JP2020101444A - Transmission electron microscope observation sample and manufacture method of the same - Google Patents

Abstract

To provide a manufacture method of TEM (transmission electron microscope) observation sample, capable of easily manufacturing a thin sample that can be easily mounted on a TEM and has thickness and visual field area suitable for measurement.SOLUTION: A sample manufacture method includes steps of: filling a hole part provided in a sheet mesh 10 loadable in a sample holder of the TEM with a composition containing powder sample and resin to obtain a curing sample; cutting the curing sample to obtain a strip-like curing sample 11; attaching the strip-like curing sample 11 to an ion milling (IM) processing device so that one of long sides of the strip-like curing sample 11 faces argon ion flow; installing a shield plate 31 provided on the IM processing device; irradiating the strip-like curing sample 11 with argon ion 41, corroding composition 21 with which front and rear faces and the hole part of the strip-like curing sample 11 is filled by the argon ion flow 41, and processing the composition 21 into thin pieces to be suitable for TEM measurement.SELECTED DRAWING: Figure 5

Description

The present invention is a transmission electron microscope observation sample used when observing a cross section of a powder with a transmission electron microscope (may be referred to as “TEM” in the present invention), and preparation of the transmission electron microscope observation sample. It is about the method.

With the development of the electronics industry, it has become necessary to obtain precise information about the physical properties, the state of change, etc. of various material powders used in the field. Observation by TEM is considered to be an effective means for obtaining such information.
Here, when observing various powder samples by TEM, it is required to use the powder samples as TEM observation samples.
Specifically, the powder sample and an appropriate resin (preferably an epoxy resin or the like) are kneaded and cured to obtain a molded body. Then, the molded body is sliced using a focused ion beam processing apparatus (may be referred to as “FIB” in the present invention) or an ion milling apparatus (may be referred to as “IM” in the present invention). To produce a sample for TEM observation.
For example, according to Patent Document 1, a TEM observation sample having a field of view of about 10 μm that can be observed with a TEM can be manufactured. Further, in Patent Document 2, a kneaded product obtained by kneading a powder sample and an epoxy resin is sandwiched between silicon substrates and cured to obtain a cured product. Then, after the cured product is polished, it is processed by IM to prepare a sample for TEM observation.

JP, 2007-47053, A Japanese Patent No. 4594156

In TEM observation, when a large number of powder particles constituting a powder sample are desired to be observed, it is required to secure a wide observation visual field. In such a case, in the method for producing a TEM observation sample described in Patent Document 1 described above, the area that can be processed by one operation is small (usually, the width of a thin sample that can be processed by IM is 0.5 mm). ), repeated processing is required.
Further, with the development of the electronics industry, more precise information has been demanded regarding the physical properties of powder particles, the state of change, etc., and a thinner TEM observation sample has been demanded. In such a case, in the method for producing a sample for TEM observation described in Patent Document 2 described above, it takes skill to make a molded body by polishing to have a thickness of, for example, 0.1 mm. difficult. Further, since the silicon substrate is likely to be cracked by rough polishing, there is a problem that the molded body is easily damaged.

Further, in the method for producing a sample for TEM observation described in Patent Document 1, a sheet mesh filled with the mixed composition of the powder sample and the resin is used to expose the cross section of the mixed composition of the powder sample and the resin. It includes a step of cutting. Then, it is described that the cutting step uses a knife or the like to perform cutting so as not to damage the sample.
However, mechanical properties such as hardness and brittleness are different between the mixed composition and the sheet mesh. Therefore, the cutting step is actually a highly difficult step and has low productivity, and in some cases, the mixed composition as a sample is mechanically damaged.

The present invention has been made under such circumstances, and the problem to be solved by the present invention is to easily prepare a thin sample that can be easily mounted on a TEM and has a thickness and a visual field area suitable for measurement by the TEM. It is to provide a method for producing a sample for TEM observation that can be performed.

The present inventors have conducted research in order to solve the above problems. Then, attention was paid to a commercially available sheet mesh having a plurality of holes used for loading the observation sample into the TEM.
That is, the plurality of holes provided in the sheet mesh is filled with a composition obtained by mixing and kneading a powder sample and a kneading resin, and the kneading resin is cured to form a sheet mesh and a composition. A cured sample in which the product is integrated is obtained. Then, a cured sample in which the sheet mesh and the composition are integrated is irradiated with an argon ion flow to erode, and the composition is thinned into a thickness suitable for measurement by a transmission electron microscope. Was completed.
Furthermore, the present inventors also conceived a configuration in which a cured sample in which the sheet mesh and the composition are integrated is cut along a suitable cutting line to form a strip-shaped cured sample.

That is, the first invention for solving the above problems is
A hole provided in a sheet mesh that can be loaded into a sample holder of a transmission electron microscope, a step of filling a composition containing a powder sample and a resin, and curing the resin to obtain a cured sample,
Cutting the cured sample along an appropriate cutting line to obtain a strip-shaped cured sample,
A step of loading the strip-shaped cured sample into an ion milling apparatus so that one of the long side surfaces of the strip-shaped cured sample faces the argon ion flow;
The shield plate provided in the ion milling apparatus is installed along the long side of the long side surface on the long side surface facing the ion flow in the strip-shaped cured sample loaded in the ion milling apparatus. Process,
Irradiating the strip-shaped cured sample with argon ions, eroding the composition filled in the front and back surfaces and holes of the strip-shaped cured sample by the argon ion flow, and filling the strip-shaped cured sample in one or more places of the hole. And a step of thinning the above composition, and a method for preparing a sample for observation with a transmission electron microscope.
The second invention is
Irradiating the strip-shaped cured sample with argon ions, in the step of thinning the filled composition into a thickness suitable for measurement by a transmission electron microscope,
In a predetermined condition, after eroding the composition filled in the front and back surfaces and holes of the strip-shaped cured sample with an argon ion flow, the argon ion irradiation is stopped, and the strip-shaped cured sample is removed from the ion milling apparatus. Process,
The strip-shaped cured sample that had been irradiated with argon ions was loaded into an ion milling device so that the long side surface that did not face the argon ion flow in the strip-shaped cured sample that had been irradiated with the argon ions faced the argon ion flow. The process of
The strip-shaped cured sample irradiated with the argon ion is irradiated with argon ions without providing the shielding plate, and the composition filled in the front and back surfaces and the hole of the strip-shaped cured sample is eroded by the argon ion flow. The method for producing a sample for observation with a transmission electron microscope according to the first invention, further comprising the step of thinning the filled composition at one or more locations of the hole.
The third invention is
The resin is a liquid or gel when mixed with a powder sample, and is a resin that cures at room temperature, heat cures, or UV after being filled in the holes provided in the sheet mesh. It is a method for producing a sample for observation with a transmission electron microscope according to the first or second invention.
The fourth invention is
The method for producing a sample for observation with a transmission electron microscope according to any one of the first to third inventions, characterized in that the resin is an epoxy resin.
The fifth invention is
The method for producing a sample for transmission electron microscope observation according to any one of the first to fourth inventions, characterized in that the powder sample is mixed with a resin in a volume ratio of 1:1 or more.
The sixth invention is
The method for producing a sample for transmission electron microscope observation according to any one of the first to fifth inventions, characterized in that a sheet mesh having a plurality of holes and a thickness of 10 μm or more and 50 μm or less is used as the sheet mesh. is there.
The seventh invention is
A strip-shaped cured sample in which a plurality of holes provided in the strip-shaped sheet mesh are filled with a cured product of a composition containing a powder sample and a resin,
The strip-shaped cured sample can be loaded into a sample holder of a transmission electron microscope,
The filled composition has been flaked by erosion by a stream of argon ions,
The sample for transmission electron microscope observation is characterized in that the filled composition is in the form of flakes at one or more locations of a plurality of holes provided in the strip-shaped cured sample.

According to the present invention, a sample for TEM observation that can be easily attached to a TEM and has a thickness of the sample and a visual field area suitable for observation by TEM can be easily manufactured.

It is a perspective view of a sheet mesh. It is a perspective view at the time of putting a composition on a sheet mesh. It is a perspective view of a hardening sample. It is a perspective view at the time of cutting a hardening sample and obtaining a strip-shaped hardening sample. It is a perspective view at the time of irradiating a strip-shaped cured sample with argon ions. It is sectional drawing which shows the state of the cross section which appears when it is assumed that the strip-shaped cured sample irradiated with the argon ion stream was cut. It is a sectional view showing a state of a section which appears when it is assumed that a strip-shaped cured sample is cut after irradiation with an argon ion flow. It is sectional drawing which shows the state of the cross section which appears when it is assumed that the strip-shaped cured sample irradiated with the argon ion stream of the 2nd time was cut. It is a sectional view showing a state of a section which appears when it is assumed that a strip-shaped cured sample is cut after the second irradiation with an argon ion flow.

Modes for carrying out the present invention: 1. A powder sample to be measured, 2. Kneading resin, 3. Sheet mesh, 4. 4. Preparation and processing of cured sample, Processing by IM, 6. The order of loading into a TEM and analysis will be described with reference to the drawings.

1. Powder sample to be measured The present invention is a metal oxide, metal hydroxide, metal carbonate, metal nitride, complex oxide, complex hydroxide, complex carbonate, complex nitride, various ceramic powder, It can be applied to various powder samples.

2. Kneading Resin The resin to be kneaded with the powder sample to be measured may be any liquid or gel in the state of being mixed and in a state capable of being mixed with the powder sample. Therefore, a room temperature curing or heat curing type resin or adhesive which is liquid or gel in an atmosphere in which the powder sample is mixed, a UV resin which is cured by UV irradiation, and the like can be preferably used. The types of these resins and adhesives are not particularly limited as long as they have a strength that does not hinder TEM observation and do not exert a chemical action on the powder sample. Of these, an epoxy resin, which is a heat-curable resin, is preferable from the viewpoint of workability.

3. Sheet mesh A sheet mesh is essentially a small disc-shaped wire net for mounting a sample to be observed with a TEM. Various materials and mesh shapes are commercially available. In the present invention, the number of holes formed by the wire mesh in the sheet mesh may be two or more. FIG. 1 shows a sheet mesh 10 having a plurality of holes.

However, when a strip-shaped cured sample is prepared in “4. Preparation of cured sample” described later, the strip-shaped cured sample 11 is formed without cutting the one or more holes and the composition 21 filled therein. It is essential to remain inside. Therefore, it is important to use a sheet mesh having holes having a number, size, and position that can leave at least one hole that is not cut by two parallel cutting lines that cut the cured sample. ..

Copper is the most common material for the sheet mesh 10. However, in addition to metals such as nickel, gold, molybdenum, and copper, carbon, polymer materials, and the like are also used. The material is not particularly limited, except that a material having a spectrum that does not overlap with the X-ray spectrum of the powder sample to be measured is selected during analysis by TEM described later.
The size of the sheet mesh 10 having an outer diameter of 3 mmφ is convenient from the viewpoint of loading in a TEM sample holder described later. Further, it is preferable that the thickness of the sheet mesh 10 is 10 μm or more and less than 30 μm, from the viewpoint that mechanical strength can be secured and the sheet mesh 10 can be directly applied to processing by IM described later.

4. Preparation of Hardened Sample A powder sample to be measured and a resin are mixed and kneaded to obtain a composition 20 containing the powder sample and the resin. The composition of the composition 20 is a mixture of a powder sample and a resin in a volume ratio of 1:1 or more and 5:1 or less, preferably 2:1 or more and 4:1 or less. This is because more particles can be observed during TEM observation and the strength as a cured sample is ensured.

FIG. 2 shows a perspective view of the composition 20 placed on the sheet mesh 10.
The composition 20 is filled into the holes provided through both the front and back surfaces of the sheet mesh 10. At that time, it is preferable that a medicine packing paper or the like is laid under the sheet mesh 10 so that the composition 20 does not rise more than the front and back surfaces of the sheet mesh 10, and the excess amount of the composition 20 is sucked into the medicine packing paper or the like for filling. This is because by preventing the composition 20 from rising above both the front and back surfaces of the sheet mesh 10, extra processing time is not required when thinning by IM as described later.

In the sheet mesh 10 from which the surplus of the composition 20 is removed, the kneading resin filled in the holes is cured by a predetermined method to obtain a cured sample. A perspective view of the cured sample is shown in FIG.
In FIG. 3, the composition 20 is filled in the holes provided in the sheet mesh 10 and cured, and the filled composition 21 is in a cured state.

Then, it is preferable that the cured sample is cut along an appropriate cutting line to obtain an arc-shaped cured sample and a strip-shaped cured sample, and the obtained strip-shaped cured sample is processed by IM described later. Of course, the cured sample can be processed by IM described later while keeping the disk shape (cylindrical shape), but it is preferable to cut it from the viewpoint of workability.
Therefore, hereinafter, a process of cutting the cured sample along an appropriate cutting line to obtain an arc-shaped cured sample and a strip-shaped cured sample will be described with a main example.

FIG. 4 shows a perspective view when the cured sample is cut along two parallel cutting lines to form arc-shaped cured samples 12 and 13 and strip-shaped cured sample 11.
Incidentally, it is convenient to cut the cured sample by using a sharp cutter knife or the like.
The obtained strip-shaped cured sample 11 has a substantially rectangular front and back surfaces, two side surfaces on the long side and two side surfaces on the short side. Here, the front surface, the back surface, the two side surfaces on the long side and the two side surfaces on the short side are substantially equal to each other. Then, the two side surfaces on the long side are the side surfaces derived from the cut surface created at the time of cutting the cured sample, and the two side surfaces on the short side consider the outer shape of the original sheet mesh 10 to be a cylindrical shape. At this time, the side surface is derived from the portion corresponding to the side surface portion of the cylindrical shape.
At this time, some of the composition 21 filled in the holes may be cut by a cutter knife or the like, but one or more holes and the composition 21 filled therein may be cut. It is important that they remain in the strip-shaped cured sample 11 without being left. Therefore, a sheet mesh having one or more holes and the number of the holes, the size and the positions of which the composition 21 filled therein can remain in the strip-shaped cured sample 11 without being cut is selected. Moreover, a cutting line is provided so that one or more holes and the composition 21 filled therein can remain in the strip-shaped cured sample 11 without being cut.

5. Processing by IM FIG. 5 shows a perspective view when the obtained strip-shaped cured sample 11 is loaded in the IM and the strip-shaped cured sample 11 is irradiated with the argon ion flow 41 for the first time.
Then, FIG. 6 shows a state of a cross section that appears when it is assumed that the strip-shaped cured sample 11 and the shielding plate 31 in FIG. 5 are cut at the position of the line AA.

First, as shown in FIG. 5, first, the strip-shaped cured sample 11 is loaded into the IM so that one of the long side surfaces of the strip-shaped cured sample 11 faces the argon ion flow. Next, the shield plate 31 mounted on the IM is installed along the long side of the long side surface of the strip-shaped cured sample 11 installed so as to face the ion flow. Install on the side of the side.

At this time, if it is assumed that the strip-shaped cured sample 11 and the shielding plate 31 are cut at the position of the line AA, it is considered that the cross section in the state shown in the cross sectional view of FIG. 6 appears. That is, in FIG. 6, reference numeral 11 is the cross section of the strip-shaped cured sample 11, reference numeral 10 is the cross section of the sheet mesh 10, reference numeral 21 is the cross section of the composition 21, and reference numeral 31 is the cross section of the shielding plate 31. is there. Further, reference numeral 41 is an argon ion flow 41 that is irradiated onto the strip-shaped cured sample 11, and is a cross section of a state when the strip-shaped cured sample 11 is irradiated with the argon ion flow 41.

Then, as shown in FIGS. 5 and 6, while the ion gun of the IM is tilted back and forth with respect to the long side surface of the strip-shaped cured sample 11, both sides of the strip-shaped cured sample 11 and both sides thereof are penetrated. The composition 21 filled in the provided holes (including those not cut by a cutter knife or the like) is irradiated with the argon ion flow 41 for the first time under predetermined conditions.

Then, the first irradiation of the argon ion flow 41 and the effect of the shield plate 31 mainly erode the composition 21 filled in the hole on the lower side from the center of the strip-shaped cured sample 11, and the irradiation of the argon ion flow is performed. FIG. 7 is a cross-sectional view showing a state of a cross section that appears when the strip-shaped cured sample is cut later, which is the state of the cross-section of the strip-shaped cured sample after irradiation with argon ions.

Here, the irradiation of the argon ion flow of IM is once stopped. Then, the strip-shaped cured sample 11 is taken out from the IM, turned upside down, loaded again into the IM, and the side surface on the long side that does not face the first time argon ion flow 41 faces the second time argon ion flow. The combination is a preferable constitution from the viewpoint of thinning the composition described later.

Therefore, from this point of view, assuming that after the first irradiation of the argon ion flow 41 under a predetermined condition, the irradiation of the argon ion flow is stopped once, and the strip-shaped cured sample after the irradiation of the argon ion flow is cut. The strip-shaped cured sample 11 in the state shown in FIG. 7, which is a cross-sectional view showing the state of the cross section appearing in FIG.

Then, the strip-shaped cured sample 11 is turned upside down, this time, the long-side side surface on the side that did not face the first time argon ion flow 41 is made to face the argon ion flow, and the strip-shaped cured sample 11 is returned again. Load IM.
However, in view of thinning of the composition described later, unlike the first time, the shielding plate 31 mounted on the IM was not installed on the long side surface in the second time, unlike the first time.

Then, while the ion gun is tilted back and forth with respect to the long-side side surface of the strip-shaped cured sample 11, the strip-shaped cured sample, which is turned upside down, is irradiated with the second argon ion flow 42. FIG. 8 is a cross-sectional view showing the state of the cross section of the strip-shaped cured sample 11 at this time when it is assumed that the strip-shaped cured sample irradiated with the second argon ion flow is cut. Show.
Then, since the shielding plate 31 was not provided, the composition 21 filled in the hole on the upper side from the center of the strip-shaped cured sample 11 was mainly eroded.
That is, the composition 21 filled in the hole that was mainly irradiated with the first argon ion flow 41 was also mainly irradiated with the second irradiation of the argon ion flow 42 from the direction opposite to the first direction, and It was eroded and exfoliated.

Even when a disc-shaped (cylindrical) cured sample is used, as in the case of the strip-shaped cured sample 11, the first irradiation of argon ions is performed to erode the composition 21 filled in the hole. Thin into pieces. After that, the disk-shaped cured sample is taken out from the IM, the disk-shaped cured sample is turned upside down and loaded into the IM again, and the second time is irradiated with argon ions, the hole is filled and corroded to form a thin piece. The emulsified composition is further eroded to form flakes.

Sectional drawing which shows the state of the cross section in the strip-shaped hardened sample 11 after the 2nd argon ion irradiation, when assuming that the strip-shaped hardened sample after the 2nd irradiation of an argon ion stream was cut|disconnected. As shown in FIG.
As shown in FIG. 9, a part of the filled composition 21 is exfoliated into the exfoliated composition 22 by the first and second argon ion flows from different directions. The exfoliated composition 22 may be perforated depending on the irradiation conditions of the argon ion flow.

Specifically, the composition 22 that has been exfoliated by being corroded twice is exfoliated to a film thickness of 0.01 to 0.1 μm, and has a thickness suitable as a sample for TEM observation. Furthermore, the thinned composition 22 has a region of about 0.5×1 mm, and can provide a sufficient visual field area as a sample for TEM observation.

On the other hand, the composition 22 that has been exfoliated by being eroded twice is extremely embrittled by being irradiated with argon ions. However, since the embrittled and exfoliated composition 22 is formed in the hole portion of the strip-shaped cured sample 11, the strip-shaped cured sample 11 is treated with almost no mechanical impact on the embrittled portion. It can be handled easily.

Even when a disk-shaped cured sample is used, the composition that has been exfoliated by being corroded twice is exfoliated to a film thickness of 0.01 to 0.1 μm and is suitable as a sample for TEM observation. It becomes the thickness. Furthermore, the thinned composition 22 also has a region of about 0.5×1 mm, and can provide a sufficient visual field area as a sample for TEM observation.
On the other hand, a composition that has been exfoliated by being eroded twice is extremely embrittled by being irradiated with argon ions. However, since the portion is formed in the hole of the disk-shaped cured sample, the portion can be easily handled with almost no mechanical impact.

6. Loading into TEM and Analysis Strip-shaped cured sample 11 having a thinned portion is taken out from IM and loaded into a sample holder of TEM.
Since the thinned composition 22 is formed in the hole of the strip-shaped cured sample 11, the thinned composition 22 is loaded into the sample holder of the TEM as it is without giving a mechanical impact to the thinned portion. ..
It is also considered that the metal element evaporated from the sheet mesh 10 portion on the ion gun side in the strip-shaped cured sample 11 thinned to argon ions is attached to the portion on the ion gun side of the thinned composition 22. .. Therefore, this problem can be avoided by selecting, as the material of the sheet mesh 10, a material having a spectrum that does not overlap with the X-ray spectrum of the powder sample to be measured.

As described above, the film thickness of the composition 22 thinned by being eroded twice is suitable as a sample for TEM observation, and has a region capable of providing a sufficient visual field. Therefore, if desired, sufficient observation can be performed precisely.

The present invention will be specifically described with reference to examples. However, the present invention is not limited to the specific example.
(Example 1)
1. Powder sample to be measured As a powder sample to be measured, an oxide powder of a transition metal having a particle size of 0.5 to 10 μm was prepared.
2. Kneading Resin An epoxy resin (G2) manufactured by GATAN was prepared as a kneading resin.
3. Sheet mesh Oken Shoji Co., Ltd. product (#09-1043, φ0.8, molybdenum) was prepared as a sheet mesh. This is a sheet mesh made of molybdenum (Mo) whose EDS spectra do not overlap with those of the powder sample to be measured, and which has a plurality of holes.

4. Preparation of Hardened Sample A powder sample and a kneading resin were mixed and mixed at a volume ratio of 3:1 to obtain a composition containing the powder sample and the resin. The composition was applied and filled in a plurality of holes provided in the sheet mesh. At this time, the sheet mesh was placed on the medicine packing paper to suppress the composition from protruding from the back side of the sheet mesh. On the other hand, the composition was coated and filled in the holes provided in the sheet mesh while suppressing the composition from protruding from the front side of the sheet mesh.
When the filling of the composition into the sheet mesh was completed, the resin in the composition was cured by heating with a hot plate at 120° C. for 10 minutes to obtain a cured sample.

After curing the kneading resin of the sheet mesh having a plurality of holes in which the excess of the composition has been removed, the cured sample is subjected to two parallel cutting lines with a width of 0.5 to 0.8 mm. The sample was cut by a method to obtain a strip-shaped cured sample having a plurality of holes. The cutting was performed using a sharp cutter knife or the like. At this time, some parts of the composition filled in the holes were cut with a cutter knife. However, a plurality of holes and the composition filled therein were not on the cutting line and remained in the strip-shaped cured sample without being cut.

5. Processing by IM The strip-shaped cured sample was placed in an ion milling device (made by JEOL Ltd., ion slicer IB09060CIS) so that one of the long side surfaces of the obtained strip-shaped cured sample faced the ion flow. A shield plate attached to the apparatus was installed on the long side surface facing the ion flow along the long side of the long side surface facing the ion flow.
Then, the strip-shaped cured sample was irradiated with argon ions for the first time while inclining the ion gun back and forth with respect to the long side surface facing the ion flow.
Then, both front and back surfaces of the strip-shaped cured sample were irradiated with an argon ion flow for 2.5 hours under the condition of 7 kV on each surface to erode the composition filled in the holes penetrating the front and back surfaces.

The irradiation of the argon ion flow was once terminated, and the strip-shaped cured sample was removed from the IM. Then, the strip-shaped cured sample was turned upside down, and this time, in the first irradiation of argon ions, the long-side side surface that did not face the argon ion flow was made to face the argon ion flow to cure the strip-shaped cured sample. The sample was loaded back into the IM. At this time, the shield plate attached to the device was not used.

Then, both front and back surfaces of the strip-shaped cured sample were irradiated with a second argon ion flow for 0.5 hours stepwise under the conditions of 6 kV, 5 kV, 4 kV, 3 kV, and 2 kV, respectively. The composition filled in the hole provided through the hole was eroded. As a result, the film thickness of the composition that had been exposed to the argon ion irradiation twice at one or more locations in the hole was thinned to 0.01 to 0.1 μm, which is a thickness suitable for measurement by TEM. However, it was brittle.

6. Loading into TEM and Analysis The cured sample that had been thinned by the flow of argon ions was removed from the IM, loaded into the sample holder of the TEM, and placed in the TEM (JEM-ARM200F, manufactured by JEOL Ltd.).
However, since the composition that had been thinned and embrittled was present in the hole of the cured sample, it was easy to load the cured sample into the TEM sample holder.
The film thickness of the flakes of the composition thinned by argon ions was suitable as a sample for TEM observation, and had a region capable of providing a sufficient visual field. I was able to make precise observations.

10: Sheet mesh 11: Strip-shaped cured sample 12: Arc-shaped cured sample 13: Arc-shaped cured sample 20: Composition 21: Filled composition 22: Exfoliated composition 31: Shielding plate 41: 1st time Argon ion flow 42: Second argon ion flow

Claims (7)

A hole provided in a sheet mesh that can be loaded into a sample holder of a transmission electron microscope, a step of filling a composition containing a powder sample and a resin, and curing the resin to obtain a cured sample,
Cutting the cured sample along an appropriate cutting line to obtain a strip-shaped cured sample,
A step of loading the strip-shaped cured sample into an ion milling apparatus so that one of the long side surfaces of the strip-shaped cured sample faces the argon ion flow;
The shield plate provided in the ion milling apparatus is installed along the long side of the long side surface on the long side surface facing the ion flow in the strip-shaped cured sample loaded in the ion milling apparatus. Process,
Irradiating the strip-shaped cured sample with argon ions, eroding the composition filled in the front and back surfaces and holes of the strip-shaped cured sample by the argon ion flow, and filling the strip-shaped cured sample in one or more places of the hole. And a step of thinning the obtained composition, and a method for producing a sample for transmission electron microscope observation, which comprises: Irradiating the strip-shaped cured sample with argon ions, in the step of thinning the filled composition into a thickness suitable for measurement by a transmission electron microscope,
In a predetermined condition, after eroding the composition filled in the front and back surfaces and holes of the strip-shaped cured sample with an argon ion flow, the argon ion irradiation is stopped, and the strip-shaped cured sample is removed from the ion milling apparatus. Process,
The strip-shaped cured sample that had been irradiated with argon ions was loaded into an ion milling device so that the long side surface that did not face the argon ion flow in the strip-shaped cured sample that had been irradiated with the argon ions faced the argon ion flow. The process of
The strip-shaped cured sample irradiated with the argon ion is irradiated with argon ions without providing the shielding plate, and the composition filled in the front and back surfaces and the hole of the strip-shaped cured sample is eroded by the argon ion flow. The method for producing a sample for observation with a transmission electron microscope according to claim 1, further comprising the step of thinning the filled composition at one or more locations of the hole. The resin is a liquid or gel when mixed with a powder sample, and is a resin that cures at room temperature, heat cures, or UV after being filled in the holes provided in the sheet mesh. The method for producing the sample for transmission electron microscope observation according to claim 1. The method for producing a sample for observation with a transmission electron microscope according to claim 1, wherein the resin is an epoxy resin. The method for producing a sample for observation by a transmission electron microscope according to claim 1, wherein the powder sample is mixed with a resin in a volume ratio of 1:1 or more. The method for producing a sample for observation by a transmission electron microscope according to claim 1, wherein the sheet mesh has a plurality of holes and has a thickness of 10 μm or more and 50 μm or less. A strip-shaped cured sample in which a plurality of holes provided in the strip-shaped sheet mesh are filled with a cured product of a composition containing a powder sample and a resin,
The strip-shaped cured sample can be loaded into a sample holder of a transmission electron microscope,
The filled composition has been flaked by erosion by a stream of argon ions,
A sample for observation with a transmission electron microscope, wherein the filled composition is in the form of flakes at one or more locations of a plurality of holes provided in the strip-shaped cured sample.

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