Textured cmp pad comprising polymeric particles

Abstract

A chemical mechanical polishing pad comprising a polishing portion, the polishing portion comprising: a polymeric body; a plurality of polymeric particles embedded within a bulk of the polymeric body, wherein at least a portion of the plurality of polymeric particles is at least partially exposed to a surface of the polymeric body; and a plurality of pores at the surface of the polymeric body.

Description

Technical Field

[0001] This disclosure is generally about polishing pads for chemical mechanical planarization, and more specifically about textured CMP pads containing polymer particles. Attached Figure Description

[0002] To aid in understanding this disclosure, reference is now made to the following description taken in conjunction with the accompanying drawings, wherein:

[0003] Figure 1 This is a diagram of an example system of chemimechanical planarization;

[0004] Figure 2A This is a diagram of an example CMP pad that reveals the content of this document;

[0005] Figure 2B yes Figure 2A A surface unfolded diagram of the CMP pad;

[0006] Figure 3 This is a block diagram illustrating the example mixture used to prepare the example CMP pad of Figure 2;

[0007] Figure 4 This is a flowchart illustrating an example method for preparing a polishing portion of a CMP pad, preparing a CMP pad having the polishing portion, and using the CMP pad;

[0008] Figure 5 This is a graph showing the relationship between average hardness and the amount of copolymer polyol (CPP) curing agent added to the mixture used to prepare CMP pad samples;

[0009] Figure 6A and 6B It is a graph showing the elastic modulus of the sample prepared at different temperatures using different amounts of CPP curing agent included in the mixture used to prepare the sample;

[0010] Figure 7A This is a SEM image of the surface of a traditional CMP pad;

[0011] Figure 7B This is a SEM image of the surface of an example of the CMP pad described in this disclosure. Detailed Implementation

[0012] First, it should be understood that although exemplary implementations of the embodiments of this disclosure are described below, this disclosure can be implemented using any number of techniques, whether currently known or unknown. This disclosure should not be limited in any way to the exemplary implementations, drawings, and techniques described below. Furthermore, the drawings are not necessarily drawn to scale.

[0013] Integrated circuits are typically formed on a substrate by sequentially depositing conductive, semiconductive, and / or insulating layers on a silicon wafer. Various manufacturing processes require planarization of at least one of these layers on the substrate. For example, for some applications (e.g., polishing metal layers to form vias, plugs, and lines in trenches of patterned layers), the overlay is planarized until the top surface of the patterned layer is exposed. In other applications (e.g., planarizing dielectric layers for photolithography), the overlay is polished until the desired thickness remains on the underlying layer. Chemical mechanical planarization (CMP) is one method of planarization. This planarization method typically involves mounting a substrate on a carrier head. The exposed surface of the substrate is typically placed against a polishing pad on a rotating stage. The carrier head provides a controlled load (e.g., applies force) on the substrate to press it against the rotating polishing pad. During polishing, a polishing liquid, such as a slurry containing abrasive particles, may also be applied to the surface of the polishing pad.

[0014] Polishing pads typically consist of a polished surface that contacts the polished surface during polishing. Previously polished surfaces of CMP pads may exhibit uneven polishing properties throughout their lifetime. For example, if the material removal rate decreases with increasing CMP pad lifetime, it may be difficult to reliably perform the CMP process. Variations in the properties of the polished surface can lead to variable and uncontrollable polishing properties in the CMP pad and corresponding variable and uncontrollable CMP results, such as inconsistent material removal rates from the planarized / polished wafer.

[0015] This disclosure identifies that controlling the properties of the microstructure of the polished surface of an improved CMP pad can provide more reliable and improved CMP performance. For example, this disclosure identifies that CMP pads with polymer particles embedded in the top polishing layer help improve the adjustability of the pad material and make the pad surface easier to clean, because as the polishing surface layer is gradually removed due to prolonged use, the embedded particles begin to be exposed. Over time, this contributes to a more consistent surface texture and correspondingly more consistent CMP performance. The embedded polymer particles also provide an increased polishing surface area through the prominent surface features caused by the polymer particles exposed on the CMP pad surface and the porous surface features caused by the polymer particles removed from the CMP pad surface (see [link to relevant documentation]). Figure 2A and 2B (and the corresponding description below). The increased surface area and roughness improve CMP performance.

[0016] Chemical mechanical planarization system

[0017] Figure 1A system 100 for performing chemical mechanical planarization is described. System 100 includes a CMP pad 200 (also referred to as a “polishing pad,” see also Figure 2 and the corresponding description below) placed on or attached to a platform 104. For example, the CMP pad 200 can be attached to the platform 104 using an adhesive layer (not shown). The platform 104 is generally rotatable during chemical mechanical planarization. A wafer 106 (e.g., a silicon wafer with or without conductive, semiconductor, and / or insulating layers as described above) is attached to the head 108 of a rotatable chuck. The wafer 106 can be attached using a vacuum and / or a reversible adhesive (e.g., an adhesive that holds the wafer 106 in place during chemical mechanical planarization but allows the wafer 106 to be removed from the head 108 after chemical mechanical planarization). Figure 1 As shown, pressure can be applied to the wafer 106 during chemical mechanical planarization (e.g., to enhance the contact between the surface of the wafer 106 and the CMP pad 200). The regulator 112 generally contacts the surface of the polishing pad 102 and removes a portion of the top layer of the polishing pad 102 to improve its performance during chemical mechanical planarization.

[0018] Example CMP pad 200 is described in Figure 2A and 2B The details are described below in more detail. In simple terms, the CMP pad 200 generally has a circular or near-cylindrical shape (i.e., a top surface, a bottom surface, and curved edges). The CMP pad 200 may comprise polyurethane (e.g., elastic or rigid polyurethane). Examples of compositions and methods for preparing the example CMP pad 200 are provided below. Figure 3 and 4 Detailed description follows. The CMP pad 200 can have any suitable thickness and any suitable diameter (e.g., for use with a CMP system, such as system 100). For example, the thickness of the CMP pad 200 can range from less than or about 0.5 mm to greater than 5 cm. In some embodiments, the thickness of the CMP pad 200 can range from 1 mm to 5 mm. The polishing pad diameter is generally selected to match or be just smaller than the diameter of the platform 104 of the polishing system 100 used. The CMP pad 200 generally has a uniform or nearly uniform thickness (e.g., a thickness varying by no more than 50%, 25%, 20%, 10%, 5%, or less in the radial range of the polishing pad).

[0019] The slurry 110 may be provided on the surface of the CMP pad 200 prior to and / or during chemical mechanical planarization. The slurry 110 may be any suitable slurry for planarizing wafer-type materials and / or layers to be planarized (e.g., removing a silicon oxide layer from the surface of the wafer 106). The slurry 110 generally comprises fluid and abrasive and / or chemically reactive particles. Any suitable slurry 110 may be used. For example, the slurry 110 may react with one or more materials removed from the planarized surface.

[0020] Adjuster 112 is a device configured to adjust the surface of the CMP pad 200. Adjuster 112 generally includes a contact layer with the top layer of the CMP pad 200 (e.g., as described below). Figure 2A and Figure 2B The conditioner 112 can be used to roughen the surface of the CMP pad 200 by removing a portion of the top layer (or top pad 202) and improving its performance during chemical mechanical planarization. For example, the conditioner 112 can roughen the surface of the CMP pad 200. The novel CMP pad 200 with polymer particles embedded in the top layer described in this disclosure may require less adjustment of the conditioner 112 than previous CMP pads because proper surface texture remains consistent as the top layer is removed and the embedded particles are exposed during the CMP process.

[0021] Example polishing pad

[0022] Figure 2A and 2B Example CMP pad 200 is illustrated from a cross-sectional side view. Example CMP pad 200 includes a top pad 202 and a bottom pad 214. The CMP pad 200 generally has a circular or approximately cylindrical shape. The thickness of the CMP pad 200 can be any suitable value, for example, in the range from about 1 mm to about 10 mm or greater. The diameter of the CMP pad 200 can be any suitable value, for example, in the range from about 500 mm to about 800 mm or greater. The CMP pad 200 generally has a uniform thickness. Uniform thickness is defined as a thickness that varies by no more than 50%, 25%, 20%, 10%, 5%, or less in the radial direction of the CMP pad 200. In other words, the thickness measured near the center of the CMP pad 200 is substantially the same as the thickness near the edge of the CMP pad 200.

[0023] The top pad 202 is the polished portion of the CMP pad 200 and interacts with the planarized / polished surface (e.g., as described above) during the CMP process. Figure 1 (Surface contact of wafer 106). Figure 2AAs depicted in the side view, the top pad 202 includes a polymeric body 206 in which a plurality of polymer particles 204 are embedded. The polymeric body 206 may be a polyurethane material, such as thermosetting polyurethane, or any other suitable material. The polymer particles 204 may be any suitable polymer. In some embodiments, the polymer particles 204 comprise poly(styrene-acrylonitrile) (SAN). The concentration of polymer particles 204 in the polymeric body 206 may be from 0.5 wt% to 40 wt% (e.g., 1 wt% to 30 wt%, 5 wt% to 25 wt%). The polymer particles 204 may be approximately spherical, with a diameter ranging from 10 nanometers to about 50 micrometers (e.g., 50 nanometers to 20 micrometers, 100 nanometers to 1000 nanometers).

[0024] like Figure 2B As shown in the unfolded diagram 210, at least a portion of the polymer particles 204 are at least partially exposed on the surface 212 of the polymer body 206 near the surface 212 of the top pad 202. The surface 212 also includes a plurality of holes 208 on the surface of the polymer body 206. When the polymer particles 204 are removed from the surface 212 (e.g., during processing, planarization / polishing processes, and / or by...), Figure 1 During adjustment of the regulator 112, the pores 208 can be formed. The presence of the polymer particles 204 provides numerous technical benefits. For example, the roughness of the surface 212 can be increased by the presence of both the pores 208 and the polymer particles 204 (see also...). Figure 7A and 7B (and the corresponding description below). Furthermore, during use of the CMP pad 200, the roughness of the surface 212 can remain at a relatively consistent value when material is removed from the top pad 202. For example, since the pores 208 and / or polymer particles 204 can be exposed more deeply within the surface 212 of the top pad 202, the roughness can remain relatively constant as material is removed from the top pad 202. In some cases, the elasticity and / or other mechanical properties of the top pad 202 can be modulated via the presence of the polymer particles 204 (see also...). Figure 5 , 6A (and 7B and the corresponding description below). For example, the concentration and / or size of the polymer particles 204 can be selected to obtain the elasticity, hardness, etc. required for a given application (e.g., for the removal and / or planarization / polishing of a given material).

[0025] The material of the top pad 202 may be porous or non-porous. The top pad 202 may be formed, for example, by forming a thermosetting polyurethane foam, or by including a filler material (e.g., as shown below) in the polyurethane composition. Figure 3The described pore-forming filler 310) or via the inclusion of hollow microspheres (e.g., as referred to below) in the polyurethane composition Figure 3 The top pad 202 is prepared using the described polymeric microsphere filler 310. Porous embodiments of the top pad 202 can have substantially any suitable porosity, for example, from about 5 to about 60 volume percentages (e.g., from about 10 to about 50 volume percentages, from about 15 to about 50 volume percentages, or from about 20 to about 40 volume percentages). Non-porous embodiments of the top pad 202 generally have a porosity of less than about 5 volume percentages.

[0026] In some cases, the surface 212 of the top pad 202 may include grooves or any other suitable structure or pattern to facilitate CMP processes. For example, grooves may facilitate the transport of any other product processed by etched material and / or CMP processes away from the surface 212 of the top pad 202 and the planarized wafer 106. The top pad 202 may have any suitable thickness. For example, the thickness of the top pad 202 may range from about 0.2 mm to about 5 mm.

[0027] The lower pad 214 can provide relatively compressible support for the upper pad 202. The lower pad 214 can be made of polyurethane material, such as thermosetting polyurethane. The lower pad 214 can have any suitable thickness. For example, the thickness of the lower pad 214 can range from about 0.2 mm to about 5 mm.

[0028] The top pad 202 and the bottom pad 214 may or may not be secured together with an adhesive to form the CMP pad 200. For example, when using an adhesive, the top pad 202 can be secured to the bottom pad 214 by a thin layer of adhesive (e.g., a layer of pressure-sensitive adhesive (e.g., tape, glue, etc.)). Other adhesives may also be used, or alternatively, as appropriate. For example, the adhesive may be a hot-melt adhesive, or the top pad 202 and the bottom pad 214 may be joined by laminating a thin layer of thermoplastic material between the top pad 202 and the bottom pad 214. For CMP, a platform adhesive can be used to secure the CMP pad 200 to... Figure 1 Platform 104 is shown in the figure.

[0029] In some embodiments, CMP pad 200 may include more or fewer layers. For example, in some embodiments, CMP pad 200 does not include the lower pad 214. In other embodiments, CMP pad 200 may include additional layers not shown in FIG2.

[0030] Composition for preparing textured CMP pad surfaces

[0031] Figure 3An example mixture 300 for preparing the top pad 202 and CMP pad 200 of FIG. 2 is described. The mixture 300 includes a prepolymer 302, a first curing agent 304 that can be mixed with polymer particles 306, a second curing agent 308, and any optional filler 310.

[0032] The prepolymer 302 may be an isocyanate-terminated urethane prepolymer. The prepolymer 302 can be prepared by reacting a polyfunctional aromatic isocyanate with a prepolymer polyol. Examples of polyfunctional aromatic isocyanates may include toluene diisocyanate (TDI) compounds such as 2,4-TDI, 2,6-TDI, and mixtures thereof; methylene diphenyl diisocyanate (MDI) compounds such as 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI (also referred to in the art as 4,4'-diphenylmethane diisocyanate) and mixtures thereof; naphthalene-1,5-diisocyanate; bitoluidine diisocyanate; terephthalic diisocyanate; phenyl dimethyl diisocyanate; and mixtures thereof. The polyol prepolymer 302 may include generally suitable diols, polyols, polyol-diols, copolymers thereof, and mixtures thereof. For example, the polyol prepolymer 302 may include polytetramethylene ether glycol (PTMEG), polypropylene ether glycol (PPG), ethylene oxide-terminated PTMEG or PPG, polycaprolactone, ester-based polyols such as ethylene glycol adipate or butylene glycol adipate, copolymers thereof, and mixtures thereof. It should be understood that suitable polyols such as PTMEG and PPG can be mixed with low molecular weight polyols (including ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, tripropylene glycol) and mixtures thereof.

[0033] The first curing agent 304 may be a copolymer polyol (CPP) curing agent. CPP is produced by polymerizing one or more unsaturated monomers in a polyol through free radical polymerization. The first curing agent 304 may be a fluid mixed with polymer particles 306. The polymer particles 306 may be the same as the polymer particles 204 in FIG. 2. For example, the polymer particles 306 may be polystyrene, copolystyrene and acrylonitrile, polyurethane or polyurea particles, etc. The polymer particles 306 are generally retained in the top pad 202 of the CMP pad 200 (e.g., in their original form or modified during the formation of the CMP pad 200 by exposure to other components 302, 308, 310 of the mixture 300 during mixing, exposure to heat, exposure to mechanical forces, etc.). Adding SAN polymer particles 306 to the mixture 300 can produce a harder and more resilient CMP pad 200 than would be achieved by using the first curing agent 304 alone.

[0034] The limited solubility of the polymer particles 306 (e.g., SAN polymer) in the first curing agent 304 leads to phase separation, resulting in the polymer particles 306 being uniformly distributed in the first curing agent 304. During polymerization (see...) Figure 4 The free radical initiator can extract hydrogen from the polyol curing agent 304 and provide free radical sites on the polyol chain. This stabilizes the polymer particles 306 in the first curing agent 304. The first curing agent 304 may include so-called "giant monomers," which are typically AB functional monomers having vinyl and hydroxyl functional groups. These giant monomers can improve the stability of the polymer particles 306 in the first curing agent 304 and prevent the aggregation of the polymer particles 306. The concentration (in solids percentage) of the polymer particles 306 in the first curing agent 304 can be as high as 50% by weight or more.

[0035] The second curing agent 308 may be a polyamine curing agent. The second curing agent 308 may comprise substantially any suitable polyamine, including, for example, diamines and other polyfunctional amines. The second curing agent 308 may be a low molecular weight polyamine curing agent. Example diamines may include aniline diamine compounds, toluene diamine compounds, aminobenzoic acid ester compounds, and mixtures thereof. Example aniline diamine compounds include 4,4-methylenebis(2-chloroaniline) (MBCA or MOCA), 4,4'-methylenebis-o-chloroaniline (MbOCA), 4,4'-methylenebis-(3-chloro-2,6-diethylaniline) (MCDEA), 4,4'-methylenebis-aniline, and 1,2-bis(2-aminophenylthio)ethane. Examples of toluenediamine compounds include dimethylthiotoluenediamine, diethyltoluenediamine, 5-tert-butyl-2,4- and 3-tert-butyl-2,6-toluenediamine, 5-tert-pentyl-2,4- and 3-tert-pentyl-2,6-toluenediamine, and chlorotoluenediamine. Examples of aminobenzoic acid ester compounds include trimethylene glycol di-p-aminobenzoate, polytetramethylene oxide di-p-aminobenzoate, polytetramethylene oxide mono-p-aminobenzoate, polypropylene oxide di-p-aminobenzoate, and polypropylene oxide mono-p-aminobenzoate. Aniline diamine compounds such as 4,4-methylenebis(2-chloroaniline) and toluenediamine compounds such as dimethylthiotoluenediamine may be preferred in some cases (although the disclosed examples are not limited in this respect).

[0036] Optional filler 310 generally includes any additional components of the mixture 300. Filler 310 can provide different physical, mechanical, and / or chemical properties to the top pad 202. Filler 310 may include lubricants and / or pore-forming agents, such as microspheres or gases. For example, filler 310 may include a pore-forming agent that forms pores in the top pad 202. Filler 310 may include a substance that reacts with polished / planarized surfaces and / or slurries applied to polished / planarized surfaces.

[0037] Figure 2A and 2B The top pad 202 shown can be manufactured using virtually any suitable pad manufacturing technique (e.g., such as...). Figure 4 As shown below (e.g., casting, molding, coating, extrusion, printing, sintering, spraying, etc.), the mixture 300 is manufactured. The disclosed pad embodiments are not limited to any particular manufacturing technique. For example, the top pad 202 can be manufactured using any of a variety of molding and casting techniques. As a non-limiting example, a first portion 312 of the mixture 300 can be prepared comprising the prepolymer 302 and any optional filler 310, and a second portion 314 of the mixture 300 can be prepared by combining the first curing agent 304 and the second curing agent 308 having polymer particles 306. The two portions 312, 314 can be prepared separately and then blended together at a predetermined blending ratio and / or temperature. The resulting mixture 300 can then be poured into a mold in which the mixture is maintained at a high temperature, for example, between about 60°C and about 160°C. The mold can optionally be arranged in a closed chamber and exposed to vacuum or pressure to expel air trapped in the poured mixture. After a predetermined time (e.g., about 10 to about 30 minutes), the top pad 202 can be removed from the mold and then cured (e.g., cured for about 6 to 12 hours at a temperature in the range of about 30°C to about 100°C).

[0038] If the CMP pad 200 includes a lower pad 214, then the appropriate lower pad 214 can be prepared simultaneously or separately using a similar molding process or any other suitable process. The top pad 202 can be attached to the lower pad 214 using any suitable mechanism (e.g., adhesive and / or heating) to prepare the CMP pad 200.

[0039] Method for preparing textured CMP pad surfaces

[0040] Figure 4 An example process 400 is described for preparing a top pad 202 having embedded polymer particles 204, a CMP pad 200 including said top pad 202, and using said CMP pad 200. The process 400 may begin at step 402, in which step 402 is prepared... Figure 3The first mixture portion 312. For example, the first mixture portion 312 can be prepared by combining the prepolymer 302 with any optional filler 310. In step 404, the second mixture portion 314 is prepared. For example, the second mixture portion 314 can be prepared by combining the first curing agent 304 having polymer particles 306 with the second curing agent 308. In step 406, the first mixture portion 312 and the second mixture portion 314 are combined to prepare mixture 300. In some embodiments, steps 402, 404, and 406 can be performed in different orders and / or combinations to prepare mixture 300.

[0041] In step 408, the top pad 202 is prepared using the mixture 300 from step 406. For example, the top pad 202 can be prepared using casting, molding, coating, extrusion, printing, sintering, spraying, etc. For example, the mixture 300 can be poured into a mold and a polymerization reaction can be initiated in the mold to form the polymeric body 206 of the top pad 202. For example, the mixture 300 can be maintained at a high temperature (e.g., between about 60°C and about 160°C). The mold can optionally be deployed in a closed chamber and exposed to vacuum or pressure to expel air trapped in the poured mixture 300. After a predetermined time (e.g., about 10 to about 30 minutes), the top pad 202 can be removed from the mold and then cured (e.g., cured for about 6 to 12 hours at a temperature ranging from about 30°C to about 100°C).

[0042] In step 410, the top pad 202 from step 408 can be combined with the bottom pad 214. The bottom pad 214 can be prepared using a process similar to or different from the process used to prepare the top pad 202. Generally, the bottom pad 214 can be prepared using casting, molding, coating, extrusion, printing, sintering, spraying, etc. The top pad 202 can be attached to the bottom pad 214 using any suitable mechanism (e.g., adhesive and / or heating) to prepare the CMP pad 200.

[0043] In step 412, the CMP pad 200 obtained from step 410 can be used for planarization / polishing processes, for example, as described above. Figure 1 Referring to FIG2, when performing a polishing / planarization process, while the embedded polymer particles 204 are exposed on the surface 212 to form exposed polymer particles 204 and / or holes 208, the surface roughness is kept relatively constant, resulting in improved and more consistent CMP results.

[0044] Example

[0045] (1) A chemical mechanical polishing pad comprising a polishing portion is provided in embodiment (1), the polishing portion comprising:

[0046] Aggregation subject;

[0047] A plurality of polymer particles embedded within the polymeric body, wherein at least a portion of the plurality of polymer particles is at least partially exposed on the surface of the polymeric body; and

[0048] Multiple pores on the surface of the polymer body.

[0049] (2) In Example (2), the chemical mechanical polishing pad of Example (1) is provided, wherein the concentration of the plurality of polymer particles embedded in the polymeric body is in the range of 0.5% by weight to 40% by weight.

[0050] (3) In Example (3), a chemical mechanical polishing pad of Example (1) or (2) is provided, wherein the polymer particles have an average size of about 10 nanometers to about 50 micrometers.

[0051] (4) A chemical mechanical polishing pad of any of the embodiments of (1) to (3) is provided in Example (4), wherein the polymeric host comprises polyurethane.

[0052] (5) A chemical mechanical polishing pad of any of the embodiments of (1) to (4) is provided in Example (5), wherein the polymer particles comprise styrene-acrylonitrile.

[0053] (6) A chemical mechanical polishing pad of any of the embodiments of (1) to (5) is provided in embodiment (6), wherein the porosity of the polished portion is in the range of about 10% to 80%.

[0054] (7) In Example (7), a chemical mechanical polishing pad of any of the embodiments of Examples (1) to (6) is provided, wherein the elastic storage modulus of the polished portion is measured at 25°C to be in the range of about 50 MPa to about 1000 MPa.

[0055] (8) A chemical mechanical polishing pad of any of the embodiments of (1) to (7) is provided in Example (8), wherein the hardness of the polished portion is in the range of about 50 Shore D scale to 80 Shore D scale.

[0056] (9) In embodiment (9), a chemical mechanical polishing pad of any of embodiments (1) to (8) is provided, which further includes a lower pad portion connected to the polishing portion.

[0057] (10) In Example (10), a method for manufacturing the polishing portion of a chemical mechanical polishing pad of any of Examples (1) to (9) is provided.

[0058] (11) The method of embodiment (10) is provided in embodiment (11), further comprising:

[0059] Prepare a first mixture containing the prepolymer;

[0060] Prepare or obtain a first curing agent containing polymer particles;

[0061] A second mixture is prepared by combining the first curing agent containing the polymer particles with a second curing agent;

[0062] Combine the first mixture with the second mixture;

[0063] Transfer the combined first and second mixtures into a mold; and

[0064] A polymerization reaction is initiated in the mold to form the polymeric body of the polishing portion of the chemical mechanical polishing pad.

[0065] (12) A composition for preparing the chemical mechanical polishing pad of any of the embodiments of (1) to (9) is provided in Example (12).

[0066] (13) The composition of Example (12) is provided in Example (13), the composition comprising:

[0067] Prepolymer;

[0068] First curing agent; and

[0069] Polymer particles.

[0070] (14) The composition of Example (13) is provided in Example (14), the composition further comprising a second curing agent and / or optionally including one or more fillers.

[0071] Example Experiment Example

[0072] Preparation of samples for mechanical property testing

[0073] The following describes an example procedure for preparing the example test samples used in this disclosure (e.g., the CMP pad 200 described above). The first set of solid or porous samples was prepared by compression molding using a 9-inch square mold with an 80 mil thickness. A mixture of filler-free prepolymer, a first CPP curing agent, and a second curing agent (dimethylthiotoluene diamine in this example) was poured into a preheated mold and compressed at 260℉ for 10 minutes. The pre-cured samples were then removed from the mold and cured in a ventilated oven at 200℉ for 12 hours. The samples were then cut into small pieces and subjected to various mechanical property tests without further surface treatment.

[0074] Preparation of CMP pads for planarization testing

[0075] The following describes another example procedure for preparing the example CMP pads (e.g., CMP pad 200 described above) used in this disclosure. The CMP pads used for planarization testing are prepared in batches using a molding system. The prepolymer is first mixed with a filler, then with a second curing agent, and the CPP curing agent is mixed with polymer particles (or not mixed with polymer particles as a control). The mixture is then transferred to a separate container of the molding system and preheated. The final mixture is dispensed to the bottom of a 30-inch diameter mold. The CMP pad is then left in the mold under a vacuum of 260℉ for 10 minutes. The amount of components dispensed, molding time, pressure, mold design, and / or substrate temperature vary between certain test compositions.

[0076] The resulting CMP pads were then removed from the mold and cured in a ventilated oven at 230℉ for 16 hours. The cured pads were then used for testing. For mechanical testing, grooves were removed by CNC grinding. For planarization and polishing testing, the pads were thinned from the back side to 65 mils, and a light, fine surface treatment was applied to the grooved sides. The surface-treated top pad was laminated with the bottom pad and platform adhesive, and a window was installed if necessary to observe certain polishing processes. All CMP pads in the examples used the same top pad thickness, bottom pad, and platform adhesive.

[0077] Mechanical testing

[0078] Hardness: The hardness (Shore D hardness) of various test samples was measured at 25°C using a standard hardness tester according to the procedures stated in ASTM 2240 and ISO 868.

[0079] Density: The density of various prepared samples was measured using a specific gravity bottle. Samples were cut into 1-inch diameter circles for testing. During testing, the samples were purged of isopropanol from the wet specific gravity bottle, and the apparent density was determined by gravimetric analysis.

[0080] Modulus: The elastic storage modulus (E') as a function of temperature was measured for various samples using Dynamic Mechanical Analysis (DMA). Cured samples were cut into 6mm x 30mm rectangular portions and mounted in tensile fixtures. The physical dimensions of each sample were measured using a micrometer prior to DMA. DMA testing was performed under dry conditions with airflow at a frequency of 1 Hz, an amplitude of 30 micrometers, and a temperature rise rate of 5°C per minute from -50°C to 180°C in standard multi-frequency controlled strain tensile mode. DMA measurements were performed according to ASTM D4065.

[0081] Surface roughness: The surface roughness of the polished pad was obtained using a digital optical microscope (IF (InfiniteFocus) measurement) configured for three-dimensional (3D) measurements on an Alicona. The surface roughness data presented in Table 1 below are the average of nine measurements taken at different locations near the center, middle, and edge of the CMP pad sample. Sa is the average surface roughness of the measurement area; Spk is the average height of the peak above the core material; and Svk is the average depth of the valley below the core material.

[0082] The embedded polymer particles in sample pad 1 have a higher surface roughness than their counterparts in the control pad. This increased roughness is due to both the protruding surface features resulting from the polymer particles exposed on the CMP pad surface and the porous surface features resulting from the polymer particles removed from the CMP pad surface. Compared to the control pad, sample pad 1 exhibits an increased surface roughness (Sa) with higher peak height (Spk) and deeper valley depth (Svk). This increased surface roughness of sample pad 1 can provide an improved removal rate (as shown below) without requiring the use of a harder material to fabricate the pad.

[0083] Table 1: Surface roughness values ​​of the control CMP pad and sample pad 1

[0084] Sa(μm) 4.54 5.32 Spk(μm) 6.40 7.40 Svk(μm) 6.60 8.02

[0085] Mechanical properties of example CMP pads prepared from different mixtures

[0086] Table 2 shows a list of various samples prepared for mechanical testing, as shown below. Figure 5 , 6A As described in 6B. Table 2 shows the properties of the curing agent 304 and polymer particles 306 used to prepare a sample of the CMP pad 200, which is used to prepare the mixture 300. In Table 2, OH# refers to the hydroxyl density per mass of material (e.g., in...). Figure 3 In component 304), the particle content refers to the SAN polymer particles (e.g., Figure 3 Component 306) in CPP curing agent (e.g., Figure 3 The nominal functionality refers to the number of functional groups on each molecule of the CPP curing agent, and the viscosity 25C / 40C refers to the viscosity of the mixture of the CPP curing agent and SAN particles (if measured) at 25°C and 40°C. Sample 1 is a polyether polyol having 10% SAN particles dispersed in a high molecular weight reactive polyol with a hydroxyl value of 30.0 ± 2.0 mg KOH / g. Sample 2 is a polyurea-filled polyether polyol. Samples 3, 4, and 5 are different formulations of grafted polyether polyols containing dispersed SAN particles of copolystyrene and acrylonitrile.

[0087] Table 2: Properties of CPP curing agent and SAN particles in different test samples

[0088]

[0089] Using different concentrations of CPP curing agent (e.g., Figure 3 Component 304) and SAN particles (e.g., Figure 3 The average hardness of the samples prepared from component 306 (Table 2) is shown in [data missing]. Figure 5 In the middle. As the amount of CPP curing agent increases, the hardness decreases. Using different concentrations of CPP curing agent (e.g., Figure 3 The elastic storage modulus (E') of the samples prepared by the first curing agent 304 in Table 2 is shown in... Figure 6A and 6B middle. Figure 6A This displays the value of the elastic storage modulus at 25°C, while Figure 6B This displays the value of the elastic storage modulus at 50°C. Similar to hardness, the elastic storage modulus decreases with increasing amount of CPP curing agent. In determining the particles described herein (e.g., Figure 3 When the content of component 306 is within a certain range, it is necessary to identify the effect of changes in hardness or modulus.

[0090] like Figure 5 , 6A As shown in 6B, when the amount of SAN particles (e.g., component 306 of mixture 300) increases, as in samples 3 and 4, a small change in hardness and elastic storage modulus is observed with increasing CPP curing agent concentration. This may be advantageous where higher hardness and elastic storage modulus may be preferred. In some cases, by adjusting the CPP curing agent (e.g., Figure 3 The concentration of component 304) and / or the SAN particles (e.g., Figure 3 Adjusting the concentration of component 306 to regulate the elastic storage modulus and / or hardness (e.g., to obtain the properties required for a given polishing / planarization application) may be possible and / or advantageous. In some cases, the elastic storage modulus of the polished portion is measured at 25°C to be in the range of about 20 MPa to about 1500 MPa, for example, from 50 MPa to about 1000 MPa measured at 25°C. Furthermore, in some cases, the elastic storage modulus is measured at 50°C to be in the range of about 20 MPa to about 400 MPa, for example, from 25 MPa to about 35 MPa measured at 50°C.

[0091] The effect of SAN particles on surface texture

[0092] To observe the effects of using the CPP curing agent (e.g., Figure 3Component 304) and SAN particles (e.g., Figure 3 The effect of component 306 on the surface texture of CMP pads was investigated by adjusting a series of samples and imaging them using scanning electron microscopy (SEM), such as... Figure 7A and 7B As shown in the image. Figure 7A SEM images show a conventional CMP pad, which, after conditioning, has no pores and limited surface texture. In contrast, when using a CPP curing agent with SAN particles (5 mol% CPP, 6.2 wt.% SAN particles in sample 4), as... Figure 7B As shown, the surface has significantly increased roughness and has pores ranging from submicron to micron in size. Figure 7B The SEM image in Figure 2 corresponds to surface 212 depicted in Figure 2, where the particles 204 and the pores 208 created by removing the particles 204 both increase the surface roughness. Further testing also confirmed that the increase in surface roughness and porosity achieved using the CPP curing agent and SAN particles is a result of the combination of the CPP curing agent and the SAN particles, and cannot be achieved by adding the CPP curing agent alone.

[0093] Chemical mechanical planarization properties

[0094] The performance of the example CMP pads was evaluated using tungsten paste (W8900, CMC Materials). The example CMP pads were evaluated using a Reflexion LK CMP polisher (available from Applied Materials) and Silyb tungsten wafers, the Silyb tungsten wafers comprising: (1) 6000 Å paste deposited using chemical vapor deposition. (2) "6k overlay wafer" of planar tungsten film; of A sample of a “2k854 patterned wafer” with tungsten film deposited on a specially patterned surface; and (3) having of A tungsten film is deposited on a specially patterned surface in a “5k 854 pattern” sample. Another example used to evaluate CMP performance is the CMP of an oxide surface using a dielectric paste (D9228, purchased from CMC Materials). The tested oxide surface is an oxide wafer covered with a tungsten film deposited from tetraethyl orthosilicate (TEOS) using chemical vapor deposition. Silicon oxide.

[0095] The CMP pad (referred to as sample pad 1) was prepared using a polyurethane prepolymer (NCO value 10.18) based on toluene diisocyanate (TDI) and polytetramethylene ether glycol (PTMEG), a CPP curing agent containing SAN particles, a second curing agent of dimethyl thiotoluene diamine, and a filler (sample 4). The formulation contained 66 parts of prepolymer, 14.5 parts of CPP curing agent, 16.5 parts of second curing agent, and 3 parts of pore filler. Pad sample 1 exhibited similar hardness and density to the CMP pad without embedded polymer particles, which was used as a control in the removal rate study. Table 3 shows a comparison of the tungsten removal performance of sample pad 1 with that of the control CMP pad. Sample pad 1 demonstrated improved tungsten removal rate (RR) on tungsten-covered wafers and patterned wafers of two different thicknesses without sacrificing performance in terms of pitting and wear.

[0096] Table 3: Example tungsten removal rate (RR) results using the inventive CMP pad (pad sample 1) and the control CMP pad.

[0097]

[0098]

[0099] Similar performance improvements were observed for oxide layer removal, as illustrated in Table 4 below, which shows a comparison of the oxide removal rate of pad sample 1 with the control and other samples without CPP curing agent (Control 2 and Control 3). Pad sample 1 exhibited a higher oxide removal rate (RR) than any other tested sample, even though its hardness and porosity (higher density) were lower than Control 2 and Control 3. Hardness and porosity are generally considered to be driving factors for the higher oxide removal rate.

[0100] Table 4: Results of oxide removal rates using the inventive CMP pads (pad sample 1 and different control CMP pads).

[0101]

[0102] Modifications, additions, or omissions may be made to the systems, apparatuses, and methods described herein. Components of the systems and apparatuses may be integrated or separated. Furthermore, the operation of the systems and apparatuses may be performed by more, fewer, or other components. The methods may include more, fewer, or other steps. Furthermore, the steps may be performed in any suitable order. Furthermore, any suitable logic may be used to operate the systems and apparatuses. As used in this document, "each" refers to each member of a set or each member of a subset of a set.

[0103] Here, "or" is inclusive rather than exclusive, unless otherwise expressly indicated or indicated in the text. Therefore, in this text, "A or B" means "A, B, or both," unless otherwise expressly indicated or indicated in the text. Furthermore, "and" is both a conjunction and a numeral, unless otherwise expressly indicated or indicated in the text. Therefore, in this text, "A and B" means "both A and B, or one of them," unless otherwise expressly indicated or indicated in the text.

[0104] The scope of this disclosure covers all changes, substitutions, variations, alterations, and modifications to the exemplary embodiments described or illustrated herein that will be understood by one of ordinary skill in the art. The scope of this disclosure is not limited to the exemplary embodiments described or illustrated herein. Furthermore, although this disclosure describes and illustrates corresponding embodiments herein as including specific components, elements, features, functions, operations, or steps, any of these embodiments may include any combination or arrangement of any of any of the components, elements, features, functions, operations, or steps described or illustrated elsewhere herein that will be understood by one of ordinary skill in the art. Furthermore, references in the appended claims to a device or system or a component of a device or system adapted to, arranged to, capable of, configured to, enabled, operable, or permissible to perform a particular function cover said device, system, or component, whether or not it or said particular function is activated, started, or unlocked, provided that said device, system, or component is so adapted, arranged, capable of, configured to, enabled, operable, or permissible. Moreover, although this disclosure describes or illustrates specific embodiments as providing specific advantages, those specific embodiments may not provide these advantages, or may provide some or all of these advantages.

[0105] The terms “a,” “an,” “the,” and “the,” and similar designations used in describing the invention (particularly in the following claims) should be interpreted to cover both singular and plural forms, unless otherwise indicated herein or clearly contradicted herein. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” should be interpreted as open-ended terms (i.e., meaning “including, but not limited to”). Unless otherwise indicated herein, the numerical ranges listed herein are intended only as shorthand to individually indicate that each independent value falls within the range, and each independent value is incorporated into this specification as if it were individually referenced herein. The use of any and all instances or exemplary language (e.g., “for example”) provided herein is intended only to better illustrate the invention and not to limit the scope of the claims.

Claims

1. A chemical mechanical polishing pad comprising a polishing portion, said polishing portion comprising: A polymeric body having a polished surface; A plurality of polymer particles embedded within the body of the polymeric body, wherein at least a portion of the plurality of polymer particles is at least partially exposed on the polished surface of the polymeric body, and the exposed portions of the polymer particles protrude from the polished surface of the polymeric body; and In the plurality of holes on the polished surface of the polymer body, in, After adjustment, the exposed portions of the polymer particles and the plurality of pores are both present on the polishing surface of the chemical mechanical polishing pad.

2. The chemical mechanical polishing pad according to claim 1, wherein the concentration of the plurality of polymer particles embedded in the polymer matrix is ​​in the range of 0.5% by weight to 40% by weight.

3. The chemical mechanical polishing pad according to claim 1, wherein the polymer particles have an average size of 10 nanometers to 50 micrometers.

4. The chemical mechanical polishing pad according to claim 1, wherein the polymeric host comprises polyurethane.

5. The chemical mechanical polishing pad of claim 1, wherein the polymer particles comprise styrene-acrylonitrile.

6. The chemical mechanical polishing pad according to claim 1, wherein the porosity of the polishing portion is in the range of 10% to 80%.

7. The chemical mechanical polishing pad according to claim 1, wherein the elastic storage modulus of the polishing portion is measured at 25°C to be in the range of 50 MPa to 1000 MPa.

8. The chemical mechanical polishing pad according to claim 1, wherein the hardness of the polished portion is in the range of 50 Shore D scale to 80 Shore D scale.

9. The chemical mechanical polishing pad of claim 1, further comprising a lower pad portion connected to the polishing portion.

10. A method for producing a polishing pad, the method comprising: Prepare a first mixture containing the prepolymer; Prepare or obtain a first curing agent containing polymer particles; The second mixture is prepared by combining the first curing agent containing the polymer particles with a second curing agent; Combine the first mixture with the second mixture; Transfer the combined first and second mixtures into a mold; and A polymeric body is formed by initiating a polymerization reaction in the mold to form a polishing portion of the chemical mechanical polishing pad. The polymeric body includes a plurality of polymer particles embedded within the body of the polymeric body. After adjustment of the polishing pad, at least a portion of the plurality of polymer particles, together with a plurality of pores, are at least partially exposed to the polishing surface of the polymeric body, and the exposed portions of the polymer particles protrude from the polishing surface of the polymeric body.

11. The method of claim 10, wherein the polymer particles have an average size of 10 nanometers to 50 micrometers.

12. The method of claim 10, wherein the polymer particles comprise styrene-acrylonitrile.

13. The method of claim 10, wherein the polymeric host comprises polyurethane.

14. A composition for preparing the polishing pad according to claim 1, the composition comprising: Prepolymer; First curing agent; and Polymer particles.

15. The composition according to claim 14, further comprising at least one of a second curing agent and one or more fillers.

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