Low-dishing oxide CMP polishing composition for shallow trench isolation applications and method of making same

Abstract

A shallow trench isolation (STI) chemical mechanical planarization (CMP) polishing composition, a method for using the same, and a system are provided. The CMP polishing composition includes an abrasive of ceria-coated inorganic oxide particles, such as ceria-coated silica, and two chemical additives to provide tunable oxide film removal rates and tunable SiN film removal rates, low oxide trench dishing, and high oxide:SiN selectivity. The two chemical additives include: (1) at least one silicone-containing compound containing at least one of ethylene oxide and propylene oxide (EO-PO) groups and at least one substituted ethylenediamine group on the same molecule; and (2) at least one nonionic organic molecule having at least two, preferably at least four, hydroxyl functional groups.

Description

[Technical Field]

[0001] Cross-reference to related patent applications This application claims the benefit of U.S. Application No. 63 / 032233, filed May 29, 2020, and U.S. Application No. 63 / 045796, filed June 29, 2020, the disclosures of which are incorporated herein by reference.

[0002] The present invention relates to CMP chemical polishing compositions and chemical mechanical planarization (CMP) for shallow trench isolation (STI) processes. [Background technology]

[0003] An important step involved in the manufacture of microelectronic devices is polishing, particularly the polishing of surfaces for chemical mechanical polishing to recover selected materials and / or planarization of substrate structures.

[0004] For example, a SiN layer is deposited under a SiO2 layer to act as a polishing stop layer. This polishing stop role is particularly important in shallow trench isolation (STI) structures. Selectivity is typically expressed as the ratio of oxide polishing rate to nitride polishing rate. One example is the adjustable polishing selectivity ratio of silicon dioxide (SiO2) or HDP film rates compared to silicon nitride (SiN).

[0005] In the global planarization of patterned STI structures, adjusting the removal rate of SiN film and adjusting oxide trench dishing are two key factors to be considered. Less trench oxide loss prevents current leakage between adjacent transistors. Uneven trench oxide loss across the die (at the die) affects transistor performance and yield of device fabrication. Severe trench oxide loss (high oxide trench dishing) causes poor isolation of transistors, leading to device defects. Therefore, it is also important to reduce trench oxide loss by reducing oxide trench dishing in STI CMP polishing compositions.

[0006] U.S. Patent No. 5,876,490 discloses a polishing composition containing abrasive particles and exhibiting a normal stress effect. The slurry further contains non-abrasive particles that cause a decrease in the polishing rate in recesses, while the abrasive particles maintain a high polishing rate at elevated positions. This results in improved planarization. More specifically, the slurry contains cerium oxide particles and a polymer electrolyte and can be used for shallow trench isolation (STI) polishing applications.

[0007] U.S. Patent No. 6,964,923 teaches a polishing composition containing cerium oxide particles and a polymeric electrolyte for shallow trench isolation (STI) polishing applications. The polymeric electrolyte used includes a salt of polyacrylic acid similar to that in U.S. Patent No. 5,876,490. Ceria, alumina, silica, and zirconia are used as abrasives. The molecular weights of the listed polyelectrolytes range from 300 to 20,000, but are generally less than 100,000.

[0008] U.S. Patent No. 6,616,514 discloses a chemical mechanical polishing slurry for use in removing a first material, preferentially relative to silicon nitride, from the surface of an article by chemical mechanical polishing. The chemical mechanical polishing slurry according to the invention includes an abrasive, an aqueous medium, and an organic polyol that does not dissociate protons, the organic polyol including a compound having at least three hydroxyl groups that are not dissociable in the aqueous medium, or a polymer formed from at least one monomer having at least three hydroxyl groups that are not dissociable in the aqueous medium.

[0009] U.S. Pat. No. 6,984,588 discloses a chemical-mechanical polishing composition containing a cerium compound soluble at a pH greater than 3 and a method for selectively polishing silicon oxide overfills in preference to silicon nitride film layers in a single step during the manufacture of integrated circuits and semiconductors.

[0010] U.S. Pat. No. 6,544,892 discloses a method for removing silicon dioxide preferentially over silicon nitride from the surface of an article by chemical mechanical polishing, the method comprising polishing the surface using a polishing pad, water, abrasive particles, and an organic compound having both a carboxylic acid functional group and a second functional group selected from an amine and a halide.

[0011] The specification of U.S. Patent No. 7,247,082 discloses a polishing composition containing an abrasive, a pH adjuster, a selectivity improver, and water, wherein the abrasive is contained in an amount of 0.5 to 30 wt%, the pH adjuster is contained in an amount of 0.01 to 3 wt%, the selectivity improver is contained in an amount of 0.3 to 30 wt%, and the water is contained in an amount of 45 to 99.49 wt%, where wt% is based on the weight of the polishing composition, and the improver is selected from methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diamine, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diamine, methylamine, ethylamine, propylamine, isopropylamine, propylamine, diethylamine, dipropylamine, dipropylamine, ... Disclosed is a polishing composition, wherein the polishing agent is one or more compounds selected from the group consisting of isopropylamine, ethylenediamine, 1,2-diaminopropane, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, 6-(dimethylamino)-1-hexanol, bis(3-aminopropyl)amine, triethylenetetraamine, diethylene glycol bis(3-aminopropyl)ether, piperazine, and piperidine.

[0012] U.S. Pat. No. 8,778,203 discloses a method for selectively removing target material on a surface of a substrate, the method comprising: providing a substrate containing target and non-target materials; dissolving oxygen in a polishing solution to achieve a predetermined dissolved oxygen concentration, the polishing solution having a pH of about 5 to about 11, the polishing solution containing a plurality of abrasive silica particles, at least some of the abrasive silica particles being functionalized with n-(trimethoxysilylpropyl)isothioronium chloride; maintaining the predetermined dissolved oxygen concentration of the polishing solution at approximately 8.6 mg / L to approximately 16.6 mg / L by continuously applying substantially pure oxygen to the polishing solution; disposing the polishing solution between a polishing pad and the surface; applying the polishing pad to the surface; and selectively removing a predetermined thickness of target material, wherein varying the dissolved oxygen content of the polishing solution during the removing step varies the removal ratio of the target material to the non-target material.

[0013] U.S. Pat. No. 6,914,001 discloses a chemical mechanical polishing method including the steps of contacting a surface of a semiconductor wafer with a surface of a polishing pad; supplying an aqueous solution containing abrasive particles, a removal rate accelerator, and different first and second passivation agents to the interface between the surface of the polishing pad and the surface of the semiconductor wafer, where the first passivation agent is an anionic, cationic, or nonionic surfactant; and rotating the surface of the semiconductor wafer against the surface of the polishing pad to remove oxide material on the semiconductor wafer.

[0014] However, these previously disclosed shallow trench isolation (STI) polishing compositions, while having adjustable oxide-to-nitride selectivity, did not address the importance of oxide film removal rate control, SiN film removal rate control, reduced oxide trench dishing, and more uniform oxide trench dishing in polished and patterned wafers.

[0015] Therefore, from the foregoing, it is readily apparent that there remains a need in the art for STI chemical mechanical polishing compositions, methods, and systems that can provide tunable oxide and HDP film removal rates, tunable SiN film removal rates, reduced oxide trench dishing, and more uniform oxide trench dishing across various sized oxide trench features when polishing patterned wafers in an STI chemical and mechanical polishing (CMP) process. Summary of the Invention

[0016] The present invention provides STI CMP polishing compositions for tunable oxide and HDP film removal rates, tunable SiN film removal rates, tunable TEOS:SiN selectivity, and reduced oxide trench dishing in polished and patterned wafers using relatively low concentrations of ceria-coated inorganic oxide abrasives.

[0017] The STI CMP polishing composition of the present invention provides tunable selectivity of oxide or HDP films over nitride films by incorporating two chemical additives for tailoring the removal rate of oxide and SiN films and reducing oxide trench dishing in chemical mechanical polishing (CMP) compositions for shallow trench isolation (STI) CMP applications over a wide pH range, including acidic, neutral, and alkaline pH conditions.

[0018] The disclosed chemical mechanical polishing (CMP) compositions for shallow trench isolation (STI) CMP applications have a unique combination of using ceria-coated inorganic oxide abrasive particles and two chemical additives suitable as removal rate modifiers for oxide and nitride films and as reducers of oxide trench dishing.

[0019] One of the additives is a silicone-containing compound that contains, on the same molecule, at least one of: (1) ethylene oxide and propylene oxide (EO-PO) groups and at least one substituted ethylenediamine group.

[0020] The other additive is a non-ionic organic molecule having at least two hydroxyl functional groups.

[0021] In one embodiment, a chemical-mechanical polishing composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; solvent; optionally Biocides; and pH adjuster and having a pH of 2 to 12, 3 to 10, 4 to 9, or 5 to 7.

[0022] In another aspect, there is provided a method of chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising a silicon oxide film, the method comprising: providing a semiconductor substrate; providing a polishing pad; 1. A chemical mechanical polishing (CMP) composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; solvent; optionally Biocides; and pH adjuster and providing a chemical mechanical polishing (CMP) composition comprising: contacting a surface of a semiconductor substrate with a polishing pad and a chemical-mechanical polishing composition; polishing at least one surface comprising silicon dioxide; A method is provided which includes:

[0023] In yet another aspect, there is provided a system for chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising silicon oxide, comprising: a semiconductor substrate; 1. A chemical mechanical polishing (CMP) composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; solvent; optionally Biocides; and pH adjuster a chemical mechanical polishing (CMP) composition comprising: Polishing pad and wherein at least one surface comprising a silicon oxide film is in contact with a polishing pad and a chemical-mechanical polishing composition.

[0024] In one embodiment, the at least one silicone-containing compound has the general molecular structure (1): [ka] wherein each of a and a' is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of a and a' is not 0; each of b and c is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of b and c is not 0; n and m may be the same or different and each is independently 1 to 12, 1 to 8, 1 to 5, or 2 to 4; The R' and R'' groups on the side chains of the molecule can be the same or different and each independently represents hydrogen; -(CH2) p CH3 alkyl group (wherein p is 1 to 12 or 2 to 5); -NH2; -NH(CH2) q -NH2 group (wherein q is 1 to 12 or 2 to 5); -(EO) group consisting of repeating ethylene oxide (EO) and propylene oxide (PO) groups e -(PO) d -OH (wherein d and e each independently represent 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, or 1 to 5); -COOH, -COOM, -COOR 1 , -R 1 COOH, -R 1 COOM, -R 1 COOR 2 , -SO3H;-R 1SO3H; -SO3M; phosphonic acid; phosphate salts selected from sodium, potassium, or ammonium salts; aromatic groups selected from benzyl, dibenzyl, or other aromatic moieties; fluorine-containing organic groups -(CF2) s CF3 (wherein s is 1 to 12 or 2 to 5), wherein R 1 and R 2 each independently represents -(CH2) m (m is 1 to 12), or -(C6H4) n - (n is 1 to 4); and M is selected from sodium, potassium, or ammonium.

[0025] Examples of at least one silicone-containing compound having the general molecular structure (1) include, but are not limited to: [ka] (In the formula, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; b and c may be the same or different and each is independently selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of b and c is not 0; e and d may be the same or different, and each is independently 1 to 12; [ka] (In the formula, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, and 0 to 5; b is selected from 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, or 1 to 5; e and d may be the same or different, and each is independently 1 to 12; and [ka] (In the formula, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; b is selected from 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, or 1 to 5 Includes.

[0026] In another embodiment, the at least one silicone-containing compound has the general molecular structure (2): [ka] wherein a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; e and d may be the same or different and each is independently 1-12.

[0027] In another embodiment, the at least one silicone-containing compound has the general molecular structure (3): [ka] wherein R' and R'' may be the same or different and each independently represents hydrogen; -(CH2) p CH3 (wherein p is 1 to 12 or 2 to 5); -NH2; -NH(CH2) q -NH2 (wherein q is 1 to 12 or 2 to 5); a group consisting of repeating ethylene oxide (EO) and propylene oxide (PO) -(EO) e -(PO) d -OH (wherein d and e are each independently selected from the group consisting of 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, and 1 to 5); -COOH; -COOM; -COOR 1 ;-R 1 COOH;-R 1 COOM;-R 1 COOR 2 ;-SO3H;-SO3M;-R 1SO3H; phosphonic acid; phosphate salt selected from sodium, potassium or ammonium salts; benzyl; di-benzyl; 1 and R 2 each independently represents -(CH2) m (m is 1 to 12) and -(C6H4) n - (n is 1-4); M is selected from the group consisting of sodium, potassium, and ammonium; x, y, and z may be the same or different and each is independently selected from 1 to 12; n1 is 2 to 13.

[0028] Solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0029] Biocides include, but are not limited to, Kathon from DuPont / Dow Chemical Co. TM , Kathon TM CG / ICP II, and Bioban from DuPont / Dow Chemical Co. They have the active ingredient 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.

[0030] Suitable pH adjusters for lowering the pH of the polishing composition include, but are not limited to, nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, hydrochloric acid, phosphoric acid, various polycarboxylic acids, and mixtures thereof. Suitable pH adjusters for raising the pH of the polishing composition include, but are not limited to, potassium hydroxide, sodium hydroxide, ammonia hydroxide, tetraethylammonium hydroxide, organic quaternary ammonium hydroxide compounds, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and other chemical agents that can be used to adjust the pH to a more alkaline direction.

[0031] The polished silicon oxide film (or simply oxide film) can be a chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP) or spin-on oxide film.

[0032] The substrate disclosed above may further comprise a silicon nitride surface. The removal selectivity of SiO2:SiN can be adjusted according to the requirements of the relevant STI CMP application. [Brief explanation of the drawings]

[0033] [Figure 1] 1 shows the removal rates (Å / min) and removal rate selectivities for HDP and SiN films and HDP:SiN using Ref. 1, Comp. 1 and Comp. 2. [Figure 2] 100 μm oxide trench dishing (Å) versus OP (over trench dishing) time (sec) using Ref. 1, Comp. 1 and Comp. 2. [Figure 3] 200 μm oxide trench dishing (Å) versus OP time (sec) using Ref. 1, Comp. 1 and Comp. 2. [Figure 4] Oxide trench dishing (Å) versus OP time (sec) using Ref.1, Ref.2 and Comp.3. [Figure 5] 3 shows the removal rate (Å / min) and removal rate selectivity for HDP:SiN films and TEOS:SiN using Ref. 4, Comp. 4, and Comp. 5. [Figure 6] 3 shows the removal rate (Å / min) and removal rate selectivity for HDP:SiN films and TEOS:SIN using Ref. 5, Comp. 6, and Comp. 7. [Figure 7] Oxide trench dishing (Å) versus OP time (sec) for 100 μm and 200 μm using Ref. 5, Comp. 6 and Comp. 7. [Figure 8]1 shows the removal rate (Å / min) and removal rate selectivity for HDP at 2.0 psi: SiN at 5.0 psi using Ref. 6, Comp. 8, Comp. 9, Comp. 10, and Comp. 11. DETAILED DESCRIPTION OF THE INVENTION

[0034] In the global planarization of patterned STI structures, tuning the SiN removal rate, reducing oxide trench dishing across oxide trench features of various sizes, tuning the oxide film removal rate, and using a relatively low concentration of ceria-coated inorganic oxide particles as an abrasive are key factors to be considered.

[0035] Less trench oxide loss prevents current leakage between adjacent transistors. Non-uniform trench oxide loss across the die (at the die) impacts transistor performance and device manufacturing yield. Significant trench oxide loss (high oxide trench dishing) causes poor transistor isolation, leading to device defects. Therefore, it is important to reduce trench oxide loss by reducing oxide trench dishing in STI CMP polishing compositions.

[0036] All references cited in this specification, including publications, patent applications, and patents, are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and to the same extent as if set forth in its entirety herein.

[0037] The use of the terms "a," "an," "the," and similar modifiers in the context of describing the present invention (particularly in the context of the claims below) is to be construed as covering both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referencing each separate value falling within that range, and, unless otherwise indicated herein, each separate value is incorporated herein to the same extent as if that value were individually set forth herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or otherwise clearly contradicted by context. Any and all examples or exemplary language (e.g., "such as") provided herein are intended merely to better illustrate the invention and do not pose a limitation on the scope of the invention, unless otherwise recited in the claims. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. The use of "comprising" in this specification and claims includes the narrower terms "consisting essentially of" and "consisting of."

[0038] Embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible combinations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0039] In all such compositions where particular components of the composition are discussed in terms of weight percent ranges that include a lower limit of zero, it is understood that such components may or may not be present in various particular embodiments of the composition; for example, when such components are present, they may be present in concentrations as low as 0.00001 weight percent, based on the total weight of the composition in which such component is used.

[0040] The present development relates to a chemical mechanical polishing (CMP) composition using chemical additives and ceria coated composite particles as an abrasive for shallow trench isolation (STI) CMP applications.

[0041] More specifically, the disclosed chemical mechanical polishing (CMP) compositions for shallow trench isolation (STI) CMP applications have a unique combination of ceria-coated inorganic oxide abrasive particles and two chemical additives for adjusting oxide film removal rate, reducing oxide trench dishing, and adjusting nitride removal rate.

[0042] The two chemical additives used in the same STI CMP polishing composition offer the advantages of achieving desired oxide film removal rates, tunable SiN film removal rates, and high and tunable oxide:SiN selectivity, reduced corrosion, SiN loss, reduced total defect load, and more importantly, significantly reduced oxide trench dishing and improved overpolishing window stability in polishing patterned wafers.

[0043] In one embodiment, a chemical-mechanical polishing composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; solvent; optionally Biocides; and pH adjuster and having a pH of 2 to 12, 3 to 10, 4 to 9, or 5 to 7.

[0044] Ceria-coated inorganic oxide particles are composite particles having inorganic oxide particles as core particles whose surfaces are coated with ceria particles.

[0045] The average particle size (MPS) of the ceria-coated inorganic metal oxide particles is 10 nm to 1000 nm, 15 nm to 800 nm, preferably 20 nm to 500 nm, more preferably 50 nm to 250 nm. The ceria particles are smaller than the core particles. The ceria particles are 5 to 40 nm.

[0046] Ceria-coated inorganic oxide particles include, but are not limited to, ceria-coated colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia, or any other ceria-coated inorganic metal oxide particles.

[0047] Preferred ceria-coated inorganic oxide particles are ceria-coated colloidal silica particles, which have silica particles as core particles whose surfaces are coated with ceria particles.

[0048] In some embodiments, the concentration of these ceria-coated inorganic oxide particles is 0.01 wt% to 20 wt%, 0.05 wt% to 10 wt%, or 0.1 wt% to 5 wt%.

[0049] In some other embodiments, the concentration of these ceria-coated inorganic oxide particles is between 0.01 wt% and 2 wt%, between 0.025 wt% and 1.0 wt%, or between 0.05 wt% and 0.5 wt%.

[0050] The first chemical additive comprises a silicone-containing compound.

[0051] In one embodiment, the at least one silicone-containing compound has the general molecular structure (1): [ka] wherein each of a and a' is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of a and a' is not 0; each of b and c is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of b and c is not 0; n and m may be the same or different and each is independently 1 to 12, 1 to 8, 1 to 5, or 2 to 4; R and R' may be the same or different and each independently represents hydrogen; -(CH2) p CH3 (wherein p is 1 to 12 or 2 to 5); -NH2; -NH(CH2) q -NH2 (wherein q is 1 to 12 or 2 to 5); a group consisting of repeating ethylene oxide (EO) and propylene oxide (PO) -(EO) e -(PO) d -OH (wherein d and e are each independently selected from the group consisting of 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, and 1 to 5); -COOH; -COOM; -COOR 1 ;-R 1 COOH;-R 1 COOM;-R 1 COOR 2 ;-SO3H;-SO3M;-R 1 SO3H; phosphonic acid; phosphate salt selected from sodium, potassium or ammonium salts; benzyl; di-benzyl; 1 and R 2 each independently represents -(CH2) m (m is 1 to 12) and -(C6H4) n (n is 1 to 4); and M is selected from the group consisting of sodium, potassium, and ammonium.

[0052] Examples of at least one silicone-containing compound having the general molecular structure (1) include, but are not limited to: [ka] (In the formula, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; b and c may be the same or different and each is independently selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of b and c is not 0; e and d may be the same or different, and each is independently 1 to 12; [ka] (In the formula, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, and 0 to 5; b is selected from 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, or 1 to 5; e and d may be the same or different, and each is independently 1 to 12; and [ka] During the ceremony, a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; b is selected from 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, or 1 to 5 Includes.

[0053] In another embodiment, the at least one silicone-containing compound has the general molecular structure (2): [ka] wherein a is selected from 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; e and d may be the same or different and each is independently 1-12.

[0054] Further, in another embodiment, the at least one silicone-containing compound has the general molecular structure (3): [ka] wherein R' and R'' may be the same or different and each independently represents hydrogen; -(CH2) pCH3 (wherein p is 1 to 12 or 2 to 5); -NH2; -NH(CH2) q -NH2 (wherein q is 1 to 12 or 2 to 5); a group consisting of repeating ethylene oxide (EO) and propylene oxide (PO) -(EO) e -(PO) d -OH (wherein d and e are each independently selected from the group consisting of 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, and 1 to 5); -COOH; -COOM; -COOR 1 ;-R 1 COOH;-R 1 COOM;-R 1 COOR 2 ;-SO3H;-SO3M;-R 1 SO3H; phosphonic acid; phosphate salt selected from sodium, potassium or ammonium salts; benzyl; di-benzyl; 1 and R 2 each independently represents -(CH2) m (m is 1 to 12) and -(C6H4) n (n is 1-4); M is selected from the group consisting of sodium, potassium, and ammonium; x, y, and z may be the same or different and each is independently selected from 1 to 12; n1 is 2 to 13.

[0055] The STI CMP composition contains 0.0001 wt % to 2.0 wt %, 0.001 wt % to 1.0 wt %, or 0.0025 wt % to 0.25 wt % of at least one silicone-containing surface-wetting compound as a chemical additive that functions primarily to adjust the removal rate of oxide films and SiN films and to reduce oxide trench dishing, the at least one silicone-containing surface-wetting compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group on the same molecule.

[0056] The second chemical additive comprises at least one non-ionic organic molecule having at least two hydroxyl functional groups.

[0057] In one embodiment, the second chemical additive has the general structure shown below: [ka] It has.

[0058] In the general molecular structure (a), n is selected from 2 to 5,000, 3 to 12, or 4 to 6.

[0059] In these general molecular structures, the R1, R2 and R3 groups may be the same or different atoms or functional groups.

[0060] R1, R2 and R3 are independently hydrogen, alkyl group C n H 2n+1 (wherein n is 1 to 12, preferably 1 to 6, more preferably 1 to 3); and can be selected from the group consisting of alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxyl ester, an organic amine group, and combinations thereof; where in the formula, at least two of R1, R2, and R3 are hydrogen atoms.

[0061] In another embodiment, the chemical additive has the general structure shown below: [ka] It has.

[0062] In this structure, one —CHO functional group is located at one end of the molecule as a terminal functional group; n is selected from 2 to 5000, 3 to 12, or 4 to 7.

[0063] Each of R1 and R2 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxylic ester, an organic amine group, and combinations thereof.

[0064] In yet another embodiment, the second chemical additive is (c), (d), or (e): [ka] The molecular structure is selected from the group comprising:

[0065] In these general molecular structures, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 may be the same or different atoms or functional groups.

[0066] They can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylates, organic carboxylic esters, organic amine groups, and combinations thereof; at least two or more, preferably four or more of them are hydrogen atoms.

[0067] Furthermore, in another embodiment, the chemical additive contains at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure or at least one six-membered ring structural motif ether linked by at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure, and at least one six-membered ring polyol. Polyols are organic compounds containing hydroxyl groups.

[0068] The general molecular structure of a chemical additive is (f): [ka] Shown below.

[0069] In the structure (f), at least one R in the groups R1 to R5 in the general molecular structure (f) is (i): [ka] wherein n and m may be the same or different, and each of n and m is independently selected from 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 to 2; R6 to R9 may be the same or different atoms or functional groups; each of R6, R7, R8, and R9 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxyl ester, an organic amine, and combinations thereof; at least two of them are hydrogen atoms; The remainder of each R in the groups R1 to R5 is independently hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid or a substituted organic sulfonate, a substituted organic carboxylic acid or a substituted organic carboxylate, an organic carboxyl ester, an organic amine, (ii): [ka] (wherein structure (ii) is R in (ii)) 11 ~R 14 By removing one R from the structure (f), it is connected to the structure (f) through an oxygen-carbon bond, and the remaining R 10 ~R 14each independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid or a substituted organic sulfonate, a substituted organic carboxylic acid or a substituted organic carboxylate, an organic carboxylic ester, an organic amine, and combinations thereof; and combinations thereof.

[0070] In some embodiments, the general molecular structure (f) has at least two, at least four, or at least six Rs, which are hydrogen atoms in the groups R1 through R9. Thus, the chemical additives contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structure.

[0071] The second chemical additive may be selected from the group consisting of (a), (b), (c), (d), (e), (f), and combinations thereof.

[0072] Examples of the second chemical additive include maltitol, lactitol, maltotriitol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(-)-fructose, sorbitan, sucrose, ribose, inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, beta-lactose, arabinose, and combinations thereof. Preferred chemical additives are maltitol, lactitol, maltotriitol, D-sorbitol, mannitol, dulcitol, iditol, D-(-)-fructose, sucrose, ribose, inositol, glucose, D-(+)-mannose, beta-lactose, and combinations thereof. More preferred chemical additives are maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(-)-fructose, beta-lactose, and combinations thereof.

[0073] Some examples of second chemical additives are listed below. [ka] D-sorbitol; and [ka] Dulcitol. [ka] maltitol; and [ka] Lactitol.

[0074] Preferred chemical additives of the second type are D-sorbitol, dulcitol, maltitol and lactitol.

[0075] The STI CMP composition further contains 0.001 wt % to 2.0 wt %, 0.0025 wt % to 1.0 wt %, or 0.05 wt % to 0.5 wt % of at least one non-ionic organic molecule having at least two hydroxyl functional groups, which primarily functions as a SiN film removal rate adjuster and an oxide film removal rate adjuster, and as an oxide trench dishing reducer.

[0076] Solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0077] The preferred solvent is DI water.

[0078] 4 The STI CMP composition may contain from 0.0001 wt% to 0.05 wt%, preferably from 0.0005 wt% to 0.025 wt%, more preferably from 0.001 wt% to 0.01 wt% of a biocide.

[0079] Biocides include, but are not limited to, Kathon from DuPont / Dow Chemical Co. TM , Kathon TMCG / ICP II, and Bioban from DuPont / Dow Chemical Co. They have the active ingredient 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.

[0080] The STI CMP composition may contain a pH adjuster.

[0081] Acidic or basic pH adjusters can be used to adjust the STI polishing composition to an optimized pH value.

[0082] Suitable pH adjusters for lowering the pH of the polishing composition include, but are not limited to, nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, hydrochloric acid, phosphoric acid, various polycarboxylic acids, and mixtures thereof. Suitable pH adjusters for raising the pH of the polishing composition include, but are not limited to, potassium hydroxide, sodium hydroxide, ammonia hydroxide, tetraethylammonium hydroxide, organic quaternary ammonium hydroxide compounds, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and other chemical agents that can be used to adjust the pH to a more alkaline direction.

[0083] The pH of the composition is 2-12, 3-10, 4-9, or 5-7.

[0084] The STI CMP composition contains 0 wt% to 1 wt%, 0.01 wt% to 0.5 wt%, or 0.1 wt% to 0.25 wt% of a pH adjuster.

[0085] In another aspect, a method is provided for chemical mechanical polishing (CMP) a substrate having at least one surface comprising silicon dioxide using the chemical mechanical polishing (CMP) composition described above in a shallow trench isolation (STI) process.

[0086] In yet another aspect, a system is provided for chemical mechanical polishing (CMP) a substrate having at least one surface comprising silicon dioxide using the chemical mechanical polishing (CMP) composition described above in a shallow trench isolation (STI) process.

[0087] The polished oxide film may be a chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP) or spin-on oxide film.

[0088] The substrate disclosed above may further comprise a silicon nitride surface. The removal selectivity of SiO2:SiN can be tailored according to the requirements of the STI CMP application.

[0089] The following non-limiting examples are provided to further illustrate the present invention. [Example]

[0090] CMP method In the examples provided below, CMP experiments were performed using the procedures and experimental conditions given below.

[0091] Terminology / Components Ceria-coated silica particles (having various sizes) were supplied by JGCC Inc., Japan. The ceria-coated silica particles have a mean particle size (MPS) of approximately 20 nanometers (nm) to 500 nanometers (nm). The MPS is measured by light scattering. The ceria particles coated on the surface of the core silica particles have a smaller size. For example, for ceria-coated silica particles with a mean particle size of approximately 120 nanometers (nm), the size of the ceria particles is greater than 13 nm.

[0092] The silicone-containing compounds used were the Silamine® series of silicone amines and Silsurf® series of silicone polyethers from Siltech Corporation, 225 Wicksteed Avenue, Toronto, Ontario, Canada. M4H 1G5.

[0093] The Silamine series (silicone amines) includes Silamine C-100 and its derivatives, Silamine C-50, Silamine AS, and Silamine C-300, and the Silsurf series (silicone polyethers) includes Silsurf A008-AC-UP, Silsurf A208, Silsurf CR 1115, Silsurf E608, and Silsurf J208-6.

[0094] The nonionic organic molecules having at least two, and preferably at least four, hydroxyl functional groups used were maltitol, D-fructose, dulcitol, D-sorbitol, and other chemical raw materials supplied by Sigma-Aldrich, St. Louis, MO, or supplied by Evonik Industries, Allentown, PA.

[0095] TEOS: Tetraethyl orthosilicate Polishing pads: Polishing pads supplied by DOW, Inc., IC1010 and other pads were used during CMP.

[0096] Parameters general Å or ​​A: Angstrom - unit of length BP: Back pressure, in psi CMP: Chemical mechanical planarization = chemical mechanical polishing CS: Carrier Speed DF: Downforce: Pressure applied during CMP, in psi min:minutes ml: milliliter mV: millivolt psi: pounds per square inch PS: Polishing tool platen rotation speed, rpm (revolutions per minute) SF: Flow rate of the composition, ml / min wt%: weight percent (of the listed component) TEOS:SiN selectivity: (TEOS removal rate) / (SiN removal rate) HDP: TEOS deposited by high density plasma TEOS or HDP removal rate: The removal rate of TEOS or HDP measured at a given down pressure. The down pressure of the CMP tool was 3.1 psi in the examples described below. SiN removal rate: The removal rate of SiN measured at a given down pressure. The down pressure of the CMP tool was 3.1 psi in the examples described below.

[0097] measurement The films were measured with a ResMap CDE, Model 168, manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA 95014. The ResMap tool is a four-point probe sheet resistance tool. A 49-point diameter scan with a 5 mm edge exclusion was taken of the film.

[0098] CMP Tools The CMP tools used were 200 mm Mirra or 300 mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, California, 95054. For platen 1, an IC1000 pad supplied by DOW, Inc., 451 Bellevue Rd., Newark, DE 19713 was used for blanket and patterned wafer investigations.

[0099] The IC1010 pads were conditioned by conditioning the pads on a conditioner for 18 minutes at 7 lbs downforce. To qualify the tool settings and pad conditioning, two tungsten monitors and two TEOS monitors were polished with Versum® STI2305 composition supplied by Versum Materials Inc. at baseline conditions.

[0100] wafer Polishing experiments were performed using PECVD or LECVD or HD TEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.

[0101] Polishing experiment In the blanket wafer study, oxide blanket wafers and SiN blanket wafers were polished under baseline conditions: table speed: 93 rpm, head speed: 87 rpm, film pressure: 3.1 psi DF, and slurry flow rate: 200 ml / min.

[0102] The compositions were used in polishing experiments on patterned wafers (MIT860) supplied by SWK Associates, Inc. 2920 Scott Blvd. Santa Clara, CA 95054. These wafers were measured on a Veeco VX300 profiler / AFM instrument. Three different size pitch features were used for oxide dishing measurements. Wafers were measured at the center, middle, and edge die locations.

[0103] The TEOS:SiN selectivity (TEOS removal rate) / (SiN removal rate) obtained from the STI CMP polishing composition was tunable.

[0104] In the following examples, an STI polishing composition containing 0.2 wt % ceria-coated silica, 0.0001 wt % to 0.05 wt % biocide, 0.15 wt % D-sorbitol, and deionized water was prepared at pH 5.35 as a reference.

[0105] Polishing working compositions were prepared under the same pH conditions using 0.2 wt% ceria-coated silica, 0.15 wt% D-sorbitol, various wt% Silamine compounds as another type of chemical additive, 0.0001 wt% to 0.05 wt% biocide, and deionized water.

[0106] Example 1 In Example 1, the polishing composition used for oxide polishing is shown in Table 1.

[0107] Reference 1 (Ref. 1) was prepared using 0.2 wt% ceria-coated silica, 0.0001 wt% to 0.05 wt% biocide, 0.15 wt% D-sorbitol, and deionized water. Working compositions were prepared by adding various wt% of Silamine compound to the reference sample. The samples had a pH of 5.35. Table 1. Effect of two chemical additives on the film removal rate (RR) (Å / min) and HDP:SiN selectivity. [Table 1]

[0108] The removal rates (RR, Å / min) of different films were tested. The results are listed in Table 1 and shown in Figure 1. As shown in Table 1 and Figure 1, the addition of Silamine to the polishing composition effectively suppressed the removal rate of LPCVD SiN films and increased the HDP:SiN polishing selectivity.

[0109] With the addition of 0.01 wt% Silamine AS, the HDP:SiN polishing selectivity increased from 102:1 to 118:1.

[0110] With the addition of 0.0075 wt% Silamine C-100, the polishing selectivity of HDP:SiN increased from 102:1 to 112:1.

[0111] Example 2 In Example 2, the same polishing composition as used in Example 1 was used for polishing the patterned oxide wafer and for 100 μm and 200 μm oxide trench dishing versus over-polishing time. The results are shown in Table 2 and illustrated in FIGS. 2 and 3.

[0112] As shown in Table 2, Figures 2 and 3, adding 0.01 wt% Silamine AS to form two additive-based polishing compositions reduced oxide trench dishing for different overpolishing times on both 100 μm and 200 μm pitch features compared to the reference sample using only ceria-coated silica abrasive and 0.15 wt% D-sorbitol. Table 2. Effect of two additive polishing compositions on oxide trench dishing (Å) versus overpolishing (OP) time (sec). [Table 2]

[0113] Adding 0.0075 wt% Silamine C-100 to form two additive-based polishing compositions significantly reduced oxide trench dishing for different overpolishing times on both 100 μm and 200 μm pitch features compared to a reference sample using only ceria-coated silica abrasive and 0.15 wt% D-sorbitol.

[0114] The effect on oxide trench dishing rate of adding 0.01 wt % Silamine AS or 0.0075 wt % Silamine C-100 to form two additive-based polishing compositions was tested, and the results are listed in Table 3. Table 3. Effect of two additives at pH 5.35 on oxide dishing rate. [Table 3]

[0115] As shown in Table 3, adding 0.01 wt% or 0.0075 wt% Silamine C-100 to form two additive-based polishing compositions significantly reduced the oxide dishing rate.

[0116] The effect of adding 0.01 wt% or 0.0075 wt% Silamine C-100 to form two additive-based polishing compositions on the slope of oxide trench dishing versus polishing volume was tested, and the results are listed in Table 4. Table 4. Effect of two additives on the slope of trench dishing versus overpolishing amount [Table 4]

[0117] As shown in Table 4, adding 0.01 wt% or 0.0075 wt% Silamine C-100 to form two additive-based polishing compositions reduced the slope of oxide dishing versus over-polishing.

[0118] Example 3 In Example 3, the same polishing composition used in Example 1 was used to test total defect load in polished TEOS and SiN wafers.

[0119] The results are shown in Table 5. Table 5. Effect of two additives vs. one additive on total defect load [Table 5]

[0120] As shown in Table 5, the total defect load in polished TEOS and LPCVD wafers decreased significantly with the addition of Silamine.

[0121] Example 4 In Example 4, the polishing composition used for oxide polishing is shown in Table 6.

[0122] Reference 2 (Ref. 2) was made using 0.2 wt% ceria-coated silica, 0.0001 wt% to 0.05 wt% biocide, 0.025 wt% Silamine C-100, and deionized water at pH 5.35.

[0123] An example composition (Comp. 3) was made using 0.2 wt% ceria-coated silica, 0.0001 wt% to 0.05 wt% biocide, 0.15 wt% D-sorbitol, 0.025 wt% Silamine C-100, and deionized water at a pH of 5.35.

[0124] The removal rate (RR, Å / min) for different films was tested. The effect of two chemical additives, Silamine C-100 and D-sorbitol-based polishing compositions versus a reference sample on the film removal rate and HDP:SiN selectivity was tested and is listed in Table 6. Table 6. Effect of two chemical additives on the membrane RR (Å / min) and HDP:SiN selectivity. [Table 6]

[0125] As shown in Table 6, Ref. 2, which uses 0.025 wt% Silamine C-100 as the only chemical additive, had the highest LPCVD SiN film removal rate, which was significantly greater than the SiN removal rates obtained from Ref. 1, which uses D-sorbitol as the only chemical additive, and the experimental sample, which uses two chemical additives, D-sorbitol and Silamine C-100. Table 7. Effect of chemical composition of two additives on oxide trench dishing (Å) versus OP time (sec). [Table 7]

[0126] The two chemical additive-based polishing compositions Comp. 3 effectively suppressed the removal rate of LPCVD SiN films and increased the polishing selectivity of HDP:SiN from 7:1 for Ref. 2 and 68:1 for Ref. 2 to 83:1.

[0127] In Example 4, the same polishing composition was used to polish patterned oxide wafers and to produce 100 μm, 200 μm, and 1000 μm oxide trench dishing versus overpolishing time, with the results shown in Table 7 and depicted in FIG. 4.

[0128] As shown in Table 7 and Figure 4, the experimental samples based on two chemical additives significantly reduced oxide trench dishing at different pitch sizes for different over-polishing times compared to the single-chemical additive-based Ref. 1 and Ref. 2 samples.

[0129] All samples were tested for oxide trench dishing rate and the results are listed in Table 8.

[0130] The two chemical additive-based polishing compositions Comp. 3 significantly reduced the oxide trench dishing rate at different size pitches compared to the oxide trench dishing rate obtained for the reference sample.

[0131] All samples were tested for the slope of oxide trench dishing versus the amount of overpolishing, and the results are listed in Table 9. Table 8. Effect of two additives on oxide dishing rate at pH 5.35 [Table 8]

[0132] All samples were tested for the slope of oxide trench dishing versus the amount of overpolishing, and the results are listed in Table 9.

[0133] As shown in Table 9, the two chemical additive-based polishing compositions (Comp. 3) reduced the slope of oxide dishing versus over-polishing compared to the slope of oxide dishing versus over-polishing obtained for the reference sample. Table 9. Effect of two additives on the slope of trench dishing versus overpolishing amount [Table 9]

[0134] Example 5 In Example 5, the polishing composition used for oxide polishing is shown in Table 10.

[0135] Reference 4 (Ref. 4) was prepared using 0.4 wt% ceria-coated silica, 0.275 wt% D-sorbitol, 0.0001 wt% to 0.05 wt% biocide, and deionized water. Working compositions Comp. 4 and Comp. 5 were prepared by adding 0.0125 wt% Silsurf E608 or Silsurf A208, respectively, to Reference 4. All samples had a pH of 5.35. Table 10. Removal Rate (RR) (Å / min); Removal Rate (RR) Selectivity for HDP:SiN and TEOS:SiN [Table 10]

[0136] The removal rates (RR, Å / min) for different films were tested, and the results are listed in Table 10 and illustrated in FIG.

[0137] As shown in Table 10 and Figure 5, adding 0.0125 wt% of Silsurf E608 or Silsurf A208 to the polishing composition effectively suppressed the removal rate of the PECVD SiN film and increased the polishing selectivity of HDP:SiN and TEOS:SiN.

[0138] With the addition of 0.0125 wt% Silsurf E608, the polishing selectivity of HDP:SiN increased from 45:1 to 67:1; the polishing selectivity of TEOS:SiN increased from 45:1 to 64:1.

[0139] With the addition of 0.0125 wt% Silsurf A208, the HDP:SiN polishing selectivity increased from 45:1 to 74:1; the TEOS:SiN polishing selectivity increased from 45:1 to 71:1.

[0140] Example 6 In Example 6, the polishing composition used for oxide polishing is shown in Table 11.

[0141] A reference sample was prepared using 0.2 wt% ceria-coated silica, 0.28 wt% lactitol, 0.0001 wt% to 0.05 wt% biocide, and deionized water. Working samples were prepared by adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 to the reference sample. All samples had a pH of 5.35. Table 11. Removal Rate (RR) (Å / min); Removal Rate (RR) Selectivity for HDP:SiN and TEOS:SiN [Table 11]

[0142] The removal rates (RR, Å / min) for different films were tested, and the results are listed in Table 11 and illustrated in FIG.

[0143] As shown in Table 11 and Figure 6, adding Silsurf E608 or Silsurf A208 to the polishing composition effectively suppressed the removal rate of the PECVD SiN film and increased the polishing selectivity of HDP:SiN or TEOS:SiN.

[0144] With the addition of 0.025 wt% Silsurf E608, the polishing selectivity of HDP:SiN increased from 39:1 to 59:1; the polishing selectivity of TEOS:SiN increased from 41:1 to 60:1.

[0145] With the addition of 0.025 wt% Silsurf A208, the polishing selectivity of HDP:SiN increased from 39:1 to 73:1; the polishing selectivity of TEOS:SiN increased from 41:1 to 77:1.

[0146] Example 7 In Example 7, the same polishing composition as used in Example 6 was used to polish the patterned oxide wafer. The oxide trench dishing of 100 μm and 200 μm versus over-polishing time is shown in Table 12 and illustrated in FIG.

[0147] As shown in Table 12 and Figure 7, adding 0.025 wt% Silsurf E608 with lactitol to form two additive-based polishing compositions reduced oxide trench dishing for different overpolishing times in both 100 μm and 200 μm pitch features compared to the reference sample using only ceria-coated silica abrasive and 0.28 wt% lactitol. Table 12. Oxide Trench Dishing (Å) vs. OP Time (sec) [Table 12]

[0148] As shown in Table 12 and Figure 7, adding 0.025 wt% Silsurf A208 with lactitol to form two additive-based polishing compositions reduced oxide trench dishing for different overpolishing times in both 100 μm and 200 μm pitch features compared to a reference sample using only ceria-coated silica abrasive and 0.28 wt% lactitol.

[0149] The effect on oxide trench dishing rate of adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 together with lactitol to form two additive-based polishing compositions was tested, and the results are listed in Table 13.

[0150] As shown in Table 13, adding Silsurf E608 or 0.025 wt% Silsurf A208, along with 0.28 wt% lactitol, to form two polishing compositions reduced the oxide dishing rate. Table 13. Oxide trench dishing rates at pH 5.35 [Table 13]

[0151] The effect on oxide trench loss rate of adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 together with 0.28 wt% lactitol to form two additive-based polishing compositions was tested, and the results are listed in Table 14.

[0152] As shown in Table 14, adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 together with 0.28 wt% lactitol to form two additive-based polishing compositions reduced the oxide trench loss rate.

[0153] The effect on the SiN loss rate of adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208, along with 0.28 wt% lactitol, to form two additive-based polishing compositions was tested, and the results are listed in Table 15. Table 14. Oxide Trench Loss Rate at pH 5.35 [Table 14]

[0154] As shown in Table 15, adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 together with 0.28 wt% lactitol to form two additive-based polishing compositions reduced the SiN loss rate. Table 15. SiN loss rate at pH 5.35 [Table 15]

[0155] The effect of adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208, along with 0.28 wt% lactitol, to form two additive-based polishing compositions on the oxide trench to blanket ratio was tested, and the results are listed in Table 16.

[0156] As shown in Table 16, adding 0.025 wt% Silsurf E608 or 0.025 wt% Silsurf A208 together with 0.28 wt% lactitol to form two additive-based polishing compositions reduced the oxide trench to blanket ratio.

[0157] Generally, the lower the trench to blanket oxide ratio, the less oxide trench dishing there is. Table 16. Oxide Trench to Blanket Ratio at pH 5.35 [Table 16]

[0158] Example 8 In general, suppressing the removal rate of SiN film and increasing the removal rate selectivity of HDP:SiN or TEOS:SiN improves STI polishing performance in reducing erosion and trench dishing.

[0159] Some chemical additives in STI polishing suppress SiN removal rate more at relatively low downforces compared to those at increased downforces. For reduced corrosion and oxide trench dishing, it is important to select chemical additives that can provide suppressed SiN removal rate and high removal rate selectivity for HDP:SiN or TEOS:SiN at both low and high applied downforces.

[0160] In Example 8, Reference 6 (Ref. 6) was prepared using 0.2 wt% ceria-coated silica, 0.28 wt% maltitol, and deionized water. Working compositions Comp. 8, Comp. 9, Comp. 10, and Comp. 11 were prepared by adding 0.025 wt% Silsurf E608, Silsurf A208, Silsurf J208-6, or Silsurf CR1115 to Reference 6. All samples had a pH of 5.35.

[0161] In Example 8, a downforce of 2.0 psi was applied to polish the HDP film. Both a downforce of 2.0 psi and a downforce of 5.0 psi were applied to polish the PECVD SiN film.

[0162] The polishing results showing the removal rates (RR) for different films and the RR selectivity at different down forces are shown in Table 17 and FIG.

[0163] As shown in Table 17 and Figure 8, all four Silsurf chemical additives effectively suppressed the PECVD SiN removal rate relative to the reference sample, especially when a high downforce of 5.0 psi was applied for polishing PECVD SiN films. Table 17. RR of films; RR selectivity of HDP:PECVD SiN [Table 17]

[0164] These Silsurf-type chemical additives increased the HDP at 2.0 psi:SiN at 5.0 psi ratio from 10:1 for the reference sample without Silsurf-type chemical additives to a range of 23:1 to 30:1 for the polishing compositions using these Silsurf-type chemical additives, respectively.

[0165] The above-described embodiments of the invention, including the working examples, are illustrative of the many embodiments that can be made from the present invention. It is contemplated that many other configurations of the process can be used and that the materials used in the process can be selected from many other materials than those specifically disclosed. The following embodiments can be given as examples of the present invention. (Appendix 1) 1. A chemical-mechanical polishing composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; solvent; Optionally, Biocides; and pH adjuster wherein the composition has a pH selected from the group consisting of 2 to 12, 3 to 10, 4 to 9, and 5 to 7; the at least one silicone-containing compound is [ka] (In the formula, each of a and a' is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of a and a' is not 0; each of b and c is independently 0 to 50, 0 to 40, 0 to 30, 0 to 20, 0 to 10, or 0 to 5; at least one of b and c is not 0; n and m may be the same or different and each is independently 1 to 12, 1 to 8, 1 to 5, or 2 to 4; R and R' may be the same or different and each independently represents hydrogen; -(CH 2 ) p CH 3 (wherein p is 1 to 12 or 2 to 5); -NH 2 ;-NH(CH 2 ) q -NH 2 (wherein q is 1 to 12 or 2 to 5); a group -(EO) in which ethylene oxide (EO) and propylene oxide (PO) are repeated e -(PO) d -OH (wherein each of d and e is independently selected from the group consisting of 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 10, and 1 to 5); -COOH; -COOM; -COOR 1 ;-R 1 COOH;-R 1 COOM;-R 1 COOR 2 ;-SO 3 H;-SO 3 M;-R 1 SO 3 H; phosphonic acid; phosphate selected from sodium, potassium or ammonium salts; benzyl; di-benzyl, wherein R1 and R 2 each independently represents -(CH 2 ) m (wherein m is 1 to 12) and -(C 6 H 4 ) n wherein n is 1 to 4; and M is selected from the group consisting of sodium, potassium, and ammonium;

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Claims

1. 1. A chemical-mechanical polishing composition comprising: at least one ceria-coated inorganic oxide particle; at least one silicone-containing compound comprising at least one selected from the group consisting of at least one ethylene oxide and propylene oxide (EO-PO) group and at least one substituted ethylenediamine group; at least one nonionic organic molecule having at least two hydroxyl functional groups; and solvent wherein the composition has a pH of 2 to 12; the at least one silicone-containing compound is 【Chemistry 1】 (In the formula, each of a and a' is independently 0 to 50; at least one of a and a' is not 0; each of b and c is independently 0 to 50; at least one of b and c is not 0; n and m may be the same or different and each independently is 1 to 12; R and R' may be the same or different and each independently represents hydrogen; -(CH ２ ) ｐ CH ３ (wherein p is 1 to 12); ２ -NH(CH ２ ) ｑ -NH ２ (wherein q is 1 to 12); a group -(EO) repeating ethylene oxide (EO) and propylene oxide (PO) ｅ - (PO) ｄ -OH (wherein each of d and e is independently 1 to 50); -COOH; -COOM; -COOR １ ;-R １ COOH; -R １ COOM;-R １ COOR ２ ;-SO ３ H; -SO ３ M;-R １ SO ３ H; phosphonic acid; phosphate selected from sodium, potassium or ammonium salts; benzyl; di-benzyl, wherein R １ and R ２ each independently represents -(CH ２ ) ｍ (wherein m is 1 to 12) and -(C ６ H ４ ) ｎ wherein n is 1 to 4; and M is selected from the group consisting of sodium, potassium, and ammonium; 【Chemistry 2】 (In the formula, a is 0 to 50; e and d may be the same or different and each is independently 1 to 12; 【Transformation 3】 (In the formula, R' and R'' may be the same or different and each independently represents hydrogen; -(CH ２ ) ｐ CH ３ (wherein p is 1 to 12); ２ -NH(CH ２ ) ｑ -NH ２ (wherein q is 1 to 12); a group -(EO) repeating ethylene oxide (EO) and propylene oxide (PO) ｅ - (PO) ｄ -OH (wherein each of d and e is independently 1 to 50); -COOH; -COOM; -COOR １ ;-R １ COOH; -R １ COOM;-R １ COOR ２ ;-SO ３ H; -SO ３ M;-R １ SO ３ H; phosphonic acid; phosphate salts selected from sodium, potassium or ammonium salts; benzyl; di-benzyl; １ and R ２ each independently represents -(CH ２ ) ｍ (wherein m is 1 to 12) and -(C ６ H ４ ) ｎ wherein n is 1 to 4; M is selected from the group consisting of sodium, potassium, and ammonium; x, y, and z may be the same or different and each is independently selected from 1 to 12; n1 is 2 to 13; and (4) Combination of (1) to (3) 1. A chemical-mechanical polishing composition having a general molecular structure selected from the group comprising:

2. A chemical mechanical polishing composition as described in claim 1, containing a biocide.

3. A chemical mechanical polishing composition as described in claim 1, containing a pH adjuster.

4. 2. The chemical mechanical polishing composition of claim 1, wherein the ceria-coated inorganic metal oxide particles are selected from the group consisting of ceria-coated colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia particles, and combinations thereof, and the particles are present in the composition in a range of 0.01 wt % to 20 wt %.

5. At least one silicone-containing compound having the general molecular structure (1) 【Chemistry 4】 (In the formula, a is 0 to 50; b and c may be the same or different and each independently ranges from 0 to 50; at least one of b and c is not 0; e and d may be the same or different and each is independently 1 to 12; 【Transformation 5】 (In the formula, a is 0 to 50; b is 1 to 50; e and d may be the same or different and each is independently 1 to 12; 【Transformation 6】 (In the formula, a is 0 to 50; b is 1 to 50; and (d) Combinations thereof The chemical-mechanical polishing composition of claim 1 selected from the group comprising:

6. 10. The chemical-mechanical polishing composition of claim 1, wherein the at least one silicone-containing compound is present in the composition at a concentration of 0.0001 wt % to 2.0 wt %.

7. the at least one nonionic organic molecule having at least two hydroxyl functional groups comprising: 【Transformation 7】 (wherein n is 2 to 5000; R １ , R ２ and R ３ groups may be the same or different and each independently represents hydrogen, an alkyl group C ｎ H ２ｎ＋１ wherein n is 1 to 12; alkoxy; an organic group having one or more hydroxyl groups; a substituted organic sulfonic acid; a substituted organic sulfonate; a substituted organic carboxylic acid; a substituted organic carboxylate; an organic carboxylic ester; an organic amine group; and combinations thereof; １ , R ２ and R ３ at least two of the groups are hydrogen atoms; 【Transformation 8】 (wherein n is 2 to 5000; R １ and R ２ may each independently be selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxylic ester, an organic amine group, and combinations thereof. 【Chemistry 9】 (In the formula, R １ , R ２ , R ３ , R ４ and R ５ may be the same or different and may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxyl ester, an organic amine group, and combinations thereof; R １ , R ２ , R ３ , R ４ and R ５ at least two of which are hydrogen atoms; 【Chemistry 10】 (In the formula, R ６ , R ７ and R ８ may be the same or different and may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxyl ester, an organic amine group, and combinations thereof; R ６ , R ７ and R ８ at least two of which are hydrogen atoms; 【Chemistry 11】 (In the formula, R ９ , R １０ , R １１ , R １２ , R １３ and R １４ may be the same or different and may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxyl ester, an organic amine group, and combinations thereof; R ９ , R １０ , R １１ , R １２ , R １３ and R １４ at least two of which are hydrogen atoms; 【Chemistry 12】 (Wherein, R in the general molecular structure (f) １ ~R ５ wherein at least one R in the group is (i): 【Chemistry 13】 where n and m may be the same or different and independently range from 1 to 5; R ６ ~R ９ may be the same or different and are independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxylic ester, an organic amine, and combinations thereof; R ６ ~R ９ at least two of are hydrogen atoms; R １ ~R ５ wherein the remainder of each R in the group is independently hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxylic ester, or an organic amine; (ii): 【Chemistry 14】 (wherein structure (ii) is R in (ii)) １１ ~R １４ is connected through an oxygen-carbon bond in structure (f) by removing one R from １０ ~R １４ each of which may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, an organic group having one or more hydroxyl groups, a substituted organic sulfonic acid, a substituted organic sulfonate, a substituted organic carboxylic acid, a substituted organic carboxylate, an organic carboxylic ester, an organic amine, and combinations thereof; (g) Combinations thereof 10. The chemical-mechanical polishing composition of claim 1, wherein the nonionic organic molecule has a general molecular structure selected from the group comprising:

8. The chemical-mechanical polishing composition of claim 1 , wherein the at least one nonionic organic molecule has at least four hydroxyl functional groups.

9. the at least one nonionic organic molecule comprising: 【Chemistry 15】 D-sorbitol; or 【Chemistry 16】 The chemical-mechanical polishing composition of claim 1 , wherein the polishing agent is dulcitol.

10. The nonionic organic molecule is 【Chemistry 17】 maltitol, or [Chemistry 18] The chemical-mechanical polishing composition of claim 1 , wherein the polishing composition is lactitol.

11. 10. The chemical-mechanical polishing composition of claim 1, wherein the solvent is selected from the group consisting of deionized water, distilled water, and alcohol-containing organic solvents.

12. 10. The chemical-mechanical polishing composition of claim 1, wherein the composition comprises 0.0001 wt % to 0.05 wt % of a biocide, and the biocide comprises 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.

13. 2. The chemical mechanical polishing composition of claim 1, wherein the composition comprises 0 wt. % to 1 wt. % of a pH adjuster for acidic pH conditions selected from the group consisting of nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, hydrochloric acid, phosphoric acid, various polycarboxylic acids, and mixtures thereof; or 0 wt. % to 1 wt. % of a pH adjuster for alkaline pH conditions selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetraethylammonium hydroxide, organic quaternary ammonium hydroxide compounds, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof.

14. ceria-coated colloidal silica; 【Chemistry 19】 (In the formula, a is 0 to 50; b and c may be the same or different and each independently ranges from 0 to 50; at least one of b and c is not 0; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 20】 (In the formula, a is 0 to 50; b is 1 to 50; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 21】 (In the formula, a is 0 to 50; b is 1 to 50), 【Chemistry 22】 (In the formula, a is 0 to 50; e and d may be the same or different and each is independently 1 to 12; and (e) Combinations thereof at least one selected from the group comprising: at least one selected from the group consisting of dulcitol, D-sorbitol, maltitol, lactitol, and combinations thereof; Deionized water 10. The chemical-mechanical polishing composition of claim 1, comprising:

15. ceria-coated colloidal silica; 【Chemistry 23】 (In the formula, a is 0 to 10; b and c may be the same or different and each independently ranges from 0 to 10; at least one of b and c is not 0; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 24】 (In the formula, a is 0 to 10; b is 1 to 10; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 25】 (In the formula, a is 0 to 10; b is 1 to 10), 【Chemistry 26】 (In the formula, a is 0 to 10; e and d may be the same or different and each is independently 1 to 12; and (e) Combinations thereof at least one selected from the group comprising: at least one selected from the group consisting of dulcitol, D-sorbitol, maltitol, lactitol, and combinations thereof; Deionized water 10. The chemical-mechanical polishing composition of claim 1, comprising:

16. ceria-coated colloidal silica; 【Chemistry 27】 (In the formula, a is 0 to 50; b and c may be the same or different and each independently ranges from 0 to 50; at least one of b and c is not 0; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 28】 (In the formula, a is 0 to 50; b is 1 to 50; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 29】 (In the formula, a is 0 to 50; b is 1 to 50), 【Transformation 30】 (In the formula, a is 0 to 50; e and d may be the same or different and each is independently 1 to 12; and (e) Combinations thereof at least one selected from the group comprising: at least one selected from the group consisting of dulcitol, D-sorbitol, maltitol, lactitol, and combinations thereof; Biocides containing 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one; Deionized water 10. The chemical-mechanical polishing composition of claim 1, comprising:

17. ceria-coated colloidal silica; 【Chemistry 31】 (In the formula, a is 0 to 10; b and c may be the same or different and each independently ranges from 0 to 10; at least one of b and c is not 0; e and d may be the same or different and each independently is 1 to 12; 【Chemistry 32】 (In the formula, a is 0 to 10; b is 1 to 10; e and d may be the same or different and each independently is 1 to 12; 【Transformation 33】 (In the formula, a is 0 to 10; b is 1 to 10), 【Transformation 34】 (In the formula, a is 0 to 10; e and d may be the same or different and each is independently 1 to 12; and (e) Combinations thereof at least one selected from the group comprising: at least one selected from the group consisting of dulcitol, D-sorbitol, maltitol, lactitol, and combinations thereof; Biocides containing 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one; Deionized water 10. The chemical-mechanical polishing composition of claim 1, comprising:

18. 1. A method for chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising a silicon oxide film, comprising: providing a semiconductor substrate; providing a polishing pad; Providing a chemical mechanical polishing (CMP) composition according to any one of claims 1 to 17; contacting the surface of the semiconductor substrate with the polishing pad and the chemical-mechanical polishing composition; and polishing at least one surface comprising said silicon oxide film; A method comprising:

19. 20. The method of claim 18, wherein the silicon oxide film is a high density plasma deposited tetraethylorthosilicate (TEOS) (HDP) film.

20. 20. The method of claim 18, wherein the semiconductor substrate further comprises a silicon nitride (SiN) surface.

21. 20. The method of claim 18, wherein the silicon oxide film is a high-density plasma deposited tetraethylorthosilicate (TEOS) (HDP) film; the semiconductor substrate further comprises a silicon nitride surface; and the HDP removal rate / SiN removal rate is 70 or greater.

22. 1. A system for chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising a silicon oxide film, comprising: a. a semiconductor substrate; b. the chemical-mechanical polishing (CMP) composition of any one of claims 1 to 17; c. Polishing pad wherein at least one surface comprising the silicon oxide film is in contact with the polishing pad and the chemical-mechanical polishing composition.

23. 23. The system of claim 22, wherein the silicon oxide film is a high density plasma deposited tetraethylorthosilicate (TEOS) (HDP) film.

24. 23. The system of claim 22, wherein the semiconductor substrate further comprises a silicon nitride surface.

25. 23. The system of claim 22, wherein the silicon oxide film is a high-density plasma deposited tetraethylorthosilicate (TEOS) (HDP) film; the semiconductor substrate further comprises a silicon nitride surface; and a HDP removal rate / SiN removal rate is 70 or greater.

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