TW200934865A - Formulations for cleaning memory device structures - Google Patents

Abstract

A removal composition and process for removing polymeric protective coating(s) from a microelectronic device having said coatings thereon. The removal composition removes the polymeric protective coating(s) from the device in a single step without substantially removing underlying layers.

Description

200934865 IX. Description of the invention: - [Technical field to which the invention pertains] The present invention relates to the removal of such photoresist layers from microelectronic devices having a photoresist layer thereon, such as devices including microelectromechanical systems (MEMS) Composition 0 [Prior Art] A thin (l〇〇_nm to 3〇〇_nm) tantalum nitride or hafnium oxide coating is usually used as a mask for pattern etching or as a mask on a substrate during a germanium etching process. The passivation layer seals the active circuit. The tantalum nitride film has been used as a protective layer or a hard mask during the 艮011 or Dinghe 11 矽 etch because of the lower etch rate compared to ruthenium. Undesirably, the nitrite needs a bismuth deposition temperature and is susceptible to damage during the remainder process. Cerium oxide has an etch rate higher than that of tantalum nitride, so it is only used as a protective/masking layer for very short etching. An ideal candidate for organic polymer based protective coatings. Polymer and coating materials have been used in the IC and MEMS industries for many years as photoresists, anti-reflective coatings, and flat layers. The materials are conveniently coated in a film form by a spin coating process and then baked or UV cured to achieve the final coating form. Disadvantageously, non-patterned, hard baked photoresists are easily etched in an alkaline solution. Polymethyl methacrylate was also evaluated as an etch mask for KOH, however, due to the saponification reaction of the ester group, the masking time of this polymer was found to be sharply reduced from 165 minutes at (10) to 15 minutes at rCT (15 minutes). Black wax (Apiez〇n® w, available from Scientific Instrument Services, Inc., New Jersey) was also used as a protective coating in the 3 wt% κ〇Η silver engraving process (70 ° C). 136561.doc 200934865 After engraving, the wax is removed using the well-known carcinogen triethylene glycol. A spin-on protective coating comprising an organic polymer has been proposed and some protective coatings have been found to be largely associated with known nitrogen. The same manner of chemically protecting the tantalum material effectively protects the tantalum material from the alkaline wet etching composition. However, there is still a problem in the removal of the protective coating such as Hi. The removal process preferably does not damage such as metal and tantalum. A single step process for the underlying layer. In addition, the removal process - preferably adheres to worldwide environmental standards and has a low cost of ownership (C00). 最佳 Optimally, the removal process includes enabling the user to process the microelectronic device in batches. Sa is a circular wet etching composition that does not substantially deposit/precipitate the removed material on the surface of the device wafer. Therefore, a significant advancement in the art is to provide microelectronics having a polymeric protective coating from above in a single step. An improved liquid composition for removing the coating material from the surface of the device wafer. SUMMARY OF THE INVENTION The present invention generally relates to the removal of the polymeric protective coating from the surface of a microelectronic device having a polymeric protective coating thereon. Liquid composition. The liquid removal composition comprises, consists of, or consists essentially of at least one organic solvent and at least one etchant source. In one aspect, the invention relates to a A removal composition comprising at least one organic solvent and at least one etchant source, wherein the removal composition is adapted to remove the material from a microelectronic device having a polymeric material thereon. In another aspect, the invention A removal composition consisting of two organic solvents and at least one etchant source, wherein the removal composition is suitable for having a polymeric material from above The material is removed from the microelectronic device. 136561.doc 200934865 In another aspect, the present invention is directed to a removal composition consisting of two organic solvents, a source of rice cooker, and a residue of polymeric material. Wherein the removal composition is adapted to remove the material from a microelectronic device having a polymeric material thereon. A further aspect of the invention relates to a method of removing the material from a microelectronic device having a polymeric material thereon, The method includes contacting the microelectronic device with the removal composition for a time sufficient to at least partially remove the material from the microelectronic device, sufficient to remove the material from the microelectronic device until the device is removed. The material includes at least one organic solvent and at least one etchant source. Another aspect of the invention relates to a removal composition consisting of a diethylene glycol monoalkyl ether, a cyclobutane, and an alkanolamine:HF complex, wherein the alkyl group is a fluorene-C6 group, and Wherein the removal composition is adapted to remove the material from a microelectronic device having a polymeric material thereon. Other aspects, features, and advantages of the present invention will be more fully apparent from the appended claims. [Embodiment] The present invention generally relates to liquid removal compositions for removing such materials from microelectronic devices having polymeric materials such as spin-on protective coatings thereon. For ease of reference, "Microelectronics" corresponds to semiconductor substrates, memory devices, flat panel displays, solar cells and photovoltaic cells, and MEMS manufactured for use in microelectronics, integrated circuits and computer wafer applications. (MEMS). It should 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 136561.doc 200934865. • As used herein, "about" Corresponding to ± 5% of the value. As used herein, "suitable" for removing the materials from the microelectronic device having the polymeric material thereon corresponds to at least partial removal of the materials from the microelectronic device. Preferably, at least 85% of the material to be removed is removed from the microelectronic device using the composition of the invention, more preferably at least 9%, even more preferably at least 95%, and optimally at least 99% Remove material. As defined herein, substantially no " corresponds to less than about 2% by weight, more preferably less than 1 weight, based on the total weight of the composition. /. And preferably less than (M% by weight of the composition. As described more fully below, the compositions of the present invention may be included in a variety of specific formulations. In all such compositions, where the particular component of the composition is Reference is made to the range of weight percentages including the lower limit of zero, it being understood that the components may or may not be present in various specific embodiments of the composition, and in the presence of such φ group injuries, they may be employed The total weight of the composition is present at a concentration as low as 0.001 wt/〇. In one aspect, the invention relates to liquid migration suitable for selective removal of polymeric materials (eg, spin-on protective coatings) from semiconductor devices. In addition to compositions. Recently, effective spin-on protective coatings have been developed to protect the underlying layer from alkaline etching compositions and/or to clean sealed active circuits, for example, as claimed by chenghong Li et al., June 30, 2006. U.S. Patent Application Serial No. 11/428,123, entitled ''Spin-On Protective Coatings for Wet-Etch Processing of Microelectronic Substrates" and to xing_Fu Zh〇ng et al. 136,561. U.S. Patent Application Serial No. 11/470,520, filed on Sep. 6, 2006, entitled, "Negative Photoresist for Silicon KOH Etch Without Silicon Nitride", both incorporated by reference in its entirety. A spin coating protective coating system comprising a surface coated on a microelectronic substrate

An undercoat layer and a photosensitive layer coated on the undercoat layer. The undercoat layer may include decane dispersed or dissolved in a solvent system. The decane may be selected from the group consisting of amino alkoxy decane, aminoalkyl alkoxy decane, anilinoalkyl alkoxy decane, phenyl decane, diphenyl decane, [aniline Alkyl] propyltrimethoxydecane, N-[3-trimethoxyoxyalkyl]propylethylenediamine, and combinations thereof. More specifically, the decane may include a substance selected from the group consisting of aminopropyltrimethoxydecane, aminopropyltriethoxy oxime, N-anilinopropyltrimethoxyxanthene , N-anilinopropyl triethoxy oxane 3 glycidoxypropyl trimethoxy decane, 2 - (3, 4-epoxycyclohexyl) ethyl dimethoxy decane, 3 - benzyl propyl -trimethoxydecane, phenyl: methoxy decane, phenyl trioxane, phenyl triethoxy decane, phenyl triethoxy hydrazine, diphenyl decyloxy (tetra), diphenyl bis气石夕,, diphenyl hydroxy diol 2 · phenylethyl trisaloxy I, p / m - gas: dimethoxy decane, p / m - bromophenyl trimethoxy decane, (pair / _ =) dikis trimethoxy ketone, 2 methoxy) phenylethyl tridecyl decane, 2- (p / m _ gas a 34-m-1 methyl) benzyl Trimethoxy decane, 3,4-monopropenyl trioxane, 3_ valerite and one oxypropyl dioxane, 3-(N-anilino)propyldimethoxy money, alkane, 3-[N-aniline propylidene = soil) ethyl diethoxy bismuth dimethoxy Xi burning stone, Ν_ [3 · Xi-trimethoxyphenyl cornerstone alkoxy 136561.doc • 10- 200934865 yl] ethylenediamine, and combinations thereof. The undercoat layer is applied to coagulate the decane molecules into a continuous film on the microelectronic substrate. The photosensitive layer is formed of a polymer dispersed or dissolved in a solvent system and a photoacid generator (PAG), wherein the polymer comprises a terpolymer selected from the group consisting of styrene polymer 'acrylonitrile single And a monomer comprising a functional group reactive with an amine. The monomer containing a functional group reactive with an amine includes a monomer containing one or more epoxy groups such as f-based glycidyl acrylate, glycidyl acrylate, and vinyl benzoyl epoxypropyl ether. The photosensitive layer is coated so that the photosensitive layer polymer forms a covalent bond with the amine or other reactive group of the base coating. After coating, the photosensitive layer is exposed to ultraviolet light which causes the PAG to produce an acid which initiates cross-linking of the polymer in the photosensitive layer (preferably via an epoxy group). In another aspect, the liquid removal composition of the present invention comprises, consists of, or consists essentially of at least one I-spot source and at least one organic solvent, wherein the combination Suitable for removing the polymeric coating material from a microelectronic device having a polymeric coating material thereon

In the broad practice of the present invention, the liquid removal composition of the present invention may comprise, consist of, or consist essentially of (1) at least one source of scenting agent and at least one organic solvent;丨) at least one source of fluoride and at least one organic solvent; (iii) at least one source of residual agent, at least one organic solvent and a residue of polymeric coating material; or (iv) at least one source of fluoride, at least one organic Solvent and polymeric coating material residues. In each case, the liquid removal composition preferably has substantially no added water. As defined herein, the polymeric coating material residue may comprise a coating and/or a photosensitive layer of the above-described bottom 136561.doc -11.200934865, wherein the polymeric coating material residue is suspended and/or dissolved in the liquid removal composition. . In addition, the polymeric coating material residue (whether dissolved and/or suspended) may be substantially polymeric or monomeric, wherein the monomer comprises the above-described decane, acrylonitrile monomer and a monomer comprising a functional group reactive with an amine. At least one of them. "Additional Water" as defined herein corresponds to water added by a user or producer of the composition of the present invention. The added water does not correspond to water or wet water that is commonly found in commercial chemicals that are mixed together to form the compositions of the present invention. The liquid removal composition comprises, consists of, or consists essentially of the following in the range of the total weight of the composition: at least one organic solvent and at least one etchant source:

Preferably, the '% by weight of organic solvent and etchant is in the range of from about 5: Torr to about 15: 1', preferably from about 7:1 to about 13:1 and most preferably from about 9:1 to about 12.5:1 〇 Importantly, all compositions are effective in removing polymeric materials from microelectronic devices (eg, spin-on polymeric protective coatings while coexisting with underlying layers (eg, metal and tantalum). The remainder of the intended use includes fluorides, Fluoride includes, but is not limited to, hydrogen peroxide (Hf), bismuth (xep2), fluorocrate (H2SlF6), fluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF4), fluoroantimonic acid Money ((NHASiF6), tetradecylammonium hexafluorophosphate, ammonium fluoride (NH4F), fluorine 136561.doc 200934865 tetraalkylammonium (NR4F), alkyl hydrogen fluoride (NRh3F), ammonium difluoride (NH5F2), Dialkylammonium hydrogen 'fluoride (NR2H2F), triaikyiammonium hydrogen flU0ride (NR3HF), trialkylammonium trihydrogen fluoride (NR3:3HF), Anhydrous hydrogen fluoride pyridine complex, anhydrous hydrogen fluoride triethylamine complex, amine: hydrogen fluoride complex and combinations thereof Wherein the ruths may be the same or different from each other and are selected from the group consisting of linear or branched qC:6 alkyl groups (eg, decyl, ethyl, propyl, butyl, pentyl, hexyl), and wherein the amine includes straight a chain or branched alkylamine, a substituted or unsubstituted c6_c(7) arylamine, a glycolamine, an alkanolamine, and an amine-N-oxide, including but not limited to: pyridine, 2-ethylpyridine , 2-methoxypyridine and its derivatives (such as 3 • decyloxypyridine), 2-indenyl bite ratio bite derivative, diterpene ratio bite, 〇辰 bite, 〇辰嗓, 三乙Amine, triethanolamine, ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine, tridecylamine, diglycolamine, monoethanolamine, triethanolamine, hydrazine 15 ethyl ethylethanolamine, N _Methylaminoethanol, Aminoethoxyethanol, Diamyl Ethoxyethanol, Diethanolamine, N-Mercaptodiethanolamine, 1-Amino-2-propanol, Isobutanol Face, # &amp Diethylethylene diamine, ° ratio 0, different P odor, 1,2,4 life, bite, chlorpyrifo, pyrazine, chlorpyrifos, quinoline, isoquinoline, 吲0 wood, imidazole, N-methylmorpholine_N_oxygen Compound (NMM〇), trimethylamine-N-oxide, diethylamine_N_oxide, 唆N_oxide, n-ethyl 淋N_oxide, N-methyl hydrazine bite- N-oxide, N-ethyl lysine, N-oxidation, 4, 1 methylhydrazone, diisopropylamine, diisobutylamine, aniline aniline, and combinations thereof. Preferably, the money engraving agent contains Nitrogen burning 136561.doc •13· m 200934865 Alcoholamine, such as triethanolamine: HF. Solvents suitable for use in the compositions of the present invention may be substantially non-polar or polar. Illustrative non-polar substances include, but are not limited to, toluene, decane, hexane (hexane, hexanes), xenon, di, benzene, odorless mineral spirits (petroleum), mineral spirits (hydrotreated heavy stones) Brain oil), phenoxy-2-propanol, ketone (pr〇Pri〇Phenone), cyclohexane, perfluoro], 2_dimethylcyclobutane,

Perfluoro-1,2-dimethylcyclohexane and perfluorohexane. Illustrative polar solvents include (but are not limited to): sterols, ethanol, ! _propanol, isopropanol, butanol, 2 · butanol, 3-methyl-1-butanol, allyl alcohol and higher alcohols (including glycols, triols, etc.), 2, 2, 3 ,3,4,4,5,5-octafluoro-1_pentanol, 1H,1H,9H_ perfluoro behenol, perfluoroheptanoic acid, 1H, 1H, 7H-dodecyl-1·heptanol, all Fluoric acid, 111,111,81811_dodecyl-1,8-octanediol, 2,2,3,3,4,4,5,5-octafluoro 1,6-hexanediol, 5H- Perfluoropentanoic acid, n-butyl heptafluorobutyrate, halohydrin (such as 3-gas-1,2-propanediol, 3-gas-1-propanethiol, 1-hydrogen-2-propanol, 2-gas _ι_ propanol, 3-a-1-1-propanol, 3-bromo-1,2-propanediol, bromo-indolyl alcohol, indole bromo-1-propanol, 3-iodo-1-propanol, 4- Gas-1-butanol, 2-gas ethanol), tetrahydrofuran (THF), N-methylpyrrolidone (nmp), N-octylpyrrolidone, N-phenylpyrrolidone, methyl decanoate, Ethyl citrate, propyl formate, butyl formate, 2-butanone, 3-pentanone, dimethyl decylamine (Dmf), diterpene (DMSO), formazan, ethanethiol, ring Tetramethylene sulfone, sulfolane, dimethylhydrazine, diethyl hydrazine, bis(2-hydroxyethyl) sulfone, decyl sulfolane, B Base ring, ethyl ether, ethyl lactate, ethyl acetate, propyl acetate, isobutyl acetate, decyl butyrate, ethyl butyrate, ethyl benzoate, acetonitrile, mercaptoisobutyl ketone, sulfhydryl Ethyl ketone, mercaptopropyl ketone, acetone, B 136561.doc -14· 200934865 diol, propylene glycol, amphiphilic substances (for example, diethylene glycol monodecyl 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 (ie, butyl card) Alcohol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol oxime ether, dipropylene glycol methyl ether, tripropylene glycol oxime ether, two Propylene glycol dioxime ether, dipropylene glycol ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol, propylene glycol, n-butylene glycol, n-propylene glycol, n-butylene glycol, n-propanediol n-butyl ether, propylene glycol phenyl ether ), dioxane, butyrolactone, butylene carbonate, ethylene carbonate, propylene carbonate, and combinations thereof. Preferably, the solvent comprises diethylene glycol monobutyl ether, sulfolane, and combinations thereof. In various preferred embodiments, the compositions of the present invention are formulated from the following formulation AF, wherein all percentages are by weight based on the total weight of the formulation: Formulation A: 70% by weight of diethylene glycol monobutyl ether 20% by weight of sulfolane, 10% by weight of triethanolamine: HF (with 73% by weight of 27% by weight) Formulation B: 80% by weight / 〇 diethylene glycol monomethyl ether, 20% by weight of triethanolamine: HF (73 %) Formulation C: 70% by weight. / 〇 diethylene glycol monomethyl ether, 20% by weight of cyclobutyl hydrazine, 10% by weight of triethanolamine: HF (73%) Formulation D: 80% by weight of sulfolane, 20% by weight of triethanolamine: HF (73 ° / 〇 Formulation E: 80% by weight NMP, 20% by weight triethanolamine: HF (73%) Formulation F: 80% by weight DMSO, 20% by weight triethanolamine: HF (73%) In a preferred embodiment, The inventive removal composition comprises, consist of, or consists essentially of: 136561.doc -15-200934865: diethylene glycol monoalkyl ether, sulfolane and alkanolamine: HF, wherein The alkyl group is a C _C6 group (for example, methyl, ethyl, propyl, butyl, pentyl or hexyl) and the alkanolamine comprises a substance selected from the group consisting of monoethanolamine, triethanolamine, Aminoethylethanolamine, N-decylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, 1-amino-2-propanol and Isobutanolamine. In a preferred embodiment, the removal composition of the present invention comprises, consists of, or consists essentially of diethylene glycol monobutyl ether, sulfolane, and triethanolamine: HF. In still another preferred embodiment, the removal composition of the present invention comprises, consists of, or consists essentially of from about 60 to about 80% by weight based on the total weight of the composition. Diethylene glycol monobutyl ether, about 15 to about 25% by weight of sulfolane and about 5 to about 15% by weight of triethanolamine: HF (which may have a certain percentage of water present due to the preparation of the TEA:HF complex) ). In a particularly preferred embodiment, the removal composition of the present invention comprises about 7% by weight, based on the total weight of the composition, of diethylene glycol monobutyl hydrazine, about 20% by weight sulfolane, and about 1% by weight. Triethanolamine: HF (73%) In each of the examples, the composition may further comprise a polymeric coating material residue, consist of or consist essentially of a polymeric coating material residue. The layer material residue (whether dissolved and/or suspended in the composition) may comprise at least one compound (whether monomer or polymerized) of the above primer layer, photosensitive layer or combination thereof. In another embodiment of the invention, Providing a concentrated liquid removal composition that can be diluted for use as a removal solution. Concentrated composition or "concentrate" conveniently allows 136561.doc -16 - 200934865 to allow the user (eg, a program engineer) to dilute the concentration at the time of use The dilution of the concentrated removal composition can range from about 1:1 to about 1 :1, wherein the removal composition is diluted with at least one organic solvent on the tool or just prior to the tool. In terms of The concentrate may be formulated to include an etchant and at least one organic solvent for transport to processing. The user may dilute the concentrate with at least one organic solvent or a different organic solvent during processing. The liquid removal composition of the present invention is readily The individual components are simply added and mixed to a uniform state for formulation. Further, the liquid removal composition can be readily formulated as a single package formulation, or formulated as a multi-part formulation that is mixed during use or prior to use, such as a multi-part formulation. Individual portions may be mixed in an upstream storage tank of the tool or tool. In the broad practice of the invention, the concentration of the individual ingredients may vary widely in a particular plurality of liquid removal compositions, i.e., more dilute or more concentrated, and It will be appreciated that the liquid removal compositions of the present invention may, in addition and in the alternative, comprise any component group consistent with the disclosure herein, consisting of any combination of ingredients consistent with the disclosure herein, or substantially consisting of any ingredients consistent with the disclosure herein. Combination composition. Therefore, another aspect of the invention relates to a kit comprising one or Preferably, one or more of the containers are suitable for forming a composition of the composition of the invention. The kit comprises at least one organic solvent and at least one etchant in one or more containers for immediate processing or use. Or the kit may comprise at least one organic solvent and at least one etchant in one or more containers for combining with at least one organic solvent during processing or during use, wherein the at least one organic solvent in the container And the at least one organic solvent added during processing or at the time of use may be the same or different from each other. c S1 136561.doc • 17· 200934865 The container of the set must be suitable for storing and carrying the removal composition, for example, NOWPak® Container (Advanced Technology Materials, Inc., Danbury, Conn., USA). The one or more containers containing the components of the removal composition preferably comprise means for fluidly communicating the components of the or the containers for blending and dispensing. By way of example, referring to a NOWPak® container, gas pressure can be applied to the outside of the liner in the or such container such that at least a portion of the contents of the liner are unloaded and thereby enable fluid communication for blending And distribution. Alternatively, gas pressure may be applied to the headspace of a conventional pressurizable container or a pump may be used to enable fluid communication. Additionally, the system preferably includes a dispensing opening for dispensing the blended removal composition to the processing tool. It is preferred to use a polymeric film material that is substantially chemically inert, free of impurities, flexibility and elasticity, such as high density polyethylene, to make the liner of the container or containers. The desired liner material is processed without the need for coextrusion or barrier layers and without any pigment, UV inhibitor or process agent that can adversely affect the purity requirements of the components to be disposed in the liner. The list of desirable liner materials includes raw (without additives) polyethylene, original polytetrafluoroethylene (PTFE), polypropylene, polyamine phthalate, polyvinylidene gas, polyethylene, polyacetal, A film of polystyrene, polyacrylonitrile, polybutene or the like. The preferred thickness of the liner material ranges from about 5 mils (0.005 inch) to about 30 mils (0.030 inch), for example, 20 mils (0.020 inch).

With respect to the containers used in the kits of the present invention, the disclosures of the following patents and patent applications are hereby incorporated by reference in their entirety in their entireties in U.S. Patent No. 7,188,644, entitled "APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE

136561.doc 18- 200934865 LIQUIDS"; US Patent No. 6,698,619, entitled "RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM"; and in the name of John EQ·Hughes, May 9, 2007 U.S. Patent Application Serial No. 60/916,966, entitled "SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION". When applied to microelectronic device fabrication operations, the liquid removal compositions of the present invention are effectively utilized to remove polymeric protective coatings, such as spin-on protective coatings, from the surface of the microelectronic device. Importantly, the liquid removal compositions of the present invention coexist with underlying layers (e.g., metal and tantalum) that are also present on the microelectronic device. Preferably, the liquid removal composition removes at least 85% of the polymeric protective coating to be removed present on the device, more preferably at least 90%, even more preferably at least 95%, and optimally at least 99% of the desired to be removed The polymeric protective coating is removed from the surface of the microelectronic device. Thus, in another aspect, the present invention is directed to a method of removing a polymeric protective coating (e.g., a spin-on protective coating) from a microelectronic device using the liquid removal composition described herein. Those skilled in the art will appreciate that the compositions described herein can be used in a single or multiple step removal process. Preferably, the polymeric protective coating is removed in a single step process. It is easy to formulate the liquid removal composition of the present invention by simply mixing the ingredients in a mixing container or a cleaning container, for example, under gentle agitation. In a removal application, the liquid removal composition is applied to the microelectronic device having the polymeric protective coating thereon in any suitable manner, such as by spraying the composition onto the surface of the device by dipping ( In a large number of the compositions) 136561.doc •19- 200934865

A device comprising a polymeric protective coating by contacting a device with another material, such as a lining or fiber sorbent applicator member, the material absorbing the composition thereon' by including a polymeric protective coating The device is in contact with the circulating composition' or any other suitable method, manner or technique by contacting the liquid removal composition with the polymeric protective layer on the microelectronic device. The removal application can be static and/or detached, as is readily apparent to those skilled in the art. In addition, the process can be used in batch or single wafer systems. After contacting the liquid removal composition with the polymeric protective layer, the liquid removal composition further comprises a suspension of the polymeric protective coating described above which is releasable and/or; The use of the compositions of the present invention to remove the polymeric protective coating from a microelectronic device having a polymeric protective coating thereon, such as in the range of from about 2.77 to about 1 pit, (4) to about 6 (TC to range) The liquid removal composition is contacted with the apparatus for a sufficient period of time from about 1 minute to about 60 minutes under sufficient conditions of temperature, preferably from about 5 minutes to about 40 minutes, and preferably from about 1 to about 10 minutes to about % of the contact time and The temperature is illustrative and any other suitable time and temperature conditions effective to at least partially remove the polymeric coating from the device may be used within the broad practice of the invention. "At least partially removed _Previously present on the device (4) Layer 'better at least 95%, and optimally at least 99 〇/〇. After achieving the desired cleaning effect, as may be required or effective in the end use application of the composition of the invention' The liquid removal composition can be readily removed (e.g., rinsed) from previously applied devices. For example, the device can be methanol*propanol, ethylene glycol, water, water' surfactant mixture or 13656 丨.doc - 20· 200934865 Its combination Thereafter, the apparatus can be dried using nitrogen, a centrifugal drying cycle, or steam drying. It will be appreciated that the specific contact conditions for the liquid removal compositions of the present invention based on the disclosure herein can be readily determined within the skill of the art. And the particular ratio of ingredients and the concentration of the ingredients in the compositions of the present invention can vary widely while achieving the desired removal of the polymeric protective coating on the surface of the microelectronic device. Yet another aspect of the present invention pertains to the present invention. Improved microelectronic devices fabricated by the method and products containing the microelectronic devices. A further aspect of the invention relates to a method of fabricating an article comprising a microelectronic device, the method comprising: removing the microelectronic device from the liquid removal composition Contacting a time sufficient to remove the polymeric protective coating from a microelectronic device having a polymeric protective coating thereon, and incorporating the microelectronic device into the article, wherein the removal composition comprises the following, Each composition consists or consists essentially of at least one organic solvent and at least one etchant source. Liquid removal combination The polymeric coating material may further comprise, consist of, or consist essentially of a polymeric coating material. Another aspect of the invention pertains to a composition comprising, consisting of, or consisting essentially of a finished article comprising: a substrate of a microelectronic device, at least one of an undercoat layer and a photosensitive layer deposited on the substrate, and a source comprising at least one organic solvent and at least one etchant, at least one organic solvent and at least one etch The liquid source composition consists of or consists essentially of at least one organic solvent and at least one source of money engraving. In one embodiment of this aspect, the liquid removal composition comprises the following 13656I.doc 200934865, It consists of or consists essentially of diethylene glycol monobutyl ether, sulfolane and triethanolamine: HF. • In another aspect, the invention relates to a method of removing the polymeric protective coating from a microelectronic device having a polymeric protective coating thereon, the method further comprising microelectronics after removal of the polymeric protective coating The surface of the device is contacted with the rework composition to render the surface hydrophilic, wherein natural oxides are grown on the surface in the presence of the rework composition. The rework composition includes a composition comprising hydrogen peroxide and other peroxides, and a gas comprising oxyhydrogen gas and ozone. After processing, the composition of the present invention can be further processed in a manufacturing facility to reduce the chemical oxygen demand (c〇D) of the wastewater stream. For example, a formulation containing an organic solvent and an inorganic biotoxic compound such as fluoride can be treated by: (1) carbon, preferably polyvinylidene gas (PVDC) having a pore size less than 丨 nm wide. Monomer carbon, which will be derived from the composition "scouring" organic solvent, (2) a metal carbonate such as an alkali metal or alkaline earth metal carbonate which reacts with fluoride ions and neutralizes any acid present, and / or (3) Calcium citrate, such as CasSiOrCkSiCU.xI^O, which reacts with fluoride ions and neutralizes any acid present. These treatments can be carried out continuously or in a single-step mixed bed process. The treated wastewater stream should be exposed to treatment until c〇d is reduced to an acceptable level for publication. The features and advantages of the present invention are more fully described by the following non-limiting examples in which all parts and percentages are by weight unless otherwise indicated. Example 1 I36561.doc -22- t S1 200934865 The core substrate having a polymeric smear coating comprising a decane undercoat layer and a sensitized layer was statically impregnated at 80 ° C as described herein. Formulation A Duration - 30 minutes. After the impregnation, the device substrate was rinsed with deionized water and dried with nitrogen. Scanning electron micrographs of the substrate of the dryer showed that the undercoat layer and the photosensitive layer were removed in a single step, in which the undergrowth was negligible; the pits were not observed and the particulate material remained on the surface. Corrosion measurements were performed to thereby immerse the wafer including the surface layer Cu, a milk, and Si in the formulation A at 80 ° C and use a Tafel curve to determine the rot rate of the surface layer materials. The corrosion rates of Cu, A, Ni, and Si were measured within 4.59, 5.12, 7.33, and 1.63, respectively, in terms of A min·丨. This indicates the compatibility of the formulation with the underlying material of the microelectronic device. The present invention has been disclosed herein with reference to illustrative embodiments and features, but it is understood that the embodiments and features described above are not intended to limit the invention, and that those skilled in the art will Other variations, changes, and other embodiments. Therefore, it is intended that the present invention cover the modifications and modifications of the embodiments of the invention. 136561.doc -23-

Claims (1)

200934865,, X. Patent application: • κ _ 移 移 i composition '彡 contains at least one organic; a container and at least one species (four) agent source 'where the removal composition is suitable for having a polymeric material from above The material is removed from the microelectronic device. 2. The removal composition of claim 1, wherein the at least one etchant comprises a fluoride source. 3. The removal composition of claim 2, wherein the at least one fluoride source comprises a group selected from the group consisting of: Substance: hydrogen fluoride, fluocenoate (H2SiF6), fluoroboric acid, tetrabutylborate tetrafluoroborate (TBA-BF4), ammonium fluorite (NHJjjSiF6), tetramethylammonium hexafluorophosphate, ammonium fluoride, Tetraalkylammonium fluoride, alkyl hydrogen fluoride, ammonium hydrogen difluoride (NH5F2), hydrogen fluoride, second courtyard, hydrogen fluoride, three-burning base, gasification, trihydrogenation, π-bite _hf complex, dimethyl 0 ratio bite-HF complex, 2-ethyl group than bite-HF complex, 2-decyloxy 0-bite-HF complex, 2-methyl n-bite-HF complex, σ-pyridine derivative -HF complex, piperidine-HF complex, piperazine-HF complex, triethylamine-HF complex, triethanolamine-HF complex, PMDETA-HF ruthenium complex, diglycolamine-HF complex, Monoethanolamine-HF complex, pyrrole-HF complex, isoxazole-HF complex, 1,2,4-triazole-HF complex, two "bite-HF complex, mouth bite-HF complex , 吼°Q-HF complex, Jian-HF complex, 啥-HF complex, iso- lin-HF complex, 吲哚-HF complex, imidazole-HF complex, ethylamine-HF complex , methylamine-HF complex, isobutylamine-HF complex, third butylamine-HF complex, tributylamine-HF complex, dipropylamine-HF complex, dimethylamine-HF complex, 1 - Mercapto imidazole-HF complex, diisopropylamine-HF complex 136561.doc 200934865 compound, diisobutylamine_HF complex, aniline-HF complex, aniline derivative-HF complex, N_mercaptomorpholine ·Ν_Oxide (Nmm〇)-HF composite, trimethylamine-N-oxide-HF composite, triethylamine-N-oxide-HF composite, pyridine oxide-HF composite, N-B Mymorpholine-N-oxide-HF complex, N_mercaptopyrrolidine_N•oxide·111? complex, N-ethylpyrrolidine_N_oxide_HF complex, difluorination氙 (XeF2) and its combination. ❹ 4. The removal composition of claim 2, wherein the fluoride source comprises a triethanolamine:HF complex. 5. The removal composition of claim 1, wherein the at least one organic solvent comprises a material selected from the group consisting of substituted aliphatic hydrocarbons, unsubstituted aliphatic alkanes, substituted cyclic alkanes Unsubstituted cyclic hydrocarbons, aromatics, alcohols, glycols, triols, functional alcohols, ethylene glycol mysteries, carbonic acid, decylamine, „bitenone, phthalate, B 6. The removal composition of any one of claims 1 to 4, wherein the at least one organic solvent comprises a substance selected from the group consisting of toluene, Phthalate, hexane (hexane, hexanes), octane, diphenylbenzene, odorless ore from fine (petroleum), mineral spirits (hydrotreated naphtha), phenoxy 2 propanol, propylbenzene Ketone, cyclohexane, perfluoro-1,2-dimethylcyclobutane, 1,2-dimethylcyclohexan, perfluoroadol, methanol, ethanol, A " internal alcohol, isopropanol , 1-butanol, 2-butanol, 3-mercapto-indolyl butanol, allyl alcohol, pentanol, glycol, triol, and ^^/yibu octafluoro-indole-pentanol ,, 1H, 1H, 9 H-perfluoro-1-nonanol, perfluoroheptanoic acid, 1 h, 1 h, 7 h T difluoro-136561.doc -2- 200934865 1-heptanol, perfluoropentanoic acid, 111,111,811,811-ten Difluoro-1,8-octanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 5H-perfluoropentanoic acid, heptafluorobutyric acid Butyl ester, 3-chloro-1,2-propanediol, 3-gas-1-propanethiol, 1-chloro-2-propanol, 2-a-1-1-propanol, 3-a-1-1-propanol, 3-bromo-1,2-propanediol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-iodo-1-propanol, 4-ox-1-butanol, 2-gas ethanol , tetrahydrofuran (THF), N-decylpyrrolidone (NMP), N-octylpyrrolidone, N-phenylpyrrolidone, methyl formate, ethyl decanoate, propyl formate, butyl formate , 2-butanone, 3-pentanone, dimethylformamide (DMF), dimethylene; 13⁄4 (DMSO), methyl sulfide, ethanethiol, tetramethylene sulfone, sulfolane, dimethyl Stone wind, diethylene stone, bis(2-hydroxyethyl) sulfone, decyl cyclobutyl hydrazine, ethyl sulfolane, diethyl ether, lactic acid ethyl acetate, ethyl acetate, propylene acetate, isobutyl acetonate, butyric acid Methyl ester, ethyl butyrate, ethyl benzoate, acetonitrile, methyl isobutyl Ketone, mercaptoethyl ketone, methyl propyl ketone, propylene glycol, ethylene glycol, propylene 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, tripropylene glycol oxime ether, dipropylene glycol dimethyl sulfonate, dipropylene glycol diethyl 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, diterpene, butyrolactone, butylene carbonate, ethylene carbonate, carbonic acid Propylene diester, acetic acid, trifluoroacetic acid, and combinations thereof. 136561.doc 200934865 The removal composition of any of the items 1 to 4 wherein the organic solvent comprises 3-ethylene glycol monomethyl ether and sulfolane. The removal composition of any of claims 4, wherein the composition is substantially free of added water. 9. A composition for removal according to π, i, comprising diethylene glycol monomethyl shim, cyclobutyl milling and triethanolamine: HF complex. 10. The removal composition of claim 1, further comprising a polymeric material residue. 11. The removal composition of claim 1, wherein the polymeric material residue comprises a material selected from the group consisting of: a silk alkaloid, an aminoalkyl alkoxy decane, an anilino group Alkyl alkoxy decane, phenyl oxime, diphenyl sinter, 3-[N-anilino]propyltrimethoxy sulphide, n-dimethoxyxanthyl] propylethylenediamine, benzene An acetamyl polymer, an acrylonitrile monomer, a monomer comprising a functional group reactive with an amine, and combinations thereof. 12. A removal composition comprising two organic solvents and at least one residual agent ’ source' wherein the removal composition is adapted to remove the material from a microelectronic device having a polymeric material thereon. 13. The removal composition of claim 12, wherein the composition is substantially free of added water. 14. The removal composition of claim 12 which consists of diethylene glycol monomethoate and triethanolamine:HF complex. 15. A removal composition comprising two organic solvents, a source to a sputum smear agent, and a residue of a polymeric material, wherein the removal composition is adapted to be removed from a microelectronic device having a polymeric material thereon The material. 136561.doc 200934865 16. The removal composition of claim 15 wherein the composition is substantially free of added water. 17. The removal composition of claim 15 which consists of diethylene glycol monomethyl shim, cyclobinder wind, diethanolamine:HF complex and polymeric material residue. 18. The removal composition of any one of claims 15-17, wherein the polymeric material residue comprises a material selected from the group consisting of: an amino alkoxylate, an amine alkyl alkoxy Base decane, anilinoalkyl alkoxy fluorene, phenyl decane, diphenyl decane, 3-[1^anilino]propyltrimethoxy decane, N-[3-trimethoxyoxyalkylene] Propyl ethylenediamine, a styrene polymer, an acrylonitrile monomer, a monomer comprising a functional group reactive with an amine, and combinations thereof. 19. A method of removing a material from a microelectronic device having a polymeric material thereon, the method comprising contacting the germanium electronic device with a removal composition under conditions sufficient to at least partially remove the material from the microelectronic device a time sufficient to at least partially remove the material from the microelectronic device, wherein the removal composition comprises at least one organic solvent and at least one etchant. 20. The composition of about 20 ° C to about the method of claim 19, Wherein the contact comprises a condition selected from the group consisting of: a time of from about 1 minute to about 6 minutes; a temperature in the range of 150 C; and combinations thereof. Wherein the source of etchant comprises at least one fluorine. 21. The source of the method of claim 19. 22. The method of claim 21, wherein the following components are comprised of the at least one fluoride source comprising a selected group of: hydrogen fluoride, fluorite 136561.doc 200934865 (H2SiF6), fluoroboric acid, tetrafluoroborate tetrabutylate Ammonium (TBA-BF4), ammonium fluoroantimonate ((NH4)2SiF6), tetramethylammonium hexafluorophosphate, ammonium fluoride, tetraalkylammonium fluoride, alkyl hydrogen fluoride, ammonium hydrogen difluoride (NH5F2), hydrogen fluoride Dialkyl sulphide, hydrogen trifluoride, fluorinated trihydrogen tricarbide, bite _ HF complex, lutidine-HF complex, 2-ethylpyridine-HF complex, 2-oxo Pyridine-HF complex, 2-methylpyridine-HF complex, β-bite derivative-HF complex, piet-HF complex, Pyrene-HF complex, triethylamine-HF complex, III Ethanolamine-HF complex, PMDETA-HF complex, diglycolamine-HF complex, monoethanolamine-HF complex, pyrrole-HF complex, isoxazole-HF complex, 1,2,4-triazole -HF complex, two alpha ratio bite-HF complex, mouth bite-HF complex, ° 嗓-HF complex, chlorazine-HF complex, 啥琳-HF complex, isoquino-HF complex吲哚-HF complex, imidazole-HF complex, ethylamine-HF complex, guanamine-HF complex, isobutylamine-HF complex, third butylamine-HF complex, tributylamine-HF complex , dipropylamine-HF complex, diamine-HF complex, 1-methylimidazole-HF complex, diisopropylamine-HF complex, diisobutylamine-HF complex, aniline-HF complex, Aniline derivative-HF complex, Ν-methylmorpholine-Ν-oxide (NMMO)-HF complex, tridecylamine-N-oxide-HF complex, triethylamine-N-oxide-HF Complex, pyridine-N-oxide-HF complex, N-ethylmorpholine-N-oxide-HF complex, N-decylpyrrolidinium-N-oxide-HF complex, N-ethyl a pyrrolidine-N-oxide-HF complex, xenon difluoride (XeF2), and combinations thereof; and wherein the at least one organic solvent comprises a substance selected from the group consisting of 136561.doc 200934865: alcohol, binary Alcohol, trihydric alcohol, glycol ether, carbonic acid vinegar, decylamine, pyrrolidone, formate, acetate, ketone, ethylene glycol, and combinations thereof. 23. The method of claim 19, further comprising Rinse the rinse composition Microelectronic device. 24. The method of claim 23, wherein the rinse composition comprises water. 25. The method of claim 23, further comprising drying the microelectronic device after contact with the rinsing composition. The method of claim 23, wherein the removing composition further comprises a polymeric material residue. 27. The method of claim 26, wherein the polymeric material residue comprises a material selected from the group consisting of: amino alkoxydecane, aminoalkyl alkoxy decane, anilinoalkyl alkoxy Base decane, phenyl decane, diphenyl decane, 3-[indolyl-anilino]propyltrimethoxydecane, ruthenium [3-trimethoxydecyl]propylethylenediamine, styrene polymer, propylene Nitrile monomer, monomer comprising a functional group reactive with an amine, and combinations thereof. 28. A removal composition consisting of a diethylene glycol single-chamber (IV), a compound and an alkanolamine:HF complex, wherein the alkyl group is.丨·. a group, and wherein the removal composition is adapted to remove the material from a device having a polymeric material thereon. The removal composition of claim 28, wherein the (tetra)amine comprises a substance selected from the group consisting of monoethanolamine, triethanolamine, aminoethanolamine, guanidine-methylamine oxime ethanol, amine Ethyl ethoxyethanol, dimethylamine ethoxyethanol, diethanolamine, decyl monoethanolamine, hydrazine-amino group 2_ 136561.doc 200934865 'Alcohol and isobutanolamine. 3. The removal composition of claim 28 or 29, wherein the hard compound comprises a substance selected from the group consisting of cyclobutanil, dimethyl sulphate, diethyl sulfoxide, bis (2-hydroxyl) Ethyl) hydrazine, methylcyclobutyl hydrazine, ethylcyclobutyl hydrazine and combinations thereof. The removal composition of claim 28, wherein the amount of the diethylene glycol monoalkyl ether is in the range of from about 60% by weight to about 80% by weight, based on the total weight of the composition, The amount of the sulfone compound ranges from about 15% by weight to about 25% by weight, and the amount of the alkanolamine:HF complex is about 5 weight%. Straight to about 15% by weight. I36561.doc 200934865 VII. Designated representative map: r (1) The representative representative figure of this case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the characteristics that can best display the invention. Chemical formula: (none) 136561.doc