KR20160114627A - Abrasive material having a structured surface - Google Patents

Abstract

A polishing material having an excellent structured surface for preventing adhesion and accumulation of foreign matter, and a method for manufacturing the same.
An abrasive material of an embodiment of the present invention is an abrasive material having an abrasive layer having a structured surface having a plurality of three-dimensional elements arranged thereon, wherein a surface treatment selected from the group consisting of fluorine treatment and silicon treatment is applied to the structured surface Wherein the fluorine treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment.

Description

[0001] ABRASIVE MATERIAL HAVING A STRUCTURED SURFACE [0002]

The present invention relates to an abrasive material having a structured surface. In particular, the present invention relates to a polishing material comprising an abrasive layer having a surface-treated structured surface.

The abrasive material may be used for rough polishing, chamfering, final polishing of various surfaces such as semiconductor wafers, magnetic recording media, glass plates, lenses, prisms, automotive painted surfaces, fiber optic connector end surfaces, And so on.

For example, in a chemical mechanical polishing (CMP) process of a semiconductor wafer, an abrasive layer having a structured surface in which a plurality of three-dimensional elements such as a three-dimensional element having a quadrangular pyramid shape, (Also referred to as a conditioner or a dresser disk) is used for rough polishing (also referred to as dressing or conditioning) of the polishing pad. The CMP process includes performing CMP by providing a slurry containing abrasive particles between the polishing pad and the semiconductor wafer. The conditioner comprises a layer of silicon carbide coated with a monolithic diamond layer as an abrasive layer, for example, attached to a support disk or ring. The polishing material roughenes the surface of the polishing pad and removes clogging of the polishing pad surface. The CMP process is stabilized in this way. This type of conditioner comprising an abrasive layer having a structured surface is superior to other conventional conditioners having abrasive particles such as cohesive diamond particles adhered on a base material by nickel plating, brazing, sintering, It is advantageous in that large scratches caused by dislodged abrasive particles do not occur on the semiconductor wafer surface.

Abrasive materials having structured surfaces are also used in the surface polishing of large glass plates used in the manufacture of liquid crystal displays and the like, in rough polishing and finishing polishing of optical fiber connector end surfaces, automotive painted surfaces and the like. For example, an abrasive material is used in which the abrasive layer comprises abrasive grains such as agglomerated diamond particles, alumina, silicon carbide, cerium oxide, and the like, and a binder such as hardened urethane acrylate, epoxy resin and the like. The portion of the abrasive layer that is in contact with the object to be polished is abraded during coarse polishing or finish polishing depending on the hardness of the object to be polished and new abrasive particles are exposed on the structured surface. For example, when an object to be polished having a hardness such as a glass plate is polished, the polishing layer is usually worn during polishing. On the other hand, when a surface having a low hardness such as an automotive painted surface using an acrylic resin, a urethane resin or the like is polished in the outermost layer, the abrasive layer may not be significantly worn.

Patent Document 1 (International Publication No. WO 2005-012592) discloses a method of manufacturing a ceramic material which comprises (a) (1) a first phase containing at least one type of ceramic material, and (2) at least one type of carbide- A base material having a surface comprising a second phase; And (b) a CVD diamond coating disposed on at least a portion of the surface of the base material.

Patent Document 2 (published in Japanese translation of PCT Application No. 2002-542057) discloses "a backing material and at least one three-dimensional abrasive coating bonded on the surface of the backing material, the abrasive coating comprising a plurality of diamonds An abrasive article that is ideal for polishing a glass or glass ceramic work piece comprising a binder formed from a cured binder precursor in which bead abrasive particles are dispersed and a filler that constitutes about 40 to about 60 weight percent of the abrasive coating, .

Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-179640) discloses an abrasive material used for polishing an optical fiber connector end surface in a predetermined shape, the abrasive material including a base material and an abrasive layer provided on the base material , The abrasive layer having abrasive composites comprising abrasive particles and a binder as constituent elements and the abrasive layer having a spatial structure constituted by a plurality of systematically arranged three-dimensional elements of a predetermined shape ".

Patent Document 1: International Publication No. WO 2005/012592

Patent Document 2: Japanese translation of Published PCT Application No. 2002-542057

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-179640

The cause is unclear, but when the urethane foam pad conditioning is performed during a CMP process using an abrasive material comprising an abrasive layer having a structured surface, the defect density of the semiconductor wafer surface may increase with increasing the conditioning period. Moreover, the accumulation of foreign objects such as abrasive particles contained in the CMP slurry, polyurethane particles away from the urethane foam pad, etc. can be observed in the valley part (concave portion) of the structured surface of the abrasive layer . Accumulation of foreign matter is believed to interfere with the smooth flow of the CMP slurry between the abrasive material and the urethane foam pad.

The accumulation of glass powder (polishing powder) dropped by the surface polishing of the glass plate in the valley portion of the structured surface, and the accumulation of glass powder (polishing powder) on the structured surface such as acrylic resin, urethane resin and the like The adhesion (in this case, the abrasive layer is not significantly worn, adhesion occurs at the protruding portion or tip of the structured surface) is preferably prevented or inhibited because the production efficiency can be reduced, This can affect product quality.

An object of the present invention is to provide an abrasive material having an excellent structured surface for preventing adhesion and accumulation of foreign matter, and a method of manufacturing the same.

An embodiment of the present invention is an abrasive material having an abrasive layer having a structured surface having a plurality of three-dimensional elements arranged thereon, the abrasive material having a surface treatment selected from the group consisting of fluorine treatment and silicon treatment, Wherein the fluorine treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment.

Another embodiment of the present invention provides a method of polishing a substrate, comprising: providing an abrasive material comprising an abrasive layer having a structured surface having a plurality of three-dimensional elements arranged thereon; And performing a surface treatment selected from the group consisting of fluorine treatment and silicon treatment on at least a portion of the structured surface of the abrasive material, wherein the fluorine treatment is performed by plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment Wherein the polishing agent is selected from the group consisting of

Yet another embodiment of the present invention is an abrasive material having an abrasive layer having a structured surface configured to have a plurality of three-dimensional elements arranged thereon, wherein at least a portion of the structured surface comprises: (a) densified fluorocarbon, A film comprising a material selected from the group consisting of silicon carbide, and silicon oxide; (b) a fluorine terminated surface; Or (c) a combination thereof.

According to the present invention, it is possible to provide an abrasive material which can be released without any foreign matter adhering or accumulating on the structured surface, especially in the valley portion (concave portion) of the structured surface.

It should be noted that the above description should not be construed as a complete disclosure of all embodiments of the invention or the advantages associated with the invention.

1 is a cross-sectional view of an abrasive material according to an embodiment of the present invention.
2 is a cross-sectional view of an abrasive material according to another embodiment of the present invention.
3A is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a triangular pyramid shape are disposed.
3B is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a quadrangular pyramidal shape are disposed.
3C is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a truncated pyramid shape are disposed.
FIG. 3D is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a hemispherical shape are disposed.
Figure 3e is a cross-sectional view of a structured surface in which the three-dimensional element is a laterally oriented and aligned triangular prism.
Figure 3f is a top surface schematic view of a structured surface having a plurality of three-dimensional elements disposed thereon with a hipped roof shape.
Figure 3g is a top surface schematic view of a structured surface in which a combination of a plurality of three-dimensional elements of various shapes is disposed.
4A to 4D are optical micrographs of structured surfaces of the abrasive materials of Examples 1 and 2 and Comparative Example 1 and Comparative Example 2, respectively, after performing the CMP dressing test.
5A is an overall photograph of polishing materials A to C of Examples 3 to 5 and Comparative Example 3 after car-coating polishing test.
5B is an optical microscope photograph of the structured surfaces of the polishing materials A to C of Examples 3 to 5 and Comparative Example 3 after performing the automotive coating polishing test.
5C is an optical microscope picture of the structured surfaces of polishing materials A to C of Examples 3 to 5 and Comparative Example 3 after car coating polishing test is performed and then with water.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following detailed description is given for the purpose of illustrating exemplary embodiments of the present invention, but these embodiments are not to be construed as limiting the present invention.

Refers to a contact surface with an object to be polished, i. E., A horizontal plane parallel to the surface of the object to be polished when the polishing material is contacted with a flat object to be polished.

The term "height" of a three-dimensional element in the present disclosure refers to the distance from the lower end surface of the three-dimensional element along the vertical line of the polishing surface to the upper end point or top surface of the three-dimensional element.

An abrasive material of an embodiment of the present invention comprises an abrasive layer having a structured surface and a plurality of three-dimensional elements are disposed on the structured surface. A surface treatment selected from the group consisting of fluorine treatment or silicon treatment is performed on at least a part of the structured surface. In the present disclosure, "fluorine treatment" refers to surface treatment using a fluorine-containing material, and "silicon treatment" refers to surface treatment using a material containing silicon. Fluorine and other atoms other than silicon, such as hydrogen, oxygen, carbon, nitrogen, etc., can contribute to the surface treatment, and these other atoms can be derived from materials containing fluorine or silicon, .

The abrasive layer can be formed using various materials. 1 illustrates a cross-sectional view of an abrasive material of an embodiment of the present invention. The abrasive material 10 illustrated in Figure 1 comprises an abrasive layer 11 and the abrasive layer 11 comprises a bulk layer 13 and a surface coating < RTI ID = 0.0 > Layer (14). The surface coating layer 14 is applied to a structured surface on which a plurality of three-dimensional elements 12 are disposed. 1, the bulk layer 13 not only determines the shape of the three-dimensional element 12, but also functions as a base material for attaching the polishing material 10 to other tools or the like. Other base materials may be attached to the surface of the bulk layer 13 on the side opposite the structured surface.

The bulk layer determines the shape of the three-dimensional element. The bulk layer may be formed of various hard materials such as an inorganic material such as sintered ceramics in consideration of the material properties and hardness of the object to be polished. The sintered ceramics may include, for example, silicon carbide, silicon nitride, alumina, zirconia, tungsten carbide, and the like. Of these, silicon carbide and silicon nitride, and particularly silicon carbide, can be advantageously used in terms of strength, hardness, abrasion resistance, and the like.

The bulk layer may be formed by mixing ceramic particles such as silicon carbide, a binder, and other materials as needed, and extruding them into a metal die having a negative pattern of the structured surface followed by sintering have.

The surface coating layer is generally formed of a material that is harder than the bulk layer and contributes to polishing the object to be polished by contacting the object to be polished during polishing. Examples of surface coating layers that can be used include diamond-like carbon (abbreviated as DLC) and other diamond materials, tungsten carbide (WC), titanium nitride (TiN), titanium carbide . The thickness of the surface coating layer is generally greater than about 0.5 占 퐉 or about 1 占 퐉 or more, and about 30 占 퐉 or less or about 20 占 퐉 or less. By setting the thickness of the surface coating layer to approximately 1 占 퐉 or more, only the surface coating layer is contacted with the object to be polished during polishing, so that the object to be polished can be protected from contact with the bulk layer. On the other hand, when the adhesion between the surface coating layer and the bulk layer is low, the thickness of the surface coating layer is preferably made relatively thin.

A film containing a diamond material can be advantageously used as a surface coating layer. The film may comprise, for example, diamond-like carbon. The diamond-like carbon is amorphous and comprises a large amount of sp ³ stabilized by hydrogen (for example, carbon atoms can be at least about 40 atomic percent, or at least about 50 atomic percent, and about 99 atomic percent or about 98 atoms %). The diamond film can be formed by a plasma enhanced chemical vapor deposition (PECVD) method, a hot wire chemical vapor deposition (HWCVD) method, an ion beam, a laser, or the like, using a gaseous carbon source such as methane or the like or a solid carbon source such as graphite, Can be deposited on the bulk layer by conventional techniques such as sputtering, ablation, RF plasma, ultrasonic, arc discharge, cathode arc plasma deposition, and the like. In some embodiments, a film having a high degree of crystallinity can be stabilized and produced, and thus the HWCVD method can be advantageously used to deposit a thick diamond film.

Figure 2 illustrates a cross-sectional view of an abrasive material of another embodiment of the present invention. The abrasive material 10 illustrated in Figure 2 includes an abrasive layer 11 comprising abrasive particles 16 and a binder 17 on a backing material 15 and the abrasive layer 11 comprises a plurality of three- And has a structured surface on which the elements 12 are disposed. The backing material 15 serves as a base material of the abrasive material 10. The abrasive grains 16 are uniformly or non-uniformly distributed throughout the binder 17. In this embodiment, when the surface of the object to be polished is polished using the abrasive material 10, the portion in contact with the object to be polished is gradually broken according to the hardness of the object to be polished, 16 are exposed.

In this embodiment, a curable composition comprising abrasive particles, a binder precursor, and an initiator is filled into a metal die having a negative pattern of the structured surface, and the composition is cured using heat or radiation, May be formed.

Examples of abrasive particles that can be used include diamond, cubic boron nitride, cerium oxide, molten aluminum oxide, heat-treated aluminum oxide, aluminum oxide made by a sol-gel process, silicon carbide, chromium oxide, silica, Zirconia, alumina zirconia, iron oxide, garnet, and mixtures thereof. The Mohs' hardness of the abrasive grains is preferably 8 or more or 9 or more. The type of abrasive particles can be selected based on the intended polishing and the diamond, cubic boron nitride, aluminum oxide and silicon carbide are advantageously used for rough polishing such as deburring and the like and for chamfering such as forming a curved surface And silica and aluminum oxide can be advantageously used for finish polishing.

The average particle size of the abrasive particles can vary within a wide range based on the type of abrasive particles, the application of abrasive materials, and the like, and is generally greater than or equal to about 10 nm, greater than or equal to about 1 탆, or greater than or equal to about 5 탆, About 200 μm or less, or about 80 μm or less. For example, abrasive grains having an average grain size of greater than about 0.5 占 퐉 and about 20 占 퐉 or less, or about 10 占 퐉 or less can be advantageously used for rough polishing such as deburring and the like, and for chamfering such as forming a curved shape, Abrasive particles having a particle size of about 10 nm or more and about 1 μm or less, about 0.5 μm or less, or about 0.1 μm or less can be advantageously used for finish polishing.

Coarse diamonds in which diamond particles having a particle size of about 1 μm to about 100 μm are dispersed in a matrix such as glass, ceramic, metal, metal oxide, organic resin, or the like can be used. The average particle size of the agglomerated diamond comprising diamond particles having a particle size of greater than 15 [mu] m is generally greater than about 100 [mu] m or greater than about 250 [mu] m and not greater than about 1000 [mu] m or not greater than about 400 [mu] m. The average particle size of the aggregated diamond comprising diamond particles having a particle size of less than or equal to 15 microns is generally greater than or equal to about 20 microns, greater than or equal to about 40 microns, or greater than or equal to about 70 microns, and less than or equal to about 450 microns, It is approximately 300 μm or less.

A curable resin that is cured by heat or radiation may be used as the binder precursor. The curable resin is generally cured by radical polymerization or cationic polymerization. Examples of binder precursors include phenol resins, resole-phenolic resins, aminoplast resins, urethane resins, epoxy resins, acrylic resins, polyester resins, vinyl resins, melamine resins, isocyanurate acrylate resins, urea-formaldehyde resins , Isocyanurate resin, urethane acrylate resin, epoxy acrylate resin, and mixtures thereof. The term "acrylate" used for the binder precursor includes acrylate and methacrylate.

Conventional thermal initiators or photoinitiators may be used as initiators. Examples of initiators include organic peroxides, azo compounds, quinones, benzophenones, nitroxo compounds, halogenated acrylics, hydrazones, mercapto compounds, pyrylium compounds, triacryl imidazole, bisimidazole, chloroalkyltriazine, Benzoin ethers, benzyl ketals, thioxanthones, acetophenones, iodonium salts, sulfonium salts, and derivatives thereof.

The abrasive particles are generally included in the curable composition in an amount of at least about 150 parts by weight, or at least about 200 parts by weight, and at most about 1000 parts by weight, or at most about 700 parts by weight, based on 100 parts by weight of the binder precursor. The initiator is generally included in the curable composition in an amount of at least about 0.1 parts by weight, or at least about 0.5 parts by weight, and at most about 10 parts by weight, or at most about 2 parts by weight, based on 100 parts by weight of the binder precursor.

The curable composition may further comprise optional components such as coupling agents, fillers, wetting agents, dyes, pigments, plasticizers, fillers, mold release agents, polishing aids and the like.

The backing material may be a polymer film such as polyester, polyimide, polyamide, etc .; paper; Cured fiber; A molded or cast elastomer, a processed nonwoven fabric or woven fabric, or the like. The backing material may be adhered to the polishing layer using an adhesive layer.

The polishing layer and the backing material may be integrally formed using a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin or the thermosetting resin include phenol resin, aminoplast resin, urethane resin, epoxy resin, ethylenic unsaturated resin, isocyanurate acrylate resin, urea-formaldehyde resin, isocyanurate resin, urethane acrylate Resins, epoxy acrylate resins, bimaleimide resins, and mixtures thereof. Among them, a polyamide resin, a polyester resin and a polyurethane resin (including a polyurethane-urea resin) can be advantageously used.

The thickness of the backing material may generally be set at about 1 mm or more, or about 0.5 cm or more, and about 2 cm or less, or about 1 cm or less. The shape tracking characteristic with the backing material as the elastic material can also be applied to the backing material. A predetermined curvature can be applied to the backing material by preforming the backing material.

The polishing function of the three-dimensional element of the abrasive material is demonstrated at its upper end. In an abrasive material having an abrasive layer comprising abrasive particles and a binder, the three-dimensional element is deteriorated from the upper portion during polishing, and unused abrasive particles are exposed. Therefore, by increasing the concentration of the abrasive particles present in the upper end portion of the three-dimensional element, the cutting property and the abrasive property of the abrasive material can be increased, and thus the abrasive material can be advantageously used. The base portion of the three-dimensional element, i.e., the lower portion of the abrasive layer that is bonded to the base material or integrally formed with the base material, does not typically require a polishing function, and thus is formed only by the binder, .

The structured surface of the abrasive layer may comprise variously shaped three-dimensional elements. Examples of the three-dimensional element shape include a cylinder, an elliptic cylinder, a prism, a hemisphere, a semi-elliptical sphere, a cone, a pyramid, a quadrangular cone, Pyramids, meeting roofs, and the like. The structured surface may also include a combination of a plurality of three-dimensional elements having various shapes. For example, the structured surface may be a combination of a plurality of columns and a plurality of pyramids. The cross-sectional shape of the base portion of the three-dimensional element may be different from the cross-sectional shape of the top portion. For example, the cross section of the base portion may be a square shape, while the cross section of the upper end portion may be a circular shape. The three-dimensional element usually has a base portion with a cross-sectional area greater than the cross-sectional area of the top portion. The base portions of the three-dimensional elements can be in contact with each other or alternately, and the base portions of the adjacent three-dimensional elements can be separated from each other at a predetermined distance.

In some embodiments, a plurality of three-dimensional elements are systematically arranged on the structured surface. In the present disclosure, three-dimensional elements having the same or similar shape "systematically" used in connection with the position of a three-dimensional element are arranged along one or more directions on a horizontal plane parallel to the polishing surface, As shown in FIG. One or more directions on a horizontal plane parallel to the polishing surface may be a linear, concentric, spiral (or vortex) direction, or a combination thereof. In embodiments where a plurality of three-dimensional elements are systematically placed on the structured surface, the space present between the three-dimensional elements, such as grooves, for example, may be structured in a pattern favorable to flow and release of slurry, abrasive powder, Can be placed on the entire surface. The plurality of three-dimensional elements may be formed by, for example, a surface treatment, a polycrystalline diamond deposition method by laser treatment, or a diamond wheel, a CVD by a cutting wheel, or an injection molding, A binder precursor is filled in the binder precursor and then cured using heat or radiation.

Structured surfaces that can be used in the abrasive material of the present invention are described by way of example with reference to Figures 3A-3G. 3A is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a triangular pyramid shape are disposed. In Fig. 3A, the symbol o represents the length of the base of the three-dimensional element 12 and the symbol p represents the distance between the upper end portions of the three- The lengths of the bases of the triangular element may be the same or different, and the lengths of the sides may be the same or different. For example, o may be set at about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p may be set to about 5 탆 or more, or about 10 탆 or more, and about 1000 탆 or less or about 500 탆 or less. Although not illustrated in Fig. 3A, the height h of the three-dimensional element 12 can be set to be about 2 탆 or more, or about 4 탆 or more, and about 600 탆 or less or about 300 탆 or less. The change in h is preferably about 20% or less of the height of the three-dimensional element 12, and more preferably about 10% or less.

3B is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a quadrangular pyramidal shape are disposed. 3B, the symbol o represents the length of the base of the three-dimensional element 12 and the symbol p represents the distance between the upper end portions of the three-dimensional element 12. The lengths of the bases of the quadrangular pyramids can be the same or different, and the lengths of the sides can be the same or different from each other. For example, o may be set at about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p may be set to about 5 탆 or more, or about 10 탆 or more, and about 1000 탆 or less or about 500 탆 or less. Although not illustrated in Fig. 3B, the height h of the three-dimensional element 12 may be set to be about 2 탆 or more, or about 4 탆 or more, and about 600 탆 or less or about 300 탆 or less. The change in h is preferably about 20% or less of the height of the three-dimensional element 12, and more preferably about 10% or less.

In another embodiment of the present invention, the three-dimensional element can be a truncated triangular pyramid or a truncated quadrangular pyramid. The upper end surface of the three-dimensional element of this embodiment generally consists of a triangular or rectangular horizontal surface parallel to the polishing surface. Substantially all upper end surfaces are preferably on a horizontal plane parallel to the polishing layer.

3C is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a truncated quadrangular pyramid are disposed. The shape of the quadrangular pyramid before cutting the upper part is illustrated in the upper left corner. 3C, the symbol o represents the length of the base of the three-dimensional element 12, the symbol u represents the distance between the bases of the three-dimensional element 12, and the symbol y represents the length of the side of the top surface. The lengths of the bases of the truncated quadrangular pyramids can be the same or different from each other, the lengths of the sides can be the same or different from each other, and the lengths of the sides of the upper surface can be the same or different from each other. For example, o may be set at about 5 μm or more, or about 10 μm or more, and about 6000 μm or less, or about 3000 μm or less. u may be set to be greater than or equal to 0 [mu] m or greater than or equal to about 2 [mu] m, and less than or equal to about 10,000 [mu] m or less than or equal to about 5000 [mu] m. y may be set at about 0.5 μm or more, or about 1 μm or more, and about 6000 μm or less, or about 3000 μm or less. Although not illustrated in FIG. 3C, the height h of the three-dimensional element 12 may be set at about 5 μm or more, or about 10 μm or more, and about 10,000 μm or less or about 5000 μm or less. The change in h is preferably about 20% or less of the height of the three-dimensional element 12, and more preferably about 10% or less.

FIG. 3D is a top surface schematic view of a structured surface in which a plurality of three-dimensional elements having a hemispherical shape are disposed. In Figure 3D, the symbol r represents the radius of the three-dimensional element 12 and the symbol p represents the distance between the centers of the three-dimensional elements 12. For example, r may be set at about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p may be set to about 5 탆 or more, or about 10 탆 or more, and about 1000 탆 or less or about 500 탆 or less. Although not illustrated in FIG. 3D, the height h of a three-dimensional element having a hemispherical shape is the same as an ordinary radius r. The change in h is preferably about 20% or less of the height of the three-dimensional element 12, and more preferably about 10% or less.

3E is a schematic cross-sectional view of another embodiment of the present invention, wherein the plurality of three-dimensional elements 12 are laterally oriented triangular prisms and have ridges. The three-dimensional element 12 is disposed on the base material 15 and comprises an abrasive layer upper portion 18 comprising abrasive particles and a binder and a lower abrasive layer portion 19 including a binder but not abrasive particles, As shown in Fig. The ridges are preferably on a horizontal plane substantially parallel to the polishing layer across the entire polishing material. In some embodiments, substantially all of the ridges are on the same horizontal plane parallel to the polishing layer. 3E, the symbol a represents the vertical angle of the three-dimensional element 12; Symbol w represents the width of the lower end portion of the three-dimensional element 12; The symbol p represents the distance between the upper end portions of the three-dimensional element 12; The symbol u represents the distance between the long bases of the three-dimensional element 12; The symbol h indicates the height of the three-dimensional element 12 from the surface of the base material 15; The symbol s indicates the height of the upper part 18 of the polishing layer. For example, alpha can be set to about 30 degrees or more, or about 45 degrees or more, and about 150 degrees or less, or about 140 degrees or less. w may be set to about 2 탆 or more, or about 4 탆 or more, and about 2000 탆 or less or about 1000 탆 or less. p may be set to about 2 탆 or more, or about 4 탆 or more, and about 4000 탆 or less or about 2000 탆 or less. u may be set to be greater than or equal to 0 [mu] m or greater than or equal to about 2 [mu] m, and less than or equal to about 2000 [mu] m or less than or equal to about 1000 [ h may be set to about 2 탆 or more, or about 4 탆 or more, and about 600 탆 or less or about 300 탆 or less. s can be set at about 5% or more, or about 10% or more, and about 95% or less or about 90% or less of the height h of the three-dimensional element 12. [ The change in h is preferably about 20% or less of the height of the three-dimensional element 12, and more preferably about 10% or less.

The individual three-dimensional elements 12 illustrated in Figure 3e can extend across the entire surface of the abrasive material. In this case, both end portions of the three-dimensional element 12 in the long base direction are near the end portions of the abrasive material, and the plurality of three-dimensional elements 12 are arranged in the band shape.

In another embodiment of the present invention, the three-dimensional element has a gathered roof shape. In the present disclosure, the "meeting roof" shape refers to a three-dimensional shape in which the side surfaces consist of two corresponding triangular shapes and two corresponding rectangular shapes, wherein the adjacent triangular side surface and the square side surface share an area, The area shared by the two rectangular side surfaces is ridge. The ridges are preferably on a horizontal plane substantially parallel to the polishing layer across the entire polishing material. In some embodiments, substantially all of the ridges are on the same horizontal plane parallel to the polishing layer. The two triangular side surfaces and the two rectangular side surfaces may have the same shape or different shapes from each other. Thus, the lower end surface of the meeting roof shape may be rectangular, trapezoidal, or the like, and the four side portions may have a square shape that is different from each other.

Figure 3f is a top surface schematic view of a structured surface on which a plurality of three-dimensional elements having a meeting roof shape are disposed. Figure 3f illustrates a meeting roof shape having a rectangular lower end surface. In Figure 3f, the symbol l represents the length of the long base of the three-dimensional element 12 and the symbol x represents the distance between the short bases of the adjacent three-dimensional elements 12. [ For example, l may be set at about 5 μm or more, or about 10 μm or more, and about 10 mm or less or about 5 mm or less. x may be set to be 0 占 퐉 or more, or about 2 占 퐉 or more, and about 2000 占 퐉 or less or about 1000 占 퐉 or less. The symbol w, the symbol p and the symbol u, and the definitions and exemplary numerical ranges of the symbol h, the symbol s, the symbol a, etc., which are not illustrated in Fig. 3f, are the same as those described in Fig. 3e.

In another embodiment, the structured surface comprises a combination of a plurality of three-dimensional elements having various shapes. Figure 3g illustrates an example of such an embodiment. The structured surface illustrated in Figure 3G includes a combination of a first triangular pyramid 121, a second triangular pyramid 122, a hexagonal horn 123, and a meeting roof 124. The length of the bases of each of the three-dimensional elements may be set at about 5 μm or more, or 10 μm or more, and about 1000 μm or less, or about 500 μm or less, and heights of about 2 μm or more or about 4 μm or more, mu m or less or about 300 mu m or less. The distance between the bases of adjacent three-dimensional elements may be set to be greater than or equal to about 0 [mu] m or greater than or equal to about 2 [micro] m, and less than or equal to about 10,000 [micro] m or less than or equal to about 5000 [micro] m. The length of the ridge of the meeting roof 124 may be set to be greater than about 0.5 占 퐉 or about 1 占 퐉 or more, and about 1000 占 퐉 or less or about 500 占 퐉 or less.

In some embodiments, the density of the three-dimensional elements of the abrasive material, in other words, the abrasive material 1, the number of three-dimensional elements are approximately 0.5-element / ㎠ or more or 1.0-element / ㎠ or more, and approximately 1 × 10 ⁷ per ㎠ dog element / ㎠ or less is approximately 4 × 10 ^6-element / ㎠ below. In embodiments where a plurality of three-dimensional elements are systematically disposed on the structured surface, the number of three-dimensional elements per cm < 2 > of abrasive material may be greater than or equal to about 0.05 element / cm 2 or greater than or equal to about 0.10 elements / 10 ⁶ elements / cm 2 or less or about 4 × 10 ⁵ elements / cm 2 or less. In this embodiment, the high polishing efficiency is achieved by arranging the three-dimensional elements at high density on the structured surface, while slurry, abrasive powder, etc., Can be efficiently released by using a space having a determined pattern and performing surface treatment on the structured surface in combination.

In the case of the abrasive material of the present invention, a fluorine treatment or a silicon treatment is performed on at least a part of the structured surface. Without being bound by any theory, it is believed that an abrasive material wherein the structured surface is covered by a surface coating layer, such as diamond-like carbon, and an abrasive material wherein the abrasive layer comprises abrasive particles and resin binder, charge-up, or surface energy of the structured surface, and thus the abrasive particles are adhered to the base material by conductive Ni plating or the like, as compared to conventional abrasive materials where the abrasive particles are adhered to the base material by electrostatic or other interactions It is easy to hang on a structured surface. According to the present invention, even though the structured surface comprises three-dimensional elements at relatively high densities, the surface energy of the structured surface can be reduced by surface treatment of such three-dimensional elements, Adhesion or accumulation of abrasive particles, organic compounds, etc., in the polishing slurry, polyurethane particles generated from the polyurethane foam pad, etc., can be prevented or suppressed.

In the present invention, the fluorine treatment can be advantageously carried out by a plasma treatment, a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method or a fluorine gas treatment.

"Plasma treatment" in accordance with the present invention refers to a treatment that changes the chemical composition of the surface of an object to be treated using a plasma activated source gas, and the reaction products, including materials derived from the object to be treated, Lt; / RTI > On the other hand, in chemical vapor deposition and physical vapor deposition, a film containing a component derived from a gas, liquid or solid raw material is formed by deposition on the surface of an object to be treated. The chemical vapor deposition method includes, for example, a thermal CVD method, a direct plasma enhanced CVD method, a remote plasma CVD method, a hot wire CVD method, and the like. Physical vapor deposition methods include sputtering, vacuum deposition, arc spraying, plasma spraying, aerosol deposition, and the like.

Without wishing to be bound by any theory, fluorination can be achieved by the fact that fluorine is doped around the surface of a surface coating layer, such as diamond-like carbon or abrasive particles, because the surface of the material is fluorine It is believed that a coating comprising densified fluorocarbon containing many CC bonds is formed on the structured surface, and the like.

In some embodiments, fluorine treatment by plasma treatment or chemical vapor deposition methods may be performed using a low pressure plasma apparatus or an atmospheric pressure plasma apparatus having a decompressible chamber. A chemical vapor deposition method using a plasma apparatus is generally referred to as a plasma enhanced CVD method. When an atmospheric pressure plasma apparatus is used, in addition to the fluorine-containing gas, nitrogen gas and / or Group 18 atoms of the periodic table, specifically helium, neon, argon, krypton, xenon and radon are used as the discharge gas. Of these, nitrogen, helium and argon can be advantageously used, and nitrogen is particularly advantageous from a cost point of view. Low pressure plasma devices are commonly used in batch treatments. When continuous processing such as long webbing is required, it may be advantageous from the viewpoint of productivity to use an atmospheric pressure plasma apparatus. Conventional methods such as corona discharge, dielectric barrier discharge, single or dual RF discharges using, for example, 13.56 MHz high frequency power, 2.45 GHz microwave discharge, arc discharge, etc., can be used as a method of generating plasma. Among these generation methods, a single RF discharge using a 13.56 MHz high frequency power source can be advantageously used.

Fluorocarbons, such as _{CF 4, C 4 F 8,} C 5 F 6, C 4 F 6, CHF 3, CH 2 F 2, CH 3 F, C 2 F 6, C 3 F 8, C 4 F 10, C ₆ F ₁₄ , nitrogen trifluoride (NF ₃ ), SF _6, and the like can be used as a fluorine-containing gas used in a plasma treatment or chemical vapor deposition method. From the standpoints of safety, reactivity and the like, C ₃ F ₈ , C ₆ F ₁₄ and CF ₄ can be advantageously used. The flow rate of the fluorine-containing gas may be set to about 20 sccm or more, or about 50 sccm or more, and about 1000 sccm or less, or about 500 sccm or less. A carrier gas, such as nitrogen, helium, or argon, having a flow rate of about 50 sccm or more and a flow rate of about 5000 sccm or less may be further included in the gas flow fed to the apparatus.

In some embodiments, it is known that a good film can be deposited by setting the raw gas C / F ratio to about 3 or less. In this case, the C / F ratio is determined by adding a non-fluorine gas such as acetylene, . In embodiments where the C / F ratio of the source gas is greater than or equal to about 2 and less than or equal to about 3, depending on the bias voltage, the surface modification due to the plasma treatment may occur preferentially or the film deposition due to the chemical vapor deposition process may preferentially Lt; / RTI > By adjusting the bias voltage in such an embodiment, the fluorine treatment can be plasma treatment or chemical vapor deposition or a combination thereof. The range of the bias voltage may vary depending on the size or design of the device, but may generally be set to about 100 V or less, about 0 V or less to about -1000 V or more, or about -100,000 V or more.

The power applied for generating the plasma can be determined based on the dimensions of the abrasive material to be treated and the power density in the discharge space is generally about 0.00003 W / cm 2 or more, or about 0.0002 W / cm 2 or more, and about 10 W / Or about 1 W / cm < 2 > or less. For example, if the dimensions of the abrasive material to be fluorinated are less than or equal to 10 cm (length) x 10 cm (width), the applied power will be about 200 W or more, or about 500 W or more, and about 4 kW or less, or about 2.5 kW or less Lt; / RTI >

The temperature of the plasma treatment or chemical vapor deposition process is preferably a temperature that does not impair the characteristics and performance of the polishing material to be treated and the like and the surface temperature of the polishing material to be treated is approximately -15 DEG C or higher, And about 400 캜 or less, about 200 캜 or less, or about 100 캜 or less. The surface temperature of the abrasive material can be measured by a thermocouple in contact with the abrasive material, a radiation thermometer, and the like.

The processing pressure when performing a plasma treatment or chemical vapor deposition method using a low pressure plasma apparatus can be set to be about 10 mTorr or more, or about 20 mTorr or more, and about 1500 mTorr or less or about 1000 mTorr or less.

The treatment time for the plasma treatment or chemical vapor deposition process can 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, or about 120 seconds or less.

In another embodiment, the remote plasma apparatus may be used as a fluorine treatment by a plasma treatment or a chemical vapor deposition method. Chemical vapor deposition methods using remote plasma devices are generally referred to as remote plasma CVD methods. In a remote plasma apparatus, the plasma is generated in a plasma excitation chamber that is different from the processing chamber, and the excited active species is generated by introducing the source gas into the plasma excitation chamber, and the excited active species generated is nitrogen, helium, neon, Is flowed into the processing chamber with the same carrier gas, thereby fluorinating the structured surface of the abrasive material.

A low pressure remote plasma apparatus or an atmospheric pressure remote plasma apparatus having a decompression chamber can be used as the remote plasma apparatus. The discharge gas and the preferred discharge gas that can be used are as described above for the low pressure plasma apparatus and the atmospheric pressure plasma apparatus. 2.45 ㎓ microwave discharge and 2.45 ㎓ microwave discharge / electron cyclotron resonance (ECR) are generally used as a plasma generation method and a 2.45 ㎓ microwave discharge and a 2.45 ㎓ microwave discharge / electron cyclotron The resonance (ECR) is advantageously used because the desired high plasma density in the remote plasma can be achieved.

Fluorocarbons, such as _{CF 4, C 4 F 8,} C 5 F 6, C 4 F 6, CHF 3, CH 2 F 2, CH 3 F, C 2 F 6, C 3 F 8, C 4 F 10, C ₆ F _14, etc., nitrogen trifluoride (NF ₃ ), SF _6, and the like can be used as a fluorine-containing gas used in a plasma treatment or chemical vapor deposition method using a remote plasma apparatus. The lifetime of the active species here is longer and safety is higher, so that NF ₃ and SF ₆ can be advantageously used. The flow rate of the fluorine-containing gas may be set to about 20 sccm or more, or about 50 sccm or more, and about 1000 sccm or less, or about 500 sccm or less. The flow rate of the carrier gas may be set to be about 100 sccm or more, or about 200 sccm or more, and about 5000 sccm or less, or about 200 sccm or less.

In some embodiments, it is known that a good film can be deposited by setting the raw gas C / F ratio to about 3 or less. In this case, the C / F ratio can be adjusted by adding a non-fluorine based gas such as acetylene, have. In embodiments where the C / F ratio of the source gas is greater than or equal to about 2 and less than or equal to about 3, depending on the bias voltage, surface modification due to the plasma treatment may occur preferentially or film deposition due to the chemical vapor deposition process may occur preferentially. By adjusting the bias voltage in such an embodiment, the fluorine treatment can be plasma treatment or chemical vapor deposition or a combination thereof. The range of the bias voltage may vary depending on the size or design of the device, but may generally be set to about 100 V or less, about 0 V or less to about -1000 V or more, or about -100,000 V or more.

The power required for generating the plasma can be set to, for example, about 1 W or more, or about 10 W or more, and about 300 kW or less or about 30 kW or less.

In a remote plasma apparatus, the fluorine treatment can be performed while keeping the polishing material to be treated at a low temperature. For example, the surface temperature of the polishing material to be treated may be set at about -15 占 폚 or higher, about 0 占 폚 or higher, or about 15 占 폚 or higher, and about 200 占 폚 or lower, about 100 占 폚 or lower, or about 50 占 폚 or lower. The surface temperature of the abrasive material can be measured by a thermocouple in contact with the abrasive material, a radiation thermometer, and the like.

The process pressure when performing a plasma treatment or chemical vapor deposition process using a low pressure remote plasma apparatus may be set to be about 1 mTorr or more, or about 10 mTorr or more, and about 1500 mTorr or less or about 1000 mTorr or less.

The treatment time for the plasma treatment or chemical vapor deposition process can 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, or about 120 seconds or less.

In another embodiment, sputtering can be used as the fluorine treatment by the physical vapor deposition method. Sputtering can be performed using a typical sputtering apparatus such as an ion sputtering apparatus, a DC magnetron sputtering apparatus, an RF magnetron sputtering apparatus, or the like.

Fluoropolymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and the like can be used as a fluorine-treated sputtering target. Fluorocarbons, such as _{CF 4, C 4 F 8,} C 5 F 6, C 4 F 6, CHF 3, CH 2 F 2, CH 3 F, C 2 F 6, C 3 F 8, C 4 F 10, Reactive sputtering can be performed by providing C ₆ F _14, etc., nitrogen fluoride (NF ₃ ), SF ₆ , and the like in the processing chamber.

The sputtering temperature may be set at about -193 ° C or higher, or about 25 ° C or higher, and about 600 ° C or lower, or about 1300 ° C or lower.

The processing pressure of the sputtering can be set to about 1 x ^10-5 Torr or more, or about 1 x ^10-3 Torr or more, and about 10 mTorr or less, or about 100 mTorr or less.

The processing time of the sputtering can be set to about 1 second or more, about 5 seconds or more, or about 10 seconds or more, and about 30 seconds or less, about 60 seconds or less, or about 180 seconds or less.

In another embodiment, vacuum deposition can be used as a fluorine treatment by physical vapor deposition. Vacuum deposition can be performed using a typical deposition apparatus, such as a resistance heating deposition apparatus, an electron beam deposition apparatus, an ion plating apparatus, or the like.

Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) and other fluoropolymers, calcium fluoride (CaF ₂ ) and other fluorine-containing organic compounds may be used as deposition sources.

The deposition temperature may be set at about -193 DEG C or higher, or about 25 DEG C or higher, and about 600 DEG C or lower, or about 1000 DEG C or lower.

The deposition processing pressure may be set to approximately 1 x ^10-6 Torr or greater, or approximately 1 x ^10-5 Torr or greater, and approximately 1 x ^10-3 Torr or less, or approximately 1 x ^10-2 Torr or less.

The treatment time for the deposition may be set to about 5 seconds or more, about 10 seconds or more, or about 30 seconds or more, and about 120 seconds or less, about 600 seconds or less, or about 1200 seconds or less.

In another embodiment, the fluorine gas (F ₂ ) treatment can be used as the fluorine treatment. The fluorine gas may be diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, etc., and may be used as is without dilution. The fluorine gas treatment is generally carried out at atmospheric pressure.

The temperature at which the fluorine gas is brought into contact with the structured surface of the abrasive material may be set to room temperature or higher, about 50 캜 or higher, or about 100 캜 or higher, and about 250 캜 or lower, about 220 캜 or lower or about 200 캜 or lower.

The treatment time of the fluorine gas treatment may be set to about 1 minute or more, or about 1 hour or more, and about 1 week or less or about 50 hours or less.

In the present invention, the silicon treatment can be advantageously carried out by a plasma treatment, a chemical vapor deposition method, a physical vapor deposition method, or an atomic layer deposition method. Without wishing to be bound by any theory, it is believed that the silicon treatment can be carried out in the polymer contained in the binder or on the surface of abrasive particles or on a surface coating such as diamond-like carbon, Si-O-Si bonds, Si- A phenomenon in which the structured surface is improved by forming bonds or the like; A phenomenon in which a coating containing silicon oxycarbide or silicon oxide having a relatively dense network structure formed through Si-O-Si bonds, Si-C-Si bonds, Si-OC bonds or the like is formed on the structured surface ≪ / RTI >

The silicon treatment by the plasma treatment or chemical vapor deposition method may be performed using the same low pressure plasma apparatus, atmospheric pressure plasma apparatus, low pressure remote plasma apparatus, atmospheric pressure remote plasma apparatus, and the like, which are the same as for the fluorine treatment described above. The discharge gas and the plasma generation method are the same as those described for the fluorine treatment.

A fluorine-containing gas such as silane (SiH ₄ ), tetramethylsilane (TMS), hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDS), tetraethoxysilane (TEOS) Containing gas. Among them, monosilane or tetramethylsilane can be advantageously used because of high reactivity and large diffusion coefficient. When an atmospheric plasma apparatus is used, tetramethylsilane, which has low boiling point and is nonflammable, is used. The flow rate of the silicon-containing gas may be set at about 20 sccm or more, or about 50 sccm or more, and about 1000 sccm or less, or about 500 sccm or less. A carrier gas, such as nitrogen, helium, or argon, having a flow rate of about 50 sccm or more and a flow rate of about 5000 sccm or less may be further included in the gas flow fed to the apparatus.

When the oxygen atom is not included in the silicon-containing gas, oxygen is added to the gas flow supplied to the plasma apparatus. Oxygen may be fed into the chamber of the plasma apparatus through a line separate from the silicon-containing gas, or may be supplied as a gaseous mixture with the silicon-containing gas through a showerhead disposed within the chamber. The flow rate of oxygen can be set to about 5 sccm or more, or about 10 sccm or more, and about 500 sccm or less, or about 300 sccm or less. The flow rate ratio of oxygen to the silicon-containing gas is about 0.1: 1 or more, about 0.2: 1 or more, or about 0.3: 1 or more, and about 5: 1 or less, about 4 : 1 or less or about 3: 1 or less. After the supply of the silicon-containing gas is stopped, the post-treatment can be performed, for example, by supplying only oxygen at a flow rate of, for example, about 5 sccm or more, or about 10 sccm or more, and about 500 sccm or less or about 300 sccm or less.

The power applied for generating the plasma can be determined based on the dimensions of the abrasive material to be treated and the power density in the discharge space is generally about 0.00003 W / cm 2 or more, or about 0.0002 W / cm 2 or more, and about 10 W / Or about 1 W / cm < 2 > or less. For example, when the dimensions of the abrasive material to be siliconized are less than or equal to 10 cm (length) x 10 cm (width), the applied power is approximately 1 W or more, or approximately 10 W or more, and approximately 300 kW or less, or approximately 30 kW or less Lt; / RTI >

The temperature of the plasma treatment or chemical vapor deposition process is preferably a temperature that does not impair the characteristics and performance of the polishing material to be treated and the like and the surface temperature of the polishing material to be treated is approximately -15 DEG C or higher, And about 400 캜 or less, about 200 캜 or less, or about 100 캜 or less. The surface temperature of the abrasive material can be measured by a thermocouple in contact with the abrasive material, a radiation thermometer, and the like.

The processing pressure when performing a plasma treatment or chemical vapor deposition method using a low pressure plasma apparatus can be set to be about 10 mTorr or more, or about 20 mTorr or more, and about 1500 mTorr or less or about 1000 mTorr or less.

The treatment time for the plasma treatment or chemical vapor deposition process can 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, or about 120 seconds or less.

In another embodiment, sputtering or vacuum deposition may be used as silicon treatment by physical vapor deposition. The silicon treatment using the physical vapor deposition method can be carried out using standard sputtering equipment, such as the same ion sputtering equipment described for fluorine treatment, DC magnetron sputtering equipment, RF magnetron sputtering equipment, or standard deposition equipment such as resistance heating deposition equipment, electron beam deposition equipment , Ion plating equipment, and the like.

The sputtering target of the silicon treatment may be silicon dioxide (SiO ₂ ). Reactive sputtering can be performed by supplying oxygen into the processing chamber when silicon (Si) is used as a sputtering target.

The sputtering temperature may be set at about -193 ° C or higher, or about 25 ° C or higher, and about 600 ° C or lower, or about 1300 ° C or lower.

The processing pressure of the sputtering can be set to about 1 x ^10-5 Torr or more, or about 1 x ^10-3 Torr or more, and about 10 mTorr or less, or about 100 mTorr or less.

The processing time of the sputtering can be set to about 1 second or more, about 5 seconds or more, or about 10 seconds or more, and about 30 seconds or less, about 60 seconds or less, or about 180 seconds or less.

Silicon dioxide (SiO ₂ ) can be used as a deposition source for vacuum deposition. Electron beam deposition can be advantageously used with silicon dioxide deposition. Silicon treatment can be performed by depositing silicon monoxide (SiO) as a deposition source, followed by deposition to perform annealing oxidation in an oxidizing atmosphere, and deposition of silicon monoxide while introducing an oxygen plasma into the deposition chamber.

The deposition temperature may be set at about -193 DEG C or higher, or about 25 DEG C or higher, and about 600 DEG C or lower, or about 1000 DEG C or lower.

The deposition processing pressure may be set to approximately 1 x ^10-6 Torr or greater, or approximately 1 x ^10-5 Torr or greater, and approximately 1 x ^10-3 Torr or less, or approximately 1 x ^10-2 Torr or less.

The treatment time for the deposition may be set to about 5 seconds or more, about 10 seconds or more, or about 30 seconds or more, and about 120 seconds or less, about 600 seconds or less, or about 1200 seconds or less.

In another embodiment, an atom layer deposition (ALD) method may be used as the silicon treatment. The atomic layer deposition method comprises providing at least two types of precursor gases alternately into the reaction chamber, depositing a single layer of such precursor gas on the structured surface each time, and reacting such precursor gas on the structured surface .

Examples of the precursor gas A that can be used include tetraethoxysilane, bis (tert-butoxy) (isopropoxy) silanol, bis (isopropoxy) (tert-butoxy) silanol, bis (Tert-butoxy) silanol, bis (tert-butoxy) silanol, bis (tert-butoxy) Pentoxy) silanol, tris (tert-pentoxy) silanol, and the like. Examples of precursor gas B include water (H ₂ O), oxygen (O ₂ ), ozone (O ₃ ), and the like.

The flow rate of the precursor gas A may be set to be about 0.1 sccm or more, or about 1 sccm or more, and about 100 sccm or less or about 1000 sccm or less. The time for introducing the precursor gas A into the reaction chamber may be about 0.01 seconds or more, or about 0.1 seconds or more, and about 10 seconds or less or about 100 seconds or less.

The flow rate of the precursor gas B may be set at about 0.1 sccm or more, or about 1 sccm or more, and about 100 sccm or less, or about 1000 sccm or less. The time for introducing the precursor gas B into the reaction chamber may be about 0.01 seconds or more, or about 0.1 seconds or more, and about 10 seconds or less or about 100 seconds or less.

Unreacted precursor gas and / or reaction by-products may be purged from the reaction chamber by introducing purge gas into the reaction chamber between introduction of the precursor gas A and introduction of the precursor gas B. The purge gas is an inert gas that will not react with the precursor gas. Examples of purge gases that may be used include nitrogen gas, helium, neon, argon, and mixtures thereof. The flow rate of the purge gas may be, for example, about 10 sccm or more, or about 50 sccm or more, and about 500 sccm or less or about 1000 sccm or less, and the introduction time of the purge gas may be about 1 second or more, 30 seconds or less, or about 60 seconds or less.

A film of silicon carbide or silicon oxide having a predetermined thickness is formed on the structured surface by changing the flow rate and the introduction time of the precursor gas A and the precursor gas B as well as the number of times of introducing the precursor gas A and the precursor gas B . After introducing precursor gas A and / or precursor gas B, the reaction between precursor gas A and precursor gas B can be performed in a variety of ways including, but not limited to, heat, plasma, pulsed plasma, helion plasma, high density plasma, inductive coupled plasma, X- Photons, remote plasmas, and the like.

The physical properties of structured surfaces that have been surface treated in this manner can be assessed, for example, by contact angles, hardness, and the like.

In some embodiments, for example, in a structured surface fluorinated embodiment, the water contact angle of the surface treated structured surface is greater than or equal to about 70 degrees, or greater than or equal to about 90 degrees, and less than or equal to about 120 degrees or less than or equal to about 150 degrees . The water contact angle can be determined by a droplet method, an expansion / contraction method, a Wilhelmy method, and the like.

In some other embodiments, for example, in embodiments wherein the structured surface is siliconized to provide a hydrophilic surface, the water contact angle of the surface treated structured surface may be greater than or equal to about 0 or greater than or equal to about 10, and less than or equal to about 30 Or about 45 degrees or less. The water contact angle can be determined by a droplet method, an expansion / contraction method, a Bill Helmi method, and the like.

In another embodiment, the hardness of the surface treated structured surface is greater than or equal to about 40 or greater than about 50, and less than or equal to about 87 or less than or equal to about 97 when converted to Shore hardness. The hardness of the surface-treated structured surface can be determined, for example, by the nano indentation method. When the hardness of the surface-treated structured surface is about 50 or more when calculated as the Shore hardness, adhesion to a structured surface of relatively soft foreign matter, such as polymer particles of polyurethane, can be prevented.

The composition of the film deposited on a structured surface or a structured surface in a fluorinated or silicon-treated modified state can be determined by x-ray photoelectron spectroscopy (XPS), or secondary ion mass spectrometry (TOF-SIMS) And the like can be evaluated qualitatively or quantitatively. The XPS spectrum can be obtained, for example, using a Kratos Axis Ultra spectrometer using a monochromatic Al K alpha photon source at an electron emission angle of 90 [deg.] To the surface. The TOF-SIMS can use a rasterized pulse 25 keV Ga + primary ion beam, for example, with a 400 x 400 micrometer area with a beam diameter of approximately 1 μm.

Another embodiment of the present invention is an abrasive material comprising an abrasive layer having a structured surface configured to have a plurality of three-dimensional elements arranged thereon, wherein at least a portion of the structured surface comprises: (a) densified fluorocarbon, A film comprising a material selected from the group consisting of silicon oxycarbide, silicon oxycarbide, and silicon oxide; (b) a fluorine terminated surface; Or (c) a combination thereof.

In the present invention, "densified fluorocarbon" refers to a fluorocarbon material comprising a dense three dimensional network structure formed to have C-C bonds as a result of containing a relatively large amount of quaternary carbon atoms. The densified fluorocarbons have high hardness and excellent abrasion resistance and adhesion in foreign matter, compared with standard fluoropolymers that are not crosslinked or crosslinked.

The densified fluorocarbon may contain other atoms such as hydrogen, oxygen, nitrogen, etc. in addition to carbon and fluorine. In some embodiments, the densified fluorocarbon comprises about 20 atomic percent or more, or about 25 atomic percent or more, and about 65 atomic percent or less or about 60 atomic percent or less of carbon atoms based on the total amount of elements other than hydrogen. In some other embodiments, the densified fluorocarbon comprises about 30 atomic percent or more, or about 35 atomic percent or more, and about 75 atomic percent or less, or about 70 atomic percent or less of carbon atoms, based on the total amount of elements other than hydrogen . Moreover, in some other embodiments, the densified fluorocarbon is present in an amount of at least about 25 atomic percent, or at least about 30 atomic percent, and no more than about 80 atomic percent or no more than about 70 atomic percent based on the total amount of the elements other than hydrogen, And a quaternary carbon atom bonded to the carbon atom. The atomic percentages of carbon atoms and fluorine atoms of the densified fluorocarbons can be determined, for example, using XPS, and the atomic percentages of the quaternary carbon atoms can be determined using, for example, 13 C-NMR.

The silicon oxycarbide is a compound that includes silicon, oxygen, and carbon but may include other atoms that are three-dimensional elements, such as hydrogen, nitrogen, and the like. The silicon oxycarbide is hard, has excellent abrasion resistance, adhesion in foreign substances, etc., and can be made hydrophilic or hydrophobic by changing the composition. In some embodiments, the silicon oxycarbide contains about 10 atomic percent or more, or about 15 atomic percent or more, and about 90 atomic percent or less, or about 80 atomic percent or less of silicon atoms based on the total amount of elements other than hydrogen. In some other embodiments, the silicon oxycarbide contains at least about 5 atomic percent, or at least about 10 atomic percent, and at least about 80 atomic percent or at most about 70 atomic percent oxygen atoms based on the total amount of the elements other than hydrogen. Moreover, in some other embodiments, the silicon oxycarbide may comprise at least about 1 atomic percent, or at least about 5 atomic percent, and at least about 90 atomic percent, or at least about 80 atomic percent carbon atoms, based on the total amount of the elements other than hydrogen do. The atomic percentages of silicon atoms, oxygen atoms and carbon atoms in silicon oxycarbide can be determined using XPS, TOF-SIOMS, and the like.

Silicon oxide is a compound that includes silicon and oxygen but can contain other atoms, such as hydrogen, nitrogen, etc., except for carbon. Silicon oxide, especially silicon oxide having Si-O-H bonds at its ends, is generally hydrophilic and can effectively prevent adhesion of hydrophobic materials to structured surfaces. In some embodiments, the silicon oxide contains about 30 atomic percent or more, or about 33 atomic percent or more, and about 55 atomic percent or less, or about 50 atomic percent or less of silicon atoms based on the total amount of elements other than hydrogen. In some other embodiments, the silicon oxycarbide contains at least about 45 atomic percent, or at least about 50 atomic percent, and at least about 70 atomic percent or at most about 67 atomic percent oxygen atoms based on the total amount of the elements other than hydrogen. The atomic percentages of silicon atoms and oxygen atoms in silicon oxide can be determined using XPS, TOF-SIOMS, and the like.

The thickness of the film comprising densified fluorocarbon, silicon oxycarbide, and silicon oxide is generally greater than or equal to about 0.05 nm or greater than or equal to 0.5 nm, and less than or equal to about 200 μm or less than or equal to about 150 μm. The film thickness can be determined using XPS, TOF-SIOMS, or the like.

The fluorine atom density of the fluorinated terminated structured surface is generally greater than about 1 x 10 ¹³ cm ^-2 or greater than about 5 x 10 ¹³ cm ^{-2 and} less than about 5 x 10 ¹⁵ cm ^-2 or less than about 3 x 10 ¹⁵ cm ^-2 or less. The fluorine atom density of the structured surface can be determined using XPS, TOF-SIOMS, and the like.

The abrasive material of the present invention can be used in a variety of applications such as rough polishing, chamfering and fine polishing of various surfaces such as semiconductor wafers, magnetic recording media, glass plates, lenses, prisms, automotive coatings, fiber optic connector terminal surfaces and the like as well as dressings for other polishing tools It can be used for various applications. The abrasive materials of the present invention may also be advantageously used for applications using abrasive slurries.

Example

In the following examples, specific embodiments of the invention are illustrated, but the invention is not limited thereto. All "parts" and "percentages" are on a mass basis unless otherwise specified.

1. CMP dressing test

Five disk-shaped abrasive materials having a diameter of 11 mm and a thickness of 3 mm in Examples 1 and 2 and Comparative Examples 1 and 2 were placed in a stainless steel disk-shaped base having a diameter of 110 mm and a thickness of 5 mm Were adhered at equal distances on the circumference at a distance of 43 mm from the center of the material and then used as CMP dressing. The disc shaped abrasive material had a silicon carbide bulk layer with a structured surface periodically arranged with square pyramids (pyramids) having a base length of 360 [mu] m and a height of 160 [mu] m, with the base portions of the square horns contacting each other. A diamond layer was coated on the silicon carbide bulk layer.

The structured surface of the abrasive material was treated with fluorine (Example 1) or silicon (Example < RTI ID = 0.0 > 1) < / RTI > using the batch type capacitively coupled plasma device WB 7000 (Plasma Therm Industrial Products, Inc.) 2). The structured surface of Comparative Example 1 was treated with a fluoropolymer 3M (registered trademark) Novec EGC 1720 (manufactured by 3M) in a solvent Novec (registered trademark) so as to have a solids fraction of 0.1% Coating solution prepared by dissolving a fluoropolymer-coated film on a structured surface using a < RTI ID = 0.0 > C-7100 < / RTI > (manufactured by 3M). Comparative Example 2 was not treated (control test). The detailed processing conditions of Example 1 and Example 2 are shown in Table 1.

The abrasive materials of Comparative Example 1 and Comparative Example 2 as well as Example 1 and Example 2 were attached to a disk and the Buehler 占 EcoMet 占 4000 (manufactured by Beuler) Respectively. Instead of CMP slurry, water was supplied to the polishing system. A CMP dressing test was conducted using a urethane foam pad ICE 1000 pad (product of Dow) having a downward force of 5 kgf (1 kgf per abrasive material) and a rotational speed of 150 RPM (disk) / 10 rpm (urethane pad) After performing for 1 hour, the disks were immersed in a water bath for 5 minutes to simulate a standard compounding treatment, with the structured surface of the abrasive material facing downward, naturally dried, and then with an optical microscope (300x magnification) The structured surface was observed and examined for accumulation of foreign material (urethane particles) (Fig. 4). In Examples 1 and 2, urethane particles were hardly accumulated, and a remarkable improvement was observed as compared with Comparative Example 2. Comparative Example 1 even had a larger amount of polyurethane particle accumulation than Comparative Example 2. < tb > < TABLE >

Next, the abrasive material was ultrasonically cleaned with water, and the structured surfaces of Example 1 and Example 2 were observed in detail using an optical microscope (magnification of 1500 times). In particular, no damage to the surface was observed in Example 1, but there was partial delamination of the silicon film in Example 2.

2. Car paint polishing test

In Examples 3 to 5 and Comparative Example 3, the following abrasive materials A to C were used as polishing pads for removing fine protrusions on the surface of automobile paint.

Abrasive material A: Trizact (R) film disc roll 466 LA-A5 (manufactured by 3M, similar to grit size # 3000).

Abrasive material B: TRIZJATT (TM) film disk roll 466 LA-A3 (manufactured by 3M, similar to grit size # 4000).

Polishing material C: Trizac (R) Diamond Disk 662 XA (manufactured by Sumitomo 3M).

The structured surfaces of the abrasive materials A to C were treated with fluorine treatment (Example 3) or silicon treatment (Example 4 and Example < RTI ID = 0.0 > 5). Comparative Example 3 was not treated (control test). The detailed processing conditions of Examples 3 to 5 are shown in Table 1.

The adhesive sheet was applied to the backside surface of the abrasive material A to the surface-treated or untreated abrasive material C, and a disc having a diameter of 32 mm was punched out. Black paints and clear paints (LX Clear, manufactured by Nippon Paint) can be painted on phosphate coated steel plates to allow sanders to operate in one horizontal direction , And one of the abrasive materials A to C was attached to the polishing surface of a 3M (registered trademark) polishing sander 3125 (manufactured by 3M) having a 3 mm orbital movement, and approximately 5000 A load of 1 kgf was applied while rotating at rpm, and the surface of the coated plate was polished back and forth five times at a speed of 1 m / min with respect to a distance of 20 cm. After polishing, the amount of abrasive powder adhered to the surfaces of the abrasive materials A to C was visually observed, and the result was confirmed by the entire photograph in Fig. 5A and by an optical microscope photograph (300x magnification) in Fig. 5B appear. The lowest amount of abrasive powder adhered to the structured surface of the siliconized abrasive material A to abrasive material C was in Example 4. [

Next, the abrasive materials A to C were washed using water, and the structured surfaces thereof were observed by an optical microscope (300x magnification) (Fig. 5C). All of Examples 3 to 5 demonstrated good cleaning properties compared to Comparative Example 3, and the siliconized Examples 4 and 5 demonstrated much better cleaning properties. In the case of automotive paint polishing applications, the surface of the abrasive material is generally washed with water after several polishing cycles, and thus an abrasive material with good cleaning properties is extremely advantageous for such applications.

3. Glass plate surface polishing test

In Comparative Example 4 as well as Example 6 and Example 7, a 9 占 퐉 (made by 3M) diamond tile pad was used as the polishing pad used to polish the glass plate surface.

The structured surface of the polishing pad was fluorinated (Example 6) or siliconized (Example 8) using a batch type capacitively coupled plasma device WB 7000 (Plasma Island Industrial Products, Inc.). Comparative Example 4 was not treated (control test). The detailed treatment conditions of Example 6 and Example 7 are shown in Table 1.

Polishing pads of Comparative Example 4 as well as Example 6 and Example 7 were attached to a disk and set on a Buller 占 ECOMET 占 4000 (manufactured by Buller). A 5% aqueous solution of LA-20 (manufactured by Neos) was applied to the polishing system as a polishing solution. Aoita Glass (manufactured by Asahi Glass) was polished for 150 minutes under the conditions of a load of 80 N, top plate rotation speed of 60 rpm, and bottom plate rotation speed of 450 rpm. No cleaning of the structured surface of the polishing pad was performed during polishing.

After polishing, the polishing pad was placed in an oven at 60 DEG C to evaporate the polishing solution. After drying, the weight of the polishing pad was measured (W ₁ ). Next, the polishing pad was washed with water, placed in an oven at 60 캜 and dried. After drying, the weight of the polishing pad was measured (W ₂ ). The amount of bonded abrasive powder was calculated by the formula W ₂ - W ₁ , which was 210 mg for Example 6 and 110 mg for Example 7, but 250 mg for Comparative Example 4. Both Example 6 and Example 7 demonstrated good cleaning properties compared to Comparative Example 4, and the siliconized Example 7 demonstrated much better cleaning properties.

[Table 1]

10 Abrasive materials
11 Polishing layer
12 three-dimensional element
13 bulk layer
14 Surface coating layer
15 backing
16 abrasive particles
17 Binder
18 Above the polishing layer
19 Lower part of the abrasive layer
121 1st triangular pyramid
122 2nd triangular pyramid
123 hexagonal horn
124 Meeting Roof Shape

Claims (9)

An abrasive material comprising an abrasive layer having a structured surface having a plurality of three-dimensional elements arranged thereon, wherein a surface treatment selected from the group consisting of fluorination and silicon treatment is applied to at least a portion of the structured surface Wherein the fluorine treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment. The abrasive material of claim 1, wherein the plurality of three-dimensional elements are periodically arranged on a structured surface. 3. The abrasive material of claim 1 or 2, wherein the silicon treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and atom layer deposition. 4. The method of any one of the preceding claims, wherein the polishing layer comprises a bulk layer comprising silicon carbide and a surface coating comprising diamond like carbon provided on at least a portion of the bulk layer ≪ / RTI > The abrasive material of any one of claims 1 to 3, wherein the abrasive layer comprises abrasive particles and a binder. 6. A method according to any one of claims 1 to 5, wherein the plurality of three-dimensional elements comprises a round cylinder, an oval cylinder, a prism, a hemisphere, a semi-ellipsoid, a shape selected from the group consisting of ellipsoid, cone, pyramid, truncated cone, truncated pyramid, hipped roof shape, and combinations thereof. Abrasive material. Providing an abrasive material comprising an abrasive layer having a structured surface configured to have a plurality of three-dimensional elements arranged thereon; And
Fluorine treatment, and silicon treatment on at least a portion of the structured surface of the abrasive material,
Wherein the fluorine treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment. 8. The method of claim 7, wherein the silicon treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and atomic layer deposition. 1. An abrasive material having an abrasive layer having a structured surface configured to have a plurality of three-dimensional elements arranged thereon, wherein at least a portion of the structured surface comprises: (a) an abrasive layer comprising a densified fluorocarbon, silicon oxycarbide, A film comprising a material selected from the group; (b) a fluorine terminated surface; Or (c) a combination thereof.

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