CN106769287A - A kind of method that utilization Graphene monocrystalline support membrane contained network realizes high efficiency liquid-packing - Google Patents
A kind of method that utilization Graphene monocrystalline support membrane contained network realizes high efficiency liquid-packing Download PDFInfo
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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
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- 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 method that utilization Graphene monocrystalline support membrane contained network realizes high efficiency liquid-packing.The method includes：After the Graphene that two panels is grown in different growth substrates respectively 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 thereon, encapsulation is completed, and is largely available for the vacuole of in-situ characterization under transmission electron microscope.The method process is simple; 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, the possibility that reaction mechanism is studied from atomic scale is substantially increased.
Description
Technical field
The invention belongs to semiconductor applications, it is related to one kind to realize that high efficiency liquid is sealed using Graphene monocrystalline support membrane contained network
The method of dress.
Background technology
Graphene be one kind by carbon atom through sp2Individual layer or the two dimensional crystal material of few layer that hydridization is formed, with excellent
Electricity, optics and mechanical property.Meanwhile, efficiently and the chemical gaseous phase depositing process of relatively low cost be high-quality graphene it is thin
Prepared by the batch of film and application is provided and ensured.Except for the routine neck such as transparent conductive film, photodetector, biology sensor
Overseas, Graphene equally has very big potentiality in transmission electron microscope representational field.The electrical conductivity and thermal conductivity of superelevation can effectively drop
The loss of low electron irradiation, the regular texture of monoatomic layer hardly introduces extra interference to sample characterization and back end signal holds
Easily deduct, mechanical strength and flexibility high ensure that Graphene can pay(useful) load sample.Graphene has sealing well simultaneously
Performance, perfect Graphene lattice only allows that proton is passed through.And the effect of π-π stackings is formed between the bilayer graphene of clean surface
There is provided stronger Van der Waals force, also cause sample is encapsulated into possibility.Wherein, encapsulation of the solution inside Graphene can use
In liquid reactive in-situ characterization and tracking under transmission electron microscope, can be provided from atomic scale resolving reaction process
Energy.
In the early time, the silicon nitride material for depending on traditional silicon technology to prepare under transmission electron microscope liquid reactive in-situ characterization is made more
Be packaging film, due to silicon nitride limited strength, realize self-supporting especially load vacuole needed for film thickness often approach
Hundred nanometers, greatly reduce the resolution ratio of imaging.Additionally, also having been reported that the table in situ for depending on open liquid cell to be reacted
Levy, but sample is generally the ionic liquid of low saturated vapour pressure, greatly limit the reaction system type that can be characterized.Using Graphene
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 type that can be encapsulated
Type is limited, and vacuole size and density are also relatively low, greatly reduces the efficiency and repeatability of fluid-tight.Therefore, how one kind is developed
High-quality, the high efficiency encapsulation in-situ characterization that carries out under transmission electron microscope of different type liquid-phase reaction system become it is particularly important and
It is extremely challenging.
The content of the invention
It is an object of the invention to provide the side that a kind of utilization Graphene monocrystalline support membrane contained network realizes high efficiency liquid-packing
Method.
The method that the utilization Graphene that the present invention is provided encapsulates liquid, comprises the following steps：
After the Graphene that two panels is grown in different growth substrates respectively 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 thereon, complete 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 instead2Reduction 5-10min, finally with 200:1 hydrogen grows 0.5-3h, and sample is detached with magnet
Go out high-temperature region fast cooling.
The Graphene is Graphene monocrystalline or Graphene large single crystal；
The class of liquids to be packaged is various, not by its evaporation rate, the limit of molecular weight, density, hydrophily, molten boiling point etc.
System.Liquid to be packaged can be nano-particle solution, salting liquid, organic solvent, inorganic solvent or contain biological sample as described
Nutrient solution；Wherein, the butyrolactone solution of the nano-particle solution concretely aqueous solution of gold nano or perovskite；It is described
Salting liquid concretely KI base lead ammonium (CH3NH3PbI3) butyrolactone solution or ammonium persulfate the aqueous solution；It is described organic
Solvent concretely ethanol, methyl alcohol etc.；The inorganic solvent concretely water；It is raw in the nutrient solution containing biological sample
Thing sample concretely but is not limited to bacterium, virus or iron oxide red albumen etc.；
The transmitting substrates are the porous carbon film micro-grid with metal grill；The micro-grid concretely load it is regular or
The commercial micro-grid of irregular porous carbon film.Common-use size includes external diameter 3mm, and inner mesh number includes 100/200/300/400
Deng different size, the metal grill is specially Au, Mo or Ni grid；Be covered with one layer of porous carbon film on metal grill, aperture from
0.6 μm to 10 μm, pitch of holes is also from 1 μm to 5 μm.The contained network of wherein hole regular distribution is German import
Quantifoil, what is be randomly distributed is domestic Grid (purchased from middle mirror tech and emerging Bry).
In the covering step, 10 microns are smaller than between two panels Graphene.
The covering be specially by the another piece of graphite alkene be added dropwise after the Graphene of liquid to be packaged contacts, 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 layer graphenes
Layer and without air exist, be now smaller than 10 microns between two panels Graphene.
Methods described also comprises the following steps：After the covering step, unnecessary liquid to be packaged is inhaled with filter paper
Remove, stand to residual it is to be packaged evaporate after, after embathing dry；
The purpose for absorbing unnecessary liquid to be packaged with filter paper is in order to excessively solute can be remained in after preventing solvent from volatilizing
Two panels Graphene outer surface, influences subsequent characterizations；
The purpose of standing is slow drying sample, residual liquid is gradually volatilized totally, increases the adhesion between graphene layer
Property and model ylid bloom action power；The time of standing is 5-20min；
Described to embathe step, dip lotion is the solvent that can dissolve the liquid to be packaged, is chosen in particular from ethanol, isopropyl
At least one in alcohol and water；Specific species can be selected according to reaction system.It is required that it can dissolve fluid-tight system remains in liquid
Steep outside excessive volatile-resistant substance, and secondary interference will not be caused to the reaction in vacuole, at the same will not to Graphene with
Contained network causes extra 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；Quickly dried up with nitrogen gun；Dried with supercritical drying instrument
Graphene contained network before encapsulation liquid etc..
Methods described also comprises the following steps：After the dropwise addition step, before covering step, by two panels Graphene profit
It is aligned with micro-mechanical arm.
Specifically, the alignment comprises the following steps：
1) by it is a piece of be loaded with the transmitting substrates of Graphene 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) the transmitting substrates face down (having the one of Graphene to face down) for being loaded with Graphene by another is fixed on
Microoperation arm top, is located at the step 1) in Graphene surface；
The step 1) in, mica sheet, quartz plate or silicon chip that the clean substrate is concretely newly peeled off；In transmission base
The purpose that beneath side places clean substrate is the cleanliness factor for guarantee system；The area of the clean substrate is not less than 0.25 square
Centimetre, such as can be 1 square centimeter.
The step 2) in fixing step, fixed method is vertical capillary after drawing fixation liquid with capillary syring
After suction pipe makes its bottom have liquid to flow out, the transmitting substrates and the drop contact and then quilt of outflow for being loaded with Graphene by another
Stabilization is drawn on the capillary syring top, then will be fixed on the microoperation arm top after capillary rotation proper angle
End, completes the fixation；
The difficult volatilization of the fixation liquid and the liquid that reaction system will not be interfered, concretely deionized water
Or butyrolactone；
The consumption of the fixation liquid is not more than 1 milliliter.
The purpose drawn with capillary syring is in order to avoid system introduces additional contamination, while realizing the position of two panels contained network
Alignment.
The micromechanics motion arm needs to implement function such as：It is not less than in X-direction and the controllable displacement of Y-direction
500 microns, stepping accuracy is not less than as 1 micron, running accuracy are 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 for transmiting contained network, it is to avoid the friendship of hanging region and metal ribs
It is folded, while realizing that the position of two panels contained network is controllable.
The method of the transfer includes：After the Graphene development in growth substrate will be grown in, used with object penetrating substrate
After low surface tension organic solvent carries out hot padding, the etching removal growth substrate, then replace the etching step with displacement liquid
Rapid etching liquid used；
The displacement liquid displacement step comprises the following steps：Water is first used, then with by low surface tension organic solvent and water
The mixed solution of composition enters line replacement.
The low surface tension organic solvent is concretely but one kind for being not limited in isopropanol, ethanol and propyl alcohol or it is more
First mixed solution；
The hot padding is specially after the surface of the two-dimensional material is added dropwise the organic solvent of the low surface tension, with
The object penetrating substrate laminating, is again heated to 50-100 DEG C (concretely 60 DEG C), keeps 5-10min；
The consumption of the low surface tension organic solvent is every transmission contained network 5-10 μ L；The every transmission contained network is equal
It is the disk of a diameter of 3mm；
The purity of the low surface tension organic solvent is chromatographic grade purity.
In the mixed solution being made up 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 up of low surface tension organic solvent and water, the low surface
In the volume ratio of tension force organic solvent and water, volume ratio of the low surface tension organic solvent in the displacement liquid is passed successively
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；
Total displacement number of times that the mixed solution being made up of low surface tension organic solvent and water enters line replacement is many
In 5 times, specially 7 times.
Specifically, in the displacement step, the body of isopropyl alcohol and water in the mixed solution being made up of isopropyl alcohol and water used
Product ratio is replaced successively 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 speed of displacement is 1-10ml/min every time, concretely 3ml/min.
The mode provided using the invention described above enters line replacement, and the surface tension and contact angle of displacement liquid can be made gradually to subtract
It is small, it is to avoid the rupture of Graphene large single crystal support membrane or complete is easily caused when being directly rinsed with water after the completion of etching
The too low major defect of degree.
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 or the aqueous solution of iron chloride of 0.1M；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 dried up after Yu Shuizhong immersions is similar.The purpose of the development is to realize stone
The fixed point transfer of black alkene large single crystal (size is more than 3mm), it is to avoid introduce crystal boundary and defect, bring 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 and is dried up with nitrogen or argon gas.
Methods described also comprises the 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 washing after bombardment removal or etching；The purpose for removing the face Graphene is anti-
Only the Graphene fragment in the face sticks to another side after Copper Foil etching, introduces extra pollution.
Specifically, the bombardment removal is removed for plasma bombardment；
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.
Due to being shifted without glue, 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..
Methods described also includes：Dried after the displacement step；In the drying steps, dry temperature specifically may be used
It is 10-70 DEG C, can is more specifically 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 by sample drying is preposition in easy volatile solvent, in super-clean bench
Air volume is opened to be air-dried in unlimited system；Dried up with nitrogen gun；Aided in supercritical drying instrument dry etc..
In addition, the Graphene for preparing according to the method described above encapsulates the product of liquid, protection model of the invention is fallen within
Enclose.
The present invention is by effectively using the big list of Graphene of integrity degree high, high-cleanness, high and the high intensity obtained without glue transfer
Brilliant film realizes the encapsulation of the controllable high efficiency reaction solution in position, and has prepared large area, high density, the Gao Ke of system
The encapsulation of repeatability such that it is able to be largely available for the vacuole of in-situ characterization under transmission electron microscope, realize related liquid phase reactor
In-situ characterization under transmission electron microscope., up to 3 microns, maximal density can for the continuous hanging area of maximum of its hanging Graphene used
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 (higher resolution is limited to transmission electron microscope imaging level in itself).Additionally, this method has very big compatibility
Property, the Graphene transmission contained network of selection can be individual layer or lack layer graphene sample, achievable to have to different liquid-phase reaction systems
Effect encapsulation, while can be used for sample in ESEM or the in-situ characterization of spectroscopy instrument, can also realize to biological sample, such as thin
Effective encapsulation of bacterium, virus, iron oxide red albumen etc..
Brief description of the drawings
Fig. 1 is the photo of the grade Graphene large single crystal isolated after developing and successfully loaded high-quality by being shifted without glue
Measure the photo of the transmission contained network of Graphene.
Fig. 2 is to transmit in contained network 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 base unit to hanging Graphene in full wafer contained network
Enlarged drawing.
Fig. 3 is that the graphene film of different farmland areas size is supported on the transmission contained network quantifoil that hanging size is 2 μm
On the contrast of average integrity degree, farmland area is smaller, and integrity degree is lower.
Fig. 4 is the high-resolution data of the hanging Graphene being transferred to without glue in transmission contained network, its clean surface, without substantially dirty
Dye thing residual.
Fig. 5 is for accurately realizing that two panels is loaded with the microoperation arm of the metal ribs close alignment of the transmission contained network of Graphene
Pictorial diagram, wherein right figure for left figure red area enlarged drawing.
Fig. 6 is the experimental principle figure of the controllable encapsulation liquid in Graphene position.
Fig. 7 be after the controllable encapsulation liquid of Graphene position the picture of the optical reflection in situ that obtains and transmission mode 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 of the different solutions that Graphene encapsulation is obtained.
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 obtained after different solutions, is divided into liquid
Only there is the class of carbon film Auxiliary support (red) two Graphene (blueness) and vacuole at least side for bubble both sides.The illustration of left figure is phase
The typical transmission electron microscopic picture of the vacuole of the large-size answered.
Figure 12 is the typical density statistics after the aqueous solution of the gold nano grain of Graphene encapsulation large-size.
Figure 13 is the allusion quotation obtained by the 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 be two isolated about 2-4 nanosizeds gold nano grain gradually reunite merging formed 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 still keeps the typical transmission electron microscopic picture of stabilization and sweeps after placing three weeks
Retouch transmission electron microscope picture.
Figure 17 is that the ammonium persulfate aqueous solution of Graphene encapsulation gradually produces bubble and the allusion quotation discharged under electron beam irradiation
Type transmission electron microscope picture.
Figure 18 be Graphene encapsulation organic inorganic hybridization perovskite --- the butyrolactone solution of KI base lead ammonium is obtained
Vacuole transmission electron micrograph and the picture of high-resolution lattice phase.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
State method and be conventional method unless otherwise instructed.The raw material can be obtained from open commercial sources unless otherwise instructed.
Experimental technique described in following embodiments, unless otherwise specified, is 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
Paper tinsel, nickel foil, corronil etc.) it is purchased from Alpha Ai Sha.Hanging graphene-based bottom is purchased from middle mirror tech and emerging Bry or by it
Bought on behalf from external (the quantifoil companies of Germany).
Embodiment 1, the high-quality graphene transmission contained network high efficiency encapsulation gold nano grain aqueous solution
1) the isolated large single crystal Graphene sample that growth is finished is taken out, in 150 DEG C of thermal station baking 3-5min, shows Graphene
Shadow, position visualization.
Graphene on Copper Foil without the one side of transfer is processed by air plasma cleaning machine and realizes bombardment removal,
Throughput is 15sccm, and power is 90W, and the time is 3min.
A face Graphene to be transferred upward, by object penetrating substrate front surface down, is positioned over Graphene sample to be transferred
Surface, due to transmitting substrates target for diameter 3mm disk, therefore be added dropwise 5-10 microlitres of chromatographic pure isopropanol, make isopropanol
Naturally volatilize, be again heated to 60 DEG C of holding 10min, it is ensured that the close contact of substrate and Graphene；
The Copper Foil that the length of object penetrating substrate will be stained with Graphene large single crystal is placed in the ammonium persulfate that concentration is 0.1M
The aqueous solution in, Copper Foil substrate 4h is etched at room temperature；
Water is first used, then the etching that etch step is remained is replaced by peristaltic pump with the mixed solution being made up of isopropyl alcohol and water
Liquid, the replacing velocity of peristaltic pump is 3ml/min；In displacement step, in the mixed solution be made up of isopropyl alcohol and water isopropanol and
The volume ratio of water as shown in table 1, is replaced successively according to volume ratio shown in table 1 is ascending, and the volume of displacement liquid used is equal every time
It is 300mL；The displacement liquid of every kind of volume ratio is only with once；During according to as above sequentially entering line replacement, the surface of corresponding displacement liquid
Tension force (unit is mN) and the numerical value of contact angle are as shown in table 1.
The displacement liquid and its corresponding surface tension and contact angle of table 1, different isopropanols and water volume ratio
Isopropanol is slowly vented after being replaced, and heating systems to 60 DEG C by sample drying, you can complete monocrystalline stone
Transfer of the black alkene by growth substrate Copper Foil to object penetrating substrate.
2) a piece of transmission contained network for being loaded with high-quality graphene is face-up positioned over and light associated with microoperation arm
Learn on platform, be placed in three-dimensional manipulating platform center position.
3) using after capillary syring top " absorption " fixation liquid deionized water, vertical capillary syring makes its bottom have water
After outflow, the transmitting substrates for being loaded with Graphene by another are drawn in capillary syring with the water drop contact for flowing out and then by stabilization
Top, then microoperation arm top will be fixed on after capillary rotation proper angle, face down is being placed on first piece contained network just
Top, using microoperation platform progressively adjust lower section two panels contained network metal ribs position, including R directions rotation and X, Y-direction
Translation, finally realize the correction of two panels contained network position.
4) the about 1-20 microlitres water-soluble drop of gold nano grain is drawn in first piece contained network with micro syringe, and by the
Two slow being displaced downwardly to of contained network contact with first piece, make the carbon film and metal ribs at the transmitting substrates edge of two panels Graphene same
There was only very thin water layer during focal plane between two layer graphenes and exist without air, now being smaller than between two panels Graphene
10 microns.
5) 5-20min to the gold nano for remaining is stood after the aqueous solution of unnecessary gold nano grain is absorbed with filter paper again
After the aqueous solution volatilization of grain, the good sample with ethanol of fluid-tight is embathed into 180s in 25 DEG C carries out embathing re-dry, completes encapsulation.Will
Vacuum is preserved after sample dries in the shade, and is remained follow-up transmission electron microscope and is characterized.
Wherein, drying means is concretely placed in former solvent by sample drying is preposition in easy volatile solvent, in super-clean bench
Air volume is inside opened in unlimited system Quick-air-drying；Quickly dried up with nitrogen gun；Before encapsulation liquid being dried with supercritical drying instrument
Graphene contained network etc..
Fig. 1 is the photo of the grade Graphene large single crystal isolated after developing and successfully loaded high-quality by being shifted without glue
Measure the photo of the transmission contained network of Graphene.
Fig. 2 is to transmit in contained network 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 base unit to hanging Graphene in full wafer contained network
Enlarged drawing.
Fig. 3 is that the graphene film of different farmland areas size is supported on the transmission contained network quantifoil that hanging size is 2 μm
On the contrast of average integrity degree, farmland area is smaller, and integrity degree is lower.
Fig. 4 is the high-resolution data of the hanging Graphene being transferred to without glue in transmission contained network, its clean surface, without substantially dirty
Dye thing residual.
Fig. 5 is for accurately realizing that two panels is loaded with the microoperation arm of the metal ribs close alignment of the transmission contained network of Graphene
Pictorial diagram, wherein right figure for 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 align during encapsulation, envelope
Sample bilayer graphene after dress directly accompanies liquid, and thickness is from several nanometers to hundred nanometers；The region stone of unencapsulated liquid
Black alkene level still has stronger Van der Waals force, it is ensured that the long-time stability of vacuole.
Fig. 7 shows that the metal ribs of two Graphene large single crystal support membrane contained networks after fixed point fluid-tight can be realized stacking completely,
Ensure that the maximization of fluid-tight sample area.As can be seen that because the absorptance of single-layer graphene is only 2.3%, Graphene liquid
Envelope region still light-permeable, also can pass through electronics.Absorption of the carbon film region to light is more, but can still be used for sample is relatively low under transmission
The sign of times pattern.
Fig. 9 is the transmission electron microscope picture of the different solutions that Graphene encapsulation is obtained, ethanol, water, various sizes of gold nano
Particle the aqueous solution and colloidal sol (<5nm, 5-10nm,>10nm), ammonium persulfate aqueous solution, butyrolactone solution of perovskite etc..Can
To find, from several nanometers to several microns, the number in every square micron is from one to tens for the size of vacuole.This
Outward, solution encapsulation obtains bigger vacuole when there is carbon film Auxiliary support in Graphene outside.Part vacuole periphery can also be seen simultaneously
Obvious liquid bridge is observed, for the circulation etc. of liquid.
Figure 10 shows the Graphene large single crystal support membrane encapsulation vacuole that the obtains generally existing on sample, and distribution density compared with
It is high.But ESEM resolution ratio in itself is limited to, the vacuole less than ten nanometers is more difficult discernable.
Figure 11 shows after Graphene encapsulation different solutions the vacuole size that obtains from several nanometers to several microns, every square
Number in micron is from one to tens.Additionally, solution encapsulation is more easy to get when there is carbon film Auxiliary support in Graphene outside
To bigger vacuole, show that the technology can be used for the sign of biological sample such as virus, cell etc..
Figure 12 is the typical density statistics after the aqueous solution of the gold nano grain of Graphene encapsulation large-size, the region liquid
The density of bubble is up to every square micron tens, and size is from several nanometers to hundreds of nanometers.Simultaneously as content liquid mistake
Many, the later stage is not cleaned, and Graphene outside has remained more gold nano grain.Figure 12 shows by two hanging region graphite
Amplification step by step after alkene encapsulation is characterized, and the vacuole size that encapsulation is obtained is distributed very intensive.But for the sample due to first
Phase draws content liquid excessively, and the later stage is not cleaned, and Graphene outside has remained more gold nano grain.
After Figure 13 shows Graphene fluid-tight reaction solution, remain to obtain high resolution up to 0.2 nanometer under F30 transmission electron microscopes
Golden (111) crystal face lattice image, it is seen then that gold (111) crystal face spacing of lattice it is high-visible.The vacuole can bear to be more than
The electron irradiation of the high dose of 3min, while electron beam can drive the movement of nano-particle, reunites and grows.
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 be by the technology trace trap.
Figure 15 shows that the vacuole of Graphene large single crystal support membrane encapsulation can for a long time keep stabilization under electron beam irradiation.
Figure 16 shows that the vacuole of Graphene large single crystal support membrane encapsulation still keeps stabilization after placing three weeks, and edge is received
The deposition of rice grain, it may be possible to caused by the slow growth of gold nano grain.
Embodiment 2：High-quality graphene large single crystal support membrane contained network high efficiency encapsulates the aqueous solution of ammonium persulfate
According to the step 1 of embodiment 1) the Graphene large single crystal film sample that finishes will be grown transmission will be transferred to by growth substrate
Electronic Speculum substrate；Step 2) -5) it is same as Example 1, only by the step 2 of embodiment 1) used by 1-20 microlitres of gold nano grain it is water-soluble
Liquid replaces with the 5-8 microlitres of aqueous solution of ammonium persulfate；By the step 5 of embodiment 1) embathe ethanol used and replace with isopropanol.
Fig. 7 shows that the metal ribs of two Graphene large single crystal support membrane contained networks after fixed point fluid-tight can be realized stacking completely,
Ensure that the maximization of fluid-tight sample area.As can be seen that because the absorptance of single-layer graphene is only 2.3%, Graphene liquid
Envelope region still light-permeable, also can pass through electronics.Absorption of the carbon film region to light is more, but can still be used for sample is relatively low under transmission
The sign of times pattern.
Fig. 9 shows that Graphene large single crystal support membrane encapsulation liquid can be realized efficiently, and the size of the vacuole for obtaining is received from several
, to several microns, the number in every square micron is from one to tens for rice.Additionally, Graphene outside has carbon film to aid in
Solution encapsulation obtains bigger vacuole during support.Part vacuole periphery can also be observed that obvious liquid bridge simultaneously, for liquid
Circulation etc..
Figure 10 shows the Graphene large single crystal support membrane encapsulation vacuole that the obtains generally existing on sample, and distribution density compared with
It is high.But ESEM resolution ratio in itself is limited to, the vacuole less than ten nanometers is more difficult discernable.
Figure 11 shows after Graphene large single crystal support membrane encapsulation different solutions the vacuole size that obtains from several nanometers to several micro-
Rice, the number in every square micron is from one to tens.Additionally, molten when having carbon film Auxiliary support on the outside of Graphene
Fluid-tight dress is more easy to obtain bigger vacuole, shows that the technology can be used for the sign of biological sample such as virus, cell etc..
Figure 17 shows that the ammonium persulfate aqueous solution of Graphene large single crystal support membrane encapsulation is gradually produced under electron beam irradiation
Bubble is simultaneously gradually migrated to liquid edge, and the generation of bubble is probably derived from the decomposition of persulfate or splitting for water under electron irradiation
Solution.
Embodiment 3：High-quality graphene large single crystal support membrane contained network high efficiency encapsulation KI base lead ammonium (CH3NH3PbI3)
Butyrolactone solution
According to the step 1 of embodiment 1) the Graphene large single crystal film sample that finishes will be grown transmission will be transferred to by growth substrate
Substrate (namely commercial transmission electron microscopy contained network)；Step 2) -5) it is same as Example 1, only by the step 2 of embodiment 1) used by 1-
The aqueous solution of 20 microlitres of gold nano grains replaces with the butyrolactone solution of KI base lead ammonium；By the step 5 of embodiment 1) embathe institute
Isopropanol is replaced with ethanol.
Fig. 7 shows that the metal ribs of two Graphene large single crystal support membrane contained networks after fixed point fluid-tight can be realized stacking completely,
Ensure that the maximization of fluid-tight sample area.As can be seen that because the absorptance of single-layer graphene is only 2.3%, Graphene liquid
Envelope region still light-permeable, also can pass through electronics.Absorption of the carbon film region to light is more, but can still be used for sample is relatively low under transmission
The sign of times pattern.
Fig. 9 show Graphene encapsulation liquid can efficiently realize, and the vacuole for obtaining size from several nanometers to several microns not
Deng per the number in square micron from one to tens.Additionally, solution envelope when there is carbon film Auxiliary support in Graphene outside
Dress obtains bigger vacuole.Part vacuole periphery can also be observed that obvious liquid bridge simultaneously, for the circulation etc. of liquid.
Figure 10 shows the Graphene large single crystal support membrane encapsulation vacuole that the obtains generally existing on sample, and distribution density compared with
It is high.But ESEM resolution ratio in itself is limited to, the vacuole less than ten nanometers is more difficult discernable.
Figure 11 shows after Graphene large single crystal support membrane encapsulation different solutions the vacuole size that obtains from several nanometers to several micro-
Rice, the number in every square micron is from one to tens.Additionally, molten when having carbon film Auxiliary support on the outside of Graphene
Fluid-tight dress is more easy to obtain bigger vacuole, shows that the technology can be used for the sign of biological sample such as virus, cell etc..
Figure 18 shows the organic inorganic hybridization perovskite of Graphene large single crystal support membrane encapsulation --- KI base lead ammonium
The transmission electron micrograph of the vacuole that butyrolactone solution is obtained and the picture of high-resolution lattice phase.
Comparative example 1：Random stacked graphene large single crystal support membrane contained network encapsulation gold nano grain solution
The Graphene large single crystal film sample that growth is finished is taken out, is slightly toasted in 170 DEG C of thermal station, Copper Foil does not change colour, and says
Bright Graphene has been covered with, and confirmation is characterized under ESEM and is individual layer region.The Graphene sample of one side to be transferred is then protected,
Process 3min to bombard the sample of removal another side by air plasma cleaning machine.
By the use of quantifoil micro-grids as Auxiliary support film, the volatile ethanol of drop is added dropwise will using capillary force
Graphene to be transferred and the porous carbon film tight adhesion on contained network surface.
The Graphene on the Copper Foil of transmitting substrates will be stained with, be placed in the ammonium persulfate etching liquid of 0.1M, carved at room temperature
Erosion Copper Foil substrate 4h, after Copper Foil etching terminates, sample is cleaned, and is then quickly dried up with nitrogen gun.
The about 5-8 microlitres water-soluble drop of low concentration ammonium persulfate is drawn in the face-up load of first piece with micro syringe
On the net, and by second contained network face down contacted with first piece.Excessive response solution is drawn with filter paper, 5-20min is stood afterwards.
The good sample of fluid-tight is embathed with isopropanol, vacuum is preserved after then sample is dried in the shade, remained follow-up transmission
Electronic Speculum is characterized.
Fig. 8 (a) shows that the random stacking of metal ribs can substantially reduce the exposed possibility in the hanging region of two panels, so as to drop
The region area of the Graphene fluid-tight reaction solution that can be characterized under low transmission Electronic Speculum.This further illustrates this method for packing has more
Packaging efficiency high, controllability and repeatability.C () substantially reduces the integrity degree of carbon film after the removal of wherein side metal ribs,
And then reduce the intensity of sample and the usable area of totality.
Comparative example 2：Contained network is transmitted using the Graphene of low integrity degree encapsulate gold nano grain solution
The polycrystalline graphite alkene film sample that growth is finished is taken out, is slightly toasted in 170 DEG C of thermal station, Copper Foil does not change colour, explanation
Graphene has been covered with, and confirmation is characterized under ESEM and is individual layer region.The Graphene sample of one side to be transferred is then protected, is led to
Air plasma cleaning machine treatment 3min is crossed to bombard the sample of removal another side.
By the use of transmission electron microscope substrate as Auxiliary support film, a drop water is added dropwise and utilizes capillary force by graphite to be transferred
Alkene is adhered to (adhesion is weaker than the intensity using ethanol or isopropanol etc.) with the porous carbon film on contained network surface.Transmission will have been adhered to
The length of substrate has the Copper Foil of Graphene, is placed in the ammonium persulfate etching liquid of 2M, and Copper Foil substrate 20min is etched at room temperature, treats copper
After paper tinsel etching terminates, sample is cleaned, then quickly dried up with nitrogen gun.
The a piece of transmission contained network for being loaded with high-quality graphene is face-up positioned over and optics associated with microoperation arm
On platform, and its position is relatively fixed.The saturating of high-quality graphene is loaded with using capillary syring top " absorption " another
Penetrate contained network and be fixed on motion arm top, face down is placed on the surface of first piece contained network, is progressively adjusted using microoperation platform
The position of whole lower section two panels contained network metal ribs, including R directions rotation and X, the translation of Y-direction, finally realize two panels contained network position
The correction put.
The about 5-8 microlitres water-soluble drop of low concentration ammonium persulfate is drawn in first piece contained network with micro syringe, and will
Second slow being displaced downwardly to of contained network contacts with first piece.Excessive response solution is drawn with filter paper, 5-20min is stood afterwards.
The good sample of fluid-tight with isopropanol embathe and is placed in super-clean bench and is quickly dried in the shade, then protect sample vacuum
Deposit, remain follow-up transmission electron microscope and characterize.
Fig. 8 (b) shows, is limited by early stage Graphene transmission contained network integrity degree, even if the metal ribs of two panels contained network are
Alignment, the region of the available Graphene Successful encapsulation vacuole for finally obtaining is also very limited.This further demonstrates high-quality
Measure importance of the integrity degree Graphene high for the final quantity for obtaining vacuole.
Claims (10)
1. a kind of method that utilization Graphene encapsulates liquid, comprises the following steps：
After the Graphene that two panels is grown in different growth substrates respectively is transferred on transmitting substrates by growth substrate, it is added dropwise
Behind liquid to be packaged to the wherein surface of piece of graphite alkene, another piece of graphite alkene is covered thereon, complete encapsulation.
2. method according to claim 1, it is characterised in that：The Graphene is Graphene monocrystalline or the big list of Graphene
It is brilliant；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 film micro-grid with metal grill；And/or,
In the covering step, 10 microns are smaller than between two panels Graphene.
3. method according to claim 1 and 2, it is characterised in that：The method of the transfer includes：To be grown in growing base
After Graphene development on bottom, after carrying out hot padding with low surface tension organic solvent with object penetrating substrate, etching removal institute
Growth substrate is stated, then etching liquid used by the etch step is replaced with displacement liquid；The use displacement liquid displacement step includes as follows
Step：Water is first used, then enters line replacement with the mixed solution being made up of low surface tension organic solvent and water.
4. method according to claim 3, it is characterised in that：The low surface tension organic solvent is selected from isopropanol, second
At least one in alcohol and propyl alcohol；And/or,
The hot padding be after the surface of the two-dimensional material is added dropwise the low surface tension organic solvent, it is saturating with the target
Substrate laminating is penetrated, 50-70 DEG C of holding 5-10min is again heated to；And/or,
The consumption of the low surface tension organic solvent is every two-dimensional material 5-10 μ L；The every two-dimensional material is directly
Footpath 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 up 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 up 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,
Total displacement number of times that the mixed solution being made up of low surface tension organic solvent and water enters line replacement is no less than 5 times
Or be 7 times；
Specifically, in the displacement step, the volume ratio of isopropyl alcohol and water in the mixed solution being made up of isopropyl alcohol and water used
Replace successively in the following order：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 or 300-600mL every time；And/or,
The speed of displacement is 1-10ml/min or 3ml/min every time.
5., according to any described methods of claim 1-4, 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 not more than
The persulfate of 0.1M or the aqueous solution of iron chloride；The persulfate is specially ammonium persulfate or sodium peroxydisulfate；
The temperature of etching is room temperature；
The time of etching is 0.5-10h；
In the development step, developing method is to toast or in water after immersion the Graphene being grown in growth substrate
Drying；And/or, in the baking procedure, temperature is 100-300 DEG C or 150 DEG C；Time is 1-10min or 3-5min；And/or,
In be set forth in water in soaking step, water temperature is 0-50 DEG C；Time is 10-200min；And/or,
The method of the transfer also comprises the 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 washing after bombardment removal or etching；
Dried after the displacement step.
6. according to any described method in claim 1-5, it is characterised in that：Methods described also comprises the following steps：Institute
After stating covering step, unnecessary liquid to be packaged is absorbed with filter paper, stand to residual it is to be packaged evaporate after, embathe
After dry；And/or,
In the standing step, the time of standing is 5-20min；And/or,
Described to embathe step, dip lotion is the solvent that can dissolve the liquid to be packaged, be chosen in particular from ethanol, isopropanol and
At least one in water；The time embathed is 30-300s or 180s；Temperature is room temperature or 10-30 DEG C or 25 DEG C.
7. according to any described method in claim 1-6, it is characterised in that：Methods described also comprises the following steps：Institute
State after dropwise addition step, before covering step, two panels Graphene is aligned using micro-mechanical arm.
8. method according to claim 7, it is characterised in that：The alignment comprises the following steps：
1) a piece of transmitting substrates of Graphene that are loaded with face-up are placed in clean substrate, are placed in three-dimensional manipulating platform center
Position；
2) the transmitting substrates face down that another is loaded with Graphene is fixed on microoperation arm top, is located at the step
It is rapid 1) in Graphene surface.
9. method according to claim 8, it is characterised in that：The step 2) in fixing step, fixed method is use
After capillary syring draws fixation liquid, after vertical capillary syring makes its bottom have liquid to flow out, graphite is loaded with by another
The transmitting substrates of alkene are drawn on the capillary syring top with the drop contact for flowing out and then by stabilization, then the capillary is revolved
The microoperation arm top is fixed on after turning proper angle, the fixation is completed；
The difficult volatilization of fixation liquid and the liquid or deionized water or butyrolactone that reaction system will not be interfered；
And/or,
The consumption of the fixation liquid is not more than 1 milliliter；And/or,
The microoperation arm can be implemented function such as：It is not less than 500 microns, stepping in X-direction and the controllable displacement of Y-direction
Precision is not less than as 1 micron, running accuracy are 1 degree and axially 360 ° of rotatable controllable selections.
10. the product that liquid is encapsulated by Graphene that any methods describeds of claim 1-9 are obtained；Or,
The product by Graphene encapsulation liquid that any methods describeds of claim 1-9 are obtained is liquid reactive under transmission electron microscope
Application in in-situ characterization.
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