CN106769287B - A method of realizing high efficiency liquid-packing - Google Patents
A method of realizing high efficiency liquid-packing Download PDFInfo
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- CN106769287B CN106769287B CN201611079512.7A CN201611079512A CN106769287B CN 106769287 B CN106769287 B CN 106769287B CN 201611079512 A CN201611079512 A CN 201611079512A CN 106769287 B CN106769287 B CN 106769287B
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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
- G01N1/2806—Means for preparing replicas of specimens, e.g. for microscopal analysis
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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
- G01N1/2853—Shadowing samples
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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
- G01N1/36—Embedding or analogous mounting of samples
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/02—Details
- H01J37/20—Means for supporting or positioning the objects or the material; Means for adjusting diaphragms or lenses associated with the support
Abstract
The invention discloses a kind of methods for realizing high efficiency liquid-packing using graphene monocrystalline support membrane support grid.This method comprises: after the graphene that two panels is grown in respectively in different growth substrates is transferred on transmitting substrates by growth substrate, after liquid to be packaged to the wherein surface of piece of graphite alkene is added dropwise, another piece of graphite alkene is covered on it, encapsulation is completed, is obtained largely for the vacuole of in-situ characterization under transmission electron microscope.This method simple process; it is repeatable high; it is repeatable high; controllability is strong; it is compatible strong; the thousands of liquid cells by graphene packaging protection can be prepared on the sample of several mm sizes in a short time, for in-situ characterization under transmission electron microscope, substantially increase the possibility from atomic scale research reaction mechanism.
Description
Technical field
The invention belongs to semiconductor fields, are related to a kind of utilization graphene monocrystalline support membrane support grid realization high efficiency liquid envelope
The method of dress.
Background technique
Graphene be one kind by carbon atom through sp2The two dimensional crystal material of single layer or few layer that hydridization is formed, has excellent
Electricity, optics and mechanical property.Meanwhile efficiently and the chemical vapor deposition method of relatively low cost be high-quality graphene
Prepared by the batch of film and application provides guarantee.Except normal for transparent conductive film, photodetector, biosensor etc.
Outside rule field, graphene equally has very big potentiality in transmission electron microscope representational field.The conductivity and thermal conductivity of superelevation can have
Effect reduces the loss of electron irradiation, and the regular texture of monoatomic layer hardly introduces additional interference and back end to sample characterization
Signal is easy to deduct, and high mechanical strength and flexibility ensure that graphene can payload sample.Graphene has fine simultaneously
Sealing performance, perfect graphene lattice only allows proton to pass through.And π-π is formed between the bilayer graphene of clean surface
Stacking effect provides stronger Van der Waals force, but also sample is encapsulated into possibility.Wherein, solution is inside graphene
Encapsulation can be used for liquid reactive in-situ characterization and tracking under transmission electron microscope, for from atomic scale resolving reaction mistake
Journey provides possibility.
In the early time, liquid reactive in-situ characterization depends on the silicon nitride material of traditional silicon technology preparation to make more under transmission electron microscope
For packaging film, due to silicon nitride limited strength, film thickness needed for realization self-supporting especially loads vacuole is often approached
Hundred nanometers, greatly reduce the resolution ratio of imaging.In addition, also having been reported that the original position reacted dependent on open liquid cell
Characterization, but sample is mostly the ionic liquid of low saturated vapour pressure, greatly limits the reaction system type that can be characterized.Utilize stone
Black alkene thin-film package liquid also has a small amount of report in recent years, but is limited by graphene quality and packaging technology, the liquid that can be encapsulated
Body limited types, vacuole size and density are also relatively low, greatly reduce the efficiency and repeatability of fluid-tight.Therefore, how to develop
The in-situ characterization that a kind of high quality, high efficiency encapsulation different type liquid-phase reaction system carry out under transmission electron microscope becomes especially to weigh
It wants and extremely challenging.
Summary of the invention
The object of the present invention is to provide a kind of sides that high efficiency liquid-packing is realized using graphene monocrystalline support membrane support grid
Method.
Method provided by the invention using graphene encapsulation liquid, includes the following steps:
After the graphene that two panels is grown in respectively in different growth substrates is transferred on transmitting substrates by growth substrate,
After liquid to be packaged to the wherein surface of piece of graphite alkene is added dropwise, another piece of graphite alkene is covered on it, completes encapsulation.
In the above method, growing method concretely anneals copper foil substrate at 1020 DEG C under 1000sccm Ar atmosphere
1-2h, after use the H of 100sccm instead25-10min is restored, finally 0.5-3h is grown with 200:1 hydrogen, sample is detached with magnet
High-temperature region fast cooling out.
The graphene is graphene monocrystalline or graphene large single crystal；
The class of liquids multiplicity to be packaged, not by its evaporation rate, the limit of molecular weight, density, hydrophily, molten boiling point etc.
System.As the liquid to be packaged can be nano-particle solution, salting liquid, organic solvent, inorganic solvent or contain biological sample
Culture solution；Wherein, the butyrolactone solution of the nano-particle solution concretely aqueous solution or perovskite of gold nano；It is described
Salting liquid concretely potassium iodide base lead ammonium (CH3NH3PbI3) butyrolactone solution or ammonium persulfate aqueous solution；It is described organic
Solvent concretely ethyl alcohol, methanol etc.；The inorganic solvent concretely water；It is raw in the culture solution containing biological sample
Object sample concretely but is not limited to bacterium, virus or iron oxide red albumen etc.；
The transmitting substrates are the porous carbon membranes micro-grid with metal grill；The micro-grid concretely load it is regular or
The commercial micro-grid of irregular porous carbon membranes.Common-use size includes outer diameter 3mm, and inner mesh number includes 100/200/300/400
Equal different sizes, the metal grill is specially Au, Mo or Ni grid；Be covered with one layer of porous carbon membranes on metal grill, aperture from
0.6 μm to 10 μm is differed, and pitch of holes also μm is differed from 1 μm to 5.Wherein the support grid of hole regular distribution is German import
Quantifoil, irregular distribution are domestic Grid (purchased from middle mirror tech and emerging Berry).
In the covering step, the spacing between two panels graphene is less than 10 microns.
The covering is specially after contacting the another piece of graphite alkene with the graphene that liquid to be packaged has been added dropwise, to make two
The carbon film and metal ribs at the transmitting substrates edge of piece graphene only have very thin water at same focal plane between two layers of graphene
Layer and without air exist, the spacing between two panels graphene is less than 10 microns at this time.
The method also includes following steps: after the covering step, extra liquid to be packaged being inhaled with filter paper
Remove, stand to it is remaining it is to be packaged evaporate after, it is dry after embathing；
The purpose that extra liquid to be packaged is absorbed with filter paper is that excessive solute can remain in after solvent volatilization in order to prevent
Two panels graphene outer surface, influences subsequent characterizations；
The purpose of standing is slow drying sample, so that residual liquid is gradually volatilized completely, increases the adherency between graphene layer
Property and model ylid bloom action power；The time of standing is 5-20min；
Described to embathe in step, dip lotion is the solvent that can dissolve the liquid to be packaged, is chosen in particular from ethyl alcohol, isopropyl
At least one of alcohol and water；Specific type can be selected according to reaction system.It is required that it, which can dissolve fluid-tight system, remains in liquid
Steep external excessive volatile-resistant substance, and secondary interference will not be caused to the reaction in vacuole, at the same will not to graphene with
Support grid causes additional breakage or introduces other pollutants.
The time embathed is 30-300s or 180s；Temperature is room temperature or 10-30 DEG C or 25 DEG C；
In the drying steps, dry method concretely by sample drying it is preposition be placed in easy volatile solvent it is former molten
Agent opens air volume in unlimited system Quick-air-drying in super-clean bench；It is quickly dried up with nitrogen gun；It is dry with supercritical drying instrument
Graphene support grid etc. before encapsulating liquid.
The method also includes following steps: after a dropping step, before covering step, by two panels graphene benefit
It is aligned with micro-mechanical arm.
Specifically, the alignment includes the following steps:
1) by it is a piece of load have graphene transmitting substrates be face-up placed in clean substrate (even if also transmitting substrates with
Clean substrate contact), it is placed in three-dimensional manipulating platform center position；
2) loading another has the transmitting substrates face down the one of graphene (have down) of graphene to be fixed on
Microoperation arm top, is located at the surface of graphene in the step 1)；
In the step 1), mica sheet, quartz plate or silicon wafer that the cleaning substrate is concretely newly removed；In transmission base
The purpose of the beneath clean substrate of side's placement is the cleanliness for guarantee system；The area of the cleaning substrate is flat not less than 0.25
Square centimetre, such as can be 1 square centimeter.
In the step 2) fixing step, fixed method is vertical capillary after drawing fixed liquid with capillary syring
After suction pipe makes its bottom have liquid outflow, another is loaded the drop contact and then quilt of the transmitting substrates and outflow that have graphene
Stablize and draw on the capillary syring top, then is fixed on microoperation arm top after the capillary is rotated proper angle
End, completes the fixation；
The fixation is difficult volatilization with liquid and will not be to the liquid that reaction system interferes, concretely deionized water
Or butyrolactone；
The dosage of the fixed liquid is not more than 1 milliliter.
It is while to realize the position of two panels support grid in order to avoid system introduces additional contamination with the purpose that capillary syring is drawn
Alignment.
The micromechanics motion arm need to can be realized following function: controllable moving distance is not less than in the x direction and the y direction
500 microns, stepping accuracy is not less than for 1 micron, running accuracy is 1 degree and axial 360 ° of rotatable controllable selections.Using micro-
The purpose of mechanically actuated arm is efficiently to carry out fluid-tight using the hanging region of transmission support grid, avoids the friendship of hanging region and metal ribs
It is folded, while realizing that the position of two panels support grid is controllable.
The method of the transfer includes: to use after the graphene being grown in growth substrate development with object penetrating substrate
After low surface tension organic solvent carries out hot padding, etching removes the growth substrate, then replaces the etching with displacement liquid and walk
Rapid etching liquid used；
The displacement liquid displacement step includes the following steps: first with water, then with by low surface tension organic solvent and water
The mixed solution of composition is replaced.
The low surface tension organic solvent concretely but one of is not limited to isopropanol, ethyl alcohol and propyl alcohol or it is more
First mixed solution；
The hot padding be specially after the organic solvent that the low surface tension is added dropwise in the surface of the two-dimensional material, with
The object penetrating substrate fitting, is again heated to 50-100 DEG C (concretely 60 DEG C), keeps 5-10min；
The dosage of the low surface tension organic solvent is every transmission support grid 5-10 μ L；The every transmission support grid is equal
The disk for being 3mm for diameter；
The purity of the low surface tension organic solvent is chromatographic grade purity.
In the mixed solution being made of low surface tension organic solvent and water, the low surface tension organic solvent and
The volume ratio of water is 0.1-100:1；
It is described to be carried out in displacement step with the mixed solution being made of low surface tension organic solvent and water, the low surface
In the volume ratio of tension organic solvent and water, volume ratio of the low surface tension organic solvent in the displacement liquid is successively passed
Increase；
The mixed solution of the low surface tension organic solvent and the water composition of every kind of volume ratio is served only for once replacing；
The total displacement number replaced with the mixed solution being made of low surface tension organic solvent and water is many
In 5 times, specially 7 times.
Specifically, in the displacement step, the body of isopropyl alcohol and water in the mixed solution used being made of isopropyl alcohol and water
Product than successively replacing in the following order: 1:1,2:1,4:1,10:1,20:1,40:1,100:1；
The volume of displacement liquid used is no less than 300mL every time, concretely 300-600mL, 400ml, 500mL or
600mL；
The rate replaced every time is 1-10ml/min, concretely 3ml/min.
It is replaced in the way of aforementioned present invention offer, the surface tension of displacement liquid and contact angle can be made gradually to subtract
It is small, avoid the rupture that graphene large single crystal support membrane is be easy to cause when being directly rinsed with water after the completion of etching or complete
Spend too low major defect.
The growth substrate is copper foil, nickel foil or corronil；
In the etch step, the etching liquid is the solution that can etch the growth substrate, and specially concentration is little
In the persulfate of 0.1M or the aqueous solution of iron chloride；The persulfate concretely ammonium persulfate or sodium peroxydisulfate；
The temperature of etching is room temperature；
The time of etching is 0.5-10h.
Due to that can be oxidized by the region that graphene is protected, and the position protected by graphene is quite different, therefore can make
Graphene farmland area displays.The development principle that Yu Shuizhong is dried up after impregnating is similar.The purpose of the development is to realize stone
The fixed point transfer of black alkene large single crystal (size is greater than 3mm), avoids introducing crystal boundary and defect, brings extra interference.The baking
In step, temperature is 100-300 DEG C or 150 DEG C；Time is 1-10min, concretely 3-5min；
In be set forth in water in soaking step, water temperature is 0-100 DEG C；Time is 10-200min；
The drying is specially to be dried up with nitrogen or argon gas.
The method also includes following steps: before the hot padding step, removal is grown in the growth substrate
The graphene of another side；The method of the removal is bombardment removal or washes after etching；The purpose for removing the face graphene is anti-
Only the graphene fragment in the face is adhered to another side after copper foil etching, introduces additional pollution.
Specifically, the bombardment removal is that plasma bombardment removes；
Throughput is 5-30sccm, concretely 15sccm；Power is 40-500W, concretely 90W；Time is 1-
10min, concretely 3min.
In the etch step, etching liquid is the aqueous solution of persulfate of the concentration not less than 1M or iron chloride；Etching
Time is less than 10min.
Since no glue shifts, the graphene of one side to be transferred need to be protected in etching, such as with polishing copper foil or aluminium foil
Encapsulation etc..
The method also includes: the drying after the displacement step；In the drying steps, dry temperature specifically may be used
It is 10-70 DEG C, more specifically can is 60-70 DEG C, so that organic solvent such as isopropanol quickly volatilizees with drying sample.
The drying means is concretely placed in former solvent for sample drying is preposition in easy volatile solvent, in super-clean bench
Air volume is opened to air-dry in unlimited system；It is dried up with nitrogen gun；With supercritical drying instrument auxiliary drying etc..
In addition, the product for the graphene encapsulation liquid being prepared according to the method described above, also belongs to protection model of the invention
It encloses.
The big list of graphene of high integrity degree, high-cleanness, high and high intensity that the present invention is shifted by effective use without glue
Brilliant film realizes the encapsulation of the controllable high efficiency reaction solution in position, and has prepared the large area, high density, Gao Ke of system
The encapsulation of repeatability, so as to obtain largely realizing related liquid phase reactor for the vacuole of in-situ characterization under transmission electron microscope
In-situ characterization under transmission electron microscope.For the continuous hanging area of the maximum of its hanging graphene used up to 3 microns, maximal density can
Up to 50-70/μm2.In the vacuole of graphene encapsulation, the resolution ratio of the high resolution TEM imaging of nano particle still may be used
Reach 0.2nm (imaging level that higher resolution is limited to transmission electron microscope itself).In addition, this method has very big compatibility
Property, the graphene transmission support grid of selection can be single layer or few layer graphene sample, it can be achieved that having to different liquid-phase reaction systems
Effect encapsulation, while can be used for sample in scanning electron microscope or the in-situ characterization of spectroscopy instrument, it can also realize to biological sample, it is such as thin
Effective encapsulation of bacterium, virus, iron oxide red albumen etc..
Detailed description of the invention
It is high-quality that Fig. 1 is that the photo and shifting by no glue of the grade graphene large single crystal isolated after development has successfully loaded
Measure the photo of the transmission support grid of graphene.
Fig. 2 is to transmit in support grid in each square net the typical scan electron microscopic picture of the hanging graphene of high quality and with side
Shape grid is integrity degree statistics and nine adjacent circular holes regions of the basic unit to graphene hanging in full wafer support grid
Enlarged drawing.
Fig. 3 is that the graphene film of different farmland areas size is supported on the vacantly transmission support grid quantifoil having a size of 2 μm
On average integrity degree comparison, farmland area is smaller, and integrity degree is lower.
Fig. 4 is transferred to the high-resolution data of the hanging graphene in transmission support grid, clean surface, without obvious dirty for no glue
Contaminate object residual.
Fig. 5 is for accurately realizing that two panels load has the microoperation arm of the metal ribs close alignment of the transmission support grid of graphene
Pictorial diagram, wherein right figure be left figure red area enlarged drawing.
Fig. 6 is the experimental principle figure of the controllable encapsulation liquid in graphene position.
Fig. 7 be the optical reflection and transmission mode in situ obtained after the controllable encapsulation liquid of graphene position picture and
The picture of transmission electron microscope.
Fig. 8 is the typical scan electron microscopic picture of control group.
Fig. 9 is the transmission electron microscope picture for the different solutions that graphene encapsulates.
Figure 10 is that graphene encapsulates the typical scanning electron microscopic picture obtained after different solutions.
Figure 11 is the histogram that graphene encapsulates the vacuole size and distribution density that obtain after different solutions, is divided into liquid
Only there are two class of carbon film Auxiliary support (red) in graphene (blue) and vacuole at least side for bubble two sides.The illustration of left figure is phase
The typical transmission electron microscopic picture of the vacuole for the larger size answered.
Figure 12 is the typical density statistics after the aqueous solution for the gold nano grain that graphene encapsulates larger size.
Figure 13 is the obtained allusion quotation of reunion growth process in-situ observation to the gold nano grain being encapsulated in inside graphene
The transmission electron microscope data of type.
Figure 14, which gradually reunites with merging for the gold nano grain of two isolated about 2-4 nanosizeds, forms five nano-scales
During nano particle, two intercrystallines away from development law.
Figure 15 is that the vacuole of graphene encapsulation keeps stable in situ TEM picture for a long time under electron beam irradiation.
Figure 16 is that the vacuole of graphene encapsulation is being placed the typical transmission electron microscopic picture for still keeping stable after three weeks and swept
Retouch transmission electron microscope picture.
Figure 17 is the allusion quotation that the ammonium persulfate aqueous solution of graphene encapsulation gradually generates bubble and is discharged under electron beam irradiation
Type transmission electron microscope picture.
Figure 18 be graphene encapsulation organic inorganic hybridization perovskite --- the butyrolactone solution of potassium iodide base lead ammonium obtains
Vacuole transmission electron microscope picture and high-resolution lattice phase picture.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
All raw materials can be bought by commercial sources in the present invention, and all reagents are chromatographic grade, wherein aurosol, calcium
Titanium ore, isopropanol, ammonium persulfate, sodium peroxydisulfate, iron chloride and hydrochloric acid etc. are purchased from Chinese medicines group.Graphene growth substrate (copper
Foil, nickel foil, corronil etc.) it is purchased from Alpha Ai Sha.Hanging graphene-based bottom is purchased from middle mirror tech and emerging Berry or by it
It is bought on behalf from foreign countries (German quantifoil company).
Embodiment 1, high-quality graphene transmission support grid high efficiency encapsulate gold nano grain aqueous solution
1) the isolated large single crystal graphene sample that growth finishes is taken out, 3-5min is toasted in 150 DEG C of thermal station, keeps graphene aobvious
Shadow, position visualization.
Graphene on copper foil without the one side of transfer is realized into bombardment removal by the processing of air plasma cleaning machine,
Throughput is 15sccm, power 90W, time 3min.
A face graphene to be transferred upward, downward by object penetrating substrate front surface, is placed in graphene sample to be transferred
Surface, due to transmitting substrates target be diameter 3mm disk, therefore be added dropwise 5-10 microlitres of chromatographic pure isopropanol, make isopropanol
Naturally it volatilizees, is again heated to 60 DEG C of holding 10min, guarantee the close contact of substrate and graphene；
The copper foil with graphene large single crystal for being stained with object penetrating substrate is placed in the ammonium persulfate that concentration is 0.1M
Aqueous solution in, at room temperature etch copper foil substrate 4h；
Water is first used, then the remaining etching of etch step is replaced by peristaltic pump with the mixed solution being made of isopropyl alcohol and water
Liquid, the replacing velocity of peristaltic pump are 3ml/min；In displacement step, in the mixed solution that be made of isopropyl alcohol and water isopropanol and
The volume ratio of water is as shown in table 1, successively replaces according to volume ratio shown in table 1 is ascending, and the volume of displacement liquid used is equal every time
For 300mL；The displacement liquid of every kind of volume ratio is only used once；When being replaced according to sequence as above, the surface of corresponding displacement liquid
The numerical value of tension (unit mN) and contact angle is as shown in table 1.
Table 1, the displacement liquid of different isopropanols and water volume ratio and its corresponding surface tension and contact angle
Isopropanol is slowly vented after being replaced, and heating systems to 60 DEG C by sample drying, monocrystalline stone can be completed
Black alkene is by the transfer on growth substrate copper foil to object penetrating substrate.
2) a piece of transmission support grid for having high-quality graphene that loads face-up is placed in and light associated with microoperation arm
It learns on platform, is placed in three-dimensional manipulating platform center position.
3) using after capillary syring top " absorption " fixed liquid deionized water, vertical capillary syring makes its bottom have water
After outflow, another is loaded the water drop contact of the transmitting substrates and outflow that have graphene and then drawn by stablizing in capillary syring
Top, then it is fixed on microoperation arm top after capillary is rotated proper angle, face down is being placed on first support grid just
Top gradually adjusts the position of lower section two panels support grid metal ribs, rotation and X including the direction R, Y-direction using microoperation platform
Translation, finally realize two panels support grid position correction.
4) the water-soluble drop of about 1-20 microlitres gold nano grain is drawn in first support grid with micro syringe, and by the
Two support grids are slowly displaced downwardly to be contacted with first, and the carbon film and metal ribs for making the transmitting substrates edge of two panels graphene are same
There was only very thin water layer when focal plane between two layers of graphene and exist without air, the spacing between two panels graphene is less than at this time
10 microns.
5) 5-20min is stood after again absorbing the aqueous solution of extra gold nano grain with filter paper to remaining gold nano
After the aqueous solution volatilization of grain, the good sample with ethanol of fluid-tight is embathed into 180s in 25 DEG C and carries out embathing re-dry, completes encapsulation.It will
Vacuum saves after sample dries in the shade, and remains subsequent transmission electron microscope characterization.
Wherein, drying means is concretely placed in former solvent for sample drying is preposition in easy volatile solvent, in super-clean bench
Air volume is inside opened in unlimited system Quick-air-drying；It is quickly dried up with nitrogen gun；Before the dry encapsulation liquid of supercritical drying instrument
Graphene support grid etc..
It is high-quality that Fig. 1 is that the photo and shifting by no glue of the grade graphene large single crystal isolated after development has successfully loaded
Measure the photo of the transmission support grid of graphene.
Fig. 2 is to transmit in support grid in each square net the typical scan electron microscopic picture of the hanging graphene of high quality and with side
Shape grid is integrity degree statistics and nine adjacent circular holes regions of the basic unit to graphene hanging in full wafer support grid
Enlarged drawing.
Fig. 3 is that the graphene film of different farmland areas size is supported on the vacantly transmission support grid quantifoil having a size of 2 μm
On average integrity degree comparison, farmland area is smaller, and integrity degree is lower.
Fig. 4 is transferred to the high-resolution data of the hanging graphene in transmission support grid, clean surface, without obvious dirty for no glue
Contaminate object residual.
Fig. 5 is for accurately realizing that two panels load has the microoperation arm of the metal ribs close alignment of the transmission support grid of graphene
Pictorial diagram, wherein right figure be left figure red area enlarged drawing.
Fig. 6 is the experimental principle figure of the controllable encapsulation liquid in graphene position, and metal ribs keep height to be aligned when encapsulation, envelope
Sample bilayer graphene after dress directly accompanies liquid, and thickness nanometer is differed from several nanometers to hundred；The region stone of unencapsulated liquid
Black alkene level still has stronger Van der Waals force, ensure that the long-time stability of vacuole.
Fig. 7 shows that the metal ribs for pinpointing two graphene large single crystal support membrane support grids after fluid-tight can realize complete stacking,
It ensure that the maximization of fluid-tight sample area.As can be seen that since the absorptance of single-layer graphene is only 2.3%, graphene liquid
Region still light-permeable is sealed, also can pass through electronics.Carbon film region is more to the absorption of light, but it is lower still to can be used under transmission sample
The characterization of times pattern.
Fig. 9 is the transmission electron microscope picture for the different solutions that graphene encapsulates, ethyl alcohol, water, various sizes of gold nano
The aqueous solution and colloidal sol (<5nm, 5-10nm,>10nm) of particle, ammonium persulfate aqueous solution, butyrolactone solution of perovskite etc..It can
With discovery, the size of vacuole differs from several nanometers to several microns, and the number in every square micron is differed from one to tens.This
Outside, solution encapsulates to obtain bigger vacuole when having carbon film Auxiliary support on the outside of graphene.Part vacuole periphery can also be seen simultaneously
Apparent liquid bridge is observed, the circulation etc. for liquid.
The vacuole that Figure 10 shows that graphene large single crystal support membrane encapsulates is generally existing on sample, and distribution density compared with
It is high.But the resolution ratio for being limited to scanning electron microscope itself, the vacuole less than ten nanometers are more difficult discernable.
Figure 11 shows that the vacuole size obtained after graphene encapsulation different solutions is differed from several nanometers to several microns, every square
Number in micron is differed from one to tens.In addition, solution encapsulation is more easy to get when having carbon film Auxiliary support on the outside of graphene
To bigger vacuole, show that the technology can be used for biological sample such as virus, the characterization of cell etc..
Figure 12 is the typical density statistics after the aqueous solution for the gold nano grain that graphene encapsulates larger size, the region liquid
The density of bubble is up to every square micron tens, and size is from several nanometers to several hundred nanometers etc..Simultaneously as content liquid mistake
More, the later period is not cleaned, has remained more gold nano grain on the outside of graphene.Figure 12 shows by two hanging region graphite
The characterization of amplification step by step after alkene encapsulation, the vacuole size encapsulated are differed, are distributed very intensive.But for the sample due to first
Phase absorption content liquid is excessive, and the later period is not cleaned, has remained more gold nano grain on the outside of graphene.
After Figure 13 shows graphene fluid-tight reaction solution, remain to obtain high resolution under F30 transmission electron microscope to receive up to 0.2
The lattice image of (111) crystal face of the gold of rice, it is seen then that the spacing of lattice of golden (111) crystal face is high-visible.The vacuole can be born greatly
In the electron irradiation of the high dose of 3min, while electron beam can drive the movement of nanoparticle, reunite and grow.
Figure 14 shows that the gold nano grain of two isolated about 2-4 nanosizeds gradually reunites with merging and forms five nano-scales
Nano particle during, two intercrystallines away from development law can pass through the technology trace trap.
Figure 15 shows that the vacuole of graphene large single crystal support membrane encapsulation can keep for a long time stable under electron beam irradiation.
Figure 16 shows that the vacuole of graphene large single crystal support membrane encapsulation is placing after three weeks still holding stabilization, and edge is received
The deposition of rice grain, it may be possible to due to caused by the slow growth of gold nano grain.
Embodiment 2: the aqueous solution of high-quality graphene large single crystal support membrane support grid high efficiency encapsulation ammonium persulfate
The graphene large single crystal film sample that growth finishes is transferred to transmission by growth substrate according to 1 step 1) of embodiment
Electronic Speculum substrate；Step 2) -5) it is same as Example 1, only by the water-soluble of 1-20 microlitres of gold nano grain used in 1 step 2) of embodiment
Liquid replaces with the aqueous solution of 5-8 microlitres of ammonium persulfate；1 step 5) of embodiment is embathed into ethyl alcohol used and replaces with isopropanol.
Fig. 7 shows that the metal ribs for pinpointing two graphene large single crystal support membrane support grids after fluid-tight can realize complete stacking,
It ensure that the maximization of fluid-tight sample area.As can be seen that since the absorptance of single-layer graphene is only 2.3%, graphene liquid
Region still light-permeable is sealed, also can pass through electronics.Carbon film region is more to the absorption of light, but it is lower still to can be used under transmission sample
The characterization of times pattern.
Fig. 9 shows that the size for the vacuole that graphene large single crystal support membrane encapsulation liquid can be realized efficiently, and be obtained is received from several
Rice is differed to several microns, and the number in every square micron is differed from one to tens.In addition, having carbon film auxiliary on the outside of graphene
Solution encapsulates to obtain bigger vacuole when support.Part vacuole periphery can also be observed that apparent liquid bridge simultaneously, be used for liquid
Circulation etc..
The vacuole that Figure 10 shows that graphene large single crystal support membrane encapsulates is generally existing on sample, and distribution density compared with
It is high.But the resolution ratio for being limited to scanning electron microscope itself, the vacuole less than ten nanometers are more difficult discernable.
Figure 11 shows after graphene large single crystal support membrane encapsulation different solutions obtained vacuole size from several nanometers to several micro-
Rice differs, and the number in every square micron is differed from one to tens.In addition, molten when having carbon film Auxiliary support on the outside of graphene
Fluid-tight dress is easier to obtain bigger vacuole, shows that the technology can be used for biological sample such as virus, the characterization of cell etc..
Figure 17 shows that the ammonium persulfate aqueous solution of graphene large single crystal support membrane encapsulation gradually generates under electron beam irradiation
Bubble is simultaneously gradually migrated to liquid edge, and the generation of bubble is probably derived from splitting for the decomposition of persulfate under electron irradiation or water
Solution.
Embodiment 3: high-quality graphene large single crystal support membrane support grid high efficiency encapsulates potassium iodide base lead ammonium
(CH3NH3PbI3) butyrolactone solution
The graphene large single crystal film sample that growth finishes is transferred to transmission by growth substrate according to 1 step 1) of embodiment
Substrate (namely commercial transmission electron microscopy support grid)；Step 2) -5) it is same as Example 1, it is only that 1 step 2) of embodiment is used
The aqueous solution of 1-20 microlitres of gold nano grain replaces with the butyrolactone solution of potassium iodide base lead ammonium；1 step 5) of embodiment is embathed
Ethyl alcohol used replaces with isopropanol.
Fig. 7 shows that the metal ribs for pinpointing two graphene large single crystal support membrane support grids after fluid-tight can realize complete stacking,
It ensure that the maximization of fluid-tight sample area.As can be seen that since the absorptance of single-layer graphene is only 2.3%, graphene liquid
Region still light-permeable is sealed, also can pass through electronics.Carbon film region is more to the absorption of light, but it is lower still to can be used under transmission sample
The characterization of times pattern.
Fig. 9 shows the size of vacuole that graphene encapsulation liquid can be realized efficiently, and be obtained from several nanometers to several microns not
It is differed from one to tens Deng, number in every square micron.In addition, solution seals when having carbon film Auxiliary support on the outside of graphene
Dress obtains bigger vacuole.Part vacuole periphery can also be observed that apparent liquid bridge simultaneously, the circulation etc. for liquid.
The vacuole that Figure 10 shows that graphene large single crystal support membrane encapsulates is generally existing on sample, and distribution density compared with
It is high.But the resolution ratio for being limited to scanning electron microscope itself, the vacuole less than ten nanometers are more difficult discernable.
Figure 11 shows after graphene large single crystal support membrane encapsulation different solutions obtained vacuole size from several nanometers to several micro-
Rice differs, and the number in every square micron is differed from one to tens.In addition, molten when having carbon film Auxiliary support on the outside of graphene
Fluid-tight dress is easier to obtain bigger vacuole, shows that the technology can be used for biological sample such as virus, the characterization of cell etc..
Figure 18 shows the organic inorganic hybridization perovskite of graphene large single crystal support membrane encapsulation --- potassium iodide base lead ammonium
The transmission electron microscope picture for the vacuole that butyrolactone solution obtains and the picture of high-resolution lattice phase.
Comparative example 1: random stacked graphene large single crystal support membrane support grid encapsulates gold nano grain solution
The graphene large single crystal film sample that growth finishes is taken out, is slightly toasted in 170 DEG C of thermal station, copper foil does not change colour, says
Bright graphene has covered with, and characterization confirmation is single layer region under scanning electron microscope.The graphene sample of one side to be transferred is then protected,
3min is handled by air plasma cleaning machine to bombard the sample of removal another side.
Using quantifoil micro-grid as Auxiliary support film, the volatile ethyl alcohol of a drop is added dropwise will using capillary force
The porous carbon membranes tight adhesion of graphene and support grid surface to be transferred.
It will be stained with the graphene on the copper foil of transmitting substrates, is placed in the ammonium persulfate etching liquid of 0.1M, carves at room temperature
Copper foil substrate 4h is lost, after being etched to copper foil, sample is cleaned, is then quickly dried up with nitrogen gun.
The water-soluble drop of about 5-8 microlitres low concentration ammonium persulfate is drawn in first face-up load with micro syringe
On the net, and by second support grid face down with first it contacts.Excessive response solution is drawn with filter paper, stands 5-20 afterwards
min。
The good sample of fluid-tight is embathed with isopropanol, vacuum saves after then sample dries in the shade, and remains subsequent transmission
Electronic Speculum characterization.
Fig. 8 (a) shows that the random stacking of metal ribs will be greatly reduced a possibility that hanging region of two panels exposes, to drop
The region area for the graphene fluid-tight reaction solution that can be characterized under low transmission Electronic Speculum.This further illustrates that this packaging method has more
High packaging efficiency, controllability and repeatability.(c) integrity degree of carbon film after the removal of wherein side metal ribs is substantially reduced,
Thereby reduce the intensity of sample and the usable area of totality.
Comparative example 2: gold nano grain solution is encapsulated using the graphene transmission support grid of low integrity degree
The polycrystalline graphite alkene film sample that growth finishes is taken out, is slightly toasted in 170 DEG C of thermal station, copper foil does not change colour, explanation
Graphene has covered with, and characterization confirmation is single layer region under scanning electron microscope.The graphene sample of one side to be transferred is then protected, is led to
Air plasma cleaning machine processing 3min is crossed to bombard the sample of removal another side.
Using transmission electron microscope substrate as Auxiliary support film, a drop water is added dropwise and utilizes capillary force by graphite to be transferred
The porous carbon membranes on alkene and support grid surface adhere to (adhesion strength is weaker than the intensity using ethyl alcohol or isopropanol etc.).Transmission will have been adhered to
The copper foil with graphene of substrate, is placed in the ammonium persulfate etching liquid of 2M, copper foil substrate 20min is etched at room temperature, to copper
After foil etches, sample is cleaned, is then quickly dried up with nitrogen gun.
The a piece of transmission support grid for having high-quality graphene that loads face-up is placed in and optics associated with microoperation arm
On platform, and its position is relatively fixed.There is the saturating of high-quality graphene using capillary syring top " absorption " another load
It penetrates support grid and is fixed on motion arm top, face down is placed on the surface of first support grid, is gradually adjusted using microoperation platform
Two panels support grid position is finally realized in the position of whole lower section two panels support grid metal ribs, the translation of rotation and X, Y-direction including the direction R
The correction set.
The water-soluble drop of about 5-8 microlitres low concentration ammonium persulfate is drawn in first support grid with micro syringe, and will
Second support grid is slowly displaced downwardly to be contacted with first.Excessive response solution is drawn with filter paper, stands 5-20min afterwards.
The good sample of fluid-tight with isopropanol embathe and is placed in super-clean bench and quickly dries in the shade, then protects sample vacuum
It deposits, remains subsequent transmission electron microscope characterization.
Fig. 8 (b) shows that being transmitted support grid integrity degree by graphene early period is limited, even if the metal ribs of two panels support grid are
Alignment, the region of the available graphene Successful encapsulation vacuole finally obtained are also very limited.This further demonstrates high-quality
High integrity degree graphene is measured for finally obtaining the importance of the quantity of vacuole.
Claims (17)
1. a kind of method using graphene encapsulation liquid, includes the following steps:
After the graphene that two panels is grown in respectively in different growth substrates is transferred on transmitting substrates by growth substrate, it is added dropwise
After liquid to be packaged to the wherein surface of piece of graphite alkene, another piece of graphite alkene is covered on it, completes encapsulation；
The method of the transfer includes: after the graphene being grown in growth substrate develops, with the low table of object penetrating substrate
After face tension organic solvent carries out hot padding, etching removes the growth substrate, then replaces the etch step institute with displacement liquid
Use etching liquid；The displacement liquid displacement step includes the following steps: first with water, then with by low surface tension organic solvent and water
The mixed solution of composition is replaced.
2. according to the method described in claim 1, it is characterized by: the graphene is graphene monocrystalline；And/or
The liquid to be packaged is nano-particle solution, salting liquid, organic solvent, inorganic solvent or the culture containing biological sample
Liquid；And/or
The transmitting substrates are the porous carbon membranes micro-grid with metal grill；And/or
In the covering step, the spacing between two panels graphene is less than 10 microns.
3. according to the method described in claim 1, it is characterized by: the low surface tension organic solvent is selected from isopropanol, second
At least one of pure and mild propyl alcohol；And/or
The hot padding is after the low surface tension organic solvent is added dropwise in the surface of two-dimensional material, with the object penetrating base
Bottom fitting, is again heated to 50-70 DEG C of holding 5-10 min；And/or
The dosage of the low surface tension organic solvent is every two-dimensional material 5-10 μ L；The every two-dimensional material is
Diameter is the disk of 3mm；And/or
The purity of the low surface tension organic solvent is chromatographic grade purity；And/or
In the mixed solution being made of low surface tension organic solvent and water, the low surface tension organic solvent and water
Volume ratio is 0.1-100:1；And/or
It is described to be carried out in displacement step with the mixed solution being made of low surface tension organic solvent and water, the low surface tension
In the volume ratio of organic solvent and water, volume ratio of the low surface tension organic solvent in the displacement liquid is incremented by successively；
And/or
The mixed solution of the low surface tension organic solvent and the water composition of every kind of volume ratio is served only for once replacing；And/or
It is described to be no less than 5 with total displacement number that the mixed solution being made of low surface tension organic solvent and water is replaced
It is secondary.
4. according to the method described in claim 3, it is characterized by: described with being made of low surface tension organic solvent and water
Total displacement number that mixed solution is replaced is 7 times；
In the displacement step, the volume ratio of isopropyl alcohol and water is according to as follows in the mixed solution used being made of isopropyl alcohol and water
Sequence is successively replaced: 1:1,2:1,4:1,10:1,20:1,40:1,100:1；And/or
The volume of displacement liquid used is no less than 300mL every time；And/or
The rate replaced every time is 1-10ml/min.
5. according to the method described in claim 4, it is characterized by: the volume of displacement liquid used is 300-600mL every time；
And/or
The rate replaced every time is 3ml/min.
6. according to the method described in claim 1, the growth substrate is copper foil, nickel foil or corronil；
In the etch step, the etching liquid is the solution that can etch the growth substrate；
The temperature of etching is room temperature；
The time of etching is 0.5-10 h；
In the development step, developing method is after toasting the graphene being grown in growth substrate or impregnating in water
Drying；And/or in the baking procedure, temperature is 100-300 DEG C；Time is 1-10min；And/or it is impregnated in be set forth in water
In step, water temperature is 0-50 DEG C；Time is 10-200min；And/or
The method of the transfer further includes following steps: before the hot padding step, removal is grown in the growth substrate
The graphene of upper another side；The method of the removal is bombardment removal or washes after etching；
It is dry after the displacement step.
7. according to the method described in claim 6, it is characterized by: the etching liquid is the persulfate that concentration is not more than 0.1M
Or the aqueous solution of iron chloride；
In the baking procedure, temperature is 150 DEG C；Time is 3-5min.
8. according to the method described in claim 7, it is characterized by: the persulfate is ammonium persulfate or sodium peroxydisulfate.
9. according to the method described in claim 1, it is characterized by: the method also includes following steps: being walked in the covering
After rapid, extra liquid to be packaged is absorbed with filter paper, stand to it is remaining it is to be packaged evaporate after, it is dry after embathing；
And/or
In the standing step, the time of standing is 5-20 min；And/or
Described to embathe in step, dip lotion is the solvent that can dissolve the liquid to be packaged；The time embathed is 30-300 s；
Temperature is room temperature.
10. according to the method described in claim 9, dip lotion is selected from ethyl alcohol, isopropyl it is characterized by: described embathe in step
At least one of alcohol and water；The time embathed is 180s；Temperature is 10-30 DEG C.
11. according to the method described in claim 10, temperature is 25 DEG C it is characterized by: described embathe in step.
12. any method in -11 according to claim 1, it is characterised in that: the method also includes following steps:
After a dropping step, before covering step, two panels graphene is aligned using micro-mechanical arm.
13. according to the method for claim 12, it is characterised in that: the alignment includes the following steps:
1) there are the transmitting substrates of graphene to be face-up placed in clean substrate a piece of load, be placed in three-dimensional manipulating platform center
Position；
2) the transmitting substrates face down for having graphene is loaded by another and be fixed on microoperation arm top, be located at the step
It is rapid 1) in graphene surface.
14. according to the method for claim 13, it is characterised in that: in the step 2 fixing step, fixed method is
After drawing fixed liquid with capillary syring, after vertical capillary syring makes its bottom have liquid outflow, another load there is into stone
It the transmitting substrates of black alkene and the drop contact of outflow and then is drawn by stablizing on the capillary syring top, then by the capillary
It is fixed on microoperation arm top after rotation proper angle, completes the fixation；
The fixation is difficult volatilization with liquid and will not be to the liquid that reaction system interferes；And/or
The dosage of the fixed liquid is not more than 1 milliliter；And/or
The microoperation arm can be realized following function: controllable moving distance is not less than 500 microns, stepping in the x direction and the y direction
Precision is 1 degree and axial 360 ° of rotatable controllable selections not less than 1 micron, running accuracy.
15. according to the method for claim 14, it is characterised in that: the fixation is deionized water or butyrolactone with liquid.
16. the product by graphene encapsulation liquid that any the method for claim 1-15 obtains.
17. the product by graphene encapsulation liquid that any the method for claim 1-15 obtains liquid phase under transmission electron microscope is anti-
The application in in-situ characterization answered.
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