IVIETHODS

BACKGROUND

Field

[0001] Embodiments of the present disclosure generally relate to a polishing pad, and methods of forming a polishing pad, and more particularly, to a polishing pad used for polishing a substrate in an electronic device fabrication process.

Description of the Related Art

[00023 Chemical mechanical polishing (CMP) is commonly used in the manufacture of high-density integrated circuits to pianarize or polish a layer of material deposited on a substrate, by contacting the material layer to be planarized with a polishing pad and moving the polishing pad and/or the substrate, and hence the material layer surface, in the presence of a polishing fluid and abrasive particles. Two common applications of CMP are planarization of a bulk film, for example pre-metal dielectric (PMD) or interiayer dielectric (ILD) polishing, where underlying features create recesses and protrusions in the layer surface, and shallow trench isolation (STi) and interiayer metal interconnect polishing, where polishing is used to remove the via, contact or trench fill material from the exposed surface (field) of the layer having the feature.

[0003] in a typical CMP process, the substrate is retained in a carrier head that presses the backside of the substrate toward the polishing pad. Material is removed across the material layer surface in contact with the polishing pad through a combination of chemical and mechanical activity that is provided by the polishing fluid and the abrasive particles. Typically, the abrasive particles are either suspended in the polishing fluid, known as a slurry, or are embedded in the polishing pad, known as a fixed abrasive polishing pad.

[0004] When abrasive particles are suspending in the polish fluid (slurry) a non-abrasive polishing pad is typically used to transport the abrasive particles to the material layer of the substrate where the abrasive particles provide mechanical action, and in some embodiments, chemical reaction, with the surface thereof. In contrast, with a fixed abrasive polishing pad, the abrasive particles are typically integrated into the polishing pad by embedding them in a supporting material (e.g., often referred to as a binder material), such as an epoxy resin. Generally, during a CMP process, the binder material fixedly holds the abrasive particles in place at the polishing pad surface where they provide mechanical polishing action to, and sometimes chemical reaction with, the material layer of the substrate during the CMP process.

[Θ0053 Generally, fixed abrasive polishing pads are superior to standard (non- fixed abrasive polishing pads) in some aspects of polishing performance, such as less undesirable erosion of planar surfaces in areas with high feature density and less undesirable dishing of the upper surface of the film material in recessed features such as trenches, contacts, and lines. However, fixed abrasive polishing pads tend to have lower lifetimes (polishes per pad), inferior substrate to substrate stability for film removai rate from the substrate surface, and inferior substrate to substrate stability for uniformity of film removal across the substrate.

[0006] Typically, fixed abrasive conditioning disks, such as diamond conditioning disks, are used with standard polishing pads to rejuvenate and planarize the polishing pad surface, and thus maintain substrate to substrate stability polishing performance. However, fixed abrasive conditioning disks are generally incompatible for use with fixed abrasive polishing pads as the disk will remove the embedded abrasive particles from the inherently brittle surface of the supporting epoxy material in which the abrasive material is embedded. This undesirable removal of the abrasive particles leaves a pad surface devoid, or nearly devoid, of the abrasive particles necessary for efficient CMP processes.

[0007] Accordingly, what is needed in the art is a polishing pad, and methods of manufacturing a polishing pad, having desirable polishing characteristics of a fixed abrasive polishing pad that is compatible with external conditioning, such as with a fixed abrasive conditioning disk. SUMMARY

[0008] Embodiments herein generally relate to an integrated abrasive (!A) polishing pad comprising abrasive particles disposed in, and chemically bonded to, the polishing material of portions of the polishing pad, and methods of forming thereof. In particular, in embodiments herein, a curable resin precursor mixture is formed with abrasive particles having a poiymerizable group chemically bonded to surfaces thereof. The curable resin precursor mixture is used in an additive manufacturing process, along with a curable resin sub-polishing material precursor composition, to form a polishing pad. In some embodiments, the polishing pad has discrete polishing elements with abrasive particles disposed in, and chemically bonded to, the polishing pad material thereof.

[0009] In one embodiment, a method of forming a polishing article includes dispensing a first plurality of droplets of a first precursor and curing the first plurality of droplets to form a first layer comprising a portion of a sub-polishing element. The method further includes dispensing a second plurality of droplets of the first precursor and a second precursor onto the first layer and curing the second plurality of droplets to form a second layer comprising portions of the sub- polishing element and portions of a plurality of polishing elements. Here, the second precursor includes functionalized abrasive particles having a poiymerizable group chemically bonded to surfaces thereof.

[0010] in another embodiment, a method of forming a polishing article includes forming a sub-polishing element from a first plurality of droplets of a first precursor and forming a plurality of polishing elements disposed in, and extending from, the sub-polishing element by dispensing a second plurality of droplets of a second precursor. Here, the second precursor comprises treated metal oxide nanoparticles having poiymerizable compounds bonded to less than about 50% of bonding sites on the surface of the metal oxide nanoparticles. The treated metal oxide nanoparticles comprise the reaction product of metal oxide nanoparticles with a silane compound, a cyanate compound, a sulfonic acid compound, a phosphoric acid compound, a carboxylic acid compound, or combinations thereof. [00113 In another embodiment, a polishing article includes a sub-polishing element comprising a first reaction product of a first precursor mixture and a plurality of polishing elements extending from the sub-polishing element. Here, the plurality of polishing elements comprise a second reaction product of a second precursor mixture, wherein the second precursor mixture comprises functionaiized abrasive particles.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. If is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

[0013] Figures 1A-1 D illustrate various properties of surface functionaiized ceria particles formed according methods set forth herein.

[0014] Figure 2A is a schematic sectional view of a polishing system using an integrated abrasive (IA) polishing pad formed according to embodiments disclosed herein.

[0015] Figures 2B-2C are schematic perspective sectional views of IA polishing pads, according to embodiments described herein.

[0016] Figure 3A is a schematic sectional view of an additive manufacturing system used to form an integrated abrasive (IA) polishing pad, such as the IA polishing pads described in Figures 2B-2C, according to one embodiment.

[0017] Figures 3B and 3C illustrate a curing process using the additive manufacturing system described in Figure 3A. [0018] Figures 4A-4B illustrate the properties of a layer formed from a precursor comprising surface functionalized abrasive particles, according to one embodiment.

[0019] Figure 5 is a flow diagram illustrating a method of forming a polishing pad, such as the integrated abrasive (IA) polishing pads described in Figure 2A- 2B, according to one embodiment.

[00203 Figures 6 is a schematic top view of an integrated abrasive (IA) polishing pad, according to another embodiment.

[0021] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements disclosed in one embodiment may be beneficially utilized on other embodiments without specific recitation.

[00223 Embodiments described herein generally relate to polishing articles and methods for manufacturing polishing articles used in a polishing process. More specifically, embodiments described herein relate to integrated abrasive (IA) polishing pads, and methods of manufacturing IA polishing pads, that have the advantageous polishing characteristics of fixed abrasive polishing pads yet allow for conditioning with a fixed abrasive conditioner, such as a diamond conditioner. The ability to condition IA polishing pads enables a polishing process that uses a non-abrasive polishing fluid yet has stable and controlled polishing performance and an extended polishing pad lifetime.

[0023] Herein the polishing articles described as polishing pads, and methods of forming thereof, are applicable to other polishing applications including, for example, buffing. Further, although the discussion herein is in relation to chemical mechanical polishing (CMP) processes, the articles and methods are also applicable to other polishing processes using both chemically active and chemically inactive polishing fluids. In addition, embodiments described herein may be used in at least the following industries: aerospace, ceramics, hard disk drive (HDD), MEMS and Nano-Tech, metalworking, optics and electro-optics manufacturing, and semiconductor device manufacturing, among others.

[0024] Embodiments of the present disclosure provide for integrated abrasive (IA) polishing pads manufactured using, at least in part, surface functionaiized abrasive particles in an additive manufacturing process, such as a two- dimensional 2D or three-dimensional 3D Inkjet printing process. Additive manufacturing processes, such as the three-dimensional printing ("3D printing") process described herein, enable the formation of polymer IA polishing pads with discrete polishing regions and/or polishing features (polishing elements) having unique properties and attributes. Generally, the polymers of the polishing elements form chemical bonds, for example covalent bonds or ionic bonds, with the polymers of adjacent polishing elements at the interfaces thereof. Because the polishing elements are linked with adjacent polishing elements through chemical bonding, the interfaces are stronger and more robust than polishing pads having discrete elements attached using other methods, such as with adhesive layers or by thermal bonding, to allow for the use of a more aggressive polishing or conditioning process when desired,

[0025] Herein, abrasive particles refer to hydroxyl terminated metal oxide nanopartides such as single or mu!ticomponent metal oxide nanopartides, for example ceria, alumina, silica, silica/alumina oxide, or combinations thereof. In other embodiments, the abrasive particles comprise metal oxide nanopartides terminated with hydroxy! groups, thiol groups, carboxylic acid groups, amino groups, or combinations thereof. A surface functionaiized abrasive particle refers to an abrasive particle comprising at least one polymerizable group chemically bonded to bonding sites on the surfaces thereof. Bonding sites refers to sites that can react with the compounds described herein to form a covalent bond with a polymerizable group.

[0026] In some embodiments, surface modification to achieve the surface functionaiized abrasive particle includes reacting the surfaces of the hydroxy! terminated abrasive particles with surface modifying organic compounds, such as organic silane compounds, sulfonic acid compounds, organic phosphoric acid compounds, carboxylic acid compounds, derivatives thereof, or combinations thereof. In embodiments described herein, the reaction product of the hydroxy! terminated abrasive particles comprises abrasive particles having surfaces terminated with both alkene and hydroxy! groups, hereafter referred to as aikene terminated abrasive particles. In other embodiments, the surfaces may be terminated with any polymerizab!e group, such as an epoxy group, for example an epoxy aldehyde group or an epoxy ketone group.

[00273 In one embodiment, the surface functionalized abrasive particles are formed by reacting the surfaces of the abrasive particles with a silane compound, such as an alkoxy silane, such as trichioro(phenyi)silane, trichloro(hexyl)silane, trichioro(octadecyl)siiane, trimethoxy(7-octen-1-yl)silane, trichloro[2-

(chioromethyl)allyijjsiiane, vinyitrimethoxysilane, chloro(dimethyi)vinylsilane, allyltrimethoxysiiane, acryloyl chloride, vinyitrimethoxysilane, or combinations thereof. The abrasive particle silane compound reaction is used to graft a desired poiymerizable group onto a hydroxyl terminated surface of the abrasive particle (i.e., circular shaped element shown below) as represented in chemical reactions (A) and (B) where R is a methyl group (CH3).

[0028] in another embodiment, the surface functionalized abrasive particles are formed by reacting the surfaces of the abrasive particles with a cyanate compound, such as an isocyanate based monomer such as tris-[3- (trimethoxysi!y!)propyj] isocyanurate or 2-(methacryloyioxy)ethyl isocyanate. For example, the isocyanate group of 2-(methacryloyloxy)ethyl isocyanate reacts with hydroxy! group and form amide bond results in covalent linkage of acrylic groups with abrasive nanopariicles as shown in chemical reaction (C) where R represents hydrogen (H) or a methyl group (CH3).

(C)

[Θ0293 In another embodiment, the surface functionahzed abrasive particles are formed by reacting the surfaces of the abrasive particles with sulfonic or phosphoric acid derivatives, such as 2-acrylamido-2-methyl-1-propanesulfonic acid as shown in reaction (D) or with vinyl phosphonate as shown in reaction (E), where R represents hydrogen (H) or a methyl group (CH ₃ ).

(

E) [0030] In another embodiment, the surface functionaiized abrasive particles are formed by reacting the surfaces of the abrasive particles with carboxylic acids that comprise acrylic groups, such as shown in chemical reaction (F) where R represents hydrogen (H) or a methyl group (CH ₃ ) and n is from 1 to 50. In some embodiments, the reactivity of the carboxylic group is increased by converting the carboxylic acid containing acrylic group to a chloride acid using thionyi chloride.

[0031] Figures 1A-1 D illustrate various properties of surface functionaiized ceria particles formed according to one embodiment. Ceria is commonly used as an abrasive particle for shallow trench isolation (STI) polishing applications in addition to other CMP applications because the hydroxyl terminated surface of ceria exhibits a high affinity for silicon oxide (SiC½) materials compared to silicon nitride materials leading to desirably high selectivity between the two films. While not wishing to be bound to a particular theory it is believed that excessive loading (% of bonding sites) of the surface of ceria particles with po!ymerizab!e groups will undesirably influence the reaction of the ceria particle with an H-terminated surface of Si02 which impacts polishing rate and selectivity performance. Therefore, it is desirable to limit the loading of functionaiized surface sites on the surfaces of the ceria particles so that sufficient hydroxyl terminated sites remain to react with the H-terminated surfaces of SiC<2. Herein, loading of the abrasive particles surfaces, such as ceria surfaces, with polymerizable groups is desirably maintained at between about 0.1 % and about 50%, such as between about 1 % and about 25%, such as between about 1 % and about 10%, such as between about 1 % and about 5%, for example between about 2% and about 5%, or where at least some of the abrasive particle surfaces are surface functionaiized by not more than about 5%. [0032] In Figures 1A-1 D ceria particles were surface functionalized by reacting the hydroxy! terminated surface sites with chioro{dimethyi)vinyisilane as shown in reaction (G).

ceria nanoparticles _c h lorodimethyl(vinyl)si lane

[0033] The reaction was carried out by mixing ceria particles with a nonaqueous solvent, such as toluene, while using a probe sonicator to agitate the mixture at 60 °C. Chioro(dimethyi)vinylsilane was added to the mixture drop by drop during sonication and the mixture was then maintained at 60 °C for about three hours to complete the reaction and provide for surface functionalized ceria particles. The surface functionalized ceria particles were purified by a combination of filtration, centrifugation, and washing with toluene to remove the unreacted chioro(dimethyl)vinylsiiane. The treated ceria particles were characterized with thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and energy dispersive x-ray (EDX) analysis to confirm functionaiization thereof.

[0034] Figure 1A shows the results of a thermogravimetric analysis (TGA) of a sample of the treated ceria particles. As the sample of treated ceria particles 107 was heated from ambient temperature to 100 °C (first range 103) it experienced rapid weight loss attributable to the evaporation of the residual toluene left from the purification process, A second range 05 of temperatures from 100 °C to 800 °C, and, in particular, from 400 °C to 800 °C show a more gradual decline in the weight of the sample of treated ceria particles which is attributable to the ignition of the hydrocarbons of the polymerizabie groups bonded to the bonding sites on the surfaces thereof. Figure 1 B shows the results of an FTIR analysis of the treated ceria particles 107 compared to untreated ceria particles 111. A CH=CH ₂ vibration 1 19 at a wavelength of about 1620 cm ^"1 and methyl antisymmetric and symmetric vibrations 17 at about 2919 cm ^"1 and 2850 cm ^"1 indicate successful surface modification, and thus surface functiona!ization, of the treated ceria particles 107 with dimethyl vinyl silane groups when compared to the untreated ceria particles 1 11. An 0~H vibration 1 5 at about 3400 cm ^"1 indicates that a portion of the hydroxy! groups on the treated ceria particles 107 have been consumed during the reaction when compared to the untreated ceria particles 1 11 , further indicating successful surface functionalization of the treated ceria particles 107 with dimethyl vinyl silane groups. However, as shown by O-H vibration 115 at least a portion of the hydroxy! groups remain bonded to bonding sites of the surfaces of the treated ceria particles 107 thus leaving sufficient hydroxy! terminated sites on the ceria particle maintain desirable polishing rates and/or selectivity performance during a CMP process, such as during an ST! polishing process where the hydroxyl terminated sites of ceria particles react with H-terminated surfaces of SiC½.

[0035] Figure 1C shows TE images 120 and 130 where drop-coated films of the treated ceria particles 107 were formed on carbon-coated copper grinds by solvent evaporation. As shown in images 120 and 130 the individual treated ceria particles have a fairly uniform mean diameter of between about 20 nm to about 50 nm. However, not unexpectedly, the individual particles formed larger agglomerations of particles that, in a typical formulation, will need to be milled, meaning the larger agglomerations of particles will need to be separated into smaller agglomerations and/or individual particles before or during formulation of the precursor mixtures used to form the !A polishing pad described herein. Figure 1 D shows selected EDX spectra of the treated ceria particles shown in image 145, where Ce, O, and Si signals are attributable to ceria particles and the bonded dimethyl vinyl silane group, indicating successful functiona!ization of the treated ceria particles' surfaces with the poiymerizabie dimethyl vinyl silane group. In another embodiment, the surfaces of the abrasive particles are reacted with the surface modifying compounds using a vapor reaction process, such as a fluidized bed.

[0036] Figure 2A is a schematic sectional view of an example polishing system 250 using an IA polishing pad 200 formed according to the embodiments described herein. Typically, the IA polishing pad 200 is secured to a platen 252 of the polishing system 250 using an adhesive, such as a pressure sensitive adhesive, disposed between the IA polishing pad 200 and the platen 252. A substrate carrier 258, facing the platen 252, and the IA polishing pad 200 mounted thereon, has a flexible diaphragm 261 configured to impose different pressures against different regions of a substrate 260 while urging the material surface of the substrate 260 against the polishing surface of the IA polishing pad 200. The substrate carrier 258 includes a carrier ring 259 surrounding the substrate 260. During polishing, a downforce on the carrier ring 259 urges the carrier ring 259 against the IA polishing pad 200 to prevent the substrate 260 from slipping from the substrate carrier 258. The substrate carrier 258 rotates about a carrier axis 264 while the flexible diaphragm 261 urges the substrate 260 against the polishing surface of the IA polishing pad 200. The platen 252 rotates about a platen axis 254 in an opposite direction from the rotation of the substrate carrier 258 while the substrate carrier 258 sweeps back and forth from an inner diameter of the platen 252 to an outer diameter of the platen 252 to, in part, reduce uneven wear of the IA polishing pad 200, Herein, the platen 252 and the IA polishing pad 200 have a surface area that is greater than a surface area of the substrate 260, however, in some polishing systems, the IA polishing pad 200 has a surface area that is less than the surface area of the substrate 260.

[0037] During polishing, a fluid 226 is introduced to the IA polishing pad 200 through a fluid dispenser 268 positioned over the platen 252. Typically, the fluid 226 is water, a polishing fluid, a polishing slurry, a cleaning fluid, or a combination thereof. Herein, the polishing fluid contains a pH adjuster and/or chemically active components, such as an oxidizing agent, to enable chemical mechanical polishing of the material surface of the substrate 280.

[0038] Typically, the polishing system 250 includes a pad conditioning assembly 270 that comprises a conditioner 278, such as a fixed abrasive conditioner, for example a diamond conditioner. The conditioner 278 is coupled to a conditioning arm 272 having an actuator 276 that rotates the conditioner 278 about its center axis, while a downforce is applied to the conditioner 278 as it sweeps across the IA polishing pad 200 before, during, and/or after polishing the substrate 260. The conditioner 278 abrades and rejuvenates the IA polishing pad 200 and/or cleans the IA polishing pad 200 by removing polish byproducts or other debris from the polishing surface thereof.

[0039] Figures 2B-2C are schematic perspective sectional views of IA polishing pads 200b-c, according to embodiments described herein. The IA polishing pads 200b-c can be used as the IA polishing pad 200 in the polishing system 250 of Figure 2A. in Figure 2B, the IA polishing pad 200b comprises a plurality of polishing elements 204b that are disposed within a sub-polishing element 206b, and extend from a surface of the sub-polishing element 206b. The plurality of polishing elements 204b have a thickness 215 the sub-polishing element 208b has a sub-thickness 212. As illustrated in Figures 2B and 2C, the polishing elements 204b, 204c are supported by a portion of the sub-polishing element 206b, 208c (e.g. , portion within region 212A). Therefore, when a load is applied to the polishing surface 201 of the IA polishing pads 200b-c (e.g., top surface) by a substrate during processing, the load will be transmitted through the polishing elements 204b, 204c and portion 212A of the sub-polishing element 206b, 206c. Herein, the plurality of polishing elements 204b include a post 205 disposed in the center of the IA polishing pad 200b and a plurality of concentric rings 207 disposed about the post 205 and extending radially outward therefrom. The plurality of polishing elements 204b and the sub-polishing element 208b define a plurality of channels 218 disposed in the IA polishing pad 200b between each of the polishing elements 204b and between a plane of the polishing surface of the IA polishing pad 200b and a surface of the sub-polishing element 206b. The plurality of channels 218 enable the distribution of fluid 268, such as a polishing fluid, across the IA polishing pad 200b and to an interface between the IA polishing pad 200b and the material surface of a substrate 260. in other embodiments, the patterns of the polishing elements 204b are rectangular, spiral, fractal, random, another pattern, or combinations thereof. Herein, a width 214 of the polishing element(s) 204b-c is between about 250 microns and about 5 millimeters, such as between about 250 microns and about 2 millimeters. A pitch 218 between the polishing eiement(s) 204b is between about 0.5 millimeters and about 5 millimeters, in some embodiments, the width 214 and/or the pitch 216 varies across a radius of the IA polishing pad 200b to define zones of pad material properties and/or abrasive particle concentration.

[0040] in Figure 2C, the polishing elements 204c are shown as circular columns extending from the sub-polishing element 206c. in other embodiments, the polishing elements 204b are of any suitable cross-sectional shape, for example columns with toroidal, partial toroidal (e.g. , arc), oval, square, rectangular, triangular, polygonal, irregular shapes, or combinations thereof, in some embodiments, the shapes and widths 214 of the polishing elements 204c, and the distances therebetween, are varied across the IA polishing pad 200c to tune hardness, mechanical strength, fluid transport characteristics, or other desirable properties of the complete IA polishing pad 200c.

[0041] Herein, the polishing elements 204b-c and the sub-polishing elements 206b-c each comprise a pad material composition of at least one of oligomeric and/or polymeric segments, compounds, or materials selected from the group consisting of: po!yamides, polycarbonates, polyesters, polyether ketones, poiyethers, polyoxymethylenes, polyether sulfone, poiyetherimides, poiyimides, poiyolefins, polysiloxanes, poiysulfones, poiyphenylenes, poiyphenylene sulfides, poiyurethanes, polystyrene, polyacrylonitriies, poiyacryiates, polymethylmethacrylates, polyurethane acrylates, polyester acrylates, polyether acrylates, epoxy acrylates, polycarbonates, polyesters, melamines, poiysulfones, polyvinyl materials, acryionitrile butadiene styrene (ABS), halogenated polymers, block copolymers and random copolymers thereof, and combinations thereof. [0042] In some embodiments, the materials used to form portions of the I A polishing pad 200b-c, such as the first polishing elements 204b-c and the sub- polishing elements 206b-c will include the reaction product of at least one ink jettable pre-poiymer composition that is a mixture of functional polymers, functional oligomers, reactive diluents, and curing agents to achieve the desired properties of an IA polishing pad 200b-c. In general, the deposited material can be exposed to heat or electromagnetic radiation, which may include ultraviolet radiation (UV), gamma radiation, X-ray radiation, visible radiation, I R radiation, and microwave radiation and also accelerated electrons and ion beams may be used to initiate polymerization reactions. For the purposes of this disclosure, we do not restrict the method of cure, or the use of additives to aid the polymerization, such as sensitizers, initiators, and/or curing agents, such as through cure agents or oxygen inhibitors, in one embodiment, two or more polishing elements, such as the polishing elements 204b-c and the sub-polishing elements 206b-c, within a unitary pad body, are formed from the sequential deposition and post deposition processing and comprise the reaction product of at least one radiation curable resin precursor composition, wherein the compositions contain functional polymers, functional oligomers, monomers, and/or reactive diluents that have unsaturated chemical moieties or groups, including but not restricted to: vinyl groups, acrylic groups, methacrylic groups, allyl groups, and acetylene groups. The hardness and/or storage modulus E' of the materials found within the polishing elements 204b-c and the sub-polishing elements 208b~c are different, such that the values hardness and/or storage modulus E' values for the polishing elements 204b-c elements are greater than the sub-polishing elements 206b-c elements, in some embodiments, the material composition and/or material properties of the polishing elements 204b-c vary from polishing element to polishing element. Individualized material composition and/or material properties allow for the tailoring of the polishing pads for specific needs.

[0043] At least a portion of the one or more of the plurality of polishing elements 204b-c include abrasive particles disposed in, and chemically bonded, either covalentiy or ionical!y, to the polishing pad material compositions thereof. Herein, the polishing elements 204b-c comprise, at least, the reaction product of a radiation curable resin precursor composition that contains functional polymers, functional oligomers, monomers, or reactive diluents that have unsaturated chemical moieties or groups, including but not restricted to: vinyl groups, acrylic groups, methacry!ic groups, ally! groups, and acetylene groups, and surface functionalized abrasive particles, such as aikene terminated abrasive particles, for example aikene terminated metal oxide nanoparticles. Typically, the concentration of the abrasive particles is less than about 70 wt.% of the polishing pad material composition of the polishing element 204b, such as less than about 50 wt.%, such as between about 1 wt.% and about 50 wt.%, between about 1 wt.% and about 40 wt.%, between about 1 wt.% and about 30 wt.%, between about 1 wt.% and about 20 wt.%, between about 1 wt.% and about 10 wt.%, for example between about 1 wt.% and about 5 wt.%. Herein, the surface functionalized abrasive particles are uniformly distributed throughout the polishing elements 204b-c.

[Θ044] in other embodiments, the surface functionalized abrasive particles are uniformly distributed in the portion of the polishing elements 204b-c extending from the surface of the sub-polishing elements 206b-c and abrasive particles are not included in the polishing pad material in the portion of the polishing element 204b-c extending beneath the surface of the sub-polishing element 208b-c. in other embodiments, the concentration of the abrasive particles increases or decreased from first ends of the polishing elements 204b-c to second ends of the polishing elements 204b-c distal from the first ends where the second ends form polishing surfaces of the IA polishing pads 200b-c. In other embodiments, the abrasive particles are disposed in abrasive layers of the polishing elements with layers of pad material (non-abrasive layers) comprising no abrasive particles, or lower concentrations of abrasive particles, disposed therebetween. In some embodiments, the IA polishing pads 200b-c further include abrasive particles disposed in, and chemically bonded to, the polishing pad material compositions of the sub-polishing elements 206b-c.

[0045] Typical polishing pad material composition properties that may be adjusted using the methods and material compositions described herein include storage modulus E, loss modulus E", hardness, tan 5, yield strength, ultimate tensile strength, elongation, thermal conductivity, zeta potential, mass density, surface tension, Poison's ratio, fracture toughness, surface roughness (R _a ), glass transition temperature (Tg) and other related properties. For example, storage modulus E', influences polishing results such as the removal rate from, and the resulting uniformity of, the material layer surface of a substrate. Typically, polishing pad material compositions having a medium or high storage modulus E' provide a higher removal rate for dielectric films used for PMD, ILD, and STI, and cause less undesirable dishing of the upper surface of the film material in recessed features such as trenches, contacts, and lines. Polishing pad material compositions having a low storage modulus E' generally provide more stable removal rates across the polishing pad lifetime, cause less undesirable erosion of a planer surface in areas with high feature density, and cause reduced micro scratching of the material surface. In general, polishing pad material compositions with a low storage modulus are unsuitable as a binder material for the abrasive particles of a conventional fixed abrasive polishing pad as the abrasive particles can more easily escape the softer pad material than with a hard, high storage modulus E\ conventional epoxy resin type of supporting material. Characterizations as a low, medium, or high storage modulus E' pad material composition at temperatures of 30 °C (E'30) and 90 °C (E'90) are summarized in Table 1 :

Table 1

[0046] Typically, the sub-polishing elements 206b-c are formed from materials different from the materials forming the polishing elements 204b-c, such as materials having a low (soft) or moderate storage modulus E ^" , The polishing elements 204b-c are typically formed from materials having a medium or high (hard) storage modulus E\ With a standard non-abrasive polishing pad and slurry process, medium or high storage modulus polishing materials are generally necessary to maintain desirable material removal rates when polishing dielectric materials, such as SiOj. This is because the harder pad materials more effectively hold or support the loose abrasive particles against the material surface of the substrate when compared to a softer pad that will allow the abrasive particles to sink below the pad surface as the pad material deforms when a downforce pushes the substrate against the surface of the polishing pad. Also, it has been found that CMP processes that use soft or low storage modulus E ^" polishing pads tend to have non-uniform pianarization results due to the relative ease that a soft or low storage modulus E' polishing pad deforms under the applied force generated by the carrier ring 259 (Figure 2A) and the applied force generated by the flexible diaphragm 261 during a CMP process. In other words, the soft, flexible and low storage modulus E' nature of the material used to form the soft or low storage modulus E' polishing pad allows the effect that the force, supplied by the carrier ring 259, to be minimized, which improves the ability of the pad to compensate for carrier ring downforce. Likewise, conventional fixed abrasive polishing pads typically utilize a material that has a high hardness value to physically hold the abrasive particles in place. However, it has been found that CMP processes that use "hard" polishing pad materials tend to have non-uniform planarization results due to edge effects found at the edge of the polished substrate 260 (Figure 2A) that specifically relate to the need to apply a force to the carrier ring 259 (Figure 2A) to compensate for a larger inherent polishing non- uniformity found at the edge of the substrate during a CMP process, if is believed that one of the benefits of the IA polishing pads described herein is the ability to maintain high removal rates and low erosion where the polishing elements 204b-c comprise a polishing pad material composition having a tuned and/or controlled low or medium storage modulus E. This is because the desirably positioned abrasive particles, will be held at the pad surface, through covalenf bonding thereto, instead of sinking into the soft pad material as with a standard soft polishing pads and slurry process. By holding the abrasive particles at the polishing surface of a soft pad material, the chemical activity between the abrasive particle and the material surface of the substrate, such as a between a ceria particle and an S1O ₂ substrate surface, can be maintained to enable a reasonable material removal rate. Therefore, in some embodiments the polishing elements 204b-c will have a low or medium storage modulus E'. However, it is also recognized that surface functionalized abrasive particles act as a crossiinking reagent between polymer chains formed from the radiation curable resin precursor composition, in some embodiments, this function as a crossiinking reagent will lead to a higher storage modulus E' for the polishing elements 204b-c, depending on the loading of the polymerizable terminated bonding sites, such as aikene terminated bonding sites, on the abrasive particle and/or the concentration of the surface functionalized abrasive particles in the radiation curable resin precursor composition. Therefore, in some embodiments, it is desirable to limit the loading (% of polymerizable group terminated bonding sites on surfaces of the abrasive particles) of the po!ymeraizable group, such as the loading of aikene terminated groups, to less than about 10%, such as less than about 5 %, for example between 2% and 5%.

[00473 in addition to anchoring abrasive particles to the polishing surfaces of the polishing elements 204b-c, by chemically bonding the abrasive particles to the polishing material thereof, functionalizing the surfaces of the abrasive particles also increases the chemical compatibility of the precursor compositions used to manufacture the polishing pads in an additive manufacturing process, such as the 3D inkjet printing process described in Figures 3A-3C.

[0048] Figure 3A is a schematic sectional view of an additive manufacturing system 350 used to form an IA polishing pad, such as IA polishing pads 200b-c, according to embodiments disclosed herein. Herein, the additive manufacturing system 350 has a first printer 360 and a second printer 370 for dispensing droplets of a first precursor composition 359 and a second precursor composition 369 through one or more dispense nozzles 335. The printers 360 and 370 move independently of one another and independently of a manufacturing support 302 during the printing process which enables the placement of droplets of the precursor compositions 359 and 369 at selected locations on the manufacturing support 302 to form a polishing pad, such as the IA polishing pads 200b-c. The selected locations are collectively stored as a CAD-compatibie printing pattern which is readable by an electronic controller 305 which directs the motion of the manufacturing support 302, the motion of the printers 360 and 370, and delivery of the droplets from the nozzles 335,

[0049] Typically, the first precursor composition 359 is used to form the sub- polishing elements 206b~c and the second precursor composition 369 is used to form the plurality of polishing elements 2Q4b-c of the IA polishing pads 200b-c shown in Figures 2B-2C. Herein, the first and second precursor compositions 359 and 369 each comprise a mixture of one or more of functional polymers, functional oligomers, monomers, and/or reactive diluents that are at least monofunctiona!, and undergo polymerization when exposed to free radicals, Lewis adds, and/or electromagnetic radiation. In some embodiments, the first and/or second precursor compositions 359 and 369 further comprise one or more photoinifiators.

[OOSQ] In embodiments described herein, the second precursor composition 369 further comprises surface functionalized abrasive particles, such as surface functionalized ceria particles, surface functionalized alumina particles, surface functionalized silica particles, surface functionaiized silica/alumina oxide particles, or combinations thereof, and one or more dispersion and/or suspension agents. In addition to enabling the chemical bonding of abrasive particles to the polishing pad materia! of the polishing elements described herein, surface functionalization of abrasive particles increases the compatibilities thereof with typical organic liquid resin precursor compositions. This increased compatibility is the result of converting at least a portion of the hydrophilic hydroxyl surface terminated sites of the abrasive particles to hydrophobic po!ymerizable organic groups. This increased compatibility enables the surface functionalized abrasive particles described herein to enter into a suspension comprising a liquid precursor composition and remain suspended therein, forming a highly stable and homogeneous suspension.

[0051] In addition, functiona!izing the surfaces of the abrasive particles desirably increases the thermal stability and/or chemical compatibility of precursor composition suspensions. While not wishing to be bound to any particular theory, it is believed that unmodified abrasive particles act as a catalyst for polymerization (by initiating a thermal curing reaction at typical dispensing temperatures) of at least a portion of the components within a precursor composition. This premature polymerization undesirably increases the viscosity of the precursor composition which creates difficulties, such as nozzle dogging, when dispensing droplets thereof. Precursor compositions comprising surface functionalized abrasive particles, with as few as less than about 5% of the abrasive particle's bonding sites bonded to po!ymerizabie groups, such as between about 2% and about 5%, have increased thermai stability and/or chemical compatibility (i.e. improved viscosity for dispensing through the printer nozzles) when compared to precursor compositions comprising untreated abrasive particles.

[0052] Herein, the concentration of the surface functionalized abrasive particles in at least the second precursor composition 389 is desirably maintained at between about 1 % and about 50% by weight, such as between about 1 wt.% and about 40 wt.%, between about 1 wt. % and about 30 wt. %, between about 1 wt.% and about 20 wt.%, between about 1 wt.% and about 10 wt.%, or between about 1 wt.% and about 5 wt.%, for example less than about 10 wt.% or less than about 5 wt.%. in other embodiments, the surface functionalized abrasives comprise less than about 70 wt.% of the first precursor composition 359. In other embodiments, surface functionalized abrasive particles and unmodified abrasive particles comprise less than about 70 wt.% of the first precursor composition 359.

[0053] Herein, functional polymers include multifunctional acrylates including di, tri, tetra, and higher functionality acrylates, such as 1 ,3,5-triacryloylhexahydro- 1 ,3,5-triazine or frimethylolpropane triacry!ate.

[0054] Functional oligomers include monofunctional and multifunctional oligomers, acrylate oligomers, such as aliphatic urethane acrylate oligomers, aliphatic hexafunctional urethane acrylate oligomers, diacrylate, aliphatic hexafunctional acrylate oligomers, multifunctional urethane acrylate oligomers, aliphatic urethane diacrylate oligomers, aliphatic urethane acrylate oligomers, aliphatic polyester urethane diacrylate blends with aliphatic diacrylate oligomers, or combinations thereof, for example bisphenoi-A ethoxyiate diacrylate or poiybutadiene diacrylate. in one embodiment, the functional oligomer comprises tetrafunctional acrylated polyester oligomer available from Al!nex Corp. of Aipharetta, GA as EB4G® and the functional oligomer comprises an aliphatic polyester based urethane diacrylate oligomer available from Sartomer USA of Exton, PA as CN991.

[0055] Monomers include both mono-functional monomers and multifunctional monomers. Mono-functional monomers include tetrahydrofurfuryl acrylate (e.g. SR285 from Sartomer®), tetrahydrofurfuryl methacryiate, vinyl caprolactam, isobornyl acrylate, isobornyl methacryiate, 2-phenoxyethy! acrylate, 2- phenoxyethyi methacryiate, 2-(2-ethoxyethoxy)ethyl acrylate, isooctyl acrylate, isodecyl acrylate, isodecyl methacryiate, iauryi acrylate, iaury! methacryiate, stearyl acrylate, stearyl methacryiate, cyclic trimethylolpropane formal acrylate, 2- [[(Butylamino) carbonyljoxyjethyl acrylate (e.g. Genomer 1122 from RAHN USA Corporation), 3,3,5-frimethylcyclohexane acrylate, or mono-functional methoxylated PEG (350) acrylate. Multifunctional monomers include diacrylates or dimethacry!ates of diois and polyether diols, such as propoxyiated neopenfyi glycol diacrylate, 1 ,8-hexanediol diacrylate, 1 ,6-hexanediol dimethacryiate, 1 ,3- bufylene glycol diacrylate, 1 ,3-butylene glycol dimethacryiate 1 ,4-butanediol diacrylate, 1 ,4-butanediol dimethacryiate, alkoxylated aliphatic diacrylate (e.g., SR9209A from Sartomer®), diethylene glycol diacrylate, diethylene glycol dimethacrylaie, dipropyiene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacr late, alkoxylated hexanediol diacrylates, or combinations thereof, for example SR582, SR563, SR564 from Sartomer®.

[0056] Reactive diluents include monoacrylate, 2-ethylhexyl acrylate, octyidecyl acrylate, cyclic trimethylo!propane formal acrylate, caprolactone acrylate, isobornyl acrylate (IBOA), or alkoxylated lauryl methacrylate.

[0057] Photoinitiators used herein include polymeric photoinitiators and/or oligomer photoinitiators, such as benzoin ethers, benzyl ketals, acetyl phenones, alkyl phenones, phosphine oxides, benzophenone compounds and thioxanthone compounds that include an amine synergist, or combinations thereof. For example, in some embodiments photoinitiators include Irgacure® products manufactured by BASF of Ludwigshafen, Germany, such as Irgacure 819, Irgacure 784, irgacure 379, Irgacure 2022, Irgacure 1173, Irgacure 500, combinations thereof, or equivalent compositions.

[0058] Dispersion and/or suspension agents are typically used to stabilize the abrasive particles within a liquid suspension, for example by increasing the electrostatic repulsion (zeta potential) between abrasive particles. Dispersion and/or suspension agents can be used to enable the homogenous suspension of surface functionalized abrasive particles in the liquid of the precursor compositions 359 and 369. Examples of dispersion and/or suspension agents include Hyper® products, such as HypermerKD4 and Hyper KD57, available from Croda, inc., of New Castle, Delaware, USA, or BYK Dis2008, BYK JET-9151 , or BYK JET-9152 available from BYK-Gardner GmbH of Germany.

[0059] Typically, layers formed of the droplets of the precursor compositions 359 and 369 dispensed by the printers 360 and 370 are cured by exposure to radiation 321 from a radiation source 320, such as an ultraviolet light (UV) source, x~ray source, or other type of electromagnetic wave source. Herein, the radiation 321 is UV radiation provided by a UV source. In other embodiments, the precursor compositions 359 and/or 369 are cured by exposure to thermal energy. [0060] Figures 3B illustrates a curing process using the additive manufacturing system 350 of Figure 3A. Figure 3B shows a portion of one or more previously formed layers 346 of a polishing element, such as polishing element 204b-c, disposed on the manufacturing support 302. During processing, the printers 380 and 370 deliver a plurality of droplets 343 of one or more precursor compositions, such as the second precursor composition 369, to a surface 346A of the one or more first layers 346. The plurality of droplets 343 form one of a plurality of second layers 348 which, in Figure 3B, includes a cured portion 348A and an uncured portion 348B where the cured portion has been exposed to radiation 321 from the radiation source 320. Herein, the thickness of the cured portion 348A of the first layer is between about 0.1 micron and about 1 mm, such as between about 5 microns and about 100 microns, for example between about 25 microns and about 30 microns.

[0061] Figure 3C is a close up cross-sectional view of a droplet 343 dispensed onto the surface 348A of the one or more previously formed layers 346. As shown in Figure 3C, once dispensed onto the surface 346A, the droplet 343 spreads to a droplet diameter 343A having a contact angle a. The droplet diameter 343A and contact angle a are a function of at least the material properties of the precursor composition, the energy at the surface 348A (surface energy) of the one or more previously formed layers 348, and time although the droplet diameter 343A and the contact angle a will reach an equilibrium after a short amount of time, for example less than about one second, from the moment that the droplet contacts the surface 346A of the one or more previously formed layers 346. In some embodiments, the droplets 343 are cured before reaching an equilibrium diameter and contact angle. Typically, the droplets 343 have a diameter of between about 10 and about 200 micron, such as between about 50 micron and about 70 microns before contact with the surface 346A and spread to between about 10 and about 500 micron, between about 50 and about 200 microns, after contact therewith.

[0062] Herein, the precursor compositions 359 and 369 are formulated to have a viscosity between about 80 cP and about 110 cP at about 25 °C, between about 15 cP and about 30 cP at about 70 °C, or between 10 cP and about 40 cP for temperatures between about 50 °C and about 150 °C so that the mixtures may be effectively dispensed through the dispense nozzles 335 of the printers 360 and 370. In some embodiments, the second precursor composition 369 is recirculated or otherwise mechanically agitated to ensure that the surface functionaiized abrasive particles remain homogenously suspended in the liquid precursor mixture.

[0063] Figures 4A-4B illustrate the properties of a layer formed from a precursor mixture comprising surface functionaiized abrasive particles formed according to embodiments described herein. Figure 4A is a TEM of a layer of polishing materia! having surface functionaiized abrasives disposed therein formed using the embodiments described in Figures 3A-3C from a precursor having a formulation described in Table 2. In this embodiment, the surface functionaiized ceria particles and a suspension agent were mixed in an acrylic monomer (I BOA) to form a mixture. The mixture was milled using a probe sonicator to break up larger agglomerations of the ceria particles into smaller agglomerations or individual particles having a mean diameter between about 30 nm and about 300 nm. In other embodiments, other types of milling processes, for example ball milling, are used to reduce larger agglomerations of abrasive particles to desirable sizes either before, during, or after mixing of the precursor. After milling, the remaining components of Table 2 were added to the mixture to form the precursor composition which was homogenized by uitrasonication so that the surface functionaiized abrasive particles were uniformly distributed therein. As shown in the images in Figure 4A the ceria particles have a uniform distribution within the printed layer. Figure 4B shows an EDX spectra of the ceria particles (shown in inset image 420) disposed in the layer formed from the precursor shown in Table 2 where Ce, O, and Si signals are attributable to ceria particles and the bonded dimethyl vinyl silane group which indicates successful surface functionalization of the treated ceria particle surfaces with the poiymerizable dimethyl vinyl silane group. Table 2

[0064] Figure 5 is a flow diagram illustrating a method 500 of forming a polishing pad, such as IA polishing pads 200b-c of Figure 2A-2B, according to embodiments described herein. At activity 510 the method includes dispensing a first plurality of droplets of a first precursor, such as the first precursor 359 described in Figures 3A-3C. Herein, the first precursor comprises a curable resin composition and is a mixture of one or more functional polymers, functional oligomers, monomers, reactive diluents, or combinations thereof. In this embodiment, the first precursor further comprises one or more photoinitiators to enable curing of the dispensed first plurality of droplets using UV radiation. Herein, the precursors used in method 500 have a viscosity between about 80 cP and about 10 cP at about 25 °C, between about 15 cP and about 30 cP at about 70 °C, or between 10 cP and about 40 cP for temperatures between about 50 °C and about 150 °C enabling droplets therefrom to be dispensed through dispense nozzles 335 of the printer 360, [0065] At activity 520 the method 500 includes curing the first plurality of droplets to form one of a plurality of first layers, such as the one or more previously formed layers 346 shown in Figures 3B-3C, the one of the plurality of first layers herein comprising a portion of a sub-polishing element, such as the sub-polishing elements 206b-c of IA polishing pads 200b-c. Herein, the plurality of first droplets are cured by exposure to UV radiation from a UV radiation source, such as radiation source 320, having a wavelength of between about 170 nm and about 500 nm,

[0066] At activity 530 the method 500 includes dispensing a second plurality of droplets of the first precursor and a second precursor onto the plurality of first layers, the second precursor comprising surface functionaiized abrasive particles having at least one polymerizable group chemically bonded to the surfaces thereof. Herein, the surface functionaiized abrasive particles comprise the reaction product of hydroxy! terminated metal oxide nanoparticles, such as ceria, with an organic compound, such as a silane organic compound, a cyanate compound, a sulfonic acid compound, a phosphoric acid organic compound, a carboxyiic acid compound, or combinations thereof. In some embodiments, the reaction product of the hydroxyl terminated metal oxide nanoparticles and the organic compound forms an alkene terminated abrasive particle. In this embodiment, the loading (% of surface sites chemically bonded to a polymerizable compound) is less than about 50%, for example less than about 50% of the surface sites are alkene terminated, and the concentration of surface functionaiized abrasive particles in the second precursor is between about 1 wt.% and about 50 wt.%. In another embodiment, the total concentration of abrasive particles, including non-functionalized abrasive particles in the second precursor is less than about 70%.

[0067] Typically, the second precursor comprises a mixture of one or more one or more functional polymers, functional oligomers, monomers, reactive diluents, or combinations thereof. in this embodiment, the second precursor further comprises a photoinitiator to enable UV curing and a dispersion and/or suspension agent to stabilize the functionaiized abrasive particles in the second precursor mixture, and to maintain their suspension therein. In this embodiment, the surface functionaiized abrasive particles, or agglomerations thereof, have a mean diameter of between about 10 nm and about 5 micron, such as between about 30 nm and 500 nm, such as between about 30 nm and 300 nm, for example between about 100 nm and about 50 nm.

[0068] At activity 540 the method 500 includes curing the second plurality of droplets to form a second layer, the second layer comprising portions of the sub- polishing element and portions of a plurality of polishing elements, such as the second polishing elements 204b-c. Herein, curing the second plurality of droplets comprises exposing the second plurality of droplets to UV radiation thereby polymerizing the second plurality of droplets and forming chemical bonds at the interfaces therebetween. In this manner, chemical bonds, such as covalent and/or ionic bonds, are formed between polymer materials comprising portions of the sub-polishing element and polymer materials comprising portions of the polishing elements at the interfaces thereof. Further, the surface functionaiized abrasive particles serve as a crosslinking reagent between reaction products of the second precursor mixture by forming chemical bonds therewith.

[0069] The method described above is used with the IA polishing pads described herein or with any polishing pad where chemically bonding abrasive particles to the polishing pad material is desired. Benefits of the method include forming IA polishing pads with tunable polishing properties that are compatible with diamond conditioning during, before, or after a CMP process. Other embodiments comprise forming IA polishing pads by delivering droplets containing different precursors that have differing concentrations of abrasive particles so that the abrasive particle concentration can be varied across the surface of the polishing pad material as shown in Figure 6.

[007Q] Figure 6 is a schematic top view of an IA polishing pad 800 used with web based or roli-to-roil type polishing system. The IA polishing pad 600 is formed using an additive manufacturing system, such as the additive manufacturing system 350 shown in Figures 3A-3B. Herein, the IA polishing pad 600 is disposed over a polishing platen 652 between a first roll 681 and a second roll 682, The IA polishing pad 600 comprises a concentration gradient of abrasive particles bonded to the polishing pad material thereof across a polishing surface 608. Herein, the IA polishing pad 600 has a first region 602 comprising a low concentration of abrasive particles, a second region 604 comprising a high concentration of abrasive particles, and intermediate regions 603 comprising intermediate concentrations of abrasive particles. The regions 602 to 604 of varying concentrations of abrasive particles are formed according to embodiments herein from a plurality of precursor compositions, each comprising a different concentration of surface functionalized abrasive particles. In other embodiments, the regions of varying concentrations are formed by alternating droplets of a precursor composition comprising a high concentration of abrasive particles with a precursor composition comprising a low concentration of abrasive particles.

[0071] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.