CN102190295A - Graphene and hexagonal boron nitride planes and associated methods - Google Patents
Graphene and hexagonal boron nitride planes and associated methods Download PDFInfo
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- CN102190295A CN102190295A CN2011100453737A CN201110045373A CN102190295A CN 102190295 A CN102190295 A CN 102190295A CN 2011100453737 A CN2011100453737 A CN 2011100453737A CN 201110045373 A CN201110045373 A CN 201110045373A CN 102190295 A CN102190295 A CN 102190295A
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Abstract
Graphene layers made of primarily sp2 bonded atoms and associated methods are disclosed. In one aspect, for example, a method of forming a graphite film can include heating a solid substrate under vacuum to a solubilizing temperature that is less than a melting point of the solid substrate, solubilizing carbon atoms from a graphite source into the heated solid substrate, and cooling the heated solid substrate at a rate sufficient to form a graphite film from the solubilized carbon atoms on at least one surface of the solid substrate. The graphite film is formed to be substantially free of lattice defects.
Description
Priority data
The application advocates U.S. the 12/713rd of filing an application on February 25th, 2010, the right of priority of No. 004 patent application case, this U.S. patent application case is the U.S. the 12/499th that files an application on July 8th, 2009, No. 647 patent application cases and the U.S. the 61/079th, No. 064 patent application case and the U.S. the 61/145th that files an application on January 19th, 2009, the case that continues of No. 707 temporary patent application cases, above-mentioned patent application case are integrated in herein with as a reference.
Technical field
The invention relates to Graphene and hexagonal boron nitride thin slice and methods involving thereof.Therefore, the present invention relates to chemistry and material science.
Background technology
Graphene is generally defined as the flat board that single atomic thickness has the carbon atom of sp2 bond, and these carbon atoms are the structures that closely are stacked into the phenyl ring with honeycomb crystal lattice.This two-dimensional material presents high electronic stability and excellent thermal conductivity on the plane of laminate structure, in majority each other the lamellar graphite alkene of parallel stacks formed by graphite.
Graphene is used in the characteristic of describing a lot of carbon-based materials (comprising graphite, large-scale soccerballene, nanotube etc.) widely, and for example, carbon nanotube can be Graphene and rolls the right cylinder that forms nano-scale.Moreover plane Graphene itself has been estimated to be and has not been present in free state (free state), and is unsettled for the formation of warp architecture (as charcoal ash (soot), soccerballene, nanotube etc.).
At present existing people attempts in conjunction with Graphene in electronic installation (as transistor), yet such trial is usually because the problem relevant with the manufacturing with the high quality graphene layer that is fit to be attached to the suitable size in this device and can't be successful.A kind of technology that produces graphene layer relates to tears Graphene from highly oriented pyrolytic graphite, make in this way, only can produce platelets, to such an extent as to their too little usually can't uses in electronic application.
Summary of the invention
Therefore, the invention provides Graphene and hexagonal boron nitride layer and methods involving thereof.For example, provide a kind of method that forms graphite linings on the one hand.This method comprises: heating one solid base material arrives a solvent temperature (solubilizing temperature) under vacuum state, and this solvent temperature is lower than the fusing point of this solid base material; To be dissolved in from the carbon atom in graphite source among this heated solid base material; And cool off this heated solid base material so that this dissolved carbon atom forms a graphite linings at least one surface of this solid base material with a competent speed.Formed graphite linings does not include lattice imperfection haply.On the one hand, this method can be nearly a step comprise and on this solid base material, remove this graphite linings.
Can be according to the present invention each side and consider to use various solid metal base materials to make graphite linings.On the one hand, the example of solid metal base material comprise and be not subject to chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), tantalum (Ta), palladium (Pd), platinum (Pt), lanthanum (La), cerium (Ce), europium (Eu), iridium (Ir), ruthenium (Ru), rhodium (Rh), its alloy with and binding substances.In a particular aspects, this solid metal base material can comprise nickel.
In addition, this solid base material can comprise a less haply active material to adjust the solubleness of carbon atom among the solid metal base material.Can consider various less haply active materials, and any this class material that is compatible with the solid metal base material and can adjusts the carbon dissolution degree is regarded as all in category of the present invention.This haply the example of less active material comprise and be not subject to gold (Au), silver (Ag), copper (Cu), plumbous (Pb), tin (Sn), zinc (Zn), its binding substances with and alloy.On the one hand, this less haply active material can comprise copper.On the other hand, this solid metal base material comprises a first metal layer and one second metal level, and wherein this first metal layer can be used for the dissolved carbon atom, and this second metal level can be used for adjusting carbon atom solubleness.Therefore, in some aspects among, this second metal level is compared the first metal layer, comprises the less haply active material of larger proportion.
When making graphene layer, can use different solvent temperatures, and can change this solvent temperature according to the characteristic of the graphene layer of the employed solid metal base material and the output of wanting.On the one hand, this solid metal base material is a nickel, and this solvent temperature is by about 500 ℃ to about 1450 ℃.On the other hand, this solid metal base material is a nickel, and this solvent temperature is by about 500 ℃ to about 1000 ℃.Again on the other hand, this solid metal base material is a nickel, and this solvent temperature is by about 700 ℃ to about 800 ℃.In addition, can change the rate of cooling of solid metal base material according to the characteristic of the graphene layer of the material of this solid metal base material and the output of wanting.On the one hand, this rate of cooling is by about 1 ℃/per second to 20 ℃/per second.
In the present invention on the other hand, a method that forms graphite linings can comprise: be arranged on a solid metal base material on one support base material and connect a graphite carbon this solid metal base material of originating.This method can further comprise: this solid metal base material of heating arrives a solvent temperature under vacuum state, and this solvent temperature is lower than the fusing point of this solid metal base material; And the carbon atom in the graphite source is dissolved among this heated solid metal base material.Then can a competent speed cool off this heated solid metal base material to be formed a graphite linings by dissolved carbon atom at least one surface of this solid metal base material, wherein this graphite linings does not have lattice imperfection haply.On the one hand, connecting the originate step of this solid metal base material of this graphite carbon comprises this graphite carbon source is arranged between this support base material and this solid metal base material.On the other hand, connecting the originate step of this solid metal base material of this graphite carbon comprises and this graphite carbon is originated that a surface of this solid metal base material is gone up and this support base material relatively.
The present invention also provides the graphene layer according to the inventive method manufacturing.In this example, the size and dimension that graphene layer can be preset and making.These graphene layers can be applicable on the various devices.Aforementioned means can comprise and not be subject to molecule sensor, photodiode, liquid-crystal display, solar panels, pressure transmitter, surface acoustic wave filter (SAWfilter), acousticresonance device, transistor, electrical condenser; Transparency electrode, ultraviolet laser (UV laser), DNA chip or the like.
Generality and more extensively describe out various feature of the present invention only now, therefore in ensuing detailed description, can further understand, and the contribution of doing in this area may have better understanding, and further feature of the present invention will become more clear from contained detailed description and accompanying drawing and claim, also may learn when implementation is of the present invention.
Description of drawings
Fig. 1 is the synoptic diagram of the Graphene lattice of one embodiment of the invention;
Fig. 2 is the sectional view of the die assembly of another embodiment of the present invention;
Fig. 3 is the Photomicrograph of the graphene layer of further embodiment of this invention;
Fig. 4 is the Photomicrograph of the graphene layer of yet another embodiment of the invention;
Fig. 5 is the present invention's Photomicrograph of the graphene layer of another embodiment again;
Fig. 6 is the Photomicrograph of the graphene layer of another embodiment of the present invention;
Fig. 7 is the present invention's sectional view of the die assembly of another embodiment again.
Embodiment
Below cooperate graphic and of the present invention preferred embodiment, further setting forth the present invention is to reach the technique means that predetermined goal of the invention is taked.
Definition
It below is the definition of the proper noun that in explanation of the present invention and claim, occurred.
Employed odd number kenel wording is as " one " and " being somebody's turn to do " in the literary composition, unless in context the well-known odd number that is designated as, not so the antecedent of these odd number kenels also comprises most objects, therefore for example " particle " comprises one or more such particles; " this material " comprises one or more this materials.
" degree of graphitization (degree of graphitization) " described herein is meant the ratio of graphite, it has the graphite plane (graphene plane) of 3.354 dusts (angstrom) of being separated by in theory, therefore, graphited degree is 1 to be meant that 100% graphite has the graphite plane spacing (d of bottom surface
(0002)) be the carbon atom sexangle reticulated structure of 3.354 dusts.Higher degree of graphitization is meant less graphite plane spacing.Degree of graphitization (G) can utilize formula 1 to calculate.
G＝(3.440-d
(0002))/(3.440-3.354) (1)
On the contrary, d
(0002)Can be according to G and use formula 2 is calculated and got.
d
(0002)＝3.354+0.086(1-G) (2)
According to formula 1,3.440 dust is amorphous carbon
The interval of bottom surface, and 3.354 dusts are pure graphite
The interval, pure graphite be can by at 3000 ℃ with the graphitisable carbon of time (as 12 hours) sintering that prolong.The greying of higher degree is corresponding to bigger crystal size, and it is by bottom surface (L
a) size and stack layer (L
c) size characterize.Note that this dimensional parameters is inversely proportional to the interval of bottom surface.One " high-graphitized " is according to employed material, is equal to or greater than about 0.8 but typically refer to graphited degree.In certain embodiments, the greying of high level is meant the degree of graphitization greater than about 0.85.
Employed in the literary composition " graphite linings " word is meant the graphene layer of most storehouses.
Employed in the literary composition " less haply activity (substantially less-reactive) " is not meant and can reacts and the element of chemical bonded refractory or the mixture of element with grapheme material significantly.The example of less active element can comprise but be not limited in gold (Au), silver (Ag), copper (Cu), plumbous (Pb), tin (Sn), zinc (Zn) and composition thereof haply.
Use " (substantially) haply " to be meant step, characteristic, character, state, structure, project or result's complete, approaching scope or degree completely in the literary composition.For example, one " haply " was meant by the object that coated that this object was coated fully or almost completely coated.And can under different situations, decide according to specific context from absolute certain admissible deviation fully.Yet, as a rule near fully as acquisition absolute or complete have identical total result fully.Used " haply " be also suitable on an equal basis when being used in negative connotation, to represent fully or near lacking step, characteristic, character, state, structure, project or result fully.For instance, one " not having (substantiallyfree of) haply " particulate composition can be and lacks particle fully, perhaps be close to very much to lack particle fully, and it influences meeting as lacking particle fully.In other words, the influence that the composition of one " not having haply " composition or element as long as do not have on the characteristic of being paid close attention to can measure can in fact still comprise such material.
Employed in the literary composition " approximately (about) " is the elasticity that may provide the numerical range end points than the numerical value of end points " higher (a little above) " or " low (a little below) " by providing.
An employed majority article, construction package, component and/or material in the literary composition, can appear in general common the enumerating based on convenient, yet these are enumerated the solid memder that may be interpreted as in enumerating and are defined separately or individually, therefore, the solid memder in enumerating like this can not be considered as any separately based on other in fact equal in identical the enumerating of the explanation of no phase antirepresentation in general group member.
Data on concentration, quantity and other numerical value are presented with the form of scope or are represented, and the use that need be appreciated that this range format is only based on accessibility and succinct, therefore when explaining, should have suitable elasticity, not only be included in the numerical value that clearly shows in the scope with as restriction, also can comprise simultaneously all discrete numerical value and the underrange in numerical range, be quoted from clearly as each numerical value and underrange.For example a numerical range " about 1 micron to about 5 microns " should be construed to comprise not only clearly that citation comes out about 1 to about 5, also be included in each numerical value and underrange in this stated limit simultaneously, therefore, be included in each numerical value in this numerical range, for example 2,3 and 4, or the underrange etc. of 1-3,2-4 and 3-5 for example, and discrete 1,2,3,4 and 5.This principle of identity is useful in the scope that citation one numerical value is only arranged, moreover no matter such explanation is in the amplitude or described feature of a scope if should be able to being applied to.
Invention
The invention relates to novel Graphene and hexagonal boron nitride layer and methods involving thereof; Furthermore, it relates to make and comprises mainly with sp
2Bond is arranged the material of the atom that forms and the method and this material of material layer.What known is that graphene layer can be made with the size that enough is used for a lot of electronic application, and graphene layer is for having sp
2The flat board of bond carbon and the single atomic thickness of tool, and as shown in Figure 1, it is the structure that closely is stacked into the phenyl ring with honeycomb crystal lattice.Carbon-to-carbon bond length in Graphene is approximately 1.45 dusts
Length than diamond
Short.Graphene is the basic structural element of other graphite material, and this graphite material comprises graphite, carbon nanotube, soccerballene etc.The term of " Graphene " comprises the Graphene of relevant single atomic shell and the Graphene of most layer stacks in it should be noted aspect of the present invention.It should be noted that " graphite linings " word can be used for describing the Graphene of most layer stacks.
Splendid Graphene only only is made up of hexagonal, and any pentagon or septangle crystal in Graphene all can constitute defective, and this defective changes the smooth character of this graphene layer.For example, single pentagon crystal can make plate bending (warp) become the cone shape, when 12 pentagon crystal can produce smooth soccerballene during in suitable position.Similarly, single septangle crystal can become plate bending saddle (saddle-shape).The bending of Graphene flat board tends to reduce electronic stability and heat conductance, and therefore be unfavorable for using these character as important use on.
As mentioned above, proved it to be to be difficult to obtain even as big as the high quality graphene layer (or graphite linings) that is used in a lot of electronics or other application.And use the fusion solvent or a solid metal sill can produce this high-quality graphene layer.In the example of fusion solvent, these materials form fusion solvents and as sintering and/or the formation of catalyst to help most Graphene lamellar bodies.For example on the one hand in, the invention provides a kind of method that forms graphene layer, this method can comprise the fusion solvent of a mixed carbon source and a horizontal orientation; The precipitation carbon source spreads all over a graphite linings in this fusion solvent with formation from this fusion solvent; And this graphite linings is separated into most graphene layers.In certain aspects, the heating of carbon source and precipitation are to finish to reduce to pollute in vacuum state.
The method of many mixed carbon sources and fusion solvent can both be considered.In some cases, this carbon source is and the fusion solvent that is molten state; In other situation, this carbon source is to be incorporated into the solvent material that just can present molten state afterwards.For example on the one hand in, mixed carbon source and this fusion solvent comprise provides this carbon source to one solidified solvent layer, and this solidified solvent layer of heating becomes a fusion solvent with this solidified solvent layer of fusion under vacuum environment, and allow the carbon atom of this fusion solvent and carbon source form a congruent melting (eutectic) liquid, this fusion solvent and carbon source then can be remained on the state of congruent melting liquid, and allow graphite linings form and spread all over haply in whole fusion solvent.In another aspect, methane can be formed graphite at sputter by pyrolysis (pyrolyze) on the nickel on the aluminum oxide substrate, and heat nickel is with liquefaction afterwards, and the carbon atom in the graphite can rearrange and form Graphene.
On the one hand, Graphene can be formed from go out molten (exsolution) the supersaturated solution of the carbon of fusion solvent by carbon, in this case, this solvent liquid has oversaturated carbon material, cool off this liquid so that carbon begins melt into kish graphite (kish graphite), this kish graphite can float over the top surface of this fusion solvent, and can repair (mend) mutually and form the high quality Graphene, can apply vibrations to of the repairing of this fusion solvent with the help graphite flake, this technology can make carbon atom effectively diffusion in supersaturation fusion solvent, therefore can be deposited in the edge of graphite lamellar body " island (islands) " easily.Carbon atom with the arrangement of six square keys knot is very stable, therefore can not be dissolved in this fusion solvent easily, on the other hand, the edge of this structure comprise can and solute atoms (as nickle atom) reaction rock key (dangling bond), therefore, dissolving and precipitin reaction at the edge are reversible, make solute atoms by bond and dissolving and recirculation, up to the carbon atom bond, and growth around the edge of this lamellar body is beneficial to six square keys and ties the unstable carbon atom and the solute atoms of carbon and then can improve this program if temperature can be controlled near equilibrium state or if temperature can circulate to remove.
In certain aspects, can use etching reagent (etchant) to remove carbon atom, and be to remove the big carbon molecule that does not meet the Graphene lattice in some cases, this etching reagent comprise but be not limited in hydrogen (H), oxygen (O), nitrogen (N), fluorine (F), chlorine (Cl) with and composition thereof.In addition, can apply methane and spread all in whole surface carbon source as a supplement, and help to repair that these Graphene lamellar bodies form is a successive laminate structure at least haply.On the one hand, etching reagent and methane can be in time and circulation is a successive laminate structure at least haply to repair that these Graphene lamellar bodies form.Moreover the quantity that is controlled at the kish alkene on surface during by repairing can promote the quality of graphene layer, and too many Graphene can produce the gap that can't repair in formed laminate structure, and Graphene very little can reduce productive rate significantly.
More particularly as shown in Figure 2, the thin layer of a high-graphitized graphite 12 can scatter (spread) and spread all in being arranged in mould 16 solidified fusion solvent layers 14, and this high-graphitized graphite comprises natural graphite.In a lot of situations, using graphite material is useful as mould, yet other material can use too, and can be known by one of ordinary skill in the art.In addition, on the one hand in, the thin layer of the graphite that this is high-graphitized can have the thickness less than about 40nm; In another aspect, this thin layer can have the thickness less than about 20nm.No less important and it should be noted that and when high-graphitized graphite is highly purified, can access preferable result, for example, the impurity in the various graphite (as oxygen and nitrogen) can utilize as carrying out chlorination to handle (chlorination treatment) in high temperature and be removed.In addition, the example of nonrestrictive high-graphitized graphite comprises pyrolytic graphite (pyrolitic graphite), sputter graphite (sputtered graphite), natural graphite (natural graphite) etc.On the one hand, the degree of graphitization of this graphite is approximately greater than 0.80; In another aspect, the degree of graphitization of this graphite is approximately greater than 0.90; In aspect another, the degree of graphitization of this graphite is approximately greater than 0.95.
After graphite intersperses among this solidified solvent layer, this die assembly can heat in vacuum oven and the fusion solvent material forms a fusion solvent, when fusion, this solvent and this graphite form congruent melting liquid, for example, if this solvent is a nickel, nickel-carbon eutectic liquids cognition forms along the border between this fusion solvent surface and this high-graphitized graphite; Then, this fusion solvent helps the Graphene lamellar body of making from high-graphitized graphite repaired each other becomes the continuity graphene layer together.This fusion solvent is made up of any material that forms that can be used in catalytic graphite alkene; For example on the one hand in, this fusion solvent can comprise chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), tantalum (Ta), palladium (Pd), platinum (Pt), lanthanum (La), cerium (Ce), europium (Eu) and associated alloys and mixture.In a particular aspects, this fusion solvent can comprise nickel.In another particular aspects, this fusion solvent can be made up of nickel haply.In another particular aspects, this fusion solvent can be formed or be made up of nickel or nickelalloy haply by nickel or nickelalloy.In a particular aspects, this fusion solvent comprises iron, nickel and cobalt.On the one hand, it is dusty material and contacting with graphite material that this fusion solvent has just begun; In another aspect, this solidified solvent can be at graphite will deposit a crust on the part, and this graphite is to put on this surface with the whole bag of tricks, comprises dry method (dry powders), puddling (slurries), sputter or the like.
In some cases, the activity that formed graphene layer can be because solvent the nickel of carbon (as have) and damaging, for example, the carbide bond can produce at the interface between this fusion solvent and the graphite material, the intensity of this bond can cause Graphene in bending (buckle) when this fusion solvent surface removes and/or tear (tear), therefore, in certain aspects, less haply active compound or material can be included in this fusion solvent, the activity that has the fusion solvent of graphite with minimizing, therefore, the active minimizing of this fusion solvent can reduce the amount of the carbide that forms along the interface, thereby helps to regain and have the Graphene that minimum is torn infringement.
Any material that can reduce the activity of this fusion solvent and allow Graphene be formed on this fusion solvent is to be regarded as category of the present invention.On the one hand, this less haply active compound can comprise as the element of gold and silver, copper, lead, tin, zinc and the combination or the alloy of element thereof.In a particular aspects, this less haply active compound is a copper.In another specific embodiment, nickel-copper alloy can be used for the catalyst surface, for this alloy, because so the cause fusion nickel of empty 3d track can dissolve graphite, so and molten copper can't be dissolved graphite because of what its 3d track had taken, ambrose alloy is that a kind of have can be 1084 ℃ of copper fusing points to the alloy of adjusting fusing point between 1455 ℃ of nickel fusing points, therefore corronel can be used in the active optimizing that makes between liquid alloy and graphite flake, this activity can be not powerful in forming carbide, but be enough to mobile carbon atom in Graphene, to touch carbon atoms such as (nudge) to the equilibrium theory of tide, the position of energy minimum just.In another aspect, can use copper-manganese alloy, it is because copper and manganese can moltenly fully mix (miscible), and makes fusing point descend, and it only has 873 ℃ when manganese content is 34.5wt%.
Therefore the making of Graphene is to allow the dull and stereotyped growth of Graphene according to unique arrangement between Graphene and the liquid metal (unique mapping), and reduces because of the unsettled defective locations of catalyst reaction.In addition, heavy melt liquid (density is near 9g/cc) can be as the iron plate (iron plane) of frangible Graphene (density is 2.5g/cc), in this case, fluidstatic balance can be by the floating big area that keeps the graphite flat board, in order to help defective carbon atom to move, can provide ultrasonic vibrations to help sintering program and grain coarsening growth; Then, can reach, and avoid convection current and very slow top cooling by keeping thermograde by allowing the method for the unlikely formation of significant crystal grain or this Graphene that has formed of distortion (buckle) cool off this melt liquid.
Having no intent to will be in conjunction with any specific theory, but believe the formation of solvent material energy catalytic graphite alkene layer, because the size of solvent atom is more much bigger than carbon atom size, the d track of this catalyst material sky can " touch (nudge) " or the guiding carbon atom almost enters the tram of carbon and forms the Graphene reticulated structure, this interaction is not strong enough to the formation carbide, but but be strong enough to carbon atom is moved, therefore solvent liquid is as being decided to be the template of carbon atom to form six side's Graphene reticulated structures, when these reticulated structures form, if being arranged, the then a lot of graphene layer storehouses of any crystal boundary produce some crystal boundaries, will be appreciated that many Graphene storehouse bodies, the graphene layer that is produced is more away from the catalyst surface, begins to produce crystal boundary then easily more.
For example liquid nickel can be arranged any other atom in the graphene layer when Graphene forms, the flowing property of this liquid state template can touch the graphite atom in circulating type ground (around), to repair the interface between the graphite flake, other still has the small detail of much repairing the mechanism of group certainly of fragment (patch) about auto-mending graphite, two different carbon atom zones must be arranged on Graphene, though the dull and stereotyped hexagon-shaped pattern that adopts of Graphene independently, most graphite linings can slight curvatures (buckled) and have Ah method (alpha) district and beta (beta) is distinguished.As long as Graphene is dull and stereotyped to be had other atom (A Faqu) to be aligned in just can to move behind the whole flat board and align, atom of other more than half part then is positioned at contiguous hexagonal central authorities.Because A Faqu is with Fan Dewa power of hearing institute bond, so the electronics that rocks is too faint can't with the nickle atom interaction, the room (vacancies) of having only the carbon atom of beta region can be subjected to the 3d track of nickel attracts, this means that Graphene repairing fragment must be towards relevant nickle atom, in itself, it can touch graphite flake and spread all in nickel surface.
Can reduce any crystal boundary by the catalytic effect of above-described fusion solvent, therefore form big zone, high-quality graphene layer, and if the words that have any crystal boundary to exist then have few crystal boundary at graphene layer.In certain aspects, this Graphene can lack crystal boundary haply or not have crystal boundary fully.Formed graphene layer usually has identical size haply with for its surface formed thereon.Therefore this fusion catalyst surface horizontal orientation accurately can help to have the formation of the graphene layer of high flat degree.It should be noted that this program can be in order to the graphene layer of the single atomic thickness that is shaped, perhaps a graphene layer or the flat board with most discrete graphene layer parallel stacks.In situation described later, the storehouse of graphene layer does not have high electron mobility and high heat conductance because of most graphene layers do not have structural crystal boundary haply.Be the thin layer that forms this graphite in some cases, and can be separated into most graphene layers.
The characteristic that the degree that the temperature of die assembly can be enhanced is desired to reach according to the character and the Graphene product of solvent and determining.Yet on the one hand, this die assembly is to be heated to greater than about 1000 ℃; In another aspect, this die assembly is to be heated to greater than about 1300 ℃; In aspect another, this die assembly is to be heated to greater than about 1500 ℃.Similarly, Graphene can be manufactured in various pressure, for example on the one hand in, the pressure in the vacuum oven be less than about 5 the holder ears (Torr); In another aspect, the pressure in the vacuum oven is from about 10
-3To about 10
-6The holder ear.
After graphene layer forms, cool off this die assembly to help removing of Graphene product.In certain aspects, evenly cooling off this surface is helpful with the Flatness of keeping the surface.On the one hand, this cooling can be by coming out heat conduction under the solvent surface, and keep heat on the solvent surface in high temperature and finish; In case the solvent cooling, graphene layer can be torn from the surface, and Graphene can be torn from the surface with individual layer shape or multilayer shape, because 3.35 dusts are arranged between laminate structure
The interval, so can produce this action of tearing.According to the size on solvent surface, graphene layer can be torn constantly and can be wound in a rolling strip device.
Fig. 3 shows the Photomicrograph of oneself Graphene described herein to Fig. 6.Fig. 3 shows the graphite linings with fold lines formed thereon, and as described, graphene layer from then on graphite linings is separated.As shown in Figure 4, the fold lines of amplification shows that graphite linings is that successive and nothing are broken haply.Fig. 5 shows the pliability of graphite linings, and Fig. 6 is presented at the density distribution of the graphene layer surface microorganism (microbe) that exposes, and the microorganism on graphene layer can be removed by being heated to about 50 ℃.This is reversible reaction, so these graphene layers can be as the inductor block of microorganism.
As mentioned above, in some cases, graphene layer can separate from the thick graphite linings that is formed at the solvent surface.The method of various these graphene layers of separation is all possible, and it all is contained in the category of the present invention.On the one hand, this graphite linings can heat in sulfuric acid, and the insertion of sulphur atom can be separated into this graphene layer most graphene layers, and each graphene layer can be purified (for example in the hydrogen or halogen environment at high temperature) and remove impurity and/or defective afterwards.
In the present invention on the other hand, can use the gasification program and eliminate defective, because defective in Graphene and crystal boundary are unsettled, the carbon atom that is positioned at terminal seat is to tend to dissolvedly, the carbon atom in the Graphene reticulated structure is then relatively stable.Oxygen after the introducing heating or steam spread all in the surface of graphene layer can cause that desiring the relevant unsettled carbon atom of crystal boundary is gasificated into carbon monoxide (CO) or carbonic acid gas (CO
2), by control CO/CO
2Ratio (dividing potential drop), carbon atom can be removed from defective locations, and grows in every way in the Graphene lamellar body.Except oxygen, halogen gas (as fluorine and chlorine) also can use.
Graphene layer can be grown in the pyrolysated mode of carbonaceous gas (for example methane, ethane, propane, butane etc.) in addition, this mode can be used in the growing high-quality Graphene, avoids the supersaturation and the quick and uncontrolled growth of carbon because the solubleness of carbon is controlled.Therefore, can add carbonaceous gas (as CO/CO
2) mixture, and the dividing potential drop of carbon monoxide and carbonic acid gas can be different, the concentration with control carbon carbon in the fusion solvent makes the defective in the graphene layer that is produced minimize by this.
Also can use the solid metal base material to make graphene layer.On the one hand, for example, a method that forms graphite linings (or graphene layer) comprises: heating one solid base material arrives a solvent temperature (solubilizingtemperature) under vacuum state, and this solvent temperature is lower than the fusing point of this solid metal base material; And will be dissolved among this heated solid metal base material from the carbon atom in graphite source.Can increase the solubleness of carbon atom in this solid metal base material in this graphite source by heating this solid metal base material, carbon atom is moved among this metal.This method can further comprise cools off with a sufficient speed that this heated solid metal base material reaches so that this dissolved carbon atom forms a graphite linings to any surface of this solid metal base material.Aforementioned surfaces can comprise in abutting connection with the surface in graphite source and/or with graphite source facing surfaces.After forming graphite linings, can remove this graphite linings by this solid metal base material.In some aspects, can when heating and/or cooling off this solid metal base material, adopt vacuum condition to avoid oxidation when forming Graphene.
Can consider various solid metal base materials, and the solid metal base material that any this class can the dissolved carbon atom is considered as all among category of the present invention.On the one hand, for example, this solid metal base material has comprised a composition, this composition be selected from chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), tantalum (Ta), palladium (Pd), platinum (Pt), lanthanum (La), cerium (Ce), europium (Eu), iridium (Ir), ruthenium (Ru), rhodium (Rh), its alloy with and binding substances.In a particular aspects, this solid metal base material comprises nickel.
In some aspects, can use a less haply active material to adjust the solubleness of carbon atom among the solid metal base material.This haply the example of less active material comprise and be not subject to gold (Au), silver (Ag), copper (Cu), plumbous (Pb), tin (Sn), zinc (Zn), its in conjunction with and alloy, as earlier aforementioned in the literary composition.Less haply active material can be attached on this solid metal base material to adjust the solubleness of carbon atom by various different modes.On the one hand, for example, this less haply active material can be mixed in the solid metal base material.Aforementionedly for example can comprise mixture and alloy or the like.On the other hand, this solid metal base material can form a multilayer (multilayer) solid metal base material.For example, on the one hand, this solid metal base material comprises a first metal layer and one second metal level, and wherein this first metal layer is a solid metal substrate material that is used for the dissolved carbon atom, and this second metal level is the less haply active material that is used for adjusting carbon atom solubleness.In a specific example, can be to a bronze medal layer in conjunction with a nickel dam.Carbon atom in this heats this matrix material, an adjacent graphite can be originated is dissolved among this nickel dam.Because carbon atom is lower haply in the solubleness of copper layer, so carbon atom will mainly concentrate among this nickel dam.
Compared to the fusion solvent, use wherein structural stability excellence next that benefit is this solid metal base material of solid metal base material than melt liquid.Among the example of fusion solvent, a metallic substance carries out the surface that the fusion Graphene is formed at this liquid metal.When this metallic substance solidifies through heating and cooling, because at least a portion surface tension change makes the metal material surface alteration of form.This surface shape changes can cause that formed graphene layer produces defective in some cases on metal material surface.See through and carbon atom to be dissolved in a heating to reach among the solid metal base material of a temperature and this temperature is lower than this base material fusing point, the profile of its growth surface and surface configuration can not change haply, and in some example, can make that graphene layer has less defects.
Temperature when therefore, this carbon atom dissolves (solvent temperature) can change according to the difference of the material that is used for this solid metal base material.Anyly keep this solid metal substrate surface shape and the temperature of solubilized carbon atom all should be considered to be included in the present invention's the category.In a particular aspects, this solid metal base material is a nickel, and this solvent temperature is by about 500 ℃ to about 1450 ℃.On the other hand, this solid metal base material is a nickel, and this solvent temperature is by about 500 ℃ to about 1000 ℃.Again on the other hand, this solid metal base material is a nickel, and this solvent temperature is by about 700 ℃ to about 800 ℃.
Also can change the rate of cooling of this solid metal base material according to the character of solid metal base material and formed Graphene.Should notice that this heated solid metal base material can carry out active or passive type cools off to reach specific rate of cooling.Rate of cooling is compared slow rate of cooling and carbon atom can be pulled out metal base quickly fast, and this may cause grapheme material that different characteristics or different lattice qualities are arranged.
In some aspects, when forming this graphene layer, this solid metal base material can be placed on the support base material.This solid metal base material can be attached on this support base material or it only is arranged on this support base material.Except providing a supporting, but this support base material also auxiliary adjustment temperature, particularly refrigerative speed.The support base material quality that is increased may be used heating power and regulate material, and this solid metal base material can cooled off aspect space and time more equably.
This graphite carbon source can be combined in each position of this solid metal base material.On the one hand, for example, this graphite carbon source can be arranged between support base material and the solid metal base material.Among this example, Graphene can be formed on this solid metallic surface and between graphite carbon source and solid metallic surface; It can be formed on the solid metal base material through moving through the mode of solid metal base material and relative graphite carbon source; Or it can be formed on these different surfaces simultaneously.On the other hand, this graphite carbon source can be arranged on the surface of this solid metal base material and this support base material relatively.In this example, Graphene can be formed on this solid metal base material and between graphite carbon source and solid metal base material; It can see through the mode that moves through the solid metal base material and be formed on this solid metal sill and relative graphite carbon source, and the solid metal base material is not joined on this support base material; Perhaps it can be formed on these different surfaces simultaneously.
Except graphite and high-graphitized graphite, also can use diamond material to be used as carbon source forming graphene layer, and this diamond can be lower than under the temperature of fusing point of solid metal base material and dissolve one with among the situation that is applied to fusion solvent and solid metal base material.Employed diamond material can comprise rough diamond, rhinestone, monocrystalline diamond, polycrystalline diamond, class bore carbon (diamond like carbon, DLC), non-crystal diamond (amorphous diamond) and other analogue.Wherein benefit of using this diamond material is can produce the graphene layer of rhombohedron (rhombohedral) sequence (ABCABC....) but not the sequence that produces traditional ABABAB.....Therefore, a method that forms the rhombohedron graphite linings can comprise on the one hand: mix the fusion solvent of a diamond source and a horizontal orientation, and the diamond that is deposited in this fusion solvent is originated to form a rhombohedron graphite linings that is dispersed throughout in the fusion solvent.
In aspect more of the present invention, the graphene layer various hotchpotchs that can mix, hotchpotch can be in order to changing the physical properties of graphene layer, and/or it can be in order to change the physical interaction among the graphene layer of graphene layer storehouse body.This doping can produce by hotchpotch is added in the fusion solvent when this graphite linings forms, and perhaps can produce by dopant deposition thing in laminate structure after graphite linings forms.For example can form P-type semiconductor by doped with boron.Various hotchpotchs can both be in order to being doped in the graphene layer, specific nonrestrictive example comprise boron, phosphorus, nitrogen with and combination.Mixing also to be used to change the electron mobility of graphite linings specific region, in laminate structure, forming circuit, the specific doping in this zone can be in a graphene layer distributed circuit figure.Moreover when graphene layer had the height electron mobility, the electroconductibility between the graphene layer in the storehouse body then can be limited.By doping metals atom or other conductive material, the electron mobility in the laminate structure of storehouse can increase.
The present invention provides the graphene layer of making according to step described herein again, and this laminate structure can comprise the storehouse body of single graphene layer or most graphene layers; Moreover, as mentioned above, graphene layer in the aspect of the present invention has high-quality material, if the words that have any crystal boundary to exist then have few crystal boundary, in addition, graphene layer can be made according to each side described herein, because the synthetic of grapheme material is to spread all over whole solvents or catalyst surface, so it has than the previous possible bigger size in aspect, but should be appreciated that the graphite linings that has a virtually any size according to manufacturing of the present invention all is considered as in category of the present invention, method of the present invention meets large-area graphene layer especially, the size of this laminate structure need be had nothing in common with each other according to the size on catalyst surface, yet in a particular aspects, the size of graphite linings can be greater than about 1.0mm
2In another aspect, the size of graphite linings is from about 1.0mm
2To about 10mm
2In aspect another, the size of graphite linings is from about 10mm
2To about 100mm
2Still in one side, the size of this graphite linings is greater than about 100mm
2In one side, the size of graphite linings is greater than about 10cm in addition
2More in one side, the size of graphite linings is greater than about 100cm
2In one side, the size of graphite linings is greater than about 1m again
2
The physical property of graphene layer makes it become a material that helps being bonded to various devices.Can consider a lot of devices and purposes, following example should not be regarded as any restriction.For example, on the one hand in, the high electron mobility of Graphene makes it can be as the assembly of unicircuit; In another aspect, Graphene can be as the transmitter of the single or most molecules of detecting (comprising gas), 2 dimension (2D) structures of graphite linings can be effectively be exposed to the integral body of the material of Graphene in the context, therefore make it become effective material of detecting molecule, this molecule detecting can measure indirectly, when gas molecule is absorbed in the surface of Graphene, the position of absorption can present local the transformation aspect resistance.Graphene is a kind of advantageous material for this detecting, because of its high conductivity with utmost point lower noise, and cause the change of resistance to be detected.In another aspect, graphite linings can be used for as surface acoustic wave filter (SAW filter), in this case, because the resonance of grapheme material, so can the transfer overvoltage signal.In aspect another, can use Graphene as pressure transmitter.In one side, graphene layer can be used for the transparency electrode as the application of photodiode (LED), liquid-crystal display (LCD) and solar panel in addition.In addition, Graphene can with insulating material (for example
) film is common reels to make electrical condenser.Moreover Graphene can be reeled to make excellent capacitor material jointly with the insulating hexagonal boron nitride.And Graphene is layed on the semiconductor material (for example silicon), and produces the electronics connection line (electricalinterconnect) of electronic installation through etching.
The present invention provides hexagonal boron nitride layer and associated method again.For example provide a kind of method that forms the hexagonal boron nitride layer on the one hand, this method can comprise the fusion solvent of mixed nitride boron source and horizontal orientation, and this boron nitride source of precipitation spreads all over hexagonal boron nitride layer in this fusion solvent with formation from this fusion solvent.On the one hand, mixed nitride boron source and fusion solvent comprise provides this boron nitride source to one solidified solvent layer, and this solidified solvent layer of heating becomes a fusion solvent with this solidified solvent layer of fusion under nitrogen environment, and allows this fusion solvent and boron and nitrogen-atoms from boron nitride source form a congruent melting (eutectic) liquid.In another aspect, this boron nitride source of precipitation comprises and keeps this fusion solvent and the boron nitride source state at congruent melting liquid from this fusion solvent, and allows the hexagonal boron nitride layer form and spread all over haply in whole fusion solvent.
More specific is is shown in Fig. 7, and boron nitride source thin layer (for example thin slice 32) can be scattered in mould 36 on the solidified fusion solvent layer 34.In a lot of situations, using boron nitride material is favourable as mould, but other material is useful too, and can know in one of ordinary skill in the art.In addition, on the one hand in, the boron nitride source thin layer can have the thickness less than about 40nm; In another aspect, the boron nitride source thin layer can have the thickness less than about 20nm.
After boron nitride being scattered in this solidified fusion solvent layer, die assembly can be heated in having the boiler of nitrogen environment to melt this solvent layer.This nitrogen environment is used to stop the nitrogen steam that forms from boron nitride, moreover, the solubleness of nitrogen is far below boron in molten metal, the solubleness of nitrogen can increase by adding nitrogen absorption agent (for example nickel, cobalt, iron, tungsten, manganese, molybdenum, chromium and composition thereof), by increasing the solubleness of nitrogen, can increase the growth rate of laminate structure, and reduce density of defects.
Therefore this catalyst surface helps the hexagonal boron nitride thin slice is the continuity hexagonal boron nitride from the boron nitride source repairing.This fusion catalyst is the material that is formed by any energy catalysis successive hexagonal boron nitride layer.For example on the one hand in, this fusion catalyst comprises lithium (Li), sodium (Na), potassium (K), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), lithium hydride (LiH), lithium nitride (Li
3N), sodium nitride (Na
3N), magnesium nitride (Mg
3N
2), CaCl2 (Ca
3N
3) and alloy and composition; In a particular aspects, this catalyst surface comprises lithium nitride; In another particular aspects, this catalyst surface is made up of lithium nitride haply.In another particular aspects, lithium hydride can use as the fusion solvent.
Any crystal boundary energy in the hexagonal boron nitride layer reduces by the catalytic effect of fusion solvent, therefore forms big area, high-quality hexagonal boron nitride layer, if the words that have any crystal boundary to exist then have few crystal boundary.Formed hexagonal boron nitride layer has identical size haply with supplying its catalyst solvent that generates thereon.The horizontal orientation that the fusion solvent is smooth helps the formation of the hexagonal boron nitride layer of elevation planeization.It should be noted that this program can be in order to form the hexagonal boron nitride layer of single atomic thickness, a perhaps hexagonal boron nitride layer, the flat board that perhaps has most discrete hexagonal boron nitride layer parallel stacks.After situation in, the storehouse body of hexagonal boron nitride layer has high electron mobility and high thermal conductivity, its be because most hexagonal boron nitride layers have the crystal boundary of unstructuredness haply.
Die assembly can heated temperature can be according to the character of fusion solvent and the desired characteristic of hexagonal boron nitride product and different.Yet on the one hand, this die assembly can be heated to greater than about 1000 ℃; Again on the other hand in, this die assembly can be heated to greater than about 1300 ℃; In aspect another, this die assembly can be heated to greater than about 1500 ℃.Similarly, hexagonal boron nitride can produce in various pressure, for example on the one hand in, the nitrogen environment in boiler is less than about 1atm.
After this hexagonal boron nitride layer formed, this die assembly can be cooled off and help removing of hexagonal boron nitride product.In certain aspects, evenly cooling surface is favourable with the Flatness of keeping this solvent surface.On the one hand, this cooling can be finished in higher temperature by conduction heat under the fusion solvent and the heat that maintains on the fusion solvent, in case the solvent cooling, the hexagonal boron nitride layer can be torn from the surface, and hexagonal boron nitride is torn and become simple layer shape structure or most laminate structure.According to the size on catalyst surface, hexagonal boron nitride can be torn constantly and can be wound in a rolling strip device.
In aspect more of the present invention, the hexagonal boron nitride layer various hotchpotch that can mix, hotchpotch can be in order to changing the physical properties of hexagonal boron nitride layer, and/or it can be in order to change the physical interaction in the hexagonal boron nitride layer of hexagonal boron nitride layer stack body.This doping can produce by hotchpotch is added in the die assembly when this hexagonal boron nitride layer forms, and perhaps can produce by dopant deposition thing in laminate structure after the hexagonal boron nitride layer forms.Various hotchpotchs can both be in order to be doped in the hexagonal boron nitride layer, and specific nonrestrictive example comprises silicon, magnesium and composition thereof.Silicon doping is formed the N-type semiconductor material in hexagonal boron nitride.
The present invention also provides according to the made hexagonal boron nitride of step described herein, and this laminate structure comprises the storehouse body of single hexagonal boron nitride layer or most hexagonal boron nitride layers.Moreover as mentioned above, these hexagonal boron nitride layers of aspect are high-quality material according to the present invention, if the words that have any crystal boundary to exist then have few crystal boundary.In addition, the hexagonal boron nitride layer can be made according to each side described herein, because the synthetic of hexagonal boron nitride material is to spread all over whole catalyst surfaces, so it has than the previous possible bigger size in aspect, but should be appreciated that the hexagonal boron nitride layer that has a virtually any size according to manufacturing of the present invention all is considered as in category of the present invention, method of the present invention meets large-area hexagonal boron nitride layer especially, the size of this laminate structure need be had nothing in common with each other according to the size on catalyst surface, yet on the one hand, the size of hexagonal boron nitride layer can be greater than about 1.0mm
2In another aspect, the size of hexagonal boron nitride layer is from about 1.0mm
2To about 10mm
2In aspect another, the size of hexagonal boron nitride layer is from about 10mm
2To about 100mm
2Still in one side, the size of hexagonal boron nitride layer is greater than about 100mm
2In one side, the size of hexagonal boron nitride layer is greater than about 10cm in addition
2More in one side, the size of hexagonal boron nitride layer is greater than about 100cm
2In one side, the size of hexagonal boron nitride layer is greater than about 1m again
2
The physical property of hexagonal boron nitride layer makes it become a material that helps being bonded to various devices.Can consider a lot of devices and purposes, following example should not be regarded as any restriction.For example, on the one hand in, hexagonal boron nitride has a high energy gap (5.97eV) and can send far ultraviolet rays yue (deep uv, about wavelength 215nm).Therefore, hexagonal boron nitride can be used for as a LED or solar cell.For example, the shortest bond length of these material tool solids
So the diamond than bidimensional is also hard, so it has very large energy gap, can launch far ultraviolet rays yue, this has in order to form white light LEDs for little shadow technology of nanometer and UV fluorescence excitation very much.Can form the P-N interface to make transistor, it is original position (in-situ) to form the Graphene inter-connected circuit.Among another embodiment, Graphene or single boron nitride also have high velocity of sound and thermal conductivity again, and therefore, it can be used for surface acoustic wave filter, supersonic speed generator and the scatterer of ultra high frequency.Because of the hexagonal symmetry, these materials also have piezoelectric properties (piezoelectric).In another embodiment, Graphene or boron nitride layer can be used for as chemisorption gas inductor block, be used for by aqueous solution electrolysis with the accurate electrode (delicate electrode) of the PPB degree of analyzing ion (as lead), have the transparency electrode of hydrogen termination etc.
Should notice that this hexagonal boron nitride can have similar arrangement by fusion nickel.As previously mentioned, liquid nickel can be arranged any other atom in the graphite linings when Graphene forms, the flowing property of this liquid state template can touch the graphite atom circulating type, to repair the interface between the graphite flake, other still has the small detail of much repairing the mechanism of group certainly of fragment (patch) about auto-mending graphite, two different carbon atom zones must be arranged on Graphene, though the dull and stereotyped hexagon-shaped pattern that adopts of Graphene independently, most graphite linings can slight curvatures and have Ah method (alpha) district and beta (beta) is distinguished.Align as long as just can move after the Graphene flat board has other atom (A Faqu) in alignment with whole flat board, atom of other more than half part then is positioned at contiguous hexagonal central authorities.Because A Faqu is with Fan Dewa power of hearing institute bond, so the electronics that rocks is too faint can't with the nickle atom interaction, the room (vacancies) of having only the carbon atom of beta region can be subjected to the 3d track of nickel attracts, this means that Graphene repairing fragment must be towards relevant nickle atom, in itself, it can touch graphite flake and spread all in nickel surface.In the situation of hexagonal boron nitride, this directivity is arranged more clear, and it is mated because of the boron atom and the nitrogen-atoms of boron nitride by the electronics complementarity.Using nickel to come catalysis in the situation of group mechanism, because the character of empty 3d orbital makes nickle atom and extra electronic energy be pushed toward the boron atom.
Hexagonal boron nitride has very broad direct gap, can discharge far ultraviolet rays yue by electric field is provided.Hexagonal boron nitride is the inherent N-type semiconductor, and it can be strengthened by the doping of beryllium (Be) or magnesium (Mg), and this negative electrode can self-excitation (selfresonate), and therefore can be used as the laser electrode, and is used for scatterer with system component (built).
Various devices all can be considered in conjunction with hexagonal boron nitride and graphene layer.For example, the hexagonal boron nitride layer has high energy gap, and is the good insulation performance body therefore.By changing Graphene and hexagonal boron nitride layer, can produce (effective capacitative) material of effective capacitance amount, this matrix material is to be curled with storehouse form, planar alignment or stratiform to form the composite cylindrical kenel and produce, and other potential purposes comprises unicircuit, automobile battery, solar cell, the battery of mobile computer and the battery of mobile phone by the interconnective three-dimensional boron nitride crystal pipe of Graphene.Because having thin cross section, this matrix material can produce the run-in index solar cell.Extra use comprises gas and microbiological sensor (microbe sensor), and DNA and protein chip.
The present invention also provides Graphene/hexagonal boron nitride matrix material.For example on the one hand in, the electronics precursor material has a matrix material, comprises a graphite linings and is arranged at hexagonal boron nitride layer on this graphite linings.In a particular aspects, this matrix material comprises most graphene layer and hexagonal boron nitride layers that are provided with at interval.These laminate structures can be used in the various electronic packages, and it is to be understood by one of ordinary skill in the art.For example, become cylindrically by most laminate structures that are provided with at interval of reeling, can be formed with the cylindrical capacitor of usefulness.
These matrix materials can use fusion solvent method described herein manufacturing, or can form the method for this laminate structure by other.For example on the one hand in, the method for making Graphene/hexagonal boron nitride matrix material comprises provides one to have graphite linings and be arranged at template on the base material; And deposition boron nitride source material on this graphite linings to form a hexagonal boron nitride layer thereon, therefore when deposition, use the template of graphite linings as the hexagonal boron nitride layer, this hexagonal boron nitride layer is sedimentary by any known method institute, comprises chemical Vapor deposition process (CVD) and physical vaporous deposition (PVD).
Be to make in an advantage of the method for this announcement and have the size that is predetermined and the Graphene and the hexagonal boron nitride of shape, because material layer can be formed on the surface that spreads all in the fusion solvent, so the size and dimension of the fusion solvent that the size and dimension of Graphene that is produced and hexagonal boron nitride layer can be by horizontal orientation determines.Therefore, by selecting mould in advance, with the fusion solvent surface that generation has specific dimensions and shape, then the shape and size of this Graphene and hexagonal boron nitride layer also can be predetermined.Therefore this size and dimension that is predetermined is not only the result who a material layer is cut to specified shape, but forms the material layer with specific and size and dimension of selecting in advance or being predetermined.
Provide the method that forms silicon carbide layer in the present invention on the other hand, this method comprises the fusion solvent of hybrid silicon carbide source and horizontal orientation, and this silicon carbide source of precipitation spreads all in the silicon carbide layer of this fusion solvent with formation from this fusion solvent.
Embodiment
Embodiment 1
One graphite block is machined and forms the discoid depressed part with about 3mm height, place one and have the pure nickel plate of about 1mm thickness in this depressed part, the graphite of ultra-high purity then intersperses among on the nickel plate, and this assembly is to be positioned in the tubulose boiler, provides about 10 in this boiler
-5The vacuum environment of holder ear; Then nickel can fusion fully in 1500 ℃, and be maintained at molten state 30 to 60 minutes, controlled temperature is so that the graphite edge exceeds 50 ℃ than these fusion nickel slurries (bath) approximately, and such temperature contrast can reduce the convection current of liquid, and may hinder the formation of the Graphene lattice of formation; This boiler can slowly cool off afterwards and the graphene layer that is produced is torn from this refrigerative nickel plate.
Embodiment 2
One graphene layer is to form according to embodiment 1, and difference is that this nickel plate is with electroless plating one nickel-phosphorus (Ni-P) layer to be arranged, and nickel-nickel phosphide (Ni-Ni
3P) Ceng eutectic point is 870 ℃, therefore can allow the Graphene flat board form in 1000 ℃.
Embodiment 3
One graphene layer is to form according to embodiment 1, and difference is that this ultrapure graphite is that mixture with the nickel compound of the carbonyl of ultrapure graphite flake and 70wt% is replaced.
Embodiment 4
Invar (Fe2Ni) powder is dispersed in the bottom of graphite jig, and the graphite of high-graphitized degree (as natural graphite) powder is to disperse along this Invar powder top, and this die assembly is in vacuum (for example 10
-5Torr) be heated in this alloy of fusion (as 1300 ℃, for the congruent melting constituent of metal-carbon).Because the density of graphite (2.25) is the density (8-9) far below alloy, so graphite flake can float over the top of molten alloy.Moreover because the platelet morphology of graphite, Graphene is dull and stereotyped can be parallel with the molten alloy surface.In the case, the Graphene fragment can be repaired together by iron alloy by catalysis, and this step is from group mechanism and self-repair mechanism, therefore can form the Graphene flat board of meter level size.
After the dull and stereotyped growth of Graphene, these fusion slurries can be lowered the temperature under its surface keeps smooth state, it can be by heat upwards conduction from the below, and keep top layer to finish in a higher temperature, in case this assembly cooling, then the Graphene flat board that may also stick on alloy is torn from bottom and since between the Graphene flat board than large-spacing
So the action of tearing can be finished with the continuity step.
Embodiment 5
The pure natural powdered graphite mixes mutually with the nickel and the copper (having same ratio) of its 10 times of weight, this mixture is positioned in the graphite jig, and under vacuum state, be heated to 1300 ℃ six hours.Graphite dissolves and in the edge precipitation, it has the abundant electronics that rocks, and formed lamellar body floats on the melt liquid.After six hours, temperature is reduced between liquidus line and the solidus curve, the feasible liquid and solid-state equilibrium state that reaches, and in this stage, unsettled carbon atom can dissolve, and more stable atom can precipitate, and this melts can solidify at leisure.Utilize hydrogen to feed in the vacuum further to remove the graphite defective by the carbon atom that gasifies.Large-scale Graphene is infiltrated in the hot sulfuric acid to be separated into graphene layer, obtain these graphene layers and engage (wafer bonding) by the wafer under 800 ℃ in a vacuum and be arranged on the Silicon Wafer that has polished, this surface further feeds fluorine with by forming CF
4Gas and remove any defective.
Embodiment 6
Pure natural hexagonal boron nitride (hBN) powder mixes in nitrogen atmosphere mutually with its lithium hydride, and be heated to more than 1300 ℃ and form hBN solution, this fusion mistake hold temperature 1300 ℃ six hours, be cooled to the temperature between liquidus line and the solidus curve afterwards, then this congruent melting melts is slowly lowered the temperature, and hydrogen introduced removing unsettled boron and nitrogen-atoms, thereby formed hBN film seethes with excitement in sulfuric acid and is separated out laminate structure.Obtained hBN layer is arranged on the graphite linings of coating Silicon Wafer in the example 5, one titanium film is deposited on the hBN layer by sputter, this titanium film of etching is with digital transistor umformer (transducer) in forming, and it is to convert electromagnetic riveting machine signal to surface acoustic wave, and vice versa.
Embodiment 7
Hexagonal boron nitride (hBN) film doping has beryllium so that it becomes P-type material; Aluminium nitride (AlN) is to be deposited on the hBN film with molecular beam epitaxy technology (MBE), and is doped with carbon atom to form n type material.Formed p-n connects face can emit ultraviolet ray (UV) immediately after accepting direct current.
Certainly, need be appreciated that above-described arrangement all only is in the application of describing principle of the present invention, many changes and different arrangement can also be under the situation that does not break away from the spirit and scope of the present invention be come out in one of ordinary skill in the art are contemplated, and application range also contains above-mentioned change and arrangement.Therefore, be the most practical above-mentioned and most preferred embodiment although the present invention is described by specific and detailed description ground, can under the situation that does not depart from principle of the present invention and viewpoint, do many as changes such as size, material, shape, pattern, function, working method, assembling and uses in one of ordinary skill in the art.
Claims (20)
1. method that forms graphite linings, it includes:
Heating one solid metal sill reaches a solvent temperature under vacuum state, and wherein this solvent temperature is lower than the fusing point of this solid metal base material;
The carbon atom in one graphite source is dissolved among the described heated solid metal base material; And
Cool off described heated solid metal base material so that described dissolved carbon atom forms a graphite linings at least one surface of described solid metal base material with a competent speed, wherein formed graphite linings does not have lattice imperfection haply.
2. the method for formation graphite linings according to claim 1, it further comprises on described solid metal base material and removes graphite linings.
3. the method for formation graphite linings according to claim 1, wherein, described graphite linings is high-graphitized.
4. the method for formation graphite linings according to claim 1, wherein, described solid metal base material comprises a composition, this composition be selected from chromium, manganese, iron, cobalt, nickel, tantalum, palladium, platinum, lanthanum, cerium, europium, iridium, ruthenium, rhodium, its alloy with and binding substances.
5. the method for formation graphite linings according to claim 1, wherein, described solid metal base material comprises nickel.
6. the method for formation graphite linings according to claim 1, wherein, described solid metal base material comprises a less haply active material and adjusts the carbon dissolution degree.
7. the method for formation graphite linings according to claim 6, wherein, described less haply active material be selected from gold and silver, copper, lead, tin, zinc, its binding substances with and alloy.
8. the method for formation graphite linings according to claim 6, wherein, described less haply active material is a copper.
9. the method for formation graphite linings according to claim 6, wherein, described solid metal base material comprises this solid metal base material and comprises a first metal layer and one second metal level, wherein this first metal layer can be used for the dissolved carbon atom, and this second metal level can be used for adjusting carbon atom solubleness.
10. the method for formation graphite linings according to claim 1, wherein, described solid metal base material is a nickel, and described solvent temperature is 500 ℃ to 1450 ℃.
11. the method for formation graphite linings according to claim 1, wherein, described solid metal base material is a nickel, and described solvent temperature is 500 ℃ to 1000 ℃.
12. the method for formation graphite linings according to claim 1, wherein, described solid metal base material is a nickel, and described solvent temperature is 700 ℃ to 800 ℃.
13. a method that forms graphite linings, it includes:
One solid metal base material is arranged on the support base material;
Connect a graphite carbon this solid metal base material of originating;
This solid metal base material of heating arrives a solvent temperature under vacuum state, and this solvent temperature is lower than the fusing point of this solid metal base material;
Carbon atom in the graphite carbon source is dissolved among this heated solid metal base material; And
Cool off this heated solid metal base material to be formed a graphite linings by dissolved carbon atom at least one surface of this solid metal base material with a competent speed, wherein, this graphite linings does not have lattice imperfection haply.
14. the method for formation graphite linings according to claim 13, wherein, the step that the described graphite carbon of described connection source is attached to described solid metal base material comprises described graphite carbon source is arranged between described support base material and the described solid metal base material.
15. the method for formation graphite linings according to claim 13, wherein, the originate step of described solid metal base material of the described graphite carbon of described connection comprises an originate surface of described solid metal base material of described graphite carbon is gone up and described relatively support base material.
16. the method for formation graphite linings according to claim 13, its size and shape that further comprises the described solid metal base material of preliminary election has the graphite linings of pre-set dimension and shape with generation.
17. a graphite linings of being made by the described method of claim 16, wherein, described graphite linings comprises a default size and shape.
18. graphite linings according to claim 17, it is integrated in the device, and this device is to be selected from molecule sensor, photodiode, liquid-crystal display, solar panels, pressure transmitter, surface acoustic wave filter, acousticresonance device, transistor, electrical condenser; Transparency electrode, ultraviolet laser, DNA chip with and combination.
19. graphite linings according to claim 17, wherein, described graphite linings is coupled on the Silicon Wafer.
20. graphite linings according to claim 19, this graphite linings is subjected to etching and forms the electronics connection line.
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| US12/713,004 US20100218801A1 (en) | 2008-07-08 | 2010-02-25 | Graphene and Hexagonal Boron Nitride Planes and Associated Methods |
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| CN103663434A (en) * | 2012-09-12 | 2014-03-26 | 铼钻科技股份有限公司 | Method and device for mass production of graphene |
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| CN113390959A (en) * | 2021-04-30 | 2021-09-14 | 西安交通大学 | Composite sensitive film and preparation method thereof, gas sensor and preparation method thereof |
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