JP2002122524A - Method of making sample for transmission electron microscope - Google Patents
Method of making sample for transmission electron microscopeInfo
- Publication number
- JP2002122524A JP2002122524A JP2000312941A JP2000312941A JP2002122524A JP 2002122524 A JP2002122524 A JP 2002122524A JP 2000312941 A JP2000312941 A JP 2000312941A JP 2000312941 A JP2000312941 A JP 2000312941A JP 2002122524 A JP2002122524 A JP 2002122524A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- sample
- electron microscope
- transmission electron
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Sampling And Sample Adjustment (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、透過電子顕微鏡に
よる微細構造観察に供する薄膜試料を、簡便かつ短時聞
で試料損傷を与えずに作製する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thin film sample for observation of a fine structure by a transmission electron microscope in a simple and short time without damaging the sample.
【０００２】[0002]
【従来の技術】異なる材料同士を組み合わせた機能材料
は、その特性に応じて様々な用途に広く用いられてお
り、その中でもガラス基板の表面に金属薄膜や化合物薄
膜などを成膜した材料は、コンピューターディスプレイ
や自動車用ガラスなどに用いられている。このような材
料の特性は、薄膜の結晶性（結晶粒のサイズ、結晶配向
性など）や薄膜中の粒界析出物の有無などの微細構造に
大きく左右されるため、材料開発においては微視的な観
点からの解析が非常に重要である。2. Description of the Related Art Functional materials obtained by combining different materials are widely used in various applications depending on their characteristics. Among them, materials formed by depositing a metal thin film or a compound thin film on the surface of a glass substrate include: It is used for computer displays and automotive glass. The properties of such materials are greatly influenced by the microstructure such as the crystallinity of the thin film (crystal grain size, crystal orientation, etc.) and the presence or absence of grain boundary precipitates in the thin film. It is very important to analyze from the viewpoint of the viewpoint.
【０００３】透過電子顕微鏡（以下、説明の便宜上「Ｔ
ＥＭ」と称する）は、材料の内部構造や結晶構造につい
ての情報を得ることができる装置であり、前記したよう
な微細構造を詳細に解析する場合に多く利用されてい
る。このＴＥＭを用いて解析を行うには、試料の厚さを
数百ｎｍ以下まで薄片化する必要があり、試料作製に多
大な労力と時間を要している。A transmission electron microscope (hereinafter referred to as "T
An EM is a device that can obtain information on the internal structure and crystal structure of a material, and is often used when analyzing the above-described fine structure in detail. In order to perform analysis using this TEM, it is necessary to reduce the thickness of the sample to several hundred nm or less, and a great deal of labor and time are required for sample preparation.
【０００４】ＴＥＭ用試料作製法は、イオンシニング
法、ミクロトーム法、電解研磨法などが一般的であり、
最近ではフォーカストイオンビーム（ＦＩＢ）法も利用
されている。イオンシニング法は、アルゴンイオンを試
料に照射して薄片化する手法であり、比較的均一に薄片
化できるという利点を有する反面、薄片化に長時開かか
るためイオン照射による試料の損傷が大きくなり、試料
本来の構造が変化してしまうケースがある。ＦＩＢ法
は、ガリウムイオンを利用して薄片試料を直接切り出す
手法であり、狙った部位のみの薄片試料を比較的短時聞
で得られるという利点があるが、前記したイオン照射に
よる試料損傷も否めない。ミクロトーム法は、ダイヤモ
ンドナイフを用いて機械的に切削する手法であり、比較
的容易に薄片化できるが、切削時に試料へ歪を与え易い
という欠点がある。電解研磨法は、金属の電解反応を利
用した手法であり、基材が導電体である場合は非常に良
好な薄片試料が得られるが、基材が絶縁体である場合に
は適用が困難である。また、これらの作製法で得られた
薄片試料は、いずれも観察可能な視野が限られているた
め、観察したい箇所が観察不可である場合は再度作製し
なければならない。また全ての作製法に共通して丁寧な
前加工が必要であるため、非常に手間がかかることも大
きな欠点である。[0004] As a method for preparing a TEM sample, an ion thinning method, a microtome method, an electrolytic polishing method and the like are generally used.
Recently, a focused ion beam (FIB) method has also been used. The ion thinning method is a method of illuminating a sample by irradiating it with argon ions, and has the advantage that it can be relatively uniformly thinned.However, since the thinning takes a long time, the sample is greatly damaged by ion irradiation. In some cases, the original structure of the sample changes. The FIB method is a method of directly cutting a slice sample using gallium ions, and has an advantage that a slice sample of only a target portion can be obtained in a relatively short time, but the sample damage due to the ion irradiation described above is undeniable. Absent. The microtome method is a method of mechanically cutting using a diamond knife, and can be relatively easily sliced, but has a disadvantage that strain is easily applied to a sample during cutting. The electropolishing method is a method utilizing an electrolytic reaction of a metal, and a very good flake sample is obtained when the substrate is a conductor, but it is difficult to apply when the substrate is an insulator. is there. Further, the slice samples obtained by these manufacturing methods have a limited observable visual field, and therefore, when a portion to be observed cannot be observed, it must be manufactured again. In addition, since a careful pre-processing is required in common to all the manufacturing methods, it is a great disadvantage that it takes much time and effort.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記した従来
法の欠点を解消するためになされたもので、ガラス基材
表面に金属薄膜あるいは化合物薄膜を成膜した材料につ
いて、面倒な前加工を施すことなく簡便、かつ短時間
で、試料に損傷を与えずにＴＥＭ観察用試料を作製する
ことができる透過電子顕微鏡用試料の作製方法を提案す
ることを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the conventional method, and requires complicated pre-processing for a material in which a metal thin film or a compound thin film is formed on a glass substrate surface. An object of the present invention is to propose a method for preparing a sample for a transmission electron microscope, which can prepare a sample for TEM observation simply and in a short time without applying any damage to the sample.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、基材であ
るガラスの端面に金属薄膜あるいは化合物薄膜を成膜し
た材料について、溶剤を用いて基材のみを溶解除去する
ことによりＴＥＭ観察用試料を得る方法が、薄膜の結晶
構造解析を行う場合に効果的であることを見い出し本発
明を完成するに至った。Means for Solving the Problems The inventors of the present invention conducted TEM observation of a material in which a metal thin film or a compound thin film was formed on an end face of glass as a base material by dissolving and removing only the base material using a solvent. The present inventors have found that a method for obtaining a sample for use is effective when analyzing the crystal structure of a thin film, and have completed the present invention.
【０００７】すなわち、本発明に係る透過電子顕微鏡用
試料の作製方法は、ガラス基材の少なくとも片端面に金
属あるいは化合物の薄膜が成膜された材料の前記基材の
みを溶剤を用いて溶解除去し、薄膜を採取することを特
徴とするものである。この方法において、前記溶剤は、
薄膜を変質することなく基材のみを溶解除去し得るもの
を選択して用いる。また基材を溶解した後に溶液中に残
った薄膜を採取する方法としては、一般的に使用される
治具（銅メッシュ、金メッシュなど）を用いてすくい取
る方式が好適である。すくい取った薄膜は充分に乾燥す
ることによりＴＥＭ観察が可能となる。ここで基材用の
溶剤としては、強アルカリ水溶液（例えば水酸化ナトリ
ウム水溶液）を用いる。That is, in the method of preparing a sample for a transmission electron microscope according to the present invention, only a substrate, which is a material in which a thin film of a metal or a compound is formed on at least one end surface of a glass substrate, is dissolved and removed using a solvent. And collecting a thin film. In this method, the solvent is
A material capable of dissolving and removing only the substrate without altering the thin film is selected and used. As a method of collecting the thin film remaining in the solution after dissolving the base material, a method of scooping using a commonly used jig (copper mesh, gold mesh, or the like) is preferable. The scooped thin film is sufficiently dried to enable TEM observation. Here, a strong alkali aqueous solution (for example, sodium hydroxide aqueous solution) is used as a solvent for the base material.
【０００８】[0008]
【発明の実施の形態】図１は本発明の一実施例を示す概
略説明図であり、１はガラス基材、２は金属あるいは化
合物の薄膜、２ａは薄膜片、３は筋、４はポリエチレン
製容器、５は溶剤、６は純水、７はアセトン、８は取出
し治具（銅メッシュ、金メッシュなど）、９はピンセッ
トである。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic explanatory view showing one embodiment of the present invention, wherein 1 is a glass substrate, 2 is a thin film of a metal or a compound, 2a is a thin film piece, 3 is a stripe, and 4 is polyethylene. 5 is a solvent, 5 is a solvent, 6 is pure water, 7 is acetone, 8 is an extraction jig (copper mesh, gold mesh, etc.), and 9 is tweezers.
【０００９】すなわち、透過電子顕微鏡用試料を作製す
る場合は、ガラス基材１の少なくとも片端面に金属ある
いは化合物の薄膜２が成膜された材料の前記薄膜２の表
面に碁盤目状の筋（キズ）３を入れた後、ポリエチレン
製容器４などに所定の溶剤５を適量入れ、その中に薄膜
２を成膜したガラス基材１を投入する。この時溶剤５は
薄膜２に付けた筋３から浸入し徐々に基材のガラスを溶
解していき、最終的には薄膜片２ａがガラス基材１から
剥離して溶剤５中に浮遊する。その後、この薄膜片２ａ
をすくい取り、純水６が入った容器中に投入して２〜３
分間放置し溶剤５を水洗除去する。その後、再びこの薄
膜片２ａをすくい取り、アセトン７が入った容器中に薄
膜片２ａを移した後、最終処理として再び純水６が入っ
た容器中に投入すると薄膜片２ａは皺や折れ曲がりも無
い状態で水面に浮く。これを取出し治具８ですくい取り
乾燥させる。この時、取出し治具８はピンセット９を使
用して把持する。乾燥したメッシュは、そのままＴＥＭ
観察に供する。That is, when preparing a sample for a transmission electron microscope, a grid-like streak () is formed on the surface of the thin film 2 made of a material in which a metal or compound thin film 2 is formed on at least one end surface of a glass substrate 1. After the flaw 3 is put, an appropriate amount of a predetermined solvent 5 is put into a polyethylene container 4 or the like, and the glass substrate 1 on which the thin film 2 is formed is put therein. At this time, the solvent 5 penetrates from the streak 3 attached to the thin film 2 and gradually dissolves the glass of the base material. Finally, the thin film piece 2 a is separated from the glass base material 1 and floats in the solvent 5. Then, this thin film piece 2a
And put into a container containing pure water 6
The solvent 5 is washed away with water. Thereafter, the thin film piece 2a is scooped again, the thin film piece 2a is transferred into a container containing acetone 7, and then put into a container containing pure water 6 again as a final treatment, so that the thin film piece 2a also has wrinkles and bends. Floats on the surface of the water without any. This is taken out and scooped with a jig 8 and dried. At this time, the removal jig 8 is gripped using tweezers 9. The dried mesh is TEM
Serve for observation.
【００１０】[0010]
【実施例】実施例 本発明を適用した実施例として、コンピュータディスプ
レイの電磁波シールド膜のＴＥＭ観察を行なった。本実
施例では、薄膜としてＡｇ−Ａｕ薄膜を、溶剤として２
０ｗｔ％−水酸化ナトリウム水溶液を用い、図１に示す
方法により薄膜片（膜厚５０〜６０ｎｍ）を作製した。
その結果、良好な薄膜片が作製されていることを確認し
た。また、試料損傷（例えば黒くなって不鮮明な領域や
粒子形状が崩れている領域など）も認められないことか
ら、実際の膜構造情報が得られていると考えられる。EXAMPLE As an example to which the present invention was applied, TEM observation of an electromagnetic wave shielding film of a computer display was performed. In this embodiment, an Ag-Au thin film is used as a thin film, and 2
Using a 0 wt% aqueous solution of sodium hydroxide, a thin film piece (film thickness 50 to 60 nm) was prepared by the method shown in FIG.
As a result, it was confirmed that a good thin film piece was produced. In addition, since no damage to the sample (for example, a region that is black and unclear or a region where the particle shape is broken) is not recognized, it is considered that actual film structure information has been obtained.
【００１１】また、本実施例における試料作製時間を、
従来の試料作製方法と比較して表１に示す。表１の結果
より明らかなごとく、本発明方法は、従来法のいずれと
比較しても格段に試料作製時間が短いことがわかる。こ
れは本発明の方法は、従来法で必要な前加工（切削や研
磨など）をほとんど行わないのに加え、基材が容易に溶
解する溶剤を選択して、薄片化の時間を大幅に短縮でき
たことによるものと推察される。The sample preparation time in this embodiment is
Table 1 shows a comparison with a conventional sample preparation method. As is clear from the results in Table 1, the method of the present invention has a significantly shorter sample preparation time than any of the conventional methods. This is because the method of the present invention does not perform pre-processing (cutting, polishing, etc.) that is required by the conventional method, and in addition, selects a solvent that easily dissolves the base material, greatly shortening the time for thinning. It is presumed that it was possible.
【００１２】また従来法では、試料損傷を与えたり、薄
片化に失敗した場合の時間的ロスが大きいなどの問題が
あったが、本発明の方法は溶剤による基材のみの溶解で
あるため、金属や化合物の薄膜には影響を及ぼさなかっ
た。さらに本発明の方法では、装置や大がかりな設備を
必要としないため、コスト面においても効果が大きい。
さらに観察視野も従来法に比べて格段に大きいので、薄
膜の全体的な結晶性評価が可能である。上記の結果よ
り、本発明方法は面倒な前加工をせずに簡便、かつ短時
開にＴＥＭ観察用試料を作製できることが確認された。In the conventional method, there are problems such as damage to the sample and a large time loss in the case of failure in thinning. However, since the method of the present invention dissolves only the substrate with a solvent, It did not affect metal or compound thin films. Furthermore, the method of the present invention does not require any equipment or large-scale equipment, and is thus highly effective in terms of cost.
Furthermore, since the observation field of view is much larger than that of the conventional method, it is possible to evaluate the overall crystallinity of the thin film. From the above results, it was confirmed that the method of the present invention can prepare a TEM observation sample simply and without any troublesome pre-processing, in a short time.
【００１３】[0013]
【表１】 [Table 1]
【００１４】比較例 前記の実施例と同一試料について、従来法（イオンシニ
ング法）で試料作製した結果、得られた試料の膜厚が数
十ｎｍと非常に薄いためにシニングが膜内にまで及び、
本来の膜構造を反映していないことが確認された。Comparative Example As a result of preparing a sample by the conventional method (ion thinning method) for the same sample as the above-mentioned example, the thickness of the obtained sample was very thin, several tens of nm, so that thinning was formed in the film. Up to,
It was confirmed that it did not reflect the original film structure.
【００１５】[0015]
【発明の効果】以上説明したごとく、本発明によれば、
ガラスの表面に金属薄膜や化合物薄膜が成膜された材料
のＴＥＭ観察用試料を、面倒な前加工をせずに簡便、か
つ短時間で試料損傷を与えずに作製する方法を提供する
ことができ、また従来法（イオンシニング法）より格段
に作業時間が短く、試料損傷も無く、さらにコストを大
幅に低減できるなどの優れた効果を奏する。As described above, according to the present invention,
It is intended to provide a method for preparing a TEM observation sample of a material in which a metal thin film or a compound thin film is formed on a glass surface, without troublesome preprocessing, and in a short time without damaging the sample. In addition, it has excellent effects such as a much shorter working time than the conventional method (ion thinning method), no sample damage, and a great reduction in cost.
【図１】本発明の一実施例を示す概略説明図である。FIG. 1 is a schematic explanatory view showing one embodiment of the present invention.
１ ガラス基材 ２ 金属あるいは化合物の薄膜 ２ａ 薄膜片 ３ 筋 ４ ポリエチレン製容器 ５ 溶剤 ６ 純水 ７ アセトン ８ 取出し治具（銅メッシュ、金メッシュなど） ９ ピンセット DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Metal or compound thin film 2a Thin film piece 3 Streak 4 Polyethylene container 5 Solvent 6 Pure water 7 Acetone 8 Removal jig (copper mesh, gold mesh, etc.) 9 Tweezers
Claims (3)
るいは化合物の薄膜が成膜された材料の前記基材のみを
溶剤を用いて溶解除去し、薄膜を採取することを特徴と
する透過電子顕微鏡用試料の作製方法。1. A transmission electron microscope characterized in that a thin film is collected by dissolving and removing only a substrate of a material in which a thin film of a metal or a compound is formed on at least one end surface of a glass substrate using a solvent. Method of preparing sample for use.
材のみを溶解除去し得るものであることを特徴とする請
求項１記載の透過電子顕微鏡用試料の作製方法。2. The method for preparing a sample for a transmission electron microscope according to claim 1, wherein the solvent is capable of dissolving and removing only the substrate without deteriorating the thin film.
用いてすくい取る方式を用いることを特徴とする請求項
１または２記載の透過電子顕微鏡用試料の作製方法。3. The method for preparing a sample for a transmission electron microscope according to claim 1, wherein a method of scooping using a jig is used as a method of collecting the thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000312941A JP2002122524A (en) | 2000-10-13 | 2000-10-13 | Method of making sample for transmission electron microscope |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000312941A JP2002122524A (en) | 2000-10-13 | 2000-10-13 | Method of making sample for transmission electron microscope |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002122524A true JP2002122524A (en) | 2002-04-26 |
Family
ID=18792433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000312941A Pending JP2002122524A (en) | 2000-10-13 | 2000-10-13 | Method of making sample for transmission electron microscope |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002122524A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360708C (en) * | 2004-05-12 | 2008-01-09 | 中国科学院金属研究所 | Method for preparing film specimen in use for transmission electron microscope |
| JP2009002768A (en) * | 2007-06-21 | 2009-01-08 | Japan Health Science Foundation | Tissue microarray preparation method |
| CN106546469A (en) * | 2016-10-31 | 2017-03-29 | 东旭科技集团有限公司 | A kind of preparation method of the electron microscopic sample of plate glass |
| US11539159B2 (en) | 2018-08-17 | 2022-12-27 | Volkswagen Aktiengesellschaft | Plug connector |
-
2000
- 2000-10-13 JP JP2000312941A patent/JP2002122524A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360708C (en) * | 2004-05-12 | 2008-01-09 | 中国科学院金属研究所 | Method for preparing film specimen in use for transmission electron microscope |
| JP2009002768A (en) * | 2007-06-21 | 2009-01-08 | Japan Health Science Foundation | Tissue microarray preparation method |
| CN106546469A (en) * | 2016-10-31 | 2017-03-29 | 东旭科技集团有限公司 | A kind of preparation method of the electron microscopic sample of plate glass |
| CN106546469B (en) * | 2016-10-31 | 2019-03-12 | 东旭科技集团有限公司 | A kind of preparation method of the electron microscopic sample of plate glass |
| US11539159B2 (en) | 2018-08-17 | 2022-12-27 | Volkswagen Aktiengesellschaft | Plug connector |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Phaneuf | Applications of focused ion beam microscopy to materials science specimens | |
| Heidenreich | Electron microscope and diffraction study of metal crystal textures by means of thin sections | |
| US7005636B2 (en) | Method and apparatus for manipulating a microscopic sample | |
| Schiffbauer et al. | Novel application of focused ion beam electron microscopy (FIB-EM) in preparation and analysis of microfossil ultrastructures: A new view of complexity in early Eukaryotic organisms | |
| US20060000973A1 (en) | Method for the removal of a microscopic sample from a substrate | |
| US20060219919A1 (en) | TEM sample holder and method of forming same | |
| JP5942873B2 (en) | Method for producing thin sample and method for observing sample | |
| JP2002174571A (en) | Thinning and working for tem sample | |
| Zhang et al. | 3D characterisation using plasma FIB-SEM: A large-area tomography technique for complex surfaces like black silicon | |
| JP2002122524A (en) | Method of making sample for transmission electron microscope | |
| JP2003194681A (en) | Tem sample preparation method | |
| CN113447339A (en) | Preparation method of sample for analyzing copper crystal grains of PCB hole | |
| JP2010230518A (en) | Thin sample preparing method | |
| Vihinen et al. | Three dimensional electron microscopy of cellular organelles by serial block face SEM and ET | |
| CN104913957A (en) | Preparation method for TEM in-situ observation material matrix/passivation film interface structure sample | |
| CN113466268B (en) | Combined sample and preparation method thereof | |
| CN114062076A (en) | Sample preparation method for copper foil crystal analysis | |
| JP2002082027A (en) | Fabrication of sample for transmission electron microscope | |
| CN105092621B (en) | The etching technics and image combining method of notableization biological tissue section membrane structure | |
| Shami et al. | Expedited large-volume 3-D SEM workflows for comparative microanatomical imaging | |
| CN113899764A (en) | Sample preparation method for electron microscopic three-dimensional reconstruction geological sample based on ion thinning | |
| JPH06288882A (en) | Preparation of sample for transmission electron microscope and apparatus for dyeing of sample | |
| Yabusaki et al. | Specimen preparation technique for microstructure analysis using focused ion beam process | |
| JPH08184537A (en) | Method for extracting sample of nonmetallic inclusion in steel | |
| CN115201519A (en) | Sample preparation method and application of transmission electron microscope containing ferrimagnetic element alloy |