Specific embodiment
The explaining in detail of the purpose of the representative embodiment for the present invention is described given below, but thisA little embodiments should not be construed as limiting the invention.
" abrasive surface " refers to the contact surface with polished object in the disclosure, in other words,Refer to when the flat polished object of abrasive contact, parallel to the level meter on the surface of polished objectFace.
In the disclosure, " highly " of three-D elements refers to basal surface the hanging down along abrasive surface of three-D elementsThe summit to three-D elements for the straight line or the distance of top surface.
The abrasive material of the embodiment of the disclosure includes the abrasive material with patterned surface, and multiple threeDimension element is arranged on patterned surface.Process the table of the group constituting selected from fluoride process or siliconFace processes and executes at least a portion of patterned surface." fluoride process " in the disclosure isRefer to the surface treatment using the material containing fluorine, and " silicon process " refers to using the material containing siliconSurface treatment.Other atoms outside fluorine removal and silicon such as hydrogen, oxygen, carbon, nitrogen etc. can be used for tableFace is processed, and these other atoms can derive from the material containing fluorine or the material containing silicon, or canFrom another kind of source.
Abrasive material can be formed using various materials.Fig. 1 illustrates the horizontal stroke of the abrasive material of the embodiment of the disclosureSectional view.Abrasive material 10 shown in Fig. 1 includes abrasive material 11, and abrasive material 11 includes body layer13 and the face coat 14 that is arranged at least a portion of body layer 13.Face coat 14 is applied inTo the patterned surface being provided with multiple three-D elements 12.The feelings of shown embodiment in FIGUnder condition, body layer 13 not only determines the shape of three-D elements 12, also serves as and is attached to abrasive material 10The matrix material of another instrument etc..Another matrix material could attach to base layer 13 and structuringThe surface of surface opposition side.
Body layer determines the shape of three-D elements.Material behavior in view of polished object and hardnessEtc., body layer can for example be formed by various hard materials, such as inorganic material, such as sinters pottery.Such as sintering pottery may include carborundum, silicon nitride, aluminum oxide, zirconium oxide, tungsten carbide etc..FromFrom the perspective of intensity, hardness, abrasion resistance etc., be advantageously used in these carborundum andSilicon nitride, and especially carborundum.
Body layer can be by mixing ceramic particle, binding agent and other of such as carborundum etc. on demandMaterial, pressure injection, in the metal die of the opposite pattern with patterned surface, is then sintering toFormed.
Face coat typically by harder than body layer and contribute to during polishing pass through contact polished thingBody is formed treating the material that polishing object is polished.The example of spendable face coat includes classDiamond carbon (being abbreviated as DLC) and other diamond, tungsten carbide (WC), titanium nitride(TiN), titanium carbide (TiC) etc..The thickness of face coat is typically about 0.5 μm or bigger or about 1 μmOr bigger, and about 30 μm or less or about 20 μm or less.By the thickness of face coat is setIt is set to about 1 μm or bigger, only face coat contacts polished object during polishing, and therefore treatsPolishing object can protected with contact-free body layer.On the other hand, if face coat and body layerAdhesion is low, then the thickness of face coat is preferably made to relative thin.
Film containing diamond can be used advantageously as face coat.Film may include such as DLCCarbon.Diamond-like-carbon is unbodied, and includes the substantial amounts of sp by stabilized hydrogen3(for example, carbon is formerSon is about 40 atom % or more or about 50 atom % or more, and about 99 atom % or less orAbout 98 atom % or less).Diamond film can on demand using such as methane etc. gaseous carbon sources orThe solid carbon source of such as graphite etc. and hydrogen are deposited in body layer by routine techniques, such technologySuch as plasma enhanced chemical vapor deposition (PECVD) method, hot-wire chemical gas-phase deposition (HWCVD)Method, ion beam, laser ablation, RF plasma, ultrasonic, arc discharge, cathode arc plasma sinkAmass etc..In some embodiments, the film with high-crystallinity can be being stabilized and produceRaw, and therefore HWCVD method is advantageously used for deposition of thick diamond film.
Fig. 2 illustrates the cross-sectional view of the abrasive material of another embodiment of the disclosure.Shown in Fig. 2Abrasive material 10 includes abrasive material 11, and abrasive material 11 includes abrasive grain 16 and on back lining materials 15Binding agent 17, and abrasive material 11 has the patterned surface being provided with multiple three-D elements 12.The back of the bodyLining material 15 serves as the matrix material of abrasive material 10.Abrasive grain 16 equably or heterogeneity be distributed inIn whole binding agent 17.In the case of this embodiment, when treating polishing object using abrasive material 10Surface when being polished, according to the hardness of polished object, contact the part of polished object by byGradually destroy, thus exposing untapped abrasive grain 16.
In the case of this embodiment, including consolidating of abrasive grain, binder precursor and initiatorChange composition to be filled in the metal die of the opposite pattern with patterned surface, and therefore may be usedForm the abrasive material including abrasive grain and binding agent.
The example of spendable abrasive grain includes diamond, cubic boron nitride, cerium oxide, melting oxygenChange aluminium, heat treated aluminum, the aluminum oxide prepared by sol-gel process, carborundum, chromium oxide, twoSilica, zirconium oxide, aluminium oxide-zirconium oxide, iron oxide, garnet and their mixture.Abrasive materialThe Mohs' hardness of particle is preferably 8 or higher or 9 or higher.The type of abrasive grain can be based on expectionPolishing selected, and diamond, cubic boron nitride, aluminum oxide and carborundum can advantageously be usedSuch as clear up burr etc. in rough polishing, and formed for chamfering such as curved surface etc., andSilica and aluminum oxide are advantageously used for finally polishing.
The average particle size particle size of abrasive grain can exist in type based on coating materials particle, application of abrasive material etc.In different scopes, and be typically about 10nm or bigger, about 1 μm or bigger, or about 5 μm orBigger, or about 500 μm or less, about 200 μm or less, or about 80 μm or less.For example,Average particle size particle size is about 0.5 μm or bigger and about 20 μm or less, or about 10 μm or lessAbrasive grain be advantageously used for rough polishing and such as clear up burr etc., and such as curved for chamferingCurved shape is formed etc., and average particle size particle size is about 10nm or bigger and about 1 μm or moreLittle, about 0.5 μm or less or about 0.1 μm or less abrasive grain are advantageously used for finally throwingLight.
It is usable in the matrix of such as glass, pottery, metal, metal oxide, organic resin etc.The cohesion diamond of the diamond particles that a size of about 1 μm to about 100 μm of middle discrete particles.Including toolThe average particle size particle size having the cohesion diamond of the diamond particles more than 15 μm of particle sizes is generallyAbout 100 μm or bigger or about 250 μm or bigger, and about 1000 μm or less or about 400 μmOr it is less.Including the diamond particles with 15 μm or more low particle size cohesion diamond flatAll particle size is typically about 20 μm or bigger, about 40 μm or bigger, or about 70 μm or bigger,And about 450 μm or less, about 400 μm or less, or about 300 μm or less.
Binder precursor be can be used as by the curable resin of heat or radiation curing.Curable resin is generalSolidified by radical polymerization or cationic polymerization.The example of binder precursor include phenolic resin,First rank phenolic aldehyde-phenol resin, amino resin, carbamate resins, epoxy resin, acrylic acid treeFat, polyester resin, vinylite, melmac, chlorinated isocyanurates acrylate,Lauxite, isocyanurate resin, urethane acrylate resin, epoxy acrylate treeFat and their mixture.Term " acrylate " for binder precursor include acrylate andMethacrylate.
Conventional thermal initiator or light trigger can be used as initiator.The example of initiator includes organic mistakeOxide, azo-compound, quinone, benzophenone, nitroxyl (nitroxo) compound, propylene halideAcid, hydrazone, sulfhydryl compound, pyrylium compound, triacrylimidazoles, double imidazoles, alkyl chlorideBase triazine, benzoin ether, benzyl ketals, thioxanthones, acetophenone, salt compounded of iodine, sulfosalt and theyDerivative.
With respect to the binder precursor of 100 mass parts, abrasive grain is typically with about 150 mass parts or moreMany or about 200 mass parts or more, and about 1000 mass parts or less or about 700 mass parts or moreFew amount is included in curable compositions.With respect to the binder precursor of 100 mass parts, initiatorGeneral with about 0.1 mass parts or more or about 0.5 mass parts or more, and about 10 mass parts or moreLess or about 2 mass parts or less amount are included in curable compositions.
Curable compositions can also include optional components, such as coupling agent, filler, wetting agent, dyeMaterial, pigment, plasticizer, filler, remover, polishing auxiliary agent etc..
Back lining materials can be polymer film, such as polyester, polyimides etc.；Paper wood；Sulfuration is fineDimension；Molding or cast elastomers, treated supatex fabric or manufacture fabric；Etc..BackingMaterial can adhere to abrasive material using adhesive phase.
Abrasive material and back lining materials can be next integrally-formed using such as thermoplastic resin or thermosetting resin.The example of thermoplastic resin or thermosetting resin includes phenolic resin, amino resin, carbamic acidEster resin, epoxy resin, olefinic unsaturated-resin, chlorinated isocyanurates acrylate, ureaformaldehyde treeFat, isocyanurate resin, urethane acrylate resin, Epocryl, doubleMaleimide resin and their mixture.Polyamide is advantageously used in these, gathersEster resin and polyurethane resin (including polyurethanes-carbamide resin).
The thickness of back lining materials can be usually set to about 1mm or thicker or about 0.5cm or bigger, andAbout 2cm or less or about 1cm or less.Also shape tracking characteristics can be applied to back lining materials, itsMiddle back lining materials are as elastomeric material.By pre-formed back lining materials, predetermined bending can be applied to the back of the bodyLining material.
The polishing function of the three-D elements of abrasive material is illustrated at its top.Have including abrasive material in abrasive materialIn the case of the abrasive material of particle and binding agent, three-D elements degrade from top section during polishing,And expose untapped abrasive grain.Therefore, deposit in the top section by increase three-D elementsAbrasive grain concentration, the cutting characteristic of abrasive material and erosion property can increase, and therefore abrasive materialCan advantageously be used.The base portion of three-D elements, in other words, abrasive material adheres to matrix materialOr the bottom integrally-formed with matrix material is not usually required to polishing function, and therefore can be only by gluingKnot dosage form becomes and does not include abrasive grain.
The patterned surface of abrasive material may include variously-shaped three-D elements.The showing of three-D elements shapeExample inclusion cylinder, elliptical cylinder, prism, hemisphere, semielliptical, cone, pyramid, the truncated cone, cutPyramid, whole hip shape etc..Patterned surface may also include multiple three-dimensional elements with various shapesThe combination of part.For example, patterned surface can be the combination of multiple cylinders and multiple pyramid.Three-D elementsThe shape of cross section of base portion can be different from the shape of cross section of top section.For example, base portion is transversalFace can be square, and the cross section of top section can be circle.Three-D elements base portion generally has horizontal strokeSectional area is more than the base portion of top section cross-sectional area.The base portion of three-D elements can connect mutually or alternatelyTouch, and the base portion of neighbouring three-D elements can be separated a predetermined distance each other.
In the case of some embodiments, multiple three-D elements are systematically arranged on patterned surfaceOn.Within the context of the present disclosure, the position with regard to three-D elements is used " systematically " meansThe three-D elements with same shape or analogous shape are along parallel on the level surface of abrasive surfaceIndividual or multiple directions are repeatedly provided on patterned surface.Parallel on the level surface of abrasive surfaceOne or more directions can for linear direction, concentric direction, spirality (spiral) direction or theyCombination.Systematically it is arranged on the situation of the embodiment on patterned surface in multiple three-D elementsUnder, the space existing between three-D elements can be conducive to slurry, abrasive powders etc. such as grooveFlowing and the pattern of discharge be arranged in the whole main body of patterned surface.Such multiple three-D elementsCan for example pass through formed below：Polycrystalline diamond sedimentation by surface treatment, laser treatment；OrPerson's diamond wheel, cut the CVD of wheel；Or injection, binder precursor is filled in structure one kindChange in the metal three-D elements of opposite pattern on surface, then using the method for heat or radiation curing, etc.Deng.
The patterned surface that can be used in the abrasive material of the disclosure is described using embodiment, with reference toFig. 3 A to 3G.Fig. 3 A is the patterned surface being provided with multiple three-D elements with triangular pyramidUpper surface schematic diagram.In figure 3 a, symbol o represents the length of the base portion of three-D elements 12, andAnd symbol p represents the distance between top section of three-D elements 12.The length of the base portion of triangular pyramid canIt is same to each other or different to each other, and the length of side can be same to each other or different to each other.For example, o may be set to about5 μm or bigger or about 10 μm or bigger, and about 1000 μm or less or about 500 μm or moreLittle.P may be set to about 5 μm or bigger or about 10 μm or bigger, and about 1000 μm or lessOr about 500 μm or less.Although not illustrating in figure 3 a, the height h of three-D elements 12 canIt is set as about 2 μm or bigger or about 4 μm or less, and about 600 μm or less or about 300 μmOr it is less.The change of h is preferably about 20% or less of the height compared to three-D elements 12, andAnd more preferably about 10% or less.
Fig. 3 B is the upper surface being provided with the patterned surface of multiple three-D elements with pyramid shapeSchematic diagram.In figure 3b, symbol o represents the length of the base portion of three-D elements 12, and symbol pRepresent the distance between top section of three-D elements 12.The length of the base portion of rectangular pyramid can be mutually the sameOr different, and the length of side can be same to each other or different to each other.For example, o may be set to about 5 μm orBigger or about 10 μm or bigger, and about 1000 μm or less or about 500 μm or less.P canIt is set as about 5 μm or bigger or about 10 μm or bigger, and about 1000 μm or less or about500 μm or less.Although not illustrating in figure 3b, the height h of three-D elements 12 can setIt is about 2 μm or higher or about 4 μm or bigger, and about 600 μm or less or about 300 μm or moreLittle.The change of h is preferably about 20% or less of the height compared to three-D elements 12, and moreIt is preferably about 10% or less.
In the case of other embodiments of the disclosure, three-D elements for cutting triangular pyramid or can cut four ribsCone.The top surface of the three-D elements of these embodiments typically by parallel to abrasive surface triangle orQuadrangle level surface structure.Essentially all top surface is preferably in the water parallel to abrasive materialOn quasi- surface.
Fig. 3 C is to be provided with the upper surface with the patterned surface of multiple three-D elements cutting rectangular pyramidSchematic diagram.Pyramid shape before cutting top is shown in upper left side.In fig. 3 c, symbol o representsThe length of the base portion of three-D elements 12, symbol u represents the distance between base portion of ternary element 12,And symbol y represents the length of the side of top surface.The length cutting the base portion of rectangular pyramid can be mutually the sameOr different, the length of side can be same to each other or different to each other, and the length of the side of top surface can be each otherIdentical or different.For example, o may be set to about 5 μm or bigger or about 10 μm or bigger, Yi Jiyue6000 μm or less or about 3000 μm or less.U may be set to 0 μm or bigger or about 2 μm orBigger, and about 10,000 μm or less or about 5000 μm or less.Y may be set to about 0.5 μmOr bigger or about 1 μm or bigger, and about 6000 μm or less or about 3000 μm or less.ThoughSo do not illustrate in fig. 3 c, but the height h of three-D elements 12 may be set to about 5 μm or bigger orAbout 10 μm or bigger, and about 10,000 μm or less or about 5000 μm or less.The change of hIt is preferably about 20% or less of the height compared to three-D elements 12, and be more preferably about10% or less.
Fig. 3 D is that the upper surface being provided with the patterned surface with hemispheric multiple three-D elements showsIt is intended to.In fig. 3d, symbol r represents the radius of three-D elements 12, and symbol p represents three-dimensionalThe distance between middle part of element 12.For example, r may be set to about 5 μm or bigger or about 10 μm orBigger, and about 1000 μm or less or about 500 μm or less.P may be set to about 5 μm or moreBig or about 10 μm or bigger, and about 1000 μm or less or about 500 μm or less.Although notIllustrate in fig. 3d, but the height h with hemispheric three-D elements is generally identical with radius r.The change of h is preferably about 20% or less of the height compared to three-D elements 12, and more preferablyGround is about 10% or less.
Fig. 3 E is the schematic cross section of another embodiment of the disclosure, and such multiple threeDimension element 12 is the triangular prism of horizontal orientation and has ridge.Three-D elements 12 are arranged on matrix materialOn 15, and be shown as including the abrasive material top 18 of abrasive grain and binding agent and include binding agent butDo not include the double-layer structure of the abrasive material bottom 19 of abrasive grain.Ridge is preferably parallel to abrasive materialOn level surface, substantially across the whole main body of abrasive material.In some embodiments, essentially allRidge is all present in identical parallel on the level surface of abrasive material.In fig. 3e, symbol α represents threeThe vertical angles of dimension element 12；Symbol w represents the width of the bottom of three-D elements 12；Symbol p representsThe distance between top section of three-D elements 12；Symbol u represent three-D elements 12 long base portion itBetween distance；Symbol h represents the height on the surface away from matrix material 15 for the three-D elements 12；And accord withNumber s represents the height on abrasive material top 18.For example, α may be set to about 30 degree or bigger or about 45Degree or bigger, and about 150 degree or less or about 140 degree or less.W may be set to about 2 μm orBigger or about 4 μm or bigger, and about 2000 μm or less or about 1000 μm or less.P canIt is set as about 2 μm or bigger or about 4 μm or bigger, and about 4000 μm or less or about2000 μm or less.U may be set to 0 μm or bigger or about 2 μm or bigger, and about 2000 μmOr it is less or about 1000 μm or less.H may be set to about 2 μm or bigger or about 4 μm or bigger,And about 600 μm or less or about 300 μm or less.S may be set to the height h of three-D elements 12About 5% or bigger or about 10% or bigger, and about 95% or less or about 90% or less.H'sChange is preferably about 20% or less of the height compared to three-D elements 12, and more preferablyAbout 10% or less.
Each three-D elements 12 shown in Fig. 3 E can extend across the whole surface of abrasive material.In this feelingsUnder condition, two ends on the long base portion direction of three-D elements 12 are all in the end sections of neighbouring abrasive materialPosition at, and such multiple three-D elements 12 with belt like shape arrange.
In another embodiment of the disclosure, three-D elements have whole hip shape.In the disclosure" whole hip " shape point out side surface with two corresponding triangles and two corresponding quadrangle structuresThe 3D shape made, wherein neighbouring triangle side surface and quadrangle side surface shared region, andIt is ridge by the region that corresponding two quadrangle side surfaces are shared.Ridge is preferably parallel to abrasive materialLevel surface on, substantially across the whole main body of abrasive material.In some embodiments, substantially instituteRidge is had all to be present in identical parallel on the level surface of abrasive material.Two triangle side surfaces and twoIndividual quadrangle side surface can have mutually the same shape or different shapes.Therefore, whole hip shapeBasal surface can be rectangle, trapezoidal etc., and the length of four sides can be pros different from each otherShape.
Fig. 3 F is the upper surface being provided with the patterned surface of multiple three-D elements with whole hip shapeSchematic diagram.Fig. 3 F shows the whole hip shape with rectangle basal surface.In Fig. 3 F, symbol lRepresent the length of the long base portion of three-D elements 12, and symbol x represents the short of neighbouring three-D elements 12The distance between base portion.For example, l may be set to about 5 μm or bigger or about 10 μm or bigger, andAbout 10mm or less or about 5mm or less.X may be set to 0 μm or bigger or about 2 μm or moreGreatly, and about 2000 μm or less or about 1000 μm or less.Symbol w, p and u and symbolThe definition of h, s, α etc. (although not shown in Fig. 3 F) and exemplary value range and Fig. 3 EDescribed in those are identical.
In the case of another embodiment, patterned surface includes thering is of different shapes multiple threeThe combination of dimension element.Fig. 3 G shows the embodiment of such embodiment.Knot shown in Fig. 3 GStructure surface includes the first triangular pyramid 121, the second rectangular pyramid 122, hexagonal pyramid 123 and whole hip124 combination.The length of the base portion of each three-D elements may be set to about 5 μm or bigger or 10 μmOr bigger, and about 1000 μm or less or about 500 μm or less, and highly can each setIt is about 2 μm or bigger or about 4 μm or bigger, and about 600 μm or less or about 300 μm or moreLittle.The distance between base portion of neighbouring three-D elements may be set to 0 μm or bigger or about 2 μm or moreGreatly, and about 10,000 μm or less or about 5000 μm or less.The length of whole hip 124 canIt is set as about 0.5 μm or bigger or about 1 μm or bigger, and about 1000 μm or less or about500 μm or less.
In the case of some embodiments, the density of the three-D elements of abrasive material, in other words, often1cm2The three-D elements number of abrasive material be about 0.5 element/cm2Or bigger or 1.0 element/cm2OrBigger, and about 1 × 107Individual element/cm2Or it is less or about 4 × 106Individual element/cm2Or it is less.?In the case that multiple three-D elements are systematically arranged on the embodiment on patterned surface, every 1cm2'sThe three-D elements number of abrasive material may be set to about 0.05 element/cm2Or bigger or about 0.10 element/cm2Or bigger, and about 1 × 106Individual element/cm2Or it is less or about 4 × 105Individual element/cm2Or moreLittle.In the case of this embodiment, passing through three-D elements with high-density arrangement in structuring tableWhen realizing high polishing efficiency on face, by using the predetermined pattern of having being present between three-D elementsSpace, such as groove, and in combination surface treatment is carried out on patterned surface can be effectiveGround discharge slurry, abrasive powders etc..
For the abrasive material of the disclosure, at least a portion of patterned surface is carried out fluoride process orSilicon is processed.Without being bound by any theory, patterned surface is by face coat diamond-like-carbon etc.Include abrasive grain in the abrasive material of covering and abrasive material and the abrasive material of resinoid bond is considered to cause to tieCharging on structure surface or the surface energy of patterned surface, and therefore, the easy electrostatic of foreign bodyGround or cling to patterned surface by another kind of interaction, such as passes through conduction compared to abrasive grainNi plate etc. adheres to the Conventional abrasives on matrix material.According to the disclosure, even if patterned surface containsThere are the three-D elements of relative high density, the surface energy of patterned surface also can pass through these three-D elementsSurface treatment is reducing, and can prevent or suppress foreign body to the adhesion of patterned surface such asThe adhesion of the abrasive grain in abrasive slurries, organic compound etc. or accumulation, polyurethanesParticle is from polyurethane foam pad generation etc..
In the disclosure, fluoride process can be advantageous by corona treatment, chemical vapor deposition(CVD) method, physical vapour deposition (PVD) (PVD) method or fluorine gas process and carry out.
Referred to using by plasma-activated raw material gas according to " corona treatment " of the disclosureStructural reform becomes the process of the chemical composition on surface of pending object, and includes from pending objectThe product of material be included on the surface of corona treatment.On the other hand, using chemistryVapour deposition and physical vapour deposition (PVD), including from gas, the component of liquid or solid raw materialFilm to be formed on the surface of pending object by being deposited on.Chemical vapour deposition technique includes for example hotCVD, direct plasma strengthen CVD, remote plasma cvd method, HF CVDMethod etc..Physical vaporous deposition includes sputtering, vacuum moulding machine, electric arc spraying, plasma sprayPainting, aerosol deposition method etc..
Without being bound by any theory it is believed that fluoride is processed produces following phenomenon, such as Fluorin doped existsAround the surface of the face coat of such as diamond-like-carbon or abrasive grain, the surface of material is due to includingIn polymer in a binder, the generation of C-F key is that fluorine blocks, coating is included containing many in knotDensified fluorocarbon of C-C key being formed on structure surface etc..
In the case of some embodiments, by the fluorine of corona treatment or chemical vapour deposition techniqueCompound is processed can be using have can the low-voltage plasma body device of decompression chamber or atmospheric pressure plasma dressPut and carry out.Chemical vapour deposition technique using plasma device generally refers to plasma enhanced CVDMethod.If using atmospheric pressure plasma device, then in addition to fluoro-gas, nitrogen and/or cycle18th race's atom of table, specifically, helium, neon, argon gas, Krypton, xenon, radon gas etc.As discharge gas.In these it may be advantageous to use nitrogen, helium and argon gas, and from costFrom the point of view of angle, nitrogen is especially advantageous.Low-voltage plasma body device is generally used for batch process.If neededWant long sideband of continuous processing etc., the use of atmospheric pressure plasma can be favourable from the point of view of yield angle's.Conventional method such as corona discharge, electric medium block discharge are such as using 13.56MHz high-frequency electricalThe single or double RF electric discharge in source, 2.45GHz microwave discharge, arc discharge etc. can be used as generating plasmaThe method of body.It may be advantageous to the list using 13.56MHz high frequency electric source in these generation methodsRF discharges.
Fluorocarbons such as CF4、C4F8、C5F6、C4F6、CHF3、CH2F2、CH3F、C2F6、C3F8、C4F10、C6F14, Nitrogen trifluoride (NF3)、SF6Etc. can be used as corona treatmentOr the fluoro-gas used in chemical vapour deposition technique.Come from the angle of security, reactivity etc.See it may be advantageous to use C3F8、C6F14And CF4.The flowrate settable of fluoro-gas is about 20sccmOr bigger or about 50sccm or bigger, and about 1000sccm or less or about 500sccm or moreLittle.It is fed in the gas stream of device that can also to include flow velocity be about 50sccm or more greatly and aboutThe carrier gas of 5000sccm or less, such as nitrogen, helium or argon gas.
In some embodiments, by being about 3 or less to make by raw gas C/F ratio setThe possibility of favourable film deposition is known, and in this case, C/F ratio can be by addingNon- fluorine base gas such as acetylene, acetone etc. are adjusting.It is about 2 in the C/F ratio of raw gasOr more greatly and in the case of about 3 or less embodiment, can preferentially occur due to plasma-based processSurface modification, or the film deposition due to chemical vapor deposition can preferentially occur, this depends on bias.LogicalCross and adjust bias in such embodiment, it can be corona treatment or chemical gaseous phase that fluoride is processedDeposition or combinations thereof.The size based on device for the scope of bias or design etc. change, but oneAs may be set to about 100V or less, about 0V or be less to about -1000V or more greatly or about -100,000V or bigger.
Plasma generates the required power that applies and can the size based on pending abrasive material determine, andPower density in discharge space typically may be selected to be about 0.00003W/cm2Or more greatly or about0.0002W/cm2Or bigger, and about 10W/cm2Or less or about 1W/cm2Or it is less.For example,If the size of the abrasive material that thing to be fluorinated is processed is 10cm (length) × 10cm (width) or less,The power of so applying may be set to about 200W or bigger or about 500W or bigger, and about 4kWOr less or about 2.5kW or less.
The temperature of corona treatment or chemical vapour deposition technique does not preferably involve pending abrasive materialFeature and performance etc. temperature, and the surface temperature of pending abrasive material may be set to about -15 DEG COr bigger, about 0 DEG C or bigger or about 15 DEG C or bigger, and about 400 DEG C or less, about 200 DEG C orLess or about 100 DEG C or less.The surface temperature of abrasive material can be connect by thermocouple, radiation thermometer etc.The device of tactile abrasive material measures.
When carrying out corona treatment or chemical vapour deposition technique using low-voltage plasma body device, placeReason pressure may be set to about 10 millitorrs or bigger or about 20 millitorrs or bigger, and about 1500 millitorrs orLess or about 1000 millitorrs or less.
The process time of corona treatment or chemical vapour deposition technique may be set to about 2 seconds or more,About 5 seconds or more or about 10 seconds or more, and about 300 seconds or shorter, about 180 seconds or shorter orAbout 120 seconds or shorter.
In the case of another embodiment, remote plasma unit can be used as by plasmaProcess or the fluoride of chemical vapour deposition technique is processed.Chemical gaseous phase using remote plasma unitSedimentation generally refers to remote plasma and strengthens CVD.Situation in remote plasma unitUnder, plasma is created in the plasma exciatiaon chambers different from processing chamber housing, excites activationMaterial passes through for raw gas to be introduced in plasma exciatiaon chamber generation, generation excite activatorMatter is flow in processing chamber housing together with carrier gas such as nitrogen, helium, neon, argon gas etc., andThe fluoride of the therefore patterned surface of abrasive material processes and is carried out.
There is low-voltage remote plasma device or the atmospheric pressure remote plasma dress of reduced pressure treatment chamberPut and can be used as remote plasma unit.Discharge gas can be used and favourable discharge gas is as aboveFor described in low-voltage plasma body device and atmospheric pressure plasma device.High frequency (13.56MHz) RF is putElectricity, 2.45GHz microwave discharge, 2.45GHz microwave discharge/electron cyclotron resonace (ECR) etc. are general to be usedMake plasma generating method, and advantageously using 2.45GHz microwave discharge and 2.45GHz microwaveElectric discharge/electron cyclotron resonace (ECR), because desired higher ion can be realized in remote plasma body weightVolume density.
Fluorocarbons such as CF4、C4F8、C5F6、C4F6、CHF3、CH2F2、CH3F、C2F6、C3F8、C4F10、C6F14Etc., Nitrogen trifluoride (NF3)、SF6Etc. can be used as using long-rangeFluoro-gas used in the corona treatment of plasma device or chemical vapour deposition technique.SwashSend out lasting a long time of the material activating, and safe, and NF is therefore advantageously used3WithSF6.The flowrate settable of fluoro-gas is about 20sccm or bigger or about 50sccm or bigger, andAbout 1000sccm or less or about 500sccm or less.The flowrate settable of carrier gas is about 100sccmOr bigger or about 200sccm or bigger, and about 5000sccm or less or about 200sccm or moreLittle.
In some embodiments, by being about 3 or less to make by raw gas C/F ratio setThe possibility of favourable film deposition is known, and in this case, C/F ratio can be by addingNon- fluorine base gas such as acetylene, acetone etc. are adjusting.It is about 2 in the C/F ratio of raw gasOr more greatly and in the case of about 3 or less embodiment, can preferentially occur due to plasma-based processSurface modification, or the film deposition due to chemical vapor deposition can preferentially occur, this depends on bias.LogicalCross and adjust bias in such embodiment, it can be corona treatment or chemical gaseous phase that fluoride is processedDeposition or combinations thereof.The size based on device for the scope of bias or design etc. change, but oneAs may be set to about 100V or less, about 0V or be less to about -1000V or more greatly or about -100,000V or bigger.
During plasma generates, required applying power may be set to e.g., from about 1W or bigger or about 10WOr bigger, and about 300kW or less or about 30kW or less.
In the case of remote plasma unit, fluoride process can be carried out and keep pending simultaneouslyAbrasive material is in low temperature.For example, the surface temperature of pending abrasive material may be set to about -15 DEG C or bigger,About 0 DEG C or bigger or about 15 DEG C or bigger, and about 200 DEG C or less, about 100 DEG C or less or about50 DEG C or less.The surface temperature of abrasive material can contact abrasive material by thermocouple, radiation thermometer etc.Device measures.
When carrying out corona treatment or chemical vapour deposition technique using low-voltage remote plasma deviceWhen, processing pressure may be set to about 1 millitorr or bigger or about 10 millitorrs or bigger, and about 1500Millitorr or less or about 1000 millitorrs or less.
The process time of corona treatment or chemical vapour deposition technique may be set to about 2 seconds or more,About 5 seconds or more or about 10 seconds or more, and about 300 seconds or less, about 180 seconds or less orAbout 120 seconds or less.
In another embodiment, sputtering can be used as at by the fluoride of physical vaporous depositionReason.Sputtering can be carried out using physical sputtering device, such as ion sputtering device, DC magnetron sputtering dressPut, RF magnetic control sputtering device etc..
Fluoropolymer such as polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF) etc. can be used asThe sputtering target that fluoride is processed.Reactive sputtering can be by providing fluorocarbons all in the processing chamberAs CF4、C4F8、C5F6、C4F6、CHF3、CH2F2、CH3F、C2F6、C3F8、C4F10、C6F14Etc., nitrogen fluoride (NF3)、SF6Etc. come to carry out.
Sputter temperature may be set to about -193 DEG C or bigger or about 25 DEG C or bigger, and about 600 DEG C orLess or about 1300 DEG C or less.
The processing pressure of sputtering may be set to about 1 × 10-5Support or bigger or about 1 × 10-3Support or bigger,And about 10 millitorr or less or about 100 millitorrs or less.
The process time of sputtering may be set to about 1 second or more, about 5 seconds or more or about 10 seconds or moreMany, and about 30 seconds or less, about 60 seconds or less or about 180 seconds or less.
In the case of another embodiment, vacuum moulding machine can be used as the fluorine by physical vapour deposition (PVD)Compound is processed.Vapour deposition can be carried out using physical deposition device, such as resistance heating deposition device,Electron beam deposition device, ion plating device etc..
Polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF) and other fluoropolymer, calcirm-fluoride(CaF2) and other fluorinated organic compound etc. can be used as sedimentary origin.
Depositing temperature may be set to about -193 DEG C or bigger or about 25 DEG C or bigger, and about 600 DEG C orLess or about 1000 DEG C or less.
The processing pressure of deposition may be set to about 1 × 10-6Support or bigger or about 1 × 10-5Support or bigger,And about 1 × 10-3Support or less or about 1 × 10-2Support or less.
Deposition process time may be set to about 5 seconds or more, about 10 seconds or more or about 30 seconds orMore, and about 120 seconds or less, about 600 seconds or less or about 1200 seconds or less.
In the case of another embodiment, fluorine gas (F2) process as fluoride process.Fluorine gas can useInert gas such as nitrogen, helium, argon gas, carbon dioxide etc. dilution, and also can not diluteIn the case of use.Fluorine gas processes and typically carries out under atmospheric pressure.
When fluorine gas is contacted with the patterned surface of abrasive material, temperature may be set to room temperature or bigger, about50 DEG C or bigger or about 100 DEG C or bigger, and about 250 DEG C or less, about 220 DEG C or less or about200 DEG C or less.
The process time that fluorine gas is processed may be set to about 1 minute or more or about 1 hour or more, withAnd about 1 week or less or about 50 hours or less.
Within the context of the present disclosure, silicon process can be advantageous by corona treatment, chemical vapor depositionArea method, physical vaporous deposition or atomic layer deposition method are carried out.Without being bound by any theory it is believed thatSilicon processes and produces following phenomenon, wherein patterned surface pass through in the polymer that includes in a binder orSi-O-Si key, Si-C- are formed on the surface of abrasive grain or face coat such as diamond-like-carbon etc.Si key, Si-O-C key etc. are improving；Including have by Si-O-Si key, Si-C-Si key,The relatively compact cancellated siloxicon that Si-O-C key etc. is formed or the coating of silica are formedOn patterned surface；Etc..
Processed by the silicon of corona treatment or chemical vapour deposition technique and can use and previously be directed to fluorinationThing process those low-voltage plasma body devices of described identical, atmospheric pressure plasma device, low pressure are remoteJourney plasma device, atmospheric pressure remote plasma unit etc..Discharge gas and plasma lifeOne-tenth method is identical with for those described in fluoride process.
Silane (SiH4), tetramethylsilane (TMS), HMDO (HMDSO), hexamethyl twoSilazane (HMDS), tetraethoxysilane (TEOS) etc. can be used as corona treatment or chemical gaseous phaseFluoro-gas used in sedimentation.In these it may be advantageous to use monosilane or tetramethylsilaneAlkane, because reactivity is high and diffusion coefficient is big.If using atmospheric pressure plasma device, thenUsing having low boiling and nonflammable tetramethylsilane.The flowrate settable of silicon-containing gas is about20sccm or bigger or about 50sccm or bigger, and about 1000sccm or less or about 500sccmOr it is less.It is fed in the gas stream of device that can also to include flow velocity be about 50sccm or more greatly and aboutThe carrier gas of 5000sccm or less, such as nitrogen, helium or argon gas.
If not including oxygen atom in silicon-containing gas, then be added to oxygen and be fed to plasma dressIn the gas stream put.Oxygen can be by being fed to the chamber of plasma apparatus with the pipeline that silicon-containing gas separateIn room, or setting shower nozzle supply in the chamber can be passed through in the mixed gas form with silicon-containing gas.The flowrate settable of oxygen is about 5sccm or bigger or about 10sccm or bigger, and about 500sccmOr less or about 300sccm or less.In the case that the flow rate set of silicon-containing gas is 1, oxygenMay be set to about 0.1 with the flow velocity ratio of silicon-containing gas:1 or bigger, about 0.2:1 or bigger or about 0.3:1Or bigger, and about 5:1 or less, about 4:1 or less or about 3:1 or less.Stopping silicon containing gasAfter the supply of body, post processing can by with e.g., from about 5sccm or bigger or about 10sccm or bigger orAbout 10sccm or bigger, and the flow velocity of about 500sccm or less or about 300sccm or less only suppliesOxygen is answered to carry out.
Plasma generates the required power that applies and can the size based on pending abrasive material determine, andPower density in discharge space typically may be selected to be about 0.00003W/cm2Or more greatly or about0.0002W/cm2Or bigger, and about 10W/cm2Or less or about 1W/cm2Or it is less.For example,If treating that the size of the abrasive material that silicon is processed is 10cm (length) × 10cm (width) or less, thenApply power and may be set to about 1W or bigger or about 10W or bigger, and about 300kW or lessOr about 30kW or less.
The temperature of corona treatment or chemical vapour deposition technique does not preferably involve pending abrasive materialFeature and performance etc. temperature, and the surface temperature of pending abrasive material may be set to about -15 DEG COr bigger, about 0 DEG C or bigger or about 15 DEG C or bigger, and about 400 DEG C or less, about 200 DEG C orLess or about 100 DEG C or less.The surface temperature of abrasive material can be connect by thermocouple, radiation thermometer etc.The device of tactile abrasive material measures.
When carrying out corona treatment or chemical vapour deposition technique using low-voltage plasma body device, placeReason pressure may be set to about 10 millitorrs or bigger or about 20 millitorrs or bigger, and about 1500 millitorrs orLess or about 1000 millitorrs or less.
The process time of corona treatment or chemical vapour deposition technique may be set to about 2 seconds or more,About 5 seconds or more or about 10 seconds or more, and about 300 seconds or less, about 180 seconds or less orAbout 120 seconds or less.
In another embodiment, sputtering or vacuum moulding machine can be used as the silicon by physical vapour deposition (PVD)Process.Process and can be carried out using following using the silicon of physical vaporous deposition, standard sputter equipment is such asWith for fluoride process described equipment identical ion sputtering equipment, DC magnetron sputtering apparatus,RF magnetron sputtering apparatus etc.；Or the such as resistance to heating vapor deposition apparatus of standard vapor deposition apparatus, electricityBeamlet vapor deposition apparatus, ion plating apparatus etc..
The sputtering target that silicon is processed can be silica (SiO2).When being used silicon (Si) as sputtering target, insteadThe sputtering of answering property can be carried out in processing chamber housing by providing a supply of oxygen to.
Sputter temperature may be set to about -193 DEG C or bigger or about 25 DEG C or bigger, and about 600 DEG C orLess or about 1300 DEG C or less.
The processing pressure of sputtering may be set to about 1 × 10-5Support or bigger or about 1 × 10-3Support or bigger,And about 10 millitorr or less or about 100 millitorrs or less.
The process time of sputtering may be set to about 1 second or more, about 5 seconds or more or about 10 seconds or moreMany, and about 30 seconds or less, about 60 seconds or less or about 180 seconds or less.
Silica (SiO2) can be used as the vapor deposition source of vacuum vapor deposition.Electron-beam vapor deposition canAdvantageously it is used together with silica vapour deposition.Silicon is processed and can be carried out, using an oxygen by followingSiClx (SiO) carries out vapour deposition as vapor deposition source, then carries out oxygen of annealing in oxidizing atmosphereChange, and oxygen plasma is being incorporated in vapor deposition chamber vapour deposition silicon monoxide simultaneously.
Depositing temperature may be set to about -193 DEG C or bigger or about 25 DEG C or bigger, and about 600 DEG C orLess or about 1000 DEG C or less.
The processing pressure of deposition may be set to about 1 × 10-6Support or bigger or about 1 × 10-5Support or bigger,And about 1 × 10-3Support or less or about 1 × 10-2Support or less.
Deposition process time may be set to about 5 seconds or more, about 10 seconds or more or about 30 seconds orMore, and about 120 seconds or less, about 600 seconds or less or about 1200 seconds or less.
In another embodiment, atomic layer deposition method (ALD) can be used as silicon process.Atomic layer depositionArea method includes alternately providing in reaction chamber by least two kinds of precursor gases, every time in knotThese precursor gases of individual layer are deposited on structure surface, and makes these precursor gases in patterned surfaceUpper reaction.
The example of spendable precursor gases A includes tetraethoxysilane, double (tert-butoxy) (isopropyl oxygenBase) silanol, double (isopropoxy) (tert-butoxy) silanol, double (tertiary amoxy) (isopropoxy) silaneAlcohol, double (isopropoxy) (tertiary amoxy) silanol, double (tertiary amoxy) (tert-butoxy) silanol, double(tert-butoxy) (tertiary amoxy) silanol, three (tertiary amoxy) silanol etc..Precursor gases B showsExample includes water (H2O), oxygen (O2), ozone (O3) etc..
The flowrate settable of precursor gases A is about 0.1sccm or bigger or about 1sccm or bigger, withAnd about 100sccm or less or about 1000sccm or less.Precursor gases A is incorporated into reaction chamberThe time of room can be about 0.01 second or longer or about 0.1 second or longer, and about 10 seconds or shorter or about100 seconds or shorter.
The flowrate settable of precursor gases B is about 0.1sccm or bigger or about 1sccm or bigger, withAnd about 100sccm or less or about 1000sccm or less.Precursor gases B is incorporated into reaction chamberTime can be about 0.01 second or longer or about 0.1 second or longer, and about 10 seconds or shorter or about100 seconds or shorter.
Untreated precursor gases and/or byproduct of reaction can be by before introducing precursor gases A and introducingBetween body gas B, purge gas are incorporated into purge out reaction chamber in reaction chamber.Purge gasFor the inert gas not reacted with precursor gases.The example of spendable purge gas includes nitrogen, heliumGas, neon, argon gas and their mixture.The flow velocity of purge gas can be e.g., from about 10sccm or moreBig or about 50sccm or bigger, and about 500sccm or less or about 1000 or less, and blowThe introducing time of scavenging body can be about 1 second or less or about 10 seconds or less, and about 30 seconds or moreLess or about 60 seconds or less.
The film of the siloxicon including predetermined thickness or silica can by change introduce precursor gases A andThe number of times of B, and the flow velocity of precursor gases A and B and introducing time shape on patterned surfaceBecome.After introducing precursor gases A and/or B, the reaction between precursor gases A and B can be passed throughUsing heat, plasma, pulsed plasma, Helicon wave plasma, high-density plasma,Inductively coupled plasma, X-ray, electron beam, photon, remote plasma etc. are promoting.
The physical characteristic of so patterned surface of surface treatment can for example pass through contact angle, hardness etc.To evaluate.
In some embodiments, such as it is in the embodiment that fluoride is processed in patterned surface,The water contact angle of the patterned surface of surface treatment is about 70 ° or higher or about 90 ° or higher, Yi Jiyue120 ° or lower or about 150 ° or lower.Water contact angle can pass through sessile drop method, expansion/shrinkage method, WilliamRice method (Wilhelmy method) etc. measures.
In some other embodiments, such as it is that silicon is processed to provide hydrophily table in patterned surfaceIn the embodiment in face, the water contact angle of the patterned surface of surface treatment is about 0 ° or higher or about 10 °Or higher, and about 30 ° or lower or about 45 ° or lower.Water contact angle can by sessile drop method, expand/Shrinkage method, Wilhelmy method (Wilhelmy method) etc. measure.
In another embodiment, the structuring expression hardness of surface treatment ought be converted into Shore hardnessShi Weiyue 40 or higher or about 50 or higher, and about 87 or lower or about 97 or lower.SurfaceThe hardness of the patterned surface processing can for example be measured by Nanoindentation.If the knot of surface treatmentThe hardness on structure surface is about 50 or higher when being calculated as Shore hardness, then relatively soft exoticThe polymer beads of body such as polyurethanes etc. can be prevented to the adhesion of patterned surfaceOnly.
It is deposited on patterned surface or patterned surface is fluorinated on the modified state that thing is processed or silicon is processedComposition can using x-ray photoelectron spectroscopy (XPS) or using the flight time secondary ion mass spectrometry (SIMS)Etc. (TOF-SIMS) qualitatively or quantitatively evaluate.XPS spectrum can be for example using Kratos Axis UltraSpectrometer obtains, and Kratos Axis Ultra spectrometer is using the list of the electron emission polar angle to 90 ° of surfaceColor Al K alpha-photon source.TOF-SIMS can be used for for example being turned to about 1 μm of beam diameter gratingThe pulse 25keV Ga+ Primary ion Beam of 400x400 um region.
The disclosure further embodiment provides a kind of abrasive material including abrasive material, abrasive material hasPatterned surface, patterned surface is configured to there is multiple three-D elements disposed above, structureAt least a portion changing surface includes：A () film, including selected from densified fluorocarbon, oxygen carbonThe material of the group of SiClx and silica composition；The surface of (b) fluorine end-blocking, or (c) combinations thereof.
In the disclosure, " densified carbon fluoride " refer to due to include relatively great amount of quaternary carbon formerSub and inclusion is formed with the fluorocarbon of the fine and close tridimensional network of C-C key.Densified carbon fluorineCompound has high rigidity, and resist excellent compared to crosslinked or noncrosslinking standard fluoropolymerAbrasiveness and anti-foreign material adhesion.
Densified fluorocarbon may include other atoms such as hydrogen, oxygen, nitrogen in addition to carbon and fluorineEtc..In some embodiments, based on the total amount of the element outside dehydrogenation, densified carbon is fluorinatedCompound includes about 20 atom % or more or about 25 atom % or more, and about 65 atom % or moreLess or about 60 atom % or less carbon atom.In some other embodiments, outside dehydrogenationElement total amount, densified fluorocarbon includes about 30 atom % or more or about 35 atom %Or more, and about 75 atom % or less or about 70 atom % or less carbon atom.Additionally,In some other embodiments, based on the total amount of the element outside dehydrogenation, densified fluorocarbonIncluding about 25 atom % or more or about 30 atom % or more, and about 80 atom % or less orAbout 70 atom % or less quaternary carbon atom being bonded to 4 neighbouring carbon atoms.Densified carbon fluorinationThe atomic percent of the carbon atom of compound and fluorine atom can be by for example being measured using XPS, and quaternary carbonThe atomic percent of atom can for example be measured using 13C-NMR etc..
Siloxicon is including silicon, oxygen and carbon compound, but it is former to may include three-D elements otherSon, such as hydrogen, nitrogen etc..Siloxicon is hard and has excellent abrasion resistance, anti-externalMaterial adhesion etc., and can make hydrophilic or hydrophobic by changing composition.IfIn dry embodiment, based on the total amount of the element outside dehydrogenation, siloxicon contain about 10 atom % orMore or about 15 atom % or more, and about 90 atom % or less or about 80 atom % or lessSilicon atom.In some other embodiments, based on the total amount of the element outside dehydrogenation, oxygen carbonizationSilicon contains about 5 atom % or more or about 10 atom % or more, and about 80 atom % or less orAbout 70 atom % or less oxygen atom.Additionally, some other embodiments in, based on dehydrogenation itThe total amount of outer element, siloxicon contains about 1 atom % or more or about 5 atom % or more, withAnd about 90 atom % or less or about 80 atom % or less carbon atom.Silicon atom in siloxicon,The atomic percent of oxygen atom and carbon atom can measure by using XPS, TOF-SIOMS etc..
Silica is the compound including silicon and oxygen, but may include the other atoms in addition to carbon, allAs hydrogen, nitrogen etc..Silica, especially end have Si-O-H key silica generally hydrophilicProperty, and hydrophobic material can be effectively prevented adhere to patterned surface.In some embodimentsIn, based on the total amount of the element outside dehydrogenation, silica contains about 30 atom % or more or about 33Atom % or more, and about 55 atom % or less or about 50 atom % or less silicon atom.?In some other embodiments, based on the total amount of the element outside dehydrogenation, it is former that siloxicon contains about 45Sub- % or more or about 50 atom % or more, and about 70 atom % or less or about 67 atom %Or less oxygen atom.In silica, the atomic percent of silicon atom and oxygen atom can be by usingXPS, TOF-SIOMS etc. measure.
Thickness including the film of densified fluorocarbon, siloxicon and silica is typically about0.05nm or bigger or about 0.5nm or bigger, and about 200 μm or less or about 150 μm or moreLittle.Film thickness can measure by using XPS, TOF-SIOMS etc..
The fluorine atom density of the patterned surface of fluorine end-blocking is typically about 1 × 1013cm-2Or it is bigger or about 5×1013cm-2Or bigger, and about 5 × 1015cm-2Or it is less or about 3 × 1015cm-2Or it is less.KnotThe fluorine atom density on structure surface can measure by using XPS, TOF-SIOMS etc..
The abrasive material of the disclosure can be used for various applications, the rough polishing on such as various surfaces, chamfering and fine polishingLight, surface such as semiconductor wafer, magnetic recording medium, glass plate, lens, prism, automotive oilPaint, joints of optical fibre end surface etc., and the finishing for other polishing tools etc..This public affairsThe abrasive material opened can also advantageously be used for the application using abrasive slurries.