WO2016069576A1 - Non-amine post-cmp compositions and method of use - Google Patents

Non-amine post-cmp compositions and method of use Download PDF

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WO2016069576A1
WO2016069576A1 PCT/US2015/057535 US2015057535W WO2016069576A1 WO 2016069576 A1 WO2016069576 A1 WO 2016069576A1 US 2015057535 W US2015057535 W US 2015057535W WO 2016069576 A1 WO2016069576 A1 WO 2016069576A1
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acid
hydroxide
ammonium
composition
ether
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PCT/US2015/057535
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French (fr)
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Jun Liu
Donald FRYE
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Entegris, Inc.
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • H01L21/02068Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02074Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0005Special cleaning and washing methods
    • C11D11/0011Special cleaning and washing methods characterised by the objects to be cleaned
    • C11D11/0023"Hard" surfaces
    • C11D11/0047Electronic devices, e.g. PCBs, semiconductors
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02Inorganic compounds
    • C11D7/04Water-soluble compounds
    • C11D7/06Hydroxides
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/261Alcohols; Phenols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/264Aldehydes; Ketones; Acetals; Ketals
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/265Carboxylic acids; Salts thereof
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3245Aminoacids
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/32Organic compounds containing nitrogen
    • C11D7/3281Heterocyclic compounds
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    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/34Organic compounds containing sulfur
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    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/36Organic compounds containing phosphorus

Abstract

A high pH composition and process for protecting cobalt-containing material layers and/or cleaning post-chemical mechanical polishing (CMP) residue and contaminants from a microelectronic device having said residue and contaminants thereon. The compositions achieve highly efficacious protection of cobalt-containing material layers and cleaning of the post-CMP residue and contaminant material from the surface of the microelectronic device without compromising the low-k dielectric material, copper interconnect material, or cobalt-containing materials.

Description

NON-AMINE POST-CMP COMPOSITIONS AND METHOD OF USE

FIELD OF THE INVENTION

[0001] The present invention relates to amine-free compositions for substantially and efficiently cleaning residue and/or contaminants from microelectronic devices having same thereon. The present invention further relates to protecting cobalt-containing material layers.

DESCRIPTION OF THE RELATED ART

[0002] It is well known that integrated circuit (IC) manufacturers have replaced aluminum and aluminum alloys with copper for advanced microelectronic applications because copper has a higher conductivity that translates to significant improvement in the interconnect performance. In addition, copper-based interconnects offer better electromigration resistance than aluminum, thereby improving the interconnect reliability. That said, the implementation of copper faces certain challenges. For example, the adhesion of copper (Cu) to silicon dioxide (S1O2) and to other dielectric materials is generally poor. Poor adhesion results in the delamination of Cu from adjoining films during the manufacturing process. Also, Cu ions readily diffuse into S1O2 under electrical bias, and increase the dielectric electrical leakage between Cu lines even at very low Cu concentrations within the dielectric. In addition, if copper diffuses into the underlying silicon where the active devices are located, device performance can be degraded.

[0003] The problem of the high diffusivity of copper in silicon dioxide (S1O2), and in other inter- metal dielectrics (IMDs)/interlevel dielectrics (ILDs), remains of great concern. To deal with this issue, an integrated circuit substrate must be coated with a suitable barrier layer that encapsulates copper and blocks diffusion of copper atoms. The barrier layer, comprising both conductive and non- conductive materials, is typically formed over a patterned dielectric layer and prior to deposition of copper. Typical materials for the barrier layer include tantalum (Ta), tantalum nitride (TaNx), tungsten (W), titanium (Ti), titanium nitride (TiN), ruthenium (Ru), cobalt (Co), molybdenum (Mo), rhenium (Rh), and alloys thereof.

[0004] In the manufacturing of deep submicron semiconductors, the copper damascene process is used to form conductive copper lines and vias in the low-k dielectric layer. One important step of the damascene process is copper chemical mechanical polishing (CMP) for the removal of excess copper above the dielectric layer surface. The CMP process involves holding and rotating a thin, flat substrate of the semiconductor device against a wetted polishing pad under controlled pressure and temperature in the presence of CMP slurries. The slurries contain abrasive materials and chemical additives as appropriate to the specific CMP process and requirements. Following the CMP process, contaminants consisting of particles from the polishing slurry, chemicals added to the slurry, and reaction by-products of the polishing slurry are left behind on the wafer surface. All contaminants must be removed prior to any further steps in the microelectronic device fabrication process to avoid degradation of device reliability and introduction of defects into the device. Often, particles of these contaminants are smaller than 0.3 μιη.

[0005] One particular issue in this respect is the residues that are left on the microelectronic device substrate following CMP processing. Such residues include CMP material and corrosion inhibitor compounds such as benzotriazole (BTA). If not removed, these residues can cause damage to copper lines or severely roughen the copper metallization, as well as cause poor adhesion of post-CMP applied layers on the device substrate. Severe roughening of copper metallization is particularly problematic, since overly rough copper can cause poor electrical performance of the product microelectronic device. Towards that end, post-CMP removal compositions have been developed to remove the post-CMP residue and contaminants.

[0006] Conventional cleaning techniques use fluid flow of a cleaning solution, e.g., alkaline solutions based on ammonium hydroxide, over the wafer surface in combination with megasonics, jetting or brushing to remove contaminants. Said cleaning solutions remove the contaminants by attacking the wafer surface or reacting with the contaminants before removing the dislodged contaminants from the wafer. Disadvantageously, some of the contaminants may be chemically inert to the chemical ingredients in the cleaning solutions. Furthermore, the amine -containing cleaning solutions known in the art smell and release amine vapors into the fab which can poison photoresist.

[0007] It would be a significant advance in the art to provide improved amine-free compositions for post-CMP cleaning of the microelectronic devices, for the substantially defect-free and substantially scratch-free removal of CMP residue and contaminants from the surface of said device. Said aqueous compositions effectuate substantial residue and contaminant removal from the surface of the device without damaging the exposed low-k dielectric material and interconnect and via materials, e.g., copper and/or aluminum containing materials.

SUMMARY OF THE INVENTION

[0008] The present invention generally relates to an amine-free composition and process for cleaning residue and/or contaminants from microelectronic devices having said residue and contaminants thereon. The residue may include post-CMP residue.

[0009] In one aspect, a method of protecting cobalt-containing material layers relative to copper- containing material layers on a microelectronic device is described, said method comprising contacting the microelectronic device with a high pH composition comprising at least one oxidizing agent, wherein the pH of the high pH composition is greater than about 10. [0010] In another aspect, a composition for cleaning residue and contaminants from a surface is described, said composition comprising at least one complexing agent, at least one basic compound, at least one solvating agent, water, at least one oxidizing agent, wherein the at least one basic compound comprise a species selected from the group consisting of (a) KOH, CsOH, ammonium hydroxide, and combinations thereof, wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes, and (b) a quaternary phosphonium hydroxide base, wherein at least one component in the composition has at least one nitrogen atom, wherein the pH is greater than about 10, and wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes.

[0011] In still another aspect, a method of cleaning residue and contaminants from a microelectronic device having said residue and contaminants thereon is described, said method comprising contacting the microelectronic device with a composition for sufficient time to at least partially clean said residue and contaminants from the microelectronic device, wherein said composition comprises at least one complexing agent, at least one basic compound, at least one solvating agent, water, at least one oxidizing agent, wherein the at least one basic compound comprise a species selected from the group consisting of (a) KOH, CsOH, ammonium hydroxide, and combinations thereof, wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes, and (b) a quaternary phosphonium hydroxide base, wherein at least one component in the composition has at least one nitrogen atom, wherein the pH is greater than about 10, and wherein the composition is substantially devoid of amines, quaternary bases, fluoride -containing sources, and abrasive material typically used in chemical mechanical polishing processes.

[0012] Other aspects, features and advantages of the invention will be more fully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with the composition of Example 1.

[0014] Figure 2A illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation B.

[0015] Figure 2B illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation C.

[0016] Figure 2C illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation D. [0017] Figure 3 A illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation E.

[0018] Figure 3B illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation F.

[0019] Figure 3C illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with formulation G.

[0020] Figure 4 illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with the composition of Example 4.

[0021] Figure 5 illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with the composition of Example 5.

[0022] Figure 6 illustrates a Tafel plot of the galvanic corrosion of copper and cobalt following contact with the composition of Example 6.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS

THEREOF

[0023] The present invention relates generally to amine-free compositions that clean post-CMP residue and contaminants from a microelectronic device having said residue and contaminants thereon. The cleaning compositions are compatible with the exposed materials, while substantially removing the post-CMP residue and contaminants from the surface of the microelectronic device. Advantageously, the cleaning compositions are highly compatible with cobalt-containing material layers. Further, the present invention relates to the protection of cobalt-containing material in general.

[0024] For ease of reference, "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, or computer chip applications. . It is to be understood that the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that will eventually become a microelectronic device or microelectronic assembly.

[0025] As used herein, "residue" corresponds to particles generated during the manufacture of a microelectronic device including, but not limited to, plasma etching, ashing, chemical mechanical polishing, wet etching, and combinations thereof.

[0026] As used herein, "contaminants" correspond to chemicals present in the CMP slurry, e.g., benzotriazole (BTA), reaction by-products of the polishing slurry, chemicals present in the wet etching composition, reaction by products of the wet etching composition, and any other materials that are the by-products of the CMP process, the wet etching, the plasma etching or the plasma ashing process. [0027] As used herein, "post-CMP residue" corresponds to particles from the polishing slurry, e.g., silica-containing particles, chemicals present in the slurry, reaction by-products of the polishing slurry, carbon-rich particles, polishing pad particles, brush deloading particles, equipment materials of construction particles, copper, copper oxides, organic residues, and any other materials that are the byproducts of the CMP process.

[0028] As defined herein, "low-k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material has a dielectric constant less than about 3.5. Preferably, the low-k dielectric materials include low-polarity materials such as silicon- containing organic polymers, silicon-containing hybrid organic/inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, carbon-doped oxide (CDO) glass, CORAL™ from Novellus Systems, Inc., BLACK DIAMOND™ from Applied Materials, Inc., SiLK™ from Dow Corning, Inc., and NANOGLASS™ of Nanopore, Inc, and the like. It is to be appreciated that the low-k dielectric materials may have varying densities and varying porosities.

[0029] As defined herein, "clean amine-free compositions" correspond to the amine-free compositions just prior to contact with the microelectronic device having post-CMP and/or contaminants thereon.

[0030] As defined herein, "complexing agent" includes those compounds that are understood by one skilled in the art to be complexing agents, chelating agents and/or sequestering agents. Complexing agents will chemically combine with or physically hold the metal atom and/or metal ion to be removed using the compositions of the present invention.

[0031] As defined herein, the term "barrier material" corresponds to any material used in the art to seal the metal lines, e.g., copper interconnects, to minimize the diffusion of said metal, e.g., copper, into the dielectric material. Conventional barrier layer materials include tantalum or titanium, their nitrides and silicides, and alloys thereof. Candidate materials that could serve as directly plateable diffusion barriers include ruthenium (Ru), cobalt (Co), tungsten (W), molybdenum (Mo), rhenium (Rh), and alloys thereof including, but not limited to, pure cobalt, CoWP, CoWB, cobalt nitrides (including cobalt nitrides comprising additional elements such as Ta or Li), CoW, CoP, CoSi, and cobalt silicide.

[0032] As defined herein, "cobalt-containing material layers" correspond to metal layers comprising cobalt and cobalt alloys.

[0033] As defined herein, "copper-containing material layers" correspond to metal layers comprising copper and copper alloys.

[0034] As used herein, "about" is intended to correspond to ± 5 % of the stated value.

[0035] "Substantially devoid" is defined herein as less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, even more preferably less than 0.1 wt. %, and most preferably 0 wt%. [0036] As defined herein, "post-etch residue" corresponds to material remaining following gas-phase plasma etching processes, e.g., BEOL dual damascene processing. The post-etch residue may be organic, organometallic, organosilicic, or inorganic in nature, for example, silicon-containing material, carbon-based organic material, and etch gas residue including, but not limited to, oxygen and fluorine. "Post-ash residue," as used herein, corresponds to material remaining following oxidative or reductive plasma ashing to remove hardened photoresist and/or bottom anti-reflective coating (BARC) materials. The post-ash residue may be organic, organometallic, organosilicic, or inorganic in nature.

[0037] It is understood to the skilled artisan that ammonium hydroxide (NH4OH) can be used interchangeably with ammonia (NH3) when the composition is aqueous.

[0038] For the purposes of this invention, an "amine" is defined as at least one primary, secondary, or tertiary amine, with the proviso that (i) an amide group, (ii) species including both a carboxylic acid group and an amine group (e.g., amino acids), (iii) ammonia, also referred to as ammonium hydroxide, (iv) surfactants that include amine groups, and (v) amine-N-oxides are not considered "amines" according to this definition. The amine formula can be represented by NR^R3, wherein R1, R2 and R3 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched Ci-Ce alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C6-C10 aryls (e.g., benzyl), straight-chained or branched Ci-Ce alkanols (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol), and combinations thereof, with the proviso that R1, R2 and R3 cannot all be hydrogen. Quaternary ammonium hydroxide compounds have the general formula R1R2R3R4NOH, where Ri, R2, R3 and R4 are the same as or different from one another and are hydrogen, Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl or hexyl), and substituted or unsubstituted C6-Ci0 aryl groups (e.g., benzyl); and alkanolamines.

[0039] As defined herein, a quaternary phosphonium hydroxide base corresponds to a compound having the formula R1R2R3R4POH, where Rb R2, R3 and R4 are the same as or different from one another and are hydrogen, Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl or hexyl), and substituted or unsubstituted C6-Ci0 aryl groups (e.g., benzyl). Quaternary phosphonium hydroxide bases include tetramethylphosphomum hydroxide, tetraethylphosphonium hydroxide, ielrapropylphosphonium hydroxide, teirabutylphosphonium hydroxide (TBPH), ietradecyltributyiphosphoiiium hydroxide, phenyltrimethylphosphoiiiu hydroxide, phenyltriethylphosphonium hydroxide and benzyltrimethylphosphonium hydroxide, corresponding anions (e.g., halides), and combinations thereof.

[0040] As used herein, "suitability" for cleaning residue and contaminants from a microelectronic device having said residue and contaminants thereon corresponds to at least partial removal of said residue/contaminants from the microelectronic device. Cleaning efficacy is rated by the reduction of objects on the microelectronic device. For example, pre- and post-cleaning analysis may be carried out using an atomic force microscope. The particles on the sample may be registered as a range of pixels. A histogram (e.g., a Sigma Scan Pro) may be applied to filter the pixels in a certain intensity, e.g., 231-235, and the number of particles counted. The particle reduction may be calculated using:

. ^ rr. (Number of PreClean Objects - Number of PostClean Objects)

Cleaning Efficacy = x 100

Number of PreClean Objects

Notably, the method of determination of cleaning efficacy is provided for example only and is not intended to be limited to same. Alternatively, the cleaning efficacy may be considered as a percentage of the total surface that is covered by particulate matter. For example, AFM's may be programmed to perform a z-plane scan to identify topographic areas of interest above a certain height threshold and then calculate the area of the total surface covered by said areas of interest. One skilled in the art would readily understand that the less area covered by said areas of interest post-cleaning, the more efficacious the cleaning composition. Preferably, at least 75% of the residue/contaminants are removed from the microelectronic device using the compositions described herein, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99% of the residue/contaminants are removed.

[0041] Compositions of the invention may be embodied in a wide variety of specific formulations, as hereinafter more fully described.

[0042] In all such compositions, wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed.

[0043] In a first aspect, the present invention relates to an amine-free composition for cleaning post- CMP residue and contaminants, said amine-free composition comprising at least one complexing agent, at least one basic compound, at least one solvating agent, at least one oxidizing agent, and water. Optionally, the amine-free composition can further comprise at least one buffering agent.

[0044] In one embodiment, the amine-free composition comprises, consists of, or consists essentially of at least one complexing agent, at least one basic compound, at least one solvating agent, at least one oxidizing agent, and water, wherein the at least one basic compound comprises KOH, CsOH, ammonium hydroxide, and combinations thereof, preferably KOH, optionally at least one buffering agent. The components in a concentrate of the amine-free composition are present in the following range of weight percents, based on the total weight of the composition,

Component weight percent preferred wt.% complexing agent(s) about 0.1 wt% to about about 0.1 wt% to about

20 wt% 10 wt%

basic compound(s) about 0.01 wt% to about about 0.01 wt% to 5 wt% about 4 wt% solvating agent(s) about 1 wt% to about 40 about 5 wt% to about wt% 30 wt%

oxidizing ; agent(s) about 0.01 wt% to about about 0.01 wt% to

10 wt% about 5 wt% water about 25 wt% to about about 51 wt% to about

98.9 wt% 94.9 wt%

optional buffering agent(s) (when about 0.01 wt% to about about 0.1 wt% to about present) 10 wt% 5 wt%

pH about 7 to about 13 about 10 to about 12

Upon dilution, the weight percent values of the components in the concentrated amine-free composition will change as a factor of the dilution factor, as readily understood by one skilled in the art. Advantageously, the compositions described herein protect the cobalt-containing material layers relative to copper-containing material layers. The water is preferably deionized. It should be appreciated that the at least one oxidizing agent, when intended to be present, can be added just upstream of or at the cleaning apparatus.

[0045] In still another embodiment, the amine-free composition comprises, consists of, or consists essentially of at least one complexing agent, at least one basic compound, at least one solvating agent, at least one oxidizing agent, and water, wherein the at least one basic compound comprises a quaternary phosphonium hydroxide base and optionally at least one buffering agent, wherein at least one component in the composition has at least one nitrogen atom. The components in a concentrate of the amine-free composition are present in the following range of weight percents, based on the total weight of the composition,

Component weight percent preferred wt.% complexing agent(s) about 0.1 wt% to about about 0.1 wt% to about

20 wt% 10 wt%

basic compound(s) about 1 wt% to about 30 about 2 wt% to about wt% 20 wt%

solvating agent(s) about 1 wt% to about 40 about 5 wt% to about wt% 30 wt%

oxidizing agent(s) about 0.01 wt% to about about 0.01 wt% to

10 wt% about 5 wt% water about 0.01 wt% to about about 35 wt% to about

97.9 wt% 92.9 wt%

optional buffering agent(s) (when about 0.01 wt% to about about 0.1 wt% to about present) 10 wt% 5 wt%

pH > about 10 > about 10

Upon dilution, the weight percent values of the components in the concentrated amine-free composition will change as a factor of the dilution factor, as readily understood by one skilled in the art. Advantageously, the compositions described herein protect the cobalt-containing material layers relative to copper-containing material layers. The water is preferably deionized. It should be appreciated that the at least one oxidizing agent, when intended to be present, can be added just upstream of or at the cleaning apparatus. It should be appreciated by the person skilled in the art that since the compositions are intended to be "amine-free," the "at least one component in the composition has at least one nitrogen atom" includes non-amine compounds that include nitrogen atoms, e.g., amino acids, aminopolycarboxylic acids, ionic compounds comprising a nitrogen atom, etc.

[0046] The compositions described herein may have utility in applications including, but not limited to, post-etch residue removal, post-ash residue removal surface preparation, post-plating cleaning, post-CMP residue removal, copper seed etching/cleaning, through silicon via (TSV) cleaning, MEMS cleaning, and cobalt and cobalt alloy surface cleaning and protection.

[0047] The complexing agents contemplated herein include organic acids, comprising at least one COOH group or carboxylate group in a salt thereof, including, but not limited to, lactic acid, maleic acid, ascorbic acid, malic acid, citric acid, benzoic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, mandelic acid, maleic anhydride, phthalic acid, glutaric acid, glycolic acid, glyoxylic acid, glycerin, acetylacetone, salicylhydroxamic acid, a salt thereof, or a partially neutralized form thereof, phenylacetic acid, quinic acid, pyromellitic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, gluconic acid, glyceric acid, formic acid, acetic acid, propionic acid, acrylic acid, adipic acid, itaconic acid, glucuronic acid, amino acids (e.g., glycine, lysine, β-alanine, histidine, phenylalanine, cysteine, leucine, serine, arginine, aspartic acid, glutamic acid, ), 8-hydroxyquinoline, 2,4-pentanedione, benzetetracarboxylic acid, pyruvic acid, tannic acid, sulfanilic acid, 2- hydroxyphosphonocarboxylic acid (HPAA), pyrocatecol, pyrogallol, gallic acid, tannic acid, ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), (1,2- cyclohexylenedinitrilo)tetraacetic acid (CDTA), iminodiacetic acid, 2-phosphonobutane- 1,2,4- tricarboxylic acid (PBTCA), other aliphatic and aromatic carboxylic acids, salts thereof as well as combinations of the foregoing acids. Other complexing agents contemplated, as an alternative or in addition to, include phosphonic acid and derivatives thereof (e.g., l,5,9-triazacyclododecane-N,N',N"- tris(methylenephosphonic acid) (DOTRP), l,4,7,10-tetraazacyclododecane-N,N',N",N"'- tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), l-hydroxyethylidene-l,l-diphosphonic acid (HEDP), bis(hexamethylene)triamine phosphonic acid, l,4,7-triazacyclononane-N,N',N"-tris(methylenephosphonic acid (NOTP), ethylenediamine tetra(methylene phosphonic acid (EDTMP)), salicylic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid and derivatives thereof, and any combination thereof. Preferably, the complexing agent for the amine-free composition comprises 5-sulfosalicylic acid, CDTA, an amino acid such as glycine, cysteine, or histidine, and any combination thereof. Advantageously, some complexing agents serve to stabilize amine-free compositions comprising at least one oxidizing agent. For example, adding just about 0.001 wt% to about 0.1 wt% CDTA to the non-amine composition comprising an oxidizing agent, e.g., urea hydrogen peroxide will stabilize the composition, substantially reducing decomposition of the oxidizing agent over time.

[0048] Oxidizing agents contemplated include ozone, nitric acid, bubbled air, cyclohexylaminosulfonic acid, hydrogen peroxide (H202), FeCl3 (both hydrated and unhydrated), oxone (2KHSO5 KHSO4 K2SO4), ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH4C102), ammonium chlorate (NH4CIO3), ammonium iodate (NH4IO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4CIO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S20g), ammonium hypochlorite (NH4CIO)), sodium perborate (NaBC^), sodium polyatomic salts (e.g., sodium persulfate (Na2S20g), sodium hypochlorite (NaCIO)), potassium polyatomic salts (e.g., potassium iodate (KIO3), potassium permanganate (KMnC^), potassium persulfate, potassium persulfate (K2S20g), potassium hypochlorite (KCIO)), tetramethylammonium polyatomic salts (e.g., tetramethylammonium chlorite ((N(CH3)4)C102), tetramethylammonium chlorate ((N(CH3)4)C103), tetramethylammonium iodate ((N(CH3)4)I03), tetramethylammonium perborate ((N(CH3)4)B03), tetramethylammonium perchlorate ((N(CH3)4)C104), tetramethylammonium periodate ((N(CH3)4)I04), tetramethylammonium persulfate ((N(CH3)4)S20g)), tetrabutylammonium polyatomic salts (e.g., tetrabutylammonium peroxomonosulfate), peroxomonosulfuric acid, ferric nitrate (Fe(N03)3), amine-N-oxides (e.g., N- methylmorpholine-N-oxide (NMMO); trimethylamine-N-oxide; triethylamine-N-oxide; pyridine-N- oxide; N-ethylmorpholine-N-oxide; N-methylpyrrolidine-N-oxide; N-ethylpyrrolidine-N-oxide) urea hydrogen peroxide ((CO(NH2)2)H202), peracetic acid (CH3(CO)OOH), periodic acid, potassium dichromate, potassium chlorate, 2-nitrophenol, 1 ,4-benzoquinone, peroxybenzoic acid, peroxyphthalic acid salts, vanadium oxides (e.g., V02, V60i3), ammonium metavanadate, ammonium tungstate, sodium nitrate, potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof. Preferably, the oxidizing agent for the amine-free composition comprises hydrogen peroxide, NMMO, urea hydrogen peroxide, and combinations thereof.

[0049] Solvating agents contemplated include, but are not limited to, 2-pyrrolidinone, l-(2- hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1 ,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (i.e., butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof. Preferably, the solvating agent for the amine-free composition comprises sulfolane (tetramethylene sulfone), 1 -(2-hydroxyethyl)-2- pyrrolidinone, and combinations thereof.

[0050] When present, buffering agents are added to stabilize the amine-free composition during dilution and manufacturing as well as achieve the appropriate compositional pH, as readily determined by the skilled artisan. Buffering agents contemplated include, but are not limited to, dipotassium phosphate, potassium carbonate, boric acid, lysine, proline, β -alanine, ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), dimethyl glyoxime, dibasic phosphate salts (e.g., (NH4)H2P04, K2HP04), tribasic phosphate salts (e.g., (NH4)3P04, K3P04), mixtures of dibasic and tribasic phosphate salts (e.g., K2HP04/K3P04), mixures of dibasic and tribasic carbonate salts (e.g., K2CO3/KHCO3), hydroxyethylidene diphosphonic acid (HEDP), and combinations thereof. Preferred buffering agents, when present, include dibasic phosphate salts (e.g., (NH4)H2P04, K2HP04), tribasic phosphate salts (e.g., (NH4)3P04, K3P04),mixtures of dibasic and tribasic phosphate salts (e.g., K2HP04/K3P04), and combinations thereof.

[0051] The amine-free compositions described herein are preferably substantially devoid of abrasive material typically used in chemical mechanical polishing processes (before the initiation of cleaning), fluoride-containing sources, amines, quaternary ammonium bases, and any combination thereof. Quaternary ammonium bases include compounds having the formula NR^R^OH, wherein R1, R2, R3 and R4 may be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched Ci-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), and substituted or unsubstituted C6-Ci0 aryl, e.g., benzyl, with the proviso at least one of R1, R2, R3 or R4 has to be a component other than hydrogen.

[0052] In a preferred embodiment, the amine-free composition comprises, consists of, or consists essentially of (i) at least one oxidizing agent comprising a species selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, NMMO, and combinations thereof, (ii) at least one basic compound comprising KOH, (iii) at least one complexing agent comprising a species selected from the group consisting of 5-sulfosalicylic acid and derivatives thereof, CDTA, glycine, histidine, cysteine, and combinations thereof, (iv) at least one solvating agent selected from the group consisting of sulfolane, l-(2-hydroxyethyl)-2-pyrrolidinone, and combinations thereof, and (v) and water, wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes, wherein the pH is in a range from about 7 to about 13. In another preferred embodiment, the amine-free composition comprises, consists of, or consists essentially of (i) at least one oxidizing agent comprising a species selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, NMMO, and combinations thereof, (ii) at least one basic compound comprising TBPH, (iii) at least one complexing agent comprising a species selected from the group consisting of 5- sulfosalicylic acid and derivatives thereof, CDTA, glycine, histidine, cysteine, and combinations thereof, (iv) at least one solvating agent selected from the group consisting of sulfolane, l-(2- hydroxyethyl)-2-pyrrolidinone, and combinations thereof, and (v) and water, wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes, wherein the pH is greater than 10, and wherein at least one component in the composition has at least one nitrogen atom. Preferably, the amine-free composition has a copper etch rate less than 5 A min 1, a cobalt etch rate less than 5 A mm 1, and a BTA removal efficiency greater than 20%, more preferably greater than 30%, and most preferably greater than 40%>. Advantageously, the compositions described herein protect the cobalt- containing material layers relative to copper-containing material layers.

[0053] In one embodiment of the first aspect, a concentrated amine-free composition is provided that can be diluted for use as a cleaning solution. A concentrated composition, or "concentrate," advantageously permits a user, e.g. CMP process engineer, to dilute the concentrate to the desired strength and acidity at the point of use. Dilution of the concentrated amine-free composition may be in a range from about 1 : 1 to about 2500: 1, preferably about 10: 1 to about 100: 1, wherein the amine- free composition is diluted at or just before the tool with solvent, e.g., deionized water.

[0054] An important feature of the amine-free composition described herein is that the non-aqueous constituents (the constituents other than water) are present in the composition in small quantities, often less than about 20 % by weight. This is an economic advantage since an effective amine-free composition can be formulated more economically, which is of importance since post-CMP amine- free compositions are used in large quantities. Furthermore, because the amine-free composition is water-based, the amine-free compositions described herein are more easily disposed of. Notably, the life of the amine-free composition is dependent only on particle loading and as such, the amine-free composition is recyclable.

[0055] In a second aspect, the amine-free compositions described herein comprise, consist of, or consist essentially of at least one complexing agent, at least one basic compound, at least one buffering agent, water, optionally at least one oxidizing agent, optionally at least one reducing agent, optionally at least one solvating agent, residue and/or contaminants. Importantly, the residue and contaminants may be dissolved and/or suspended in the amine-free composition described herein. Preferably, the residue includes post-CMP residue.

[0056] The amine-free compositions described herein are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition. Furthermore, the amine-free compositions may be readily formulated as single-package formulations or multi-part formulations that are mixed at or before the point of use, e.g., the individual parts of the multi-part formulation may be mixed at the tool or in a storage tank upstream of the tool. The concentrations of the respective ingredients may be widely varied in specific multiples of the amine-free composition, i.e., more dilute or more concentrated, in the broad practice of the invention, and it will be appreciated that the amine- free compositions can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein.

[0057] Accordingly, another aspect relates to a kit including, in one or more containers, one or more components adapted to form the compositions of the first aspect of the invention. Preferably, the kit includes, in one or more containers, at least one complexing agent, at least one basic compound, at least one solvating agent, water, optionally at least one buffering agent, for combining with additional water and the at least one oxidizing agent, at the fab or the point of use. The containers of the kit must be suitable for storing and shipping said first composition components, for example, NOWPak® containers (Advanced Technology Materials, Inc., Danbury, Conn., USA).

[0058] In a third aspect, the amine-free compositions described herein are usefully employed to clean post-CMP residue and contaminants from the surface of the microelectronic device. Importantly, the amine-free composition does not damage low-k dielectric materials, does not substantially corrode metal interconnects, e.g., copper, on the device surface, and does not substantially corrode cobalt- containing material layers. Advantageously, the compositions described herein protect the cobalt- containing material layers relative to copper-containing material layers in the galvanic couple. Preferably the amine-free composition removes at least 85 % of the residue present on the device prior to residue removal, more preferably at least 90 %, even more preferably at least 95 %, and most preferably at least 99%.

[0059] In post-CMP residue and contaminant cleaning application, the amine-free composition may be used with a large variety of conventional cleaning tools such as megasonics and brush scrubbing, including, but not limited to, Verteq single wafer megasonic Goldfinger, OnTrak systems DDS (double-sided scrubbers), SEZ single wafer spray rinse, Applied Materials Mirra-Mesa™ /Reflexion ™/Reflexion LK™, and Megasonic batch wet bench systems.

[0060] In use of the amine-free compositions for cleaning post-CMP residue and contaminants from microelectronic devices having same thereon, the amine-free composition typically is contacted with the device for a time of from about 5 sec to about 10 minutes, preferably about 15 sec to 5 min, at temperature in a range of from about 20°C to about 50°C. Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to at least partially clean the post-CMP residue/contaminants from the device. "At least partially clean" and "substantial removal" both correspond to at removal of at least 85 % of the residue present on the device prior to residue removal, more preferably at least 90 %, even more preferably at least 95 %, and most preferred at least 99 %

[0061] Following the achievement of the desired cleaning action, the amine-free composition may be readily removed from the device to which it has previously been applied, as may be desired and efficacious in a given end use application of the compositions of the present invention. Preferably, the rinse solution includes deionized water. Thereafter, the device may be dried using nitrogen or a spin-dry cycle.

[0062] Another aspect relates to a diluted cleaning composition comprising concentrated amine-free composition as described herein, diluted in a range from about 1 :1 to about 2500:1, preferably about 10:1 to about 100:1, wherein the amine-free composition is diluted at or just before the tool with solvent, e.g., deionized water.

[0063] Yet another aspect relates to the improved microelectronic devices made according to the methods described herein and to products containing such microelectronic devices.

[0064] Another aspect relates to a recycled amine-free composition. The amine-free composition may be reused until residue and/or contaminant loading reaches the maximum amount the respective composition may accommodate, as readily determined by one skilled in the art.

[0065] A still further aspect relates to methods of manufacturing an article comprising a microelectronic device, said method comprising contacting the microelectronic device with an amine- free composition for sufficient time to clean post-CMP residue and contaminants from the microelectronic device having said residue and contaminants thereon, and incorporating said microelectronic device into said article.

[0066] Another aspect relates to a method of protecting cobalt-containing material layers relative to copper-containing material layers on a microelectronic device, said method comprising contacting the microelectronic device with an amine-free composition described herein.

[0067] Another aspect relates to a method of protecting cobalt-containing material layers on a microelectronic device, said method comprising contacting the microelectronic device with an amine- free composition described herein.

[0068] Yet another aspect relates to a method of protecting cobalt-containing material layers on a microelectronic device, said method comprising contacting the microelectronic device with a high pH solution comprising at least one oxidizing agent, wherein the pH of the solution is greater than about 10. It was surprisingly discovered that a solution having a high pH comprising at least one oxidizing agent is able to protect the cobalt-containing material layer. The at least one oxidizing agent can be any of those described hereinabove in the first aspect and the amount is in a range from about 0.01 wt% to about 5 wt%. The time of contacting can be from about 15 sec to about 5 min and the temperature of contacting is in a range from about 20°C to about 50°C, as readily determined by the person skilled in the art. In order to provide the pH value greater than about 10, the composition can comprise at least one base selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, at least one amine, at least one quaternary ammonium hydroxide (e.g., tetramethylammonium hydroxide (TMAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide, tetraethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, choline hydroxide, ammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH)), trialkyl-hydroxyalkylammonium hydroxide, dialkyl-bis(hydroxyalkyl)ammonium hydroxide, tris(hydroxyalkyl)alkylammonium hydroxide, at least one quaternary phosphonium hydroxide as defined herein, and any combination thereof. It is understood by the person skilled in the art how much of the at least one base should be added to achieve a pH greater than about 10. The solution can further comprise at least one complexing agent, at least one solvating agent, and water, as defined herein. Notably, the solution is preferably substantially devoid of fluoride -containing sources and abrasive material typically used in chemical mechanical polishing processes.

[0069] The features and advantages of the invention are more fully shown by the illustrative examples discussed below.

Example 1

[0070] A composition including 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% glycine, 0.01-5 wt% KOH, 0.001-1 wt% CDTA, and 0.01-5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared and the corrosion rate of copper and cobalt was determined to be 0.153 A/min and 0.098 A/min, respectively. A Tafel plot of the galvanic corrosion of copper and cobalt is shown in Figure 1, where it can be seen that cobalt is protected relative to copper in the galvanic couple.

Example 2

[0071] A composition 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% cysteine, 0.01-5 wt% KOH, balance water, pH approximately 10-12, was prepared, hereinafter Formulation B. A second composition 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% cysteine, 0.01-5 wt% KOH, 0.1-5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared, hereinafter Formulation C. A third composition 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% cysteine, 0.01-5 wt% KOH, 0.1- 5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared, hereinafter Formulation D. The concentration of urea hydrogen peroxide in Formulation D was greater than that in Formulation C. Tafel plots of the galvanic corrosion of copper and cobalt is shown in Figures 2A (formulation B), 2B (formulation C) and 2C (formulation D), where it can be seen that cobalt is protected relative to copper in the galvanic couple as the concentration of urea hydrogen peroxide increases. Example 3

[0072] A composition 20-40 wt% l-(2-hydroxyethyl)-2-pyrrolidinone, 0.01-2 wt% tartaric acid, 0.01-2 wt% glycine, 0.1-5 wt% histidine, 0.01-5 wt% KOH, balance water, pH approximately 10-12, was prepared, hereinafter Formulation E. A second composition 20-40 wt% l-(2-hydroxyethyl)-2- pyrrolidinone, 0.01-2 wt% tartaric acid, 0.01-2 wt% glycine, 0.1-5 wt% histidine, 0.01-5 wt% KOH, 0.1-5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared, hereinafter Formulation F. A third composition 20-40 wt% l-(2-hydroxyethyl)-2-pyrrolidinone, 0.01-2 wt% tartaric acid, 0.01-2 wt% glycine, 0.1-5 wt% histidine, 0.01-5 wt% KOH, 0.1-5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared, hereinafter Formulation G. The concentration of urea hydrogen peroxide in Formulation G was greater than that in Formulation F. Tafel plots of the galvanic corrosion of copper and cobalt is shown in Figures 3A (formulation E), 3B (formulation F) and 3C (formulation G), where it can be seen that cobalt is protected relative to copper in the galvanic couple as the concentration of urea hydrogen peroxide increases.

Example 4

[0073] A composition including 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% glycine, 2-12 wt% TBPH, 0.001-1 wt% CDTA, and 0.01-5 wt% urea hydrogen peroxide, balance water, pH approximately 10-12, was prepared and the etch rate of copper and cobalt was determined to be about 11-12 A/min and <1 A/min, respectively. A Tafel plot of the galvanic corrosion of copper and cobalt is shown in Figure 4, where it can be seen that cobalt is protected relative to copper in the galvanic couple.

Example 5

[0074] A composition 10-20 wt% sulfolane-W, 0.01-2 wt% 5-sulfosalicylic acid dihydrate, 0.01-2 wt% cysteine, 1-7 wt% TBPH, balance water, pH approximately 10-12, was prepared and the etch rate of copper and cobalt were both determined to be about 1 A/min. A Tafel plot of the galvanic corrosion of copper and cobalt is shown in Figure 5, where it can be seen that cobalt was not protected relative to copper in the galvanic couple. It is expected that as oxidizing agent is added to this formulation, e.g., as in Example 2, that the protection will switch.

Example 6

[0075] A composition 20-40 wt% l-(2-hydroxyethyl)-2-pyrrolidinone, 0.01-2 wt% tartaric acid, 0.01-2 wt% glycine, 0.1-5 wt% histidine, 12-25 wt% TBPH, balance water, pH approximately 10-12, was prepared and the etch rate of copper and cobalt was determined to be about 2 A/min and 20 A min, respectively. A Tafel plot of the galvanic corrosion of copper and cobalt is shown in Figure 6, where it can be seen that cobalt was not protected relative to copper in the galvanic couple. It is expected that as oxidizing agent is added to this formulation, e.g., as in example 3, that the protection will switch.

[0076] Although the invention has been variously disclosed herein with reference to illustrative embodiments and features, it will be appreciated that the embodiments and features described hereinabove are not intended to limit the invention, and that other variations, modifications and other embodiments will suggest themselves to those of ordinary skill in the art, based on the disclosure herein. The invention therefore is to be broadly construed, as encompassing all such variations, modifications and alternative embodiments within the spirit and scope of the claims hereafter set forth.

Claims

THE CLAIMS What is claimed is:
1. A method of protecting cobalt-containing material layers on a microelectronic device, said method comprising contacting the microelectronic device with a high pH composition comprising at least one oxidizing agent, wherein the pH of the high pH composition is greater than about 10.
2. The method of claim 1, wherein the at least one oxidizing agent comprises a species selected from the group consisting of ozone, nitric acid, bubbled air, cyclohexylaminosulfonic acid, hydrogen peroxide, FeCl3, oxone (2KHSO5 KHSO4 K2SO4), ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium perborate, sodium persulfate, sodium hypochlorite, potassium iodate, potassium permanganate, potassium persulfate, potassium persulfate, potassium hypochlorite, tetramethylammomum chlorite, tetramethylammomum chlorate, tetramethylammomum iodate, tetramethylammomum perborate, tetramethylammomum perchlorate, tetramethylammomum periodate, tetramethylammomum persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, N-methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine -N-oxide, N-ethylmorpholine-N-oxide, N- methylpyrrolidine-N-oxide, N-ethylpyrrolidine -N-oxide, urea hydrogen peroxide, peracetic acid, periodic acid, potassium dichromate, potassium chlorate, 2-nitrophenol, 1,4-benzoquinone, peroxybenzoic acid, peroxyphthalic acid salts, vanadium oxides, ammonium metavanadate, ammonium tungstate, sodium nitrate, potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof.
3. The method of claim 1, wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, NMMO, urea hydrogen peroxide, and combinations thereof.
4. The method of any of the preceding claims, wherein the high pH composition further comprises at least one basic compound selected from the group consisting of (a) a species selected from the group consisting of KOH, CsOH, ammonium hydroxide, and combinations thereof, wherein the composition is substantially devoid of amines, quaternary bases, fluoride -containing sources, and abrasive material typically used in chemical mechanical polishing processes, (b) a quaternary phosphonium hydroxide base, wherein at least one component in the composition has at least one nitrogen atom, and wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes, and (c) at least one species selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, at least one amine, at least one quaternary ammonium hydroxide (e.g., tetramethylammonium hydroxide (TMAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide, tetraethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, choline hydroxide, ammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide, (2-hydroxyethyl) triethylammonium hydroxide, (2-hydroxyethyl) tripropylammonium hydroxide, (1-hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH)), trialkyl- hydroxyalkylammonium hydroxide, dialkyl-bis(hydroxyalkyl)ammonium hydroxide, tris(hydroxyalkyl)alkylammonium hydroxide, at least one quaternary phosphonium hydroxide, and combinations thereof, wherein the composition is substantially devoid of fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes.
5. The method of claim 4, wherein the composition further comprises at least one complexing agent, at least one solvating agent, and water.
6. The method of any of the preceding claims, wherein the amount of the at least one oxidizing agent is in a range from about 0.01 wt% to about 5 wt%.
7. The method of any of the preceding claims, wherein the contacting comprises time in a range from about 15 sec to about 5 min and the temperature in a range from about 20°C to about 50°C.
8. A composition for cleaning residue and contaminants from a surface, said composition comprising at least one complexing agent, at least one basic compound, at least one solvating agent, water, at least one oxidizing agent, wherein the at least one basic compound comprise a species selected from the group consisting of (a) KOH, CsOH, ammonium hydroxide, and combinations thereof, wherein the composition is substantially devoid of amines, quaternary bases, fluoride- containing sources, and abrasive material typically used in chemical mechanical polishing processes, and (b) a quaternary phosphonium hydroxide base, wherein at least one component in the composition has at least one nitrogen atom, wherein the pH is greater than about 10, and wherein the composition is substantially devoid of amines, quaternary bases, fluoride-containing sources, and abrasive material typically used in chemical mechanical polishing processes.
9. The composition of claim 8, wherein pH is in a range from 7 to about 13, preferably about 9 to about 12.
10. The composition of claim 8, wherein the at least one phosphonium hydroxide base comprises tetramethylphosphoaium hydroxide, tetraetkylpkospkonium hydroxide, tetrapropylpkospkonium hydroxide, teti'abutylpkospkoniuin hydroxide (TBPH), tetradecyitributylpkospkoniuin hydroxide, phenyltrimethylphosphonium hydroxide, pketiyitrietkylpkospkoniujxi hydroxide and benzyltriraetkylpkospkomum hydroxide, corresponding anions, and combinations thereof.
11. Tke composition of any of claims 8-10, wkerein tke at least one complexing agent comprises a species selected from tke group consisting of lactic acid, maleic acid, ascorbic acid, malic acid, citric acid, benzoic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, mandelic acid, maleic ankydride, pktkalic acid, aspartic acid, glutamic acid, glutaric acid, glycolic acid, glyoxylic acid, glycerin, acetylacetone, salicylkydroxamic acid, a salt tkereof, or a partially neutralized form tkereof, pkenylacetic acid, quinic acid, pyromellitic acid, tartaric acid, terepktkalic acid, trimellitic acid, trimesic acid, gluconic acid, glyceric acid, formic acid, acetic acid, propionic acid, acrylic acid, adipic acid, itaconic acid, glucuronic acid, glycine, lysine, β -alanine, kistidine, pkenylalanine, cysteine, leucine, serine, 8-kydroxyquinoline, 2,4-pentanedione, benzetetracarboxylic acid, pyruvic acid, tannic acid, sulfanilic acid, 2-kydroxypkospkonocarboxylic acid (HPAA), pyrocatecol, pyrogallol, gallic acid, tannic acid, etkylenediamine tetraacetic acid (EDTA), dietkylenetriaminepentaacetic acid (DTPA), (l,2-cyclokexylenedinitrilo)tetraacetic acid (CDTA), iminidiacetic acid, 2- pkospkonobutane-l,2,4-tricarboxylic acid (PBTCA), pkospkonic acid, 1,5,9-triazacyclododecane- N,N',N"-tris(metkylenepkospkonic acid) (DOTRP), l,4,7,10-tetraazacyclododecane-N,N',N",N"'- tetrakis(metkylenepkospkonic acid) (DOTP), nitrilotris(metkylene)tripkospkonic acid, dietkylenetriaminepenta(metkylenepkospkonic acid) (DETAP), aminotri(metkylenepkospkonic acid), l-kydroxyetkylidene-l,l-dipkospkonic acid (HEDP), bis(kexametkylene)triamine pkospkonic acid, l,4,7-triazacyclononane-N,N',N"-tris(metkylenepkospkonic acid (NOTP), etkylenediamine tetra(metkylene pkospkonic acid (EDTMP), salicylic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid and derivatives tkereof, and any combination tkereof.
12. Tke composition of any of claims 8-11, wkerein tke at least one oxidizing agent comprises a species selected from tke group consisting of ozone, nitric acid, bubbled air, cyclokexylaminosulfonic acid, kydrogen peroxide, FeCl3, oxone (2KHSO5 KHSO4 K2SO4), ammonium peroxomonosulfate, ammonium cklorite, ammonium cklorate, ammonium iodate, ammonium perborate, ammonium percklorate, ammonium periodate, ammonium persulfate, ammonium kypocklorite, sodium perborate, sodium persulfate, sodium kypocklorite, potassium iodate, potassium permanganate, potassium persulfate, potassium persulfate, potassium kypocklorite, tetrametkylammonium cklorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, N- methylmorpholine-N-oxide, trimethylamine-N-oxide, triethylamine-N-oxide, pyridine -N-oxide, N- ethylmorpholine-N-oxide, N-methylpyrrolidine-N-oxide, N-ethylpyrrolidine-N-oxide, urea hydrogen peroxide, peracetic acid, periodic acid, potassium dichromate, potassium chlorate, 2-nitrophenol, 1,4- benzoquinone, peroxybenzoic acid, peroxyphthalic acid salts, vanadium oxides, ammonium metavanadate, ammonium tungstate, sodium nitrate, potassium nitrate, ammonium nitrate, strontium nitrate, sulfuric acid, and combinations thereof.
13. The composition of any of claims 8-12, wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, NMMO, urea hydrogen peroxide, and combinations thereof.
14. The composition of any of claims 8-13, wherein the at least one solvating agent comprises a species selected from the group consisting of 2-pyrrolidinone, l-(2-hydroxyethyl)-2-pyrrolidinone, glycerol, 1 ,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n- butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof.
15. The composition of any of claims 8-14, wherein the at least one solvating agent comprises sulfolane, l-(2-hydroxyethyl)-2-pyrrolidinone, and combinations thereof.
16. The composition of any of claims 8-15, wherein the residue and contaminants comprise post- CMP residue and contaminants selected from the group consisting of particles from a CMP polishing slurry, chemicals present in the CMP polishing slurry, reaction by-products of the CMP polishing slurry, carbon-rich particles, polishing pad particles, copper, and copper oxides.
17. The composition of any of claims 8-16, further comprising post-CMP residue and contaminants.
18. A method of cleaning residue and contaminants from a microelectronic device having said residue and contaminants thereon, said method comprising contacting the microelectronic device with the composition of any of claims 8-17 for sufficient time to at least partially clean said residue and contaminants from the microelectronic device.
19. The method of claim 18, wherein said residue and contaminants comprise post-CMP residue and contaminants.
20. The method of claims 18 or 19, wherein said contacting comprises a condition selected from the group consisting of: time of from about 15 seconds to about 5 minutes; temperature in a range of from about 20°C to about 50°C; and combinations thereof.
PCT/US2015/057535 2014-10-31 2015-10-27 Non-amine post-cmp compositions and method of use WO2016069576A1 (en)

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Citations (5)

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US20130053291A1 (en) * 2011-08-22 2013-02-28 Atsushi Otake Composition for cleaning substrates post-chemical mechanical polishing
WO2013123317A1 (en) * 2012-02-15 2013-08-22 Advanced Technology Materials, Inc. Post-cmp removal using compositions and method of use
WO2013142250A1 (en) * 2012-03-18 2013-09-26 Advanced Technology Materials, Inc. Post-cmp formulation having improved barrier layer compatibility and cleaning performance
US20130296214A1 (en) * 2010-07-16 2013-11-07 Advanced Technology Materials, Inc. Aqueous cleaner for the removal of post-etch residues

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050126588A1 (en) * 2003-11-04 2005-06-16 Carter Melvin K. Chemical mechanical polishing slurries and cleaners containing salicylic acid as a corrosion inhibitor
US20130296214A1 (en) * 2010-07-16 2013-11-07 Advanced Technology Materials, Inc. Aqueous cleaner for the removal of post-etch residues
US20130053291A1 (en) * 2011-08-22 2013-02-28 Atsushi Otake Composition for cleaning substrates post-chemical mechanical polishing
WO2013123317A1 (en) * 2012-02-15 2013-08-22 Advanced Technology Materials, Inc. Post-cmp removal using compositions and method of use
WO2013142250A1 (en) * 2012-03-18 2013-09-26 Advanced Technology Materials, Inc. Post-cmp formulation having improved barrier layer compatibility and cleaning performance

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