Chemical additives for chemical mechanical planarization (cmp) polishing compositions

Abstract

This invention provides chemical mechanical planarization (CMP) polishing compositions, methods, and systems for polishing copper. The CMP polishing compositions contain specific amino alcohol compounds that have a weak inhibitory effect on copper polishing to protect low-lying areas during the removal of protrusion features, thereby maintaining planarization efficiency in advanced node Cu CMP processes.

Description

Cross-referencing of related patent applications

[0001] This application claims the benefit of U.S. Application No. 63 / 607,266, filed December 7, 2023. The disclosure of that application is hereby incorporated herein by reference. Background Technology

[0002] This invention relates to chemical additives for chemical mechanical planarization (CMP) polishing compositions. More specifically, this invention relates to amino alcohol compounds used as chemical additives in copper CMP polishing compositions. The invention also relates to CMP polishing methods and systems using these copper CMP polishing compositions.

[0003] In the semiconductor industry, semiconductor devices have structured layers and multilayer interconnect structures composed of stacked thin films containing one or more of the following materials: copper (Cu), tantalum (Ta), titanium (Ti), titanium nitride (TiN), aluminum-copper (Al-Cu), aluminum-silicon (Al-Si), tungsten (W), doped polycrystalline silicon (poly-Si), and various combinations thereof.

[0004] Typically, different materials are deposited on top of each other in complex structures. Semiconductor device deposition is accomplished using various methods. However, CMP (Continuous Metallurgical Processing) is required after each deposition step to ensure the deposited layer is flat and has a low surface roughness, preparing it for the next deposition step.

[0005] In advanced node Cu CMP processes, the Cu linewidth on the patterned wafer is significantly reduced, leading to a substantial increase in the Cu step height difference between the array and the field region after electroplating. Therefore, achieving high planarization efficiency is crucial for minimizing these step height variations between different feature sizes.

[0006] Therefore, in the Cu CMP process, it is crucial to enhance the depression level to the desired level while maintaining planarization efficiency. This allows for a reduction in overall processing time while ensuring the desired depression level is achieved according to process requirements.

[0007] Furthermore, in a typical CMP process step, a rotating wafer saddle brings the wafer to be polished into contact with a polishing pad. The CMP polishing composition is typically applied between the wafer and the polishing pad.

[0008] Therefore, it is the combination of a high removal rate of the material to be planarized and a low removal rate of the material to be retained that limits the effectiveness of the CMP polishing composition.

[0009] There remains a need in this field because the known Cu CMP polishing slurries cannot provide the performance required to meet all the requirements. Summary of the Invention

[0010] This invention addresses this need by using chemical additives in chemical mechanical planarization (CMP) polishing compositions; more specifically, by using amino alcohol compounds as chemical additives in copper chemical mechanical planarization (CMP) polishing compositions.

[0011] In one aspect (Aspect 1), a CMP polishing composition is provided, comprising, substantially comprising, or comprising the following: a) Abrasive; b) Chemical additives; and c) Water-soluble solvents; and Optionally, at least one of the following: d) Chelating agents; e) Corrosion inhibitors; f) Biocides; g) Organic quaternary ammonium salts; h) Oxidizing agents; and i) pH adjuster; The pH range of the CMP polishing composition is 3 to 11, 4 to 10, 5 to 9, or 6 to 8.

[0012] The abrasive can be any known abrasive particle, including but not limited to inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof.

[0013] Chemical additives include, but are not limited to, amino alcohol compounds having the structure A shown below: A In structure A, R1 and R2 are each independently including, but not limited to: H; OH; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol; and R3, R4 and R5 are each independently including, but not limited to: H; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol.

[0014] Some examples of chemical additives include, but are not limited to, 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-1-butanol.

[0015] Optional chelating agents include, but are not limited to, amino acids and their derivatives, as well as amines.

[0016] Amino acids and amino acid derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0017] Optional corrosion inhibitors include, but are not limited to, families of heteroaromatic compounds containing a nitrogen atom in their aromatic rings, such as 1,2,4-triazoles, benzotriazoles and benzotriazole derivatives, tetrazolium and tetrazolium derivatives, imidazoles and imidazole derivatives, benzimidazoles and benzimidazole derivatives, pyrazoles and pyrazole derivatives, and tetrazolium and tetrazolium derivatives.

[0018] The optional biocide can be any biocide that provides an active ingredient to prevent biological growth and thus provides a more stable shelf life for the CMP polishing composition.

[0019] Examples of biocides include, but are not limited to, Kathon from Dow Chemical Co. TM and Kathon TM CG / ICP II; its active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and Neolone from CHEMPOINT, Bellevue, WA 98004 USA. TM M10; its active ingredient is methylisothiazolinone.

[0020] Optional organic quaternary ammonium salts include, but are not limited to, choline salts, such as choline bicarbonate, or all other salts formed between choline and other anionic counterions.

[0021] Optional oxidizing agents include, but are not limited to, peroxides selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate, and ammonium persulfate; and non-peroxides selected from ferrous nitrite, KClO4, KBrO4, and KMnO4; and combinations thereof.

[0022] Optional pH adjusters include, but are not limited to (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and mixtures thereof for lowering pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof for raising pH.

[0023] The water-soluble solvent is selected from deionized (DI) water, distilled water, and alcoholic organic solvents.

[0024] In another aspect (Aspect 2), a CMP polishing method is provided for chemically and mechanically planarizing a semiconductor substrate comprising at least one Cu-containing surface, the method comprising, substantially comprising, or comprising the following steps: Make at least one surface contact the polishing pad; Chemical-mechanical planarization polishing composition for delivery aspect 1; The at least one Cu-containing surface is polished using a chemical mechanical planarization composition.

[0025] In another aspect (aspect 3), a CMP polishing system is provided, comprising, substantially comprising, or consisting of the following: A semiconductor substrate comprising at least one Cu-containing surface; Polishing pads; and Aspect 1: Chemomechanical planarization composition; The at least one Cu-containing surface is in contact with the polishing pad and the chemimechanical planarization composition.

[0026] The at least one surface may also include at least one second material, which can be any material used together with copper for a semiconductor substrate or patterned wafer; including but not limited to Ta; Ti; TaN; TiN; Ta; TaN; Ti; TiN, Co, Ru; dielectric materials such as SiO2, SiN, SiC; and low-k and ultra-low-k materials; such as different Black Diamond materials. TM membrane.

[0027] Other aspects, features, and embodiments of the invention will become more apparent from the following disclosure and the appended claims.

[0028] The embodiments of the present invention can be used alone or in combination with each other. Detailed Implementation

[0029] As industry standards trend toward smaller device features, there is a continued need to develop new Cu CMP polishing compositions that enhance recess levels to minimize step height variations between different feature sizes while maintaining planarization efficiency of Cu CMP processes in a wide range of advanced node applications.

[0030] The present invention addresses this need by providing a novel Cu CMP polishing composition using an amino alcohol compound as a chemical additive, and by providing a method and system for using the CMP polishing composition.

[0031] In one aspect (Aspect 1), a CMP polishing composition is provided, comprising, substantially comprising, or comprising the following: a) Abrasive; b) Chemical additives; and c) Water-soluble solvents; and Optionally, at least one of the following d) Chelating agents; e) Corrosion inhibitors; f) Biocides; g) Organic quaternary ammonium salts; h) Oxidizing agents; and i) pH adjuster; The pH range of the CMP polishing composition is 3 to 11, 4 to 10, 5 to 9, or 6 to 8.

[0032] Abrasives include, but are not limited to, inorganic oxide particles, inorganic oxide particles coated with metal oxides, organic polymer particles, organic polymer particles coated with metal oxides, and combinations thereof.

[0033] The abrasive particles used in the Cu bulk CMP polishing compositions disclosed herein include, but are not limited to, the following: colloidal silica or high-purity colloidal silica; colloidal silica particles doped with other metal oxides within the colloidal silica lattice, such as alumina-doped silica particles; silica sols of sodium silicates and / or potassium silicates; fumed silica; colloidal alumina, including α-, β-, and γ-type aluminum oxides; colloidal and photoactive titanium dioxide; cerium oxide; colloidal cerium oxide; nanoscale inorganic metal oxide particles, such as alumina, titanium dioxide, zirconium oxide, cerium oxide, etc.; nanoscale diamond particles; nanoscale silicon nitride particles; single-peak, bi-peak, and multi-peak colloidal abrasive particles; organic polymer-based soft abrasives; surface-coated or modified abrasives; or other composite particles, and mixtures thereof.

[0034] The CMP polishing composition contains 0.0025% to 25% by weight of abrasive; the preferred concentration range of the abrasive is 0.0025% to 2.5% by weight. The most preferred concentration range of the abrasive is 0.005% to 1.0% by weight.

[0035] Chemical additives include, but are not limited to, amino alcohol compounds.

[0036] Amino alcohol compounds include, but are not limited to, compounds having the general structure A shown below: A; In structure A, R1 and R2 each independently include, but are not limited to: H; OH; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol; and R3, R4 and R5 in structure A each independently include, but are not limited to: H; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol.

[0037] Examples of amino alcohol compounds include, but are not limited to, 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-1-butanol.

[0038] Amino alcohol compounds can be used alone or in combination.

[0039] Amino alcohols are characterized by their unique steric hindrance structure. Unbound from theory, in the case of these amino alcohol compounds, the steric hindrance structure is believed to exhibit the ability to provide weak protection in the low-lying regions of the pattern, thereby contributing to improved planarization efficiency (PE). PE can be evaluated by examining the change in film thickness at the bottom and top of the feature. It is determined by plotting the amount of step height reduction for a specific feature (e.g., 100 nm line / spacing) against the thickness of the removed copper (Cu) film. The slope of this plot reflects the achieved planarization efficiency, taking into account the combination of chemicals and mechanical polishing parameters used in the composition during the polishing process.

[0040] Simultaneously, due to their relatively mild chelating ability, these compounds promote metal dissolution during the polishing process, thereby modulating the level of Cu line depression. This dual-functionality allows these amino alcohol compounds to be used as effective chemical additives in Cu CMP polishing compositions to manipulate and customize the depression effect while maintaining planarization efficiency.

[0041] The range of chemical additives is 0.0001-0.5% by weight, 0.0005-0.25% by weight, 0.00075-0.1% by weight, 0.001-0.075% by weight, 0.0015-0.06% by weight, or 0.002-0.05% by weight.

[0042] Optional chelating agents include, but are not limited to, the amino acids and derivatives and amines disclosed in US11401441BB, the disclosure of which is incorporated herein by reference.

[0043] Amino acids and amino acid derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0044] The CMP polishing composition contains 0.1% to 18% by weight, 0.5% to 10% by weight, or 0.75% to 2.5% by weight of a chelating agent.

[0045] Optional corrosion inhibitors include, but are not limited to, families of heteroaromatic compounds containing nitrogen atoms in the aromatic ring, such as 1,2,4-triazoles, benzotriazoles and their derivatives (e.g., 5-methyl-benzotriazole); tetrazolium and its derivatives; imidazoles and their derivatives; benzimidazoles and their derivatives; pyrazoles and their derivatives; and tetrazolium and its derivatives.

[0046] The CMP polishing composition contains 0.005% to 1.0% by weight of corrosion inhibitor; the preferred concentration range is 0.01% to 0.5% by weight; the most preferred concentration range is 0.02% to 0.2% by weight.

[0047] The optional biocide can be any biocide that provides an active ingredient to prevent biological growth, thereby providing a more stable shelf life for the CMP polishing composition.

[0048] Examples of biocides include, but are not limited to, Kathon from Dow Chemical Co. TM Kathon TM CG / ICP II; its active ingredients are 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and Neolone from CHEMPOINT, Bellevue, WA 98004 USA. TM M10; its active ingredient is methylisothiazolinone.

[0049] The CMP polishing composition contains 0.0001% to 0.05% by weight of a biocide; the preferred concentration range is 0.0002% to 0.025% by weight; the most preferred concentration range is 0.002% to 0.01% by weight.

[0050] Optional organic quaternary ammonium salts include, but are not limited to, choline salts, such as choline bicarbonate, or all other salts formed by choline with other anionic counterions, as disclosed in US11401441, the disclosure of which is incorporated herein by reference.

[0051] Optional oxidizing agents include, but are not limited to, peroxides selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate, and ammonium persulfate; and non-peroxides selected from ferrous nitrite, KClO4, KBrO4, and KMnO4; and combinations thereof.

[0052] The CMP polishing composition contains 0.1% to 10% by weight of an oxidant; the preferred concentration range is 0.25% to 3% by weight; the most preferred concentration range is 0.5% to 2.0% by weight.

[0053] Optional pH adjusters include, but are not limited to (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and mixtures thereof for lowering pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof for raising pH.

[0054] The CMP polishing composition contains 0% to 1% by weight of a pH adjuster; the preferred concentration range is 0.01% to 0.5% by weight; the most preferred concentration range is 0.1% to 0.25% by weight.

[0055] The water-soluble solvent is selected from deionized (DI) water, distilled water, and alcoholic organic solvents.

[0056] In another aspect (Aspect 2), a CMP polishing method is provided for chemically and mechanically planarizing a semiconductor substrate comprising at least one Cu-containing surface, the method comprising, substantially comprising, or comprising the following steps: Make at least one surface contact the polishing pad; Chemical-mechanical planarization polishing composition for delivery aspect 1; The at least one Cu-containing surface was polished using a chemimechanical planarization composition.

[0057] In another aspect (aspect 3), a CMP polishing system is provided, comprising, substantially comprising, or consisting of the following: A semiconductor substrate comprising at least one Cu-containing surface; Polishing pads; and Aspect 1: Chemomechanical planarization composition; The at least one Cu-containing surface is in contact with the polishing pad and the chemimechanical planarization composition.

[0058] The at least one surface may also comprise at least one second material, which can be any material used together with Cu for a semiconductor substrate or patterned wafer; including but not limited to Ta; Ti; TaN; TiN; Ta; TaN; Ti; TiN, Co, Ru; dielectric materials such as SiO2, SiN, SiC; and low-k and ultra-low-k materials; such as different Black Diamon TM membrane.

[0059] The following non-limiting embodiments are used to further illustrate the present invention.

[0060] Glossary Components All raw material chemicals, such as glycine, alanine, benzotriazole, and nitric acid, were supplied by MilliporeSigma, St. Louis, MO.

[0061] The Cu pattern MIT754 was provided by SKORPIOS, Albuquerque, NM 87109-4358.

[0062] Colloidal silica (such as PL-1M) was supplied by Fuso Chemical Co., LTD, Japan.

[0063] CMP Methodology parameter General Å or ​​A: angstrom - a unit of length BP: Back pressure, unit: psi CMP: Chemical Mechanical Planarization = Chemical Mechanical Polishing CS: Carrier speed DF: Downforce: The pressure applied during CMP, unit: psi min: minutes ml: milliliters mV: millivolt mM: millimoles psi: pounds per square inch PS: Polishing equipment table speed, unit rpm (revolutions per minute). SF: Composition flow rate, ml / min Wt.%: (Weight percentage of the listed components) Cu:Ta selectivity: (Cu removal rate) / (Ta removal rate) Removal rate: The removal rate measured at a given pressure. In the examples, the pressure of the CMP device is 2.0, 3.0, 4.0, or 4.8 psi.

[0064] Metrology The membrane was measured using a ResMap CDE (model 168) manufactured by Creative Design Engineering, Inc., 20565 Alves Dr., Cupertino, CA 95014. The ResMap instrument is a four-probe thin-film resistance instrument. A 49-point diameter scan of the membrane was performed with 5 mm edge exclusion.

[0065] CMP equipment For Examples 1 and 2, the RR of the blanket-coated Cu film and the RR of the blanket-coated Ta film were measured using a TriboLab CMP polishing apparatus from Bruker, and the Cu:Ta polishing selectivity (Cu removal rate / Ta removal rate) was calculated accordingly; as well as Cu depressions on a 300 mm Cu patterned wafer MIT 754.

[0066] Polishing conditions were as follows: DuPont DGK pad; Kinik 34J in-situ dressing disc; downforce = 4.8 psi; T / H RPM = 80 / 70 rpm; composition flow rate = 250 ml / min; test membrane size: 4 x 4 cm sample; indentation data were collected 20 seconds after the end of polishing. For Examples 3, 4, and 5, copper recesses on a 300mm Cu patterned wafer MIT 754 were also measured using an Ebara device.

[0067] Polishing conditions were as follows: DuPont DGK pad; Kinik 34J in-situ dressing disc; downforce = 1.5 psi; T / H RPM = 80 / 70 rpm; composition flow rate = 350 ml / min; depression data were collected 20 seconds after the end of polishing. Polishing experiment Polishing experiments were conducted to evaluate the relative yield (RR) of blanket-coated Cu and Ta films, as well as the planarization efficiency (PE) and depression level on Cu patterned wafers. These tests were performed using a reference Cu CMP polishing composition and compared with samples containing different amino alcohols as chemical additives.

[0068] Example 1 In Example 1, the blanket-coated Cu and Ta films were polished. The Cu:Ta selectivity was calculated.

[0069] The reference polishing composition (Ref.) contains 1.125 wt% glycine, 0.125 wt% alanine, 0.067 wt% 1,2,4-triazole, 0.0025 wt% 5-methylbenzotriazole, and 0.003 wt% methylisothiazolinone. Colloidal silica (PL-1M, cocoon-shaped, primary particle size 15 nm) is added at 0.1 wt%. 1.0 wt% H₂O₂ is added before use. The pH of the reference sample is adjusted to 6 to 8 using nitric acid or potassium hydroxide.

[0070] The working polishing composition (WC) is obtained by adding 0.0025% by weight to 0.01% by weight of the disclosed different amino alcohol compounds having the disclosed general structure A to Reference Ref.: 2-(dimethylamino)-2-methyl-1-propanol for WC 1, 2-amino-2-methyl-1-propanol for WC 2, 2-amino-2-ethyl-1,3-propanediol for WC 3, 3-amino-4-octanol for WC 4, and 2-amino-2-hydroxymethyl-1,3-propanediol for WC 5. The different amino alcohol compounds are supplied by Angus Chemicals (now Advancion Corporation).

[0071] The polishing results of blanket-coated Cu and Ta films and the Cu:Ta selectivity by adding the same amount (0.005 wt%) of different amino alcohol compounds to the reference are listed in Table 1.

[0072] Table 1. Reactivity and selectivity of Cu, Ta, and TaN membranes

[0073] As the results show, the addition of the disclosed amino alcohol compound reduced the removal rate of Cu, Ta, and TaN films due to the weak passivation effect during the Cu CMP process.

[0074] This passivation effect is stronger for Ta and TaN films than for Cu films, resulting in improved Cu:Ta / TaN selectivity.

[0075] By using the different amino alcohol compounds disclosed, the Cu:Ta selectivity was improved from 207:1 to a range of 234:1 to 1395:1.

[0076] Example 2 The Cu patterned wafer was polished on a mini polisher to observe the planarization efficiency (PE%) and Cu line depressions on smaller Cu line features.

[0077] PE% is determined by measuring the step height reduction of a 100 mm line / spacing feature relative to the copper (Cu) film removal thickness after 30 seconds of polishing.

[0078] The same Ref. and working compositions WC1 to WC5 used in Example 1 were used in Example 2.

[0079] The results are listed in Table 2.

[0080] Table 2. PE% and line depressions on Cu patterned wafers

[0081] As shown in Table 2, the PE ratio was at least maintained and mostly increased by the disclosed amino alcohol compounds compared to the reference sample.

[0082] Importantly, the use of the disclosed amino alcohol compounds does indeed promote Cu pitting to varying degrees.

[0083] Please note that the chemical additives using the disclosed amino alcohol compounds intentionally increase the Cu line depression level to meet the critical requirements of advanced node Cu CMP processes.

[0084] Example 3 The Cu patterned wafer was polished using an Ebara device to observe the planarization efficiency (PE%) and Cu line depressions on smaller Cu line features.

[0085] PE% was determined by measuring the step height reduction of a 100mm line / spacing feature relative to the copper (Cu) film removal thickness after 30 seconds of polishing.

[0086] The same Ref. and working compositions WC1 to WC5 used in Example 1 were used in Example 3.

[0087] The new working compositions WC6 to WC8 are obtained by adding the same amount (0.005 wt%) of the disclosed amino alcohol having the disclosed general structure A to Ref.: amino-2-propanol for WC6, 2-(isopropylamino)ethanol for WC7, and 2-(methylamino)ethanol for WC8.

[0088] The comparative composition (CC) was obtained by adding the same amount (0.005 wt%) of an amino alcohol that does not have the disclosed general structure A to Ref.: 2-(2-aminoethoxy)ethanol for CC1 and 3-morpholinopropylamine for CC2, respectively.

[0089] The results are listed in Table 3.

[0090] Table 3. PE% and line depressions on Cu patterned wafers

[0091] The results from the Ebara device shown in Table 3 are consistent with those from the mini polisher shown in Table 2. The use of the disclosed amino alcohol compound with structure A significantly improves PE% relative to the reference sample and promotes Cu indentation to varying degrees.

[0092] In comparison, amino alcohol compounds (for CC1 and CC2) that do not have sterically hindered groups as shown in structure A do not provide the same performance.

[0093] Example 4 The Cu patterned wafer was polished using an Ebara device to observe the planarization efficiency (PE%) and Cu line depressions on smaller Cu line features.

[0094] PE% is determined by measuring the step height reduction of the 100mm line / spacing feature relative to the copper (Cu) film removal thickness after 30 seconds of polishing.

[0095] The same Ref. and working composition WC1 used in Example 1 were used in Example 4.

[0096] Working compositions WC9 and WC10 were obtained by adding 0.0075 wt% and 0.01 wt% of 2-(dimethylamino)-2-methyl-1-propanol to Ref., respectively.

[0097] The results are shown in Table 4.

[0098] Table 4. PE% and line depressions on Cu patterned wafers

[0099] The results in Table 4 show that using different concentrations of 2-(dimethylamino)-2-methyl-1-propanol increased the PE% relative to the reference sample and promoted Cu indentation at the 2 μm line. The increased amount of amino alcohol did not promote Cu indentation at the 0.18 μm line.

[0100] Example 5 The Cu patterned wafer was polished using an Ebara device to observe the planarization efficiency (PE%) and Cu line depressions on smaller Cu line features.

[0101] PE% is determined by measuring the step height reduction of the 100 mm line / spacing feature relative to the Cu film thickness removed after 30 seconds of polishing.

[0102] The new reference polishing composition (Ref. 1) comprises 1.125 wt% glycine, 0.125 wt% alanine, 0.050 wt% 1,2,4-triazole, 0.0025 wt% 5-methylbenzotriazole, and 0.003 wt% methylisothiazolinone. Colloidal silica (PL-1M, cocoon-shaped, primary particle size 15 nm) is added at 0.1 wt%. 0.9 wt% H₂O₂ is added upon use. The pH of the reference sample is adjusted to 6 to 8 using nitric acid or potassium hydroxide.

[0103] The working compositions WC11 to WC14 were obtained by adding 0.0025 wt%, 0.005 wt%, 0.0075 wt%, and 0.01 wt% of 2-(dimethylamino)-2-methyl-1-propanol to Ref. 1, respectively.

[0104] The results are shown in Table 5.

[0105] Table 5. PE% and line depressions on Cu patterned wafers

[0106] The results in Table 4 show that the use of the disclosed amino alcohol compound improved the PE relative to Ref. 1.

[0107] Importantly, the use of the disclosed amino alcohol compound within the tested amount range significantly promoted the indentation.

[0108] In this invention, specific amino alcohol compounds with sterically hindered groups at positions R1 and R2, as shown in general structure A, are used. These amino alcohol compounds have been shown to have a weak inhibitory effect on the removal rate (RR) of Cu, Ta, and TaN. This weak inhibition serves as an indicator of protecting low-lying areas during the removal of protruding features, thereby maintaining planarization efficiency.

[0109] Furthermore, the reduction in Ta and TaN RR enhances Cu's selectivity for Ta / TaN, thereby improving control over the level of depression during the overpolishing step.

[0110] Please note that the chemical additives using the disclosed amino alcohol compounds intentionally improve the Cu line depression level to meet the critical requirements of advanced node Cu CMP processes.

[0111] The embodiments of the present invention listed above, including working examples, are examples of numerous embodiments that can be implemented by the present invention. It is conceivable that many other configurations of the method can be used, and the materials used in the process can be selected from a wide range of materials other than those specifically disclosed.

Claims

1. A chemical mechanical planarization polishing composition comprising, substantially comprising, or comprising the following: a) Abrasive; b) Chemical additives; and c) Water-soluble solvents; Optionally, at least one of the following: d) Chelating agents; e) Corrosion inhibitors; f) Biocides; g) Organic quaternary ammonium salts; h) Oxidizing agents; and i) pH adjuster; The chemical additives mentioned above include amino alcohol compounds. The water-soluble solvent is selected from deionized (DI) water, distilled water, and alcoholic organic solvents; and The pH range of the CMP polishing composition is 3 to 11, 4 to 10, 5 to 9, or 6 to 8.

2. The chemical mechanical planarization polishing composition according to claim 1, wherein... The amino alcohol compound has the following general structure A: A； R1 and R2 are each independently selected from H; OH; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol; and R3, R4 and R5 are each independently selected from H; C1-C12, C1-C8 or C1-C4 alkyl; or C1-C12, C1-C8 or C1-C4 alkyl alcohol.

3. The chemimechanical planarization polishing composition according to any one of claims 1-2, wherein the chemical additive is selected from 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-1-butanol, and combinations thereof.

4. The chemimechanical planarization polishing composition according to any one of claims 1-3, wherein the chemical additive is selected from 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, 2-amino-2-hydroxymethyl-1,3-propanediol, and combinations thereof.

5. The chemical mechanical planarization polishing composition according to any one of claims 1-4, wherein the concentration range of the chemical additive is 0.0001-0.1 wt%, 0.0005-0.08 wt%, 0.001-0.06 wt%, 0.0015-0.04 wt%, 0.002-0.03 wt%, 0.0025-0.02 wt%, 0.003-0.01 wt%, or 0.0035-0.008 wt%.

6. The chemical mechanical planar polishing composition according to any one of claims 1-5, wherein the abrasive is selected from colloidal silica; colloidal silica particles doped with other metal oxides within a colloidal silica lattice; silica sol selected from sodium silicates, potassium silicates, and combinations thereof; fumed silica; colloidal alumina selected from α-, β-, and γ-type aluminum oxides; colloidal and photoactive titanium dioxide, cerium oxide, colloidal cerium oxide; nanoscale diamond particles; nanoscale silicon nitride particles; organic polymer-based soft abrasives; surface-coated or modified abrasives; and combinations thereof.

7. The chemical mechanical planarization polishing composition according to any one of claims 1-6, wherein the abrasive is selected from colloidal silica; colloidal silica particles doped with other metal oxides within a colloidal silica lattice; surface-coated or modified colloidal silica; and combinations thereof.

8. The chemical mechanical planarization polishing composition according to any one of claims 1-7, wherein the abrasive is selected from colloidal silica; surface-coated or modified colloidal silica; and combinations thereof.

9. The chemical mechanical planar polishing composition according to any one of claims 1-8, wherein the concentration of the abrasive is in the range of 0.0001-0.5 wt%, 0.0005-0.25 wt%, 0.00075-0.1 wt%, 0.001-0.075 wt%, 0.0015-0.06 wt%, or 0.002-0.05 wt%.

10. The chemimechanical planarization polishing composition according to any one of claims 1-9, wherein the chelating agent is selected from amino acids and their derivatives, amines, and combinations thereof.

11. The chemical mechanical planar polishing composition according to any one of claims 1-10, wherein the chelating agent is an amino acid or a derivative thereof, selected from glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

12. The chemimechanical planar polishing composition according to any one of claims 1-11, wherein the chelating agent is a combination of at least two amino acids or derivatives thereof, wherein the amino acids or derivatives thereof are selected from glycine, D-alanine, L-alanine, DL-alanine, β-alanine, valine, leucine, isoleucine, phenylalanine, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

13. The chemimechanical planar polishing composition according to any one of claims 1-12, wherein the chelating agent is a combination of at least two amino acids or their derivatives, selected from glycine, D-alanine, L-alanine, DL-alanine, β-alanine, their derivatives, and combinations thereof.

14. The chemimechanical planarization polishing composition according to any one of claims 1-13, wherein the concentration of the chelating agent ranges from 0.1% to 18% by weight, 0.5% to 10% by weight, or 0.75% to 2.5% by weight.

15. The chemimechanical planarization polishing composition according to any one of claims 1-14, wherein the corrosion inhibitor is a heteroaromatic compound containing a nitrogen atom in an aromatic ring.

16. The chemimechanical planarization polishing composition according to any one of claims 1-15, wherein the corrosion inhibitor is selected from 1,2,4-triazole, benzotriazole and benzotriazole derivatives, tetrazolium and tetrazolium derivatives, imidazole and imidazole derivatives, benzimidazole and benzimidazole derivatives, pyrazole and pyrazole derivatives, tetrazolium and tetrazolium derivatives, and combinations thereof.

17. The chemimechanical planarization polishing composition according to any one of claims 1-16, wherein the corrosion inhibitor is selected from 1,2,4-triazole, benzotriazole and benzotriazole derivatives and combinations thereof.

18. The chemical mechanical planarization polishing composition according to any one of claims 1-17, wherein the concentration range of the corrosion inhibitor is 0.005 wt% to 1.0 wt%, 0.01 wt% to 0.5 wt%, or 0.02 wt% to 0.2 wt%.

19. The chemimechanical planarization polishing composition according to any one of claims 1-18, wherein the biocide comprises an ingredient selected from 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and combinations thereof.

20. The chemimechanical planarization polishing composition according to any one of claims 1-19, wherein the concentration of the biocide ranges from 0.0001 wt% to 0.05 wt%, 0.0002 wt% to 0.025 wt%, or 0.002 wt% to 0.01 wt%.

21. The chemical mechanical planar polishing composition according to any one of claims 1-20, wherein the oxidant is a peroxide compound selected from hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, peroxypropionic acid, substituted or unsubstituted peroxybutyric acid, hydroperoxyacetaldehyde, potassium periodate, ammonium persulfate; and a non-peroxide compound selected from ferrous nitrite, KClO4, KBrO4, KMnO4; and combinations thereof.

22. The chemical mechanical planarization polishing composition according to any one of claims 1-21, wherein the oxidant is hydrogen peroxide.

23. The chemical mechanical planarization polishing composition according to any one of claims 1-22, wherein the concentration of the oxidant ranges from 0.10% to 10.00% by weight, 0.25% to 3.00% by weight, or 0.50% to 2.00% by weight.

24. The chemimechanical planar polishing composition according to any one of claims 1-23, wherein the pH adjuster is selected from (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and mixtures thereof, for lowering pH; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine and mixtures thereof, for raising pH.

25. The chemimechanical planarization polishing composition according to any one of claims 1-24, wherein the concentration range of the pH adjuster is 0.00% to 1.00% by weight, 0.01% to 0.50% by weight, or 0.10% to 0.25% by weight.

26. The chemical mechanical planarization polishing composition according to any one of claims 1-25, wherein the chemical mechanical planarization polishing composition comprises at least one silica sol selected from colloidal silica, fumed silica, sodium silicate or potassium silicate; at least one selected from glycine and alanine; at least one selected from 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-1-butanol and combinations thereof; and the pH is 5 to 9 or 6 to 8.

27. A chemical mechanical planarization polishing method for polishing a semiconductor substrate comprising at least one Cu-containing surface, comprising the following steps, substantially comprising the following steps, or comprising the following steps: Make at least one surface contact the polishing pad; Deliver the chemical mechanical planarization polishing composition according to any one of claims 1-26; Polish the at least one Cu-containing surface using the chemimechanical planarization composition.

28. The chemical mechanical planarization polishing method of claim 27, wherein the semiconductor substrate comprises at least one other surface containing a second material; the removal selectivity of Cu relative to the second material is >1, >5, or >6; and the second material is selected from Ta; Ti; TaN; TiN; Ta; TaN; Ti; TiN; SiO2, SiN, SiC; and low-k and ultra-low-k materials.

29. A chemical mechanical planar polishing system, comprising: Semiconductor substrate having at least one Cu-containing surface; Polishing pad; as well as The chemical mechanical planarization polishing composition according to any one of claims 1 to 26; The at least one Cu-containing surface is in contact with the polishing pad and the chemimechanical planarization composition.

30. The chemical mechanical planarization polishing system according to claim 29; The semiconductor substrate includes at least one other surface containing a second material; the removal selectivity of Cu relative to the second material is >1, >5, or >6; and The second material is selected from Ta; Ti; TaN; TiN; Ta; TaN; Ti; TiN; SiO2; SiN; SiC; as well as low-k and ultra-low-k materials.

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