Oxide chemical mechanical planarization (CMP) polishing compositions

Abstract

This invention provides a chemical mechanical planar polishing (CMP) composition for shallow trench isolation (STI) applications. The CMP composition contains cerium dioxide-coated inorganic metal oxide particles as an abrasive, such as cerium dioxide-coated silica particles; chemical additives selected from a first group of nonionic organic molecules having multiple hydroxyl functional groups in the same molecule; chemical additives selected from a second group of aromatic organic molecules having sulfonic acid groups or sulfonate functional groups and combinations thereof; a water-soluble solvent; and optionally a biocide and a pH adjuster; wherein the pH of the composition is 2 to 12, preferably 3 to 10, more preferably 4 to 9.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 716,784 and U.S. Provisional Patent Application No. 62 / 716,769, filed August 9, 2018, which are incorporated herein by reference as if fully set forth. Technical Field

[0003] This application relates to oxide or doped oxide film chemical mechanical planarization (CMP) compositions, methods and systems for polishing oxide or doped oxide films. Background Technology

[0004] In the fabrication of microelectronic devices, an important step is polishing, especially for chemical mechanical polishing / planarization of surfaces, in order to recover selected materials and / or planarize the structure.

[0005] For example, a SiN layer can be deposited under a SiO2 layer to serve as a polishing stop layer. This polishing stop effect is particularly important in shallow trench isolation (STI) structures. Selectivity is characteristically expressed as the ratio of oxide polishing rate to nitride polishing rate. One example is the increased polishing rate selectivity of silicon dioxide (SiO2) compared to silicon nitride (SiN).

[0006] In the global planarization of patterned STI structures, improving the oxide removal rate, reducing the SiN film removal rate, and minimizing oxide trench depression are three key factors to consider. Lower trench oxide loss will prevent current leakage between adjacent transistors. Non-uniform trench oxide loss across the die (within the die) 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 necessary to reduce trench oxide loss by minimizing oxide trench depression in oxide or doped oxide film CMP polishing compositions.

[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 at depressions, while the abrasive particles maintain a high polishing rate at heights. 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 electrolyte used includes a salt 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 weight of this polyelectrolyte ranges from 300 to 20,000, but is generally less than 100,000.

[0009] US Patent 6,616,514B1 discloses a chemical mechanical polishing slurry for removing a first substance from the surface of an article preferentially over silicon nitride by chemical mechanical polishing. The chemical mechanical polishing slurry according to this invention comprises an abrasive, which is calcined cerium dioxide particles, 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 the aqueous medium, or a polymer formed from at least one monomer having at least three non-dissociatable hydroxyl groups in the aqueous medium. Polyols used as chemical additives include mannitol, mannose, xylitol, sorbitol, etc. This prior art claims to achieve high oxide:SiN selectivity by using these chemical additives with calcined cerium dioxide abrasive in the polishing composition. However, polishing test results using the two chemical additives at concentrations listed in this prior art show very low oxide removal rates at pH 9.5 and with 1.0% calcined cerium dioxide and 2.0% chemical additives. Patterned wafer data are not listed at all in this prior art.

[0010] US Patent 9,293,344B2 discloses a chemical mechanical polishing slurry that uses calcined cerium dioxide as an abrasive and a water-soluble polymer as a chemical additive. This water-soluble polymer is prepared using a monomer containing at least one carboxylic acid with a double bond and a salt. This slurry is used to remove a dielectric film from the surface of an article preferentially over silicon nitride via chemical mechanical polishing. The chemical mechanical polishing slurry according to this invention comprises an abrasive, an aqueous medium, and a water-soluble organic polymer.

[0011] U.S. Patent 7,091,164B2 discloses a chemical mechanical polishing slurry that uses cerium dioxide and / or titanium dioxide as abrasives, and chemical additives having carboxyl groups and electrophilic functional groups. These chemical additives are primarily amino acids or amino acid derivatives. This prior art achieves an oxide:SiN selectivity of approximately 5:1. The pH range listed in this prior art is from 6 to approximately 11.

[0012] U.S. Patent Application 2019 / 0062593A1 discloses a chemical mechanical polishing slurry that uses 0.5 to 30% by weight of elongated, curved, or nodular silica particles as abrasives and cationic polymers (diallyl alkylamine salts, diallyl alkyl ammonium chlorides) or mixed copolymers having carboxyl and electrophilic functional groups as chemical additives. This polishing slurry provides good oxide:SiN selectivity.

[0013] However, those previously disclosed shallow trench isolation (STI) polishing compositions did not address the importance of oxide film removal rate, SiN film removal rate suppression, and oxide trench depression reduction during the same polishing process, as well as more uniform oxide trench depression on the polished patterned wafer and high oxide-nitride selectivity.

[0014] Therefore, it should be clear from the above that there is still a need in the art for compositions, methods, and systems for STI chemical mechanical polishing that can provide increased oxide film removal rates, reduced SiN film removal rates, and reduced oxide trench depressions in STI chemical and mechanical polishing (CMP) processes, as well as more uniform oxide trench depressions on oxide trench features of different sizes on polished patterned wafers, in addition to high silica removal rates and high silica selectivity for silicon nitride. Summary of the Invention

[0015] This overview is provided to introduce selected concepts in a simplified form, which will be further described in the detailed embodiments below. This overview is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0016] The embodiments described below and as defined in the appended claims include oxide or doped oxide film polishing compositions that provide increased oxide film removal rate, suppressed SiN film removal rate, improved TEOS:SiN selectivity, and reduced oxide trench depressions on polished patterned wafers.

[0017] The oxide or doped oxide film CMP polishing composition of the present invention also provides high oxide-to-nitride selectivity by introducing two different types of chemical additives as oxide film removal rate enhancers, SiN film removal rate inhibitors, and oxide trench depression reducers in a wide pH range (including acidic, neutral, and alkaline pH conditions) in a chemical mechanical polishing (CMP) composition for shallow trench isolation (STI) CMP applications.

[0018] The disclosed chemical mechanical polishing (CMP) composition for CMP polishing applications of oxide or doped oxide films has a unique combination of using cerium dioxide-coated inorganic oxides as abrasive particles and suitable chemical additives as oxide trench reduction agents, oxide film removal rate enhancers and nitride inhibitors.

[0019] In addition, several specific aspects of the systems and methods of the subject matter are disclosed.

[0020] Aspect 1: A chemimechanical planarization (CMP) composition comprising:

[0021] a. Abrasive;

[0022] b. The first additive, which consists of an organic compound containing multiple hydroxyl functional groups;

[0023] c. A second additive, which consists of an aromatic organic compound containing a sulfonate or sulfonic acid functional group;

[0024] d. Solvent.

[0025] Aspect 2: The CMP composition according to aspect 1, wherein the abrasive is selected from cerium dioxide-coated inorganic oxides, cerium dioxide-coated organic polymer particles, and combinations thereof.

[0026] Aspect 3: The CMP composition according to Aspect 2, wherein the abrasive is a cerium dioxide-coated inorganic oxide selected from: cerium dioxide-coated colloidal silica; cerium dioxide-coated high-purity colloidal silica; cerium dioxide-coated alumina; cerium dioxide-coated titanium dioxide; cerium oxide-coated zirconium oxide; and combinations thereof.

[0027] Aspect 4: The CMP composition according to any one of Aspects 1-3, wherein the range of the abrasive is from 0.05 to 10% by weight of the CMP composition based on the total weight of the composition.

[0028] Aspect 5: The CMP composition according to any one of Aspects 1-4, wherein the aromatic organic compound comprising a sulfonate or sulfonic acid functional group comprises a sulfonate or sulfonic acid functional group directly bonded to the aromatic ring or connected to the aromatic ring via an alkyl bridging group.

[0029] Aspect 6: The CMP composition according to any one of Aspects 1-5, wherein the solvent is selected from water, ether, and alcohol.

[0030] Aspect 7: The CMP composition according to any one of aspects 1-6 further comprises at least one of a biocide and a pH adjuster.

[0031] Aspect 8: The CMP composition according to any one of Aspects 1-7, wherein the pH range of the composition is 3 to 10.

[0032] Aspect 9: The CMP composition according to any one of aspects 1-8, wherein the pH range of the composition is 4.5 to 7.5.

[0033] Aspect 10: The CMP composition according to any one of aspects 1-9, wherein the general molecular structure of the first additive is:

[0034]

[0035] Wherein: n is selected from 2 to 5,000, and R1, R3 and R2 in each occurrence are 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 and organic amine groups.

[0036] Aspect 11: The CMP composition according to aspect 10, wherein R1, R2 and R3 are hydrogen.

[0037] Aspect 12: The CMP composition according to aspect 10, wherein n is selected from 3 to 12.

[0038] Aspect 13: The CMP composition according to aspect 10, wherein the first additive is selected from: ribitol, xylitol, mesoerythritol, D-sorbitol, mannitol, euonymus alcohol, idotitol, and combinations thereof.

[0039] Aspect 14: The CMP composition according to any one of aspects 1-13, wherein the general molecular structure of the first additive is:

[0040]

[0041] Wherein n is selected from 2 to 5,000, and R2 and each occurrence of R1 are 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, and organic amine groups.

[0042] Aspect 15: The CMP composition according to aspect 14, wherein n is selected from 3 to 12.

[0043] Aspect 16: The CMP composition according to aspect 14, wherein R1 and R2 are hydrogen and n is selected from 3 to 4.

[0044] Aspect 17: The CMP composition according to any one of aspects 1-16, wherein the general molecular structure of the first additive is selected from:

[0045] (a)

[0046] (b) and

[0047] (c)

[0048] R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 are 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, and organic amine groups, provided that at least two occurrences of R1 to R14 in each structure are hydrogen.

[0049] Aspect 18: The CMP composition according to aspect 17, wherein the first additive is selected from: D-(-)-fructose, sorbitol, sucrose, β-lactose, D-ribose, inositol, glucose, and combinations thereof.

[0050] Aspect 19: The CMP composition according to any one of aspects 1-17, wherein the general molecular structure of the first additive is:

[0051]

[0052] R1 to R5 are 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 and organic amine groups.

[0053] Aspect 20: The CMP composition according to aspect 19, wherein at least one of R1 to R5 is a polyol molecular unit having the following structure:

[0054]

[0055] Wherein n and m are independently selected from 1 to 5, and R6 to R9 are 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 and organic amines.

[0056] Aspect 21: The CMP composition according to aspect 20, wherein n and m are independently selected from 1 to 3.

[0057] Aspect 22: The CMP composition according to aspect 20, wherein at least one of R1 to R5 is a six-membered cyclic polyol having the following structure:

[0058]

[0059] R10, R11, R12, R13 and R14 are 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 and organic amines.

[0060] Aspect 23: The CMP composition according to aspect 22, wherein at least two of R1 to R9 are hydrogen atoms.

[0061] Aspect 24: The CMP composition according to aspect 22, wherein at least six of R1 to R9 are hydrogen atoms.

[0062] Aspect 25: The CMP composition according to aspect 19, wherein the first additive is selected from maltitol, lactitol and maltotritol.

[0063] Aspect 26: The CMP composition according to any one of Aspects 1-25, wherein the range of the first additive is from 0.005 to 1.0 by weight based on the total weight of the composition.

[0064] Aspect 27: The CMP composition according to any one of aspects 1-26, wherein the general molecular structure of the second additive is:

[0065]

[0066] Wherein R is selected from hydrogen, sodium ion, potassium ion, and ammonium ion; and R′ is attached at the α-position, meta-position, or para-position relative to the sulfonic acid or sulfonate group, and contains C. n H 2n+1 alkyl groups of the structure, wherein n is selected from 1 to 18.

[0067] Aspect 28: The CMP composition according to aspect 27, wherein the second additive is selected from: 4-dodecylbenzenesulfonic acid or its ammonium, sodium or potassium salt; 4-methylbenzenesulfonic acid or its ammonium, sodium or potassium salt; and combinations thereof.

[0068] Aspect 29: A method for chemical mechanical polishing (CMP) of a semiconductor substrate having at least one surface comprising a silicon oxide film, the method comprising:

[0069] a. Contacting the at least one silicon oxide-containing surface with a CMP polishing pad and a CMP composition according to any one of aspects 1-28; and

[0070] b. Polish the at least one surface containing silicon dioxide.

[0071] Aspect 30: The method according to aspect 29, wherein the silicon oxide film is selected from chemical vapor deposition (CVD), plasma enhanced CVD (PECVD), high density deposition CVD (HDP), and spin-on silicon oxide films.

[0072] Aspect 31: According to the method of aspect 30, the silicon oxide film is a SiO2 film.

[0073] Aspect 32: According to the method of aspect 31, the semiconductor substrate further comprises a silicon nitride surface; and step (b) comprises selectively polishing the at least one silicon dioxide-containing surface with a silicon oxide:silicon nitride removal of greater than 60. Attached Figure Description

[0074] Figure 1 Chemical additives on membrane RR The effect of TEOS: SiN selectivity.

[0075] Figure 2 D-sorbitol and BSA additives for oxide groove depressions The impact relative to OP time (seconds).

[0076] Figure 3 The effect of D-sorbitol and BSA additives on the rate of oxide trench loss The impact.

[0077] Figure 4 The effect of D-sorbitol and BSA additives on SiN loss rate The impact.

[0078] Figure 5 The effect of D-sorbitol and BSA additives on the rate of oxide trench indentation The impact.

[0079] Figure 6 The effect of D-sorbitol and BSA on the slope of the depression relative to OP.

[0080] Figure 7 Maltitol and BSA on membrane RR The effect of TEOS: SiN selectivity.

[0081] Figure 8 Maltitol and BSA additives for oxide groove depressions The impact relative to OP time (seconds).

[0082] Figure 9 Maltitol and BSA additives affect the rate of oxide trench loss. The impact.

[0083] Figure 10 Maltitol and BSA additives affect the SiN loss rate. The impact.

[0084] Figure 11 Maltitol and BSA additives affect the rate of oxide trench indentation. The impact.

[0085] Figure 12 The effect of maltitol and BSA on the slope of the indentation relative to the amount of OP. Detailed Implementation

[0086] The following detailed description provides only preferred exemplary embodiments and is not intended to limit the scope, applicability, or configuration of the claimed invention. Rather, the subsequent detailed description of preferred exemplary embodiments will provide those skilled in the art with a feasible description of how to implement the preferred exemplary embodiments. Various changes may be made to the function and arrangement of the elements without departing from the spirit and scope of the invention as set forth in the appended claims.

[0087] All terms defined herein shall be given their broadest possible interpretation, including any implied meanings implied by reading the specification and any words that a person skilled in the art and / or a dictionary, paper, or similar authority would assign a particular meaning to. Furthermore, it should be noted that, as stated in the specification and appended claims, unless otherwise stated, the singular forms “a,” “an,” and “the” include plural indicators. Additionally, when used herein, the terms “comprising” and “including” specify that certain features are present in the embodiment, but should not be construed as excluding the presence or addition of additional features, components, operations, and / or combinations thereof.

[0088] This paper discloses CMP polishing compositions for polishing oxide materials, along with related methods and systems, meeting the needs of polishing semiconductor wafers containing silicon oxide structures. In the global planarization of patterned STI structures, suppressing SiN removal rates and reducing oxide trench depressions on oxide trench features of various sizes are key considerations. Lower trench oxide losses prevent current leakage between adjacent transistors. Non-uniform trench oxide losses within the die (within the die) affect transistor performance and device manufacturing yield. Severe trench oxide losses (high oxide trench depressions) lead to poor transistor isolation, resulting in device failure. Therefore, it is important to reduce trench oxide losses by minimizing oxide trench depressions in the STI CMP polishing composition.

[0089] This invention relates to chemical mechanical polishing (CMP) compositions for polishing oxide or doped oxide films using CMP applications. The CMP compositions disclosed herein are particularly suitable for planarization of patterned STI structures.

[0090] More specifically, the disclosed chemical mechanical polishing (CMP) composition for polishing oxide or doped oxide films in CMP applications has a unique formulation comprising abrasives and two types of additives acting as oxide trench reduction agents, oxide film removal rate enhancers, and nitride removal rate inhibitors. The CMP composition also contains a solvent. Other optional components such as biocides and pH adjusters may also be present in the formulation.

[0091] In a preferred embodiment, the abrasive comprises cerium dioxide-coated inorganic oxide particles or cerium dioxide-coated organic polymer particles. Preferably, the first additive is a nonionic and non-aromatic organic molecule with multiple hydroxyl functional groups, while the second additive is an organic aromatic molecule with sulfonic acid or sulfonate functional groups.

[0092] The components of the CMP formulation will be discussed in more detail below. The following paragraph headings are for the purpose of providing an organizational description of this disclosure only and are not intended to limit the scope of the claimed invention in any way.

[0093] abrasive

[0094] In one embodiment, the abrasive comprises cerium dioxide-coated organic polymer particles, including but not limited to cerium dioxide-coated polystyrene particles, cerium dioxide-coated polyurethane particles, cerium dioxide-coated polyacrylate particles, or any other cerium dioxide-coated organic polymer particles.

[0095] In a preferred embodiment, the abrasive comprises cerium dioxide-coated inorganic oxide particles, including but not limited to 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. Preferably, the cerium dioxide-coated inorganic oxide particles are cerium dioxide-coated colloidal silica particles.

[0096] In this embodiment, the cerium dioxide-coated inorganic metal oxide particles have a particle size ranging from 2 to 1,000 nanometers. A preferred average particle size range is 5 to 500 nanometers, more preferably 20 to 250 nanometers.

[0097] In this embodiment, based on the total weight of the CMP composition, the concentration of the cerium dioxide-coated inorganic metal oxide particles ranges from 0.01 to 20% by weight. Preferably, this concentration ranges from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight.

[0098] First Additive

[0099] In this embodiment, the first additive is a nonionic and nonaromatic organic molecule having multiple hydroxyl functional groups.

[0100] In one embodiment, the first additive comprises the following general molecular structure:

[0101]

[0102] Wherein: n is selected from 2 to 5,000, preferably 3 to 12, and more preferably 4 to 7. R1, R3, and each occurrence of R2 are 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, and organic amine groups. R1, R2, and R3 can be the same or different groups. Preferably, two or more occurrences of R1, R2, and R3 are hydrogen atoms. More preferably, four or more occurrences of R1, R2, and R3 are hydrogen atoms. When R1, R2, and R3 are the same and are hydrogen atoms, the chemical additive has multiple hydroxyl functional groups.

[0103] Preferred examples of first additives having the general molecular structure of Formula 1 include, but are not limited to, ribitol, xylitol, mesoerythritol, D-sorbitol, mannitol, euonymus alcohol and idotitol.

[0104] In another embodiment, the first additive comprises the following general molecular structure:

[0105]

[0106] In this embodiment, the carbonyl (CHO) functional group is located at one end of the molecule as a terminal functional group, and n ranges from 2 to 5,000, preferably from 3 to 12, more preferably from 4 to 7. R2 and each occurrence of R1 are 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.

[0107] In a preferred embodiment, n = 3, and R2 and all of R1 are hydrogen atoms. In this embodiment, the first additive is D-arabinose or L-arabinose. In another preferred embodiment, n = 4, and R2 and all of R1 are hydrogen atoms. In this embodiment, the first additive is D-mannose or L-mannose.

[0108] In another embodiment, the general molecular structure of the first additive is selected from:

[0109] (a)

[0110] (b)

[0111] (c) and its combinations,

[0112] Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, and R14 are 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, and organic amine groups, provided that at least two occurrences of R1 to R14 in each structure are hydrogen. Preferably, at least three occurrences of R1 to R14 in each structure are hydrogen. More preferably, at least four occurrences of R1 to R14 in each structure are hydrogen (where possible).

[0113] Preferred examples of the first additive having the structure of this embodiment include, but are not limited to, D-(-)-fructose, sorbitol, sucrose, β-lactose, D-ribose, inositol, and glucose.

[0114] In another embodiment, the first additive contains at least one six-membered ring ether structural unit bonded to at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure, or at least one polyol molecular unit containing multiple hydroxyl functional groups in its molecular unit structure and at least one six-membered ring polyol. As used herein, a polyol is an organic compound containing more than two hydroxyl groups.

[0115] The general molecular structure of the first additive in this embodiment is:

[0116]

[0117] R1, R2, R3, R4 and R5 are 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 and organic amine groups.

[0118] In a preferred embodiment, at least one R in the group of R1 to R5 in the general molecular structure (d) is a polyol molecular unit having the structure shown in (e):

[0119]

[0120] Wherein n and m are independently selected from 1 to 5, preferably 1 to 4, more preferably 1 to 3, and most preferably 1 to 2. R6, R7, R8 and R9 are 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 and organic amine groups.

[0121] In another embodiment, at least one R in the group of R1 to R5 in the general molecular structure (d) is a polyol molecular unit having the structure shown in (e); at least one R in the group of R1 to R5 in the general molecular structure is a six-membered ring polyol as shown in (f):

[0122]

[0123] R10, R11, R12, R13 and R14 are each 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 and organic amine groups.

[0124] In a general molecular structure, the R in the group of R1 to R9 appears at least twice, preferably four times, and more preferably six times as a hydrogen atom. In a general molecular structure, when only one R (e.g., R5 in the group of R1 to R5) is a polyol molecular unit (b) with n=2 and m=1, and all the remaining R in the group of R1 to R9 are hydrogen atoms, the following two chemical additives are obtained: maltitol and lactitol.

[0125] When one R (e.g., R5) is a polyol molecular unit (b) with n=2 and m=1, and one R (e.g., R2) is a six-membered ring polyol and all the remaining Rs in the group of R1 to R14 are hydrogen atoms, the following chemical additive is obtained: maltotriose alcohol.

[0126] Preferred first additives include, but are not limited to, maltitol, lactitol, maltotriol, 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, maltotriol, 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, maltotriol, D-sorbitol, mannitol, euonymus alcohol, D-(-)-fructose, β-lactose, and combinations thereof.

[0127] Based on the total weight of the CMP composition, the CMP composition contains 0.0001% to 2.0% by weight, preferably 0.001% to 1.0% by weight, and preferably 0.0025% to 0.5% by weight of a first additive.

[0128] Second additive

[0129] In a preferred embodiment, the second additive is an organic aromatic molecule having sulfonic acid or sulfonate functional groups, represented by the following general structural formula:

[0130]

[0131] Where -R can be a hydrogen atom or a metal ion; or

[0132]

[0133] Where -R′ can be a hydrogen atom or a metal ion; and n can range from 1 to 12, representing different lengths of the alkyl linking group -CH2-; and combinations of (g) and (h). When R or -R′ is a hydrogen atom, the chemical additive is benzenesulfonic acid. When -R or -R′ is a metal ion such as sodium ion, potassium ion, or ammonium ion, the chemical additive is benzenesulfonate.

[0134] In another embodiment, the general molecular structure (i) of the second group of chemical additives is an organic aromatic molecule having a sulfonic acid or sulfonate functional group attached to one position of the aromatic ring and other functional groups at other positions of the aromatic ring, as shown in formula (i):

[0135]

[0136] Where -R can be a hydrogen atom or a metal ion; when -R is a hydrogen ion, the additive is a benzenesulfonic acid molecular derivative; when -R can be a metal ion, such as a sodium ion, potassium ion, or ammonium ion, the additive is a benzenesulfonate molecular derivative. -R′ is another functional group that can be attached at the α, meta, or para position relative to the sulfonic acid or sulfonate group. Typically, -R′ has a -C n H 2n+1 The alkyl group of the structure has a carbon chain length ranging from -C1 to -C18.

[0137] Some examples of the second group of chemical additives are 4-dodecylbenzenesulfonic acid and 4-methylbenzenesulfonic acid, or their ammonium, sodium, or potassium salts.

[0138] In an embodiment, the CMP composition contains 0.0001% to 2.0% by weight, preferably 0.001% to 1.5% by weight, and more preferably 0.002% to 1.0% by weight of a second additive.

[0139] solvent

[0140] The CMP composition contains a solvent. Preferably, the solvent is water or a water-soluble solvent. Preferred solvents include, but are not limited to, deionized (DI) water, distilled water, and alcohols. More preferably, DI water is a more preferred solvent.

[0141] Optional ingredients

[0142] Optionally, the CMP contains a biocidal agent. Preferred biocides include, but are not limited to, Kathon, which is available from DuPont / Dow Chemical Co. TM Kathon TM CG / ICP II and Bioban. Preferred biocides comprise at least one of the active ingredients 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. The STI CMP composition may contain 0.0001% to 0.05% by weight; preferably 0.0005% to 0.025% by weight; and more preferably 0.001% to 0.01% by weight of the biocide.

[0143] STI CMP compositions may optionally contain a pH adjuster. Acidic or alkaline pH adjusters can be used to adjust the STI polishing composition to an optimized pH value. Preferred pH adjusters include, but are not limited to, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof. Preferred pH adjusters also include alkaline pH adjusters, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic quaternary ammonium hydroxides, organic amines, and other chemical reagents that can be used to adjust the pH to a more alkaline direction. When a pH adjuster is present, the CMP composition contains 0% to 1% by weight, preferably 0.01% to 0.5% by weight, more preferably 0.1% to 0.25% by weight of the pH adjuster.

[0144] How to use

[0145] In some embodiments, the CMP polishing composition may be prepared as two or more components and mixed upon use.

[0146] In one embodiment, 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 in a shallow trench isolation (STI) process.

[0147] The polished oxide film can be chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), spin-coated silicon oxide film or flowable CVD oxide film, carbon-doped oxide film or nitrogen-doped oxide film.

[0148] The substrates disclosed above may also include a silicon nitride surface. The SiO2:SiN removal selectivity is greater than 30, preferably greater than 60, and more preferably greater than 80.

[0149] 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 in a shallow trench isolation (STI) process. The polished oxide film can be a CVD oxide, a PECVD oxide, a high-density oxide, or a spin-coated oxide film.

[0150] The following non-limiting embodiments are provided to further illustrate the invention.

[0151] CMP method

[0152] In the embodiments given below, CMP experiments are performed using the procedures and experimental conditions described below.

[0153] Vocabulary

[0154] Components

[0155] Cerium dioxide-coated silica: used as an abrasive, with a particle size of about 100 nanometers (nm); the particle size range of such cerium dioxide-coated silica particles can be from about 2 nanometers (nm) to 1000 nanometers (nm);

[0156] The cerium dioxide-coated silica particles (of different sizes) were supplied by JGC Inc. of Japan.

[0157] Chemical additives, such as benzenesulfonic acid or its salts; and maltitol, D-fructose, euonymus alcohol, D-sorbitol and other chemical raw materials are supplied by Sigma-Aldrich, St. Louis, MO.

[0158] TEOS: Tetraethyl orthosilicate

[0159] Polishing pads: Polishing pads IC1000, IC1010 and other pads used during CMP are supplied by DOW, Inc.

[0160] parameter

[0161] General

[0162] Or A: Angstrom - a unit of length

[0163] BP: Back pressure, unit: psi

[0164] BSA: Benzenesulfonic acid

[0165] CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing

[0166] CS: Carrier speed

[0167] DF: Downward force: The pressure applied during CMP, in psi.

[0168] min: minutes

[0169] ml: milliliters

[0170] mV: millivolt

[0171] psi: pounds per square inch

[0172] PS: The table rotation speed of the polishing equipment is in rpm (revolutions per minute).

[0173] SF: Composition flow rate, ml / min

[0174] % by weight: (by weight of the listed components)

[0175] TEOS: SiN Selectivity: (TEOS Removal Rate) / (SiN Removal Rate)

[0176] HDP: High-density plasma-deposited TEOS

[0177] TEOS or HDP removal rate: The TEOS or HDP removal rate measured at a given downpressure. In the examples listed above, the downpressure of the CMP device is 3.0 psi.

[0178] 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.

[0179] Measurement

[0180] The membrane 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 membrane, a 49-point diameter scan was performed (excluding the 5mm edge).

[0181] CMP equipment

[0182] The CMP equipment used was a 200mm Mirra or 300mm Reflexion manufactured by Applied Materials, 3050 Boweres 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.

[0183] Run in the IC1010 pad or other pads by allowing them to dress for 18 minutes. Apply a 7 lbs downforce on the conditioner. To ensure proper equipment setup and pad running-in, use the equipment provided by Versum Materials Inc. under baseline conditions. The STI2305 composition was used to polish two tungsten monitors and two TEOS monitors.

[0184] Chips

[0185] 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.

[0186] Polishing experiment

[0187] In the blank wafer study, oxide and SiN blank wafers were polished under baseline conditions. The baseline equipment conditions were: stage speed: 87 rpm; head speed: 93 rpm; film pressure: 3.0 psi DF; composition flow rate: 200 ml / min. The polishing pads used for testing were IC1010 pads supplied by Dow Chemicals.

[0188] In the working examples, deionized water is used as the solvent in the composition.

[0189] The composition was used in 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.

[0190] The TEOS:SiN selectivity (TEOS removal rate) / (SiN removal rate) obtained from the STI CMP polishing composition is adjustable.

[0191] Working Example

[0192] In the following working examples, an STI polishing composition comprising 0.2 wt% cerium dioxide-coated silica particles, 0.0001 wt% to 0.05 wt% biocide, and deionized water was prepared as a reference (reference), with the pH adjusted to 5.35, or having other selected pH conditions.

[0193] Polishing compositions were prepared using a reference (0.2 wt% cerium dioxide-coated silica, 0.0001 wt% to 0.05 wt% biocide and deionized water) and either a Class I or Class II chemical additive or a mixture of Class I and Class II chemical additives, at a pH of 5.35 or other selected pH conditions.

[0194] Example 1

[0195] In Example 1, the polishing composition used for oxide polishing is shown in Table 1. The reference sample was prepared using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and DI water.

[0196] The first-class chemical additive, D-sorbitol, was used at 0.15% by weight and mixed with the reference sample.

[0197] The second type of chemical additive, benzenesulfonic acid, is used at 0.10% by weight and mixed with the reference sample.

[0198] The first-class chemical additive, D-sorbitol, was used at 0.15% by weight, and the second-class chemical additive, benzenesulfonic acid, was used at 0.10% by weight, and both were mixed with the reference sample.

[0199] All reference and test samples had the same pH value of approximately 5.35.

[0200] The removal rates (RR) for polishing different films were tested. The effects of chemical additives on membrane removal rate and TEOS:SiN membrane selectivity were observed and are listed in Table 1 and described in the figure. Figure 1 middle.

[0201] Table 1. Effects of chemical additives on membrane RR And TEOS: The effect of SiN selectivity

[0202]

[0203] The polishing conditions used were: Dow IC1010 pads, 3.0psi DF, table / head speed of 87 / 93rpm, and non-in-situ finishing.

[0204] As shown in Table 1 and Figure 1 The results shown demonstrate that adding D-sorbitol as a chemical additive to the polishing composition effectively suppressed the SiN film removal rate and improved the HDP film removal rate. Therefore, the TEOS:SiN selectivity was significantly enhanced.

[0205] Adding benzenesulfonic acid to the polishing composition not only inhibited the SiN film removal rate but also improved both the TEOS and HDP film removal rates. Therefore, a further improvement in TEOS:SiN selectivity was achieved compared to the selectivity obtained from the reference sample.

[0206] When both the first type of additive, D-sorbitol, and the second type of additive, BSA, are added to the same polishing composition, the removal rates of both TEOS and HPD films are still increased, while the removal rate of the SiN film is further suppressed. Therefore, the highest TEOS:SiN selectivity is achieved when both types of additives are used in the same polishing composition, compared to the TEOS:SiN selectivity obtained by using these additives alone or without using either of them.

[0207] Table 2. Effects of D-sorbitol and BSA additives on oxide grooves and depressions Impact of relative OP time (seconds)

[0208]

[0209] When comparing TEOS:SiN selectivity, the polishing composition using two chemical additives provided a selectivity of 73:1, which is significantly higher than the 9:1 selectivity obtained from the reference sample.

[0210] Example 2

[0211] In Example 2, the polishing composition used for the polishing test is shown in Table 2. The reference sample was prepared at pH 5.35 using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water.

[0212] In the test samples, D-sorbitol or benzenesulfonic acid (BSA) were used alone or together at 0.15% by weight or 0.1% by weight, respectively.

[0213] All reference and test samples had the same pH value of approximately 5.35.

[0214] The effects of D-sorbitol, benzenesulfonic acid (BSA), or D-sorbitol + BSA on the relatively different overpolishing times of oxide trench depressions were tested. The results are listed in Table 2 and described in [the table / plot]. Figure 2 middle.

[0215] As shown in Table 2 and Figure 2 The results shown indicate that, compared to the oxide groove depressions obtained from the reference sample with respect to different overpolishing times, the addition of the first-class additive D-sorbitol as the chemical additive to the polishing composition significantly reduced the oxide groove depressions with respect to different overpolishing times.

[0216] Compared to the reference sample, the addition of the second type of additive, BSA, provided slightly worse oxide trench depressions with a relative over-polishing time.

[0217] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition, a significant reduction in oxide groove indentation relative to overpolishing time was achieved compared to the reference sample.

[0218] Compared to using either of these two additives alone, the polishing composition based on dual chemical additives provides a more stable overpolishing window.

[0219] The effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the oxide trench loss rate were tested. The effects are shown in Table 3 and depicted in... Figure 3 middle.

[0220] Table 3. Effects of D-sorbitol and BSA additives on oxide trench loss rate Impact

[0221]

[0222]

[0223] As shown in Table 3 and Figure 3 The results shown indicate that, compared to the oxide trench loss rate obtained from the reference sample, the addition of D-sorbitol, a Class I additive, to the polishing composition as the chemical additive significantly reduced the oxide trench loss rate.

[0224] Adding BSA (a type II additive) to the polishing composition provided a slightly increased rate of oxide trench loss compared to the reference sample.

[0225] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition, a significant reduction in oxide trench loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest oxide trench loss rate among all tested polishing compositions and the reference sample.

[0226] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0227] The effects of D-sorbitol, benzenesulfonic acid (BSA), or D-sorbitol + BSA on the SiN loss rate on patterned features of different sizes were tested. The effects are shown in Table 4 and depicted in... Figure 4 middle.

[0228] Table 4. Effects of D-sorbitol and BSA additives on SiN loss rate Impact

[0229]

[0230]

[0231] As shown in Table 4 and Figure 4 The results shown indicate that, compared to the SiN film loss rate obtained from the reference sample, the addition of D-sorbitol, a first-class additive, as the chemical additive in the polishing composition significantly reduced the SiN film loss rate.

[0232] Adding a second-class additive, BSA, to the polishing composition provided an improved SiN film loss rate compared to the reference sample.

[0233] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition, a significant reduction in SiN film loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest SiN film loss rate among all tested polishing compositions and the reference sample.

[0234] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0235] The oxide trench indentation rates on patterned features of different sizes were tested using D-sorbitol, benzenesulfonic acid (BSA), or D-sorbitol + BSA. The effects are shown in Table 5 and described in... Figure 5 middle.

[0236] Table 5. Effects of D-sorbitol and BSA additives on oxide groove indentation rate Impact

[0237]

[0238] As shown in Table 5 and Figure 5The results shown indicate that, compared to the oxide trench indentation rate obtained from the reference sample, the addition of D-sorbitol, a Class I additive, to the polishing composition as the chemical additive significantly reduced the oxide trench indentation rate.

[0239] Adding a second-class additive, BSA, to the polishing composition provided an increased oxide trench indentation rate compared to the reference sample.

[0240] When D-sorbitol and BSA were used as dual chemical additives in the polishing composition, a significant reduction in oxide trench indentation rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest oxide trench indentation rate among all tested polishing compositions and the reference sample.

[0241] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0242] The effects of D-sorbitol, benzenesulfonic acid (BSA), or D-sorbitol + BSA on the slope of the relative overpolishing removal of grooves and depressions on patterned features of different sizes were tested. The results are listed in Table 6 and plotted on... Figure 6 middle.

[0243] Table 6. Effects of D-sorbitol and BSA on the slope of the depression relative to OP amount

[0244]

[0245] As shown in Table 6 and Figure 6 The results shown indicate that the slope of the groove depression relative to overpolishing was significantly reduced compared to that obtained from the reference sample when either Class I additive D-sorbitol or Class II additive BSA was added to the polishing composition, whether alone or together as a chemical additive in the polishing composition.

[0246] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0247] Example 3

[0248] In Example 3, the polishing composition used for the polishing test is shown in Table 7. The reference sample was prepared using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water. In the test sample, maltitol and BSA were used alone or together at 0.28 wt% and 0.10 wt%, respectively.

[0249] All reference and test samples had the same pH value of approximately 5.35.

[0250] The removal rates (RR) for polishing different films were tested. The effects of chemical additives maltitol and BSA on membrane removal rate and TEOS:SiN selectivity were observed and listed in Table 7. Figure 7 Described in the text.

[0251] Polishing components and conditions were: Dow IC1010 polishing pads, 3.0psi DF, non-in-situ finishing, and table / head speed of 87 / 93rpm.

[0252] Table 7. Effects of maltitol and BSA on membrane RR And TEOS: The effect of SiN selectivity

[0253]

[0254] As shown in Table 7 and Figure 7 The results show that adding maltitol as a first-class chemical additive to the polishing composition effectively suppressed the SiN film removal rate and slightly increased the HDP film removal rate. Therefore, the TEOS:SiN selectivity was significantly increased.

[0255] Adding benzenesulfonic acid (BSA) as a second-class chemical additive to the polishing composition not only suppressed the SiN film removal rate but also improved both the TEOS and HDP film removal rates. Therefore, a further improved TEOS:SiN selectivity was achieved compared to the selectivity obtained from the reference sample.

[0256] When both the first-class additive maltitol and the second-class additive BSA were added to the same polishing composition, the removal rates of both TEOS and HPD films were still increased, while the removal rate of SiN films was further suppressed. Therefore, the highest TEOS:SiN selectivity was achieved when both classes of additives were used in the same polishing composition, compared to the TEOS:SiN selectivity obtained by using these additives alone or without using either of them.

[0257] When comparing the TEOS:SiN selectivity, the polishing composition using both types of chemical additives simultaneously provided a selectivity of 80:1, which is significantly higher than the 9:1 selectivity obtained from the reference sample.

[0258] Example 4

[0259] Table 8. Effects of maltitol and BSA additives on oxide grooves and depressions The impact relative to OP time (seconds).

[0260]

[0261]

[0262] In Example 4, the polishing composition used for the polishing test is shown in Table 8. The reference sample was prepared using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water. In the test sample, maltitol and BSA were used alone or together at 0.28 wt% and 0.10 wt%, respectively.

[0263] All reference and test samples had the same pH value of approximately 5.35.

[0264] The effects of maltitol, benzenesulfonic acid (BSA), or maltitol + BSA on oxide trench retractions with different overpolishing times were tested. The results are listed in Table 8 and plotted in [the table]. Figure 8 middle.

[0265] As shown in Table 8 and Figure 8 The results show that, compared to the oxide trench depressions obtained from the reference sample at different overpolishing times, the addition of maltitol, a first-class additive, to the polishing composition as the chemical additive significantly reduced the oxide trench depressions at different overpolishing times.

[0266] Compared to the reference sample, the addition of the second-class additive BSA resulted in slightly worse oxide trench depressions with a relative overpolishing time.

[0267] When maltitol and BSA are used as dual chemical additives in the same polishing composition, a significant reduction in oxide trench depressions at different overpolishing times was achieved compared to the reference sample on patterned features of different sizes.

[0268] The effects of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on the rate of oxide trench loss were tested. The effects are shown in Table 9 and depicted in... Figure 9 middle.

[0269] Table 9. Effects of maltitol and BSA additives on oxide trench loss rate Impact

[0270]

[0271]

[0272] As shown in Table 9 and Figure 9The results shown indicate that, compared to the oxide trench loss rate obtained from the reference sample, the addition of maltitol, a Class I additive, to the polishing composition as the chemical additive significantly reduced the oxide trench loss rate.

[0273] Adding BSA (a type II additive) to the polishing composition provided a slightly increased rate of oxide trench loss compared to the reference sample.

[0274] When maltitol and BSA are used as dual chemical additives in the polishing composition, a significant reduction in oxide trench loss rate is achieved compared to the reference sample.

[0275] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0276] The effects of maltitol, benzenesulfonic acid (BSA), or maltitol + BSA on the SiN loss rate on patterned features of different sizes were tested. The effects are shown in Table 10 and depicted in... Figure 10 middle.

[0277] Table 10. Effects of maltitol and BSA additives on SiN loss rate Impact

[0278]

[0279]

[0280] As shown in Table 10 and Figure 10 The results shown indicate that, compared to the SiN film loss rate obtained from the reference sample, the addition of maltitol, a first-class additive, to the polishing composition as the chemical additive significantly reduced the SiN film loss rate.

[0281] Adding a second-class additive, BSA, to the polishing composition provided an improved SiN film loss rate compared to the reference sample.

[0282] When maltitol and BSA were used as dual chemical additives in the same polishing composition, a significant reduction in SiN film loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest SiN film loss rate among all tested polishing compositions and the reference sample.

[0283] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ adjustment.

[0284] The oxide trench indentation rates on patterned features of different sizes were tested using maltitol or benzenesulfonic acid (BSA) or maltitol + BSA. The effects are shown in Table 11 and depicted in... Figure 11 middle.

[0285] Table 11. Effects of maltitol and BSA additives on oxide groove indentation rate Impact

[0286]

[0287]

[0288] As shown in Table 11 and Figure 11 The results shown indicate that, compared to the oxide trench indentation rate obtained from the reference sample, the addition of maltitol, a first-class additive, to the polishing composition as the chemical additive significantly reduced the oxide trench indentation rate.

[0289] Adding a second-class additive, BSA, to the polishing composition provided a slightly lower oxide trench indentation rate compared to the reference sample.

[0290] When maltitol and BSA are used as dual chemical additives in the polishing composition, a significant reduction in oxide trench indentation rate is achieved compared to the reference sample.

[0291] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0292] The effects of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on the slope of the relative overpolishing removal of grooves on patterned features of different sizes were tested. The results are listed in Table 12 and plotted on... Figure 12 middle.

[0293] Table 12. Effects of maltitol and BSA on the slope of the indentation relative to OP.

[0294]

[0295] As shown in Table 12 and Figure 12 The results shown indicate that the slope of the groove depression relative to overpolishing was significantly reduced compared to the slope obtained from the reference sample when either the first type additive maltitol or the second type additive BSA was added to the polishing composition, whether alone or together as a chemical additive in the polishing composition.

[0296] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0297] Example 5

[0298] As noted in the preceding description, the oxide or doped oxide CMP polishing compositions of the present invention can be used in a wide pH window to provide high oxide film removal rates, suppressed SiN removal rates, improved oxide:SiN selectivity, and low oxide trench depressions.

[0299] In Example 5, the polishing composition of the present invention was tested under acidic pH conditions of 4.5.

[0300] In Example 5, the polishing composition used for the polishing test is shown in Table 13. The reference sample was prepared at pH 4.5 using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water.

[0301] In the test samples, D-sorbitol or benzenesulfonic acid (BSA) were used alone or together at 0.15% by weight or 0.1% by weight, respectively.

[0302] All reference and test samples had the same pH value of approximately 4.5.

[0303] The effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the removal rate and TEOS:SiN selectivity of various membrane types were tested, and the results are listed in Table 13.

[0304] Table 13. Effects of chemical additives on membrane RR at pH 4.5 The effect of TEOS: SiN selectivity.

[0305]

[0306]

[0307] The polishing conditions used were: Dow IC1010 pads, 3.0psi DF, table speed / head speed 87 / 93rpm, and non-in-situ finishing.

[0308] As shown in Table 13, the addition of D-sorbitol as a chemical additive to the polishing composition effectively suppressed the SiN film removal rate and improved the HDP film removal rate. Therefore, the TEOS:SiN selectivity was significantly improved.

[0309] Adding benzenesulfonic acid as the sole chemical additive to the polishing composition not only improved the removal rate of the SiN film, but also improved the removal rates of both the TEOS and HDP films. Therefore, a further reduction in the TEOS:SiN selectivity was achieved compared to the selectivity obtained from the reference sample.

[0310] When both the first type of additive, D-sorbitol, and the second type of additive, BSA, were added to the same polishing composition at pH 4.5, the removal rates of both TEOS and HPD films were still increased, while the removal rate of the SiN film was further suppressed. Therefore, the highest TEOS:SiN selectivity was achieved using both types of additives in the same polishing composition compared to the TEOS:SiN selectivity obtained at pH 4.5 using either of these additives alone or without them.

[0311] When comparing TEOS:SiN selectivity, the polishing composition using two classes of chemical additives provided a selectivity of 132:1, which is significantly higher than the 8:1 selectivity obtained from the reference sample at pH 4.5.

[0312] Furthermore, in Example 5, maltitol was used as an oxide trench reduction agent and BSA as an oxide film removal rate enhancer in the polishing composition used for polishing tests, as shown in Table 14. The reference sample was prepared at pH 4.5 using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water.

[0313] In the test samples at pH 4.5, maltitol was used alone or together with benzenesulfonic acid (BSA) at 0.28% by weight and / or 0.1% by weight, respectively.

[0314] All reference and test samples had the same pH value of approximately 4.5.

[0315] The effects of maltitol or maltitol plus benzenesulfonic acid (BSA) on membrane removal rate and TEOS:SiN selectivity were tested, and the results are listed in Table 14.

[0316] Table 14. Effects of chemical additives on membrane RR at pH 4.5 The effect of TEOS: SiN selectivity.

[0317]

[0318] As shown in Table 14, the addition of maltitol as a chemical additive to the polishing composition effectively suppressed the SiN film removal rate and improved the HDP film removal rate. Therefore, the TEOS:SiN selectivity was significantly increased.

[0319] At pH 4.5, adding benzenesulfonic acid as the sole chemical additive to the polishing composition not only improved the removal rate of the SiN film, but also improved the removal rates of both the TEOS and HDP films. Therefore, a further reduced TEOS:SiN selectivity was obtained compared to the selectivity obtained from the reference sample.

[0320] When both the first-class additive maltitol and the second-class additive BSA were added to the same polishing composition at pH 4.5, the removal rates of both TEOS and HPD films were still increased, while the removal rate of the SiN film was further suppressed. Therefore, at pH 4.5, the highest TEOS:SiN selectivity was achieved using both classes of additives in the same polishing composition compared to the TEOS:SiN selectivity obtained by using these additives alone or without using either of them.

[0321] When comparing TEOS:SiN selectivity, the polishing composition using two chemical additives provided a selectivity of 93:1, which is significantly higher than the 8:1 selectivity obtained from the reference sample at pH 4.5.

[0322] In Example 5, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on oxide trench depressions at pH 4.5 were tested, and the results are listed in Table 15.

[0323] Table 15. Effects of D-sorbitol and BSA additives on oxide trench depressions at pH 4.5 Impact of relative OP time (seconds)

[0324]

[0325] As shown in Table 15, compared to the relative overpolishing time of the resulting oxide trench depressions obtained from the reference sample, the addition of the first-class additive D-sorbitol as the chemical additive to the polishing composition at pH 4.5 significantly reduced the relative overpolishing time of the oxide trench depressions.

[0326] Compared to the reference sample, the addition of the second additive BSA at pH 4.5 resulted in poorer oxide trench depression relative overpolishing time.

[0327] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 4.5, a significant reduction in oxide groove indentation relative to overpolishing time was achieved compared to the reference sample.

[0328] Compared to using either of these two additives alone, the polishing composition based on dual chemical additives at pH 4.5 provides a more stable overpolishing window.

[0329] In Example 5, the effects of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on oxide trench depressions at pH 4.5 were tested for different overpolishing times, and the results are listed in Table 16.

[0330] Table 16. Effects of maltitol and BSA additives on oxide groove depressions at pH 4.5 Impact of relative OP time (seconds)

[0331]

[0332] As shown in Table 16, compared with the relative overpolishing time of oxide trench depressions obtained from the reference sample, the addition of maltitol as a Class I additive to the polishing composition at pH 4.5 significantly reduced the relative overpolishing time of oxide trench depressions.

[0333] Compared to the reference sample, the addition of the second-generation additive BSA at pH 4.5 resulted in poorer relative overpolishing time for oxide trench depressions.

[0334] When maltitol and BSA were used as dual chemical additives in the same polishing composition at pH 4.5, a significant reduction in oxide trench pits with different overpolishing times was achieved compared to the reference sample.

[0335] Compared to using either of these two additives alone, the polishing composition based on dual chemical additives at pH 4.5 provides a more stable overpolishing window.

[0336] In Example 5, the effect of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the rate of oxide trench loss was tested at pH 4.5. The effects are shown in Table 17.

[0337] Table 17. Effects of D-sorbitol and BSA additives on oxide trench loss rate Impact

[0338]

[0339] As shown in Table 17, the addition of D-sorbitol, a Class I additive, to the polishing composition at pH 4.5 significantly reduced the oxide trench loss rate compared to the oxide trench loss rate obtained from the reference sample.

[0340] At pH 4.5, the addition of BSA (a type II additive) to the polishing composition provided a significantly increased oxide trench loss rate compared to the reference sample.

[0341] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 4.5, a significant reduction in oxide trench loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest oxide trench loss rate among all tested polishing compositions and the reference sample.

[0342] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0343] In Example 5, the effect of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on the rate of oxide trench loss was tested at pH 4.5. The effects are shown in Table 18.

[0344] Table 18. Effects of maltitol and BSA additives on oxide trench loss rate at pH 4.5 Impact

[0345]

[0346] As shown in Table 18, the addition of maltitol as a Class I additive to the polishing composition at pH 4.5 significantly reduced the oxide trench loss rate compared to the oxide trench loss rate obtained from the reference sample.

[0347] Adding the second-class additive BSA to the polishing composition at pH 4.5 provided a significantly increased oxide trench loss rate compared to the reference sample.

[0348] When maltitol and BSA were used as dual chemical additives in the same polishing composition at pH 4.5, a significant reduction in oxide trench loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest oxide trench loss rate among all tested polishing compositions and the reference sample.

[0349] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0350] In Example 5, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the SiN loss rate of patterned features of different sizes were tested at pH 4.5. The effects are shown in Table 19.

[0351] Table 19. Effects of D-sorbitol and BSA additives on SiN loss rate at pH 4.5 Impact

[0352]

[0353] As shown in Table 19, compared with the SiN film loss rate obtained from the reference sample, the addition of the first type additive D-sorbitol as the chemical additive to the polishing composition at pH 4.5 significantly reduced the SiN film loss rate.

[0354] Adding a second type of additive, BSA, to the polishing composition provided an increased SiN film loss rate compared to the reference sample.

[0355] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 4.5, a significant reduction in SiN film loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest SiN film loss rate among all tested polishing compositions and the reference sample.

[0356] In Example 5, the effect of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the oxide trench indentation rate of patterned features of different sizes was tested at pH 4.5. The effects are shown in Table 20.

[0357] Table 20. Effects of D-sorbitol and BSA additives on oxide trench indentation rate at pH 4.5 Impact

[0358]

[0359] As shown in Table 20, the addition of D-sorbitol, a Class I additive, to the polishing composition at pH 4.5 significantly reduced the oxide trench indentation rate compared to that obtained from the reference sample.

[0360] Adding a second-class additive, BSA, to the polishing composition at pH 4.5 provided a greater oxide trench indentation rate compared to the reference sample.

[0361] When D-sorbitol and BSA were used as dual chemical additives in the polishing composition at pH 4.5, a significant reduction in oxide trench indentation rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest oxide trench indentation rate among all tested polishing compositions and the reference sample.

[0362] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0363] In Example 5, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the slope of the relative overpolishing removal of grooves on patterned features of different sizes were tested at pH 4.5, and the results are listed in Table 21.

[0364] Table 21. Effects of D-sorbitol and BSA on the slope of the depression relative to OP at pH 4.5

[0365]

[0366] As shown in Table 21, compared with the slope obtained from the reference sample, the addition of the first type additive D-sorbitol as the chemical additive to the polishing composition at pH 4.5 significantly reduced the slope of the groove depression relative to the overpolishing amount.

[0367] Compared to the slope obtained from the reference sample, the slope of the groove depression relative to the overpolishing amount increased when BSA, a second type of additive, was added as a chemical additive to the polishing composition at pH 4.5.

[0368] When D-sorbitol and BSA were used as dual chemical additives in the polishing composition at pH 4.5, a significantly reduced slope of groove retraction relative to oxide film overpolishing was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest slope of oxide retraction relative to oxide film overpolishing among all tested polishing compositions and the reference sample.

[0369] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0370] Example 6

[0371] As noted in the preceding description, the oxide or doped oxide CMP polishing compositions of the present invention can be used in a wide pH window to provide high oxide film removal rates, suppressed SiN removal rates, improved oxide:SiN selectivity, and low oxide trench depressions.

[0372] In Example 6, the polishing composition of the present invention was tested under alkaline pH conditions of 7.5.

[0373] In Example 6, the polishing composition used for the polishing test is shown in Table 22. The reference sample was prepared at pH 7.5 using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water.

[0374] In the test samples, D-sorbitol or benzenesulfonic acid (BSA) were used alone or together at 0.15% by weight and / or 0.1% by weight, respectively.

[0375] All reference and test samples had the same pH value of approximately 7.5.

[0376] At pH 7.5, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the removal rate and TEOS:SiN selectivity of various membrane types were tested, and the results are listed in Table 22.

[0377] Table 22. Effects of chemical additives on membrane RR at pH 7.5 The effect of TEOS: SiN selectivity.

[0378]

[0379]

[0380] The polishing conditions used were: Dow IC1010 pads, 3.0psi DF, table speed / head speed 87 / 93rpm, and non-in-situ finishing.

[0381] As shown in Table 22, the addition of D-sorbitol as a chemical additive to the polishing composition at pH 7.5 effectively suppressed the SiN film removal rate. Therefore, the TEOS:SiN selectivity was significantly improved.

[0382] Adding benzenesulfonic acid as the sole chemical additive to the polishing composition at pH 7.5 not only improved the removal rate of the SiN film, but also improved the removal rates of both the TEOS and HDP films. Therefore, a further decrease in the TEOS:SiN selectivity was observed compared to the selectivity obtained from the reference sample.

[0383] When both the first-class additive D-sorbitol and the second-class additive BSA were added to the same polishing composition at pH 7.5, the removal rates of both TEOS and HPD films were still increased, while the removal rate of SiN films was further suppressed. Therefore, the highest TEOS:SiN selectivity was achieved when both classes of additives were used in the same polishing composition, compared to the TEOS:SiN selectivity obtained at pH 7.5 using either of these additives alone or without them.

[0384] When comparing TEOS:SiN selectivity, the polishing composition using two classes of chemical additives provided a selectivity of 89:1, which is significantly higher than the 8:1 selectivity obtained from the reference sample at pH 7.5.

[0385] Furthermore, in Example 6, maltitol was used as an oxide trench reduction agent and BSA as an oxide film removal rate enhancer in the polishing composition used for polishing tests at pH 7.5, as shown in Table 23. The reference sample was prepared at pH 7.5 using 0.2 wt% cerium dioxide-coated silica particles, a very low concentration of biocide, and deionized water.

[0386] In the test samples, maltitol was used alone or in combination with benzenesulfonic acid (BSA) at 0.28% by weight and / or 0.1% by weight, respectively.

[0387] All reference and test samples had the same pH value of approximately 7.5.

[0388] The effects of maltitol, BSA, or maltitol plus benzenesulfonic acid (BSA) on membrane removal rate and TEOS:SiN selectivity were tested, and the results are listed in Table 23.

[0389] Table 23. Effects of chemical additives on membrane RR at pH 7.5 The effect of TEOS: SiN selectivity.

[0390]

[0391] As shown in Table 23, the addition of maltitol as a chemical additive to the polishing composition at pH 7.5 effectively suppressed the SiN film removal rate. Therefore, the TEOS:SiN selectivity was significantly improved.

[0392] At pH 7.5, adding benzenesulfonic acid as the sole chemical additive to the polishing composition not only improved the removal rate of the SiN film, but also improved the removal rates of both the TEOS and HDP films. Therefore, a further decrease in the TEOS:SiN selectivity was observed compared to the selectivity obtained from the reference sample.

[0393] When both the first-class additive maltitol and the second-class additive BSA were added to the same polishing composition at pH 7.5, the removal rates of both TEOS and HPD films were still increased, while the removal rate of the SiN film was further suppressed. Therefore, at pH 7.5, the highest TEOS:SiN selectivity was achieved when using both classes of additives in the same polishing composition, compared to the TEOS:SiN selectivity obtained by using these additives alone or without using either of them.

[0394] When comparing TEOS:SiN selectivity, the polishing composition using two classes of chemical additives provided a selectivity of 83:1, which is significantly higher than the 8:1 selectivity obtained from the reference sample at pH 7.5.

[0395] In Example 6, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on oxide trench depressions at pH 7.5 were tested, and the results are listed in Table 24.

[0396] Table 24. Effects of D-sorbitol and BSA additives on oxide groove depressions at pH 7.5 Impact of relative OP time (seconds)

[0397]

[0398] As shown in Table 24, compared with the oxide groove depressions obtained from the reference sample at different overpolishing times, the addition of the first-class additive D-sorbitol as the chemical additive to the polishing composition at pH 7.5 significantly reduced the oxide groove depressions at different overpolishing times.

[0399] Compared to the reference sample, the addition of the second additive BSA at pH 7.5 resulted in poorer oxide trench depression relative overpolishing time.

[0400] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 7.5, a significant reduction in oxide groove indentation relative to overpolishing time was achieved compared to the reference sample.

[0401] Compared to using either of these two classes of additives alone, the polishing composition based on dual chemical additives at pH 7.5 provides a more stable overpolishing window.

[0402] In Example 6, the effects of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on oxide trench depressions at pH 7.5 were tested for different overpolishing times, and the results are listed in Table 25.

[0403] Table 25. Effects of maltitol and BSA additives on oxide groove depressions at pH 7.5 Impact of relative OP time (seconds)

[0404]

[0405] As shown in Table 25, compared with the oxide trench depressions obtained from the reference sample at different overpolishing times, the addition of maltitol as a Class I additive to the polishing composition at pH 7.5 significantly reduced the oxide trench depressions at different overpolishing times.

[0406] Compared to the reference sample, the addition of the second-generation additive BSA at pH 7.5 resulted in poorer oxide trench depression relative overpolishing time.

[0407] When maltitol and BSA were used as dual chemical additives in the same polishing composition at pH 7.5, a significant reduction in oxide trench indentation with relative overpolishing time was achieved compared to the reference sample.

[0408] Compared to using either of these two classes of additives alone, the polishing composition based on dual chemical additives at pH 7.5 provides a more stable overpolishing window.

[0409] In Example 6, the effect of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the rate of oxide trench loss was tested at pH 7.5. The effects are shown in Table 26.

[0410] Table 26. Effects of D-sorbitol and BSA additives on oxide trench loss rate at pH 7.5 Impact

[0411]

[0412] As shown in Table 26, the addition of D-sorbitol, a Class I additive, to the polishing composition at pH 7.5 significantly reduced the oxide trench loss rate compared to the oxide trench loss rate obtained from the reference sample.

[0413] Adding the second-class additive BSA to the polishing composition at pH 7.5 provided a significantly increased oxide trench loss rate compared to the reference sample.

[0414] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 7.5, a significantly reduced oxide trench loss rate was achieved compared to the reference sample. At pH 7.5, the dual chemical additives in the same polishing composition provided the lowest oxide trench loss rate among all tested polishing compositions and the reference sample.

[0415] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0416] In Example 6, the effect of maltitol or benzenesulfonic acid (BSA) or maltitol + BSA on the rate of oxide trench loss was tested at pH 7.5. The effects are shown in Table 27.

[0417] Table 27. Effects of maltitol and BSA additives on oxide trench loss rate at pH 7.5 Impact

[0418]

[0419] As shown in Table 27, the addition of maltitol as a Class I additive to the polishing composition at pH 7.5 significantly reduced the oxide trench loss rate compared to the oxide trench loss rate obtained from the reference sample.

[0420] Adding the second-class additive BSA to the polishing composition at pH 7.5 provided a significantly increased oxide trench loss rate compared to the reference sample.

[0421] When maltitol and BSA were used as dual chemical additives in the same polishing composition at pH 7.5, a significantly reduced oxide trench loss rate was achieved compared to the reference sample. At pH 7.5, the dual chemical additives in the same polishing composition provided the lowest oxide trench loss rate among all tested polishing compositions and the reference sample.

[0422] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0423] In Example 6, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the SiN loss rate of patterned features of different sizes were tested at pH 7.5. The effects are shown in Table 28.

[0424] Table 28. Effects of D-sorbitol and BSA additives on SiN loss rate at pH 7.5 Impact

[0425]

[0426] As shown in Table 28, the addition of D-sorbitol, a Class I additive, to the polishing composition at pH 7.5 significantly reduced the SiN film loss rate compared to that obtained from the reference sample.

[0427] Adding a second-class additive, BSA, to the polishing composition at pH 7.5 provided an increased SiN film loss rate compared to the reference sample.

[0428] When D-sorbitol and BSA were used as dual chemical additives in the same polishing composition at pH 7.5, a significantly reduced SiN film loss rate was achieved compared to the reference sample. The dual chemical additives in the same polishing composition provided the lowest SiN film loss rate among all tested polishing compositions and the reference sample.

[0429] In Example 6, the effect of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the oxide trench indentation rate of patterned features of different sizes was tested at pH 7.5. The effects are shown in Table 29.

[0430] Table 29. Effects of D-sorbitol and BSA additives on oxide groove indentation rate at pH 7.5 Impact

[0431]

[0432] As shown in Table 29, the addition of D-sorbitol, a Class I additive, to the polishing composition at pH 7.5 significantly reduced the oxide trench indentation rate compared to that obtained from the reference sample.

[0433] Adding a second-class additive, BSA, to the polishing composition at pH 7.5 provided an increased oxide trench indentation rate compared to the reference sample.

[0434] When D-sorbitol and BSA were used as dual chemical additives in the polishing composition at pH 7.5, a significantly reduced oxide trench indentation rate was achieved compared to the reference sample. At pH 7.5, the dual chemical additives in the same polishing composition provided the lowest oxide trench indentation rate among all tested polishing compositions and the reference sample.

[0435] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0436] In Example 6, the effects of D-sorbitol or benzenesulfonic acid (BSA) or D-sorbitol + BSA on the slope of the relative overpolishing removal of grooves on patterned features of different sizes were tested at pH 7.5, and the results are listed in Table 30.

[0437] Table 30. Effects of D-sorbitol and BSA on the slope of the depression relative to OP at pH 7.5

[0438]

[0439] As shown in Table 30, compared to the results obtained from the reference sample, the addition of the first-class additive D-sorbitol as the chemical additive to the polishing composition at pH 7.5 significantly reduced the slope of the groove depression relative to the overpolishing amount.

[0440] Compared to the reference sample, when BSA (a type II additive) was added as a chemical additive to the polishing composition at pH 7.5, the slope of the groove depression relative to the overpolishing amount was slightly reduced.

[0441] When D-sorbitol and BSA were used as dual chemical additives in the polishing composition at pH 7.5, the slope of groove retraction relative to oxide film overpolishing was significantly reduced compared to the reference sample. The dual chemical additives in the same polishing composition at pH 7.5 provided the lowest slope of groove retraction relative to oxide film overpolishing among all tested polishing compositions and the reference sample.

[0442] The polishing conditions for patterned wafer polishing are: Dow IC1010 pads, 3.0 psi downward force, stage speed / head speed of 87 / 93 rpm, and in-situ finishing.

[0443] The embodiments of the invention listed above, including working examples, are examples of numerous embodiments that can be made 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 planarization (CMP) composition for a semiconductor substrate having at least one surface comprising a silicon oxide film, comprising: a. 0.05 to 10% by weight of abrasive, selected from cerium dioxide-coated inorganic oxides, cerium dioxide-coated organic polymer particles, and combinations thereof; b. 0.005 to 1.0% by weight of a first additive, selected from maltitol or D-sorbitol; c. A second additive, wherein the second additive is benzenesulfonic acid; d. A solvent selected from water, ether, and alcohol; and optionally... e. Biocides and pH adjusters; The pH range of the composition is 3 to 10.

2. The CMP composition according to claim 1, wherein the abrasive is a cerium dioxide-coated inorganic oxide selected from: 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; and combinations thereof.

3. The CMP composition according to claim 1 or 2, wherein the first additive is D-sorbitol.

4. 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. Contacting the at least one silicon oxide-containing surface with a CMP polishing pad and the CMP composition according to any one of claims 1-3; and b. Polish the at least one surface containing silicon oxide.

5. The method according to claim 4, wherein the silicon oxide film is selected from chemical vapor deposition (CVD), plasma-enhanced CVD (PECVD), high-density deposition CVD (HDP), and spin-coated silicon oxide films.

6. The method according to claim 4 or 5, wherein the silicon oxide film is a SiO2 film.

7. The method of claim 4 or 5, wherein the semiconductor substrate further comprises a silicon nitride surface; and step (b) comprises selectively polishing the at least one silicon dioxide-containing surface with a silicon oxide:silicon nitride removal ratio greater than 60.

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