CMP compositions for polishing dielectric materials
A modified silica-based CMP slurry with a nucleating agent and cationic surfactant addresses the issue of high defectivity in ceria-based polishing, achieving improved removal rates and surface finishes for dielectric materials.
Patent Information
- Application Number
- JP2023562852
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2021-04-16
- Filing Date
- 2022-04-12
- Publication Date
- 2025-10-06
- Estimated Expiration
- 2042-04-12
AI Technical Summary
Conventional ceria-based slurries for polishing dielectric materials like glass result in high defectivity due to deep scratches, leading to poor surface finishes and high defect rates.
A CMP slurry composition comprising silica abrasive modified with a nucleating agent and a percompound coating, combined with a cationic surfactant, enhances polishing performance by improving removal rates while reducing surface defects.
The composition achieves higher removal rates and better surface finishes with reduced scratches, providing a more reliable polishing process for dielectric materials.
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Abstract
Description
[Technical Field]
[0001] The present invention relates generally to improved compositions and methods for polishing glass and other dielectric surfaces. [Background technology]
[0002] Microelectronic wafers are used to form integrated circuits and comprise a substrate, such as silicon, that is patterned with areas for the deposition of various insulating, conductive, or semiconductive materials.
[0003] Materials such as glass and other dielectric materials are used as light-transmitting screens for computers, smartphones, and other electronic devices, as well as in microelectronic devices.
[0004] To achieve accurate patterning, excess material used in forming layers on the substrate must be removed. Furthermore, preparing a flat or planar microelectronic wafer surface prior to subsequent processing is often critical to fabricating functional and reliable circuits. Therefore, certain surfaces of microelectronic device wafers must be planarized and / or polished. Additionally, in the case of optical devices, it may be necessary to smooth the surface or remove subsurface damage for light transmission.
[0005] Chemical-mechanical polishing or planarization ("CMP") is a process in which material is removed from the surface of a microelectronic device wafer and the surface is planarized and polished by combining physical processes, such as grinding, with chemical processes, such as oxidation and chelation. In its most basic form, CMP involves applying a slurry, e.g., a solution of an abrasive and an active chemistry, to a polishing pad that buffs the surface of the microelectronic device wafer, thereby achieving the removal, planarization, and polishing processes. Typically, to achieve rapid and uniform removal, it is not desirable for the removal or polishing process to consist of purely physical or purely chemical action, but rather a synergistic combination of both. In integrated circuit fabrication, CMP slurries must also be capable of preferentially removing films, including composite layers of metals and other materials, to produce highly planar surfaces for subsequent photolithography, patterning, etching, and thin-film processing. In a conventional CMP operation, a substrate carrier or polishing head is attached to a carrier assembly and placed in contact with a polishing pad within a CMP apparatus. The carrier assembly applies a controllable pressure to the substrate to press it against the polishing pad, which is moved relative to the substrate.
[0006] The industry standard abrasive used in polishing dielectric materials such as glass, silica, and silica-silicon nitride structures is ceria (CeO). Ceria generally exhibits high reactivity with the surface being polished, resulting in relatively high removal rates. However, ceria tends to produce poor surface finishes on these substrates due to the formation of unacceptable deep scratches throughout, resulting in a high defectivity of the final surface area. Therefore, improved abrasives and slurries containing such abrasives are needed for use in polishing dielectric materials such as glass. Summary of the Invention
[0007] In summary, the present invention provides improved slurry compositions useful for CMP polishing of dielectric materials. In one embodiment, the dielectric material is glass. In one aspect, the compositions of the present invention are comprised of water, a silica abrasive optionally modified with a nucleating agent followed by a coating obtained by treatment with a percompound, and a cationic surfactant. Such compositions are useful as performance-enhancing additives added to conventional ceria slurry compositions to form the compositions of the present invention. Thus, the present invention provides slurry compositions that achieve high removal rates while limiting the levels of defectivity typically observed when utilizing ceria slurries alone. [Brief explanation of the drawings]
[0008] [Figure 1] 1 shows the removal rate in microns per minute of a glass surface comparing ceria alone, silica alone, and a composition of the present invention. [Figure 2] FIG. 1 shows the removal rates in microns per minute of a TEOS surface comparing ceria alone, silica alone (i.e., unmodified colloidal silica), and ceria plus additive 2, as specified in the Examples. [Figure 3] FIG. 1 is a comparative surface finish diagram showing a glass surface polished with a standard ceria slurry (Ra (average roughness): 0.81 nm). [Figure 4] FIG. 1 is a comparative surface finish diagram showing a glass surface polished with a composition of the present invention (Ra: 0.54 nm). DETAILED DESCRIPTION OF THE INVENTION
[0009] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally utilized in its sense including "and / or" unless the context clearly dictates otherwise.
[0010] The term "about" generally refers to a range of numbers considered equivalent to a recited value (e.g., having the same function or result). In many instances, the term "about" may include numbers that are rounded to the nearest significant figure.
[0011] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
[0012] The composition of the present invention is useful as a CMP polishing composition (i.e., slurry) for dielectric materials such as glass. Further examples of such materials include, for example, tetraethyl orthosilicate (TEOS), fluoride silica glass, carbon-doped silicon glass, glass ceramics, zirconium silicate, barium titanate, silicon nitride, silicon oxynitride, and carbon-doped silicon oxide (SiOC). These substrate materials may be polycrystalline or amorphous and may have more than one phase. The substrate material may be in the form of an epitaxial layer or may include a bulk substrate single crystal.
[0013] Thus, in a first aspect, the present invention provides a method for producing a composition comprising: a. Water, b. a silica abrasive; c. a cationic surfactant; d. Ceria abrasive and A composition comprising:
[0014] In the compositions of the present invention, the term "silica" refers to unmodified silica selected from commercially available colloidal silicas with an average particle size of about 20 nm to about 150 nm, available from Fuso Chemical Co., Ltd., Ecolab, and Nouryon, to name a few. In this disclosure, "average size" refers to the average value of the particle size distribution, based on volume or weight distribution. Colloidal silica particles are defined as particles made from silicic acid precursors, such as sodium silicate or potassium silicate. Colloidal silica is known to have bound hydroxyl ions that impart a negative charge under neutral pH conditions. The concentration of silica particles can vary from 0.000001 to 50 weight percent, or from about 0.05 to about 20 weight percent, based on the total weight of the composition (i.e., slurry).
[0015] The ceria particles, i.e., CeO2, used in the composition of the second aspect are of a size and size distribution typically used in CMP operations, generally ranging in size (i.e., diameter) from about 1 nm to about 100 microns. The concentration of the ceria particles can vary from 0.000001 weight percent to 50 weight percent based on the total weight of the composition, or from about 0.05 weight percent to about 10 weight percent based on the total weight of the composition (i.e., slurry). In one embodiment, the average particle size of ceria used in microelectronic applications is from about 10 nm to about 250 nm. In another embodiment, for applications requiring polishing of optical devices, the average particle size is from about 250 nm to about 10 μm. Ceria abrasives are well known in the CMP field and are commercially available from Nyacol Nano Technologies, Inc., Cabot, and Ferro, to name a few. Examples of suitable ceria abrasives include wet ceria, calcined ceria, and metal-doped ceria, among others. The composition can contain one type of ceria abrasive particle or multiple different types of abrasive particles based on size, composition, preparation method, particle size distribution, or other mechanical or physical properties. The ceria abrasive particles can be made by a variety of different processes. For example, the ceria abrasive particles can be precipitated ceria particles or condensation-polymerized ceria particles, including colloidal ceria particles.
[0016] In certain embodiments, component b. of the compositions of the present invention consists of a modified silica abrasive. In further embodiments, component b. comprises a mixture of a silica abrasive and a modified silica abrasive.
[0017] The modified silica abrasive material has a film or coating of one or more colloidal metal oxides. Such coating covers at least a portion of the surface area of the silica particle. In one embodiment, the modified silica abrasive material can be prepared by first treating the silica particle with a nucleating agent. In one embodiment, the nucleating agent is selected from substituted glycine compounds that are believed to function as nucleating agents on the surface of the silica. In certain embodiments, the substituted glycine compound has the formula TIFF0007749692000001.tif20170 (wherein R is selected from hydrogen or C1-C6 alkyl having one or two hydroxyl groups; R 1 is selected from C1-C6 alkyl having one or two hydroxyl groups.
[0018] In other embodiments, the substituted glycine compound is selected from 2-(bis-2-hydroxyethyl)amino)acetic acid, commonly known as bicine, and N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine, commonly known as tricine.
[0019] The silica product is then treated with a percompound. Typical examples of percompound types include permanganate, peroxide, perchlorate, and persulfate compounds. One particular type of percompound is an alkali metal permanganate (e.g., sodium, lithium, potassium, or barium), or a mixture of a percompound with one component being permanganate. In such cases, the colloidal metal oxide coating or film will contain manganese oxide. Optionally, hydrogen permanganate can also be used. Permanganate is the permanganate(VII) ion, MnO -4 is a general term for chemical compounds containing manganese. Because the manganese in permanganate is in the +7 oxidation state, the permanganate ion is a strong oxidizing agent. The term persulfate (sometimes known as peroxysulfate or peroxodisulfate) refers to the anion SO5 2- or S2O8 2- refers to an ion or compound containing
[0020] Examples of specific per-based compounds (oxidizers) include potassium permanganate (KMnO), sodium permanganate (NaMnO), potassium peroxoborate (KBO), potassium peroxochromate (KCrO), potassium peroxodisulfate (KSO), and potassium perrhenate (KReO). The oxidation state of manganese in these permanganates is +7, which is the highest oxidation state of manganese. Mixtures of per-compounds can also be used. In one embodiment, the per-compound is potassium permanganate. The concentration of the per-compound can vary from about 0.1 mM to about 5 mM in certain embodiments.
[0021] Thus, in another embodiment, the colloidal metal oxide coating is a coating obtained by treating silica with a nucleating agent and a percompound.
[0022] The resulting modified silica material is then combined with other desired ingredients and mixed with a cationic surfactant. As used herein, the term "surfactant" refers to an organic compound that reduces the surface tension (or interfacial tension) between two liquids or between a liquid and a solid, typically an organic amphiphilic compound containing a hydrophobic group (e.g., a hydrocarbon (e.g., alkyl) "tail") and a hydrophilic group. The surfactants described herein can be used individually or in mixtures. Generally, the concentration of surfactant used in the compositions of the present invention depends on the type of surfactant utilized, the surface of the specific abrasive particle, and the substrate material being polished.
[0023] Cationic surfactants are essentially surface-active molecules that have at least one positively charged moiety. In one embodiment, cationic surfactants include C6-C 18 Ammonium halides are selected from C6 to C 18 The modifier " refers to the number of carbon atoms in the surfactant, which may include aliphatic and aromatic moieties. In another embodiment, the cationic surfactant is 12 ~C 18The ammonium halide is selected from the group consisting of ammonium halides.
[0024] Exemplary cationic surfactants include cetyltrimethylammonium bromide (CTAB) (also known as hexadecyltrimethylammonium bromide), hexadecyltrimethylammonium chloride (CTAC), heptadecanefluorooctanesulfonic acid, tetraethylammonium halide, stearyltrimethylammonium chloride, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridinium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyl Examples of suitable cationic surfactants include, but are not limited to, dimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, didodecyldimethylammonium bromide, di(hydrogenated tallow)dimethylammonium chloride, tetraheptylammonium bromide, tetrakis(decyl)ammonium bromide, and oxyphenonium bromide, dimethyldioctadecylammonium chloride, dimethyldihexadecylammonium bromide, and di(hydrogenated tallow)dimethylammonium chloride. In one embodiment, the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0025] In certain embodiments of the present invention, the composition further comprises, in addition to the cationic surfactant, at least one additional surfactant selected from anionic and nonionic surfactants.
[0026] When present, the anionic or nonionic surfactant is, in certain embodiments, from about 0.0001% to about 5% by weight (wt), or from about 0.001% to about 2% by wt, relative to the total weight of the composition.
[0027] Anionic surfactants are generally surfactants characterized by a negatively charged hydrophilic polar group. Exemplary anionic surfactants include polyacrylic acid, polymethacrylic acid, polystyrene-acrylic acid copolymer, acrylic acid-maleic acid copolymer, acrylic acid-ethylene copolymer, acrylic acid-acrylamide copolymer, and acrylic acid-polyacrylamide copolymer. The weight-average molecular weight of such anionic surfactants can be 1,000 to 30,000. In other embodiments, the weight-average molecular weight of the anionic surfactant is about 1,000 to about 25,000, or about 1,500 to about 25,000, or about 1,500 to about 20,000.
[0028] Other examples of anionic surfactants include carboxylates, sulfonates such as alkylbenzene sulfonates, sulfates, phosphates, etc. Further examples include dioctyl sodium sulfosuccinate (DOSS), perfluorooctane sulfonate (PFOS), linear alkylbenzene sulfonates, sodium lauryl ether sulfate, lignosulfonates, and sodium stearate.
[0029] Exemplary nonionic surfactants include PolyFox PF-159 (OMNOVA Solutions), polyethylene glycol) ("PEG"), poly(propylene glycol) ("PPG"), ethylene oxide / propylene oxide block copolymers such as Pluronic F-127 (BASF), polysorbate polyoxyethylene (20) sorbitan monooleate (Tween™ 80) (Croda Americas), polyoxyethylene (20) sorbitan monostearate (Tween™ 60), polyoxyethylene (20) sorbitan monopalmitate (Tween™ 40), polyoxyethylene (20) sorbitan monolaurate (Tween™ 20), polyoxypropylene / polyoxyethylene block copolymers (e.g., Pluronic L31, Plutonic 31R1, Pluronic 25R2, and Pluronic 25R4), polyoxyethylene glycol octylphenol ether, polyoxyethylene glycol alkylphenol ether, and combinations thereof.
[0030] The compositions of the present invention may optionally contain one or more additional ingredients, such as conditioners, dispersants, and pH modifiers such as acids and bases.
[0031] The slurry can further include a pH stabilizer. Both organic and inorganic pH stabilizers can be used. Examples of inorganic pH stabilizers include phosphates, phthalates, bicarbonates, and silicates. Examples of organic pH stabilizers include amines, glycine, and N-cyclohexyl-2-aminoethanesulfonic acid. In certain embodiments, the pH of the composition of the present invention is about 3 to about 13. In other embodiments, the pH of the composition is about 9 to about 11.
[0032] The slurry composition may further include a fungicide, examples of which include tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, alkylbenzyldimethylammonium chloride, and alkylbenzyldimethylammonium hydroxide, 3,5-di-methyltetrahydro-1,3,5,2H-thiadiazine-2-thione, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, sodium chlorite, and sodium hypochlorite.
[0033] The polishing process can be carried out at temperatures from about 15°C to about 100°C. Higher temperatures are expected to increase the polishing rate of glass and other dielectric materials. In one embodiment, the temperature range is from about 25°C to about 65°C. One way to achieve higher temperatures is to preheat the slurry before feeding it into the CMP tool.
[0034] Generally, any type of polymer-based polishing pad can be used as the polishing pad. Examples of polishing pads are based on polyurethane pads and suede pads. The thickness of the pad can vary from 0.1 mm to 25 mm. The hardness of the suede pad can vary from Asker C 5 to Asker 95. The compressibility of the suede pad can be 0.1% to 40%. The pore size of the microporous suede pad can vary from 2 microns to 100 microns, and in one embodiment, the pore size is in the range of 20 to 60 microns. The microporous pad layer can have a backing pad layer of poly(ethylene terephthalate) (PET) or a foam or nonwoven material with a thickness of 30 microns to 25 mm.
[0035] In addition to microporous pads, polyurethane pads can also be used. Examples of polyurethane-based pads include Cabot Microelectronics' D-100 pad and Dow Electronics Materials' IC and Suba series. The hardness of such pads ranges from 5 to 99 Shore D. The porosity of such pads can vary from 0.1% to 40%. Overall, it should be noted that any other type of polymer material can be used with the slurry. In addition to using porous pads, metal pads (cast iron, copper, tin, etc.), granite, or resin surfaces can also be used as pads.
[0036] Suitable equipment for chemical mechanical polishing is commercially available. The method of the present invention generally includes mixing a slurry composition containing the above-mentioned ingredients, placing the dielectric substrate to be polished in a CMP apparatus having a rotating pad, and then performing chemical mechanical polishing using the slurry composition of the present invention. In this polishing method, at least a portion of the surface of the dielectric substrate is removed or ground away, thereby obtaining a suitably polished dielectric substrate.
[0037] Thus, in another aspect, the present invention provides a method for chemical mechanical polishing a substrate having a surface comprising a dielectric material, the method comprising: a. contacting a substrate with a composition of the present invention; b. transferring the composition relative to the substrate; and c. Grinding the substrate to remove a portion of the dielectric surface to obtain a polished dielectric surface. The present invention provides a method comprising:
[0038] The compositions of the present invention are easily formulated by simply adding each component and mixing until uniform. The compositions may be easily formulated as single-package or multi-part formulations that are mixed at the time of use or before use. The concentration of each component may vary widely depending on the specific multiple of the composition, i.e., whether it is more dilute or more concentrated, and it will be recognized that the compositions described herein may variously and alternatively comprise, consist of, or consist essentially of any combination of components consistent with the present disclosure.
[0039] Thus, in another aspect, the present invention provides a kit comprising components selected from a., b., c., and d. above in one or more containers for combination at the time of use. [Example]
[0040] Example 1 Optical glass wafers were polished using a 12-inch Buehler polisher with a platen speed of 150 RPM and an applied downforce. DuPont Suba800 pads were selected for polishing glass substrates. The downpressure was varied between 2 and 6 psi. The polishing media flow rate was maintained constant at 30 ml / min, and the polishing time was fixed at 5 minutes. The polishing media contained one embodiment of hybrid particles consisting of two abrasives: ceria and functionalized colloidal silica particles (i.e., "modified silica" as referred to herein). The size of the ceria particles was 1.5 microns. The concentration of the ceria particles was kept constant at 1 wt%. The concentration of the functionalized silica particles was varied from 0.05 wt% to 3.5 wt%. An IR thermometer was used to measure the temperature rise on the pad during the polishing process. Removal rates were determined at pH 9 and 4.5 and were used to evaluate the performance of each slurry composition. The pH of the polishing media was adjusted using an aqueous solution of potassium hydroxide and nitric acid.
[0041] Colloidal silica particles were functionalized prior to blending with ceria abrasive to formulate hybrid particles. To functionalize the colloidal silica, the silica particles were treated with potassium permanganate. The potassium permanganate concentration was maintained at 3.8 mM. Bicine was used as a nucleating agent to promote the formation of colloidal manganese dioxide particles, which were then coated onto the silica particles. Cetyltrimethylammonium bromide (CTAB) was used as a cationic surfactant. The CTAB concentration was maintained at 2 mM throughout the slurry. Secondary alkyl sulfonate (SAS) was used as a rheology modifier. The SAS concentration was maintained at 0.2 wt% of the slurry. Two additives were prepared for testing purposes, hereafter referred to as Additive 1 (functionalized silica without SAS) and Additive 2 (functionalized silica with SAS).
[0042] Performance metrics included (a) removal rate, (b) surface finish, (c) scratch profile / depth, and (d) additive stability (determined over time based on additive settling in a test tube). Removal rate was determined based on the weight loss of the glass wafer during the polishing process. A factor was calculated to convert the weight loss in grams to a removal rate in μm / hour. This factor takes into account the surface area and material density of the glass wafer. The surface roughness and scratch depth resulting from each polish were determined by scanning the polished glass surface with an atomic force microscope. A scan size of 50 μm × 50 μm was selected for the analysis.
[0043] Table 1 shows the removal rate data for ceria particles alone (control) and hybrid particles prepared with two different silica particles as a function of drop pressure. The data confirm that polishing follows Prestonian behavior.
[0044] Table 2 presents removal rate data for the same set of slurry compositions as a function of volume % of additive. The higher the volume % of additive, the higher the removal rate.
[0045] Figure 1 shows the surface roughness profile of a glass wafer after polishing. Polishing with ceria alone results in a higher surface roughness and a deeper scratch profile. The glass surface polished with the hybrid particles exhibits a lower Ra value and shallower, fewer scratches.
[0046] Table 1: Removal rate data for ceria alone and hybrid particles at pH 11 as a function of downforce. Silica additive was maintained at 10% by volume. TIFF0007749692000002.tif27170
[0047] Table 2: Removal rate data at pH 11 in hybrid particle slurries as a function of volume percent of functionalized silica additive at 6 psi. TIFF0007749692000003.tif38170
[0048] Example 2 In this example, several polishing slurries were prepared using ceria abrasives of various particle sizes and their effect on the removal rate of glass substrates was tested using the same protocol as specified in Example 1. Particle size was varied from 1.5 microns to 5 microns. All ceria particles were sourced from various sources. Each slurry had the same percentage of Additive 1, which was 10 vol% of the total volume of the slurry. Table 3 shows the removal rates obtained by applying a 6 psi pressure drop at a pH of 11. It was observed that the removal rate decreased as the particle size of the ceria abrasive increased.
[0049] Table 3: Removal rate data at 6 psi and pH 11 as a function of ceria particle size. TIFF0007749692000004.tif27170
[0050] Example 3 In this example, several polishing slurries were prepared using various concentrations of ceria particles and tested for their effect on removal rate under the polishing conditions specified in Example 1. The ceria concentration was varied from 0.1 wt% to 1.5 wt%. Each slurry had the same proportion of Additive 1, which was 10 vol% of the total slurry volume. Table 4 shows the removal rate data for glass substrates using ceria abrasive alone and in the presence of the two additives.
[0051] Table 4: Removal rate data at 6 psi and pH 11 as a function of ceria concentration in weight percent. TIFF0007749692000005.tif73170
[0052] Example 4 In this example, the removal rates of various films deposited on optical glass substrates were compared to investigate the selectivity of polishing slurries on various substrates. Polishing rate selectivity can be an important parameter in various CMP applications. The removal rates of TEOS and SiN films were compared to that of optical glass. Both TEOS and SiN films were deposited on silicon substrates by PECVD and obtained from DK Nanotechnology. Square specimens measuring 1.5 inches by 1.5 inches were cut for polishing in the presence of the tested slurries. Polishing rate selectivity was tested by applying a 4 psi drop pressure. Table 5 shows the removal rates in μ / hr for all tested substrates. The presented data confirm that the selectivity of TEOS polishing in the presence of additives was consistently unaffected, while the selectivity of silicon nitride improved by up to 4:1 compared to TEOS or optical glass.
[0053] Table 5: Removal rate data at 4 psi for various substrates TIFF0007749692000006.tif43170
[0054] Aspects In a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a. Water, b. a silica abrasive; c. a cationic surfactant; d. Ceria abrasive and A composition comprising:
[0055] In a second aspect, the present invention provides a composition of the first aspect, wherein the silica abrasive is at least partially coated with a colloidal metal oxide.
[0056] In a third aspect, the present invention provides a composition of the second aspect, wherein the colloidal metal oxide coating is a coating obtained by treating silica with a nucleating agent and a percompound.
[0057] In a fourth aspect, the present invention provides the composition of the second, third, or fourth aspect, wherein the metal oxide is manganese oxide.
[0058] In a fifth aspect, the present invention provides a method for preparing a nucleating agent having the formula TIFF0007749692000007.tif20170 (wherein R is selected from hydrogen or C1-C6 alkyl having one or two hydroxyl groups; R 1 is selected from C1-C6 alkyl having one or two hydroxyl groups, A composition of the third aspect is provided.
[0059] In a sixth aspect, the present invention provides the composition of any one of the third to fifth aspects, wherein the nucleating agent is selected from 2-(bis-2-hydroxyethyl)amino)acetic acid and N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine.
[0060] In a seventh aspect, the present invention provides the composition of any one of the second to sixth aspects, wherein the per-compound is selected from potassium permanganate, sodium permanganate, potassium perborate, potassium perchromate, potassium peroxodisulfate, and potassium perrhenate, or mixtures thereof.
[0061] In an eighth aspect, the present invention provides a cationic surfactant having a C6 to C 18 The composition of any one of the first to seventh aspects is provided, wherein the ammonium halide is selected from the group consisting of ammonium halides.
[0062] In a ninth aspect, the present invention provides a cationic surfactant, 12 ~C 18 The composition of any one of the first to eighth aspects is provided, wherein the ammonium halide is selected from the group consisting of ammonium halides.
[0063] In a tenth aspect, the present invention provides the composition of any one of the first to ninth aspects, wherein the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0064] In an eleventh aspect, the present invention provides a composition of any one of the first to tenth aspects, further comprising one or more surfactants selected from anionic surfactants and nonionic surfactants.
[0065] In a twelfth aspect, the present invention provides a method for chemical mechanical polishing a substrate having a surface comprising a dielectric material, the method comprising: A.The substrate, Water, b. Silica abrasives, c. cationic surfactants, and d. Ceria abrasive contacting with a composition comprising B. transferring the composition relative to the substrate; and C. Grinding the substrate to remove a portion of the dielectric surface to obtain a polished dielectric surface. The present invention provides a method comprising:
[0066] In a thirteenth aspect, the present invention provides the method of the twelfth aspect, wherein the silica abrasive is at least partially coated with a colloidal metal oxide.
[0067] In a fourteenth aspect, the present invention provides the method of the thirteenth aspect, wherein the metal oxide is manganese oxide.
[0068] In a fifteenth aspect, the present invention provides a cationic surfactant, 12 ~C 18 The method of any one of the twelfth to fourteenth aspects is provided, wherein the ammonium halide is selected from the group consisting of ammonium halides.
[0069] In a sixteenth aspect, the present invention provides the method of any one of the twelfth to fifteenth aspects, wherein the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0070] In a seventeenth aspect, the present invention provides the method of any one of the thirteenth to sixteenth aspects, wherein the colloidal metal oxide coating is a coating obtained by treating silica with a nucleating agent and a percompound.
[0071] In an eighteenth aspect, the present invention provides a method for preparing a nucleating agent having the formula TIFF0007749692000008.tif20170 (wherein R is selected from hydrogen or C1-C6 alkyl having one or two hydroxyl groups; R 1 is selected from C1-C6 alkyl having one or two hydroxyl groups.
[0072] In a nineteenth aspect, the present invention provides the method of the twelfth, seventeenth, or eighteenth aspects, wherein the nucleating agent is selected from 2-(bis-2-hydroxyethyl)amino)acetic acid and N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine.
[0073] In a twentieth aspect, the present invention provides the method of any one of the seventeenth to nineteenth aspects, wherein the per-compound is selected from potassium permanganate, sodium permanganate, potassium perborate, potassium perchromate, potassium peroxodisulfate, and potassium perrhenate, or a mixture thereof.
[0074] In a twenty-first aspect, the present invention provides the method of any one of the thirteenth to twentieth aspects, wherein the metal oxide is manganese oxide.
[0075] In a twenty-second aspect, the present invention provides a cationic surfactant, 12 ~C 18 The method of any one of the twelfth to twenty-first aspects is provided, wherein the ammonium halide is selected from the group consisting of ammonium halides.
[0076] In a twenty-third aspect, the present invention provides the method of any one of the twelfth to twenty-second aspects, wherein the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0077] In a twenty-fourth aspect, the invention provides the method of any one of the twelfth to twenty-third aspects, wherein the dielectric surface is selected from glass, tetraethyl orthosilicate, fluorinated silica glass, carbon-doped silicon glass, glass-ceramics, zirconium silicate, barium titanate, silicon nitride, silicon oxynitride, and carbon-doped silicon oxide.
[0078] In a twenty-fifth aspect, the present invention provides the method of any one of the twelfth to twenty-fourth aspects, wherein the dielectric surface is glass.
[0079] In a 26th aspect, the present invention provides a kit comprising components selected from components a., b., c., and d. of any one of the first aspect and the seventh to eleventh aspects in one or more containers.
[0080] In a twenty-seventh aspect, the present invention provides the kit of the twenty-sixth aspect, wherein component b. is silica and component c. is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0081] In a twenty-eighth aspect, the present invention provides the kit of the twenty-sixth aspect, wherein component b. is a silica abrasive at least partially coated with magnesium oxide, and component c. is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
[0082] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily recognize that still other embodiments may be made and used within the scope of the appended claims. The numerous advantages of the present disclosure, which are encompassed by this specification, are set forth in the foregoing description. It will be understood, however, that this disclosure is in many respects merely illustrative. The scope of the present disclosure will, of course, be defined in the language in which the appended claims are expressed.
Claims
1. a. Water; b. a silica abrasive at least partially coated with a colloidal metal oxide; c. a cationic surfactant; d. Ceria abrasive and A composition comprising:
2. 2. The composition of claim 1, wherein the colloidal metal oxide coating is a coating obtained by treating silica with a nucleating agent and a percompound.
3. The composition of claim 1 wherein the metal oxide is manganese oxide.
4. The nucleating agent is of the formula wherein R is hydrogen or a C 1 -C 2 -C 3 -C 4 -C 5 -C 6 -C 7 -C 8 -C 9 -C 10 -C 11 -C 12 -C 13 -C 14 -C 15 -C 16 -C 17 -C 18 -C 19 -C 20 -C 21 -C 22 -C 23 -C 24 -C 25 -C 26 - 1 ~C 6 alkyl, and R 1 is a C having one or two hydroxyl groups 1 ~C 6 3. The composition of claim 2, wherein the alkyl is selected from the group consisting of aryl, arylsulfonyl, arylalkyl, arylsulfonyl ...
5. The composition of claim 2, wherein the nucleating agent is selected from 2-(bis-2-hydroxyethyl)amino)acetic acid and N-(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)glycine.
6. 3. The composition of claim 2, wherein the percompound is selected from potassium permanganate, sodium permanganate, potassium perborate, potassium perchromate, potassium peroxodisulfate, and potassium perrhenate, or mixtures thereof.
7. The cationic surfactant is C 6 ~C 18 The composition of claim 1 , wherein the ammonium halide is selected from the group consisting of ammonium halides.
8. The cationic surfactant is C 12 ~C 18 The composition of claim 1 , wherein the ammonium halide is selected from the group consisting of ammonium halides.
9. 2. The composition of claim 1, wherein the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
10. 10. The composition of claim 1, further comprising one or more surfactants selected from anionic surfactants and nonionic surfactants.
11. 1. A method for chemical mechanical polishing a substrate having a surface comprising a dielectric material, comprising: A. The substrate a. water, b. a silica abrasive at least partially coated with a colloidal metal oxide; c. a cationic surfactant, and d. Ceria abrasive contacting with a composition comprising B. transferring the composition relative to the substrate; and C. Grinding the substrate to remove a portion of the dielectric surface to obtain a polished dielectric surface. A method comprising:
12. 12. The method of claim 11, wherein the metal oxide is manganese oxide.
13. The cationic surfactant is C 12 ~C 18 12. The method of claim 11, wherein the ammonium halide is selected from the group consisting of ammonium halides.
14. 12. The method of claim 11, wherein the cationic surfactant is selected from hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and benzalkonium chloride.
15. 12. The method of claim 11, wherein the dielectric surface is selected from glass, tetraethyl orthosilicate, fluorinated silica glass, carbon-doped silicon glass, glass-ceramics, zirconium silicate, barium titanate, silicon nitride, silicon oxynitride, and carbon-doped silicon oxide.
16. The method of claim 11 , wherein the dielectric surface is glass.
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