JP2017503670A - Abrasive material having a structured surface - Google Patents

Abstract

Providing an abrasive material having a structured surface that has an excellent ability to prevent the adhesion and deposition of foreign objects, and a method of manufacturing the same. An abrasive material of an embodiment of the present disclosure is an abrasive material having an abrasive layer with a structured surface having a plurality of three-dimensional elements disposed thereon, and is selected from the group consisting of fluorine treatment and silicon treatment A surface treatment is performed on at least a portion of the structured surface, and the fluorine treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and fluorine gas treatment. [Selection] Figure 1

Description

Detailed Description of the Invention

[Field of the Invention]
The present disclosure relates to an abrasive material having a structured surface. Specifically, the present disclosure relates to an abrasive material that includes an abrasive layer having a surface-treated structured surface.

[background]
Abrasive materials include rough polishing, chamfering, final polishing, and various surfaces such as semiconductor wafers, magnetic storage media, glass plates, lenses, prisms, automotive painted surfaces, fiber optic connector end surfaces, and the like. Widely used in similar products.

  For example, in a chemical mechanical polishing (CMP) process of a semiconductor wafer, a structured surface in which a plurality of three-dimensional elements are systematically arranged, such as a three-dimensional element having a quadrangular pyramid shape, a hemispherical shape, or the like. A polishing material (also referred to as a conditioner or dresser disk) comprising a polishing layer having the following is used for the purpose of 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 a polishing pad and a semiconductor wafer. The conditioner includes a silicon carbide layer coated with a monolithic diamond layer as an abrasive layer and is attached to, for example, a support disk or support ring. The polishing material roughens the surface of the polishing pad and removes clogging of the polishing pad surface. The CMP process is thus stabilized. This type of conditioner, which includes an abrasive layer with a structured surface, has other abrasive particles such as bulk diamond particles deposited on the substrate by nickel plating, soldering, sintering, or the like. Compared to conventional conditioners, it is advantageous in that large scratches caused by detached abrasive particles do not occur on the semiconductor wafer surface.

  Abrasive materials with structured surfaces include large glass plates for surface polishing used in the manufacture of liquid crystal displays and the like, rough and final polishing of optical fiber connector end surfaces, painted surfaces of automobiles, and Also used for similar items. For example, an abrasive material in which the abrasive layer contains abrasive particles such as massive diamond particles, alumina, silicon carbide, cerium oxide, and the like, and a binder such as cured urethane acrylate, epoxy resin, and the like. used. The portion of the polishing layer that contacts the object to be polished wears during rough polishing or final polishing depending on the hardness of the object to be polished, exposing new abrasive particles on the structured surface. For example, when a polishing object having hardness such as a glass plate or the like is polished, the polishing layer is usually worn during polishing. On the other hand, when polishing a low-hardness surface such as a painted surface of an automobile that uses an acrylic resin, urethane resin, or the like for the outermost layer, the polishing layer may not wear significantly.

  Patent Document 1 (International Publication No. 2005-012592) is (a) a substrate, (1) a first phase including at least one of ceramic materials, and (2) a carbide forming material. A substrate having a surface comprising a second phase comprising at least one; and (b) a CVD diamond coating composite comprising a chemical vapor deposition diamond coating disposed on at least a portion of the surface of the substrate. ing.

  Patent Document 2 (Japanese Published Publication No. 2002-542057 of published PCT application) states: “Glass or glass comprising a backing and at least one three-dimensional abrasive coating bonded on the surface of the backing. An abrasive article ideal for polishing ceramic workpieces, the abrasive coating comprising a plurality of diamond bead abrasive particles and a filler comprising from about 40% to about 60% by weight of the abrasive coating. “Abrasive article comprising a binder formed from a dispersed cured binder precursor” is described.

  Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-179640) states that “a polishing material used for polishing an optical fiber connector end surface into a predetermined shape. A polishing layer comprising a polishing composite comprising abrasive particles and a binder as constituents, wherein the polishing layer is a plurality of systematically arranged solid elements of a predetermined shape Abrasive material having a spatial structure constituted by:

International Publication No. 2005/012592 Japanese translation of PCT publication No. 2002-542057 JP 2001-179640 A

[Summary of Invention]
The cause is not clear, but when the urethane foam pad conditioning was performed during the CMP process using a polishing material containing a polishing layer with a structured surface, defects on the surface of the semiconductor wafer linked to an increase in the conditioning cycle The density may increase. In addition, deposits of foreign matter such as abrasive particles contained in the CMP slurry, polyurethane particles scraped from the urethane foam pad, and the like are seen in valleys (recesses) on the structured surface of the polishing layer. May be. The accumulation of foreign material is believed to interfere with the smooth flow of CMP slurry between the abrasive material and the urethane foam pad.

  During rough polishing and final polishing of automotive painted surfaces (in this case, the polishing layer does not wear significantly and adhesion occurs at the protruding part or at the tip of the structured surface) and is scraped off by surface polishing of the glass plate. Glass powder (abrasive powder) deposition in the valleys of structured surfaces and adherence to structured surfaces such as acrylic, urethane, or the like reduces production efficiency and thus product quality It is preferable to prevent or suppress it.

  It is an object of the present disclosure to provide an abrasive material having a structured surface that has an excellent ability to prevent the adhesion and deposition of foreign objects, and a method for manufacturing the same.

[Summary of Invention]
Embodiments of the present disclosure provide an abrasive material having an abrasive layer having a structured surface with a plurality of three-dimensional elements disposed thereon, the surface treatment being selected from the group consisting of fluorine treatment and silicon treatment Is performed on at least a portion of the structured surface, and 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 disclosure provides a method of manufacturing an abrasive material comprising an abrasive layer having a structured surface having a plurality of three-dimensional elements disposed thereon, Performing a surface treatment selected from the group consisting of a fluorine treatment and a silicon treatment on at least a portion of the structured surface of the abrasive material, wherein the fluorine treatment comprises plasma treatment, chemical vapor deposition, physical vapor deposition, and A method is provided that is selected from the group consisting of fluorine gas treatment.

  Yet another embodiment of the present disclosure is an abrasive material having an abrasive layer comprising a structured surface configured with a plurality of three-dimensional elements disposed thereon, wherein at least a portion of the structured surface comprises: Polishing having (a) a film comprising a material selected from the group consisting of densified fluorocarbon, silicon oxycarbide, and silicon oxide, (b) a surface terminated with fluorine, or (c) a combination thereof. Provide material.

[Effect of the invention]
According to the present disclosure, it is possible to provide an abrasive material that can be discharged without adhering or depositing foreign matter in a structured surface, particularly a valley (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 of the advantages associated with the invention.

1 is a cross-sectional view of an abrasive material according to an embodiment of the present disclosure. FIG. 6 is a cross-sectional view of an abrasive material according to another embodiment of the present disclosure. FIG. 4 is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a triangular pyramid shape are arranged. FIG. 6 is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a quadrangular pyramid shape are arranged. FIG. 4 is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a truncated pyramid shape are arranged. FIG. 2 is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a hemispherical shape are arranged. FIG. 3 is a cross-sectional view of a structured surface that is a triangular prism with three-dimensional elements oriented and aligned in a lateral direction. FIG. 4 is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a dormitory roof shape are arranged. FIG. 3 is a top surface schematic view of a structured surface on which a combination of a plurality of three-dimensional elements of various shapes is disposed. It is the optical microscope photograph after implementing the CMP dressing test of the structured surface of the polishing material of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. It is the optical microscope photograph after implementing the CMP dressing test of the structured surface of the polishing material of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. It is the optical microscope photograph after implementing the CMP dressing test of the structured surface of the polishing material of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. It is the optical microscope photograph after implementing the CMP dressing test of the structured surface of the polishing material of Examples 1 and 2 and Comparative Examples 1 and 2, respectively. It is the whole photograph after implementing the automobile coating grinding | polishing test of polishing material AC of Examples 3-5 and Comparative Example 3. It is an optical micrograph of the structured surface after implementing the automobile coating grinding | polishing test of polishing material AC of Examples 3-5 and Comparative Example 3. It is an optical microscope photograph of the structured surface after implementing the automobile coating grinding | polishing test of polishing material AC of Examples 3-5 and Comparative Example 3, and then wash | cleaning with water.

[Detailed description]
Detailed descriptions are given below to illustrate representative embodiments of the present invention, but these embodiments should not be construed as limiting the present invention.

  In the present disclosure, the “polishing surface” refers to a contact surface with an object to be polished, in other words, a reference plane parallel to the surface of the object to be polished when the polishing material contacts the flat object to be polished.

  In the present disclosure, the “height” of a three-dimensional element refers to the distance from the bottom surface of the three-dimensional element to the apex or top surface of the three-dimensional element along the normal of the polishing surface.

  An abrasive material of an embodiment of the present disclosure includes a polishing 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 portion of the structured surface. In this disclosure, “fluorine treatment” refers to a surface treatment using a material containing fluorine, and “silicon treatment” refers to a surface treatment using a material containing silicon. Other atoms, excluding fluorine and silicon, such as hydrogen, oxygen, carbon, nitrogen, and the like may contribute to the surface treatment, and these other atoms may be fluorine-containing materials or silicon May be derived from a material containing or may be derived from another source.

  A variety of materials can be used to form the polishing layer. FIG. 1 illustrates a cross-sectional view of an abrasive material of an embodiment of the present disclosure. The polishing material 10 illustrated in FIG. 1 includes a polishing layer 11, and the polishing layer 11 includes a bulk layer 13 and a surface coating layer 14 disposed on at least a portion of the bulk layer 13. The surface coating layer 14 is applied to a structured surface on which a plurality of three-dimensional elements 12 are arranged. With the embodiment illustrated in FIG. 1, the bulk layer 13 not only determines the shape of the three-dimensional element 12, but also as a substrate for attaching the abrasive material 10 to another tool or the like. Also works. Another substrate 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 can be formed of various hard materials such as inorganic materials (eg, sintered ceramics) in consideration of the material properties and hardness of the object to be polished and the like. Examples of the sintered ceramic include silicon carbide, silicon nitride, alumina, zirconia, tungsten carbide, and the like. Of these, silicon carbide and silicon nitride, particularly silicon carbide, can be advantageously used from the viewpoint of strength, hardness, abrasion resistance, and the like.

  The bulk layer is a mixture of ceramic particles such as silicon carbide or the like, a binder, and other materials as needed, and pressure injected into a metal die having a negative pattern of structured surfaces; It can then be formed by sintering.

  The surface coating layer is generally formed of a material harder than the bulk layer, and contributes to polishing of the polishing object by contacting the polishing object 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 (TiC), and There are similar ones. The thickness of the surface coating layer is generally about 0.5 μm or more or about 1 μm or more and about 30 μm or less or about 20 μm or less. By setting the thickness of the surface coating layer to about 1 μm or more, only the surface coating layer comes into contact with the object to be polished during polishing, and thus 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 weak, the thickness of the surface coating layer is preferably relatively thin.

Advantageously, a film comprising a diamond material can be used as the surface coating layer. This film can include, for example, diamond-like carbon. Diamond-like carbon is amorphous and contains large amounts of sp ³ stabilized by hydrogen (eg, about 40 atomic percent or more, or about 50 atomic percent or more, and about 99 atomic percent or less, or about 98 atomic percent or less). By conventional techniques such as plasma enhanced chemical vapor deposition (PECVD), hot wire chemical vapor deposition (HWCVD), ion beam, laser ablation, RF plasma, ultrasound, arc discharge, cathodic arc plasma deposition, and the like, A diamond film may be deposited on the bulk layer using a gaseous carbon source such as methane or the like, or a solid carbon source such as graphite or the like, and optionally hydrogen. it can. In some embodiments, highly crystalline films can be stabilized and produced, and therefore HWCVD methods can be used to deposit advantageously thick diamond films.

  FIG. 2 illustrates a cross-sectional view of an abrasive material of another embodiment of the present disclosure. 2 includes a polishing layer 11 including abrasive particles 16 and a binder 17 on a backing 15, and the polishing layer 11 has a structure in which a plurality of three-dimensional elements 12 are arranged. Having a surface. The backing 15 acts as a base material for the abrasive material 10. The abrasive particles 16 are dispersed uniformly or non-uniformly through the binder 17. With this embodiment, when the surface of the object to be polished is polished using the polishing material 10, a portion in contact with the object to be polished is gradually destroyed, and thus unused due to the hardness of the object to be polished. The abrasive particles 16 are exposed.

  With this embodiment, a curable composition comprising abrasive particles, a binder precursor, and an initiator is loaded into a metal die having a structured surface negative pattern and using heat or radiation. This composition is cured, thus forming an abrasive layer comprising abrasive particles and a binder.

  Examples of abrasive particles that can be used include diamond, cubic boron nitride, cerium oxide, molten aluminum oxide, heat treated aluminum oxide, aluminum oxide prepared 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 particles is preferably 8 or more or 9 or more. The type of abrasive particles can be selected based on the intended polishing, and diamond, cubic boron nitride, aluminum oxide, and silicon carbide are advantageously used for rough polishing such as deburring or the like, And can be used for chamfering such as curved surface formation or the like, and silica and aluminum oxide can be advantageously used for final polishing.

  The average particle size of the abrasive particles may be within a different range based on the type of abrasive particles, the application of the abrasive material, and the like, and is generally about 10 nm or more, about 1 μm or more, or about 5 μm or more, and It is about 500 μm or less, about 200 μm or less, or about 80 μm or less. For example, abrasive particles having an average particle size of about 0.5 μm or more and about 20 μm or less or about 10 μm or less are advantageously used for rough polishing such as deburring or the like and for forming a curved shape or the like. Abrasive particles that can be used for chamfering such as those having an average 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 are advantageously used for final polishing. Can be used for.

  Bulk diamond in which diamond particles having a particle size of about 1 μm to about 100 μm are dispersed in a base material such as glass, ceramic, metal, metal oxide, organic resin, and the like can be used. The average particle size of the block diamond comprising diamond particles having a particle size greater than 15 μm is generally about 100 μm or more or about 250 μm or more and about 1000 μm or less or about 400 μm or less. The average particle size of the block diamond containing diamond particles having a particle size of 15 μm or less is generally about 20 μm or more, about 40 μm or more, or about 70 μm or more, and about 450 μm or less, about 400 μm or less, or about 300 μm or less.

  As the binder precursor, a curable resin cured by heat or radiation can be used. The curable resin is generally cured by radical polymerization or cationic polymerization. Examples of the binder precursor include phenol resin, resol phenol resin, aminoplast resin, urethane resin, epoxy resin, acrylic resin, polyester resin, vinyl resin, melamine resin, isocyanurate acrylate resin, urea formaldehyde resin, isocyanurate resin, Examples include urethane acrylate resins, epoxy acrylate resins, and mixtures thereof. The term “acrylate” used in the binder precursor includes acrylate and methacrylate.

  As the reaction initiator, a conventional thermal reaction initiator or photoinitiator can be used. Examples of reaction initiators include organic peracids, azo compounds, quinones, benzophenones, nitroso compounds, halogenated acrylics, hydrazones, mercapto compounds, pyrylium compounds, triacrylimidazoles, bisimidazoles, chloroalkyltriazines, benzoin ethers, benzyl ketals. Thioxanthone, acetophenone, iodonium salt, sulfonium salt, and derivatives thereof.

  The abrasive particles are generally in the curable composition in an amount of about 150 parts by weight or more or about 200 parts by weight or more and about 1000 parts by weight or less or about 700 parts by weight or less based on 100 parts by weight of the binder precursor. included. The reaction initiator is generally in the curable composition at least about 0.1 parts by weight or more than about 0.5 parts by weight and not more than about 10 parts by weight or about 2 parts by weight with respect to 100 parts by weight of the binder precursor. It is included in the amount of parts or less.

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

  The backing can be a polymer film such as polyester, polyimide, polyamide, and the like; paper; vulcanized fiber; molded or cast elastomer; treated non-woven or fine fabric; and the like. An adhesive layer can be used to adhere the backing to the polishing layer.

  The polishing layer and the backing material can be integrally formed using a thermoplastic resin or a thermosetting resin. Examples of thermoplastic resins or thermosetting resins include phenolic resin, aminoplast resin, urethane resin, epoxy resin, ethylenically unsaturated resin, isocyanurate acrylate resin, urea formaldehyde resin, isocyanurate resin, urethane acrylate resin, epoxy Examples include acrylate resins, bimaleimide resins, and mixtures thereof. Advantageously, among these, polyamide resins, polyester resins, and polyurethane resins (including polyurethane urea resins) can be used.

  The thickness of the backing can generally be set to about 1 mm or more or about 0.5 cm or more and about 2 cm or less or about 1 cm or less. By using an elastic material for the backing, shape tracking characteristics may be further applied to the backing. A predetermined curvature may be applied to the backing by preforming the backing.

  The polishing function of the three-dimensional element of the abrasive material is demonstrated at the top. With an abrasive material having an abrasive layer containing abrasive particles and a binder, the three-dimensional element is degraded from the top during polishing, exposing unused abrasive particles. Thus, by increasing the concentration of abrasive particles present in the top of the three-dimensional element, the cutting and abrasive properties of the abrasive material can be increased, and therefore the abrasive material can be used advantageously. The base of the three-dimensional element, in other words the lower part of the abrasive layer attached to or integrally formed with the substrate, usually does not require a polishing function and is therefore formed only by the binder without abrasive particles. can do.

  The structured surface of the polishing layer can include three-dimensional elements of various shapes. Examples of the shape of the three-dimensional element include a cylinder, an elliptic cylinder, a prism, a hemisphere, a semi-elliptical sphere, a cone, a pyramid, a truncated cone, a truncated pyramid, a dormitory roof, and the like. The structured surface may further 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 cylinders and a plurality of pyramids. The cross-sectional shape of the base of the three-dimensional element may be different from the cross-sectional shape of the top. For example, the cross section of the base may be square, but the cross section of the top may be circular. Typically, the three-dimensional element has a base having a cross-sectional area that is larger than the cross-sectional area of the top. The bases of the three-dimensional elements may be in contact with each other or alternately, and the bases of adjacent three-dimensional elements can be separated from each other by a predetermined distance.

  With some embodiments, the plurality of three-dimensional elements are systematically arranged on the structured surface. With this disclosure, “systematically” used in reference to the position of a three-dimensional element is a reference where a three-dimensional element having the same or similar shape is on the structured surface and parallel to the polishing surface. It means that they are repeatedly arranged along one or more directions on the surface. The direction or directions on the reference plane parallel to the polishing surface can be a linear direction, a concentric direction, a helical (spiral) direction, or a combination thereof. With embodiments in which a plurality of three-dimensional elements are systematically arranged on the structured surface, a space, such as a groove, that exists between the three-dimensional elements is patterned on the entire body of the structured surface. This is advantageous for flowing and discharging slurry, abrasive powders, and the like. Multiple three-dimensional elements can be formed by polycrystalline diamond deposition by surface treatment, laser treatment, or CVD by diamond wheel, cutting wheel, or injection molding, which structures the binder precursor Filling into a three-dimensional element of metal having a surface negative pattern and then curing using, for example, heat or radiation, and the like.

  Structured surfaces that can be used with the abrasive materials of the present disclosure are described using examples and with reference to FIGS. 3A-3G. FIG. 3A is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a triangular pyramid shape are arranged. 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 tops of the three-dimensional element 12. The lengths of the bases of the triangular pyramids may be the same or different from each other, and the lengths of the sides may be the same or different from each other. For example, o can be set to about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p can be set to about 5 μm or more or about 10 μm or more and about 1000 μm or less or about 500 μm or less. Although not shown in FIG. 3A, the height h of the three-dimensional element 12 can be set to about 2 μm or more, or about 4 μm or more, and about 600 μm or less, or about 300 μm or less. The variation of h is preferably about 20% or less, more preferably about 10% or less of the height variation of the three-dimensional element 12.

  FIG. 3B is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a quadrangular pyramid shape are arranged. In FIG. 3B, the symbol o represents the base length of the three-dimensional element 12 and the symbol p represents the distance between the tops of the three-dimensional element 12. The lengths of the bases of the quadrangular pyramids may be the same or different from each other, and the lengths of the sides may be the same or different from each other. For example, o can be set to about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p can be set to about 5 μm or more or about 10 μm or more and about 1000 μm or less or about 500 μm or less. Although not shown in FIG. 3A, the height h of the three-dimensional element 12 can be set to about 2 μm or more or about 4 μm or more and about 600 μm or less or about 300 μm or less. The variation of h is preferably about 20% or less, more preferably about 10% or less of the height variation of the three-dimensional element 12.

  With other embodiments of the present disclosure, the three-dimensional element can be a triangular frustum or a quadrangular frustum. The top surfaces of the three-dimensional elements of these embodiments are generally comprised of a triangular or quadrangular reference plane parallel to the polishing surface. Substantially all of the top surface is preferably on a reference surface parallel to the polishing layer.

  FIG. 3C is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a quadrangular frustum shape are arranged. A quadrangular pyramid shape before cutting the apex is shown in the upper left. In FIG. 3C, symbol o represents the length of the bottom of the three-dimensional element 12, symbol u represents the distance between the bottoms of the three-dimensional element 12, and symbol y represents the length of the top surface. The length of the bases of the truncated pyramid may be the same or different from each other, the lengths of the sides may be the same or different from each other, and the length of the side of the top surface May be the same or different from each other. For example, o can be set to about 5 μm or more or about 10 μm or more, and about 6000 μm or less or about 3000 μm or less. u can be set to about 0 μm or more, or about 2 μm or more, and about 10,000 μm or less, or about 5000 μm or less. y can be set to 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 shown in FIG. 3C, the height h of the three-dimensional element 12 can be set to 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 variation of h is preferably about 20% or less, more preferably about 10% or less of the height variation of the three-dimensional element 12.

  FIG. 3D is an upper surface schematic view of a structured surface on which a plurality of three-dimensional elements having a hemispherical shape are arranged. In FIG. 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 can be set to about 5 μm or more, or about 10 μm or more, and about 1000 μm or less, or about 500 μm or less. p can be set to about 5 μm or more or about 10 μm or more and about 1000 μm or less or about 500 μm or less. Although not shown in FIG. 3D, the height h of a three-dimensional element having a hemispherical shape is usually the same as the radius r. The variation of h is preferably about 20% or less, more preferably about 10% or less of the height variation of the three-dimensional element 12.

  FIG. 3E is a cross-sectional schematic view of another embodiment of the present disclosure, wherein the plurality of three-dimensional elements 12 are laterally oriented triangular prisms having a ridge. The three-dimensional element 12 is illustrated as a two-layer structure disposed on a substrate 15 and comprising a polishing layer upper part 18 containing abrasive particles and a binder and an abrasive layer lower part 19 containing a binder but no abrasive particles. . The ridge is preferably on a reference plane parallel to the polishing layer, substantially over the entire body of polishing material. In some embodiments, substantially all ridges are on the same reference plane parallel to the polishing layer. In FIG. 3E, the symbol α represents the vertical angle of the three-dimensional element 12, the symbol w represents the width of the bottom of the three-dimensional element 12, and the symbol p represents the distance between the tops 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 represents the height of the three-dimensional element 12 from the surface of the substrate 15, and the symbol s represents the top of the polishing layer 18. Represents the height. For example, α can be set to about 30 ° or more or about 45 ° or more, and about 150 ° or less or about 140 ° or less. w can be set to about 2 μm or more, or about 4 μm or more, and about 2000 μm or less, or about 1000 μm or less. p can be set to about 2 μm or more, or about 4 μm or more, and about 4000 μm or less, or about 2000 μm or less. u can be set to about 0 μm or more or about 2 μm or more and about 2000 μm or less or about 1000 μm or less. h can be set to about 2 μm or more, or about 4 μm or more, and about 600 μm or less, or about 300 μm or less. s can be set to about 5% or more or about 10% or more of the height h of the three-dimensional element 12 and about 95% or less or about 90% or less. The variation of h is preferably about 20% or less, more preferably about 10% or less of the height variation of the three-dimensional element 12.

  The individual three-dimensional elements 12 illustrated in FIG. 3E may extend across the entire surface of the abrasive material. In this case, both ends in the longitudinal direction of the base of the three-dimensional element 12 are in the vicinity of the end of the abrasive material, and the plurality of three-dimensional elements 12 are arranged in a band shape.

  With another embodiment of the present disclosure, the three-dimensional element has a dormitory roof shape. In the present disclosure, the “boarding roof” shape refers to a three-dimensional shape with side surfaces composed of two corresponding triangular shapes and two corresponding square shapes, where adjacent triangular side surfaces and rectangular side surfaces are areas. The area shared by two corresponding rectangular sides is the ridge. The ridge is preferably on a reference plane parallel to the polishing layer, substantially over the entire body of polishing material. In some embodiments, substantially all ridges are on the same reference 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. Therefore, the bottom surface of the dormitory roof shape may be rectangular, trapezoidal, or the like, and the lengths of the four sides may be different from the square shape.

  FIG. 3F is a schematic top view of a structured surface on which a plurality of three-dimensional elements having a laid roof shape are arranged. FIG. 3F illustrates a dormitory roof shape having a rectangular bottom surface. In FIG. 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 adjacent three-dimensional elements 12. For example, l can be set to about 5 μm or more or about 10 μm or more, and about 10 mm or less or about 5 mm or less. x can be set to about 0 μm or more, or about 2 μm or more, and about 2000 μm or less, or about 1000 μm or less. Definitions of symbols w, p, and u and exemplary numerical ranges, not shown in FIG. 3F, are the same as those described in FIG. 3E, although symbols h, s, α, and the like are similar. is there.

  With another embodiment, the structured surface includes a combination of a plurality of three-dimensional elements having various shapes. FIG. 3G illustrates an example of such an embodiment. The structured surface illustrated in FIG. 3G includes a combination of a first triangular pyramid 121, a second triangular pyramid 122, a hexagonal pyramid 123, and a dormitory roof 124. The length of the base of each three-dimensional element can be set to about 5 μm or more or 10 μm or more, and about 1000 μm or less or about 500 μm or less, and the height is about 2 μm or more or about 4 μm or more, respectively. It can be set to 600 μm or less or about 300 μm or less. The distance between the bases of adjacent three-dimensional elements can be set to 0 μm or more or about 2 μm or more, and about 10,000 μm or less or about 5000 μm or less. The length of the ridge portion of the dormitory roof 124 can be set to about 0.5 μm or more or about 1 μm or more and about 1000 μm or less or about 500 μm or less.

With some embodiments, the density of the three-dimensional elements of the abrasive material, in other words, the number of three-dimensional elements per cm ^{2 of the} abrasive material is about 0.5 element / cm ² or more, or 1.0 element / Cm ² or more and about 1 × 10 ⁷ elements / cm ² or less or about 4 × 10 ⁶ elements / cm ² or less. Using embodiments in which a plurality of three-dimensional elements are systematically arranged on the structured surface, the number of three-dimensional elements per cm ^{2 of} abrasive material is greater than or equal to about 0.05 elements / cm ² or about 0. .10 element / cm ² or more and about 1 × 10 ⁶ element / cm ² or less, or about 4 × 10 ⁵ element / cm ² or less. With this embodiment, a high polishing efficiency is achieved by arranging three-dimensional elements at a high density on the structured surface, while a space having a predetermined pattern that exists between the three-dimensional elements. Slurries, abrasive powders, and the like can be efficiently discharged by using (e.g., grooves) and combining and performing a surface treatment on the structured surface.

  For the abrasive materials of the present disclosure, a fluorination or silicon treatment is performed on at least a portion of the structured surface. Without being bound by any theory, an abrasive material whose structured surface is covered by a surface coating layer such as diamond-like carbon or the like, and an abrasive material wherein the abrasive layer comprises abrasive particles and a resin binder Is believed to produce a charge on the structured surface or to produce surface energy of the structured surface, and thus a conventional abrasive material having abrasive particles deposited on a substrate by conductive nickel plating or the like In comparison, foreign objects tend to adhere to structured surfaces due to static electricity or other interactions. According to the present disclosure, even if the structured surface contains three-dimensional elements at a relatively high density, surface treatment of these three-dimensional elements can reduce the surface energy of the structured surface and polish Prevent or inhibit the adherence of foreign matter on structured surfaces such as abrasive particles in slurries, organic compounds, and the like, polyurethane particles generated from polyurethane foam pads, and the like, or the like. Can do.

  In the present disclosure, the fluorine treatment can be advantageously performed by plasma treatment, chemical vapor deposition (CVD), physical vapor deposition (PVD), or fluorine gas treatment.

  “Plasma treatment” according to the present disclosure refers to a treatment that changes the chemical composition of the surface of a processing object using a raw material gas activated by plasma, and is derived from the processing object on the plasma-treated surface. Reaction products including materials are included. On the other hand, a film containing components derived from gas, liquid, or solid raw materials is formed by depositing on the surface of the object to be processed using chemical vapor deposition and physical vapor deposition. Examples of the chemical vapor deposition method include a thermal CVD method, a direct plasma enhanced CVD method, a remote plasma CVD method, a hot wire CVD method, and the like. Examples of physical vapor deposition include sputtering, vacuum vapor deposition, arc spraying, plasma spraying, aerosol deposition, and the like.

  Without being bound by any theory, it is due to the formation of C—F bonds in the polymer that is doped with fluorine around the surface of the surface coating layer such as diamond-like carbon or abrasive particles and contained in the binder. Thus, the fluorine treatment creates a phenomenon in which the surface of the material is terminated with fluorine and a dense fluorocarbon coating containing many C—C bonds is formed on the structured surface and the like. it is conceivable that.

  With some embodiments, a fluorine treatment by plasma treatment or chemical vapor deposition can be performed using a low pressure plasma device with a depressurizable chamber or an atmospheric pressure plasma device. 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, as a discharge gas, in addition to fluorine-containing gas, nitrogen gas and / or Group 18 element of the periodic table, specifically helium, neon, argon, krypton, xenon, Radon and the like are used. Among these, nitrogen, helium, and argon can be advantageously used, and nitrogen is particularly advantageous from the viewpoint of cost. A low-pressure plasma apparatus is generally used for batch processing. If continuous processing of long webbings or the like is required, the use of an atmospheric pressure plasma device may be advantageous from a productivity standpoint. As a method for generating plasma, corona discharge, dielectric barrier discharge such as single RF discharge or dual RF discharge using a 13.56 MHz high frequency power source, 2.45 GHz microwave discharge, arc discharge, or the like Conventional methods can be used. Among these generation methods, a single RF discharge using a 13.56 MHz high frequency power supply can be advantageously used.

As fluorine-containing gas used in plasma treatment or chemical vapor deposition, 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), may be used a fluorocarbon such as SF _6, and the like thereto. From the viewpoints 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 can 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 between about 50 sccm and about 5000 sccm may be further included in the gas stream supplied to the apparatus.

  In some embodiments, the possibility of depositing a preferred film by setting the C / F ratio of the raw material gas to about 3 or less is known, in which case acetylene, acetone, and the like The C / F ratio can be adjusted by adding a non-fluorine-based gas. When using an embodiment in which the C / F ratio of the raw material gas is about 2 or more and about 3 or less, depending on the bias voltage, surface modification by plasma treatment may occur selectively, or chemical vapor deposition In some cases, film deposition may occur selectively. In such an embodiment, the fluorine treatment can be plasma treatment or chemical vapor deposition, or a combination thereof, by adjusting the bias voltage. The range of the bias voltage varies based on the size or design of the device or the like, which can generally be set to about 100V or less, about 0V or less to about −1000V or more, or about −100,000V or more. it can.

The applied power required for plasma generation can be determined based on the dimensions of the abrasive material being processed, and the power density in the radiation space is generally greater than or equal to about 0.00003 W / cm ² or about .0. 0002W / cm ² or more, and to be about 10 W / cm ² or less, or about 1W / cm ² or less can be selected. For example, when the dimension of the polishing material to be fluoride-treated is 10 cm (length) × 10 cm (width) or less, the applied power is about 200 W or more or about 500 W or more, and about 4 kW or less or about 2.5 kW or less. Can be set.

  The temperature of the plasma treatment or chemical vapor deposition method is preferably a temperature that does not impair the characteristics and performance of the abrasive material to be treated and the like, and the surface temperature of the abrasive material to be treated is about −15 ° C. or more, about It can be set to 0 ° C or higher, or about 15 ° C or higher, and about 400 ° C or lower, about 200 ° C or lower, or about 100 ° C or lower. The surface temperature of the abrasive material can be measured by a thermocouple, radiation thermometer, or the like that contacts the abrasive material.

  When performing plasma treatment or chemical vapor deposition using a low-pressure plasma apparatus, the treatment pressure is about 10 mTorr (0.001 kPa) or more or about 20 mTorr (0.003 kPa) or more and about 1500 mTorr (0.20 kPa) or less, or It can be set to about 1000 mTorr (0.1 kPa) or less.

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

  With another embodiment, a remote plasma device can be used for plasma treatment or fluorine treatment by chemical vapor deposition. A chemical vapor deposition method using a remote plasma apparatus is generally called a remote plasma CVD method. When a remote plasma apparatus is used, plasma is generated in a plasma excitation chamber different from the processing chamber, and excited active species are generated by introducing a raw material gas into the plasma excitation chamber. The generated excited active species are nitrogen, It flows into the processing chamber with a carrier gas such as helium, neon, argon, or the like, and thus a fluorination of the structured surface of the abrasive material is performed.

  A low pressure remote plasma device using a reduced pressure processing chamber or an atmospheric pressure remote plasma device can be used as the remote plasma device. Discharge gases that can be used and preferred discharge gases are those described above for the low pressure plasma apparatus and the atmospheric pressure plasma apparatus. High frequency (13.56 MHz) RF discharge, 2.45 GHz microwave discharge, 2.45 GHz microwave discharge / electron cyclotron resonance (ECR), and the like are commonly used as plasma generation methods and are desirable for remote plasma Since high plasma density can be achieved, 2.45 GHz microwave discharge and 2.45 GHz microwave discharge / electron cyclotron resonance (ECR) are advantageously used.

_{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, Fluorocarbon, nitrogen trifluoride (NF ₃ ), SF ₆ , and the like, and the like, as fluorine-containing gas used in plasma processing or chemical vapor deposition using a remote plasma apparatus Can be used. The lifetime of the excited active species is longer and safer, so NF ₃ and SF ₆ can be used advantageously. The flow rate of the fluorine-containing gas can 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 can be set to 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, the possibility of depositing a preferred film by setting the C / F ratio of the raw material gas to about 3 or less is known, in which case acetylene, acetone, and the like The C / F ratio can be adjusted by adding a non-fluorine gas. When using an embodiment in which the C / F ratio of the raw material gas is about 2 or more and about 3 or less, depending on the bias voltage, surface modification by plasma treatment may occur selectively, or chemical vapor deposition The film deposition by the method may occur selectively. In such embodiments, by adjusting the bias voltage, the fluorine treatment can be plasma treatment or chemical vapor deposition, or a combination thereof. The range of the bias voltage varies based on the size or design of the device or the like, which can generally be set to about 100V or less, about 0V or less to about −1000V or more, or about −100,000V or more. it can.

  The applied power required for plasma generation 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.

  When a remote plasma apparatus is used, fluorine treatment can be performed while maintaining the polishing material to be processed at a low temperature. For example, the surface temperature of the polishing material to be treated may be set to about −15 ° C. or higher, about 0 ° C. or higher, or about 15 ° C. or higher, and about 200 ° C. or lower, about 100 ° C. or lower, or about 50 ° C. or lower. it can. The surface temperature of the abrasive material can be measured by a thermocouple, radiation thermometer, or the like that contacts the abrasive material.

  When performing plasma processing or chemical vapor deposition using a low-pressure remote plasma apparatus, the processing pressure is about 1 mTorr (0.0001 kPa) or more or about 10 mTorr (0.001 kPa) or more and about 1500 mTorr (0.2 kPa) or less. Alternatively, it can be set to about 1000 mTorr (0.1 kPa) or less.

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

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

Fluoropolymers such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and the like can be used as a fluorine-treated sputtering target. _{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, And reactive sputtering may be performed by supplying carbon fluoride, nitrogen fluoride (NF ₃ ), SF ₆ , and the like into the processing chamber.

  The sputtering temperature can be set to 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 sputtering is about 1 × 10 ⁻⁵ Torr (1 × 10 ⁻⁶ kPa) or more or about 1 × 10 ⁻³ Torr (1 × 10 ⁻⁴ kPa) or more and about 10 mTorr (0.001 kPa) or less, or It can be set to about 100 mTorr (0.01 kPa) or less.

  The sputtering treatment time 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.

  With another embodiment, vacuum deposition can be used as the fluorination treatment by physical vapor deposition. Vacuum deposition can be performed using typical deposition equipment such as resistance heating deposition equipment, electron beam deposition equipment, ion plating equipment, or the like.

Use polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and other fluoropolymers, calcium fluoride (CaF ₂ ), other fluorine-containing organic compounds, and the like as deposit sources can do.

  The deposition temperature can be set to about −193 ° C. or higher or about 25 ° C. or higher and about 600 ° C. or lower or about 1000 ° C. or lower.

The processing pressure for the deposition is about 1 × 10 ⁻⁶ Torr (1 × 10 ⁻⁷ kPa) or more, or about 1 × 10 ⁻⁵ Torr (1 × 10 ⁻⁶ kPa) or more, and about 1 × 10 ⁻³ Torr (1 × 10 ⁻⁴ kPa) or less or about 1 × 10 ⁻² Torr (1 × 10 ⁻³ kPa) or less.

  Deposition processing time can 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.

With another embodiment, fluorine gas (F ₂ ) treatment is used as the fluorine treatment. The fluorine gas may be diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide, and the like, or may be used as it is without being diluted. The fluorine gas treatment is generally performed at atmospheric pressure.

  The temperature at which the fluorine gas contacts the structured surface of the abrasive material is set to room temperature or higher, about 50 ° C. or higher, or about 100 ° C. or higher, and about 250 ° C. or lower, about 220 ° C. or lower, or about 200 ° C. or lower. be able to.

  The treatment time of the fluorine gas treatment can 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.

  With the present disclosure, silicon treatment can be advantageously performed by plasma treatment, chemical vapor deposition, physical vapor deposition, or atomic layer deposition. Without being bound by any theory, silicon treatment can be performed in Si—in a binder or in a polymer contained on the surface of abrasive particles or on a surface coating such as diamond-like carbon or the like. The formation of O-Si bonds, Si-C-Si bonds, Si-O-C bonds, and the like is considered to cause the phenomenon that the structured surface is improved, and Si-O-Si A coating comprising silicon oxycarbide or silicon oxide having a relatively dense network formed through a bond, Si-C-Si bond, Si-O-C bond, or the like is a structured surface or It is formed on something similar.

  Silicon treatment by plasma treatment or chemical vapor deposition is performed using the same low pressure plasma device, atmospheric pressure plasma device, low pressure remote plasma device, atmospheric pressure remote plasma device, and the like as those for fluorine treatment described above. can do. The discharge gas and plasma generation methods are the same as described for the fluorine treatment.

Silane (SiH ₄ ), Tetramethylsilane (TMS), Hexamethyldisiloxane (HMDSO), Hexamethyldisilazane (HMDS), Tetraethoxysilane (TEOS), and the like can be obtained by plasma treatment or chemical vapor deposition. It can be used as the fluorine-containing gas used. Among these, monosilane or tetramethylsilane can be advantageously used because it has high reactivity and a large diffusion coefficient. When an atmospheric pressure plasma apparatus is used, tetramethylsilane having a low boiling point and nonflammability is used. The flow rate of the silicon-containing gas can 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 at a flow rate between about 50 sccm and about 5000 sccm may be further included in the gas stream supplied to the apparatus.

  If the silicon-containing gas does not contain oxygen atoms, oxygen is added to the gas stream supplied to the plasma device. Oxygen may be supplied into the chamber of the plasma device through a conduit separate from the silicon-containing gas, or supplied as a mixed gas with the silicon-containing gas through a showerhead disposed in the chamber. Can do. 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. When the flow rate of the silicon-containing gas is set to 1, the flow rate ratio of oxygen to 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 stopping the supply of the silicon-containing gas, the post-treatment may be performed, for example, by supplying only oxygen at a flow rate of about 5 sccm or more or about 10 sccm or more and about 500 sccm or less or about 300 sccm or less.

The applied power required for plasma generation can be determined based on the dimensions of the abrasive material being processed, and the power density in the radiation space is generally greater than or equal to about 0.00003 W / cm ² or about .0. 0002W / cm ² or more, and to be about 10 W / cm ² or less, or about 1W / cm ² or less can be selected. For example, when the size of the polishing material to be silicon-treated is 10 cm (length) × 10 cm (width) or less, the applied power is set to about 1 W or more or about 10 W or more, and about 300 kW or less or about 30 kW or less. Can do.

  The temperature of the plasma treatment or chemical vapor deposition method is preferably a temperature that does not impair the characteristics and performance of the abrasive material to be treated and the like, and the surface temperature of the abrasive material to be treated is about −15 ° C. or more, about It can be set to 0 ° C. or higher, or about 15 ° C. or higher, and about 400 ° C. or lower, about 200 ° C. or lower, or about 100 ° C. or lower. The surface temperature of the abrasive material can be measured by a thermocouple, radiation thermometer, or the like that contacts the abrasive material.

  When performing plasma treatment or chemical vapor deposition using a low-pressure plasma apparatus, the treatment pressure is about 10 mTorr (0.001 kPa) or more or about 20 mTorr (0.003 kPa) or more and about 1500 mTorr (0.20 kPa) or less, or It can be set to about 1000 mTorr (0.1 kPa) or less.

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

  In another embodiment, sputtering or vacuum deposition can be used as the silicon treatment by physical vapor deposition. Silicon treatment using physical vapor deposition is the same ion sputtering equipment, DC magnetron sputtering equipment, RF magnetron sputtering equipment, and the like as described for fluorine treatment, or standard heating equipment such as resistance heating deposition It can be performed using standard vapor deposition equipment such as equipment, electron beam vapor deposition equipment, ion plating equipment, and the like.

The silicon-treated sputtering target can be silicon dioxide (SiO ₂ ). Reactive sputtering may be performed by supplying oxygen into the processing chamber when using silicon (Si) as a sputtering target.

  The sputtering temperature can be set to 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 sputtering is about 1 × 10 ⁻⁵ Torr (1 × 10 ⁻⁶ kPa) or more or about 1 × 10 ⁻³ Torr (1 × 10 ⁻⁴ kPa) or more and about 10 mTorr (0.001 kPa) or less, or It can be set to about 100 mTorr (0.01 kPa) or less.

  The sputtering treatment time 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 advantageously be used with silicon dioxide deposition. Silicon treatment may be performed by vapor deposition using silicon monoxide (SiO) as a vapor deposition source, followed by annealing oxidation in an oxidizing atmosphere and monoxide while introducing oxygen plasma into the vapor deposition chamber. Silicon deposition may be performed.

  The deposition temperature can be set to about −193 ° C. or higher or about 25 ° C. or higher and about 600 ° C. or lower or about 1000 ° C. or lower.

The processing pressure for the deposition is about 1 × 10 ⁻⁶ Torr (1 × 10 ⁻⁷ kPa) or more, or about 1 × 10 ⁻⁵ Torr (1 × 10 ⁻⁶ kPa) or more, and about 1 × 10 ⁻³ Torr (1 × 10 ⁻⁴ kPa) or less or about 1 × 10 ⁻² Torr (1 × 10 ⁻³ kPa) or less.

  Deposition processing time can 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, atomic layer deposition (ALD) can be used as the silicon treatment. Atomic layer deposition involves alternately providing at least two precursor gases into the reaction chamber, each time depositing a single layer of these precursor gases on the structured surface, Reacting a precursor gas on the structured surface.

Examples of precursor gas A that can be used include tetraethoxysilane, bis (tert-butoxy) (isopropoxy) silanol, bis (isopropoxy) (tert-butoxy) silanol, bis (tert-pentoxy) (iso Propoxy) silanol, bis (isopropoxy) (tert-pentoxy) silanol, bis (tert-pentoxy) (tert-butoxy) silanol, bis (tert-butoxy) (tert-pentoxy) silanol, tris (tert-pentoxy) silanol, And the like. Examples of the 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 can be set to 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 can 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 can be set to 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 can 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.

  By introducing a purge gas into the reaction chamber between the introduction of precursor gas A and the introduction of precursor gas B, unreacted precursor gas and / or reaction byproducts can be purged from the reaction chamber. The purge gas is an inert gas that does not react with the precursor gas. Examples of purge gases that can be used include nitrogen gas, helium, neon, argon, and mixtures thereof. The purge gas flow rate can 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 purge gas introduction time is about 1 second or more, or about 10 seconds or more, and about It can be 30 seconds or less, or about 60 seconds or less.

  By varying the number of introductions of the precursor gas A and the precursor gas B, and the flow rates and introduction times of the precursor gas A and the precursor gas B, a film containing silicon oxycarbide or silicon oxide having a predetermined thickness is obtained. It can be formed on a structured surface. After introducing the precursor gas A and / or precursor gas B, heat, plasma, pulse plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, electron beam, photon, remote plasma, and the like Can be used to promote the reaction between precursor gas A and precursor gas B.

  The physical properties of the structured surface treated in this way can be evaluated, for example, by contact angle, hardness, and the like.

  In some embodiments, for example, in embodiments where the structured surface is fluoride treated, the water contact angle of the surface treated structured surface is about 70 ° or more, or about 90 ° or more, and about 120 ° or less. Or about 150 ° or less. The contact angle of water can be determined by the droplet method, expansion / contraction method, Wilhelmy method, or the like.

  In some other embodiments, for example, in embodiments where the structured surface is siliconized to provide a hydrophilic surface, the water contact angle of the surface treated structured surface is about 0 ° or greater, or It was about 10 ° or more and about 30 ° or less, or about 45 ° or less. The contact angle of water can be determined by the droplet method, expansion / contraction method, Wilhelmy method, or the like.

  In another embodiment, the hardness of the surface treated structured surface was about 40 or more, or about 50 or more, and about 87 or less, or about 97 or less when converted to Shore hardness. The hardness of the surface treated structured surface can be determined by the nanoindentation method. When the hardness of the surface-treated structured surface is about 50 or more when calculated as Shore hardness, the adhesion of relatively soft foreign matter such as polyurethane or similar polymer particles to the structured surface is prevented. be able to.

The composition of the film deposited on the structured surface, or the modified state of the fluoride or silicon treated structured surface is determined by secondary ion mass spectrometry using X-ray photoelectron spectroscopy (XPS) or time of flight. It can be evaluated qualitatively or quantitatively using a method (TOF-SIMS) and the like. For example, a XPS spectrum can be obtained using a Kratos Axis Ultra spectrometer using a monochromatic Al K α photon source with an electron emission polar angle of 90 ° to the surface. TOF-SIMS can use, for example, a pulsed 25 keV (4.0 × 10 ⁻¹⁵ ) Ga + primary ion beam rasterized by a 400 μm × 400 μm area with a beam diameter of about 1 μm.

  Yet another embodiment of the present disclosure is an abrasive material comprising an abrasive layer having a structured surface configured with a plurality of three-dimensional elements disposed thereon, wherein at least a portion of the structured surface comprises: Polishing comprising (a) a film comprising a material selected from the group consisting of densified fluorocarbon, silicon oxycarbide, and silicon oxide, (b) a surface terminated with fluorine, or (c) a combination thereof. Provide material.

  In the present disclosure, “densified fluorocarbon” refers to a fluorocarbon material that includes a dense three-dimensional network structure formed by C—C bonds as a result of containing a relatively large amount of quaternary carbon atoms. Point to. Densified fluorocarbons have high hardness and superior wear resistance and foreign matter adhesion resistance compared to standard or non-crosslinked standard fluoropolymers.

  The densified fluorocarbon may contain other atoms in addition to carbon and fluorine, such as hydrogen, oxygen, nitrogen, and the like. In some embodiments, the densified fluorocarbon is 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, based on the total amount of elements other than hydrogen. Of carbon atoms. In some other embodiments, the densified fluorocarbon is about 30 atomic percent or more, or about 35 atomic percent or more, and about 75 atomic percent or less, or about 70 atoms based on the total amount of elements other than hydrogen. % Carbon atom or less. Further, in some other embodiments, the densified fluorocarbon is about 25 atomic percent or more, or about 30 atomic percent or more, and about 80 atomic percent or less, or about about based on the total amount of elements other than hydrogen. Contains quaternary carbon atoms bonded to four adjacent carbon atoms, up to 70 atomic percent. For example, by using XPS, the atomic percentages of carbon and fluorine atoms of a densified fluorocarbon can be determined, for example, using quaternary carbon atoms using 13C-NMR or the like. The atomic percentage of can be determined.

  Silicon oxycarbide is a compound containing silicon, oxygen, and carbon, but may contain three-dimensional elements and other atoms (such as hydrogen, nitrogen, and the like). Silicon oxycarbide is hard and has excellent wear resistance, foreign matter adhesion resistance, and the like, and can be made either hydrophilic or hydrophobic by changing the composition. In some embodiments, the silicon oxycarbide is 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 silicon atoms based on the total amount of elements other than hydrogen. including. In some other embodiments, the silicon oxycarbide is about 5 atomic percent or more, or about 10 atomic percent or more, and about 80 atomic percent or less, or about 70 atomic percent or less, based on the total amount of elements other than hydrogen. Contains oxygen atoms. In yet some other embodiments, the silicon oxycarbide is about 1 atomic percent or more, or about 5 atomic percent or more, and about 90 atomic percent or less, or about 80 atomic percent or less, based on the total amount of elements other than hydrogen. Of carbon atoms. The atomic percentage 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 containing silicon and oxygen, but may contain other atoms (except carbon) such as hydrogen, nitrogen, and the like. Silicon oxide, particularly silicon oxide having a Si—O—H bond at the end, is generally hydrophilic and may effectively prevent adhesion of the hydrophobic material to the structured surface. In some embodiments, the silicon oxide comprises 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 silicon atoms based on the total amount of elements other than hydrogen. Including. In some other embodiments, the silicon oxycarbide is about 45 atomic% or more, or about 50 atomic% or more, and about 70 atomic% or less, or about 67 atomic% or less, based on the total amount of elements other than hydrogen. Contains oxygen atoms. The atomic percentage of silicon and oxygen atoms in the silicon oxide can be determined using XPS, TOF-SIOMS, and the like.

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

The fluorine atom density of the fluorine-terminated structured surface is generally about 1 × 10 ¹³ cm ⁻² or higher, or about 5 × 10 ¹³ cm ⁻² or higher, and about 5 × 10 ¹⁵ cm ⁻² or lower, or about 3 ×. 10 ¹⁵ cm ⁻² or less. By using XPS, TOF-SIOMS, and the like, the fluorine atom density on the structured surface can be determined.

  Abrasive materials of the present disclosure include rough polishing, chamfering, and precision polishing of various surfaces such as semiconductor wafers, magnetic storage media, glass plates, lenses, prisms, automotive coatings, fiber optic connector terminal surfaces, and the like. Can be used for various applications, as well as dressings for other abrasive tools and the like. The abrasive materials of the present disclosure can also be advantageously used in applications that use abrasive slurries.

  The following examples illustrate certain embodiments of the present disclosure, but the invention is not limited thereto. Unless otherwise specified, all “parts” and “%” are based on mass.

1. CMP dressing test In Examples 1 and 2 and Comparative Examples 1 and 2, five disc-shaped abrasive materials having a diameter of 11 mm and a thickness of 3 mm were formed into a stainless steel disk shape having a diameter of 110 mm and a thickness of 5 mm. It was deposited at equal intervals on the circumference at a distance of 43 mm from the center of the substrate and then used as a CMP dressing. The disc-shaped abrasive material has a silicon carbide bulk layer with a structured surface having regular square pyramids (pyramids), the regular pyramids having a base length of 360 μm and a height of 160 μm, arranged periodically The bases of regular square pyramids were in contact with each other. A diamond layer was coated on the silicon carbide bulk layer.

  The structured surface of the abrasive material is subjected to fluoride treatment (Example 1) or silicon treatment (Example 2) using a batch type capacitively coupled plasma plasma apparatus (WB 7000 (Plasma Therm Industrial Products, Inc.)). It was. The structured surface of Comparative Example 1 was prepared by adding a fluoropolymer (3M (registered trademark) Novec (registered trademark) EGC 1720 (manufactured by 3M)) to a solvent (Novec (registered trademark) 7100 (manufactured by 3M). )), A coating solution prepared by dissolving so as to have a solid content of 0.1% by mass was applied to form a fluoropolymer coating film. Comparative Example 2 was untreated (control test). Detailed processing conditions of Examples 1 and 2 are shown in Table 1.

  The abrasive materials of Examples 1 and 2 and the abrasive materials of Comparative Examples 1 and 2 were attached to a disk and set in a Bühler (R) EcoMet (R) 4000 (Buehler). The polishing system was supplied with water instead of CMP slurry. Using a urethane foam pad (ICE 1000 pad (Dow product)), 5 kgf (50 N) (1 kgf (10 N) per abrasive material) and 150 RPM (disk) / 10 rpm (urethane pad) rotation At a speed, a CMP dressing test is performed for 1 hour, then the disc is immersed in a water bath for 5 minutes to mimic a standard compounding process, and is naturally dried with the structured surface of the abrasive material facing down, The structured surface was then observed using an optical microscope (magnified 300x) to check for deposits of foreign matter (urethane particles) (Figure 4). In Examples 1 and 2, there was almost no accumulation of urethane particles, and a clear improvement was observed compared to Comparative Example 2. Comparative Example 1 had a large amount of polyurethane particle deposition even compared to Comparative Example 2.

  The abrasive material was then ultrasonically cleaned using water and the structured surfaces of Examples 1 and 2 were observed in detail using an optical microscope (enlarged 1500 times). Although no surface damage was particularly observed for Example 1, there was partial peeling of the silicon film for Example 2.

2. Automotive 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 microscopic protrusions on the surface of automobile paint.

Abrasive material A: Trizact (registered trademark) film disc roll 466 LA-A5 (3M, equivalent to grit size # 3000)
Abrasive material B: Trizact (registered trademark) film disk roll 466 LA-A3 (manufactured by 3M, equivalent to grit size # 4000)
Polishing material C: Trizact (registered trademark) diamond disk 662 XA (manufactured by Sumitomo 3M)

  The structured surfaces of the abrasive materials A-C were treated with fluoride (Example 3) or silicon (Example 4) using a batch-type capacitively coupled plasma apparatus (WB 7000 (Plasma Therm Industrial Products, Inc.)). And 5). Comparative Example 3 was untreated (control test). Table 1 shows the detailed processing conditions of Examples 3 to 5.

  An adhesive sheet with or without surface treatment was applied to the back surface of the abrasive materials A to C, and a disk having a diameter of 32 mm was punched out. A plate coated with black paint and clear paint (LX Clear made by Nippon Paint Co., Ltd.) on a bonde steel plate is attached to an apparatus capable of operating the sander in one horizontal direction. Is attached to the polishing surface of a 3M® polishing sander 3125 (manufactured by 3M) with a 3 mm circular motion, a load of 1 kgf (10 N) is applied simultaneously with rotation of about 5000 rpm, and the coated plate The surface was polished 5 times back and forth at a distance of 20 cm at a speed of 1 m / min. After polishing, the amount of polishing powder adhering to the surfaces of the polishing materials A to C was visually observed, and the results were shown by the overall photograph of FIG. 5A and the optical micrograph (enlarged 300 times) of FIG. 5B. In Example 4, the amount of abrasive powder adhered to the structured surfaces of the siliconized abrasive materials A to C was minimal.

  Next, the polishing materials A to C were washed with water, and the structured surface was observed with an optical microscope (enlarged 300 times) (FIG. 5C). Examples 3-5 all showed favorable cleaning properties compared to Comparative Example 3, and siliconized Examples 4 and 5 showed even more preferable cleaning properties. For automotive paint polishing applications, the surface of the abrasive material is generally washed after being polished several times, and therefore abrasive materials having favorable cleaning properties are very advantageous in this application.

3. Glass plate surface polishing test In Examples 6 and 7 and Comparative Example 4, a Trizact (registered trademark) diamond tile pad 9 μm (manufactured by 3M) was used as a polishing pad used for polishing the surface of the glass plate. It was.

  The structured surface of the polishing pad was fluoride treated (Example 6) or silicon treated (Example 8) using a batch type capacitively coupled plasma device (WB 7000 (Plasma Thermal Industrial Products, Inc.)). . Comparative Example 4 was untreated (control test). The detailed processing conditions of Examples 6 and 7 are shown in Table 1.

  The polishing pads of Examples 6 and 7 and the polishing pad of Comparative Example 4 were attached to a disk and set in a Buehler (registered trademark) EcoMet (registered trademark) 4000 (manufactured by Buehler). As a polishing solution, a 5% aqueous solution of LA-20 (Neos) was applied to the polishing system. Blue plate glass (manufactured by Asahi Glass Co., Ltd.) was polished for 150 minutes under conditions of a load of 80 N, an upper plate rotation speed of 60 rpm, and a lower plate rotation speed of 450 rpm. During polishing, the structured surface of the polishing pad was not cleaned.

After polishing, the polishing pad was placed in a furnace at 60 ° C. to evaporate the polishing solution. The weight after drying of the polishing pad was measured (W ₁ ). Next, the polishing pad was washed with water, placed in a 60 ° C. oven, and dried. The weight after drying of the polishing pad was measured (W ₂ ). The amount of attached abrasive powder was calculated by the formula: W ₂ -W ₁ , and the value was 210 mg for Example 6 and 110 mg for Example 7 but 250 mg for Comparative Example 4. Example 6 and Example 7 both showed favorable cleaning properties compared to Comparative Example 4, and siliconized Example 7 showed even more preferable cleaning properties.

Claims (9)

  A polishing material comprising a polishing layer having a structured surface on which a plurality of three-dimensional elements are disposed, wherein a surface treatment selected from the group consisting of a fluorine treatment and a silicon treatment comprises at least the structured surface. An abrasive material implemented over a portion, 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 disposed on the structured surface.   The polishing material according to claim 1 or 2, wherein the silicon treatment is selected from the group consisting of plasma treatment, chemical vapor deposition, physical vapor deposition, and atomic layer deposition.   The said polishing layer comprises a bulk layer comprising silicon carbide, and the surface coating layer comprises diamond-like carbon provided on at least a portion of the bulk layer. Abrasive material.   The abrasive material according to any one of claims 1 to 3, wherein the abrasive layer contains abrasive particles and a binder.   The plurality of three-dimensional elements are selected from the group consisting of a cylindrical shape, an elliptical cylindrical shape, a prism, a hemisphere, a semi-ellipsoid, a cone, a pyramid, a truncated cone, a truncated pyramid, a ridge roof shape, and combinations thereof. The abrasive material according to any one of claims 1 to 5, which has a shape. A method for producing an abrasive material, comprising:
Providing an abrasive material comprising an abrasive layer having a structured surface configured with a plurality of three-dimensional elements disposed thereon;
Performing a surface treatment selected from the group consisting of a fluorine treatment and a silicon treatment on at least a portion of the structured surface of the abrasive material,
The method 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. A polishing material comprising a polishing layer comprising a structured surface comprising a plurality of three-dimensional elements disposed thereon, wherein at least a portion of the structured surface is (a) a densified fluorocarbon A polishing material comprising: a film comprising a material selected from the group consisting of: silicon oxycarbide, and silicon oxide; (b) a fluorine terminated surface; or (c) a combination thereof.