CN101426966A - Chemically attached diamondoids for CVD diamond film nucleation - Google Patents

Abstract

Provided is a novel method for nucleating the growth of a diamond film. The method comprises providing a substrate having a diamondoid chemically attached to it, which serves as a superior nucleation site, and then facilitating the growth of the diamond film.

Description

The diamantane that is used for the chemistry connection of CVD diamond film nucleation

Disclosed is improving one's methods of diamond film nucleation growth.The invention still further relates to the new application of this diamond-film-like.

Background of invention

Can obtain diamantane (diamondoid) with multiple shape and size.Diamantane is bridge-ring naphthenic hydrocarbon.Lower diamondoids: single diamantane (adamantane), two diamantane (diamantane) and three diamantane (triamantane) are made of 1,2 and 3 diamond-like crystal cage respectively.The higher diamondoids from four diamantane to ten diamantane of recent findings is made of 4-11 diamond-like crystal cage.United States Patent (USP) 6,815,569; 6,843,851; 6,812,370; 6,828,469; 6,831,202; 6,812,371; 6,844,477; With 6,743, such higher diamondoids has been described in 290, as a reference at this full content of quoting these patents.

Attempt to use chemical vapor deposition (CVD) technology diamond synthesis film can trace back to before the eighties in 20th century.The result of these effort is the carbon that new form occurred, and it mainly is unformed in essence, yet it contains the sp of height ³-hybrid bond, and therefore show a lot of adamantine features.Created term " diamond-like carbon " (DLC) for describing such film, though the not definition accurately in the literature of this term.In " the marvellous world of carbon ", Prawer instructs because most of diamond-like materials show as the mixture of of bonding, (or the sp of four-coordination ³Hydridization) ratio of carbon atom is measuring of described material " quasi-diamond " content.United States Patent (USP) 6,783 has been described the generation of successful CVD diamond film in 589, quotes its full content as a reference at this.Other publication that diamond film growth is discussed comprises Spitsyn, B.V., " nucleation and the nanostructure of diamond in gas phase Diamond filmSynthetic ", NATOScience Series II:Mathematics, Physics and Chemistry 155 (coating that nano structure membrane and nano-dispersed are strengthened), 123-136 (2004), Soga, T.; Sharda, T.; Jimbo, T., " precursor of the CVD growth of nanocrystalline diamond, " Physics of the Solid State (Translation of Fizika Tverdogo Tela (Sankt-Peterburg), 46 (4), 720-725 (2004); Jager, W.; Jiang, X., " diamond hetero epitaxy-nucleation, interface structure, film growth, " Acta MetallurgicaSinica (English alphabet) 14 (6), 425-434 (2004); Jiang, X., " the CVD diamond film of texture and hetero epitaxy, " semi-conductor and semi-metal 76 (diamond film I), 1-47 (2003); Iijima, S., Aikawa, Y.﹠amp; Baba K. " growth of the diamond particles in the chemical vapour deposition, " J Mater Res.6,1491-1497 (1991); Philip J., Hess, P, Feygelson T., Butler J.E., Chattopadhyay S., Chen K.B., and ChenL.C, " elasticity of nanocrystalline diamond film, machinery and thermal characteristics, " Journal of Appl.Physics is #3 (2003) V.93.

The potentiality of diamond-like materials in microelectronics and other application are unlimited.Produce the adamantine good method of CVD although exist really, require further improvement always.Nucleation method in the past is subject to them can only produce the polycrystalline diamond film.The application of polycrystalline film, special is limited for electronics application, because diamond crystallites shows multiple orientation with regard to its internal crystal framework skeleton, and is separated by the border of non-diamond crystal grain.In addition, former method shows limited nucleation density, and this can produce limited surface coverage and because the uneven surface that the formation of big crystallite causes.

Summary of the invention

On the base material that before the CVD deposition diamantane chemistry is connected to hope, remarkable enhancing CVD diamond production method is provided and has made the CVD diamond lattic structure have the possibility of new purposes.There have several different methods that diamantane is play a part to be unique.

Have been found that before deposition, the diamantane chemistry to be connected on the base material and have many good qualities.These comprise: (1) seed density maximum, produce less crystallite dimension, and reduce surfaceness; (2) alleviate lamination problem, improve heat transfer characteristic simultaneously; (3) described base material does not have surface abrasion; (4) ability of CVD patterned growth; (5) CVD that has strengthened specific diamond plane surface grows, and allows to improve greatly the homoepitaxy growth of diamond film performance, makes new electronics application become possibility; (6) can select the accurate dimension of nucleation crystal seed; (7) growth of doped diamond; (8) coating of non conductive substrate; (9) radiating uses.Before leaning against nucleation the diamantane chemistry is connected on the described film growth base material thereon, has realized all aforementioned advantages in practice of the present invention, this provides the novel method of diamond film nucleation growth.

Brief description

Fig. 1 has shown the CVD diamond crystalline film of using diamondoid seed crystals to form.

Fig. 2 has shown the diamantane molecule that connects from the teeth outwards as oriented seed crystal.

Fig. 3 has shown the diamantane that is bonded on the metallic surface.

Fig. 4 A, B and C have shown by silyl ether bond and have been connected to diamantane on the silicon face.

Fig. 5 A, B and C have shown how ten diamantane molecules are connected on the silicon face.

Fig. 6 has shown the reactor that sublime diamondoids is used for CVD in the gas phase.

DESCRIPTION OF THE PREFERRED

The definition of diamantane

Term " diamantane " refers to replacement and the unsubstituted cage compound of diamantane series, described diamantane series comprises single diamantane, two diamantane, three diamantane, four diamantane, five diamantane, six diamantane, seven diamantane, eight diamantane, nine diamantane, ten diamantane, 11 diamantane etc., comprises their all isomer and steric isomer.Compound has " diamantane " topological framework, means that their carbon atom arrangement is added on the FCC diamond lattice segment.The diamantane that replaces comprises 1～10, and preferred 1～4 independent alkyl substituent of selecting.Diamantane comprises " lower diamondoids " and " higher diamondoids ", term, and the mixture of any combination of rudimentary and higher diamondoids just as herein defined.

Term " lower diamondoids " is meant all derivatives that do not replace and replace of single diamantane, two diamantane and three diamantane and any and/or single diamantane, two diamantane and three diamantane.Be different from " higher diamondoids ", these lower diamondoids components show as no isomer or chirality feature and are easy to synthesize.

Term " higher diamondoids " is meant any and/or all replacements and unsubstituted four diamantane components; Any and/or all replacements and unsubstituted five diamantane components; Any and/or all replacements and unsubstituted six diamantane components; Any and/or all replacements and unsubstituted seven diamantane components; Any and/or all replacements and unsubstituted eight diamantane components; Any and/or all replacements and unsubstituted nine diamantane components; Any and/or all replacements and unsubstituted ten diamantane components; Any and/or all replacements and unsubstituted 11 diamantane components; And the isomer and the steric isomer of the mixture of said components and four diamantane, five diamantane, six diamantane, seven diamantane, eight diamantane, nine diamantane, ten diamantane, 11 diamantane.

From petroleum, separate diamantane

Contain the raw material of the higher diamondoids of recyclable amount, comprise, for example the refinery stream of generations such as natural gas condensate and cracking, rectifying, coking process.Particularly preferred raw material stems from the Norphlet rock stratum and the Canadian LeDuc rock stratum in the Gulfian.

These raw materials contain the lower diamondoids (often up to about 2/3rds) of vast scale and less but a considerable number of higher diamondoids (often up to about 0.3～0.5wt%).Can realize the processing of these raw materials is also separated (if desired) with senior and lower diamondoids to remove non-diamantane by using following technology (only illustrating): size separation techniques is film, molecular sieve etc. for example; Evaporation and heat separator under normal pressure or the decompression; Extractor; Static separator; Crystallization; Chromatography; Well head separator etc.

Preferred separation method generally comprises the distillation of raw material.This can remove lower boiling non-diamondoid components.This can also shift out or tell boiling point and be lower than the rudimentary or higher diamondoids component that the boiling point of isolating higher diamondoids is wanted in selection.Under any situation, lower cuts will be enriched in lower diamondoids and the lower boiling non-diamondoid materials.Carry out distillation procedure so that the cut in several interested temperature ranges to be provided, with the initial gross separation of higher diamondoids that affirmation is provided.The cut that is enriched in higher diamondoids or the interested diamantane is remained, and may need further purification.Other is removed impurity and also can comprise following limiting examples to the further method of purifying of the cut that is rich in diamantane: evaporation, distillation, crystallization, chromatography, well head separator, flash distillation, fixed bed and fluidized-bed reactor, decompression under size separation techniques, normal pressure or the decompression, or the like.

The removing of non-diamondoid components also can comprise the Pintsch process step before or after the distillation.Pintsch process is the effective ways that remove dealkylation, non-diamondoid components from raw material.It by at least about 390 ℃, most preferably from about under 410～450 ℃, the described raw material of heating is implemented in vacuum condition or inert atmosphere.Pintsch process is long enough under sufficiently high temperature, so that the non-diamondoid components thermolysis in the raw material before the Pintsch process is at least about 10wt%.More preferably at least about 50wt%, in addition more preferably at least the non-diamondoid components of 90wt% be thermal decomposited.

Although Pintsch process is preferred in one embodiment, it is always unessential for the recovery, separation or the purification that promote diamantane.For some given raw material, other method allows to make concentration of diamondoids enough high, so that can use direct separation method, for example chromatography (comprising preparation gas-chromatography and high performance liquid chromatography), crystallization, fractional sublimation separate diamantane.

Even after distillation or Pintsch process/distillation, the material of may wishing further to purify is to provide the selected diamantane that uses in the composition that uses in the present invention.This purification techniques comprises chromatogram, crystallization, thermal diffusion technology, zone refining, progressively recrystallization, apart or the like.For example, in a method, the raw material that reclaims is carried out following additional step: the 1) gravity column chromatography of carrying out with the silica gel of Silver Nitrate dipping; 2) twin columns prepare capillary gas chromatography to separate diamantane; 3) crystallization.

Alternative methods is to use single-column or multicolumn liquid chromatography, comprises high performance liquid chromatography, separates interested diamantane.As above, can use a plurality of posts with different choice.Use the further processing of these methods to allow meticulousr separation, this can cause purified basically component.

The U.S. Provisional Patent Application of submitting in January 19 calendar year 2001 60/262,842, the U.S. Provisional Patent Application of submitting to June 21 calendar year 2001 60/300,148 and the U.S. Provisional Patent Application 60/307,063 submitted to July 20 calendar year 2001 in stated and handled raw material to obtain the detailed method of higher diamondoids composition.At this full content of quoting these applications as a reference.

Unlike through being commonly used for the bigger diamond particle of the sedimentary crystal seed of diamond CVD, diamantane is easy to be derived by chemical group, and this chemical group can be used as described diamantane is chemically bonded to lip-deep connector (linker).Example is diamantane-thiol derivative and for example golden being connected in metallic surface.Another is that diamantane leads to being connected of peroxide bridge with silicon face.The method that diamantane is connected with silicon wafer is the silylanizing ligation.Silylation reactive is used for connecting the hydrocarbon structure part for a long time on silicon-dioxide and glass surface.Trimethylsilyl ethers is to be used to derive glass and the silicon-dioxide reagent with the routine that forms non-wettable surface.Be extensive use of alkyl silicon ether form have the enhanced thermostability derivative so that helpful in high temperature mass spectrometry, as Denney, R.C. is discussed at " being used for the stratographic sillylation reagent " Spec.Chem.6 (1983).Layer like this is heat-staple under the CVD service temperature.A kind of method of attachment relates to and forms the sillylation reagent contain diamantane, its can with siloxy-(siloxyl) the structure division reaction on the silicon face of oxidation.These class methods can use the sillylation reagent that for example contains concrete diamantane or alkyl diamondoids as one of alkyl on trialkyl halosilanes or other trialkylsilkl reagent.Silylation reactive relates to conventional base-catalyzed method.The chemical bonding method of passing through cytotoxic compounds that also can use other to be fit to.

Also described diamantane can be joined together to form dimer, tripolymer etc., be connected on the described base material by chemical linkers with forms such as dimer, tripolymers then.Also have, can at first diamantane be connected on the described base material, link together by the orientation of another kind of linking group then, for example make homoepitaxy become possibility with hope by a kind of linking group.

Because the quality of CVD diamond film is the function of seed density, diamantane is guaranteed the seed density of maximum possible and the film of best in quality as the diamond units of possible minimum.Little CVD crystal seed promotes effective nucleation and has the more uniform CVD diamond film of excellent mechanical properties, electric property (for example field emission), optics and heat conductivility.

At present by before described CVD method, realizing the CVD nucleation with friction of melee particulate or scratch-off surface (for example Pao Guang silicon).Iijima, S., Aikawa, Y.﹠amp; BabaK. show in " growth of diamond particles in the chemical vapour deposition " (J.Mater.Res.6,1491-1497 (1991)) that this friction techniques is embedded in the described silicon face tiny diamond chips (being of a size of tens nanometers).These crystal seeds have multiple orientation, make to produce homoepitaxy.These diamond chips are as the crystal seed of CVD growth.People such as Iijima (1991) have determined that the highest possible nucleation density of using this friction techniques to obtain is 10 ¹⁰-10 ¹¹/ cm ²Diamantane is the diamond particles of possible minimum, and it is of a size of the 1-2 nanometer.The minimum size of diamantane makes brings up to 10 with nucleation density ¹³-10 ¹⁴/ cm ²Become possibility, compare the nucleation density that might obtain and be significantly improved with above-mentioned technology.Can before the CVD method, diamantane be deposited from the teeth outwards with physics or chemical process (with diamondoid derivatives).Fig. 1 has shown CVD diamond crystal film (the CVD condition: 6% 50 Ton, 5KW, 333H2, SCCM/22 C1-I that use diamantane (four diamantane) crystal seed forms ₄, 700 ℃, 8 hours).

CVD layer and its base material layering are problems, and are the obstacles of potential CVD applications of diamond.Described diamantane is connected to the form of single sheet chemistry will be provided huge number (order of magnitude will be 10 on the base material ¹³-10 ¹⁴/ cm ²) anchor point, therefore and will relax or eliminate described lamination problem.This also can improve the heat transfer through described interface.

Do not need as diamond particulate seeds, to use the rubbing method (scraping or ultrasonic method) on physical damage surface that diamantane is embedded in the surface with the physics method.Therefore, by eliminating surface abrasion before the CVD diamondoid seed crystals chemistry being connected on the surface.The prevention or reduce surface damage in application, for example in the production of microtronics and microelectronics-mechanical system (MEMS), be even more important.

Can the diamantane chemistry be connected on the surface with various modes.For example, on the metallic surface, draw electronic circuit with diamantane-mercaptan so that nano-photoetching.In addition, these patterns can use or be used as the crystal seed of the diamond CVD growth of patterning by original state.In addition, so that have only concrete pattern to expose on the surface, can realize the CVD deposition of patterning by masked surface (for example Pao Guang silicon).For example, contain diamantane silylating agent can with the reaction of siloxy-structure division on the described exposed silicon surface, thereby form intensive, the predetermined pattern of CVD diamond seeds.In case diamantane is finished via the bonding that silicon ether connects, remove covert and use high temperature CVD method depositing diamond.The CVD diamond makes the ultra-thin insulation layer of novel microelectronic application examples widely such as production high thermal conductivity and the application of for example producing the MEMS component of being made up of diamond become possibility with predetermined pattern deposition.Diamond is because its intensity, resistance to abrasion and low-friction coefficient are the MEMS structured materials of high desirability.

Except forming pattern, diamantane can be connected on the described base material to induce the growth of CVD diamond on specific diamond face.For example, described diamantane can anchor on the described base material to induce along the growth of described (111) face, produces very flat diamond surface.Use current seeding method (for example Russian Nano diamond), the crystal face of described crystal seed is a random orientation.These orientations at random cause forming the polycrystalline cvd film.Homoepitaxy is to use unique possibility of the diamond plane surface nucleation of orientation.Use diamondoid derivatives might control the orientation of the diamond plane surface that is used for the CVD diamond nucleation.In order to control diamond orientations fully, be connected to described lip-deep diamantane and can be connected to each other with the result who guarantees to want to make the film of best homoepitaxy.

The chemical bonding (Fig. 2 and 3) on the diamantane before the CVD and surface makes the predetermined orientation of diamond plane surface of described crystal seed become possibility.Fig. 4 A shown with silicon face on the firm alkyl structure part of [1 (2,3) 4] five metals of siloxy-bonding.Described [1 (2,3) 4] five diamantane are incorporated on the described surperficial siloxy-by alkyl silicon ether connecting key via the end of the bridge tertiary carbon.[1 (2,3) 4] five diamantane and described surface bonding have by this way exposed its diamond (111) surface and have been used for CVD nucleation/diamond deposition.

Use other diamantane structure, also can use described { 100} and { the 110} diamond face is for the relative effectiveness of CVD nucleation.Fig. 4 B has shown that the firm alkyl structure of [12 (3) 4] five metals part is incorporated on the siloxy-on the silicon face by alkyl silicon ether connecting key via the end of the bridge tertiary carbon.Described [12 (3) 4] five diamantane and described surface bonding by this way are exposed to the CVD reactant with its (100) surface.Similarly, Fig. 4 C has shown [123] the four adamantane structure parts that are incorporated into the siloxy-group on the silicon face via the end of the bridge tertiary carbon by alkyl silicon ether connecting key.Its (110) face is come out on [123] four diamantane and surface bonding by this way.[123] four diamantane that show among Fig. 4 C provide the unique opportunity that utilizes the crystal seed chirality in forming the adamantine nucleation of CVD.Described [123] four diamantane are the soluble chiral molecules (it not only shows left-handed but also show dextral primary helix structure) with primary helix.

Fig. 2 has shown the diamantane molecule 1, and it connects from the teeth outwards the oriented seed crystal as CVD diamond nucleation/production.The 2nd, the surface, for example metal, silicon, glass, pottery, organic polymer, can be bonded to any material on 1, wherein 1 is lower diamondoids, higher diamondoids, assorted diamantane or other diamondoid derivatives.Described diamantane structure division 1 is bonded on 2 by linking group (4), and this linking group (4) is connected on the described surface by key 3, and is connected on the described diamantane by key 5.Perhaps, described diamantane can be bonded directly on the described surface.

Fig. 3 has shown the example of diamantane.In this case, [1231241 (2) 3] ten diamantane are incorporated on the metallic surface by the mercaptan connecting key, for example on the gold.

Fig. 4 shows by the silicon ehter bond and is connected to diamantane on the silicon face.Fig. 4 A is [1 (2,3) 4] five diamantane, and its (111) face exposes.Fig. 4 B is [12 (3) 4] five diamantane, and its (100) face exposes.Fig. 4 C is chirality [123] four diamantane, and the enantiomorph that (110) face exposes is right.

Fig. 5 A, 5B and 5C show [1231241 (2) 3] ten diamantane molecules are how to be connected in many ways on the silicon face to expose concrete diamond plane surface.Fig. 5 A shown be how by silicon ether connect expose (111) diamond face, Fig. 5 B exposes (100) diamond face and Fig. 5 C exposes (110) face.By this way, diamantane can either be with deciding high preferred orientation and the crystalline size again can be with the homogeneity that decides CVD diamond nucleation crystal seed, thereby might carry out homoepitaxy.High-quality diamond in the production microelectronic applications needs the diamond film of homoepitaxy.This can be connected to each other and realize by using suitable chemical linkers will be connected to described lip-deep diamantane.

Diamantane can obtain with the multiple size of 1-11 diamond crystal cage.This provides the ability of selecting the accurate dimension of nucleation crystal seed, and this is the ability that other CVD nucleation method can not have.In some applications, wish the greater or lesser a little crystal seed of use has proper property and quality with production diamond layer.

With nitrogen or boron or other structure division diamantane of can deriving.In surface diamondoid seed, introduce these derivatives and cause the CVD diamond film in lattice, to mix n-type or p-type unit, doping CVD is provided adamantine novel method.

The use of chemistry interconnection technique makes diamond to grow on non-conductor or friable surface.At first coated with diamondoids is used the low temperature CVD method diamond layer of growing then to produce highdensity nucleation site layer on described surface.

The diamantane chemistry is connected to the surface goes up the formation individual layer, this individual layer can be made thinner and more uniform diamond film, and need not process relevant surface heating with CVD thus by radiation to produce the diamond-like layer.

In case diamantane is connected on the described base material as crystal seed, people can use the CVD method of standard.Methane, ethane, ethene, acetylene and other gaseous carbon sources can be used for the CVD method of standard.Hydrogen also can be with described carbon-source gas, and preferably with rare gas element for example nitrogen or argon gas mix, be used in this nucleation method.

In another embodiment, in case the diamantane chemistry that will want be connected on the described surface, can use then in the United States Patent (USP) 6783589 technology described with sublime diamondoids to the gas phase that is used for CVD.Employed exemplary reactor is shown in 400 places among Fig. 6 usually.Reactor 400 comprises the processing space 402 that reactor wall 401 surrounds.Gas inlet pipe 403 is used for guiding processing gas to enter in the described processing space 402, and described processing gas comprises methane, hydrogen and optional rare gas element, for example argon gas.Sublime diamondoids or volatilization device 404 are similar to quartz transpirator discussed above, also can be used for containing the gaseous volatilization of diamantane and being injected in the described reactor 400.Described volatilizer 404 can comprise the device of introducing carrier gas (for example hydrogen, nitrogen, argon gas) or rare gas element (for example rare gas except that argon gas), and it can contain other carbon precursor gases, for example methane, ethane or ethene.

Consistent with conventional CVD reactor, described reactor 400 can have the waste gas outlet 405 that is used for shifting out from described processing space 402 processing gas; Energy is applied to the energy source that also bombards in the processing space 402 from the plasma body in the processing gas of processing space 402; Hydrogen molecule is converted into the filament 407 of mon-H; Growth has the susceptor 408 that contains diamantane film 409 above; Rotate described susceptor 408 to strengthen the described sp that contains diamantane film 409 ³The inhomogeneity device 410 of-hydridization; With Controlling System 411, it is used for regulating and controlling following content: gas apply to the amount of the energy the described processing space 402 through the flow of inlet 403, from source 406 and be injected into the amount of the diamantane in the described processing space 402, the atomize of the hydrogen of the amount of the processing gas of discharging by waste gas outlet 405, described filament 407 and rotate the device 410 of described susceptor 408.In exemplary embodiment, described plasma energy source 406 comprises ruhmkorff coil so that the energy that applies in the processing gas in the processing space 402 produces plasma body 412.

Diamondoid precursor (it can be three diamantane or higher diamondoids) is passed be used for the volatilize volatilizer 404 of described diamantane to be injected into according to embodiments of the present invention in the reactor 400.Can use carrier gas (for example methane or argon gas) to promote to be entrained in the transmission of the diamantane in the carrier gas that enters in the described processing space 402.Unlike the conventional plasma CVD diamond technology that once only increases a carbon atom on the film of growth, this injection of diamantane can promote the growth of the diamond film 409 of CVD growth by allowing carbon atom at every turn with about 10-100 or bigger deposited at rates.Growth velocity can improve 2-3 times at least, and in certain embodiments, growth velocity can improve at least one the order of magnitude.

In certain embodiments, methane and/or the hydrogen that is injected is necessary " filling " to the diamond between the diamantane, and/or the material area of " holding back " between the lip-deep diamantane aggregation of " repairing " film 409 in described growth.Hydrogen by the PECVD technology by stablizing the sp of the diamond surface in the described growth ³-key characteristic participates in adamantine synthetic.As what discuss in the above-cited document, but people such as A.Erdemir have instructed hydrogen also to control capturing hydrogen, can insert sp in the generation of the carbon radicals of condensation (condensable) in the dissolving of the size of incipient nucleus, carbon and the gas phase, the lip-deep hydrocarbon of the diamond film from be connected to described growth ³The generation in the room of the carbon precursor of bonding.Hydrogen attack is carved two keys or the sp of great majority from the diamond film surface in the growth ²The carbon of-bonding, therefore and hinder the formation of graphite and/or decolorizing carbon.Hydrogen also etches away less diamond particles and suppresses nucleation.Therefore, the diamond film that the CVD that has enough hydrogen to exist grows causes such diamond coatings, and it mainly contains the macrobead with highly many-sided (faceted) surface.Such film shows the surfaceness of about 10% film thickness.In the present embodiment, there is no need to stablize the surface of described film, because the carbon on the sedimentary diamantane outside surface has been sp ³Stabilization.

Diamantane can be used as the carbon precursor of CVD diamond film, this means that each carbon of the diamantane that injects described processing space 402 joins on the described diamantane film with complete substantially form.Except that this effect, the diamantane 413 that injects described reactor 400 from described volatilizer 404 can only be used for the CVD diamond film nucleation according to the routine techniques growth.In this case, described diamantane 413 is entrained in the carrier gas, the latter can comprise methane, hydrogen and/or argon gas, and when deposition process begins, be injected in the described reactor 400 and become diamond film with nucleation, its will be in step subsequently from as growth the methane (being not diamantane) of carbon precursor.In certain embodiments, select the specific isomer of specific diamantane can promote under conventional environment, to be difficult to the growth of the diamond film of the crystalline orientation that obtains, have hope.Perhaps, for the purpose of above-mentioned discussion, to reactor 400, introduce the ultracrystallite form that the diamantane nucleator can be used to promote the film in the described growth from volatilizer 404.

The weight of the diamantane of diamantane and replacement, the function (weight of wherein said diamondoid functional groups is included in the described diamantane part) as the gross weight of described CVD film can be the about 99.9wt% of about 1-in one embodiment.In another embodiment, the content of the diamantane of diamantane and replacement is the about 99wt% of about 10-.In another embodiment, diamantane and to replace diamantane be about 25-95wt% with respect to the ratio of described film gross weight in the described CVD film.

Though described the present invention with reference to specific embodiment, the application is intended to cover multiple change and the replacement of being made by those skilled in the art under the spirit and scope of not leaving appended claim.

Claims (42)

1. the method for diamond film nucleation growth comprises providing described film to treat nucleation base material thereon that wherein at least a diamantane chemistry is connected on the described base material.

2. the process of claim 1 wherein that described diamantane is a lower diamondoids.

3. the method for claim 2, wherein said lower diamondoids is selected from single diamantane, two diamantane and three diamantane.

4. the process of claim 1 wherein that described diamantane is a higher diamondoids.

5. the method for claim 4, wherein said higher diamondoids is selected from four diamantane, five diamantane, six diamantane, seven diamantane, eight diamantane, nine diamantane, ten diamantane and 11 diamantane.

6. the process of claim 1 wherein that described diamantane derives with nitrogen or boron.

7. the method for diamond film nucleation growth said method comprising the steps of:

A) provide reactor with airtight processing space;

B) in described processing space, place base material, and the diamantane chemistry is connected on the described base material;

C) introduce processing gas to described processing space; With

D) energy is applied to the described processing space from energy source.

8. the method for claim 7, wherein said method also comprise injects at least a higher diamondoids in described processing space, wherein said at least a higher diamondoids makes described diamond film nucleating growth on described base material.

9. the method for claim 7, wherein said method also comprise injects at least a diamantane in described processing space, wherein said at least a higher diamondoids is derived with nitrogen or boron.

10. the method for claim 7, wherein said method also comprise injects at least a lower diamondoids in described processing space, wherein said at least a lower diamondoids makes described diamond film nucleating growth on described base material.

11. the method for claim 7, wherein said reactor disposes for implementing the chemical vapor deposition (CVD) technology.

12. the method for claim 11, wherein said chemical vapour deposition technique are plasma body enhanced chemical vapour deposition (PECVD) technology.

13. the method for claim 8, wherein said at least a higher diamondoids are the higher diamondoids that replaces.

14. the method for claim 7, wherein said nucleogenesis does not rely on the character of described base material.

15. being carbide, the method for claim 7, wherein said base material form (carbideforming) base material.

16. the method for claim 15, wherein said base material is selected from Si and Mo.

17. being non-carbide, the method for claim 7, wherein said base material form (non-carbide forming) base material.

18. the method for claim 17, wherein said base material is selected from Ni and Pt.

19. the method for claim 7, wherein said processing gas comprises methane and hydrogen.

20. the method for claim 19, wherein said processing gas also comprises rare gas element.

21. the method for claim 20, wherein said rare gas element is an argon gas.

The energy that applies in the described processing space 22. the method for claim 7, wherein said energy source comprise ruhmkorff coil produces plasma body.

23. the method for claim 19 also comprises the step that the hydrogen in the described processing space is converted into mon-H.

It is sublimate in the gas phase 24. the method for claim 8, wherein said implantation step comprise by the described at least a higher diamondoids of heated volatile.

25. the method for claim 24, wherein said implantation step are included in the higher diamondoids of carrying described distillation in the carrier gas of introducing in the described Processing Room secretly.

26. the method for claim 25, wherein said carrier gas are at least a gas that is selected from hydrogen, nitrogen, rare gas element and carbon precursor gases.

27. the method for claim 26, wherein said rare gas element are rare gas and wherein said carbon precursor gases is at least a gas that is selected from methane, ethane and ethene.

28. the method for claim 7, wherein said nucleation density is at least 10 ¹³Cm ^-2

29. the method for claim 8, the injection of wherein said at least a higher diamondoids make the growth velocity of described diamond film be increased at least 2～3 times.

30. the method for claim 10, the injection of wherein said at least a lower diamondoids make the growth velocity of described diamond film be increased at least 2～3 times.

31. the method for claim 8 also comprises the growth with the diamond film of the crystalline orientation that promotes to have hope of the step of selecting concrete higher diamondoids.

32. the method for claim 7, the wherein described base material of rotation in the process of growth of the described diamond film of at least a portion.

33. having chemistry before nucleogenesis, the diamond film of nucleation on base material, described base material be connected to diamantane on the described base material.

34. the diamond film of claim 33, wherein said diamantane is derived with nitrogen or boron.

35. the diamond film of claim 33, wherein said diamantane is a higher diamondoids.

36. the diamond film of claim 33, wherein said diamantane is a lower diamondoids.

37. by the diamond film of following steps nucleation, described step comprises:

A) provide reactor with airtight processing space;

B) place base material in described processing space, described base material has the diamantane that chemistry is connected thereto;

C) in described processing space, introduce processing gas; With

D) energy is applied to the described processing space from energy source.

38. the diamond film of claim 37, wherein said diamond film are super nanocrystal films.

39. the diamond film of claim 38, wherein said super nanocrystal film has the microstructure that comprises the 3-5 nanocrystal size.

40. the diamond film of claim 37, wherein said diamantane is derived with nitrogen or boron.

41. the diamond film of claim 37, wherein said diamantane are selected from single diamantane, two diamantane, three diamantane, four diamantane, five diamantane, six diamantane, seven diamantane, eight diamantane, nine diamantane, ten diamantane and 11 diamantane.

42. the diamond film of claim 37, wherein said higher diamondoids are selected from single diamantane, two diamantane, three diamantane, four diamantane, five diamantane, six diamantane, seven diamantane, eight diamantane, nine diamantane, ten diamantane and 11 diamantane.

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