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    • 专利摘要:
    The present invention relates to aqueous chemical mechanical planarization (CMP) polishing compositions having a pH of from 2.5 to 5.3 and comprising a mixture of spherical colloidal silica particles and from 30 to 99% by weight, based on based on the total weight of silica solids in the aqueous CMP polishing composition, elongated, curved or nodular silica particles where the colloidal silica particles and elongated, curved or nodular silica particles differ in their size from one another weight average particle (CPS) of less than 20 nm, wherein at least one type of particles among the spherical colloidal silica particles and the elongated, curved or nodular silica particles contains one or more cationic nitrogen atoms. The present invention further relates to methods of using the compositions in CMP polishing applications with a high backing force.
    公开号:FR3057565A1
    申请号:FR1759855
    申请日:2017-10-19
    公开日:2018-04-20
    发明作者:Yi Guo；David Mosley；Matthew Van Hanehem
    申请人:Rohm and Haas Electronic Materials CMP Holdings Inc；
    IPC主号:
    专利说明:

    Holder (s): ROHM AND HAAS ELECTRONIC MATERIALS CMP HOLDINGS, INC ..
    Extension request (s)
    Agent (s): CABINET BEAU DE LOMENIE.
    FR 3 057 565 - A1 (54) AQUEOUS COMPOSITION OF LITTLE ABRASIVE SILICA PARTICLES.
    The present invention relates to aqueous polishing compositions by chemical mechanical planarization (CMP) having a pH ranging from 2.5 to 5.3 and comprising a mixture of spherical colloidal silica particles and from 30 to 99% by weight, based on the total weight of silica solids in the aqueous CMP polishing composition, of elongated, curved or nodular silica particles where the colloidal silica particles and the elongated, curved or nodular silica particles differ from each other in the weight average particle size (CPS) of less than nm, where at least one type of particle from spherical colloidal silica particles and elongated, curved or nodular silica particles contains one or more cationic nitrogen atoms. The present invention further relates to methods of using the compositions in CMP polishing applications with high bearing force.
    AQUEOUS COMPOSMON OF LITTLE ABRASIVE SILICA PARTICLES
    TECHNICAL AREA
    The present invention relates to aqueous chemical mechanical planarization (CMP) polishing compositions comprising a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles where at least one type of particle among the spherical colloidal silica particles and the elongated, curved or nodular silica particles contains one or more cationic nitrogen atoms.
    STATE OF THE ART
    Currently, users of aqueous chemical mechanical planarization (CMP) polishing compositions used with CMP polishing pads for polishing substrates wish to reduce costs by reducing the solids content of the aqueous abrasive suspensions used in such polishing to levels from 1 to 10% by weight of solids. However, these compositions of aqueous suspensions of silica for CMP do not behave in a satisfactory manner, in particular under conditions of high support forces such as those which are necessary for the substrates constituted by hard dielectric wafers such as chips or memory modules. In CMP polishing with high contact force, the space between a substrate constituted by a wafer and the surface of a polishing pad is substantially reduced, which results in a defect in transport of the abrasive particles during polishing, from the edge of the tampon towards its center. This results in a noticeable lack of flatness of the polished substrates by means of CMP polishing with high bearing force, which has a negative impact on the efficiency of planarization. In addition, the friction between the pad and the substrate during polishing increases appreciably, which increases the polishing temperature and leads to abrasion or wear of the pad rather than to the polishing of the substrate and leads to a lifetime of the pad. polishing which is shortened. In addition, with increasing bearing force, the rate of substrate removal when using known aqueous silica suspensions can stagnate or even decrease.
    Patent application US2011 / 0163262 A1, in the name of Higuchi et al. describes compositions containing a mixture of colloidal silica and, as secondary particles, branched or curved silica particles, as well as methods of producing such silica-based compositions. Higuchi emphasizes the purity of the resulting aqueous suspension compositions. However, none of the Higuchi compositions makes it possible to treat, and even less to solve, the problem posed by the excessive friction which appears during polishing or the lack of flatness of the substrates resulting from polishing by CMP with high bearing force.
    The present applicant has endeavored to solve the problem posed by the production of aqueous silica compositions by CMP which make it possible to obtain more uniform substrate polishing performance at low solids contents of silica in high strength applications. 'high support.
    STATEMENT OF THE INVENTION
    Thus, the present invention relates to the following:
    1. An aqueous chemical mechanical planarization (CMP) polishing composition which comprises a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ from one another in weight average particle size (CPS) of less than 20 nm, the composition having a pH ranging from 2.5 to 5.3 or, preferably, from 3 to 5, where at least one type of particle among the spherical colloidal silica particles and the elongated silica particles , curved or nodular contains one or more cationic nitrogen atoms, and, in addition, where the quantity of elongated, curved or nodular silica particles ranges from 30 to 99% by weight, or from 30 to 95% by weight, or preferably 40 to 90% by weight, or more preferably 40 to 85% by weight, based on the total weight of silica solids in the aqueous CMP polishing composition.
    2. The aqueous CMP polishing composition according to point 1, above, where one or more cationic nitrogen atoms comes from an aminosilane which contains one or more cationic nitrogen atoms at the pH of the aqueous composition. polishing by CMP, so that at least one type of particle among the spherical colloidal silica particles and the elongated, curved or nodular silica particles are silica particles containing one or more aminosilane groups, preferably where the particles of Elongated, curved or nodular silica additionally contain a protonated amine or a quaternary ammonium.
    3. The aqueous CMP polishing composition according to any one of points 1 and 2, above, where the aminosilane is chosen from an aminosilane containing one or more tertiary amine groups, such as N, N- (diethylaminomethyl) triethoxysilane (DEAMS), or one or more secondary amine groups, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (AEAPS) or N-aminoethylamino-ethylaminopropyltrimethoxysilane (DETAPS), preferably an aminosilane containing one or more groups tertiary amine.
    4. The aqueous CMP polishing composition according to any one of points 2 and 3, above, where the amount of aminosilane ranges from 0.0020 to 0.25% by weight, or, preferably, from 0.003 to 0.1% by weight or, more preferably, from 0.003 to 0.02% by weight, based on the total silica solids in the aqueous CMP polishing composition.
    5. The aqueous CMP polishing composition according to any one of points 1, 2, 3 and 4, above, further comprising a compound containing two quaternary ammonium groups, such as dihydroxides or hexabutyl Ci-Cg salts alkanediammonium, such as their dihalides, for example, N, N, N, N, N ', N', N'-hexabutyl-1-6hexanediammonium, or, preferably, N, N, N,, 'dihydroxide , Ν ', N'hexabutyl-1,4-butanediammonium (HBBAH).
    6. The aqueous chemical-mechanical planarization (CMP) polishing composition according to point 5, above, where the amount of compound containing two quaternary ammonium groups ranges from 1 to 2000 ppm or, preferably, from 5 to 500 ppm or, more preferably, from 10 ppm to 200 ppm, based on the total silica solids in the aqueous CMP polishing composition.
    7. The aqueous chemical mechanical planarization polishing composition (CMP) according to any one of points 1, 2, 3, 4, 5 and 6, above, where the one or more cationic nitrogen atoms originates from '' a protonated amine or quaternary ammonium which is contained in the elongated, curved or nodular silica particles or, preferably, where the one or more cationic nitrogen atoms comes from the protonated amine or quaternary ammonium which is contained in the elongated, curved or nodular silica particles and also of any one of an aminosilane, a compound containing two quaternary ammonium groups, or both an aminosilane and a compound containing two quaternary ammonium groups .
    8. The aqueous chemical mechanical planarization polishing composition (CMP) according to any one of points 1, 2, 3, 4, 5, 6 and 7, above, where the average particle size by weight (CPS) ) silica particles range from 10 nm to 200 nm, or, preferably, from 25 nm to 80 nm.
    9. The aqueous chemical mechanical planarization polishing composition (CMP) according to any one of points 1 to 8, above, further comprising a buffer, which is a carboxylate of a (di) carboxylic acid of pKa from 3 to 7, or preferably pKa from 3 to 6, in an amount from 0 to 50 millimoles per kg (mmol / kg), or, preferably, from 0.1 to 10 mmol / kg of the composition (wet) total.
    10. The aqueous chemical mechanical planarization polishing composition (CMP) according to any one of points 1 to 9, above, intended for use in the polishing of substrates containing dielectrics or oxides, where the composition does not contains no oxidizing compound, such as hydrogen peroxide. by CMP
    11. The aqueous chemical-mechanical planarization (CMP) polishing composition according to any one of points 1 to 10, above, where the total amount of silica particles ranges from 1 to 30% by weight, or preferably 15 to 30% by weight, based on the total weight of the composition.
    12. According to another aspect, the present invention relates to methods for producing an aqueous CMP polishing composition comprising the mixture (i) of an aqueous suspension of spherical colloidal silica particles and (ii) from 30 to 99%. by weight, or from 30 to 95% by weight, or, preferably from 40 to 90% by weight, or, more preferably, from 40 to 85% by weight, based on the total weight of silica solids in the aqueous composition for polishing by CMP, of an aqueous suspension of elongated, curved or nodular silica particles such that the suspensions (i) and (ii) differ from each other in the weight average particle size (CPS) of less than 20 nm, and the adjustment of the pH of the resulting mixture to a value of 2.5 to 5.3 or, preferably, from 3 to 5, with a buffer or a carboxylic acid, preferably succinic acid, to form the aqueous CMP polishing composition, where at least one type of particle among the spherical colloidal silica particles and the elongated, curved or nodular silica particles, or both types of particles, contains one or more cationic nitrogen atoms or, preferably, the elongated, curved or nodular silica particles comprise a protonated amine or a quaternary ammonium which provides one or more additional cationic nitrogen atoms.
    13. The methods according to the present invention for producing an aqueous CMP polishing composition according to point 12, above, in which at least one of the aqueous suspensions (i) and (ii), or both, is formed by treating the particles with an aqueous aminosilane at a pH of 6 to 9, preferably 7 to 8, and vigorously shaking the mixture for 5 to 180 minutes, for example, for up to 60 minutes, to form a composition of silica particles containing one or more aminosilane groups containing one or more cationic nitrogen atoms, and adjusting the pH of the resulting composition to 2.5 to 5.2 or, preferably, to 3 to 5.
    14. The methods according to the present invention for producing an aqueous CMP polishing composition according to item 13, the methods further comprising mixing a compound containing two quaternary ammonium groups to produce the aqueous CMP polishing composition.
    15. The methods according to the present invention for producing an aqueous CMP polishing composition according to point 12, where at least one of the aqueous suspensions (i) and (ii), or both, is formed by combination of the suspension aqueous with a compound containing two quaternary ammonium groups to form silica particles which contain one or more cationic nitrogen atoms.
    16. The methods according to the present invention for producing an aqueous CMP polishing composition according to any one of points 13, 14 and 15, above, wherein the aqueous aminosilane comprises an aminosilane containing one or more tertiary amine groups, such as N, N (diethylaminomethyl) triethoxysilane (DEAMS), or one or more secondary amine groups, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (AEAPS) or N-aminoethylaminoethyl-aminopropyltrimethoxysilane (DEAPS also known as l 'abbreviation DETAPS).
    17. The methods according to the present invention for producing an aqueous CMP polishing composition according to any one of points 14 and 15, in which the compound containing two quaternary ammonium groups is chosen from the dihydroxides of hexabutyl Ci-C 8 alkanediammonium and their salts, such as dihalides, preferably Ν, Ν, Ν, Ν ', Ν', Ν'hexabutyl-1,4-butanediammonium dihydroxide (HBBAH).
    18. The methods according to the present invention for producing an aqueous CMP polishing composition according to any one of items 11 to 17 above, wherein each of the aqueous suspensions (i) and (ii) has a solids content of 15 to 30% by weight.
    19. The methods according to the present invention for producing an aqueous CMP polishing composition according to point 18 above, further comprising diluting the aqueous CMP polishing composition to a total content of silica particles from 1 to 10%. by weight, based on the total weight of the composition.
    20. In yet another aspect, the present invention relates to methods of polishing a CMP substrate, such as a semiconductor, memory or optical dielectric substrate, with a CMP polishing pad and an aqueous CMP polishing composition which comprise polishing the substrate with the buffer and an aqueous CMP polishing composition according to any one of items 1 to 11, above.
    21. The processes for polishing a CMP substrate according to point 20 above, where the contact force for polishing ranges from 20.7 kPa (3 psi) to 41.5 kPa (6 psi) or, preferably from 24.15 kPa (3.5 psi) to 36 kPa (5.2 psi). DETAILED DESCRIPTION
    Unless otherwise specified, the temperature and pressure conditions are room temperature and standard pressure. All the ranges indicated are inclusive and combinable.
    Unless otherwise indicated, any term containing parentheses may refer to the entire term containing parentheses and the term without parentheses, and combinations of each alternative. Thus the term (poly) isocyanate means isocyanate, polyisocyanate, or mixtures thereof. All the ranges indicated are inclusive and combinable. For example, the term a range of 5xl0 ' 2 to 3 Pa.s (50 to 3000 cP), or 10' 1 Pa.s (100 cP) or more includes 5xl0 ' 2 to 10' 1 Pa.s (50 at 100 cP), 5 × 10 ' 2 to 3 Pa.s (50 to 3000 cP) and 10 1 to 3 Pa.s (100 to 3000 cP).
    As used herein, the term ASTM refers to publications by ASTM International, West Conshohocken, PA.
    As used herein, the term colloidally stable means that a given composition does not gel or precipitate, and remains clear from visual inspection after a given time and at a given temperature.
    As used herein, the term strong base refers to metal hydroxides, including hydroxides of alkali and alkaline earth metals, such as NaOH, KOH or Ca (OH) 2 .
    As used herein, the term ISO refers to publications of the International Organization for Standardization, Geneva, CH.
    As used herein, the term particle size (CPS) means the weight average particle size of a composition as determined by a centrifugal disc system from CPS Instruments (Netherlands). The particles are separated by size using centrifugal force in a solvent and are quantified by optical light scattering.
    As used herein, the term solid of silica particles or solid of silica means, for a given composition, the total amount of spherical silica particles, plus the total amount of elongated, curved or nodular silica particles, including any substance with which any of these particles are treated.
    As used herein, the term solids means any substance other than water or ammonia that does not evaporate under conditions of use, regardless of its physical state. Thus, silanes or liquid additives which do not evaporate under the conditions of use are considered to be solid.
    As used herein, the term strong acid denotes a protic acid having a pKa of 2 or less, such as inorganic acids such as sulfuric acid or nitric acid.
    As used herein, the term conditions of use refers to the temperature and pressure at which a given composition is used, including increases in temperature and pressure during use or as a result of use.
    As used herein, the term fraction by weight of silica denotes% by total weight of silica, based on the total weight of the composition / 100%. Thus, 30% by weight of silica is equivalent to a fraction by weight of 0.3.
    As used herein, the term% by weight represents percent by weight. As used herein, the term zeta potential denotes the charge of a given composition as measured by a Malvern Zetasizer instrument. All the zeta potential measurements were made on (diluted) suspension compositions as described in the examples. The value indicated was deduced from an averaged measurement of zeta potential values using more than 20 acquisitions made by the instrument for each composition indicated.
    The Applicant has surprisingly found that an aqueous CMP polishing composition comprising a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ from one another in weight average particle size (CPS) less than 20 nm (colloidal size), and where at least one type of particle among elongated, curved or nodular silica particles and spherical colloidal silica particles contains a cationic nitrogen atom can reduce friction during polishing and lower the polishing temperature during polishing. In addition, the mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles improves the uniformity of the withdrawal speed (VR) and the uniformity of the withdrawal profiles when the bearing force polishing increases. In addition, the composition of the present invention also allows a significantly reduced polishing temperature which promotes less wear of the texture of the polishing pad. When evaluating the performance of the aqueous CMP polishing composition of the present invention, a graph of VR (y) as a function of pressure (x) gives a straight line when the polishing downforce is increased. In addition, the mixture of spherical silica particles and elongated, curved or nodular silica particles allows an improved uniformity of the VR when moving on the substrate, from the center to the edge. The aqueous CMP polishing composition of the present invention thus allows good polishing performance for a low solids content of abrasive from 1 to 5% by weight of solids.
    As used herein, the term elongated, curved, or nodular silica particles denotes silica particles having an aspect ratio of the largest dimension to the diameter perpendicular to the largest dimension of 1.8: 1 to 3 : 1.
    Suitable elongated, curved or nodular silica particles are produced by suspension polymerization by hydrolytic condensation of silanols formed in a known manner from precursors such as tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS). Methods for producing elongated, curved or nodular silica particles are known and can be found, for example, in U.S. Patent no. 8,529,787 in the name of Higuchi et al. The hydrolytic condensation comprises the reaction of the precursors in an aqueous suspension in the presence of a basic catalyst such as an alkylammonium hydroxide, an alkylamine or KOH, preferably tetramethylammonium hydroxide; the hydrolytic condensation process can introduce one or more cationic nitrogen atoms into the elongated, curved or nodular silica particles. Preferably, the elongated, curved or nodular silica particles are cationic at a pH of 4.
    Suitable curved or nodular silica particles are available from Fuso Chemical Co., Ltd., Osaka, JP (Fuso) under the trade names of suspensions HL-2, HL-3, HL-4, PL-2, PL- 3 or BS-2 and BS-3. The particles of the HL and BS series from Fuso contain one or more nitrogen atoms which confer a cationic charge at pH 4.
    To guarantee the colloidal stability of the aqueous CMP polishing composition of the present invention, the composition has a pH ranging from 2.5 to 5.3 or, preferably, from 3 to 5. The composition tends to lose its stability beyond the desired pH range.
    Preferably, according to the present invention, the aqueous CMP polishing composition comprises a compound containing two quaternary ammonium groups, such as Ν, Ν, Ν, Ν ', Ν', Ν'-hexabutyl1,4-butane-diammonium dihydroxide (HBBAH). Such compounds increase the stability of the aqueous CMP polishing composition during storage, transportation and thermal aging while maintaining a high shrinkage rate.
    According to the present invention, the suitable compounds containing two quaternary ammonium groups can comprise the dihydroxides of hexabutyl Ci-Ce alkanediammonium or their salts, like the dihalides, or, preferably, the dihydroxide of N, N, N, Ν ', Ν ', N'hexabutyl-1,4-butanediammonium (HBBAH).
    According to the present invention, the appropriate amount of compound containing two quaternary ammonium groups is from 1 to 2000 ppm or, preferably, from 5 to 500 ppm or, more preferably, from 10 ppm to 200 ppm, based on the solids of total silica, in the composition. This amount should be sufficient to guarantee a stabilizing effect. A larger amount of compound containing two quaternary ammonium groups is required to stabilize concentrates and compositions which have a higher concentration of silica and / or a lower concentration of aminosilane. More is also needed to stabilize the smaller medium-sized particles due to their increased surface area and their ability to oligomerize or gel.
    According to the present invention, suitable aminosilanes intended for use in the production of silica particles containing one or more aminosilane groups of the present invention are aminosilanes containing one or more tertiary amine groups and aminosilanes containing one or more secondary amine groups. Suitable aminosilanes for use in the aqueous CMP polishing composition of the present invention include an aminosilane containing one or more tertiary amine groups, such as N, N- (diethylaminomethyl) triethoxysilane (DEAMS), or one or more amine groups secondary, such as N- (2-amino-ethyl) -3-aminopropyltrimethoxysilane (AEAPS) or Naminoethylaminoethylamino-propyltrimethoxysilane (DEAPS also known by the abbreviation DETAPS).
    Appropriate amounts of aminosilane for use in the aqueous CMP polishing composition according to the present invention range from 0.0020 to 0.25% by weight, based on the total silica solids in the aqueous polishing composition by CMP.
    The composition according to the present invention is intended for polishing dielectrics such as interlayer dielectrics (ILD).
    EXAMPLES
    The following examples illustrate the various features of the present invention.
    In the following examples, unless otherwise indicated, the temperature and pressure conditions are room temperature and standard pressure.
    The following substances were used in the examples:
    HBBAH = N, N, N, N ', N', N ', N'-hexabutyl-1,4-butane-diammonium dihydroxide, 98% by weight (Sachem, Austin, TX).
    AEAPS = N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 98% (Gelest Inc., Morrisville, PA);
    DEAMS = (N, N-diethylaminomethyl) triethoxysilane, 98% (Gelest Inc.).
    The different silica particles used in the examples are presented in Table A, below.
    Table A: silica particles
    Aqueous suspension of silica Source pH 5 Particle size (CPS, nm) Morpho-house Materialsraw Concentration (% by weight of solids) SuspensionAT Klebosol ™ ' 1 1598-B25 7.7 38 Spherical Na silicate 30 SuspensionB Klebosol ™ - 1 1598-B12 7.7 25 Spherical Na silicate 30 SuspensionVS Klebosol ™ ' 1 30H50 2.5 75 Spherical Na silicate 30 SuspensionG HL-3 ™ ' 3 7.8 55 Elongated cationic particle 4 TMOS 20 SuspensionH HL-2 ™ ' 3 7.8 45 Elongated cationic particle 4 TMOS 20 SuspensionJ PL-2 ™> 3 7.8 45 Lying down TMOS 20 SuspensionK PL-3 ™ ' 3 7.1 55 Lying down TMOS 20 SuspensionL BS-3 ™ ' 3 - 6 7.3 53 Elongated cationic particle 4 TMOS 20 SuspensionM BS-2 ™ ' 3 7.1 45-48 Elongated cationic particle 4 TMOS 20 SuspensionNOT PL-2L ™ ' 3 7.4 42 spherical TMOS 20 Suspension0 PL-3L ™ ' 3 7.4 52 spherical TMOS 20
    1 Merck KgAA, Lamotte, France; 3 Fuso Chemical, Osaka, JP; 4 Charge determined at pH 4.0 and cationic particles formed with TMOS and an alkaline catalyst containing an amine, such as tetramethylammonium hydroxide; 5 pH as supplied by the source; 6 Fuso BS-3 particles were originally supplied as BS-2H particles but are now marketed as BS-3 particles.
    The following abbreviations have been used in the following examples:
    PU: point of use; VR: withdrawal speed.
    The following test methods were used in the following examples:
    pH at PU: the pH at the point of use (pH at PU) was that measured during the test concerning the speed of withdrawal after dilution of the concentrate compositions indicated with water at the indicated solid content. Non-uniformity: standard deviation of the mean withdrawal speed values deduced from the withdrawal speeds measured at multiple locations from the center to the edge of the pad.
    Withdrawal speed: the test concerning the withdrawal speed in the polishing of the indicated substrate was performed using the indicated polishing device, such as the Strasbaugh 6EC 200 mm or 6EC RR wafer polishing device (Axus Technology Company, Chandler, AZ ) or an Applied Materials Mirra ™ 200mm or Mirra RR polishing machine (Applied Materials, Santa Clara, CA), as indicated, at the indicated contact force and the rotational speeds of the table and support (rpm) indicated, and with the indicated CMP polishing pad and the indicated abrasive suspension, at a given abrasive suspension flow rate of 200 ml / min. A Diagrid ™ AD3BG-150855 diamond pad conditioner (Kinik Company, Taiwan) was used to condition the polishing pad. The polishing pad was run in with the pad conditioner using a 6.35 kg (14.0 lb) pressing force for 20 minutes and was then conditioned again before polishing using a pressing force of 4.1 kg (9 lb) for 10 minutes. The polishing pad was conditioned still in situ during polishing at 10 scans / min from 4.32 cm to 23.37 cm from the center of the polishing pad with a pressing force of 4.1 kg (9 lb ). The withdrawal rates were determined by measuring the film thickness before and after polishing using a KLA-Tencor ™ FX200 metrology tool (KLA Tencor, Milpitas, CA) using a 49 point spiral scan with an edge exclusion of 3 mm.
    Zeta potential: the zeta potential of the indicated compositions was measured using a Malvern Zetasizer ™ instrument (Malvern Instruments, Malvern,
    UK) in the form of concentrates at 15-30% by weight. The indicated value was deducted from a single measurement for each composition indicated.
    Example 1: polishing
    In a shrinkage speed test, a Mirra ™ (Applied Materials) polisher with VP6000 ™ K7 + R32 pad with circular grooves having a pitch of 1778 micrometers (70 mils (70 x 10 ' 3 inch; 1 inch) = 25.4 mm)) and overlapping radial grooves (The Dow Chemical Company, Midland, MI (Dow)) was used to polish a TEOS substrate using the CMP polishing compositions shown in Table IA, below below, at a suspension flow rate of 200 ml / min, a speed of rotation of the plate of 123 rpm and a speed of rotation of the support of 117 rpm. The polishing compositions were used at a total solids content of 1 to 2% by weight. The final pH was measured just after dilution with PU.
    Table IA: formulations (all proportions are in% by weight, based on total solids)
    Ex. SuspensionAT SuspensionL SuspensionG DEAMS HBBAH PHfinal PH titration agent Spherical, 38 nm Elongated, cationic, 55 nm Elongated, cationic, 55 nm 1 * 1 4 H 3 PO 4 2 * 1 0.0053 0.00042 4.5 Addsucdnique 3 0.5 1 0.008 0.000625 4.5 Addsucdnique 4 1 1 0.0107 0.00083 4.5 Addsucdnique 5 * 1.5 0.008 0.000625 4.5 Addsucdnique 6 0.5 1.5 0.0107 0.00083 4.5 Addsucdnique 7 * 2 0.0107 0.00083 4.5 Addsucdnique 8 * 1.125 0.006 0.0005 4.5 Addsucdnique
    * - Designates a comparative example.
    Table IB: removal speed performance
    Ex. TEOS RV (13.79 kPa, Â (10 ' 10m ) / min) TEOS RV (20.68 kPa, Â / min) TEOS RV (27.58 kPa, Â / min) TEOS RV (34.47 kPa, Â / min) No-TEOS uniformity (34.47 kPa,%) 1 * 2138 2407 2216 1533 13.0 2 * 2151 2736 2673 1345 23.9 3 2089 2839 3496 3976 3.8 4 2107 2916 3511 3945 4.4 5 * 2320 3245 3795 2552 12.5 6 2290 3157 3900 4571 4.6 7 * 2435 3413 4238 3766 4.3 8 * 2358 3070 3211 2261 11.7
    * - Designates a comparative example
    Table IC: polishing wear
    Example 13.79 kPaPolishing T (° C) 20.68kPaPolishing T (° C) 27.58kPaPolishing T (° C) 34.47kPaPolishing T (° C) 1 * 38.7 47.7 55.9 62.8 2 * 37.3 45.3 54.6 63.5 3 35.3 40.5 46.7 53.7 4 34.5 38.7 43.2 48.3 5 * 36.7 43.7 52.3 61.8 6 35.1 40.9 46.5 52.4 7 * 36.5 42.6 50.0 60.2 8 * 37.5 45.6 54.1 62.1
    As shown in Tables IB and IC, above, the compositions according to the present invention all have an improved removal speed at a higher polishing support force, a more uniform polishing (uniformity) and a reduced temperature, and therefore reduced wear of the pad, during polishing, slow profiles at the center less pronounced and a bending behavior of the VR curve as a function of the pressing force (curve P) reduced among the groups of suspensions. In Comparative Examples 1, 2, 5, 7 and 8, without mixing spherical silica particles containing DEAMS in suspension A and elongated, curved or nodular silica particles in suspension G or suspension K, none of the formulations of The aqueous CMP polishing composition did not exhibit a linear P curve in which the removal speed increased or remained constant as the contact force increased. In addition, at 34.47 kPa, the aqueous CMP polishing compositions of Comparative Examples 1, 2, 5, 7 and 8 with only suspensions of elongated, curved or nodular silica particles exhibited a profile of nonuniformity> 10%. At the same time, Examples 3, 4 and 6 according to the present invention, containing a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ from one another in weight average particle size (CPS) less than 20 nm, all exhibited a non-uniformity at 34.47 kPa of less than 5% and a more linear P curve with higher withdrawal speeds at higher support forces. In addition, the polishing temperatures of the aqueous CMP polishing compositions according to the present invention are substantially lower than those of compositions comprising only elongated, curved or nodular silica particles, which implies less wear of the texture of the pads. and a potentially longer buffer life.
    Example 2: Polishing of larger pads
    In a test concerning the speed of removal, a Reflexion ™ polishing device (Applied Materials) with an IC1000 ™ K7 + R32 buffer (Dow) was used to polish a TEOS substrate using the CMP polishing compositions defined in the Table 2A, below, at a suspension flow rate of 300 ml / min, a speed of rotation of the plate of 93 rpm and a speed of rotation of the support of 87 rpm. The polishing compositions were used at a total solids content of 1 - 2% by weight. The final pH was measured just after dilution with PU.
    Table 2A: formulations (all proportions are in% by weight, based on total solids)
    Suspension L Suspension G Suspension A Suspension C DEAMS HBBAH pHfinal pH titrating agent Ex. Elongated 53 nm Cation elongation 55 nm Spheri-than38 nm Spheri-than75 nm 11 * 1.125 0.006 0.0005 4.5 Acidsuccini-than 12 1 1 0.0107 0.00083 4.5 Acidsuccini-than 13 * 5 1 0.05 3 Acidnitric
    * - Designates a comparative example
    Table 2B: removal speed performance
    Ex. TEOS RV (6.895 kPa, Â / min) TEOS RV (13.79 kPa, Â / min) TEOS RV (20.68 kPa, Â / min) TEOS RV (27.58 kPa, Â / min) TEOS RV (34.47 kPa, Â / min) 11 * 1305 2414 3395 4115 4182 12 1245 2217 2991 3748 4316 13 * 1164 2114 2909 3401 3717
    * - Designates a comparative example
    Table 2C: polishing wear
    Ex. 6.895 kPaPolishing T (° C) 13.79 kPaPolishing T (° C) 20.68 kPaPolishing T (° C) 27.58 kPaPolishing T (° C) 34.47 kPaPolishing T (° C) 11 * 28.5 37.2 47.2 56.8 65.6 12 27.2 34.6 41.7 48.7 56.1 13 * 25.1 33.9 41.9 48.5 55.0
    * - Designates a comparative example
    As shown in Tables 2B and 2C, above, the aqueous CMP polishing composition of Example 12 (2%) at a weight ratio of solids
    1: 1 from spherical colloidal silica to elongated, curved or nodular silica gave a linear P curve and VR profile at 34.47 kPa (5 psi) flat when compared to an acidic suspension of spherical colloidal silica having much higher solid content of particles in Comparative Example 13 (6%). The problem of slowness in the center of suspension 11 (1.125%) at 34.47 kPa (5 psi) remained. It should be noted that the polishing temperature of the aqueous CMP polishing compositions according to the present invention of Example 12 remained low when compared to that of an aqueous CMP polishing composition with low solids content. comparative example 11.
    Example 3: Polishing compositions with different aminosilanes In a test concerning the speed of removal, a Mirra ™ polishing device (Applied Materials) with a VP6000 ™ K7 + R32 buffer (Dow) was used to polish a TEOS substrate using the CMP polishing compositions defined in Table 3A, below, at a suspension flow rate of 200 ml / min, a speed of rotation of the plate of 93 rpm and a speed of rotation of the support of 87 rpm . The polishing compositions were used at a total silica solids content of 2% by weight. The final pH was measured just after dilution with PU.
    Table 3A: formulations (all proportions are in% by weight, based on total solids)
    Ex. SuspensionL SuspensionAT DEAMS AEAPS HBBAH PHfinal Titration AgentPH Lying down53 nm 38 nm spherical 14 1 1 0.011 0.0008 4.5 Acidsuccinic 15 1 1 0.004 0.0008 4.5 Acidsuccinic 16 1 1 0.005 0.0008 4 f 5 Acidsuccinic
    Table 3B: removal speed performance
    Ex. TEOS RV (20.68 kPa, Â / min) TEOS RV (34.47 kPa, Â / min) TEOS non-uniformity (20.68 kPa,%) TEOS non-uniformity (34.47 kPa,%) 14 2408 3364 6.5 4.7 15 2235 2962 7.3 3.9 16 2208 2969 7.2 4.9
    With the use of an aminosilane containing a secondary amine group (AEAPS), the compositions of Examples 15 and 16 according to the present invention exhibited a behavior of withdrawal speed and uniformity similar to that of the composition of Example 14 , containing an aminosilane containing a tertiary amine group (DEAMS). All of the examples had a weight ratio of suspensions of 1: 1. The P curves (withdrawal speed curves) are reasonably linear and the 34.47 kPa (5 psi) withdrawal profiles of the compositions containing AEAPS are as uniform at a higher pressing force (34.47 kPa) than the compositions containing DEAMS, even if their withdrawal speeds are slightly lower.
    Example 4: polishing performance
    In a test concerning the speed of removal, a Mirra ™ polishing device (Applied Materials) with a VP6000 ™ K7 + R32 buffer (Dow) was used to polish a TEOS substrate using the CMP polishing compositions defined in the Table 4A, below, at a suspension flow rate of 200 ml / min, a speed of rotation of the plate of 123 rpm and a speed of rotation of the support of 117 rpm. The polishing compositions were used at a total silica solids content of 1-2% by weight. The final pH was measured just after dilution with PU.
    Table 4A: formulations (all proportions are% by weight, based on total solids)
    In all of Examples 17, 18, 19, 20 and 21, below, Formulations 5 contain HBBAH in an amount of 0.001% by weight or 10 ppm and
    DEAMS in an amount of 0.011% by weight.
    Ex. Suspension A Suspension J Suspension N Suspension O Suspension L PHfinal pH titrating agent spherical 38 nm elongated 45 nm spherical 42 nm spherical 52 nm Elongated, cationic 45-48 nm 17 1 1 4.5 Acidsucci-fuck 18 * 1 1 4.5 Acidsucci-fuck 19 1 1 4.5 Acidsucci-fuck 20 1 1 4.5 Acidsuccinice 21 * 2 4.5 Acidsucci-fuck
    * - Designates a comparative example
    Table 4B: removal speed performance
    Ex. TEOS RV(13.79 kPa, Â / min) TEOS RV (20.68 kPa, Â / min) TEOS RV (27.58 kPa, Â / min) TEOS RV (34.47 kPa, Â / min) NoTEOS uniformity (34.47 kPa,%) 17 2062 2817 3395 3817 5.0 18 * 2053 2878 2890 1260 19.9 19 1966 2669 3374 3799 5.6 20 1540 1961 2401 2866 4.2 21 * 2422 3280 3335 1753 19.0
    * - Designates a comparative example
    Table 4C: polishing wear
    Example 13.79 kPa T polishing (° C) 20.68kPa T polishing (° C) 27.58kPa T polishing (° C) 34.47kPa T polishing (° C) 17 35.1 39.9 45.0 49.7 18 * 37.8 44.4 55.1 66.0 19 36.2 41.2 47.9 55.1 20 33.9 38.2 44.3 53.5 21 * _ 457 55.3 65.2
    * - Designates a comparative example
    As shown in Tables 4B and 4C, above, the mixture according to the present invention of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ from one another in weight average particle size (CPS) less than 20nm gives higher removal speed and uniformity in polishing and allows polishing with reduced pad wear. As shown in Comparative Examples 18 and 21, respectively, the fact of mixing two types of elongated silica particles or using only one type of particles does not allow effective polishing at a high bearing force. When spherical silica particles were introduced into the formulation of elongated, curved or nodular silica particles, the non-uniformity of the polished wafers was significantly reduced. Comparing Examples 19-20 to Example 17 according to the present invention, it appears that the spherical silica particles produced from water glass give superior polishing wear results and more uniform polishing results, for example at 27.58 kPa, as spherical silica particles which are produced by suspension polymerization from tetraalkoxysilicates, such as TMOS and TEOS.
    Example 5: polishing with alternative formulations
    In a test concerning the withdrawal speed, a polishing device
    Mirra ™ (Applied Materials) with VP6000 ™ K7 + R32 buffer (Dow) was used to polish a TEOS substrate using the CMP polishing compositions defined in Table 5A, below, at a rate of suspension of 200 ml / min, a speed of rotation of the plate of 123 rpm and a speed of rotation of the support of 117 rpm. The polishing compositions were used at a total silica solids content of 1-2% by weight and are shown in Table 5A, below. The final pH was measured just after dilution with PU.
    Table 5A: formulations (all proportions are% by weight, based on total solids)
    Suspension M Suspension L DEAMS Suspension A Suspension L DEAMS PHfinal AgentofpH titration Ex. __ __ __ __ 22 * 2 0.0107 4.5 Acidsucci-fuck 23 * 2 0.0107 4.5 Acidsucci-fuck 24 1 0.00535 1 0.00535 4.5 Acidsucci-fuck 25 1 1 0.00535 4.5 Acidsucci-fuck 26 * 1 1 0.00535 4.5 Acidsucci-fuck 27 * 1 0.00535 28 * L5 0.008
    * - Designates a comparative example
    Table 5B: removal speed performance
    Ex. TEOS RV (20.68 kPa, Â / min) TEOS RV (27.58 kPa, Â / min) TEOS RV (34.47 kPa, Â / min) TEOS non-uniformity (34.47 kPa,%) 22 * 1974 2356 2623 3.8 23 * 3372 4265 3200 5.2 24 2839 3420 3897 5.4 25 2857 3401 3871 4.2 26 * 3518 4198 3274 9.6 27 * 2948 3120 1734 19.8 28 * 3302 4093 3826 2.9
    * - Designates a comparative example
    Table 5C: polishing wear
    Example 20.68 kPaPolishing T (° C) 27.58 kPaPolishing T (° C) 34.47 kPaPolishing T (° C) 22 * 35.4 38.6 41.7 23 * 43.8 49.6 61.8 24 40.7 43.5 47.9 25 41.9 46.0 52.2 26 * 45.6 53.1 63.2 27 * 42.2 49.5 58.9 28 * 44.7 53.3 62.4
    * - Designates a comparative example
    As shown in Tables 5B and 5C, above, the compositions of Examples 24 and 25 according to the present invention which comprise a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ from each other in the weight average particle size (CPS) of less than 20 nm greatly exceed in performance the compositions of Comparative Examples 22-23 and 26 in which there is no mixture of silica particles (Comparative Examples 22-23) or wherein the mixture comprises only elongated silica particles (Comparative Examples 26-27). Comparative example 28 gives good removal speed performance but gives off heat, and the possibility of increased wear during polishing. As shown in Table 5B, above, the polishing performance of the compositions of Examples 24 and 25 according to the present invention are improved at the high polishing support forces.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Aqueous chemical mechanical planarization (CMP) polishing composition comprising a mixture of spherical colloidal silica particles and elongated, curved or nodular silica particles which differ less in weight average particle size (CPS) from 20 nm, the composition having a pH ranging from 2.5 to 5.3, where at least one type of particle among the spherical colloidal silica particles and the elongated, curved or nodular silica particles contains one or more atoms of cationic nitrogen, and where the amount of elongated, curved or nodular silica particles is from 30 to 99% by weight, based on the total weight of silica solids in the aqueous CMP polishing composition.
    [2" id="c-fr-0002]
    2. Aqueous CMP polishing composition according to claim 1, wherein the amount of elongated, curved or nodular silica particles ranges from 40 to 90% by weight, based on the total weight of silica solids in the aqueous composition of CMP polishing.
    [3" id="c-fr-0003]
    3. Aqueous CMP polishing composition according to claim 1 or claim 2, in which the one or more cationic nitrogen atoms comes from an aminosilane which contains one or more cationic nitrogen atoms at the pH of the aqueous composition. polishing of CMP, so that at least one type of particles among the spherical colloidal silica particles and the elongated, curved or nodular silica particles are silica particles containing an aminosilane group.
    [4" id="c-fr-0004]
    4. An aqueous CMP polishing composition according to claim 3, in which the aminosilane is chosen from an aminosilane containing one or more tertiary amine groups, or one or more secondary amine groups.
    [5" id="c-fr-0005]
    5. Aqueous CMP polishing composition according to claim 4, wherein the amount of aminosilane ranges from 0.0020 to 0.25% by weight, based on the total weight of silica solids in the aqueous polishing composition from CMP.
    [6" id="c-fr-0006]
    6. An aqueous CMP polishing composition according to any one of the preceding claims, which further comprises a compound containing two quaternary ammonium groups.
    [7" id="c-fr-0007]
    7. Aqueous CMP polishing composition according to claim 6, wherein the amount of the compound containing two quaternary ammonium groups is from 1 to 2000 ppm, based on the total weight of silica solids in the aqueous CMP polishing composition. .
    [8" id="c-fr-0008]
    8. Aqueous CMP polishing composition according to any one of the preceding claims, characterized in that the weight average particle size (CPS) of the silica particles ranges from 10 nm to 200 nm.
    [9" id="c-fr-0009]
    9. An aqueous CMP polishing composition according to any one of the preceding claims, which further comprises a buffer, which is a carboxylate of a pKa (di) carboxylic acid from 3 to 7 in an amount of 0 to 50 millimoles per kg (mmol / kg) of the total (wet) composition.
    [10" id="c-fr-0010]
    10. An aqueous CMP polishing composition according to any one of the preceding claims, wherein the total amount of silica particles is from 1 to 30% by weight, based on the total weight of the composition.
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    同族专利:
    公开号 | 公开日
    US9783702B1|2017-10-10|
    FR3057565B1|2020-07-24|
    DE102017009708A1|2018-04-19|
    KR20180043178A|2018-04-27|
    JP2018070870A|2018-05-10|
    CN107964374A|2018-04-27|
    TW201815674A|2018-05-01|
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    优先权:
    申请号 | 申请日 | 专利标题
    US15/297,716|US9783702B1|2016-10-19|2016-10-19|Aqueous compositions of low abrasive silica particles|
    US15297716|2016-10-19|
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