And (3) purge gas treatment: 8 seconds, purge gas flow 96SCCM
And (3) water vapor treatment: 0.5 second, steam flow 0.75SCCM
And (3) purge gas treatment: 10 seconds, purge gas flow 96SCCM
The set of treatments was carried out in a reaction chamber at a temperature of 150℃and a vacuum of 225mPa, and repeated for 20 cycles, with a total reaction time of about 30 minutes. An observation sample that can be covered with a metal film of about 2nm was obtained by ALD treatment.
Comparative example 2
(production of sheet)
A sheet prepared under the same conditions as the sheet sample of example 2 but not subjected to ALD treatment was used as the sheet of comparative example 2.
(STEM observation)
STEM observations were performed on both the sheet sample of example 2 and the sheet of comparative example 2 on the day of flaking and after 10 days.
STEM observations were performed on the sheet sample of example 1 and the sheet of comparative example 1 using a scanning transmission electron microscope ARM200F (manufactured by japan electronics corporation). The acceleration voltage in STEM observation was set to 200kV, and the observation magnification was set to 1000000 times, whereby the observation sample was photographed.
STEM photographs taken of the sheet sample of example 2 and the sheet of comparative example 2 on the day of flaking and after 10 days are shown in fig. 4. As shown in fig. 4, in the sheet sample of example 2 (ALD-treated), no deformation or diffusion of silver particles was observed, whereas in the sheet sample of comparative example 2, silver particles contained in the sheet were found to be deformed or diffused after 10 days.
(evaluation of contaminants)
The sample was dropped onto a STEM electron microscope carrier net, and then ALD treatment was performed on the sample together with the carrier net, whereby the observation sample of example 3 and the sample of comparative example 3 were produced.
[ example 3 ]
ZnCuInS/ZnS Quantum Dots (manufactured by PlasmaChem Co., ltd.) as a sample was dropped onto a 150-mesh carrier mesh (diameter: 3mm, copper carrier mesh, manufactured by Japanese Industrial science Co., ltd.) for STEM electron microscope, on which a carbon thin film as an organic film was formed, and then ALD treatment was performed on ZnCuInS/ZnS together with the carrier mesh.
(ALD processing)
The TEM observation screen was fixed in a reaction chamber of an ALD apparatus AT-400 (manufactured by Anric Technologies corporation) and ALD treatment was performed, to obtain a sample of example 3. The ALD process conditions are as follows.
Precursor gas: trimethylaluminum (TMA)
Oxidant gas: h 2 O
Purge gas: n (N) 2
Temperature in the reaction chamber: 150 DEG C
The set of steps for continuously performing the precursor gas treatment step, the precursor gas purge step, the vapor gas treatment step, and the vapor gas purge step was set to 1 cycle, and 20 cycles were performed, whereby the total 30 minutes of treatment was performed.
Precursor gas treatment: 0.5 second, TMA flow 0.75SCCM
And (3) purge gas treatment: 8 seconds, purge gas flow 96SCCM
And (3) water vapor treatment: 0.5 second, steam flow 0.75SCCM
And (3) purge gas treatment: 10 seconds, purge gas flow 96SCCM
The set of treatments was carried out in a reaction chamber at a temperature of 150℃and a vacuum of 225mPa, and repeated for 20 cycles, with a total reaction time of about 30 minutes. An observation sample covered with a metal film of about 2nm was obtained by ALD treatment.
(STEM observation)
STEM observation of the sample of example 3 was performed using a scanning transmission electron microscope ARM200F (manufactured by japan electronics corporation). The acceleration voltage in STEM observation was set to 200kV, and the observation magnification was set to 5000000 times, whereby the observation sample was photographed. Fig. 5 shows STEM photographs obtained by taking photographs of the observation sample of example 3 subjected to ALD treatment and the sample of comparative example 3 not subjected to ALD treatment under these conditions.
As shown in fig. 5, the image of the electron micrograph of the observation sample formed by ALD-treated quant Dots (manufactured by PlasmaChem) is clear, whereas the image of the electron micrograph of quant Dots (manufactured by PlasmaChem) not treated by ALD is not clear. From this, it is clear that contamination of the STEM device with contaminants can be suppressed by ALD processing, and an electron microscopic photograph image can be clearly taken.
Claims (18)
1. A method for producing a sample, wherein the sample is a sample observed by an electron microscope,
the manufacturing method comprises the following steps:
a 1 st treatment step of forming a layer of a gaseous metal compound by adhering the metal compound to a surface of a material for producing the sample; and
a 2 nd treatment step of reacting the metal compound with a gaseous oxidizing agent to form a metal oxide layer or a metal layer from the metal compound layer,
wherein,
the material contains a 1 st component, which causes a decrease in the accuracy of observation due to receiving an electron beam from an electron microscope, or which deforms with the passage of time.
2. The method for producing a sample according to claim 1, wherein,
The 1 st component is selected from silver, halogen, silver halide, lead-tin alloy, fluorine resin, sulfur compound and organic compound.
3. The method for producing a sample according to claim 2, wherein,
the material further comprises a 2 nd component other than the 1 st component,
the material comprises a layer of a transparent electrode material as the 2 nd component and a layer containing the fluorine-based resin as the 1 st component,
the fluorine-based resin is a vinylidene fluoride-based resin,
the transparent electrode material is selected from tin oxide and indium oxide.
4. The method for producing a sample according to claim 2, wherein,
the material further comprises a 2 nd component other than the 1 st component,
the material contains the silver particles and the fluorine-based resin as the 1 st component and contains a carbon carrier as the 2 nd component,
the fluorine-based resin is a fluorine-based ionomer.
5. The method for producing a sample according to claim 2, wherein,
the material further comprises a 2 nd component other than the 1 st component,
the material comprises:
the organic compound as the 1 st component; and
as the alloy of the component 2, there is mentioned an alloy containing tin and an element selected from the group consisting of gold, silver, silicon, bismuth and antimony,
The organic compound includes at least 1 organic compound selected from a resin, a surfactant, and an organic solvent.
6. The method for producing a sample according to claim 2, wherein,
the material contains the lead-tin alloy and the organic compound as the 1 st component,
the organic compound includes at least 1 organic compound selected from a resin, a surfactant, and an organic solvent.
7. The method for producing a sample according to claim 2, wherein,
the material is a dispersion containing the 1 st component,
the material comprising the organic compound as the 1 st component,
the organic compound includes at least 1 organic compound selected from a resin, a plasticizer, a surfactant, and an organic solvent.
8. The method for producing a sample according to claim 2, wherein,
the material further comprises a 2 nd component other than the 1 st component,
the material comprises:
the sulfur compound as the 1 st component; and
as the 2 nd component, a material selected from alumina (Al 2 O 3 ) Silicon dioxide (SiO) 2 ) Silica-alumina (SiO) 2 -Al 2 O 3 ) Titanium dioxide (TiO) 2 ) At least 1 of magnesium oxide (MgO), zeolite, ceria-zirconia composite oxide, zirconia, activated carbon, graphite, boron nitride, and carbon nitride.
9. The method for producing a sample according to any one of claims 1 to 8, further comprising the steps of:
before the 1 st processing step, a part of the material is cut out by a focused ion beam, thereby obtaining a sheet of the material.
10. 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 hafnium, zirconium, aluminum, silicon, and titanium.
11. The method for producing a sample according to claim 10, wherein,
the metal compound is trimethylaluminum.
12. 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.
13. The method for producing a sample according to any one of claims 1 to 12, wherein,
in the 1 st and 2 nd treatment steps, the metal compound is reacted with the oxidizing agent at a temperature in the range of 20 to 200 ℃.
14. The method for producing a sample according to any one of claims 1 to 13, wherein,
the 1 st processing step and the 2 nd processing step are repeated as a set of steps.
15. The method for producing a sample according to claim 14, wherein,
the set of processes further comprises:
and a purging step of purging an unreacted product of the gaseous metal compound and an unreacted product of the gaseous oxidizing agent with an inert gas during a period from the 1 st treatment step to the 2 nd treatment step and a period from the 2 nd treatment step to the 1 st treatment step.
16. A method of viewing a sample, comprising:
a manufacturing step of manufacturing a sample by performing the method for manufacturing a sample according to any one of claims 1 to 15; and
and an observation step of observing the sample with an electron microscope.
17. 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.
18. The method for observing a sample according to claim 16 or 17, wherein,
the specimen was observed by the electron microscope at an acceleration voltage in the range of 30 to 300 kV.
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| JP2021127590A JP2022058178A (en) | 2020-09-30 | 2021-08-03 | Sample manufacturing method and sample observation method |
| JP2021-127590 | 2021-08-03 | ||
| PCT/JP2022/012281 WO2023013142A1 (en) | 2020-09-30 | 2022-03-17 | Method for manufacturing sample, and method for observing sample |
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| KR (1) | KR20240039138A (en) |
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| TWI438953B (en) * | 2008-01-30 | 2014-05-21 | Osram Opto Semiconductors Gmbh | Method for manufacturing electronic components and electronic components |
| JP5224347B2 (en) * | 2008-06-23 | 2013-07-03 | フィルジェン株式会社 | Method for forming metal thin film on spectroscopic sample for scanning electron microscope |
| JP2011198885A (en) * | 2010-03-18 | 2011-10-06 | Mitsui Eng & Shipbuild Co Ltd | Atomic layer deposition method and method therefor |
| JP2014157123A (en) * | 2013-02-18 | 2014-08-28 | Toshiba Corp | Sample, sample preparation device and sample observation method |
| JP6120760B2 (en) * | 2013-12-11 | 2017-04-26 | 三菱電機株式会社 | Manufacturing method of solar cell |
| US10128078B2 (en) | 2014-01-29 | 2018-11-13 | Japan Science And Technology Agency | Protective agent for electron microscopic observation of biological sample in water-containing state, kit for electron microscopic observation, methods for observation, diagnosis, evaluation, and quantification by electron microscope, and sample stage |
| JP2015187974A (en) * | 2014-03-14 | 2015-10-29 | 日本電子株式会社 | Method of producing sample support film |
| JP6137553B2 (en) * | 2014-07-28 | 2017-05-31 | 日本電信電話株式会社 | Phase separation structure observation method |
| JP6818346B2 (en) | 2016-04-28 | 2021-01-20 | 国立大学法人浜松医科大学 | Detection kits and methods for direct identification and quantification of nanoparticles by electron microscopy |
| JP6680143B2 (en) * | 2016-08-22 | 2020-04-15 | 住友電気工業株式会社 | Method for preparing sample for interface analysis and method for interface analysis |
| EP3456859A1 (en) * | 2017-09-13 | 2019-03-20 | Rolex Sa | Protective coating for a complex watch component |
| TWI707058B (en) * | 2019-12-19 | 2020-10-11 | 汎銓科技股份有限公司 | A method of preparing a sample for physical analysis |
| JP2022025001A (en) * | 2020-07-28 | 2022-02-09 | 株式会社住化分析センター | Sample preparation method and sample observation method |
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