WO2020116990A1 - Composite de graphène pour observation microscopique d'électrons et procédé de fabrication de substrat d'échantillon - Google Patents

Composite de graphène pour observation microscopique d'électrons et procédé de fabrication de substrat d'échantillon Download PDF

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Publication number
WO2020116990A1
WO2020116990A1 PCT/KR2019/017192 KR2019017192W WO2020116990A1 WO 2020116990 A1 WO2020116990 A1 WO 2020116990A1 KR 2019017192 W KR2019017192 W KR 2019017192W WO 2020116990 A1 WO2020116990 A1 WO 2020116990A1
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graphene
sample
layer
microscope
support layer
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PCT/KR2019/017192
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English (en)
Korean (ko)
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이정오
정두원
황준연
이경은
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한국화학연구원
한국과학기술연구원
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Publication of WO2020116990A1 publication Critical patent/WO2020116990A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00—Microscopes
    • G02B21/24—Base structure
    • G02B21/26—Stages; Adjusting means therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/02—Details
    • H01J37/20—Means for supporting or positioning the objects or the material; Means for adjusting diaphragms or lenses associated with the support

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  • the present invention relates to a graphene complex for electron microscopy that can observe a sample to be observed clearly and accurately.
  • the crystalline phase of a specific material allows the characteristics of the material to be grasped in more detail, and the material made of the crystalline phase has superior physical and chemical properties compared to the amorphous material.
  • a very high temperature is required to form a crystalline phase of a material, or it is performed in a solution phase, because it undergoes a process of reassembling the constituent molecules of the material.
  • a solution phase it is relatively easy to produce a single crystal of a soluble material, because crystal growth is made by homogeneous nucleation, and in the case of heterogeneous nucleation that forms crystals on a solid substrate, there is a problem that it is difficult to greatly increase the crystal size. do.
  • graphene having a large sheet shape composed of hybridized SP 2 bonds of carbon atoms is a perfectly flat and defect-free material. Therefore, since the discovery of graphene, it has attracted attention as the best template material for epitaxial growth of various 2D materials.
  • An object of the present invention is to provide a graphene complex for electron microscope observation that can observe a sample to be observed clearly and accurately.
  • Graphene complex for electron microscopic observation including a graphene layer and a support layer located on one surface of the graphene layer.
  • the graphene complex is a graphene complex in which the sample to be observed is located on the other surface of the graphene layer.
  • the sample to be observed is at least one graphene complex selected from the group consisting of oligonucleotides, proteins, polypeptides, cells, organelles, protozoa, viruses, metals, polymers and semiconductors.
  • the support layer is a graphene composite made of an amorphous material.
  • the support layer is a graphene composite made of a crystalline material.
  • the crystalline material is at least one selected from the group consisting of metal, silica, quartz, ceramic, paper, plastic, polymer, cloth and composites thereof Graphene composite.
  • the microscope is a graphene complex selected from the group consisting of transmission electron microscope, scanning electron microscope, scanning probe microscope, scanning tunneling microscope, confocal microscope, X-ray microscope, optical microscope and tomography microscope. .
  • a method of manufacturing an electron microscope sample substrate comprising forming a crystalline sample on the other surface of the graphene layer of the composite of 5 above.
  • the crystalline sample is at least one selected from the group consisting of oligonucleotides, proteins, polypeptides, cells, organelles in the cell, protozoa, viruses, metals, polymers, and semiconductors.
  • a sample to be observed can be accurately and clearly observed.
  • a sample to be observed in the case of a graphene composite supported by a support layer made of a crystalline material, a sample to be observed can be crystallinely formed, and in the case of a graphene composite supported by a support layer made of an amorphous material, an insulating bio sample The back can be accurately and clearly observed, and even in the case of a sample that could not be placed on a single graphene layer, it has the advantage of being stably placed due to the chemical transparency of graphene.
  • FIG. 1 is a SEM sample obtained by placing a section sample on a Kapton film without carbon coating (A), a SEM observation by coating the sample surface with carbon (B), and a graphene layer positioned on top using a Kapton film as a support layer. It shows the SEM observation result (C) by placing a target section sample on the graphene composite of the invention.
  • FIG. 2 and 3 are the results of imaging each of the cases in which the present invention graphene complex was used (FIG. 2) and the kapton film alone was not used (FIG. 3).
  • 5 to 7 shows the growth pattern of gold crystals over time after PECVD as a support layer (copper foil, SiO 2 /Si), as a result of observation under a microscope by growing gold crystals using the graphene composite of the present invention.
  • the thickness of the gold thin film was grown to 1 nm, 3 nm, 3.4 nm, 4.5 nm, 5 nm, and 7 nm, and the current resistance exhibited by the thin film was measured as 145 ⁇ for 3 nm and 75 ⁇ for 5 nm.
  • FIG. 8 shows an atomic force microscope (AFM) picture of the gold crystal film formed on the graphene of FIG. 6.
  • FIG. 9 shows that a crystal film having a thickness of about 3 nm was formed as a result of showing the thickness according to the position (horizontal) of the gold crystal film of FIG.
  • 11 shows the UV/VIS spectrum of the gold single crystal layer formed on the graphene layer supported on the quartz support layer to evaluate the optical properties of the gold crystal film. 11, the transmittance decreases as the gold crystal layer deposition thickness increases.
  • 12 and 13 are electron microscope images showing the growth of an indium single crystal formed on a graphene layer supported on a copper foil support layer, which is formed at 277K and 100K, respectively.
  • FIG. 14 shows an AFM image of crystals after transferring the indium single crystal layer of FIG. 12 to a silicon substrate with PMMA.
  • 15 is a graph showing the thickness according to the position (horizontal) of the indium single crystal layer of FIG. 14, and it can be seen that 10-30 nm thick crystals were grown.
  • 16 is an electron microscope image showing single crystal growth of tin formed on a graphene layer supported on a copper foil support layer.
  • 17 to 19 are electron microscopic images showing the growth of Pd, Pt, and Co single crystals formed on the graphene layers supported on the copper foil support layers, respectively.
  • the present invention provides a graphene complex for electron microscopic observation, including a graphene layer and a support layer located on one surface of the graphene layer.
  • the graphene composite is a sample supporting substrate for electron microscopy observation, and the sample to be observed can be clearly and precisely observed due to the excellent conductivity and chemical transparency of the graphene layer made of carbon, and the bio sample having insulating properties is also clearly observed. It has the advantage that it is possible.
  • the sample to be observed may be located on the upper surface, the lower surface, and both sides of the graphene complex in a range capable of observing the electron microscope, but specifically, the other surface of the graphene layer That is, it may be located on a surface that is not supported as a support layer among both surfaces of the graphene layer.
  • oligonucleotides, proteins, polypeptides, cells, organelles, protozoa, viruses, metals, polymers, organic molecules and semiconductors It may be at least one selected from the group consisting of.
  • the support layer can be used without limitation as long as it is used as a sample support layer for an electron microscope in the prior art, and can be varied depending on the type of electron microscope or the nature of the sample to be observed. It may be a crystalline support layer made of a material or an amorphous support layer made of a material that is not crystalline.
  • a material constituting the crystalline support layer may be at least one selected from the group consisting of metal, silica, quartz, ceramic, paper, plastic, polymer, cloth, and composites thereof. , It is not particularly limited.
  • a sample that has already been prepared may be placed on the graphene layer, but it may be observed by forming a crystalline sample on the graphene layer.
  • the crystallinity of the crystalline sample can be further improved to more clearly observe the internal structure such as the crystal structure.
  • a sample substrate in the case of using a crystalline support layer as an embodiment of the present invention may be prepared by including a step of forming a crystalline sample on the graphene layer of the present invention graphene composite.
  • the crystalline sample may be at least one selected from the group consisting of oligonucleotides, proteins, polypeptides, cells, intracellular organelles, protozoa, viruses, metals, polymers, organic molecules and semiconductors, but is not limited thereto, and crystallinity Any sample to be observed can be freely selected and formed on the graphene layer.
  • the crystalline sample can be applied without any particular limitation on the method of forming the sample as an observation subject of an electron microscope.
  • a chemical vapor deposition method, sputtering, etc. may be mentioned, but an appropriate method may be applied depending on the material.
  • a material constituting the amorphous support layer may be at least one selected from the group consisting of amorphous polymers, amorphous inorganic materials and composites thereof, but is not particularly limited thereto.
  • the graphene layer included in the graphene composite may be a single graphene layer, a double graphene layer, or multiple graphene layers, but is preferably a single graphene layer or a thin graphene layer in terms of forming a thin graphene composite for microscopic observation.
  • the graphene layer is located on one surface of the support layer, and is not limited to a specific surface such as upper, lower, or both sides of the support layer, but considering the aspect of placing the target material on the graphene layer during electron microscope observation , It is preferably located on the upper portion of the support layer.
  • the graphene layer is located on one surface of the support layer by at least one method from the group consisting of chemical vapor deposition, vapor deposition, molecular beam deposition, vacuum deposition, activation reaction deposition, mechanical separation, fluid collision separation, and chemical separation. It may be, but is not limited thereto, and any method known in the art can be freely selected as long as it can effectively position the graphene layer on the support layer.
  • the graphene composite is a graphene composite for electron microscope observation, and has no particular limitation on its thickness, and may be set in various ranges depending on the type of electron microscope and the nature of the support layer, but has a thinner thickness to improve electron permeability, etc. To obtain the effect of, for example, it may be 5 to 70, 6 to 65, 7 to 60, 8 to 55, 9 to 55, 10 to 50 mm 2, preferably 10 to 50 mm thick.
  • the graphene composite is a graphene composite for electron microscopic observation, and is based on chemical transparency of graphene and conductivity of a carbon-based material. Therefore, as a kind of microscope, TEM (transmission electron microscope), SEM (scanning electron microscope), AFM (scanning probe microscope), STM (scanning tunneling microscope), confocal microscope (confocal microscope), X-ray microscope, optical microscope and It may be one selected from the group consisting of a tomographic microscope (tomography microscope), but is not limited thereto.
  • Example 1 Observation of a bio sample using a graphene complex supported on a flexible support layer
  • the graphene material is grown for about 1 hour in a methane and hydrogen atmosphere at 1000° C. using a copper foil cleaned with a nickel etchant in a hot wall furnace as a catalyst. More specifically, graphene was manufactured on a 4.8 ⁇ m thick copper thin film (Alfa Aesar) by low pressure chemical vapor deposition (CVD). Prior to synthesis, the copper film was immersed in a nickel etchant (transene, TFB) and washed.
  • the specific growth conditions are as follows.
  • a copper thin film was put in a reactor, and the pressure was reduced, followed by heating to 1000° C. and annealing for 20 minutes under 100 sccm H 2 conditions. 30 sccm CH 4 and 30 sccm H 2 were introduced for 40 minutes to promote graphene growth.
  • the furnace was cooled to room temperature.
  • the graphene material grown on the copper foil as described above can be used as an electron microscope substrate capable of growing crystals without additional treatment, but when optical transparency is required, the graphene grown on the copper foil is transferred to a transparent substrate. use.
  • the image of the biosample of the present invention was used by transferring a graphene sample grown on a copper foil onto a kapton foil via PMMA or by transferring a graphene sample onto a kapton foil using an electrostatic film.
  • Cell sections are made by staining cell membranes with osmium, uranium, lead, etc., and forming thin sections of tens of nanometers in flexible membranes (Kapton films, etc.) with clean surfaces using ultra-thin sectioning machines using biothin tissue embedded in resin. It was used in experiments to observe the microstructure of.
  • the graphene material grown on the copper foil on the glass substrate was transferred and used as a substrate for growing the lysozyme protein.
  • the structure of the target sample can be confirmed by reducing the charging phenomenon, but carbon on the sample
  • the result of reducing the resolution of the observed image is somewhat reduced, resulting in a difference in the image resolution of each sample according to the degree of sample coating, and additional experiments such as immunostaining after imaging cannot be additionally performed. This exists.
  • a sample of a target fragment is placed on the graphene complex of the present invention in which a graphene layer is positioned on a Kapton film as a support layer, and the results observed by SEM can be confirmed.
  • the charging phenomenon has been eliminated, and the resolution of the image is very high enough to clearly identify the structure.
  • additional experimental processes such as immunostaining after imaging.
  • FIG. 2 shows that when using the graphene composite of the present invention, the microstructure of biological tissues, such as cell membranes, is well shown in various sample thicknesses and various acceleration voltages, it can be utilized regardless of sample thickness and acceleration voltage.
  • Figure 3 shows the effect of improving the conductivity of the graphene coating at the boundary coated with the graphene composite of the present invention on the surface.
  • the conductivity is increased compared to the case where it is not, so the charging phenomenon does not appear, and the effect of improving the conductivity is to remove the excess electrons accumulated in the biological tissue sample having insulating characteristics, thereby removing the sample.
  • the charging phenomenon clear observation of the microstructure is possible.
  • the lysozyme protein crystal is grown using a graphene complex and the results observed under a microscope can be confirmed.
  • nucleation is easier than in the case where it is not. It can be seen that the crystal growth is fast and large.
  • Example 2 Growth and observation of a metal single crystal using a graphene composite supported on a crystalline support layer
  • Graphene was prepared on a 4.8 ⁇ m thick copper thin film (Alfa Aesar) by low pressure chemical vapor deposition (CVD). Prior to synthesis, the copper film was immersed in a nickel etchant (transene, TFB) and washed.
  • TFB nickel etchant
  • a copper thin film was put in a reactor, and the pressure was reduced, followed by heating to 1000° C. and annealing for 20 minutes under 100 sccm H 2 conditions. 30 sccm CH 4 and 30 sccm H 2 were introduced for 40 minutes to promote graphene growth.
  • the furnace was cooled to room temperature.
  • PMMA is coated on the graphene surface and transferred to a desired substrate by etching copper, or after attaching an electrostatic film to the graphene surface and etching the copper to the desired substrate.
  • the method of transcription was used.
  • transfer the graphene coated with PMMA onto the SiO 2 /Si or quartz support layer dry it sufficiently at room temperature to remove water, and then dry it completely at a temperature of 100°C or less to improve adhesion.
  • the PMMA was soaked and removed in acetone to complete the graphene complex.
  • the electrostatic film a graphene layer attached to the electrostatic film was attached to the target substrate, and then the electrostatic film was compressed to transfer and remove the graphene.
  • the graphene composite supported by the copper foil support layer and the SiO 2 /Si or quartz support layer All supported graphene composites correspond to graphene composites supported by a crystalline support layer.
  • Metal crystals were grown through vacuum thermal vapor deposition on the graphene composite surface thus manufactured.
  • the vacuum thermal evaporation chamber was depressurized to 2.0 X 10 -6 mbar, and pure metal pellets (99.999%, iTASCO T) were placed in a molybdenum boat (iTASCO) and then evaporated.
  • the deposition was performed at room temperature (300K) or low temperature (277K ⁇ 100K). The thickness of the thin film was monitored with a quartz crystal microbalance (QCM).
  • FIG. 5 shows an electron microscope image of a gold single crystal formed on a graphene layer supported on a copper foil support layer.
  • gold is deposited on the graphene layer supported on the crystalline copper foil support layer, it can be seen that fractal crystals grow.
  • the connectivity of crystals was significantly reduced on the graphene surface left in the atmosphere for a long time (Fig. 5, 18h, 1-2 weeks exposed).
  • FIGS. 6 and 7 show electron microscope images of gold single crystals formed on a graphene layer supported on a SiO 2 /Si support layer. Again, it can be seen that the crystals in the form of fractals grow as if supported on the copper foil support layer. However, the size of the crystal is smaller than that of the graphene supported on the crystalline support layer.
  • FIG. 8 and 9 show AFM images and thicknesses of gold crystals grown on the graphene of FIG. 5, respectively.
  • FIG. 10 shows XRD analysis results of the gold single crystal film of FIG. 6. It can be seen that the Au ⁇ 111> plane occupies the majority, and it can be seen from the Laue pattern of the Au ⁇ 111> peak of the right enlarged image that the crystal film is composed of 2-3 layers of gold atoms.
  • FIG. 11 shows the UV/VIS spectrum of the grown gold crystal layer. Referring to this, as the deposition thickness increases, the transparency of the film decreases, and it can be seen that the location of the resonance peak shifts slightly to a long wavelength. This means that the crystal size increases with increasing deposition thickness.
  • FIG. 12 and 13 are electron microscope images showing the growth of an indium single crystal formed on a graphene layer supported on a copper foil support layer, which is formed at 277K and 100K, respectively.
  • the crystal of FIG. 13 is formed in a very small size compared to the crystal of FIG. 12 because the metal atoms lose kinetic energy due to the low temperature of the substrate and crystallize as soon as it hits the substrate. On a substrate close to room temperature, metal atoms move relatively freely to form a larger crystal phase.
  • 16 is an electron microscope image showing single crystal growth of tin formed on a graphene layer supported on a copper foil support layer. Referring to this, increasing the deposition thickness increases the crystal size, but there was no significant difference in crystals formed at 277K and 307K. Thus, it can be seen that the temperature of the substrate is preferably 0 degrees Celsius or more in order to maximize the crystal size.
  • 17 to 19 are electron microscopic images showing the growth of Pd, Pt, and Co single crystals formed on the graphene layers supported on the copper foil support layers, respectively.
  • Pd, Pt, and Co small crystals in a fractal form are grown, but in the case of Pd, Pt, and Co, the binding energy with graphene is higher than in the case of Au, In, Sn, and the crystal size is high.

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Abstract

Lorsqu'elle est utilisée dans une observation microscopique d'électrons, un composite de graphène de la présente invention peut permettre une observation précise et nette d'un échantillon à observer. En particulier, dans le cas d'un composite de graphène supporté par une couche de support constituée d'un matériau cristallin, un échantillon à observer peut être formé pour être cristallisé, et, dans le cas d'un composite de graphène supporté par une couche de support constituée d'un matériau non cristallin, un échantillon biologique isolant ou analogue peut être observé de manière précise et nette, et même un échantillon qui ne peut pas être monté sur une seule couche de graphène peut être monté de façon stable sur le composite de graphène du fait de la transparence chimique du graphène.
PCT/KR2019/017192 2018-12-06 2019-12-06 Composite de graphène pour observation microscopique d'électrons et procédé de fabrication de substrat d'échantillon WO2020116990A1 (fr)

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KR102484419B1 (ko) 2020-11-04 2023-01-03 재단법인대구경북과학기술원 그래핀을 이용하여 세포가 살아있는 생체 시료의 세포막 구조 및 성분을 분석하는 이미징 분석 방법 및 장치
KR102558793B1 (ko) * 2021-11-26 2023-07-25 (주)엠씨케이테크 그래핀 복합 구조체 제조방법 및 이로부터 제조되는 그래핀 복합 구조체

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