KR20140082816A - Non-amine post-cmp composition and method of use - Google Patents

Abstract

A cleaning composition and method for cleaning such residues and contaminants from a microelectronic device on top of chemical mechanical polishing (CMP) -containers and contaminants is disclosed. The cleaning composition is substantially free of amine and ammonium-containing compounds, such as quaternary ammonium bases. This composition achieves highly effective cleaning of CMP-after-residue and contaminants from the surface of microelectronic devices without including low-k dielectric materials or copper interconnect materials.

Description

NON-AMINE POST-CMP COMPOSITION AND METHOD OF USE < RTI ID = 0.0 >

The present invention generally relates to compositions for cleaning them from microelectronic devices where residues and / or contaminants are on top.

Microelectronic device wafers are used to form integrated circuits. The microelectronic device wafer includes a substrate, e.g., silicon, and is patterned for deposition of different materials having insulating, conductive, or semi-conductive properties in this region.

To obtain the correct pattern, the excess material used to form the layer on the substrate must be removed. In addition, it is important to fabricate flat or planar microelectronic wafer surfaces before subsequent fabrication to fabricate functional reliable circuits. As such, it is necessary to remove and / or polish the specific surface of the microelectronic device wafer.

Chemical mechanical polishing or planarization ("CMP") is a process that removes material from the surface of a microelectronic device wafer and combines physical processes, such as abrasion, with chemical processes such as oxidation or chelation, (More specifically, planarization). In its most basic form, CMP involves applying a slurry, e.g., a solution of abrasive and active chemicals, to a polishing pad that buffers the surface of a microelectronic device wafer to achieve removal, planarization, and polishing processes. In order to achieve rapid and uniform removal in the removal or polishing process, the case of pure or pure chemical action is not preferable compared to the synergistic combination of the two. In the fabrication of integrated circuits, CMP slurries can also be used to preferentially remove films comprising a layer of metal and other materials to form a highly planar, flat surface for subsequent photolithography, So that the surface can be generated.

Recently, copper has been increasingly used for metal interconnects in integrated circuits. In a copper damascene process commonly used for metallization of circuits in microelectronic fabrication, the layer to be removed and planarized is a copper layer having a thickness of about 1 to 1.5 [mu] m, and a copper layer of about 0.05 to 0.15 [mu] m And a copper seed layer having a thickness. These copper layers are typically separated from the dielectric material surface by a layer of barrier material about 50-300 A thick, which prevents copper from diffusing into the oxide dielectric material. One solution to obtain good uniformity across the wafer surface after polishing is to use a CMP slurry with accurate removal selectivity for each material.

Prior processing operations, including wafer substrate surface preparation, deposition, plating, etching, and chemical-mechanical polishing, are commonly used to remove contaminants The cleaning operation is required. Often, the particles of these contaminants are smaller than less than 0.3 microns.

One particular problem in this regard is the residue remaining on the microelectronic device substrate after the CMP process. Such residues include CMP materials and corrosion inhibitor compounds such as benzotriazole (BTA). If not removed, these residues may cause damage to the copper wire or severely roughen the copper metal sheath, as well as result in poor adhesion of the CMP-applied layer on the device substrate. The severe roughness of copper metal sheathing is particularly problematic because excessively coarse copper can lead to poor electrical performance of microelectronic device products.

Another residue-generating process, which is common in microelectronic fabrication, involves gas-phase plasma etching that transfers a pattern of a developed photoresist coating to the underlying layer, which includes a hardmask, an interlevel dielectric (ILD) , And an etch stop layer. The gaseous plasma etch-after residue, which may include chemical elements present on the substrate and in the plasma gas, is typically deposited on a back end of the line structure and, if not removed, Can be prevented. Conventional cleaning chemicals often damage the ILD and are absorbed into the pores of the ILD to increase the dielectric constant and / or to corrode the metal structure.

The present invention generally relates to compositions and methods for cleaning such residues and / or contaminants from microelectronic devices with residues and contaminants on top. The cleaning composition of the present invention is substantially free of amine and ammonium species. The residue may comprise CMP-after, after-etch, and / or ash-after-residue.

In one embodiment, a cleaning composition is disclosed which comprises at least one basic salt, at least one organic solvent, at least one complexing agent, and water, wherein substantially no amine and ammonium-containing salts are present.

In another embodiment, a cleaning composition is described which consists essentially of at least one basic salt, at least one organic solvent, at least one complexing agent, and water, wherein substantially no amine and ammonium-containing salts are present .

In another embodiment, cleaning compositions comprising at least one basic salt, at least one organic solvent, at least one complexing agent, and water, wherein substantially no amine and ammonium-containing salt are present, are described.

Another aspect relates to a kit comprising one or more of the following reagents to form a cleansing composition in one or more containers, wherein the one or more reagents comprises at least one basic salt; At least one organic solvent; At least one chelating agent; And optionally at least one surfactant; Wherein the kit is configured to form a composition.

Another aspect relates to a method for removing residues and contaminants from a microelectronic device having residues and contaminants thereon, the method comprising at least partially cleaning the residues and contaminants from the microelectronic device Contacting the microelectronic device with the cleaning composition for a sufficient time, wherein the cleaning composition comprises at least one basic salt; At least one organic solvent; At least one chelating agent; Optionally at least one surfactant; And water.

Other aspects, features, and advantages will become more fully apparent from the ensuing disclosure and appended claims.

The present invention relates to compositions useful for removing such material (s) from microelectronic devices with residues and contaminants on top. Such compositions are particularly useful for removal of residues after CMP-, after-etching, and / or after sintering.

For ease of reference, "microelectronic devices" refer to semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and the like, all of which are fabricated for use in microelectronics, panel and other products such as substrates for solar cells, photovoltaics, and microelectromechanical systems (MEMS). Substrates for solar cells include, but are not limited to, silicon, amorphous silicon, multicrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. The substrate for solar cell may or may not be doped. The term "microelectronic device" is not meant to be limiting in any way, and should be understood to include any substrate that will ultimately be a microelectronic device or microelectronic assembly.

As used herein, "residue" refers to particles generated during fabrication of a microelectronic device, including, but not limited to, plasma etching, ashing, chemical mechanical polishing, wet etching, and combinations thereof.

As used herein, "contaminant" refers to a chemical present in a CMP slurry, a reaction by-product of a polishing slurry, a chemical present in the wet etching composition, a reaction by-product of the wet etch composition, and a CMP process, Corresponding to any other material that is a by-product of the plasma crystallization process.

As used herein, the term "post-CMP residue" refers to particles from a polishing slurry, such as silica-containing particles, chemicals present in the slurry, reaction by-products of the polishing slurry, carbon- Brushing deloading particles, constituent materials of constituent particles, copper, copper oxide, organic residues, and any other material that is a by-product of the CMP process.

As defined herein, a "low-k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, where such material has a dielectric constant of less than about 3.5. Preferably, low-k dielectric materials include low-polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorosilicate glass (FSG) Silicon dioxide, and carbon-doped oxide (CDO) glasses. It should be appreciated that low-k dielectric materials can have varying densities and varying porosity.

As defined herein, "complexing agents" include compounds known to those skilled in the art to be complexing agents, chelating agents and / or sequestering agents. The complexing agent will chemically combine or physically retain the metal atoms and / or metal ions that are removed using the compositions described herein.

As defined herein, the term "barrier material" is used in the art to minimize diffusion of the metal, e. G. Copper, into the dielectric material to seal the metal wire, e. G. It corresponds to any material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, tungsten, other refractory metals and their nitrides and silicides, and combinations thereof.

As defined herein, "post-etch residue" corresponds to a material that remains after a gas-phase plasma etch process, such as a BEOL dual damascene process, or a wet etch process. The post-etch residue can be naturally organic, organometallic, organosilicon, or inorganic and can be, for example, a silicon-containing material, a carbon-based organic material, and an etch gas residue such as oxygen and fluorine have.

As defined herein, "post-differentiation residue ", as used herein, refers to an oxidative or < RTI ID = 0.0 > Corresponding to the remaining material after the reductive plasma crystallization. The post-differentiation residues can be naturally organic, organometallic, organosilicon, or inorganic.

"Substantially non-existent" is defined as less than 2 wt%, preferably less than 1 wt%, more preferably less than 0.5 wt%, most preferably less than 0.1 wt%, based on the total weight of the composition .

As used herein, "about" is intended to correspond to +/- 5% of the stated value.

As used herein, "fitness" for cleaning residues and contaminants from microelectronic devices with residues and contaminants on top corresponds to removing at least a portion of the residue / contaminants from the microelectronic device . The cleaning efficacy is graded by the reduction of the object on the microelectronic device. For example, a cleaning analysis-transfer and a cleaning-after-analysis can be performed using an atomic force microscope. Particles on the sample can be recorded as a range of pixels. A histogram (e.g., Sigma Scan Pro) can be applied to filter out specific intensities, for example, 231-235 pixels, and the number of counted particles. The particle reduction can be calculated using the following equation: Cleaning efficacy = [(number of objects before cleaning - number of objects after cleaning) / number of objects before cleaning] × 100. In particular, methods for determining the cleaning efficacy are provided, for example, but not by way of limitation. Alternatively, the cleaning efficacy can be considered as a percentage of the total surface covered by the particulate material. For example, the AFM is programmed to perform a z-plane scan to identify a geographical area of interest higher than a certain height threshold, and then to calculate the total surface area covered by the area of interest. It will be readily apparent to one of ordinary skill in the art that the less area covered by the area of interest after cleaning, the more effective the cleaning composition is. Preferably, at least 75% of the residue / contaminant is removed from the microelectronic device using the composition described herein, more preferably at least 90%, even more preferably at least 95% of the residue / contaminant , And most preferably at least 99%.

The compositions described herein may be embodied in a variety of specific formulations, as will be described in greater detail below.

In all such compositions in which certain components of the composition are discussed with respect to a weight percent range including zero lower limits, such components may or may not be present in the various specific embodiments of the composition, and when such components are present, Lt; RTI ID = 0.0 > 0.001% < / RTI > by weight based on the total weight of the composition.

The cleaning composition comprises, consists of, consists essentially of, or consists essentially of, at least one basic salt, at least one organic solvent, at least one complexing agent, water, and optionally at least one surfactant do. Preferably the water is deionized. The cleaning composition is particularly useful for cleaning residues and contaminants, such as CMP-post-residues, post-etch residues, post-differentiation residues, and contaminants from microelectronic device structures.

In one embodiment, the cleaning composition comprises, consists essentially of, or consists essentially of at least one basic salt, at least one organic solvent, at least one complexing agent, and water. In another embodiment, the cleaning composition comprises, consists of, or consists of at least one basic salt, at least one organic solvent, at least one complexing agent, water, and at least one surfactant Lt; / RTI > In another embodiment, the cleaning composition comprises, consists essentially of, or consists essentially of at least one basic salt, at least one organic solvent, at least two complexing agents, and water.

Regardless of the embodiment, the cleaning composition is substantially free of amine and ammonium-containing salts, such as quaternary ammonium bases. Also, the composition before use, for example, the cleaning chemistry, preferably contains an oxidizing agent; A fluoride-containing source; Abrasive materials; Alkaline earth metal base; Crosslinked polymer particles; And combinations thereof, are substantially absent. Also, the cleaning composition should not be solidified to form a polymeric solid, e.g., a photoresist. For purposes of the present invention, an "amine" is a compound that is a mixture of at least one primary, secondary, or tertiary amine, ammonium, and / or a quaternary ammonium hydroxide compound (eg, ammonium hydroxide, alkylammonium hydroxide, (Ii) a species containing both a carboxylic acid group and an amine group, (iii) a surfactant containing an amine group, and (iv) a species in which the amine group is a substituent (e.g., For example, bonded to aryl and heterocyclic moieties, are not considered "amines" according to this definition. The amine formula is represented by NR ¹ R ² R ³ wherein R ¹ , R ² and R ³ may be the same or different and are selected from hydrogen, straight or branched C ₁ -C ₆ alkyl (eg, methyl, ethyl (For example, methyl, ethyl, propyl, butyl, pentyl, hexyl), C ₆ -C ₁₀ aryl (for example benzyl), straight or branched C ₁ -C ₆ alkanols , Hexanol), and combinations thereof, provided that R ¹ , R ² and R ³ can not all be hydrogen. The quaternary ammonium hydroxide compound has the general formula R ₁ R ₂ R ₃ R ₄ NOH wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and are selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl (E.g., methyl, ethyl, propyl, butyl, pentyl or hexyl), and substituted or unsubstituted C ₆ -C ₁₀ aryl groups (e.g., benzyl); And alkanolamines.

For purposes of the compositions and methods described herein, the at least one basic salt is selected from the group consisting of cesium hydroxide, rubidium hydroxide, potassium hydroxide, and combinations thereof, preferably cesium hydroxide and / or rubidium hydroxide, Cesium. Preferably, the at least one basic salt is formulated so that the composition described herein retains substantially its initial pH, even after several dilutions, for example, diluted pH = initial pH ± 2 pH units, more preferably Is selected such that diluted pH = initial pH +/- about 1 pH unit.

The at least one organic solvent is preferably a polyol, a sulfone, or a combination thereof wherein the polyol is selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, glycerin (also known as glycerol), diethylene glycol, dipropylene glycol , 1,4-butanediol, 2,3-butylene glycol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 3-methyl- A combination thereof, and the like. The sulfone may be at least one selected from the group consisting of tetramethylene sulfone (sulfolane), dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, methyl sulfolane, ethyl sulfolane, . Preferably, the at least one organic solvent comprises tetramethylene sulfone, glycerin, propylene glycol, ethylene glycol as a single solvent or any combination thereof. Most preferably, the at least one organic solvent is methylenesulfone.

The complexing agent may be selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid (CDTA), glycine, ascorbic acid, iminodiacetic acid But are not limited to, acetic acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, , Acrylic acid, adipic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutaric acid, glyceric acid, glycolic acid, glyoxylic acid, isophthalic acid, itaconic acid, lactic acid, Or a salt thereof with an organic acid such as malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phthalic acid, proline, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, sorbitol, succinic acid, tartaric acid, terephthalic acid, The N, N "-tris (methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane (Methylenephosphonic acid) (DOTP), nitrilotris (methylene) triphosphonic acid, diethylenetriamine penta (methylenephosphonic acid) (DETAP), aminotri (Methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), bis (hexamethylene) triaminephosphonic acid, 1,4,7-triazacyclononane- , N "-tris (methylenephosphonic acid) (NOTP), salts and derivatives thereof, and combinations thereof. Preferably, the at least one complexing agent comprises iminodiacetic acid, boric acid, gallic acid, HEDP as a single complexing agent or any combination thereof. Most preferably, the at least one complexing agent comprises a combination of boric acid, HEDP, or boric acid and HEDP.

Exemplary surfactants for use in the compositions described herein include, but are not limited to, amphipathic salts, cationic surfactants, anionic surfactants, fluoroalkyl surfactants, nonionic surfactants, and combinations thereof, But are not limited to, SURFONYL 104, TRITON CF-21, ZONYL TM UR, ZONYL FSO-100, ZONYL FSN, -100, 3M Fluorad fluorosurfactants (i.e. FC-4430 and FC-4432), dioctylsulfosuccinate salts, 2,3-dimercapto-1-propanesulfonate, dodecylbenzenesulfonate with acid, polyethylene glycol, polypropylene glycol, polyethylene or polypropylene glycol ethers, carboxylic acid salts, R ₁ benzene sulfonic acid or a salt thereof (wherein, R ₁ is straight-chain or branched-chain C ₈ -C ₁₈ alkyl group), amphiphilic fluoro Polymers, polyethylene glycols, polypropylene Recycled, polyethylene or polypropylene glycol ethers, carboxylic acid salts, dodecylbenzene sulfonic acid, polyacrylate polymers, dinonylphenyl polyoxyethylene, silicone or modified silicone polymers, acetylenic diols or modified acetylenic diols, alkylammonium or Modified alkyl ammonium salts as well as combinations comprising at least one of the foregoing surfactants, sodium dodecyl sulfate, zwitterionic surfactants, aerosol -OT (AOT) and fluorinated analogues thereof, alkyl Perfluoropolyether surfactants, 2-sulfosuccinate salts, phosphate-based surfactants, sulfur-based surfactants, and acetoacetate-based polymers. In one preferred embodiment, the surfactant comprises an alkyl benzene sulfonic acid, more preferably dodecyl benzene sulfonic acid.

The pH of the cleaning composition described herein is greater than 7, preferably in the range of from about 8 to about 14, more preferably in the range of from about 8 to about 13.

In one preferred embodiment, the cleaning composition comprises, consists essentially of, or consists essentially of at least one basic salt, at least one organic solvent, at least two complexing agents, and water. For example, the cleaning composition comprises, consists essentially of, or consists of CsOH, at least one organic solvent, at least two complexing agents, and water. In another embodiment, the cleaning composition comprises, consists essentially of, or consists of CsOH, sulfone, at least two complexing agents, and water. In another embodiment, the cleaning composition comprises, consists essentially of, or consists of CsOH, sulfone, phosphonic acid, and at least one additional complexing agent, and water.

In a particularly preferred embodiment, the cleaning composition comprises (a) cesium hydroxide, glycerin, iminodiacetic acid and water, (b) cesium hydroxide, glycerin, boric acid and water, (c) cesium hydroxide, propylene glycol, (E) cesium hydroxide, propylene glycol, boric acid, and water, and (f) cesium hydroxide, HEDP, tetramethylenesulfone, boric acid, and water, Or consist essentially of these. In each case, the composition includes an amine and an ammonium-containing salt such as a quaternary ammonium base; Oxidant; A fluoride-containing source; Abrasive materials; Alkaline earth metal base; And combinations thereof are substantially absent.

Examples of compositions described herein are selected from the group consisting of Formulations A through R.

Formulation A: 4.0 wt% CsOH (50%), 12 wt% ethylene glycol, 0.8 wt% IDA, 83.2 wt% water, pH concentrated = 12.22, pH diluted (30: 1) = 10.36

Formulation B: 7.1 wt% CsOH (50%), 5 wt% ethylene glycol, 1.6 wt% IDA, 86.3 wt% water, pH concentrated = 11.88, pH diluted (30: 1) = 10.27

Formulation C: 5.7 wt% CsOH (50%), 12 wt% ethylene glycol, 0.8 wt% IDA, 1 wt% ascorbic acid, 80.5 wt% water, pH concentrated = 11.41, pH diluted (30: 9.89

Formulation D: 9.1 wt% CsOH (50%), 12 wt% ethylene glycol, 1.6 wt% IDA, 1 wt% ascorbic acid, 76.3 wt% water, pH concentrated = 11.16, pH diluted (30: 10.1

Formulation E: 3.9 wt% CsOH (50%), 5.0 wt% glycerin, 0.8 wt% IDA, 90.3 wt% water, pH concentrated = 12.0, pH diluted (30: 1) = 10.16

Formulation F: 4.0% by weight CsOH (50%), 12.0% by weight glycerin, 0.8% by weight IDA, 83.2% by weight Water, pH concentrated = 11.1, pH diluted (30:

Formulation G: 7.1% by weight CsOH (50%), 5.0% by weight glycerin, 1.6% by weight IDA, 86.3% by weight water, pH concentrated = 11.5, pH diluted (30:

Formulation H: 5.7 wt% CsOH (50%), 12.0 wt% glycerin, 0.8 wt% IDA, 1.0 wt% ascorbic acid, 80.5 wt% water, pH concentrated = 10.8, pH diluted (30: 1) = 9.61

Formulation I: 8.8 wt% CsOH (50%), 5.0 wt% glycerin, 1.6 wt% IDA, 1.0 wt% ascorbic acid, 83.6 wt% water, pH concentrated = 12.3, pH diluted (30:

Formulation J: 7.4 wt% CsOH (50%), 12.0 wt% glycerin, 1.6 wt% IDA, 79.0 wt% water, pH concentrated = 10.7, pH diluted (30: 1) = 9.81

Preparation K: 6.3 wt% CsOH (50%), 4.8 wt% Propylene glycol, 2 wt% Glycine, 86.9 wt% Water, pH Concentrated = 9.71

Formulation L: 6.6 wt% CsOH (50%), 10 wt% propylene glycol, 2 wt% gallic acid, 81.4 wt% water, pH concentrated = 10.32

Formulation M: 15.7 wt% CsOH (50%), 4.8 wt% propylene glycol, 5 wt% gallic acid, 74.5 wt% water, pH concentrated = 10.14

Formulation N: 16.2 wt% CsOH (50%), 4.8 wt% propylene glycol, 5 wt% gallic acid, 1 wt% ascorbic acid, 73 wt% water, pH concentrated = 9.28

Formulation O: 2.1 wt% CsOH (50%), 8.5 wt% glycerin, 0.4 wt% iminodiacetic acid, 89.0 wt% water

Formulation P: 2.5 wt% CsOH (50%), 12 wt% ethylene glycol, 0.6 wt% iminodiacetic acid, 84.9 wt% water

Formulation Q: 4 wt% CsOH (50%), 12 wt% glycerin, 3.3 wt% boric acid, 80.7 wt% water, pH concentrated = 7.17, pH diluted (100:

Formulation R: 4 wt% CsOH (50%), 4.8 wt% propylene glycol, 3.3 wt% boric acid, 87.9 wt% water, pH concentrated = 8.4, pH diluted (100:

Preparation S: 3 wt% CsOH, 1.2 wt% HEDP, 9 wt% tetramethylene sulfone, 0.25 wt% boric acid, 86.55 wt% water

The concentrations of the components in the concentrate are preferably as follows:

With respect to the amount of composition, the weight percentages of each component are preferably: from about 0.1: 1 to about 10: 1 basic salt complexing agent, preferably from about 0.5: 1 to about 4: 1, Most preferably from about 1: 1 to about 3: 1; And from about 0.1: 1 to about 25: 1, and preferably from about 1: 1 to about 20: 1, and most preferably from about 2: 1 to about 15: 1.

The range of weight percentages of the components will cover all possible enriched or diluted embodiments of the composition. Finally, in one embodiment, there is provided a concentrated cleaning composition which can be diluted for use as a cleaning composition. The concentrated composition, or "concentrate" advantageously allows a user, e.g., a CMP process engineer, to dilute the concentrate to the desired strength and pH at the point of use. Dilution of the concentrated cleaning composition may range from about 1: 1 to about 2500: 1, preferably from about 5: 1 to about 1500: 1, and most preferably from about 10: 1 to about 1000: 1, The cleaning composition is diluted with a solvent, for example, deionized water, just before entering the equipment or equipment. It will be understood by one of ordinary skill in the art that the range of weight percent relative to another component of a given ingredient after dilution should be maintained unchanged.

The compositions described herein may have utility in the field of application, including, but not limited to, post-etch residue removal, residue post-differentiation removal surface preparation, post-plating cleaning, and post-CMP residue removal.

In yet another preferred embodiment, the cleaning composition described herein further comprises residues and / or contaminants. Significantly, residues and contaminants can be dissolved and / or suspended in the composition. Preferably, the residue comprises CMP-after-residue, post-etch residue, post-differentiation residue, contaminant, or a combination thereof. For example, the cleaning composition may comprise at least one basic salt, at least one organic solvent, at least one complexing agent, water, optionally at least one surfactant, and residuals and / or contaminants , Or may consist essentially of these.

The cleaning composition can be easily formulated by simply adding the individual components and mixing to homogeneous conditions. In addition, the compositions may be readily formulated as single-packaged formulations, or as multi-part formulations to be mixed at the time of use or prior to use, for example, individual portions of the multi-part formulation may be mixed in the equipment, Lt; RTI ID = 0.0 > upstream < / RTI > The concentration of the individual components can vary widely, i.e., to be more diluted or more concentrated, and the compositions described herein can be variously and alternatively, any combination of the components consistent with the disclosure herein Or may consist essentially of, < RTI ID = 0.0 > and / or < / RTI >

Accordingly, another aspect relates to a kit comprising one or more ingredients in one or more containers adapted to form the compositions described herein. The kits may comprise at least one basic salt, at least one organic solvent, at least one complexing agent, optionally at least one surfactant, and optionally water, in one or more containers, And may be included to combine with additional water. The container of the kit may be adapted to store and ship the removal composition and may include, for example, a NOWPak (R) container (Advanced Technology Materials, Inc., Danbury, Connecticut, USA].

The one or more vessels comprising the components of the stripping composition preferably comprise means for fluid communication of the components in the one or more vessels for blending and dispensing. For example, in a NOWPAC (registered trade mark) container, gas pressure is applied to a liner in the one or more containers to cause at least a portion of the contents of the liner to be released, thereby providing fluid communication for blending and dispensing . Alternatively, the gas pressure may be applied to the head space of a conventional pressurized vessel, or a pump may be used to enable fluid communication. In addition, such a system preferably includes a dispensing port for dispensing the blended removal composition to process equipment.

A substantially chemically inert, impurity-free, soluble and resilient polymeric film material, such as high density polyethylene, is used to make the liner for the one or more containers. Preferred liner materials are processed without any pigments, UV inhibitors, or processing agents that may have a detrimental effect on the purity requirements for the components located in the liner without requiring a coextrusion or barrier layer. A preferred list of liner materials includes virgin (additive-free) polyethylene, virgin polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacetal, polystyrene, Rhenitrile, polybutylene, and the like. The preferred thickness of such a liner material is in the range of about 5 mils (0.005 inches) to about 30 mils (0.030 inches) and is, for example, 20 mils (0.020 inches) thick.

With regard to containers for kits, the disclosures of the following patents and patent applications are incorporated herein by reference in their entirety: "APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF " US Patent No. 7,188,644 entitled " PARTICLES IN ULTRAPURE LIQUIDS "; U. S. Patent No. 6,698, 619 entitled " RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM " &Quot; SYSTEM AND METHODS FOR MATERIAL BLENDING & DISTRIBUTION "filed on May 9, 2007, U.S. Patent Application No. 60 / 916,966 to John E. Q. Hughes; PCT / US08 / 63276, filed on May 9, 2008, entitled " SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION ".

When applied to microelectronic manufacturing operations, the cleaning compositions described herein are usefully used to clean residues (e.g., CMP-after-residues) and / or contaminants from the surface of a microelectronic device. Importantly, the cleaning composition does not damage the low-k dielectric material or corrode the metal interconnects on the device surface. Moreover, the cleaning composition does not easily remove silicon or silicon material. Preferably, the cleaning composition removes at least 85%, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99% of the residues present on the device prior to removal of the residue.

In the field of CMP-post-residue and contaminant cleaning, the cleaning composition can be applied to a wide variety of conventional cleaning equipment, such as megasonics and brush scrubbing, including but not limited to VERTEC single wafer megasonic gold fingers Verteq single wafer megasonic Goldfinger, OnTrak systems DDS, SEZ or other single wafer spray cleaning, Applied Materials Mirra-Mesa (trademark) / Reflexion Reflexion: registered trademark) / Reflexion LK (registered trademark) and megasonic batch batch wet bench systems.

In using the compositions described herein to clean them from CMP-post-residue, post-etch residue, post-distillation residue and / or contaminant microelectronic devices on top, the cleaning composition typically comprises about Deg.] C to about 90 [deg.] C, preferably from about 20 [deg.] C to about 50 [deg.] C for a time of from about 5 seconds to about 10 minutes, preferably from about 1 second to about 20 minutes, Lt; RTI ID = 0.0 > temperature. Such contact times and temperatures are exemplary and any other suitable time and temperature conditions effective to at least partially clean the CMP-residue / contaminants from the apparatus within a wide range of implementations of the method may be employed. At least partially cleaned "and" substantial removal "both require at least 85%, more preferably at least 90%, even more preferably at least 95%, most preferably at least 99% of the residues present in the device prior to residue removal. % ≪ / RTI >

After achieving the desired cleaning action, the cleaning composition can be easily removed from previously applied equipment if desired and effective at the desired end use application of the compositions described herein. Preferably, the cleaning solution comprises deionized water. The apparatus can then be dried using a nitrogen or spin-dry cycle.

Advantages of the compositions and methods of the present invention include, but are not limited to, substantial removal of particles from the surface, substantial removal of organic and metallic residues from the surface, immobilized metals, e.g., copper surfaces, Low-k dielectric, and low metal surface roughness. In addition, the composition is preferably environmentally friendly.

Yet another aspect relates to an improved microelectronic device made according to the methods described herein, and to an article of manufacture comprising such a microelectronic device.

Another aspect relates to a regenerative cleaning composition, wherein the cleaning composition can be applied to the cleaning composition until the residue and / or contaminant load reaches the maximum amount that the cleaning composition can accommodate, as readily determined by those skilled in the art Can be reproduced.

A further aspect relates to a method of fabricating a product comprising a microelectronic device, the method comprising the steps of: providing a microelectronic device for a period of time sufficient to clean residues and contaminants from the microelectronic device Contacting the cleaning composition with a cleaning composition; And incorporating the microelectronic device into the article using the cleaning composition described herein.

In another aspect, a method is disclosed for removing CMP-after-residue and contaminants from a microelectronic device thereon, the method comprising: polishing the microelectronic device with a CMP slurry; At least one basic salt, at least one organic solvent, at least one complexing agent, optionally at least one surfactant, and at least one surfactant for a period of time sufficient to remove CMP- Contacting the microelectronic device with a cleaning composition comprising, consisting essentially of, or consisting essentially of water to form a CMP-after-residue-containing composition; And continuously contacting the microelectronic device with the residue-containing composition after CMP for a period of time sufficient to effect substantial cleaning of the microelectronic device, wherein the cleaning composition comprises an amine and an ammonium- For, quaternary ammonium base; Oxidant; A fluoride-containing source; Abrasive materials; Alkaline earth metal base; And combinations thereof are substantially absent.

Another aspect relates to an article of manufacture comprising a cleaning composition, a microelectronic device wafer, and a material selected from the group consisting of residues, contaminants, and combinations thereof, wherein the cleaning composition comprises at least one basic salt, at least one At least one complexing agent, optionally at least one surfactant, and water, wherein the remainder comprises at least one of CMP-post-residue, post-etch-residue, and post-sintering- One.

While the present invention has been variously described herein with reference to exemplary embodiments and features, it is to be understood that the above-described embodiments and features are not intended to limit the invention, and other variations, modifications, and other embodiments may be made without departing from the teachings of the present disclosure And will be proposed to those skilled in the art per se. Accordingly, the invention should be broadly construed as embracing all such variations, modifications and alternative embodiments within the spirit and scope of the appended claims.

Claims (20)

1. A cleaning composition comprising at least one basic salt, at least one organic solvent, at least one complexing agent, and water, wherein the amine and the ammonium-containing salt are substantially absent. The method according to claim 1,
Wherein the at least one basic salt comprises a species selected from the group consisting of cesium hydroxide, rubidium hydroxide, potassium hydroxide, and combinations thereof. The method according to claim 1,
Wherein the at least one basic salt comprises cesium hydroxide. 4. The method according to any one of claims 1 to 3,
Wherein the at least one organic solvent comprises glycol, sulfone, or combinations thereof. 5. The method of claim 4,
Wherein the at least one organic solvent is selected from the group consisting of ethylene glycol, propylene glycol, neopentyl glycol, glycerin, diethylene glycol, dipropylene glycol, 1,4-butanediol, 2,3-butylene glycol, (2-hydroxyethyl) sulfone, methylsulfolane (methylsulfolane), diethylsulfone, diethylsulfone, diethylsulfone, , Ethylsulfolane, and combinations thereof. ≪ Desc / Clms Page number 13 > 5. The method of claim 4,
Wherein the at least one organic solvent comprises a species selected from the group consisting of ethylene glycol, propylene glycol, glycerin, tetramethylene sulfone, and combinations thereof. 7. The method according to any one of claims 1 to 6,
At least one complexing agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid (CDTA), glycine, ascorbic acid, iminodiacetic acid (IDA) But are not limited to, nitrilotriacetic acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, But are not limited to, acetone oxime, acrylic acid, adipic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutaric acid, glyceric acid, glycolic acid, glyoxylic acid, isophthalic acid, Examples of the acid addition salts include salts of organic acids such as acetic acid, anhydrous maleic acid, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phthalic acid, proline, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, sorbitol, succinic acid, , N, N ', N''- tris (methylenephosphonic acid) (DOTRP), 1,4,7,10-tetramethylcyclohexanecarboxylic acid, (DOTP), nitrilotris (methylene) triphosphonic acid, diethylenetriamine penta (methylenephosphonic acid) (methylenephosphonic acid) DETAP), aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), bis (hexamethylene) triaminephosphonic acid, 1,4,7-triazacyclononane Wherein the cleaning composition comprises species selected from the group consisting of N, N ', N "-trismethylene phosphonic acid (NOTP), salts and derivatives thereof, and combinations thereof. 8. The method of claim 7,
Wherein the at least one complexing agent comprises iminodiacetic acid (IDA), gallic acid, boric acid, HEDP, or a combination thereof. 9. The method according to any one of claims 1 to 8,
Oxidant; A fluoride-containing source; Abrasive materials; Alkaline earth metal base; Crosslinked organic polymer particles; ≪ / RTI > and combinations thereof. The method according to claim 1,
(b) cesium hydroxide, glycerin, boric acid and water; (c) cesium hydroxide, propylene glycol, gallic acid and water, (c) cesium hydroxide, ethylene glycol, Wherein the cleaning composition is selected from the group consisting of acetic acid and water, (e) cesium hydroxide, propylene glycol, boric acid, and water, and (f) cesium hydroxide, HEDP, tetramethylene sulfone, boric acid, and water. 11. The method according to any one of claims 1 to 10,
Residuals and contaminants, wherein the residue is removed after chemical-mechanical polishing or planarization ("CMP"), after residue after etching, after residue after recrystallization, or And combinations thereof. 12. The method according to any one of claims 1 to 11,
Wherein the cleaning composition is diluted to a range of about 10: 1 to about 1000: 1. 13. The method according to any one of claims 1 to 12,
And is not solidified to form polymer solids. 14. The method according to any one of claims 1 to 13,
A cleaning composition further comprising at least one surfactant. 15. The method according to any one of claims 1 to 14,
wherein the pH is in the range of about 8 to about 14. In one or more containers, one or more basic salts; At least one organic solvent; One or more chelating agents; And optionally at least one reagent for forming a cleaning composition selected from the group consisting of at least one surfactant, and is configured to form the composition of any one of claims 1 to 15. Contacting the microelectronic device with the cleaning composition according to any one of claims 1 to 15 for a time sufficient to at least partially clean the residue and contaminants from the microelectronic device at the top with residues and contaminants A method for removing such residues and contaminants from a microelectronic device in which the residue and contaminants are in the upper portion. 18. The method of claim 17,
Wherein the residue comprises a CMP-after residue, an after-etch residue, a post-sinter residue, or a combination thereof. The method according to claim 17 or 18,
Wherein the contacting step comprises a time selected from the group consisting of a time of from about 15 seconds to about 5 minutes, a temperature in the range of from about 20 DEG C to about 50 DEG C, and combinations thereof. The method according to any one of claims 17 to 19,
Further comprising diluting the cleaning composition with a solvent at the point of use or prior to the point of use.