WO2024130991A1 - 具有改进颗粒的化学机械抛光组合物 - Google Patents

具有改进颗粒的化学机械抛光组合物 Download PDF

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Publication number
WO2024130991A1
WO2024130991A1 PCT/CN2023/101110 CN2023101110W WO2024130991A1 WO 2024130991 A1 WO2024130991 A1 WO 2024130991A1 CN 2023101110 W CN2023101110 W CN 2023101110W WO 2024130991 A1 WO2024130991 A1 WO 2024130991A1
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composition
acid
abrasive particles
abrasive
particles
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PCT/CN2023/101110
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English (en)
French (fr)
Inventor
马庭轩
贾仁合
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昂士特科技(深圳)有限公司
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Publication of WO2024130991A1 publication Critical patent/WO2024130991A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents

Definitions

  • the invention belongs to the technical field of chemical engineering, and in particular relates to a chemical mechanical polishing composition with improved particles.
  • CMP compositions are commonly used in the integrated circuit and micro-electromechanical systems industries for chemical mechanical polishing of substrates such as wafers by a combination of chemical and mechanical forces. These compositions are typically aqueous solutions containing various chemical additives and abrasive particles dispersed in the composition. CMP compositions are also referred to as polishing slurries, CMP slurries, or polishing compositions. CMP compositions greatly affect many factors in the polishing and smoothing of substrates, such as material removal rate, planarization, and defectivity of the substrate.
  • the substrate in the interlayer dielectric (ILD) layer typically comprises dielectric silicon.
  • dielectric silicon Common silicon-containing dielectric substrates used in the industry are silicon dioxide, tetraethyl orthosilicate (TEOS), and silicon nitride. Silicon-containing dielectric substrates are often polished with CMP compositions containing ceria abrasives. For many dielectric silicon applications, a CMP composition comprising cerium oxide (ceria) abrasives having a high material removal rate is desired. However, ceria abrasives having a high material removal rate often result in more undesirable defects, such as scratches, in the substrate during the CMP process.
  • ceria cerium oxide
  • ceria abrasives are widely used for polishing dielectric silicon substrates, there is still a need for a CMP composition comprising ceria abrasives that is suitable for polishing materials containing silicon oxides and exhibits an increased material removal rate and a reduced number of defects in the substrate during the CMP process.
  • An object of the present invention is to overcome the problems of the prior art. Specifically, an object of the present invention is to provide a novel CMP composition for polishing a substrate containing silicon oxide, which on the one hand exhibits a high material removal rate during the CMP process, and on the other hand causes fewer defects in the substrate, such as scratches.
  • the CMP composition of the present invention comprises cerium dioxide abrasive particles, wherein the cerium dioxide abrasive particles have a cubic morphology, the zeta potential at pH 1-pH 6 in the composition is at least 10 mV, and the steepness factor is at least 34.
  • the CMP composition (referred to herein as the "composition") comprises abrasive particles dispersed in an aqueous carrier, the abrasive particles aiding in the removal of material from the surface of the substrate during the polishing process.
  • the abrasive particles are selected from cerium oxide
  • the abrasive particles are metal oxides of cerium dioxide (cerium dioxide), aluminum oxide (aluminum oxide), silicon oxide (silicon dioxide), zirconium oxide (zirconium oxide), titanium oxide (titania), germanium oxide (germanium oxide), magnesium oxide (magnesium oxide), nickel oxide, gallium oxide (gallium oxide), yttrium oxide (yttrium oxide) and combinations thereof.
  • the abrasive particles contain at least 72 wt% (weight) of cerium dioxide, more preferably at least 83 wt%, more preferably at least 91 wt%, more preferably at least 96 wt%, and most preferably at least 98 wt%.
  • the abrasive particles are cerium dioxide abrasive particles.
  • cerium dioxide refers to the oxide of the rare earth metal cerium, also known as cerium oxide, cerium oxide or cerium dioxide.
  • the ceria abrasive grains are doped ceria abrasive grains.
  • Suitable dopants are, for example, metal ions (such as Ca, Mg, Zn, Zr, Sc, Y) or lanthanides (such as lanthanum, praseodymium, neodymium, promethium or samarium).
  • metal ions such as Ca, Mg, Zn, Zr, Sc, Y
  • lanthanides such as lanthanum, praseodymium, neodymium, promethium or samarium.
  • the ceria abrasive grains are preferably substantially free of dopants.
  • Dopants may be present in the abrasive grains as impurities, which may originate from the raw materials or starting materials used to prepare the abrasive grains.
  • substantially free of component X refers to a composition that does not substantially contain the component X, i.e., the component may at most be present in the composition as an impurity or contaminant, but is not added to the composition as a single component. This means that the component X is not added in substantial amounts.
  • substantially amounts of the present invention are amounts less than 30 ppm, more preferably less than 20 ppm, more preferably less than 10 ppm, and most preferably less than 1 ppm.
  • Ppm as used herein refers to ppm by weight.
  • the composition preferably contains at least 0.001 wt%, more preferably at least 0.03 wt%, more preferably at least 0.06 wt%, more preferably at least 0.09 wt%, and most preferably at least 0.14 wt% of abrasive particles.
  • the term "when used” refers to when the composition is applied to the surface of the substrate during the CMP process. If the concentration of abrasive particles is too high, the particles will aggregate, which will shorten the shelf life of the composition and cause undesirable surface defects on the substrate during the CMP process.
  • the composition when used, preferably contains at most 21.7 wt%, more preferably at most 18.9 wt%, more preferably at most 16.8 wt%, more preferably at most 13.3 wt%, and most preferably at most 10.8 wt% of abrasive particles.
  • the composition contains 0.03 wt% to 18.9 wt%, more preferably 0.06 wt% to 16.8 wt%, and more preferably 0.09 wt% to 13.3 wt% of abrasive particles.
  • the abrasive particles can be present in the composition as individual particles, aggregates, agglomerates and mixtures thereof. Individual particles can be attached to each other, for example, by van der Waals forces, thereby forming aggregates of more than one individual particle. Aggregates themselves can further attach to each other, for example, by physical interactions, forming agglomerates of more than one aggregate. The formation of aggregates and agglomerates is reversible.
  • the term abrasive particles as used herein refers to individual particles, aggregates and agglomerates.
  • the number of individual particles and aggregates and agglomerates can be determined by a person skilled in the art through transmission electron microscopy (TEM) or scanning electron microscopy (SEM) images. The analysis should be based on a statistically significant number of randomly selected particles, such as at least 300.
  • the sum of the aggregates and agglomerates of the abrasive particles is at most 68.9wt% of the abrasive particles, more preferably at most 56.7wt%, more preferably at most 45.4wt%, more preferably at most 32.3wt%, and most preferably at most 22.1wt%. Fewer aggregates and agglomerates can be achieved, for example, by deagglomeration such as filtering, grinding and other processes known to those skilled in the art.
  • the abrasive particles of the present invention should have a suitable morphology.
  • the morphology of the particles affects the surface reactivity of the particles and affects the material removal rate.
  • the morphology can be determined by a person skilled in the art, for example, using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) image. It has been found that particles with a spherical morphology exhibit a lower material removal rate.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the term spherical morphology is not limited to a perfect sphere, and refers to any rounded morphology without substantial edges and vertices (corners), such as spherical, elliptical, grape-like structures, etc.
  • the amount of the abrasive particles having a spherical morphology is at most 34.6wt% of the abrasive particles, more preferably at most 24.9wt%, more preferably at most 13.8wt%, more preferably at most 6.8wt%, and most preferably at most 3.1wt%.
  • abrasive particles having at least one vertex can exhibit higher material removal rates.
  • the abrasive particles have a morphology selected from the group consisting of cubes, quadrangular pyramids, triangular prisms, dodecahedrons, icosahedrons, octahedrons, hexagonal pyramids, hexagonal prisms, pentagonal prisms, cones, tetrahedrons, cuboids, rhombuses, hexagonal rhombuses, and mixtures thereof.
  • the abrasive particles have a cubic morphology. It has been found that abrasive particles with a cubic morphology can exhibit higher material removal rates.
  • the term cubic morphology refers to any cube-like morphology and is not limited to a perfect cube.
  • one or more edges of the abrasive particles may be slightly rounded, one or more vertices of the abrasive particles may be slightly rounded, one or more opposite edges of the abrasive particles may be slightly tilted (not completely parallel), one or more dihedral angles of the abrasive particles may be slightly greater than or less than 90°, and other differences from a perfect cube.
  • the abrasive particles have a cubic morphology in an amount of at least 31.3 wt % of the abrasive particles, more preferably at least 49.2 wt %, more preferably at least 68.4 wt %, more preferably at least 76.3 wt %, more preferably at least 86.7 wt %, more preferably at least 93.8 wt %, and most preferably at least 98 wt %.
  • the average particle size (diameter) of the abrasive particles will affect the material removal rate.
  • the average particle size can be obtained by laser diffraction measurement (e.g. using LA-960 from Horiba). The curve graph obtained by this measurement provides the cumulative volume percentage of particles of a certain size.
  • the average particle size (D50) is the particle size at which 50% by volume of the particles have a particle size less than this value. A smaller D50 will reduce the material removal rate.
  • the abrasive has a D50 of at least 5 nm, more preferably at least 11 nm, more preferably at least 23 nm, more preferably at least 33 nm, and most preferably at least 48 nm measured by laser diffraction.
  • the abrasive should have a smaller average particle size.
  • the abrasive has a D50 of at most 380 nm, more preferably at most 221, more preferably at most 181 nm, more preferably at most 151 nm, and most preferably at most 125 nm measured by laser diffraction.
  • the abrasive has a D50 of 11 nm to 221 nm, more preferably 23 nm to 181 nm, more preferably 33 nm to 151 nm, and more preferably 48 nm to 125 nm measured by laser diffraction. It is generally believed that abrasive particles with a larger D50 will result in a higher material removal rate during a CMP process. However, it is surprisingly found that the abrasive particles of the present invention can achieve a high material removal rate even with a smaller D50.
  • D10 is the particle size at which 10% by volume of the particles have a particle size less than this value.
  • the abrasive has a D10 of at least 3 nm, more preferably at least 9 nm, more preferably at least 18 nm, more preferably at least 28 nm, and most preferably at least 39 nm as measured by laser diffraction.
  • a smaller D10 of the abrasive increases the particle packing density (reduces the void volume) on the surface of the substrate during the CMP process, which helps to improve the material removal rate.
  • the abrasive preferably has a D10 of at most 320 nm, more preferably at most 211, more preferably at most 152 nm, more preferably at most 112 nm, and most preferably at most 87 nm as measured by laser diffraction.
  • the abrasive has a D10 of 9 nm to 211 nm, more preferably 18 nm to 152 nm, more preferably 28 nm to 112 nm, and most preferably 39 nm to 87 nm as measured by laser diffraction.
  • D90 is the particle size at which 90% of the particles by volume have a particle size less than this value.
  • a higher D90 of the abrasive particles will increase the material removal rate during the CMP process.
  • the abrasive particles have a D90 of at least 24 nm, more preferably at least 41 nm, more preferably at least 76 nm, more preferably at least 83 nm, and most preferably at least 99 nm measured by laser diffraction.
  • the D90 of the abrasive particles is too high, more undesirable defects such as scratches will appear during the CMP process.
  • the abrasive particles preferably have a D90 of at most 489 nm, more preferably at most 376, more preferably at most 269 nm, more preferably at most 219 nm, and most preferably at most 194 nm measured by laser diffraction.
  • the abrasive particles have a D90 of 41 nm to 376 nm, more preferably 76 nm to 269 nm, more preferably 83 nm to 219 nm, and most preferably 99 nm to 194 nm measured by laser diffraction.
  • a wide particle size distribution results in higher material removal rates due to a higher number of larger particles and better loading of the abrasive during the CMP process.
  • a wide particle size distribution is often associated with a lack of The number of defects is relatively large.
  • the width of the particle size distribution can be described by a particle size distribution factor.
  • the particle size distribution factor used herein refers to the value obtained by the formula (D90-D10)/D50.
  • D90, D10 and D50 can be obtained by laser diffraction as described above.
  • the abrasive particles have a particle size distribution factor of at most 1.8, more preferably at most 1.3, more preferably at most 1.0, more preferably at most 0.9, and most preferably at most 0.8.
  • the abrasive particles should have a large steepness factor.
  • the steepness factor used herein refers to the value obtained by the formula (D30/D70)*100.
  • D30 and D70 can be obtained by laser diffraction as described above.
  • D30 is the particle size at which 30% by volume of the particles have a particle size less than this value.
  • D70 is the particle size at which 70% by volume of the particles have a particle size less than this value.
  • a wide particle size distribution provides a small steepness factor, while a narrow particle size distribution provides a large steepness factor.
  • the abrasive particles with a large steepness factor of the present invention exhibit a high material removal rate while achieving fewer defects in the substrate, such as scratches, during the CMP process.
  • the abrasive particles have a steepness factor of at least 34, more preferably at least 48, more preferably at least 56, more preferably at least 67, and most preferably at least 74.
  • the abrasive particles preferably have a steepness factor of at most 98, more preferably at most 97, more preferably at most 96, and most preferably at most 95.
  • the abrasive particles have a D30 of 4 nm to 353 nm, more preferably 20 nm to 168 nm, and most preferably 44 nm to 103 nm, as measured by laser diffraction.
  • the abrasive particles have a D70 of 16 nm to 421 nm, more preferably 43 nm to 218 nm, and most preferably 62 nm to 137 nm, as measured by laser diffraction.
  • the abrasive particles should have a small slope factor.
  • slope factor refers to the absolute value of the rising slope of the particle size distribution diagram divided by the falling slope (meaning that its sign is not taken into account).
  • the particle size distribution diagram can be obtained by particle size distribution measurement as described above, wherein the particle size (x-axis) is plotted relative to the volume percentage of the particle (y-axis).
  • rising slope refers to the slope of the tangent (straight line) drawn from P_D01 to P_max.
  • falling slope refers to the slope of the tangent (straight line) drawn from P_max to P_D99.
  • P_D01 refers to the point in the particle size distribution diagram where the particle size is equal to D01.
  • D01 is the particle size obtained by laser diffraction as described above, and 1% by volume of the particles have a particle size less than D01.
  • P_D99 refers to the point in the particle size distribution diagram where the particle size is equal to D99.
  • D99 is the particle size obtained by laser diffraction as described above, and 99% by volume of the particles have a particle size less than D99.
  • P_max refers to the absolute maximum value of the particle size distribution, that is, the point in the particle size distribution with the largest volume % of particles.
  • a small slope factor can be, for example, As a result of a wider distribution of smaller particles than larger particles, this improves particle packing during CMP processing.
  • the abrasive particles have a slope factor of at most 18.6, more preferably at most 10.3, more preferably at most 7.7, more preferably at most 5.2, and most preferably at most 3.8.
  • a crystallite can be a crystal or a region of a crystal structure.
  • a crystallite can be located anywhere within the abrasive grain, such as in the center of the abrasive grain or exposed on the surface of the abrasive grain.
  • An abrasive grain can contain a single crystallite, two crystallites, or a plurality of crystallites.
  • the abrasive should have a high degree of crystallinity.
  • crystallinity refers to the volume % of crystallites contained in the abrasive.
  • a suitable degree of crystallinity can be obtained by controlling parameters during the synthesis of the abrasive, such as temperature.
  • the degree of crystallinity can be obtained from a dry powder of the abrasive by X-ray diffraction (XRD), for example, using a D8 X-ray diffractometer (Bruker Corp). It was found that a higher degree of crystallinity results in a higher material removal rate of the substrate during the CMP process.
  • the abrasive preferably has a crystallinity of at least 56% by volume, more preferably at least 78% by volume, more preferably at least 86% by volume, and most preferably at least 96% by volume of the abrasive.
  • the abrasive is a single crystallite.
  • the abrasive should have a coefficient of linear thermal expansion (CTELP) with suitable lattice parameters.
  • CTELP refers to the expansion of the atomic spacing within the abrasive in response to a specific temperature change.
  • CTELP can be measured by X-ray diffraction (XRD), for example, using a D8 X-ray diffractometer (Bruker Corp) during multiple (such as at least four) heating and cooling cycles.
  • XRD X-ray diffraction
  • Bruker Corp D8 X-ray diffractometer
  • CTELP can be calculated from the slope of the curve of expansion relative to the average temperature of the heating and cooling cycles.
  • CTELP refers to the average coefficient of linear thermal expansion in the temperature range of 20°C to 400°C.
  • the abrasive of the present invention preferably has at least CTELP at a particle size of 40nm. More preferably at least More preferably at least More preferably at least More preferably at least Most preferably at least Preferably, the abrasive particles have a CTELP of at most More preferably at most More preferably at most Most preferably at most In a preferred embodiment, the abrasive particles have a CTELP of 1.2*10 -5 to 40 nm. More preferably, 2.6*10 -5 to More preferred to CTELP.
  • the ceria abrasive particles may have lattice planes exposed on the surface of the abrasive particles, such as ⁇ 100 ⁇ , ⁇ 110 ⁇ , ⁇ 111 ⁇ , ⁇ 220 ⁇ , ⁇ 422 ⁇ and combinations thereof.
  • the desired lattice planes can be achieved, for example, by suitable particle shape, particle size, and parameters (such as temperature) during the synthesis of the ceria abrasive particles.
  • the lattice planes can be measured by X-ray diffraction, such as by measuring the dry powder of the abrasive particles using a D8 X-ray diffractometer (Bruker Corp).
  • the lattice plane ⁇ 100 ⁇ exposed on the surface of the ceria abrasive particles leads to more oxygen vacancies. More oxygen vacancies on the surface of the ceria abrasive particles can increase the movement of oxygen atoms within the crystallites, which can increase the surface reactivity of the abrasive particles. It has been found that a higher percentage of the lattice plane ⁇ 100 ⁇ exposed on the surface of the ceria abrasive particles can increase the material removal rate of the substrate during CMP processing.
  • preferably at least 26%, more preferably at least 42%, more preferably at least 52%, more preferably at least 64%, more preferably at least 71%, more preferably at least 83%, and most preferably at least 94% of the lattice planes exposed on the surface of the cerium dioxide abrasive are ⁇ 100 ⁇ .
  • the abrasive grains should have a suitable lattice parameter a.
  • the lattice parameter a refers to the average (arithmetic mean) length of the unit cells in the lattice of the abrasive grains along the x-axis.
  • the lattice parameter can be obtained by X-ray diffraction, for example, using a D8 X-ray diffractometer (Bruker Corp), and calculated from each reflection (hkl) relative to cos 2 ⁇ .
  • a suitable lattice parameter a can induce favorable mechanical stress in the abrasive grains.
  • the abrasive grains have at least More preferably at least Most preferably at least
  • the abrasive particles preferably have a lattice parameter a of at most More preferably at most Most preferably at most The lattice parameter a of .
  • the abrasive preferably has a low band gap Eg.
  • the band gap Eg refers to the minimum energy required to excite an electron from the valence band to the conduction band.
  • the band gap Eg can be obtained from the ultraviolet visible (UV-Vis) absorption spectrum of a 1 wt% solution of the abrasive, for example, using a Varian Cary 5E spectrophotometer (Agilent Technologies) at 25°C, scanning wavelengths from 300 to 1000 nm.
  • a Tauc curve can be plotted by ( ⁇ h ⁇ ) 2 (Y axis) and (h ⁇ ) (X axis), where ⁇ is the linear absorption coefficient, h is the Planck constant, and ⁇ is the frequency of light.
  • the linear portion of the graph can be extrapolated, and the intersection with the extrapolated X axis corresponds to the band gap Eg.
  • a smaller band gap Eg results in an increased formation of reactive oxygen species (ROS) such as superoxide, singlet oxygen, hydroxyl radicals, and hydrogen peroxide. ROS may contribute to higher surface reactivity during CMP processing. It was found that a lower band gap Eg may be associated with a higher material removal rate during CMP processing.
  • ROS reactive oxygen species
  • the abrasive grains preferably have a band gap of at most 3.40 eV, more preferably at most 3.34 eV, more preferably at most 3.31 eV, more preferably at most 3.27 eV, more preferably at most 3.20 eV, and most preferably at most 3.11 eV.
  • the abrasive grains have a band gap of at least 2.36 eV, more preferably at least 2.40 eV, more preferably at least
  • the abrasive grains have a band gap E g of 2.36 eV to 3.40 eV, more preferably 2.40 eV to 3.34 eV, more preferably 2.46 eV to 3.31 eV, more preferably 2.51 eV to 3.27 eV, and more preferably 2.57 eV to 3.20 eV.
  • Smaller band gap E g can be achieved by suitable particle size distribution, particle morphology and microcrystalline structure of the abrasive grains.
  • the ceria abrasive grains have a narrow F 2g peak as assessed by visible Raman spectroscopy.
  • Visible Raman spectra can be obtained, for example, at 25°C using a FRS 27 Raman spectrometer (Bruker Corp.) with a 532 nm laser on a dry powder of ceria abrasive grains.
  • the F 2g peak appears near 464 cm -1 and corresponds to Ce-O vibrations.
  • the Raman spectra should be baseline corrected and normalized to the intensity of the F 2g peak.
  • the full width at half maximum (FWHM) can be used to describe the width of the F 2g peak at half maximum height.
  • the FWHM is the wavelength difference at which the F 2g peak intensity is equal to half the maximum intensity of the visible Raman spectrum measured at 532 nm.
  • a smaller FWHM is associated with a larger ceria abrasive grain crystallite size.
  • a smaller number of defect sites can help reduce the FWHM.
  • Crystal surface defects affect the oxygen mobility within the crystallites and can change the surface reactivity during the CMP process. Surprisingly, it was found that a smaller FWHM can be associated with an increased material removal rate.
  • the cerium oxide abrasive grain preferably has an F 2g peak having a FWHM of at most 26.97 cm -1 , more preferably at most 22.16 cm -1 , more preferably at most 18.02 cm -1 , more preferably at most 15.62 cm -1 , most preferably at most 13.06 cm -1 as measured by Raman spectroscopy at a wavelength of 532 nm.
  • FWTM full width at 1/3 maximum peak
  • FWTM is the wavelength difference when the F2g peak intensity is equal to 1/3 of the maximum intensity of the visible Raman spectrum measured at 532nm.
  • Smaller FWTM values are associated with larger abrasive grain crystallite sizes and the presence of crystal surface defects. Surprisingly, it was found that smaller FWTM can be associated with increased material removal rates.
  • the cerium dioxide abrasive preferably has a F2g peak with a FWTM of at most 35.78cm -1 , more preferably at most 28.34cm -1 , more preferably at most 24.11cm -1 , more preferably at most 21.23cm -1 , and most preferably at most 19.17cm -1 measured by Raman spectroscopy at a wavelength of 532nm.
  • the ceria abrasive grains should have a high ratio of D50 to FWHM.
  • the ratio of D50 to FWHM is the absolute value of D50 of the ceria abrasive grain divided by the absolute value of FWHM of the F 2g peak of the ceria abrasive grain measured by Raman spectroscopy at a wavelength of 532 nm.
  • the D50 and FWHM of the F 2g peak of the ceria abrasive grains can be obtained as described above.
  • a higher ratio of D50 to FWHM is associated with a larger crystallite size relative to the abrasive grain size.
  • a lower number of crystal plane defects also helps to increase the ratio of D50 to FWHM of the F 2g peak.
  • the ceria abrasive grains preferably have a D50 of at least 4.51, more preferably at least 5.12, more preferably at least 5.72, more preferably at least 6.1, and most preferably at least 7.
  • the ratio of D50 of at least 6.68 to the FWHM of the F2g peak measured by Raman spectroscopy at a wavelength of 532 nm.
  • the ceria abrasive grains should have a high D50 to FWTM ratio.
  • the D50 to FWTM ratio is the absolute value of the D50 of the ceria abrasive grain divided by the FWTM of the F 2g peak of the ceria abrasive grain measured by Raman spectroscopy at a wavelength of 532 nm.
  • the D50 and FWTM of the F 2g peak of the ceria abrasive grains can be obtained as described above.
  • a higher ratio of D50 to the FWTM of the F 2g peak is associated with a larger crystallite size relative to the abrasive grain size.
  • a lower number of crystal face defects also helps to increase the D50 to the FWTM of the F2g peak ratio.
  • the cerium dioxide abrasive grain preferably has a ratio of D50 to FWTM of the F 2g peak measured by Raman spectroscopy at a wavelength of 532 nm of at least 1.47, more preferably at least 2.15, more preferably at least 3.64, more preferably at least 3.95, more preferably at least 4.13, and most preferably at least 4.81.
  • the abrasive particles have a positive charge.
  • the charge refers to the zeta potential, which can be measured, for example, by a Mastersizer S (Malvern Instruments).
  • the zeta potential refers to the potential at the interface between a moving fluid within a composition and a stabilizing layer of fluid attached to the abrasive particles dispersed in the composition.
  • the zeta potential depends on the pH of the composition. A higher zeta potential leads to a stronger electrostatic repulsion between the particles, thereby increasing the stability of the dispersion of the particles in the composition.
  • the abrasive particles have a zeta potential of at least 10 mV, more preferably at least 15 mV, more preferably at least 20 mV, more preferably at least 28 mV, most preferably at least 34 mV in the composition at a pH of 1 to 6.
  • the abrasive particles have a zeta potential of at most 80 mV, more preferably at most 75 mV, more preferably at most 70 mV, most preferably at most 60 mV in the composition at a pH of 1 to 6.
  • the abrasive particles have a zeta potential of 10 mV to 80 mV, more preferably 15 mV to 75 mV, more preferably 20 mV to 70 mV, more preferably 28 mV to 60 mV at a pH of 1 to 6 in the composition.
  • the composition should have a suitable viscosity.
  • the viscosity can be measured in mPa*s (milliPascal seconds) at 25°C using a NDJ-8S viscometer (Shanghai Lichen Instrument Technology Co., Ltd.). Higher viscosity can reduce the aggregation and agglomeration of abrasive particles, thereby achieving fewer defects in the substrate.
  • the composition has a viscosity of at least 0.08 mPa*s, more preferably at least 0.24 mPa*s, and most preferably at least 0.72 mPa*s when measured as a 2% solution at 25°C.
  • the composition preferably has a viscosity of at most 28.3 mPa*s, more preferably at most 15.3 mPa*s, and most preferably at most 7.8 mPa*s when measured as a 2% solution at 25°C.
  • abrasive particles having the characteristics described herein advantageously exhibit high material removal rates while inducing fewer defects.
  • compositions comprising abrasive particles as described herein dispersed in an aqueous carrier The composites can show advantageously high material removal rates even without the addition of chemical additives.
  • the composition further comprises one or more chemical additives.
  • the chemical additives may interact, for example, with the abrasive particles and/or with the substrate and/or with the polishing pad during the CMP process.
  • the interaction may be based on, for example, hydrogen bonds, van der Waals forces, electrostatic forces, etc.
  • the chemical additives may be any component suitable for use as, for example, a removal rate promoter, a polishing rate inhibitor, a surfactant, a thickener, a conditioning agent, a complexing agent, a chelating agent, a biocide, a dispersant, an oxidant, a film former, an etching inhibitor, a catalyst, a termination compound, a dissolution inhibitor, a corrosion inhibitor, or a combination thereof.
  • the composition comprises an aqueous carrier.
  • the abrasive particles and chemical additives are suspended in the aqueous carrier.
  • the aqueous carrier enables the abrasive particles and chemical additives to contact the substrate and the polishing pad during the CMP process.
  • the aqueous carrier can be any component suitable for suspending the abrasive particles and chemical additives.
  • Examples of the aqueous carrier include water, ethers (such as dimethicone, ...
  • the aqueous carrier contains at least 50 wt % water, more preferably at least 70 wt % water, more preferably at least 90 wt % water, more preferably at least 95 wt % water, and most preferably at least 99 wt % water.
  • the water is deionized water.
  • the composition comprises a pH adjusting agent when used.
  • the pH adjusting agent helps the composition to achieve a suitable pH.
  • the pH adjusting agent can be an acid or a salt thereof.
  • the acid or a salt thereof can be an organic acid, an inorganic acid or a combination thereof.
  • organic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, methylbutyric acid, caproic acid, dimethylbutyric acid, ethylbutyric acid, methylvaleric acid, heptanoic acid, methylhexanoic acid, caprylic acid, ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, malic acid, phthalic acid, tartaric acid, citric acid, lactic acid, diglycolic acid, furancarboxylic acid, tetrahydrofuranic acid, methoxyacetic acid, methoxyphenylacetic acid, phenoxyacetic acid, methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid,
  • inorganic acids examples include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, carbonic acid, hypophosphorous acid, phosphorous acid, phosphoric acid, and combinations thereof.
  • the pH adjusting agent is an organic acid.
  • the organic acid is selected from maleic acid, malic acid, tartaric acid, citric acid, acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and combinations thereof.
  • the composition may comprise a pH adjusting agent at a concentration suitable for achieving the pH of the present invention.
  • the composition may also optionally include a pH buffer.
  • the pH buffer helps maintain a suitable pH for the composition.
  • the pH buffer may be any suitable buffer.
  • the pH buffer may be, for example, phosphate, sulfuric acid Salts, acetates, borates, ammonium salts or combinations thereof.
  • the composition may include a pH buffer at a concentration suitable for maintaining the pH of the present invention.
  • the pH of the composition affects the removal rate of the substrate during the CMP process. It has been found that alkaline pH leads to lower material removal rates. Therefore, the composition preferably has a pH of at most 7.0, more preferably at most 6.5, more preferably at most 6.0, more preferably at most 5.5, more preferably at most 5.0, and most preferably at most 4.5 when used.
  • the composition comprises a monoacid.
  • the monoacid is an organic compound having one acid group.
  • the monoacid may be in the form of an acid, a conjugate acid, a salt or a combination thereof.
  • Suitable acid groups include, for example, carboxyl, sulfonic acid and phosphonic acid.
  • the monoacid is a monocarboxylic acid.
  • the monocarboxylic acid may, for example, be a straight chain monocarboxylic acid, a branched monocarboxylic acid, a saturated monocarboxylic acid, an unsaturated monocarboxylic acid, a substituted monocarboxylic acid, an aromatic monocarboxylic acid and a combination thereof.
  • the example of the monocarboxylic acid has nicotinic acid, isonicotinic acid, quinaldic acid, acetic acid, picolinic acid, hydroxybenzoic acid, formic acid, carbonic acid, glycolic acid, glyoxylic acid, lactic acid, glyceric acid, pyruvic acid, oxopropionic acid, hydroxypropionic acid, oxopropionic acid, glycidic acid, butyric acid, isobutyric acid, butyric acid, propionic acid, crotonic acid, isocrotonic acid, acrylic acid, methacrylic acid, vinylacetic acid, butynoic acid, hydroxybutyric acid, oxobutyric acid, valeric acid, isovaleric acid, neopentanoic acid, caproic acid, sorbic acid, benzoic acid, salicylic acid, octanoic acid, nonanoic acid, cinnamic acid, capric
  • the monoacid is selected from propionic acid, butyric acid, acetic acid, valeric acid, caproic acid, picolinic acid and combinations thereof.
  • the monoacid is different from pH adjusting agent, meaning that they are not identical compounds.
  • the composition comprises at least 0.0001wt%, more preferably at least 0.001wt%, more preferably at least 0.007wt%, more preferably at least 0.013wt%, most preferably at least 0.021wt% of monoacid when used.
  • the composition comprises at most 9.7wt%, more preferably at most 4.4wt%, more preferably at most 2.3wt%, more preferably at most 1.2wt%, most preferably at most 0.14wt% of monoacid when used.
  • the composition comprises 0.0001wt% to 9.7wt%, more preferably 0.001wt% to 4.4wt%, more preferably 0.007wt% to 2.3wt%, more preferably 0.013wt% to 1.2wt% of monoacid.
  • the composition may also optionally include one or more biocides.
  • the biocide may be a compound that prevents, inhibits, reduces the growth, inhibits the activity, or eliminates unwanted microorganisms.
  • biocides are sodium hypochlorite, methylisothiazolinone, benzisothiazolinone, chloromethylisothiazolinone, and combinations thereof.
  • the composition preferably comprises at least 0.6 ppm by weight, more preferably at least 1.6 ppm by weight, more preferably at least 2.7 ppm by weight, more preferably at least 3.8 ppm by weight, and most preferably at least 4.6 ppm by weight of the biocide.
  • High concentrations of biocide may result in the biocide and the composition being mixed. Undesirable interactions occur between other components and the substrate, therefore, the composition preferably comprises at most 98 ppm by weight, more preferably at most 83 ppm by weight, more preferably at most 74 ppm by weight, most preferably at most 69 ppm by weight of biocide.
  • the present invention also provides a method for chemical mechanical polishing of a substrate comprising a silicon oxide material, the method comprising the following steps: (a) providing a chemical mechanical polishing composition; (b) contacting the substrate with the chemical mechanical polishing composition and a polishing pad; (c) moving the polishing pad relative to the substrate with the composition located therebetween; and (d) removing at least a portion of the substrate.
  • the CMP composition provided in step (a) is a composition of the present invention.
  • the method may optionally include other steps.
  • the abrasive particles can be prepared by any suitable method known to those skilled in the art to impart the above-mentioned properties to the abrasive particles.
  • the cerium oxide abrasive particles can be prepared by precipitation of cerium nitrate and by thermal growth of the particles. The particles can then be centrifuged, washed and dried. The particles can be deagglomerated by further processing, such as filtering, grading, crushing, grinding, milling, ultrasonic treatment and combinations thereof. The particles are dispersed and used to formulate a composition.
  • Useful dispersion processes can be, for example, high shear mixing, ultrasonic treatment and other processes known to those skilled in the art.
  • the composition can be prepared using suitable techniques known to those skilled in the art.
  • the abrasive particles and other chemical additives as described above can be added to the aqueous carrier in any order and in suitable amounts to achieve the desired concentration.
  • the abrasive particles and chemical additives can be mixed and stirred in the aqueous carrier.
  • the pH value can be adjusted using the above-mentioned pH adjusting agents and pH buffers to obtain and maintain the desired pH.
  • the abrasive particles and chemical additives can be added at any time before use (e.g., one month, one day, one hour or one minute) or during the CMP process.
  • the composition can be provided as a one-part system, a two-part system, or a multi-part system.
  • the first part can include abrasive particles and the second part can include one or more chemical additives.
  • the first part and the second part can be mixed at any time before the CMP treatment (e.g., one month, one day, one hour, or one minute) or during the CMP treatment, such as when a polishing apparatus having multiple supply paths for the CMP composition is used.
  • the composition may be provided as a concentrate and may be diluted with a suitable amount of water prior to use.
  • concentration of the components in the composition may be any suitable concentration, for example 2, 3, 10 or 25 times the above concentrations for use.
  • the concentrate may contain abrasive particles and chemical additives in concentrations such that upon dilution with a suitable amount of water, the abrasive particles and chemical additives are present in the composition at the above concentrations.
  • the composition is provided, for example, as a two-part system, one or both parts may be provided as a concentrate. Two parts It may be provided in different concentrations, for example a first part having a three-fold concentration and a second part having a five-fold concentration. The two parts may be diluted in any order before mixing.
  • the composition should achieve high material removal rates for substrates comprising silicon oxide materials during CMP processing.
  • substrates comprising silicon oxide materials are silicon wafers comprising high density plasma (HDP) oxide, plasma enhanced tetraethyl orthosilicate (PETEOS), spin-on glass (SOG), and tetraethyl orthosilicate (TEOS).
  • HDP high density plasma
  • PETEOS plasma enhanced tetraethyl orthosilicate
  • SOOG spin-on glass
  • TEOS tetraethyl orthosilicate
  • the composition exhibits at least / minute, more preferably at least / minute, more preferably at least / minute, preferably at least
  • the material removal rate of the substrate comprising silicon oxide material is 0.0447 W/min.
  • the present invention also relates to the use of the composition of the present invention.
  • the composition of the present invention is used for chemical mechanical polishing of a substrate comprising a silicon oxide material.
  • chemical mechanical polishing refers to a process in which a substrate is placed in a CMP apparatus so that it contacts a polishing pad and a CMP composition located therebetween. The polishing pad moves relative to the substrate to remove a portion of the substrate.
  • silicon oxide materials are polycrystalline silicon, silicon oxide, tetraethyl orthosilicate (TEOS), silicon nitride, doped silicon oxide materials such as carbon doped silicon oxide materials, high density plasma (HDP) oxides, phosphosilicate glass (PSG), borophosphosilicate glass (BPSG), high aspect ratio process (HARP) oxides, spin-on dielectric (SOD) oxides, chemical vapor deposition (CVD) oxides, plasma enhanced tetraethyl orthosilicate (PETEOS), thermal oxides, undoped silicate glass, and combinations thereof.
  • HDP high density plasma
  • PSG phosphosilicate glass
  • BPSG borophosphosilicate glass
  • HTP high aspect ratio process
  • SOD spin-on dielectric
  • CVD chemical vapor deposition
  • PETEOS plasma enhanced tetraethyl orthosilicate
  • thermal oxides undoped silicate glass, and combinations thereof.
  • the compositions of the present invention are used for chemical mechanical polishing of substrates comprising silicon oxide materials and silicon nitride materials.
  • the composition exhibit a particular material removal selectivity for silicon oxide relative to silicon nitride.
  • the material removal rate of silicon oxide preferably exceeds the material removal rate of silicon nitride by at least 2 times, more preferably at least 6 times, more preferably at least 18 times, more preferably at least 37 times, more preferably at least 57, and most preferably at least 71.
  • the material removal rate of silicon nitride preferably exceeds the material removal rate of silicon oxide by at least 2 times, more preferably at least 9 times, and most preferably at least 18 times.
  • the compositions of the present invention are used to polish substrates comprising silicon oxide and polycrystalline silicon.
  • the composition may be desirable for the composition to exhibit a particular material removal selectivity for silicon oxide relative to polycrystalline silicon.
  • the material removal rate of silicon oxide preferably exceeds the material removal rate of polycrystalline silicon by at least 2 times, more preferably by at least 11 times, more preferably by at least 37 times, and most preferably by at least 72 times.
  • Figure 1 is the UV-visible absorption spectra of cerium oxide particles from compositions E7 and A11-A12 in the wavelength range of 300nm to 1000nm, with the x-axis showing the wavelength in nm and the y-axis showing the absorbance in arbitrary units (a.u.).
  • compositions E8 and A13-15 are visible Raman spectrum of ceria particles from compositions E8 and A13-15 in the wavelength range of 200 cm -1 to 700 cm -1 , with the x-axis showing the wave number in cm -1 and the y-axis showing the intensity in arbitrary units (au).
  • cerium oxide abrasive grains were synthesized as follows: 1000 g of Ce(NO 3 ) 3 *6H 2 O and 90 g of NaOH were dissolved in deionized water, respectively. The two solutions were mixed and stirred to form an emulsion slurry. Subsequently, the emulsion slurry was heated at different temperatures of at least 393 K for different time periods of at least 12 hours. The fresh white precipitate formed by the above treatment was separated by centrifugation. The separated precipitate was washed several times with water and ethanol, and then dried overnight in air at at least 373 K.
  • compositions of the following examples were prepared as follows: 0.5 grams of ceria abrasive grains were dispersed and diluted with deionized water to achieve a concentration of 0.05 wt %. Biocide KATHON TM LX150 (Dow Inc.) was added at 30 ppm by wt, and the pH of each composition was adjusted to about 3.5 with acetic acid.
  • PE-TEOS blank plasma enhanced tetraethyl orthosilicate
  • compositions E1-E2 and compositions A1-A2 were evaluated.
  • Compositions E1-E2 included ceria having cubic morphology and compositions A1-A2 included ceria having spherical morphology.
  • the morphology was evaluated by TEM using a Talos F200x transmission electron microscope.
  • the ceria and each composition were prepared as described above.
  • the PE-TEOS wafer was polished with the compositions on a CTS-AP300 polishing tool for 60 seconds as described above.
  • the RR values in Table 1 are expressed in angstroms/minute. Material removal rates are listed in units of .
  • LA960 measures particle size D50 by laser diffraction.
  • compositions E1 and E2 comprising ceria in cubic morphology exhibited higher PE-TEOS material removal rates than compositions A1 and A2 comprising ceria in spherical morphology.
  • compositions E3-E4 and A3-A6 were evaluated. As listed in Table 2, compositions E3-E4 and A3-A4 include cerium dioxide having a cubic morphology and different particle size distributions. Composition A5 includes cerium dioxide in a spherical morphology. Cerium dioxide particles of compositions E3-E4 and A3-A5 were prepared as described above. Composition A6 includes commercial cerium dioxide purchased from Solvay SA, which has a hexagonal morphology and a particle size listed in Table 2. All compositions were prepared as described above. The morphology of the particles was evaluated by SEM using a Nova Nano450 scanning electron microscope.
  • particle sizes D10, D30, D50, D70, and D90 were obtained by laser diffraction using a Horiba LA960.
  • Particle size distribution factors, steepness factors, and slope factors were calculated as described above.
  • PE-TEOS wafers were polished with the compositions on a CTS-AP300 polishing tool for 60 seconds.
  • the values in Table 2 are expressed in angstroms per minute.
  • the material removal rate is listed in units.
  • compositions E3 and E4 of the present invention have small particle size distribution factors, large steepness factors and small slope factors, and both compositions advantageously show higher PE-TEOS removal rates compared to compositions A3-A6.
  • composition A3 shows a slightly higher D50 compared to compositions E3 and E4 (which is expected to be associated with a higher material removal rate)
  • composition A3 shows a significantly lower PE-TEOS material removal rate.
  • composition A3 has an unfavorable large slope factor.
  • composition A4 has an unfavorable large particle size distribution factor, an unfavorable low steepness factor and an unfavorable large slope factor, and shows a lower PETEOS removal rate.
  • compositions A5 containing spherical cerium oxide and compositions A6 containing hexagonal cerium oxide have a small particle size distribution factor, a high steepness factor and a small slope factor
  • the PE-TEOS material removal rate is lower than compositions E3-E4 containing cubic cerium oxide.
  • cubic morphology, small particle size distribution factor, large steepness factor, and small slope factor are associated with favorable high PE-TEOS material removal rate.
  • compositions E5-E6 and A7-A10 were evaluated for PE-TEOS material removal rate and intra-wafer non-uniformity (WIWNU).
  • Compositions E5-E6 included ceria in cubic morphology, while composition A7 included ceria in spherical morphology.
  • Ceria abrasive grains for compositions E5-E6 and A7 were prepared as described above.
  • Compositions A8-A10 included commercial ceria purchased from Solvay SA having a hexagonal morphology with a D50 of 71.17 nm, 81.47 nm, and 94.62 nm, respectively, as measured by laser diffraction using a Horiba LA960. All compositions were prepared as described above.
  • PE-TEOS wafers were polished with the compositions on a CTS-AP300 polishing tool for 60 seconds as described above.
  • the values in angstroms/minute in Table 3 Material removal rates are listed in units of .
  • NU Non-uniformity
  • NU can be used to describe the surface quality of a polished wafer. Higher surface uniformity is associated with lower NU. Higher NU can be the result of localized areas of excessive removal and defects such as spots, pits, and scratches.
  • the material removal rate on the diagonal of the PE-TEOS wafer was measured under the same conditions as above to obtain the diagonal removal rate distribution. For each measurement point, the standard deviation of the thickness difference of the PE-TEOS wafer before and after polishing was obtained. Compared with the total average thickness difference of the PE-TEOS wafer before and after polishing, NU was calculated as the size of the standard deviation. NU is listed in percentage in Table 3.
  • compositions E5 and E6 of the present invention comprising cubic cerium oxide show significantly higher PE-TEOS material removal rates compared to the compositions A7 comprising spherical cerium oxide and the compositions A8-A10 comprising hexagonal cerium oxide.
  • the compositions E5-E6 comprising cubic cerium oxide advantageously show less heterogeneity than the compositions A8-A10 comprising hexagonal cerium oxide, indicating that the polished PE-TEOS wafer has a higher surface quality and fewer surface defects.
  • compositions E7 and A11-A12 included ceria particles in cubic morphology prepared as described above.
  • Compositions A11-A12 included commercial ceria purchased from Solvay SA having a hexagonal morphology with D50s of 71.17 nm and 81.47 nm, respectively, as measured by laser diffraction using a Horiba LA960.
  • the compositions were prepared as described above.
  • PE-TEOS wafers were polished with the compositions on a CTS-AP300 polishing tool for 60 seconds as described above.
  • the band gaps in Table 4 are in angstroms/minute.
  • the material removal rate is listed in units of .
  • UV-visible absorption spectra were obtained from the corresponding cerium oxide particles of compositions E7 and A11-A12, as shown in Figure 1.
  • a solution sample of 1 wt % cerium oxide particles dispersed in deionized water was prepared and measured at 25°C using a Cary-60 UV-visible spectrometer (Agilent Technologies Inc.). As described above, based on Tauc Curve estimation of the band gap.
  • composition E7 of the present invention comprising cubic cerium oxide exhibits a lower band gap and exhibits a higher PE-TEOS material removal rate.
  • composition E8 includes ceria having a cubic morphology
  • composition A13 includes ceria having a spherical morphology
  • compositions 14-A15 include commercial ceria having a hexagonal morphology purchased from Solvay SA.
  • the D50 of compositions E8 and A13-A15 was measured by laser diffraction using a Horiba LA960 and is listed in Table 5. Particles of compositions E8 and A13 and compositions E8 and A13-A15 were prepared as described above.
  • PE-TEOS wafers were polished with the compositions on a CTS-AP300 polishing tool for 60 seconds as described above.
  • the values in Table 5 are expressed in angstroms/minute.
  • the material removal rate is listed in units.
  • Raman spectroscopy the cerium dioxide particles were centrifuged, the supernatant was removed, and the particles were dried at 60°C overnight.
  • Raman spectroscopy was applied to the dried powder using a Horiba iHR550 spectrometer (Horiba) at 25°C using a 532nm laser.
  • the spectra were baseline corrected using iterative reweighted least squares and normalized to the intensity of the F2g peak.
  • the Raman spectra of compositions E8 and A13-15 are shown in Figure 2.
  • FWHM full width at half maximum
  • FWTM full width at 1/3 maximum peak
  • the ratio of D50 to FWHM and the ratio of D50 to FWTM were calculated as described above and are listed in Table 5.
  • the composition E8 containing cubic cerium oxide exhibited a higher PE-TEOS material removal rate than the composition A13 containing spherical cerium oxide and the compositions A14-A15 containing hexagonal cerium oxide.
  • the cerium oxide particles of the composition E8 showed a smaller FWHM, a smaller FWTM, a higher D50 to FWHM ratio, and a higher D50 to FWTM ratio than the cerium oxide particles of the compositions A13-A15.

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Abstract

一种化学机械抛光组合物和用相同组合物对包含硅氧化物材料的基材进行化学机械抛光的方法。涉及包含二氧化铈磨粒的化学机械抛光组合物，所述磨粒的特征在于立方形态、在组合物中在1-6的pH下至少为10mV的zeta电位以及至少为34的陡度因子。CMP组合物，其在CMP处理过程中一方面展现出高材料去除率，另一方面引起基材中更少的缺陷，如划痕。

Description

具有改进颗粒的化学机械抛光组合物 技术领域
本发明属于化工技术领域，具体涉及一种具有改进颗粒的化学机械抛光组合物。
背景技术
化学机械抛光(CMP)组合物通常用于集成电路和微机电***工业中，用于通过化学和机械力的组合对诸如晶片的基材进行化学机械抛光。这些组合物通常是水溶液，包含分散在组合物中的各种化学添加剂和磨粒。CMP组合物也称为抛光浆料、CMP浆料或抛光组合物。CMP组合物极大地影响基材抛光和平滑化过程中的许多因素，例如基材的材料去除率、平坦化和缺陷率。
在诸如浅沟槽隔离的CMP应用中，层间介电(ILD)层中的基材通常包含电介质硅。工业中常用的含硅介电基材为二氧化硅、原硅酸四乙酯(TEOS)和氮化硅。含硅介电基材经常用含有二氧化铈磨粒的CMP组合物抛光。对于许多介电硅应用，需要包含具有高材料去除率的铈氧化物(二氧化铈)磨粒的CMP组合物。然而，具有高材料去除率的二氧化铈磨粒常常会导致在CMP处理期间基材中出现更多不希望的缺陷，例如划痕。尽管二氧化铈磨粒广泛用于抛光介电硅基材，但仍然需要包含二氧化铈磨粒的CMP组合物，其适合用于抛光含有硅氧化物的材料，在CMP处理过程中表现出材料去除率提高和基材中缺陷数目降低。
发明内容
本发明的一个目的是克服现有技术的问题。具体来说，本发明的一个目的是提供一种用于抛光含有硅氧化物的基材的新型CMP组合物，其在CMP处理过程中一方面展现出高材料去除率，另一方面引起基材中更少的缺陷，如划痕。
本发明通过如下方案解决了上述问题：本发明的CMP组合物包含二氧化铈磨粒，其中所述二氧化铈磨粒具有立方形态，在组合物中pH1-pH6下的zeta电位至少为10mV，陡度因子(steepness factor)至少为34。
CMP组合物(本文称为“组合物”)包含分散在水性载体中的磨粒，所述磨粒有助于在抛光过程中从基材表面去除材料。优选地，所述磨粒是选自铈氧化 物(二氧化铈)、铝氧化物(氧化铝)、硅氧化物(二氧化硅)、锆氧化物(氧化锆)、钛氧化物(二氧化钛)、锗氧化物(氧化锗)、镁氧化物(氧化镁)、镍氧化物、镓氧化物(氧化镓)、钇氧化物(氧化钇)及其组合的金属氧化物磨粒。优选所述磨粒包含至少72wt(重量)％、更优选至少83wt％、更优选至少91wt％、更优选至少96wt％、最优选至少98wt％的二氧化铈。在特别优选的实施方案中，所述磨粒是二氧化铈磨粒。如本领域技术人员所知，二氧化铈是指稀土金属铈的氧化物，也称为氧化铈、铈氧化物或二氧化铈。
在一些实施方案中，所述二氧化铈磨粒是掺杂二氧化铈磨粒。合适的掺杂剂例如是金属离子(如Ca、Mg、Zn、Zr、Sc、Y)或镧系元素(如镧、镨、钕、钷或钐)。然而，发现本发明的磨粒即使在没有掺杂剂的情况下也可以表现出高去除率。因此，所述二氧化铈磨粒优选基本上不含掺杂剂。掺杂剂可作为杂质存在于磨粒中，杂质可源自用于制备磨粒的原料或起始材料。
本文所用术语“基本上不含组分X”是指组合物，其实质上不包含所述组分X，即该组分至多可以作为杂质或污染物存在于所述组合物中，但不是作为单个组分添加到所述组合物中的。这意味着所述组分X没有以实质量添加。本发明的非实质量是小于30ppm，更优选小于20ppm，更优选小于10ppm，最优选小于1ppm的量。本文所用ppm是指重量ppm。
在使用时，所述组合物优选包含至少0.001wt％、更优选至少0.03wt％、更优选至少0.06wt％、更优选至少0.09wt％、最优选至少0.14wt％的磨粒。本文所用术语“使用时”是指在CMP过程中将所述组合物应用到基材表面的时候。如果磨粒的浓度太高，则颗粒会聚集，这会缩短组合物的保质期并在CMP处理过程中导致基材出现不希望的表面缺陷。因此，在使用时，所述组合物优选包含至多21.7wt％、更优选至多18.9wt％、更优选至多16.8wt％、更优选至多13.3wt％，最优选至多10.8wt％的磨粒。在优选的实施方案中，所述组合物包含0.03wt％至18.9wt％，更优选0.06wt％至16.8wt％，更优选0.09wt％至13.3wt％的磨粒。
所述磨粒可以作为单个颗粒、聚集体、附聚物及其混合物存在于所述组合物中。单个颗粒可以例如通过范德华力彼此附着，从而形成超过一个的单个颗粒的聚集体。聚集体自身可以例如通过物理相互作用进一步彼此附着，形成一个以上聚集体的附聚物。聚集体和附聚物的形成是可逆的。本文所用的术语磨粒是指单个颗粒、聚集体和附聚物。
已发现在CMP处理过程中，单个颗粒的大量聚集和附聚会导致基材表面上出现更多缺陷，如划痕和凹坑。单个颗粒以及聚集体和附聚物的数目可以由本领域技术人员通过透射电子显微镜(TEM)或扫描电子显微镜(SEM)图像确定。分析应基于统计学上有意义的大量随机选择的颗粒，例如至少300个。优选所述磨粒的聚集体和附聚物的总和至多为磨粒的68.9wt％，更优选至多56.7wt％，更优选至多45.4wt％，更优选至多32.3wt％，最优选至多22.1wt％。较少的聚集体和附聚物可以例如通过解聚如过滤、研磨和本领域技术人员已知的其他过程来实现。
本发明的磨粒应具有合适的形态。颗粒的形态会影响颗粒的表面反应性并且影响材料去除率。所述形态可由本领域技术人员例如使用透射电子显微镜(TEM)或扫描电子显微镜(SEM)图像确定。已发现具有球形形态的颗粒表现出较低的材料去除率。术语球形形态不限于完美的球体，是指没有实质性边缘和顶点(角)的任何圆形形态，例如球状、椭圆状、葡萄状结构等。优选所述磨粒具有球形形态的量至多为磨粒的34.6wt％，更优选至多为24.9wt％，更优选至多为13.8wt％，更优选最多为6.8wt％，最优选至多为3.1wt％。
已发现具有至少一个顶点的磨粒可表现出较高的材料去除率。优选所述磨粒具有选自立方体、四角锥、三棱柱、十二面体、二十面体、八面体、六角锥、六角棱柱、五角棱柱、圆锥、四面体、长方体、菱形、六角菱形及其混合物的形态。
在特别优选的实施方案中，所述磨粒具有立方体形态。已发现具有立方体形态的磨粒可以表现出更高的材料去除率。术语立方体形态是指任何类似立方体的形态，并不限于完美的立方体。例如，磨粒的一个或多个边缘可以稍微圆化，磨粒的一个或多个顶点可以稍微圆化，磨粒的一个或多个对棱可以稍微倾斜(不完全平行)，磨粒的一个或多个二面角可以略大于或小于90°，以及与完美立方体的其他差异。略微可指与完美立方体的偏差至多30％，更优选至多20％，最优选至多10％。优选所述磨粒具有立方体形态的量为磨粒的至少31.3wt％，更优选至少49.2wt％，更优选至少68.4wt％，更优选至少76.3wt％，更优选至少86.7wt％，更优选至少93.8wt％，最优选至少98wt％。
所述磨粒的平均粒径(直径)会影响材料去除率。如本领域技术人员所知，平均粒径可以通过激光衍射测量(例如使用来自Horiba的LA-960)获得。通过 该测量获得的曲线图提供了具有一定尺寸的颗粒的累积体积百分比。平均粒径(D50)是50体积％颗粒的粒径小于该值的粒径。D50较小会使材料去除率降低。优选所述磨粒具有激光衍射测量为至少5nm、更优选至少11nm、更优选至少23nm、更优选至少33nm、最优选至少48nm的D50。然而，如果D50太大，则在CMP处理过程中，基材表面会出现大量不希望有的缺陷，如划痕。因此，所述磨粒应具有较小的平均粒径。优选所述磨粒具有激光衍射测量的至多380nm、更优选至多221、更优选至多181nm、更优选至多151nm、最优选至多125nm的D50。在优选的实施方案中，所述磨粒具有激光衍射测量为11nm至221nm，更优选23nm至181nm，更优选33nm至151nm，更优选48nm至125nm的D50。通常认为具有较大D50的磨粒会在CMP处理过程中导致较高的材料去除率。然而，令人惊奇地发现，本发明的磨粒即使具有较小的D50也可以实现高材料去除率。
D10是10体积％颗粒的粒径小于该值的粒径。优选所述磨粒具有激光衍射测量为至少3nm、更优选至少9nm、更优选至少18nm、更优选至少28nm、最优选至少39nm的D10。磨粒的D10较小会增加CMP处理过程中基材表面上的颗粒堆积密度(减少空隙体积)，这有助于提高材料去除率。因此，所述磨粒优选具有激光衍射测量为至多320nm、更优选至多211、更优选至多152nm、更优选至多112nm、最优选至多87nm的D10。在优选的实施方案中，所述磨粒具有激光衍射测量的9nm至211nm、更优选18nm至152nm、更优选28nm至112nm、最优选39nm至87nm的D10。
D90是90体积％颗粒的粒径小于该值的粒径。磨粒的较高D90会提高CMP处理过程中的材料去除率。优选所述磨粒具有激光衍射测量的至少24nm、更优选至少41nm、更优选至少76nm、更优选至少83nm、最优选至少99nm的D90。然而，如果磨粒的D90过高，则在CMP处理过程中会出现更多不希望有的缺陷，如划痕。因此，所述磨粒优选具有激光衍射测量的至多489nm、更优选至多376、更优选至多269nm、更优选至多219nm、最优选至多194nm的D90。在优选的实施方案中，所述磨粒具有激光衍射测量的41nm至376nm，更优选76nm至269nm，更优选83nm至219nm，最优选99nm至194nm的D90。
通常，粒径分布宽会使材料去除率更高，这是由于较大颗粒的数目更多，以及在CMP处理过程中磨粒更好装载。然而，粒径分布宽通常与基材表面中缺 陷数量较多有关。令人惊奇地发现，本发明的磨粒即使具有窄的粒径分布也可以使材料去除率增加。粒径分布的宽度可以用粒径分布因子来描述。本文所用的粒径分布因子是指通过公式(D90-D10)/D50获得的值。粒径分布宽提供大的粒径分布因子，而粒径分布窄提供小的粒径分布因子。D90、D10和D50可以如上所述通过激光衍射获得。发现较小的粒径分布因子与较高的材料去除率有关，同时在CMP处理过程中引起更少的基材表面缺陷。粒径分布因子小可以是例如较少的颗粒聚集和附聚的结果。优选所述磨粒具有至多1.8、更优选至多1.3、更优选至多1.0、更优选至多0.9，最优选至多0.8的粒径分布因子。
所述磨粒应该具有大的陡度因子。本文所用的陡度因子指的是通过公式(D30/D70)*100得到的值。D30和D70可以如上所述通过激光衍射获得。D30是30体积％颗粒的粒径小于该值的粒径。D70是70体积％颗粒的粒径小于该值的粒径。粒径分布宽提供小的陡度因子，而粒径分布窄提供大的陡度因子。令人惊奇地发现，本发明的具有大陡度因子的磨粒表现出高材料去除率，同时在CMP处理过程中实现了基材中更少的缺陷，如划痕。优选所述磨粒具有至少34，更优选至少48，更优选至少56，更优选至少67，最优选至少74的陡度因子。然而，如果陡度因子过大，CMP处理过程中材料去除率会降低。因此，所述磨粒优选具有至多98，更优选至多97，更优选至多96，最优选至多95的陡度因子。
优选所述磨粒具有激光衍射测量的4nm至353nm、更优选20nm至168nm、最优选44nm至103nm的D30。优选所述磨粒具有激光衍射测量的16nm至421nm、更优选43nm至218nm、最优选62nm至137nm的D70。
所述磨粒应具有小的斜率因子。本文所用的术语斜率因子指的是粒径分布图的上升斜率除以下降斜率的绝对值(意思是不考虑其符号)。如本领域技术人员已知的，粒径分布图可以如上所述由粒径分布测量获得，其中相对于颗粒的体积百分比(y轴)对粒径(x轴)作图。本文使用的术语上升斜率是指从P_D01到P_max绘制的切线(直线)的斜率。本文使用的术语下降斜率是指从P_max到P_D99绘制的切线(直线)的斜率。P_D01是指粒径分布图中粒径等于D01的点。D01是如上所述通过激光衍射获得的粒径，1体积％的颗粒具有小于D01的粒径。P_D99是指粒径分布图中粒径等于D99的点。D99是如上所述通过激光衍射获得的粒径，99体积％的颗粒具有小于D99的粒径。P_max是指粒径分布图的绝对最大值，即粒径分布图中具有最大体积％颗粒的点。斜率因子较小例如可以是 较小颗粒比较大颗粒的分布更宽的结果，这会改善CMP处理过程中的颗粒堆积。发现斜率因子较小使基材中的缺陷较少，同时仍表现出高材料去除率。较小的斜率因子可以例如通过改善颗粒的分散以及之后较少聚集和附聚的颗粒来实现。优选所述磨粒具有至多18.6、更优选至多10.3、更优选至多7.7、更优选至多5.2、最优选至多3.8的斜率因子。
在合成所述磨粒的过程中，颗粒中会形成微晶。微晶可以是晶体或晶体结构的区域。微晶可位于磨粒内的任何位置，例如在磨粒的中心或暴露于磨粒的表面。一个磨粒可包含单个微晶、两个微晶或多个微晶。通过控制磨粒合成过程中的条件，例如温度，可以获得磨粒中所需数量和尺寸的微晶。
所述磨粒应具有高结晶度。本文所用的术语结晶度是指所述磨粒包含微晶的体积％。通过控制磨粒合成过程中的参数，例如温度，可以获得合适的结晶度。如本领域技术人员所知，结晶度可以通过X射线衍射(XRD)例如使用D8X射线衍射仪(Bruker Corp)由磨粒的干燥粉末得到。发现结晶度较高会导致CMP处理过程中基材的材料去除率较高。因此，所述磨粒优选具有至少56体积％。，更优选至少78体积％，更优选至少86体积％，最优选至少96体积％磨粒的结晶度。在特别优选的实施方案中，所述磨粒是单个微晶。
所述磨粒应具有合适的晶格参数的线性热膨胀系数(CTELP)。CTELP是指磨粒内的原子间距响应于特定的温度变化而膨胀。CTELP可以通过X射线衍射(XRD)测量，例如在多个(如至少四个)加热和冷却循环期间用D8X射线衍射仪(Bruker Corp)测量。如本领域技术人员所知，CTELP可以由膨胀相对于加热和冷却循环的平均温度的曲线的斜率来计算。CTELP是指在20℃至400℃的温度范围内的线性热膨胀的平均系数。令人惊奇地发现，CTELP较高会使CMP处理过程中基材的材料去除率增加。因此，本发明的磨粒优选在40nm的粒径下具有至少更优选至少更优选至少更优选至少更优选至少最优选至少的CTELP。优选所述磨粒在40nm的粒径下具有至多更优选至多更优选至多更优选至多最优选至多的CTELP。在优选的实施方案中，所述磨粒在40nm的粒径下具有1.2*10-5至更优选2.6*10-5至更优选至的CTELP。
二氧化铈磨粒可具有暴露在磨粒表面的晶格面，例如{100}、{110}、{111}、{220}、{422}及其组合。期望的晶格面可以例如通过二氧化铈磨粒合成期间合适的颗粒形状、颗粒尺寸以及参数(如温度)来实现。如本领域技术人员所知，晶格面可以通过X射线衍射测量，例如用D8X射线衍射仪(Bruker Corp)由磨粒的干燥粉末测量。与暴露在二氧化铈磨粒表面的其他晶格面如{111}和{110}相比，暴露在二氧化铈磨粒表面的晶格面{100}会导致更多的氧空位。二氧化铈磨粒表面更多的氧空位可以增加微晶内氧原子的运动，这可以增加磨粒的表面反应性。已发现暴露在二氧化铈磨粒表面的晶格面{100}的百分比更高可以增加CMP处理过程中基材的材料去除率。在实施方案中，优选暴露在二氧化铈磨粒表面的晶格面的至少26％、更优选至少42％、更优选至少52％、更优选至少64％、更优选至少71％、更优选至少83％、最优选至少94％是{100}。
所述磨粒应具有合适的晶格参数a。晶格参数a是指磨粒的晶格内沿x轴方向的晶胞的平均(算术平均)长度。如本领域技术人员所知，晶格参数可以由X射线衍射，例如用D8X射线衍射仪(Bruker Corp)获得，并由相对cos2θ的每个反射(hkl)计算。合适的晶格参数a可以在磨粒内引起有利的机械应力。优选所述磨粒在40nm的粒径下具有至少更优选至少最优选至少的晶格参数a。优选所述磨粒在40nm的粒径下具有至多更优选至多最优选至多的晶格参数a。
优选所述磨粒具有低带隙Eg。如本领域技术人员所知，带隙Eg是指将电子从价带激发到导带所需的最小能量。带隙Eg可以由磨粒的1wt％溶液的紫外可见(UV-Vis)吸收光谱获得，例如在25℃使用Varian Cary 5E分光光度计(Agilent Technologies)，扫描波长300至1000nm。基于紫外可见吸收光谱，可以由(αhν)2(Y轴)和(hγ)(X轴)绘制Tauc曲线，其中α是线性吸收系数，h是Planck常数，ν是光的频率。图的线性部分可以外推，与外推的X轴的交点对应于带隙Eg。较小的带隙Eg会导致活性氧类(ROS)如超氧化物、单线态氧、羟基自由基和过氧化氢的形成增加。ROS可能有助于CMP处理过程中更高的表面反应性。发现较低的带隙Eg可能与CMP处理过程中较高的材料去除率相关。因此，所述磨粒优选具有至多3.40eV、更优选至多3.34eV、更优选至多3.31eV、更优选至多3.27eV、更优选至多3.20eV、最优选至多3.11eV的带隙。优选所述磨粒具有至少2.36eV、更优选至少2.40eV、更优选至少 2.46eV、更优选至少2.51eV、最优选至少2.57eV的带隙Eg。优选所述磨粒具有2.36eV至3.40eV、更优选2.40eV至3.34eV、更优选2.46eV至3.31eV、更优选2.51eV至3.27eV、更优选2.57eV至3.20eV的带隙。较小的带隙Eg可通过磨粒的合适粒径分布、粒子形态和微晶结构来实现。
优选所述二氧化铈磨粒具有可见拉曼光谱评估的窄F2g峰。可见拉曼光谱可以例如在25℃下使用FRS 27拉曼光谱仪(Bruker Corp.)用532nm激光在二氧化铈磨粒的干粉上获得。如本领域技术人员所知，F2g峰出现在464cm-1附近并且对应于Ce-O振动。拉曼光谱应进行基线校正并归一化为F2g峰的强度。半峰全宽(FWHM)可用于描述F2g峰在半峰高处的宽度。FWHM是F2g峰强度等于在532nm处测量的可见拉曼光谱的最大强度一半时的波长差。较小的FWHM与较大的二氧化铈磨粒微晶尺寸有关。此外，较少数目的缺陷点会有助于减小FWHM。晶体表面缺陷影响微晶内的氧迁移率，并会在CMP处理过程中改变表面反应性。令人惊讶的是，发现较小的FWHM可与增加的材料去除率相关。因此，二氧化铈磨粒优选具有拉曼光谱在532nm波长下测量的FWHM为至多26.97cm-1、更优选至多22.16cm-1、更优选至多18.02cm-1、更优选至多15.62cm-1、最优选至多13.06cm-1的F2g峰。
1/3最大峰值处的全宽(FWTM)可用于描述峰下部的F2g峰的宽度。FWTM是F2g峰强度等于在532nm处测量的可见拉曼光谱最大强度1/3时的波长差。较小的FWTM值与较大的磨粒微晶尺寸以及晶体表面缺陷的存在有关。令人惊讶的是，发现较小的FWTM可与材料去除率增加相关。因此，二氧化铈磨粒优选具有拉曼光谱在532nm波长下测量的FWTM为至多35.78cm-1、更优选至多28.34cm-1、更优选至多24.11cm-1、更优选至多21.23cm-1、最优选至多19.17cm-1的F2g峰。
二氧化铈磨粒应具有高的D50与FWHM之比。D50与FWHM之比是二氧化铈磨粒的D50绝对值除以拉曼光谱在532nm波长下测量的二氧化铈磨粒的F2g峰的FWHM的绝对值。二氧化铈磨粒的D50和F2g峰的FWHM可以如上所述获得。D50与FWHM之比较高与相对于磨粒粒径微晶尺寸较大有关。晶面缺陷数目较少也有助于提高D50与F2g峰的FWHM之比。已发现D50与F2g峰的FWHM之比较高可与CMP处理过程中基材的材料去除率增加有关。因此，二氧化铈磨粒优选具有至少4.51、更优选至少5.12、更优选至少5.72、更优选至少6.1、最优选至 少6.68的D50与拉曼光谱在532nm波长下测量的F2g峰的FWHM之比。
二氧化铈磨粒应具有高的D50与FWTM之比。D50与FWTM之比是二氧化铈磨粒的D50绝对值除以拉曼光谱在532nm波长下测量的二氧化铈磨粒的F2g峰的FWTM。二氧化铈磨粒的D50和F2g峰的FWTM可以如上所述获得。D50与F2g峰的FWTM之比较高与相对于磨粒粒径微晶尺寸较大相关。晶面缺陷数目较少也有助于提高D50与F2g峰的FWTM之比。已发现D50与F2g峰的FWTM之比较高可与材料去除率增加相关。因此，二氧化铈磨粒优选具有至少1.47、更优选至少2.15、更优选至少3.64、更优选至少3.95、更优选至少4.13、最优选至少4.81的D50与拉曼光谱在532nm波长下测量的F2g峰的FWTM之比。
优选所述磨粒带有正电荷。电荷是指zeta电位，可以通过例如Mastersizer S(Malvern Instruments)测量。如本领域技术人员所知，zeta电位是指在组合物内的移动流体与附着于分散在所述组合物中的磨粒上的流体稳定层之间的界面处的电位。zeta电位取决于组合物的pH值。zeta电位更高导致粒子之间静电排斥更强，从而增加粒子在组合物中分散体的稳定性。优选磨粒在组合物中在1至6的pH下具有至少10mV、更优选至少15mV、更优选至少20mV、更优选至少28mV、最优选至少34mV的zeta电位。优选磨粒在组合物中在1至6的pH下具有至多80mV、更优选至多75mV、更优选至多70mV、最优选至多60mV的zeta电位。优选磨粒在组合物中在1至6的pH下具有10mV至80mV、更优选15mV至75mV、更优选20mV至70mV、更优选28mV至60mV的zeta电位。
所述组合物应具有合适的粘度。粘度可以用NDJ-8S粘度计(上海力辰仪器科技有限公司)在25℃下以mPa*s(毫帕秒)为单位测量。较高的粘度可以减少磨粒的聚集和附聚，从而实现基材中较少的缺陷。优选所述组合物在25℃下作为2％溶液测量时具有至少0.08mPa*s、更优选至少0.24mPa*s、最优选至少0.72mPa*s的粘度。然而，如果粘度过高，则颗粒和化学添加剂在组合物中的移动会受到限制，会导致去除率降低。因此，所述组合物在25℃下作为2％溶液测量时优选具有至多28.3mPa*s、更优选至多15.3mPa*s、最优选至多7.8mPa*s的粘度。
已发现具有本文所述特征的磨粒有利地表现出高材料去除率，同时引起的缺陷更少。令人惊奇地发现，包含分散在水性载体中的如本文所述的磨粒的组 合物即使不添加化学添加剂，也能表现出有利的高材料去除率。
优选所述组合物还包含一种或多种化学添加剂。该化学添加剂可以在CMP处理过程中例如与磨粒和/或与基材和/或与抛光垫相互作用。该相互作用可以基于例如氢键、范德华力、静电力等。所述化学添加剂可以是适合用作例如去除率促进剂、抛光率抑制剂、表面活性剂、增稠剂、调节剂、络合剂、螯合剂、生物杀灭剂、分散剂、氧化剂、成膜剂、蚀刻抑制剂、催化剂、终止化合物、溶解抑制剂、腐蚀抑制剂或其组合的任何组分。
所述组合物包含水性载体。所述磨粒和化学添加剂悬浮在水性载体中。该水性载体使磨粒和化学添加剂能够在CMP处理过程中与基材和抛光垫接触。该水性载体可以是适合用于悬浮磨粒和化学添加剂的任何组分。该水性载体的实例有水、醚类(如二烷和四氢呋喃)、醇类(如甲醇和乙醇)以及它们的组合。优选该水性载体含至少50wt％水、更优选至少70wt％水、更优选至少90wt％水、更优选至少95wt％水、最优选至少99wt％水。优选所述水是去离子水。
优选所述组合物在使用时包含pH调节剂。该pH调节剂帮助组合物实现合适的pH。该pH调节剂可以是酸或其盐。该酸或其盐可以是有机酸、无机酸或其组合。
有机酸的实例有甲酸、乙酸、丙酸、丁酸、戊酸、甲基丁酸、己酸、二甲基丁酸、乙基丁酸、甲基戊酸、庚酸、甲基己酸、辛酸、乙基己酸、苯甲酸、乙醇酸、水杨酸、甘油酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、马来酸、苹果酸、邻苯二甲酸、酒石酸、柠檬酸、乳酸、二甘醇酸、呋喃羧酸、四氢呋喃酸、甲氧基乙酸、甲氧基苯乙酸、苯氧基乙酸、甲磺酸、乙磺酸、磺基琥珀酸、苯磺酸、甲苯磺酸、苯基膦酸、羟乙基二膦酸及其组合。
无机酸的实例有盐酸、硫酸、硝酸、氢氟酸、硼酸、碳酸、次磷酸、亚磷酸、磷酸及其组合。
优选所述pH调节剂是有机酸。在特别优选的实施方案中，所述有机酸选自马来酸、苹果酸、酒石酸、柠檬酸、乙酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸及其组合。所述组合物可以包含浓度适合于实现本发明的pH的pH调节剂。
所述组合物还任选包含pH缓冲剂。该pH缓冲剂帮助维持组合物合适的pH。该pH缓冲剂可以是任何合适的缓冲剂。该pH缓冲剂可以例如是磷酸盐、硫酸 盐、乙酸盐、硼酸盐、铵盐或其组合。所述组合物可以包含浓度适合维持本发明的pH的pH缓冲剂。
所述组合物的pH影响CMP处理过程中基材的去除率。已发现碱性pH会导致较低的材料去除率。因此，该组合物优选在使用时具有至多7.0、更优选至多6.5、更优选至多6.0、更优选至多5.5、更优选至多5.0、最优选至多4.5的pH。
优选所述组合物包含一元酸。该一元酸是具有一个酸基的有机化合物。该一元酸可以是酸、共轭酸、盐或其组合的形式。合适的酸基有例如羧基、磺酸基和膦酸基。优选所述一元酸是单羧酸。该单羧酸例如可以是直链单羧酸、支链单羧酸、饱和单羧酸、不饱和单羧酸、取代单羧酸、芳族单羧酸及其组合。
所述单羧酸的实例有烟酸、异烟酸、喹哪啶酸、乙酸、皮考啉酸、羟基苯甲酸、甲酸、碳酸、乙醇酸、乙醛酸、乳酸、甘油酸、丙酮酸、氧代丙酸、羟基丙酸、氧代丙酸、缩水甘油酸、酪酸、异丁酸、丁酸、丙酸、巴豆酸、异巴豆酸、丙烯酸、甲基丙烯酸、乙烯基乙酸、丁炔酸、羟基丁酸、氧代丁酸、戊酸、异戊酸、新戊酸、己酸、山梨酸、苯甲酸、水杨酸、辛酸、壬酸、肉桂酸、癸酸、肉豆蔻酸、棕榈酸、硬脂酸及其组合。在特别优选的实施方案中，所述一元酸选自丙酸、丁酸、乙酸、戊酸、己酸、皮考啉酸及其组合。优选所述一元酸不同于pH调节剂，意味着它们不是相同的化合物。
优选所述组合物在使用时包含至少0.0001wt％、更优选至少0.001wt％、更优选至少0.007wt％、更优选至少0.013wt％、最优选至少0.021wt％的一元酸。优选所述组合物在使用时包含至多9.7wt％、更优选至多4.4wt％、更优选至多2.3wt％、更优选至多1.2wt％、最优选至多0.14wt％的一元酸。在优选的实施方案中，所述组合物包含0.0001wt％至9.7wt％、更优选0.001wt％至4.4wt％、更优选0.007wt％至2.3wt％、更优选0.013wt％至1.2wt％的一元酸。
所述组合物还任选包含一种或多种生物杀灭剂。该生物杀灭剂可以是防止、抑制、减少生长、抑制活性或消除不需要的微生物的化合物。生物杀灭剂的实例是次氯酸钠、甲基异噻唑啉酮、苯并异噻唑酮、氯甲基异噻唑啉酮及其组合。
所述组合物优选包含按重量计至少0.6ppm、更优选按wt计至少1.6ppm、更优选按wt计至少2.7ppm、更优选按wt计至少3.8ppm、最优选按wt计至少4.6ppm的生物杀灭剂。高浓度的生物杀灭剂会导致生物杀灭剂与组合物的 其他组分以及基材之间发生不希望的相互作用，因此，所述组合物优选包含按wt计至多98ppm、更优选按wt计至多83ppm、更优选按wt计至多74ppm、最优选按wt计至多69ppm的生物杀灭剂。
本发明还提供了一种化学机械抛光包含硅氧化物材料的基材的方法，该方法包括以下步骤：(a)提供化学机械抛光组合物；(b)使基材与化学机械抛光组合物和抛光垫接触；(b)相对于基材移动抛光垫，组合物位于两者之间；(c)除去至少一部分基材。步骤(a)提供的CMP组合物是本发明的组合物。该方法可以任选包括其他步骤。
所述磨粒可以用本领域技术人员已知的任何合适方法制备，以赋予磨粒上述特性。在实施方案中，二氧化铈磨粒可通过硝酸铈沉淀和通过使颗粒受热生长来制备。颗粒之后可以离心、洗涤和干燥。所述颗粒可通过进一步加工，如过滤、分级、压碎、研磨、碾磨、超声处理及其组合来解附聚。所述颗粒被分散并用于配制组合物。有用的分散过程可以是例如高剪切混合、超声处理和本领域技术人员已知的其他过程。
所述组合物可以用本领域技术人员已知的合适技术来制备。如上所述的磨粒和其他化学添加剂可以以任何顺序以合适的量添加到水性载体中以达到所需的浓度。所述磨粒和化学添加剂可以在水性载体中混合和搅拌。pH值可以用上述pH调节剂和pH缓冲剂进行调节，以获得并保持希望的pH。所述磨粒和化学添加剂可以在使用前任何时间(例如一个月、一天、一小时或一分钟)或CMP处理过程中添加。
所述组合物可以作为单部分***、两部分***或多部分***提供。例如，作为双部分***，第一部分可包括磨粒，第二部分可包括一种或多种化学添加剂。第一部分和第二部分可以在CMP处理之前的任何时间(例如一个月、一天、一小时或一分钟)或在CMP处理过程中混合，例如当使用具有多个CMP组合物的供给路径的抛光设备时。
所述组合物可以作为浓缩物提供，并且可在使用前用适量的水稀释。所述组合物中各组分的浓缩度可以是任何合适的，例如上述使用时浓度的2倍、3倍、10倍或25倍。例如，所述浓缩物所含磨粒和化学添加剂的浓度使得在用适量水稀释后，磨粒和化学添加剂以上述浓度存在于组合物中。如果所述组合物例如作为两部分***提供，则一个或两个部分可以作为浓缩物提供。两部分 可以不同的浓缩度提供，例如第一部分的浓缩度为三倍，第二部分的浓缩度为五倍。两部分在混合之前可以按任何顺序稀释。
在CMP处理过程中，所述组合物应实现包含硅氧化物材料的基材的高材料去除率。包含硅氧化物材料的基材的示例有包含高密度等离子体(HDP)氧化物、等离子体增强的原硅酸四乙酯(PETEOS)、旋涂玻璃(SOG)和原硅酸四乙酯(TEOS)的硅晶片。优选所述组合物在CMP处理过程中表现出至少/分钟、更优选至少/分钟、更优选至少/分钟、最优选至少/分钟的包含硅氧化物材料的基材的材料去除率。
本发明还涉及本发明的组合物的用途。优选本发明的组合物用于化学机械抛光包含硅氧化物材料的基材。如本领域技术人员所知，化学机械抛光是指将基材放置在CMP装置内，使其与抛光垫和位于两者之间的CMP组合物接触的过程。所述抛光垫与基材相对移动，以除去部分基材。硅氧化物材料的实例是多晶硅、氧化硅、原硅酸四乙酯(TEOS)、氮化硅、掺杂氧化硅材料如碳掺杂氧化硅材料、高密度等离子体(HDP)氧化物、磷硅酸盐玻璃(PSG)、硼磷硅酸盐玻璃(BPSG)、高深宽比工艺(HARP)氧化物、旋涂电介质(SOD)氧化物、化学气相沉积(CVD)氧化物、等离子增强原硅酸四乙酯(PETEOS)、热氧化物、未掺杂硅酸盐玻璃及其组合。
在一些实施方案中，本发明的组合物用于化学机械抛光包含硅氧化物材料和硅氮化物材料的基材。根据应用不同，可能希望所述组合物相对于硅氮化物而言表现出特定的对硅氧化物的材料去除选择性。在某些实施方案中，硅氧化物的材料去除率优选超过硅氮化物的材料去除率至少2倍、更优选至少6倍、更优选至少18倍、更优选至少37倍、更优选至少57、最优选至少71。在其他实施方案中，硅氮化物的材料去除率优选超过硅氧化物的材料去除率至少2倍、更优选至少9倍、最优选至少18倍。
在一些实施方案中，本发明的组合物用于抛光包含硅氧化物和多晶硅的基材。根据应用不同，可能希望所述组合物相对于多晶硅而言表现出特定的对硅氧化物的材料去除选择性。在某些实施方案中，硅氧化物的材料去除率优选超过多晶硅的材料去除率至少2倍、更优选至少11倍、更优选至少37倍、最优选至少72倍。
附图说明
图1是来自组合物E7和A11-A12的二氧化铈颗粒在300nm至1000nm波长范围内的紫外可见吸收光谱，x轴显示以nm为单位的波长，y轴显示任意单位(a.u.)的吸光度。
图2是来自组合物E8和A13-15的二氧化铈颗粒在200cm-1至700cm-1波长范围内的可见拉曼光谱，x轴显示以cm-1为单位的波数，y轴显示任意单位(a.u.)的强度。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
在以下实施例中，二氧化铈磨粒如下合成：将1000g Ce(NO3)3*6H2O和90g NaOH分别溶解在去离子水中。将两种溶液混合并搅拌以形成乳状浆液。随后，将乳状浆液在至少393K的不同温度下加热至少12小时的不同时间段。通过离心分离上述处理形成的新鲜白色沉淀物。分离的沉淀物用水和乙醇洗涤数次，随后在空气中至少373K干燥过夜。
以下实施例的组合物如下制备：将0.5克二氧化铈磨粒用去离子水分散并稀释，以达到0.05wt％的浓度。按wt计以30ppm添加生物杀灭剂KATHONTM LX150(Dow Inc.)，用乙酸将每种组合物的pH调节至约3.5。
在以下实施例中，由TopVendor获得空白等离子增强原硅酸四乙酯(PE-TEOS)晶片并包括TEOS层。用CTS-AP300抛光工具(可从CTS Co.获得)在100rpm的研磨平台速度、85rpm的载具速度、3.3psi的膜下压压力和150ml/min的浆料流速下将PE-TEOS晶片抛光60秒。
实施例1
评估组合物E1-E2和组合物A1-A2的PE-TEOS材料去除率(RR)。组合物E1-E2包括具有立方形态的二氧化铈，组合物A1-A2包括具有球形形态的二氧化铈。用Talos F200x透射电子显微镜通过TEM评估形态。如上所述制备二氧化铈和各组合物。如上所述，将PE-TEOS晶片在CTS-AP300抛光工具上用组合物抛光60秒。表1中以埃/分钟为单位列出了材料去除率。用Horiba  LA960通过激光衍射测量粒径D50。
表1
从表1可以看出，包含立方形态二氧化铈的组合物E1和E2表现出比包含球形形态二氧化铈的组合物A1和A2更高的PE-TEOS材料去除率。
实施例2
评估组合物E3-E4和A3-A6的PE-TEOS材料去除率。如表2中所列，组合物E3-E4和A3-A4包括具有立方形态和不同粒径分布的二氧化铈。组合物A5包括球形形态的二氧化铈。如上所述制备组合物E3-E4和A3-A5的二氧化铈颗粒。组合物A6包括购自Solvay S.A.的商品二氧化铈，其具有六方形态和表2中所列的粒径。所有组合物均如上所述制备。用Nova Nano450扫描电子显微镜通过SEM评估颗粒的形态。如上所述，粒径D10、D30、D50、D70和D90使用Horiba LA960通过激光衍射获得。如上所述计算粒径分布因子、陡度因子和斜率因子。如上所述，将PE-TEOS晶片在CTS-AP300抛光工具上用组合物抛光60秒。表2中以埃每分钟为单位列出了材料去除率。
表2

从表2中可以看出，本发明的组合物E3和E4具有小的粒径分布因子、大的陡度因子和小的斜率因子，并且与组合物A3-A6相比，这两种组合物都有利地表现出更高的PE-TEOS去除率。尽管组合物A3显示出与组合物E3和E4相比略高的D50(这预计与较高的材料去除率有关)，但组合物A3表示出显著较低的PE-TEOS材料去除率。从表2可以看出，组合物A3具有不利的大斜率因子。与组合物E3-E4相比，组合物A4具有不利的大粒径分布因子、不利的低陡度因子和不利的大斜率因子，并且表现出较低的PETEOS去除率。从表2中可以看出，尽管含有球形二氧化铈的组合物A5和含有六方二氧化铈的组合物A6具有小的粒径分布因子、高的陡度因子和小的斜率因子，但是PE-TEOS材料去除率与包含立方形态二氧化铈的组合物E3-E4相比较低。从表2中可以看出，立方形态、小粒径分布因子、大陡度因子和小斜率因子与有利的高PE-TEOS材料去除率相关。
实施例3
评估组合物E5-E6和A7-A10的PE-TEOS材料去除率和晶片内不均匀性(WIWNU)。组合物E5-E6包括立方形态的二氧化铈，而组合物A7包括球形形态的二氧化铈。如上所述制备组合物E5-E6和A7的二氧化铈磨粒。组合物A8-A10包括购自Solvay S.A.的商品二氧化铈，其具有六方形态，用Horiba LA960通过激光衍射测量的D50分别为71.17nm、81.47nm和94.62nm。如上所述制备所有组合物。如上所述，将PE-TEOS晶片在CTS-AP300抛光工具上用组合物抛光60秒。表3中以埃/分钟为单位列出了材料去除率。不均匀性(NU)可用于描述抛光晶片的表面质量。较高的表面均匀性与较低的NU有关。较高的NU可能是局部区域去除率过高和有缺陷(如斑点、凹坑和划痕)的结果。为 了获得NU，在与上述相同的条件下测量PE-TEOS晶片对角线上的材料去除率，以获得对角去除率分布。对于每个测量点，获得抛光前后PE-TEOS晶片厚度差的标准偏差。相比抛光前后PE-TEOS晶片的总平均厚度差，计算NU，做为该标准偏差的大小。表3中以百分比列出了NU。
表3
从表3中可以看出，与包含球形形态二氧化铈的组合物A7、包括六方形态二氧化铈的组合物A8-A10相比，本发明的包含立方形态二氧化铈的组合物E5和E6表现出显著更高的PE-TEOS材料去除率。此外，与包含六方形态二氧化铈的组合物A8-A10相比，包含立方形态二氧化铈的组合物E5-E6有利地显示出更小的不均匀性，表明抛光的PE-TEOS晶片具有更高的表面质量和更少的表面缺陷。
实施例4
评估组合物E7和A11-A12的PE-TEOS材料去除率和相应二氧化铈颗粒的带隙。组合物E7包括如上所述制备的立方形态的二氧化铈颗粒。组合物A11-A12包括购自Solvay S.A.的商品二氧化铈，其具有六方形态，用Horiba LA960通过激光衍射测量的D50分别为71.17nm和81.47nm。如上所述制备组合物。如上所述，将PE-TEOS晶片在CTS-AP300抛光工具上用组合物抛光60秒。表4中以埃/分钟为单位列出了材料去除率。对于带隙评估，从组合物E7和A11-A12的相应二氧化铈颗粒获得紫外可见吸收光谱，如图1所示。制备分散在去离子水中的1wt％二氧化铈颗粒的溶液样品，并在25℃下用Cary-60紫外可见光谱仪(Agilent Technologies Inc.)进行测量。如上所述，基于Tauc 曲线估计带隙。
表4
从表4中可以看出，与包含六方形态二氧化铈颗粒的组合物A11-A12相比，本发明的包含立方形态二氧化铈的组合物E7显示出较低的带隙，并且表现出较高的PE-TEOS材料去除率。
实施例5
评估组合物E8和A13-A15的PE-TEOS材料去除率和相应二氧化铈颗粒的拉曼光谱。组合物E8包括具有立方形态的二氧化铈，组合物A13包括具有球形形态的二氧化铈，组合物14-A15包括购自Solvay S.A.的具有六方形态的商品二氧化铈。组合物E8和A13-A15的D50用Horiba LA960通过激光衍射测量并列于表5中。如上所述制备组合物E8和A13的颗粒以及组合物E8和A13-A15。如上所述，将PE-TEOS晶片在CTS-AP300抛光工具上用组合物抛光60秒。表5中以埃/分钟为单位列出了材料去除率。对于拉曼光谱，将二氧化铈颗粒离心，去除上清液，并将颗粒在60℃下干燥过夜。用Horiba iHR550光谱仪(Horiba)在25℃下使用532nm激光对干燥的粉末应用拉曼光谱。使用迭代重加权最小二乘法对光谱进行基线校正，并归一化为F2g峰的强度。组合物E8和A13-15的拉曼光谱如图2所示。如上所述计算FWHM(半峰全宽)、FWTM(1/3最大峰值处的全宽)、D50与FWHM之比以及D50与FWTM之比，并列在表5中。
表5

从表5中可以看出，与包含球形形态二氧化铈的组合物A13和包含六方形态二氧化铈的组合物A14-A15相比，包含立方形态二氧化铈的组合物E8表现出更高的PE-TEOS材料去除率。与组合物A13-A15的二氧化铈颗粒相比，组合物E8的二氧化铈颗粒显示出更小的FWHM、更小的FWTM、更高的D50与FWHM之比以及更高的D50与FWTM之比。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种包含二氧化铈磨粒的化学机械抛光组合物，其中所述二氧化铈磨粒具有：
    立方形态，
    在所述组合物中在1-6的pH下至少为10mV的zeta电位，和
    至少为34的陡度因子。
  2. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有至多1.8的粒径分布因子。
  3. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有至多18.6的斜率因子。
  4. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有F2g峰，其通过拉曼光谱在532nm波长下测量的FWHM为至多26.97cm-1。
  5. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有F2g峰，其通过拉曼光谱在532nm波长下测量的FWTM为最多35.78cm-1。
  6. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有至少4.51的D50与F2g峰的FWHM之比，所述FWHM通过拉曼光谱在532nm的波长下测量。
  7. 根据权利要求1所述的组合物，其特征在于，所述磨粒具有至少1.47的D50与F2g峰的FWTM之比，所述FWTM通过拉曼光谱在532nm波长下测量。
  8. 根据权利要求1所述的组合物，其特征在于，所述组合物的pH至多为7.0。
  9. 根据权利要求1-8中任一项所述的组合物，其特征在于，所述磨粒具有至多3.40eV的带隙。
  10. 一种对含有硅氧化物材料的基材进行化学机械抛光的方法，该方法包括以下步骤：
    a.提供根据权利要求1-9中任一项所述的化学机械抛光组合物；
    b.使所述基材与化学机械抛光组合物和抛光垫接触；
    c.相对于所述基材移动抛光垫，所述组合物位于两者之间；
    d.除去至少一部分基材。
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