Chemical mechanical planarization slurry and method for polishing a substrate

Abstract

A chemical mechanical polishing (CMP) slurry can include a plurality of particles dispersed in a carrier, and at least a portion of the plurality of particles can have a body including a core containing zirconia and a shell covering at least a portion of the core, and the shell includes silica, an oxidizing agent, and a carrier. The CMP slurry can include at least one of a hydrogen peroxide stability % reduction rate of 50% or less and a high copper material removal rate.

Description

Technical Field

[0001] The following is directed to a chemical mechanical polarization (CMP) slurry and a method of using the CMP slurry to polish a substrate.

Background Art

[0002] Compositions for use in material removal operations are known. Such abrasive compositions can include fixed abrasive compositions in which an aggregate of abrasive particles is attached to a body or substrate. Alternatively, certain abrasive compositions can include free abrasive agents, where the abrasive particles do not attach to the body or substrate but are contained within a liquid carrier as a slurry or mixture. Depending on the type of material removal operation, one can choose to use a fixed abrasive or a free abrasive.

[0003] Conventional polishing slurries are most frequently used in the polishing of materials such as glass, metal, etc. The electronic device manufacturing industry uses polishing slurries for chemical mechanical planarization (CMP). In a typical CMP process, a substrate (e.g., a wafer) is placed in contact with a moving polishing pad, e.g., a rotating polishing pad attached to a platen. In addition, other industries also seek polishing compositions.

Brief Description of the Drawings

[0004] The present disclosure can be better understood by reference to the accompanying drawings, and numerous features and advantages thereof will be apparent to those of ordinary skill in the art.

Figure 1

Figure 2

Figure 3

Figure 4

Mode for Carrying Out the Invention

[0005] The following is directed to microparticles or a plurality of particulate particles, including, for example, a plurality of abrasive particles including the particulate particles of the embodiments herein. In another embodiment, the microparticles can be part of a batch of abrasive particles including the microparticles. In yet another aspect, a CMP slurry that can include the microparticles is disclosed. As used herein, a plurality of particles, a batch of abrasive particles, or a CMP slurry can include minor impurities, major impurities, or can consist of the microparticles.

[0006] According to one aspect, the microparticles can include a core and a shell covering the core. FIG. 1 includes a cross-sectional view of a microparticle 100 including a core 101 and a shell 103 covering at least a portion of the core 101.

[0007] FIG. 2 includes a TEM image of a particle having a core and a shell. The image can be a representative image used to measure the average thickness of the shell. A suitable number of similar images of the particles of the embodiments herein can be taken to create a suitable sample dataset for calculating the average thickness of the shell.

[0008] The formation of the particles can include first forming the core. According to one embodiment, a raw material having a zirconium-containing material such as zirconium oxychloride is calcined to form zirconia (ZrO 2) can be formed. After forming the core particles, the distribution of the core particles can be controlled using sieving. The selected core particles can then be processed to create a shell that covers the core. In one embodiment, the process for forming the shell can include the chemical synthesis of a silica-containing material from an organosilicon-containing material (e.g., silane). In a particular embodiment, the formation of the shell layer can include the reaction of a silicon-containing precursor, such as silane, with other reactants to form a silica-containing shell layer that covers the core. Methods for forming the shell can include, for example, but are not limited to, sol-gel and co-precipitation processes, TEOS / TMOS processes, or any process that uses an organo-containing compound as a precursor, pickering processes, spray coating, mechanofusion processes, deposition processes (e.g., CVD, ALD, etc.), or any combination thereof, and can include various techniques. The process for forming the shell can be a process suitable for creating any of the shell characteristics as disclosed in any of the embodiments herein. For example, in one non-limiting case, the process for forming the shell can include a deposition technique for creating a shell having a particular chemical nature, morphology, and / or thickness. In one embodiment of the microparticles, the process for forming a shell on the core particles includes using a silicon-containing source such as an organosilicon source (e.g., TMOS, TEOS). The organosilicon source can be added to water that can cause the release of the silicon material. The core particles can be added to the water and the silicon source to create a mixture. The pH of the mixture can be adjusted to control the deposition of the silicon source onto the surface of the core particles such that a particulate material having a core and a shell structure is created.

[0009] According to one embodiment, the core may include zirconia and may also include Cl-containing species. Without wishing to be bound by any particular theory, the Cl-containing species may be particularly beneficial for forming a shell having certain characteristics and / or performance of the fine particles. In certain cases, the core may include Cl-containing species such as chlorine as an intergranular or grain boundary material within the zirconia. According to one embodiment, the content of the Cl-containing species may be at least 1 ppm, such as at least 5 ppm, or at least 10 ppm, or at least 20 ppm, or at least 50 ppm, or at least 75 ppm, or at least 100 ppm, or at least 125 ppm, or at least 150 ppm, or at least 200 ppm, or at least 300 ppm, or at least 400 ppm, or at least 500 ppm, or at least 600 ppm, or at least 700 ppm, or at least 800 ppm, or at least 900 ppm. In another embodiment, the Cl-containing species may be present in an amount of 3000 ppm or less, or 2500 ppm or less, or 2000 ppm or less, or 1800 ppm or less, or 1500 ppm or less, or 1200 ppm or less, or 1000 ppm or less. It will be understood that the content of the Cl-containing species may be within a range including any of the above minimum and maximum values, for example, but not limited to, within a range of at least 1 ppm and 3000 ppm or less, or at least 10 ppm and 2000 ppm or less, or even within a range including at least 200 ppm and 1000 ppm or less.

[0010] According to another embodiment, the core may include zirconia. In some cases, the core may include a combination of oxide-containing species, such as, for example, but not limited to, zirconia, alumina, etc. In yet another embodiment, the core may include at least 50 wt% zirconia, or at least 75 wt% zirconia, or at least 80 wt% zirconia, or at least 90 wt% zirconia, or at least 95 wt% zirconia, or at least 98 wt% zirconia, or at least 99 wt% zirconia, or at least 99.5 wt% zirconia, etc., of zirconia based on the total weight of the core.

[0011] In another embodiment, the core may consist essentially of zirconia, such that some minor impurities may be present, but such impurities do not substantially affect the performance or properties of the core. In yet another non-limiting embodiment, the core consists entirely of zirconia and the total content of non-zirconia species is 1% or less, or 0.8% or less, or 0.5% or less, or 0.3% or less, or 0.2% or less, or 0.18% or less, or 0.15% or less. According to another non-limiting embodiment, the core consists essentially of zirconia and Cl-containing species. In yet another embodiment, the core includes polycrystalline abrasive grains.

[0012] In one aspect, the microparticles can be part of a plurality of microparticles, and a minority, majority, or all of the plurality of microparticles have the characteristics of the microparticles according to one embodiment. In one example, the microparticles can include a core having a D50 within a range of at least 1 nm to 2000 nm or less. For example, the core can have a D50 of at least 2 nm, or at least 5 nm, or at least 10 nm, or at least 25 nm, or at least 50 nm, or at least 75 nm, or at least 100 nm, or at least 120 nm, or at least 140 nm. Note that in another non-limiting embodiment, the core can have a D50 of 1500 nm or less, or 1200 nm or less, or 1000 nm or less, or 900 nm or less, or 800 nm or less, or 700 nm or less, or 600 nm or less, or 500 nm, or 400 nm or less, or 300 nm or less. It will be understood that the core can have a D50 within a range including any of the above minimum and maximum values, including, for example, but not limited to, within a range of at least 1 nm to 1500 nm or less, or at least 2 nm to 1000 nm or less, or at least 10 nm to 500 nm or less, or at least 20 nm to 300 nm or less.

[0013] In one aspect, the particle size distribution can be a unimodal or single-mode distribution. As used herein, a distribution is unimodal or single-mode if, for a value "m", it increases monotonically for x ≤ m and decreases monotonically for x ≥ m. In that case, the maximum value of f(x) is f(m), and there are no other maxima.

[0014] The particle size distribution characteristics related to any of the embodiments of this specification are measured by laser scattering using Horiba LA950. Deionized water is used as the circulating bath medium. A refractive index of 1.66 with an imaginary value of 0.0i is used. The sample is prepared by providing a suitable amount of particulate material in a 50 ml beaker. The beaker is filled to the fill line with a solution of deionized water containing 0.25% to 0.35% sodium hexametaphosphate (SHMP) such that the slurry contains approximately 1 to 3 wt% solid particulate material in a mixture of deionized water and SHMP. The sample is then sonicated for 30 seconds. The pH of the water is set to 8 - 10. During the analysis, the sonication function of the Horiba analyzer is on. The sample is pipetted into the circulating bowl in 2 - 3 drops (about 1 - 3 ml) at a time until the Lamp% reaches 80 - 85%. The data from the analysis is imported into suitable computer software (e.g., Microsoft Excel) that can provide statistical analysis. The data analysis function of the software is used to analyze the distribution details.

[0015] In another embodiment, the plurality of particles can have a specific particle size distribution that can promote improved manufacturing and / or performance. For example, in one embodiment, the core (i.e., the uncoated particle) can have D10 - D90 values in the range of at least 1 nm to 5000 nm or less. In certain embodiments, the D10 - D90 values can be at least 1 nm, or at least 10 nm, or at least 25 nm, or at least 50 nm, or at least 75 nm, or at least 100 nm, or at least 120 nm, or at least 140 nm, or at least 260 nm, or at least 300 nm, or at least 400 nm, or at least 500 nm. In addition, in another non-limiting embodiment, the D10 - D90 values can be 4500 nm or less, or 4000 nm or less, or 3000 nm or less, or 2000 nm or less, or 1000 nm or less, or 800 nm or less, or 600 nm or less, or 400 nm or less, or 200 nm or less, or 150 nm or less. It will be understood that the D10 - D90 values can be, for example, but not limited to, within a range that includes at least 10 nm to 3000 nm or less, or within a range of at least 25 nm to 1000 nm or less, or within a range of at least 50 nm to 500 nm or less, or even within a range that includes at least 50 nm to 150 nm or less, including any of the above minimum and maximum values.

[0016] In another embodiment, the particulate material or materials (i.e., core and shell) may have a D50 of at least 1 nm, or at least 2 nm, or at least 5 nm, or at least 10 nm, or at least 25 nm, or at least 50 nm, or at least 75 nm, or at least 100 nm, or at least 120 nm, or at least 140 nm. In another non-limiting embodiment, the core may have a D50 of 1500 nm or less, or 1200 nm or less, or 1000 nm or less, or 900 nm or less, or 800 nm or less, or 700 nm or less, or 600 nm or less, or 500 nm, or 400 nm or less, or 300 nm or less. The core may have a D50 within a range including, for example, but not limited to, any of the above minimum and maximum values within a range of at least 1 nm to 1500 nm or less, or at least 2 nm to 1000 nm or less, or at least 10 nm to 500 nm or less, or at least 20 nm to 300 nm or less.

[0017] According to one embodiment, the particulate material may have a specific surface area that can promote the production and / or improve the performance of the particulates. For example, in one embodiment, the core (i.e., the uncoated particle) has at least 1 m 2 / g to 100 m 2 / g or less, for example, at least 10 m 2 / g, or at least 15 m 2 / g, or at least 20 m 2 / g, and 80 m 2 / g or less, or 50 m 2 / g or less, 30 m 2 / g or less, or 25 m 2 / g or less.

[0018] In one aspect, the shell can be formed to have certain characteristics that promote improved performance of the microparticles. For example, in one non-limiting embodiment, the average thickness of the shell can be formed to provide suitable stability against certain oxidation species while also providing suitable material removal performance. According to one embodiment, the shell includes an average thickness of at least 0.5% and at most 20% of the median diameter (D50) of the core. In one non-limiting embodiment, the average thickness of the shell is at least 0.06% of the D50 of the core, such as at least 0.07% of the D50 of the core, or at least 0.08% of the D50 of the core, or at least 0.09% of the D50 of the core, or at least 0.1% of the D50 of the core, or at least 0.13% of the D50 of the core, or at least 0.15% of the D50 of the core, or at least 0.18% of the D50 of the core, or at least 0.2% of the D50 of the core, or at least 0.3% of the D50 of the core, or at least 0.4% of the D50 of the core, or at least 0.5% of the D50 of the core, or at least 0.6% of the D50 of the core, or at least 0.7% of the D50 of the core, or at least 0.8% of the D50 of the core, or at least 0.9% of the D50 of the core, or at least 1% of the D50 of the core, or at least 2% of the D50 of the core, or at least 3% of the D50 of the core, or at least 4% of the D50 of the core, or at least 5% of the D50 of the core. Also, in another non-limiting embodiment, the average thickness of the shell is at most 18% of the D50 of the core, or at most 17% of the D50 of the core, or at most 16% of the D50 of the core, or at most 15% of the D50 of the core, or at most 14% of the D50 of the core, or at most 13% of the D50 of the core, or at most 12% of the D50 of the core, or at most 11% of the D50 of the core, or at most 10% of the D50 of the core, or at most 9% of the D50 of the core, or at most 8% of the D50 of the core, or at most 7% of the D50 of the core, etc., and can be at most 19% of the D50 of the core. The average thickness of the shell can be, for example, but not limited to, within a range including any of the above minimum and maximum percentages, including within a range of at least 0.5% and at most 19% of the D50 of the core, or within a range of at least 0.5% and at most 15% of the D50 of the core, or within a range of at least 1% and at most 10% of the D50 of the core.

[0019] The process of measuring the average thickness of the shell can be performed by TEM image analysis such as the images provided in Figure 2. Multiple particles are imaged at a magnification suitable for clearly resolving the shell layer, such as a field of view of approximately 100 nm. For randomly selected particles or portions of particles, 10 photographs are taken at the same magnification. A statistically relevant sample set is created by making a suitable number of measurements from the images (e.g., making 4 measurements for any shell regarding at least 10 different particles, for a total of 40 measurements). Image analysis software such as ImageJ can be used to evaluate the average thickness of the layer. The average shell thickness is calculated as the average from all of the shell thickness measurements made. The average shell thickness value is then compared to the D50 of the core, and the average thickness of the shell is calculated as a percentage of the core D50.

[0020] Any reference to an average value herein can refer to the average value from a single particle, multiple microparticles, or a batch of abrasive grains or microparticles from a CMP slurry. The measurements necessary to determine the average value should be obtained from a statistically relevant sample size.

[0021] According to another embodiment, the shell layer can include a silica-containing species having a specific content, also referred to herein as "SiOx". In certain embodiments, the silica-containing species can include a silane or a silane-containing compound. In certain embodiments, the silica-containing species consists essentially of silica (SiO 2 ). As used herein, consisting essentially of silica means that at least 99% by weight of the shell layer is silica based on the total weight of the shell.

[0022] In one embodiment, the shell layer can include a plurality of films, such as a first film that is in direct contact with the outer surface of the core, and such a first film can include silica. In another embodiment, the shell layer can include a second film that covers at least a portion of the first film such that at least a portion of the first film is disposed between the core and the second film. In one example, the second film can include a silane or a silane-containing species.

[0023] In another embodiment, the shell can have a specific composition that can promote improved performance. For example, in one embodiment, the shell can include at least 90 volume % of SiOx, such as at least 95 volume % of SiOx or at least 98 volume % of SiOx, based on the total volume of the shell. In a particular embodiment, the shell can consist essentially of SiOx such that a small amount of impurities that do not substantially change the characteristics or properties of the shell can be present. In another embodiment, the shell can consist entirely of SiOx. Such percentages can also be average percentages for a plurality of abrasive grains or batches of abrasive grains.

[0024] In another embodiment, the shell can include certain species of content that can be considered impurities. Examples of such impurity species can include silicon carbide, diamond, cubic boron nitride, boron carbide, ceria, titania, yttria, rare earth oxides, aluminosilicates, transition metals, transition metal oxides, oxides (e.g., alumina or transition alumina), sulfates (e.g., transition metal sulfates), nitrates (e.g., transition metal nitrates) or any combination thereof.

[0025] According to one embodiment, the content of such impurity species can be 9 weight % or less based on the total volume of the shell, such as 7 weight % or less of impurities, or 5 weight % or less of impurities, or 2 weight % or less of impurities, or 1 weight % or less of impurities, or 0.5 weight % or less of impurities. In a non-limiting embodiment, the shell can include at least 0.001 weight % of impurities. The impurities in the shell can be within a range that includes either the above minimum percentage or the above maximum percentage. Such percentages can also be average percentages for a plurality of abrasive grains or batches of abrasive grains.

[0026] Regarding another aspect of the microparticles, in some examples, the microparticles can have a specific percentage of the core covered by a shell, which can promote the improved performance of the microparticles. For example, in one embodiment, the shell can cover at least 50%, such as at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99% of the total surface area of the core. In one particular embodiment, the shell can be a thin conformal coating that essentially covers the entire core. Such a percentage can also be the average percentage for a plurality of abrasive particles or batches of abrasive particles.

[0027] In another embodiment, the shell can have a specific thickness that can promote improved manufacturing and / or the performance of the microparticles. For example, in one embodiment, the shell can have an average thickness of at least 0.1 nm and 50 nm or less. In another embodiment, the shell can have an average thickness of at least 0.5 nm, or at least 0.8 nm, or at least 1 nm, or at least 1.5 nm, or at least 2 nm, or at least 3 nm, or at least 4 nm, or at least 5 nm. In another non-limiting embodiment, the shell can have an average thickness of 45 nm or less, or 40 nm or less, or 35 nm or less, or 30 nm or less, or 25 nm or less, or 20 nm or less, or 18 nm or less, or 15 nm or less, or 14 nm or less, or 13 nm or less, or 12 nm or less. It will be understood that the shell can have an average thickness within a range including any of the above minimum and maximum values, for example, but not limited to, at least 0.5 nm and 30 nm or less, or at least 0.5 nm and 20 nm or less.

[0028] In a particular aspect, the average (D50) particle size of the particles can be from 150 nm to 250 nm, and the thickness of the shell can be from 4 nm to 20 nm, or from 6 nm to 15 nm.

[0029] According to one embodiment, the particulate material is at least 3 g / cm 3 ~7 g / cm 3It may have a density within the following ranges. In one non-limiting embodiment, the density of the particulate material is at least 3.5 g / cm 3 , or at least 3.8 g / cm 3 , or at least 4.0 g / cm 3 , or at least 4.2 g / cm 3 , or at least 4.5 g / cm 3 , or at least 4.8 g / cm 3 , or at least 5.0 g / cm 3 , or at least 5.2 g / cm 3 , or at least 5.5 g / cm 3 , such as at least 3.2 g / cm 3 and may be. In another non-limiting embodiment, the particulate material may have a density of 6.8 g / cm 3 or less, or 6.5 g / cm 3 or less, or 6.2 g / cm 3 or less, or 6.0 g / cm 3 or less, or 5.8 g / cm 3 or less, or 5.5 g / cm 3 or less. The density may be, for example, but not limited to, at least 3.5 g / cm 3 and 6.5 g / cm 3 or less, or at least 4 g / cm 3 and 6 g / cm 3 or less, or within a range including at least 5 g / cm 3 and 6 g / cm 3 or less, and may be within a range including any of the above minimum and maximum values.

[0030] In certain examples, the microparticles can be relatively dense with little porosity. For example, the microparticles can have a porosity of 20 volume % or less, such as 15 volume % or less, or 12 volume % or less, or 10 volume % or less, or 8 volume % or less, or 5 volume % or less, or 3 volume % or less, or 2 volume % or less, or 1 volume % or less, or 0.5 volume % or less, or 0.1 volume % or less, relative to the total volume of the microparticles, which can promote improved performance of the composition. In another non-limiting embodiment, the microparticles can have a porosity of at least 0.1 volume %, or at least 0.5 volume %, or at least 1 volume %, or at least 5 volume %, or even at least 15 volume %. The porosity of the particulate material can be within a range that includes either of the above minimum and maximum percentages.

[0031] According to one embodiment, the plurality of abrasive grains can include at least one or more microparticles described in any of the embodiments herein. The plurality of abrasive grains can include a small or large content of microparticles. In at least one example, the plurality of abrasive grains includes at least 50 wt%, or at least 60 wt%, or at least 70 wt%, or at least 80 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt% of microparticles. In one example, the plurality of abrasive grains consists entirely of microparticles. In another non-limiting embodiment, the plurality of abrasive grains includes a batch of abrasive particles that can be used for material removal operations or incorporation into a fixed abrasive. According to one embodiment, the batch of abrasive grains can have a weight of at least 10 grams, but can include abrasive grains of larger weights, including contents of kilograms or more.

[0032] In yet another aspect, a chemical mechanical planarization (CMP) slurry can include a carrier and a plurality of particles including the microparticles of any one or more combinations of the features of the microparticles herein. The plurality of particles can include a plurality of abrasive grains including any of the features of the embodiments herein.

[0033] The CMP slurry can be formed according to the following non-limiting methods. Other additives in other contents may be used, and it will be understood that the following process is merely an illustration of the CMP slurry according to one embodiment. The process for making the CMP slurry may include obtaining 10,546 grams of deionized water and adding it to a mixing container. 3,809 grams of the core-shell particles (e.g., abrasive particles) of the embodiment of the present specification are added to the deionized wafer and mixed for approximately 10 minutes to produce a first mixture. 480 grams of tartaric acid are added, 8 grams of 1,2,4-triazole are added to the first mixture, and it is mixed for approximately 20 minutes to produce a second mixture. Approximately 914 grams of hydrogen peroxide (H 2 O 2 ) is added to the second mixture and mixed for approximately 5 minutes to produce a CMP mixture. The pH of the CMP mixture can be adjusted to approximately 7.5 using KOH. The final CMP mixture contains approximately 2 wt% particulate material, 2 wt% H 2 O 2 , 3% tartaric acid, and 0.05 wt% 1,2,4-triazole.

[0034] The CMP slurry may contain other additives in addition to the carrier and the plurality of particles. For example, in certain examples, the CMP slurry may further include at least one of a surfactant, a dispersant, a wetting agent, a thickening agent, an antifoaming agent, an antibacterial agent, a suspending aid, a stabilizer, a lubricant, a rheology modifier, or any combination thereof. For example, certain optional additives can include an oxidizing agent, a dispersant, a surfactant, a lubricant, or any combination thereof. Some suitable examples of oxidizing agents include peroxides (e.g., H 2 O 2 ), persulfides (e.g., H 2 S 2 ), perchlorates (e.g., KClO 4 ), periodates (e.g., KIO 4 ), perbromates (e.g., KBrO 4 ), permanganates (e.g., KMnO 4 NaMnO 4 ), chromates (e.g., K 3CrO 8 ) ammonium cerium nitrate (e.g., (NH 4 ) 2 Ce(NO 3 ) 6 ), ferrocyanide (e.g., K 4 Fe(CN) 6 ), persulfate, or any combination thereof may be included. Some suitable examples of dispersants include potassium hexametaphosphate, polyvinylpyrrolidone, potassium polynaphthalenesulfonate, potassium polymethacrylate, ammonium polymethacrylate, potassium polyacrylate, ammonium polyacrylate, potassium ligninsulfonate. In some limited applications, a dispersant having sodium (e.g., any of the dispersants listed above) may be used, but it is not typical for all applications (e.g., the electronics industry). Some suitable examples of surfactants include oleic acid, cetyltrimethylammonium bromide, dodecanethiol, oleylamine, sodium dodecyl sulfate, hydroxymethylphosphonoacetic acid, or any combination thereof. Some suitable examples of lubricants include fluorosurfactants, zinc stearate, manganese dioxide, molybdenum disulfide, aluminosilicate, organosilicon copolymer, or any combination thereof. In another embodiment, one or more optional complexing agents (e.g., malonic acid, tartaric acid, citric acid, and amino acids) may be added. In another embodiment, an optional corrosion inhibitor (e.g., BTA, triazole (e.g., 1,2,4-triazole), phosphonic acid, etc.) may be added. The CMP slurry may contain any one or more of the aforementioned additives.

[0035] The CMP slurry can have high stability with respect to the presence of hydrogen peroxide. In one embodiment, the % reduction rate of hydrogen peroxide stability of the CMP slurry can be 50% or less. As used herein, the phrase "hydrogen peroxide stability % reduction rate" means the reduction of the hydrogen peroxide content of the slurry after 7 days expressed as a percentage. As illustrated in Figure 3, the CMP slurry containing plain zirconia particles without a silica shell could not maintain any hydrogen peroxide even for 1 day, but as the thickness of the shell containing silica increased, it was found that the H 2 O 2 content could be significantly maintained. The CMP slurry of the present disclosure can combine the use of modified zirconia particles with the desired advantages for polishing while enabling high stability of H 2 O 2 contained in the slurry.

[0036] In certain other examples, the composition can be a dry or wet composition. The wet composition can include a CMP slurry containing a liquid carrier that promotes the dispersion of a plurality of abrasive grains in the carrier. That is, a plurality of abrasive grains can be suspended in a liquid carrier to form a CMP slurry. After forming the dry powder composition, it may be transported to the customer, and the customer can add a liquid carrier to make a polishing composition in the form of a slurry. However, in other examples, the dry powder composition can be dispersed in the liquid carrier before being sent to the customer. Some suitable examples of the liquid carrier can include polar or non-polar liquid materials. In one embodiment, the carrier can include water, can consist essentially of water, and more specifically, can consist essentially of deionized water.

[0037] The compositions of the embodiments can be used in various industries, particularly in the electronics industry for chemical mechanical planarization. In at least one embodiment, the CMP slurry can be used to finish the surface of a substrate where both metal and ceramic parts are exposed. In one non-limiting embodiment, the CMP slurry containing particulate material is a dielectric material (e.g., silica), nitride (Si 3 N4 ), carbides (e.g., SiC), metals or metal alloys (e.g., W, Al, Cu, Co, Ta, Ru, Au), etc., and can be used on workpieces containing such materials. According to certain embodiments, the fine particles of the embodiments herein can be suitable for use in a CMP slurry configured for use in copper barrier polishing.

[0038] In one particular aspect, the CMP slurry can have a particularly small difference in material removal rate between certain types of materials. For example, the CMP slurry can have an ST material removal rate percentage difference of 300% or less, such as 200% or less, or 100% or less. As used herein, the ST material removal rate percentage difference is the difference in the material removal rate of a CMP slurry for polishing a silica (SiO2) substrate and a tantalum nitride (TaN) substrate.

[0039] As further demonstrated in the examples, the CMP slurry can have high efficiency in polishing substrates containing copper (Cu). In certain aspects, the Cu material removal rate can be at least 1500 Å / min. In certain aspects, the CMP slurry can have a removal rate of at least 100 Å / min for both TaN material and SiO2 material and a copper removal rate of at least 1500 Å / min while having high stability with respect to hydrogen peroxide.

[0040] Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, those skilled in the art will understand that those aspects and embodiments are merely illustrative and do not limit the scope of the present invention. Embodiments can conform to any one or more of the embodiments listed below.

[0041] Embodiments Embodiments include any combination of any one or more of the features described herein.

[0042] Embodiment 1. A chemical mechanical polishing (CMP) slurry, It includes a plurality of particles dispersed in a carrier, and at least a part of the plurality of particles has a main body including a core containing zirconia and a shell covering at least a part of the core. The shell contains silica, an oxidizing agent, and a carrier, and the CMP slurry is A hydrogen peroxide stability % reduction rate of 50% or less, where the hydrogen peroxide stability % reduction rate is calculated according to [( %H on the 0th day 2 O 2 - %H on the 7th day 2 O 2 ) / %H on the 0th day 2 O 2 × 100%, the hydrogen peroxide stability % reduction rate A SiO2 material removal rate of at least 100 Å / min A Cu material removal rate of at least 1500 Å / min A TaN material removal rate of at least 100 Å / min A chemical mechanical planarization (CMP) slurry including at least one of a ST material removal rate percentage difference of 300% or less.

[0043] Embodiment 2. The slurry is A hydrogen peroxide stability % reduction rate of 50% or less A SiO2 material removal rate of at least 100 Å / min A Cu material removal rate of at least 1500 Å / min A TaN material removal rate of at least 100 Å / min, and The CMP slurry according to Embodiment 1, including a combination of two or more of a ST material removal rate percentage difference of 300% or less.

[0044] Embodiment 3. The slurry is A hydrogen peroxide stability % reduction rate of 50% or less A SiO2 material removal rate of at least 100 Å / min A Cu material removal rate of at least 1500 Å / min A TaN material removal rate of at least 100 Å / min, and The CMP slurry according to Embodiment 2, consisting of each combination of a ST material removal rate percentage difference of 300% or less.

[0045] Embodiment 4. The CMP slurry according to any one of Embodiments 1 to 3, wherein the hydrogen peroxide stability % reduction rate is 45% or less, or 40% or less, or 35% or less, or 30% or less, or 25% or less, or 20% or less, or 18% or less, or 16% or less, or 14% or less, or 12% or less, or 10% or less, or 8% or less, or 6% or less, or 4% or less.

[0046] Embodiment 5. The CMP slurry according to any one of Embodiments 1 to 4, wherein the hydrogen peroxide stability % reduction rate is at least 0.1%, or at least 0.5%, or at least 1%.

[0047] Embodiment 6. The CMP slurry according to any one of Embodiments 1 to 5, wherein the SiO2 material removal rate is at least 125 Å / min, or at least 150 Å / min, or at least 175 Å / min, or at least 200 Å / min, or at least 225 Å / min according to the CMP test.

[0048] Embodiment 7. The CMP slurry according to any one of Embodiments 1 to 6, wherein the SiO2 material removal rate is 600 Å / min or less, or 500 Å / min or less, or 400 Å / min or less according to the CMP test conditions provided in Table 3.

[0049] Embodiment 8. The CMP slurry according to any one of Embodiments 1 to 7, wherein the copper material removal rate is at least 1550 Å / min, or at least 1575 Å / min, or at least 1600 Å / min, or at least 1650 Å / min, or at least 1700 Å / min, or at least 1750 Å / min according to the CMP test conditions provided in Table 3.

[0050] Embodiment 9. The CMP slurry according to any one of Embodiments 1 to 8, wherein the copper material removal rate is 4000 Å / min or less, or 3000 Å / min or less, or 2500 Å / min or less according to the CMP test conditions provided in Table 3.

[0051] Embodiment 10. The CMP slurry according to any one of Embodiments 1 to 9 herein, wherein when the TaN material removal rate is measured according to the CMP test conditions provided in Table 3, it is at least 125 Å / min, or at least 150 Å / min, or at least 175 Å / min, or at least 200 Å / min, or at least 225 Å / min, or at least 250 Å / min, or at least 300 Å / min.

[0052] Embodiment 11. The CMP slurry according to any one of Embodiments 1 to 10, wherein the ST removal rate percentage difference is 250% or less, or 225% or less, or 200% or less, or 150% or less, or 125% or less, or 100% or less.

[0053] Embodiment 12. The CMP slurry according to any one of Embodiments 1 to 11, wherein the core comprises at least 50% by volume of zirconia, or at least 75% by volume of zirconia, or at least 80% by volume of zirconia, or at least 90% by volume of zirconia, or at least 95% by volume of zirconia, or at least 98% by volume of zirconia, or at least 99% by volume of zirconia, or at least 99.5% by volume of zirconia, or consists essentially of zirconia, or consists of zirconia.

[0054] Embodiment 13. The CMP slurry according to any one of Embodiments 1 to 12, wherein the core contains polycrystalline abrasive grains.

[0055] Embodiment 14. The CMP slurry according to any one of Embodiments 1 to 13, wherein the shell has an average thickness of at least 0.5% and 20% or less, or at least 1% and 10% or less based on the average (D50) size of the core.

[0056] Embodiment 15. The CMP slurry according to any one of Embodiments 1 to 14, wherein the shell contains at least 90% by volume, or at least 95% by volume, or at least 98% by volume of silica with respect to the total volume of the shell, or consists essentially of silica, or consists of silica.

[0057] Embodiment 16. The CMP slurry according to any one of Embodiments 1 to 15, wherein the shell contains 9% by weight or less, or 7% by weight or less, or 5% by weight or less, or 2% by weight or less, or 1% by weight or less, or 0.5% by weight or less of impurities.

[0058] Embodiment 17. The CMP slurry according to any one of Embodiments 1 to 16, wherein the shell covers at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 99% of the total surface area of the core.

[0059] Embodiment 18. The CMP slurry according to any one of Embodiments 1 to 17, wherein the shell has an average thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 6 nm, or at least 7 nm, or at least 8 nm, or at least 9 nm, or at least 10 nm, or at least 15 nm.

[0060] Embodiment 19. The CMP slurry according to any one of Embodiments 1 to 18, wherein the shell has an average thickness of 45 nm or less, or 40 nm or less, or 35 nm or less, or 30 nm or less, or 25 nm or less, or 20 nm or less, or 18 nm or less, or 15 nm or less, or 14 nm or less, or 13 nm or less, or 12 nm or less.

[0061] Embodiment 20. A CMP slurry composition, wherein the shell has an average thickness of at least 4 nm and 20 nm or less.

[0062] Embodiment 21. The CMP slurry according to any one of Embodiments 1 to 20, wherein each of the plurality of particles includes a core containing zirconia and a shell containing silica.

[0063] Embodiment 22. The CMP slurry according to any one of Embodiments 1 to 21, wherein the average particle size of the plurality of particles is at least 30 nm, or at least 50 nm, or at least 70 nm, or at least 90 nm, or at least 100 nm, or at least 120 nm, or at least 150 nm, or at least 170 nm.

[0064] Embodiment 23. The CMP slurry according to any one of Embodiments 1 to 22, wherein the average particle size of the plurality of particles is 500 nm or less, or 400 nm or less, or 300 nm or less, or 250 nm or less, or 200 nm or less.

[0065] Embodiment 24. The CMP slurry according to any one of Embodiments 1 to 23, wherein the average particle size (D50) of the plurality of particles is in the range of at least 50 nm to 300 nm or less.

[0066] Embodiment 25. The CMP slurry according to any one of Embodiments 1 to 24, wherein the amount of the plurality of particles is at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight, or at least 3% by weight, or at least 5% by weight based on the total weight of the CMP slurry.

[0067] Embodiment 26. The CMP slurry according to any one of Embodiments 1 to 25, wherein the amount of the plurality of particles is 10% by weight or less, or 8% by weight or less, or 6% by weight or less, or 4% by weight or less based on the total weight of the CMP slurry.

[0068] Embodiment 27. The CMP slurry according to any one of Embodiments 1 to 26, wherein the pH of the CMP slurry is at least 2.5, or at least 3.0, or at least 3.5, or at least 4.0, or at least 4.5, or at least 5.0, or at least 5.5, or at least 6.0, or at least 6.5, or at least 7.0, or at least 7.5, or at least 8.0.

[0069] Embodiment 28. The CMP composition according to any one of Embodiments 1 to 27, wherein the pH of the CMP slurry is 10 or less, or 9 or less, or 8 or less, or 7 or less, or 6.5 or less, or 6 or less, or 5.5 or less, or 5 or less.

[0070] Embodiment 29. The CMP slurry according to Embodiment 26 or 27, wherein the pH is in the range of 5 to 8.

[0071] Embodiment 30. The CMP slurry according to any one of Embodiments 1 to 29, further comprising an oxidizing agent, a complexing agent, a corrosion inhibitor, a pH adjuster, or any combination thereof.

[0072] Embodiment 31. The CMP slurry according to Embodiment 30, wherein the oxidizing agent comprises a peroxide, a persulfate, or a permanganate.

[0073] Embodiment 32. The CMP slurry according to Embodiment 31, wherein the oxidizing agent comprises hydrogen peroxide (H 2 O 2 ).

[0074] Embodiment 33. The CMP slurry according to any one of Embodiments 1 to 32, wherein the amount of the oxidizing agent is at least 0.5 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2.0 wt%, or at least 3.0 wt%, or at least 5 wt%, or at least 7 wt% based on the total weight of the slurry.

[0075] Embodiment 34. The CMP slurry according to any one of Embodiments 1 to 33, wherein the amount of the oxidizing agent is 15% by weight or less, or 10% by weight or less, or 5% by weight or less based on the total weight of the slurry.

[0076] Embodiment 35. The CMP slurry according to Embodiment 30, wherein the complexing agent contains malonic acid, tartaric acid, citric acid, an amino acid, or any combination thereof.

[0077] Embodiment 36. The CMP slurry according to Embodiment 30, wherein the corrosion inhibitor contains benzotriazole (BTA), triazole, phosphonic acid, or any combination thereof.

[0078] Embodiment 37. The CMP slurry according to any one of Embodiments 1 to 36, wherein the carrier contains water.

[0079] Embodiment 38. A method for polishing a substrate, comprising providing a substrate and a CMP slurry, and polishing the substrate with the CMP slurry using a polishing pad, wherein the CMP slurry contains a plurality of particles dispersed in a carrier, an oxidizing agent, and a carrier, and at least a portion of the plurality of particles has a main body including a core containing zirconia and a shell covering at least a portion of the core, and the shell contains silica.

[0080] Embodiment 39. The method according to Embodiment 38, wherein the substrate contains a ceramic material, a metal, a metal alloy, diamond, a polymer, a group III-V compound, or a group IV-IV compound.

[0081] Embodiment 40. The method according to Embodiment 39, wherein the substrate contains a dielectric material, a nitride, a carbide, a metal, or a metal alloy.

[0082] Embodiment 41. The method according to Embodiment 39 or 40, wherein the substrate contains copper, silica, tantalum nitrate (TaN), or any combination thereof.

[0083] Embodiment 42. The method according to any one of Embodiments 38 to 40, configured for copper barrier polishing.

[0084] Embodiment 43. The method according to any one of Embodiments 38 to 42, further comprising adjusting the pH of the CMP slurry before polishing.

[0085] Embodiment 44. The pH of the CMP slurry is at least 2.5, or at least 3.0, at least 3.5, at least 4.0, at least 4.5, at least 5.0, or at least 5.5, or at least 6.0, or at least 6.5, or at least 7.0, or at least 7.5, or at least 8.0, the method according to any one of Embodiments 38 to 43.

[0086] Embodiment 45. The pH of the CMP slurry is 10 or less, or 9 or less, or 8 or less, or 7 or less, or 6.5 or less, or 6 or less, or 5.5 or less, or 5 or less, the method according to any one of Embodiments 38 to 44.

[0087] Embodiment 46. At least one oxidizing agent includes peroxide, persulfate, permanganate, chlorite, nitrite, perchlorate, hypochlorite, manganese oxide, or any combination thereof, the method according to any one of Embodiments 38 to 45.

[0088] Embodiment 47. The oxidizing agent includes peroxide, persulfate, permanganate, or a combination thereof, the method according to any one of Embodiments 38 to 46.

[0089] Embodiment 48. The oxidizing agent includes hydrogen peroxide (H 2 O 2 ), the method according to any one of Embodiments 38 to 47.

[0090] Embodiment 49. SiO 2The method according to any one of Embodiments 38 to 48, wherein the material removal rate is at least 100 Å / min, or at least 125 Å / min, or at least 150 Å / min, or at least 175 Å / min, or at least 200 Å / min, or at least 225 Å / min according to the CMP test.

[0091] Embodiment 50. SiO 2 The method according to any one of Embodiments 38 to 48, wherein the material removal rate is 600 Å / min or less, or 500 Å / min or less, or 400 Å / min or less according to the CMP test.

[0092] Embodiment 51. The method according to any one of Embodiments 38 to 50, wherein the copper material removal rate is at least 1500 Å / min, or at least 1550 Å / min, or at least 1575 Å / min, or at least 1600 Å / min, or at least 1650 Å / min, or at least 1700 Å / min, or at least 1750 Å / min according to the CMP test.

[0093] Embodiment 52. The method according to any one of Embodiments 38 to 51, wherein the copper material removal rate is 4000 Å / min or less, or 3000 Å / min or less, or 2500 Å / min or less according to the CMP test.

[0094] Embodiment 53. The method according to any one of Embodiments 38 to 52, wherein the TaN material removal rate, when measured according to the CMP test, is at least 100 Å / min, or at least 125 Å / min, or at least 150 Å / min, or at least 175 Å / min, or at least 200 Å / min, or at least 225 Å / min, or at least 250 Å / min, or at least 300 Å / min.

[0095] Embodiment 54. The method according to any one of Embodiments 38 to 53, wherein the ST removal rate percentage difference is 300% or less, or 250% or less, or 225% or less, or 200% or less, or 150% or less, or 125% or less, or 100% or less.

[0096] Embodiment 55. The method according to any one of Embodiments 38 to 54, wherein the average particle size of the plurality of particles is at least 30 nm, or at least 50 nm, or at least 70 nm, or at least 90 nm, or at least 100 nm, or at least 120 nm, or at least 150 nm, or at least 170 nm.

[0097] Embodiment 56. The method according to any one of Embodiments 38 to 55, wherein the average particle size of the plurality of particles is 500 nm or less, or 400 nm or less, or 300 nm or less, or 250 nm or less, or 200 nm or less.

[0098] Embodiment 57. The method according to any one of Embodiments 38 to 56, wherein the average particle size (D50) of the plurality of particles is in the range of at least 50 nm to 300 nm or less.

[0099] Embodiment 58. The method according to any one of Embodiments 38 to 57, wherein the shell has an average thickness of at least 1 nm, or at least 3 nm, or at least 5 nm, or at least 6 nm, or at least 7 nm, or at least 8 nm, or at least 9 nm, or at least 10 nm, or at least 15 nm.

[0100] Embodiment 59. The method according to any one of Embodiments 38 to 58, wherein the shell has an average thickness of 45 nm or less, or 40 nm or less, or 35 nm or less, or 30 nm or less, or 25 nm or less, or 20 nm or less, or 18 nm or less, or 15 nm or less, or 14 nm or less, or 13 nm or less, or 12 nm or less.

[0101] Embodiment 60. The method according to any one of Embodiments 38 to 59, wherein the average (D50) particle size of the plurality of particles is in the range of 100 nm to 250 nm, and the thickness of the shell is in the range of 3 nm to 20 nm, or 5 nm to 15 nm.

Examples

[0102] Example 1: The following non-limiting examples illustrate the present invention.

[0103] The zirconia raw material particularly suitable for use as a core was obtained from Saint - Gobain as Product Code 9839 / 9840, sometimes called Zirpol Nano. The characteristics of the particle size distribution are provided in Table 1.

[0104]

Table 1

[0105] After obtaining the core material, it was processed to form a silica shell covering at least a portion of the core. The process for forming the shell included a deposition process. The process for forming the shell on the core particles included forming a silica coating using a silicon - containing source such as an organosilicon source (e.g., TMOS, TEOS). The organosilicon source was added to water to release the silicon material. The core particles were added to the water and the silicon source to make a mixture. The pH of the mixture can be adjusted to control the deposition of the silicon source onto the surface of the core particles such that particulate material having a core zirconia core and a silica shell structure is produced.

[0106] The coated particles of Sample S1 were formed such that the shell had an average thickness of approximately 1 nm.

[0107] Example 2: A sample of particulate having a core - shell structure was formed according to the process of Example 1, except that the shell was formed to have an average thickness of approximately 3 nm.

[0108] Example 3: A sample of particulate having a core - shell structure was formed according to the process of Example 1, except that the shell was formed to have an average thickness of approximately 12 nm.

[0109] Example 4: Samples S1, S2, and S3 were subjected to H according to the following test procedures2 O 2 Tested for compliance: Of the particulate material sample, 0.4 g was weighed (to ±0.001 g) and recorded as W g. 150 mL of sulfuric acid (1:19) was measured into a 500 mL Erlenmeyer flask and cooled to below 10 °C using a laboratory refrigerator or freezer. When the temperature of the solution reached below 10 °C, approximately 3 drops of ferroin indicator solution were added, and then titrated with ammonium cerium nitrate solution (0.1 N) contained in a burette until the indicator changed to blue. Thereafter, a 0.4 g measured sample of the particulate material was added to the cold solution. The number of grams of the sample = (40 mL × 0.1 N × 1.701) / %C, where %C is the estimated concentration of hydrogen peroxide and 1.701 is the weight per milliequivalent of hydrogen peroxide × 100, and it was swirled and mixed as calculated. It was then rapidly titrated with ammonium cerium nitrate solution (0.1 N) until it became the same blue color. The titration result, mL Ce+3, is calculated by subtracting the initial volume from the final volume of the ammonium cerium nitrate used. The percent concentration of hydrogen peroxide in the sample was calculated using the following formula: H 2 O 2 Concentration % = (ml Ce+3) × (N Ce+3) × 1.701 / grams of sample.

[0110] Calculation example: Titrant volume: Final 40.49 mL - Initial 1.52 mL = 38.97 mL of titrant H 2 O 2 Concentration %: (38.97 mL Ce+3 × 0.0950 mol equivalent / L Ce+3 × 1.701) / 17.80 g sample = 0.3538%

[0111] Figure 3 includes plots of H 2 O 2 over time (0 - 7 days) to evaluate the stability and compliance of samples S1, S2, and S3, as well as uncoated zirconia particles (sample C1), and a 3% H 2 O 2 %. As demonstrated, samples S1, S2, and S3, compared to sample C1, have H 2O 2 had better compatibility and stability with. Sample S1 had a 0-day %H of 3% 2 O 2 and a 7-day %H of 1.8% 2 O 2 and had an approximate hydrogen peroxide stability % reduction rate of 40% when calculated. Thus, [(3.0 - 1.8) / 3.0]×100% = 40%. Sample S2 had a 0-day %H of 3% 2 O 2 and a 7-day %H of 1.8% 2 O 2 and had an approximate hydrogen peroxide stability % reduction rate of 40% when calculated. Thus, [(3.0 - 1.8) / 3.0]×100% = 40%. Sample S3 had a 0-day %H of 3% 2 O 2 and a 7-day %H of 2.55% 2 O 2 and had an approximate hydrogen peroxide stability % reduction rate of 15% when calculated. Thus, [(3.0 - 2.55) / 3.0]×100% = 15%.

[0112] The best H over time 2 O 2 stability was had by Sample S3, which had the thickest silica coating of 6 nm.

[0113] The experiments were conducted using each slurry containing zirconia particles with silica shell thicknesses of 9 nm and 12 nm, which showed even better H over time 2 O 2 stability (lower H 2 O 2 stability % reduction rate).

[0114] Example 5 Samples S1, S2, and S3 were tested as CMP slurries to evaluate their material removal rates on a glass substrate.

[0115] The CMP slurries were prepared using the fine particles from samples S1, S2, and S3, and the CMP slurry samples are referred to herein as CMP S1, CMP S2, and CMP S3, respectively. Each CMP slurry was prepared by adding 1870 grams of deionized water to a mixing container. Then, 1.2 grams of polyalkylene oxide-modified heptamethyltrisiloxane was added to the deionized water and mixed for approximately 5 minutes to produce a first mixture. Next, 120 grams of core-shell particles (e.g., abrasive particles of S1, S2, or S3) were added to the first mixture and mixed for approximately 30 minutes to produce one of the representative CMP mixtures of CMP S1, CMP S2, and CMP S3. The pH of each CMP mixture was adjusted to approximately 5.5 using nitric acid. Each sample contained approximately 1.5 wt% particulate material and 0.05 wt% polyalkylene oxide-modified heptamethyltrisiloxane.

[0116] Each CMP sample was tested twice according to the conditions provided in Table 2.

[0117]

Table 2

[0118] The results of the glass polishing tests are shown in Figure 4, illustrating the glass removal rates for both tests for each sample.

[0119] Example 6: Three new abrasive particle samples (i.e., Sample S4, S5, and S6) were fabricated according to the process of Example 1, except that the average thickness of each sample was adjusted. Sample S4 had an average shell thickness of 3 nm. Sample S5 had an average shell thickness of 6 nm. Sample S6 had an average shell thickness of 9 nm. Using each sample of abrasive particles, three new CMP slurries, namely CMP S4, CMP S5, and CMP S6, were fabricated respectively. The CMP slurries were formed according to the following procedure. First, 1950 grams of core-shell particles (e.g., abrasive particles of Sample S4, S5, or S6) were added to 5214 grams of deionized water and mixed for approximately 15 minutes to produce a first mixture. Then, 240 grams of tartaric acid was added to the first mixture and mixed for approximately 15 minutes to produce a second mixture. Next, approximately 4 grams of 1,2,4-triazole was added to the second mixture and mixed for approximately 15 minutes to produce a third mixture. Then, approximately 457 grams of hydrogen peroxide (H 2 O 2 ) was added to the third mixture and mixed for approximately 5 minutes to produce one of CMP samples CMP S4, CMP S5, or CMP S6. The pH of each CMP sample was adjusted to approximately 7 - 8 using KOH. Each of the CMP samples contained approximately 2 wt% particulate material (S4, S5, or S6), 2 wt% H 2 O 2 , 3% tartaric acid, and 0.05 wt% 1,2,4-triazole.

[0120] The polishing efficiency of the CMP samples was tested using copper wafers, TaN wafers, and silica wafers having a diameter of 6 inches as substrates. Each CMP slurry was tested twice for each substrate wafer type according to the conditions provided in Table 3, which is also referred to herein as a "CMP test". For copper polishing, a copper wafer manufactured by Advantive Technologies with an upper copper layer of 15,000 Å and lot number GM033018-1 was used. For TaN polishing, a TaN wafer manufactured by Advantive Technologies with an upper TaN layer of 3000 Å and lot number GM111819-6 was used. For silicon dioxide polishing, a silicon dioxide wafer manufactured by Advantive Technologies with a thickness of 20,000 Å and lot number 349547-1 was used.

[0121]

Table 3

[0122] The material removal rate was measured according to the following technique. For the copper wafers, the material removal rate of the CMP slurry was calculated by using a four-point probe from a CDE ResMap178. The thickness was calculated from the sheet resistance and resistivity of the metal over 49 points across the entire wafer. The measurements were taken before and after performing the CMP test. The difference between before and after the measurement is the metal removal divided by the polishing time to yield the material removal rate.

[0123] For TaN wafers, the removal rate was measured from the weight loss, wafer area, and density. The TaN weight of the wafer was measured before and after the CMP test. Then, the changes in weight, wafer area, and density were used to calculate the material removal rate over the test time. For oxide wafers, the material removal rate of the CMP slurry was measured with a Filmetrics F20 instrument. This measures the wafer thickness at seven points through the center of the wafer using an integrated spectrometer / source unit. This is done both before and after polishing. The difference, which results in the metal removal rate, is the metal removal divided by the polishing time.

[0124] For silicon oxide wafers, the material removal rate was measured with a Filmetrics F20 instrument. This measures the wafer thickness at seven points through the center of the wafer using an integrated spectrometer / source unit. This was done both before and after polishing. The difference, which results in the glass removal rate, is the metal removal divided by the polishing time.

[0125] The results of the material removal rates for each of the CMP samples, CMP S4, CMP S5, and CMP S6, are summarized in Table 4.

[0126]

Table 4

[0127] From the data shown in Table 4, the percent differences in the ST material removal rates between the polishing of silica wafers and TaN wafers were calculated: for CMP sample S4, a value of 20% was calculated; for CMP sample S5, a value of 30% was calculated; and for CMP sample S6, a value of 10% was calculated.

[0128] From the data in Table 4, it can be further seen that as the shell thickness increases, the removal rates of copper, TaN, and SiO 2 decrease.

[0129] Experiments were conducted on slurry compositions having shell thicknesses of 12 nm, 15 nm, and 20 nm to confirm this trend.

[0130] Without being bound by theory, a specific range of silica coating thickness with respect to the zirconia core may have advantages in obtaining a desired material removal rate and having a stable polishing slurry in terms of the mode of H 2 O 2 decomposition.

[0131] The subject matter disclosed above should be considered illustrative rather than limiting, and the appended claims are intended to encompass all such modifications, enhancements, and other embodiments that fall within the true scope of the invention. Accordingly, to the maximum extent permitted by law, the scope of the invention should be determined by the broadest permissible interpretation of the following claims and their equivalents, and should not be limited or restricted by the foregoing detailed description.

[0132] The abstract is provided to comply with patent law and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Additionally, in the foregoing "Detailed Description of the Invention," various features may be grouped together or described in a single embodiment for the purpose of simplifying the disclosure. The disclosure should not be interpreted as reflecting an intention that the claimed embodiments require more features than are explicitly recited in each claim. Rather, the subject matter of the invention may be directed to less than all of the features of any of the disclosed embodiments, as reflected in the following claims. Accordingly, the following claims are incorporated into the "Detailed Description of the Invention," and each claim stands on its own as defining a separately claimed subject matter.

Claims

1. A chemical mechanical planarization (CMP) slurry, comprising a plurality of particles dispersed in a carrier, at least a portion of said plurality of particles having a body comprising a core containing zirconia and a shell covering at least a portion of said core, said shell comprising silica, an oxidizing agent, and a carrier, wherein said CMP slurry has a hydrogen peroxide stability % reduction rate of 50% or less, SiO at a rate of at least 100 Å / min ２ material removal rate a Cu material removal rate of at least 1500 Å / min, a TaN material removal rate of at least 100 Å / min, or a chemical mechanical planarization (CMP) slurry comprising at least one of a ST material removal rate percent difference of 300% or less.

2. The CMP slurry according to claim 1, wherein the ST removal rate percent difference is 100% or less.

3. The CMP slurry according to claim 1, wherein said core contains at least 80% by volume of zirconia based on the total volume of said core.

4. The CMP slurry according to claim 1, wherein said shell has an average thickness of at least 1% and 10% or less based on the average (D50) size of said core.

5. The CMP slurry according to claim 1, wherein said shell has an average thickness of at least 3 nm and 20 nm or less.

6. The CMP slurry according to claim 1, wherein the average particle size of said plurality of particles is at least 50 nm and 500 nm or less.

7. The CMP slurry according to claim 1, wherein the amount of said plurality of particles is at least 1% by weight and 10% by weight or less.

8. The CMP slurry according to claim 1, wherein the pH is in the range of 5 to 9.

9. The CMP slurry according to claim 1, wherein said oxidizing agent comprises a peroxide, a persulfate, a permanganate, or a combination thereof.

10. The CMP slurry according to claim 9, wherein said oxidizing agent comprises hydrogen peroxide.

11. The CMP slurry according to claim 1, wherein said carrier comprises water.

12. The CMP slurry according to claim 1, wherein the average (D50) particle size of said plurality of particles is in the range of 100 nm to 250 nm, and the thickness of said shell is in the range of 3 nm to 20 nm.

13. A method of polishing a substrate, comprising: providing a substrate and a CMP slurry; and polishing said substrate with said CMP slurry using a polishing pad. The CMP slurry includes a plurality of particles dispersed in a carrier, an oxidizing agent, and a carrier, and at least a portion of the plurality of particles has a main body including a core containing zirconia and a shell covering at least a portion of the core, and the shell includes silica, method.

14. The method according to claim 13, wherein the oxidizing agent includes hydrogen peroxide.

15. The method according to claim 13, wherein the copper material removal rate is at least 1500 Å / min according to the CMP test.

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