CN113358558A - Method for bonding nano material in-situ electron microscope - Google Patents
Method for bonding nano material in-situ electron microscope Download PDFInfo
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- CN113358558A CN113358558A CN202110601370.0A CN202110601370A CN113358558A CN 113358558 A CN113358558 A CN 113358558A CN 202110601370 A CN202110601370 A CN 202110601370A CN 113358558 A CN113358558 A CN 113358558A
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- electron microscope
- adhesive
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N19/00—Investigating materials by mechanical methods
- G01N19/04—Measuring adhesive force between materials, e.g. of sealing tape, of coating
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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
- G01N23/02—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 transmitting the radiation through the material
- G01N23/04—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 transmitting the radiation through the material and forming images of the material
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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
-
- 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
- G01N23/20025—Sample holders or supports therefor
Abstract
The invention provides a method for bonding nano materials in an in-situ electron microscope, which utilizes the electron beam dosage of 15e/nm2And s, the adhesive is cured to realize the bonding of the nano materials. The adhesive is EMIMBr-AlCl3Ionic liquid prepared by reacting AlCl3Mixing the solid powder with EMIMBr in a molar ratio of 1.3:1, and magnetically stirring to obtain the EMIMBr powder. The method can be used for carrying out nondestructive bonding on the nano material under the low-dose electron beam irradiation, has wide application range, is particularly suitable for the nano material which is not resistant to electron beam irradiation and is not heat-resistant, and has simple use method and low cost.
Description
Technical Field
The invention belongs to the technical field of novel welding, and particularly relates to a method for bonding a nano material in an in-situ electron microscope.
Background
In recent years, along with the development and the rise of nano materials, people have more and more intensive research on the performance of the nano materials, and the invention of the simple, effective and practical nano material adhesive has important significance for researching the mechanical property of single nano materials. In conventional research, the connection or fixation of nanomaterials often relies on advanced equipment such as focused ion beam welding and environmental electron microscope chemical reaction welding. The focused ion beam welding of the nanometer material has great damage to the nanometer material structure at the welding position, the welding point is easy to break, and the Pt for welding seriously pollutes the material. The welding of the nano material by the environmental electron microscope is realized by the chemical reaction of the nano material and the solder under the irradiation of the electron beam, and the structure of the nano material is damaged by the electron beam irradiation and the heat release in the reaction process. Moreover, both the focused ion beam and the environmental electron microscope are expensive large-scale equipment, the operation is complex, and the use difficulty is high.
Therefore, the method which is low in price, wide in application range and capable of performing nondestructive bonding on the nano material under low-dose electron beam irradiation has important practical value.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a method for bonding nanomaterials in situ under electron microscope irradiation with low dose of electron beam, wherein the adhesive is cured under low dose of electron beam irradiation, and there is no strong chemical reaction during the curing process.
In order to achieve the purpose, the invention provides the following scheme:
a method for adhering nano material in-situ electron microscope with electron beam dosage of 15e/nm2s, the adhesive is solidified to realize the bonding of the nano material; the adhesive is EMIMBr-AlCl3An ionic liquid.
Preferably, the electron beam dose is 0-2 e/nm2s, contacting the nano material with adhesive, and adjusting the electron beam dose to 15e/nm2And s, moving the electron beam to irradiate the contact position of the nano material and the adhesive.
Preferably, the preparation method of the adhesive comprises the following steps: mixing AlCl3Mixing with EMIMBr solid powderStirring with a magnetic stirrer.
Preferably, the AlCl is3Molar ratio to EMIMBr 1.3: 1.
Preferably, the time for magnetic stirring is 4 h.
Preferably, the adhesive is prepared in an argon atmosphere and can be contacted with air when transferred into an in-situ electron microscope.
Preferably, the time for the adhesive to contact air when transferred into an in situ electron microscope is within 20 seconds.
Preferably, the in-situ electron microscope is an in-situ transmission electron microscope or an in-situ scanning electron microscope.
Compared with the prior art, the invention has the following beneficial effects:
1) the raw materials for preparing the adhesive are convenient to purchase, the price is low, the using amount is small, the adhesive is simple to prepare, the solidification time is short, especially the electron beam irradiation dose required by solidification is low, no violent reaction is generated in the solidification process, and the structure of the nano material at the adhesion part is completely preserved.
2) The invention can be used in a common transmission electron microscope without large-scale equipment with special functions, and is particularly suitable for nanometer materials which are not resistant to electron beam irradiation and are not heat-resistant.
3) The invention has simple use method, wide application range and low cost.
Drawings
FIG. 1 is a schematic diagram of the method for bonding nanomaterials in an in-situ electron microscope according to the present invention;
FIG. 2 is a TEM image after Au is snapped in example 2 of the present invention;
FIG. 3 is a TEM image after h-CNT is broken in example 3 of the present invention;
FIG. 4 is a TEM image after Cu breaking in example 4 of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The invention provides a method for bonding nano materials in an in-situ electron microscope, wherein the bonding agent used in the method is EMIMBr-AlCl3Ionic liquids, preparation processes such asThe following:
mixing aluminum trichloride (AlCl)3) Mixing the two solid powders with brominated 1-ethyl-3-methylimidazolium salt (EMIMBr) at a molar ratio of 1.3:1, stirring for 4h with a magnetic stirrer to allow AlCl3And mixing the mixture with EMIMBr uniformly to obtain a light yellow solution, namely the nano material adhesive.
In an in-situ electron microscope, when the nano material is contacted with the adhesive, the dosage of the electron beam is controlled to be less than 2e/nm2s, the adhesive is liquid and can be operated in situ without curing, and then the electron beam dose is adjusted to 15e/nm2And s, moving the contact position of the electron beam irradiation nanometer material and the adhesive, and quickly solidifying the adhesive (5s) to complete good and stable adhesion.
The adhesive needs to be in an Ar atmosphere glove box (H)2O<0.01PPm,O2<0.01PPm), can be contacted with air for a short time within 20s when being transferred into a transmission electron microscope.
Preparing an adhesive:
in a glove box under Ar atmosphere, 0.18g of AlCl is added3And 0.2g of EMIMBr were placed in a 5ml glass bottle and magnetically stirred for 4 hours to obtain a pale yellow viscous liquid, i.e., an adhesive.
Example 1
1) In an Ar atmosphere glove box, a CuO nanowire is adhered to a substrate on one side by silver glue, a copper bar with the thickness of 0.3mm is adopted as a substrate on the other side, a small amount of adhesive is dipped at the front end of the copper bar substrate, the copper bar substrate is assembled according to the figure 1 and is arranged in a transmission electron microscope sample rod, and then the transmission electron microscope is arranged.
2) At an electron beam intensity of 2e/nm2And s, moving the copper rod substrate to enable the adhesive to be in contact with the CuO nanowire, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm2And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The copper rod substrate is withdrawn, the nanowire can be broken, the fracture position can not occur at the bonding position, and the bonding process is proved not to damage the structure of the CuO nanowire.
Example 2
1) In an Ar atmosphere glove box, a gold rod with the diameter of 0.3mm is adopted as a substrate on one side, and a nanometer polycrystalline Au column with the diameter of 200nm and the length of 8 mu m is obtained by etching the front end by FIB (focused ion beam); and (3) still using a 0.3mm copper bar on the other side of the substrate, dipping a small amount of adhesive, assembling and loading the substrate into a transmission electron microscope sample rod according to the figure 1, and then loading the sample rod into a transmission electron microscope.
2) At an electron beam intensity of 2e/nm2And s, moving the copper rod substrate to enable the adhesive to be in contact with the front ends of the Au nanorods, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm2And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The Au nanorods can be broken by withdrawing the copper rod substrate, the fracture appears in the middle of the nanorods, and the fracture position does not occur at the bonding position, which proves that the bonding process does not damage the structure of the Au nanorods, as shown in FIG. 2.
Example 3
1) In an Ar atmosphere glove box, a semi-copper net with the diameter of 3mm is adopted as a substrate on one side, the upper half part of the semi-copper net is used for attracting the hollow carbon nano-tubes by static electricity, and the lower half part is dipped in an adhesive; and (3) adhering an AFM (atomic force microscope) probe on the other side substrate by using Ag, assembling and installing the AFM probe into a transmission electron microscope sample rod, and then installing the transmission electron microscope sample rod into the transmission electron microscope.
2) In transmission electron microscope, a small amount of adhesive is dipped by AFM tip and contacted with one end of hollow carbon nanotube with intensity of 15e/nm2s electron beam irradiation, adhesive solidification, AFM tip adhering single hollow carbon nanotube, contacting the other end of the hollow carbon nanotube with the adhesive in the lower half of the semi-copper mesh substrate with strength of 15e/nm2s electron beam irradiation, the adhesive is solidified.
3) The substrate was withdrawn and the bond strength was measured to be > 1.5GPa, as shown in FIG. 3.
Example 4
1) Welding a Cu nanorod on an AFM probe by FIB, adhering the AFM probe to a substrate on one side, using a Cu rod with the thickness of 0.3mm as a substrate on the other side, dipping a small amount of adhesive on the copper rod substrate, assembling and loading the copper rod substrate into a transmission electron microscope sample rod according to the figure 1, and then loading the transmission electron microscope sample rod into the transmission electron microscope.
2) At an electron beam intensity of 2e/nm2s, moving the copper rod substrate to make the adhesive and the Cu nano rod contact, wherein the adhesive is liquid.
3) The electron beam intensity was adjusted to 15e/nm2And s, moving the electron beam to irradiate the contact position of the adhesive and the nanowire, so that the adhesive can be rapidly solidified.
4) The substrate was withdrawn and the bond strength was measured to be > 610Mpa, as shown in figure 4.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.
Claims (8)
1. A method for bonding nano materials in an in-situ electron microscope is characterized in that in the in-situ electron microscope, the dosage of electron beams is 15e/nm2s, the adhesive is solidified to realize the bonding of the nano material; the adhesive is EMIMBr-AlCl3An ionic liquid.
2. The method for bonding the nano-materials in the in-situ electron microscope as claimed in claim 1, wherein the electron beam dose is 0-2 e/nm2s, contacting the nano material with adhesive, and adjusting the electron beam dose to 15e/nm2And s, moving the electron beam to irradiate the contact position of the nano material and the adhesive.
3. The method for bonding the nano-materials in the in-situ electron microscope according to claim 1, wherein the preparation method of the adhesive is as follows: mixing AlCl3Mixing with EMIMBr two solid powders, and stirring with magnetic stirrer.
4. The method of claim 3The method for bonding the nano material in the in-situ electron microscope is characterized in that the AlCl is3Molar ratio to EMIMBr 1.3: 1.
5. The method for bonding the nano-materials in the in-situ electron microscope according to claim 3, wherein the time of magnetic stirring is 4 h.
6. The method for bonding the nano-materials in the in-situ electron microscope according to any one of claims 3 to 5, wherein the adhesive is prepared in an argon atmosphere and can be contacted with air when being transferred into the in-situ electron microscope.
7. The method for bonding nanomaterials in-situ electron microscopy as claimed in claim 6, wherein the time for the adhesive to contact air when transferred into the in-situ electron microscopy is within 20 s.
8. The method for bonding nanomaterials in an in-situ electron microscope according to claim 1, wherein the in-situ electron microscope is an in-situ transmission electron microscope or an in-situ scanning electron microscope.
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