Low Oxide Trench Dishing Chemical Mechanical Polishing

Information

  • Patent Application
  • 20200002607
  • Publication Number
    20200002607
  • Date Filed
    June 24, 2019
    5 years ago
  • Date Published
    January 02, 2020
    5 years ago
Abstract
Chemical mechanical planarization (CMP) polishing compositions, methods and systems are provided to reduce oxide trench dishing and improve over-polishing window stability. High and tunable silicon oxide removal rates, low silicon nitride removal rates, and tunable SiO2: SiN selectivity are also provided. The compositions use a unique combination of abrasives, such as ceria coated silica particles; and the chemical additives, such as maltitol, lactitol, maltotritol, 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 reducing additives.
Description
BACKGROUND OF THE INVENTION

This invention relates to the chemical mechanical planarization (CMP) for polishing oxide and doped oxide films.


In the fabrication of microelectronics devices, an important step involved is polishing, especially surfaces for chemical-mechanical polishing for the purpose of recovering a selected material and/or planarizing the structure.


For example, a SiN layer is deposited under a SiO2 layer to serve as a polish stop. The role of such polish stop is particularly important in Shallow Trench Isolation (STI) structures. Selectivity is characteristically expressed as the ratio of the oxide polish rate to the nitride polish rate. An example is an increased polishing selectivity rate of silicon dioxide (SiO2) as compared to silicon nitride (SiN).


In the global planarization of patterned structures, reducing oxide trench dishing is a key factor to be considered. The lower trench oxide loss will prevent electrical current leaking between adjacent transistors. Non-uniform trench oxide loss across die (within Die) will affect transistor performance and device fabrication yields. Severe trench oxide loss (high oxide trench dishing) will cause poor isolation of transistor resulting in device failure. Therefore, it is important to reduce trench oxide loss by reducing oxide trench dishing in CMP polishing compositions.


U.S. Pat. No. 5,876,490 discloses the polishing compositions containing abrasive particles and exhibiting normal stress effects. The slurry further contains non-polishing particles resulting in reduced polishing rate at recesses, while the abrasive particles maintain high polish rates at elevations. This leads to improved planarization. More specifically, the slurry comprises cerium oxide particles and polymeric electrolyte, and can be used for Shallow Trench Isolation (STI) polishing applications.


U.S. Pat. No. 6,964,923 teaches the polishing compositions containing cerium oxide particles and polymeric electrolyte for Shallow Trench Isolation (STI) polishing applications. Polymeric electrolyte being used includes the salts of polyacrylic acid, similar as those in U.S. Pat. No. 5,876,490. Ceria, alumina, silica & zirconia are used as abrasives. Molecular weight for such listed polyelectrolyte is from 300 to 20,000, but in overall, <100,000.


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


However, those prior disclosed Shallow Trench Isolation (STI) polishing compositions did not address the importance of oxide trench dishing reducing.


It should be readily apparent from the foregoing that there remains a need within the art for compositions, methods and systems of chemical mechanical polishing that can afford the reduced oxide trench dishing and improved over polishing window stability in a chemical and mechanical polishing (CMP) process, in addition to high removal rate of silicon dioxide as well as high selectivity for silicon dioxide to silicon nitride.


BRIEF SUMMARY OF THE INVENTION

The present invention provides Chemical mechanical polishing (CMP) polishing compositions, methods and systems for a reduced oxide trench dishing and thus improved over polishing window stability by introducing chemical additives as oxide trench dishing reducing additives compositions at wide pH range including acidic, neutral and alkaline pH conditions.


The present invention also provides the benefits of achieving high oxide film removal rates, low SiN film removal rates, high and tunable Oxide: SiN selectivity, lower total defect counts post-polishing, and excellent mean particle size (nm) stability.


In one aspect, there is provided a CMP polishing composition comprises:


abrasive particles selected from the group consisting of ceria-coated inorganic metal oxide particles, ceria-coated organic polymer particles, and combinations thereof;


chemical additive as oxide trenching dishing reducer,


a solvent; and


optionally


biocide; and


pH adjuster;


wherein the composition has a pH of 2 to 12, preferably 3 to 10, and more preferably 4 to 9.


The ceria-coated inorganic metal oxide particles include, but are not limited to, ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia, or any other ceria-coated inorganic metal oxide particles.


The ceria-coated organic polymer particles include, but are not limited to, ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, or any other ceria-coated organic polymer particles.


The solvent includes but is not limited to deionized (DI) water, distilled water, and alcoholic organic solvents.


The chemical additives as oxide trenching dishing reducers contain at least two or more, preferably four or more, more preferably six or more hydroxyl functional groups in their molecular structures.


In one embodiment, the chemical additive has a general molecular structure as shown below:




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In the general molecular structure, n is selected from 2 to 5,000, from 3 to 12, preferably from 4 to 7.


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


Each of Rs in the group of R1 to R3 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof; wherein, at least two or more, preferably four of them are hydrogen atoms.


When R1, R2, and R3 are the same and are hydrogen atoms, the chemical additive bears multi hydroxyl functional groups.


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




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In another embodiment, the chemical additive has a structure shown below:




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


Each of R1 and R2 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof.


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




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When R1 and R2 are all hydrogen atoms, and n=4, the chemical additive is D-mannose or L-mannose.




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In yet another embodiment, the chemical additive has a molecular structure selected from the group comprising of at least one (f), at least one (g), at least one (h) and combinations thereof;




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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.


They can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof; wherein, at least two or more, preferably four or more of them are hydrogen atoms.


When R1, R2, R3 R4, R5, R6, R7 R8, R9, R10, R11, R12, R13, and R14 are all hydrogen atoms which provide the chemical additives bearing multi hydroxyl functional groups.


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




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Yet, in another embodiment, the chemical additives contain at least one six-member ring structure motif ether bonded with at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures or at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures and at least one six-member ring polyol. A polyol is an organic compound containing hydroxyl groups.


The chemical additives as oxide trenching dishing reducers contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structures.


The general molecular structure for the chemical additives is shown in (a):




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




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


the rest of Rs in the group of R1 to R5 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof.


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




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wherein each of R10, R11, R12, R13 and R14 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof;


and the rest of Rs in the group of R1 to R5 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof.


In the general molecular structure, at least two, preferably four, more preferably six of the Rs in the group of R1 to R9 are hydrogen atoms.


When only one R, such as R5 in the group of R1 to R5 in the general molecular structure is a polyol molecular unit (b) having n=2 and m=1; and all rest of Rs in the group of R1 to R9 are all hydrogen atoms, the following two chemical additives are obtained:




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When one R, such as R5 is a polyol molecular unit (b) having n=2 and m=1; and one R, such as R2 is a six-member ring polyol; and all rest of Rs in the group of R1 to R14 are all hydrogen atoms, the following chemical additive is obtained:




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The chemical additive comprises maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, ribose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, beta-lactose, arabinose, and combinations thereof. The preferred chemical additives are maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sucrose, ribose, Inositol, glucose. D-(+)-mannose, beta-lactose, and combinations thereof. The more preferred chemical additives are maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(−)-Fructose, beta-lactose, and combinations thereof.


In some embodiments, the CMP polishing compositions can be made into two or more parts and mixed at the point of use.


In another aspect, there is provided a method of chemical mechanical polishing (CMP) a substrate having at least one surface comprising silicon dioxide (such tetraethyl orthosilicate or TEOS) using the chemical mechanical polishing (CMP) composition described above.


In yet another aspect, there is provided a system of chemical mechanical polishing (CMP) a substrate having at least one surface comprising silicon dioxide using the chemical mechanical polishing (CMP) composition described above.

    • The polished oxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD (HDP), spin on oxide films or flowable CVD oxide film, carbon doped oxide film, or nitrogen doped oxide film.


The substrate disclosed above can further comprises a silicon nitride (SiN) surface. The removal selectivity of SiO2: SiN is greater than 10, preferably greater than 20, and more preferably greater than 30.







DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the Chemical mechanical polishing (CMP) compositions, methods and systems for polishing oxide.


In the global planarization of patterned structures, reducing oxide trench dishing is a key factor to be considered. The lower trench oxide loss will prevent electrical current leaking between adjacent transistors. Non-uniform trench oxide loss across die or/and within Die will affect transistor performance and device fabrication yields. Severe trench oxide loss (high oxide trench dishing) will cause poor isolation of transistor resulting in device failure. Therefore, it is important to reduce trench oxide loss by reducing oxide trench dishing in CMP polishing compositions.


The CMP compositions comprise the unique combination of abrasive and the suitable chemical additives.


This invention provides a reduced oxide trench dishing and thus improved over polishing window stability by introducing chemical additives as oxide trench dishing reducing additives in the Chemical mechanical polishing (CMP) compositions at wide pH range including acidic, neutral and alkaline pH conditions.


The Chemical Mechanical Polishing (CMP) compositions provide high oxide film removal rates, low SiN film removal rates and high SiO2: SiN selectivity.


The Chemical Mechanical Polishing (CMP) composition also further provides excellent mean particle size and size distribution stability for the abrasive particles which is very important in maintaining robust CMP polishing performances with minimized polishing performance variations.


In one aspect, there is provided a CMP polishing composition comprises:


abrasive particles selected from the group consisting of ceria-coated inorganic metal oxide particles, ceria-coated organic polymer particles, and combinations thereof;


chemical additives as oxide trenching dishing reducers,


a solvent; and


optionally


biocide; and


pH adjuster;


wherein the composition has a pH of 2 to 12, preferably 3 to 10, and more preferably 4 to 9.


The ceria-coated inorganic metal oxide particles include, but are not limited to, ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia, or any other ceria-coated inorganic metal oxide particles.


The ceria-coated organic polymer particles include, but are not limited to, ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, or any other ceria-coated organic polymer particles.


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


The concentrations of abrasive particles range from 0.01 wt. % to 20 wt. %, the preferred concentrations range from 0.05 wt. % to 10 wt. %, the more preferred concentrations range from 0.1 wt. % to 5 wt. %.


The preferred abrasive particles are ceria-coated inorganic metal oxide particles; more preferred abrasive particles are ceria-coated silica particles.


The solvent includes but is not limited to deionized (DI) water, distilled water, and alcoholic organic solvents.


The preferred solvent is DI water.


The CMP slurry may contain biocide from 0.0001 wt. % to 0.05 wt. %; preferably from 0.0005 wt. % to 0.025 wt. %, and more preferably from 0.001 wt. % to 0.01 wt. %.


The biocide includes, but is not limited to, Kathon™, Kathon™ CG/ICP II, from Dupont/Dow Chemical Co. Bioban from Dupont/Dow Chemical Co. They have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-isothiazolin-3-one.


The CMP slurry may contain a pH adjusting agent.


An acidic or basic pH adjusting agent can be used to adjust the polishing compositions to the optimized pH value.


The pH adjusting agents include, but are not limited to nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof.


pH adjusting agents also include the basic pH adjusting agents, such as sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and other chemical reagents that can be used to adjust pH towards the more alkaline direction.


The CMP slurry contains 0 wt. % to 1 wt. %; preferably 0.01 wt. % to 0.5 wt. %; more preferably 0.1 wt. % to 0.25 wt. % pH adjusting agent.


The CMP slurry contains 0.01 wt. % to 20 wt. %, 0.025 wt. % to 10 wt. %, 0.05 wt. % to 5 wt. %, or 0.1 to 3.0 wt. % of the chemical additives as oxide trenching dishing and total defect count reducers.


The chemical additives as oxide trenching dishing reducers contain at least two or more, preferably four or more, more preferably six or more hydroxyl functional groups in their molecular structures.


In one embodiment, the chemical additive has a general molecular structure as shown below:




embedded image


In the general molecular structure, n is selected from 2 to 5,000, from 3 to 12, preferably from 4 to 7.


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


Each of Rs in the group of R1 to R3 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof; wherein, at least two or more, preferably four of them are hydrogen atoms.


When R1, R2, and R3 are the same and are hydrogen atoms, the chemical additive bears multi hydroxyl functional groups.


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




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In another embodiment, the chemical additive has a structure shown below:




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


R1 and R2 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof.


When R1 and R2 are all hydrogen atoms, and n=3, the chemical additive is D-arabinose or L-arabinose.




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When R1, R2 and R3 are all hydrogen atoms, and n=4, the chemical additive is D-mannose or L-mannose.




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




embedded image


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.


They can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid, substituted organic sulfonic acid salt, substituted organic carboxylic acid, substituted organic carboxylic acid salt, organic carboxylic ester, organic amine groups, and combinations thereof; wherein, at least two or more, preferably four or more of them are hydrogen atoms.


When R1, R2, R3 R4, R5, R6, R7 R8, R9, R10, R11, R12, R13, and R14 are all hydrogen atoms which provide the chemical additives bearing multi hydroxyl functional groups.


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




embedded image


Yet, in another embodiment, the chemical additives contain at least one six-member ring structure motif ether bonded with at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures or at least one polyol molecular unit containing multiple hydroxyl functional groups in the molecular unit structures and at least one six-member ring polyol. A polyol is an organic compound containing hydroxyl groups.


The chemical additives as oxide trenching dishing reducers contain at least two, at least four, or at least six hydroxyl functional groups in their molecular structures.


The general molecular structure for the chemical additives is shown in (a):




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




embedded image


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


the rest of Rs in the group of R1 to R5 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof.


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




embedded image


wherein each of R10, R11, R12, R13 and R14 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof;


and the rest of Rs in the group of R1 to R5 can be independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof.


In the general molecular structure, at least two, preferably four, more preferably six of the Rs in the group of R1 to R9 are hydrogen atoms.


When only one R, such as R5 in the group of R1 to R5 in the general molecular structure is a polyol molecular unit (b) having n=2 and m=1; and all rest of Rs in the group of R1 to R9 are all hydrogen atoms, the following two chemical additives are obtained:




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When one R, such as R5 is a polyol molecular unit (b) having n=2 and m=1; and one R, such as R2 is a six-member ring polyol; and all rest of Rs in the group of R1 to R14 are all hydrogen atoms, the following chemical additive is obtained:




embedded image


The chemical additive comprises maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, ribose, beta-lactose, and combinations thereof. The preferred chemical additives are maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sucrose, ribose, Inositol, glucose. D-(+)-mannose, beta-lactose, and combinations thereof. The more preferred chemical additives are maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(−)-Fructose, beta-lactose, and combinations thereof.


In some embodiments, the CMP polishing compositions can be made into two or more parts and mixed at the point of use.


In another aspect, there is provided a method of chemical mechanical polishing (CMP) a substrate having at least one surface comprising silicon dioxide using the chemical mechanical polishing (CMP) composition described above. The polished oxide films can be CVD oxide, PECVD oxide, High density oxide, Spin on oxide films, flowable CVD oxide film, carbon doped oxide film, or nitrogen doped oxide film.


The polished oxide films can be Chemical vapor deposition (CVD), Plasma Enhance CVD (PECVD), High Density Deposition CVD (HDP), or spin on oxide films.


The substrate disclosed above can further comprises a silicon nitride surface. The removal selectivity of SiO2: SiN is greater than 10, preferably greater than 20, and more preferably greater than 30.


Dishing performance of the CMP compositions can also be characterized by the ratio of oxide trench dishing rate (Å/min.) vs the blanket HDP film removal rate (Å/min.).


The smaller of this ratio is, the lower oxide trench dishing is. The CMP compositions having the ratio of 0.1, 0.08, 0.06, 0.05, 0.03, or 0.02 provide good oxide dishing performance.


In CMP polishing compositions, it is very important to keep abrasive particles stable to assure consistent desired CMP polishing performance.


When using the chemical additives in the CMP polishing compositions, these chemical additives can have some impacts on the stability of abrasive particles in the compositions.


For example, when maltitol, lactitol or their derivatives, are used as oxide trench reducing agents in polishing compositions, these chemical additives can have some impacts on the stability of ceria-coated inorganic oxide abrasives in the CMP polishing compositions.


Typically, the abrasive particle stability is tested by monitoring the mean particle size (MPS) (nm) and particle size distribution parameter D99 (nm) changes vs the times or at elevated temperatures.


Particle size distribution may be quantified as a weight percentage of particles that has a size lower than a specified size. For example, parameter D99 (nm) represents a particle size (diameter) where 99 wt. % of all the slurry particles would have particle diameter equal to or smaller than the D99 (nm). That is, D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.


The smaller of MPS (nm) and D99 (nm) changes, the more stable of the abrasive particles are and thus the CMP polishing compositions are.


Particle size distribution can be measured by any suitable techniques such as imaging, dynamic light scattering, hydrodynamic fluid fractionation, disc centrifuge etc.


MPS (nm) and D99 (nm) are both measured by dynamic light scattering in this application.


CMP compositions providing abrasive particle stability have the changes for MPS (nm) and D99 (nm)≤6.0%, 5.0%, 3.0%, 2.0%, 1.0%, 0.5%, 0.3% or 0.1% for a shelf time of at least 30 days, 40 days, 50 days, 60 days, 70 days or 100 days at a temperature ranging from 20 to 60° C., 25 to 50° C.


The following non-limiting examples are presented to further illustrate the present invention.


CMP Methodology

In the examples presented below, CMP experiments were run using the procedures and experimental conditions given below.


Glossary
Components

Ceria-coated Silica: used as abrasive having a particle size of approximately 100 nanometers (nm); such ceria-coated silica particles can have a particle size of ranged from approximately 5 nanometers (nm) to 500 nanometers (nm);


Ceria-coated Silica particles (with varied sizes) were supplied by JGC Inc. in Japan.


Chemical additives, such as D-sorbitol, dulcitol, fructose, maltitol, lactitol and other chemical raw materials were supplied by Sigma-Aldrich, St. Louis, Mo.


TEOS: tetraethyl orthosilicate


Polishing Pad: Polishing pad, IC1010 and other pads were used during CMP, supplied by DOW, Inc.


Parameters
General

Å or A: angstrom(s)—a unit of length


BP: back pressure, in psi units


CMP: chemical mechanical planarization=chemical mechanical polishing


CS: carrier speed


DF: Down force: pressure applied during CMP, units psi


min: minute(s)


ml: milliliter(s)


mV: millivolt(s)


psi: pounds per square inch


PS: platen rotational speed of polishing tool, in rpm (revolution(s) per minute)


SF: slurry flow, ml/min


Wt. %: weight percentage (of a listed component)


TEOS: SiN Selectivity: (removal rate of TEOS)/(removal rate of SiN)


HDP: high density plasma deposited TEOS


TEOS or HDP Removal Rates: Measured TEOS or HDP removal rate at a given down pressure. The down pressure of the CMP tool was 2.0, 3.0 or 4.0 psi in the examples listed above.


SiN Removal Rates: Measured SiN removal rate at a given down pressure. The down pressure of the CMP tool was 3.0 psi in the examples listed.


Metrology

Films were measured with a ResMap CDE, model 168, manufactured by Creative Design Engineering, Inc, 20565 Alves Dr., Cupertino, Calif., 95014. The ResMap tool is a four-point probe sheet resistance tool. Forty-nine-point diameter scan at 5 mm edge exclusion for film was taken.


CMP Tool

The CMP tool that was used is a 200 mm Mirra, or 300 mm Reflexion manufactured by Applied Materials, 3050 Boweres Avenue, Santa Clara, Calif., 95054. An IC1000 pad supplied by DOW, Inc, 451 Bellevue Rd., Newark, Del. 19713 was used on platen 1 for blanket and pattern wafer studies.


The IC1010 pad or other pad was broken in by conditioning the pad for 18 mins. At 7 lbs. down force on the conditioner. To qualify the tool settings and the pad break-in two tungsten monitors and two TEOS monitors were polished with Versum® STI2305 slurry, supplied by Versum Materials Inc. at baseline conditions.


Wafers

Polishing experiments were conducted using PECVD or LECVD or HD TEOS wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 2985 Kifer Rd., Santa Clara, Calif. 95051.


Polishing Experiments

In blanket wafer studies, oxide blanket wafers, and SiN blanket wafers were polished at baseline conditions. The tool baseline conditions were: table speed; 87 rpm, head speed: 93 rpm, membrane pressure; 3.0 psi, inter-tube pressure; 3.1 psi, retaining ring pressure; 5.1 psi, slurry flow; 200 ml/min.


The slurry was used in polishing experiments on patterned wafers (MIT860), supplied by SWK Associates, Inc. 2920 Scott Blvd. Santa Clara, Calif. 95054). These wafers were measured on the Veeco VX300 profiler/AFM instrument. The 3 different sized pitch structures were used for oxide dishing measurement. The wafer was measured at center, middle, and edge die positions.


TEOS: SiN Selectivity: (removal rate of TEOS)/(removal rate of SiN) obtained from the CMP polishing compositions were tunable.


WORKING EXAMPLES

In the following working examples, a polishing composition comprising 0.2 wt. % cerium-coated silica, a biocide ranging from 0.0001 wt. % to 0.05 wt. %, and deionized water was prepared as reference (ref.).


The polishing compositions were prepared with the reference (0.2 wt. % cerium-coated silica, a biocide ranging from 0.0001 wt. % to 0.05 wt. %, and deionized water) plus a chemical additive in 0.01 wt. % to 2.0 wt. %.


All examples, except pH condition examples the composition had a pH at 5.35.


pH adjusting agent used for acidic pH condition and alkaline pH condition were nitric acid and ammonium hydroxide respectively.


Example 1

The working slurries has 0.15 wt. % chemical additives added to the reference slurry.


The effects of various selected chemical additives on the film removal rates and selectivity were observed.


The removal rates (RR at Å/min) for different films were tested. The test results were listed in Table 1.


As the results showed in Table 1, the slurries based on ceria-coated silica offered higher removal rate for TEOS.









TABLE 1







Effects of Chemical Additives


on Film RR (A/min.) & TEOS: SiN Selectivity












TEOS-RR
HDP-RR
SiN-RR
TEOS: SiN


Samples
(ang/min)
(ang/min)
(ang/min)
Selectivity














0.2 wt. % Ceria-coated
3279
2718
349
9


Silica (Ref.)


Ref. + 0.15 wt. %
2394
2299
75
32


D-Sorbitol


Ref. + 0.15 wt. %
2741
2372
124
22


D-Mannitol


Ref. + 0.15 wt. %
2839
2104
148
19


D-(+)-Mannose


Ref. + 0.15 wt. %
2694
2256
109
25


Xylitol


Ref. + 0.15 wt. %
2808
2064
366
8


meso-Erythritol









As the results further showed in Table 1, the chemical additives D-sorbitol,


D-mannitol, D-mannose, and xylitol, except meso-erythritol suppressed SiN removal rates comparing with the Ref., while still afforded high TEOS and HDP film removal rates and provided high Oxide: SiN selectivity.


Example 2

In Example 2, 0.2 wt. % ceria-coated silica abrasive based formulation without chemical additives was used as reference.


The chemical additives were used at 0.15 wt. % (0.15×) concentrations respectively with 0.2 wt. % ceria-coated silica as abrasives in the working slurries.


The test results were listed in Table 2. HDP RR (Å/min.) from Table 1 was also listed in Table 2.


Table 3 listed the ratio of oxide trench dishing rate (Å/min.) vs the blanket HDP film removal rate (Å/min.),









TABLE 2







Effects of Chemical Additives on Oxide Trench Dishing & HDP RR (A/min.)















Blanket HDP RR


Compositions
OP Time (sec.)
100 um pitch dishing
200 um pitch dishing
(A/min.)














0.2% Ceria-coated Silica pH 5.35
0
165
291
2718



60
857
1096



120
1207
1531


0.2% Ceria-coated Silica + 0.15X D-Sorbitol
0
137
276
2299



60
247
411



120
380
544


0.2% Ceria-coated Silica + 0.15X D-mannitol
0
162
285
2372



60
368
580



120
563
816


0.2% Ceria-coated Silica + 0.15X D-(+)-
0
181
272
2401


Mannose
60
660
973



120
1121
1553


0.2% Ceria-coated Silica + 0.15X Xylitol
0
144
258
2256



60
485
800



120
760
1166


0.2% Ceria-coated Silica + 0.15X meso-
0
131
265
2064


Erythritol
60
732
896



120
1125
1392









The test results were listed in Table 2. HDP RR (Å/min.) from Table 1 was also listed in Table 2.


Table 3 listed the ratio of oxide trench dishing rate (Å/min.) vs the blanket HDP film removal rate (Å/min.),









TABLE 3







The Ratio of Trench Dishing Rate (Å)/Blanket HDP RR (Å/min.)










P100
P200



Dishing Rate
Dishing Rate



(Å/min.)/Blanket
(Å/min.)/Blanket


Compositions
HDP RR (Å/min.)
HDP RR (Å/min.)












0.2% Ceria-coated Silica pH 5.35
0.13
0.16


0.2% Ceria-coated Silica + 0.15X
0.06
0.06


D-Sorbitol


0.2% Ceria-coated Silica + 0.15X
0.08
0.12


D-mannitol


0.2% Ceria-coated Silica + 0.15X
0.2
0.24


D-(+)-Mannose


0.2% Ceria-coated Silica + 0.15X
0.12
0.16


Xylitol


0.2% Ceria-coated Silica + 0.15X
0.19
0.24


meso-Erythritol









As the results shown in Tables 2 and 3, the addition of various chemical additives as oxide trench dishing reducer in polishing compositions showed different effects.


The polishing compositions using D-sorbitol and D-mannitol provided significant oxide trench dishing reductions on both 100 μm pitch and 200 μm pitch respectively, comparing to the reference.


The polishing composition using xylitol showed no impact on oxide trench dishing in polishing comparing to the reference. The polishing compositions using D-(+)-mannose or meso-erythritol had the oxide trench dishing worse than the reference.


The effects of chemical additives on the slopes of oxide trenching dishing vs over polishing removal amounts were listed in Table 4.









TABLE 4







Effects of Chemical Additives on Slopes of Dishing vs OP Removal


Amount











P100
P200
P1000



dishing/OP
dishing/OP
dishing/OP


Compositions
Amt Slope
Amt Slope
Amt Slope





0.2X Ceria-coated Silica
0.19
0.23
0.25


0.2X Ceria-coated Silica +
0.05
0.06
0.08


0.15x D-Sorbitol


0.2X Ceria-coated Silica +
0.08
0.11
0.40


0.15x D-Mannitol


0.2X Ceria Coated + 0.15x D-
0.20
0.27
0.38


(+)-Mannose


0.2X Ceria-coated Silica +
0.14
0.20
0.41


0.15x Xylitol









As the results shown in Table 4, the polishing composition using D-sorbitol or D-mannitol afforded much lower slope values of oxide trench dishing vs over polishing amounts on 100 μm and 200 μm features while comparing to the reference.


The other additives offered no dishing improvements comparing to the reference.


Example 3

The effects of various selected chemical additives on the film removal rates (RR at Å/min) and selectivity were observed. These chemical additives were used at 0.1 wt. % concentrations respectively with 0.2 wt. % ceria-coated silica as abrasives.


The test results were listed in Table 5.









TABLE 5







Effects of Chemical Additives on Film RR (A/min.) & TEOS: SiN


Selectivity












TEOS-RR
HDP-RR
SiN-RR
TEOS: SiN


Samples
(ang/min)
(ang/min)
(ang/min)
Selectivity














0.2% Ceria-Coated
3279
2718
349
9.4


Silica


+0.1x D-Sorbitol
2968
2814
92
32.3


+0.1x D-(−)-Fructose
1662
1781
34
48.9


+0.1x Maltitol
2834
2679
38
74.6


+0.1x Dulcitol
3127
2995
45
69.5









As the results showed in Table 5, these chemical additives D-sorbitol, D-(−)-Fructose, Maltitol and Dulcitol suppressed SiN removal rates while comparing with reference, and still afforded high TEOS and HDP film removal rates.


CMP composition having D-(−)-fructose suppressed removal of TEOS in addition of SiN, but still afforded high TEOS: SiN selectivity.


The effects of various selected chemical additives on the oxide trenching dishing vs over polishing times were observed.


The test results were listed in Table 6. HDP RR (Å/min.) from Table 5 was also listed in Table 6.









TABLE 6







Effects of Chemical Additives on Oxide Trench Dishing & HDP RR


(A/min.)














100 um
200 um
1000 um
Blanket



OP Time
pitch
pitch
pitch
HDP RR


Samples
(Sec.)
dishing
dishing
dishing
(A/min.)















0.2% Ceria-
0
165
291
1013
2718


coated Silica
60
857
1096
1821



120
1207
1531
2392


0.2% Ceria-
0
98
184
432
2814


coated Silica +
60
261
383
1494


0.1x D-Sorbitol
120
418
583
1936


0.2% Ceria-
0
123
229
694
1781


coated Silica +
60
315
372
962


0.1x D-(−)-
120
458
527
1175


Fructose


0.2% Ceria-
108
218
620
620
2679


coated Silica +
228
355
873
873


0.1x Maltitol
333
482
1068
1068


0.2% Ceria-
0
152
252
770
2995


coated Silica +
60
238
370
10


0.1x Dulcitol
120
366
495
1081









As the oxide trench dishing vs over polishing time results showed in Table 6, the CMP compositions with chemical additives afforded lower oxide trench dishing on 100 um pitch, and 200 um pitch, respectively. The compositions provided significant oxide trench dishing reductions comparing to the reference composition.


Table 7 listed the ratio of oxide trench dishing rate (Å/min.) vs the blanket HDP film removal rate (Å/min.),


As the results shown in Table 7, the addition of the chemical additives to the polishing compositions significantly reduced the ratio of trench dishing rate vs the blanket HDP film removal rates than the ratio obtained from the reference sample at pH 5.35.









TABLE 7







The Ratio of Trench Dishing Rate (Å)/Blanket HDP RR (Å/min.)










P100 Dishing Rate
P200 Dishing Rate



(Å/min.)/Blanket HDP
(Å/min.)/Blanket HDP


Compositions
RR (Å/min.)
RR (Å/min.)





0.2X Ceria-coated Silica
0.13
0.16


+0.1x D-Sorbitol
0.06
0.07


+0.1x D-(−)-Fructose
0.08
0.09


+0.1x Maltitol
0.05
0.07


+0.1x Dulcitol
0.04
0.04









The slopes of the various sized pitch dishing vs oxide over polishing amounts were listed in Table 8.









TABLE 8







Effects of Chemical Additives on Slopes of Dishing vs OP Removal


Amount











P100
P200
P1000



dishing/OP
dishing/OP
dishing/OP


Compositions
Amt Slope
Amt Slope
Amt Slope





0.2X Ceria-coated Silica
0.19
0.23
0.25


+0.1x D-Sorbitol
0.06
0.07
0.27


+0.1x D-(−)-Fructose
0.09
0.08
0.14


+0.1x Maltitol
0.04
0.05
0.08


+0.1x Dulcitol
0.04
0.04
0.05









As the results of slopes of the various sized pitch dishing vs oxide over polishing amounts showed in Table 8, the chemical additives and ceria-coated silica abrasives based CMP polishing compositions afforded much lower slope values comparing to those slope values obtained from the reference.


Example 4

In Example 4, the removal rates, and TEOS: SiN selectivity were tested tests were performed with CMP polishing compositions with chemical additives having different concentrations at pH 5.35.


The test results were listed in Table 9.









TABLE 9







Effects of Additive Conc. on Film RR (A/min.) & Selectivity of Oxide:


SiN












TEOS-RR
HDP-RR
SiN-RR
TEOS:


Samples
(ang/min)
(ang/min)
(ang/min)
SiN Sel.














0.2% Ceria-coated Silica +
3595
3128
110
33


0.05x D-Sorbitol


0.2% Ceria-coated Silica +
3821
3425
112
34


0.1x D-Sorbitol


0.2% Ceria-coated Silica +
3651
3517
83
44


0.15x D-Sorbitol









As the results showed in Table 9, when the concentration of D-sorbitol used in the compositions increased, similar TEOS removal rates were obtained, and HPD film removal rates were increased and TEOS: SiN selectivity were also increased slightly or significantly.


The effects on the oxide trenching dishing vs over polishing times from the selected chemical additive D-sorbitol concentrations on the various sized pitch features were tested.


The test results were listed in Table 10.









TABLE 10







Effects of Chemical Additive D-Sorbitol Conc. On Oxide Trench


Dishing vs OP Times(sec.)














200 um
Blanket



Polish Time
100 um pitch
pitch
HDP


Compositions
(Sec.)
dishing
dishing
RR














0.2% Ceria-coated
0
198
332
3128


Silica + 0.05x D-
60
453
690


Sorbitol
120
573
842


0.2% Ceria-coated
0
182
288
3425


Silica + 0.1x D-Sorbitol
60
355
551



120
499
736


0.2% Ceria-coated
0
132
246
3517


Silica + 0.15x D-
60
269
423


Sorbitol
120
423
595









As the results showed in Table 10, all 3 tested CMP polishing compositions contained D-sorbitol with different concentrations gave low oxide trench dishing on both 100 μm pitch and 200 μm pitch.


Also, as the chemical additive D-sorbitol concentrations increased, the oxide trench dishing are further reduced.


As the results showed in Table 10, all 3 tested CMP polishing compositions contained D-sorbitol with different concentrations gave low oxide trench dishing on both 100 μm pitch and 200 μm pitch.


Also, as the chemical additive D-sorbitol concentrations increased, the oxide trench dishing are further reduced.


Table 11 listed the ratio of Trench Dishing Rate (A)/Blanket HDP RR (Å/min.)


from the compositions with different concentrations of D-Sorbitol.









TABLE 11







Ratio of Trench Dishing Rate (Å)/Blanket HDP RR (Å/min.) vs Conc. of


D-Sorbitol










P100 Dishing Rate
P200 Dishing Rate



(Å/min.)/
(Å/min.)/



Blanket HDP
Blanket HDP


Compositions
RR (Å/min.)
RR (Å/min.)





0.2% Ceria-coated Silica +
0.04
0.05


0.05X D-Sorbitol


0.2% Ceria-coated Silica +
0.04
0.05


0.1X D-Sorbitol


0.2% Ceria-coated Silica +
0.04
0.05


0.15X D-Sorbitol









As the results shown in Table 11, D-sorbitol used in the composition at pH 5.35, all significantly reduced the ratio of trench dishing rate vs the blanket HDP film removal rates across the different tested concentrations.


Therefore, D-sorbitol can be used as an effective oxide trench dishing reducer in the wide concentration range.


The slopes of the various sized pitch dishing vs oxide over polishing amounts were tested and the results were listed in Table 12.









TABLE 12







Effects of Additive Conc. on Slopes of Dishing vs OP Removal Amount










P100 dishing/OP Amt
P200 dishing/OP


Compositions
Slope
Amt Slope





STI2305 (Reference)
0.01
0.01


0.2% Ceria-coated Silica +
0.06
0.08


0.05x D-Sorbitol


0.2% Ceria-coated Silica +
0.05
0.07


0.1x D-Sorbitol


0.2% Ceria-coated Silica +
0.04
0.05


0.15x D-Sorbitol









As the results of slopes of the various sized pitch dishing vs oxide over polishing amounts showed in Table 12, different concentrations of D-sorbitol in CMP polishing compositions all afforded similar slope values comparing to the reference sample.


Also, as the D-sorbitol concentration increased, the slopes of the various sized pitch dishing vs oxide over polishing while at over polishing time at zero seconds gradually decreased.


Example 5

In Example 5, the tests were performed with CMP polishing compositions having different pH values.


The composition composed of 0.2 wt. % ceria-coated silica as abrasives and 0.1 wt. % D-sorbitol as chemical additive was tested at three different pH conditions.


The removal rates (RR at Å/min) for different films were tested. The test results were listed in Table 13.









TABLE 13







Effects of pH on Film RR (A/min.) & Selectivity of Oxide: SiN











0.2% Ceria-coated






Silica + 0.1% D-
TEOS-RR
HDP-RR
SiN-RR
TEOS:


Sorbitol
(ang/min)
(ang/min)
(ang/min)
SiN Sel.














pH 5.35
3821
3425
112
34


pH 6
3759
3415
131
29


pH 8
2932
3084
94
31









As the results showed in Table 10, the compositions showed a consistent performance by offering high TEOS and HDP film removal rates, low SiN removal rates, and high TEOS: SiN selectivity in acidic, neutral or alkaline pH conditions..


The test results on the effects of pH conditions using the CMP polish compositions on oxide trench dishing vs over polishing times were performed.


The results were listed in Table 14.


As the results showed in Table 14, similar oxide trenching dishing vs over polishing times and HDP film removal rates were obtained for the same concentration of ceria-coated silica as abrasives and D-sorbitol as oxide trenching dishing reducing agent at 3 different pH conditions.









TABLE 14







Effects of pH Conditions on Oxide Trench Dishing vs Over Polishing


Times (sec.) & HDP Film RR (A/min.)













100 um
200 um




Polish Time
pitch
pitch
Blanket


Compositions & pH
(Sec.)
dishing
dishing
HDP RR














0.2% Ceria-coated Silica +
0
182
288
3425


0.1x D-Sorbitol (pH
60
355
551


5.35)
120
499
736


0.2% Ceria-coated Silica +
0
169
325
3415


0.1x D-Sorbitol (pH 6)
60
354
566



120
506
800


0.2% Ceria-coated Silica +
0
193
360
3084


0.1x D-Sorbitol (pH 8)
60
391
615



120
537
814









Table 15 showed the results of the ratio of Trench Dishing Rate (A)/Blanket HDP RR (Å/min.),









TABLE 15







Ratio of Trench Dishing Rate (Å)/Blanket HDP RR (Å/min.) at Different


pH










P100 Dishing Rate
P200 Dishing Rate



(Å/min.)/Blanket
(Å/min.)/Blanket


Compositions
HDP RR (Å/min.)
HDP RR (Å/min.)





0.2% Ceria-coated Silica +
0.04
0.05


0.1X D-Sorbitol (pH 5.35)


0.2% Ceria-coated Silica +
0.04
0.07


0.1X D-Sorbitol (pH 6)


0.2% Ceria-coated Silica +
0.05
0.06


0.1X D-Sorbitol (pH 7)









As the results shown in Table 15, the addition of the chemical additives, D-sorbitol, used as oxide trench dishing reducer in polishing compositions at different pH conditions, showed significantly reduction of the ratio which indicated that D-sorbitol can be used as a very effective oxide trench dishing reducing agent at wide pH window.


Example 6

In Example 6, the effects of various selected chemical additives from afore listed several types of chemical additives on the film removal rates and selectivity were observed.


The same molar concentrations of all tested chemical additives at 8.132 mM was used respectively.


All examples, except examples for the pH condition test had a pH at 5.35.


For the examples used in the pH condition test, pH adjusting agent was used for acidic pH condition and alkaline pH condition were nitric acid and ammonium hydroxide respectively.


The removal rates (RR at Å/min) and removal selectivity for different films were tested. The test results were listed in Table 16.


As the results showed in Table 16, these chemical additives, when used at 8.132 mM concentrations in the polishing compositions afforded similar TEOS film removal rates, HDP film removal rates, slightly or significantly suppressed SiN removal rates comparing with the reference.









TABLE 16







Effects of 8.132 mM Concentration of Chemical Additives on Film RR


(A/min.) & TEOS: SiN Selectivity












TEOS
HDP RR
PECVO SiN
TEOS SiN


Compositions
RR (A/min.)
(A/min.)
RR (A/min.)
Selectivity














0.2% Ceria-coated
2754
1886
432
6.4


Silica


0.2% Ceria-coated
2609
2493
45
58.4


Silica + 8.132 mM


Maltitol


0.2% Ceria-coated
2862
2512
114
25.1


Silica + 8.132 mM


Ribose


0.2% Ceria-coated
2963
1985
393
7.5


Silica + 8.132 mM


Arabinose


0.2% Ceria-coated
2913
2186
115
25.3


Silica + 8.132 mM


Beta-lactose


0.2% Ceria-coated
2899
2028
201
14.4


Silica + 8.132 mM


Myo-inositol









The Oxide: SiN selectivity was fluctuating from slightly increased (arabinose, myo-inositol) to significantly increased (maltitol, ribose and beta-lactose). Among these tested chemical, maltitol showed as the most efficient SiN removal rate suppressing chemical additive, and ribose and beta-lactose also showed as quite efficient SiN removal rate suppressing additives.


Example 7

The following chemical additives, maltitol, D-sorbitol, lactitol, ribose, and beta-lactose were used in the polishing compositions with 0.2 wt. % ceria-coated silica abrasives at pH 5.35 to have conducted polishing tests on polishing oxide patterned wafers. The chemical additives were used at 0.15 wt. % in the compositions.


The effects of various chemical additives on the film removal rates and selectivity were observed.


The test results were listed in Table 17.


As the results showed in Table 17, all compositions afforded similar high TEOS film removal rates, increased HDP film high removal rates, significantly suppressed SiN removal rates, significantly increased Oxide: SiN selectivity comparing with the reference sample.









TABLE 17







Effects of Chemical Additives on Film RR (A/min.) & TEOS: SiN


Selectivity












TEOS
HDP RR
SiN RR
TEOS: SiN


Composition
RR (A/min)
(A/min)
(A/min)
Selectivity














0.2% Ceria-coated
4310
3047
557
8


Silica pH 5.35


0.2% Ceria-coated
3605
3992
65
36


Silica + 0.15%


D-sorbitol


0.2% CPOP +
4505
4203
61
39


0.15% Maltitol


0.2% CPOP +
4563
4183
85
41


0.15% Lactitol


0.2% CPOP +
4517
4325
103
39


0.15% Ribose


0.2% CPOP +
4716
4049
80
46


0.15% Beta-Lactose









The effects of various chemical additives on the oxide trenching dishing vs over polishing times were observed. These chemical additives were used at 0.15 wt. % (0.15×) concentrations respectively with 0.2 wt. % ceria-coated silica as abrasive, and with all formulations at pH 5.35.


The test results were listed in Table 18.









TABLE 18







Effects of Chemical Additives on Oxide


Trench Dishing & HDP RR (A/min.)











OP Time
100 um
200 um


Compositions
(sec.)
pitch dishing
pitch dishing













0.2% Ceria-coated Silica
0
165
291


pH 5.35
60
857
1096



120
1207
1531


0.2% Ceria-coated Silica +
0
94
222


0.15% Sorbitol
60
216
351



120
314
475


0.2% Ceria-coated Silica +
0
135
261


0.15% Maltitol
60
293
463



120
413
641


0.2% Ceria-coated Silica +
0
120
193


0.15% Lactitol
60
313
436



120
468
646


0.2% Ceria-coated Silica +
0
88
176


0.15% Ribose
60
290
409



120
441
606


0.2% Ceria-coated Silica +
0
141
259


0.15% Beta-Lactose
60
387
587



120
579
870









As the oxide trench dishing vs over polishing time results showed in Table 18, all of these chemical additives, when used with ceria-coated silica abrasives in the CMP polishing compositions, afforded largely reduced oxide trench dishing vs over polishing times at 60 seconds or 120 seconds respectively on 100 μm pitch and 200 μm pitch features, and provided significant oxide trench dishing reductions comparing to the reference.


Table 19 showed the results of the ratio of Trench Dishing Rate (A)/Blanket HDP RR (Å/min.),









TABLE 19







Ratio of Trench Dishing Rate (Å)/Blanket HDP RR (Å/min.)












P100 Dishing
P200 Dishing




Rate
Rate




(Å/min.)/
(Å/min.)/




Blanket HDP
Blanket HDP



Compositions
RR (Å/min.)
RR (Å/min.)






0.2% Ceria-coated Silica
0.13
0.16



pH 5.35





0.2% Ceria-coated Silica +
0.02
0.03



0.15% Sorbitol





0.2% Ceria-coated Silica +
0.05
0.04



0.15% Maltitol





0.2% Ceria-coated Silica +
0.04
0.05



0.15% Lactitol





0.2% Ceria-coated Silica +
0.03
0.05



0.15% Ribose





0.2% Ceria-coated Silica +
0.05
0.07



0.15% Beta-Lactose









As the results shown in Table 19, all tested polishing compositions using chemical additives showed significantly reduction of the ratio of trench dishing rate vs the blanket HDP film removal rates which indicated that all these chemical additives can be used as very effective oxide trench dishing reducing agents in the invented CMP polishing compositions.


Working Example 8

The polishing compositions were prepared with the reference (0.2 wt. % ceria-coated silica, a biocide ranging from 0.0001 wt. % to 0.05 wt. %, and deionized water) and maltitol or lactitol were used at 0.28 wt. %.


All example compositions had a pH at 5.35.


The removal rates (RR at Å/min) for different films were tested. The effects of two selected chemical additives, maltitol and lactitol on the film removal rates and selectivity were observed.


The test results were listed in Table 20.









TABLE 20







Effects of Maltitol or Lactitol on Film RR (Å/min.)


& TEOS: SiN Selectivity












TEOS
HDP
SiN
TEOS:



Film RR
Film RR
Film RR
SiN


Compositions
(Å/min.)
(Å/min.)
(Å/min.)
Selectivity














0.2% Ceria-coated Silica
3279
2718
349
9.4


pH 5.35






0.2% Ceria-coated Silica +
2623
2639
46
57.0


0.28% Maltitol pH 5.35






0.2% Ceria-coated Silica +
2630
2547
55
47.8


0.28% Lactitol pH 5.35













As the results shown in Table 20, the addition of the chemical additives, maltitol or lactitol, in the polishing compositions, significantly suppressed SiN removal rates while still afforded high TEOS and HDP film removal rates, thus, significantly increased Oxide: SiN film polishing selectivity.


Example 9

The example compositions in Example 8 were used in this Example.


Oxide trenching dishing for without/or with different over polishing times were tested. The effects of maltitol or lactitol on the oxide trenching dishing vs over polishing times were observed.


The test results were listed in Table 21.









TABLE 21







Effects of Maltitol or Lactitol on Oxide


Trench Dishing vs OP Times (Sec.)











OP Times
100 um
200 um


Compositions
(Sec.)
pitch dishing
pitch dishing













0.2% Ceria-coated Silica
0
165
291


pH 5.35 Ref.
60
857
1096



120
1207
1531


0.2% Ceria-coated Silica +
0
408
616


0.28% Maltitol pH 5.35
60
480
713



120
542
803


0.2% Ceria-coated Silica +
0
349
563


0.28% Lactitol pH 5.35
60
438
702



120
510
779









As the results shown in Table 21, the polishing compositions with the addition of the chemical additives, maltitol or lactitol, afforded low oxide trench dishing on 100 μm pitch, and 200 μm pitch respectively when 60 second or 120 second over polishing times were applied.


The compositions provided significant oxide trench dishing reductions comparing to the reference composition which did not have the chemical additives, maltitol or lactitol.


Table 22 showed the results of the ratio of Trench Dishing Rate (A)/Blanket HDP RR (Å/min.),









TABLE 22







The Ratio of Trench Dishing Rate (A)/


Blanket HDP RR (A/min.)












P100 Dishing
P200 Dishing




Rate
Rate




(Å/min.)/
(Å/min.)/




Blanket HDP
Blanket HDP



Compositions
RR (A/min.)
RR (A/min.)






0.2% Ceria-coated Silica
0.13
0.16



pH 5.35





0.2% Ceria-coated Silica +
0.02
0.03



0.28% Maltitol pH 5.35





0.2% Ceria-coated Silica +
0.03
0.03



0.28% Lactitol pH 5.35









As the results shown in Table 22, the addition of either maltitol or lactitol as oxide trench dishing reducer in polishing compositions significantly reduced the ratio of trench dishing rate vs the blanket HDP film removal rates, the lower of this ratio is, the lower of oxide trench dishing is.


The slopes of oxide trench dishing vs the OP removal amount was showed in Table 23.









TABLE 23







Effects of Maltitol or Lactitol on Slopes


of Dishing vs OP Removal Amount











P100
P200
P1000



dishing/OP
dishing/OP
dishing/OP


Compositions
Amt Slope
Amt Slope
Amt Slope





0.2% Ceria-coated Silica
0.19
0.23
0.25


pH 5.35 Ref.





0.2% Ceria-coated Silica +
0.04
0.05
0.08


0.28% Maltitol pH 5.35





0.2% Ceria-coated Silica +
0.04
0.06
0.09


0.28% Lactitol pH 5.35









The results listed in Table 23 indicated that the compositions with chemical additives, maltitol or lactitol provided lower slopes which indicated good over polishing window for maintaining low oxide trench dishing even more oxide film removed in over polishing steps.


As showing in Table 23, these chemical additives, maltitol or lactitol, and ceria-coated silica based CMP polishing compositions again showed much lower slope values comparing to those slope values obtained for the ceria-coated silica abrasive based reference sample.


Example 10

In Example 10, the trench oxide loss rates were compared for the polishing compositions using maltitol or lactitol and reference as listed in Table 24.









TABLE 24







Effects of Maltitol or Lactitol on Trench Loss Rates (Å/min.)












P100Trench
P200Trench




Loss Rate
Loss Rate



Compositions
(Å/sec.)
(Å/sec.)














0.2% Ceria-coated Silica
18.5
19.3



pH 5.35 Ref.





0.2% Ceria-coated Silica +
2.0
2.5



0.28% Maltitol pH 5.35





0.2% Ceria-coated Silica +
2.3
2.6



0.28% Lactitol pH 5.35











As the results shown in Table 24, the addition of maltitol or lactitol as oxide trench dishing reducing agent into the polishing compositions, the trench loss rates were significantly reduced vs the reference sample without using any chemical additives.


Example 11

The compositions were prepared as shown in Table 19.


The compositions used of 0.2 wt. % ceria-coated silica as abrasives, 0.28 wt. % lactitol as chemical additive, biocide, DI water, and a pH adjusting agent to provide different pH conditions.


The removal rates (RR at Å/min) for different films were tested. The effects of pH conditions on the film removal rates and selectivity were observed.


The test results were listed in Table 25.









TABLE 25







Effects of pH on Film RR (Å/min) & Selectivity of Oxide: SiN












TEOS
HDP
SiN
TEOS:



Film RR
Film RR
Film RR
SiN


Compositions
(Å/min.)
(Å/min.)
(Å/min.)
Selectivity














0.2% Ceria-coated Silica
3279
2718
349
9.4


pH 5.35






0.2% Ceria-coated Silica +
2623
2639
46
57.0


0.28% Lactitol pH 5.35






0.2% Ceria-coated Silica +
2524
2517
56
45.1


0.28% Lactitol pH 7.0






0.2% Ceria-coated Silica +
2401
2417
52
46.2


0.28% Lactitol pH 8.0













As the results shown in Table 25, the addition of lactitol as oxide trench dishing reducing agent into the polishing compositions at three different pH conditions, (acidic, neutral or alkaline) gave similar TEOS and HDP film removal rates, very effectively suppressed SiN film removal rates, and yielded much higher TEOS: SiN selectivity than the reference sample without using lactitol as chemical additive.


Oxide trenching dishing for without/or with lactitol as chemical additive over polishing times were tested.


The effects of lactitol containing polishing composition at different pH conditions on the oxide trenching dishing vs over polishing times were observed.


The test results were listed in Table 26.


As the results shown in Table 26, the polishing compositions with the addition of lactitol, at different pH conditions afforded low oxide trench dishing on 100 μm pitch, and 200 μm pitch respectively when 60 second or 120 second over polishing times were applied.


The compositions with lactitol as oxide trench dishing reducing agent provided significant oxide trench dishing reductions comparing to the reference polishing composition which did not have the chemical additive, lactitol.









TABLE 26







Effects of Lactitol at Different pH Conditions on


Oxide Trench Dishing vs OP Times (Sec.)











OP Times
100 um
200 um


Compositions
(Sec.)
pitch dishing
pitch dishing













0.2% Ceria-coated Silica
0
165
291


pH 5.35 Ref.
60
857
1096



120
1207
1531


0.2% Ceria-coated Silica +
0
349
563


0.28% Lactitol pH 5.35
60
438
702



120
510
779


0.2% Ceria-coated Silica +
0
73
182


0.28% Lactitol pH 7.0
60
222
390



120
346
532


0.2% Ceria-coated Silica +
0
269
386


0.28% Lactitol pH 8.0
60
425
576



120
568
766









Table 27 depicted the ratio of Trench Dishing Rate (A)/Blanket HDP RR (Å/min.) at Different pH.









TABLE 27







Ratio of Trench Dishing Rate (A)/Blanket


HDP RR (A/min.) at Different pH












P100 Dishing
P200 Dishing




Rate
Rate




(Å/min.)/
(Å/min.)/




Blanket HDP
Blanket HDP



Compositions
RR (A/min.)
RR (A/min.)






0.2% Ceria-coated Silica
0.13
0.16



pH 5.35





0.2% Ceria-coated Silica +
0.03
0.03



0.28% Lactitol pH 5.35





0.2% Ceria-coated Silica +
0.05
0.06



0.28% Lactitol pH 7.0





0.2% Ceria-coated Silica +
0.06
0.08



0.28% Lactitol pH 8.0









As the results shown in Table 27, the addition of lactitol as oxide trench dishing reducer in polishing composition significantly reduced the ratio of trench dishing rate vs the blanket HDP film removal rates at different pH conditions than that ratio obtained for reference sample at pH 5.35.


The slopes of oxide trench dishing vs the OP removal amount at different pH conditions was showed in Table 28.









TABLE 28







Effects of Lactitol at Different pH on Slopes


of Dishing vs OP Removal Amount












P100
P200




dishing/OP
dishing/OP



Compositions
Amt Slope
Amt Slope






0.2% Ceria-coated Silica
0.19
0.23



pH 5.35





0.2% Ceria-coated Silica +
0.04
0.06



0.28% Lactitol pH 5.35





0.2% Ceria-coated Silica +
0.06
0.08



0.28% Lactitol pH 7.0





0.2% Ceria-coated Silica +
0.06
0.08



0.28% Lactitol pH 8.0









The results listed in Table 28 indicated that the compositions with chemical additive lactitol at different pH conditions provided lower slopes of trench dishing vs the over polishing removal amounts which indicated good over polishing window for maintaining low oxide trench dishing even more oxide film removed in over polishing steps.


As showing in Table 28, lactitol and ceria-coated silica based CMP polishing compositions again showed much lower slope values at different pH conditions comparing to those slope values obtained for the ceria-coated silica abrasive based reference sample at pH 5.35.


In Example 11, the trench oxide loss rates were compared for the polishing compositions using lactitol at different pH conditions or without using lactitol at pH 5.35 and listed in Table 29.









TABLE 29







Effects of Lactitol at Different pH Conditions


on Trench Loss Rates (Å/min.)












P100Trench
P200Trench




Loss Rate
Loss Rate



Compositions
(Å/sec.)
(Å/sec.)














0.2% Ceria-coated Silica
18.5
19.3



pH 5.35 Ref.





0.2% Ceria-coated Silica +
2.3
2.6



0.28% Lactitol pH 5.35





0.2% Ceria-coated Silica +
3.3
4.0



0.28% Lactitol pH 7.0





0.2% Ceria-coated Silica +
3.7
4.2



0.28% Lactitol pH 8.0











As the results shown in Table 29, the addition of lactitol as oxide trench dishing reducing agent into the polishing compositions at different pH conditions, the trench loss rates were significantly reduced vs the reference sample without using lactitol as chemical additive.


The polishing test results obtained at different pH conditions using lactitol as oxide trench dishing reducer proved that the CMP polishing compositions can be used in wide pH range including acidic, neutral or alkaline pH conditions.


Example 12

When using the suitable chemical additives, such as maltitol or lactitol or their derivatives, as oxide trench reducing agents in polishing compositions, these chemical additives can have some impacts on the stability of ceria-coated inorganic oxide abrasives in the CMP polishing compositions. In CMP polishing compositions, it is very important to have good abrasive particle stability to assure constant and desirable CMP polishing performances.


Typically, the abrasive particle stability is tested through monitoring the MPS (nm) (=mean particle size) and D99 (nm) changes vs the times or at elevated temperatures. The smaller of MPS (nm) and D99 (nm) changes, the more stable of the invented polishing compositions are.


In this example, the stability of ceria-coated silica abrasive particles in the compositions having chemical additives was monitored by measuring the change of the mean particles size and the change of particle size distribution D99.


The testing samples were made using 0.2 wt. % or other wt. % ceria-coated silica abrasive; very low concentration of biocide; 0.15 wt. % maltitol, 0.15 wt. % lactitol or 0.0787 wt. % Myo-inositol as oxide trench dishing reducer; and with pH adjusted to 5.35.


The abrasive stability tests on the polishing compositions were carried out at 50° C. for at least 10 days or more.


The MPS (nm) or D99 (nm) of the tested polishing compositions were measured using DLS technology (DLS=dynamic light scattering).


The stability test results of the used ceria-coated silica abrasives with the chemical additives were listed in Table 30.









TABLE 30







Particle Size Stability (MPS) Test Results @ 50° C. − D99 (nm)















Compositions/Days
0
1
2
3
4
11
18
32


















0.2% Ceria-coated Silica + 0.15% Maltitol
179.6
179.6
178.4
179.6
180

183



0.2% Ceria-coated Silic + 0.15% Lactitol
180
178.8
180.9
179.6
180.6


182.3


0.2% Ceria-coated Silic + 0.0787% Myo-inositol
180.8
178.5
179.6
180.4
181.5
182.3









By day 4 at 50° C., 0.2 wt. % ceria-coated silica particles had MPS changes of 0.23%, 0.34% and 0.39% in the compositions having 0.15 wt. % maltitol, 0.15 wt. lactitol and 0.0787 wt. % myo-inositol respectively.


0.2 wt. % ceria-coated silica particles in the composition having 0.15 wt. maltitol had a mean particle size change of less than 1.9% by day 18 at 50° C.


0.2 wt. % ceria-coated silica particles in the composition having 0.0787 wt. % myo-inositol had a mean particle size change of less than 0.83% by day 11 at 50° C.


0.2 wt. % ceria-coated silica particles in the composition having 0.15 wt. % lactitol had a mean particle size change of less than 1.3% by day 32 at 50° C.


More stability test were listed in Table 31.









TABLE 31







Particle Size Stability Test Results @ 50° C. − MPS (nm) & D99 (nm)


















Particle Sizes











Compositions
(nm)
Day 0
Day 1
Day 4
Day 8
Day 15
Day 22
Day 33
Day 40
Day 62




















0.2% Ceria-coated Silica +
MPS (nm)
120
121.1
122.8
123
123.2
121.5
121.9
120.6
119.9


0.15% Maltitol pH 5.35
D99 (nm)
176.3
178
180.9
180.4
180
172.4
178.3
176.2
177.4









0.2 wt. % ceria-coated silica particles in the composition having 0.15 wt. % maltitol had a mean particle size and D99 changes of less than 8.34×10−4 and 0.63 respectively by day 62 at 50° C.


Furthermore, the particle stability tests were also conducted at 50° C. on polishing compositions comprised more concentrated ceria-coated silica abrasives (more than 0.2 wt. %) and more concentrated maltitol (more than 0.15 wt. %) as oxide trench dishing reducer.


The test results were listed in Table 32.


Data showed that 0.8 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 0.41% and less than 0.23% respectively by day 42 at 50° C. in the composition having 0.6 wt. % of maltitol respectively.









TABLE 32







Particle Size Stability Test Results @ 50° C. − MPS (nm) & D99 (nm)

















Particle Sizes










Compositions
(nm)
Day 0
Day 3
Day 5
Day 7
Day 14
Day 19
Day 25
Day 42



















0.8% Ceria-coated Silica +
MPS (nm)
122
122
121.9
122
121
121
121.4
122.5


0.6% Maltitol pH 5.35
D99 (nm)
180.5
179.5
180
179.6
185.3
185.3
179.6
180.9


1.6% Ceria-coated Silica +
MPS (nm)
121.2
122.1
122.1
121.5
121.3
121.2
121.4
122.6


1.2% Maltitol pH 5.35
D99 (nm)
179.5
180
180
179.2
179.6
179.6
180.5
182.3


2.4% Ceria-coated Silica +
MPS (nm)
122.1
121.9
121.5
121.1
121
121
122
122.5


1.8% Maltitol pH 5.35
D99 (nm)
180.5
180
179.2
178
180.1
180.1
180.5
180.9









Data also showed that 0.8 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 0.41% and less than 0.23% respectively by day 42 at 50° C. in the composition having 0.6 wt. % of maltitol respectively.


1.6 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 1.2% and less than 1.6% respectively by day 42 at 50° C. in the composition having 1.2 wt. % of maltitol respectively.


2.4 wt. % of the ceria-coated silica particles had MPS and D99 changes of less than 0.33% and less than 0.23% respectively by day 42 at 50° C. in the composition having 1.8 wt. % of maltitol respectively.


As the results shown in Table 30 to 32, when maltitol, lactitol or Myo-inositol used as oxide trench dishing reducer with ceria-coated silica particles as abrasives, the polishing compositions showed very good particle size stability of MPS (nm) and D99 (nm) even at elevated testing temperatures.


The polishing compositions comprised of ceria-coated colloidal silica abrasives and more concentrated maltitol as oxide trench dishing reducer all showed very good particle size stability of MPS (nm) and D99 (nm) at elevated temperatures.


Example 13

Another key benefit of using the present invented CMP polishing compositions is the reduced total defect counts through and post-polishing which is resulted in by using the ceria-coated colloidal silica composite particles as abrasives instead of using calcined ceria particle as abrasives.


The following three polishing compositions were prepared for defects testing. The first sample was made using 0.5 wt. % calcined ceria abrasives, 0.05 wt. % polyacrylate salt and low concentration of biocide; the second sample was made using 0.2 wt. % ceria-coated silica abrasives, 0.28 wt. % maltitol and low concentration of biocide; the third sample was made using 0.2 wt. % ceria-coated silica abrasives, 0.28 wt. % lactitol and low concentration of biocide. In order to obtain similar dielectric film removal rates to be compared, higher concentration of calcinated ceria abrasive was used in sample 1.


All three formulations have pH valued at 5.35.


The total defect counts on polished TEOS and SiN wafers were compared by using three afore listed polishing compositions. The total defect count results were listed in Table 33.


As the total defect count results shown in Table 33, the polishing compositions using ceria-coated silica particles as abrasives and either of maltitol or lactitol as trench dishing reducing agent afforded significantly lower total defect counts on the polished TEOS and SiN wafers than the total defect counts obtained using the polishing composition comprised of calcined ceria abrasives and polyacrylate salt as chemical additive.









TABLE 33







Effects of Different Polishing Compositions


on TEOS & SiN Total Defect Counts










TEOS Total
SiN Total



Defect
Defect



Count@0.13 μm
Count@0.13 μm


Compostions
LPD
LPD












0.2% Calcined Ceria +
3847
498


0.05% Polyacrylate Salt pH 5.35




0.2% Ceria-coated Silica +
438
73


0.28% Maltitol pH 5.35




0.2% Ceria-coated Silica +
493
73


0.28% Lactitol pH 5.35











Example 14

The following four polishing compositions were prepared for the defects testing.


The first two polishing compositions used calcined ceria abrasives, 0.28 wt. % maltitol or 0.28 wt. % lactitol as oxide trenching dishing reducing agent and low concentration of biocide; the other two polishing compositions were made using ceria-coated silica abrasives, 0.28 wt. % maltitol or 0.28 wt. % lactitol as oxide trenching dishing reducing agent and low concentration of biocide. All four formulations have pH valued at 5.35.


All chemical additives used at the same wt. %, but different types of abrasives were used, e.g., calcined ceria vs ceria-coated silica particles as abrasives.


The effects of different types of abrasives on the film removal rates and TEOS: SiN selectivity were observed and the results were listed in table 34.









TABLE 34







Effects of Different Types of Abrasives


on Film RR & TEOS: SiN Selectivity












TEOS RR
HDP RR
SiN RR
TEOS: SiN


Compositions
(A/min.)
(A/min.)
(A/min.)
Selectivity





Calcined Ceria +
1774
1839
38
43


0.28% Maltitol






Calcined Ceria +
1997
1996
37
54


0.28% Lactitol






Ceria-coated Silica +
3085
2956
60
51


0.28% Maltitol






Ceria-coated Silica +
3188
2885
69
46


0.28% Lactitol









As the results shown in Table 34, the polishing compositions that used ceria-coated silica as abrasives did afford much higher TEOS and HDP film removal rates than those film removal rates obtained from the polishing compositions which used calcined ceria as abrasives.


The normalized total defect counts on polished TEOS and SiN wafers were compared by using four afore listed polishing compositions. The normalized total defect count results were listed in Table 35.









TABLE 35







Effects of Different Types of Abrasives on Normalized


TEOS & SiN Total Defect Counts














PECVD
PECVD



TEOS
TEOS
SiN
SiN



0.07 um
0.13 um
0.1 um
0.13 um


Compositions
LPD
LPD
LPD
LPD





Calcined Ceria +
1.00
1.00
1.00
1.00


0.28% Maltitol






Calcined Ceria +
1.03
0.64
0.96
1.04


0.28% Lactitol






Ceria-coated Silica +
0.21
0.07
0.25
0.58


0.28% Maltitol






Ceria-coated Silica +
0.43
0.10
0.49
0.58


0.28% Lactitol









As the normalized total defect count results shown in Table 35, the polishing compositions using ceria-coated silica particles as abrasives and either maltitol or lactitol as trench dishing reducing agent afforded significantly lower normalized total defect counts on the polished TEOS and SiN wafers than the normalized total defect counts obtained using the polishing composition comprised of calcined ceria abrasives, and either maltitol or lactitol as oxide trench dishing reducing chemical additive.


The embodiments of this invention listed above, including the working example, are exemplary of numerous embodiments that may be made of this invention. It is contemplated that numerous other configurations of the process may be used, and the materials used in the process may be elected from numerous materials other than those specifically disclosed.

Claims
  • 1. A Chemical Mechanical Polishing (CMP) composition comprising: abrasive particles selected from the group consisting of ceria-coated inorganic oxide particles selected from the group consisting of ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia particles and combinations thereof;ceria-coated organic polymer particles selected from the group consisting of ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, and combinations thereof; andcombinations thereof;chemical additive;solvent selected from the group consisting of deionized (DI) water, distilled water, and alcoholic organic solvents; andoptionallybiocide; andpH adjuster;whereinthe composition has a pH of 2 to 12; andthe chemical additive is selected from the group consisting of(A) a molecular structure (a):
  • 2. The Chemical Mechanical Polishing (CMP) composition of claim 1, wherein the abrasive particles range from 0.05 wt. % to 10 wt. % and have mean particle size ranging from 5 nm to 500 nm;the chemical additive ranges from 0.01 wt. % to 20.0% wt. % and has at least four hydroxyl functional groups in its molecular structure; andthe composition has a pH of 3 to 10.
  • 3. The Chemical Mechanical Polishing (CMP) composition of claim 2, wherein the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.
  • 4. The Chemical Mechanical Polishing (CMP) composition of claim 1, wherein the abrasive particles having mean particle size ranging from 5 nm to 500 nm, and have a concentration from 0.05 wt. % to 10 wt. %;the chemical additive (a) has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (1), and ranges from 0.05 wt. % to 5 wt. %;the composition has a pH of 3 to 10; andthe ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.
  • 5. The Chemical Mechanical Polishing (CMP) composition of claim 4, wherein the polyol molecular unit (b) has n=2 and m=1; and rest of Rs in the group of R1 to R9 are all hydrogen atoms, as shown below:
  • 6. The Chemical Mechanical Polishing (CMP) composition of claim 1, wherein the abrasive particles having mean particle size ranging from 5 nm to 500 nm, and have a concentration from 0.05 wt. % to 10 wt. %;the chemical additive (a) has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (2), and range from 0.05 wt. % to 5 wt. %;the composition has a pH of 3 to 10; andthe ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.
  • 7. The Chemical Mechanical Polishing (CMP) composition of claim 6, wherein the polyol molecular unit (b) which has n=2 and m=1; and rest of Rs in the group of R1 to R14 are all hydrogen atoms, as shown below:
  • 8. The Chemical Mechanical Polishing (CMP) composition of claim 1, wherein the abrasive particles range from 0.05 wt. % to 10 wt. % and have mean particle size ranging from 5 nm to 500 nm;the chemical additive ranges from 0.01 wt. % to 20.0% wt. % and is selected from the group comprising maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, Inositol, glucose, D-arabinose, L-arabinose, L-mannose, D-mannose, L-mannose, meso-erythritol, ribose, beta-lactose, and combinations thereof.the composition has a pH of 3 to 10.
  • 9. The Chemical Mechanical Polishing (CMP) composition of claim 1, wherein the abrasive particles are ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm, and have a concentration from 0.05 wt. % to 10 wt. %;the chemical additive ranges from 0.05 wt. % to 5 wt. %, and is selected from the group comprising maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sucrose, Inositol, glucose, L-mannose, D-mannose, beta-lactose, and combinations thereof.the composition has a pH of 3 to 10; andthe ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.
  • 10. The chemical mechanical polishing composition of claim 1, wherein the composition comprises ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm, and have a concentration from 0.05 wt. % to 10 wt. %; the chemical additive selected from the group consisting of maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(−)-Fructose, beta-lactose, and combinations thereof; andthe ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤2.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.
  • 11. The chemical mechanical polishing composition of claim 1, wherein the composition comprises one selected from the group consisting of from 0.0001 wt. % to 0.05 wt. % of the biocide having active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-1-isothiazolin-3-one, and combinations thereof; from 0 wt. % to 1 wt. % of the pH adjusting agent selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof for acidic pH conditions; or selected from the group consisting of sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and combinations thereof for alkaline pH conditions; and combinations thereof.
  • 12. A method of chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising silicon oxide film, comprising (a) providing the semiconductor substrate;(b) providing a polishing pad;(c) providing a chemical mechanical polishing (CMP) composition comprising 0.05 wt. % to 10 wt. % abrasive particles selected from the group consisting of ceria-coated inorganic oxide particles selected from the group consisting of ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia particles and combinations thereof; ceria-coated organic polymer particles selected from the group consisting of ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, and combinations thereof; andcombinations thereof;0.01 wt. % to 20.0% wt. % chemical additive;solvent selected from the group consisting of deionized (DI) water, distilled water, andalcoholic organic solvents; andoptionallybiocide; andpH adjuster;whereinthe composition has a pH of 2 to 12; andthe chemical additive is selected from the group consisting of(A) a molecular structure (a):
  • 13. The method of claim 12; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm; wherein the ceria-coated inorganic oxide particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive having at least four hydroxyl functional groups in its molecular structure; andthe chemical mechanical polishing (CMP) composition has a pH of 3 to 10.
  • 14. The method of claim 12; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm;wherein the ceria-coated inorganic oxide particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive (a) has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (1), and ranges from 0.05 wt. % to 5 wt. %; andthe composition has a pH of 3 to 10.
  • 15. The method of claim 14, wherein the polyol molecular unit (b) in the chemical additive has n=2 and m=1; and rest of Rs in the group of R1 to R9 are all hydrogen atoms, as shown below:
  • 16. The method of claim 12; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles ceria-coated colloidal silica particles or ceria particles having mean particle size ranging from 5 nm to 500 nm;the chemical additive has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (2);the ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;andthe composition has a pH of 3 to 10.
  • 17. The method of claim 16, wherein the polyol molecular unit (b) in the chemical additive has n=2 and m=1; and rest of Rs in the group of R1 to R14 are all hydrogen atoms, as shown below:
  • 18. The method of claim 12, wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm; wherein the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive is selected from the group comprising maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, ribose, beta-lactose, and combinations thereof; andthe composition has a pH of 3 to 10.
  • 19. The method of claim 12; wherein the chemical mechanical polishing (CMP) composition comprises ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm; wherein the ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive has at least five hydroxyl functional groups in its molecular structure; and is selected from the group comprising maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sucrose, ribose, Inositol, glucose. D-(+)-mannose, beta-lactose, and combinations thereof;water; andthe composition has a pH of 3 to 10.
  • 20. The method of claim 12; wherein the chemical mechanical polishing (CMP) composition comprises ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm; wherein the ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤2.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive selected from the group consisting of maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(−)-Fructose, beta-lactose, and combinations thereof; andwater;the composition has a pH of 3 to 10.
  • 21. The method of claim 12, wherein the chemical mechanical polishing (CMP) composition comprises one selected from the group consisting of from 0.0001 wt. % to 0.05 wt. % of the biocide having active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-1-isothiazolin-3-one, and combinations thereof; from 0 wt. % to 1 wt. % of the pH adjusting agent selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof for acidic pH conditions; or selected from the group consisting of sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and combinations thereof for alkaline pH conditions; and combinations thereof.
  • 22. The method of claim 12; wherein the semiconductor substrate further comprises a silicon nitride surface; and removal selectivity of silicon oxide: silicon nitride is ≥20.
  • 23. A system of chemical mechanical polishing (CMP) a semiconductor substrate having at least one surface comprising silicon oxide film, comprising a. the semiconductor substrate;b. a polishing pad; andc. a chemical mechanical polishing (CMP) composition comprising 0.05 wt. % to 10 wt. % 0.05 wt. % to 10 wt. % abrasive particles selected from the group consisting of ceria-coated inorganic oxide particles selected from the group consisting of ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia particles and combinations thereof;ceria-coated organic polymer particles selected from the group consisting of ceria-coated polystyrene particles, ceria-coated polyurethane particle, ceria-coated polyacrylate particles, and combinations thereof; andcombinations thereof;0.01 wt. % to 20.0% wt. % chemical additive;solvent selected from the group consisting of deionized (DI) water, distilled water, and alcoholic organic solvents; andoptionallybiocide; andpH adjuster;whereinthe composition has a pH of 2 to 12; andthe chemical additive has at least four hydroxyl functional groups and is selected fromthe group consisting of(A) a molecular structure (a):
  • 24. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm; wherein the c particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive having at least four hydroxyl functional groups in its molecular structure;the chemical mechanical polishing (CMP) composition has a pH of 3 to 10.
  • 25. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm; wherein the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive (a) has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (1), and ranges from 0.05 wt. % to 5 wt. %; andthe composition has a pH of 3 to 10.
  • 26. The system of claim 25, wherein the polyol molecular unit (b) in the chemical additive has n=2 and m=1; and rest of Rs in the group of R1 to R9 are all hydrogen atoms, as shown below:
  • 27. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles are ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm; wherein the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤5.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive (a) has at least six hydroxyl functional groups in its molecular structure and R1, R2, R3, R4 and R5 (Rs in group R1 to R5) selected from (2); andthe composition has a pH of 3 to 10.
  • 28. The system of claim 27; wherein the polyol molecular unit (b) in the chemical additive has n=2 and m=1; and rest of Rs in the group of R1 to R14 are all hydrogen atoms, as shown below:
  • 29. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises the abrasive particles having mean particle size ranging from 5 nm to 500 nm; wherein the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive is selected from the group comprising maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, ribose, beta-lactose, and combinations thereof; andthe composition has a pH of 3 to 10.
  • 30. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm; wherein the ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive has at least five hydroxyl functional groups in its molecular structure; and is selected from the group comprising maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sucrose, ribose, Inositol, glucose. D-(+)-mannose, beta-lactose, and combinations thereof;water;the composition has a pH of 3 to 10.
  • 31. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises ceria-coated colloidal silica particles having mean particle size ranging from 5 nm to 500 nm; wherein the ceria-coated colloidal silica particles have changes of mean particle size MPS (nm) and D99 (nm)≤2.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under;the chemical additive selected from the group consisting of maltitol, lactitol, maltotritol, D-sorbitol, mannitol, dulcitol, D-(−)-Fructose, beta-lactose, and combinations thereof; andwater;the composition has a pH of 3 to 10.
  • 32. The system of claim 23; wherein the chemical mechanical polishing (CMP) composition comprises one selected from the group consisting of from 0.0001 wt. % to 0.05 wt. % of the biocide having active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-1-isothiazolin-3-one, and combinations thereof; from 0 wt. % to 1 wt. % of the pH adjusting agent selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof for acidic pH conditions; or selected from the group consisting of sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and combinations thereof for alkaline pH conditions; and combinations thereof.
CROSS REFERENCE TO RELATED PATENT APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. § 119(e) to earlier filed U.S. patent applications Ser. Nos. 62/692,633, and 62/692,639 filed on Jun. 29, 2018, which are entirely incorporated herein by reference.

Provisional Applications (2)
Number Date Country
62692633 Jun 2018 US
62692639 Jun 2018 US