Pad-in-a-Bottle and Single-Platen Chemical Mechanical Planarization for Back-End Applications

Abstract

A single-platen chemical mechanical planarization (CMP) process using a novel pad-in-a-bottle (PIB) technology and PIB-type CMP slurries for back-end CMP applications is described, which replaces multiple (e.g., three) platen chemical mechanical planarization (CMP) processes for back-end CMP applications. A single platen with a single polishing pad is used for the entire back-end CMP process, including metal bulk, metal soft landing, and metal barrier CMP.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 278,049, filed November 10, 2021, which is incorporated by reference.

[0002] The present disclosure relates to a single platen CMP process having multiple polishing steps, such as for back-end applications. [Background technology]

[0003] The single platen CMP process uses a novel pad-in-a-bottle (PIB) technology and PIB-type advanced metal (such as Cu or Co) bulk, PIB-type metal (such as Cu or Co) soft landing, and PIB-type metal (such as Cu or Co) barrier chemical mechanical planarization (CMP) slurry, system, and method using a single platen for three polishing steps in back-end applications. A single selected polishing pad (hard or soft) on the platen completes all three steps of subsequent polishing.

[0004] Traditionally, in back-end CMP applications, metal bulk, metal soft landing, and metal barrier CMP slurries are used in three different polishing steps on three different platens on a CMP polishing tool for the entire polishing process, as shown in the top part of Figure 1. Typically, three different platens are used with at least two different types of polishing pads for the three CMP slurries.

[0005] Therefore, the traditional three-platen CMP process for the back-end CMP process has several weaknesses, such as: (a) three different platens are used in the CMP polisher, which makes the polishing tool large and complicated; (b) in the three-platen CMP process, at least two different types of polishing pads are required on each platen; and (c) the wafer transfer time between the three different platens reduces the device manufacturing efficiency.

[0006] The cost of ownership of expensive polyurethane polishing pads and the cost of electronic device manufacturing are also important concerns in the semiconductor industry's CMP process.

[0007] In CMP, the irregularities on the polyurethane (PU) pad are irreversibly deformed by wafer contact and also worn away by composition particles. Therefore, to ensure process stability, the pad surface needs to be continuously renewed with a diamond disk. Since the diamond disk needs to cut the pad surface to remove the old irregularities and create new ones, the pad also gradually becomes thinner, forcing its replacement.

[0008] The role of the pad asperities is fulfilled by high quality micron-sized polyurethane (PU) beads, the size of which is comparable to the size of the pores and asperities in commercial polishing pads. PIB type CMP slurries contain PU beads.

[0009] In the newly invented single platen CMP process (as shown in the bottom of FIG. 1) for back-end CMP application, a selected first PIB type Cu bulk CMP slurry is first used to remove the desired thickness of excess thickness of Cu capping layer film, after step 1, a selected second PIB type Cu soft landing CMP slurry is used in step 2 to remove the remaining Cu capping layer to stop on barrier and dielectric films to obtain low Cu line dishing, and in step 3, a selected third PIB type Cu barrier is used to remove barrier, dielectric and Cu films with the desired polishing selectivity among different films being polished to achieve Cu dishing and erosion compensation to obtain further low Cu dishing and erosion to improve electronic device manufacturing yield. Summary of the Invention

[0010] This need is met by using the single platen CMP process disclosed herein, where a single platen is used with a single selected polishing pad for all three different PIB type CMP slurries used in the back-end CMP process: PIB type Cu bulk, PIB type Cu soft landing, and PIB type Cu barrier CMP slurry.

[0011] The single platen CMP process of the present invention for back-end CMP applications reduces CMP processing time and increases throughput in semiconductor device manufacturing.

[0012] In one embodiment, a PIB type Cu bulk CMP polishing composition is provided in the first step of polishing in a single platen CMP process. The PIB type Cu bulk CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition is 3.0 to 12.0, 5.5 to 7.5, or 6.0 to 7.5.

[0013] In another embodiment, a PIB type Cu soft landing CMP polishing composition is provided in the second step of polishing in a single platen CMP process. The PIB type Cu soft landing CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; Cu dishing reduction additive; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition is 3.0 to 12.0, 5.5 to 7.5, or 6.0 to 7.5.

[0014] In a third aspect, a PIB-type Cu barrier CMP polishing composition is provided in a third step of polishing in a single platen CMP process. The PIB-type Cu barrier CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; a barrier or dielectric film removal rate enhancing additive; A liquid carrier such as water; Optionally, A Cu dishing reduction additive; A corrosion inhibitor; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition can be acidic or alkaline. For acidic pH, the pH is 2.0-6.5, and for alkaline pH PIB-type CMP polishing compositions, the pH range is 8-11.

[0015] In another aspect, a single platen CMP polishing method is provided, comprising: Providing a single platen having a single cost-effective polishing pad; providing a semiconductor patterned wafer having at least one film of copper, barrier, through silicon via (TSV), copper low-k, ultra low-k and / or other dielectric film; Providing a PIB type Cu bulk CMP polishing composition as described above; polishing a copper film to a controlled thickness, where at least a portion of the copper film is in contact with both the polishing pad and a PIB type Cu bulk CMP polishing composition; Providing a PIB type Cu soft landing CMP polishing composition as described above; polishing the copper film remaining from the last polish, stopping on the barrier film, where at least a portion of the copper film remaining from the last polish is in contact with both the polishing pad and the PIB type Cu soft landing CMP polishing composition; Providing a PIB type Cu barrier CMP polishing composition as described above; and polishing at least one film selected from the group consisting of barrier, through silicon via (TSV) copper films, low-k, ultra low-k and / or other dielectric films, wherein at least a portion of the at least one film is in contact with both the polishing pad and the PIB type Cu barrier CMP polishing composition.

[0016] In another aspect, a single platen CMP polishing system is provided. The single platen CMP polishing system includes: Providing a single platen having a single cost-effective polishing pad; Providing a semiconductor patterned wafer having at least copper, barrier, through silicon via (TSV), copper low-k, ultra low-k and / or other dielectric films; providing a PIB type Cu bulk CMP polishing composition as described above to polish a copper film to a controlled thickness, wherein at least a portion of the copper film is in contact with both the polishing pad and the PIB type Cu bulk CMP polishing composition; Providing a PIB type Cu soft landing CMP polishing composition as described above, polishing the copper film remaining from the last polishing, stopping on the barrier film, where at least a portion of the copper film remaining from the last polishing is in contact with both the polishing pad and the PIB type Cu soft landing CMP polishing composition; providing the above-mentioned PIB type Cu barrier CMP polishing composition to polish at least one film selected from the group consisting of barrier, through silicon via (TSV) copper film, low-k film, ultra low-k film and / or other dielectric film, wherein at least a portion of the at least one film is in contact with both the polishing pad and the PIB type Cu barrier CMP polishing composition.

[0017] Abrasive particles include, but are not limited to, 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; colloidal aluminum oxide, including α-, β-, and γ-type aluminum oxide; colloidal photoactive titanium dioxide, cerium oxide, colloidal cerium oxide, nano-sized inorganic metal oxide particles, such as alumina, titania, zirconia, ceria, and the like; nano-sized diamond particles, nano-sized silicon nitride particles; monomodal, bimodal, and multimodal colloidal abrasive particles; organic polymer-based soft abrasives, surface coated or modified abrasives, or other composite particles, and mixtures thereof.

[0018] Silicone-containing dispersants include, but are not limited to, silicone polyethers that contain both a water-insoluble silicone backbone and several water-soluble polyether pendant groups; such as repeat units of ethylene oxide (EO) and propylene oxide (PO) (EO-PO) functional groups that provide surface wetting.

[0019] Corrosion inhibitors include, but are not limited to, the family of heteroaromatic compounds containing a nitrogen atom in the aromatic ring, such as 1,2,4-triazole, amitrole (3-amino-1,2,4-triazole), benzotriazole and its derivatives, tetrazole and its derivatives, imidazole and its derivatives, benzimidazole and its derivatives, pyrazole and its derivatives, and tetrazole and its derivatives.

[0020] Chelating agents (or chelating agents) include, but are not limited to, amino acids, amino acid derivatives, and organic amines.

[0021] Amino acids and amino acid derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, beta-alanine, valine, leucine, isoleucine, phenylamines, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0022] Organic amines include, but are not limited to, 2,2-dimethyl-1,3-propanediamine and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and the like.

[0023] An organic diamine compound having two primary amine moieties can be described as a binary chelating agent.

[0024] Biocides include, but are not limited to, Kathon™, Kathon™ CG / ICP II, manufactured by Dow Chemical, which have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.

[0025] The Cu dishing reducing agent may include, but is not limited to, non-ionic organic surfactants such as acetylene ethoxylate type surfactants Dynol607 (trademark), Dynol604 (trademark), or polyglycol ether structure Tergitol (trademark) type non-ionic surfactants such as Tergitol (trademark) Min Form 1x, Tergitol (trademark) L-62, Tergitol (trademark) L-64, or anionic surfactants such as organic alkyl sulfonates, organic alkyl phosphates, or organic carboxylates. Examples of anionic surfactants include dodecyl sulfonate ammonium or potassium salt, octyl phosphate ammonium or potassium salt, and octyl carboxylate ammonium or potassium salt.

[0026] Barrier or dielectric film removal rate enhancing additives include, but are not limited to, various salts of silicates such as ammonium silicate, sodium silicate, potassium silicate or tetraalkyl silicates.

[0027] Oxidizing agents include, but are not limited to, periodic acid, hydrogen peroxide, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, and mixtures thereof.

[0028] Organic quaternary ammonium salts as Cu removal rate enhancers and defect reducers include, but are not limited to, choline salts with different counter ions, such as choline bicarbonate, choline hydroxide, choline dihydrogen citrate salt, choline ethanolamine, choline bitartrate, etc.

[0029] pH adjusters include, but are not limited to, the following: nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof. pH adjusters also include basic pH adjusters such as sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and other chemical reagents that can be used to adjust the pH to a more alkaline direction. [Brief description of the drawings]

[0030] [Figure 1] A conventional three-platen CMP process is compared to the single-platen CMP process of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0031] The present disclosure teaches single platen CMP polishing with a single same polishing pad using PIB type metal bulk, PIB type metal soft landing, and PIB type metal barrier CMP slurries for back-end CMP applications such as a 3-step Cu CMP process.

[0032] This application discloses a new technology in which the role of pad irregularities is fulfilled by high quality micron-sized polyurethane (PU) beads, the size of which is comparable to the size of pores and irregularities in commercial polishing pads.

[0033] The beads are suspended in a Cu CMP polishing composition having abrasive particles such as calcined ceria, colloidal silica, or composite particles with the aid of a wetting agent (or surfactant) as a dispersant to disperse the polyurethane beads in the aqueous composition.

[0034] The beads contact the wafer surface by means described below and facilitate polishing in much the same way as conventional asperities.

[0035] By selecting both the size of the beads and their concentration in the composition, much better control of the height, curvature, and area density of the "peaks" that contact the wafer is achieved, significantly reducing the process variability associated with traditional asperity contacts.

[0036] The use of beads still requires a second surface, or counter surface, on which polishing occurs, which in the present case continues to be a traditional polyurethane-based pad, but which requires minimal conditioning since it is not the primary surface on which polishing occurs. Alternatively, an inexpensive, partially conditioned pad can be used as the counter surface.

[0037] Polishers typically use three platens with two to three pads and three different CMP polishing compositions for back-end CMP applications. In this disclosure, a single platen process using the same polishing pad and three different CMP slurries is used to replace a three-platen CMP process for back-end CMP applications. The single platen process provides significant cost savings in the semiconductor device manufacturing process and increases throughput in semiconductor device manufacturing efficiency.

[0038] It can take several hours to remove a used pad and install and qualify a new one, so tool down time and engineering and product loss due to consumables used to qualify the new pad are also significant. Using a single-platen process with the same polishing pad, the changeover time for such a pad can be significantly reduced compared to a three-platen process using two to three different polishing pads.

[0039] For polishing pads, only about two-thirds of the pad thickness is used before the pad needs to be peeled off and discarded. For conditioners, only a few hundred of the tens of thousands of diamonds control the product life, after which the conditioner needs to be discarded. Furthermore, the pad and conditioner do not have regeneration or reuse options available. The inventors' research addresses the above EHS issues and provides a novel solution to the current standard CMP process by eliminating the use of multiple pads and diamond disk conditioners.

[0040] The polyurethane beads used in the three different types of CMP polishing compositions disclosed for single platen back-end CMP applications have sizes ranging from 2 to 100 μm, 10 to 80 μm, 20 to 70 μm, or 30 to 50 μm.

[0041] Some specific aspects of the invention are outlined below.

[0042] In one embodiment, a PIB type Cu bulk CMP polishing composition is provided in the first step of polishing in a single platen CMP process. The PIB type Cu bulk CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition is 3.0 to 12.0, 5.5 to 7.5, or 6.0 to 7.5.

[0043] In another embodiment, a PIB type Cu soft landing CMP polishing composition is provided in the second step of polishing in a single platen CMP process. The PIB type Cu soft landing CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A Cu dishing reduction additive; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition is 3.0 to 12.0, 5.5 to 7.5, or 6.0 to 7.5.

[0044] In a third aspect, a PIB-type Cu barrier CMP polishing composition is provided in a third step of polishing in a single platen CMP process. The PIB-type Cu barrier CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; a barrier or dielectric film removal rate enhancing additive; A liquid carrier such as water; Optionally, A Cu dishing reduction additive; A corrosion inhibitor; A pH adjuster, an oxidizing agent added at the time of use; The pH of the composition can be acidic or alkaline. For acidic pH, the pH is 2.0-6.5, and for alkaline pH PIB-type CMP polishing compositions, the pH range is 8-11.

[0045] In another aspect, a single platen CMP polishing method is provided, comprising: Providing a single platen having a single cost-effective polishing pad; providing a semiconductor patterned wafer having at least one film selected from the group consisting of copper, barrier, through silicon via (TSV), copper low-k, ultra low-k and / or other dielectric films; Providing a PIB type Cu bulk CMP polishing composition as described above; polishing a copper film to a controlled thickness, where at least a portion of the copper film is in contact with both the polishing pad and a PIB type Cu bulk CMP polishing composition; Providing a PIB type Cu soft landing CMP polishing composition as described above; polishing the copper film remaining from the last polish, stopping on the barrier film, where at least a portion of the copper film remaining from the last polish is in contact with both the polishing pad and the PIB type Cu soft landing CMP polishing composition; Providing a PIB type Cu barrier CMP polishing composition as described above; and polishing at least one film selected from the group consisting of barrier, through silicon via (TSV) copper films, low-k, ultra low-k and / or other dielectric films, wherein at least a portion of the at least one film is in contact with both the polishing pad and the PIB type Cu barrier CMP polishing composition.

[0046] In yet another aspect, a CMP polishing system is provided. The single platen CMP polishing system includes: Providing a single platen having a single cost-effective polishing pad; Providing a semiconductor patterned wafer having at least copper, barrier, through silicon via (TSV), copper low-k, ultra low-k and / or other dielectric films; providing a PIB type Cu bulk CMP polishing composition as described above to polish a copper film to a controlled thickness, wherein at least a portion of the copper film is in contact with both the polishing pad and the PIB type Cu bulk CMP polishing composition; Providing a PIB type Cu soft landing CMP polishing composition as described above, polishing the copper film remaining from the last polishing, stopping on the barrier film, where at least a portion of the copper film remaining from the last polishing is in contact with both the polishing pad and the PIB type Cu soft landing CMP polishing composition; providing the above-mentioned PIB type Cu barrier CMP polishing composition to polish at least one film selected from the group consisting of barrier, through silicon via (TSV) copper film, low-k film, ultra low-k film and / or other dielectric film, wherein at least a portion of the at least one film is in contact with both the polishing pad and the PIB type Cu barrier CMP polishing composition.

[0047] The abrasive particles are nano-sized particles and include, but are not limited to, 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; colloidal aluminum oxide, including α-, β-, and γ-type aluminum oxide; colloidal photoactive titanium dioxide, cerium oxide, colloidal cerium oxide, nano-sized inorganic metal oxide particles such as alumina, titania, zirconia, ceria, and the like; nano-sized diamond particles, nano-sized silicon nitride particles; monomodal, bimodal, and multimodal colloidal abrasive particles; organic polymer-based soft abrasives, surface coated or modified abrasives, or other composite particles, and mixtures thereof.

[0048] Colloidal silica can be made from silicates, and high purity colloidal silica can be made from TEOS or TMOS. Colloidal silica or high purity colloidal silica can have a narrow or wide particle size distribution with monomodal or multimodal, various sizes and various shapes such as spherical, cocoon, aggregate, and other shapes.

[0049] The nano-sized particles can also have different shapes, such as spherical, cocoon-shaped, aggregate-shaped, and the like.

[0050] The particle size of the abrasive used in the Cu CMP slurry is in the range of 5 nm to 500 nm, 10 nm to 250 nm, or 25 nm to 100 nm.

[0051] The Cu CMP polishing composition includes 0.0025 wt % to 25 wt %, 0.0025 wt % to 2.5 wt %, 0.005 wt % to 0.5 wt % of an abrasive.

[0052] The CMP polishing composition includes a silicone-containing dispersant for dispersing polyurethane beads in an aqueous solution, the silicone-containing dispersant also functioning as a surface wetting agent dispersant.

[0053] Silicone-containing dispersants include, but are not limited to, silicone polyethers that contain both a water-insoluble silicone backbone and several water-soluble polyether pendant groups; for example, repeat units of EO-PO functional groups that provide surface wetting properties.

[0054] Examples of silicone-containing dispersants include silsurf® E608, silsurf® J208-6, silsurf® A208, silsurf® CR1115, silsurf® A204, silsurf® A004-UP, silsurf® A008-UP, silsurf® B608, silsurf® C208, silsurf® C410, silsurf® D208, silsurf® D208, silsurf® D208-30, silsurf® Di-1010, silsurf® D208-20, silsurf® D208-10, silsurf® D208-20, silsurf® D208-30, silsurf® Di-10 ... rf® Di-1510, silsurf® Di-15-I, silsurf® Di-2012, silsurf® Di-5018-F, silsurf® G8-I, silsurf® J1015-O, silsurf® J1015-O-AC, silsurf® J208, silsurf® J208-6, siltech® OP-8, siltech® OP-11, siltech® OP-12, siltech® OP-15, siltech® OP-20; products from Siltech; 225 Wicksteed Avenue, Toronto Ontario, Canada M4H 1G5.

[0055] The concentration range of the silicone-containing dispersant is 0.01% to 2.0% by weight, 0.025% to 1.0% by weight, or 0.05% to 0.5% by weight.

[0056] The CMP slurry contains polyurethane beads of various sizes.

[0057] The concentration range of the polyurethane beads is 0.01% to 2.0% by weight, 0.025% to 1.0% by weight, or 0.05% to 0.5% by weight.

[0058] Organic quaternary ammonium salts as Cu removal rate enhancing and defect reducing agents include, but are not limited to, choline salts, such as choline bicarbonate, or any other salt formed between choline and other anionic counterions.

[0059] The CMP slurry contains 0.005% to 0.5% by weight, 0.001% to 0.25% by weight, or 0.002% to 0.1% by weight of a quaternary ammonium salt.

[0060] The CMP slurry contains 0.1 wt % to 18 wt %, 0.5 wt % to 15 wt %, or 1.0 wt % to 10.0 wt % of at least one chelating agent, dual chelating agent, or tri-chelating agent.

[0061] Chelating agents (or chelating agents) include, but are not limited to, amino acids, amino acid derivatives, and organic amines.

[0062] Amino acids and amino acid derivatives include, but are not limited to, glycine, D-alanine, L-alanine, DL-alanine, beta-alanine, valine, leucine, isoleucine, phenylamines, proline, serine, threonine, tyrosine, glutamine, asparagine, glutamic acid, aspartic acid, tryptophan, histidine, arginine, lysine, methionine, cysteine, iminodiacetic acid, and combinations thereof.

[0063] Organic amines include, but are not limited to, 2,2-dimethyl-1,3-propanediamine and 2,2-dimethyl-1,4-butanediamine, ethylenediamine, 1,3-diaminepropane, 1,4-diaminebutane, and the like.

[0064] An organic diamine compound having two primary amine moieties can be described as a binary chelating agent.

[0065] The corrosion inhibitor may be any known reported corrosion inhibitor.

[0066] Corrosion inhibitors include, but are not limited to, the family of heteroaromatic compounds containing a nitrogen atom in the aromatic ring, such as, for example, 1,2,4-triazole, amitrole (3-amino-1,2,4-triazole), benzotriazole and its derivatives, tetrazole and its derivatives, imidazole and its derivatives, benzimidazole and its derivatives, pyrazole and its derivatives, and tetrazole and its derivatives.

[0067] The CMP slurry contains 0.005% to 1.0% by weight, 0.01% to 0.5% by weight, or 0.025% to 0.25% by weight of a corrosion inhibitor.

[0068] A biocide having an active ingredient to provide a more stable shelf life for the Cu chemical mechanical polishing composition can be used.

[0069] Biocides include, but are not limited to, Kathon™, Kathon™ CG / ICP II, manufactured by Dow Chemical, which have active ingredients of 5-chloro-2-methyl-4-isothiazolin-3-one and / or 2-methyl-4-isothiazolin-3-one.

[0070] The CMP slurry contains 0.0001% to 0.05%, 0.0001% to 0.025%, or 0.0001% to 0.01% by weight of a biocide.

[0071] Acidic or basic compounds or pH adjusters can be used to make it possible to adjust the pH of the CMP polishing composition to an optimized pH value.

[0072] pH adjusters include, but are not limited to, the following: nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof. pH adjusters also include basic pH adjusters such as sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide, organic amines, and other chemical reagents that can be used to adjust the pH to a more alkaline direction.

[0073] The CMP slurry contains 0 to 1% by weight, 0.01 to 0.5% by weight, or 0.1 to 0.25% by weight of a pH adjuster.

[0074] The Cu dishing reducing agent may include, but is not limited to, non-ionic organic surfactants such as acetylene ethoxylate type surfactants Dynol607 (trademark), Dynol604 (trademark), or polyglycol ether structure Tergitol (trademark) type non-ionic surfactants such as Tergitol (trademark) Min Form 1x, Tergitol (trademark) L-62, Tergitol (trademark) L-64, or anionic surfactants such as organic alkyl sulfonates, organic alkyl phosphates, or organic carboxylates. Examples of anionic surfactants include dodecyl sulfonate ammonium or potassium salt, octyl phosphate ammonium or potassium salt, and octyl carboxylate ammonium or potassium salt.

[0075] The concentration of the Cu dishing reducing additive is in the range of 0.0005% by weight to 0.25% by weight, preferably 0.001% by weight to 0.125% by weight, and more preferably 0.025% by weight to 0.10% by weight.

[0076] Barrier or dielectric film removal rate enhancing additives include, but are not limited to, various salts of silicates such as ammonium silicate, sodium silicate, potassium silicate or tetraalkyl silicates.

[0077] The CMP slurry contains 0% to 2%, 0.1% to 1.5%, or 0.25% to 1% by weight of a barrier or dielectric film removal rate enhancing additive.

[0078] The pH of the PIB type Cu bulk and Cu soft landing polishing compositions is about 3.0 to about 12.0, with a preferred pH range of 5.5 to 7.5, and a most preferred pH range of 6.0 to 7.5.

[0079] The pH of the PIB-type Cu barrier CMP polishing composition may be acidic or alkaline. For acidic pH, the pH is 2.0-6.5, and for alkaline pH PIB-type CMP polishing composition, the pH range is 8-11. Experimental Section Parameters: Å: Angstrom - unit of length BP: Back pressure, in psi CMP: chemical mechanical planarization = chemical mechanical polishing CS: Carrier Speed DF: Downforce: pressure applied during CMP, unit: psi min:minutes ml: milliliter mV: millivolt psi: pounds per square inch PS: Platen rotation speed of the polishing tool, unit: rpm (revolutions per minute) SF: flow rate of polishing composition, ml / min Removal rate (RR): Cu RR 0.5psi Copper removal rate measured at 0.5 psi down pressure on the CMP tool Cu RR 1.0psi Copper removal rate measured at 1.0psi down pressure on the CMP tool Cu RR 2.0psi Copper removal rate measured at 2.0psi down pressure on CMP tool Cu RR 2.5psi Copper removal rate measured at 2.5 psi down pressure on a CMP tool TEOS RR 0.5psi TEOS removal rate measured at 0.5psi down pressure on the CMP tool TEOS RR 1.0psi TEOS removal rate measured at 1.0psi down pressure on the CMP tool TEOS RR 2.0psi TEOS removal rate measured at 2.0psi down pressure on a CMP tool TaN RR 0.5psi TaN removal rate measured at 0.5psi down pressure on CMP tool TaN RR 1.0psi TaN removal rate measured at 1.0psi down pressure on CMP tool TaN RR 2.0psi TaN removal rate measured at 2.0psi down pressure on CMP tool BD RR 0.5psi BD removal rate measured at 0.5 psi down pressure on the CMP tool BD RR 1.0psi BD removal rate measured at 1.0psi down pressure on the CMP tool BD RR 2.0psi BD removal rate measured at 2.0psi down pressure on the CMP tool TiN RR 1.0psi TiN removal rate measured at 1.0psi down pressure on CMP tool TiN RR 2.0psi TiN removal rate measured at 2.0psi down pressure on CMP tool

[0080] General Experimental Procedures Unless otherwise indicated, all percentages in compositions are percentages by weight.

[0081] In the examples presented below, CMP experiments were performed using the procedures and experimental conditions shown below. The CMP tool used in the examples was a 300 mm APD-800® polisher manufactured by Fujikoshi Machinery Corporation (Nagano Japan). Pad break-in was performed by polishing 25 dummy oxide (deposited by plasma-enhanced CVD from a TEOS precursor, PETEOS) wafers. To qualify the tool settings and pad break-in, two PETEOS monitors were polished at baseline conditions with Syton® OX-K colloidal silica provided by a planarization platform from Versum Materials, Inc. The polishing experiments were performed using blanket Cu, TEOS, TaN, TiN and BD wafers. These blanket wafers were purchased from Silicon Valley Microelectronics, 1150 Campbell Ave, CA, 95126. The polishing pads, hard polishing pads, IC1010, were supplied by DuPont, USA. The soft Fujibo pads were supplied by Fujibo Corporation, Japan. The hard polishing pads are made of a hard microporous polyurethane material. The hard polishing pads may be IC1010 with a compressibility of about 0.5%-4.0% and a hardness (Shore D) of about 52-62. Both hard and soft polishing pads were used on a single platen in the Cu bulk, Cu soft landing and barrier blanket wafer experiments, respectively. EXAMPLES

[0082] Example 1 - Use of Rigid IC1010 Pad in Single Platen Process For single platen processing, the PIB Cu bulk CMP polishing composition consisted of 5.20 wt% glycine, 2.40 wt% alanine, 0.016 wt% amitrole, 0.0231 wt% choline bicarbonate, 0.0016 wt% Neolone M10 biocide, 0.2705 wt% high purity colloidal silica particles as abrasive, 0.050 wt% Silsurf E608 as dispersant, and 0.10 wt% 35 micron sized polyurethane beads.

[0083] Silsurf E608, which contains EO-PO wetting functionality, was used as the silicone-containing dispersant.

[0084] For single platen processing, the PIB Cu soft landing CMP polishing composition consisted of EMD Electronics Cu soft landing slurry, Cu3086, with the addition of 0.050 wt. % Silsurf E608 and 0.10 wt. % 35 micron sized polyurethane beads as dispersants.

[0085] For single platen processing, the PIB barrier CMP polishing composition consisted of EMD Electronics, BAR6610R slurry with the addition of 0.050 wt. % Silsurf E608 as a dispersant and 0.25 wt. % 35 micron sized polyurethane beads.

[0086] 2.5% by weight H 2 O 2 was added to a PIB Cu bulk CMP composition at the point of use for polishing tests on a single platen.

[0087] 1.0% by weight H 2 O 2 was added to a PIB Cu soft landing CMP composition at the point of use for polishing tests on a single platen.

[0088] 1.0% by weight H 2 O 2was added to the PIB BAR6610R barrier CMP composition at the point of use for polishing tests on a single platen.

[0089] The polishing tests were performed with a hard IC1010 pad in a single platen process at different applied down forces and sliding speeds.

[0090] Polishing results using a hard IC1010 polishing pad in a single platen process are shown in Tables 1-3. [Table 1]

[0091] The highest Cu removal rate is achieved with the Cu PIB bulk CMP slurry at 2.5 psi down force and 1.5 m / s sliding speed on a single platen process using a hard IC1010 pad, as the polishing results are listed in Table 1. The PIB type Cu bulk slurry in a single platen process provides Cu:TEOS polishing selectivity of over 4500:1 and Cu:TaN polishing selectivity of over 1200:1 at 2.0 psi down force and 1.5 m / s sliding speed.

[0092] After completing the PIB type Cu bulk slurry CMP polishing process on the single platen, the Cu soft landing CMP slurry is subsequently used for the step 2 CMP process in the single platen process. The results are listed in Table 2. [Table 2]

[0093] As the polishing results are listed in Table 2, the highest Cu removal rate is achieved with the Cu PIB bulk CMP slurry on the single platen process at a down force of 1.0 psi and a sliding speed of 1.0 m / sec. The PIB type Cu soft landing slurry in the single platen process provides high Cu:TEOS polishing selectivity, high Cu:BD polishing selectivity, and good Cu:TaN polishing selectivity. The PIB type Cu soft landing CMP slurry used in the single platen process provides almost completely stopped CMP polishing performance for polishing dielectric films, TEOS and BD while using a hard IC1010 polishing pad.

[0094] After completing the PIB type Cu soft landing slurry CMP polishing process on the single platen, the PIB type barrier CMP slurry is subsequently used for the CMP process of step 3 in the single platen process. The results are listed in Table 3. [Table 3]

[0095] Higher TiN removal rates are achieved at four different combinations of applied down force and sliding speed, as the polishing results are listed in Table 3. The PIB barrier slurry also provides full stop CMP polishing performance in polishing Cu and BD films at different combinations of applied down force and sliding speed with a hard IC1010 polishing pad in a single platen process. The PIB type barrier CMP slurry in a single platen process provides reasonable TEOS and TaN removal rates while using a hard IC1010 polishing pad.

[0096] Example 2 - Use of soft Fujibo pads in a single platen process For single platen processing, the PIB Cu bulk CMP polishing composition consisted of 5.20 wt% glycine, 2.40 wt% alanine, 0.016 wt% amitrole, 0.0231 wt% choline bicarbonate, 0.0016 wt% Neolone M10 biocide, 0.2705 wt% high purity colloidal silica particles as abrasive, 0.050 wt% Silsurf E608 as dispersant, and 0.10 wt% 35 micron sized polyurethane beads.

[0097] Silsurf E608, which contains EO-PO wetting functionality, was used as the silicone-containing dispersant.

[0098] For single platen processing, the PIB Cu soft landing CMP polishing composition consisted of EMD Electronics Cu soft landing slurry, Cu3086, with the addition of 0.050 wt. % Silsurf E608 and 0.10 wt. % 35 micron sized polyurethane beads as dispersants.

[0099] For single platen processing, the PIB barrier CMP polishing composition consisted of EMD Electronics, BAR6610R slurry with the addition of 0.050 wt. % Silsurf E608 as a dispersant and 0.25 wt. % 35 micron sized polyurethane beads.

[0100] 2.5% by weight H 2 O 2 was added to a PIB Cu bulk CMP composition at the point of use for polishing tests on a single platen.

[0101] 1.0% by weight H 2 O 2 was added to a PIB Cu soft landing CMP composition at the point of use for polishing tests on a single platen.

[0102] 1.0% by weight H 2 O 2was added to the PIB BAR6610R barrier CMP composition at the point of use for polishing tests on a single platen.

[0103] The polishing tests were performed with a soft Fujibo pad in a single platen process at different applied down forces and sliding speeds.

[0104] Tables 4 to 6 show the polishing results using a soft Fujibo polishing pad in a single platen process. [Table 4]

[0105] As the polishing results are listed in Table 4, the highest Cu removal rate is achieved with the Cu PIB bulk CMP slurry on the single platen process using the soft Fujibo pad at a down force of 2.5 psi and a sliding speed of 1.5 m / s. The Cu removal rate obtained using the soft Fujibo pad is even higher than that obtained using the hard IC1010 pad at the same down force and sliding speed. The PIB type Cu bulk slurry in the single platen process provides a very high Cu:TEOS polishing selectivity of over 7900:1 and a Cu:TaN polishing selectivity of about 1450:1 at a down force of 2.0 psi and a sliding speed of 1.5 m / s using the soft Fujibo pad. Thus, when the same PIB type Cu bulk slurry is used with the same applied down force and sliding speed, the soft Fujibo pad provides higher Cu:TEOS and Cu:TaN selectivity than that obtained with the hard IC1010 pad.

[0106] After completing the single platen PIB type Cu bulk slurry CMP polishing process, the Cu soft landing CMP slurry is subsequently used for step 2 CMP process in a single platen process using a soft Fujibo pad. The results are listed in Table 5. [Table 5]

[0107] As the polishing results are listed in Table 5, the highest Cu removal rate is achieved with the Cu PIB bulk CMP slurry at 1.0 psi down force and 1.0 m / sec sliding speed in a single platen process using a soft Fujibo pad. The PIB type Cu soft landing slurry in a single platen process provides very high Cu:TEOS polishing selectivity, very high Cu:BD polishing selectivity, and very high Cu:TaN polishing selectivity. The PIB type Cu soft landing CMP slurry used in a single platen process provides full stop CMP polishing performance for polishing dielectric films, TEOS and BD while using a soft Fujibo polishing pad.

[0108] After completing the PIB type Cu soft landing slurry CMP polishing process on a single platen using a soft Fujibo pad, the PIB type barrier CMP slurry is subsequently used for step 3 CMP process in a single platen process. The results are listed in Table 6. [Table 6]

[0109] Higher TiN removal rates are achieved at four different combinations of applied down force and sliding speed, as the polishing results are listed in Table 5. The PIB barrier slurry also provides desirable Cu removal rates, good TEOS, TaN and BD film removal rates.

[0110] The polishing results in Tables 1 to 6 listed above were obtained using either the hard IC1010 pad or the soft Fujibo pad under different applied down force and sliding speed conditions, and these different CMP polishing compositions, PIB Cu bulk, PIB Cu soft landing, and PIB barrier slurries, can be successfully used in a single platen CMP process for back-end CMP applications.

[0111] The embodiments of the invention listed above are illustrative of the numerous embodiments that may be made from the present invention. It is contemplated that numerous other configurations of the process may be used and that the materials used in the process may be selected from numerous materials other than those specifically disclosed.

Claims

1. 1. A single platen chemical mechanical planarization (CMP) polishing method for back-end copper processes, comprising: Providing a single platen having a single polishing pad; providing a semiconductor patterned wafer having at least one film comprising a copper film, a barrier film, a through silicon via (TSV) copper film, a low-k film, an ultra low-k film, and / or another dielectric film; Providing a PIB type Cu bulk CMP polishing composition; polishing the copper film to a controlled thickness, wherein at least a portion of the copper film is in contact with both the single polishing pad and the PIB-type Cu bulk CMP polishing composition; Providing a PIB type Cu soft landing CMP polishing composition; polishing the copper film remaining from the last polish and stopping polishing on the barrier film, wherein at least a portion of the copper film remaining from the last polish is in contact with both the single polishing pad and the PIB-type Cu soft landing CMP polishing composition; Providing a PIB type Cu barrier CMP polishing composition; A single platen chemical mechanical planarization (CMP) polishing method comprising polishing at least one film selected from the group consisting of barrier films, through silicon via (TSV) copper films, low-k films, ultra low-k films, and / or other dielectric films, wherein at least a portion of the at least one film is in contact with both the single polishing pad and the PIB-type Cu barrier CMP polishing composition.

2. The PIB type Cu bulk CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster; and an oxidizing agent added at the time of use; 10. The single platen chemical mechanical planarization (CMP) polishing method of claim 1, wherein the pH of the composition is from 3.0 to 12.0, from 5.5 to 7.5, or from 6.0 to 7.

5.

3. 10. The single platen chemical mechanical planarization (CMP) polishing method of claim 1, wherein the single polishing pad comprises a microporous polyurethane material.

4. The PIB type Cu soft landing CMP polishing composition is An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A Cu dishing reducing additive; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster; and an oxidizing agent added at the time of use; 10. The single platen chemical mechanical planarization (CMP) polishing method of claim 1, wherein the pH of the composition is from 3.0 to 12.0, from 5.5 to 7.5, or from 6.0 to 7.

5.

5. The PIB type Cu barrier CMP polishing composition is An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; a barrier or dielectric film removal rate enhancing additive; A liquid carrier such as water; Optionally, A Cu dishing reducing additive; A corrosion inhibitor; A pH adjuster; and an oxidizing agent added at the time of use; 2. The single platen chemical mechanical planarization (CMP) polishing method of claim 1, wherein the pH of the composition is between 2.0 and 6.5 for an acidic pH and between 8 and 11 for an alkaline pH.

6. 2. The single platen chemical mechanical planarization (CMP) polishing method of claim 1, wherein the micron-sized polyurethane (PU) beads have a size in the range of 30 to 50 μm.

7. 1. A single platen chemical mechanical planarization (CMP) polishing system for back-end copper processing, comprising: Providing a single platen with a single cost-effective polishing pad; providing a semiconductor patterned wafer having at least one film comprising a copper film, a barrier film, a through silicon via (TSV) copper film, a low-k film, an ultra low-k film, and / or another dielectric film; providing a PIB type Cu bulk CMP polishing composition to polish the copper film to a controlled thickness, wherein at least a portion of the copper film is in contact with both the polishing pad and the PIB type Cu bulk CMP polishing composition; providing a PIB type Cu soft landing CMP polishing composition to polish the copper film remaining from the last polish and stopping polishing on the barrier film, wherein at least a portion of the copper film remaining from the last polish is in contact with both the polishing pad and the PIB type Cu soft landing CMP polishing composition; 1. A single platen chemical mechanical planarization (CMP) polishing system comprising: providing a PIB-type Cu barrier CMP polishing composition to polish at least one film selected from the group consisting of a barrier film, a through silicon via (TSV) copper film, a low-k film, an ultra low-k film, and / or other dielectric film, wherein at least a portion of the at least one film is in contact with both the polishing pad and the PIB-type Cu barrier CMP polishing composition.

8. The PIB type Cu bulk CMP polishing composition comprises: An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster; and an oxidizing agent added at the time of use; 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the pH of the composition is from 3.0 to 12.0, from 5.5 to 7.5, or from 6.0 to 7.

5.

9. 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the single polishing pad comprises a microporous polyurethane material.

10. The PIB type Cu soft landing CMP polishing composition is An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; A Cu dishing reducing additive; A liquid carrier such as water; Optionally, a chelating agent, a dual chelating agent, or a tri-chelating agent; A corrosion inhibitor; an organic quaternary ammonium salt; A biocide; A pH adjuster; and an oxidizing agent added at the time of use; 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the pH of the composition is from 3.0 to 12.0, from 5.5 to 7.5, or from 6.0 to 7.

5.

11. The PIB type Cu barrier CMP polishing composition is An abrasive; micron-sized polyurethane (PU) beads having a size in the range of 2-100 μm, 10-80 μm, 20-70 μm, or 30-50 μm; a silicone-containing dispersant; a barrier or dielectric film removal rate enhancing additive; A liquid carrier such as water; Optionally, A Cu dishing reducing additive; A corrosion inhibitor; A pH adjuster; and an oxidizing agent added at the time of use; 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the pH of the composition is between 2.0 and 6.5 for an acidic pH and between 8 and 11 for an alkaline pH.

12. 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the single polishing pad comprises a microporous polyurethane material.

13. 8. The single platen chemical mechanical planarization (CMP) polishing system of claim 7, wherein the micron-sized polyurethane (PU) beads have a size in the range of 30 to 50 μm.

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