Low oxide trench recess chemical mechanical polishing

Abstract

Chemical mechanical planarization (CMP) polishing compositions, methods, and systems are provided to reduce oxide trench dishing and improve overpolish window stability. Also provided are high and tunable silicon oxide removal rates, low silicon nitride removal rates, and tunable SiO2:SiN selectivity. The compositions use unique chemical additives, such as maltitol, lactitol, maltitol trihydrate, 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, or combinations thereof, as oxide trench dishing reduction additives.

Description

[0001] Cross-referencing of related patent applications

[0002] This application claims the priority of earlier filed U.S. patent application serial numbers 62 / 692,633 and 62 / 692,639 (filed June 29, 2018) under 35 U.S.SC §119(e), which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention relates to the chemimechanical planarization (CMP) of oxide and doped oxide films. Background Technology

[0004] In the fabrication of microelectronic devices, an important step is polishing, especially for surfaces that are chemically and mechanically polished, with the aim of restoring the selected material and / or planarizing the structure.

[0005] For example, a SiN layer can be deposited under a SiO2 layer to serve as a polishing stop. This polishing stop 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 improved polishing selectivity of silicon dioxide (SiO2) compared to silicon nitride (SiN).

[0006] In the overall planarization of patterned structures, reducing oxide trench dishing is a critical factor to consider. Lower trench oxide loss prevents current leakage between adjacent transistors. Non-uniform trench oxide loss across modes (within the mode) will affect transistor performance and device manufacturing yield. Severe trench oxide loss (high oxide trench dishing) will lead to poor transistor isolation, resulting in device failure. Therefore, it is important to reduce trench oxide loss by minimizing oxide trench dishing in the CMP polishing composition.

[0007] U.S. Patent 5,876,490 discloses a polishing composition containing abrasive particles and exhibiting a normal stress effect. The slurry also contains non-polishing particles, resulting in a reduced polishing rate in recesses, while the abrasive particles maintain a high polishing rate in elevations. This leads to improved planarization. More specifically, the slurry comprises cerium oxide particles and a polymer electrolyte and can be used in shallow trench isolation (STI) polishing applications.

[0008] U.S. Patent 6,964,923 teaches a polishing composition containing cerium oxide particles and a polymeric electrolyte for shallow trench isolation (STI) polishing applications. The polymeric electrolytes used include salts of polyacrylic acid, similar to those in U.S. Patent 5,876,490. Cerium dioxide, alumina, silica, and zirconium oxide are used as abrasives. The molecular weights of the polyelectrolytes listed thus range from 300 to 20,000, but are generally <100,000.

[0009] U.S. Patent 6,616,514 discloses a chemical mechanical polishing slurry for removing a first substance from the surface of an article by chemical mechanical polishing, preferentially over silicon nitride. The chemical mechanical polishing slurry according to this invention comprises an abrasive, an aqueous medium, and a non-dissociating organic polyol, said organic polyol comprising a compound having at least three hydroxyl groups that are non-dissociatable in an aqueous medium, or a polymer formed from at least one monomer having at least three non-dissociatable hydroxyl groups in an aqueous medium.

[0010] U.S. Patent 6,544,892 teaches a polishing composition comprising an abrasive and an organic compound having a carboxylic acid functional group and a secondary functional group selected from amines and halides. Cerium dioxide particles are used as the abrasive.

[0011] However, those previously disclosed shallow trench isolation (STI) polishing compositions did not address the importance of reducing oxide trench depressions.

[0012] As is readily apparent from the foregoing, there remains a need in the art for chemical mechanical polishing compositions, methods, and systems that, in addition to the high removal rate of silica and the high selectivity of silica for silicon nitride, can also provide reduced oxide trench depressions and improved overpolishing window stability during chemical and mechanical polishing (CMP) processes. Summary of the Invention

[0013] The present invention provides chemical mechanical polishing (CMP) compositions, methods, and systems for reducing oxide trench depressions and thus improving the stability of overpolished windows by introducing chemical additives as oxide trench depression reduction additive compositions over a wide pH range (including acidic, neutral, and alkaline pH conditions).

[0014] The present invention also provides the benefits of achieving high oxide film removal rate, low SiN film removal rate, high and tunable oxide:SiN selectivity, low total defect count after polishing and excellent average particle size (nm) stability.

[0015] In one aspect, a CMP polishing composition is provided, the composition comprising:

[0016] Abrasive particles, selected from inorganic oxide particles, metal-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof.

[0017] Chemical additives used as oxide trench depression reducers;

[0018] Solvent; and

[0019] Optional

[0020] biocides; and

[0021] pH adjuster;

[0022] The pH of the composition is 2 to 12, preferably 3 to 10, and more preferably 4 to 9.

[0023] Inorganic oxide particles include, but are not limited to, cerium dioxide, colloidal silica, high-purity colloidal silica, colloidal cerium dioxide, aluminum oxide, titanium dioxide, and zirconium oxide particles.

[0024] An example of cerium dioxide particles is calcined cerium dioxide particles. An example of calcined cerium dioxide particles is calcined cerium dioxide particles manufactured through a grinding process.

[0025] Examples of colloidal cerium dioxide particles are typically produced by chemical reactions and crystallization processes.

[0026] Metal-coated inorganic oxide particles include, but are not limited to, cerium dioxide-coated inorganic oxide particles, such as cerium dioxide-coated colloidal silica, cerium dioxide-coated high-purity colloidal silica, cerium dioxide-coated alumina, cerium dioxide-coated titanium dioxide, cerium dioxide-coated zirconium oxide, or any other cerium dioxide-coated inorganic oxide particles.

[0027] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0028] The metal-coated organic polymer particles are selected from cerium dioxide-coated organic polymer particles, zirconium oxide-coated organic polymer particles, silica-coated organic polymer particles, and combinations thereof.

[0029] Preferred abrasive particles are cerium dioxide-coated inorganic oxide particles and cerium dioxide particles. More preferred abrasive particles are cerium dioxide-coated silica particles and calcined cerium dioxide particles.

[0030] Solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0031] Chemical additives used as oxide trench reduction agents contain at least two or more, preferably four or more, more preferably six or more hydroxyl functional groups in their molecular structure.

[0032] In one embodiment, the chemical additive has the following general molecular structure:

[0033]

[0034] In this general molecular structure, n is selected from 2 to 5,000, 3 to 12, and preferably 4 to 7.

[0035] R1, R2, and R3 can be the same or different atoms or functional groups.

[0036] Each R in the group of R1 to R3 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylate salts, organic carboxylic acid esters, organic amine groups, and combinations thereof; wherein at least two or more, preferably four of them, are hydrogen atoms.

[0037] When R1, R2, and R3 are the same and are hydrogen atoms, the chemical additive carries multiple hydroxyl functional groups.

[0038] The molecular structures of some examples of such chemical additives are listed below:

[0039]

[0040]

[0041] In another embodiment, the chemical additive has the following structure:

[0042]

[0043] In this structure, a -CHO functional group is located at one end of the molecule as a terminal functional group; n is selected from 2 to 5,000, 3 to 12, preferably 4 to 7.

[0044] Each of R1 and R2 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylate salts, organic carboxylic acid esters, organic amine groups, and combinations thereof.

[0045] When R1 and R2 are both hydrogen atoms and n = 3, the chemical additive is D-arabinose or L-arabinose:

[0046]

[0047] When R1 and R2 are both hydrogen atoms and n = 4, the chemical additive is D-mannose or L-mannose:

[0048]

[0049] In yet another embodiment, the chemical additive has a molecular structure selected from the group consisting of at least one (f), at least one (g), at least one (h), and combinations thereof:

[0050]

[0051]

[0052] In these general molecular structures, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 can be the same or different atoms or functional groups.

[0053] They may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylic acids, organic carboxylic esters, organic amine groups, and combinations thereof; wherein at least two or more, preferably four or more, of them are hydrogen atoms.

[0054] When R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 are all hydrogen atoms, they provide chemical additives carrying multiple hydroxyl functional groups.

[0055] The molecular structures of some examples of such chemical additives are listed below:

[0056]

[0057]

[0058]

[0059] In another embodiment, the chemical additive contains at least one six-membered ring motif ether bonded to at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure, or bonded to at least one polyol molecular unit containing multiple hydroxyl functional groups and at least one six-membered ring polyol. The polyol is an organic compound containing hydroxyl groups.

[0060] Chemical additives used as oxide trench reduction agents contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structure.

[0061] The general molecular structure of chemical additives is shown in (a):

[0062]

[0063] In one embodiment, in a general molecular structure, at least one R from the group of R1 to R5 is a polyol molecular unit having the structure shown in (b):

[0064]

[0065] Wherein n and m can be the same or different. m or n is independently selected from 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 to 2; and R6 to R9 can be the same or different atoms or functional groups; and

[0066] The remaining Rs in groups R1 to R5 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines, and combinations thereof.

[0067] In another embodiment, in the general molecular structure, at least one R of the group R1 to R5 is a polyol molecular unit having the structure shown in (b); in the general molecular structure, at least one R of the group R1 to R5 is a six-membered ring polyol as shown in (c):

[0068]

[0069] in

[0070] In structure (c), one of the ORs in groups OR11, OR12, OR13, and OR14 is replaced by an O; and

[0071] Each of the other Rs in the group consisting of R10 and R10, R11, R12, R13 and R14 is independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines and combinations thereof.

[0072] Furthermore, the remaining R in groups R1 to R5 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines, and combinations thereof.

[0073] In a typical molecular structure, at least two, preferably four, and more preferably six of the R atoms in the group R1 to R9 are hydrogen atoms.

[0074] In a typical molecular structure, when only one R (e.g., R5) in the group R1 to R5 is a polyol molecular unit with n=2 and m=1 (b), and all the remaining Rs in the group R1 to R9 are hydrogen atoms, the following two chemical additives are obtained:

[0075]

[0076] When one R (e.g., R5) is a polyol unit (b) with n=2 and m=1, and one R (e.g., R2) is a six-membered ring polyol and the remaining Rs in the group of R1 to R14 are all hydrogen atoms, the following chemical additives are obtained:

[0077]

[0078] Chemical additives include maltitol, lactitol, malttriol, ribitol, D-sorbitol, mannitol, euonymus alcohol, idoteol, D-(-)-fructose, dehydrated sorbitol, sucrose, ribose, inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, mesoerythritol, β-lactose, arabinose, and combinations thereof. Preferred chemical additives are maltitol, lactitol, malttriol, D-sorbitol, mannitol, euonymus alcohol, idoteol, D-(-)-fructose, sucrose, ribose, inositol, glucose, D-mannose, L-mannose, β-lactose, and combinations thereof. More preferred chemical additives are maltitol, lactitol, malttriol, D-sorbitol, mannitol, euonymus alcohol, D-(-)-fructose, β-lactose, and combinations thereof.

[0079] In some embodiments, the CMP polishing composition may be prepared in two or more parts and mixed upon use.

[0080] On the other hand, a method is provided for chemically mechanically polishing (CMP) a substrate having at least one surface containing silicon dioxide (e.g., tetraethyl orthosilicate or TEOS) using the above-described chemical mechanical polishing (CMP) composition.

[0081] On another aspect, a system is provided for performing chemical mechanical polishing (CMP) on a substrate having at least one surface containing silicon dioxide using the above-described chemical mechanical polishing (CMP) composition.

[0082] The polished oxide film can be chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), spin-on silicon oxide, flowable CVD oxide film, carbon-doped oxide film, nitrogen-doped oxide film, or a combination thereof.

[0083] The substrate disclosed above may also include a silicon nitride (SiN) surface. The SiO2:SiN removal selectivity is greater than 10, preferably greater than 20, and more preferably greater than 30. Attached Figure Description

[0084] Figure 1 The effect of the cerium dioxide-coated silica / D-sorbitol ratio on the membrane RR (A / min) was depicted.

[0085] Figure 2 The effect of the silica / D-sorbitol ratio in cerium dioxide coating on oxide trench depressions was depicted. Detailed Implementation

[0086] This invention relates to chemical mechanical polishing (CMP) compositions, methods, and systems for polishing oxide and doped oxide films.

[0087] In the overall planarization of patterned structures, reducing oxide trench depression is a key consideration. Lower trench oxide loss prevents current leakage between adjacent transistors. Non-uniform trench oxide loss across modes and / or within modes will affect transistor performance and device manufacturing yield. Severe trench oxide loss (high oxide trench depression) will lead to poor transistor isolation, resulting in device failure. Therefore, it is important to reduce trench oxide loss by minimizing oxide trench depression in the CMP polishing composition.

[0088] The CMP composition comprises a unique combination of abrasive particles and suitable chemical additives (such as maltitol, lactitol, and malttriol, or any other chemical molecule with similar molecular structure and functional groups).

[0089] This invention provides reduced oxide trench depression and thus improved overpolishing window stability by introducing chemical additives as oxide trench depression reducing additives into chemical mechanical polishing (CMP) compositions over a wide pH range (including acidic, neutral and alkaline pH conditions).

[0090] Chemical mechanical polishing (CMP) compositions offer high oxide film removal rates, low SiN film removal rates, and high SiO2:SiN selectivity.

[0091] When compared with CMP polishing compositions that use calcined cerium dioxide particles as abrasives, this chemical mechanical polishing (CMP) composition also provides a significant reduction in total defect count.

[0092] Chemical mechanical polishing (CMP) compositions further provide excellent average grain size and size distribution stability for abrasive particles, which is crucial for maintaining robust CMP polishing performance and minimizing polishing performance variations.

[0093] In one aspect, a CMP polishing composition is provided, the composition comprising:

[0094] Abrasive particles, selected from inorganic oxide particles, metal-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof.

[0095] Chemical additives used as oxide trench depression reducers;

[0096] Solvent; and

[0097] Optional

[0098] biocides; and

[0099] pH adjuster;

[0100] The pH of the composition is 2 to 12, preferably 3 to 10, and more preferably 4 to 9.

[0101] Inorganic oxide particles include, but are not limited to, cerium dioxide, colloidal silica, high-purity colloidal silica, colloidal cerium dioxide, aluminum oxide, titanium dioxide, and zirconium oxide particles.

[0102] An example of cerium dioxide particles is calcined cerium dioxide particles. An example of calcined cerium dioxide particles is calcined cerium dioxide particles manufactured through a grinding process.

[0103] Examples of colloidal cerium dioxide particles are typically produced by chemical reactions and crystallization processes.

[0104] Metal-coated inorganic oxide particles include, but are not limited to, cerium dioxide-coated inorganic oxide particles, such as cerium dioxide-coated colloidal silica, cerium dioxide-coated high-purity colloidal silica, cerium dioxide-coated alumina, cerium dioxide-coated titanium dioxide, cerium dioxide-coated zirconium oxide, or any other cerium dioxide-coated inorganic oxide particles.

[0105] Organic polymer particles include, but are not limited to, polystyrene particles, polyurethane particles, polyacrylate particles, or any other organic polymer particles.

[0106] The metal-coated organic polymer particles are selected from cerium dioxide-coated organic polymer particles, zirconium oxide-coated organic polymer particles, silica-coated organic polymer particles, and combinations thereof.

[0107] The average particle size (MPS) of abrasive particles ranges from 2 to 1,000 nm, 5 to 500 nm, 15 to 400 nm, or 25 to 250 nm. MPS refers to the diameter of the particles and is measured using dynamic light scattering (DLS) technology.

[0108] The concentration of these abrasive particles ranges from 0.01 wt% to 20 wt%, preferably from 0.05 wt% to 10 wt%, and more preferably from 0.1 wt% to 5 wt%.

[0109] Preferred abrasive particles are cerium dioxide-coated inorganic oxide particles and cerium dioxide particles. More preferred abrasive particles are cerium dioxide-coated silica particles and calcined cerium dioxide particles.

[0110] Solvents include, but are not limited to, deionized (DI) water, distilled water, and alcoholic organic solvents.

[0111] The preferred solvent is DI (dihydrate).

[0112] CMP slurry may contain 0.0001% to 0.05% by weight; preferably 0.0005% to 0.025% by weight, more preferably 0.001% to 0.01% by weight of a biocide.

[0113] Biocides include, but are not limited to, Kathon from Dupont / Dow Chemical Co. TM Kathon TM CG / ICP II, from Bioban of Dupont / Dow Chemical Co. Their active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.

[0114] CMP slurries may contain pH adjusters.

[0115] The polishing composition can be adjusted to an optimized pH value using acidic or alkaline pH adjusters.

[0116] pH adjusters include, but are not limited to, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof.

[0117] pH adjusters also include alkaline pH adjusters, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic quaternary ammonium hydroxide, organic amines, and other chemical reagents that can be used to adjust the pH value towards a more alkaline direction.

[0118] CMP slurry contains 0% to 1% by weight, preferably 0.01% to 0.5% by weight, more preferably 0.1% to 0.25% by weight of pH adjuster.

[0119] CMP slurry contains 0.01% to 20% by weight, 0.025% to 10% by weight, 0.05% to 5% by weight, or 0.1% to 3.0% by weight of chemical additives as oxide trench and total defect count reducers.

[0120] Chemical additives used as oxide trench reduction agents contain at least two or more, preferably four or more, more preferably six or more hydroxyl functional groups in their molecular structure.

[0121] In one embodiment, the chemical additive has the following general molecular structure:

[0122]

[0123] In this general molecular structure, n is selected from 2 to 5,000, 3 to 12, and preferably 4 to 7.

[0124] R1, R2, and R3 can be the same or different atoms or functional groups.

[0125] Each R in the group of R1 to R3 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylic acids, organic carboxylic esters, organic amine groups, and combinations thereof; wherein at least two or more, preferably four, of them are hydrogen atoms.

[0126] When R1, R2, and R3 are the same and are hydrogen atoms, the chemical additive carries multiple hydroxyl functional groups.

[0127] The molecular structures of some examples of such chemical additives are listed below:

[0128]

[0129]

[0130] In another embodiment, the chemical additive has the following structure:

[0131]

[0132] In this structure, a -CHO functional group is located at one end of the molecule as a terminal functional group; n is selected from 2 to 5,000, 3 to 12, preferably 4 to 7.

[0133] R1 and R2 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylic acids, organic carboxylic acid esters, organic amine groups, and combinations thereof.

[0134] When R1 and R2 are both hydrogen atoms and n = 3, the chemical additive is D-arabinose or L-arabinose:

[0135]

[0136] When R1 and R2 are both hydrogen atoms and n = 4, the chemical additive is D-mannose or L-mannose:

[0137]

[0138] In yet another embodiment, the chemical additive has a molecular structure selected from the group consisting of at least one (f), at least one (g), at least one (h), and combinations thereof:

[0139]

[0140] In these general molecular structures, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 can be the same or different atoms or functional groups.

[0141] They may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids, substituted organic sulfonates, substituted organic carboxylic acids, substituted organic carboxylic acids, organic carboxylic esters, organic amine groups, and combinations thereof; wherein at least two or more, preferably four or more, of them are hydrogen atoms.

[0142] When R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 are all hydrogen atoms, they provide chemical additives carrying multiple hydroxyl functional groups.

[0143] The molecular structures of some examples of such chemical additives are listed below:

[0144]

[0145]

[0146] In yet another embodiment, the chemical additive contains at least one six-membered ring motif ether bonded to at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure, or bonded to at least one polyol molecular unit containing multiple hydroxyl functional groups and at least one six-membered ring polyol. The polyol is an organic compound containing hydroxyl groups.

[0147] Chemical additives used as oxide trench reduction agents contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structure.

[0148] The general molecular structure of chemical additives is shown in (a):

[0149]

[0150] In one embodiment, in a general molecular structure, at least one R from the group of R1 to R5 is a polyol molecular unit having the structure shown in (b):

[0151]

[0152] Wherein n and m can be the same or different. m or n is independently selected from 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 to 2; and R6 to R9 can be the same or different atoms or functional groups; and

[0153] The remaining Rs in groups R1 to R5 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines, and combinations thereof.

[0154] In another embodiment, in the general molecular structure, at least one R from the group of R1 to R5 is a polyol molecular unit having the structure shown in (b); in the general molecular structure, at least one R from the group of R1 to R5 is a six-membered ring polyol as shown in (c):

[0155]

[0156] in

[0157] In structure (c), one of the ORs in groups OR11, OR12, OR13, and OR14 is replaced by an O; and

[0158] Each of the other Rs in the group consisting of R10 and R10, R11, R12, R13 and R14 is independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines and combinations thereof.

[0159] Furthermore, the remaining R in groups R1 to R5 may be independently selected from hydrogen, alkyl, alkoxy, organic groups having one or more hydroxyl groups, substituted organic sulfonic acids or salts, substituted organic carboxylic acids or salts, organic carboxylic acid esters, organic amines, and combinations thereof.

[0160] In a typical molecular structure, at least two, preferably four, and more preferably six of the R atoms in the group R1 to R9 are hydrogen atoms.

[0161] In a typical molecular structure, when only one R (e.g., R5) in the group R1 to R5 is a polyol molecular unit with n=2 and m=1 (b), and all the remaining Rs in the group R1 to R9 are hydrogen atoms, the following two chemical additives are obtained:

[0162]

[0163] When one R (e.g., R5) is a polyol unit (b) with n=2 and m=1, and one R (e.g., R2) is a six-membered ring polyol and the remaining Rs in the group of R1 to R14 are all hydrogen atoms, the following chemical additives are obtained:

[0164]

[0165] Chemical additives include maltitol, lactitol, malttriol, ribitol, D-sorbitol, mannitol, euonymus alcohol, idoteol, D-(-)-fructose, dehydrated sorbitol, sucrose, inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, mesoerythritol, ribose, β-lactose, and combinations thereof. Preferred chemical additives are maltitol, lactitol, malttriol, D-sorbitol, mannitol, euonymus alcohol, idoteol, D-(-)-fructose, sucrose, ribose, inositol, glucose, D-(+)-mannose, β-lactose, and combinations thereof. More preferred chemical additives are maltitol, lactitol, malttriol, D-sorbitol, mannitol, euonymus alcohol, D-(-)-fructose, β-lactose, and combinations thereof.

[0166] In some embodiments, the CMP polishing composition may be prepared in two or more parts and mixed upon use.

[0167] On the other hand, a method is provided for chemically mechanically polishing (CMP) a substrate having at least one surface containing silicon dioxide using the above-described chemical mechanical polishing (CMP) composition. The polished oxide film can be a CVD oxide, a PECVD oxide, a high-density oxide, or a spin-formed oxide film.

[0168] The polished oxide film can be chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), spin-formed oxide film, flowable CVD oxide film, carbon-doped oxide film, nitrogen-doped oxide film, or a combination thereof.

[0169] The substrate disclosed above may also include a silicon nitride (SiN) surface. The SiO2:SiN removal selectivity is greater than 10, preferably greater than 20, and more preferably greater than 30.

[0170] The indentation properties of CMP compositions can also be assessed by the indentation rate of oxide trenches. Removal rate of blank HDP membrane It is characterized by the ratio.

[0171] The smaller the ratio, the lower the oxide trench depression.

[0172] CMP compositions with ratios of ≤0.1, 0.08, 0.06, 0.05, 0.03, or 0.02 provide good oxide pitting properties.

[0173] In CMP polishing compositions, it is important to maintain the stability of abrasive particles to ensure consistent desired CMP polishing performance.

[0174] When chemical additives are used in CMP polishing compositions, these additives may have some effect on the stability of the abrasive particles in the composition.

[0175] For example, when maltitol, lactitol, or their derivatives are used as oxide groove reducers in polishing compositions, these chemical additives can have some impact on the stability of cerium dioxide-coated inorganic oxide abrasives in CMP polishing compositions.

[0176] Typically, abrasive particle stability is tested by monitoring changes in average particle size (MPS) (nm) and particle size distribution parameter D99 (nm) relative to time or at elevated temperatures.

[0177] Particle size distribution can be quantified as the weight percentage of particles with a size smaller than a specified size. For example, the parameter D99(nm) represents the particle size (diameter) of 99% by weight of all slurry particles. In other words, D99(nm) is the particle size at which 99% by weight of the particles fall below D99(nm).

[0178] The smaller the variation in MPS (nm) and D99 (nm), the more stable the abrasive particles, and therefore the more stable the CMP polishing composition.

[0179] Particle size distribution can be measured using any suitable technique, such as imaging, dynamic light scattering, fluid dynamics, fluid classification, disc centrifuges, etc.

[0180] In this application, both MPS (nm) and D99 (nm) are measured by dynamic light scattering.

[0181] The CMP compositions providing abrasive particle stability exhibit changes in MPS (nm) and D99 (nm) of ≤6.0%, 5.0%, 3.0%, 2.0%, 1.0%, 0.5%, 0.3%, or 0.1% over a shelf life of at least 30, 40, 50, 60, 70, or 100 days at temperatures of 20 to 60°C and 25 to 50°C, respectively.

[0182] The following non-limiting embodiments are provided to further describe the invention.

[0183] CMP method

[0184] In the embodiments given below, CMP experiments are performed using the procedures and experimental conditions described below.

[0185] Vocabulary

[0186] Components

[0187] Calcined cerium dioxide particles: used as abrasives with a particle size of about 150 nanometers (nm); the particle size range of these cerium dioxide-coated silica particles can be from about 5 nanometers (nm) to 500 nanometers (nm).

[0188] Cerium dioxide-coated silica: used as an abrasive with a particle size of about 100 nanometers (nm); the particle size of such cerium dioxide-coated silica particles can be from about 5 nanometers (nm) to 500 nanometers (nm).

[0189] The cerium dioxide-coated silica particles (of different sizes) were supplied by JGC Inc. of Japan.

[0190] Chemical additives, such as D-sorbitol, euonymus alcohol, fructose, maltitol, lactitol, and other chemical raw materials, are supplied by Sigma-Aldrich, St. Louis, MO.

[0191] TEOS: Tetraethyl orthosilicate.

[0192] Polishing pads: Polishing pads IC1010 and other pads are used in the CMP process and are supplied by DOW, Inc.

[0193] parameter

[0194] General

[0195] Or A: Angstrom—a unit of length

[0196] BP: Back pressure, unit: psi

[0197] CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing

[0198] CS: Carrier speed

[0199] DF: Downward force: The pressure applied during CMP, in psi.

[0200] min: minutes

[0201] ml: milliliters

[0202] mV: millivolt

[0203] psi: pounds per square inch

[0204] PS: The table rotation speed of the polishing equipment is in rpm (revolutions per minute).

[0205] SF: Slurry flow rate, ml / min

[0206] % by weight: (the weight percentage of the listed components)

[0207] TEOS:SiN Selectivity: (TEOS Removal Rate) / (SiN Removal Rate)

[0208] HDP: High-density plasma-deposited TEOS

[0209] TEOS or HDP removal rate: The TEOS or HDP removal rate measured at a given downpressure. In the examples, the downpressure of the CMP device is 2.5 psi, 3.0 psi, 3.3 psi, or 4.3 psi.

[0210] SiN removal rate: The SiN removal rate measured at a given downpressure. In the listed examples, the downpressure of the CMP device is 3.0 psi.

[0211] Measurement

[0212] The film was measured using a ResMap CDE, Model 168, manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA 95014. The ResMap device is a four-point probe thin-film resistance instrument. For the film, a 49-point diameter scan was performed (excluding the 5mm edge).

[0213] CMP equipment

[0214] The CMP equipment used was a 200mm Mirra or 300mm Reflexion manufactured by Applied Materials, 3050 Bowers Avenue, Santa Clara, California, 95054. IC1000 pads supplied by DOW, Inc., 451 Bellevue Rd., Newark, DE 19713 were used on stage 1 for blank and patterned wafer studies.

[0215] Run in the IC1010 pad or other pads by conditioning the pad for 18 minutes. Apply a 7 lbs downforce on the conditioner. To determine the suitability of the equipment setup and pad run-in, use the equipment provided by Versum Materials Inc. under baseline conditions. STI2305 slurry was used to polish two tungsten monitoring objects and two TEOS monitoring objects.

[0216] Chips

[0217] Polishing experiments were conducted using PECVD, LECVD, or HD TEOS wafers. These blank wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, CA 95051.

[0218] Polishing experiment

[0219] In the blank wafer study, oxide blank wafers and SiN blank wafers were polished under baseline conditions. The equipment baseline conditions were: stage speed: 87 rpm; head speed: 93 rpm; membrane pressure: 2.5 psi, 3.0 psi, 3.3 psi, or 4.3 psi; tube pressure: 3.1 psi or other; holding ring pressure: 5.1 psi or other.

[0220] The paste was used for polishing experiments on patterned wafers (MIT860) supplied by SWK Associates, Inc. 2920 Scott Blvd. Santa Clara, CA 95054. These wafers were measured using a Veeco VX300 analyzer / AFM instrument. Three different pitch structures were used for oxide recess measurements. Measurements were taken at the center, middle, and edge die locations.

[0221] The TEOS:SiN selectivity obtained from the CMP polishing composition, : (TEOS removal rate) / (SiN removal rate), is adjustable.

[0222] Working Example

[0223] In the following working examples, a polishing composition comprising 0.2 wt% cerium dioxide-coated silica, 0.0001 wt% to 0.05 wt% biocide and deionized water was prepared as a reference (comparison).

[0224] A polishing composition was prepared using a reference (0.2 wt% cerium dioxide-coated silica, 0.0001 wt% to 0.05 wt% biocide and deionized water) plus 0.01 wt% to 2.0 wt% chemical additives.

[0225] Except for the pH condition examples, the pH of the compositions in all examples was 5.35.

[0226] The pH adjusters used for acidic and alkaline pH conditions are nitric acid and ammonium hydroxide, respectively.

[0227] Example 1

[0228] The working slurry contains 0.15% by weight of chemical additives, which are added to the reference slurry.

[0229] The effects of various selected chemical additives on membrane removal rate and selectivity were observed.

[0230] Test the removal rate (RR) for different membranes. (Calculation). The test results are listed in Table 1.

[0231] Table 1. Effects of chemical additives on membrane RR The effect of TEOS:SiN selectivity

[0232]

[0233]

[0234] As shown in Table 1, the slurry based on cerium dioxide-coated silica provides a higher removal rate for TEOS.

[0235] As further shown in Table 1, compared to the reference, the chemical additives D-sorbitol, D-mannitol, D-mannose and xylitol, in addition to meso-erythritol, inhibited the SiN removal rate while still providing high TEOS and HDP membrane removal rates and high oxide:SiN selectivity.

[0236] Example 2

[0237] In Example 2, a formulation based on 0.2% by weight of cerium dioxide coated with silica abrasive without chemical additives was used as a reference.

[0238] Chemical additives were used at a concentration of 0.15% by weight (0.15X), of which 0.2% by weight of cerium dioxide-coated silica served as an abrasive in the working slurry.

[0239] The effects of various selected chemical additives on the relative overpolishing time of oxide groove depressions were observed.

[0240] The test results are listed in Table 2. The HDP RR in Table 1... Also listed in Table 2.

[0241] Table 2. Effects of chemical additives on oxide trench depressions and HDP RR Impact

[0242]

[0243] Table 3. Trench Indentation Rate / Blank HDP RR ratio

[0244]

[0245] Table 3 lists the oxide trench indentation rates. Removal rate compared with blank HDP membrane The ratio.

[0246] As shown in Tables 2 and 3, the addition of various chemical additives to the polishing composition as oxide groove and depression reducing agents exhibits different effects.

[0247] Compared to the reference, the polishing compositions using D-sorbitol and D-mannitol provided significant reductions in oxide groove depressions at both 100 μm and 200 μm pitches.

[0248] Compared to the reference, the polishing composition using xylitol showed no effect on oxide groove depression during polishing. The oxide groove depression was worse than the reference when using polishing compositions using D-(+)-mannose or racemic erythritol.

[0249] Table 4 lists the effect of chemical additives on the slope of the relative over-polishing removal of oxide grooves and depressions.

[0250] Table 4. Effect of chemical additives on the slope of relative OP removal from depressions

[0251]

[0252]

[0253] As shown in Table 4, the polishing compositions using D-sorbitol or D-mannitol provided much lower slope values ​​for the relative overpolishing of oxide trenches at the 100 μm and 200 μm features compared to the reference.

[0254] Compared to the reference, other additives did not provide improvement in depressions.

[0255] Example 3

[0256] Observe the effect of various selected chemical additives on membrane removal rate (RR, in terms of...) The effects of (calculation) and selectivity. These chemical additives were used at a concentration of 0.1% by weight, of which 0.2% by weight of cerium dioxide-coated silica was used as an abrasive.

[0257] The test results are listed in Table 5.

[0258] Table 5. Effects of chemical additives on membrane RR The effect of TEOS:SiN selectivity

[0259]

[0260] The results are shown in Table 5. Compared with the reference, these chemical additives, D-sorbitol, D-(-)-fructose, maltitol and euonymus alcohol, inhibited the SiN removal rate, but still provided high TEOS and HDP membrane removal rates.

[0261] Table 6. Effects of chemical additives on oxide trench depressions and HDP RR Impact

[0262]

[0263]

[0264] CMP compositions containing D-(-)-fructose inhibit the removal of TEOS in addition to SiN, but still provide high TEOS:SiN selectivity.

[0265] The effects of various selected chemical additives on the relative overpolishing time of oxide groove depressions were observed.

[0266] The test results are listed in Table 6. The HDP RR in Table 5... Also listed in Table 6.

[0267] As shown in Table 6, the results of oxide trench retraction relative to overpolishing time indicate that the CMP composition with chemical additives provides lower oxide trench retraction at both 100 μm and 200 μm pitches. Compared to the reference composition, this composition provides a significant reduction in oxide trench retraction.

[0268] Table 7 lists the oxide trench indentation rates. Relative removal rate of blank HDP membrane The ratio.

[0269] Table 7. Trench Indentation Rate / Blank HDP RR ratio

[0270]

[0271] As shown in Table 7, the addition of chemical additives to the polishing composition significantly reduced the ratio of trench indentation rate to blank HDP film removal rate compared to the ratio obtained from the reference sample at pH 5.35.

[0272] Table 8 lists the slope of the relative oxide overpolishing amount for various sizes of pitched recesses.

[0273] As shown in Table 8, the slope results of the spacing recesses of various sizes relative to oxide overpolishing indicate that the CMP polishing compositions based on chemical additives and cerium dioxide-coated silica abrasives provide slope values ​​that are much lower than those obtained for the reference samples.

[0274] Table 8. Effect of chemical additives on the slope of relative OP removal from depressions

[0275]

[0276] Example 4

[0277] In Example 4, the removal rate and TEOS:SiN selectivity were tested at pH 5.35 with CMP polishing compositions containing different concentrations of chemical additives.

[0278] The test results are listed in Table 9.

[0279] Table 9. Effect of additive concentration on membrane RR Effect of oxides on SiN selectivity

[0280]

[0281] As shown in Table 9, similar TEOS removal rates were obtained when the concentration of D-sorbitol used in the composition increased, and the HPD membrane removal rate increased, and the TEOS:SiN selectivity was also slightly or significantly improved.

[0282] The effect of the concentration of the selected chemical additive D-sorbitol on the relative overpolishing time of oxide grooves was tested for various size spacing features.

[0283] The test results are listed in Table 10.

[0284] Table 10. Effect of D-sorbitol concentration on relative OP time (seconds) of oxide groove depressions

[0285]

[0286] As shown in Table 10, all three CMP polishing compositions containing different concentrations of D-sorbitol exhibited low oxide trench depressions at both 100 μm and 200 μm pitches.

[0287] Furthermore, as the concentration of the chemical additive D-sorbitol increases, the oxide groove depressions are further reduced.

[0288] Table 11. Trench Indentation Rate / Blank HDP RR The ratio relative to the concentration of D-sorbitol

[0289]

[0290] Table 11 lists the groove indentation rates of compositions with different concentrations of D-sorbitol. / Blank HDP RR The ratio.

[0291] As shown in Table 11, the D-sorbitol used in the composition at pH 5.35 significantly reduced the ratio of trench indentation rate to blank HDP membrane removal rate at different test concentrations.

[0292] Therefore, D-sorbitol can be used as an effective oxide groove and pit reduction agent over a wide concentration range.

[0293] The slope of the relative oxide overpolishing amount for various sizes of pitched recesses was tested, and the results are listed in Table 12.

[0294] Table 12. Effect of additive concentration on the slope of relative OP removal in depressions

[0295]

[0296] As shown in Table 12, the slope results of the spacing recesses of various sizes relative to the amount of oxide overpolishing are similar to those of the reference sample, with different concentrations of D-sorbitol in the CMP polishing composition providing similar slope values.

[0297] Furthermore, with increasing D-sorbitol concentration, the slope of the spacing recesses of various sizes relative to oxide overpolishing (although at an overpolishing time of zero seconds) gradually decreased.

[0298] Example 5

[0299] In Example 5, CMP polishing compositions with different pH values ​​were used for testing.

[0300] Compositions comprising 0.2 wt% cerium dioxide-coated silica as an abrasive and 0.1 wt% D-sorbitol as a chemical additive were tested under three different pH conditions.

[0301] Test the removal rate (RR) of different membranes. (Calculation). The test results are listed in Table 13.

[0302] Table 13. pH effect on membrane RR Effect of oxides on the selectivity of SiN

[0303]

[0304] As shown in Table 10, the composition exhibits consistent performance by providing high TEOS and HDP membrane removal rates, low SiN removal rates, and high TEOS:SiN selectivity under acidic, neutral, or alkaline pH conditions.

[0305] Table 14 lists the test results of the effect of pH conditions on the relative overpolishing time of oxide trench depressions using the CMP polishing composition.

[0306] As shown in Table 14, similar oxide trench reduction relative overpolishing time and HDP film removal rate were obtained for silica coated with cerium dioxide as an abrasive and D-sorbitol as an oxide trench reduction agent at the same concentration under three different pH conditions.

[0307] Table 14. Effects of pH conditions on relative overpolishing time (seconds) of oxide trenches and HDP film RR Impact

[0308]

[0309] Table 15 shows the trench indentation rate. / Blank HDP RR The result of the ratio.

[0310] Table 15. Groove indentation rate at different pH values / Blank HDP RR ratio

[0311]

[0312] As shown in Table 15, the addition of D-sorbitol, a chemical additive used as an oxide groove indentation reducer, to the polishing composition under different pH conditions showed a significantly reduced ratio, indicating that D-sorbitol can be used as a very effective oxide groove indentation reducer over a wide pH window.

[0313] Example 6

[0314] In Example 6, the effects of various selected chemical additives from the types of chemical additives listed above on membrane removal rate and selectivity were observed.

[0315] All test chemical additives were used at the same molar concentration of 8.132 mM.

[0316] Except for the examples tested under pH conditions, the pH for all examples was 5.35.

[0317] For the examples used in pH condition testing, the pH adjusters for acidic and alkaline pH conditions are nitric acid and ammonium hydroxide, respectively.

[0318] The removal rates (RR) of different membranes were tested. (Calculation) and removal of selectivity. The test results are listed in Table 16.

[0319] Table 16.8. Effects of 132 mM concentration of chemical additives on membrane RR The effect of TEOS:SiN selectivity

[0320]

[0321] As shown in Table 16, when these chemical additives were used in the polishing composition at a concentration of 8.132 mM, they provided similar TEOS film removal rates, HDP film removal rates, and slightly or significantly suppressed SiN removal rates compared to the reference.

[0322] Oxides: SiN selectivity fluctuated from slightly increased (arabinose, inositol) to significantly increased (maltitol, ribose, and β-lactose). Among the chemicals tested, maltitol showed to be the most effective SiN removal rate inhibitor, while ribose and β-lactose also showed to be very effective SiN removal rate inhibitors.

[0323] Example 7

[0324] The following chemical additives were used in the polishing composition: maltitol, D-sorbitol, lactitol, ribose, and β-lactose, along with 0.2% by weight of cerium dioxide-coated silica abrasive at pH 5.35, for polishing oxide-patterned wafers in polishing tests. The chemical additives were used in the composition at 0.15% by weight.

[0325] The effects of various chemical additives on membrane removal rate and selectivity were observed.

[0326] The test results are listed in Table 17.

[0327] Table 17. Effects of chemical additives on membrane RR The effect of TEOS:SiN selectivity

[0328]

[0329] As shown in Table 17, all compositions provided similar high TEOS membrane removal rates, increased HDP membrane removal rates, significantly suppressed SiN removal rates, and significantly improved oxide:SiN selectivity compared to the reference samples.

[0330] The effects of various chemical additives on the relative overpolishing time of oxide trench depressions were observed. These chemical additives were used at a concentration of 0.15 wt% (0.15X), with 0.2 wt% cerium dioxide-coated silica as the abrasive, and all formulations were at a pH of 5.35.

[0331] The test results are listed in Table 18.

[0332] As shown in Table 18, the results of oxide trench retraction relative to overpolishing time show that when used in CMP polishing compositions with cerium dioxide-coated silica abrasives, all these chemical additives provide significantly reduced oxide trench retraction relative to 60 seconds or 120 seconds for 100 μm and 200 μm pitch features, respectively, compared to the reference, and provide a significant reduction in oxide trench retraction.

[0333] Table 18. Effects of chemical additives on oxide trench depressions and HDP RR Impact

[0334]

[0335] As shown in Table 18, the results of oxide trench retraction relative to overpolishing time show that when used in CMP polishing compositions with cerium dioxide-coated silica abrasives, all these chemical additives provided significantly reduced oxide trench retraction relative to overpolishing times of 60 seconds and 120 seconds, respectively, for 100 μm and 200 μm pitch features, compared to the reference, and provided a significant reduction in oxide trench retraction.

[0336] Table 19 shows the trench indentation rate. / Blank HDP RR The result of the ratio.

[0337] Table 19. Trench Indentation Rate / Blank HDP RR ratio

[0338]

[0339] As shown in Table 19, all the tested polishing compositions using chemical additives exhibited a significant reduction in the ratio of trench indentation rate to blank HDP film removal rate, indicating that all these chemical additives can be used as very effective oxide trench indentation reduction agents in the CMP polishing compositions of the present invention.

[0340] Working Example 8

[0341] A polishing composition was prepared using a reference (0.2 wt% cerium dioxide-coated silica, 0.0001 wt% to 0.05 wt% biocide and deionized water), with maltitol or lactitol used at 0.28 wt%.

[0342] The pH of all example compositions was 5.35.

[0343] Test the removal rate (RR) of different membranes. (Calculation). The effects of two selected chemical additives—maltitol and lactitol—on membrane removal rate and selectivity were observed.

[0344] The test results are listed in Table 20.

[0345] Table 20. Effects of maltitol or lactitol on membrane RR The effect of TEOS:SiN selectivity

[0346]

[0347] As shown in Table 20, the addition of chemical additives—maltitol or lactitol—to the polishing composition significantly inhibited the SiN removal rate while still providing high TEOS and HDP film removal rates, thus significantly improving the polishing selectivity of oxide:SiN films.

[0348] Example 9

[0349] The example composition from Example 8 is used in this example.

[0350] Test oxide trench retractions with / without chemical additives at different overpolishing times. Observe the effect of maltitol or lactitol on oxide trench retractions relative to overpolishing time.

[0351] The test results are listed in Table 21.

[0352] Table 21. Effect of maltitol or lactitol on relative OP time (seconds) of oxide groove depression

[0353]

[0354] As shown in Table 21, the polishing compositions with added chemical additives—maltitol or lactitol—provided low oxide trench depressions at 100 μm and 200 μm pitches, respectively, when an overpolishing time of 60 seconds or 120 seconds was applied.

[0355] Compared to reference compositions that do not contain chemical additives—maltitol or lactitol—this composition provides a significant reduction in oxide groove depressions.

[0356] Table 22 shows the trench indentation rate. / Blank HDP RR The result of the ratio.

[0357] Table 22. Trench Indentation Rate / Blank HDP RR ratio

[0358]

[0359] As shown in Table 22, the addition of maltitol or lactitol to the polishing composition as an oxide trench reduction agent significantly reduced the ratio of trench indentation rate to blank HDP film removal rate. The lower the ratio, the lower the oxide trench indentation.

[0360] The slope of oxide trench depression relative to OP removal is shown in Table 23.

[0361] Table 23. Effect of maltitol or lactitol on the slope of relative OP removal in the depression

[0362]

[0363] The results listed in Table 23 indicate that compositions with chemical additives—maltitol or lactitol—provide a lower slope, which suggests a good overpolishing window for maintaining low oxide trench depressions, even when more oxide film is removed during the overpolishing step.

[0364] As shown in Table 23, the CMP polishing compositions based on these chemical additives—maltitol or lactitol—and cerium-coated silica again exhibit much lower slope values ​​compared to the slope values ​​obtained for reference samples based on cerium-coated silica abrasives.

[0365] Example 10

[0366] In Example 10, the rate of groove oxide loss using maltitol or lactitol and a reference polishing composition was compared, as shown in Table 24.

[0367] Table 24. Effects of maltitol or lactitol on trench loss rate Impact

[0368]

[0369] As shown in Table 24, the addition of maltitol or lactitol to the polishing composition as an oxide groove reduction agent significantly reduced the groove loss rate compared to the reference sample without any chemical additives.

[0370] Example 11

[0371] The compositions were prepared as shown in Table 19.

[0372] The composition uses 0.2 wt% cerium dioxide-coated silica as an abrasive, 0.28 wt% lactitol as a chemical additive, a biocide, deionized water, and a pH adjuster to provide different pH conditions.

[0373] Test the removal rate (RR) of different membranes. (Calculation). Observe the effect of pH conditions on membrane removal rate and selectivity.

[0374] The test results are listed in Table 25.

[0375] Table 25. pH effect on membrane RR Effect of oxides on SiN selectivity

[0376]

[0377] As shown in Table 25, adding lactitol as an oxide trench reduction agent to the polishing composition under three different pH conditions (acidic, neutral, or alkaline) yielded similar TEOS and HDP film removal rates, effectively suppressed SiN film removal rates, and produced much higher TEOS:SiN selectivity than the reference sample without lactitol as a chemical additive.

[0378] The relative overpolishing time of oxide trenches with / without lactitol as a chemical additive was tested.

[0379] The effect of lactitol-containing polishing compositions on the relative overpolishing time of oxide grooves under different pH conditions was observed.

[0380] The test results are listed in Table 26.

[0381] As shown in Table 26, the polishing compositions with lactitol added under different pH conditions provided low oxide trench depressions at 100 μm and 200 μm pitches, respectively, when applied with overpolishing times of 60 seconds or 120 seconds.

[0382] Compared to a reference polishing composition without the chemical additive lactitol, the composition having lactitol as an oxide trench reduction agent provides a significant reduction in oxide trenches.

[0383] Table 26. Effect of lactitol on relative OP time (seconds) of oxide trench depression under different pH conditions

[0384]

[0385] Table 27 depicts the trench indentation rate at different pH values. / Blank HDP RR The ratio.

[0386] Table 27. Trench indentation rate at different pH values / Blank HDP RR ratio

[0387]

[0388] As shown in Table 27, compared with the ratio obtained for the reference sample at pH 5.35, the addition of lactitol as an oxide trench reduction agent to the polishing composition significantly reduced the ratio of trench indentation rate to blank HDP membrane removal rate under different pH conditions.

[0389] Table 28 shows the slope of the relative OP removal amount of oxide trench depressions under different pH conditions.

[0390] Table 28. Effect of lactitol on the slope of relative OP removal in depressions at different pH levels

[0391]

[0392] The results listed in Table 28 show that compositions with the chemical additive lactitol provided a lower slope for the relative overpolishing removal of groove depressions under different pH conditions, indicating a good overpolishing window for maintaining low oxide groove depressions, even when more oxide film is removed in the overpolishing step.

[0393] As shown in Table 28, the CMP polishing compositions based on lactitol and cerium-coated silica again exhibited much lower slope values ​​under different pH conditions compared to the slope values ​​obtained for the reference sample of cerium-coated silica abrasive at pH 5.35.

[0394] In Example 11, the groove oxide loss rate of polishing compositions using lactitol under different pH conditions or without lactitol at pH 5.35 was compared and is listed in Table 29.

[0395] Table 29. Effects of lactitol on trench loss rate under different pH conditions Impact

[0396]

[0397] As shown in Table 29, compared with the reference sample without lactitol as a chemical additive, adding lactitol as an oxide groove reduction agent to the polishing composition under different pH conditions significantly reduced the groove loss rate.

[0398] Polishing test results obtained using lactitol as an oxide groove reduction agent under different pH conditions demonstrate that the CMP polishing composition can be used over a wide pH range, including acidic, neutral, or alkaline pH conditions.

[0399] Example 12

[0400] When suitable chemical additives (such as maltitol or lactitol or their derivatives) are used as oxide trench reducers in polishing compositions, these chemical additives can have some effect on the stability of cerium dioxide-coated inorganic oxide abrasives in CMP polishing compositions.

[0401] In CMP polishing compositions, good abrasive particle stability is crucial to ensure consistent and ideal CMP polishing performance.

[0402] Typically, abrasive particle stability is tested by monitoring changes in MPS (nm) (mean particle size) and D99 (nm) relative to time or at elevated temperatures. The smaller the changes in MPS (nm) and D99 (nm), the more stable the polishing composition of the present invention.

[0403] In this embodiment, the stability of cerium dioxide-coated silica abrasive particles in a composition with chemical additives is monitored by measuring changes in average particle size and particle size distribution D99.

[0404] The test sample was prepared using the following: 0.2 wt% or other wt% cerium dioxide-coated silica abrasive; very low concentration of biocide; 0.15 wt% maltitol, 0.15 wt% lactitol or 0.0787 wt% inositol as an oxide trench reduction agent; and the pH was adjusted to 5.35.

[0405] The abrasive stability of the polishing composition was tested at 50°C for at least 10 days or longer.

[0406] The MPS (nm) or D99 (nm) of the tested polishing composition was measured using DLS technology (DLS = Dynamic Light Scattering).

[0407] The stability test results of the cerium dioxide-coated silica abrasives used with chemical additives are listed in Table 30.

[0408] Table 30. Particle size stability (MPS) test results @50℃ - D99 (nm)

[0409]

[0410] By day 4, at 50°C, the MPS changes of 0.2% by weight cerium dioxide coated silica particles in compositions containing 0.15% by weight maltitol, 0.15% by weight lactitol, and 0.0787% by weight inositol were 0.23%, 0.34%, and 0.39%, respectively.

[0411] By day 18, at 50°C, the average particle size change of 0.2% by weight cerium dioxide-coated silica particles in the composition containing 0.15% by weight maltitol was less than 1.9%.

[0412] By day 11, at 50°C, the average particle size change of 0.2 wt% cerium dioxide-coated silica particles in the composition having 0.0787 wt% inositol was less than 0.83%.

[0413] By day 32, at 50°C, the average particle size change of 0.2% by weight cerium dioxide-coated silica particles in the composition containing 0.15% by weight lactitol was less than 1.3%.

[0414] Table 31 lists more stability tests.

[0415] Table 31. Particle size stability test results @50℃ - MPS (nm) and D99 (nm)

[0416]

[0417] By day 62, at 50°C, the average particle size and D99 changes of 0.2 wt% cerium dioxide-coated silica particles in the composition containing 0.15 wt% maltitol were less than 8.34 × 10⁻⁶. -4 and 0.63%.

[0418] In addition, particle stability tests were also conducted at 50°C on polishing compositions containing a higher concentration of cerium dioxide-coated silica abrasive (greater than 0.2% by weight) and a higher concentration of maltitol (greater than 0.15% by weight) as an oxide trenching reducer.

[0419] The test results are listed in Table 32.

[0420] Table 32. Particle size stability test results @50℃ - MPS (nm) and D99 (nm)

[0421]

[0422] Data shows that by day 42, at 50°C, the MPS and D99 changes of 0.8 wt% cerium dioxide-coated silica particles in a composition containing 0.6 wt% maltitol were less than 0.41% and less than 0.23%, respectively.

[0423] The data also showed that by day 42, at 50°C, the MPS and D99 changes of 0.8 wt% cerium dioxide-coated silica particles in the composition containing 0.6 wt% maltitol were less than 0.41% and less than 0.23%, respectively.

[0424] By day 42, at 50°C, the MPS and D99 changes of 1.6% by weight of cerium dioxide-coated silica particles in the composition containing 1.2% by weight of maltitol were less than 1.2% and less than 1.6%, respectively.

[0425] By day 42, at 50°C, the MPS and D99 changes of 2.4 wt% cerium dioxide-coated silica particles in the composition containing 1.8 wt% maltitol were less than 0.33% and less than 0.23%, respectively.

[0426] As shown in Tables 30 to 32, when maltitol, lactitol, or inositol are used as oxide trench reduction agents with cerium dioxide-coated silica particles as abrasives, the polishing compositions exhibit very good particle size stability of MPS (nm) and D99 (nm) even at elevated test temperatures.

[0427] Polishing compositions containing cerium dioxide-coated colloidal silica abrasives and higher concentrations of maltitol as an oxide trenching reducer both exhibited very good particle size stability (MPS, nm) and D99 (nm) at elevated temperatures.

[0428] Example 13

[0429] Another key benefit of using the CMP polishing composition of the present invention is the reduction in the total defect count during and after polishing, which is achieved by using cerium dioxide-coated colloidal silica composite particles as abrasives instead of calcined cerium dioxide particles.

[0430] Three polishing compositions were prepared for defect testing. The first sample was prepared using 0.5 wt% calcined cerium dioxide abrasive, 0.05 wt% polyacrylate, and a low concentration of biocide; the second sample was prepared using 0.2 wt% cerium dioxide-coated silica abrasive, 0.28 wt% maltitol, and a low concentration of biocide; the third sample was prepared using 0.2 wt% cerium dioxide-coated silica abrasive, 0.28 wt% lactitol, and a low concentration of biocide. To obtain similar dielectric film removal rates for comparison, a higher concentration of calcined cerium dioxide abrasive was used in sample 1.

[0431] The pH value of all three formulations was 5.35.

[0432] The total defect counts on polished TEOS and SiN wafers were compared using the three polishing compositions listed above. The total defect count results are listed in Table 33.

[0433] Table 33. Effect of different polishing compositions on the total defect count of TEOS and SiN

[0434]

[0435] As shown in Table 33, the total defect count results show that, compared to the total defect count obtained using a polishing composition containing calcined cerium dioxide abrasive and polyacrylate as a chemical additive, the polishing composition using cerium dioxide-coated silica particles as abrasive and maltitol or lactitol as a trench recess reducer provides a significantly lower total defect count on polished TEOS and SiN wafers.

[0436] Example 14

[0437] The following four polishing compositions were prepared for defect testing.

[0438] The first two polishing compositions used calcined cerium dioxide abrasive, 0.28 wt% maltitol or 0.28 wt% lactitol as an oxide trench reducer and a low concentration of biocide; the other two polishing compositions used cerium dioxide-coated silica abrasive, 0.28 wt% maltitol or 0.28 wt% lactitol as an oxide trench reducer and a low concentration of biocide. All four formulations had a pH of 5.35.

[0439] All chemical additives were used in the same weight percentage, but different types of abrasives were used, such as calcined cerium dioxide and cerium dioxide-coated silica particles as abrasives.

[0440] The effects of different types of abrasives on the film removal rate and TEOS:SiN selectivity were observed, and the results are listed in Table 34.

[0441] Table 34. Effects of different types of abrasives on the selectivity of RR and TEOS:SiN films

[0442]

[0443] As shown in Table 34, the polishing composition using cerium-coated silica as an abrasive does indeed provide much higher TEOS and HDP film removal rates compared to those obtained by polishing compositions using calcined cerium dioxide as an abrasive.

[0444] The normalized total defect counts on polished TEOS and SiN wafers were compared using the four polishing compositions listed above. The results of the normalized total defect counts are listed in Table 35.

[0445] Table 35. Effects of different types of abrasives on standardized TEOS and total defect count of SiN

[0446]

[0447] As shown in Table 35, the normalized total defect count results indicate that the polishing composition using cerium dioxide-coated silica particles as abrasive and maltitol or lactitol as a trench reduction chemical additive provides a significantly lower normalized total defect count on polished TEOS and SiN wafers compared to the total defect count obtained using a polishing composition containing calcined cerium dioxide abrasive and maltitol or lactitol as a trench reduction chemical additive.

[0448] Example 15

[0449] In Example 15, a polishing composition based on calcined cerium dioxide and cerium dioxide-coated silica particles was tested.

[0450] Compositions containing calcined cerium dioxide particles but without chemical additives were used as a reference.

[0451] Calcined cerium dioxide or cerium dioxide-coated silica particles are used at 1.0% by weight, and D-sorbitol and D-mannitol are used at 2.0% by weight, respectively.

[0452] All samples were alkaline at pH 9.5. IC1010 was used as a polishing pad, and a downward force of 3.3 psi was applied.

[0453] The membrane removal rate results are listed in Table 36.

[0454] Table 36. Membrane Removal Rate vs Polishing Composition

[0455]

[0456] As shown in Table 36, the polishing composition with 1.0 wt% calcined cerium dioxide abrasive provided high TEOS and HDP film removal rates at pH 9.5 when no chemical additives were used in the polishing composition.

[0457] At pH 9.5, using 2.0% by weight of D-sorbitol or D-mannitol as a chemical additive in the polishing composition yielded significantly lower TEOS and HDP membrane removal rates.

[0458] Polishing compositions with such low TEOS and HDP film removal rates appear to be insufficient to meet oxide film removal rate requirements in CMP applications.

[0459] Determining the appropriate concentration range and suitable ratio of abrasive / chemical additives, as well as optimizing pH conditions, in CMP polishing compositions is crucial to provide sufficiently high oxide film removal rates and high TEOS:SiN selectivity to meet the requirements of CMP applications.

[0460] Example 16

[0461] In Example 16, the effect of the weight % ratio of cerium dioxide-coated silica to the chemical additive D-sorbitol on the polishing removal rate of various films and the relative overpolishing time of oxide trenches was tested.

[0462] In the compositions, cerium dioxide-coated silica abrasive was used at 0.2% to 0.4% by weight, and D-sorbitol was used at 0.0% to 0.30% by weight; this resulted in a ratio of 0.0% by weight of cerium dioxide-coated silica abrasive to 0.0% by weight of the chemical additive D-sorbitol. The pH of all tested compositions was 5.35.

[0463] The test results are depicted in Figure 1 and 2 middle.

[0464] Please note that the three points at 0 in the two figures refer to compositions containing only abrasive particles, i.e., the ratio of silica to D-sorbitol not used for cerium dioxide coating, since D-sorbitol is not used in the composition.

[0465] like Figure 1 and 2 The results shown indicate that TEOS and HDP membrane removal rates are high when the weight % ratio of cerium dioxide-coated silica to D-sorbitol ranges from 0.0 to 4.0.

[0466] However, even at a ratio of 0.0, the SiN removal rate is still high, therefore, the selectivity of TEOS:SiN is low.

[0467] When the ratio of cerium dioxide-coated silica to D-sorbitol is in the range of 0.7 to 2.0, high TEOS and HDP film removal rates, low SiN removal rates, and high TEOS:SiN selectivity are achieved.

[0468] When the ratio > 2.0, the SiN removal rate gradually increases and the TEOS:SiN selectivity decreases.

[0469] Figure 2The oxide trench depressions shown relative to overpolishing time also indicate that a ratio of cerium oxide-coated silica to D-sorbitol in the range of 0.7–2.0 wt% is more suitable for achieving high oxide film removal rates, low SiN removal rates, high TEOS:SiN selectivity, and low oxide trench depressions.

[0470] Test results show that selecting a suitable range of cerium dioxide-coated silica abrasive weight % relative to chemical additive D-sorbitol weight % allows for high oxide film removal rates, low SiN film removal rates, high oxide:SiN film selectivity, and low oxide trenching.

[0471] Example 17

[0472] In this embodiment, polishing performance was compared at pH 5.35 using calcined cerium dioxide as an abrasive and different concentrations of polyacrylate (PAA salt) and sorbitol as chemical additives. A downward force of 3.0 psi was applied in these polishing tests. Compositions without chemical additives were used as a reference.

[0473] The test results are listed in Table 37.

[0474] Table 37. Effect of additive concentration on membrane RR Effect of oxides on SiN selectivity

[0475]

[0476] As shown in Table 37, the chemical additive PAA salt in the formulation based on calcined cerium dioxide particles inhibited the removal rates of TEOS and HDP films and reduced the removal rate of SiN films and the TEOS:SiN selectivity.

[0477] The chemical additive D-sorbitol, when used at three different concentrations in CMP polishing compositions based on calcined cerium dioxide particles, also inhibited the removal rates of TEOS and HDP films, but significantly reduced the SiN removal rate and thus increased the TEOS:SiN selectivity from about 20:1 to about 30:1.

[0478] The effects of abrasive polishing compositions based on the chemical additive PAA salt and three different concentrations of D-sorbitol, plus the same concentration of calcined cerium dioxide, on the relative overpolishing time of oxide grooves and depressions of various sizes were observed. The results are listed in Table 38.

[0479] As shown in Table 38, the results indicate that the chemical additive PAA salt in the formulation based on calcined cerium dioxide particles reduced oxide groove depressions compared to a reference based on calcined cerium dioxide alone.

[0480] Table 38. Effects of Additives or Concentrations on Oxide Groove Depressions Impact

[0481]

[0482] The chemical additive D-sorbitol, when used in three different concentrations in CMP polishing compositions based on calcined cerium dioxide particles, also reduced oxide groove depressions on three different size features.

[0483] When D-sorbitol is used at a concentration of 0.15X or 0.3X, a much lower oxide trench depth relative to a 60-second overpolishing time is obtained compared to when D-sorbitol is used at a concentration of 0.05X.

[0484] Example 18

[0485] In Example 18, the CMP polishing composition was tested at different pH values.

[0486] The composition contains only 0.5% by weight of calcined cerium dioxide as an abrasive or 0.15% by weight of D-sorbitol as a chemical additive.

[0487] Membrane removal rates were tested under two different pH conditions.

[0488] The membrane removal rate, TEOS:SiN selectivity, and oxide trench depression were tested.

[0489] The results are listed in Tables 39 and 40, respectively.

[0490] Table 39. Effect of pH on membrane removal rate and TEOS:SiN selectivity

[0491]

[0492] As shown in Table 39, when the STI polishing composition contains 0.5 wt% calcined cerium dioxide particles as an abrasive and 0.15 wt% D-sorbitol as a chemical additive, a slightly lower TEOS removal rate is obtained at acidic pH, a slightly higher HDP film removal rate is obtained at alkaline pH, and the SiN removal rate decreases from pH 5.35. Lowered to pH 9.39

[0493] Table 40. Effects of pH conditions on oxide trench depressions Impact

[0494]

[0495] As shown in Table 40, when the polishing composition contained 0.5 wt% calcined cerium dioxide particles as the abrasive and 0.15 wt% D-sorbitol as the chemical additive, low oxide trench retractions were obtained at 100 μm and 200 μm spacings at both pH values. Even at pH 9.39, the 0.5 wt% calcined cerium dioxide particles as the abrasive and the 0.15 wt% D-sorbitol as the chemical additive still provided more stable oxide trench retractions relative to the increase in overpolishing time.

[0496] Therefore, the CMP polishing composition provides good indentation properties for CMP applications over a wide pH range.

[0497] Example 19

[0498] In Example 19, polishing tests were performed on various films using a CMP polishing composition prepared at pH 5.35 using calcined cerium dioxide particles or cerium dioxide-coated silica particles as abrasives and maltitol or lactitol as chemical additives.

[0499] The polishing pad used was the Dow IC1010 pad, and the downward force used for the polishing test was 3.0 psi.

[0500] The test results for various membrane removal rates and TEOS:SiN selectivity are listed in Table 41.

[0501] Table 41. Membrane RR Comparison with TEOS:SiN selectivity

[0502]

[0503] As shown in Table 41, the polishing composition with chemical additives maltitol or lactitol and calcined cerium dioxide particles or cerium dioxide-coated silica particles provides high TEOS and good HDP film removal rates, significantly suppresses SiN film removal rates, and thus significantly improves TEOS:SiN selectivity.

[0504] The relative overpolishing time of oxide trench depressions was tested at pH 5.35.

[0505] Table 42. Effect of chemical additives on relative OP time (seconds) of groove depression

[0506]

[0507] The polishing pad used was the Dow IC1010 pad, and the downward force used for the polishing test was 3.0 psi.

[0508] Table 42 lists the test results for oxide trench depression relative to overpolishing time.

[0509] As shown in Table 42, regardless of whether calcined cerium dioxide or cerium dioxide-coated silica particles are used as abrasives, polishing compositions with low or high concentrations of maltitol or lactitol are very effective in reducing the relative overpolishing time of oxide trench features of various sizes, and also provide a more uniform and stable overpolishing window.

[0510] Example 20

[0511] The pH of all tested CMP polishing compositions was 5.35. Dow's IK4140 pads were used as an alternative to Dow's IC1010.

[0512] When using Dow's IK4140 pads, apply a DF of 4.3 psi for polishing with a polishing composition based on calcined cerium dioxide abrasive, and apply a DF of 2.5 psi for polishing compositions based on cerium dioxide-coated silica abrasive. For all polishing compositions, apply the same table / head speed of 50 / 48 rpm.

[0513] Table 43 lists the test results of polishing various types of blank wafers using Dow's IK4140H polishing pad.

[0514] Table 43. Relative film RR of various polishing compositions under different polishing DF conditions and selectivity

[0515]

[0516] As shown in Table 43, when different polishing downforces were used to polish various blank films with different polishing compositions, very similar HDP film removal rates were obtained.

[0517] Compared to the HDP film removal rate obtained by the polishing composition using calcined cerium dioxide-based abrasives at 4.3 psi DF, the polishing composition using cerium dioxide-coated silica abrasives gave a similar HDP film removal rate even at much lower applied downforce and lower abrasive concentration.

[0518] Furthermore, overall, when comparing the SiN removal rates obtained under different polishing forces, the polishing composition containing cerium dioxide-coated silica abrasives gave a lower SiN removal rate than the polishing composition using cerium dioxide particles as the abrasive.

[0519] Table 44 lists the polishing test results of patterned wafers polished under different downward forces.

[0520] Table 44. Various polishing compositions for polishing patterned wafers under different polishing DF conditions

[0521]

[0522] As shown in Table 44, the patterned wafer polishing results show that, compared to polishing compositions using calcined cerium dioxide particles as abrasives and polyacrylate as chemical additives, polishing compositions using cerium dioxide-coated silica particles as abrasives and D-sorbitol or maltitol as chemical additives give similar P200 oxide trench loss rates, lower P200SiN loss rates, and lower SiN / HDP blank ratios.

[0523] In another set of tests shown in Table 45, Dow's IK4250UH pad was also used with 3.0psi DF for both polishing compositions. For this polishing test, the same table / head speed was applied at 87 / 93 rpm.

[0524] The polishing test results of polishing various types of blank wafers using Dow's IK4250UH polishing pad are listed in Table 45.

[0525] Table 45. Relative Film Reduction (RR) of Various Polishing Compositions and selectivity

[0526]

[0527] As shown in Table 45, when using Dow's IK4250UH polishing pad, under the same pH conditions, compared to the results of using a polishing composition containing 0.5 wt% calcined cerium dioxide particles as abrasive and 0.0506 wt% polyacrylate as an additive, a more suppressed SiN removal rate was obtained when using 0.2 wt% cerium dioxide-coated silica particles as abrasive and 0.15 wt% D-sorbitol as an additive, and an HDP film removal rate 118% higher was achieved.

[0528] Meanwhile, the HDP film:SiN selectivity increased from 13.9:1 to 51.9:1.

[0529] The patterned wafers were also polished using Dow's IK4250UH pads. The polishing results and polishing compositions are listed in Table 46.

[0530] Table 46. Various polishing compositions for polishing patterned wafers

[0531]

[0532] As shown in Table 46, when cerium dioxide-coated silica particles are used as abrasives and D-sorbitol is used as a chemical additive, lower P200 oxide trench loss rate, lower P200SiN loss rate, and lower SiN / HDP blank ratio are obtained.

[0533] The embodiments of the invention listed above (including working examples) are examples of many implementations that can be carried out by the invention. Many other configurations of the method are contemplated, and the materials used in the method can be selected from a wide range of materials in addition to those specifically disclosed.

Claims

1. A chemical mechanical polishing (CMP) composition, said composition comprising: Abrasive particles, selected from inorganic oxide particles, metal-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof. Chemical additives; Solvents selected from deionized (DI) water, distilled water, and alcoholic organic solvents; and Optional biocides; and pH adjuster; in The pH of the composition is 2 to 12; The inorganic oxide particles are selected from cerium dioxide, colloidal silica, alumina, titanium dioxide, zirconium oxide particles, and combinations thereof; The metal-coated inorganic oxide particles are selected from cerium dioxide-coated inorganic oxide particles, specifically from cerium dioxide-coated colloidal silica, cerium dioxide-coated alumina, cerium dioxide-coated titanium dioxide, cerium dioxide-coated zirconium oxide particles, and combinations thereof. The organic polymer particles are selected from polystyrene particles, polyurethane particles, polyacrylate particles, and combinations thereof. The metal-coated organic polymer particles are selected from cerium dioxide-coated organic polymer particles, zirconium oxide-coated organic polymer particles, silica-coated organic polymer particles, and combinations thereof; and The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof.

2. The chemical mechanical polishing (CMP) composition according to claim 1, wherein the cerium dioxide is colloidal cerium dioxide.

3. The chemical mechanical polishing (CMP) composition according to claim 1, wherein... The abrasive particles range from 0.05% by weight to 10% by weight, and the average particle size is from 5 nm to 500 nm. The range of the chemical additives is from 0.01% by weight to 20.0% by weight; and The pH of the composition is 3 to 10.

4. The chemical mechanical polishing (CMP) composition according to claim 3, wherein the abrasive particles exhibit a variation of ≤5.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days at a temperature ranging from 20 to 60°C; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below.

5. The chemical mechanical polishing (CMP) composition according to any one of claims 1-4, wherein... The abrasive particles have an average particle size of 5 nm to 500 nm and a concentration of 0.05 wt% to 10 wt%. The range of the chemical additive is from 0.05% by weight to 5% by weight; The pH of the composition is 3 to 10; and The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) within a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it.

6. The chemical mechanical polishing (CMP) composition according to claim 5, wherein... The chemical additive is Maltitol; The solvent is deionized (DI) water; and The variation of the average particle size MPS (nm) and D99 (nm) of the abrasive particles is ≤2.0%.

7. The chemical mechanical polishing (CMP) composition according to any one of claims 1-4, wherein... The abrasive particles have an average particle size of 5 nm to 500 nm and a concentration of 0.05 wt% to 10 wt%. The range of the chemical additive is from 0.05% by weight to 5% by weight; The pH of the composition is 4 to 9; and The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) within a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it.

8. The chemical mechanical polishing (CMP) composition according to any one of claims 1-4, wherein The abrasive particles have an average particle size of 5 nm to 500 nm and range from 0.05 wt% to 10 wt%. The chemical additives range from 0.01% to 20.0% by weight and are selected from maltitol, euonymus alcohol, and combinations thereof; and The pH of the composition is 3 to 10.

9. The chemical mechanical polishing (CMP) composition according to any one of claims 1-4, wherein... The abrasive particles are cerium dioxide-coated colloidal silica particles or cerium dioxide particles with an average particle size of 5 nm to 500 nm and a range of 0.05 wt% to 10 wt%. The chemical additives range from 0.05% to 5% by weight and are selected from maltitol, euonymus alcohol, and combinations thereof; The pH of the composition is 3 to 10; and The cerium dioxide-coated colloidal silica particles or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) within a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it.

10. The chemical mechanical polishing (CMP) composition according to any one of claims 1-4, wherein the composition comprises cerium dioxide-coated colloidal silica particles or cerium dioxide particles; the chemical additive is selected from maltitol, euonymus alcohol, and combinations thereof; and water; and The cerium dioxide-coated colloidal silica particles or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤2.0% in average particle size MPS (nm) and D99 (nm) within a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it.

11. The chemical mechanical polishing composition according to any one of claims 1-4, wherein the composition comprises a selection from: 0.0001% to 0.05% by weight of a biocide, the active ingredient of which is selected from 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and combinations thereof; 0% to 1% by weight of a pH adjuster, the pH adjuster being selected for acidic pH conditions from nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof; or for alkaline pH conditions from sodium hydroxide, potassium hydroxide, ammonium hydroxide, organic quaternary ammonium hydroxides, organic amines, and combinations thereof; and combinations thereof.

12. The chemical mechanical polishing composition according to claim 11, wherein the organic quaternary ammonium hydroxide is tetraalkylammonium hydroxide.

13. A method for chemical mechanical polishing (CMP) of a semiconductor substrate having at least one surface comprising a silicon oxide film, the method comprising: (a) Providing the semiconductor substrate; (b) Provide a polishing pad; (c) Providing the chemical mechanical polishing (CMP) composition according to claim 1; (d) Contacting the surface of the semiconductor substrate with the polishing pad and the chemical mechanical polishing composition; and (e) Polishing the at least one surface containing a silicon oxide film; The silicon oxide film is selected from chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), spin-formed silicon oxide film, flowable CVD oxide film, carbon-doped oxide film, nitrogen-doped oxide film, and combinations thereof.

14. The method of claim 13, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm. The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤5.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it; The range of the chemical additive is from 0.05% by weight to 5% by weight; and The pH of the composition is 3 to 10.

15. The method of claim 14, wherein The chemical additive is Maltitol; The solvent is deionized (DI) water; and The variation of the average particle size MPS (nm) and D99 (nm) of the abrasive particles is ≤2.0%; and The ratio of oxide trench indentation rate (Å / min) to blank HDP membrane removal rate (Å / min) is ≤0.

1.

16. The method of claim 13, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm; The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below; and The pH of the composition is 3 to 10.

17. The method according to claim 13 or 14, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm; The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; and The pH of the composition is 3 to 10.

18. The method according to claim 13 or 14, wherein the chemical mechanical polishing (CMP) composition comprises: Cerium dioxide coated colloidal silica particles or cerium dioxide particles with an average particle size of 5 nm to 500 nm. The cerium dioxide-coated colloidal silica particles or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; water; The pH of the composition is 3 to 10.

19. The method according to claim 13 or 14, wherein the chemical mechanical polishing (CMP) composition comprises: Cerium dioxide coated colloidal silica particles or cerium dioxide particles with an average particle size of 5 nm to 500 nm. The cerium dioxide-coated colloidal silica particles or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤2.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; and Water; and The pH of the composition is 3 to 10.

20. The method according to any one of claims 13-16, wherein the semiconductor substrate further comprises a silicon nitride surface; and the silicon oxide:silicon nitride removal selectivity is ≥20.

21. A system for chemical mechanical polishing (CMP) of a semiconductor substrate having at least one surface comprising a silicon oxide film, the system comprising: (a) The semiconductor substrate; (b) Polishing pad; and (c) The chemical mechanical polishing (CMP) composition as described in claim 1; in The silicon oxide film is selected from chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), spin-formed silicon oxide films, flowable CVD oxide films, carbon-doped oxide films, nitrogen-doped oxide films, and combinations thereof; and The at least one surface containing a silicon oxide film is in contact with the polishing pad and the chemical mechanical polishing composition.

22. The system of claim 21, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm. The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤5.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it; The range of the chemical additive is from 0.05% by weight to 5% by weight; and The pH of the composition is 3 to 10.

23. The system of claim 22, wherein... The chemical additive is Maltitol; The solvent is deionized (DI) water; and The variation of the average particle size MPS (nm) and D99 (nm) of the abrasive particles is ≤2.0%.

24. The system of claim 21, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm. The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤5.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it; The range of the chemical additive is from 0.05% by weight to 5% by weight; and The pH of the composition is 4 to 9.

25. The system of claim 21, wherein the chemical mechanical polishing (CMP) composition comprises: The abrasive particles have an average particle size of 5 nm to 500 nm. The abrasive particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; and The pH of the composition is 3 to 10.

26. The system of claim 21 or 22, wherein the chemical mechanical polishing (CMP) composition comprises: Cerium dioxide coated colloidal silica or cerium dioxide particles with an average particle size of 5 nm to 500 nm. The cerium dioxide-coated colloidal silica or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤3.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; water; The pH of the composition is 3 to 10.

27. The system of claim 21 or 22, wherein the chemical mechanical polishing (CMP) composition comprises: Cerium dioxide coated colloidal silica or cerium dioxide particles with an average particle size of 5 nm to 500 nm. The cerium dioxide-coated colloidal silica or cerium dioxide particles, at a temperature of 20 to 60°C, exhibit a change of ≤2.0% in average particle size MPS (nm) and D99 (nm) over a shelf life of ≥30 days; wherein D99 (nm) is the particle size at which 99% by weight of the particles fall below it. The chemical additives are selected from maltitol, euonymus alcohol, and combinations thereof; and water; The pH of the composition is 3 to 10.

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