CN114964968A - Preparation method of nano-scale pinpoint transmission electron microscope sample - Google Patents
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- 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
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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
- G01N1/286—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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
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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
- G01N1/286—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
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Abstract
The invention discloses a preparation method of a nano-scale pinpoint transmission electron microscope sample. The method comprises the following main steps: (1) depositing a carbide protective layer in a target area, and cutting to obtain a cuboid sample; (2) transferring the cuboid sample to a micro-column, and fixing the cuboid sample in the center of the top of the micro-column by platinum carbide deposition; (3) utilizing focused ion beams to annularly thin the cuboid sample to prepare a micron-sized cylindrical sample with an annular protective layer; (4) and gradually thinning the top end of the cylindrical sample by adopting focused ion beams to prepare the nano-scale pinpoint transmission electron microscope sample with the tip diameter smaller than 30nm, the cone angle smaller than 30 degrees and the length of the thin area (the diameter is smaller than 80nm) larger than 50 nm. The technology solves the problems that the tip of the transmission electron microscope sample is easy to shake and bend and damage, can effectively prepare the nano-scale tip sample with an extremely thin tip, and realizes the high-resolution analysis of three-dimensional space information of sample bubbles, pore canals and precipitated phases.
Description
Technical Field
The invention belongs to the field of preparation of transmission electron microscope samples, and particularly relates to a preparation method of a nano-scale pinpoint transmission electron microscope sample.
Background
The transmission electron microscopic analysis technology is an important method for exploring the microstructure of a material, and the preparation technology of a sample is a key premise for obtaining related target microscopic information. The conventional sheet-like transmission electron microscope sample can provide two-dimensional spatial information of a material microstructure, but the three-dimensional spatial information is often covered, so that the judgment deviation of the structure and the appearance of the material is caused. Especially, when three-dimensional spatial information of a nano-scale micropore, bubble and precipitated equal structure in a material is analyzed, a nano-scale pinpoint transmission electron microscope sample needs to be prepared. Therefore, the development of the preparation technology of the nano-scale pinpoint transmission electron microscope sample has obvious application value.
Currently, the preparation of a needle-tip-shaped sample is mainly based on the cutting of a block-shaped sample by a focused ion beam technology. CN 109307784B discloses a semiconductor tip sample preparation technology for three-dimensional atom probes, which can prepare a tip sample with a tip diameter of 100 nm. CN113899765 reports a transmission electron microscope sample preparation method for three-dimensional reconstruction of geological samples, and the needle tip dimension is 50-200 nm. However, it is still difficult to efficiently obtain high-resolution three-dimensional spatial information of structures such as micropores, nanobubbles (<5nm) and nanoprecipitates in the material. In order to meet the analysis requirement of the transmission electron microscope with the nano structure, a preparation technology of a nano needle-tip-shaped sample with an extremely thin tip region (the diameter is less than 30nm) needs to be developed. However, the related art still has the following challenges: on one hand, the nano-scale pinpoint sample is easy to shake in the preparation process, and the tip is difficult to be effectively thinned; on the other hand, a needle-tip sample with a small diameter and a long length is easy to bend and even break, so that the sample is damaged. The problems are more obvious when the material containing rich pore channels, bubbles and precipitated phases is prepared, the preparation of a nano-scale pinpoint transmission electron microscope sample of the related material is severely limited, and the three-dimensional spatial information of the microstructure of the nano-scale pinpoint transmission electron microscope sample is difficult to obtain.
In summary, the existing techniques for preparing a transmission electron microscope sample with a pinpoint shape still have difficulty in overcoming the problems that the material shakes during sample preparation and is easy to bend or break after sample preparation, and a nano-scale pinpoint transmission electron microscope sample with a very small tip diameter cannot be effectively obtained, so that the analysis of the three-dimensional structure of nano-scale pore canals, bubbles and precipitated phases in the sample is limited.
Therefore, there is a need to develop a method for preparing a nano-scale pinpoint sample, which can specifically solve the technical problems of easy bending and shaking of the sample during sample preparation.
Disclosure of Invention
In view of the above, the invention provides a method for preparing a nano-scale pinpoint-shaped transmission electron microscope sample, which aims to overcome the defects that the nano-scale pinpoint-shaped transmission electron microscope sample is easy to shake in the preparation process and is easy to bend and break after sample preparation, prepare a stable pinpoint-shaped transmission electron microscope sample with a small tip diameter, and realize high-resolution analysis on three-dimensional space information of bubbles, pores and precipitated phases in the sample.
A preparation method of a nano-scale pinpoint transmission electron microscope sample comprises the following steps:
s10 preparation of cuboid sample: depositing a platinum carbide protective layer in a target sample preparation area of the material, and cutting off the front side, the rear side, the bottom and the right side area of the target area by adopting a focused ion beam to preliminarily form a cuboid structure; depositing platinum carbide between the sample transfer needle and the cuboid structure to enable the sample transfer needle to be adhered to the cuboid structure, and finally cutting off the left area of the sample by adopting a focused ion beam to finish extraction of the cuboid sample;
s20 immobilization of cuboid sample: moving the sample transfer needle adhered with the cuboid sample to the position above the central microcolumn of the micro-grid for the transmission electron microscope, keeping a certain gap, and depositing platinum carbide in the gap between the cuboid sample and the microcolumn to adhere the cuboid sample and the microcolumn; cutting off the adhesion area of the cuboid sample and the sample moving needle by using a focused ion beam, and taking out the sample transfer needle;
s30 preparation of diameter micron cylindrical samples: cutting a cuboid sample for multiple times from top to bottom by adopting an annular focused ion beam to form a columnar structure with the diameter of micron order and the appearance of stepped shaft shape and the diameter of which is continuously reduced;
s40 preparation of diameter nanoscale needle-tip samples: the cylindrical sample is thinned step by step from top to bottom by adopting the annular focused ion beam, namely, the outer diameter in an annular area cut by the focused ion beam is gradually reduced along with the thinning process, the cutting depth is gradually reduced, the intensity of the beam is gradually reduced, the diameter of the tip of the sample is gradually reduced, meanwhile, a certain thickness is reserved at the bottom to effectively support the sample, and finally, a stable needle tip sample with the nanoscale tip diameter is formed.
Optionally, the height of the rectangular parallelepiped sample in step S10 ranges from 3 μm to 10 μm, and the length and thickness ranges from 2 μm to 5 μm.
Optionally, the step S20 of fixing the sample to the microcolumn further includes performing deposition and fixing on the back surface of the cuboid sample; if a gap exists between the cuboid sample and the microcolumn, directly depositing platinum carbide in the gap to completely bond and fix the sample; if the gap between the cuboid sample and the microcolumn is too small or gapless, the focused ion beam is adopted to cut the bottom edge of the cuboid sample until the gap area between the cuboid sample and the microcolumn is exposed, and platinum carbide is deposited in the gap to completely bond and fix the sample.
Optionally, when the cuboid sample and the microcolumn are fixed, a gap of 0.5-1 μm needs to be maintained.
Optionally, in the step S30, in the process of cutting the stepped shaft-shaped columnar structure, the outer diameter of the annular region cut by the focused ion beam each time is smaller than the inner diameter of the annular region at the previous time, so that an annular protective layer is reserved around each layer of the cylindrical step, and it is ensured that the sample is not shaken and bent in the subsequent thinning process.
Optionally, in step S30, the inner diameter of the annular focused ion beam ranges from 1 μm to 6 μm, and the beam intensity ranges from 2 μm to 8 μm and is 0.5nA to 2 nA.
Optionally, in step S30, the annular protection layer refers to a concentric annular structure around the center of the sample, and has a diameter ranging from 1 μm to 8 μm and a thickness ranging from 0.5 μm to 2 μm.
Optionally, the inner diameter range of the annular region in the step-by-step cutting and thinning process in step S40 is 0.2 μm to 1 μm, the outer diameter range is 0.3 μm to 2 μm, the cutting depth range is 0.5 μm to 5 μm, and the beam intensity range is 15pA to 0.5 nA.
Optionally, the diameter range of the tip of the needle tip observation area is 20-30 nm, the cone angle is 20-30 degrees, the length range of the observation area is 50-100 nm, and the diameter of the bottom end of the observation area is 50-80 nm.
The invention has the beneficial effects that: on the basis of preparing a pinpoint sample by the existing focused ion beam method, aiming at the problem that the sample is easy to shake, a strategy of reserving a certain number of annular protective layers near the pinpoint sample is firstly proposed on the basis of effectively fixing the sample, so that the structural stability of the pinpoint sample is effectively enhanced, and the thinning efficiency and the thinning degree of the pinpoint sample are improved; meanwhile, aiming at the problem that a needle point-shaped sample is easy to bend, the invention firstly provides a step-by-step thinning strategy, namely, the inner diameter, the outer diameter, the cutting depth and the beam intensity of a focusing ion beam annular area are gradually reduced along with thinning, and a certain bottom thickness is kept under the condition that the diameter of a tip is effectively reduced so as to effectively fix and support the needle point. The preparation method provided by the invention solves the problems of shaking during sample preparation and bending and breaking after sample preparation of the pinpoint sample, prepares the nanoscale pinpoint transmission electron microscope sample which is stable in structure and not easy to bend, has the tip diameter smaller than 30nm, the cone angle smaller than 30nm and the length of a thin area (the thickness is smaller than 80nm) larger than 50nm, and realizes high-resolution analysis of three-dimensional space information of sample bubbles, pore channels and precipitated phases.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing a nano-scale pinpoint sample according to the present invention;
FIG. 2 is a scanning electron microscope image of a nanosized pinpoint sample of titanium hydride completed in the present invention;
FIG. 3 is a transmission electron microscope image of a lateral scanning of a nano-sized tip sample of titanium hydride prepared in the present invention;
FIG. 4 is a scanning transmission electron microscope image of a nano-sized tip of a titanium hydride sample completed in the present invention;
FIG. 5 is a scanning transmission electron microscope image of a metallic titanium nanosized needle point shaped sample tip completed in the present invention;
in the figure: 1. cuboid sample, 2 annular protective layer, 3 needle tip.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creating any labor.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
The preparation method of the nano-scale pinpoint transmission electron microscope sample, as shown in figure 1, comprises the following steps:
(1) preparation of cuboid samples
Depositing a platinum carbide protective layer in a target sample preparation area of the material, and cutting off front, rear, bottom and right side areas of the target area by adopting a focused ion beam to form a cuboid structure with the height ranging from 3 mu m to 10 mu m and the length and thickness ranging from 2 mu m to 5 mu m; depositing platinum carbide to make the sample transfer needle adhere to the cuboid sample, and finally cutting off the left area of the sample by adopting a focused ion beam to finish the extraction of the cuboid sample;
(2) fixing a cuboid sample
Moving the sample transfer needle adhered with the cuboid sample to the position above the central microcolumn of the micro-grid for the transmission electron microscope, and preferably keeping a gap of 0.5-1 mu m, and depositing platinum carbide in the gap to adhere the cuboid sample and the microcolumn; cutting off the adhesion area of the sample and the sample moving needle by using a focused ion beam, and taking out the sample transfer needle; in order to ensure that a cuboid sample is firmly fixed, the back of the sample needs to be fixed; turning to the other side of the cuboid sample, namely the back of the cuboid sample, which is not deposited and fixed, and directly depositing platinum carbide in a gap between the cuboid sample and the microcolumn to completely bond and fix the sample if the gap is between 0.5 and 1 mu m; if the gap between the cuboid sample and the microcolumn is too small or gapless, cutting the bottom edge of the cuboid sample by adopting a focused ion beam until a gap area between the cuboid sample and the microcolumn is exposed, and depositing platinum carbide in the gap to completely bond and fix the sample;
(3) preparation of diameter micron cylindrical sample
Cutting a cuboid sample for multiple times from top to bottom by adopting an annular focused ion beam to form a columnar structure with the diameter of micron order and the appearance of stepped shaft shape and the diameter of which is continuously reduced, so that the sample forms a columnar structure with the diameter of micron order; wherein the inner diameter range of the annular focused ion beam is 1-6 mu m, and the beam intensity of 2-8 mu m in the outer diameter range is 0.5-2 nA; in the cutting process, the outer diameter of the annular area cut by the focused ion beam every time is smaller than the inner diameter of the annular area at the last time, so that an annular protective layer is reserved around the cylindrical sample, the diameter range of the annular protective layer is 1-8 mu m, the thickness range of the annular protective layer is 0.5-2 mu m, and the sample is ensured not to shake and bend in the subsequent thinning process;
(4) preparation of a sample with a nanometer diameter and a needle-point shape
The cylindrical sample is thinned step by step from top to bottom by adopting an annular focused ion beam, namely the outer diameter in an annular area cut by the focused ion beam is gradually reduced along with the thinning process, the inner diameter range is 0.2-1 mu m, the outer diameter range is 0.3-2 mu m, the cutting depth is gradually reduced, the depth range is 0.5-5 mu m, the beam intensity is gradually reduced, and the intensity range is 15 pA-0.5 nA; finally, the diameter of the tip of the sample is gradually reduced to 20-30 nm, the cone angle is 20-30 degrees, the length range of an observation area is 50-100 nm, the diameter of the bottom end of the observation area is 50-80 nm, and meanwhile, a certain thickness is reserved at the bottom of the observation area to effectively support the sample, so that a needle-tip-shaped sample with the tip diameter being nano-scale is formed.
The focused ion beam microscope apparatus used in the present invention is as follows:
focusing an ion beam microscope: the block sample is annularly thinned by adopting a Scios 2 HiVac focused ion beam microscope of Thermofisher Scientific company in America; the microscopic structure of the prepared electron microscope sample was analyzed by using a Scios 2 HiVac double-spherical aberration correction scanning Transmission Electron Microscope (TEM) of Thermofish Scientific, USA, and the accelerating voltage was 300 kV.
Experimental results show that the preparation method of the nanoscale pinpoint transmission electron microscope sample is a transmission electron microscope sample preparation method with extremely small pinpoint diameter, insusceptibility to bending and high success rate, and effectively solves the problems that the sample is easy to bend, shake, overlarge in thickness (diameter) and the like in the existing pinpoint sample preparation method. The diameter of the transmission electron microscope sample needle tip prepared by the method is less than 30nm, and the analysis requirement of a high-resolution transmission electron microscope with a related nano-scale structure can be met; meanwhile, the thin region (the thickness is less than 80nm) is long, the cone angle is small, the stability is good, and the three-dimensional reconstruction analysis requirements of related structures can be met. Therefore, the method provides important technical support for the three-dimensional spatial information of the nano or sub-nano structure in the transmission electron microscope analysis sample, and has important application prospect in the technical research field of material transmission electron microscopy analysis.
Example 1
In this embodiment, a nano-scale transmission electron microscope sample of titanium hydride containing nano-bubbles is prepared by the following specific steps:
s11 preparation of cuboid sample
Depositing a platinum carbide protective layer in a target sample preparation area of the material, and cutting areas at the front, back, bottom and right sides of the target area by adopting a focused ion beam to ensure that the height of a target cuboid sample 1 is 6 mu m and the length and thickness are 4 mu m; depositing platinum carbide to enable the sample transfer needle to be adhered to the cuboid sample 1, cutting off a reserved area on the left side of the sample by adopting a focused ion beam, and extracting the cuboid sample 1; depositing a platinum carbide protective layer in a target sample preparation area of the material, and cutting off front, rear, bottom and right side areas of the target area by adopting a focused ion beam to form a cuboid sample 1 with the height range of 6 mu m and the length and thickness ranges of 4 mu m; depositing platinum carbide to enable the sample transfer needle to be adhered to the cuboid sample 1, and finally cutting off the left area of the sample by adopting a focused ion beam to finish the extraction of the cuboid sample 1;
s12 fixing cuboid sample
Moving the sample transfer needle adhered with the cuboid sample to the position above the central microcolumn of the micro-grid for the transmission electron microscope, and preferably keeping a gap of 0.5-1 mu m, and depositing platinum carbide in the gap to adhere the cuboid sample and the microcolumn; cutting off the adhesion area of the sample and the sample moving needle by using a focused ion beam, and taking out the sample transfer needle; in order to ensure that a cuboid sample is firmly fixed, the back of the sample needs to be fixed; turning to the other side of the cuboid sample, namely the back of the cuboid sample, which is not deposited and fixed, and directly depositing platinum carbide in a gap between the cuboid sample and the microcolumn to completely bond and fix the sample if the gap is between 0.5 and 1 mu m; if the gap between the cuboid sample and the microcolumn is too small or gapless, cutting the bottom edge of the cuboid sample by adopting a focused ion beam until a gap region between the cuboid sample and the microcolumn is exposed, and depositing platinum carbide in the gap to completely bond and fix the sample;
s13 preparation of diameter micron-sized cylindrical sample
Cutting a cuboid sample for multiple times from top to bottom by adopting an annular focused ion beam, wherein the inner diameter of the annular focused ion beam is gradually reduced to 1 mu m from 6 mu m, the outer diameter is gradually reduced to 2 mu m from 8 mu m, and the beam intensity is gradually reduced to 1nA from 5nA, so that the sample forms a cylindrical structure with the diameter of 1 mu m; in the cutting process, the outer diameter of the annular area cut by the focused ion beam each time is smaller than the inner diameter of the annular area at the last time, so that a plurality of annular protective layers are reserved around the cylindrical sample, the diameters of the annular protective layers are respectively 8 microns, 4 microns and 2 microns, and the thickness of the annular protective layers is 0.5 micron;
s14 preparation of diameter nanometer level pinpoint sample
The cylindrical sample is gradually thinned from top to bottom by adopting an annular focused ion beam, namely the outer diameter in an annular area cut by the focused ion beam is gradually reduced along with the thinning process, the inner diameter is gradually reduced from 1 mu m to 0.2 mu m, the outer diameter is gradually reduced from 2 mu m to 0.3 mu m, the cutting depth is gradually reduced, the cutting depth is reduced from 4 mu m to 0.5 mu m, the intensity of the used beam is gradually reduced, and the intensity of the beam is gradually reduced from 0.5nA to 15 pA; finally, the diameter of the tip of the sample is gradually reduced to 20-30 nm, the cone angle is 20-30 degrees, the length range of an observation area is 50-100 nm, the diameter of the bottom end of the observation area is 50-80 nm, and meanwhile, a certain thickness is reserved at the bottom of the observation area so as to effectively support the sample, and a needle-tip-shaped sample with the diameter of the tip of nanometer is formed.
The test results are as follows:
FIG. 2 is a scanning electron microscope image of a nano-scale pinpoint sample of metal titanium during preparation, which shows that the pinpoint sample has a small tip diameter and a typical annular protective layer 2 structure, and the sample is not bent, shaken and broken obviously during and after preparation. FIG. 3 is a scanning transmission electron microscope image of the prepared sample, and the visible sample has a typical needle-tip shape and has no obvious bending damage phenomenon. FIG. 4 shows a scanning transmission electron microscope image of a thin region at the tip of the sample, from which it can be seen that the diameter of the tip is 24nm, the thickness at the position of 100nm in length is 56nm, and the cone angle is 20 degrees, and the obtained image can clearly distinguish the injected nano-bubbles in the material and the derived micropores and defects thereof, which indicates that the needle-tip-shaped sample can effectively meet the requirements of nano-structure analysis and can effectively realize the three-dimensional spatial information analysis of the relevant structure and morphology.
Example 2
The preparation method of the nano-scale pinpoint transmission electron microscope sample of the metal titanium containing the nano bubbles comprises the following specific steps:
in this embodiment, a nano-scale transmission electron microscope sample of metal titanium containing nano-bubbles is prepared, and the specific implementation manner is substantially the same as that in embodiment 1, and the main difference is as follows: the length, the thickness and the height of the block sample are respectively 2.5 mu m, 2.5 mu m and 5 mu m, the diameter of the annular protective layer is 2.5 mu m and 1.5 mu m, the outer diameter of the annular area is reduced from 3 mu m to 0.1 mu m in the gradual thinning process, the difference between the inner diameter and the outer diameter is reduced from 0.8 mu m to 0.1 mu m, and the cutting depth is reduced from 4 mu m to 0.5 mu m.
The test results are as follows:
FIG. 5 shows a scanning transmission electron microscope image of the sample, and it can be seen that the sample has a typical needle-tip-like morphology with thin zone tip diameter < 20nm, thin zone (thickness < 50nm) length > 100nm, cone angle < 15 °. Based on the images, the nano bubble structures in the sample can be distinguished at high resolution, and the nano needle-tip transmission electron microscope sample preparation method provided by the invention is proved to be capable of effectively meeting the analysis requirement of the three-dimensional spatial information of the nano structure in the material.
Claims (9)
1. A preparation method of a nano-scale transmission electron microscope sample with a pinpoint shape is characterized by comprising the following steps:
s10 preparation of cuboid sample: depositing a platinum carbide protective layer in a target sample preparation area of the material, and cutting off the front side, the rear side, the bottom and the right side area of the target area by adopting a focused ion beam to preliminarily form a cuboid structure; depositing platinum carbide between the sample transfer needle and the cuboid structure to enable the sample transfer needle to be adhered to the cuboid structure, and finally cutting off the left area of the sample by adopting a focused ion beam to finish extraction of the cuboid sample;
s20 immobilization of cuboid sample: moving the sample transfer needle adhered with the cuboid sample to the position above the central microcolumn of the micro-grid for the transmission electron microscope, keeping a certain gap, and depositing platinum carbide in the gap between the cuboid sample and the microcolumn to adhere the cuboid sample and the microcolumn; cutting off the adhesion area of the cuboid sample and the sample moving needle by using a focused ion beam, and taking out the sample transfer needle;
s30 preparation of diameter micron cylindrical samples: cutting a cuboid sample for multiple times from top to bottom by adopting an annular focused ion beam to form a columnar structure with the diameter of micron order and the appearance of stepped shaft shape and the diameter of which is continuously reduced;
s40 preparation of diameter nanoscale needle-tip samples: the cylindrical sample is thinned step by step from top to bottom by adopting the annular focused ion beam, namely, the outer diameter in an annular area cut by the focused ion beam is gradually reduced along with the thinning process, the cutting depth is gradually reduced, the intensity of the beam is gradually reduced, the diameter of the tip of the sample is gradually reduced, meanwhile, a certain thickness is reserved at the bottom to effectively support the sample, and finally, a stable needle tip sample with the nanoscale tip diameter is formed.
2. The method for preparing a nano-scaled transmission electron microscope sample with a pinpoint shape according to claim 1, wherein the height of the rectangular parallelepiped sample in step S10 is in the range of 3 μm to 10 μm, and the length and thickness are in the range of 2 μm to 5 μm.
3. The method for preparing a nano-scale transmission electron microscope sample with a pinpoint shape according to claim 1, wherein the step S20 comprises fixing the sample to the microcolumn, and further comprises depositing and fixing the sample on the back of the cuboid sample; if a gap exists between the cuboid sample and the microcolumn, directly depositing platinum carbide in the gap to completely bond and fix the sample; if the gap between the cuboid sample and the microcolumn is too small or gapless, the focused ion beam is adopted to cut the bottom edge of the cuboid sample until the gap area between the cuboid sample and the microcolumn is exposed, and platinum carbide is deposited in the gap to completely bond and fix the sample.
4. The method for preparing a nano-scale transmission electron microscope sample with a pinpoint shape according to claim 1 or 3, wherein a gap of 0.5 μm to 1 μm is required to be maintained when the cuboid sample is fixed to the microcolumn.
5. The method for preparing a nano-scale transmission electron microscope sample with a pinpoint shape according to claim 1, wherein in the step S30, in the process of cutting the stepped shaft-shaped columnar structure, the outer diameter of the annular region cut by the focused ion beam each time is smaller than the inner diameter of the annular region at the previous time, so that an annular protection layer is reserved around each layer of the columnar step, and the sample is ensured not to be bent by shaking in the subsequent thinning process.
6. The method for preparing a nano-scale transmission electron microscope sample with a pinpoint shape according to claim 1, wherein in step S30, the inner diameter of the ring-shaped focused ion beam ranges from 1 μm to 6 μm, and the beam intensity ranges from 0.5nA to 2nA from 2 μm to 8 μm.
7. The method for preparing a nano-scale transmission electron microscope sample with a pinpoint shape according to claim 5, wherein the ring-shaped protection layer in step S30 refers to a concentric ring-shaped structure around the center of the sample, the diameter ranges from 1 μm to 8 μm, and the thickness ranges from 0.5 μm to 2 μm.
8. The method for preparing a nano-scale pinpoint-shaped transmission electron microscope sample according to claim 1, characterized in that the inner diameter range of the annular region in the step-by-step cutting and thinning process in the step S40 is 0.2 μm to 1 μm, the outer diameter range is 0.3 μm to 2 μm, the cutting depth range is 0.5 μm to 5 μm, and the beam intensity range is 15pA to 0.5 nA.
9. The method for preparing a nano-scale pinpoint-shaped transmission electron microscope sample according to claim 1, characterized in that the diameter of the tip of the pinpoint observation area of the pinpoint-shaped sample is 20nm to 30nm, the cone angle is 20 degrees to 30 degrees, the length of the observation area is 50nm to 100nm, and the diameter of the bottom of the observation area is 50nm to 80 nm.
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| CN115448251A (en) * | 2022-09-29 | 2022-12-09 | 中国科学院合肥物质科学研究院 | Nanowire preparation method |
| CN115448251B (en) * | 2022-09-29 | 2023-12-12 | 中国科学院合肥物质科学研究院 | Nanowire preparation method |
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