Within-die non-uniformity in planarization

Abstract

The present invention provides a chemical mechanical planarization (CMP) polishing composition for barrier layer applications, particularly for improving within-die non-uniformity (WID-NU), comprising 2.0 wt. % or more of an abrasive, a planarizing agent selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, polymers thereof, derivatives thereof, and combinations thereof, wherein the polymers have a molecular weight of 10 Daltons to 5 million Daltons, preferably 50 Daltons to 1 million Daltons, a corrosion inhibitor, a water-soluble solvent, and optionally, a rate enhancer, a pH adjuster, an oxidizer, and a chelating agent.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 62 / 904,861, filed September 24, 2019, which is incorporated herein by reference. [Background technology]

[0002] The present invention relates to barrier chemical mechanical planarization ("CMP") polishing compositions (or slurries) used in the manufacture of semiconductor devices, and polishing methods for performing chemical mechanical planarization. In particular, the present invention relates to barrier polishing compositions suitable for use in polishing patterned semiconductor wafers comprised of multiple films, such as a metal layer, a barrier film, and an underlying interlayer dielectric (ILD) structure or patterned dielectric layer.

[0003] Typically, a barrier layer covers the patterned dielectric layer, and a metal layer covers the barrier layer, the metal layer having a thickness at least sufficient to fill the patterned trenches with metal to form circuit interconnects.

[0004] The barrier is typically a metal, metal alloy, or intermetallic compound, such as a Ta- or Ti-containing film, e.g., TaN, Ti, TiN, or TiW. The barrier forms a layer that prevents migration or diffusion between layers within the wafer. For example, the barrier prevents the diffusion of interconnect metals, such as copper, cobalt, or silver, into adjacent dielectrics. The barrier material must be resistant to corrosion by most acids and thereby resist dissolution in the polishing composition of the CMP fluid. Furthermore, the barrier material can exhibit the toughness to withstand removal by abrasion of abrasive particles in the CMP composition and from the fixed polishing pad.

[0005] With respect to CMP, the current state of the art involves multiple steps, for example, a two-step process to achieve local and global planarization.

[0006] During step 1 of a typical CMP process, metal layers, such as overburden copper layers, are usually removed, leaving a smooth, flat surface on the wafer with metal-filled lines, vias, and trenches that provide planar circuit interconnects relative to the polished surface. Thus, step 1 serves to remove excess interconnect metal, such as copper or cobalt. Step 2 of a typical CMP, often referred to as a barrier CMP process, then continues to remove the barrier layer and excess metal layers and other films on the surface of the patterned wafer, achieving both local and global planarization of the surface over the dielectric layer.

[0007] Chemical mechanical planarization (CMP) of the barrier layer is a critical step in the wafer damascene process.

[0008] Within-die non-uniformity (WID-NU) is the overall process height deviation on a patterned wafer that can impair the performance of functional dies. WID-NU is more pronounced when the initial differences in pattern density between various structures are more pronounced. Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, there is a need to create CMP slurries that have higher removal rates as well as improved planarization, such as better within-die non-uniformity (WID-NU), and that are more reliable, consistent, and uniform. [Means for solving the problem]

[0010] The present invention provides a stable CMP slurry with better within-die planarity. Barrier CMP compositions, systems, and methods for polishing are described and disclosed herein. The compositions disclosed herein provide improved, better within-die non-uniformity (WID-NU).

[0011] In one embodiment, Abrasives, flattening agent, corrosion inhibitors, Aqueous solvents, Optionally, Wetting agents, Speed ​​enhancers, pH adjuster, an oxidizing agent, and chelating agents, A barrier chemical mechanical planarization polishing composition comprising: Polishing compositions having a pH of about 2 to about 12, preferably about 3 to about 12, more preferably about 7 to 12, and most preferably about 8 to 12, are described.

[0012] In another aspect, there is provided a polishing method for chemical mechanical planarization of a semiconductor device including at least one surface having at least a barrier layer and a dielectric layer, the method comprising the steps of: a. contacting the at least one surface with a polishing pad; b. dispensing a polishing composition described herein onto the at least one surface; and c. polishing the at least one surface with the polishing composition; wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof.

[0013] In yet another aspect, the present invention provides a semiconductor device comprising at least one surface having at least a barrier layer and a dielectric layer; A polishing pad, and The polishing composition described herein, a chemical mechanical planarization system including: wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof; The at least one surface is then in contact with the polishing pad and the polishing composition.

[0014] Examples of abrasives include, but are not limited to, colloidal silica, alumina, ceria, germania, silica, titania, zirconia, alumina-doped colloidal silica, organic polymer particles, composite particles of inorganic and organic particles, surface-modified inorganic / organic particles, and combinations thereof.

[0015] The abrasive is used in an amount of 0.1% by mass to about 25.0% by mass, 0.1% by mass to 20.0% by mass, 1% by mass to 20.0% by mass, 2.0% by mass to 15.0% by mass, or 3.0% by mass to 15.0% by mass, preferably ≧2.0% by mass, and more preferably ≧3.5% by mass.

[0016] Examples of planarizing agents include, but are not limited to, ethylene oxide, propylene oxide, butylene oxide, their polymers, their derivatives, and chemical mixtures containing them as components. These polymers have a molecular weight ranging from 10 to 5 million Daltons (Da), preferably from 50 to 1 million Da.

[0017] The leveling agent is used in an amount ranging from about 0.0001% to about 10.0% by weight, 0.0005% to 5.0% by weight, 0.0001 to 3.0% by weight, or 0.005% to 2.0% by weight.

[0018] Examples of planarizing agents include, but are not limited to, ethanol, 2-[(1-dodecylcyclohexyl)oxy]-; poly(oxy-1,2-ethanediyl), α-(1-nonyldecyl)-ω-hydroxy-; poly(oxy-1,2-ethanediyl), α-(1-decylcyclohexyl)-ω-hydroxy-; ethanol, 2-(cyclotridecyloxy)-; poly(ethylene oxide) (Mw ranging from 10 to 5 million DA, preferably 50 to 1 million DA); poly(propylene oxide) (Mw ranging from 10 to 5 million DA, preferably 50 to 1 million DA); Tergitol™ 15s9; Tergitol™ 15s7; Surfyol™ 485, Surfyol™ 465; Zetasperse™ 179; and combinations thereof.

[0019] Examples of corrosion inhibitors include, but are not limited to, benzotriazole or benzotriazole derivatives, 3-amino-1,2,4-triazole, 3,5-diamine-1,2,4-triazole, and combinations thereof in the range of about 0.0001% to about 2.0% by weight; about 0.0005% to about 1.0% by weight, or about 0.001% to about 0.5% by weight.

[0020] Examples of aqueous solvents include, but are not limited to, DI water, polar solvents, and mixtures of DI water and polar solvents. The polar solvent can be any alcohol, ether, ketone, or other polar reagent. Examples of polar solvents include alcohols, such as isopropyl alcohol, ethers, such as tetrahydrofuran and diethyl ether, and ketones, such as acetone.

[0021] Examples of wetting agents include, but are not limited to, a) nonionic surface wetting agents, b) anionic surface wetting agents, c) cationic surface wetting agents, d) amphoteric surface wetting agents, and combinations thereof, in amounts of about 0.0001% to about 10.0% by weight; 0.001% to about 5.0% by weight; 0.005% to 2.0% by weight, or 0.001% to 1.0% by weight.

[0022] Speed ​​enhancers may include, but are not limited to, potassium silicate, sodium silicate, ammonium silicate, tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof.

[0023] The rate enhancer is used in an amount ranging from about 0.001% to about 20.0% by weight; 0.01% to about 15.0% by weight, or 0.1% to about 10.0% by weight.

[0024] Examples of 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 combinations thereof for lowering the pH of the polishing composition, and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof for raising the pH of the polishing composition, in amounts of about 0.0001% by weight to about 5.0% by weight; 0.001% by weight to about 3.0% by weight; or 0.01% by weight to about 2.0% by weight, and the polishing composition has a pH of about 2 to about 12, preferably about 3 to 12, more preferably about 7 to 12, and most preferably about 8 to 12.

[0025] Examples of oxidizing agents include, but are not limited to, hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, amine compounds, and combinations thereof, in an amount ranging from about 0.05% to about 10.0% by weight; preferably from about 0.2% to about 2.0% by weight.

[0026] Suitable chelating agents include, but are not limited to, organic acids and their salts; polymeric acids and their salts; water-soluble copolymers and their salts; copolymers containing at least two different types of acid groups selected from carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and pyridine acids in the same molecule of the copolymer and their salts; polyvinyl acids and their salts; polyethylene oxide; polypropylene oxide; pyridine, pyridine derivatives, bipyridine, bipyridine derivatives, and combinations thereof.

[0027] Examples of chelating agents include, but are not limited to, potassium citrate, benzosulfonic acid, 4-tolylsulfonic acid, 2,4-diamino-benzosulfonic acid, malonic acid, itaconic acid, malic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid, amino acids, polycarboxyamino acids, phosphonic acids, salts thereof, and combinations thereof.

[0028] The chelating agent is used in an amount ranging from about 0.001% to about 10.0% by weight; preferably from about 0.05% to about 10.0% by weight; preferably from about 0.05% to about 5.0% by weight; and more preferably from 0.01% to 1.0% by weight.

[0029] All percentages are by weight based on the total weight of the CMP composition unless otherwise specified. [Brief explanation of the drawings]

[0030] [Figure 1] FIG. 1 shows quartz crystal microbalance (QCM) data for chemical A, chemical B, and chemical C.

[0031] [Figure 2] FIG. 2 shows quartz crystal microbalance (QCM) data for chemical G, chemical H, chemical K, and chemical N. DETAILED DESCRIPTION OF THE INVENTION

[0032] The present invention provides stable CMP slurries with higher barrier and ILD removal rates. Barrier CMP compositions, systems, and methods for polishing are described and disclosed herein. The compositions disclosed herein increase barrier film and ILD removal rates.

[0033] Described herein are stable CMP slurries for polishing semiconductor substrates or devices having a conductive metal layer, an underlying barrier film, and a dielectric layer with embedded metal interconnect structures.

[0034] The conductive metal layer may include, for example, Cu, CuMn, Co, CoMo, Al, AlCo, Ru, RuTa, RuTiN, Mn, and combinations thereof. The barrier and liner layers may include tantalum or titanium-containing films selected from the group consisting of Ta, TaN, Ti, TiN, TiW, or TiWN. The underlying interlayer dielectric (ILD) layer may include an oxide film, for example, SiO2, TEOS, low-K dielectric materials, and combinations thereof.

[0035] All percentages are by weight based on the total weight of the CMP composition unless otherwise specified.

[0036] The barrier chemical mechanical planarization polishing composition comprises: Abrasives, flattening agent, corrosion inhibitors, Aqueous solvents, Optionally, Wetting agents, Speed ​​enhancers, pH adjuster, an oxidizing agent, and chelating agents, It contains The polishing composition has a pH of about 2 to about 12, preferably about 3 to 12, more preferably about 7 to 12, and most preferably about 8 to 12.

[0037] The polishing composition of the present invention comprises an abrasive. Suitable abrasives for the polishing composition include nano-sized particles, such as, but not limited to, nano-sized colloidal silica or high-purity colloidal silica particles; nano-sized inorganic metal oxide particles, such as alumina, titania, zirconia, ceria, and combinations thereof; nano-sized diamond particles; nano-sized silicon nitride particles; unimodal, bimodal, or multimodal colloidal abrasive particles; organic polymer-based soft abrasives; surface-coated or surface-modified abrasives; and combinations thereof.

[0038] Surface-coated or surface-modified abrasives include, but are not limited to, colloidal silica particles doped with other metal oxides within the colloidal silica lattice, such as alumina-doped silica particles, colloidal aluminum oxide, including alpha-, beta-, and gamma-type aluminum oxide, colloidal and photoactive titanium dioxide, cerium oxide, colloidal cerium oxide, nano-sized diamond particles, nano-sized silicon nitride particles, unimodal, bimodal, and multimodal colloidal abrasive particles, zirconium oxide, organic polymer-based soft abrasives, surface-coated or surface-modified abrasives, and combinations thereof.

[0039] The nano-sized particles have a narrow or broad particle size distribution, various sizes, and various shapes, including spherical, cocoon-shaped, agglomerated, and other shapes of the abrasives.

[0040] The abrasive particles can be purified using a suitable method to remove metal impurities, such as ion exchange, which may help improve colloidal stability. Alternatively, high-purity silica abrasive particles made from precursors other than metal silicates can be used.

[0041] Preferred abrasives include, but are not limited to, high purity colloidal silica (colloidal silica), alumina, ceria, germania, silica, titania, zirconia, alumina-doped colloidal silica, and combinations thereof. Colloidal silica is the most preferred abrasive particle.

[0042] The silica can be precipitated silica, fumed silica, pyrogenic silica, silica doped with one or more adjuvants, or any other silica-based compound. In other embodiments, the silica can be produced by a process selected from the group consisting of, for example, a sol-gel process, a hydrothermal process, a plasma process, a fuming process, a precipitation process, and any combination thereof.

[0043] Preferably, the average particle size is 10 nm to 300 nm, or more preferably 20 nm to 200 nm, and even more preferably 30 nm to 100 nm, as measured by disc centrifugation (DC) particle classification.

[0044] Generally, the above abrasive particles can be used alone or in combination with each other. Two or more types of abrasive particles having different sizes can also be combined to obtain superior performance.

[0045] Typically, the abrasive particles are present in the compositions of the present invention in an amount ranging from about 0.1% to about 25.0% by weight; 0.1% to 20.0% by weight; 1.0% to 20.0% by weight; 2.0% to 15.0% by weight; or 3.0% to 15.0% by weight; preferably ≧2.0% by weight, more preferably ≧3.5% by weight.

[0046] Examples of water-soluble solvents include, but are not limited to, DI water, polar solvents, and mixtures of DI water and polar solvents. The polar solvent can be any alcohol, ether, ketone, or other polar reagent. Examples of polar solvents include alcohols, such as isopropyl alcohol, ethers, such as tetrahydrofuran and diethyl ether, and ketones, such as acetone.

[0047] Examples of planarizing agents include, but are not limited to, ethylene oxide, its derivatives, and polymers thereof; propylene oxide, its derivatives, and polymers thereof; butylene oxide, its derivatives, and polymers thereof; and combinations thereof.

[0048] These polymers have a molecular weight ranging from 10 to 5 million Daltons (Da), preferably from 50 to 1 million Da. The planarizing agent is used in an amount ranging from about 0.0001% to about 10.0% by weight, 0.0005% to 5.0% by weight, 0.0001 to 3% by weight, or 0.005% to 2.0% by weight.

[0049] Planarizing agents include, but are not limited to, ethanol, 2-[1-dodecylcyclohexyl]oxy]-; poly(oxy-1,2-ethanediyl), α-(1-nonyldecyl)-ω-hydroxy-; poly(oxy-1,2-ethanediyl), α-(1-decylcyclohexyl)-ω-hydroxy-; cyclic oligosaccharides; ethanol, 2-(cyclotridecyloxy)-; poly(ethylene oxide) (Mw ranging from 10 to 5 million Da, preferably from 50 to 1 million Da); poly(propylene oxide) (Mw ranging from 10 to 5 million Da, preferably from 50 to 1 million Da), and combinations thereof.

[0050] Surfactants such as Dow Chemical's Tergitol™ 15s9 and Tergitol™ 15s7; BASF's Polysorbate 20, e.g., Tween® 20; BASF's Cyclodextrin, Pluronic® F-108; have a secondary alcohol ethoxylate as the primary active chemical in the surfactant.

[0051] Surfyol® surfactants, Surfyol® 485, Surfyol® 465, Dynol™ 801, Dynol™ 980, and Zetasperse® 179 are surfactants from Evonik Industries. The primary active chemical in these surfactants is polyethylene oxide.

[0052] Surfactants can be used as surface wetting agents in barrier CMP slurries, and suitable wetting agents that can be added to barrier CMP slurries as surface wetting agents include any of a number of nonionic, anionic, cationic, or amphoteric surfactants known to those skilled in the art. One example of a nonionic surfactant is tricosaethylene glycol dodecyl ether.

[0053] Additionally, examples of wetting agents include, but are not limited to, sodium dodecyl sulfate, sodium lauryl sulfate, ammonium dodecyl sulfate, secondary alkane sulfonates, alcohol ethoxylates, acetylenic surfactants, and any combination thereof.

[0054] Ethoxylated acetylenic gemini surfactants, Dynol™ 607 and Dynol™ 604 from Evonik, are used as wetting agents.

[0055] When used, the amount of wetting agent typically ranges from 0.0001% to about 10.0% by weight, from 0.001% to about 5.0% by weight, from 0.005% to 2.0% by weight, or from 0.001% to 1.0% by weight.

[0056] Examples of corrosion inhibitors include, but are not limited to, benzotriazole or benzotriazole derivatives, 3-amino-1,2,4-triazole, 3,5-diamine-1,2,4-triazole, and combinations thereof.

[0057] The corrosion inhibitor is used in an amount ranging from about 0.0001% to about 2.0% by weight; from about 0.0005% to about 1% by weight, or from about 0.001% to about 0.5% by weight.

[0058] Speed ​​enhancers may include, but are not limited to, potassium silicate, sodium silicate, ammonium silicate, tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof.

[0059] The rate enhancer is used in an amount ranging from about 0.001% to about 20.0% by weight; 0.01% to about 15.0% by weight, or 0.1% to about 10.0% by weight.

[0060] Examples of 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 combinations thereof for lowering the pH of the polishing composition, and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof for raising the pH of the polishing composition, which are used in amounts of about 0.0001% by weight to about 5.0% by weight; 0.001% by weight to about 3.0% by weight; or 0.01% by weight to about 2.0% by weight, and the polishing composition has a pH of about 2 to about 12, preferably about 3 to 12, more preferably about 7 to 12, and most preferably about 8 to 12.

[0061] Examples of oxidizing agents include, but are not limited to, hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, amine compounds, and combinations thereof.

[0062] The oxidizing agent is used in an amount ranging from about 0.05% to about 10.0% by mass; preferably from about 0.2% to about 2.0% by mass.

[0063] Suitable chelating agents include, but are not limited to, organic acids and their salts; polymeric acids and their salts; water-soluble copolymers and their salts; copolymers containing at least two different types of acid groups selected from carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, and pyridine acids in the same molecule of the copolymer and their salts; polyvinyl acids and their salts; polyethylene oxide; polypropylene oxide; pyridine, pyridine derivatives, bipyridine, bipyridine derivatives, and combinations thereof.

[0064] Examples of chelating agents include, but are not limited to, potassium citrate, benzosulfonic acid, 4-tolylsulfonic acid, 2,4-diaminobenzosulfonic acid, malonic acid, itaconic acid, malic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid, amino acids, polycarboxyamino acids, phosphonic acids, salts thereof, and combinations and salts thereof.

[0065] The chelating agent is used in an amount ranging from about 0.001% to about 10.0% by weight; preferably from about 0.05% to about 5.0% by weight; and more preferably from 0.01% to 1.0% by weight.

[0066] The present invention also provides a polishing method for chemical mechanical planarization of a semiconductor device including at least one surface having at least a barrier layer and a dielectric layer, the method comprising the steps of: a. contacting the at least one surface with a polishing pad; b. dispensing a polishing composition described herein onto the at least one surface; and c. polishing the at least one surface with the polishing composition; wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof.

[0067] The present invention further comprises: a semiconductor device comprising at least one surface having at least a barrier layer and a dielectric layer; A polishing pad, and The polishing composition described herein, a system for chemical mechanical planarization comprising: wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof, and the at least one surface is in contact with the polishing pad and the polishing composition. [Example]

[0068] General Experimental Procedures All percentages are by weight unless otherwise specified. Water is added to bring the composition to 100% by weight.

[0069] In the examples presented below, CMP experiments were carried out using the procedures and experimental conditions set out below.

[0070] Polishing was performed on a 300 mm Reflection LK, Atec, at 1.1 psi, 93 RPM table speed, 300 mL / min flow rate, Fujibo H800 pad, Cu / TEOS pattern in MIT layout.

[0071] Silica particles of approximately 60 nm (measured by light scattering) were purchased from Fuso Chemical Co. LTD (Japan).

[0072] Example 1 The chemical compositions used in the slurries are shown in Table 1. Slurries B, D, E, and F had a leveling agent in them, while slurries A and C only had a wetting agent in them.

[0073] DI water was added to make the composition 100% by weight. The pH of the slurry was about 10. [Table 1]

[0074] These slurries were prepared at room temperature for each component with a short break (a few minutes).

[0075] These slurries were used for polishing (at the point of use) after 1.0 wt % hydrogen peroxide was added to them as an oxidizer.

[0076] The polishing results for dishing and etching on Cu / TEOS patterned wafers of the MIT layout are shown in Table 2. [Table 2]

[0077] 10x10 μm are features on the Cu / TEOS pattern of the MIT layout, 10 μm Cu and 10 μm TEOS.

[0078] As shown in Table 2, across all different feature sizes, the slurries with planarizing agents (Slurries B, D, E, and F) provide better dishing compared to the slurries without planarizing agents (Slurries A and C).

[0079] Similarly, as shown in Table 2, across all different feature sizes, the slurries with planarizing agents (Slurries B, D, E, and F) result in less corrosion compared to the slurries without planarizing agents (Slurries A and C).

[0080] Therefore, the data for these slurries shows that the addition of a planarizing agent can improve within-die uniformity.

[0081] Furthermore, data from these slurries indicates that the addition of wetting agents fails to improve in-die uniformity.

[0082] Example 2 The chemical compositions used in the slurries are shown in Table 3. Slurries H, I, J and K have a leveling agent in them, while slurry G has only a wetting agent in it.

[0083] DI water was added to bring the composition to 100% by weight. The pH of these slurries was approximately 10. [Table 3]

[0084] These slurries were prepared at room temperature with a short break (a few minutes) between each component.

[0085] These slurries were used for polishing after 1.0 mass % hydrogen peroxide was added to them as an oxidizing agent.

[0086] The polishing results for dishing and etching on Cu / TEOS patterned wafers of the MIT layout are shown in Table 4. [Table 4]

[0087] 10x10 μm are features on the Cu / TEOS pattern of the MIT layout, 10 μm Cu and 10 μm TEOS.

[0088] As shown in Table 4, across all different feature sizes, the slurries with planarizing agents (Slurries H, I, J, and K) provide better dishing compared to the slurry without planarizing agents (Slurry G).

[0089] Similarly, as shown in Table 4, across all different feature sizes, the slurries with planarizing agents (Slurries H, I, J, and K) result in less corrosion compared to the slurry without planarizing agents (Slurry G).

[0090] Thus, Example 2 shows that the addition of a planarizing agent can improve within-die uniformity.

[0091] Example 3 The chemical compositions used in the slurries are shown in Table 5. Slurries M, N, O and P have a leveling agent in them, while slurry L has only a wetting agent in it.

[0092] DI water was added to bring the composition to 100% by weight. The pH of these slurries was approximately 10. [Table 5]

[0093] These slurries were prepared at room temperature with a short break (a few minutes) between each component.

[0094] These slurries were used for polishing after 1.0 mass % hydrogen peroxide was added to them as an oxidizing agent.

[0095] The polishing results for dishing and etching on Cu / TEOS patterned wafers of the MIT layout are shown in Table 6. [Table 6]

[0096] 10x10 μm are features on the Cu / TEOS pattern of the MIT layout, 10 μm Cu and 10 μm TEOS.

[0097] table 6 As shown in Figure 1, across all different feature sizes, the slurries with planarizing agents (Slurries M, N, O, and P) provide better dishing compared to the slurry without planarizing agents (Slurry L).

[0098] Similarly, Table6 As shown in Figure 1, across all different feature sizes, the slurries with planarizing agents (Slurries M, N, O, and P) result in less corrosion compared to the slurry without planarizing agents (Slurry L).

[0099] Thus, Example 3 shows that the addition of a planarizing agent can improve within-die uniformity.

[0100] Example 4 Characterization of leveling and wetting agents To characterize the difference between the wetting agent and the planarizing agent, a quartz crystal microbalance (QCM) was used to measure the molecular adsorption.

[0101] Chemicals diluted with DI water were prepared as shown in Table 7.

[0102] The sensor used in this experiment was a QSX303 SiO2 with a 14 mm oxide diameter with gold electrodes on both sides.

[0103] The experiment was set to run for a total time of 30 minutes (mins). The pump was set to run at a flow rate of 1 mL / min. DI water was set to pass over the sensor for the very first 2 minutes before the chemical was passed over the sensor at the same rate for 5 minutes, and then DI water was set to pass over the sensor for the remainder of the experiment. [Table 7]

[0104] The results are shown in Figure 1.

[0105] As shown in Figure 1, chemical B exhibited rapid adsorption with a larger ΔF, while chemicals A and C exhibited slower adsorption with relatively smaller ΔF.

[0106] Without wishing to be bound by any theory or explanation, it is believed that rapid adsorption provides protection to exposed dielectric surfaces, reducing corrosion in those areas, especially in the high density copper areas (i.e., 9 x 1 μm). Reducing corrosion, in turn, improves WID-NU.

[0107] All three solutions were shown to rinse completely with DI water alone.

[0108] Chemical B was used as a planarizing agent.

[0109] Chemicals A and C were used as wetting agents only.

[0110] Example 5 Characterization of leveling and wetting agents A quartz crystal microbalance (QCM) was used to characterize the differences between the wetting and planarizing agents.

[0111] Chemicals diluted with DI water were prepared as shown in Table 8.

[0112] The sensor used in this experiment was a QSX303 SiO2 with a 14 mm oxide diameter with gold electrodes on both sides.

[0113] The experiment was set to run for a total time of 20 minutes. The pump was set to run at a flow rate of 1 mL / min. DI water was set to pass over the sensor for the very first 2 minutes before the chemical was passed over the sensor at the same rate for 5 minutes, and then DI water was set to pass over the sensor for the remainder of the experiment. [Table 8]

[0114] The results are shown in FIG.

[0115] As shown in Figure 2, chemicals H, K, and N exhibited rapid adsorption with larger ΔF, while chemical G exhibited slower adsorption with a relatively smaller ΔF.

[0116] Rapid adsorption provides protection to exposed dielectric surfaces, reducing corrosion in those areas, especially in the high-density copper areas (i.e., 9 x 1 μm). Reducing corrosion, in turn, improves WID-NU.

[0117] All three solutions were shown to rinse completely with DI water alone.

[0118] Chemicals H, K and N were used as planarizing agents.

[0119] Chemical G was used only as a wetting agent.

[0120] The foregoing examples and description of embodiments should be taken as illustrative, rather than limiting, of the invention defined by the claims. As will be readily appreciated, many variations and combinations of the features described above can be used without departing from the invention as defined in the claims. Such variations are intended to be encompassed within the scope of the appended claims.

Claims

1. 1. A barrier chemical mechanical planarization (CMP) polishing composition comprising: an abrasive selected from the group consisting of silica, alumina, ceria, germania, titania, zirconia, alumina-doped colloidal silica, and combinations thereof; Leveling agent, the leveling agent is selected from the group consisting of ethanol, 2-[(1-dodecylcyclohexyl)oxy]-; cyclic oligosaccharides; poly(oxy-1,2-ethanediyl), α-(1-nonyldecyl)-ω-hydroxy-; poly(oxy-1,2-ethanediyl), α-(1-decylcyclohexyl)-ω-hydroxy-; ethanol, 2-(cyclotridecyloxy)-; polypropylene oxide having a molecular weight ranging from 50 Daltons to 1 million Daltons; and combinations thereof. corrosion inhibitors, an aqueous solvent, the aqueous solvent being selected from the group consisting of DI water, a polar solvent, and a mixture of DI water and a polar solvent, the polar solvent being selected from the group consisting of an alcohol, an ether, and a ketone; Speed ​​enhancers, Optionally, a wetting agent, said wetting agent being selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and combinations thereof; pH adjusters, an oxidizing agent, and chelating agents, comprising The polishing composition has a pH of 7 to 12. Barrier chemical mechanical planarizing polishing composition.

2. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the abrasive is colloidal silica, and the colloidal silica has an average particle size of 20 nm to 200 nm.

3. The barrier chemical mechanical planarizing polishing composition of claim 1 , wherein the planarizing agent is polypropylene oxide.

4. 2. The barrier chemical mechanical planarizing polishing composition of claim 1, wherein the corrosion inhibitor is selected from the group consisting of benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamine-1,2,4-triazole, and combinations thereof, and the corrosion inhibitor is present in an amount of 0.0005 wt % to 1.0 wt %.

5. The barrier chemical mechanical planarization polishing composition of claim 1 , wherein the wetting agent is present in the polishing composition.

6. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the wetting agent is selected from the group consisting of acetylenic diol surfactants, alcohol ethoxylate surfactants, and combinations thereof, and the surfactant is present in an amount of 0.005 wt.% to 2.0 wt.%.

7. 2. The barrier chemical mechanical planarizing polishing composition of claim 1, wherein the rate enhancing agent is selected from the group consisting of potassium silicate, sodium silicate, ammonium silicate, tetramethylammonium silicate, tetrabutylammonium silicate, tetraethylammonium silicate, and combinations thereof, and the rate enhancing agent is used in an amount ranging from 0.01 wt.% to 15.0 wt.%.

8. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the pH adjuster is selected from the group consisting of: (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids, and combinations thereof, for lowering the pH of the polishing composition, and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof, for raising the pH of the polishing composition, and the pH adjuster is used in an amount of 0.001% by weight to 3.0% by weight.

9. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, an amine compound, and combinations thereof, and the oxidizing agent is used in an amount ranging from 0.2% by weight to 2.0% by weight.

10. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the chelating agent is selected from the group consisting of potassium citrate, benzosulfonic acid, 4-tolylsulfonic acid, 2,4-diaminobenzosulfonic acid, malonic acid, itaconic acid, malic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid, amino acids, polycarboxyamino acids, phosphonic acids, salts thereof, and combinations thereof, and the chelating agent is used in an amount ranging from 0.05% to 5.0% by weight.

11. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the barrier chemical mechanical planarization polishing composition comprises 2% by weight or more of colloidal silica, benzotriazole, the planarizing agent comprises a secondary alcohol ethoxylate, and the barrier chemical mechanical planarization polishing composition has a pH of 8 to 12.

12. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the barrier chemical mechanical planarization polishing composition comprises 2% by weight or more of colloidal silica, benzotriazole, the planarizing agent comprises a secondary alcohol ethoxylate, potassium silicate, and nitric acid or potassium hydroxide, and the barrier chemical mechanical planarization polishing composition has a pH of 8 to 12.

13. 2. The barrier chemical mechanical planarization polishing composition of claim 1, wherein the barrier chemical mechanical planarization polishing composition comprises 2% by weight or more of colloidal silica, the planarization agent comprises a wetting agent selected from the group consisting of secondary alcohol ethoxylates, acetylenic diol surfactants, alcohol ethoxylate surfactants, and combinations thereof, nitric acid, or potassium hydroxide, and the barrier chemical mechanical planarization polishing composition has a pH of 8 to 12.

14. 1. A polishing method for chemical mechanical planarization of a semiconductor device including at least one surface having at least a barrier layer and a dielectric layer, comprising the steps of: a. dispensing the polishing composition of any one of claims 1-13 onto the at least one surface; b. polishing the at least one surface with the polishing composition by using a polishing pad; comprising wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof.

15. 1. A system for chemical mechanical planarization, comprising: a semiconductor device comprising at least one surface having at least a barrier layer and a dielectric layer; A polishing pad, and The polishing composition according to any one of claims 1 to 13. comprising wherein the barrier layer comprises a tantalum or titanium-containing film selected from the group consisting of tantalum, tantalum nitride, tantalum tungsten silicon carbide, titanium, titanium nitride, titanium-tungsten, titanium tungsten nitride, and combinations thereof, and a dielectric layer selected from the group consisting of an oxide film, a low-K material, and combinations thereof, and at least one surface contacts the polishing pad and the polishing composition. system.

Images