WO2015023026A1 - Method and device for producing a transmission electron microscopy specimen - Google Patents

Method and device for producing a transmission electron microscopy specimen Download PDF

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Publication number
WO2015023026A1
WO2015023026A1 PCT/KR2013/009165 KR2013009165W WO2015023026A1 WO 2015023026 A1 WO2015023026 A1 WO 2015023026A1 KR 2013009165 W KR2013009165 W KR 2013009165W WO 2015023026 A1 WO2015023026 A1 WO 2015023026A1
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sample
transmission electron
specimen
electron microscope
epoxy
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PCT/KR2013/009165
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French (fr)
Korean (ko)
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이종훈
김나연
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국립대학법인 울산과학기술대학교 산학협력단
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Publication of WO2015023026A1 publication Critical patent/WO2015023026A1/en

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    • 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
    • G01N1/32—Polishing; Etching
    • 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
    • G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
    • G01N2001/2873—Cutting or cleaving

Definitions

  • the present invention relates to a method and apparatus for manufacturing a specimen for transmission electron microscope, and more particularly, to a method and apparatus for preparing a specimen for transmission electron microscope that can be used to prepare specimens such as porous materials and fiber materials.
  • Transmission Electron Microscopy is a type of electron microscope that uses an electron beam and an electron lens instead of a light source and a light source lens in an optical microscope.
  • the operating principle of the transmission electron microscope is basically the same as that of an optical microscope, whereas the light source of the optical microscope is light, while the light source of the transmission electron microscope transmits the specimen through the accelerating electron beam, and the action of the electron lens is adjusted to the full length to control the magnification of the image. .
  • a technique for manufacturing a transmission electron microscope specimen having a thickness of at least 100 nm or less is very important.
  • the thinner the thickness of the specimen the higher the image quality. As it becomes high, it is essential to process the thickness of the sample thinly.
  • a method for producing a transmission electron microscope specimen for sectional image observation of inorganic pigments In this method, a mixture of G-1 epoxy and powder is put into a copper tube, and then heated on a hot plate heated to about 130 degrees, and then the copper tube is cut into thin pieces and polished to obtain a thickness of about 55 to 75 ⁇ m. After making it thinner enough, the work called dimpling makes the area you want to see very thin. And the work called ion milling makes the area you want to see thinner.
  • the micropores are not completely filled, making the specimen impossible.
  • the presence of pores means that the crystals are separated, and if dimpled in this state, the crystals may be separated.
  • the amount of the epoxy is relatively greater than the amount of powder, the probability of finding powder in the region processed by dimpled, etc., and even if the powder is found, the probability of finding a powder having the desired size and thickness is low.
  • increasing the amount of powder and reducing the amount of epoxy do not mix well with each other, so the maximum powder ratio is not only as low as 20%, but the time required to make one specimen is also very long, about 20 hours.
  • an object of the present invention is to provide a method and apparatus for preparing a transmission electron microscope specimen suitable for preparing a specimen such as a porous material in which micropores exist while reducing the time required for fabrication.
  • a method for fabricating a transmission electron microscope specimen comprising: bonding a multilayer silicon substrate with epoxy mixed with a sample, preparing a laminated sample cured by applying heat and pressure, and preparing the laminated sample. Polishing to a predetermined thickness, cutting the polished laminated sample into a disk shape in a direction perpendicular to the stacking direction, and manufacturing a commercially available disk type filled in a copper tube, and focusing a specific area on the commercially available disk type Etching using an ion beam, to prepare a specimen for transmission electron microscope.
  • the transmission electron microscope specimen manufacturing apparatus for achieving the above object, a body portion for receiving the epoxy mixed with the sample in a cylindrical receiving space formed therein, coupled to the upper portion of the body portion, the receiving space It is connected to the upper body portion for applying pressure to the upper portion of the epoxy mixed with the sample contained in the sample, the lower body portion for applying pressure to the lower portion of the epoxy mixed with the sample contained in the receiving space, and the lower body portion It includes a vacuum pump for sucking the epoxy in the receiving space.
  • the present invention provides a transmission electron microscope specimen prepared by the manufacturing method.
  • the epoxy fills the micropores up to the nano-size, prevents damage of the specimen by gallium ions during etching by the focused ion beam, it is possible to prepare a specimen for a sample that was impossible with the conventional specimen manufacturing method.
  • the time required for the production of the specimen is short, the probability of seeing the desired sample in the produced specimen is also increased.
  • the heterogeneous fine powder sample can be produced in one specimen, and facilitates the fabrication of specimens for porous or fibrous materials in which micropores exist.
  • Figure 4 is an image of the specimen produced by the specimen manufacturing method according to the invention.
  • FIG. 5 is a view showing an image after vision using a focused ion beam
  • FIG. 7 is a view referred to in the description of the specimen manufacturing apparatus according to an embodiment of the present invention.
  • FIG. 1 is a flow chart provided in the description of the method for manufacturing a transmission electron microscope specimen according to an embodiment of the present invention
  • Figure 2a to 2d is a description of the method for manufacturing a transmission electron microscope specimen according to an embodiment of the present invention Reference is made to the drawing.
  • the transmission electron microscope specimen manufacturing method the laminated sample preparation (S100), polishing (S110), copper specimens in the form of disks (S120), using a focused ion beam Including the process of time (S130), the finished specimen may be analyzed by the transmission electron microscope (S140).
  • a laminated sample is produced (S100).
  • the laminated sample is produced by joining a multilayer silicon wafer substrate 201 using an epoxy 211.
  • the epoxy 213 mixed with the sample powder is placed in at least one of the silicon wafer substrate. Then, it is cured by applying heat and pressure to make a laminated sample 230 as shown in Fig. 2B.
  • the heat and time required to make the stacked sample 230 may be performed by referring to a graph as shown in FIG. 3.
  • a graph as shown in FIG. 3 When making the laminated sample 230, there is no quantitative value for the pressure applied, but basically the higher the pressure, the better.
  • the epoxy is counted out by the heat and pressure from the laminated sample 230 is removed, to make a thickness suitable for using the focused ion beam.
  • the disk-shaped specimen is loaded on the focused ion beam to find a portion where the sample powder is located, and the desired region 235 is visualized (S130).
  • Focused Ion Beam features pinpoint observation of micro-areas as a target and uniform processing of different types of materials through micro-machining ranging from micro to hundreds of nanoscales with etching of focused ion beams. It can be polished to a thickness and can quickly produce a sample.
  • the transmission electron microscope specimen After the etching of the desired region is finished using the focused ion beam, the transmission electron microscope specimen is manufactured, the specimen analysis may be performed by the transmission electron microscope (S140).
  • the specimen preparation method according to the invention it is possible to produce a sample of different fine powder into one specimen. That is, when bonding a multilayer silicon wafer substrate, by using an epoxy mixed with different sample powder between each silicon wafer, it is possible to produce one specimen containing different types of sample powder.
  • the specimen in the case of a fiber material as well as a sample in a powder form, the specimen may be manufactured in the same manner according to the above-described procedure.
  • 4 to 6 is a specimen image for transmission electron microscopy of the positive electrode material of the charged and discharged battery produced by the test piece manufacturing method according to the present invention.
  • the image shown in Figure 4 is an image of the specimen actually produced by the specimen manufacturing method according to the present invention.
  • 5 shows that the epoxy fills the micropores inside the anode material as an image of the specimen after etching using the focused ion beam.
  • 6 shows an image of a transmission electron microscope for a specimen.
  • the specimen produced according to the method according to the present invention can be observed that the epoxy is wrapped not only large pores but also pores up to fine nano size. Epoxy also serves to prevent and protect the specimen from damage by gallium ions when the specimen is manufactured using a focused ion beam. Accordingly, it is possible to prepare a specimen for a sample in which micropores exist that were impossible with the conventional method.
  • FIG. 7 is a view showing a transmission electron microscope specimen manufacturing apparatus according to an embodiment of the present invention.
  • the core of the specimen manufacturing method according to the present invention is to fill the micropores up to nano size by applying heat and pressure.
  • the range of heat applied is fixed, but the higher the pressure, the smaller the pores can fill, so there is no specific range. Accordingly, there is a need for an apparatus capable of applying a higher pressure, reducing the amount of epoxy, and making a sample having a large amount of sample powder.
  • the apparatus 300 includes an upper body 310, a body 320, a lower body 330, and a vacuum pump 340.
  • a cylindrical receiving space is formed inside the monche 320, and accommodates the epoxy 400 mixed with the sample in the receiving space.
  • the upper body part 310 is coupled to the upper part of the body part 320 to apply pressure to the upper part of the epoxy mixed with the sample contained in the receiving space.
  • the lower body part 330 is coupled to the lower part of the body part 320 to apply pressure to the lower part of the epoxy mixed with the sample contained in the receiving space.
  • a lower pump 340 is connected to the lower body 330 to suck extra epoxy from the receiving space.
  • the body 320 is provided with a heating unit 323 using a heating band or a heating wire to apply heat to the receiving space.
  • the transmission electron microscope specimen manufacturing method according to the invention is not limited to the configuration and method of the embodiments described as described above, the embodiments are all or all of the embodiments so that various modifications can be made Some may be optionally combined.
  • the present invention can be used to produce specimens for transmission electron microscopy, such as porous materials and fiber materials.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

The present invention relates to a method and a device for producing a transmission electron microscopy specimen. The method for producing a transmission electron microscopy specimen, according to the present invention, produces a transmission electron microscopy specimen by: joining multiple layers of silicon substrates using an epoxy that has been mixed with a sample, and then applying heat and pressure thus preparing a hardened laminated sample; polishing the prepared laminated sample to a prescribed thickness, cutting the polished laminated sample into a disk shape in the direction vertical to the lamination direction of the sample, thus producing a disk-shaped specimen filled into a copper tube; and then etching a specific area of the disk-shaped specimen using a focused ion beam. The present invention enables specimens for porous materials and fibrous materials to be rapidly produced.

Description

투과전자현미경용 시편 제작방법 및 장치Specimens manufacturing method and apparatus for transmission electron microscope
본 발명은 투과전자현미경용 시편 제작방법 및 장치에 관한 것으로, 더욱 상세하게는 다공성 재료 및 섬유 재료 등의 시편을 제작하는데 사용할 수 있는 투과전자현미경용 시편 제작방법 및 장치에 관한 것이다.The present invention relates to a method and apparatus for manufacturing a specimen for transmission electron microscope, and more particularly, to a method and apparatus for preparing a specimen for transmission electron microscope that can be used to prepare specimens such as porous materials and fiber materials.
투과전자현미경(Transmision Electron Microscopy,TEM)은 전자현미경의 한 종류로 광학 현미경에서의 광원과 광원 렌즈 대신에 전자빔과 전자 렌즈를 사용하는 현미경이다. 투과전자현미경의 작동원리는 기본적으로 광학 현미경과 같으나, 광학현미경의 광원이 빛인데 반하여 투과전자현미경의 광원은 가속 전자빔으로 시편을 투과하고, 상의 배율 조절을 위해 전자 렌즈의 작용을 전장으로 조절한다. Transmission Electron Microscopy (TEM) is a type of electron microscope that uses an electron beam and an electron lens instead of a light source and a light source lens in an optical microscope. The operating principle of the transmission electron microscope is basically the same as that of an optical microscope, whereas the light source of the optical microscope is light, while the light source of the transmission electron microscope transmits the specimen through the accelerating electron beam, and the action of the electron lens is adjusted to the full length to control the magnification of the image. .
전자빔이 물질에 입사되면 시편과 전자가 상호작용하여 다양한 현상이 발생하며, 투과전자현미경은 이중에서 시편의 얇은 부분을 투과한 전자들을 이용한다. 즉, 관찰하고자 하는 재료의 파장보다 작은 가속 전자를 발생하여 매질에 투과시키면 결정면이나 결함 등의 정도에 따라 투과할 수 있는 전자빔의 세기 차가 발생하게 되고, 투과된 빔 세기 차이는 형광스크린에서 명암으로 나타나는 것이다. When the electron beam is incident on the material, various phenomena occur due to the interaction between the specimen and the electron, and the transmission electron microscope uses electrons transmitted through a thin portion of the specimen. In other words, if the accelerated electrons smaller than the wavelength of the material to be observed are transmitted through the medium, the difference in the intensity of the electron beam that can be transmitted is generated according to the degree of crystal plane or defect, etc. Appear.
이러한 투과전자현미경을 이용하여 특정 물질을 효과적으로 분석하기 위해서는 최소 100㎚ 이하의 두께를 가지는 투과전자현미경용 시편을 제작하는 기술이 매우 중요하며, 투과전자현미경은 시편의 두께가 얇을수록 이미지의 품질이 높아지기 때문에 시료의 두께를 얇게 가공하는 것이 필수적이다. In order to effectively analyze a specific material using such a transmission electron microscope, a technique for manufacturing a transmission electron microscope specimen having a thickness of at least 100 nm or less is very important. In the transmission electron microscope, the thinner the thickness of the specimen, the higher the image quality. As it becomes high, it is essential to process the thickness of the sample thinly.
이와 관련하여, 무기안료 등의 단면 이미지 관찰을 위한 투과전자현미경 시편 제작방법이 있다. 이 방법은, 먼저 G-1 에폭시(epoxy)와 파우더를 섞은 것을 구리 튜브에 넣은 뒤, 약 130도 정도로 가열된 hot plate 위에서 열을 가한 후 구리 튜브를 얇게 자르고, 폴리싱을 하여 약 55 ~ 75㎛ 정도로 더 얇게 만든 후, 딤플링(dimpling)이라는 작업을 통해 가운데 보고자 하는 영역만 매우 얇게 만들어준다. 그리고, 이온 밀링(ion milling)이라는 작업을 통해 보고자 하는 영역을 더 얇게 만들어준다.In this regard, there is a method for producing a transmission electron microscope specimen for sectional image observation of inorganic pigments. In this method, a mixture of G-1 epoxy and powder is put into a copper tube, and then heated on a hot plate heated to about 130 degrees, and then the copper tube is cut into thin pieces and polished to obtain a thickness of about 55 to 75 μm. After making it thinner enough, the work called dimpling makes the area you want to see very thin. And the work called ion milling makes the area you want to see thinner.
그런데, 이와 같은 방법은 파우더 내에 미세 기공이 존재하는 경우, 미세 기공이 완벽하게 채워지지 않아, 시편의 제작을 불가능하게 한다. 즉, 기공이 존재한다는 의미는 결정들이 분리되어있는 상태인데, 이 상태에서 딤플링 등을 진행하게 되면 결정들이 분리되어 나갈 수 있다. 또한, 에폭시의 양이 파우더의 양보다 상대적으로 많아, 딤플링 등을 통해 가공한 영역에서 파우더를 찾을 수 있는 확률이 낮고, 파우더를 찾더라도 원하는 크기와 두께를 가지는 파우더를 찾을 확률도 낮다. 그리고, 파우더의 양을 늘리고 에폭시의 양을 줄이게 되면 서로 잘 섞이지 않으므로, 최대 파우더 비율은 20% 정도로 낮을 뿐만 아니라, 시편을 하나 만드는데 소요되는 시간도 대략 20시간으로 매우 길다. By the way, in the case where the micropores are present in the powder, the micropores are not completely filled, making the specimen impossible. In other words, the presence of pores means that the crystals are separated, and if dimpled in this state, the crystals may be separated. In addition, the amount of the epoxy is relatively greater than the amount of powder, the probability of finding powder in the region processed by dimpled, etc., and even if the powder is found, the probability of finding a powder having the desired size and thickness is low. In addition, increasing the amount of powder and reducing the amount of epoxy do not mix well with each other, so the maximum powder ratio is not only as low as 20%, but the time required to make one specimen is also very long, about 20 hours.
따라서, 이러한 방법은 충방전을 거친 배터리 양극 재료 등과 같이 미세 기공이 존재하는 다공성 재료에 대한 시편 제작에는 적합하지 않으므로, 새로운 시편 제작방법을 모색할 필요가 있다. Therefore, such a method is not suitable for fabricating specimens for porous materials in which micropores exist, such as battery anode materials, which have been charged and discharged, and thus, it is necessary to search for a new specimen fabrication method.
따라서, 본 발명의 목적은, 제작에 소요되는 시간을 단축하면서 미세 기공이 존재하는 다공성 재료 등의 시편 제작에 적합한 투과전자현미경 시편 제작방법 및 장치를 공함에 있다. Accordingly, an object of the present invention is to provide a method and apparatus for preparing a transmission electron microscope specimen suitable for preparing a specimen such as a porous material in which micropores exist while reducing the time required for fabrication.
상기 목적을 달성하기 위한 본 발명에 따른 투과전자현미경 시편 제작방법은, 시료와 혼합한 에폭시로 다층 실리콘 기판 사이를 접합시킨 뒤, 열과 압력을 가하여 경화시킨 적층 시료를 제조하는 단계, 상기 적층 시료를 소정 두께로 폴리싱하는 단계, 상기 폴리싱된 적층 시료를 적층 방향에 수직한 평향으로 디스크 형태로 커팅하여 구리 튜브에 채워넣은 디스크 형태의 시판을 제작하는 단계, 및 상기 디스크 형태의 시판에서 특정 영역을 집속 이온빔을 이용하여 식각하여, 투과전자현미경용 시편을 제작하는 단계를 포함한다.In another aspect of the present invention, there is provided a method for fabricating a transmission electron microscope specimen, comprising: bonding a multilayer silicon substrate with epoxy mixed with a sample, preparing a laminated sample cured by applying heat and pressure, and preparing the laminated sample. Polishing to a predetermined thickness, cutting the polished laminated sample into a disk shape in a direction perpendicular to the stacking direction, and manufacturing a commercially available disk type filled in a copper tube, and focusing a specific area on the commercially available disk type Etching using an ion beam, to prepare a specimen for transmission electron microscope.
또한, 상기 목적을 달성하기 위한 본 발명에 따른 투과전자현미경 시편 제작장치는, 내부에 형성된 원통형의 수용공간에 시료와 혼합한 에폭시를 수용하는 몸체부, 상기 몸체부의 상부에 결합하여, 상기 수용공간에 수용된 시료와 혼합한 에폭시의 상부에 압력을 가하는 상체부, 상기 몸체부의 하부에 결합하여, 상기 수용공간에 수용된 시료와 혼합한 에폭시의 하부에 압력을 가하는 하체부, 및 상기 하체부와 연결되어, 상기 수용공간에서 여부의 에폭시를 흡입하는 베큠 펌프를 포함한다. In addition, the transmission electron microscope specimen manufacturing apparatus according to the present invention for achieving the above object, a body portion for receiving the epoxy mixed with the sample in a cylindrical receiving space formed therein, coupled to the upper portion of the body portion, the receiving space It is connected to the upper body portion for applying pressure to the upper portion of the epoxy mixed with the sample contained in the sample, the lower body portion for applying pressure to the lower portion of the epoxy mixed with the sample contained in the receiving space, and the lower body portion It includes a vacuum pump for sucking the epoxy in the receiving space.
그리고, 상기 목적을 달성하기 위하여 본 발명에서는, 상기 제조방법에 의해 제조되는 투과전자현미경용 시편을 제공한다. And, in order to achieve the above object, the present invention provides a transmission electron microscope specimen prepared by the manufacturing method.
본 발명에 따르면, 에폭시가 나노 사이즈까지의 미세 기공을 채워주며, 집속이온빔에 의한 식각시 갈륨 이온에 의한 시편의 손상을 막아주어 기존의 시편 제작방법으로 불가능하였던 시료에 대한 시편 제작이 가능해 진다. 또한, 시편의 제작에 소요되는 시간이 짧고, 제작된 시편에서 원하는 시료를 볼 수 있는 확률도 높아진다. 또한, 이종 미세 분말 시료를 하나의 시편으로 제작할 수 있으며, 미세 기공이 존재하는 다공성 재료나 섬유 재료에 대한 시편 제작을 용이하게 한다.According to the present invention, the epoxy fills the micropores up to the nano-size, prevents damage of the specimen by gallium ions during etching by the focused ion beam, it is possible to prepare a specimen for a sample that was impossible with the conventional specimen manufacturing method. In addition, the time required for the production of the specimen is short, the probability of seeing the desired sample in the produced specimen is also increased. In addition, the heterogeneous fine powder sample can be produced in one specimen, and facilitates the fabrication of specimens for porous or fibrous materials in which micropores exist.
도 1은 본 발명의 일실시예에 따른 시편 제작방법에 대한 설명에 제공되는 흐름도,1 is a flow chart provided in the description of the specimen manufacturing method according to an embodiment of the present invention,
도 2a 내지 도 2d는 본 발명의 일실시예에 따른 시편 제작방법에 대한 설명에 참조되는 도면,2a to 2d is a view referred to in the description of the specimen manufacturing method according to an embodiment of the present invention,
도 3은 적층된 시편 제작시 에폭시의 경화 온도와 시간에 참조되는 그래프, 3 is a graph referred to the curing temperature and time of the epoxy when the laminated specimen is manufactured,
도 4는 본 발명에 따른 시편 제작방법에 의해 제작된 시편의 이미지,Figure 4 is an image of the specimen produced by the specimen manufacturing method according to the invention,
도 5는 집속이온빔을 이용한 시각 후 이미지를 나타낸 도면, 5 is a view showing an image after vision using a focused ion beam,
도 6은 시편에 대한 투과전자현미경의 이미지를 나타낸 도면, 그리고6 shows an image of a transmission electron microscope for a specimen, and
도 7은 본 발명의 일실시예에 따른 시편 제작장치에 대한 설명에 참조되는 도면이다. 7 is a view referred to in the description of the specimen manufacturing apparatus according to an embodiment of the present invention.
이하에서는 도면을 참조하여 본 발명을 보다 상세하게 설명한다.Hereinafter, with reference to the drawings will be described the present invention in more detail.
도 1은 본 발명의 일 실시예에 따른 투과전자현미경 시편 제작방법에 대한 설명에 제공되는 흐름도이고, 도 2a 내지 도 2d는 본 발명의 일실시예에 따른 투과전자현미경 시편 제작방법에 대한 설명에 참조되는 도면이다. 1 is a flow chart provided in the description of the method for manufacturing a transmission electron microscope specimen according to an embodiment of the present invention, Figure 2a to 2d is a description of the method for manufacturing a transmission electron microscope specimen according to an embodiment of the present invention Reference is made to the drawing.
도 1을 참조하면, 본 실시예에 따른 투과전자현미경 시편 제작방법은, 적층된 시료 제작(S100), 폴리싱(S110), 구리 튜브에 채원진 디스크 형태의 시편 제작(S120), 집속이온빔을 이용한 시각(S130) 과정을 포함하며, 완성된 시편은 투과전자현미경을 통해 시편 분석이 진행될 수 있다(S140).Referring to Figure 1, the transmission electron microscope specimen manufacturing method according to the present embodiment, the laminated sample preparation (S100), polishing (S110), copper specimens in the form of disks (S120), using a focused ion beam Including the process of time (S130), the finished specimen may be analyzed by the transmission electron microscope (S140).
도 1에 도시한 각 단계별 과정을 설명하면 다음과 같다. 먼저, 적층된 시료를 제작한다(S100). 적층된 시료는, 도 2a에 도시한 바와 같이, 다층의 실리콘 웨이퍼 기판(201)을 에폭시(211)를 이용하여 접합하여 제작한다. 이때, 실리콘 웨이퍼 기판 사이 중 적어도 하나에 시료 분말과 섞은 에폭시(213)를 넣는다. 그리고, 열과 압력을 가하여 경화시켜, 도 2b에 도시한 바와 같은, 적층된 시료(230)를 만든다.Referring to each step process shown in Figure 1 as follows. First, a laminated sample is produced (S100). As shown in FIG. 2A, the laminated sample is produced by joining a multilayer silicon wafer substrate 201 using an epoxy 211. FIG. At this time, the epoxy 213 mixed with the sample powder is placed in at least one of the silicon wafer substrate. Then, it is cured by applying heat and pressure to make a laminated sample 230 as shown in Fig. 2B.
적층된 시료(230)를 만들기 위하여 가하는 열과 필요한 시간은, 도 3에 도시한 바와 같은 그래프를 참조하여 수행할 수 있다. 적층된 시료(230)를 만들때, 가해지는 압력에 대한 정량적인 값은 존재하지 않으나, 기본적으로 압력은 높으면 높을수록 좋다. The heat and time required to make the stacked sample 230 may be performed by referring to a graph as shown in FIG. 3. When making the laminated sample 230, there is no quantitative value for the pressure applied, but basically the higher the pressure, the better.
다음으로 폴리싱 작업을 수행하여(S110), 적층된 시료(230)에서 열과 압력에 의해 밖으로 세어 나오는 에폭시들을 제거하고, 집속 이온빔 이용에 알맞은 두께로 만든다. Next, by performing a polishing operation (S110), the epoxy is counted out by the heat and pressure from the laminated sample 230 is removed, to make a thickness suitable for using the focused ion beam.
그리고, 디스크 커팅을 통해, 적층된 시료(230)를 적층된 방향에 수직 방향으로 디스크 형태로 자른 뒤, 도 2c에 도시한 바와 같이, 구리 튜브(250)에 자른 시료(233)를 끼워 넣어, 디스크 형태의 시편을 제작한다(S120). 이와 같은 작업은 시간이 경과하면서, 접합한 실리콘 웨이퍼 기판의 틈이 벌어지는 것을 막기 위해서이다. Then, after cutting the laminated sample 230 in the form of a disc in the direction perpendicular to the stacked direction through the disk cutting, as shown in Figure 2c, the cut sample 233 is inserted into the copper tube 250, A disk-shaped specimen is produced (S120). This operation is to prevent the gap of the bonded silicon wafer substrate from opening over time.
그리고, 디스크 형태의 시편을 집속 이온빔에 로딩하여 시료 분말이 있는 부분을 찾아 원하는 영역(235)을 시각한다(S130). Then, the disk-shaped specimen is loaded on the focused ion beam to find a portion where the sample powder is located, and the desired region 235 is visualized (S130).
집속 이온빔(Focused Ion Beam, FIB)의 특징은 미소영역을 타킷으로 핀 포인트 관찰을 가능케 하고, 집속 이온빔의 에칭 기능으로 수마이크로에서 수백 나노 사이즈에 이르는 미세 가공을 통해 다른 종류의 여러 재료를 균일한 두께로 연마할 수 있으며, 신속하게 시료를 제작할 수 있다는 점이다.Focused Ion Beam (FIB) features pinpoint observation of micro-areas as a target and uniform processing of different types of materials through micro-machining ranging from micro to hundreds of nanoscales with etching of focused ion beams. It can be polished to a thickness and can quickly produce a sample.
집속 이온빔을 이용하여 원하는 영역에 대한 식각이 종료하여 투과전자현미경 시편이 제작되면, 투과전자현미경을 통한 시편 분석을 진행할 수 있다(S140).After the etching of the desired region is finished using the focused ion beam, the transmission electron microscope specimen is manufactured, the specimen analysis may be performed by the transmission electron microscope (S140).
이와 같은 과정에 의해, 투과전자현미경 시편을 빠르게 제작할 수 있다. 예컨대, 본 발명에 따른 시편 제작방법을 사용하면 4시간에 한 개 정도의 시편을 제작할 수 있다. 이는 통상적으로 하나의 시편의 제작에 20시간 정도가 소요되는 것에 비하여 빠른 시간이다.By such a process, it is possible to quickly produce a transmission electron microscope specimen. For example, using the specimen manufacturing method according to the present invention can produce about one specimen every four hours. This is typically a faster time than about 20 hours to produce one specimen.
또한, 본 발명에 따른 시편 제작방법에 의해, 이종 미세 분말의 시료를 하나의 시편으로 제작 가능하다. 즉, 다층 실리콘 웨이퍼 기판을 접합할 때, 각 실리콘 웨이퍼 사이에 서로 다른 시료 분말과 섞은 에폭시를 이용함으로써, 다른 종류의 시료 분말이 포함된 하나의 시편을 제작할 수 있다. In addition, by the specimen preparation method according to the invention, it is possible to produce a sample of different fine powder into one specimen. That is, when bonding a multilayer silicon wafer substrate, by using an epoxy mixed with different sample powder between each silicon wafer, it is possible to produce one specimen containing different types of sample powder.
그리고, 분말 형태의 시료 뿐만 아니라, 섬유(fiber) 재료의 경우에도, 상기한 과정에 따라 동일한 방식으로 시편을 제작할 수 있다. In addition, in the case of a fiber material as well as a sample in a powder form, the specimen may be manufactured in the same manner according to the above-described procedure.
도 4 내지 도 6은 본 발명에 따른 시편 제작 방법에 의해 제작한 충방전 한 배터리 양극재료의 투과전자현미경용 시편 이미지이다. 4 to 6 is a specimen image for transmission electron microscopy of the positive electrode material of the charged and discharged battery produced by the test piece manufacturing method according to the present invention.
도 4에 나타낸 이미지가 본 발명에 따른 시편 제작방법에 의해 실제로 제작한 시편의 이미지이다. 도 5는 집속이온빔을 이용하여 식각 후 시편의 이미지로 에폭시가 양극재료 내부의 미세 기공을 채우고 있음을 볼 수 있다. 도 6은 시편에 대한 투과전자현미경의 이미지를 나타낸 것이다.The image shown in Figure 4 is an image of the specimen actually produced by the specimen manufacturing method according to the present invention. 5 shows that the epoxy fills the micropores inside the anode material as an image of the specimen after etching using the focused ion beam. 6 shows an image of a transmission electron microscope for a specimen.
도 4 내지 도 6에서 알 수 있는 바와 같이, 본 발명에 따른 방법에 따라 제작된 시편은 큰 기공뿐만 아니라 미세한 나노 사이즈까지의 기공을 에폭시가 싸고 있음을 관찰할 수 있다. 에폭시는 집속 이온빔을 이용하여 시편 제작시, 갈륨 이온에 의한 시편의 손상을 막고 보호하는 역할도 한다. 이에 따라, 기존의 방법으로는 불가능하였던 미세 기공이 존재하는 시료에 대한 시편 제작이 가능하다. As can be seen in Figures 4 to 6, the specimen produced according to the method according to the present invention can be observed that the epoxy is wrapped not only large pores but also pores up to fine nano size. Epoxy also serves to prevent and protect the specimen from damage by gallium ions when the specimen is manufactured using a focused ion beam. Accordingly, it is possible to prepare a specimen for a sample in which micropores exist that were impossible with the conventional method.
도 7은 본 발명의 일실시예에 따른 투과전자현미경 시편 제작 장치를 나타낸 도면이다. 7 is a view showing a transmission electron microscope specimen manufacturing apparatus according to an embodiment of the present invention.
전술한 바와 같이, 본 발명에 따른 시편 제작방법의 핵심은 열과 압력을 가하여, 나노 사이즈까지의 미세 기공을 채우는 것이다. 가해지는 열의 범위는 정해져 있으나 압력은 높을수록 더 미세한 기공까지 채울 수 있으므로 특정 범위가 정해져 있지는 않다. 이에 따라, 좀더 높은 압력을 가하고, 에폭시 양을 줄여, 시료 분말의 양이 많은 시료를 제작할 수 있는 장치가 필요하다.As described above, the core of the specimen manufacturing method according to the present invention is to fill the micropores up to nano size by applying heat and pressure. The range of heat applied is fixed, but the higher the pressure, the smaller the pores can fill, so there is no specific range. Accordingly, there is a need for an apparatus capable of applying a higher pressure, reducing the amount of epoxy, and making a sample having a large amount of sample powder.
도 7을 참조하면, 본 실시예에 따른 장치(300)는, 상체부(310), 몸체부(320), 하체부(330), 및 베큠 펌프(vacuum pump)(340를 포함한다. Referring to FIG. 7, the apparatus 300 according to the present embodiment includes an upper body 310, a body 320, a lower body 330, and a vacuum pump 340.
몬체부(320) 내부에는 원통형의 수용공간이 형성되어 있으며, 이 수용공간에 시료와 혼합한 에폭시(400)를 수용한다. 상체부(310)는 몸체부(320)의 상부에 결합하여, 수용공간에 수용된 시료와 혼합한 에폭시의 상부에 압력을 가한다. A cylindrical receiving space is formed inside the monche 320, and accommodates the epoxy 400 mixed with the sample in the receiving space. The upper body part 310 is coupled to the upper part of the body part 320 to apply pressure to the upper part of the epoxy mixed with the sample contained in the receiving space.
하체부(330)는 몸체부(320)의 하부에 결합하여, 수용공간에 수용된 시료와 혼합한 에폭시의 하부에 압력을 가한다. 또한, 하체부(330)에는 베큠 펌프(340)가 연결되어, 수용공간에서 여분의 에폭시를 흡입한다. The lower body part 330 is coupled to the lower part of the body part 320 to apply pressure to the lower part of the epoxy mixed with the sample contained in the receiving space. In addition, a lower pump 340 is connected to the lower body 330 to suck extra epoxy from the receiving space.
몸체부(320)에는 히팅 밴드(heating band) 또는 전열선 등을 사용한 발열부(323)을 설치하여, 수용공간에 열을 가한다. The body 320 is provided with a heating unit 323 using a heating band or a heating wire to apply heat to the receiving space.
이와 같은 구성에 의해, 좀더 높은 압력을 가하면서, 여분의 에폭시 양을 줄여, 시료 분말의 양이 보다 많은 시편을 제작할 수 있다.With such a configuration, it is possible to produce a specimen having a larger amount of sample powder while reducing the amount of excess epoxy while applying a higher pressure.
한편, 본 발명에 따른 투과전자현미경 시편 제작방법은 상기한 바와 같이 설명된 실시예들의 구성과 방법이 한정되게 적용될 수 있는 것이 아니라, 상기 실시예들은 다양한 변형이 이루어질 수 있도록 각 실시예들의 전부 또는 일부가 선택적으로 조합되어 구성될 수도 있다.On the other hand, the transmission electron microscope specimen manufacturing method according to the invention is not limited to the configuration and method of the embodiments described as described above, the embodiments are all or all of the embodiments so that various modifications can be made Some may be optionally combined.
또한, 이상에서는 본 발명의 바람직한 실시예에 대하여 도시하고 설명하였지만, 본 발명은 상술한 특정의 실시예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술분야에서 통상의 지식을 가진자에 의해 다양한 변형실시가 가능한 것은 물론이고, 이러한 변형실시들은 본 발명의 기술적 사상이나 전망으로부터 개별적으로 이해되어서는 안될 것이다.In addition, although the preferred embodiment of the present invention has been shown and described above, the present invention is not limited to the specific embodiments described above, but the technical field to which the invention belongs without departing from the spirit of the invention claimed in the claims. Of course, various modifications can be made by those skilled in the art, and these modifications should not be individually understood from the technical spirit or the prospect of the present invention.
본 발명은 다공성 재료 및 섬유 재료 등의 투과전자현미경용 시편을 제작하는데 사용할 수 있다.The present invention can be used to produce specimens for transmission electron microscopy, such as porous materials and fiber materials.

Claims (9)

  1. 시료와 혼합한 에폭시로 다층 실리콘 기판 사이를 접합시킨 뒤, 열과 압력을 가하여 경화시킨 적층 시료를 제조하는 단계; Preparing a laminated sample that is cured by applying heat and pressure after bonding between the multilayer silicon substrate with epoxy mixed with the sample;
    상기 적층 시료를 소정 두께로 폴리싱하는 단계; Polishing the laminated sample to a predetermined thickness;
    상기 폴리싱된 적층 시료를 적층 방향에 수직한 평향으로 디스크 형태로 커팅하여 구리 튜브에 채워넣은 디스크 형태의 시판을 제작하는 단계; 및 Manufacturing a commercially available disk type in which the polished laminated sample is cut into a disk shape in a direction perpendicular to the stacking direction and filled into a copper tube; And
    상기 디스크 형태의 시판에서 특정 영역을 집속 이온빔을 이용하여 식각하여, 투과전자현미경용 시편을 제작하는 단계를 포함하는 투과전자현미경 시편 제작방법.A method of manufacturing a transmission electron microscope specimen comprising etching a specific region using a focused ion beam in a commercially available disk form, to prepare a specimen for transmission electron microscope.
  2. 제1항에 있어서,The method of claim 1,
    상기 다층 실리콘 기판 사이에는 서로 다른 시료와 혼합한 에폭시로 접합하는 것을 특징으로 하는 투과전자현미경 시편 제작방법.A method for fabricating a transmission electron microscope specimen, wherein the multilayer silicon substrate is bonded by epoxy mixed with different samples.
  3. 제1항에 있어서,The method of claim 1,
    상기 시료는 분말 형태의 다공성 재료인 것을 특징으로 하는 투과전자현미경 시편 제작방법.The sample is a transmission electron microscope specimen manufacturing method characterized in that the powder is a porous material.
  4. 제1항에 있어서,The method of claim 1,
    상기 시료는 섬유 재료인 것을 특징으로 하는 투과전자현미경 시편 제작방법.The sample is a transmission electron microscope specimen manufacturing method, characterized in that the fiber material.
  5. 제1항 내지 제4항 중 어느 한 항의 제조방법에 의해 제조되는 투과전자현미경용 시편.Specimens for transmission electron microscope prepared by the method of any one of claims 1 to 4.
  6. 내부에 형성된 원통형의 수용공간에 시료와 혼합한 에폭시를 수용하는 몸체부; A body portion accommodating the epoxy mixed with the sample in a cylindrical receiving space formed therein;
    상기 몸체부의 상부에 결합하여, 상기 수용공간에 수용된 시료와 혼합한 에폭시의 상부에 압력을 가하는 상체부;Coupled to the upper portion of the body portion, the upper portion for applying pressure to the upper portion of the epoxy mixed with the sample contained in the receiving space;
    상기 몸체부의 하부에 결합하여, 상기 수용공간에 수용된 시료와 혼합한 에폭시의 하부에 압력을 가하는 하체부; 및A lower body part coupled to the lower part of the body part to apply pressure to a lower part of the epoxy mixed with a sample contained in the receiving space; And
    상기 하체부와 연결되어, 상기 수용공간에서 여부의 에폭시를 흡입하는 베큠 펌프를 포함하는 투과전자현미경 시편 제작장치.Transmissive electron microscope specimen manufacturing apparatus connected to the lower body, including a vacuum pump for sucking the epoxy in the receiving space.
  7. 제6항에 있어서,The method of claim 6,
    상기 몸체부에 설치되어, 상기 수용공간에 열을 가하는 발열부를 더 포함하는 투과전자현미경 시편 제작장치.It is installed on the body portion, the transmission electron microscope specimen manufacturing apparatus further comprising a heating unit for applying heat to the receiving space.
  8. 제6항에 있어서,The method of claim 6,
    상기 시료는, 분말 형태의 다공성 재료인 것을 특징으로 하는 투과전자현미경 시편 제작장치.The sample is a transmission electron microscope specimen manufacturing device, characterized in that the powder is a porous material.
  9. 제6항에 있어서,The method of claim 6,
    상기 시료는 섬유 재료인 것을 특징으로 하는 투과전자현미경 시편 제작장치.The transmission electron microscope specimen manufacturing device, characterized in that the sample is a fiber material.
PCT/KR2013/009165 2013-08-14 2013-10-14 Method and device for producing a transmission electron microscopy specimen WO2015023026A1 (en)

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KR20060076106A (en) * 2004-12-29 2006-07-04 동부일렉트로닉스 주식회사 Method for manufacturing specimen for analyzing by transmission electron microscope
KR20060089109A (en) * 2005-02-03 2006-08-08 엘지전자 주식회사 Tem specimen preparation method to analyze the specified section
KR20070037884A (en) * 2005-10-04 2007-04-09 삼성전자주식회사 The method of manufacturing semiconductor slice sample for transmission electron microscope
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KR20050070685A (en) * 2003-12-30 2005-07-07 동부아남반도체 주식회사 Tem specimen manufacturing method
KR20060076106A (en) * 2004-12-29 2006-07-04 동부일렉트로닉스 주식회사 Method for manufacturing specimen for analyzing by transmission electron microscope
KR20060089109A (en) * 2005-02-03 2006-08-08 엘지전자 주식회사 Tem specimen preparation method to analyze the specified section
KR20070037884A (en) * 2005-10-04 2007-04-09 삼성전자주식회사 The method of manufacturing semiconductor slice sample for transmission electron microscope
KR20080111573A (en) * 2007-06-19 2008-12-24 현대자동차주식회사 Manufacturing method of specimen for transmission electron microscopy

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