Chemical mechanical planarization slurry and method of polishing substrate

Abstract

A chemical mechanical polishing (CMP) slurry may include: a plurality of particles distributed in a carrier, where at least a portion of the particles of the plurality of particles may have a body including a core including zirconia and a shell covering at least a portion of the core, where the shell includes silica; an oxidant; and a carrier. The CMP slurry may include at least one of: a hydrogen peroxide stability reduction percentage of no greater than 50%; and a high copper material removal rate.

Description

Technical Field

[0001] The following relates to chemical mechanical polishing (CMP) slurries and methods of using CMP slurries for polishing substrates. Background Art

[0002] Compositions for material removal operations are known. Such abrasive compositions can include fixed abrasive compositions where a collection of abrasive particles is attached to a body or substrate. Alternatively, certain abrasive compositions can contain free abrasives where the abrasive particles are not attached to a body or substrate but are contained within a liquid carrier as a slurry or mixture. Depending on the type of material removal operation, either fixed abrasives or free abrasives can be selected for use.

[0003] Conventional abrasive slurries are most commonly used for polishing materials such as glass, metals, etc. The electronics 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). Additionally, other industries also require polishing compositions. Brief Description of the Drawings

[0004] The present disclosure can be better understood by reference to the accompanying drawings, and many features and advantages of the present disclosure will become apparent to those skilled in the art.

[0005] Figure 1 Cross-sectional view of a particulate including a core and a shell according to an embodiment.

[0006] Figure 2 TEM image of a particulate including a core and a shell, which can be used to evaluate the average thickness of the shell.

[0007] Figure 3 Plot of the percentage of H2O2 for various samples, some of which contain particulates representative of embodiments herein.

[0008] Figure 4 Plot of material removal for various samples, some of which contain particulates representative of embodiments herein. Detailed Description

[0009] The following relates to a particulate or particulates, which includes, for example, a plurality of abrasive particles including particulates representative of embodiments herein. In another embodiment, the particulate can be a part of a batch of abrasive particles including the particulate. In yet another aspect, a CMP slurry is disclosed, which can contain the particulate. As used herein, a plurality of particles, a batch of abrasive particles, or a CMP slurry can contain a small amount, a large amount of particulates, or consist of particulates.

[0010] According to one aspect, the particulate may include a core and a shell covering the core. Figure 1 Cross-sectional view of particulate 100, which includes a core 101 and a shell 103 covering at least a portion of the core 101.

[0011] Figure 2 TEM image of a particle having a core and a shell. This image represents an image that can be 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 generate a suitable sample data set, from which the average thickness of the shell is calculated.

[0012] The formation of the particle may include first forming the core. According to one embodiment, a raw material having a zirconium-containing material (such as zirconium oxychloride) may be calcined to form zirconia (ZrO2). After forming the core particles, sieving may be used to control the distribution of the core particles. The sorted core particles may then be processed to produce a shell covering the core. In one embodiment, the method for forming the shell may include chemically synthesizing a silica-containing material from an organosilicon material (such as silane). In a particular embodiment, the formation of the shell layer may include the reaction of a silicon-containing precursor (such as silane) with other reactants to form a silica-containing shell layer covering the core. The methods for forming the shell may include various techniques, which include, for example, but are not limited to, sol-gel and co-precipitation methods, TEOS / TMOS methods, or any method using an organic compound as a precursor, pickering method, spraying, mechanical fusion method, deposition methods (such as CVD, ALD, etc.), or any combination thereof. The method for forming the shell may be a method suitable for producing any of the shell characteristics disclosed in any of the embodiments herein. For example, in a non-limiting example, the method for forming the shell may include a vapor deposition technique for producing a shell having a specific chemistry, morphology, and / or thickness. In one particulate embodiment, the method for forming a shell on the core particles includes using a silicon source, such as an organosilicon source (such as TMOS, TEOS). The organosilicon source may be added to water, which may cause the release of silicon material. The core particles may be added to the water and the silicon source to produce a mixture. The pH of the mixture may 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 produced.

[0013] According to one embodiment, the core may comprise zirconia and may also comprise a Cl-containing substance. Without being bound by a particular theory, the Cl-containing substance may be particularly beneficial for forming a shell having certain characteristics and / or properties of the microparticles. In a particular instance, the core may comprise a Cl-containing substance (such as chlorine) as an interstitial or grain boundary material within the zirconia. According to one embodiment, the content of the Cl-containing substance 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. Further, in another embodiment, the Cl-containing substance may be present in an amount not greater than 3000 ppm or not greater than 2500 ppm or not greater than 2000 ppm or not greater than 1800 ppm or not greater than 1500 ppm or not greater than 1200 ppm or not greater than 1000 ppm. It should be understood that the content of the Cl-containing substance may be within a range including any one of the above minimum and maximum values, including for example but not limited to at least 1 ppm and not greater than 3000 ppm, or in the range of at least 10 ppm and not greater than 2000 ppm, or even in the range including at least 200 ppm and not greater than 1000 ppm.

[0014] According to another embodiment, the core may comprise zirconia. In some instances, the core may comprise a combination of oxide-containing substances, including for example but not limited to zirconia, alumina, etc. Further, in another embodiment, the core may comprise a specific content of zirconia, such as at least 50 wt% of zirconia based on the total weight of the core, or at least 75 wt% of zirconia or at least 80 wt% of zirconia or at least 90 wt% of zirconia or at least 95 wt% of zirconia or at least 98 wt% of zirconia or at least 99 wt% of zirconia or at least 99.5 wt% of zirconia.

[0015] 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 properties or characteristics of the core. In yet another non-limiting embodiment, the core consists entirely of zirconia, wherein the total content of non-zirconia substances is not greater than 1% or not greater than 0.8% or not greater than 0.5% or not greater than 0.3% or not greater than 0.2% or not greater than 0.18% or not greater than 0.15%. According to another non-limiting embodiment, the core consists essentially of zirconia and a Cl-containing substance. In yet another embodiment, the core comprises polycrystalline abrasive microparticles.

[0016] In one aspect, the particulate can be part of a plurality of particulates, where a minority, majority, or all of the plurality of particulates have the characteristics of the particulate according to the embodiments. In one example, the particulate can include a core having a D50 in the range of at least 1 nm to no greater than 2000 nm. 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. Additionally, in another non-limiting embodiment, the core can have a D50 of no greater than 1500 nm or no greater than 1200 nm or no greater than 1000 nm or no greater than 900 nm or no greater than 800 nm or no greater than 700 nm or no greater than 600 nm or no greater than 500 nm or no greater than 400 nm or no greater than 300 nm. It should be understood that the core can have a D50 in a range including any of the above minimum and maximum values, including, for example but not limited to, in the range of at least 1 nm to no greater than 1500 nm or in the range of at least 2 nm and no greater than 1000 nm or in the range of at least 10 nm to no greater than 500 nm or in the range of at least 20 nm to no greater than 300 nm.

[0017] In one aspect, the particle size distribution can be a unimodal / monomodal distribution. As used herein, a distribution is unimodal / monomodal if for a certain value “m”, the distribution is monotonically increasing for x ≤ m and monotonically decreasing for x ≥ m. In this case, the maximum value of f(x) is f(m) and there are no other local maxima.

[0018] The particle size distribution characteristics of any of the embodiments in the present embodiments are measured by laser scattering using a Horiba LA 950. Deionized water is used as the circulating bath medium. A refractive index of 1.66 is used, where the imaginary value is 0.0i. A sample is prepared by providing an appropriate amount of particulate material to a 50 ml beaker. The beaker is filled with deionized aqueous solution containing 0.25% to 0.35% sodium hexametaphosphate (SHMP) up to the fill line such that the slurry contains approximately 1 wt% to 3 wt% of solid particulate material in the mixture of deionized water and SHMP. The sample is then sonicated for 30 seconds. The pH of the water is set to 8 to 10. During the analysis, the sonication function of the Horiba analyzer is turned on. The sample is pipetted into the circulating bowl in 2 to 3 drops (about 1 ml to 3 ml) at a time until the Lamp% is 80% to 85%. The data from this analysis is imported into a suitable computer software (such as Microsoft Excel) capable of providing statistical analysis. The data analysis function of the software is used to analyze the distribution details.

[0019] In another embodiment, the plurality of particles can have a specific particle size distribution that can facilitate improved manufacturing and / or performance. For example, in one embodiment, the core (i.e., the uncoated particle) can have a D10-D90 value in the range of at least 1 nm to no greater than 5000 nm. In a specific embodiment, the D10-D90 value 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 microns or at least 300 nm or at least 400 nm or at least 500 nm. Additionally, in another non-limiting embodiment, the D10-D90 value can be no greater than 4500 nm or no greater than 4000 nm or no greater than 3000 nm or no greater than 2000 nm or no greater than 1000 nm or no greater than 800 nm or no greater than 600 nm or no greater than 400 nm or no greater than 200 nm or no greater than 150 nm. It should be understood that the D10-D90 value can be in a range that includes any one of the above minimum and maximum values, including, for example but not limited to, at least 10 nm to no greater than 3000 nm, or in the range of at least 25 nm to no greater than 1000 nm, or in the range that includes at least 50 nm to no greater than 500 nm, or even in the range that includes at least 50 nm to no greater than 150 nm.

[0020] In another embodiment, the particulate material or materials (i.e., the core and the shell) can 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. Additionally, in another non-limiting embodiment, the core can have a D50 of no greater than 1500 nm or no greater than 1200 nm or no greater than 1000 nm or no greater than 900 nm or no greater than 800 nm or no greater than 700 nm or no greater than 600 nm or no greater than 500 nm or no greater than 400 nm or no greater than 300 nm. It should be understood that the core can have a D50 in a range that includes any one of the above minimum and maximum values, including, for example but not limited to, in the range of at least 1 nm to no greater than 1500 nm or in the range of at least 2 nm and no greater than 1000 nm or in the range of at least 10 nm to no greater than 500 nm or in the range of at least 20 nm to no greater than 300 nm.

[0021] According to one embodiment, the particulate material can have a specific surface area that can facilitate improved manufacturing and / or performance of the particulate. For example, in one embodiment, the core (i.e., the uncoated particle) can have an area of at least 1 m 2 / g to no greater than 100 m 2 / g, such as at least 10 m 2 / g, or at least 15 m 2 / g or at least 20 m 2 / g, and not greater than 80 m 2 / g, or not greater than 50 m 2 / g, not greater than 30 m 2 / g, or not greater than 25 m 2 specific surface area within the range of / g.

[0022] In one aspect, the housing can be formed to have certain characteristics that are beneficial for improved performance of the microparticles. For example, in a non-limiting embodiment, the average thickness of the housing can be formed to provide suitable stability with respect to certain oxidizing substances while also providing suitable material removal performance. According to one embodiment, the housing comprises the following average thickness, which is at least 0.5% and not greater than 20% of the median size (D50) of the core. In a non-limiting embodiment, the average thickness of the housing can be at least 0.06% of the D50 of the core, such as at least 0.07% or at least 0.08% or at least 0.09% or at least 0.1% or at least 0.13% or at least 0.15% or at least 0.18% or at least 0.2% or at least 0.3% or at least 0.4% or at least 0.5% or at least 0.6% or at least 0.7% or at least 0.8% or at least 0.9% or at least 1% or at least 2% or at least 3% or at least 4% or at least 5% of the D50 of the core. Additionally, in another non-limiting embodiment, the average thickness of the housing can be not greater than 19% of the D50 of the core, such as not greater than 18% or not greater than 17% or not greater than 16% or not greater than 15% or not greater than 14% or not greater than 13% or not greater than 12% or not greater than 11% or not greater than 10% or not greater than 9% or not greater than 8% or not greater than 7% of the D50 of the core. It should be understood that the average thickness of the housing can be within a range including any one of the above minimum and maximum percentages, including for example but not limited to at least 0.5% and not greater than 19% of the D50 of the core, or within the range of at least 0.5% and not greater than 15% of the D50 of the core, or within the range of at least 1% and not greater than 10% of the D50 of the core.

[0023] The method for measuring the average thickness of the housing can be by TEM image analysis (such as Figure 2It is carried out by means of the images provided in [reference]. Multiple particles are imaged at a suitable magnification to clearly resolve the shell layer, such as a field of view of about 100 nm. At the same magnification, ten photos are taken of randomly selected particles or parts of particles. A statistically relevant sample set is generated by making a suitable number of measurements from the images (e.g., 4 measurements for any shell of at least 10 different particles, thus making 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 of all the shell thickness measurements made. Then the average shell thickness value is compared with the D50 of the core to calculate the average thickness of the shell as a percentage of the core D50.

[0024] Any average value referred to herein can refer to the average value from a single particle, the average value from multiple fine particles of a CMP slurry, or a batch of abrasive particles or fine particles. The measurements necessary to determine the average value should be taken from a statistically relevant sample size.

[0025] According to another embodiment, the shell layer can contain a certain content of silica-containing material, also referred to herein as "SiOx". In some aspects, the silica-containing material can contain silane or silane-containing compounds. In a particular aspect, the silica-containing material consists essentially of silica (SiO2). As used herein, consisting essentially of silica means that based on the total weight of the shell, at least 99 wt% of the shell layer is silica.

[0026] In one embodiment, the shell layer can include a multi-layer film, which includes, for example, a first film in direct contact with the outer surface of the core, and such a first film can contain silica. In another embodiment, the shell layer can include a second film covering at least a part of the first film, such that at least a part of the first film is disposed between the core and the second film. In one example, the second film can contain silane or silane-containing material.

[0027] In another embodiment, the shell can have a specific composition that can be beneficial for improved performance. For example, in one embodiment, the shell can contain at least 90 vol% of SiOx, such as at least 95 vol% of SiOx or at least 98 vol% of SiOx, based on the total volume of the shell. In a particular embodiment, the shell can consist essentially of SiOx, such that impurities can be present in a small amount that does not substantially change the characteristics or properties of the shell. In another embodiment, the shell can consist entirely of SiOx. Such percentages can also be the average percentages for multiple abrasive particles or a batch of abrasive particles.

[0028] In another embodiment, the shell can contain a certain amount of substances that can be considered impurities. Examples of such impurity substances can include silicon carbide, diamond, cubic boron nitride, boron carbide, cerium dioxide, titanium dioxide, yttrium oxide, 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.

[0029] According to one embodiment, the content of such impurity substances can be no more than 9 wt% of the total volume of the shell, such as no more than 7 wt% of impurities or no more than 5 wt% of impurities or no more than 2 wt% of impurities or no more than 1 wt% of impurities or no more than 0.5 wt% of impurities. In a non-limiting embodiment, the shell can contain at least 0.001 wt% of impurities. The impurities in the shell can be within a range including any one of the above minimum and maximum percentages. Such percentages can also be the average percentage of a plurality of abrasive particles or a batch of abrasive particles.

[0030] Referring to another aspect of the particulate, in some instances, the particulate can have a certain percentage of the core covered by the shell, which can be beneficial for the improved performance of the particulate. For example, in one embodiment, the shell can cover at least 50% of the total surface area of the core, such as or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95% or at least 99%. In a particular embodiment, the shell can be a thin conformal coating that substantially covers the entire core. Such percentages can also be the average percentage of a plurality of abrasive particles or a batch of abrasive particles.

[0031] In another embodiment, the shell can have a specific thickness, which can be beneficial for the improved manufacture and / or performance of the particulate. For example, in one embodiment, the shell can have an average thickness of at least 0.1 nm and no more than 50 nm. 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 no more than 45 nm or no more than 40 nm or no more than 35 nm or no more than 30 nm or no more than 25 nm or no more than 20 nm or no more than 18 nm or no more than 15 nm or no more than 14 nm or no more than 13 nm or no more than 12 nm. It should be understood that the shell can have an average thickness within a range including any one of the above minimum and maximum values, including for example but not limited to at least 0.5 nm and no more than 30 nm or at least 0.5 nm and no more than 20 nm.

[0032] In a particular aspect, the average (D50) particle size 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.

[0033] According to one embodiment, the particulate material can have a density in the range of at least 3 g / cm 3 to not greater than 7 g / cm 3 . In a non-limiting embodiment, the density of the particulate material can be at least 3.2 g / cm 3 , such as 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 . In another non-limiting embodiment, the particulate material can have a density of not greater than 6.8 g / cm 3 or not greater than 6.5 g / cm 3 or not greater than 6.2 g / cm 3 or not greater than 6.0 g / cm 3 or not greater than 5.8 g / cm 3 or not greater than 5.5 g / cm 3 . It should be understood that the density can be in a range including any one of the above minimum and maximum values, including for example but not limited to at least 3.5 g / cm 3 and not greater than 6.5 g / cm 3 , or in a range including at least 4 g / cm 3 and not greater than 6 g / cm 3 , or in a range including at least 5 g / cm 3 and not greater than 6 g / cm 3 .

[0034] In some instances, the particulates can be relatively dense with little to no porosity. For example, the particulates can have a porosity that can be beneficial for improved properties of the composition, such as a porosity that is no greater than 20 volume percent, such as no greater than 15 volume percent or no greater than 12 volume percent or no greater than 10 volume percent or no greater than 8 volume percent or no greater than 5 volume percent or no greater than 3 volume percent or no greater than 2 volume percent or no greater than 1 volume percent or no greater than 0.5 volume percent or no greater than 0.1 volume percent of the total volume of the particles. Additionally, in another non-limiting embodiment, the particulates can have a porosity of at least 0.1 volume percent or at least 0.5 volume percent or at least 1 volume percent or at least 5 volume percent or even at least 15 volume percent. The porosity of the particulate material can be within a range that includes any of the aforementioned minimum and maximum percentages.

[0035] According to one embodiment, the plurality of abrasive grains can include at least one or more particulates as described in any of the embodiments herein. The plurality of abrasive grains can include a small or large amount of particulates. In at least one instance, the plurality of abrasive grains includes at least 50 weight percent or at least 60 weight percent or at least 70 weight percent or at least 80 weight percent or at least 90 weight percent or at least 95 weight percent or at least 99 weight percent of particulates. In one instance, the plurality of abrasive grains consists entirely of particulates. In another non-limiting embodiment, the plurality of abrasive grains includes a batch of abrasive grains that can be used in a material removal operation or incorporated 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 greater weight, including kilograms or more.

[0036] In yet another aspect, a chemical mechanical planarization (CMP) slurry can include a carrier and a plurality of particles, the plurality of particles including the particulates of the embodiments herein, the particulates including any one or more combinations of the characteristics of the particulates. The plurality of particles can include a plurality of abrasive grains, the plurality of abrasive grains including any of the characteristics of the embodiments herein.

[0037] The CMP slurry can be formed according to the following non-limiting method. It should be understood that other additives in other contents can be used, and the following method only illustrates the CMP slurry according to one embodiment. The method for preparing the CMP slurry can include the steps of 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 embodiments herein are added to the deionized water and mixed for about 10 minutes to produce a first mixture. 480 grams of tartaric acid and 8 grams of 1,2,4-triazole are added to the first mixture and mixed for about 20 minutes to produce a second mixture. About 914 grams of hydrogen peroxide (H2O2) is added to the second mixture and mixed for about 5 minutes to produce a CMP mixture. KOH can be used to adjust the pH of the CMP mixture to about 7.5. The final CMP mixture contains about 2 wt% of particulate material, 2 wt% of H2O2, 3% of tartaric acid, and 0.05 wt% of 1,2,4-triazole.

[0038] The CMP slurry may include other additives in addition to the carrier and the plurality of particles. For example, in certain instances, the CMP slurry may further include at least one of a surfactant, a dispersant, a wetting agent, a thickening agent, an antifoaming agent, an antimicrobial agent, a suspension aid, a stabilizer, a lubricant, a rheology modifier, or any combination thereof. For example, certain optional additives may include an oxidizing agent, a dispersant, a surfactant, a lubricant, or any combination thereof. Some suitable examples of the oxidizing agent may include peroxides (e.g., H2O2), persulfides (e.g., H2S2), perchlorates (e.g., KClO4), periodates (e.g., KIO4), perbromates (e.g., KBrO4), permanganates (e.g., KMnO4, NaMnO4), chromates (e.g., K3CrO8), ammonium cerium nitrate (e.g., (NH4)2Ce(NO3)6), ferrocyanides (e.g., K4Fe(CN)6), persulfates, or any combination thereof. Some suitable examples of the dispersant include potassium hexametaphosphate, polyvinylpyrrolidone, potassium polynaphthalenesulfonate, potassium polymethacrylate, ammonium polymethacrylate, potassium polyacrylate, ammonium polyacrylate, potassium lignosulfonate. In some limited applications, a dispersant having sodium (e.g., any of the dispersants listed above) may be used, but it is not typical in all applications (e.g., the electronics industry). Some suitable examples of the surfactant may include oleic acid, cetyltrimethylammonium bromide, dodecanethiol, oleylamine, sodium dodecyl sulfate, hydroxyphosphinyl-acetic acid, or any combination thereof. Some suitable examples of the lubricant may include fluorosurfactants, zinc stearate, manganese dioxide, molybdenum disulfide, aluminosilicate, silicone 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 anti-corrosion agent (e.g., BTA, triazole (e.g., 1,2,4-triazole), phosphonic acid, etc.) may be added. The CMP slurry may include one or more of any of the foregoing additives.

[0039] The CMP slurry may have high stability in the presence of hydrogen peroxide. In one embodiment, the percentage reduction in hydrogen peroxide stability of the CMP slurry may be no greater than 50%. As used herein, the phrase "percentage reduction in hydrogen peroxide stability" means the reduction in the hydrogen peroxide content of the slurry after seven days expressed as a percentage. As Figure 3 shown, it can be seen that the CMP slurry containing pure zirconia particles without a silica shell cannot retain any hydrogen peroxide even for one day, while as the thickness of the silica-containing shell increases, the H2O2 content of the CMP slurry can be retained to a greater extent. The CMP slurry of the present disclosure can combine the advantages desired for polishing using modified zirconia particles while allowing high stability of the H2O2 contained in the slurry.

[0040] In some other instances, the composition can be a dry composition or a wet composition. The wet composition can comprise a CMP slurry that includes a liquid carrier, which facilitates the dispersion of the plurality of abrasive particles in the carrier. That is, the plurality of abrasive particles can be suspended in the liquid carrier to form a CMP slurry. After forming the dry powder composition, it can be shipped to the customer, and the customer can add the liquid carrier to produce a polishing composition in the form of a slurry. However, in other instances, 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 and can consist essentially of water, and more particularly, can consist essentially of deionized water.

[0041] The compositions of the embodiments can be used in various industries and particularly in the electronics industry for chemical mechanical planarization. In at least one embodiment, the CMP slurry can be used to polish the surface of a substrate having both exposed metal portions and ceramic portions. In one non-limiting embodiment, the CMP slurry containing particulate material can be used on a workpiece that includes materials such as dielectric materials (e.g., silicon dioxide), nitrides (Si3N4, GaN), carbides (e.g., SiC), metals or metal alloys (e.g., W, Al, Cu, Co, Ta, Ru, Au). According to a particular embodiment, the particulates of the embodiments herein can be suitable for use in a CMP slurry that is configured for copper barrier polishing.

[0042] In a particular aspect, the CMP slurry can have a particularly small difference in the material removal rate between certain types of materials. For example, the CMP slurry can have an ST material removal rate percentage difference of no greater than 300%, such as no greater than 200% or no greater than 100%. As used herein, the ST material removal rate percentage difference is the difference in the material removal rates of a CMP slurry for polishing a silicon dioxide (SiO2) substrate and a tantalum nitride (TaN) substrate.

[0043] As further shown in the examples, the CMP slurry can have a high efficiency in polishing a substrate containing copper (Cu). In a particular aspect, the Cu material removal rate can be at least In a certain particular aspect, the CMP slurry can have at least a removal rate for both TaN material and SiO2 material and at least a copper removal rate, while having a high stability to hydrogen peroxide.

[0044] Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, one skilled in the art will understand that those aspects and embodiments are merely exemplary and do not limit the scope of the invention. Embodiments may be in accordance with any one or more of the embodiments listed below.

[0045] Embodiment

[0046] Embodiments include any one or more combinations of any of the features described herein.

[0047] Embodiment 1. A chemical mechanical planarization (CMP) slurry, comprising:

[0048] A plurality of particles distributed in a carrier, wherein at least a portion of the particles in the plurality of particles have a body that includes a core containing zirconia and a shell covering at least a portion of the core, wherein the shell contains silica; an oxidizing agent; and a carrier, wherein the CMP slurry comprises at least one of the following:

[0049] A percentage reduction in hydrogen peroxide stability of no more than 50%, the percentage reduction in hydrogen peroxide stability being calculated according to [(percentage of H2O2 on day zero - percentage of H2O2 on day seven) / percentage of H2O2 on day zero]×100%;

[0050] At least Of the SiO2 material removal rate;

[0051] At least Of the Cu material removal rate;

[0052] At least Of the TaN material removal rate;

[0053] A percentage difference in the ST material removal rate of no more than 300%.

[0054] Embodiment 2. The CMP slurry according to Embodiment 1, wherein the slurry comprises a combination of two or more of the following:

[0055] A percentage reduction in hydrogen peroxide stability of no more than 50%;

[0056] At least Of the SiO2 material removal rate;

[0057] At least Of the Cu material removal rate;

[0058] At least Of the TaN material removal rate; and

[0059] A percentage difference in the ST material removal rate of not more than 300%.

[0060] Embodiment 3. The CMP slurry according to Embodiment 2, wherein the slurry consists of a combination of each of the following:

[0061] A percentage reduction in hydrogen peroxide stability of not more than 50%;

[0062] At least The removal rate of SiO2 material;

[0063] At least The removal rate of Cu material;

[0064] At least The removal rate of TaN material; and

[0065] A percentage difference in the ST material removal rate of not more than 300%.

[0066] Embodiment 4. The CMP slurry according to any one of the foregoing embodiments, wherein the percentage reduction in hydrogen peroxide stability is not more than 45% or not more than 40% or not more than 35% or not more than 30% or not more than 25% or not more than 20% or not more than 18% or not more than 16% or not more than 14% or not more than 12% or not more than 10% or not more than 8% or not more than 6% or not more than 4%.

[0067] Embodiment 5. The CMP slurry according to any one of the foregoing embodiments, wherein the percentage reduction in hydrogen peroxide stability is at least 0.1% or at least 0.5% or at least 1%.

[0068] Embodiment 6. The CMP slurry according to any one of the foregoing embodiments, wherein according to the CMP test, the SiO2 material removal rate is at least Or at least Or at least Or at least Or at least

[0069] Embodiment 7. The CMP slurry according to any one of the foregoing embodiments, wherein according to the CMP test conditions provided in Table 3, the SiO2 material removal rate is not more than Or not more than Or not more than

[0070] Embodiment 8. The CMP slurry according to any one of the foregoing embodiments, wherein according to the CMP test conditions provided in Table 3, the copper material removal rate is at least Or at least Or at least or at least or at least or at least

[0071] Embodiment 9. The CMP slurry according to any one of the foregoing embodiments, wherein according to the CMP test conditions provided in Table 3, the copper material removal rate is not greater than or not greater than or not greater than

[0072] Embodiment 10. The CMP slurry according to any one of the foregoing embodiments herein, wherein as measured according to the CMP test conditions provided in Table 3, the TaN material removal rate is at least or at least or at least or at least or at least or at least or at least

[0073] Embodiment 11. The CMP slurry according to any one of the foregoing embodiments, wherein the ST removal rate percentage difference is not greater than 250% or not greater than 225% or not greater than 200% or not greater than 150% or not greater than 125% or not greater than 100%.

[0074] Embodiment 12. The CMP slurry according to any one of the foregoing embodiments, 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 wherein the core consists of zirconia, based on the total volume of the core.

[0075] Embodiment 13. The CMP slurry according to any one of the foregoing embodiments, wherein the core comprises polycrystalline abrasive particles.

[0076] Embodiment 14. The CMP slurry according to any one of the foregoing embodiments, wherein based on the average (D50) size of the core, the shell comprises an average thickness of at least 0.5% and not greater than 20%, or at least 1% and not greater than 10%.

[0077] Embodiment 15. The CMP slurry according to any one of the foregoing embodiments, wherein the shell comprises at least 90% by volume of silica, or at least 95% by volume of silica or at least 98% by volume of silica, or consists essentially of silica, or consists of silica, based on the total volume of the shell.

[0078] Embodiment 16. The CMP slurry according to any one of the foregoing embodiments, wherein the shell contains no more than 9% by weight of impurities, or no more than 7% by weight of impurities, or no more than 5% by weight of impurities, or no more than 2% by weight of impurities, or no more than 1% by weight of impurities or no more than 0.5% by weight of impurities.

[0079] Embodiment 17. The CMP slurry according to any one of the foregoing embodiments, 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.

[0080] Embodiment 18. The CMP slurry according to any one of the foregoing embodiments, 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.

[0081] Embodiment 19. The CMP slurry according to any one of the foregoing embodiments, wherein the shell has an average thickness of no more than 45 nm, or no more than 40 nm, or no more than 35 nm, or no more than 30 nm, or no more than 25 nm, or no more than 20 nm, or no more than 18 nm, or no more than 15 nm, or no more than 14 nm, or no more than 13 nm or no more than 12 nm.

[0082] Embodiment 20. A CMP slurry composition, wherein the shell has an average thickness of at least 4 nm and no more than 20 nm.

[0083] Embodiment 21. The CMP slurry according to any one of the foregoing embodiments, wherein each of the plurality of particles comprises a core containing zirconia and a shell containing silica.

[0084] Embodiment 22. The CMP slurry according to any one of the foregoing embodiments, 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.

[0085] Embodiment 23. The CMP slurry according to any one of the foregoing embodiments, wherein the average particle size of the plurality of particles is no more than 500 nm, or no more than 400 nm, or no more than 300 nm, or no more than 250 nm or no more than 200 nm.

[0086] Embodiment 24. The CMP slurry according to any one of the foregoing embodiments, wherein the average particle size (D50) of the plurality of particles is in the range of at least 50 nm to not greater than 300 nm.

[0087] Embodiment 25. The CMP slurry according to any one of the foregoing embodiments, wherein based on the total weight of the CMP slurry, the amount of the plurality of particles is at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or at least 3 wt% or at least 5 wt%.

[0088] Embodiment 26. The CMP slurry according to any one of the foregoing embodiments, wherein based on the total weight of the CMP slurry, the amount of the plurality of particles is not greater than 10 wt%, or not greater than 8 wt%, or not greater than 6 wt% or not greater than 4 wt%.

[0089] Embodiment 27. The CMP slurry according to any one of the foregoing embodiments, wherein 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.

[0090] Embodiment 28. The CMP composition according to any one of the foregoing embodiments, wherein the pH of the CMP slurry is not greater than 10, or not greater than 9, or not greater than 8, or not greater than 7, or not greater than 6.5, or not greater than 6, or not greater than 5.5 or not greater than 5.

[0091] Embodiment 29. The CMP slurry according to Embodiment 26 or 27, wherein the pH is in the range between 5 and 8.

[0092] Embodiment 30. The CMP slurry according to any one of the foregoing embodiments, the slurry further comprising an oxidizing agent, a complexing agent, an anti-corrosion agent, a pH regulator or any combination thereof.

[0093] Embodiment 31. The CMP slurry according to Embodiment 30, wherein the oxidizing agent comprises a peroxide, a persulfate or a permanganate.

[0094] Embodiment 32. The CMP slurry according to Embodiment 31, wherein the oxidizing agent comprises hydrogen peroxide (H2O2).

[0095] Embodiment 33. The CMP slurry according to any one of the foregoing embodiments, wherein based on the total weight of the slurry, 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%.

[0096] Embodiment 34. The CMP slurry according to any one of the foregoing embodiments, wherein based on the total weight of the slurry, the amount of the oxidizing agent is not greater than 15 wt%, or not greater than 10 wt% or not greater than 5 wt%.

[0097] Embodiment 35. The CMP slurry according to Embodiment 30, wherein the complexing agent comprises malonic acid, tartaric acid, citric acid, amino acid, or any combination thereof.

[0098] Embodiment 36. The CMP slurry according to Embodiment 30, wherein the corrosion inhibitor comprises benzotriazole (BTA), triazole, phosphonic acid, or any combination thereof.

[0099] Embodiment 37. The CMP slurry according to any one of the foregoing embodiments, wherein the carrier comprises water.

[0100] Embodiment 38. A method of polishing a substrate, the method comprising: providing a substrate and a CMP slurry; and polishing the substrate with the CMP slurry using a polishing pad; wherein the CMP slurry comprises a plurality of particles, an oxidizing agent, and a carrier distributed in the carrier, wherein at least a portion of the particles in the plurality of particles has a body, the body comprising a core containing zirconia and a shell covering at least a portion of the core, and the shell comprises silica.

[0101] Embodiment 39. The method according to Embodiment 38, wherein the substrate comprises a ceramic material, a metal, a metal alloy, diamond, a polymer, a III-V compound, or a IV-IV compound.

[0102] Embodiment 40. The method according to Embodiment 39, wherein the substrate comprises a dielectric material, a nitride, a carbide, a metal, or a metal alloy.

[0103] Embodiment 41. The method according to Embodiment 39 or 40, wherein the substrate comprises copper, silica, tantalum nitride (TaN), or any combination thereof.

[0104] Embodiment 42. The method according to any one of Embodiments 38 to 40, wherein the method is configured for copper barrier polishing.

[0105] Embodiment 43. The method according to any one of Embodiments 38 to 42, wherein the method further comprises adjusting the pH of the CMP slurry before polishing.

[0106] Embodiment 44. The method according to any one of embodiments 38 to 43, wherein 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.

[0107] Embodiment 45. The method according to any one of embodiments 38 to 44, wherein the pH of the CMP slurry is not greater than 10, or not greater than 9, or not greater than 8, or not greater than 7, or not greater than 6.5, or not greater than 6, or not greater than 5.5 or not greater than 5.

[0108] Embodiment 46. The method according to any one of embodiments 38 to 45, wherein the at least one oxidant includes peroxide, persulfate, permanganate, chlorite, nitrite, perchlorate, hypochlorite, manganese oxide or any combination thereof.

[0109] Embodiment 47. The method according to any one of embodiments 38 to 46, wherein the oxidant includes peroxide, persulfate, permanganate or a combination thereof.

[0110] Embodiment 48. The method according to any one of embodiments 38 to 47, wherein the oxidant includes hydrogen peroxide (H2O2).

[0111] Embodiment 49. The method according to any one of embodiments 38 to 48, wherein according to the CMP test, the removal rate of the SiO2 material is at least or at least or at least or at least or at least or at least

[0112] Embodiment 50. The method according to any one of embodiments 38 to 48, wherein according to the CMP test, the removal rate of the SiO2 material is not greater than or not greater than or not greater than

[0113] Embodiment 51. The method according to any one of embodiments 38 to 50, wherein according to the CMP test, the removal rate of the copper material is at least or at least or at least or at least or at least or at least or at least

[0114] Embodiment 52. The method according to any one of Embodiments 38 to 51, wherein according to the CMP test, the removal rate of the copper material is not greater than or not greater than or not greater than

[0115] Embodiment 53. The method according to any one of Embodiments 38 to 52, wherein the removal rate of the TaN material is at least or at least or at least or at least or at least or at least or at least or at least

[0116] Embodiment 54. The method according to any one of Embodiments 38 to 53, wherein the percentage difference in the ST removal rate is not greater than 300%, or not greater than 250%, or not greater than 225%, or not greater than 200%, or not greater than 150%, or not greater than 125% or not greater than 100%.

[0117] 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.

[0118] Embodiment 56. The method according to any one of Embodiments 38 to 55, wherein the average particle size of the plurality of particles is not greater than 500 nm, or not greater than 400 nm, or not greater than 300 nm, or not greater than 250 nm or not greater than 200 nm.

[0119] Embodiment 57. The method according to any one of Embodiments 38 to 56, wherein the average particle size (D50) of the plurality of particles ranges from at least 50 nm to not greater than 300 nm.

[0120] Embodiment 58. The method according to any one of Embodiments 38 to 57, wherein the housing 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.

[0121] Embodiment 59. The method according to any one of embodiments 38 to 58, wherein the shell has an average thickness of no greater than 45 nm, or no greater than 40 nm, or no greater than 35 nm, or no greater than 30 nm, or no greater than 25 nm, or no greater than 20 nm, or no greater than 18 nm, or no greater than 15 nm, or no greater than 14 nm, or no greater than 13 nm or no greater than 12 nm.

[0122] Embodiment 60. The method according to any one of embodiments 38 to 59, wherein the average (D50) particle size of the plurality of particles ranges from 100 nm to 250 nm, and the thickness of the shell ranges from 3 nm to 20 nm or from 5 nm to 15 nm.

[0123] Example :

[0124] Example 1 :

[0125] The following non-limiting examples illustrate the present invention.

[0126] The zirconia raw material especially used as the core was purchased from Saint-Gobain under the product code 9839 / 9840, which can also be referred to as Zirpol Nano. The particle size distribution characteristics of the particles are provided in Table 1.

[0127] Table 1 :

[0128]

[0129] After obtaining the core material, it was processed to form a silica shell covering at least a part of the core. The method for forming the shell includes a deposition method. The method for forming the shell on the core microparticles includes using a silicon source, such as an organosilicon source (e.g., TMOS, TEOS), to form a silica coating. The organosilicon source was added to water to cause the release of the silicon material. The core particles were added to the water and the silicon source to produce 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 microparticle materials having a core zirconia core and a silica shell structure are produced.

[0130] Coated particles of sample S1 were formed such that the shell has an average thickness of about 1 nm.

[0131] Example 2 :

[0132] Samples of microparticles having a core-shell structure were formed according to the method of Example 1, except that the shell was formed to have an average thickness of about 3 nm.

[0133] Example 3 :

[0134] A sample of microparticles having a core - shell structure was formed according to the method of Example 1, except that the shell was formed to have an average thickness of about 12 nm.

[0135] Example 4 :

[0136] Samples S1, S2, and S3 were tested for H2O2 compatibility according to the following test procedure:

[0137] For a sample of the particulate material, 0.4 g (to ±0.001 g) was weighed and recorded as Wg. 150 mL of sulfuric acid (1:19) was measured into a 500 mL conical flask and cooled to below 10 °C using a laboratory chiller or freezer. When the temperature of the solution was below 10 °C, approximately three drops of o - phenanthroline ferrous ion indicator solution were added and then titrated with ammonium cerium(IV) nitrate solution (0.1 N) contained in a burette until the indicator turned blue. Then, the 0.4 g of the measured particulate material sample was added to the cold solution. As calculated according to grams of sample=(40 mL×0.1 N×1.701) / %C, where %C is the estimated concentration of hydrogen peroxide and 1.701 is the weight of hydrogen peroxide per milliequivalent×100, and vortexed to mix. It was rapidly titrated with ammonium cerium(IV) nitrate solution (0.1 N) to the same blue color. The titration result (mL Ce+3) was calculated by subtracting the final volume of ammonium cerium(IV) nitrate used from the initial volume. The following formula was used to calculate the percentage concentration of hydrogen peroxide in the sample: Percentage concentration of H2O2=(ml Ce+3)×(N Ce+3)×1.701 / grams of sample.

[0138] Example calculation:

[0139] Titrant volume: 40.49 mL final – 1.52 mL initial = 38.97 mL titrant

[0140] Percentage concentration of H2O2=(38.97 mL Ce+3×0.0950 mol.eq. / LCe+3×1.701) / 17.80 g sample = 0.3538%

[0141] Figure 3Plots of H2O2 percentage over time (day 0 to day 7) were included to evaluate the stability and compatibility of samples S1, S2, and S3, uncoated zirconia particles (sample C1), and 3% H2O2 solution. As shown, samples S1, S2, and S3 had better compatibility and stability with H2O2 compared to sample C1. Sample S1 had an approximately 40% reduction percentage in hydrogen peroxide stability, calculated as [(3.0 - 1.8) / 3.0]×100% = 40% based on a H2O2 percentage of 3% on day 0 and 1.8% on day 7. Sample S2 had an approximately 40% reduction percentage in hydrogen peroxide stability, calculated as [(3.0 - 1.8) / 3.0]×100% = 40% based on a H2O2 percentage of 3% on day 0 and 1.8% on day 7. Sample S3 had an approximately 15% reduction percentage in hydrogen peroxide stability, calculated as [(3.0 - 2.55) / 3.0]×100% = 15% based on a H2O2 percentage of 3% on day 0 and 2.55% on day 7.

[0142] The best H2O2 stability over time was with sample S3, which had the thickest silica coating of 6 nm.

[0143] Experiments were conducted with the respective slurries containing zirconia particles with silica shell thicknesses of 9 nm and 12 nm, which showed even better H2O2 stability (lower H2O2 stability reduction percentage) over time.

[0144] Example 5 :

[0145] Samples S1, S2, and S3 were tested as CMP slurries to evaluate their material removal rates on glass substrates.

[0146] Particles from samples S1, S2, and S3 were used to produce CMP slurries, and the CMP slurry samples are referred to herein as CMP S1, CMP S2, and CMP S3, respectively. Each slurry in the CMP slurries 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 about 5 minutes to produce a first mixture. Then, 120 grams of core-shell particles (e.g., abrasive particles of S1, S2, or S3) was added to the first mixture and mixed for about 30 minutes to produce one of the representative CMP mixtures of CMP S1, CMP S2, and CMP S3. Nitric acid was used to adjust the pH of each mixture in the CMP mixture to about 5.5. Each sample in the samples included about 1.5 wt% of particulate material and 0.05 wt% of polyalkylene oxide-modified heptamethyltrisiloxane.

[0147] Each CMP sample was tested twice according to the conditions provided in Table 2.

[0148] Table 2 :

[0149] Machine: SpeedFam GPAW 36” Pad: Suba X Substrate: Glass Downward pressure: 2 psi Platen speed (RPM): 40 Slurry flow rate: 100 ml / min Polishing time: 10 min

[0150] The results of the glass polishing tests are shown in Figure 4 which shows the glass removal rates of two tests for each sample.

[0151] Example 6 :

[0152] Using the method of Example 1, three new abrasive particle samples (i.e., Samples S4, S5, and S6) were produced, differing in the average thickness of each sample in the sample. Sample S4 has an average shell thickness of 3 nm. Sample S5 has an average shell thickness of 6 nm. Sample S6 has an average shell thickness of 9 nm. Each sample of abrasive particles was used to produce three new CMP slurries, namely CMP S4, CMP S5, and CMP S6. 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 about 15 minutes to produce a first mixture. Then, 240 grams of tartaric acid were added to the first mixture and mixed for about 15 minutes to produce a second mixture. Then, about 4 grams of 1,2,4-triazole were added to the second mixture and mixed for about 15 minutes to produce a third mixture. Then, about 457 grams of hydrogen peroxide (H2O2) were added to the third mixture and mixed for about 5 minutes to produce one of CMP samples CMP S4, CMP S5, or CMP S6. KOH was used to adjust the pH of each sample in the CMP sample to about 7 to 8. Each sample in the CMP sample contains about 2 wt% of particulate material (S4, S5, or S6), 2 wt% of H2O2, 3% tartaric acid, and 0.05 wt% of 1,2,4-triazole.

[0153] Copper wafers, TaN wafers, and silicon dioxide wafers with a 6-inch diameter were used as substrates to test the polishing efficiency of the CMP samples. According to the conditions provided in Table 3, each CMP slurry was tested twice on each type of substrate wafer, which is also referred to herein as the "CMP test". For copper polishing, a copper wafer with product lot number GM033018-1 from Advantive Technologies can be used, which has an upper copper layer; for TaN polishing, a TaN wafer with product lot number GM111819-6 from Advantive Technologies, which has an upper TaN layer; and for silicon dioxide polishing, a silicon dioxide wafer with product lot number 349547-1 from Advantive Technologies, which has a thickness of.

[0154] Table 3 :

[0155] Machine: IPEC 472 Pad: IC1000 A2 Regulating disc: Kinik (O-Pyradia, 350 Tips) Platen diameter: 22.5 inches Running time: 1 min Downward pressure: 3 psi Platen speed: 103 rpm Slurry flow rate: 180 ml / min Carrier speed: 97 rpm

[0156] The material removal rate was measured according to the following technique:

[0157] For copper wafers, the material removal rate of the CMP slurry was calculated by using a four-point probe from CDE ResMap 178. The thickness was calculated from the sheet resistance and resistivity of the metal at 49 points across the entire wafer. Measurements were taken before and after the CMP test. The difference between before and after the measurement was the metal removal divided by the polishing time to yield the material removal rate.

[0158] 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 change in weight, wafer area, and density was 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. It uses an integrated spectrometer / light source unit to measure the wafer thickness at 7 points across the center of the wafer. This was done before and after polishing. The difference was the metal removal divided by the polishing time to yield the metal removal rate.

[0159] For silicon oxide wafers, the material removal rate was measured with a Filmetrics F20 instrument. It uses an integrated spectrometer / light source unit to measure the wafer thickness at 7 points across the center of the wafer. This was done before and after polishing. The difference was the metal removal divided by the polishing time to yield the glass removal rate.

[0160] The material removal rate results for each of CMP samples CMP S4, CMP S5, and CMP S6 are summarized in Table 4.

[0161] Table 4 :

[0162]

[0163] From the data shown in Table 4, the percentage difference in the ST material removal rate between the polishing of silicon oxide wafers and the polishing of TaN wafers was calculated: for CMP sample S4, the calculated value was 20%, for CMP sample S5, the value was 30%, and for CMP sample S6, the value was 10%.

[0164] It can also be seen from the data in Table 4 that as the thickness of the shell increases, the removal rates of copper, TaN, and SiO2 decrease.

[0165] Experiments were conducted on slurry compositions with shell thicknesses of 12 nm, 15 nm, and 20 nm, and this experiment confirmed this trend.

[0166] Without being bound by theory, a specific range of silica coating thickness relative to the zirconia core can have advantages in terms of obtaining the desired material removal rate and having a stable polishing slurry in terms of H2O2 degradation.

[0167] The subject matter disclosed above should be considered illustrative rather than restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments that fall within the true scope of the present invention. Accordingly, to the maximum extent permitted by law, the scope of the present invention will be determined by the broadest permissible interpretation of the appended claims and their equivalents, and should not be restricted or limited by the foregoing detailed description.

[0168] The abstract of the specification is provided to comply with the 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, for the purpose of simplifying the disclosure, various features may be grouped together or described in a single embodiment. The present disclosure should not be construed as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as reflected in the following claims, the subject matter of the present invention may lie in less than all of the features of any of the disclosed embodiments. Accordingly, the appended claims are incorporated into the detailed description, where each claim independently defines a separately claimed subject matter.

Claims

1. A chemical mechanical planarization (CMP) slurry, the slurry comprising: A plurality of particles distributed in a carrier, wherein at least a portion of the particles among the plurality of particles has a body, the body including a core containing zirconia and a shell covering at least a portion of the core, wherein the shell contains silica; An oxidizing agent; and A carrier, wherein the CMP slurry comprises at least one of the following: A percentage reduction in hydrogen peroxide stability of not more than 50%; At least The removal rate of SiO2 material; At least The removal rate of Cu material; At least The removal rate of TaN material; or A percentage difference in the removal rate of ST material of not more than 300%.

2. The CMP slurry according to claim 1, wherein the percentage difference in the ST removal rate is not more than 100%.

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

4. The CMP slurry according to claim 1, wherein based on the average (D50) size of the core, the shell comprises an average thickness of at least 1% and not more than 10%.

5. The CMP slurry according to claim 1, wherein the shell has an average thickness of at least 3 nm and not more than 20 nm.

6. The CMP slurry according to claim 1, wherein the average particle size of the plurality of particles is at least 50 nm and not more than 500 nm.

7. The CMP slurry according to claim 1, wherein the amount of the plurality of particles is at least 1% by weight and not more than 10% by weight.

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

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

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

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

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

13. A method of polishing a substrate, the method comprising: Provide a substrate and a CMP slurry; and polish the substrate using the CMP slurry with a polishing pad, wherein the CMP slurry comprises a plurality of particles distributed in a carrier, an oxidizing agent, and a carrier, wherein at least a portion of the particles among the plurality of particles has a body, the body includes a core containing zirconia and a shell covering at least a portion of the core, and the shell contains silica.

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

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

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